Characterization of Low Melting Temperature, Low-Ag,

Bi-Containing, Pb-Free Solder Alloys

by

Eva Kosiba

A thesis submitted in conformity with the requirements

for the degree of Masters of Applied Science
Materials Science and Engineering
University of Toronto

© Copyright by Eva Kosiba 2016

 Characterization of Low Melting Temperature, Low-Ag, Bi-
Containing, Pb-Free Solder Alloys

Eva Kosiba

Masters of Applied Science

Materials Science and Engineering

University of Toronto

2016

Abstract
Restrictions of lead in solder lead to adoption of SAC305 in consumer products. While

high reliability applications use SnPb, supply constraints are driving the adoption of a

replacement. SAC305 has reliability concerns related to elevated process temperatures

and the formation of Ag3Sn.

Reliability performance of three low-Ag, Bi-containing, low melting temperature alloys

were compared to SAC305. All three alloys under test performed as well or better for

consumer applications. Drop testing and accelerated thermal cycling revealed no

differences that would preclude use of these alloys in production. They allow for the use

of lower Tg printed wire boards materials, which have been shown reliable.

These alloys show promise for high reliability applications. In accelerated thermal

cycling, all alloys outperformed the circuit boards. Bi precipitation resulted in less

degradation to the bulk microstructure. Bi did not impact the IMC formation or growth, a

small amount of Ag mitigated growth of Cu3Sn.

ii
 Acknowledgments
I would like to express my gratitude to Professor Doug Perovic, Dr Polina Snugovsky

and John McMahon for their guidance, generosity and support. Their knowledge of

various aspect of this research was an inspiration.

I would also like to thank Lorna Devereux and Marianne Romansky for reading through

the many revisions and offering clarity to my often confusing prose. The following

people provided much laboratory assistance and support for which I am grateful: Russell

Brush, Subramaniam Suthakaran, Michael Thomson, Hissan Syed, André Delhaise and

Salvatore Boccia. I would also like to thank Professor Erb and Professor Wang for

agreeing to participate on the review committee on short notice.

Finally I would like to acknowledge the support of the Quality and Reliability Laboratory

at Celestica and the Department of Materials Science and Engineering at the University

of Toronto.

iii
 Table of Contents

Abstract… ................................................................................................................... ii
Acknowledgments ..................................................................................................... iii
List of Tables ............................................................................................................ vii
List of Figures ............................................................................................................ ix
List of Acronyms ..................................................................................................... xiii

Chapter 1 Background ................................................................................................ 1

1 Introduction ................................................................................................. 1
2 Need for New Low Melt Solder.................................................................. 2
2.1 Legislative Changes .................................................................................... 2
2.2 SAC305 and Current Issues with Existing Alloys ...................................... 3
2.3 Search for Replacement Solder ................................................................... 6
2.3.1 Binary Alloys .............................................................................................. 6
2.3.2 Ternary and higher order alloy options ....................................................... 9
2.4 Celestica’s Low Melt Solder Research Program ...................................... 12
2.4.1 Phase 1: Alloy Selection ........................................................................... 13
2.4.1.1 Requirement Formulation ......................................................................... 14
2.4.1.2 Literature Search and Phase Diagram Analysis6 ...................................... 15
2.4.1.3 Preliminary Alloy Selection6 .................................................................... 20
2.4.1.4 Metallurgical Analysis: DSC and Microstructural Evaluation6 ................ 21
2.4.2 Phase 2: Manufacturing Feasibility Study ................................................ 25
2.4.3 Phase 3: Screening Experiments ............................................................... 25
2.4.3.1 Aerospace and Defense, ............................................................................ 26
2.4.3.1.1 Screening Experiment Structure ............................................................... 27
2.4.3.1.2 Microstructural Assessment ...................................................................... 28
2.4.3.1.3 Accelerated Thermal Cycling (ATC)........................................................ 29
2.4.3.1.4 Vibration ................................................................................................... 33
2.4.3.1.5 Summary of Findings ................................................................................ 34
3 Objective of Thesis: Low Melt Solders for Consumer Sector .................. 34
4 References ................................................................................................. 37

Chapter 2 Solder Joints after Reflow (As Manufactured) ........................................ 41

1 Introduction ............................................................................................... 41
2 Bulk Solder Microstructure – Solidification Process................................ 41
2.1 Cu Dissolution in Molten Solder .............................................................. 41
2.2 Bulk Solder Solidification......................................................................... 43
2.3 Undercooling During Solidification ......................................................... 45
2.4 Formation of Facetted IMCs in Bulk Solder............................................. 47
2.5 Bi in Solution and as a Precipitate ............................................................ 48
3 Sn-Cu Reaction and Formation of Interfacial IMC .................................. 49
4 Cu-Ni-Sn Interface .................................................................................... 53
iv
5 Experimental Set Up ................................................................................. 54
5.1 Test Vehicle Assembly ............................................................................. 54
5.2 Test Matrix ................................................................................................ 55
5.3 Test Method .............................................................................................. 56
6 Microstructural Evaluation ....................................................................... 56
6.1 Comparison of Bulk Microstructure ......................................................... 56
6.1.1 Bulk Microstructure of QFP Solder Joints................................................ 57
6.1.2 Bulk Microstructure of BGAs ................................................................... 61
6.2 Comparison of Interfacial IMC Layers ..................................................... 67
7 Summary of Findings ................................................................................ 73
8 References ................................................................................................. 74

Chapter 3 Accelerated Thermal Cycling................................................................... 77

1 Accelerated Testing for Reliability Analysis ............................................ 77
2 Microstructural Evolution ......................................................................... 82
2.1 Changes to Bulk Solder ............................................................................ 82
2.2 Changes to Interfacial IMC during Accelerated Thermal Cycling ........... 85
2.3 Effects of Bi .............................................................................................. 86
3 Experimental Setup ................................................................................... 87
3.1 Materials ................................................................................................... 88
3.2 Test Vehicle .............................................................................................. 89
3.3 Test Strategy ............................................................................................. 90
3.3.1 0-100C Thermal Cycling ......................................................................... 91
3.3.2 Harsh Environment (-55C to 125C) Thermal Cycling .......................... 92
3.4 Post ATC Evaluation and Failure Analysis .............................................. 93
4 Results ....................................................................................................... 94
4.1 Reliability and Failure Analysis Results ................................................... 94
4.1.1 0C to 100C Accelerated Thermal Cycling............................................. 94
4.1.2 -55C to 125C Accelerated Thermal Cycling ....................................... 101
4.2 Microstructure Evaluation ...................................................................... 109
4.2.1 Bulk Microstructure ................................................................................ 109
4.2.2 IMC Growth during Thermal Cycling .................................................... 111
5 Summary of Findings and Conclusions .................................................. 122
5.1 Findings Based on Reliability Data ........................................................ 122
5.2 Findings Based on Microstructural Observations ................................... 122
6 References ............................................................................................... 124

Chapter 4 Tin Whisker Testing ............................................................................... 126

1 Introduction ............................................................................................. 126
1.1 Whisker Growth Kinetics ....................................................................... 128
1.2 Sources of Compressive Stress ............................................................... 130
1.3 Morphology of Sn Whiskers ................................................................... 132
1.4 The Effects of Bi in Solder on Whisker Formation ................................ 133
2 Experimental Set Up ............................................................................... 135
2.1 Materials ................................................................................................. 136
v
2.2 High Temperature High Humidity .......................................................... 136
2.3 Thermal Shock ........................................................................................ 137
2.4 Post Exposure Evaluation ....................................................................... 138
3 Results ..................................................................................................... 139
3.1 High Temperature High Humidity Results ............................................. 139
3.2 Thermal Shock Results ........................................................................... 139
4 Summary of Findings and Conclusions .................................................. 152
5 References ............................................................................................... 154

Chapter 5 Mechanical (Drop) Shock Testing ......................................................... 156

1 Introduction ............................................................................................. 156
2 Experimental Set Up ............................................................................... 157
2.1 Materials ................................................................................................. 158
2.2 Test Vehicle ............................................................................................ 158
2.3 Assembly................................................................................................. 160
2.4 Test Strategy ........................................................................................... 160
3 Reliability Results ................................................................................... 164
4 Failure Analysis and Microstructural Evaluation ................................... 168
4.1 Dye and Pry Procedure ........................................................................... 169
4.2 Failure Isolation Procedure ..................................................................... 169
4.3 Evaluation of High Tg Board after Drop Testing .................................... 169
4.4 Evaluation of Normal Tg Board after Drop Testing ............................... 173
5 Summary of Findings and Conclusion .................................................... 175
6 References ............................................................................................... 177

Chapter 6 Summary of Findings and Conclusions ................................................. 178

Chapter 7 Future Work ........................................................................................... 182

1 Celestica/Indium Sponsored Whisker Resistant Solder Paste ................ 182
2 ReMap M1: Lower Temperature Soldering Alloys with Improved
Mechanical and Thermal Fatigue Reliability.......................................................... 184
3 ReMap M2: Alloys, Board and Component Surface Finish Interactions
with Reduced Propensity for Whisker Growth ....................................................... 184
4 ReMap M3: Aging Effect of New Lead-Free Materials on Reliability .. 186
5 References ............................................................................................... 190

vi
 List of Tables
Table 1: Sn-based eutectic alloys ........................................................................................ 8
Table 2: Preliminary alloy selection10,6............................................................................. 21
Table 3: DSC analysis of proposed alloys with 75% SAC305 ......................................... 23
Table 4: Alloys for screening experiments ....................................................................... 26
Table 5: Latin square of paste and finish, and board materials ........................................ 27
Table 6: Build matrix showing number of assemblies...................................................... 28
Table 7: Resultant BGA interconnect composition .......................................................... 29
Table 8: ATC failures on 170C Tg board material .......................................................... 30
Table 9: Reliability results on 170C Tg boards after ATC .............................................. 31
Table 10: ATC failures on 150C Tg board material ........................................................ 31
Table 11: Reliability results on 150C Tg boards after ATC ............................................ 32
Table 12: Vibration failures after 2G testing .................................................................... 33
Table 13: Vibration failures after 5G testing .................................................................... 34
Table 14: Consumer alloys under test ............................................................................... 36
Table 15: Build matrix for as assembled analysis ............................................................ 55
Table 16: Table of components evaluated by cross sectioning......................................... 55
Table 17: Composition of QFPs (wt%) ............................................................................ 57
Table 18: Experimental composition of BGA solder joint ............................................... 62
Table 19: Theoretical composition of BGA solder joint .................................................. 62
Table 20: Results of ANOVA test for equal variance and compare means of IMC
thickness of the BGA IMC layer ...................................................................... 69
Table 21: Results of ANOVA test for equal variance and compare means of IMC
thickness of the QFP IMC layer........................................................................ 70
Table 22: IMC type ........................................................................................................... 71
Table 23: Sample of temperature cycling requirements Table 4-1 in IPC-9701A6 .......... 81
Table 24: Worst case use environments of SMT6 ............................................................. 81
Table 25: Build matrix for ATC testing ............................................................................ 89
Table 26: Monitored components for ATC testing ........................................................... 90
Table 27: Test matrix for 0C to 100C ATC ................................................................... 91
Table 28: Test matrix for -50-125C ATC ....................................................................... 92
Table 29: Summary of QFP failures after 0C to 100C ATC ......................................... 95
Table 30: Summary of BGA failures after 0C to 100C ATC ........................................ 99
Table 31: Summary of QFP failures after -55C to 125C ATC .................................... 102
Table 32: Summary of BGA failures after -55C to 125C ATC ................................... 105
Table 33: Results of Levine-Test to compare the variance () of IMC measurement and
2-sided t-Test to compare the means (µ) of IMC measurements .................... 115
Table 34: Results of Levine-Test to compare the variance () of Cu3Sn measurement and
2-sided t-Test to compare the means (µ) of Cu3Sn measurements ................. 115
Table 35: Results of ANOVA test to equal variance and compare means ..................... 116
Table 36: CTE values for common materials in solder joints ........................................ 131
Table 37: JESD22A121.01 test conditions4 .................................................................... 135
Table 38: Alloys screened for whisker growth ............................................................... 136
vii
Table 39: Summary of whisker growth after 1610 cycles thermal shock....................... 140
Table 40: Results of ANOVA test for equal variance and compare means of IMC
thickness of the QFP IMC layer after 1610 cycles thermal shock. ................. 149
Table 41: Build matrix for drop shock testing ................................................................ 158
Table 42: Monitored components for drop testing ......................................................... 160
Table 43: Drop test results .............................................................................................. 166
Table 44: Failures of BGA on High Tg boards ............................................................... 171
Table 45: Failures of BGA on Normal Tg boards .......................................................... 174
Table 46: Solder paste test matrix ................................................................................... 183
Table 47: ReMap M2 test matrix .................................................................................... 186
Table 48: ReMap M3 test matrix .................................................................................... 189

viii
 List of Figures
Figure 1: Schematic of a BGA solder joint ......................................................................... 1
Figure 2: Image of a QFP solder joint3 ............................................................................... 2
Figure 3: Pad crater defect seen in a) cross section – indicated by arrows, and b) viewed
from above .......................................................................................................... 4
Figure 4: Ag3Sn platelets seen in a) cross sectioned solder joint and b) SEM image of
solder joint after removal of Sn phase .............................................................. 5
Figure 5: Sn Whisker growing from SAC305 solder ......................................................... 6
Figure 6: Sn-Cu phase diagram........................................................................................... 7
Figure 7: a) SAC ternary phase diagram and b) Sn-rich corner of SAC ternary phase
diagram ............................................................................................................. 11
Figure 8: Head in pillow defect ........................................................................................ 12
Figure 9: a) gull wing leaded solder joint, b) BGA solder joint ....................................... 13
Figure 10: Solder joint formed with leadless component ................................................. 15
Figure 11: SnBi phase diagram ......................................................................................... 16
Figure 12: a) SnAgBi ternary phase diagram and b) Sn-rich corner of SnAgBi phase
diagram ............................................................................................................. 17
Figure 13: a) SnCuBi ternary phase diagram and b) Sn-rich corner of SnCuBi phase
diagram ............................................................................................................. 18
Figure 14: Example of ternary phase diagram31 ............................................................... 19
Figure 16: DSC scan of Sn20%Bi10, ................................................................................. 22
Figure 17: Microstructure of solder joint formed with SAC305 solder ball and a no-Ag
solder paste alloy6 ............................................................................................. 25
Figure 18: Honeywell test vehicle, medium complexity board ........................................ 26
Figure 19: Example of wetting on OSP, QFP240 ............................................................. 28
Figure 22: New approach proposing to use solder with no or low-Ag content ................ 35
Figure 23: Typical reflow profile for SAC305 ................................................................. 42
Figure 24: Copper dissolution of BGA solder joint after a) 1 replacement b) 3
replacements and c) 5 replacements ................................................................. 43
Figure 25: SnAgCu phase diagram with SAC305 equilibrium solidification path .......... 44
Figure 26: A 3D phase diagram of Sn rich portion of Sn-Ag-Cu ternary system ............ 46
Figure 27: SAC solder joint viewed a) in cross section and b) after selective
electrochemical etching to remove Sn phase .................................................. 48
Figure 28: Solder joint between Sn-based solder and Cu a) rod shaped Cu6Sn5 () ...... 50
Figure 29: SnPb solder jointed to Cu substrate a) showing Kirkendall voids b) showing
Pb phase pooling at IMC/solder interface (cross section by Zohreh Bagheri) . 51
Figure 30: Typical morphologies of Cu6Sn5 grains formed on single crystal ................. 52
Figure 31: IMC formed between SAC solder and Ni(P)Au23 ........................................... 54
Figure 32: Test vehicle...................................................................................................... 55
Figure 33: Area for EDX compositional analysis of a) bulk BGA solder joint, ............... 56
Figure 34: Optical images QFP a) SAC305 b) Senju M42 c) Sunrise and d) Sunflower . 59
Figure 35: Bi present in a) eutectic colonies in Sunrise and b) throughout bulk solder
(eutectic colonies and Sn dendrite arms) of Sunflower .................................. 59
ix
Figure 36: QFP solder joint as seen a) optically b) SE SEM and c) BSE SEM ............... 60
Figure 38: SEM image of Sunflower BGA solder joint ................................................... 63
Figure 39: EDX mapping of intermetallic in Sunflower showing a) image ..................... 64
Figure 42: Polarized light images BGA a) SAC305 b) Senju M42 .................................. 67
Figure 44: IMC measurements of QFP solder joints after reflow (U2) ............................ 70
Figure 45: IMC bond layers formed on a) QFP components and b) BGA components ... 71
Figure 46: IMC formed on BGA at component side ........................................................ 72
Figure 47: Typical morphology of a) Cu6Sn5 IMC as formed on a QFP solder joint with
Sunflower b) and c) (Cu,Ni)6Sn5 and Ni23Cu33Sn44 IMCs respectively both
formed on a BGA with SAC305 solder paste ................................................... 72
Figure 49: Hysteresis loop for thermal cycle .................................................................... 80
Figure 50: SnPb solder a) before testing and b) after 3000 cycles -55C to 125C ......... 83
Figure 51: SAC305 solder a) before testing and b) after 3000 cycles -55C to 125C12 . 84
Figure 52: SAC305 after ATC shown with a)polarized light and b)EBSD mapping 13 ... 85
Figure 53: Test vehicle with monitored components ........................................................ 89
Figure 54: Card set up in thermal cycling chamber .......................................................... 90
Figure 55: Chamber profile for 0C to 100C thermal cycling ........................................ 91
Figure 57: Weibull plots of SAC305 QFP solder joints after 6010 Cycles 0 to 100C
comparing High Tg to Normal Tg boards .......................................................... 96
Figure 58: Probability Density Function for SAC305 QFP solder joints after 6010 Cycles
0 to 100C comparing High Tg to Normal Tg boards ...................................... 96
Figure 59: QFP fracture of SAC305 on High Tg board a) optically and b) cross section 97
Figure 60: Fracture surface of QFP solder joint with SAC305 on High Tg board after
6010 cycles........................................................................................................ 98
Figure 61: Fracture initiation in QFP a) Sunflower b) Senju M42 after 6010 cycles ....... 99
Figure 62: Weibull plots of BGA solder joints on Normal Tg boards after 6010 Cycles 0
to 100C cycles comparing Four Alloys ......................................................... 100
Figure 63: BGA failures after 0 to 100C ATC a) failure in board material by via plating
crack and b) partial failure through bulk solder (SAC305) near component side
IMC ................................................................................................................. 101
Figure 64: Weibull plots of QFP failures on High Tg boards after 1000 cycles -55 -125C
103
Figure 65: Probability Density Function for QFP failures on High Tg boards after 1000
cycles -55 -125C ............................................................................................ 103
Figure 66: Weibull plots of QFP failures on Normal Tg boards after 1000 Cycles -55-
125C .............................................................................................................. 104
Figure 67: QFP176 fractures in a) Sunflower and b) Senju M42 after 1000 cycles Harsh
testing .............................................................................................................. 105
Figure 68: BGA failures after -55 to 125C ATC failures in board material by via plating
crack in a) boards built with Sunrise and b) boards built with Sunflower ...... 106
Figure 70: Weibull plots of BGA solder joints after 1000 Cycles -55 to 125C cycles
comparing two board materials ....................................................................... 107
Figure 71: Weibull plot for QFP solder joints on Normal Tg boards comparing two test
conditions ........................................................................................................ 108

x
Figure 72: Probability Density Function for QFP failures on Normal Tg boards
comparing two test conditions ........................................................................ 108
Figure 73: SAC305 at Time 0 a) optically and b) SEM image and after b) 3148 cycles
and ................................................................................................................... 109
Figure 74: Senju M42 at 1000x after a) 3148 cycles and b) 6010 cycles ....................... 110
Figure 75: Sunrise after 6010 cycles 0-100C at a) 500x and b) 1000x ......................... 110
Figure 76: Sunflower at a) Time 0 and b) after 6010 cycles 0-100C at 500x ............... 111
Figure 77: IMC layers formed on QFP176 solder joints between the board side Cu layer
and solder paste a) sunrise and b) SAC305 after 438 cycles of Harsh thermal
cycling. Location 1 shows the Cu3Sn layer, location 2 shows the Cu6Sn5 layer
112
Figure 78: IMC growth at the board side of QFP during thermal cycling ...................... 114
Figure 80: Interval plot of IMC thickness at the board side of QFP after ATC ............. 117
Figure 81: Interval plot of Cu3Sn thickness at board side of QFP after ATC ................ 117
Figure 83: Main effects plot of IMC thickness at the board side QFP during 0-100C . 119
Figure 85: Main effects plot of Cu3Sn thickness board side of QFP during 0-100C ... 120
Figure 86: Interaction plot of IMC thickness at the board side of QFP after ATC ........ 121
Figure 88: Pb "cap" on whisker from SnPb component finish2 ...................................... 127
Figure 89: a) Schematic for a typical solder joint of a leaded component using SnPb
solder, b) cross section showing solder joint formed with Pb-free solder ...... 128
Figure 90: Cyclic Dynamic Recrystallization resulting in whisker formation ............... 129
Figure 91: Source of compressive stress contributing to whisker growth ...................... 130
Figure 92: Ag3Sn oxide zone with whisker6 .................................................................. 132
Figure 93: Whisker morphology a) long, thin whiskers and b) short, kinked whiskers16
133
Figure 94: Cross sections of plating surface made with SEM FIB of a) Sn and b) SnPb19
133
Figure 95: Samples in HTHH chamber .......................................................................... 136
Figure 96: Two stage, air to air, chamber for thermal shock testing .............................. 137
Figure 97: Thermal shock temperature profile ............................................................... 138
Figure 98: Schematic showing locations on lead where whiskers formed ..................... 140
Figure 99: Two adjacent leads with Sunflower solder paste after 1610 thermal shocks 141
Figure 100: Whisker growth on SAC305 after 1610 thermal shocks. a) and b) whisker
growth in location 4 c) massive deformation and d) whisker growth in location1
142
Figure 101: Whisker growth on Senju M42 after 1610 thermal shocks. a) and b) location
4 with short, thick whisker surrounded by many, very short whisker nucleation
sites c) and d) short, thick whiskers growing at site of contamination in
location4 .......................................................................................................... 143
Figure 102: Whisker growth on Sunrise after 1610 thermal shocks. a) and b) location 2
with short, thick whisker c) location 4 and d) location 1 with many, very short
whisker nucleation sites short ......................................................................... 144
Figure 103: Whisker growth on Sunflower after 1610 thermal shocks. a) and b) location 1
with short, thick whisker c) some, very short whisker nucleation sites at
location 4 and d) longest whisker observed at location1 ................................. 145
xi
Figure 104: Whisker growing from Sunflower at grain boundary of recrystallized grains
146
Figure 105: Hillock growing from Sunrise after thermal shock ..................................... 146
Figure 106: Senju M42 bulk recrystallization ................................................................ 147
Figure 107: IMC measurements of QFP solder joints after 1610 cycles thermal shock
(U1) ................................................................................................................. 148
Figure 108: Interval plot of IMC thickness at the lead side of QFP after thermal shock 149
Figure 109: IMC layer at lead with a) SAC305 and b) Sunrise after 1610 cycles of
thermal shock .................................................................................................. 150
Figure 111: Bi content at various locations of a Sunrise solder joint ............................. 151
Figure 112: Cross section of Sunflower showing Bi accumulating at grain boundaries 152
Figure 113: Test vehicle with monitored components .................................................... 159
Figure 114: Solder mask defined vs. non-solder mask defined ...................................... 160
Figure 115: Example of accelerometer secured with RTV silicone ............................... 162
Figure 116: Test set up .................................................................................................... 162
Figure 117: Target pulse shock defined by JESD22-B110 service condition B............. 163
Figure 118: Sample of pulse shock achieved during test ................................................ 164
Figure 119: Individual value plot of drops to fail, BGA (SAC305 + alloy) (U205) ...... 167
Figure 120: Individual value plot of drops to fail, QFP (U2) ......................................... 167
Figure 121: Failure modes of solder joint as defined by IPC/JEDEC-9702 ................... 169
Figure 122: BGA failure by pad cratering, Sunflower on High Tg boards ..................... 170
Figure 123: D&P mapping of Senju M42 on High Tg board, with images of ................ 171
Figure 124: Schematic of Quad-Flat-Package (QFP) ..................................................... 172
Figure 125: QFP failures in Sunflower on High Tg boards ............................................ 172
Figure 126: D&P mapping of Sunrise on Normal Tg board, with images of ................. 173
Figure 127: BGA failure in Sunflower on Normal Tg boards ......................................... 174
Figure 128: QFP failures in Sunflower on Normal Tg boards ........................................ 175
Figure 129: QFP failure in Sunrise on Normal Tg board ................................................ 175
Figure 130: Orchid at a) Time 0 and b) after 3000 cycles ATC ..................................... 187
Figure 131: Sunrise solder joint after 1000 hrs HTHH followed by 2 years ambient
storage ............................................................................................................. 188

xii
 List of Acronyms
AF: Accelerating Factor
Ag: Silver
ALT: Accelerated Life Testing
ANOVA: analysis of variance
ATC: Accelerated Thermal Cycling
ATHH: Ambient Temperature High Humidity
Au: Gold
BGA: Ball Grid Array
Bi: Bismuth
BSE: Backscatter Electron
CBGA: Ceramic Ball Grid Array
Cd: Cadmium
CTE: Coefficient of Thermal Expantion
Cu: Copper
D&P: Dye and Pry
DI: De-Ionized
DRX: Dynamic Recrystallization
DSC: Differential Scanning Calorimeter
EDX: Energy Dispersive X-Ray Spectroscopy
ENEPIG: Electroless Nickel Electroless Palladium Immersion Gold
ENIG: Electronless Nickel Immersion Gold
FA: Failure Analysis
FR4: flame retardant level
H0: null hypothesis
Ha: alternate hypothesis
HiP: Head in Pillow
HTHH: High Temperature High Humidity
ICT: In Circuit Testing
IMC: Intermetallic Compound
In: Indium
iNEMI: International Electronics Manufacturing Initiative
JEDEC: Joint Electron Device Engineering Council
LQFP: Low Profile Quad Flat Pack
MLF: Micro Lead Frame
MTTF: Mean Time To Failure
Ni: Nickel
NTC: Number of Thermal Cycles
OSP: Organic Solderability Preservatives
Pb: Lead
Pb-free: Lead free
PBGA: Plastic Ball Grid Array
PDF: probability density function
PWB: Printed Wire Board
xiii
QFP: Quad Flat Package
RoHS: Restriction of Hazardous Substances
SAC: Tin-Silver-Copper (SnAgCu)
SE: Secondary Electron
SEM: Scanning Electron Microscope
SiC: Silicon Carbide
SMT: Surface Mount Technology
Sn: Tin
SnPb: Tin Lead (usually eutectic Tin Lead)
Tg: Glass Transition Temperature
Th: Homologous Temperature
Tm: melting temperature
Vacc: Acceleration Voltage
Zn: Zinc

xiv
 Chapter 1
Background

1 Introduction
A solder joint is formed when two metal conductors with high melting temperatures,
usually copper (Cu) which melts at 1085C, are joined with another metal having a low
melting temperature. Tin (Sn) comprises the majority of materials used as solder because
of its low melting temperature (231.9°C), and its unique ability to form intermetallics
with many different joining substrates.1 In the case of electronic surface mount
technology (SMT), which is the focus of this study, these bonds act as electrical,
mechanical and thermal bonds. The solder joint is comprised of two interfaces between
the copper and solder as well as the bulk solder, which is filler material between the two
interfaces. The interfaces are chemical bonds between the Sn from the solder and the Cu
from the connecting conductors.2 In some cases, an intermediary nickel (Ni) layer will
also be present. The intermetallic compound (IMC) layer, which forms during the reflow
and solidification processes, tends to be more brittle than either the Cu or the bulk solder.

Figure 1 is a schematic of a typical ball grid array (BGA) type of component solder joint
and Figure 2 is an image of a solder joint formed using a quad flat package (QFP) type of
leaded component with gull winged shaped leads. Both are attached to the printed wire
board (PWB) by the formation of a solder joint. The solder joints formed using these two
types of components represent two of the main ways in which solder is used to form
electrical contacts.

Figure 1: Schematic of a BGA solder joint3

1
 Figure 2: Image of a QFP solder joint3

2 Need for New Low Melt Solder

2.1 Legislative Changes
In 2006 The Restriction of Hazardous Substances Directive or RoHS (2002/95/EC) took
effect for electronic products put onto the market across the European Union.4 Each of
the six substances restricted within this legislation (with some exemptions) pose some
degree of challenge to the electronic manufacturing industry. However, it is the ban of
lead (Pb) which presents the greatest disruption to traditional manufacturing processes.
Some 50 years of manufacturing knowledge based on eutectic tin-lead (SnPb) solder
requires revision, update and change. Due to the global nature of the electronic
manufacturing sector, this change has impacted all electronic manufacturing whether the
products are destined for European markets or elsewhere.

Furthermore, the European Union revised the legislation in 2011, as part of the RoHS
recast,5 and expressed an ongoing commitment to review legislation regularly, in
particular material exemptions. Any replacement to SnPb solder therefore needs to
consider the toxicity and downstream environmental impacts of the new materials.

2
2.2 SAC305 and Current Issues with Existing Alloys
The search for a replacement alloy for electronic assemblies has lead to the current
industry standard of tin-silver-copper alloys, (Sn-Ag-Cu or SAC); the most widely used
are SAC305 and SAC405, both contain 0.5wt% Cu and 3wt% and 4wt% silver (Ag)
respectively. Although these Sn-based alloys are in wide use, there remain a number of
technical and environmental limitations, which necessitate the continued search for a
more ideal replacement to SnPb. Some of the key issues with SAC305 and SAC405 are
summarized below.6

Both SAC305 and SAC405 are non-eutectic alloys with melting ranges of 217-220C and
217-221C respectively; considerably higher than the 183C melting point of eutectic
SnPb. Process temperatures for SAC alloys currently run at 240C, which is higher than
the typical process temperatures of SnPb (220C). This increase in process temperature
results in higher energy usage of reflow ovens, and consequently increased CO2
emissions, negating some of the environmental benefits of a less toxic substance.

The process temperature employed for manufacturing with SAC alloys is much closer to
the melting range, narrowing the process window and thus requiring greater process
control. While SnPb is routinely run at approximately 40C above the solder melting
temperature, such a superheat temperature would prove damaging to the overall product
when applied to products using SAC alloys. Both the PWB laminate material and some
of the more temperature sensitive components would not be able to withstand these
higher temperatures. Kelly et al.7 showed that in standard SAC reflow processes, the
component body temperature reached as high as 244.5C. It is expected that smaller
components may reach temperatures as high as 250C. Rework processes, or any wave
soldering, may require even higher temperatures, up to 260C, for compatibility with the
current Pb-free processes.8 Component suppliers have indicated that moisture sensitivity
of components may change in response to these high temperature requirements and may
necessitate preconditioning before reflow. All additional processes increase production
cost and potentially compromise the overall component reliability.

3
Moreover, the laminate materials typically used in conjunction with SnPb solders have
been replaced by new materials which have a higher glass transition temperature (Tg) in
order to withstand the higher processing temperatures needed for SAC alloys. The
development of these new materials involved changing the epoxy resin and curing agents
for additional crosslinking, as well as the inclusion of ceramic particle fillers.9 The
unintended consequence of these changes has been the introduction of a new failure
mode known as pad cratering. The harder and stiffer laminate materials fail as they
separate from the conductive copper traces within the PWB (Figure 3). These laminates
are also more susceptible to warpage, delamination and may require additional baking
processes.

Figure 3: Pad crater defect seen in a) cross section – indicated by arrows, and b)
viewed from above

This failure mode is dangerous as it may not be readily identifiable during in- circuit-
testing (ICT) within the factory, but may lead to reliability concerns in the field as the
fracture propagates, potentially severing the copper trace and causing eventual electrical
failure. This is primarily a concern for products required to withstand damage by drop
shock, such as consumer electronics (e.g. mobile phones), which are prone to being
repeatedly dropped over the course of useful life. It would therefore be preferable for any
new alloy to be compatible with older laminate materials similar to those used with
traditional SnPb solders, in which this failure mode was not prevalent.

4
The mechanical properties of SAC solder alloys also have disadvantages. In addition to
requiring a laminate material with a higher elastic modulus (E), the alloy itself is stiffer
than SnPb.10. SnPb has an E value of 40GPa at 25C and SAC305 has a value 50GPa at
25C.11 Finally, there is potential for the formation of undesirable intermetallic
compounds (IMC), i.e. Ag3Sn (Figure 4). This intermetallic may in some cases be
present as a large, sharp platelet which can potentially behave as a stress raiser or provide
a path along which cracks may more easily propagate, thereby negatively impacting the
materials’ resistance to drop shock.6

In addition to the aforementioned thermo-mechanical issues, the high cost of Ag makes

its inclusion as an alloying element undesirable for the cost-sensitive market of consumer
electronics.

Figure 4: Ag3Sn platelets seen in a) cross sectioned solder joint and b) SEM image of
solder joint after removal of Sn phase12

Finally, Sn whiskers discussed in detail in Chapter Chapter 4, present a reliability

concern for all Sn-based solders. Although the presence of Pb in high concentration does
not eliminate the potential for growth of Sn whiskers completely, Pb does mitigate the
formation of long whiskers, and therefore is not considered a reliability risk. The move
to high Sn solder compositions coincides with the further miniaturization of components,
solder joints and solder joint spacing. These factors all increase the risk of whisker
growth to a length at which bridging and hence short-circuiting of solder joints would be
5
a concern. While this risk presents a reliability concern for all products using Pb-free
solders, it is of particular concern to the aerospace and defense sectors, for which these
reliability concerns present an unacceptable level of risk.10 Figure 5 shows a Sn whisker
growing from SAC305 solder on the surface of a solder joint.

Figure 5: Sn Whisker growing from SAC305 solder

In spite of these concerns, at the time of RoHS implementation in 2006, near-eutectic

SAC alloys provided the best compromise in a supply chain where Pb containing
components used in printed circuit boards were still common.

2.3 Search for Replacement Solder

2.3.1 Binary Alloys
Prior to implementing SAC as an alternative to SnPb, an attempt to find an optimal
replacement began with the exploration of binary alloy options. A number of binary
alloys were initially considered (ideally near the eutectic point) but all had associated
issues, which disqualified them as viable alternatives.13,14

Tin (Sn) was selected as one of the two binary elements in all cases due to its low
toxicity, relatively low cost, resistance to oxidation and contribution to the melting point
or range of an alloy. Much of this analysis was performed by reviewing the equilibrium
phase diagrams of various Sn-based alloys. Information pertaining to the temperature at

6
the eutectic point, as well as IMCs that may form, was weighed against a number of
factors associated with the individual alloying elements.

Figure 6: Sn-Cu phase diagram15

SnCu has a eutectic point at 0.7% Cu close to the melting temperature of pure tin at
approximately 227C, (Figure 6) which is still more than 40C higher than that the SnPb
eutectic temperature.16 While this alloy presents some advantages, the melting
temperature is still too high to be considered a viable binary compound alternative.
Regardless, the SnCu alloy must be considered in the development of a replacement alloy
due to the interaction of solder with a copper pad on the PWB. In some cases, there will
be a barrier between the copper pad and the Sn-based solder, for example a nickel (Ni)
barrier layer. In other cases, the Sn-based solder will be exposed directly to a solid
copper substrate, which would represent the “worst case scenario” in terms of copper
dissolution. Whichever alloy is selected to replace SnPb, it is likely that the Sn-Cu
reaction will play a large role. This will be discussed further in Chapter Chapter 2.

7
Other binary alloys formed with Sn were also considered and dismissed for several
reasons. A summary of Sn-based eutectic alloys, their melting temperatures and their
eutectic compositions is provided (Table 1).

Table 1: Sn-based eutectic alloys17

System Eutectic Temperature (C) Eutectic Composition (wt%)

Sn-Cu 227 0.7
Sn-Ag 221 3.5
Sn-Au 217 10.0
Sn-Zn 198.5 9.0
Sn-Pb 183 38.1
Sn-Cd 177 32.2518
Sn-Bi 139 57.0
Sn-In 120 51.0

SnIn, SnAg and SnAu all present very expensive options. The alloying elements are
comparatively scarce and therefore do not provide attractive alternatives to SnPb.
Further, the eutectic composition of SnAg and SnAu, as well as that of SnCu is
predominately Sn. These systems will therefore form intermetallic compounds within the
Sn matrix, introducing inhomogeneity into the microstructure.17 Additionally, Ag3Sn
precipitates, which are primarily present as a network of small, rod like structures, may
also form as an undesirable platelet structure as already described above and illustrated in
Figure 4.

SnZn and SnCd both have melting temperatures close to that of SnPb, however both have
been disqualified as viable options. SnZn readily oxidizes;10 this alloy would require
processing in an inert gas environment and the addition of an excessive amount of flux.
Since the oxide forms so easily, it would also potentially form a very weak solder joint.
The main issue with SnCd is the toxicity of Cd; any replacement to SnPb should not
present the same environmental concerns as the original alloy.

8
The binary SnBi eutectic alloy was initially rejected as a viable replacement to SnPb
because of the possibility of forming a dangerously low melting intermetallic compound
when combined with Pb. Moon et al.19 showed that even a 0.1% Pb contamination
content was sufficient to reduce the melting temperature by between 38 and 55C.
During the initial transition to lead free solders, it was anticipated that this contamination
could be introduced when using SnPb tinned leaded parts within a lead-free assembly.
The potential for this contamination within the supply chain was deemed to be too great
and therefore all bismuth (Bi) containing alloys were avoided. As the legislation has now
been in place for almost a decade, this contamination has been deemed to be less likely to
occur and therefore Bi is being reconsidered a suitable alloying element.20 Research on
eutectic SnBi alloy continues. It has also been has been adopted in high volume
production for special applications; flat screen televisions are built using a combination
of SAC and eutectic SnBi. However, there remains concern due to the brittle nature of the
eutectic and its resulting poor performance in drop shock testing;21 this study will instead
consider Bi as an alloying element within a predominately Sn-based alloy system.

2.3.2 Ternary and higher order alloy options

Once it was determined that binary eutectic Sn-based alloys would not meet the needs of
a SnPb replacement, ternary alloys were explored. The International Electronics
Manufacturing Initiative (iNEMI) proposed the following criteria for the selection of a
replacement alloy:
 “Have melting point as close to Sn-Pb eutectic as possible
 Be eutectic or very close to eutectic
 Contain no more than three elements (ternary composition)
 Avoid using existing patents, if possible (for ease of implementation)
 Have the potential for reliability equal to or better than SnPb eutectic.”22

Further criteria were added for narrowing down a suitable ternary alloy. These include22:

 Liquidus temperature as close as possible to 183C

 Solidus temperature as close as possible to liquidus temperature (small pasty range)

9
  Solidus temperature significantly higher than the solder joints maximum operating
temperature

SnAgCu, SnBiCu, and SnAgBi were all considered. Based on the possibility of forming
very low melting temperature eutectics in the presence of Pb (BiPb eutectic at 125.9C,
SnPbBi ternary eutectic at 98C), Bi was ruled out during the initial transition period and
SnAgCu alloys became standard. However, now that the supply chain has been largely
purged of SnPb components, Bi containing alloys are being reconsidered. Bi-rich alloys
continue to be considered for some specialty applications, for example Sn-88%Bi and Sn-
59%Bi-1.2%Ag. However, as they have a melting temperature closer to 138C, they fail
the third criteria listed above for applications which may be exposed to harsh operating
environments of up to 125C.

The SnAgCu eutectic system is of the composition Sn-3.5Ag-0.9Cu by wt% with a

eutectic melting temperature of 217.4±0.8C. The system forms a ternary eutectic made
up of faceted Cu6Sn5 and non-faceted Ag3Sn internetallics within a Sn matrix. The
melting temperature of this eutectic is 10C lower than that of eutectic SnCu. Near
eutectic compounds of SnAgCu are currently the preferred solders in use today,
specifically SAC305, SAC405 and to a lesser extent SAC105. Where cost is a driving
force (i.e. consumer products) the preference is for a lower quantity of Ag. At the other
end of the spectrum, Ag is limited due to the potential formation of undesirable Ag3Sn
platelets.

Figure 7 shows the phase diagram of SAC alloys and specifically the Sn-rich region,
which highlights the formation of a Sn - Sn+Ag3Sn-Sn - Cu6Sn5 ternary compound.

10
a. b.
Figure 7: a) SAC ternary phase diagram and b) Sn-rich corner of SAC ternary
phase diagram23

SAC105 has been considered as an alternative to SAC305 or SAC405 as it reduces the

amount of expensive Ag, and also reducing the possible formation of the dangerous
Ag3Sn platelets. However, the reduction of Ag also coincides with an increase in
liquidus temperature to 227C.6 The corresponding increase in required reflow, rework
and other processing temperatures offsets any potential benefit gained by this slightly less
stiff, higher fracture toughness alloy. The introduction of this alloy into the ball grid
array (BGA) supply chain, where it was combined with a paste alloy of SAC305 or SnPb
(in the case of mixed metallurgy builds early in the transition to Pb-Free) lead to issues of
incomplete melting of the solder ball. This incomplete melting resulted in a Head-in-
Pillow (HiP) defect (Figure 8), since the manufacturing reflow temperatures were
generally set to accommodate the SAC305 paste.

11
 Figure 8: Head in pillow defect24

2.4 Celestica’s Low Melt Solder Research Program

Celestica, in partnership with the University of Toronto, set up a low melt research
program in 2009 with the main goal of introducing a solder alloy which would allow for
the use of conventional flame-retardant level 4 (FR4) laminate printed wire board (PWB)
material with SnPb solder. This combination would require a process temperature of
approximately 10C lower than SAC305 and potentially reduce failures via pad cratering.
This new solder paste would need to be compatible with both leaded and discrete
components - where the solder paste makes up the majority of the solder joint, and with
ball grid array components (BGA) where the paste is mixed with industry standard
SAC305 or SAC105 to form a solder joint which has the composition made up of
approximately 25% by volume paste, and approximately 75% by volume BGA alloy10
(Figure 9).

12
 Figure 9: a) gull wing leaded solder joint, b) BGA solder joint

Celestica’s program was divided into a number of phases as follows:

 Alloy Selection
 Manufacturing Feasibility
 Screening Experiments:
o Aerospace and Defense Sector
o Consumer Sector
o Telecommunications Sector
 Reliability Testing

This work explored the alloys selected for both the Consumer and Telecommunications
sector portions of the screening experiments. The Aerospace and Defense sector program
is described here in order to provide context for the current project. The remainder of
this chapter summarizes the prior work and provides context for the work in this thesis.

2.4.1 Phase 1: Alloy Selection

The initial work, described in Snugovsky et al.6, outlines the process by which various
alloys were selected for further study. This alloy selection phase of the project was
divided further into the following stages:

13
  Requirement Formulation
 Literature Search and Phase Diagram Analysis
 Preliminary Alloy Selection
 Metallurgical Analysis: Differential Scanning Calorimetry (DSC) and Microstructural
Evaluation of:
o Alloy
o Alloy plus Cu – simulate solder on board with leaded or leadless
component
o Alloy plus Cu plus SAC305/SAC105 – simulate solder on board with
BGA solder ball

2.4.1.1 Requirement Formulation

The following requirements were established:

 220-222C process temperature, at least 10C lower than SAC305

 Approximately 10-15C pasty range

 Compatible with SAC305/105 solder balls as well as with leaded and discrete
components
 Low Ag content6
 Equal or better thermo-mechanical properties than SAC305.

As described in section 2.2, an ideal replacement to SAC solders needs to be compatible

with temperature sensitive components. It should also be compatible with laminate PWB
material used with SnPb solder, which is less expensive than newer, high temperature
laminate material, requires less baking and processing prior to build and reduced adverse
mechanical properties associated with these new materials; pad cratering, de-lamination
and warpage.

The pasty range is also important as a narrow range ensures good wettability due to less
oxide formation and reduces the possibility of forming HiP defects if the paste does fully

14
melt and mix with the BGA solder ball. HiP may also result from excessive warpage in
the laminate material. A small pasty range also prevents composition gradients and
unexpected concentrations driven by thermal gradients in the cooling cycle.

Finally, any new low melt solder should form an interconnection which exhibits equal or
better properties in mechanical and thermo-mechanical testing than SAC305 and
comparable to SnPb solder. The interconnection includes the solder paste, the board
material (copper pad and any surface finish material), and either the BGA solder ball, the
lead material of a leaded component (Figure 9), or a terminal finish of a leadless
component (e.g. a capacitor) (Figure 10).

Figure 10: Solder joint formed with leadless component25

The reduction of Ag will reduce the cost of the alloy and also may improve mechanical
properties, particularly in drop shock testing. It should also be noted that the ideal Ag
content for drop shock performance may not be optimal in thermal cycling.26 It is
therefore necessary to balance these requirements.

2.4.1.2 Literature Search and Phase Diagram Analysis6

Bi containing alloys are the focus of this study. It has been shown that the addition of Bi
will improve thermal and thermo-mechanical properties over conventional SAC
alloys.27,28 These benefits can be attributed to solid solution and precipitate strengthening
which will be described further in Chapter Chapter 2. Additionally, Bi may reduce the
propensity for whisker growth in a Sn rich alloy.6 The Bi addition was intended to
depress the melting temperature but not to enter the very low melting temperature regime
around the SnBi eutectic (Figure 11). The Bi content is tuned in conjunction with altering
15
the amount of Ag and/or Cu in order to maximize the temperature depressing
characteristic of the Bi, without introducing the very low melting temperature (~137-
138C) ternary eutectics (Figure 12 and Figure 13).

Figure 11: SnBi phase diagram29

Since alloys of higher order than ternary are difficult to illustrate using phase diagrams,
the combined knowledge of the existing ternary and binary eutectic temperatures and
compositions can be compared to determine an ideal range for the proposed alloys. Since
a melting temperature of approximately 138C is well below the outlined criteria, alloys
which do not have any liquid component around this temperature are viable candidates. A
slice along the z-axis, which represents temperature, of a 3D ternary phase diagram
(Figure 14) can be used to explore the eutectic region of a particular alloy system.

The solubility limit of Bi in Sn is 21%, however this is reduced with the addition of
other alloying elements, namely Ag and/or Cu. An examination of the Sn-Ag-Bi, Sn-Cu-
Bi and Sn-Ag-Cu systems is required.

16
a. b.

Figure 12: a) SnAgBi ternary phase diagram and b) Sn-rich corner of SnAgBi phase
diagram30

From Figure 12 and Equations 1-1 and 1-2, a ternary eutectic (Point ‘E’) of Sn-Ag-Bi
exists at 137.1C, at a composition of Sn-0.68%Ag-43.47%Bi, and a binary eutectic
(Point ‘A’) at 220.3C with a composition of Sn-3.73%Ag is seen.

L -> Ag3Sn + (Bi) + (Sn) 2-1

L -> Ag3Sn + (Sn) 2-2

Upon cooling along the binary eutectic line from point A, highlighted in blue in Figure
12, both Sn and Ag3Sn are formed simultaneously. At point E (the ternary eutectic point
defined in Equation 1-1) all remaining liquid forms simultaneously into Sn, Ag3Sn and
Bi.31 Compositions along this line were explored in the development of proposed new
alloys.

17
a. b.

Figure 13: a) SnCuBi ternary phase diagram and b) Sn-rich corner of SnCuBi phase
diagram 32

Similarly, from Figure 13 and Equation 1-3, we can see that a ternary eutectic exists at
138.8C at a composition of Sn-0.01%Cu-43.09%Bi and a binary eutectic at 226.8C
with a composition of Sn-0.89%Cu.

L -> Cu6Sn5 + (Sn) + (Bi) 2-3

L -> Cu6Sn5 + (Sn) 2-4

Exploring the binary eutectic line following cooling towards the ternary eutectic from
point A in Figure 13 to point E for the SnCuBi system gives a starting point for
determining ideal alloys.

Figure 15 is an isothermal projection of the SnBiAg phase diagram at 138.4C. The area
highlighted in yellow represents an area where ternary eutectic is present at this
temperature. Compositions from within these triangles should be avoided in order to
avoid melting in the low temperature range. Additionally, the ternary eutectic of the Sn-
Ag-Bi system should be avoided because Bi is present in the eutectic as a primary
precipitate. These primary particles may be large. It is preferable to have small Bi

18
particles, the type which will likely precipitate out of solid solution after initial
solidification.

Finally, it should also be noted that current production processes such as reflow ovens
and hand solder rework, provide rapid cooling environments and do not allow for
equilibrium solidification. Other possible effects of cooling, such as Bi segregation,
should be accounted for in the development of any new alloy.

Figure 14: Example of ternary phase diagram31

19
 Figure 15: SnAgBi ternary phase diagram, isothermal section33

2.4.1.3 Preliminary Alloy Selection6

Based on examination of phase diagrams as described in section 2.4.1.2, 23 Bi-containing
alloys were selected for further evaluation including those listed in Table 2. The first two
alloys in the table, J.Hwang and Senju M42, are currently available in industry. Of these
four industry available alloys, none fully meet the criteria outlined in section 2.4.1.1 but
were included for study because they met most criteria and for purposes of comparison.

20
 Table 2: Preliminary alloy selection10,6

Published Melting Experimental Melting

Composition Temperatures (C) Temperatures (C)
Alloy
(wt%) Pasty Pasty
Min Max Min Max
Range Range

J. Hwang34 Sn3.1%Ag0.5%Cu3.1%Bi 209 212 3 209 216 7

Senju M4235 Sn2%Ag0.75%Cu3%Bi 207 218 11 207 217 10

Paul27,28 Sn3.4%Ag4.8%Bi 201 215 14 206 217 11

Orchid Sn2%Ag7%Bi 191 216 25 190 215 25

Violet Sn2.25%Ag0.5%Cu6%Bi 205 216 11

Sunflower Sn0.7%Cu7%Bi 200 219 19 209 219 10

Cornflower Sn0.7%Cu10%Bi 191 215 24

Sunrise Sn1%Ag0.7%Cu7%Bi 199 215 16

2.4.1.4 Metallurgical Analysis: DSC and Microstructural Evaluation 6

Alloys from Table 2 were evaluated using the thermoanalytical technique, differential
scanning calorimetery (DSC). DSC measurements of the alloys were made in two forms:
alloy alone representing the solder paste used in the production of a typical leaded or
leadless solder joint, and the alloy combined with SAC305 in approximately 25%-75%
ratio to represent the solder joint formed when the paste is used with a BGA component
(Figure 9). DSC measures the difference in energy input into a cell containing the sample
within a sample holder vs. a reference cell, usually the sample holder (minus the
sample).36 By plotting the heat flow (J/g*min) vs. temperature (C) it is possible to
determine the onset of a phase transformation by the decrease in heat flow, the
temperature range over which this transition occurs and the total enthalpy of the reaction.
In the case of solder in this experiment, the onset of melting and the pasty range could be
21
determined. Table 2 summarizes both the published values of melting temperature and
range as well as values determined in this study. DSC can also be used to determine if
there are any additional, undesirable phase changes that occur in the alloys. As the
selected alloys were close to the eutectic compositions, only one peak is desirable. Figure
16 is a good example of an alloy with an undesirable hypoeutectic composition. Note that
the saturation point of Bi in Sn is at 21wt% Bi. The eutectic composition is
approximately 57wt% Bi. As the alloy is heated from room temperature, the first peak is
encountered at approximately 139C (point A), which is the solid solubility limit for Bi in
Sn as well as the initiation of melting. This is characterized on the DSC curve by a sharp
peak indicating an invariant phase change. Continued heating of this alloy shows that it
passes through a melting range characterized on the DSC curve by a secondary peak, at
point B (liquidus).37

Figure 16: DSC scan of Sn20%Bi10,38

Table 3 summarizes the DSC analysis performed on the proposed alloys combined with
75% SAC305 to simulate the composition of the solder paste mixed with a SAC305
solder ball of a BGA.
22
 Table 3: DSC analysis of proposed alloys with 75% SAC305
Experimental Melting
Composition Temperatures (C)
Alloy
(wt%)
Min Max Pasty Range

J. Hwang39 Sn3.1%Ag0.5%Cu3.1%Bi 216 218 2

Senju M4240 Sn2%Ag0.75%Cu3%Bi 216 218 2

Paul27,28 Sn3.4%Ag4.8%Bi 214 217 3

Orchid Sn2%Ag7%Bi 214 218 4

Violet Sn2.25%Ag0.5%Cu6%Bi 214 217 3
Sunflower Sn0.7%Cu7%Bi 212 215 3
Sunrise Sn1%Ag0.7%Cu7%Bi 211 215 4

Microstructural evaluation was performed by cross sectioning the alloyed samples and
examining the microstructure using a scanning electron microscope (SEM) and energy-
dispersive X-ray spectroscopy (EDX). This evaluation was done using three forms of the
proposed alloys:
 Alloy
 Alloy reflowed onto a copper foil
 Alloy reflowed onto a copper foil with SAC305

The second and third scenarios represent the alloy reflowed onto a copper pad found on a
PWB and a BGA mixed with the alloy onto a copper pad respectively. Using the above
three scenarios, each of the alloys were evaluated based on the following microstructural
factors: intermetallic thickness and morphology, microstructural uniformity and
coarseness of the overall microstructure.

The intermetallic formed between the solder alloy and the copper pad creates both the
mechanical and electrical bond of the solder joint. The formation is discussed further in
Chapter Chapter 2. Both Cu6Sn5 and Cu3Sn are possible intermetallics that form during
solder reflow, and are substantially more brittle than Sn or Cu alone and have facetted
23
morphologies. During a typical reflow of Sn based solder onto a copper foil, it is
typically the Cu6Sn5 IMC layer in a scalloped morphology which forms the interconnect.
A continued solid-state reaction between the Sn in the solder, the Cu6Sn5 layer and the Cu
may persist at elevated temperatures (including those present in service conditions)
causing the Cu6Sn5 layer to grow and possibly resulting in the formation of a Cu3Sn layer
between the Cu6Sn5 and Cu over time. In this study, the initial IMC formation processes
were compared. There should be a sufficient, continuous IMC formed with no
interruptions to ensure a proper bond has formed. Conversely, the IMC layer thickness
should be minimized as it is the most brittle portion of the solder joint and prone to
fracture. Thicknesses will vary based on solder composition, PWB surface finish, reflow
profile (time and temperature) and post reflow exposure. An optimal thickness definition
does not currently exist in industry.

Microstructural uniformity and grain coarseness were also examined. The microstructure
plays a role in the materials ability to resist creep by allowing the induced load to be
uniformly distributed over the specimen thereby reducing strain-induced grain growth
and crack initiation.41 Solder joints can readily reach temperatures of approximately 0.3-
0.5 of the melting temperature (Tm) during normal operation. This temperature range may
result in both the coarsening of the primary grain structure, in this case the Sn matrix
grains, as well as growth of Ag3Sn platelets.42 In this study, the alloy itself, as well as the
alloy mixed with SAC305 in a 1:3 ratio were examined to simulate a solder joint formed
with the proposed alloy and a SAC305 BGA solder ball, as shown in Figure 17.

24
Figure 17: Microstructure of solder joint formed with SAC305 solder ball and a no-
Ag solder paste alloy6

2.4.2 Phase 2: Manufacturing Feasibility Study43

Manufacturing feasibility, or solder paste performance, was tested at Celestica. The
pastes were tested for printability, wettability and performance in the screening process.
In general, the performance of a solder paste is driven largely by the size and morphology
of the solder powder, the composition and volume of flux and the overall rheology of the
paste. These variables are largely alloy independent and therefore not considered in detail
during this study. This study concluded that the paste variables have been sufficiently
addressed and optimized in order to move to further stages of evaluation, which would
better distinguish between alloys.

2.4.3 Phase 3: Screening Experiments

From the alloys described in 2.4.1, it was determined that no one alloy would meet the
needs of the three market segments of interest. It was therefore proposed that a number of
screening experiments be performed in order to down-select the number of alloys which
would undergo full reliability studies. Table 4 summarizes the alloys selected for each of
the screening experiments for different market segments.

25
 Table 4: Alloys for screening experiments
Process
Composition Pasty
Market Segment Alloy Temperature
(wt%) Range (C)
(C)
Paul Sn3.4%Ag4.8%Bi 206 11
Aerospace and
Violet Sn2.25%Ag0.5%Cu6%Bi 205 10
Defense
Orchid Sn2%Ag7%Bi 190 25
Sunflower Sn0.7%Cu7%Bi 226 10
Consumer Sunrise Sn1%Ag0.7%Cu7%Bi 222 16
Senju M42 Sn2%Ag0.75%Cu3%Bi 224 10
Violet Sn2.25%Ag0.5%Cu6%Bi 205 10
Sunflower Sn0.7%Cu7%Bi 226 10
Telecommunications
Sunrise Sn1%Ag0.7%Cu7%Bi 222 16
Senju M42 Sn2%Ag0.75%Cu3%Bi 224 10

2.4.3.1 Aerospace and Defense44,45

The screening experiments for the three alloys selected for the aerospace and defense
sector, as listed in Table 4, were performed between 2011 and 2013 by Celestica in
partnership with Honeywell. In these screening experiments, three alloys were compared
against baselines of both SAC305 and SnPb. Both BGA, using SAC305 solder balls,
except with SnPb solder in which case SnPb solder balls were used, and leaded
components typical of those used in aerospace and defense assemblies were investigated
using a medium complexity board designed by Honeywell, as shown in Figure 18.

Figure 18: Honeywell test vehicle, medium complexity board

26
2.4.3.1.1 Screening Experiment Structure
A Latin squares approach was used in this screening experiment.46 This approach allowed
for the most information to be obtained without testing every possible combination,
which would be cost prohibitive. Three factors were identified: board material, board
finish: Organic Solderability Preservative (OSP), Electroless Nickel Immersion Gold
(ENIG) and Electroless Nickel Electroless Palladium Immersion Gold (ENEPIG) and
paste (Violet, Orchid and Paul), in nine combinations rather than the full 27
combinations. Since only two Tg levels were of interest, instead of three, as with the
other factors, the higher Tg was repeated, as summarized in Table 5. Boards with Tg of
150C and 170C were used. The overall build matrix is summarized in Table 6. No
clean solder paste of the experimental alloys was prepared by a major solder paste
supplier for the purposes of this experimental work (Table 6). Boards were built at
Celestica. Two different reflow temperatures were used in the manufacturing process.
One with a peak temperature was 240C, was used with the SAC305 alloy and one with a
peak temperature of 222C for all other alloys. Both had a time above liquidus of
approximately 70-90 seconds.

Table 5: Latin square of paste and finish, and board materials

Finish
Alloy
OSP ENIG ENEPIG
Paul 150 170 170
Violet 170 150 170
Orchid 170 170 150

27
 Table 6: Build matrix showing number of assemblies

Surface Finish
PWB Material Alloy
ENEPIG ENIG OSP
SnPb 2 3
SAC305 2 2
Normal Tg
Paul 4
(150 °C)
Violet 4
Orchid 4
SnPb 2 3
SAC305 2 1 3
High Tg
Paul 4 4
(170 °C)
Violet 4 4
Orchid 4 4

2.4.3.1.2 Microstructural Assessment

A detailed discussion on the microstructural evaluation can be found in Snugovsky et
al.44 and in Juarez et al.45. All of the assemblies were inspected optically and with x-ray
radiography, to ensure that no major anomalies or concerns existed prior to further
testing. Figure 19 illustrates wetting of the solder paste on quad flat pack (QFP) leaded
components on OSP board finish. SnPb exhibited the best wetting properties, while
SAC305 showed the worst. All three experimental alloys showed some degree of
improved wetting over SAC305. Figure 20 shows the cross section evaluation performed
on solder joints made with all solder pastes on OSP board material. All BGAs showed
good mixing characteristics between the solder paste and the SAC305 solder ball.

Figure 19: Example of wetting on OSP, QFP240

28
 Figure 20: BGA and QFP solder joints on OSP

Table 7 summarizes the composition of the resulting interconnect BGA solder ball after
assembly. This final BGA solder ball composition is a mixture of the paste alloy and the
original component SAC305 solder ball. The compositional measurements were made
using the semi-quantitative method of SEM-EDX and are provided here for comparative
purposes only.

Table 7: Resultant BGA interconnect composition

Paste Surface Ball Composition (wt%)
Alloy Finish Sn Ag Cu Bi Pb
SnPb OSP 70.2 0 0.4 0 29.4
SAC305 OSP 96.2 2.8 1.0 0 0
Paul OSP 95.0 2.6 0.8 1.7 0
Violet OSP 95.7 2.1 0.7 1.5 0
Orchid OSP 94.7 2.3 1.0 2.0 0
SAC305 ENIG 96.7 2.8 0.5 0 0
Paul ENIG 95.9 3.0 0.3 0.8 0
Violet ENIG 95.5 2.2 0.6 1.7 0
Orchid ENIG 95.0 2.5 0.4 2.1 0
Paul ENEPIG 95.0 2.5 0.4 2.1 0
Violet ENEPIG 95.1 2.8 0.6 1.5 0
Orchid ENEPIG 95.5 2.2 0.4 1.9 0

2.4.3.1.3 Accelerated Thermal Cycling (ATC)

17 assemblies of various paste, board finish, and board material combinations, were
exposed to upwards of 3000 cycles of harsh temperature thermal cycling in accordance

29
 with IPC-9701A: Performance Test Methods and Qualification Requirements for Surface
Mount Solder Attachments47 using Test Condition 1 (-55C to 125C) for 3000 cycles.
Table 8 and Table 10 summarize the number of failures over the course of the entire test.
Mean Time to Failure (MTTF) is defined by Equation 1-5 and the failure rate () is
defined by Equation 1-6.48
iN
1
MTTF 
N
T
i 1
i 2-5

1 N
  iN 2-6
 Ti
MTTF
i 1

Table 9 and Table 11 attempts to quantify the time to failure over the course of the 3,000
plus cycles in spite of the lack of a full statistical set of test data.

Table 8: ATC failures on 170C Tg board material

Paste type SnPb SAC305 Paul Violet Orchid
ENEPI ENEPI ENEPI ENI ENEP
OSP OSP OSP ENIG OSP
Finish G G G G IG
352 BGA 2/2 2/2
240 QFP

30
 Table 9: Reliability results on 170C Tg boards after ATC
Alloy Finish Component MTTF R(3039) =Failure/cycle
352 BGA - 1 0
ENEPIG
240 QFP - 1 0
SnPb
352 BGA 1611 0 0.00062
OSP
240 QFP - 1 0
352 BGA - 1 0
ENEPIG
240 QFP - 1 0
SAC305
352 BGA - 1 0
OSP
240 QFP - 1 0
352 BGA - 1 0
ENEPIG
240 QFP - 1 0
Paul
352 BGA - 1 0
ENIG
240 QFP - 1 0
352 BGA - 1 0
ENEPIG
240 QFP - 1 0
Violet
352 BGA 2271 0 0.00044
OSP
240 QFP - 1 0
352 BGA - 1 0
ENIG
240 QFP - 1 0
Orchid
352 BGA - 1 0
OSP
240 QFP - 1 0

Table 10: ATC failures on 150C Tg board material

Solder Alloy SnPb SAC305 Paul Violet Orchid
Finish ENEPIG OSP ENEPIG OSP OSP ENIG ENEPIG
352 BGA 2/2 2/2 2/2 2/2 1/2
240 QFP 1/2 2/2 2/2 2/2 1/2 1/2

31
 Table 11: Reliability results on 150C Tg boards after ATC
Alloy Finish Component MTTF R(3039) =Failure/cycle
352 BGA 2310 0 0.00043
ENEPIG
240 QFP 4466 0.5 0.00022
SnPb
352 BGA 1336 0 0.00075
OSP
240 QFP 1313 0 0.00076
352 BGA - 1 0
ENEPIG
240 QFP - 1 0
SAC305
352 BGA 551 0 0.00182
OSP
240 QFP 802 0 0.00125
352 BGA 1055 0 0.00095
Paul OSP
240 QFP 1169 0 0.00086
352 BGA 4988 0.5 0.00020
Violet ENIG
240 QFP 5748 0.5 0.00017
352 BGA - 1 0
Orchid ENEPIG
240 QFP 4536 0.5 0.00022

In the above ATC testing, there are only two replicates of each condition. Even if both
fail, there is insufficient data to plot failure rates using Weibull, or any other type of
statistical distribution. Accordingly, MTTF and failure rate () were used to quantify the
data from this screening experiment and to describe the length of time for which each
condition survived. All combinations using the 170C Tg boards survived beyond the
1000 cycles required by the Aerospace and Defense sector. SnPb and Violet BGAs both
experienced failures with a MTTF of 1611 and 2271 respectively on OSP boards. As
OSP is not a finish that is favored by this sector, the results on the ENIG and ENEPIG
finish boards, which survived in all cases, show promise.

Combinations on the 150C Tg boards experienced more failures on all board finishes.
Only the SAC305 combinations on OSP show MTTF below the required 1000 cycles:
551 for BGAs and 802 for QFPs. Again, the boards with OSP finish failed earlier than
boards with other finishes. Upon further investigation, these failures were found to be in
the board material, in the form of barrel cracks, rather than in the solder joint
interconnect.

32
 2.4.3.1.4 Vibration
Seventeen (17) assemblies of various paste, board finish and board material combinations
were exposed to two force levels of vibration testing. The test procedure, a discussion of
the failure modes, as well as a detailed discussion of the reliability results, can be found
in Juarez et al.45

Chart of % Failure

50

40
% Failure

30

20

10

0
Alloy et ul id e t
Pb ul id 05
ol Pa ch ol Sn Pa ch C3
Vi Or Vi Or A
S
Vibration Level (G) 2 5

Figure 21: Failures in vibration testing

Figure 21 provides a summary of the number of failures that occurred during vibration
testing, at two different levels of acceleration, 2G and 5G respectively. The table
illustrates that all three experimental alloys outperform SAC305, with Violet even
outperforming SnPb. Table 12 and Table 13 summarize the failures that occurred based
on varying conditions and test combinations. A more comprehensive discussion of the
survival times can be found in the original work referenced above.

Table 12: Vibration failures after 2G testing

Alloy Paul Violet Orchid
Finish OSP ENIG ENEPIG OSP ENIG ENEPIG OSP ENIG ENEPIG
Board Material 150 170 170 170 150 170 170 170 150
352 BGA
240 QFP 2/2 2/2 2/2 2/2 1/2
33
 Table 13: Vibration failures after 5G testing
Alloy Paul Violet Orchid
ENEPI
OSP ENIG ENEPIG OSP ENIG OSP ENIG ENEPIG
Finish G
Board Material 150 170 170 170 150 170 170 170 150
352 BGA 2/2 2/2 1/2 2/2 2/2 2/2 2/2 1/2
240 QFP 2/2 2/2 2/2 2/2 2/2 2/2 2/2 2/2
Alloy SAC305 SnPb
Finish OSP OSP ENEPIG ENEPIG OSP OSP ENEPIG ENEPIG
Board Material 150 170 150 170 150 170 150 170
352 BGA 2/2 2/2 2/2 2/2 2/2 2/2
240 QFP 2/2 2/2 2/2 2/2 2/2 2/2 2/2

2.4.3.1.5 Summary of Findings

The three alloys compared against SAC305 and SnPb in the Aerospace and Defense
Sector screening experiments showed acceptable manufacturability characteristics with
improved wetting and voiding over SAC305. Two of the alloys, Paul and Orchid, did not
form proper intermetallics with ENIG or ENEPIG board finishes while Violet did. This
is finding is attributed to the lack of Cu present in these alloys.

All three experimental alloys met the Aerospace qualification of 1000 cycles of harsh
thermal cycling. Only SAC305 on 150C Tg boards with OSP finish failed to meet the
criteria, however, the failures were determined to be via failures within the board. This
good performance is attributed to the fact that Bi particles evenly precipitate into the Sn
matrix during thermocycling, reducing grain coarsening and microstructural degradation.

In vibration testing, all experimental alloys showed an improved performance over

SAC305, both Violet and Paul performed equally or better than SnPb.

3 Objective of Thesis: Low Melt Solders for

Consumer Sector
The screening experiments for the three alloys selected for the Consumer Sector, as listed
in Table 4 and Table 14, are the focus of this thesis. While SAC305 has been widely

34
adopted by the industry during the initial transition to Pb-free, desired improvements in
mechanical and thermal performance, as well as cost reductions, continue to drive
research into new alloys.

Figure 22 illustrates the process for developing requirements for a new replacement alloy
for the consumer sector. The figure outlines the main shortcomings of the current market
available Pb-free solution based on SAC alloys, namely the high cost and poor
drop/shock performance. These shortcomings, in all probability could be overcome by a
new alloy, which is both less stiff and has a lower process temperature. The lower
process temperature would allow for “normal” Tg board material – that which has been
used with SnPb solders for many years – to again be used, eliminating collateral failure
modes such as pad cratering and an increased susceptibility to moisture delamination.

New Pb-Free Solder

Lower Process Temperature

Less Stiff

Normal Tg Board Material

No Moisture
Delamination/Cracks
No Pad Cratering

Improved Drop/Shock
Less Expensive
Performance

Figure 22: New approach proposing to use solder with no or low-Ag content6

Any replacement alloy for the consumer sector should perform better than SAC305 with
respect to drop/shock performance and thermal cycling. Both tests are representative of
service conditions that would likely be experienced by any consumer electronic product.
35
The following accelerated test conditions are accepted by industry as representative of
life conditions for these products:
 ATC in accordance with IPC-9701A Performance Test Methods and Qualification
Requirements for Surface Mount Solder Attachments47
 Drop/Shock Testing in accordance with the Joint Electron Device Engineering
Council (JEDEC) Standard JESD22-B110A Subassembly Mechanical Shock Test49

Table 14: Consumer alloys under test

Alloy Composition Assembly Temperature

SAC305 Sn 3%Ag 0.5%Cu 240C
Senju M42 Sn 2%Ag 0.75%Cu 3%Bi 224C
Sunrise Sn 1%Ag 0.7%Cu 7%Bi 222C
Sunflower Sn 0.7%Cu 7%Bi 226C

This thesis presents the results of both ATC and Drop Shock testing of the alloys selected
for consumer electronics applications (Table 4 and Table 14). These alloys were also
tested for a lower probability of Sn whisker formation according to JESD22A121.

36
4 References

1
K. Sweatman, J. Read, T. Nishimura, and K. Nogita “The Effect of Microalloy
Additions on the Morphology and Growth of Interfacial Intermetallic in Low-Ag
and No-Ag Pb-Free Solders”, presented at SMTAI, Chicago, Il, 2011.
2
K-N. Tu “Copper Tin Reactions in Bulk Samples” in Solder Joint Technology :
Materials, Properties and Reliability New York, Springer, 2007, ch. 1, pp. 1-32
3
IPC-A-610E “Acceptability of Electronic Assemblies” April 2010.
4
Directive 2002/95/EC of the European Parliament and of the Council of 27 January
2003 on the restriction of the use of certain hazardous substances in electrical and
electronic equipment
5
Directive 2011/65/EUof the European Parliament and of the Council of 8 June 2011 on
the restriction of the use of certain hazardous substances in electrical and
electronic equipment
6
P. Snugovsky, S. Bagheri, M. Romansky, D. Perovic, L. Snugovsky, J. Rutter “New
Generation of Pb-Free Solder Alloys: Possible Solution to Solve Current Issues
with Main Stream Pb-Free Soldering,” SMTA Journal Volume 25 Issue 3, 2012.
7
M. Kelly, D. Colnago, V. Sirtori, C. Grosskopf, K. Lyjak, C. Ravenelle, E. Kobeda, J.
Bath, S.K. Tan, and L.H. Teo “Component Temperature Study on Tin-Lead and
Lead-Free Assemblies”, Journal of SMT, Volume 15 Issue 4, 2002.
8
IPC/JEDEC J-STD-020D.1 “Moisture/Reflow Sensitivity Classification for
Nonhermetic Solid State Surface Mount Devices” March 2008.
9
B.Gray “Correlation of Printed Circuit Board Properties to Pad-Crate Defects Under
Monotonic Spherical Bend”, M.A.Sc. thesis, Dept. Mech. Eng., Ryerson
University, Toronto, Ontario. 2012.
10
P. Snugovsky “Low Melt Pb-Free Solder to Solve Pb-Free Transition Challenges”
11
T. Sawamura and T. Igarashi “Difference between Various Sn/Ag/Cu Solder
Compositions”, Almit Ltd. June 2005.
12
K.S. Kim, S.H. Huh, K. Suganuma “Effects of intermetallic compound on properties of
Sn-Ag-Cu lead free solder joints” Journal of Alloys and Compounds 1 (2002)
13
L. Turbini. “Process and material issues related to Lead-free soldering”, J Mater Sci:
Mater Electron (2007) 18:147-154
14
U. Kattner, “Phase Diagrams for Lead-Free Solder Alloys” JOM December 2002 pp.
45-51
15
http://www.metallurgy.nist.gov/phase/solder/cusn-w.jpg

37
16
C. Handwerker. “Fundamental Properties of Pb-Free Solder Alloys”, in Pb-Free
Soldering, Springer 2007, ch.2, pp. 21-74
17
K-N. Tu “Introduction” in Solder Joint Technology : Materials, Properties and
Reliability New York, Springer, 2007, sec. 1.2.1, pp. 6
18
J. Dutkiewicz, L.A. Zabdyr, Z. Moser and J. Salawa. ASM Handbook Volume 3 Alloy
Phase Diagrams Materials Park, OH: ASM International 1992 pp. 2129
19
K.-W. Moon, W.J. Boettinger, U.R. Kattner, C.A. Handwerker, and D-J. Lee. “The
Effect of Pb Contamination on the Solidification Behavior of Sn-Bi Solders”,
Journal of Electronic Materials, Vol. 30, No. 1, 2001
20
M. Ribas S. Chegudi, A. Kumar, S. Mukherjee, S. Sarkar, R. Pandher, R. Raut, and B.
Singh. “Low Temperature Alloy Development For Electronics Assembly – Part
II”
21
P. Vianco, J. Rejent and R. Grant “Development of Sn-Based, Low Melting
Temperature Pb-Free Solder Alloys” Materials Transactions, Vol 45. No. 3
(2004) pp. 765-775
22
C. Handwerker. “Fundamental Properties of Pb-Free Solder Alloys”, in Pb-Free
Soldering, Springer 2007, ch.2, pp. 21-74
23
http://www.metallurgy.nist.gov/phase/solder/agcusn-l.jpg
24
http://www.empf.org/empfasis/2008/mar08/pillow.html
25
Acceptability of Electronic Assemblies IPC-A-610 Revision D February 2005 pp. 8-17
26
D.A. Shnawah, M.F.M. Sabri, I.A. Badruddin “A review on thermal cycling and drop
impact reliability of SAC solder joint in portable electronics products,”
Department of Mechanical Engineering, University of Malaya, Kuala Lumpur,
Microelectronics Reliability 52 (2012) pp. 90-99
27
P.T. Vianco, J.A. Rejent “Properties of Ternary Sn-Ag-Bi Solder Alloys: Part 1 –
Thermal Properties and Microstructural Analysis”, Journal of Electronic
Materials, Vol.28, No.10, pp. 1127-1137, 1999
28
P.T. Vianco, J.A. Rejent “Properties of Ternary Sn-Ag-Bi Solder Alloys: Part 2 –
Wettability and Mechanical Properties Analysis”, Journal of Electronic Materials,
Vol.28, No.10, pp. 1138-1143, 1999
29
http://www.metallurgy.nist.gov/phase/solder/bisn-w.jpg
30
http://www.metallurgy.nist.gov/phase/solder/agbisn.html
31
D.A. Porter and K.E.Easterling, “Thermodynamics and Phase Diagrams” in Phase
Transformations in Metals and Alloys, 2nd ed. UK: Chapman & Hall, 1992, ch. 1,
pp 48-55.
32
http://www.metallurgy.nist.gov/phase/solder/bicusn.html
38
33
http://www1.asminternational.org/asmenterprise/APD/SearchAPD.aspx
34
J.S. Hwang “A Strong Lead-free Candidate: the Sn/Ag/Cu/Bi System”, SMT
Magazine, August 1, 2000.
35
http://www.senju.com/images/pdf/Senju%20ECO%20Solder.pdf
36
S.W. Chen, C-C Lin, C. Chen “Determination of the Melting and Solidification
Characteristics of Solders Using Differential Scanning Calorimetry”,
Metallurgical and Materials Transactions A, Volume 29A, July 1998 pp. 1965-
1972
37
L. Rycerz. “Practical remarks concerning phase diagrams determination on the basis of
differential scanning calorimetry measurements” J Therm Anal Calorim, 113,
2013 pp. 231-238
38
M. H. Kaye, K.M. Jaansalu and W.T. Thompson “Condensed Phases in Inorganic
Materials: Metallic Systems” in Measurement of the Thermodynamic Properties
of Multiple Phases, R.D. Weir and Th.W. deLoos, Ed. San Diego, Elsevier Inc.,
2005, pp. 227-305
39
J.S. Hwang “A Strong Lead-free Candidate: the Sn/Ag/Cu/Bi System”, SMT
Magazine, August 1, 2000.
40
http://www.senju.com/images/pdf/Senju%20ECO%20Solder.pdf
41
J.W. Evans “Introduction to Solder Alloys and Their Properties” in A Guide to Lead-
free Solders: Physical Metallurgy and Reliability, Silver Spring, MD: Springer,
2005, pp. 1-27
42
J.W. Evans “Microstructural Instability in Solders” in A Guide to Lead-free Solders:
Physical Metallurgy and Reliability, Silver Spring, MD: Springer, 2005, pp. 79-
95
43
E. Kosiba S. Bagheri, Z. Bagheri, P. Snugovsky, and D. Perovic “Assembly Feasibility
and Property Evaluation of Low Ag, Bi-Containing Solder Alloys” in ICSR
SMTA Conference, Toronto, ON, 2012
44
P. Snugovsky, E. Kosiba, J. Kennedy, Z. Bagheri, M. Romansky, M. Robinson, J.M.
Juarez, Jr., J.Heebink “Manufacturability and Reliability Screening of Lower
Melting Point Pb-free Alloys Containing Bi,” in IPC APEX EXPO Conference,
San Deigo, CA, 2013.
45
J. Juarez Jr., M. Robinson, J. Heebink, P. Snugovsky, E. Kosiba, J. Kennedy, Z.
Bagheri, S. Suthakaran, M. Romansky “Reliability Screening of Lower Melting
Point Pb-Free Alloys Containing Bi,” in IPC APEX EXPO Conference, Las
Vegas, NV, 2014.
46
D.C. Montgomery. “Design and Analysis of Experiments”, 8th Edition. Jonh Wiley &
Sons, 2012.
39
47
IPC-9701A Performance Test Methods and Qualification Requirements for Surface
Mount Solder Attachments, February 2006
48
J. Bentley “Introduction to Reliability and Quality Engineering”, 2nd Ed, Essex,
England, Pearson Education Limited, 1999, ch. 2, pp 28-43
49
Subassembly Mechanical Shock, JESD22-B110A, November 2004.

40
 Chapter 2
Solder Joints after Reflow (As Manufactured)

1 Introduction
The formation of a solder joint is influenced by the conditions at which the chemical
bond is formed: primarily, the maximum temperature of the reflow, the time above
solidus and the cooling rate. Therefore, the melting temperature and pasty range are
primary characteristics which differentiate solder alloys. The solder joint microstructure
further evolves when exposed to elevated temperatures for a prolonged period of time or
if exposed to other forms of stress, due to solid-state diffusion and other physical effects
described below. The microstructural properties described in this chapter, which result
from the solidification of liquid solders, will have an influence on the mechanical and
thermo-mechanical properties of the solder joint and therefore impact the reliability in
field conditions.

2 Bulk Solder Microstructure – Solidification Process

Slight changes to the alloy composition may result in different solidification regimes
within the solder joint and therefore significantly change properties. It is therefore of
interest to examine the factors which govern this process.

2.1 Cu Dissolution in Molten Solder

As the molten solder comes into contact with the solid Cu pad layer on the PWB board,
Cu will dissolve into the liquid solder. For this reason, the overall concentration of Cu
within the molten solder will increase at a rate that is dependant on the time spent above
the solidus temperature. SAC305, as an example, has an initial Cu concentration of
0.5wt% however, by the time cooling is initiated, the Cu concentration may be as high as
1wt%. Figure 23 shows a typical SAC305 reflow profile in which a particular solder joint
experienced 71 seconds above 217C, the solidus temperature for SAC305. This Cu
dissolution during the liquid phase of solder joint formation will continue, given enough

41
time, until the liquids solubility limit is reached. This reaction has been characterized by
the Nernst-Brunner equation (Equation 2-1):

X s  X 0 KAt
ln  2-1
XS X V

where XS represents the solubility limit, X0 represents the initial concentration, K is the
temperature-dependent Nernst-Brunner dissolution rate constant, A is the contact area at
the interface, V is the total volume of solder, t is time.1

Figure 23: Typical reflow profile for SAC305

If dissolution kinetic conditions are satisfied (for example if a very high temperature is
maintained over a sufficient length of time), the Cu present in the board material can be
dissolved into the solder up to a very high concentration. Potentially the entire copper pad
region on the PWB can be consumed by the intermetallic and bulk solder. Figure 24
shows the Cu pad being progressively consumed by the IMC layer after successive
rework/replacement cycles. In this example, the solder joint is repeatedly heated above
the solder alloy liquidus temperature.

42
 Figure 24: Copper dissolution of BGA solder joint after a) 1 replacement b) 3
replacements and c) 5 replacements2

It has been shown that an increase in copper concentration within a Sn-based solder alloy
from 0.5%Cu to 0.7%Cu decreases the amount of copper dissolution from the PWB
material, which is attributed to the reduction in the concentration gradient.3 This is the
primary reason for the presence of Cu in the SAC system of alloys and in the alloys
proposed in this study. The Cu dissolution described above typically results in a
concentration within the hypereutectic region of the Cu-Sn phase diagram (Figure 6). As
the solder cools Cu6Sn5 particles will begin to nucleate within the liquid.

As the Cu dissolution into the liquid solder occurs, a competing process is taking place in
which the Cu and liquid solder react to form a chemical bond at the interface, which takes
the form of an intermetallic compound – the interfacial IMC. This reaction is discussed in
3.

2.2 Bulk Solder Solidification

Within the bulk solder, the equilibrium solidification of SAC305 follows the path
outlined in red, in Figure 25, where non-faceted Sn grains begin to form a dendritic
structure. As the liquid continues to be consumed by the new Sn structure, the
remaining liquid composition moves along the red line from A towards B. At B, a
eutectic of Sn + Ag3Sn forms in the interdendritic spaces of the already solidified Sn
dendrite. This eutectic solidification continues, and the liquid compositions following the
eutectic valley from B towards E. At this point, any remaining liquid is now at the ternary
43
equilibrium composition (point E) and will solidify as a ternary eutectic of Sn + Ag3Sn
+ Cu6Sn5.4

Figure 25: SnAgCu phase diagram with SAC305 equilibrium solidification path5

The solidification path described above does not account for Cu dissolving into the bulk
solder from the board side Cu pad and, in the case of a leaded component, from the lead
itself. The Cu concentration in the bulk liquid is therefore increasing; the blue line in
Figure 25 indicates a concentration of approximately 1wt% Cu. In this case, the Cu6Sn5
begins to solidify before the Sn. The Cu6Sn5 continues to form until the concentration
reaches the eutectic line and a binary eutectic of Sn + Cu6Sn5 forms. Additionally,
Cu6Sn5 IMC, which has already formed at the Cu-liquid solder interface, and will be
described in section 3, may break off and move through the bulk solder.

As the Sn dendritic arms grow, the composition of the liquid at the Sn/liquid interface
changes and becomes Cu rich. In the Cu rich regions, a binary of Sn + Cu6Sn5 will
begin to nucleate and grow. The remaining liquid at the Sn + Cu6Sn5 eutectic/liquid
interface will be Ag rich. At this point, the remaining liquid will either solidify as a

44
eutectic of Sn + Ag3Sn to form the “double binary eutectic”6, or as a ternary eutectic of
Sn + Cu6Sn5 + Ag3Sn.

2.3 Undercooling During Solidification

The solidification path described above assumes equilibrium cooling conditions, in which
sufficient time is allowed for all processes to occur. In reality, cooling rates are usually
faster than equilibrium conditions resulting in some effects of undercooling. A number
of different structural morphologies can be expected with different cooling rates. For
example, a quick quench after melting of a SAC alloy resulted in a fine Sn dendrite
structure with very fine, non-faceted ternary eutectic structure in the interdendritic
spaces.7

Figure 23 shows that in a typical SMT reflow process, the solder alloy cools relatively
quickly after reaching maximum temperature. This cooling profile will induce
microstructures more typical of undercooling conditions than of equilibrium cooling as
described above. In the case of a SAC alloy, in which Sn, Cu6Sn5 and Ag3Sn all form,
cooling below the eutectic temperature of 217C would represent an undercooling
condition for all three of the solid phases. As one of these phases begins to nucleate and
grow, the composition of the remaining liquid changes. A move away from the eutectic
point would represent a condition of even further undercooling of one of the phases, as,
in all cases the liquidus surface increases away from the eutectic point. As the second
phase nucleates, the remaining liquid again shifts in concentration until the nucleation of
the third and final phase occurs. This is referred to as constitutional undercooling,
describing the changing conditions of the liquid at the solidification front.

As described above, it is expected that a SAC305 solder, cooled quickly below the
ternary eutectic point of 217C, would initially form a Sn phase, followed by Sn +
Ag3Sn5 eutectic and finally the ternary Sn + Ag3Sn5 + Cu6Sn5 eutectic. As the
concentration of Cu in the molten solder is increased, Cu6Sn5 is favored to solidify first.
This implies that the primary phase to solidify will be the one with the highest liquidus
temperature, however there are a number of other factors to consider including:
45
  nucleation from undercooled liquid
 the growth kinetics of facetted vs. non-facetted phases
 the availability of Cu and Ag within the volume to form corresponding phases.6

Figure 26 shows a 3D phase diagram in the Sn rich portion of a SAC alloy. The liquidus
surfaces are extended below the eutectic point to help visualize the solidification of the
three phases in undercooling situations. The red line shows the equilibrium solidification
of a particular Ag rich alloy, while the white line shows the solidification path of the
same alloy in non-equilibrium, undercooling conditions. In this scenario, Ag3Sn
continues to form until the composition reaches the eutectic of Ag3Sn + Cu6Sn5.

The undercooling of SAC305 with further dissolved Cu (Cu concentration of ~1wt%)

would result in a solidification path along the Cu6Sn5 surface below the eutectic point.
As the temperature is significantly lower than the liquidus temperature for this phase,
Cu6Sn5 will nucleate and grow. The composition of the liquid will then change and move
to another area on the phase diagram. The next phase to solidify will be the one with the
highest liquidus temperature, and therefore the greatest degree of undercooling. This will
continue until all liquid has solidified.

Figure 26: A 3D phase diagram of Sn rich portion of Sn-Ag-Cu ternary system8

46
The growth kinetics of the three phases also plays a role in the solidification process.
While this process is beyond the scope of this work, it should be considered that both
Ag3Sn and Cu6Sn5 have facetted structures and are therefore restricted to grow in specific
crystallographic directions, while the non-facetted Sn can grow through the fluid in a
more unrestricted fashion.6

Finally, the volume fraction of elements in the liquid needs to be considered. As one
phase solidifies, its growth is further restricted by the availability of atoms of the correct
type. The final volume fraction of the Ag3Sn and Cu6Sn5 phase is therefore limited by
the availability of Ag and Cu atoms respectively within the liquid. Ag3Sn requires a
localized concentration of 73.2wt% Ag within a total volume with a concentration of only
3wt% in SAC305 and even lower in the other alloys considered in this study. This would
require significant diffusion of Ag through the liquid, which may not occur in
undercooling conditions. Similarly Cu6Sn5 requires a local concentration of 39.1wt% Cu
within a liquid with only approximately 1wt% Cu. Sn, by contrast, will likely have a
ready supply of Sn at the solidification fronts of the other two phases since it makes up
the vast majority of the volume fraction.

2.4 Formation of Facetted IMCs in Bulk Solder

The presence of large, faceted IMCs in the bulk solder, Ag3Sn and Cu6Sn5, may present a
reliability concern as they can act as stress risers and paths along which cracks
propagate.9 Large, primary Cu6Sn5 particles form when the total concentration of Cu in
the liquid is high and Cu6Sn5 is the first phase to solidify (Figure 25). Some undercooling
is also required, however the undercooling required to nucleate Cu6Sn5 is less than that
required to nucleate Sn.10 This phase has a facetted structure of hexagonal morphology,
often hollow on the inside. The structure then grows in a rod, forming a structure similar
to a pencil – a hexagonal tube with a facetted center (Figure 27). As a primary phase
solidifying from liquid, this facetted rod structure will be surrounded by a liquid whose
composition moving along the blue line shown in Figure 25 until a eutectic of Sn +
Cu6Sn5 forms together. Since the base phase (Cu6Sn5) is a more complex crystal

47
structure, it dictates the final shape of the eutectic colony. In this case, the Cu6Sn5 portion
of the eutectic may form as branches of the original rod like structure.11

Ag3Sn IMCs form within the bulk solder. Similar to the Cu6Sn5 structures, Ag3Sn may
form as primary phases, or as part of a binary or ternary eutectic solidification regime
depending on the alloy composition and cooling rate. At compositions below
approximately 3.7wt% Ag, Ag3Sn particles are not expected to form as a primary phase.
It is more likely that the Ag3Sn will form in the interdendritic spaces of the Sn and/or
Cu6Sn5 phases and as part of a eutectic with one of both of the other two phases. In a
typical cross-section view, the Ag3Sn IMC will appear as small particles. In fact, these
particles have a fine, fibrous structure (Figure 27), which can be seen after selectively
etching away the Sn phase. The network of fibers typically appears to surround the Sn
dendrite arms, indicating that they form in the interdendritic spaces during eutectic
solidification. 12

Figure 27: SAC solder joint viewed a) in cross section and b) after selective
electrochemical etching to remove Sn phase13

2.5 Bi in Solution and as a Precipitate

As discussed in Section 2.4.1.2, the three experimental alloys shown in Table 15 were
selected from outside the ternary eutectic triangles of the ternary Sn-Ag-Bi and Sn-Bi-Cu
alloys so as not to form any ternary eutectic phase with Bi. This is both to avoid the
48
formation of a low melting temperature (~138C) phase, as well as to avoid the formation
of primary Bi particles, which form directly from the liquid state. Depending on the
amount of Bi in the overall composition, favourable Bi particles may be produced in the
final solder joint microstructure; however these particles are the result of solid solution
precipitation from within the Sn. Bi precipitation from solid solution has been
confirmed by the DSC curve for each studied alloy. In all cases, only one main peak
appears, indicating that all liquid was consumed prior to the ternary eutectic solidification
which could have resulted in a primary Bi phase.

Bi, as an alloying element in a Sn based solder, differs from Ag and Cu in two significant
ways: Bi has high solubility in Sn (up to 21wt%), and Bi does not form any intermetallics
with Sn. It should also be noted that Sn is not soluble in Bi; any Bi particles that form
will therefore be 100% Bi.

3 Sn-Cu Reaction and Formation of Interfacial IMC

The chemical bond which forms between Sn and Cu provides a strong interaction
between the solder and the substrate. As described earlier, this bond provides a chemical,
mechanical and electrical bond between the two materials. Both Cu6Sn5 () and Cu3Sn
() phases can potentially form during solidification at the interface. It has been shown
that the formation of the  IMC layer increases with increased temperature.14 This
generally occurs up to a thickness of approximately 2.5µm at which point the IMC
appears to form as more needle like faceted rods, initially at the interface, and then
through the bulk solder (Figure 28). The  phase was not shown to form at initial
solidification, but rather occurred over time as an effect of aging. This will be discussed
further in Chapter Chapter 3.

Many studies looking at the Sn-Cu diffusion couples considered two solid substrates in
contact while exposed to heat. When considering a solid Cu with a molten Sn coupling
to form a molten-Sn/solid-/solid-Cu interface, two rate dependent steps need to be
considered:14

49
  Diffusion of Sn through  to solid Cu interface

 Reaction of Cu and Sn at this interface

Figure 28: Solder joint between Sn-based solder and Cu a) rod shaped Cu6Sn5 ()

b) scallop shaped Cu6Sn5 () IMC layer

SAC305 has solidus and liquidus temperatures of 217C and 220C respectively. A
typical reflow profile (Figure 23) will have a time above solidus of anywhere from 60 to
90 seconds and a maximum temperature of approximately 240C. The initial formation
of the interfacial IMC layer between the Cu and  phase is governed by time, temperature
and contact area. While the contact area is fixed for a particular build, both the time and
temperature can be varied by altering the solder reflow profile or solder alloy
composition.

Although covered in Chapter Chapter 3, it is worth noting that the interfacial IMC will
continue to grow at rates determined by time and temperature. At lower aging
temperatures (ambient temperature to about 70C), the  layer grows preferentially
indicating that the Cu diffuses at these temperatures, while at higher storage temperatures
(above 135C) both the  and  layer will form and grow, indicating that Sn diffusion
begins to dominate at these increased temperatures.15 Another possibility is that the Sn
supply between the  phase and the copper interface is inadequate for the formation of
the  phase.16 The morphology of the /solder interface in a typical solder joint tends to
be scalloped in shape (Figure 28b) but may flatten to a more planar interface as it grows
50
upon aging. The  phase, which is sandwiched between the  and the Cu (resulting in a
//Cu interfaces), tends to form a more planar morphology.16,19

It has also been observed that microvoids may form between the copper and  interface17.
These Kirkendall voids18 form as the Cu diffuses into the  layer leaving behind voids
(Figure 29a). These present a long-term reliability concern as they weaken the interface.
Another consideration is the morphology of the interface that is formed.

In the SnPb solder system joined to a copper substrate, the Sn is consumed from the area
close to the solid copper forming the Cu6Sn5 intermetallic compound. This can leave a
localized region of Pb in direct contact with the intermetallic (Figure 29b). This effect
may continue under aging conditions as the Cu6Sn5 continues to grow, and the Sn in the
immediate vicinity is depleted.19 This presents a potential reliability concern; the Cu6Sn5
being brittle and the segregated Pb providing a convenient path for crack propagation and
eventual fracture. This combination has been observed to fracture predominately along
the /solder interface.19

Figure 29: SnPb solder jointed to Cu substrate a) showing Kirkendall voids20 b)

showing Pb phase pooling at IMC/solder interface (cross section by Zohreh Bagheri)

In this manner, Bi has been found to behave in a similar way as Pb. SnBi eutectic solders
may therefore have the same reliability concerns related to the pooling of one phase, Bi,
along the Cu6Sn5 interfacial IMC. The lower level of Bi used in this study, between 3-
7wt%, is not expected to result in this condition.

51
The scallop shaped morphology, typically associated with the Cu6Sn5 IMC bond layer, is
a result of the solidification of the molten solder and dissolved Cu6Sn5 at the interface. A
fast, non-equilibrium cooling rate typical in a solder reflow profile will result in a
scalloped morphology. A slower rate will allow for the interfacial IMC layer to form in a
smoother morphology and a faster rate will result in a more complicated dendritic, or
“coral” shaped structure. It has also been shown that the structure of the base Cu is a
contributing factor to the morphology of the interfacial IMC layer.21 It was found that
Cu6Sn5 grows in a prism-type morphology from single crystal Cu with (001) or (111)
grain orientations (Figure 30). Other crystallographic orientations result in a scallop-type
structure similar to that found in a polycrystalline Cu substrate. Since the board side Cu
pad is polycrystalline and not single crystal, it will form a scallop shaped IMC layer.
However, in localized areas where a Cu grain may have a (001) or (111) orientation, a
prism structure may form amongst smooth scallops.

Figure 30: Typical morphologies of Cu6Sn5 grains formed on single crystal

a) (001) Cu and b) (011) Cu21

Growth of the IMC bonding layers can also occur by solid-state diffusion during aging
conditions. This will be considered in Chapter Chapter 3.

52
4 Cu-Ni-Sn Interface
Because of the tendency for Cu to oxidize, protective layers on the Cu surfaces of PWBs
are used. For this project an OSP finish was used which is dissolved by the flux in the
solder paste during the reflow, and does not need to be considered when evaluating the
resulting solder joint. Other board finishes utilize layers of Ni, Au, Pd or other inert
metals as protective barriers. These are usually present in very thin layers, often in
combination. For example, an ENIG finish is made up of a thin Au layer (0.05µm) over
an electroless Ni layer (3-6µm). Additionally, it is common to find an electrolytic Ni
barrier layer used between the Cu pad on a BGA component and the attached solder ball;
it is for this reason that the Cu-Ni-Sn interaction is important in solder joints formed in
this study. Ni also has a much slower diffusion rate than Cu in molten solder therefore it
serves as a diffusion barrier to Cu. With a SnPb solder, it was found that a scallop shaped
Ni3Sn4 intermetallic formed, however with SAC alloys this phase appeared to be
suppressed in favour of a (Cu,Ni)6Sn5 IMC bonding layer. It is the Cu from within the
solder which is present in the final IMC composition.22 This is verified by examining a
similar IMC formed using a SnPb solder, in which no Cu is present; it forms a Ni6Sn5
IMC with no Cu present. The (Cu,Ni)6Sn5 phase is made up of many needle-like,
hexagonal cylinders with pointy tips or, when seen as a layer has a “coral” type
morphology (Figure 31).23,24

Snugovsky et al. 25 showed that in the Sn rich corner of the Cu-Ni-Sn system, two quasi-
peritectic reactions exist:
L+(Ni,Cu)3Sn4 ↔ Ni23Cu33Sn44+Sn at 229.1C 4-1

L+Ni23Cu33Sn44 ↔ (Cu,Ni)6Sn5+Sn at 228.1C 4-2

Therefore the IMC bond layer formed at the component side of the BGA, which is
formed from the Ni barrier layer, and both Sn and Cu from the SAC305 alloy will likely
be one of the compounds listed in Equation 2-2 and 2-3. Additionally, the IMC which
forms towards the board side of the BGA component will be formed primarily from the
Cu layer and the Sn from within the SAC305 solder ball and paste. Ni, which has

53
diffused through the molten solder, may also be present. The Ni23Cu33Sn44 intermetallic
has a smooth, cellular morphology. 26 The formation of Kirkendall voids is also a concern
at the (Cu,Ni)6Sn5 – Ni(P) interface.

Figure 31: IMC formed between SAC solder and Ni(P)Au23

5 Experimental Set Up
5.1 Test Vehicle Assembly
Celestica’s RIA3 test vehicle (Figure 32) was used for the work described in this paper. It
was originally designed to simulate a typical, medium complexity assembly. It is an
8”x10” surface made up of 12 Cu layers for a total thickness of 0.093” with an OSP
finish. This board is one which is often used to test new, lead-free solders and other
material parameters. LQFP176, PBGA256, CBGA64 and MLF20 components were
populated, two of each on each board. The BGA components all employed SAC305 ball
alloy. The board and SMT components were attached with solder pastes of the alloys of
interest. The solder paste alloys were experimental formulations of the alloy and paste
flux suitable for the process temperatures. The SAC305 and Senju M42 pastes were
commercially formulated by Indium Corp. The reflow was performed in an air
environment in a 10 zone oven. One board from each combination listed in Table 15 was
held for evaluation of the “As Assembled” microstructure.

54
 Figure 32: Test vehicle

Table 15: Build matrix for as assembled analysis

Alloy Composition Assembly Temperature
SAC305 Sn 3%Ag 0.5%Cu 240C
Senju M42 Sn 2%Ag 0.75%Cu 3%Bi 224C
Sunrise Sn 1%Ag 0.7%Cu 7%Bi 222C
Sunflower Sn 0.7%Cu 7%Bi 226C

5.2 Test Matrix

Each of the four components listed in Table 16 was cross sectioned to evaluate the solder
mixing, shape of the solder joint, degree of voiding and any possible anomalies.

Table 16: Table of components evaluated by cross sectioning

Component Reference Designator
BGA-256 U204
BGA-256 U205
QFP-176 U1
QFP-176 U2

55
5.3 Test Method
Components were cut from the test vehicle shown in Figure 32 and mounted in epoxy for
cross-sectioning. Each cross-section was ground and polished through the following
sequence: 500 and 1200 grade SiC paper, polishing with 6 µm and 1 µm DiaPro diamond
suspensions (Struers), and an oxide polish (Struers OP-S). Optical microscopy was
performed using a Nikon Measurescope MM-11. Prior to SEM analysis, the samples
were carbon coated using an Emitech K950X. SEM microscopy was performed using a
Hitachi S-4500 and Hitachi S-3000N with the following EDX systems: Oxford and
ThermoScientific respectively.

6 Microstructural Evaluation
6.1 Comparison of Bulk Microstructure
EDX was used to evaluate both the overall composition of the bulk material in the solder
joint and the composition of Sn grains within the solder joint (Figure 33). Although EDX
is a semi-quantitative approach, it was deemed sufficient for purposes of comparison.
Scans of the bulk solder joints were taken of cross sectioned samples as seen in Figure 33
a) and b) as well as of the Sn grain (Figure 33c) for each alloy. The results are tabulated
in Table 17 and Table 18. Each value represents an average of 3-5 measurements.

Figure 33: Area for EDX compositional analysis of a) bulk BGA solder joint,

b) bulk QFP solder joint and c) Sn grain

56
6.1.1 Bulk Microstructure of QFP Solder Joints
Table 17: Composition of QFPs (wt%)
Composition of Bulk Solder Sn Grain
Paste Alloy Paste Alloy (wt%) (wt%)
(wt%) Sn Ag Cu Bi Sn Bi
SAC305 Sn 3%Ag 0.5%Cu 96.8 2.2 1.0 0.0 100 0
Sn 2%Ag 0.75%Cu
Senju M42 94.5 1.8 1.2 2.5 98.0 2.0
3%Bi
Sunrise Sn 1%Ag 0.7%Cu 7%Bi 92.7 0.9 1.0 5.6 95.0 4.0
Sunflower Sn 0.7%Cu 7%Bi 93.8 0.0 1.0 5.2 94.5 5.5

The bulk composition of the QFP solder joints is close to that of the original paste
composition with the exception of increased Cu concentration and a very small increase
in the Sn content. The increase in Cu concentration is expected due to Cu dissolution
from the board side Cu pad and from the lead. The leads are plated with a thin layer of
Sn, which melts during the reflow process and combines with the bulk solder. It is also
expected that the concentration of Bi within the Sn grain would be lower than in the
overall composition as can be seen in two of the three Bi-containing alloys in Table 17,
Senju M42 and Sunrise. This is a result of the off-eutectic solidification in which primary
Sn dendrite arms form prior to the final eutectic solidification of the remaining liquid.
The primary Sn grain will continue to grow, driving the Bi content of the liquid at the
solid/liquid interface to increase. Finally, the remaining liquid solidifies as a eutectic
structure within the interdendritic spaces. The Bi concentration of the eutectic portion of
the Sn will therefore be greater than that of the primary Sn dendrite arms. Over time
and with the precipitation of Bi from solid solution, it is expected that this concentration
gradient will diminish. The Sunflower alloy has a composition which lies on the eutectic
line on the Sn-Bi-Cu phase diagram (Figure 13). In this case, a eutectic of Sn + Cu6Sn5
will solidify, instead of the nucleation and growth of Sn grains prior to solidification of
other phases. The Bi content of the Sn dendritic arms in Sunflower is similar to the
overall final composition of the solder joint, as seen in Table 17.

Figure 34a and b show the microstructures of SAC305 and Senju M42 solder joints
respectively. Both have very similar microstructures with fine Sn dendritic arms
57
surrounded by fine Ag3Sn and Cu6Sn5 IMCs solidified as either binary or ternary
eutectics with Sn in the interdendritic spaces. In the case of Senju M42, all Bi appears to
be in solid solution with Sn, with no visible Bi precipitates.

Figure 34c and d show cross sectional images of Sunrise and Sunflower respectively.
Both have larger Sn dendritic arms and Cu6Sn5 IMCs. Sunrise shows a small amount of
Ag3Sn particles, while Sunflower does not have any due to the lack of Ag in the paste
composition. In Sunrise, while Bi particles are visible and believed to have precipitated
from solid solution of the interdendritic Sn, which exists as either a binary eutectic with
Sn + Ag3Sn, Sn + Cu6Sn5, or a ternary eutectic of Sn + Ag3Sn + Cu6Sn5. As described
above, this interdentritic, eutectic Sn, rather than that found in the primary Sn dendrite
arms, has a higher Bi content resulting from the solidification of the off eutectic alloy
(Table 17). Sunrise shows an overall composition with 5.6wt% Bi, and only 4.0wt% in
the primary Sn dendrite arms. The bulk of the Bi, therefore is in the Sn within the
interdendritic, eutectic colonies (Figure 35a). Sunflower on the other hand shows the
presence of Bi in both interdendritic and within the Sn dendritic arms (Figure 35b).

58
 Figure 34: Optical images QFP a) SAC305 b) Senju M42 c) Sunrise and d)
Sunflower

Figure 35: Bi present in a) eutectic colonies in Sunrise and b) throughout bulk

solder (eutectic colonies and Sn dendrite arms) of Sunflower

59
The presence of Bi, as well as the distinction between Cu6Sn5 and Ag3Sn, are visible
optically (Figure 36a) however are better distinguished in scanning electron images,
particularly in backscatter electron (BSE) images (Figure 36c) in which differences in
atomic numbers are more visible. In Figure 36b and c, the Bi is shown in light colour
corresponding to a higher atomic number (83) than the surrounding Sn (50). In the
secondary electron (SE) image (Figure 36b), Cu6Sn5 and Ag3Sn appear indistinguishable,
however in BSE (Figure 36c), Cu6Sn5 appears significantly darker while Ag3Sn becomes
difficult to distinguish from the Sn.

Figure 36: QFP solder joint as seen a) optically b) SE SEM and c) BSE SEM

The Bi precipitating from the interdendritic Sn appears in both Sunrise and Sunflower
as both large particles and as fine dispersions (Figure 37). It is expected that the Bi atoms
within the Sn matrix will diffuse together to form a small volume of Bi precipitate, and
then will rearrange themselves into the Bi crystal structure.27 Bi, unlike Cu6Sn5 and
Ag3Sn, has a non-faceted structure.

60
Figure 37: BSE images of a) Sunrise QFP solder joint and b) Sunflower QFP solder
joint

6.1.2 Bulk Microstructure of BGAs

The final composition of a BGA solder joint is made up of both the screened solder paste
as well as the component solder ball. The BGA-256, which was examined in this study,
is made up of SAC305 solder spheres with a diameter of 30 mil and solder paste of each
of the four alloys screened using a 5 mil stencil and a 30 mil aperture. This results in a
volume composition of approximately 87% SAC305 solder sphere and 13% solder paste.
Table 19 provides a summary of the expected final composition of the solder joint formed
from the original solder sphere and the screen solder paste. Table 18 provides a summary
of the composition as measured using EDX as shown in Figure 33a. As with the QFPs,
the composition is close to the expected composition with the exception of an increased
Cu concentration. This is the expected result due to Cu dissolution from the board side
Cu pad. The Cu content increase in SAC305 is greater than that of the other three alloys,
which can be attributed to the higher process temperature. Cu dissolution from the
component side of the solder joint would be mitigated by the Ni barrier layer described in
Section 4. Table 22 indicated that some Ni was present in the board side IMC. This
would indicate that Ni from the component side would diffuse through the solder during
liquid phase mixing and may be present in the final bulk solder composition. Ni was not
found to be present and may therefore be present in trace amounts only.

61
 Table 18: Experimental composition of BGA solder joint
Paste Composition of Bulk Solder Sn Grain
Alloy Paste Alloy (wt%) (wt%)
(wt%) Sn Ag Cu Bi Sn Bi
SAC305 Sn 3%Ag 0.5%Cu 95.5 2.7 1.8 0.0 100 0
Senju Sn 2%Ag 0.75%Cu
96.2 2.4 0.9 0.5 99.7 0.3
M42 3%Bi
Sn 1%Ag 0.7%Cu
Sunrise 95.6 2.6 0.8 1.0 99.3 0.7
7%Bi
Sunflower Sn 0.7%Cu 7%Bi 95.8 2.2 1.0 1.0 99.1 0.9

Table 19: Theoretical composition of BGA solder joint

Theoretical Composition
Composition of
of Bulk Solder
Paste Alloy Paste Alloy
(wt%)
(wt%)
Sn Ag Cu Bi
SAC305 Sn 3%Ag 0.5%Cu 96.5 3.0 0.5 0.0
Sn 2%Ag 0.75%Cu
Senju M42 96.2 2.9 0.5 0.4
3%Bi
Sunrise Sn 1%Ag 0.7%Cu 7%Bi 95.8 2.7 0.5 0.9
Sunflower Sn 0.7%Cu 7%Bi 96.0 2.6 0.5 0.9

Table 19 gives the expected final composition of BGA solder joint based on the volume
of paste versus the SAC305 solder ball. This calculation does not take into account Cu
dissolution. Table 18 is the observed composition measured by EDX. Of note is the
increase in Cu content. Senju M42, Sunrise and Sunflower all have similar Cu
concentrations between 0.8-1.0wt%, which is also similar to that found in the QFPs. The
solder joint formed fully of SAC305 has almost tripled the Cu content at 1.8wt%. This is
likely due to the increase in process temperature; the boards built with SAC305 solder
paste reached a maximum temperature of 240C where as the other solder pastes reached
maximum process temperatures between 222 and 226C.

Good mixing of these two constituent materials is demonstrated in Figure 38 and Figure
39. These images show a portion of a BGA solder joint, formed between SAC305 solder
62
ball and Sunflower solder paste, close to the board side IMC. The EDX mapping shows
the presence of Ag at the lower end of the solder joint. As the screened solder paste,
Sunflower, contributed no Ag to the composition, this indicates good mixing from the
solder ball.

Figure 38: SEM image of Sunflower BGA solder joint

63
 Figure 39: EDX mapping of intermetallic in Sunflower showing a) image

b) Sn c) Ag and d) Cu

In all solder joints shown in Figure 40, there are no visible precipitates of Bi found in any
of the BGAs solder joints formed. With an overall composition of up to 1wt% Bi, it is not
expected that Bi would precipitate from solid solution under equilibrium conditions.

BGA solder joints formed between SAC305 solder balls and each of the four alloys under
investigation all exhibited Cu6Sn5 flower shaped structures, which were a complex
dendritic structure of the Cu6Sn5 pencil shaped rods with branches of the same shape
(Figure 41). These are primary IMCs that form directly from liquid, indicating some
undercooling conditions. The equilibrium phase diagram of Sn-Ag-Cu (Figure 25)
indicates that Cu6Sn5 would be the first phase to solidify and continue for a short time
before the solidification of Sn + Cu6Sn5 eutectic. The presence of large and highly

64
branched Cu6Sn5 faceted structures indicates some degree of undercooling during the
solidification process. In this case, the Cu6Sn5 would continue to grow for an extended
period prior to the formation of other phases. These Cu6Sn5 flowers appeared in solder
joints formed with all four examined solder pastes.

Figure 40: Optical images BGA formed with SAC305 solder balls and paste with the
following alloys a) SAC305 b) Senju M42 c) Sunrise and d) Sunflower

65
 Figure 41: Cu6Sn5 flower structures seen in BGA solder joints made up of SAC305
and a) SAC305 and b) Sunflower solder paste

Figure 42 shows the cross sectional image of a number of BGA solder joints under
polarized light. Polarized light is used to reveal the grain structure of the solder joint. As
is expected from this size of solder joint, a small number of grains comprised the entire
solder joint. While Figure 42b appears to show many small grains, it is more likely to be
interlaced dendrite arms from two to three grains.28 If cross-sectioned through another
plane, this solder joint would likely look similar to the other 3 alloys. The addition of Bi
to the solder does not appear to have a noticeable impact on the number of grains. Further
study is needed to understand the impact of Bi on the size and structure of Sn grains.

66
 Figure 42: Polarized light images BGA a) SAC305 b) Senju M42

c) Sunrise and d) Sunflower

6.2 Comparison of Interfacial IMC Layers

IMC bond layer thicknesses are difficult to measure because of their uneven
morphologies; scalloped in the case of Cu6Sn5 and a needle shaped “coral” structure in
the case of (Cu,Ni)6Sn5. In order to determine a representative thickness, the following
method was used. For BGA solder joints, a cross-section was evaluated using the SEM.
Three solder joints were selected, one from each side and one from the middle of the
component. For each joint, three locations were selected, again one from each side and
one in the middle of the solder joint. For these nine locations, an image was recorded at
3000x magnification. This image was divided along the horizontal length into six equal
segments. Five measurements were then taken between the six segments. A total of 45
measurements were taken, representing various locations across the component. This
methodology allows for any difference in IMC thickness, due to thermal differentials
67
across a component, to be captured. Also, it ensures random locations are selected as
opposed to exclusively selecting the high or low points for measurement. This same
process was used for determining the IMC thickness of the QFP solder joints, however
only two leads were analyzed, resulting in a total of 30 measurements.

There is no statistically significant difference in the thickness measurements of the IMC

layers formed using each of the four alloys on the board side of the BGA. Each solder
paste formed a board side interfacial IMC layer with a normally distributed thickness of
approximately equal variance. The variation in thickness (Figure 43) is large, which can
be attributed to the scalloped shape of the (Cu,Ni)6Sn5 IMC bond layer, which forms at
the solder/board interface (Figure 45b). Table 20 and Table 21 provide a summary of test
for equal variance () and analysis of variance (ANOVA) testing of the means (µ) of the
various alloys for BGA and QFP solder joints respectively. These tables provide
probability (p-values) for each test. In all cases, the null hypothesis (H0) and alternate
hypotheses (Ha) are as follows:

H0: µSAC305=µSenju M42=µSunrise=µSunflower and SAC305=Senju M42=Sunrise=Sunflower

Ha: at least one µ is different and at least one  is different

Values in Table 20 and Table 21 which are bold italicized represent points with a p-value
less than 0.05. This indicates that, within a 95% CI, the H0 is rejected and the Ha is
assumed to be valid.

In the case of the board side IMC layer of BGA solder joints, the H0 is valid, the IMC
layers are statistically similar.

In the case of the component side IMC bond layer, there is a statistical difference in the
thickness measurements: H0 is rejected due to the very low probability. SAC305 and
Sunrise appear to have a greater mean thickness than Senju M42 and Sunflower, however
there are many outliers within the distribution, corresponding to the random, long,
“needle-shaped” shapes which occur in the (Cu,Ni)6Sn5 phase (Figure 46). These points
were removed and the analysis was performed a second time. The new distribution was
68
also found to that the mean IMC thicknesses where not equal however this time, it was
only Sunflower exhibited a greater mean thickness. The new analysis also included many
new outliers. The jagged nature of these IMC layers makes it very difficult to compare
mean thicknesses of the component side IMC; the analysis was deemed to be
inconclusive.

6
IMC Thickness (µm)

SAC305 Senju M42 Sunrise Sunflower SAC305 Senju M42 Sunrise Sunflower
Board Side Component Side

Figure 43: IMC measurements of BGA solder joints after reflow (U204)

Table 20: Results of ANOVA test for equal variance and compare means of IMC
thickness of the BGA IMC layer
Total IMC
Variable / p value Equal
ANOVA
variance
Board Side 0.36* 0.366

Location 0.09** 0.005 (with outliers)

Component Side
0.07** 0.011 (without outliers)
*Bartlett’s Test for equal variance used since distributions where found to be Normal.
**Levene’s Test for equal variance used since distributions was found to be non-Normal.
69
The mean thicknesses of the IMC bond layer formed in the QFP solder joints are similar
for all four alloys in the “as manufactured” state (Figure 44). It should be noted that
SAC305 has a thicker IMC layer than the other three alloys at t = 0 if a 93% CI is used.
This is expected since the process temperature is higher than for the other three alloys.

6
IMC Thickness (µm)

0
SAC305 Senju M42 Sunrise Sunflower SAC305 Senju M42 Sunrise Sunflower
Board Side Lead Side

Figure 44: IMC measurements of QFP solder joints after reflow (U2)

Table 21: Results of ANOVA test for equal variance and compare means of IMC
thickness of the QFP IMC layer
Total IMC
Variable / p value Equal
ANOVA
variance
Board Side 0.60 0.07
Location Component Side 0.30 0.15

70
 Figure 45: IMC bond layers formed on a) QFP components and b) BGA
components

The composition of the IMC bond layers was determined using EDX analysis. Although
EDX provides only a semi-quantitative analysis of the composition, it has been deemed
sufficient for the purpose of identifying phases. The Sn portion of this IMC layer is
contributed from the solder, all four solder alloys contain between 91.3 and 96.5 wt%
Sn. The Cu portion of the IMC is contributed from both the solder (all four solder alloys
contain between 0.5 to 0.75 wt% Cu), and the joining material (lead or board side Cu
pad).

Table 22: IMC type

BGA QFP
Paste Alloy Component
Board Side Board Side Lead Side
Side
Ni23Cu33Sn44,
SAC305 (Cu,Ni)6Sn5 Cu6Sn5 Cu6Sn5
(Cu,Ni)6Sn5
Ni23Cu33Sn44,
Senju M42 (Cu,Ni)6Sn5 Cu6Sn5 Cu6Sn5
(Cu,Ni)6Sn5
Ni23Cu33Sn44,
Sunrise (Cu,Ni)6Sn5 Cu6Sn5 Cu6Sn5
(Cu,Ni)6Sn5
Ni23Cu33Sn44,
Sunflower (Cu,Ni)6Sn5 Cu6Sn5 Cu6Sn5
(Cu,Ni)6Sn5

The IMC bond layers which form on the BGA components are a combination of the
solder paste (one of the four tested alloys), SAC305 from the component solder ball, and
71
the material finish at both the component interface and the board side interface (Figure
45b). The component side interface consists of a Cu pad with a Ni finish
barrier/combined solder (paste alloy + ball alloy). On the board side, the interface
consists of a Cu pad/combined solder. EDX analysis shows that the IMC formed at the
component side is some combination of Ni23Cu33Sn44 and (Cu,Ni)6Sn5 (Figure 46). The
morphology of these needle-like, “coral” shaped IMCs accounts for the large spread in
thickness measurements (component side of Figure 43) and the number of large values
found outside of the 75% quartile denoted as “*” in Figure 43.

Figure 46: IMC formed on BGA at component side

spectrum 1) Ni23Cu33Sn44 and spectrum 2) (Cu,Ni)6Sn5

Figure 47: Typical morphology of a) Cu6Sn5 IMC as formed on a QFP solder joint
with Sunflower b) and c) (Cu,Ni)6Sn5 and Ni23Cu33Sn44 IMCs respectively both
formed on a BGA with SAC305 solder paste
72
7 Summary of Findings
Each of the four alloys under investigation produced solder joints of good shape and
acceptable degree of mixing on both QFPs and BGAs. The Bi content of the three Bi-
containing alloys allowed for melting temperatures of 14-18C lower than that of
SAC305 without negatively impacting the resulting solder joint formation. Differences in
microstructure have been observed related to the decrease in Ag content, addition of Bi
and varying amounts of Cu dissolution resulting from different process temperatures.

The QFP solder joints formed with Senju M42 were very similar to those formed with
SAC305, with all of the Bi present in the Sn phase. This dissolved Bi may act as a solid
solution strengthener, the effect of which needs to be verified in mechanical testing. Both
Sunflower and Sunrise showed some degree of Bi precipitating out of solid solution. Both
fine and medium sized particles were observed. This may achieve some precipitation
hardening within the solder joints, but again will need to be verified by further testing.

The final composition of BGAs was similar to that of SAC305, which was the main
contributing alloy to the final composition, and in all cases having a final Bi
concentration of 1wt% or less. All of the Bi was present in solution within the Sn
phase. The presence of many large, complex Cu6Sn5 flower-shaped imtermetallics
indicates some degree of undercooling in solder joints formed in the BGAs using
SAC305 as the ball material and each of the four alloys as the paste material.

The QFP interfacial IMCs at the board interface and lead interface were similar for all
four alloys. SAC305 results in a thicker IMC layer forming within a 93%CI. In all cases
Cu6Sn5 was identified. The BGA also showed no difference in the type of interfacial
IMCs that formed at both the board side and at the component side. There appears to be
no statistically significant difference in the layer thicknesses of the IMC formed on BGA,
although this is harder to evaluate with the Ni23Cu33Sn44 layer that forms at the
component side of the BGA due to the variable nature of the IMC shape.

73
8 References

1
A. Zbrzezny “Characterization and Modeling of Microstructural Evolution of Near-
Eutectic Sn-Ag-Cu Solder Joints” Ph.D. Thesis, Dept. MSE, Univ. Toronto,
Toronto, Canada, 2004.
2
L. Nie M. Osterman and M. Pecht “Copper Pad Dissolution and Microstructure
Analysis of Reworked Plastic Grid Array Assemblies”, at IPC APEX EXPO
Conference, Las Vegas, NV, 2009.
3
M. Kelly, C. Hamilton and P. Snugovsky “Have High Cu Dissolution Rates of
SAC305/405 Alloys Forced a Change in the Lead Free Alloy Used During PTH
Processes”, SMTA Proc. Pan Pacific Microelectronic Jan. 2007.
4
D.A. Porter and K.E.Easterling, “Thermodynamics and Phase Diagrams” in Phase
Transformations in Metals and Alloys, 2nd ed. UK: Chapman & Hall, 1992, ch. 1,
pp 48-55.
5
http://www.metallurgy.nist.gov/phase/solder/agcusn-ll.jpg
6
L.Snugovsky, P. Snugovsky, D. Perovic; T. Sack; J. W. Rutter “Some aspects of
nucleation and growth in Pb free Sn–Ag–Cu solder”, Mater. Sci. Technol. 21
(2005) 53-60.
7
A.R. Zbrzezny “Microstructure Characterization of Sn-Ag-Cu Lead-Free Solder
Solidified at Different Cooling Speeds”, Microsc. Microanal. 8 (Suppl. 2), 2002.
8
T-K. Lee, T. Bieler, C-U Kim, H. Ma “Phase Equilibria and Microstructure of Sn–Ag–
Cu Alloys” in Fundamentals of Lead-Free Solder Interconnect Technology, New
York, Springer, 2015 ch 3, pp. 64
9
Y Takamatsu, H Esaka, K Shinozuka “Formation Mechanism of Eutectic Cu6sn5 and
Ag3Sn after Growth of Primary –Sn in SN-Ag-Cu Alloy”, Materials
Transactions Vol. 52, No. 2, pp. 189-195, 2011.
10
J.W. Elmer, E.D. Specht, M. Kumar “Microstructure and In Situ Observations of
Undercooling for Nucleation of -Sn Relevant to Lead-Free Solder Alloys”,
Journal of Electronic Materials, Vol. 39, No.3, 2010.
11
P. Snugovsky, Z. Bagheri, C. Hamilton “Microstructure and Reliability Comparison of
Different Pb-Free Alloys Used for Wave Soldering and Rework”, Journal of
Electronic Materials, Vol. 38, No. 12, 2009.
12
T. Hurtony A Bonyár, P Gordon, G Harsányi “Investigation of intermetallic
compounds (IMCs) in electrochemically stripped solder joints with SEM”
Microelectronics Reliability 52, 2012.

74
13
T. Hurtony, A Bonyár, P Gordon, G Harsányi. “Investigation of intermetallic
compounds (IMCs) in electrochemically stripped solder joints with SEM”
Microelectronics Reliability 52, 2012.
14
A. So and Y.C. Chan “Reliability Studies of Surface Mount Solder Joints – Effect of
Cu-Sn Intermetallic Compounds” IEEE Transactions on Components, Packaging,
and Manufacturing Technology – Part B, Vol 19, No 3, August 1996.
15
Z Mei, A.J. Sunwoo, J.W. Morris “Analysis of Low-Temperature Intermetallic Growth
in Copper-Tin Diffusion Couples”. Metallurgical Transactions A , Volume 23A,
March 1992.
16
K.H. Prakash, T Sritharan “Interface Reaction Between Copper and Molten Tin-Lead
Solder”, Acta Mater. 49 (2001) 2481-2489.
17
S. Kumar, C.A. Handwerker and M.A. Dayananda “Intrinsic and Interdiffusion in Cu-
Sn Systems”, Journal of Phase Equilibria and Diffusion Vol. 32 No. 4, 2011.
18
K-N. Tu “Copper Tin Reactions in Bulk Samples” in Solder Joint Technology :
Materials, Properties and Reliability New York, Springer, 2007, ch. 2, sec. 2.6.1,
pp. 58-59
19
A.J. Sunwoo, J.W. Morris, G.K. Lucey, “The Growth of Cu-Sn Intermetallics at a
Pretinned Copper-Solder Interface”, Metallurgical Transactions A, Volume 23A,
April 1992
20
S. Kumar, J. Smetana, D. Love, J. Watkowski, R.Parker, C.A. Handwerker,
“Microvoid Formation at Electrodeposited Copper-Solder Interface During
Annealing: A Systematic Study of Root Cause”, presented at SMTAI, Chicago, Il,
2008.
21
H.F. Zou, H.J. Yang, Z.F. Zhang “A Study on the Orientation Relationship Between
the Scallop-Type Cu6Sn5 Grains and (011) Cu Substrate using Electron
Backscattered Diffraction” Journal of Applied Physics, 106, 113512 (2009)
22
K-N. Tu “Solder Reactions on Nickel, Palladium, and Gold” in Solder Joint
Technology: Materials, Properties and Reliability New York, Springer, 2007, ch.
7, pp. 183-204.
23
J-Y Tsai and J. Gaida “The Interaction between SnAgCu Solder and Ni(P)Au,
Ni(P)PdAu UBMS”
24
K Sweatman, J. Read, T. Nishimura and k. Nogita “The Effect of Microalloy Additions
on the Morphology and Growth of Interfacial Intermetallic in Low-Ag and No-Ag
Pb-Free Solders”, presented at SMTAI, Chicago, Il, 2011.
25
L. Snugovsky, P. Snugovsky, D.D. Perovic, J. W. Rutter “Phase Equilibria in Sn Rich
Corner of Cu-Ni-Sn System” Materials Science and Technology, 2006, Vol 22,
No 8. pp. 899-902

75
26
P. Snugovsky, E. Kosiba, J. Kennedy, Z. Bagheri, M. Romansky, M. Robinson, J.M.
Juarez, Jr., J.Heebink “Manufacturability and Reliability Screening of Lower
Melting Point Pb-free Alloys Containing Bi,” in IPC APEX EXPO Conference,
San Deigo, CA, 2013.
27
D.A. Porter and K.E.Easterling, “Diffusional Transformation in Solids” in Phase
Transformations in Metals and Alloys, 2nd ed. UK: Chapman & Hall, 1992, ch. 5,
pp 263-381.
28
B. Arfaei, N. Kim and E.J. Cotts “Dependence of Sn Grain Morphology of Sn-Ag-Cu
Solder on Solidification Temperature”, Journal of Electronic Materials, Vol. 41,
No. 2. 2012.

76
 Chapter 3
Accelerated Thermal Cycling

1 Accelerated Testing for Reliability Analysis

Reliability can be defined as the probability of a product to meet specifications over a
given time period while subjected to determined environmental conditions.1 The
reliability of any electronic assembly depends on the reliability of each individual
element. An assembly is likely to fail due to component failure in the short term and due
to solder attach failure in the long term.2 The solder attach, which include the solder joint
and the material to which it adheres, particularly in the case of surface mount devices,
presents a complicated situation in that it acts as both the electrical contact as well as the
mechanical attachment.3 In field operation, a solder attach will experience loading
conditions in the form of: (i) mechanical load, (ii) vibration, (iii) thermal shock and (iv)
differential thermal expansion. The accumulated damage caused by one or more of these
stress conditions will eventually lead to wear-out failure. Therefore, determination of the
useful life of an electronic product is contingent upon the understanding of the failure rate
of the surface mount solder attach.

Accelerated testing is used to obtain more information than would be practical, or even
possible, under normal field conditions where years may pass before a sufficient number
of failures occur to determine the reliability of a product. Accelerated testing is also
essential in determining the effects of changes to product design through its design cycle.
Accelerated conditions may include a test environment in which conditions are more
severe than that experienced during normal equipment use or by increasing the frequency
in which a condition is applied to a product. In both cases, care should be taken to avoid
the introduction of failure mechanisms, which would not be encountered in field
operation of a product.4 If failure mechanisms are maintained, the accelerated data can be
used to extrapolate the expected failure rates in field conditions.2

Of the four loading conditions described above, thermomechanical fatigue resulting from
cyclic differential thermal expansion is the primary failure mechanism of surface mount
77
solder joints and the focus of this chapter.3,5 This form of fatigue is the combination of
plastic and creep deformation which occurs as a solder attach is exposed to cyclical
heating and cooling through powering on and off, as well as exposure to environmental
conditions. Accelerated Thermal Cycling (ATC) is used to test the response of a product
to rapidly repeating changes in temperature to a level higher than normally experienced
by a product in field conditions. In this case, the applied cyclical stress is in the form of
differential thermal expansion and contraction between the various materials within a
circuit board. These differences are defined by the coefficient of thermal expansion
(CTE) of the differing materials that make up the system. In a circuit board, there are two
levels of recognized differential thermal expansion:

1. Global: thermal expansion mismatch between components and substrate, as illustrated

in Figure 48.

2. Local: thermal expansion mismatch between solder and material to which it is

bonded6

Figure 48: Representation of stress generated in circuit due to CTE mismatch 7

Stress-strain hysterisis loops, such as the one illustrated in Figure 49, are often used to
describe the cumulative stress history experienced by a solder attach during ATC. As the
temperature increases, the differential expansion of the various materials results in the

78
initial applied stress, which leads to plastic deformation. During the hot dwell (or hold)
period, which generates stresses lower than the yield strength of the solder, creep and
stress relaxation within the solder material occur. During accelerated testing, there may
or may not be enough time allotted for full stress relaxation as would likely exist in field
conditions. Stress is then applied in the opposite direction – the stress axis representing
an absolute value – during the cold cycle. As the cycles are repeated, the solder joint
fails due to low-cycle fatigue and can be described by the Coffin-Manson relationship
given in Equation 3-1:

N f  C1 ( p )
1 m
1-1

where N f is the average number of cycles to failure, C1 and m are material constants.8

Greater temperature fluctuations or greater differences in CTE mismatch will result in

higher values of plastic shear strain (  p ). This value will also be impacted by

component geometry. For example leaded components will result in lower shear plastic
strain than leadless components. Ramp rate and dwell time, at the temperature extremes,
will also impact the shape of the hysteresis loop and the strain level. The Coffin-Manson
model assumes that plastic strain is the main deformation mechanism. This simplified
model has since been revised to include the more dominant creep effect, as well as
cyclical parameters. These models are presented in IPC-SM-785 and take into account
such factors as component and solder fillet geometry, potential cyclic fatigue damage at
complete stress relaxation, and fatigue ductility coefficients. These models are also
presented with numerous caveats indicating which conditions are required for each model
and what limitations may exist.2 Modeling of complex creep-fatigue in solder attach,
particularly for new solder alloys, is a continuing field of research.

79
 Figure 49: Hysteresis loop for thermal cycle9

In order to relate the results of ATC testing, or any Accelerated Life Testing (ALT), to
life condition, data from at least two conditions need to be used to establish a trend line in
order to extrapolate to field condition. Low-level and a high-level acceleration condition
should be chosen. Three or more conditions would allow for determination of non-linear
relationships. Low-level acceleration should produce a mean time-to-failure (MTTF) of
about 10-20 times shorter than the actual field life. High-level acceleration should
produce a MTTF of approximately 100-500 times shorter than actual field life.2
Acceleration Factors (AF) are then calculated as the ratio between the two conditions and
then extrapolated from the chosen conditions to field conditions.

ATC qualification test conditions for various applications have been determined and
compiled in specification IPC-9701A6. These tests have been devised as minimum
criteria for accelerated testing for qualification purposes. While Appendix 1 of this
specification does provide guidance and examples for determining AF, it is not necessary
to determine these for every test. Rather, the minimum requirements per industry have
been established. This specification also states at least 32 samples per condition should
be tested and the test should run for the required duration or at least until 63.2% failure in
order to characterize the failure distribution. Tests that are stopped at the end of the

80
required Number of Thermal Cycle (NTC) level with insufficient (or no) failures will be
characterized by failure analysis (FA) alone. FA is to be performed on a minimum of
three randomly chosen samples. Table 23 provides a summary of the test conditions laid
out in this standard and Table 24 provides some examples of worst-case scenarios for
various products in field conditions.

Table 23: Sample of temperature cycling requirements Table 4-1 in IPC-9701A6

Low High
Test Mandated Temperature
Test Duration Temperature Temperature
Condition Condition Ramp Rate
Dwell Dwell

NTC-E

0C to
TC1 6,000 cycles
100C (preferred for
TC1) 10 minutes 10 minutes
20C/minute
NTC-C (+0C/-5C) (+5C/-0C)

-55C to
TC4 1,000 cycles
125C (preferred for
TC4)

Table 24: Worst case use environments of SMT6

Tmin Tmax T Typical service Acceptable

Application Cycles/year
(C) (C) (C) life (years) failure risk (%)
Consumer 0 60 35 365 1-3 1
Military Aircraft
a) 40 100
-55 125 10-20 0.01
b) 60 100
c) 80 65

81
Note in Table 24, T is not simply the difference between Tmax and Tmin representing the
absolute maximum and minimum temperatures experienced in the given environment,
but rather the expected worse-case scenarios which occur in a given service condition.2

Solder in ATC testing has been shown to fail according to a creep-fatigue model resulting
from the applied thermomechanical fatigue stresses. The mechanical properties of solder
are temperature dependent and therefore change continuously over the course of a fatigue
cycle, both in the bulk microstructure of the solder as well as in the IMC layer formed
between the solder and the Cu substrate. There are also cumulative effects of repeated
cycles.10 The total strain (T) can be expressed by Equation 3-2 where e and p are the
elastic and plastic strains respectively and c represents creep strain.

T   e   p   c 1-2

During the high temperature dwell period of the thermal cycle, creep and stress relaxation
are the dominant strain evolution mechanisms. During ramp up and down, plastic and
elastic strain deformations are dominant unless this transition is slow enough to allow for
full stress relaxation, which is not typically the case in accelerated testing. It is the
repeated plastic and elastic strain which constitutes fatigue fracture.

2 Microstructural Evolution
2.1 Changes to Bulk Solder
Notably, many of the tests and models described above have been developed for SnPb
solders, which have been tested over decades. It has been shown that the microstructural
response to creep and fatigue behavior of Sn based SAC alloys is very different than that
of SnPb.11 Therefore, it is possible the models and even the applicable test conditions
need to be updated. In SnPb solder joints, the initial response to applied
thermomechanical stress is grain coarsening in an attempt to reduce the internal energy in
the smaller grains. Both the applied shear strain which results from CTE mismatch and
the elevated temperature aid in grain coarsening. In eutectic SnPb, the Sn rich regions and

82
Pb regions will coalesce into larger islands. During coarsening, it should be noted that
the IMC attach layer also thickens – a Cu3Sn region may form between the Cu substrate
and the Cu6Sn5. Immediately adjacent to the IMC a layer of Pb-rich phase will form as
the local Sn has been consumed in the IMC growth process. Pb also tends to pool around
the grain boundaries of the Sn rich phase. Grain coarsening is accomplished via grain
boundary sliding and grain boundary diffusion-induced migration.5 Microvoids begin to
appear along grain boundaries, interphase boundaries and interfaces with IMCs.
Microvoids continue to propagate along grain boundaries or other interfaces until they
connect to form microcracks and eventually catastrophic macro level cracks. Figure 50
illustrates a typical SnPb solder attach a) before any accelerated testing and b) after 3000
cycles of harsh ATC. These images, taken at the same magnification, illustrate the
degree of grain coarsening, IMC growth and phase coalescence that occurs during
repeated stress cycles. While this joint did not fail catastrophically after 3000 cycles, a
large crack is propagating through the bulk solder along a Pb-rich region and, if testing
had continued, would have lead to a full electrical and mechanical fail.

Figure 50: SnPb solder a) before testing and b) after 3000 cycles -55C to 125C12

The microstructure of solder attach formed with SAC type alloys are found to behave
differently from that of eutectic SnPb. As described in Chapter Chapter 2, these solders
are made up of up to 98% Sn with small amounts of Ag and Cu present as intermetallics.
The Sn matrix, as well as the Ag3Sn and Cu6Sn5 precipitates all influence the creep
response of the solder attach. As the strain increases, an initial coarsening of the IMC
particles occurs. Recrystallization of the Sn grains takes place in the area of high strain,
83
usually close to the bulk solder interface with the attach IMCs. The grain boundaries
formed between these new grains, as well as some large precipitates, provide sites along
which voids can form (at the triple points) and fractures can easily propagate.10,13
Additionally, it is during the hot dwell cycle that the brittle IMC attach layer may grow.7

Figure 51 shows a solder attach made up of SAC305 a) before testing and b) after 3000
cycles of harsh testing. From Figure 51a) we can see the dendritic arms of the Sn
appear relatively small and evenly spaced with small dispersiods of Ag3Sn in the
interdendritic spacing. After ATC, the Ag3Sn particles appear to have coalesced into
fewer, larger particles. Additionally, the IMC layers formed between the lead and solder
as well as between the solder and copper pad have increased in size and appear to have
two phases, Cu3Sn and Cu6Sn5 as seen in Figure 51b). A Cu3Sn layer was not detectable
at zero time. Finally, the dendritic structure does not appear to be well defined after
thermal cycling. Polarized light or electron backscatter diffraction (EBSD) is needed to
properly view the grain structure. Figure 52 shows an example of a BGA solder joint that
failed during thermal cycling; recrystallized grains appear in the region where high shear
strength is experienced, and where the final crack propagated. Using EBSD, it has been
proposed that this recrystallization occurs ahead of the propagating crack.10 Fractures can
easily propagate along the regions created under creep conditions, notably between grain
boundaries and along the bulk solder/IMC interface.

Figure 51: SAC305 solder a) before testing and b) after 3000 cycles -55C to 125C12
84
Figure 52: SAC305 after ATC shown with a)polarized light and b)EBSD mapping 13

2.2 Changes to Interfacial IMC during Accelerated Thermal

Cycling
A good interfacial IMC layer is required for a properly formed solder joint, as it provides
the mechanical, electrical and thermal connection between the bulk solder and the Cu
substrate. This layer, however tends to be brittle and if a very thick layer forms or
develops, it may become a reliability concern. Interface layers also tend to be preferential
sites for crack formation and propagation. Additionally, the IMC layer in solder joints
may be a reliability concern because it consumes Cu from the substrate, Cu being the
dominant diffusing species.14 The consumption of Cu may result in a weakened Cu pad
as described in 2.1.

Cu3Sn was not detected upon initial solidification (Chapter Chapter 2); it forms as a result
of solid-state reaction during thermal aging at temperatures above 60C.17 The Cu3Sn
growth occurs between the Cu6Sn5 and the Cu substrate and is governed by the
availability of Cu from the substrate and Sn either from the already present Cu6Sn5 as
described in equation 3-3 or Sn from the bulk solder diffusing through the Cu6Sn5
substrate as described in equation 3-4. The initial formation of Cu6Sn5, and its continued
growth are dependent on Sn from the bulk solder and Cu from the substrate. The Cu is
either present during the initial solidification reaction, or diffuses through the Cu3Sn
layer. Both are described by equation 3-5.15

85
 Cu6Sn5 + 9Cu  5Cu3Sn 2-1

3Cu + Sn  Cu3Sn 2-2

6Cu + 5Sn  Cu6Sn5 2-3

The Cu3Sn layer is of concern for three reasons: it is a brittle layer more so than Cu6Sn5
or bulk solder, it is associated with large volume shrinkage, and the growth of a Cu3Sn
layer next to Cu is often accompanied by Kirkendall voids along the interface of the two
phases.16 These small voids may form a weak interface.

Both Ag and Cu additives to the solder have been found to be beneficial in suppressing
the growth of the Cu3Sn layer.17 Ag does not participate in the interfacial IMC layer at all
and can therefore only act as an influence by retarding the diffusivity of Sn through the
bulk solder towards the IMC layer. Other alloying elements (e.g. Ni, Zn) have also been
found to retard the growth of Cu3Sn and in some instances Cu6Sn5. In these cases, trace
amounts of the element are found in, or at the interface of the IMC layer and therefore are
thought to participate directly in the reaction or provide a diffusion barrier between the
layers.18

The change in thickness of the intermetallic layers can be described by the Arrhenius
equation (3-6) where x is the thickness, x0 is the initial thickness in m, t is time in s, T is
temperature in K, R is the universal gas constant (8.314 kJ/mol K) and A, Q and n are
material constants. 20

x  x0  At n exp(  Q ) 2-4
RT

2.3 Effects of Bi
Bi as an alloying element is expected to have an overall influence on the reliability of a
solder joint in two ways. The first is the reduced process temperature due to the addition
of Bi, which may result in a reduced thickness of the interfacial IMC layer as well as

86
reducing some of the deleterious effects of high temperature on both board material and
components.19

The second involves modification of the bulk solder microstructure. Sn phase is
considered to have most potential for modification with alloying as it makes up most of
the volume within a SAC solder joint. Alloys with Bi have been explored as a means to
improve thermomechanical properties through solid solution strengthening and
precipitate hardening.20 In a previous study, for example, after 3000 cycles harsh
environment ATC (-55C to 125C), Bi which was previously present in solid solution
with Sn precipitated out in an evenly distributed manner, reducing microstructural
degradation.12 Other studies have shown that Bi segregates at the grain boundaries,
potentially reducing creep resistance.21

The influence of Bi on the formation of interfacial IMC layers has also been explored. It
has been shown that Bi does not participate in the formation of either intermetallic
compound layers (Cu6Sn5 or Cu3Sn), but there is a higher concentration within the Sn
close to the Cu6Sn5 suggesting that Bi is rejected from the Sn as Sn is contributed to the
formation of Cu6Sn5.22

In this thesis, the behavior of Bi containing alloys is investigated. Also, the impact of
reducing the amount of Ag in SAC-based solders is also examined.

3 Experimental Setup
The work in this section forms a screening experiment in which the performance of
selected alloys was evaluated during thermal cycling under two different conditions. The
intention was to provide data for determining the suitability of these solders for more
statistically relevant reliability testing, which is too costly to perform on all combinations
of solder, board material and temperature conditions. These tests were performed in
accordance with test conditions outlined in IPC-9701A6 and IPC-SM-7852. The statistical
requirements of these specifications were not adhered to due to limited resources.

87
ATC testing assumes that solder joints were properly formed and no wetting issues exist,
which would result in infant mortality due to defective solder joints.6 The quality of
solder joints used in this study was demonstrated to be satisfactory in Chapter Chapter 2.
In addition to testing a statistically relevant number of samples, IPC-9701A states that the
duration of testing would ideally generate at least 63.2% failures within that sample set in
order to properly evaluate reliability and possibly determine acceleration factors. This
specification states that if an insufficient number of failures, or no failures at all, are
generated at the end of the number of thermal cycles (NTC) level, then failure analysis
should be performed on a random selection of parts (a minimum of three per test
variation) to verify that no failure occurred. This failure analysis can also be useful in
determining whether or not any microstructural changes occurred during the testing.
Finally, as this testing is intended to address solder joint reliability, only those failures
determined to be the result of thermomechanical component/board interaction will be
considered. Board level failures such as via cracks, delamination, will not be included in
the data set for any solder joint reliability calculations.6

3.1 Materials
Three Bi-containing alloys, Senju M42 containing 3%Bi and Sunrise and Sunflower each
containing 7wt% Bi, with low or no Ag, were tested against SAC305. Two board
materials were tested; a normal Tg material– one which is typically used for SnPb
applications around 150C, and a high Tg material– one which is now required for most
Pb-free applications at around 170C. Table 25 summarizes the combinations of solder
and board material tested. As described in 2.2, the lower Tg board materials that had been
previously used with SnPb solders had a lower elastic modulus and were less susceptible
to pad cratering, delamination and warpage failures.

88
 Table 25: Build matrix for ATC testing
Alloy Composition Board Material Assembly Temperature
SAC305 Sn 3%Ag 0.5%Cu 240C
Senju M42 Sn 2%Ag 0.75%Cu 3%Bi High Tg 224C
Sunrise Sn 1%Ag 0.7%Cu 7%Bi (170C) 222C
Sunflower Sn 0.7%Cu 7%Bi 226C
SAC305 Sn 3%Ag 0.5%Cu 240C
Senju M42 Sn 2%Ag 0.75%Cu 3%Bi Normal Tg 224C
Sunrise Sn 1%Ag 0.7%Cu 7%Bi (150C) 222C
Sunflower Sn 0.7%Cu 7%Bi 226C

3.2 Test Vehicle

Celestica’s RIA3 test vehicle, shown in Figure 53, was selected as the test vehicle. It was
designed to simulate a typical, medium complexity SMT assembly. It is an 8”x10”
surface made up of 12 copper layers for a total thickness of 0.093” with an Organic
Solderability Preservative (OSP) finish. This board is often used to test new, lead-free
solders and other material parameters. LQFP176, PBGA256, CBGA64 and MLF20s were
populated, two of each per board. The BGA components all had SAC305 ball alloy and
all component groups were reflowed in an air environment. Figure 53 and Table 26
shows the test vehicle and highlights the monitored components.

Figure 53: Test vehicle with monitored components

89
 Table 26: Monitored components for ATC testing
Component Reference Designator
1206 1206-A1
1206 1206-B1
0402 R400-R419
0402 R420-R439
CSP64 U208
CSP64 U209
MLF20 U5
MLF20 U6
PBGA256 U204
PBGA256 U205
QFP176 U1
QFP176 U2

3.3 Test Strategy

All components were monitored using electrical data loggers; failures were defined as a
20% increase in nominal resistance over five consecutive scans. Failures were cut from
the boards, and then the rest of the components were returned to the chamber for further
testing. Each of the two thermal profiles was allowed to run for a preset number of
cycles.

Figure 54: Card set up in thermal cycling chamber

90
3.3.1 0-100C Thermal Cycling
This portion of the testing was done in accordance with IPC-9701A Test Condition 1
(TC1) of 0C (+0/-5C) to 100C (+5/-0C) for Number of Thermal Cycles (NTC-E),
which is preferred for TC1, of 6000 cycles. The boards under test, listed in Table 27 were
set up in a chamber using a racking system which allowed for airflow around the boards
(Figure 54). The final thermal cycle profile is shown in Figure 55.

Table 27: Test matrix for 0C to 100C ATC

Alloy Composition Board Material # of Boards Tested
High Tg (170C) 4
SAC305 Sn 3%Ag 0.5%Cu
Normal Tg (150C) 3
Sn 2%Ag 0.75%Cu High Tg (170C) 6
Senju M42
3%Bi Normal Tg (150C) 5
High Tg (170C) 5
Sunrise Sn 1%Ag 0.7%Cu 7%Bi
Normal Tg (150C) 6
High Tg (170C) 5
Sunflower Sn 0.7%Cu 7%Bi
Normal Tg (150C) 5

Figure 55: Chamber profile for 0C to 100C thermal cycling

91
3.3.2 Harsh Environment (-55C to 125C) Thermal Cycling
This portion of testing was done in accordance with IPC-9701A Test Condition 1 (TC4)
of -55C (+0/-5C) to 125C (+5/-0C) for NTC-C of 1000 cycles. Notably, the
maximum temperature selected for the thermal cycle profile should be 25C lower than
the Tg of the board material.6 In this case the Normal Tg board material is 150C, while it
is exactly 25C lower than the Tg, does not allow for the 10C leeway on the hot end of
the cycle making the board material vulnerable to damage during testing. The boards
under test are listed in Table 28. The final thermal cycle profile is shown in Figure 56.

Table 28: Test matrix for -50-125C ATC

Alloy Composition Board Material # of Boards Tested
High Tg (170C) 3
SAC305 Sn 3%Ag 0.5%Cu
Normal Tg (150C) 3
High Tg (170C) 5
Senju M42 Sn 2%Ag 0.75%Cu 3%Bi
Normal Tg (150C) 5
High Tg (170C) 5
Sunrise Sn 1%Ag 0.7%Cu 7%Bi
Normal Tg (150C) 6
High Tg (170C) 5
Sunflower Sn 0.7%Cu 7%Bi
Normal Tg (150C) 5

92
 Figure 56: Profile for -55C to 125C thermal cycling

3.4 Post ATC Evaluation and Failure Analysis

Samples from groups exposed to each of the two ATC profiles were evaluated to
determine both the failure modes and to examine the changing microstructure over the
course of the test. Samples were selected at time of failure, at the halfway point of each
test and at the completion of each test. Each sample was mounted in epoxy, and then
ground and polished through the following sequence: 500 and 1200 grade SiC paper,
polishing with 6 µm and 1 µm DiaPro diamond suspensions (Struers), and an oxide
polish (Struers’ OP-S). Optical microscopy was performed using a Nikon Measurescope
MM-11. Prior to SEM analysis, the samples were carbon coated using an Emitech
K950X. SEM microscopy was performed using a Hitachi S-4500 and Hitachi S-3000N
with Oxford and ThermoScientific EDX systems respectively.

93
4 Results
4.1 Reliability and Failure Analysis Results
Using IPC-9701A as a guideline, this test focuses on solder joint reliability; other modes
of failure, for example those attributed to the laminate material, were removed from
consideration in the reliability calculations. Therefore any identified failures that were
removed from the test prior to completion and later found to be attributed to something
other than solder joint fatigue should be identified as “censored”. Finally, testing was
suspended after a predetermined amount of time whether or not failures were identified.
Parts that did not fail were identified as “censored”. This type of data censoring is
referred to as Type 1, or time censored data in which a test is concluded after a
predetermined amount of time, in spite of the fact that failures may not have occurred.23

4.1.1 0C to 100C Accelerated Thermal Cycling

A total of 6010 cycles of ATC from 0-100C were completed. The test was periodically
stopped and the failures, which have been recorded using a data logger, were removed
and verified by manual resistance measurement. If the failure was determined to be
within the test vehicle, as opposed to a cabling issue, the component was cut out of the
board for future failure analysis. The remaining components on the test vehicle where
returned to the chamber and the testing continued. Because no failures had been
identified at the halfway point of the test, four boards, one for each alloy, were removed
for metallurgical analysis. This occurred after 3157 cycles had been completed. These
components were identified as “censored”.

Table 29 summarizes the number of cycles to first failure of the QFP176s monitored
during the 6010 cycles of the test. There are not enough failures at the end of 6010
cycles to plot failure distribution charts for each alloy. Only SAC305 experienced failures
when built on High Tg (170C) board material and those occurred towards the end of the
test. Figure 57 shows the distribution of failures of solder joints built on High Tg boards

94
compared with those built on Normal Tg boards. A two-parameter Weibull distribution is
used.

The shape parameter determines the shape of the probability distribution and can be
viewed by plotting the probability density function (PDF). At values between 3 and 4, the
shape parameter approximates a normal distribution. Shape parameter values higher than
4, as shown in Figure 58 results in a near-normal distribution with a left tail. The scale
parameter (or slope on the Weibull distribution) described the range of the distribution, or
the rate of at which the failure rate increases.

It can be seen that the High Tg boards are expected to survive much longer than those
built with Normal Tg when using SAC305 as the solder paste.

Table 29: Summary of QFP failures after 0C to 100C ATC

Component High Tg Normal Tg

Senju Senju
type SAC305 Sunrise Sunflower SAC305 Sunrise Sunflower
M42 M42
2/6 0/10 0/7 0/8 6/6 0/10 1/12 0/10
QFP176
33.3% -- -- -- 100% -- 8.3% --
5792 3534 5416
5994 4349
Failure 4653
Cycle 4782
5223
5251

95
Figure 57: Weibull plots of SAC305 QFP solder joints after 6010 Cycles 0 to 100C
comparing High Tg to Normal Tg boards

Figure 58: Probability Density Function for SAC305 QFP solder joints after 6010
Cycles 0 to 100C comparing High Tg to Normal Tg boards

Figure 59 shows the failure occurred as a result of fracture initiating in the bulk solder
and propagating along the lead side IMC layer. This is further illustrated in Figure 60
which shows the fracture surface of a similar solder joint made up of SAC305 on High Tg
96
board material. The area highlighted in red shows the crack initiation. The area
highlighted in green illustrates the point at which the fracture moves along the IMC layer.
Within the green area, EDX scans were taken of area 1, which was shown to be pure Sn
indicating bulk solder and area 2: which was shown to be Cu6Sn5 indicating the IMC
layer. Finally, the area highlighted in blue shows a ductile fracture, which likely occurred
as a result of overload on the remaining area.

Figure 59: QFP fracture of SAC305 on High Tg board a) optically and b) cross
section

97
 Figure 60: Fracture surface of QFP solder joint with SAC305 on High Tg board
after 6010 cycles

Figure 61 shows that fractures had initiated in solder joints formed with the other three
alloys on high Tg board material, but by 6010 cycles had not yet propagated far enough
into the solder joint to cause an electrical failure. It is expected that these solder joints
would ultimately fail in the same manner as shown in Figure 59 and Figure 60 if the
testing had continued.

98
 Figure 61: Fracture initiation in QFP a) Sunflower b) Senju M42 after 6010 cycles
As described in 6.1.2, the BGA solder joints were made up of paste from the
experimental alloy and SAC305 solder balls. This resulted in a solder joint composition
closer to SAC305 and with no more than 0.9wt% Bi. No failures occurred within the
6010 cycles of the test when high Tg board material was used. A number of failures
occurred for each of the paste alloys when normal Tg board material was used as outlined
in Table 30. Using resistance probing, these were all found to be the result of failure
within the component-solder-board system; either in the board circuit pattern beneath the
component, the solder connecting the component to the board or within the component
itself. It is not possible to determine where within this system the failure occurred
without destructive techniques. Each component was therefore cut from the board and
cross-sectioned to find the point of failure.
Table 30: Summary of BGA failures after 0C to 100C ATC

Normal Tg
Component type
SAC305 Senju M42 Sunrise Sunflower
Fraction of components failed 5/6 9/10 8/12 6/10
% of components failed 83.3% 90.0% 66.7% 60.0%
4168 4079 4534 3623
4612 4540 4619 3930
5168 4629 4725 4607
5168 4680 4855 4902
Cycles to Failure 5278 4861 5153 5086
5497 5452 5169
5674 5455
5679 5536
5871
99
Figure 62 illustrates that there is no significant difference in the reliability performance of
the solder joints formed using paste of the four alloys on Normal Tg boards. All BGA
failures were found to result from board failures, specifically via cracks within the
laminate material. The probability distributions for each alloy in this test exhibit similar
shape and scale parameters, which is to be expected since all failures are characteristics
of the board material and construction, rather than the solder alloy.

Figure 62: Weibull plots of BGA solder joints on Normal Tg boards after 6010 Cycles 0 to
100C cycles comparing Four Alloys

Figure 63 illustrates a) a typical via barrel failure and b) a bulk solder fracture – although
incomplete failure – near the component side IMC.

100
 Figure 63: BGA failures after 0 to 100C ATC a) failure in board material by via
plating crack and b) partial failure through bulk solder (SAC305) near component
side IMC

4.1.2 -55C to 125C Accelerated Thermal Cycling

A total of 1000 cycles of ATC from -55C to 125C, or Harsh Environment ATC, were
completed. The test was periodically stopped and the failures, recorded using a data
logger, were removed and verified by manual resistance measurement. If, during the
course of testing, the failure was determined to be within the test vehicle, as opposed to a
cabling issue, the component was cut out of the board for future failure analysis. The
remaining components on the test vehicle were returned to the chamber and the testing
continued. Four boards, one for each alloy, were removed for metallurgical analysis near
the halfway point of the test, after 438 cycles completed. Table 31 summarizes the
number of cycles to first failure of the QFP176s monitored during the 1000 cycles of the
test.

101
 Table 31: Summary of QFP failures after -55C to 125C ATC

Component High Tg Normal Tg

Senju Senju
type SAC305 Sunrise Sunflower SAC305 Sunrise Sunflower
M42 M42
Fraction of
components failed
3/4 6/10 4/9 4/10 4/5 6/8 10/12 5/10
% of components 75.0
failed
75.0% 60.0% 44.4% 40.0% 80.0% 83.3% 50.0%
%
457 406 81 493 304 428 83 23
514 446 212 689 544 439 83 480
820 485 526 897 721 561 285 662
535 595 909 918 637 459 697
Cycles to 621 643 528 783
Failure 634 680 601
726
744
843
924

Figure 64 and Figure 65 show probability distribution plots and the probability density
functions of the four alloys on High Tg board materials respectively. Sunrise showed
some early fails, resulting in a different shape of the PDF.

Figure 66 shows probability distribution plots of the four alloys on Normal Tg board
materials respectively. In all cases, the distribution of failures occurred within
overlapping confidence intervals; there is insufficient data to distinguish between the
alloys after 1000 cycles of testing on Normal Tg boards.

102
Figure 64: Weibull plots of QFP failures on High Tg boards after 1000 cycles -55 -
125C

Figure 65: Probability Density Function for QFP failures on High Tg boards after
1000 cycles -55 -125C

103
Figure 66: Weibull plots of QFP failures on Normal Tg boards after 1000 Cycles -55-
125C

Just as in the 0 to 100C cycling test, all QFPs experienced solder fracture initiating in
the bulk solder and propagating along the lead side IMC (Figure 67). These however did
not result in complete fracture, and would not account for the electrical failure. Further
testing, by probing various test points in the test vehicle, determined that the likely cause
of electrical failure was the copper trace separating from the board material. Copper trace
fractures result in electrical open circuits.

104
 Figure 67: QFP176 fractures in a) Sunflower and b) Senju M42 after 1000 cycles
Harsh testing

The BGA components that underwent harsh thermal cycling experienced many failures
(Table 32). Upon cross sectional failure analysis however, these failures were found to be
the result of board damage, as in the 0-100C test, specifically via cracks within the
laminate material (Figure 68). While there are enough data points to plot probability
distributions, this did not provide a means of distinguishing between alloys.

Table 32: Summary of BGA failures after -55C to 125C ATC

High Tg Normal Tg
Component type Senju Senju
SAC305 Sunrise Sunflower SAC305 Sunrise Sunflower
M42 M42
Fraction of 5/6 10/10 6/6 9/10 4/6 10/10 12/12 10/10
components failed
% of components 83.3% 100.0% 100.0% 90.0% 66.7% 100.0% 100.0% 100.0%
failed
407 702 376 522 498 387 325 425
449 757 518 575 581 459 425 469
455 772 537 670 615 461 443 561
815 783 757 692 655 464 447 600
847 783 783 693 541 467 643
798 823 696 552 471 672
Cycles to Failure
878 864 570 491 705
924 968 597 494 804
985 999 600 575 837
999 696 587 934
848
897
105
 Figure 68: BGA failures after -55 to 125C ATC failures in board material by via
plating crack in a) boards built with Sunrise and b) boards built with Sunflower

Further examination of the solder joints revealed some crack initiation in the solder joints
towards the component side of the BGA solder joint. These crack initiation sites (Figure
69) were less significant than the damage observed after 6010 cycles of 0-100C thermal
cycling and would not account for a failure reading. Electrical failures, just as in the case
of 0-100C thermal cycling, occurred as a result of via cracks in the board material
(Figure 68). A probability plot comparing all failures on the two different board materials
(Figure 70) illustrates that the board material was a more significant distinguishing factor
than the various solder alloys.

Figure 69: BGA solder crack initiation after -55 to 125C ATC in solder joints
formed with SAC305 solder balls and a) Sunflower and b) Sunrise

106
 Figure 70: Weibull plots of BGA solder joints after 1000 Cycles -55 to 125C cycles
comparing two board materials

QFP solder joint failures on Normal Tg board material was used to compare the two test
conditions, 0-100C for 6010 cycles and -55 to 125C for 1000 cycles. The Harsh
environment test (-55 to 125C) produced many failures over the 1000 cycles, including a
few early failures. This resulted in a Weibull distribution with a shape parameter of 1.26,
a PDF with a right tail. The 0-100C was less severe and therefore resulted in fewer
failures and no early failures. The shape parameter of 5.59 indicates that the failure rate
increases over time.

107
Figure 71: Weibull plot for QFP solder joints on Normal Tg boards comparing two
test conditions

Figure 72: Probability Density Function for QFP failures on Normal Tg boards
comparing two test conditions

108
4.2 Microstructure Evaluation
4.2.1 Bulk Microstructure
SAC305, before thermal cycling (Figure 73a and 73b) appears as small dendrite arms
surrounded by small Ag3Sn and Cu6Sn5 particles. After thermal cycling from 0 to 100C
for 3148 and 6010 cycles (Figure 73c and 73d respectively) the intermetallic particles
coalesced into fewer, larger particles. Senju M42 behaved in the same manner. In both
cases, the bulk of the microstructural transition occurred between 0 and 3148 cycles, with
little change between 3148 and 6010 cycles. With 3% Bi in Senju M42, there does not
appear to be any significant Bi precipitation from the solid solution (Figure 74).

Figure 73: SAC305 at Time 0 a) optically and b) SEM image and after b) 3148 cycles
and d) 6010 cycles of 0-100C ATC

109
 Figure 74: Senju M42 at 1000x after a) 3148 cycles and b) 6010 cycles

Sunrise and Sunflower solder paste alloys, which both contain 7wt% Bi, showed a
significant amount of Bi precipitation after ATC. In both cases large, uneven particles of
Bi were present upon solidification, as seen in Chapter 2. After ATC, Sunrise showed
many, very small particles precipitated throughout the bulk, evenly dispersed from the
Sn grains (Figure 75). Sunflower also exhibited some Bi accumulation along the grain
boundaries (Figure 76). In both cases, there did not appear to be any significant
accumulation of Bi along the interface with the interfacial IMC layer.

Figure 75: Sunrise after 6010 cycles 0-100C at a) 500x and b) 1000x

110
 Figure 76: Sunflower at a) Time 0 and b) after 6010 cycles 0-100C at 500x

4.2.2 IMC Growth during Thermal Cycling

The interfacial IMC layers were measured as described in section 6.2. A comparison of
the board side IMC layer of a QFP176 component follows. This IMC layer formed
during the reflow process in which a bond was formed between the board side copper pad
and the molten solder. The Time 0 results reference this IMC layer after reflow but
before any thermal cycling. As described in section 6.2, only Cu6Sn5 was identified at
Time 0. Measurements were made after approximately the halfway point and again at the
completion of the two thermal cycling regimes. For the 0-100C test, measurements were
completed after 3157 cycles and then again after 6010 cycles. For the harsh environment
test (-55C to 125C) measurements were taken at 438 cycles and then again at 1000
cycles. After exposure to thermal cycling, both Cu6Sn5 and Cu3Sn species were identified
(Figure 77).

111
 Figure 77: IMC layers formed on QFP176 solder joints between the board side Cu
layer and solder paste a) sunrise and b) SAC305 after 438 cycles of Harsh thermal
cycling. Location 1 shows the Cu3Sn layer, location 2 shows the Cu6Sn5 layer

Figure 78 provides a comparison of the overall IMC thickness at the various test
intervals; Figure 79 provides a comparison of the Cu3Sn layer within the IMC at various
test intervals. Table 33 and Table 34 provide a summary of results from two-sided T-test
to compare the mean values and Levine-test to compare the variance of the IMC and
Cu3Sn thicknesses respectively. These tables are provided in order to examine the
changes in thickness of the overall IMC and the Cu3Sn layers, for each alloy, over the
course of the two thermal cycling conditions. The tables provide probability (p-values)
for each test. In all cases, the null and alternate hypotheses are as follows:

H0: µ1=µ2 and 1=2

Ha: µ1≠µ2 and 1≠2

Values in Table 33 and Table 34 which are bold italicized represent points with a p-value
less than 0.05. This indicates that H0 should be rejected at a 95% confidence level and
the Ha is assumed to be valid. In this case, it assumes that the mean value has changed.
These results show that between 0 and 1000 cycles of Harsh testing, the IMC layers for
each alloy increased significantly. For Senju M42 and Sunrise, this occurred primarily
within the first 438 cycles. For SAC305 and Sunflower the increase continued throughout

112
the test. In 0-100C ATC testing, the IMC layer for all alloys except SAC305 increased
throughout the test. The IMC thickness for SAC305 increased most significantly during
the first half of the test.

All t-tests of the µ in Table 34 result in rejecting the H0. This indicates that the thickness
of the Cu3Sn layer continues to increase throughout the course of the two tests.

Table 35 provides a summary of test for equal variance and ANOVA testing of the
various alloys. This test compares the IMC and Cu3Sn thicknesses of all four alloys, at a
given point during ATC. This table provides probability for each test. In all cases, the
null and alternate hypotheses are as follows:

H0: µSAC305=µSenju M42=µSunrise=µSunflower and SAC305=Senju M42=Sunrise=Sunflower

Ha: at least one µ is different and at least one  is different

The result of ANOVA testing, indicated in Table 35: Results of ANOVA test to equal
variance and compare means, show that while the total IMC thickness increased
relatively consistently among the four alloys, the increase in the thickness of the Cu3Sn
layer was different in at least one alloy. Figure 79 clearly shows that Sunflower exhibited
a significantly thicker Cu3Sn layer after Time 0 in both test conditions.

113
 Figure 78: IMC growth at the board side of QFP during thermal cycling

Figure 79: Cu3Sn (portion of IMC) growth at board side of QFP during thermal
cycling
114
 Table 33: Results of Levine-Test to compare the variance () of IMC measurement
and 2-sided t-Test to compare the means (µ) of IMC measurements
Test HARSH
(0 to 100C)
Condition (-55 to 125C)
0 to 438 0 to 1000 438 to 1000 0 to 3157 0 to 6010 3157 to
Comparison
cycles cycles cycles cycles cycles 6010 cycles
Variable /
 µ  µ  µ  µ  µ  µ
p value
SAC305 0.40 0.00 0.21 0.00 0.04 0.03 0.23 0.00 0.11 0.00 0.74 0.56
Senju M42 0.72 0.00 0.17 0.00 0.11 0.49 0.53 0.00 0.97 0.00 0.61 0.04
Sunrise 0.03 0.00 0.13 0.00 0.43 0.85 0.53 0.00 0.02 0.00 0.40 0.00
Sunflower 0.28 0.00 0.75 0.00 0.26 0.00 0.31 0.00 0.87 0.00 0.39 0.00

Table 34: Results of Levine-Test to compare the variance () of Cu3Sn measurement
and 2-sided t-Test to compare the means (µ) of Cu3Sn measurements
Test HARSH
(0 to 100C)
Condition (-55 to 125C)
Comparison 438 to 1000 cycles 3157 to 6010 cycles
variable  µ  µ
SAC305 0.40 0.00 0.72 0.00
Senju M42 0.70 0.00 0.99 0.00
Sunrise 0.17 0.04 0.17 0.00
Sunflower 0.01 0.00 0.04 0.00

115
 Table 35: Results of ANOVA test to equal variance and compare means
Total IMC Cu3Sn
Variable / p value Equal Equal
ANOVA ANOVA
variance variance
(µ) (µ)
() ()
Time 0 0.60 0.07 -- --
438 cycles
0.20 0.04 0.01 0.00
HARSH (-55 to 125C)
1000 cycles
0.35 0.24 0.00 0.00
Test HARSH (-55 to 125C)
Condition 3157 cycles
0.65 0.30 0.56 0.00
(0 to 100C)
6010 cycles
0.13 0.43 0.01 0.00
(0 to 100C)

Figure 80 through Figure 87 provide details of the ANOVA analysis. The interval plot
Figure 80 and Figure 81 show the 95% confidence intervals for the mean overall IMC
layer thickness and the mean Cu3Sn layer thickness respectively. While it appears that
SAC305 has a thicker overall IMC layer at Time 0, the interval plot shows substantial
overlap between the 95% CIs of all four alloys and therefore indicates that the difference
in thickness is not statistically significant. Further analysis indicates that there is a
difference in Time 0 thicknesses within a 93% confidence level. The thicker IMC layer
of SAC305 is a result of the higher processing temperature (240C). The intervals for the
Cu3Sn layer thickness of Sunflower do not overlap with any of the 95% CI of the other
alloys, thereby indicating a significant difference in thickness.

116
Figure 80: Interval plot of IMC thickness at the board side of QFP after ATC

Figure 81: Interval plot of Cu3Sn thickness at board side of QFP after ATC

117
The main effects plots in Figure 82 to Figure 85 are used to de-couple the main factors in
the measurements to better understand their individual contributions. Figure 82 and
Figure 83 show the condition, or time at exposure to thermal cycling, has a greater
influence on the overall IMC thickness than do the particular alloys. SAC305 has a Time
0 IMC thickness greater than the mean of the other three alloys, which all have mean
values closer to the grand mean.

Figure 84 and Figure 85 show that the condition is also a greater influence on the mean
overall thickness of the mean Cu3Sn layer than the alloys. The difference between Cu3Sn
thicknesses amongst the alloys shows the same pattern: SAC305 and Senju M42 have
mean thicknesses close to the grand mean, Sunrise has a mean lower than the grand mean
and Sunflower is significantly greater than the grand mean.

Figure 82: Main effects plot of IMC thickness at the board side QFP during HARSH
(-55 to 125C) ATC

118
Figure 83: Main effects plot of IMC thickness at the board side QFP during 0-100C

Figure 84: Main effects plot of Cu3Sn thickness at board side of QFP during
HARSH (-55 to 125C) ATC

119
 Figure 85: Main effects plot of Cu3Sn thickness board side of QFP during 0-100C

Interaction plots found in Figure 86 and Figure 87 tests the factors to identify any
interactions. Parallel, or near parallel lines, as seen in both cases indicate there are no
clear interactions; the influence of one factor is not dependent on the other. The mean
thickness of the IMC layer for SAC305 at Time 0 is greater than that of the other alloys,
however over the course of ACT testing under two test conditions, this distinction seems
to disappear, the mean IMC thicknesses are no longer distinguishable between alloys.

120
Figure 86: Interaction plot of IMC thickness at the board side of QFP after ATC

Figure 87: Interaction Plot of Cu3Sn Thickness at Board Side of QFP after ATC

121
5 Summary of Findings and Conclusions
5.1 Findings Based on Reliability Data
During two different thermal cycling regimes the only failures which could be attributed
to solder joint fatigue failures occurred in SAC305 during 0 to 100C cycling; one
sample of Sunrise, which failed but only after 5416 cycles. All other electrical failures
were attributed to failures within the board material. In the case of BGAs, this occurred
due to cracks within via barrels; in QFPs it was the result of copper trace fractures.
Thermal cycling did not significantly distinguish between the reliability performances of
the four alloys. High Tg board material appeared to outperform Normal Tg board material.
It can be concluded that the three lower process temperature solders performed as well as,
or better than SAC305 during accelerate thermal cycling. All solders survived longer
than the board materials.

5.2 Findings Based on Microstructural Observations

Bi had a beneficial impact on the bulk microstructure. It precipitated from the bulk solder
evenly in very small particles. This favorable influence of Bi only appeared when the
concentration was 7wt%; the 3wt% Bi of Senju M42 did not appear to have the same
impact. Senju M42 appeared to have the same aging characteristics as SAC305. There
was some degree of Bi segregation along the grain boundary observed in the Sunflower
alloy; however there did not appear to be full segregation of the phases.

The interfacial IMC layer () Cu6Sn5, formed during solidification, was similar in
thickness for all alloys. During thermal cycling, the total thickness of the interfacial IMC
continued to increase, as well as () Cu3Sn layer formation. While the overall thickness
increased similarly for all four alloys, the Cu3Sn layer of the Sunflower alloy was much
thicker than the other alloys. This alloy has no Ag, which indicates that Ag plays a role
in suppressing Cu3Sn growth. This is in spite of the fact that Ag does not participate in
the IMC formation; no Ag-containing species exists at the interfacial IMC. It has
previously been shown that eutectic SnAg solder exhibited a lower layer-growth

122
coefficient for Cu6Sn5 than for Cu3Sn.24 This was believed to be the result of the Sn
diffusion in SnAg being slower than the Sn diffusion in, for example eutectic SnPb
solder, in turn favoring the growth of Cu3Sn. It appears, through this study, that even
small amounts of Ag in the solder (1%, 2% and 3%) are sufficient to suppress the
diffusion of Sn to the growing interfacial IMC layers. Bi alloying did not significantly
change the growth rates of either intermetallic compound. The increased growth of the
Cu3Sn phase in the Sunflower alloy did not correspond to any decrease in reliability
during ATC.

SAC305, which was processed at a higher temperature, initially had a larger interfacial
IMC layer. This effect however did not continue during thermal cycling where the IMC
layers of all four alloys formed and increased to similar overall thicknesses.

123
6 References

1
J. Bentley “Introduction to Reliability and Quality Engineering”, 2nd Ed, Essex,
England, Pearson Education Limited, 1999, ch. 2, pp 28-43.
2
IPC-SM-785 Guidelines for Accelerated Reliability Testing of Surface Mount Solder
Attachments, November 1992
3
W. Engelmaier “Solder Attachment Reliability, Accelerated Testing, and Results
Evaluation” in Solder Joint Reliability J.H. Lau, Ed. New York, Springer 1991,
ch.17. pp. 545-587
4
Blueprints for Product Reliability, The Reliability Information Analysis Center (RIAC),
http://theriac.org/DeskReference/viewDocument.php?id=280&Scope=blueprints
&Deskref=blueprint1#3point4
5
J.W.Evans “Thermomechanical Fatigue” in A Guide to Lead-free Solder: Physical
Metallurgy and Reliability, W. Engelmaier, Ed. London, UK, Springer 2007, ch.7,
pp. 145-185
6
IPC-9701A: Performance Test Methods and Qualification Requirements for Surface
Mount Solder Attachments, February 2006
7
A. MacDiarmid “Thermal Cycling Failure – Part One of Two” in The Journal of the
Reliability Information Analysis Center, January 2011
8
J-P.M. Clech and J.A. Augis “Surface Mount Attachment Reliability and Figures of
Merit for Design for Reliability in Solder Joint Reliability J.H. Lau, Ed. New
York, Springer 1991, ch.18. pp. 588-613
9
J.W.Evans “Introduction to Solder Alloys and Their Properties” in A Guide to Lead-free
Solder: Physical Metallurgy and Reliability, Ed. London, UK, Springer 2007,
ch.1, pp. 1-27
10
A. Zbrzezny “Characterization and Modeling of Microstructural Evolution of Near-
Eutectic Sn-Ag-Cu Solder Joints” Ph.D. Thesis, Dept. MSE, Univ. Toronto,
Toronto, Canada, 2004.
11
R. Coyle, R. Parker, M. Osterman, S. Longgood, K. Sweatman, E. Benedetto, A. Allen,
E. George, J. Smetana, K. Howell, J. Arnold “iNemi Pb-Free Alloy
Characterization Project Report: Part V – The Effect of Dwell Time on Thermal
Fatigue Reliability” presented at SMTAI, Chicago, Il, 2013
12
J. Juarez Jr., M. Robinson, J. Heebink, P. Snugovsky, E. Kosiba, J. Kennedy, Z.
Bagheri, S. Suthakaran, M. Romansky “Reliability Screening of Lower Melting
Point Pb-Free Alloys Containing Bi,” in IPC APEX EXPO Conference, Las
Vegas, NV, 2014.

124
13
B. Arfaei, M. Anselm, S. Joshi, S. Mahin-Shirazi, P. Borgesen, E. Cotts, J. Wilcox, and
R. Coyle “Effect of Sn Grain Morphology on Failure Mechanism and Reliability
of Lead-Free Solder Joints in Thermal Cycling Tests”, presented at SMTAI,
Chicago, Il, 2013
14
K-N. Tu “Copper Tin Reactions in Thin-Film Samples” in Solder Joint Technology :
Materials, Properties and Reliability New York, Springer, 2007, ch. 3, pp. 73-
108.
15
N. Mookam and K. Kanlayasiri “Evolution of Intermetallic Compounds between Sn-
0.3Ag-0.7Cu Low-Ag Lead-free Solder and Cu Substrate during Thermal Aging”
J. Mater. Sci. Technol., 2012, 28(1), 53-59.
16
C. Yu, Y.Yang, P. Li, J. Chen, H. Lu “Suppression of Cu3Sn and Kirkendall voids at
Cu/Sn-3.5Ag solder joints by adding a small amount of Ge”, J.Mater Sci: Mater
Electron (2012) 23:56-60
17
C. Yu Chen, Kai-Yun Wang, Jing-Qing Chen, Hao Lu “Suppression effect of Cu and
Ag on Cu3Sn layer in solder joints”, J Mater Sci: Mater Electron (2013) 24:4690-
4635
18
G.C. Moon, S.K. Kang, D-Y Shin and H.M. Lee “Effects of Minor Additions of Zn on
Interfacial Reactions of Sn-Ag-Cu and Sn-Cu Solders with Various Cu Substrates
during Thermal Aging” Journal of Electronic Materials, Vol. 36, no. 11, 2007.
19
P. Snugovsky, E. Kosiba, J. Kennedy, Z. Bagheri, M. Romansky, M. Robinson, J.M.
Juarez, Jr., J.Heebink “Manufacturability and Reliability Screening of Lower
Melting Point Pb-free Alloys Containing Bi,” in IPC APEX EXPO Conference,
San Deigo, CA, 2013.
20
P. Vianco, and J.A. Rejent “Properties of Ternary Sn-Ag-Bi Solder Alloys: Part 1 –
Thermal Properties and Microstructural Analysis”, Journal of Electronic
Materials, Vol.28, No.10, pp. 1127-1137, 1999
21
D.Witkin “Creep Behavior of Bi-Containing Lead-Free Solder Alloys” Journal of
Electronic Materials, Vol. 41, No. 2, 2012.
22
P. Vianco, and J.A. Rejent “Properties of Ternary Sn-Ag-Bi Solder Alloys: Part 1 –
Thermal Properties and Microstructural Analysis”, Journal of Electronic
Materials, Vol.28, No.10, pp. 1127-1137, 1999
23
CRE Primer, Chapter IX: Data Collection, p. IX-5, Quality Council of Indiana. 2009.
24
D.Kwon “Intermetallic Formation and Growth” in A Guide to Lead-free Solders:
Physical Metallurgy and Reliability, Silver Spring, MD: Springer, 2005, pp. 97-
126

125
 Chapter 4
Tin Whisker Testing

1 Introduction
Whiskers, spontaneous columnar or cylindrical filaments which emanate from a surface,
are found to form from various metals including Ag, Zn, Cd and Sn.1,2 The danger posed
within an electronic system is that whiskers are both conductive and grow spontaneously.
It is therefore challenging to predict where they could form, and if they would grow long
enough to cause potential electrical bridging issues. Electrical bridges can form by
whiskers growing long enough to cross the minimum gap, or by whiskers broken off
from the surface and falling freely around the electronic assembly. Furthermore, there is a
potential for two whiskers to grow sufficiently close together to allow for electrical
arcing between them. As the demand for increasingly small electrical components
continues, and the minimum lead-to-lead gap shrinks, the risk whiskers pose increases
with miniaturization.

Sn whiskers tend to have the following characteristics: growth over time, thicknesses
varying from sub-micron to just above a few microns, tough and electrically conductive.3
Although Sn whiskers were first observed shortly after WWII in telephone transmission
line channel filters1, they were not extensively studied since Pb in Sn (at least 1wt%) was
found to be an effective form of mitigation. Although whiskers can grow from SnPb
solder, they were observed as short and often topped with a Pb-rich “cap” (Figure 88),
which appeared to limit their growth.

126
 Figure 88: Pb "cap" on whisker from SnPb component finish2

Initial investigations of whisker formation focused on Sn plating of electronic

components. As whiskers are a surface, rather than a bulk, phenomenon, a thin coating of
matte Sn found on most Pb-free components, was initially thought to be the main area of
concern. Correspondingly, most standards developed for testing, measuring and
qualifying new materials focused on component surface finishes.4,5

During assembly using a SnPb solder, the solder is expected to wet a portion of the lead
and form a fillet (represented by E in Figure 89a) while the rest of the lead maintains its
original plating material. Due to the higher reflow temperatures used to assemble SAC
solders, the electroplated Sn on the lead frame melts. The solder is therefore likely to
completely wet and cover the lead (Figure 89b).6 With SnPb solder assemblies, using
matte Sn plated components; the risk of whisker formation exists on the exposed Sn area
of the lead. Originally it was thought that whiskers grow primarily from thin film
coatings, however it has been shown they also grow from bulk solder; whiskers have
been observed growing from bulk SAC305 and SAC405.7 This indicates the risk of
whisker growth now spans the entire solder joint surface on a Pb-free assembly. It is
believed however, that areas where a thin layer of solder exists are of greatest concern.

127
Figure 89: a) Schematic for a typical solder joint of a leaded component using SnPb
solder8, b) cross section showing solder joint formed with Pb-free solder

1.1 Whisker Growth Kinetics

Currently there is no widely accepted explanation for the mechanism causing Sn
whiskers; however it is widely agreed that the driving force for whisker nucleation and
growth involves local compressive stresses. It is accepted that Sn whiskers are one of the
forms of stress relaxation within the localized region.6 It is also understood that whiskers
are a surface stress relief mechanism; when relaxation occurs within the bulk
microstructure, whiskers will not grow.9 Therefore areas with thin solder coating, or thin
plating material appear to be more susceptible to whisker formation. For example, on an
assembly of Sn plated components built with SAC305 solder, whiskers grew from areas
where the solder was less than 25µm thick.10

Complicating matters, it has been shown that the total length of the whisker does not
correlate to the applied stress, thereby indicating the mechanism is not one of bulk
diffusion. Additionally, whiskers appear to originate from newly formed grains at the
surface. For these reasons, one of the currently accepted models, proposed by Vianco,
describes whisker growth as a process of cyclic dynamic recrystallization (DRX).2,11

This model suggests that whiskers grow under specific conditions requiring both a cyclic
DRX, in order to nucleate a new grain at the surface of a thin film, and a mass transport

128
mechanism to facilitate the supply of Sn. In both case the driving force is applied
compressive stress. This model also proposes that stress relaxation will occur by means
of recrystallization rather than recovery when the homologous temperature (Th) is
approximately 0.6. Sn, even at room temperature, has a homologous temperature of 0.59.
The formation of whisker growth is further dependent on strain rate where a slower strain
rate will favor whisker formation over a high strain rate. Finally if the applied stress is
too high, even at a low strain rate, whiskers will not likely form.

As compressive stress is applied to a surface, strain within the localized system

accumulates, usually in the form of dislocations at pre-existing grain boundaries. Once
this strain energy pile-up exceeds a certain limit, a new grain will nucleate and grow in a
process known as DRX. This process differs from a dynamic recovery process in which
the dislocations will either annihilate each other or be absorbed within the grain
boundaries instead of forming new grains. The growth of grains in the form of whiskers
represents a surface phenomenon rather than grain growth within the bulk of a material.
Strain rate, temperature and grain size all factor into the cyclic DRX model and
subsequently whisker growth.2

Compressive Stress

Work Hardening
Creep Deformation Dynamic Stress Relaxation

Recrystallization Recovery
Th= ~0.6 (DRX) – no whiskers Th= 0.2-0.3

Slow strain rate Cyclic DRX Continuous DRX

– no whiskers Fast strain rate

X < σ < 5 MPa σ > 5 MPa

– no whiskers

Figure 90: Cyclic Dynamic Recrystallization resulting in whisker formation12

– no whiskers

129
1.2 Sources of Compressive Stress
Sn whisker growth is initiated by self generating compressive stress within the material
and can be mechanical, thermal or chemical in nature.9 An IMC layer growing between
the lead frame material and the plating material, or solder, is usually irregular, or scallop
shaped (Chapter 3). The growth of this layer and any IMC particles, which subsequently
break off into the bulk material, introduce compressive stresses into the bulk material. In
the case of Sn plated leads, the Sn layer is often found to have a columnar shape, with
IMC particles accumulating along the grain boundaries.

Figure 91: Source of compressive stress contributing to whisker growth13

When exposed to various temperature cycling environments, stress induced into the Sn
plating or solder is attributed to the mismatch in the Coefficient of Thermal Expansion
(CTE) between the Sn and the lead frame material. Localized compressive stresses may
occur and increase the whisker propensity where thin layers of solder exist. Also, the
uneven interfacial IMCs, which continue to grow during the heating portion of the
thermal cycle, may introduce compressive stresses into the solder. There may not be
sufficient time to relieve stress before the cold portion of the cycle occurs. Previous work
found that CTE mismatch and corresponding whisker growth was greater for Alloy 42
lead frame materials than for Cu.10,13 (Table 36).

130
 Table 36: CTE values for common materials in solder joints
Coefficient of Thermal Expansion
Material Composition (CTE) ppm/C
Lead Finish Sn Sn 22.0
Solder Paste SnPb Sn - 37Pb 21.6
Materials SAC305 Sn - 3Ag0.5Cu 21.6
Alloy 42 Fe - 42Ni 5.8
Cu - 2.1-2.6Fe-0.015-
Cu194 17.5
Lead Frame 0.15P-0.05-0.2Zn
Materials Cu151 Cu - 0.1Zr 17.7
Cu - 2.2-4.2Ni0.25-
Cu7025 17.3
1.2Si0.05-0.3Mg

The formation of oxides on the surface of a solder joint or plated lead has also been
associated with whisker growth. 9,14 In this case, the compressive stresses are related to
the volume expansion caused by the formation of oxides, which can lead to a volume
expansion of approximately 29 to 34% as observed in many studies testing samples in
humid conditions. 15 Oxidation can also be associated with the presence of IMC particles.
For example, when exposed to humidity and chloride contamination, Ag3Sn IMC
particles found at the surface of a SAC305 solder joint are found to exhibit corrosion
within the interdendritic spaces (Figure 92). This is attributed to the differing chemical
potentials of the IMC and the surrounding bulk solder, which facilitate galvanic
corrosion.6,16 Sn-based solders are particularly susceptible due to the roughness of the
surface; shrinkage voids resulting from the dendritic solidification of these solders leaves
a very rough surface which can easily entrap contaminates during the manufacturing
process or during field use. Cu-based lead frame materials have been shown to be more
susceptible to these types of compressive stresses than Alloy 42.16

131
 Figure 92: Ag3Sn oxide zone with whisker6

Mechanically-induced residual stresses also result in whisker formation. For example, the
compressive stresses generated in the Sn plating of a leaded component have been
attributed to the bending or stretching processes used to form leads into their final shape
after plating.17 Studies show that whiskers growing as a result of these mechanically
induced stresses tend to have a higher growth rate than those resulting from room
temperature IMC internal stresses.18

1.3 Morphology of Sn Whiskers

As stated in 1.1, a correlation between applied stress and resulting whisker length has not
been found. Whisker growth is, to date, unpredictable as is the final morphology of the
whisker. Long, thin, straight whiskers are often found alongside short, kinked whiskers of
various thicknesses (Figure 93). The long, fine whiskers have been found to contain only
Sn, usually of a single crystal structure. Shorter, thicker whiskers, hillocks and shell
shaped protrusions are made up of mainly Sn but may contain Ag3Sn and Cu6Sn5 IMC
particles.7 It is the long, thin, straight whiskers which are of most concern as they have
132
the highest potential of bridging a gap between electrical contacts. However, it is not
currently possible to predict the form or total length of whiskers.

Figure 93: Whisker morphology a) long, thin whiskers and b) short, kinked
whiskers16

1.4 The Effects of Bi in Solder on Whisker Formation

SnPb solder and plating finish has long been used in electronics without major reliability
concerns related to Sn whiskers. Eutectic SnPb plating over a Cu surface forms an
equiaxed grain structure rather than the columnar grain structure typical of Sn plating
(Figure 94). This equiaxed structure is believed to allow stress relaxation to occur by
incorporating displaced Sn grains more readily at grain boundaries, which lie parallel to
the surface. This would allow for the material to relieve the compressive stresses in a
uniform creep.19,20 Jadhav et al.19 showed that both the grain structure and the
concentration of Bi had an affect on the overall stress relaxation of a thin film over Cu.

Figure 94: Cross sections of plating surface made with SEM FIB of a) Sn and b)
SnPb19
133
Small amounts of Pb, as small as 1wt%, result in grain refinement and subsequently the
suppression of whisker growth. It was found that hillocks grow instead and that these
hillocks are of limited length.18 As Pb is no longer available as an alloying agent in
solder, other alloying elements are being explored for the same grain refinement, creep
resistance and ultimately whisker suppression characteristics. In this work, the focus is on
Bi alloying.

Section 1.2 identified the growth of an uneven, scalloped interfacial IMC layer as one of
the sources of compressive stress within a solder joint, particularly in areas with thin
solder coverage. Jo found that the IMC layer, which continued to grow during room
temperature storage and high temperature high humidity conditions, became more
uniform (i.e. less scalloped) with increasing concentrations of Bi.18 Annealing has also
been proposed as a means of creating a more uniform IMC layer. If the IMC layer were
to become more uniform in shape, it would introduce less compressive stress into the
system, thereby eliminating one possible source of stress. The surface area of the IMC
would also be reduced, which in turn would reduce the diffusion rate of Cu into the bulk
solder. The Cu6Sn5 IMC particles within the bulk solder are another source of internal
compressive stress on the localized system. Additionally, Jo found that as little as 0.5wt%
Bi reduced whisker propensity. Other researchers have indicated that as much as 3-5wt%
Bi is required for whisker suppression.1,21

The three main mechanisms by which Bi is thought to mitigate against whisker growth
are:
 Refining the grain size
 Altering the grain structure from a typical Sn columnar structure to an equiaxed
structure more similar to that found in SnPb
 Reducing growth and irregularity of interfacial IMC18

134
2 Experimental Set Up
The work describes in this section formed a screening experiment in which the selected
alloys were screened for whisker mitigation properties. The results were intended to
determine which, if any, of these alloys would be good candidates for further testing.

Table 37 provides a list of test conditions recommended by JEDEC for qualifying plating
finishes on components. It should be noted that there is no current test or qualification
guideline for assessing the propensity of solder alloys in an assembly to grow whiskers.
Further, it has been found that suspension of some tests, particularly those involving
humidity storage, will impact the total whisker growth and lead to under-reporting of
whisker length. When tests are restarted, new whiskers nucleate and grow rather than
existing whiskers continuing to grow. Therefore, in order to understand the time
dependence of whisker length, each successive inspection interval needs to be made after
an increased amount of uninterrupted exposure.6 The guidelines set out in Table 37 were
used as the basis for developing this works test conditions, however the conditions were
also augmented by further study. In high temperature/humidity storage conditions for
example, it was found that whisker nucleation occurred faster at 85C than at 50-70C.22
Table 37: JESD22A121.01 test conditions4

Recommendations
Ref.
Stress Type Test Conditions Inspection Minimum
Spec.
Interval Duration
Min Temperature
-55 to -40 (+0/-10)C
JESD22 Max Temperature
Temperature Cycling 500 cycles 1000 cycles
-A104 +85 (+10/-10)C
air to air: 5 to 10 minute soak;
~3 cycles/hour
Ambient
Temperature/Humidity 302C and 603%RH 1000 hours 3000 hours
Storage
High
Temperature/Humidity 602C and 87 +3/-2%RH 1000 hours 3000 hours
Storage

135
2.1 Materials
Two alloys with low Ag (Senju M42 and Sunrise), and one alloy with no Ag (Sunflower),
and varying amounts of Bi, were tested against SAC305 (Table 38). The alloy selection
method was described in Chapter Chapter 1. QFP components (U1) were cut from the
test vehicle described in 5.1.

Table 38: Alloys screened for whisker growth

Alloy Composition Assembly Temperature

SAC305 Sn 3%Ag 0.5%Cu 240C
Senju M42 Sn 2%Ag 0.75%Cu 3%Bi 224C
Sunrise Sn 1%Ag 0.7%Cu 7%Bi 222C
Sunflower Sn 0.7%Cu 7%Bi 226C

2.2 High Temperature High Humidity

Two samples of each alloy, consisting of 176 leads each, were placed in a humidity
chamber. Teflon cabling was used to suspend the samples (Figure 95) and de-ionized
(DI) water was used to generate the humidity conditions so as not to introduce possible
contaminates into the system. The samples were exposed to 85C/85%RH for 1000
hours.

Figure 95: Samples in HTHH chamber

136
2.3 Thermal Shock
Two samples of each alloy, consisting of 176 leads each, were placed in a two stage, air-
to-air, thermal shock chamber (Figure 96). The samples were exposed to -55C to 85C
thermal shocks using the profile shown in Figure 97 for a total of 1610 shock cycles.

Figure 96: Two stage, air to air, chamber for thermal shock testing

137
 120

100

80

60

40
Temperature in °C

20

-20

-40

-60
8: :04
8: :04
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5
:0
09
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51
53
55
57
59
01
03
05
07
09
11
13
-80
8:

Cold Chamber Hot Chamber Sample

Figure 97: Thermal shock temperature profile

2.4 Post Exposure Evaluation

After each of the two exposures, components were inspected for whiskers using a
variable pressure SEM (Hitachi S-3000N) at 15 kV acceleration voltage (Vacc), and
25MPa vacuum pressure. All leads on the components where examined at low
magnifications, between 100x and 250x. Areas which showed signs of irregularity,
nucleation and/or whiskers growth, where then further examined at higher magnifications
of 1000 to 5000x.

The samples exposed to thermal shock, which subsequently showed whisker growth,
were then further evaluated by cross section. Each sample was first mounted in epoxy,
and then ground and polished through the following sequence: 500 and 1200 grade SiC
paper, polishing with 6 µm and 1 µm DiaPro diamond suspensions (Struers), and an
oxide polish (Struers’ OP-S). Optical microscopy was performed using a Nikon
Measurescope MM-11. Prior to SEM analysis, the samples were carbon coated using an

138
Emitech K950X. SEM microscopy on cross-sectioned samples was performed using a
Hitachi S-4500 and Hitachi S-3000N with the following EDX systems: Oxford and
ThermoScientific respectively.

3 Results
3.1 High Temperature High Humidity Results
No whiskers were found on any of the four alloys tested after 1000 hours exposure to
85C/85% RH. Further exposure, for at least an additional 3000 hours in the same
conditions is recommended to distinguish between the whisker growth propensities
amongst the test alloys. This would be closer to the conditions set out in
JESD22A121.01, however due to resource constraints was not completed as part of this
work.

3.2 Thermal Shock Results

The results of whisker inspection are summarized in Table 39 including the location of
whiskers, as described in Figure 98 and a summary of the Bi content found in the location
of whisker growth. All alloys were found to form whiskers under the thermal shock
conditions. All whiskers (or hillocks) where short, less than 10µm and would therefore
not be considered to fail JEDEC Standard No. 201A for class 2 components, which
requires that no whisker to exceed 45µm after 1000 cycles of thermal shock.5 While this
specification is intended for component finishes rather than soldered components, it is the
only currently available guideline by which to make a comparison.

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 Table 39: Summary of whisker growth after 1610 cycles thermal shock
wt% Bi at
Alloy Composition Whisker Location | Morphology
Location

SAC305 Sn 3%Ag 0.5%Cu Yes 1,4 few hillocks 0

1,4 few, hillocks
Senju Sn 2%Ag 0.75%Cu Yes many, very small, 1.3, 1.8
M42 3%Bi 1,4
whisker nucleation sites
2 few, hillocks 3.7
Sn 1%Ag 0.7%Cu Yes many, very small
Sunrise
7%Bi 1,4 3.3, 3.3
whisker nucleation sites
1,2,4 few, hillocks 2.9, 4.1, 3.3

Sunflower Sn 0.7%Cu 7%Bi Yes some, very small

4 3.3
whisker nucleation sites

Figure 98: Schematic showing locations on lead where whiskers formed

140
Along with the observed whisker growth, other competing stress relaxation mechanisms
were found in all solder alloys. Figure 99 shows two adjacent leads, each with very
different surface morphologies after 1610 thermal cycles. The lead on the left shows
massive, bulk deformation and volume recrystallization. The lead on the right exhibits
very little deformation and appears unaffected by the local stresses. Massive eruptions
and protrusions of bulk IMC particles were also observed.

Figure 99: Two adjacent leads with Sunflower solder paste after 1610 thermal
shocks

SAC305 solder joints exhibited a small amount of whisker growth after 1610 cycles
(Figure 100), however there were no whiskers longer than 10µm. Short, thick whiskers –
which can be classified as hillocks, were found in locations 1 and 4 (Figure 98). Location
1 is of greater concern as it has a short bridging distance with the adjacent lead. Both
locations are known to have thin solder coverage; a thin solder layer is more susceptible
to whisker growth as compared to an area with a larger volume of bulk solder which may
relieve internal stresses by competing mechanisms. Unlike the Bi containing alloys,
SAC305 did not exhibit any area with many, small leads or “fields” of very short and thin
whiskers.

All three of the Bi containing alloys exhibited some degree of hillocks growing amongst
fields of very short, very thin whisker nucleation sites. This was most often found in
locations 1 and 4 (Figure 101 to Figure 103). Sunflower exhibited the least area of these
141
fields but had the two single longest whiskers seen in this study. Both however were still
shorter than 10µm.

Figure 100: Whisker growth on SAC305 after 1610 thermal shocks. a) and b)
whisker growth in location 4 c) massive deformation and d) whisker growth in
location1

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 Figure 101: Whisker growth on Senju M42 after 1610 thermal shocks. a) and b)
location 4 with short, thick whisker surrounded by many, very short whisker
nucleation sites c) and d) short, thick whiskers growing at site of contamination in
location4

143
 Figure 102: Whisker growth on Sunrise after 1610 thermal shocks. a) and b)
location 2 with short, thick whisker c) location 4 and d) location 1 with many, very
short whisker nucleation sites short

144
 Figure 103: Whisker growth on Sunflower after 1610 thermal shocks. a) and b)
location 1 with short, thick whisker c) some, very short whisker nucleation sites at
location 4 and d) longest whisker observed at location1

Figure 104 shows a whisker growing from Sunflower solder after 1610 cycles of thermal
shock. The base of the new whisker grain is located at the intersection of three surface
grains. This finding aligns with the dynamic recrystallization model. A cross section of a
hillock formed from Sunrise (Figure 105), shows that the hillock forms from a new grain
or grains. Figure 106 shows mass bulk recrystallization of the Senju M42 alloy in
location 2, where the volume of solder is greater and more susceptible to bulk
deformation. Whiskers, being a surface phenomena, will not likely form in these regions.
The stress relaxation will likely occur as a result of one of the competing mechanisms.

145
Figure 104: Whisker growing from Sunflower at grain boundary of recrystallized
grains

Figure 105: Hillock growing from Sunrise after thermal shock

146
 Figure 106: Senju M42 bulk recrystallization

Interfacial IMC layer growth has been identified as a potential source of compressive
stresses (section 1.2). The IMC may continue to grow during testing, particularly during
the high temperature portion of the cycle. If this growth continues in an irregular, scallop
shape, it will continue to drive compressive stress into the solder.

Figure 107 provides a comparison of IMC thicknesses after exposure. The IMC layers,
which form and grow at the board side of the solder joint, do not show significant
distinction between the solders. Table 40 provides a summary of test for equal variance
and ANOVA testing of the various alloys. This table provides probability (p-values) for
each test. In all cases, the null (H0) and alternate hypotheses (Ha) are as follows:

H0: µSAC305=µSenju M42=µSunrise=µSunflower and SAC305=Senju M42=Sunrise=Sunflower

Ha: at least one µ is different and at least one  is different

There is no statistically significant difference in the thickness measurements of the IMC

layers formed using each of the four alloys on the board side of the QFP after 1610 cycles
of Thermal Shock. However there is a difference in the thickness of the layer that at the
component side of the solder joint after Thermal Shock. In the case of the board side IMC

147
layer, the H0 is assumed to be valid while in the case of the component side, it is rejected.
The difference in variance of measurements for each alloy is not significant as
determined by a p-value  0.05. The difference in the mean (µ) thickness measurement at
the component side, in which SAC305 and Senju M42 have similar distributions, Sunrise
and Sunflower have similar, and smaller thickness distributions (Figure 108). This
suggests that the Bi content has some impact on the growth of the IMC layer under
thermal shock conditions. At the lead side, the mean of the IMC layer height is lower in
Sunrise and Sunflower than in SAC305 and Senju M42, which have roughly the same
overall height. The lead side IMC is of more interest than the board side as the whisker
growth has been observed mainly in locations 1, 3 and 4 (Figure 98) where a thin layer of
solder and the IMC layer interact potentially creating ideal conditions for whisker
growth. The board side IMC interacts with a larger volume of solder, at location 2. This
allows for more bulk recrystallization and massive deformation and may not drive the
growth of whiskers.

6
IMC Thickness (µm)

0
SAC305 Senju M42 Sunrise Sunflower SAC305 Senju M42 Sunrise Sunflower
Board Side Lead Side

Figure 107: IMC measurements of QFP solder joints after 1610 cycles thermal
shock (U1)

148
Table 40: Results of ANOVA test for equal variance and compare means of IMC
thickness of the QFP IMC layer after 1610 cycles thermal shock.
Total IMC
Variable / p value Equal
ANOVA
variance
Board Side 0.597 0.771
Location Lead Side 0.477 0.007

95% CI for the Mean - Lead Side

2.50

2.25
IMC Thickness (µm)

2.00

1.75

1.50

SAC305 Senju M42 Sunflower Sunrise

The pooled standard deviation was used to calculate the intervals.

Figure 108: Interval plot of IMC thickness at the lead side of QFP after thermal
shock

149
 Figure 109: IMC layer at lead with a) SAC305 and b) Sunrise after 1610 cycles of
thermal shock

Figure 110 shows a whisker growing from SAC305 at location 4. The image on the right
shows that a thin layer of solder, approximately 10µm where the relative influence of the
IMC layer, which ranges from 1-4µm, may be great.

Figure 110: Whisker growing from SAC305 after thermal shock

An examination of the solder surface as well as cross sections revealed that the Bi is not
uniformly distributed through the solder joint. Figure 111 shows the Bi concentration at
various locations along the solder joint formed using Sunrise solder paste after 1610
cycles of thermal shock. The Bi content is lowest in the thin areas of the lead, those most
susceptible to whisker formation.

150
 Figure 111: Bi content at various locations of a Sunrise solder joint

In both Sunrise and Sunflower, where the concentration of Bi is 7wt%, the Bi

precipitates, seen as the lighter areas in Figure 112, have been found around the grain
boundaries. Bi is also seen precipitating out of the primary Sn dendritic structure and
can be seen as fine particles, particularly visible in the top two images of Figure 112.

151
 Figure 112: Cross section of Sunflower showing Bi accumulating at grain
boundaries

4 Summary of Findings and Conclusions

The whisker testing executed comprised a screening experiment. A systemic count and
measuring scheme, similar to those carried out in other studies10,13,16 is required to
provide statistical conclusions. In this study, two samples of each alloy, consisting of
176 leads each were tested in each environmental condition. This provides a large
enough sample size, however it was found that the length of test, specifically the HTHH
produced an insufficient number of whiskers and no whiskers of excessive length, which
would be of concern. The current required length of test is 3000 hours; in this
experiment, only 1000 hours was completed. From previous work6, it is known that
interruption of test corresponds to the interruption of whisker growth. It is therefore
recommended that the samples be reexamined after an additional 3000 hours of HTHH.

1610 cycles of Thermal Shock testing is sufficient to meet the requirements for whisker
testing. In this case, all four alloys passed the requirements set out in JEDEC Standard

152
No. 201A for class 2 components. It is believed that the internal, compressive stresses
induced by this type of thermal shock are very high (Figure 90) and may favor another
form of stress relaxation over whisker growth, like massive bulk deformation.10

The whiskers which formed on the surface of the three Bi-containing alloys all differed
from those seen on SAC305. While all four alloys showed a small amount of hillock
growth, particularly in locations 1, 2 and 4, the Bi containing alloys also showed a
significant amount of small whisker nucleation sites. Further study is needed to quantify
this behavior, however it is believed that stress relief through many, short whiskers
presents less of an overall reliability concern. If sufficient stress is relieved through many
short whiskers, it is believed that the likelihood of one whisker continuing to grow to a
catastrophic length may be reduced.

Another observation of this study worthy of further consideration, is the local presence of
Bi at the site of whisker growth. It was found that the final composition of the solder,
which is a combination of the solder paste, the tin plating on the component and any
diffused Cu from the lead and board, is not uniform along the entire length of the lead. In
areas which have the greatest risk of whisker growth, those along the upper lead where
the solder is thin, also have the lowest overall composition of Bi. In solder joints formed
with Senju M42, which has an initial concentration of 3wt% Bi, the Bi concentration at
areas of whisker growth was experimentally found to be between 1.3 and 1.8wt%. Solder
joints formed from Sunflower and Sunrise, which have an initial concentration of 7wt%
Bi had between 2.9 and 4.1 wt% Bi in areas of whisker growth.

Finally, in Sunrise and Sunflower, each of which have 7wt% Bi, the Bi was found to have
precipitated from the Sn, likely from the interdendritic eutectic region. This process was
shown, in section 6.1.1, to have started during solidification. Over the course of the
thermal cycling, the Bi particles have been observed along the grain boundaries.
Additionally, very fine precipitates appear to have formed during the course of thermal
cycling. Therefore it is not known what the overall impact of Bi content in the solders is
on the overall propensity for whisker growth.

153
5 References

1
JP002: Current Tin Whisker Theory and Mitigation Practices Guideline, March 2006.
2
P.T. Vianco “Dynamic Recystallization (DRX) as the Mechanism for Sn Whisker
Development. Part I: A Model” ” in Journal of Electronic Materials, Vol. 38, No.
9, 2009.
3
L. Panashchenko “Evaluation of Environmental Tests For Tin Whisker Assessment”
M.Sc. Thesis, Dept. Mech. Eng., University of Maryland, College Park,
Maryland. 2009.
4
JESD22-A121A: Test Method for Measuring Whisker Growth on Tin and Tin Alloy
Surface Finishes, July 2008
5
JESD201A: Environmental Acceptance Requirements for Tin Whisker Susceptibility of
Tin and Tin Alloy Surface Finishes, September 2008
6
P.Snugovsky, S. Meschter, Z. Bagheri, E.Kosiba, M.Romansky, J. Kennedy “Whisker
Formation Induced by Component and Assembly Ionic Contamination” in the
Journal of Electronic Materials, Vol. 41, No. 2, 2012.
7
P.Snugovsky, Z. Bagheri, M. Romansky “Whisker Growth on SAC Solder Joints:
Microstructure Analysis” in ICSR SMTA Conference, Toronto, ON, 2008
8
IPC-A-610E-2010: Acceptability of Electronic Assemblies
9
K-N. Tu “Spontaneous Tin Whisker Growth: Mechanism and Prevention” in Solder
Joint Technology : Materials, Properties and Reliability New York, Springer,
2007, ch. 6, pp. 153-181
10
S.J. Meschter, P. Snugovsky, J. Kennedy, Z. Bagheri, and E.Kosiba “Strategic
Environmental Research and Development Program (SERDP) Tin Whisker
Testing and Modeling: Thermal Cycling Testing” presented at International
Conference on Solder Reliability, Toronto, Ontario, Canada, 2014.
11
P.T. Vianco “Dynamic Recystallization (DRX) as the Mechanism for Sn Whisker
Development. Part II: Experimental Study” in Journal of Electronic Materials,
Vol. 38, No. 9, 2009.
12
P.Snugovsky, S. Meschter, Z. Bagheri, E. Kosiba, M. Romansky, J. Kennedy “Whisker
Formation on SAC305 Assemblies” in TMS Conference, San Diego CA, 2014
13
S.J. Meschter, P. Snugovsky, J. Kennedy, Z. Bagheri, and E. Kosiba “SERDP Tin
Whisker Testing: Low Stress Conditions” presented at International Conference
on Solder Reliability, Toronto, Ontario, Canada, 2012.

154
14
D.Kwon “Packaging Architecture and Assembly Technology” in A Guide to Lead-free
Solders: Physical Metallurgy and Reliability, Silver Spring, MD: Springer, 2005,
pp. 35-36
15
A.Baated , K-S. Kim, K. Suganuma, S. Huang, B. Jurcik, S. Nozawa, B. Stone, M.
Ueshima. “Effects of Reflow Atmosphere and Flux on Tin Whisker Growth of
Sn-Ag-Cu Solder” presented at SMTAI, Chicago, Il, 2009
16
P.Snugovsky, E. Kosiba, S. Meschter, Z. Bagheri, J. Kennedy “Assembly Cleanliness
and Whisker Formation” presented at IPC APEX EXPO Conference, San Diego,
CA, 2015.
17
M.Osterrnan “Mitigation Strategies for Tin Whiskers” prepared for CALCE Working
Group, 2002.
18
J-L Jo “Tin Whisker Growth Mechanism and Mitigation for Lead-Free Electronics”
Ph.D. Thesis, Dept. of Adaptive Machine System, Osaka University, Japan. 2013.
19
N.Jadhav, M. Williams, F.Pei, G. Stafford, E. Chason. “Altering the Mechanical
Properties of Sn Films by Alloying with Bi: Mimicking the Effect of Pb to
Suppress Whiskers” ” in Journal of Electronic Materials, Vol. 42, No. 2, 2013.
20
W.J. Bottinger , C.E. Johnson, L.A. Bendersky, K.-W. Moon, M.E. Williams, G.R.
Stafford “Whisker and Hillock Formation on Sn, Sn-Cu and Sn-Pb
electrodeposits” in Acta Materialia, Vol. 53 pp. 5033-5050, 2005.
21
GEIA-HB-0005-2: Standard for Mitigating the Effects of Tin Whiskers in Aerospace
and High Performance Electronic Systems, January 2007.
22
S.Meschter, P. Snugovsky, J. Kennedy, S. McKeown and E. Kosiba “Tin Whisker
Testing and Risk Modeling Project” SMTA Journal Volume 24, Issue 3 (2011)

155
 Chapter 5
Mechanical (Drop) Shock Testing

1 Introduction
The proliferation of hand held devices and complex portable electronic devices occurred
at the same time as the requirement of Pb-free solders took effect.1 This confluence of
usage and regulation has introduced some significant issues related to the drop shock
response of new Pb-free solder alloys. These devices are particularly susceptible to
accidental drops over the course of their life time. At the same time SAC305 solder,
which is currently the favorite amongst commercial product manufacturers, is
significantly stiffer than traditional SnPb solder, and therefore tends to perform poorly in
response to drop shock.

As described in Chapter Chapter 1, new alloys are being explored with the intent of
improving upon SAC305. Within a SAC alloy, the Sn phase exhibits the lowest elastic
modulus and yield strength, and is therefore the most ductile phase within the SAC
solder. The IMCs which form within the bulk solder act to increase the overall strength
and reduce the ductility of the solder. In drop shock conditions, this higher strength and
lower acoustic impedance allow for the stress to more readily transfer to the solder-
copper interface, the more brittle IMC layer.2 Brittle fracture along the IMC is the typical
failure mode in drop shock conditions of a SAC solder joint as opposed to a more ductile
type fracture of SnPb solder joints, which typically failed within the bulk solder or a
combination of bulk solder and interface fracture.3 Additionally, an increased amount of
Ag can lead to the formation of platelet shaped IMC, as opposed to the finer particles
found with low concentrations of Ag. These platelets may act as stress concentrators,
reducing the overall performance of the solder joint in drop shock testing. It has been
shown that improved drop shock performance can be attributed to lowering of the Ag
component of an alloy, i.e. from SAC405 to SAC105. This transition to better
performance occurs around the 3% Ag level, alloys with Ag below 3% perform better

156
than those with Ag above 3%.4 Lowering the Ag content will reduces the yield strength
and consequently increases the bulk solder joints ability to dissipate high plastic energy.1

Finally the higher process temperature required for proper formation of SAC solder joints
presents two additional problems, which impact the solder joints resistance to drop shock:
increased exposure to higher temperatures may lead to a thickening of the brittle IMC
interface layer abdrequiring higher Tg board materials to withstand the higher
temperature. These new board materials are more prone to a failure mode which has not
been typically seen with SnPb alloys – pad cratering. Any new alternative alloy will
therefore need to address both failure modes.

Bi as an alloying element has typically been used to reduce the melting temperature of
the main alloy. Bi may also suppress the formation of Ag3Sn platelets and reduce
intermetallic compound (IMC) growth. Furthermore, Bi acts to refine the grain structure
of the bulk solder when added to a SAC solder joint.2

This work considers a number of low (or no) Ag Pb-free alloys with differing degrees of
Bi. All of these alloys have melting temperatures between 10 and 18C lower than that
of SAC305 allowing for the use of a lower Tg board material. It is believed that the
improved properties of the new, low melt alloys, along with the lower Tg board material
will have a combined effect of improving the mechanical strength of the overall solder
joint.

In this screening experiment the drop shock testing was performed on boards with an
OSP finish. It should be noted that the board finish, and subsequent interconnection IMC,
may greatly influence the performance of an alloy. Future testing should therefore be
performed on other surface finishes.

2 Experimental Set Up
The work presented in this section forms a screening experiment in which the selected
alloys were screened for drop shock response; the results are intended to determine
which, if any, of these alloys would be good candidates for further testing.
157
2.1 Materials
Two alloys with low Ag (Senju M42 and Sunrise), and one alloy with no Ag (Sunflower),
and varying amounts of Bi, were tested against SAC305. The alloy selection method was
described in Chapter Chapter 1. The board material was also a factor in these screening
experiments. Two board materials were tested; a normal Tg material– one which is
typically used for SnPb applications around 150C, and a high Tg material– one which is
now required for most Pb-free applications at around 170C.

Table 41: Build matrix for drop shock testing

Alloy Composition Board Material Assembly Temperature
SAC305 Sn 3%Ag 0.5%Cu 240C
Senju M42 Sn 2%Ag 0.75%Cu 3%Bi High Tg 224C
Sunrise Sn 1%Ag 0.7%Cu 7%Bi (170C) 222C
Sunflower Sn 0.7%Cu 7%Bi 226C
Sunrise Sn 1%Ag 0.7%Cu 7%Bi Normal Tg 222C
Sunflower Sn 0.7%Cu 7%Bi (150C) 226C

2.2 Test Vehicle

Celestica’s RIA3 test vehicle, shown in Figure 113, was used. It was originally designed
to simulate a typical, medium complexity assembly. It is an 8”x10” PWB made up of 12
copper layers for a total thickness of 0.093” with an Organic Solderability Preservative
(OSP) finish. This board is one which is often used to test new, lead-free solders and
other material parameters. LQFP176, PBGA256, CBGA64 and MLF20s were populated,
two of each on each board. The BGA components all had SAC305 ball alloy and the
reflow was performed in an air environment. While this test vehicle was not originally
designed for evaluating consumer electronics, it served the needs of the screening
experiment in that it provided for monitoring a variety of component types.

158
 Figure 113: Test vehicle with monitored components

Pad cratering has been identified as the main failure mode for Pb-free solders in
mechanical testing. This is due to the changes in laminate materials required to survive a
higher reflow temperature. PWB manufacturers have had to change the epoxy resins as
well as increase the amount of ceramic particle filler material in order to reduce the
coefficient of thermal expansion (CTE).5 To mitigate this failure mode in the drop shock
portion of testing, Solder Mask Defined (SMD) BGA pads were used. Figure 114
illustrates how the SMD boards introduce a sharp corner to the solder joints. It was
intended that this corner act as a stress concentrator within the solder joint and drive any
failure into the solder as opposed to within the laminate material, thereby allowing for a
comparison of the different solder alloys. SMD pads are also used in many commercial
applications such as cell phones and are therefore representative of commercial products
where drop strength would be a requirement.

159
 6
Figure 114: Solder mask defined vs. non-solder mask defined

2.3 Assembly
The assembly process utilized surface mount technology (SMT) parts, as described
above, placed and then reflowed with target reflow profiles outlined in Table 41. Primary
SMT was performed with No Clean flux in a ten-zone oven. 42 RIA3 boards were built
with an OSP finish and solder mask defined (SMD) copper pads. The RIA3 card was cut
in half in order to better represent the smaller board sizes used in commercial applications
(i.e. smart phones). One half of the board (RIA3-1) had five monitored components,
while the other half (RIA3-2) had only one monitored component as per Table 42 and
Figure 113.

2.4 Test Strategy

Five boards of each combination were exposed to drop shock testing, one was used for
Time 0 analysis, and one was held back as a “do nothing” board for possible verification
purposes which may arise in the future.

Table 42: Monitored components for drop testing

Board Component Reference Designator
RIA3-1 BGA-256 U204
RIA3-1 BGA-256 U205
RIA3-1 QFP-176 U1
RIA3-2 QFP-176 U2
RIA3-1 CSP-64 U208
RIA3-1 CSP-64 U209
160
In order to test the mechanical strength of the solder joints, board level drop testing,
based on JESD22-B110A7, was performed. This test method aims to evaluate a
subassembly’s ability to “withstand moderately severe shocks as a result of suddenly
applied forces or abrupt change in motion”. Within a subassembly there are four basic
types of failure which typically resulting from drop shock:
1) Fracture, or permanent deformation, caused by high applied stress
2) Chatter created by high acceleration levels, e.g. causing bolts to loosen
3) Impact between adjacent objects, caused by high displacement
4) Momentary electrical failure associated with a shock pulse8

In this test, condition 1 is the most likely and desired failure mode. Conditions 2 and 3
are mitigated by the test set up in which all resistance cables, strain gages and
accelerometers are secured using room temperature vulcanization (RTV) silicone, as seen
in Figure 115, and loaded within a fixture allowing for sufficient spacing to avoid impact
with other objects as seen in Figure 116. Condition 4 presents a problem as a momentary
electrical failure, which recovers after a shock pulse, and may be the result of an
electrical response. This is mitigated by using an event detector to monitor failures,
which require an increase of 300 for at least 200ns. An electrical pulse less than this
would not be recorded as a failure.

161
 Table Accelerometer

Figure 115: Example of accelerometer secured with RTV silicone

Figure 116: Test set up

As per JESD22-B110, the subassembly was supported in a manner which is

representative of field conditions, in this case allowing the PWB to flex during the drop
shock. The parameters are a peak acceleration of 1500G with a 0.5ms duration defined in
162
JESD22-B110 Service Condition B in a half-sine waveform. Figure 117 and Figure 118
show the target and the achieved half-sine waveform respectively. In Figure 118 the red
line represents the acceleration experienced by the drop table, monitored by an
accelerometer attached directly to the table. A limited amount of rebound was measured
immediately after the drop. This may be attributed to the movement of the accelerometer
relative to the board (or table) to which it is affixed, which should be minimized by use of
RTV silicone or a noise in the collected signal. It may also be the result of poor
dampening. Compared to the initial drop shock signal, this rebound is relatively small
and therefore not considered a significant contributing factor. The green line in Figure
118 represents the acceleration experienced by the PWB itself and is monitored via an
accelerometer attached directly to the board, generally directly opposite the monitored
component shown in Figure 113. As the card is secured to the fixture by posts at the four
corners of the board, it was allowed to freely flex back and forth after the initial shock
impulse. Per JESD22-B110, this back and forth flexure is representative of a subassembly
life condition and therefore a desired part of the test set up. An Analysis Tech STD-256
event detector was used to monitor the resistance threshold of the components under test
during the mechanical shock. A failure was recorded when the channel resistance
increased by 300 or more for at least 200ns. The testing was stopped as soon as an
electrical failure was detected (first failure).

Figure 117: Target pulse shock defined by JESD22-B110 service condition B

163
 Figure 118: Sample of pulse shock achieved during test

While the method outlined for this test can be used to calculate the change in velocity and
the displacement of the monitored items, in this project it was used to compare the
response of the various alloys. Specifically, the number of drops required to produce an
electrical failure was measured, while all other parameters were monitored to ensure
consistency of test conditions.

3 Reliability Results
Drop shock testing as described above was performed on five boards of each combination
described in Table 41. Each of the two halves was tested separately. It was initially
intended that all components would be monitored to failure allowing for 10 failures to be
recorded for each component type. This would provide a small sample size, but one
sufficient to produce basic Weibull plots. A number of events occurred during the testing
which reduced the number of components tested. These events are outlined below:
 Based on similar tests performed in the past, it was deemed that additional weights
were needed to increase the strain and help induce failure in the solder joints. Two
220g weights were added to the center of each board.9 After testing five cards, it
was determined the weight was not needed to induce failure. The resulting data
164
 associated with RIA3-1 portion of five boards was not used in the analysis. Testing
then continued with no additional weight added to the remaining boards.
 The process of attaching the weights described above involved drilling into the
laminate material to securely attach the additional weight. The resulting hole was
located very close to U1 on RIA3-1. It was therefore decided not to use any data
obtained from the monitoring of U1 as it could not be determined whether the
failure was due to the drilling process or the drop shock, or a combination of the
two. No drilling was performed on RIA3-2 and therefore all data from U2 was used
in this evaluation.
 The CSP components, as well as the BGA, did not fail. These components were
located towards the edge and corners of the test vehicle and would therefore not
experience the same degree of strain as those located in the centre of the test
vehicle.

Therefore, data from a total of 25 out of 30 BGAs and from all 30 QFPs was available for
evaluation. The results are given in Table 43 and in Figure 119 and Figure 120.

165
 Table 43: Drop test results
Board Material Drops to Failure
Alloy Board Number
(Tg) BGA (U205) QFP (U2)
22 --* 66
24 17 65
SAC305 26 25 63
27 16 52
28 8 72
1 16 56
2 19 42
Senju M42 3 10 60
4 9 37
High Tg 6 11 51
(170C) 15 9 38
16 --* 45
Sunrise 19 15 62
20 8 50
21 --* 56
8 7 55
10 --* 57
Sunflower 11 14 46
13 20 65
14 10 46
36 23 59
38 8 82
Sunrise 40 26 56
41 34 57
Normal Tg 42 8 76
(150C) 29 20 73
30 13 63
Sunflower 31 11 65
34 46 79
35 --* 84
* Samples removed for reasons provided on page 164

166
Figure 119: Individual value plot of drops to fail, BGA (SAC305 + alloy) (U205)

Figure 120: Individual value plot of drops to fail, QFP (U2)

167
The results of testing, albeit with a small sample size, indicate the board material was a
more significant factor in drop shock performance rather than the alloy. Normal Tg
boards outperformed High Tg boards in all cases.

The data also indicates that SAC305 outperformed the other alloys when comparing the
High Tg board materials. This is particularly significant in the QFPs, likely due to the
fact that the QFP solder joints are made up of 100% test alloy, the BGA solder joints are
made up of 13% test alloy and 87% SAC305 from the component solder ball. There is
therefore less of a difference in the overall composition of the BGA solder joints.

Among the three test alloys, it appears that Sunflower performed the best; however there
is not enough data for a conclusive determination. A larger sample size and perhaps a
more appropriate test vehicle would be able to provide a greater distinction between the
alloys.

It is important to note that the limited reliability data provides only a cursory view,
providing information only on which solder joints failed during the drop testing. For a
better understanding of what occurred, failure analysis of the solder joints was required to
form a clearer picture of the drop shock response. Both reliability and failure analysis
need to be assessed together for a complete understanding.

4 Failure Analysis and Microstructural Evaluation

Failure analysis of the drop shock test boards was performed by one of two methods:
 Dye and Pry (D&P) Testing: This method provides an overall image of the extent of
the failures across an entire component, as well as allowing for the determination of
the failure mode
 Cross Sectional Analysis: This method provides a clearer observation of the failure
mode in the solder joint; however, it limits the number of solder joints to be
examined.

168
4.1 Dye and Pry Procedure
Dye and Pry testing was performed per Celestica’s procedure DOC0018652 “Dye and
Pry Testing”10. The boards were immersed in red dye and subjected to a vacuum in order
to force the dye into any pre-existing cracks, which occurred during drop testing. The
dye was cured prior to component removal. The fracture surfaces were then inspected for
the presence of dye – a percentage of dye penetration for each solder joint was
determined, as was the mode of failure (refer to Figure 121).

Figure 121: Failure modes of solder joint as defined by IPC/JEDEC-970211

4.2 Failure Isolation Procedure

The location of failures was isolated by probing the daisy chain pattern using vias on the
bottom side of the PWB for BGAs, or between leads for QFPs. Cross sections were then
prepared at locations where electrical failures were found to have occurred.

4.3 Evaluation of High Tg Board after Drop Testing

Evaluation performed using D&P and cross sectioning showed that BGAs on high Tg
boards failed exclusively by pad cratering. Figure 122 illustrates a pad crater from a cross
sectional perspective. The solder joint remains completely intact; no cracking was seen
along the IMC or within the bulk solder is observed, furthermore there was no separation
between the IMC and the copper pad. All stress was dissipated through the laminate
material, which failed between the epoxy and the layers of glass weave within the board
material.
169
 Figure 122: BGA failure by pad cratering, Sunflower on High Tg boards

Dye and pry results allow for an overall view of the failures within a component, both the
number of failed solder joints and the extent to which the fracture penetrated through the
solder joint. It is important to note that pad cratering may not result in an electrical
failure. Partial fractures, as indicated by the various shades of yellow/orange in the D&P
mapping, allow for some electrical contact to be retained. Even complete fractures,
indicated by red, may still have intact copper traces associated with them. These types of
failures are particularly insidious because they are not readily identifiable but do present
a real reliability threat as the soft copper trace continues to be stressed. Figure 123 shows
the D&P mapping of one component with accompanying images of representative
failures in specific solder joints. The number within each cell of the map corresponds to
a failure mode described in Figure 121. Table 44 provides a summary of the failures, as
seen by D&P of all the alloys tested on High Tg board material. % Fracture corresponds
to the total area of the fracture surface, which was penetrated by dye. This indicates the
degree to which the fracture penetrated through the solder joint prior to the pry process.
The next four columns show the number of solder joints, as a percentage of the solder
joints on the component, which showed some degree of dye penetration. From this we see
that Senju M42 showed the least amount of damage. All of the components selected for
D&P failed between 8 and 10 drops and all showed complete dye penetration within
many of the solder joints on the outer edge of the component closest to the center of the

170
board. All solder joints which did not show any dye penetration resisted fracture up to
the point of first failure.

Figure 123: D&P mapping of Senju M42 on High Tg board, with images of

board side and b) component side of the fracture surface

Table 44: Failures of BGA on High Tg boards

High Tg Board
% Fractured
SAC305 Senju M42 Sunrise Sunflower
75-100% 7% 4% 7% 6%
50-75% 5% 1% 3% 4%
25-50% 7% 5% 9% 7%
5-25% 5% 1% 4% 5%
Total: 24% 11% 23% 21%

The QFPs on high Tg boards did not exhibit any pad cratering. This was likely due to the
structure of the part, as illustrated in Figure 124, which is much more compliant than a
BGA. With copper leads on all four sides, the component itself is able to efficiently
dissipate stress.12 Electrical failures were mainly associated with damaged leads, as seen
in Figure 125a, which after a number of drops failed at the “knee” where large repetitive

171
strain would have occurred. Although no complete mechanical failure through the bulk
solder was observed on QFPs, the beginning of IMC failure was observed in a number of
the solder joints. The crack would begin on the outside of the solder fillet and move to
the copper lead where it would continue to propagate along the brittle IMC layer as seen
in Figure 125b.

Figure 124: Schematic of Quad-Flat-Package (QFP)13

Figure 125: QFP failures in Sunflower on High Tg boards

a) fractured lead b) solder fillet fracture

172
4.4 Evaluation of Normal Tg Board after Drop Testing
Sunrise and Sunflower alloys were tested on Normal Tg boards, as seen in Figure 119
and Figure 120. Both alloys survived, on average, more drops to first failure than on High
Tg boards. Failure analysis also revealed differences in the failure mode and the degree
of damage occurring within the component and within each individual solder joint.
Figure 126 shows the D&P mapping of Sunrise on a Normal Tg board. While a small
amount of pad cratering was visible on one edge of the component, the dominant failure
mode was between the IMC interfaces with the bulk solder material towards the board
side of the component. Figure 127 shows this same failure mode, between the IMC and
bulk solder, as seen in a cross section of a BGA solder joint formed between SAC305
(BGA ball) and Sunflower (paste). Finally, Table 45 summarizes the degree of failure
which occurred in BGAs using these two alloys. While the amount of failure appeared
relatively similar between the two alloys, it is significantly less damage than was
observed on the High Tg boards using the same alloys.

Figure 126: D&P mapping of Sunrise on Normal Tg board, with images of

board side and b) component side of the fracture surface

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 Table 45: Failures of BGA on Normal Tg boards
Normal Tg Board
% Fractured
Sunrise Sunflower
75-100% 1% 1%
50-75% 2% 1%
25-50% 1% 0%
5-25% 4% 4%
Total: 8% 6%

Figure 127: BGA failure in Sunflower on Normal Tg boards

The QFPs, as in the case of High Tg boards, failed via lead fracture as seen in Figure
128a. No pad cratering was observed. Fracture, initiating in the solder fillet and
propagating along the IMC was observed, however no complete fracture of this type was
observed.

174
 Figure 128: QFP failures in Sunflower on Normal Tg boards

a) fractured lead b) solder fillet fracture

The solder alloy may be a factor in failures caused by fractured leads; the cracks appear
to originate in the solder material and then propagate through the lead at a point of high
mechanical strain.14 This is illustrated in Figure 129.

Figure 129: QFP failure in Sunrise on Normal Tg board

5 Summary of Findings and Conclusion

The drop testing carried out comprised a screening experiment. While the sample size
may not be statistically significant, it does show some promising results. Many of the
results relate to the board material rather than to the solder material. This is significant as
175
lower Tg board materials are a viable option for lower melting temperature solders,
SAC305 often requires higher Tg board material.
 Normal Tg boards appear to outperform High Tg boards independent of solder alloy.
 High Tg boards failed exclusively by pad cratering, which is a latent defect and
therefore not readily detectable. Pad craters present a reliability concern because
they will propagate through the laminate and eventually sever the copper trace. Pad
craters will not be detectable until the copper trace is broken leading to electrical
failure. Even if the laminate defect could be detected at manufacturing, it is not
readily repairable.
 Normal Tg boards survived longer. While the solder joints built on Normal Tg boards
exhibited mixed failure modes (sometimes failing by pad cratering and other times
by solder fracture at the IMC) there were also significantly less failed solder joints,
and they primarily failed at the IMC interface.

Additionally, there were some differences among the solder alloys used in drop shock
testing. On the High Tg board material, there is not enough data to properly distinguish
between the performances of each alloys in terms of drops to first fail, however Senju
M42 does appear to have sustained the least amount of damage. Furthermore, when
comparing Sunflower to Sunrise on both High and Normal Tg board materials, it appears
that Sunflower slightly outperforms Sunrise.

The following are recommendations for further testing based on this screening
experiment:
 The ideal test vehicle would have one component at the centre of the board, which
could be monitored to failure.
 Each solder/board material combination should include 32 repeats, of which at least
63% are tested to failure in order to provide sufficient data for reliability plots
 Using both SAC305 and SnPb as a baseline for comparison would provide a better
understanding of how low-melt, Bi-containing alloys perform against current
industry standards.

176
6 References

1
D.A. Shnawah, M.Sabri, I.A. Badruddin “A review on thermal cycling and drop impact
reliability of SAC solder joint in portable electronic products”, Microelectronics
Reliability, 52 (2012) pp. 90-99
2
P. Ranjit and T. Lawlor., “Effects of Silver in common lead-free alloys”
3
T. A. Woodrow and J. Bath “Lead-Free Reliability in Aerospace/Military
Environments” in Lead-Free Solder Process Development, New York, Wiley,
2011
4
G. Henshall, R. Healey, R. Pandher, K. Sweatman, K. Howell, R. Coyle, T. Sack, P. Snugovsky, S.
Tisdale, F. Hua. “iNEMI Pb-Free Alloy Alternatives Project Report: State of the Industry,”
proceedings SMTAI, p. 109 (2008).
5
B.Gray “Correlation of Printed Circuit Board Properties to Pad-Crate Defects Under
Monotonic Spherical Bend”, M.A.Sc. thesis, Dept. Mech. Eng., Ryerson
University, Toronto, Ontario. 2012.
6
PCB Layout Recommendations for BGA Packages, Lattice Semiconductor Corp. Oct.
2005
7
Subassembly Mechanical Shock, JESD22-B110A, November 2004.
8
D.S. Steinberg “Designing Electronics for Shock Environment”, in Vibration Analysis
for Electronic Equipment, 3rd ed. New York, Wiley, 2000. ch. 11, pp.248-298
9
W.Liu, N-C, Lee, S. Bagheri, p. Snugovsky, R.Brush, J.Bragg, B.Harper. “Drop Test
Performance of BGA Assembly using SAC105Ti Solder Spheres” in IPC APEX
EXPO Proceedings, 2011
10
Dye and Pry Testing, Celestica DOC0018652, 2014.
11
Monotonic Bend Characterization of Board-Level Interconnects, IPC/JEDEC-9702,
June 2004.
12
P. Snugovsky, J. Bragg, E. Kosiba, M. Thomson, B. Lee, R. Brush, S. Subramaniam,
M. Romansky, A. Ganster, W. Russell, J. P. Tucker, C.A. Handwerker, D.D.
Fritz. “Drop Test Performance of A Medium Complexity Lead-Free Board After
Assembly and Rework” in the IPC APEX EXPO Conference Proceedings, 2010.
13
http://www.practicalcomponents.com/Dummy-Components/
14
J. Juarez Jr., M. Robinson, J. Heebink, P. Snugovsky, E. Kosiba, J. Kennedy, Z.
Bagheri, S. Suthakaran, M. Romansky “Reliability Screening of Lower Melting
Point Pb-Free Alloys Containing Bi,” in IPC APEX EXPO Conference, Las
Vegas, NV, 2014.

177
 Chapter 6
Summary of Findings and Conclusions
This work explored the reliability performance and microstructural differences of three
low melting temperature, low-Ag, Bi-containing alloys compared with SAC305. From
the current work, the following conclusions can be made:
 The three low melting temperature, low-Ag, Bi-containing alloys under investigation
all produced good solder joints with QFP type components. BGA components with
SAC305 solder balls also formed good solder joints when built with these pastes;
all examined solder joints had an acceptable degree mixing. Differences in
microstructure have been observed related to the addition of Bi, decrease in Ag-
content, and varying amounts of Cu dissolution resulting from different process
temperatures.
 Solder joints with final Bi concentrations of less the ~3wt% showed no detectable Bi
precipitates. This includes QFP solder joints formed with Senju M42 and all BGA
solder joints formed with a combination of paste and SAC305 solder balls. In these
cases, all the Bi was present within the Sn phase upon solidification.

 Bi was observed to precipitate out of solid solution from “as assembled” solder joints
with Bi compositions of greater than 7wt%. This is the case with QFP solder joints
formed using Sunrise and Sunflower solder pastes. Bi also remains present in the
Sn phase, observed through EDX analysis. It is therefore likely that the Bi
precipitates are formed from the binary, ternary or double binary eutectic regions
within the interdendritic spaces of the Sn phase where the concentration of Bi in
Sn is highest. Both fine and medium sized particles were observed. In
Sunflower, the concentration of Bi within the Sn dendrites and within the Sn
portion of the binary eutectic (Sn + Cu6Sn5) within the interdendritic spaces
appeared to be approximately equal.
 Bi concentrations greater then 7wt% had a beneficial impact on the changes to bulk
microstructure, which occurred during accelerated thermal cycling. The Bi
precipitated from the bulk solder evenly in very small particles. This favorable
178
 influence did not appear when the Bi concentration was 3wt%. There was some
degree of Bi segregate along the grain boundary observed in the Sunflower alloy;
however there did not appear to be full segregation of the phases.
 After exposure to thermal shock, Bi particles were observed along the grain
boundaries in solder joints formed with alloys containing 7wt% Bi. Additionally,
very fine precipitates appear to have formed during the course of thermal shock.

 Cu6Sn5 () interfacial IMC layers that form between the studied solders and the Cu
pad of the board or the lead material of the QFP solder joint during solidification
were not statistically distinguishable in terms of thickness. No other species was
detected at the solder/Cu interface.
 In the BGA solder joint, the interfacial IMC layer that formed between the combined
solder paste/SAC305 solder ball and the Cu pad of the board was found to be
(Cu,Ni)6Sn5. The Ni is contributed to this system from the component side IMC and
diffuses through the bulk solder prior to solidification. Using a 93% CI, SAC305
appeared to have a thicker IMC layer upon solidification. This can be attributed to
the higher process temperature. The interfacial IMC layer that formed between the
Cu/Ni/(paste/SAC305 solder ball) was found to be (Cu,Ni)6Sn5 and Ni23Cu33Sn44.
Due to the irregular shape of this IMC layer, it was difficult to compare the mean
thicknesses of the IMC layer that formed when using different solder paste alloys.
 During thermal cycling, the total thickness of the interfacial IMC continued to
increase, and a () Cu3Sn layer formed. While the overall thickness increased
similarly for all four alloys, the Cu3Sn layer of the Sunflower alloy was much
thicker than the other alloys. This alloy has no Ag, which indicates that Ag plays a
role in suppressing Cu3Sn growth. Bi concentration did not appear to significantly
change the growth rates of either intermetallic compound. The increased growth of
the Cu3Sn phase in the Sunflower alloy did not correspond to any decrease in
reliability during ATC.

179
 SAC305, which was processed at a higher temperature, initially had a slightly thicker
interfacial IMC layer. During thermal cycling, the IMC layers formed in solder
joints using the various alloys increased to similar overall thicknesses.
 The three lower process temperature solders performed as well as, or better than
SAC305 during accelerate thermal cycling. During two different thermal cycling
regimes (0 to 100C and -55 to 125C) the only failures which could be attributed
to solder joint fatigue failures occurred in SAC305 during 0 to 100C cycling and
one sample of Sunrise, which failed towards the end of the test. All other electrical
failures were attributed to failures within the board material. High Tg board material
appeared to outperform Normal Tg board material during ATC.

 High Temperature, High Humidity conditions (85C, 85%RH) produced an

insufficient number of whiskers and no whiskers which would fail the requirements
of JEDEC Standard No. 201A for class 2 components. This test was run for 1000
hours, while current required length of test is 3000 hours. It would therefore be
worthwhile to continue testing.
 1610 cycles of Thermal Shock testing is sufficient to meet the requirements for
whisker testing. In this case, all four alloys passed the requirements set out in
JEDEC Standard No. 201A for class 2 components.
 The whiskers which formed on the surface of the three Bi containing alloys during
thermal shock all differed from those seen on SAC305. All alloys showed a small
amount of hillock growth, the Bi containing alloys also showed a significant
amount of small whisker nucleation sites. This may prove beneficial as many short
whiskers may effectively reduce the stress in the system and decrease the likelihood
of one whisker continuing to grow to a catastrophic length.
 The final composition of the solder, formed between the solder paste and the
dissolving Sn finish, is not uniform along the entire length of the lead on a QFP
component. In areas which have the greatest risk of whisker growth, those along
the upper lead where the solder is thin, also have the lowest overall concentration of
Bi.

180
  Normal Tg boards appear to outperform High Tg boards in drop testing, independent
of solder alloy. This is significant as lower Tg board materials are a viable option
for lower melting temperature solders where as SAC305 often requires higher Tg
board material. The manner in which boards fail varies according to board Tg: High
Tg boards failed exclusively by pad cratering, Normal Tg boards, which survived
longer, than High Tg boards, exhibited mixed failure mode of pad cratering and/or
brittle fracture at the IMC.
 While there was not enough data to distinguish the different solder paste alloys based
on number of drops to failure, there was some interesting information gleaned
during failure analysis regarding the degree or number of solder joints which failed
per component. When analysing High Tg boards, Senju M42 appears to have
sustained the least amount of damage. The other three alloys were not
distinguishable. Furthermore, when comparing Sunflower to Sunrise on both High
and Normal Tg board materials, it appears that Sunflower slightly outperforms
Sunrise. Significantly fewer solder joints per component failed when using Normal
Tg boards.

Based on comparisons to the mainstream consumer alloy –SAC305, which has a

minimum reflow temperature of 223C and a Ag concentration of 3wt%, the new, low
melting temperature, low-Ag, Bi-containing alloys may be recommended as viable
replacements.

181
 Chapter 7
Future Work
The work in this thesis, as well as that in the proposed future work, is a continuation of
the research collaboration between Celestica Inc and U of T into the development of a
reliable solder alloys, that will conform with the requirements of their respective end use
environments while meeting the environmental lead (Pb)-free constraints imposed on the
commercial supply base.

1 Celestica/Indium Sponsored Whisker Resistant

Solder Paste
It has been shown that component and assembly cleanliness affect the propensity of a
solder joint to grow whiskers, particularly in high humidity environments. It was found
that contamination impacted the degree to which corrosion formed at the surface, and
consequently the extent of internal compressive stresses applied at the surface of the
solder, which is a required element in whisker nucleation and growth.1 In the production
process, a major source of contamination is the flux residue, which may remain on the
product after the build. The role of flux is to provide an oxide-free surface for the solder
to bond with a base metal, usually copper. It is intended that the flux should be fully
consumed, or burned off, by the end of the reflow process. In practice however, it is
possible that some residue remains after production. This flux residue now behaves as a
contaminate. Various flux types have been formulated to reduce the corrosive impact of
the flux residue depending on the end use of the electronic product.

In addition to RoHS legislation, the electronics industry is undertaking further

environmental initiatives, including the reduction of halogens from electronic products.2,3
This initiative restricts the use of chlorides and bromides throughout the electronic supply
chain including the solder paste flux formulations. Halides have been used in fluxes in
order to rapidly reduce the metal oxide and allow for the formation of a robust solder
joint. Any remaining halide may, however, behave as a corroding agent if not fully

182
utilized in the reflow process. In a “halogen-free” solder paste, it is still unclear whether
the alternative agents will be more, or less corrosive.

In developing solder pastes for low melt applications with three to four elements (Sn, Cu,
Bi and sometimes Ag), Indium and Celestica are working to optimize the solder flux as
well as the alloy. It is therefore important to identify the corrosion mechanism(s) which
may affect the various elements and compounds within a particular solder. For example,
it is hoped that this work will determine whether the dominant form of corrosion is
intergranular, galvanic or some other form.

23 flux/paste combinations will be tested according to the matrix outlined in Table 46

with the goal of better understanding the interaction of the flux/paste combination.

Table 46: Solder paste test matrix

Alloy
Flux SAC305 Violet Sunflower
Sn 3%Ag 0.5%Cu Sn 2.25%Ag 0.5%Cu 6%Bi Sn 0.7%Cu 7%Bi
Base BaA1 BaA2 BaA3
Resistively 1 R1A1 R1A2 R1A3
Resistively 2 R2A1
MPU 1 M1A1 M1A2 M1A3
MPU 2 M2A1
Corrosion 1 C1A1 C1A2 C1A3
Corrosion 2 C2A1
pH (1) P1A1
pH (2) P2A1 P2A2 P2A3
pH (3) P3A1 P3A2 P3A3
pH (4) P4A1

183
2 ReMap M1: Lower Temperature Soldering Alloys
with Improved Mechanical and Thermal Fatigue
Reliability
The ReMap M1 project has two main goals: to develop a test protocol for testing alloys in
a combined thermal mechanical reliability test, and to evaluate Bi containing alloys
according to this protocol.

Currently, reliability tests exist for thermally induced stress (i.e. thermal cycling) and for
mechanical stress (e.g. vibration testing, drop testing) separately. There is currently no
existing industry standard test protocol for examining the interaction of these stress types.
Electronic assemblies, particularly those intended for high reliability applications, are
often exposed to a various stresses and often at the same time. It is believed that the
material behavior resulting from thermal stress will impact the material response to
mechanical stress. The mechanical behavior at various temperatures is therefore thought
to be significantly different. Also, the behavior of the material as it cycles through
different thermal regimes may also affect the response to mechanical stresses.

It is believed that the inclusion of Bi in these alloys will result in material strengthening
by one or more of the following mechanisms: solid-solution strengthening or
precipitation hardening. The mechanism will likely dependent on the amount of Bi
present in the alloy.4

The aim of this project is to correlate reliability data with the metallurgical findings in
order to better understand the behavior of various alloys under combined stress
conditions.

3 ReMap M2: Alloys, Board and Component Surface

Finish Interactions with Reduced Propensity for
Whisker Growth
The current work presented a preliminary assessment of the whisker mitigation properties
of a number of Bi containing alloys. This will be further developed in the ReMap M2
184
project, in which a number of Bi containing alloys will be tested (Table 47), and assessed
according to statistically accepted guidelines, in a variety of conditions, for whisker
growth characteristics. These findings will also be compared to the microstructural
properties of the alloys, as they have evolved in the listed conditions.

In previous work, it has been shown that internal stresses are created from a variety of
sources. High Temperature High Humidity (HTHH) and Ambient Temperature High
Humidity (ATHH) where selected to evaluate how internal, compressive stresses are
created at the surface of a solder joint by oxidation. This has been shown to affect Cu
leaded solder joints more than Alloy 42. ATHH with contamination is an extension of
the evaluation by oxidation, which is further enhanced by an ion-contaminated
environment. Thermal cycling, at two different levels, will also be evaluated in order to
study the affects of internal compressive stresses created from a mismatch of CTE
amongst the various materials within a solder joint. It has been shown that Alloy 42 is
affected more than Cu based lead frame alloys due to the larger difference in
CTE.5,6,7,8,9,10

It is believed that Bi mitigates the nucleation and growth of whiskers in a variety of ways.
Even a small amount of Bi has been shown to lead to a more equiaxed grain structure.
This is thought to elevate some of the internal compressive stresses on specific, columnar
grain boundaries, which have been observed in plating material. Bi also acts as a grain
refiner, by providing more grain boundaries, there is the possibility to annihilate
dislocations and therefore absorb stress internally. Finally, with the lower process
temperatures of Bi containing alloys, the scallop shaped interfacial IMC layer is likely to
be suppressed. Due to its irregular shape, this IMC layer is a major contributor to the
internal compressive stress of a thin film or a thin layer of solder.11,12

185
 Table 47: ReMap M2 test matrix
Test Condition
ATHH Thermal Thermal
Surface
Alloy HTHH ATHH (25C/85% RH) Cycling Cycling
Finish
(85C/85% RH)(25C/85% RH) + (-55C to (-20C to
contamination 80C) 100C)

SAC305 3x 3x 3x 3x 3x
Senju M42 3x 3x 3x 3x 3x
ENIG
Sunflower 3x 3x 3x 3x 3x
Violet 3x 3x 3x 3x 3x
SAC305 3x 3x 3x 3x 3x
Senju M42 3x 3x 3x 3x 3x
OSP
Sunflower 3x 3x 3x 3x 3x
Violet 3x 3x 3x 3x 3x

4 ReMap M3: Aging Effect of New Lead-Free

Materials on Reliability
The current work has focused on understanding the properties of Bi containing alloys in
the short term, with respect to time from manufacture. In reality, all of the testing took
place over 4 years and started approximately one year after the initial build, during which
time all samples were stored at ambient conditions. The effects of aging in this study are
therefore not well understood.

It has been shown in a number of studies that both SnPb alloys and SAC based alloys
exhibit significant deterioration of mechanical properties upon aging. This has been
found to occur at both room temperature and elevated storage conditions, with SAC
based solders exhibiting a deterioration of mechanical properties in the order of 25 times
greater than that experienced by SnPb.13 It is believed that the microstructural coarsening
is the main mechanism responsible for the reduction in mechanical properties; coarsening
186
occurs on both SnPb and SAC based alloys (Figure 50,Figure 51)14. In previous work, it
appears that Bi containing alloys may actually improve the mechanical properties by
reducing the amount of microstructural coarsening and through either solution hardening
(in the case of low concentrations of Bi) or precipitation hardening (in the case of higher
Bi content).15 Figure 130 illustrates the microstructural change that occurred in Orchid
(Sn2%Ag7%Bi) after 3000 cycles of harsh environment ATC (-55C to 125C).
Significant growth of the Sn dendrites was not observed, and while the other IMC
particles did appear to coalesce to some degree, the main observed change is that the Bi
precipitated out of the Sn, likely from the interdendritic eutectic first, and remained as
small, evenly spaced precipitates.

Figure 130: Orchid at a) Time 0 and b) after 3000 cycles ATC

Lower melting point alloys, specifically those containing Bi, may also improve the
mechanical properties of a solder joint by suppressing the growth of the interfacial IMC
layer. The increased reflow temperatures associated with SAC alloys, as well as the
continuous growth of the interfacial IMC over time, has been identified as a major
contributing factor to the reduced reliability of these alloys.16

While these initial findings are promising, more study is required. Potential pitfalls of Bi
precipitation also exist. If the Bi begins to coalesce into larger particles, it will no longer
present the benefits associated with a small evenly spaced particles. Also, there is a
danger that the Bi will preferentially locate along grain boundaries or along the interfacial
IMCs, similar to the known issue with SnPb solders discussed in Section 3.
187
During the course of this study, unexpected behavior was observed. Approximately two
years after the High Temperature High Humidity exposure described in Section 2.2,
samples, which had been stored at ambient conditions, where re-examined for further
whisker growth. While a small amount of whisker nucleation was observed on the sides
of the leads, a more interesting observation was that the Bi appeared to be precipitating
out of the solder (Figure 131).

Figure 131: Sunrise solder joint after 1000 hrs HTHH followed by 2 years ambient storage

Through the ReMap M3 project, the team will investigate the evolution of three Bi
containing alloys through a number of different aging conditions (Table 48). The
microstructure and hardness of each alloy, exposed to each different test condition will be
evaluated. The samples will then be down selected for reliability study. A subset of
alloys and aging conditions will be tested in both ATC and vibration conditions, and
possibly a combined environment as described in Section 2.

188
 Table 48: ReMap M3 test matrix
Aging Conditions
Surface
Alloy 25 hours 300 hours
Finish
25C ~60-70C 125C 25C ~60-70C 125C
SnPb 3x 3x 3x 3x 3x 3x
SAC305 3x 3x 3x 3x 3x 3x
ENIG Sunflower 3x 3x 3x 3x 3x 3x
Senju M42 3x 3x 3x 3x 3x 3x
Orchid 3x 3x 3x 3x 3x 3x
SnPb 3x 3x 3x 3x 3x 3x
SAC305 3x 3x 3x 3x 3x 3x
OSP Sunflower 3x 3x 3x 3x 3x 3x
Senju M42 3x 3x 3x 3x 3x 3x
Orchid 3x 3x 3x 3x 3x 3x

189
5 References

1
P.Snugovsky, S. Meschter, Z. Bagheri, E.Kosiba, M.Romansky, J. Kennedy “Whisker
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2
Directive 2002/95/EC of the European Parliament and of the Council of 27 January
2003 on the restriction of the use of certain hazardous substances in electrical and
electronic equipment
3
R. Flinders “Halogen-Free Electronics: An Overview” presented at IEEE PSES Orange
County Chapter Meeting Irvine, CA August 26, 2008
4
P.Snugovsky “ReMap M1 Project Proposal: Lower Temperature Soldering Alloys with
Improved Mechanical and Thermal Fatigue Reliability” April 2014.
5
P.Snugovsky, Z. Bagheri, M. Romansky “Whisker Growth on SAC Solder Joints:
Microstructure Analysis” in ICSR SMTA Conference, Toronto, ON, 2008.
6
S.J. Meschter, P. Snugovsky, J. Kennedy, Z. Bagheri, and E.Kosiba “Strategic
Environmental Research and Development Program (SERDP) Tin Whisker
Testing and Modeling: Thermal Cycling Testing” presented at International
Conference on Solder Reliability, Toronto, Ontario, Canada, 2014.
7
P.Snugovsky, S. Meschter, Z. Bagheri, E. Kosiba, M. Romansky, J. Kennedy “Whisker
Formation on SAC305 Assemblies” in TMS Conference, San Diego CA, 2014
8
S.J. Meschter, P. Snugovsky, J. Kennedy, Z. Bagheri, and E. Kosiba “SERDP Tin
Whisker Testing: Low Stress Conditions” presented at International Conference
on Solder Reliability, Toronto, Ontario, Canada, 2012.
9
P.Snugovsky, E. Kosiba, S. Meschter, Z. Bagheri, J. Kennedy “Assembly Cleanliness
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CA, 2015.
10
S.Meschter, P. Snugovsky, J. Kennedy, S. McKeown and E. Kosiba “Tin Whisker
Testing and Risk Modeling Project” SMTA Journal Volume 24, Issue 3 (2011)
11
N. Jadhav, M. Williams, F. Pei, G. Stafford, E. Chason “Altering the Mechanical
Properties of Sn Films by Alloying with Bi: Mimicking the Effect of Pb to
Suppress Whiskers” ” in Journal of Electronic Materials, Vol. 42, No. 2, 2013.
12
J-L Jo “Tin Whisker Growth Mechanism and Mitigation for Lead-Free Electronics”
Ph.D. Thesis, Dept. of Adaptive Machine System, Osaka University, Japan. 2013.
13
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Temperature Aging on Reliability of Lead Free Solder Joints”, in ECTC
Conference, Sparks, NV, 2007

190
14
J. Juarez Jr., M. Robinson, J. Heebink, P. Snugovsky, E. Kosiba, J. Kennedy, Z.
Bagheri, S. Suthakaran, M. Romansky “Reliability Screening of Lower Melting
Point Pb-Free Alloys Containing Bi,” in IPC APEX EXPO Conference, Las
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P.Snugovsky. “ReMap M3 Project Proposal: Aging Effects of New Lead-Free
Materials on Overall Reliability” April 2014.
16
Z. Hai, J.Zhang, C. Shen, J.L.Evans, M.J.Bozack ”Long-Term Aging Effects on
Reliability Performance of Lead-Free Solder Joints”, presented at SMTAI,
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191