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ORGANIC SOLDERABILITY PRESERVATIVES:

BENZOTRIAZOLES AND SUBSTITUTED BENZIMIDAZOLES

Joseph D. DeBiase
Enthone-OMI Inc.
New Haven, CT

INTRODUCTION HASL has limited success in processing PCMCIA cards


The acceptance and use of Organic Solderability and thin PCBS. It is not uncommon for HASL to produce
Preservatives (OSPS) as replacements for Hot Air Solder boards with inconsistent solder coating thicknesses, thus
Leveling (HASL) continues to grow. OSPS selectively causing “crowned” SMT attachment areas and reduced
protect and maintain the solderability of a PCB’S copper clearance of through-holes. These deficiencies result in
features (i.e. NUT pads, through-holes) by providing subsequent rework and rejects at assembly and reduce first-
thermal protection against degradation during assembly. pass assembly yields. Conversely, OSPS are known to
Historically one class of OSP, the benzotriazole inhibitors, consistently produce thin coatings. Other problems
has been successfully used by a number of major OEMS in associated with the HASL process include: intermetallic
select assembly applications requiring a single heat compounds formation (Cu/Sn) and the potential for poor
excursion. During the past five years a new upgraded class solderabilty; warpage due to changes in temperature; and
of OSP, the substituted benzimidazole, has proven to yield thermal shock which jeopardizes PCB integrity while
additional benefits to PCB fabricators while addressing a escalating the potential for increased ionic contamination
diversity of processing challenges encountered by PCB levels.
assemblers and OEMS.
This article will examine the considerations required in
Environmental and economic factors, as well as selecting benzotriazole and substituted-benzimidazole
advancements in PCB technology are the three major OSPS for implementation in PCB manufacturing.
drivers which have ignited the change from HASL to
OSPS. Environmental concerns include the desire to OSPS IN PCB FABRICATION
eliminate hazardous materials (e.g. lead) from the By implementing OSP technology the PCB fabricator
fabrication production environment, as well as the need to replaces a hazardous, difficult to control process (HASL)
address potential legislation restricting the use of lead on with a lead-free, easy to control, aqueous process. Figures 1
the local, state, and national levels. Since OSPS are and 2 outline typical benzotriazole and substituted
aqueous-based and do not produce hazardous waste, benzimidazole process cycles.
environmental compliance is made easier.
The front end of each process, referred to as the “pre-clean
Economically, the OSP process is substantially less cycle”, is quite similar. During this cycle the PCB is first
expensive than HASL, which is a labor intensive and a immersed in a cleaner (typically an acid cleaner) to remove
high maintenance process. When one considers that the any finger oils or other contaminants. Some copper oxide
HASL process produces solder dross (considered a removal also occurs. During the microetching step the
hazardous material), the disposal of the dross is both an copper oxide is fully removed and a total of 20-40
economic and environmental burden that the PCB microinches of copper is etched away. The resultant copper
fabricator would welcome the opportunity to eliminate. topography has an increased surface area due to the
When one compares actual processing cost, reworkhepair microroughened surface. This surface results in an
cost, and the cost of rejects, current users of substituted increased number of attachmenthonding sites for the OSP.
benzimidazole-based OSPS have experienced a total cost Additionally, the associated high sutiace energy of the
savings of 25 to 50°/0 versus HASL. For benzotriazole- copper will result in a high solderability level. The result of
based coatings the savings are even more impressive. poor or insufficient microetching is a non-uniform, less
than ideal coating appearance. This may also negatively
Finally, technology advancements evidenced by the advent allect solderability during wave soldering. The acid rinse
of new and complex packaging designs such as fine-pitch, step is used to neutralize any microetchant salts not fully
ball grid arrays (BGAs), chip scale, and flip chip have rinsed off, as well as a sacrificial bath to inhibit any
necessitated flat, planar surfaces. Another processing contaminants from entering the OSP solution. A 5-10°/0
concern is the trend towards thinner pCBS. sulfhric acid (H2S04)solution is typically employed for this
operation.

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-. —.
After the copper is properly prepared, OSP application can should suflice since the copper PCB surface topography
occur. The benzotriazole coating is deposited by immersing originally created will remain intact over time.
the PCB in a 1.0 to 2.5% concentration solution for 60~30
seconds. The solution temperatures can range from room The recommended procedures for packaging OSP-coated
temperature to 49”C. A heated solution will aid in drying PCBS for shipping to the assembler are quite similar to
the PCB. The most critical coating control parameter is those for HASL. The PCBS should be stacked 10 to 25
maintaining the solution pH above 3.0. The resultant high, depending on size, without individual slip sheets
deposit is a monolayer approximately 50 to 150 Angstroms between each PCB. An outer slip sheet, made from sulfbr-
thick. A thicker deposit is not possible. See Figure 3 for a free materials, should be placed on the top and bottom
benzotriazole bonding mechanism onto copper. PCBS in the stack. A “shrink wrap” should be applied to
tightly seal the PCB stack. The PCB stacks should be
The substituted benzimidazole coating is deposited by placed in a box which includes desiccant. During the
immersing the PCB in a 100 ~ 10°/0concentration solution packaging step operators should wear impermeable gloves
for 45 to 90 seconds. The solution temperature is set at in order to eliminate the possibility of ionic contamination
-43°C and the pH at -2.7. The resulting coating thickness and coating degradation (especially for benzotriazole -
is 0.35 ~ 0.15 microns (3500 ~ 1500 ‘A’). The protective coated PCBS).
layer is formed initially through a completing reaction
with copper to form an organometallic bond, followed by a RELIABILITY OF THE OSP COATINGS
build-up of the benzimidazole to the requisite final The reliability of OSP coatings can be defined by how
thickness. The deposition process is controlled via the durable they are prior to assembly (i.e. shelf life, handling,
coating thickness. The solution temperature and dwell time robustness, etc.) and by their long term electrical insulative
are kept constant during operation. The solution properties.
concentration and pH/total acidity will change over time,
and thus are monitored and replenished accordingly. See Durability
Figure 4 for a substituted benzimidazole bonding Historically one of the main concerns with the use of OSPS
mechanism onto copper. has been their limited shelf life and low tolerance to being
handled. The benzotriazole coating is a thin, monolayer
The $inal step in the OSP application process is PCB deposit that is quite fragile. This coating is susceptible to
drying. Drying should be performed in an in-line dryer and high humidity conditions and the best case storage/shelf
should be of sufficient temperature (60-80”C), air reflow life is typically 3 to 6 months. Finger prints or other
and duration to ensure that all PCB holes and vias are free similar handling soils will adversely affixt the
of water. This step is critical for achieving maximum shelf benzotriazole coatings. Furthermore, the coating’s
life and solderability of the OSP-coated PCBS. protective properties are severely diminished when exposed
to temperatures exceeding 100”C. After one soldering heat
These OSP coating processes can be pefiormed either in a excursion (e.g. SMT reflow) this coating rapidly degrades
vertical dip line or in an automated horizontal line. For and severe oxidation of the emaining copper stiaces
maximum consistency and throughput, especially of small follows, thus rendering assembly of the PCB’S second side
PCBS or PCBS containing small holes @ 0.015”), a improbable.
horizontal process is recommended. Horizontal processing
equipment for both types of OSPS is quite similar. The only Over 20 years of industry production experience has well
major difference is that benzotriazoles can be applied via documented the limitations of the benzotriazole coatings.
spraytechnology, whereas substituted benzimidazoles, due Despite these limitations, numerous OEMs/assemblers
to their long molecular structures, can not. Benzimidazoles have successfully used these coatings as HASL alternatives
are successfully being deposited in production via a by optimizing their assembly processes to compensate for
horizontal flood immersion module being used in the OSP these shortcomings. These coatings have been most widely
coating step. See Figure 5 for an example of a typical used in the computer and telecommunications sectors in
horizontal immersion processing line. conjunction with single soldering assembly processes,
highly active soldering materials and/or inerted soldering
Unlike HASL, and other metallic PCB surface finishes, processes.
OSP-coated PCBS are reworkable by simply re-processing
them through the original application process. If necessa~, Through six years of worldwide production experience the
rework of the OSP coatings can occur several times substituted benzimidazoles have been demonstrated to be
without concern for the integrity of the PCB. The only substantially more robust than previous OSPS. Accelerated
critical parameter to monitor is the total amount of copper aging, along with actual production experience, has found
removed during the microetch steps. Once a total of 60 to that these coatings maintain solderability for a minimum of
80# inches has been removed it is best to skip the twelve months, at typical assembly shop conditions (e.g. s
microetch step if subsequent reworks are required. This 35°C, < 80°A R.H.). 1 Companies that have pefiormed

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accelerating type tests have learned not to use steam aging, subjected to 96 hours at 35”C, 85-90’XOR.H. and a 45-50
but rather more moderate conditions. VDC bias. Insulation resistance measurements were taken
every 24 hours at a 100 VDC test voltage. After 96 hours
For many years, steam aging has been used to artificially the final insulation resistance was >3 x 1012ohms (Pass=
accelerate the storageishelf life conditions of solder coated 1.2 x 10” ohms). See Table 2 for actual readings.
PCBS. The steam conditions (90-96”C) were ideal for
inducing the growth of the non-solderable Cu-Sn The same test was petiorrned but after the test coupons
intermetallic compounds (IMCS) found on PCBS coated were coated they were subjected to one SMT reflow in an
with solder. In a relatively short time (8 -24 hours) a shelf Ill/convection oven in an air atmosphere. The final
ltie period of more than one year could be simulated. insulation resistance for the “soldered” coupons was >7 x
Companies looking to use this method on OSPS have found 1012ohms (Pass = 1.2 x 1011ohms). 5
that it is not suitable. Since IMCS are not present in a OSP
coated PCB, the steam aging only serves to degrade the . Modljied Bellcore TR-NWT-000078 Surface
organic coating and oxidize the copper. Therefore other Insul&”on Resistance
means of accelerated testing are necessitated. Testing has IPC-B-25 comb patterns with 12.5 roils lines/spaces were
been reported with 35”C, 95’XO R.H. for 96 days, 65”C, 95’%0 coated with a substituted benzimidazole coating and were
R.H. for 24 hours and 40”C, 90% R.H. for 1000 hours. 2’3 subjected to various reflowlwave soldering conditions prior
These conditions all simulated 12 to 24 months of storage to electrical testing. The SIR test conditions were 35”C, 85-
life. 90’XO R.H. 45-50 VDC bias for 28 days. Insulation
resistance measurements were taken at 100 VDC test
Although metallic PCB surface finishes tend to be more voltage every two days. The minimum acceptable
robust to handling then OSPS, the substituted insulation resistance is 2 x 1010ohms.
benzimidazole coatings are significantly more tolerant than
the benzotriazoles. Production experience at numerous Condition 1 : Coating subjected to one SMT reflow.
contract assemblers in the U.S. has shown that these Final I.R. was> 3 x 1012ohms.
coatings can withstand the routine handling that PCBS are
subjected to during assembly without the need for gloves. Condition 2: Coating subjected to five SMT reflows.
Of course proper handling of PCBS by their edges should Final I.R. was> 4 x 1012ohms.
always be stressed, regardless of PCB surface finish, in
order to minimize the potential for ionic contamination. Condition 3: Coating subjected to one WIT reflow
This is most important for PCBS to be used in no-clean plus wave soldered with a low solids,
assembly processes. no-clean flux
Final I.R. was> 3 x 10” ohms.
Long Term Electrical Reliability
To date, numerous reliability tests have been performed to Condition 4: Coating subjected to five SMT reflows
characterize the effect of the presence of the substituted plus wave soldered with slow solids, no-
benzimidazole coating on the long term electrical clean flux.
properties of the PCB. These tests were performed to Final I.R. was> 3 x 1011ohms.
determine the reliability of the coating “as deposited” as
well as after one or more heat excursions (soldering See Table 3 for actual readings.
operations). Following is a summary of some of these tests:
Through the use of numerous SMT reflows it was proven
. JIS Z-3197 Surface Insul&”on Resistance that the coating is highly inert even after expsure to
JIS Z-3197 Type 2, interlocking comb patterns with 12.5 elevated temperature excursions. The introduction of the
mil lines/spaces and a 0.62” overlap length of the fingers low solids flux demonstrated the suitability of the no-clean
were coated with a substituted benzimidazole coating and system, which incorporates the use of the substituted
subjected to 1000 hours at 40”C, 90°/0 R.H. Insulation benzimidazole coating in a no-clean, mixed technology
resistance measurements were taken at 100 VDC test assembly.
voltage every 200 hours. After 1000 hours the final
insulation resistance was 2 x 1013ohms. See Table 1 for Furthermore, Condition 4 simulates the worst case scenario
actual readings.4 of having exposedhon-wetted copper present with tin-lead
along with no-clean flux residues, which could occur when
. Bellcore TR-NWT-000078 Surface Insulation fhll wetting is not achieved during wave soldering. The test
Resistance results prove this to be an inert system and probably most
IPC-B-25 comb patterns with 25 mil lines/50 mil spaces dependent on the activity of the no-clean flux used.
were coated with a substituted benzimidazole coating and

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— ———. ———. —.—-


● Bellcore TR-NWT-000078 Electromigration No failures were attributed to solder mask degradation.
Resistance The failure analysis did suggest that the presence of the
IPC-B-25 comb patterns with 25 rnil lines/50 mil spaces solder mask was responsible for entrapping some
were coated with a substituted benzimidazole coating. Half constituents from the HASL flux during the high
of the coupons were subjected to one SMT reflow. All of temperature coating operation. As the solder mask softened
the samples were stabilized at 85°C, 85V0 R.H. for 96 at the elevated temperature, cycling and bias of the test,
hours. Initial insulation resistance measurements were these potentially ionic materials were released.
made using 100 VDC test voltage. The coupons were then
subjeeted to 500 hours at the 85°C, 85 R.H. and 10 VDC Although the benzotriazole coatings have been used for
bias conditions. The final results showed no decrease in the many years, the volume of published reliability data is not
insulation resistance as a result of the applied bias. substantial. Most large users have determined the coating
Additionally, at 10X magnification there was no evidence to be reliable via similar tests to the ones deseribed above,
of electromigration or dendritic growth. G but have never released the results into the public domain.
See Table 2 for the results of one Bellcore SIR test.
Q!!!PQ! Initial LR Final LR
Control 6.4 x 108Q 3.6 X 108Q OSPS IN PCB ASSEMBLY
As Coated 3.8 X 108f2 1.2 X109Q The SMT Process
Reflowed 7.2 X 108Q 1.1 X109Q The major benefit of OSPS to the assembler is the flat PCB
soldering pads. Unlike HASL-coated PCBS there is no
. Mod&iedBellcore TR-NW-000078 solder bump on these pads to interfere in solder paste
Electromigr&”on Resistance deposition and component placement. The flat surface
IPC-B-25 comb patterns A, B and C were coated with a allows the assembler maximum control in depositing an
substituted benzimidazole coating and subjected 85°C, 85°/0 accurate, consistent volume of solder paste. This results in
R.H. for 1000 hours at three different applied voltages. a higher transfer efllciency of the solder paste especially
Each group of coupons had their own uncoated copper for stencils with small apertures (i.e. FPT, UFPT, BGA,
control comb patterns. micro-BGA, flip chip). This “cleaner” solder paste deposit
AEll!N significantly reduces the incidence of lateral smear of the
Test Board Combs Voltaze Bias solder paste on the underside of the stencil and of solder
Pattern A 6 mil lineskpaces 50 VDc paste bridging of tight pitch soldering pads. With finer
Pattern B 12.5 mil lines/spaces 100 VDc pitches (< 0.020”) this will minimize the need to reduce
Pattern C 25 mil lines/50 rnil spaces 500 VDc stencil apertures, which will aid printability, without
concern for bridging. If minimizing the amount of
Initial insulation resistance for all comb patterns, including exposedhon-wetted copper on the periphery of an SMT
controls, were -1 x 1014 ohms. Mer 1000 hours all the pad is important, then the stencil aperture/SMT pad ratio
coated coupons were measured at >5 x 109 ohms, with the should be maintained at 1:1. The recommended maximum
control coupons all within less than a decade difference. At reduction for FPT apertures (in air reflow) is 20°/0 (i.e. 8
10X magnification no evidence of any electromigration or mil wide paste deposit on a 10 mil wide pad). Aperture
dendritic growth was reported. See Table 4 for actual reductions in the lengthwise direction are unnecessary and
readings.’ not recommended.

. Moisture and Insul&”on Resistance - Due to the high color contrast of the materials in use, (e.g.
MIL-STD-202E, Method 106D OSP-coated copper, the solder mask and solder paste),
Per MIL-STD-202E IPC-B-25 comb patterns were additional in-process benefits are realized. Alignment of
prepared with a liquid photoimageable solder mask. Half the stencil to the PCB during screen printing set-up is
were coated with a substituted benzimidazole and the facilitated due to the copper color of the SMT pads. Any
remainder with HASL. The coupons were first cycled from missed or skipped solder paste deposits onto the PCB will
25°C, 90V0R.H. to 65°C, 95’%0R.H. for ten 16 hour cycles. be easily detected because of the copper pad to solder paste
Once pre-eonditioned the comb patterns were measured for color contrast. This will allow earlier deteetion of poor
initial insulation resistance and then subjected to 65°C, printing and will preclude these PCBS from being filly
95’XOR.H. for 139 hours with a 100 VDC bias. The assembled, only to require subsequent rework. Finally, the
specifkation requirement is that the final insulation flat non-reflective topology of OSP<oated fiducial marks
resistance must be >5 x 108ohms. allows more consistent recognition by the assembly
equipment’s machine vision.
m Initial I.R Final I.R
HASL 2.0 x 10’2Q 6.0 X 107G? Production experience to date has exhibited excellent
OSP 1.3 x 10’3Q 4.0 x 10’1Q compatibility of most solder pastes, regardless of the flux

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vehicle activity (i.e. OA, RMA, no-clean, low residue) with Production experience has shown that hold times of one to
the benzotriazole and substituted benzimidazole coatings. seven days are typical and should not be of a concern. The
In converting to the OSP processes there is no need to variables listed above will dictate the acceptable hold times
adjust the thickness of the solder paste deposited. Normally for PCBS in a particular process. One major OEM has
the same thickness used with HASL PCBS will suflice. experienced hold times greater than one month without
Most of the solder from the HASL process remains under solderability degradation.8
the NUT leads during reflow and does not contribute to the
solder fillets formation. The Wave Soldering Process
Production experience to date of single pass through-hole
Existing SMT reflow profiles used for HASL - coated wave soldering of benzotriazole and substituted
PCBS should work well for both OSP types, Although, benzimidazole coatings has exhibited excellent
some optimization to the profile will enhance second side compatibility of most flux types, regardless of activity (i.e.
solderability. Maintaining the peak temperature that the OA, RA, RMA, SA, low solids no-clean, VOC-free no
PCB experiences (in air) during first side reflow below clean) or flux application technique. For mixed technology
240”C will be beneficial for subsequent soldering assembly, where wave soldering occurs after prior heat
operations. Similarly, increasing the post-reflow PCB cool- excursions, the more active flux types will be fidly
down rate to reach 100”C as quickly as possible is also compatible with the substituted benzimidazole coatings.
advantageous (not to exceed cooldown rate specified for Low activity soldering materials such as low solids and
ceramic components). These optirnizations will increase VOC-free no-clean fluxes may require some process
the process window for substituted benzimidazole coatings optimization. Benzotriazole coatings are not recommended
for multiple heat excursion assembly. Utiortunately this for use in mixed technology processes.
beneficial effect does not extend to the benzotriazole
coatings. After one heat excursion the second side copper Successfid implementation of low activity fluxes requires
is considerably oxidized. Consistent second side soldering some scrutiny of the wave soldering process. Typically the
is unlikely, even with highly active soldering materials. major areas to be analyzed are the flux formulation, the
effectiveness of the flux application method/equipment and
One consideration that is required during SMT assembly of the assembly process parameters. The choice of flux and
substituted benzimidazole coated PCBS is the selection of how it is applied to the PCB’S plated through-holes (PTHs)
solvents used to wipe down misprinted solder paste. These are major factors in determining the level of hole fill and
coatings are soluble to varying degrees in most solvents top side wetting achieved. The wetting mechanism for
(acidic or basic). Even though some amount of coating may OSPS differs from HASL. In order to achieve good wetting
be removed by a chosen solvent, this does not equate to a the flux needs to be applied where the solder needs to flow.
loss of solderability. Careiid selection of an appropriate The flux is instrumental in penetrating the coating ahead
wipedown and cleaning solvent will eliminate potential of the molten solder. The more complete the flux
incompatibilities. The benzotriazole coating, as a result of penetration into the PTHs, the more likely that fill hole fill
its strong monolayer bond to copper, is not similarly and top side wetting of the annular ring will occur. Flux
tiected. application techniques like wave fluxing and foam fluxing
are effective at delivering a suitable level of flux transfer to
In most in-line assembly processes all of the soldering the PTHs. These techniques result in excellent hole fill and
steps will occur within a few hours (if not minutes) of each top side wetting even with the lowest activity fluxes.
other. At times, due to equipment breakdown or Conversely, most spray fluxing equipment is limited in its
component shortages, partially assembled PCBS may incur ability to deliver flux far enough up into the PTHs.
substantial hold times prior to subsequent soldering. Additionally, spray fluxing significantly reduces the
Typically, for substituted benzimidazole coated PCBS if quantity of flux applied to the PCBS. For these reasons
these delays are a matter of hours or even days, unoptimized spray processes will typically yield poor top
solderability of the second side will not be compromised. side solder fillets.
Several variables will impact the maximum hold time
allowable: Low solids and VOC-free no-clean fluxes specifically
1. Time at elevated temperature during the first solder formulated for OSPS are now available from numerous flux
paste reflow. manufacturers. These fluxes typically offset some of these
2. Maximum temperature the PCB reached during the flux application shortcomings by being slightly more
first reflow. active, having superior capillary action or being more
3. Reflow environment used (N2 vs. Air). effective at penetrating the OSP. A new flux application
4. Cleaning of the PCB and what type of solvent used. technique, the JetFlux@ System, uses the principles of ink
5. Solder paste wipe down for misprint. jet printing to achieve superior flux transfer to the PTHs.
6. Activity of soldering material to be used for side tsvo. The flux is delivered in liquid micro streams that deposit
well up into the PTHs to be soldered. This technique helps
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achieve excellent top side fillets while applying a flux some oxygen diffusion will occur through the coating. The
quantity similar to spray fluxing. use of a nitrogen atmosphere will reduce this condition.
When the PCB temperature is reduced after reflow, the
In converting to mixed technology assembly of substituted coating will “close its pores”, and thus not allow any
benzimidazole coated PCBS with low solids or VOC-free further degradation. By reducing the quantity of oxygen
no-clean fluxes, several process parameters should be diffhsed through the coating on PCB side 2 during SMT
reviewed and optimized: reflow, the second side soldering operation will experience
a wider operating range. For this reason, OSPS retain
1. Improve PCB first side SMT reflow process control by solderability through more heat excursions in nitrogen
minimizing the peak reflow temperature and versus air. When nitrogen is used in wave soldering, but
increasing the PCB cooldown rate. not during SMT reflow, one will experience some increase
2. Minimize PCB hold times between soldering in process latitude. This will not be as significant an
operations. improvement as when nitrogen is used during SMT reflow
3. Maintain wave fluxing PCB top side pre-heat alone. OSP-coated PCBS soldered in air will remain
temperature at 100-12O”C. effective through 3 to 5 mass heat excursions (depending
4. Maintain solder pot temperature at 245 to 260”C. on the activity of the soldering materials) plus any
5. Use air knife after flux applicator to assist flux localized soldering (i.e. hand soldering, rework, etc.). In
penetration up the PTHs. nitrogen (< 500 ppm 02), more than 5 mass heat excursions
6. Use turbulent type wave cordlguration (e.g. chip wave) are possible.
to maximize hole fill.
7. Increase wave contact time and PCB depth in solder to Production experience has shown that the use of nitrogen is
maximize hole fill. not required for successfid mixed technology assembly of
OSP-coated (substituted benzimidazole) PCBS in a no-
Optimization of the above listed common wave soldering clean environment. The key is proper process optimization.
parameters, along with selection of the appropriate flux
and application technique will result in successful no- APPLICABILITY TO NEW
clean, mixed technology assembly with OSPS. See Table 5 PACKAGING TECHNOLOGIES
for a summary of OSP compatibility with various assembly In general both types of OSPS will be beneficial to any
process and soldering materials. packaging technology where soldering to a flat attachment
area is required. The following is a summary of
Effect of Nitrogen Inerting applicability to various new technologies.
Historically, nitrogen inerting of SMT reflow has been
used to maximize first-pass assembly yields for processes Ultra Fine-Pitch
using low activity soldering (no-clean) solder pastes. Most Ultra fine-pitch is defined as lead-to-lead spacing of 0.016”
recently nitrogen, in the form of a “blanket” surrounding or finer. Work to date has shown that the pad flatness
the solder pot, has been used in wave soldering with low afforded by the OSPS, in conjunction with finer mesh
solids, no-clean fluxes. In this case the benefits stem more solder paste powder (-400/+500, -500/+635) makes
from the reduction of dross formation on the solder pot production level processes fmsible below 0.015” pitch.
than increased solderability. In the case of OSPS nitrogen With the recent advances in stencil manu-facturing and
inerting of the entire assembly process is beneficial. screen printer accuracyhepeatability, pitches down to
0.010” may be feasible.
Some assemblers have found that by inerting the SMT
reflow process they are able to “extend the effectiveness of Ball Grid Arrays (BGAs)
benzotriazoles for some multi-heat excursion processes. To date a substantial amount of production work has been
When inerting is coupled with the use of highly aggressive petiormed with various BGA configurations soldered to
water soluble wave solder fluxes and short hold times OSP-coated PCBS. A recent study by a major OEM found
between soldering operations, some success with mixed that the use of certain types of substituted benzimidazole
technology assembly may occur. Only a few companies OSPS resulted in the highest solder joint reliability for
have ever succeeded in consistently achieving this. BGAs. This test compared HASL, various Ni-Au coatings,
Sn-Bi, Ni-Pd, and various OSPS.
The use of nitrogen (< 500 ppm Oz) in the SMT reflow of
substituted benzimidazole coated PCBS will improve the The flat pad attachment areas offer the potential for every
wave soldering hole fill with low activity fluxes. During BGA solder joint to be virtually identical in solder volume.
SMT reflow of the top side of the PCB, the bottom side By improving the probability of forming consistent solder
also experiences the elevated temperature and thus the joints the opportunities for costly rework are virtually
coating on this side also “opens its pores”, but does not eliminated. For ideal compatibility with OSPS, the BGAs
come in contact with the flux vehicle. During this period need to have eutectic solder balls which will be attached to

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the PCB via fluxholder paste or high temperature alloy Several of these tests comparing substituted benzimidazole
solder balls which will use solder paste for attachment. OSPS to metallic surface finishes are summarized below.
Micro-BGAs, mini-BGAs, and other BGA configurations
will all benefit similarly. Pull Strength Test
Numerous companies have performed comparative pull
Flip Chip tests for solder joints formed OSP and HASL-coated PCBS.
Flip chips, due to their low profile solder bumps, will also A major U.S. computer manufacturer performed the
benefit from consistent, flat pads. Flat pads will tolerate following test:
any lack in bump coplanarity better than a poorly
controlled HASL deposit. In a similar manner to BGAs, PCB preconditioning: Thermal cycling from-lo” C to
any flip chip configuration where the bump is made of an 110”C, 30°C/rninute ramp
alloy that will melt during standard reflow will be filly rate, 1 minute dwell at
compatible with OSPS. extremes for 4000 cycles.

Tape-Automated-Bonding (TAB) Pull and peel tests were performed on 7000 solder joints.
Soldering of TAB components normally requires that the All recorded strengths for the OSP formed solder joints
solder be pre-deposited on the attachment pads (which are were equal to or greater than for the HASL ones.
typically 0.010” pitch or finer). OSPS are not directly
compatible with TAB attachment but they may be of use by Vibration Test
creating a flat solderable surface for applying the pre- The same computer manufacturer fabricated test vehicles
deposited solder. The solid solder techniques often used in that incorporated daisy chained devices. The test vehicles
this application would be compatible with the OSPS. were subjected to a vibration stress range of 10 to 2000
hertz on 3 axes at 12G’s for 20 hours. No opens were
Chip-on-Board Wire Bonding found for either the OSP or HASL-formed solder joints.g
The OSPS will not be directly compatible with any type of
wire bonding. OSPS maybe usefid for PCBS requiring both Bend Flex Test (3 Point)
wire bonding and solderability. Wire bonding needs to A major telecommunications company petiormed the
occur to a noble metal like gold, but often the gold following test to compare HASL, Ni-Au and OSP-coated
thickness employed could be detrimental to the formation PCBS.
of metallurgically sound solder joints. Therefore OSPS can
be used for PCBS requiring two surface finishes. Once the Test Vehicle; A 41 I/O ceramic BGA (0.52” x
PCBS have been gold plated in the wire bond attachment 0.47”) with 0.30” solid spheres
areas they can be processed through the OSP coating (Sn62/Pb36/Ag2) was reflowed
operation. Unlike HASL and other metallic finishes, onto an 0.045” thick FR-4 PCB.
masking of the gold is not necessary.
Pre-Conditioning: The assembled PCBS were than
.PCMCIA Cards - Thin Cards subjected to an additional SMT’
Most PC card designs use a 0.016 to 0.018” thick PCB reflow to simulate second side
with numerous fine pitch components. These PCBS are assembly. The PCBS
typically fabricated in 18’ x 24” panels. It is very difIlcult were then artificially aged for 24
to HASL such large, thin panels consistently. The use of hours at 100”C.
OSPS on such designs results in increased first-pass yields
of the fine-pitch components by reducing the incidence of Test: A known load (force) was
bridging. Additionally the mild temperatures of the OSP placed on the PCBS and
process will not alter the dimensional integrity of the thin increased until a fracture of the
C Cards. The thermal shock associated with the HASL joints was detected.
process can distort the physical dimension of the PC cards
in a non-linear manner. This distortion, albeit relatively Results:
small (.1 to 2 roils), can be enough to affect the screen Load (lbs)
printer and component placement accuracy, thus impacting .,TyPq ,, .,Mean ~ta~dat~ ,~yiatio+
fine pitch assembly yields. HASL 87 11
OSP 107 6
SOLDER JOINT RELIABILITY NifAu 62 24
One of the primary issues in considering new PCB surface
finishes is the reliability of the resulting solder joints. The solder joints formed from OSP coated NUT pads were
Numerous reliability tests have been performed by significantly stronger than those joints formed with HASL
automotive, computer, and telecommunication OEMS.
769
or Ni/Au. The standard deviation results showed that OSP Substituted Benzimidazoles
formed solder joints were also most consistent. During Substituted benzimidazoles have been successfully used in
HASL, a thick, non-uniform Cu-Sn intermetallic all major sectors of the electronics industry including:
compound (IMC) layer is formed at the copper-solder computers, telecommunications, automotive, consumer
interface, an area prone to solder joint fracture. In the case electronics, instrumentation and business equipment. Some
of Ni/Au, the ftilure occurred at the copper-nickel of the high volume manufacturing processes currently
interface. The nickel deposit exhibited poor ductility and using these OSPS include:
was the weak point in the solder joint. Solder joints formed
from OSP-coated pads have seen only one thermal cycle ● A major instrumentation OEM has been assembling
(that during reflow). This cycle is well controlled in time network display monitor PCBS for 2 years in a mixed
and temperature and thus allows formation of IMCS with a technology process using a no-clean solder paste and a
fine, homogeneous crystalline structure. This leads to low solids, no-clean flux in an air atmosphere. The
stronger, more ductile solder joints. flux is applied via a spray fluxer.
● A major manufacturer of industrial controls for
Thermal Shock Test automation is assembling PCBS in a mixed technology
The same telecommunications company performed a process using no-clean solder paste and a VOC-free,
thermal shock test comparing HASL, various Ni-Au no-clean flux in an air atmosphere. The flux is applied
finishes, Sn-Bi, Ni-Pd and two OSPS. via foam and wave fluxers.
● A major contract assembler has been manufacturing
Test Vehicle; Same BGA vehicle as used in the lap top computers for 4 years in a double sided SMT
3 Point Bend Flex Test. process using water soluble solder pastes in an air
atmosphere.
Pre-Conditioning; Same ● A major contract assembler has been manufacturing
desk top computers for 2 years in a mixed technology
Test: PCBS were subjected to a liquid to process using a no-clean solder paste and a VOC-free,
liquid thermal shock from -55 to no-clean flux in an air environment. The flux is
125°C with a 5 inute dwell at applied via foaming.
extremes. ● A major automotive electronics OEM is
mantiacturing control modules in a mixed technology
At 250 cycles 3 of the Ni-Au finishes and the Ni-Pd all had process using a no-clean solder paste and a low solids,
experienced some level ofjoint cracking. Anywhere from 4 no-clean flux. The flux is applied via wave fluxing and
to 12’XOof these solder joints had experienced cracks which the solder pot uses a nitrogen blanket.
covered 50°/0 of the joint area. They were removed from ● A major telecommunication OEM has been
further cycling. At the end of the test (450 cycles) the manufacturing personal pagers for 4 years in a double
fourth Ni-Au finish exhibited 30% of the joints as cracked, sided SMT process using no-clean solder paste in a
Sn-Bi had 12Y0,one of the OSPS had 13%, HASL had 6% nitrogen atmosphere.
and the second OSP had none. This OSP was the same one ● A major computer disk drive manufacturer has been
that excelled in the 3 point bend flex test. using OSPS for 2 years in a mixed technology process
using a no-clean solder paste and a low solids no-clean
All reliability testing performed to date has exhibited flux in an air atmosphere. The flux is applied via foam
substituted benzimidazole OSPS as being equal to or better, or spray.
in solder joint strength and consistency than HASL and
other metallic surface finishes. 10 SUMMARY
Organic coatings such as benzotriazoles and substituted
OSPS IN PRODUCTION benzimidazoles have been successfdy used for a number
Benzotriazoles of years in the electronics industry. They have proven to be
Benzotriazoles have been successfully used as a HASL- not only reliable alternatives to HASL but down right
altemative for nearly 25 years by the computer, essential for achieving acceptable first-pass yields for
telecommunications and consumer electronics industry. certain complex packaging technologies, The
Products as diverse as laptop computers, telephones and benzotriazoles will probably always have a niche in the
television remote controls are manufactured with PCBS industxy. Meanwhile many satisfied users predict that the
coated with benzotriazoles. The manufacturing limitation best of the substituted benzimidazoles will be the high
with benzotriazole coated PCBS is that the design must volume, low cost coating alternative to HASL for years to
involve only one heat excursion or that soldering be come.
petiormed in an inert atmosphere with high activity fluxes
for double sided or mixed technology designs.

770
REFERENCES 5. Trace Laboratories Test Report for Enthone-OMI,
1. Banerji, K. And Bradley, E. “Manufacturability and October 1993
Reliability of Products Assembled with New PCB 6. Ibid 5
Finishes,” Proceedings Surface Mount International, 7. Tamura Kaken Internal Report, 1992
1994, pp. 584-595 8. Platt, S. and Brantingham, J., “Determination of
2. Short, B. and Reilly, D., “Switching From Tin/Lead to Product Characteristics and Process Configuration for
Copper Finishes,” Proceedings Nepcon West, 1993, Organic Solderability Preservatives,” 1994, pp. P13-4-
pp. 405-415 1 through P13-4-8
3. Parker, J.L. and Horton, J.S., “Assembly Pefiormance 9. Ibid 2
of Printed Wiring Boards Coated with an Organic 10. Ibid 1
Solderability Preservative,” Proceedings Surface
Mount International, 1992, pp. 499-513 @ JetFlux is a registered trademark of Precision
4. Tamura Kaken Internal Report, 1991 Dispensing Equipment, Inc., Bay Village, Ohio

771

—— —
Insulation Resistance (Q)
Test
Board Initial 200 Hours 400 Hours 600 Hours 800 Hours 1000 Hours

OSP IX10’4 4X10’3 4X10’3 3X10’3 2X10’3 2X10’3

Control IX10’4 6X10’3 6X10’3 5X10’3 5X10’3 4X10’3

TABLE 1. Surface Insulation Resistance (SIR) - JIS Z 3197

Average Log (Q)

+ Ban Copper control

4 -a- Benzotriazole

m -A- substituted
12- Benzimidazole

11 I I I I I I 1 I I I

o 24 6 8 10 12 14 16 18

Days

TABLE 2. Surface Insulation Resistance (SIR) - Bellcore

772

. ..
Average Log (K2)
14

13
+ 5 Reflow
+ I Reflow
12 I

I + 5 Reflow w/LsF
A + I Reflow w/LsF
11 4
+ copper control

1
-m- AS coated
10

9 1 1 I I I I I I [ I I I I I I I 1
O 4 8 12 16 20 24 28

Days

TABLE 3. Surface Insulation Resistance (SIR)


Bellcore With Low Solids, No-Clean Flux

Insulation Resistance (Q)

Test Board Initial 250 Hours 500 Hours 1000 Hours

OSP Pattern A * 7.5 x 10’3 I.oxlo’” 7.5 x 109 5.3 x 109

Control A 8.1x 10’3 5.0 x 109 3.8 X 109 2.9 X 109

OSP Pattern B* 9.3 x 10’3 1.2x lo’0 I.lx lo’” 9.2 X 109

Control B 1.2 X10’4 1.3x lo’0 I.ox lo’” 9.3 x 109

OSP Pattern C* 2.7 X 10’4 lmoxlo’o 8.2 X 109 6.0 X 10g

Control C 2.4 X 10’4 I.oxlo’” 8.9 X 109 6.7 X 109

* No evidence of electromigration

TABLE 4. Electromigration Resistance - Various Voltages

773
Assembly Substituted
Type Benzotriazoles Benzimidazoles

Single-sided SMT
Rosin E E
No-Clean E E P = Poor
Water-Soluble E E F = Fair
G = Good
SingleSided Wave E=
Rosin E E
No-Clean G E
Water-soluble E E

Double-Sided SMT
Rosin P E
No-Clean P E
Water-soluble F E

Mixed Technology
Rosin P E
No-Clean P G
Water-Soluble F E

TABLE 5. Organic Coatings - Assembly Compatibility

HZO HZO HZO DI


Acid
Clean

3040”C
-b
Rinse
Micro
Etch

25-30°C
~

Rinse
Acid
Rinse

!%lo!ioH2SOd
Rinse
OSP
Coat

40-45°C
-L-
Rinse
Dry

60-60”C
3045 sec. 30-4s Sec 20-25°C 45-90 sec.
20-40 pinch 15-30 sec. 90-1109’0Concentration
removal
90-120?40
0.24J.5 Microns Thick

FIGURE 1. Typical Substituted Benzimidazole Application Process

774
HZO

-El
H20 HZO DI
Acid Micro Acid OSP
Dry
Clean Rinse Etch Rinse Rinse Rinse Coat Rinse
-i I I I

30-40”C 25-30”C 5-10% H#Od 20-49°C 60”C


3045 sec. 3045 sec 20-25°C 30-90 sec.
2040 pinch 15-30 sec. pH >3.0
removal
1.O-2.5?40Concentration

50-150 ~ Thick

FIGURE 2. Typical Benzotriazole Application Process

H H H H

● ● ●

Cu Cu Cu Cu Cu Cu Cu Cu

FIGURE 3. Benzotriazole Coating On Copper

775
● O ● 0 ● 0
,.

‘.
.“++ ‘ .“+”+ ‘ CU++ .“++

. .. . .

IA ‘.
., - ““ “ - ~ ‘“

Cu Cu Cu Cu Cu Cu Cu Cu

FIGURE 4. Substituted Coating On Copper

FIGURE 5. Horizontal Immersion Equipment For OSPS

776