Wet Etching and Cleaning:

Surface Considerations and Process Issues

Dr. Srini Raghavan

Dept. of Chemical and Environmental Engineering
University of Arizona

 1999 Arizona Board of Regents for The University of Arizona

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Outline

• Etching and cleaning solutions/processes

• Particle adhesion theory

• Surface charge and chemistry

• Contamination

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Etching and Cleaning Solutions
• HF Solutions
– Dilute HF (DHF) solutions - prepared by diluting 49% HF
with dionized water
– Buffered HF solutions - prepared by mixing 49% HF and
40% NH4F in various proportions
• example: Buffered Oxide Etch (BOE) - patented form of buffered
HF solution
– May contain surfactants for improving wettability of silicon
and penetration of trenches containing hydrophobic base
• nonionic or anionic
• hydrocarbon or fluorocarbon

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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Etch Rate (Å/min)
at constant temp.
Etch Rate of SiO2

Etch Rate (Å/min)

Temperature
0 Weight % HF 100 More NH4F Less NH4F
NH4F/HF Ratios

Etch rate of SiO2 increases with increasing weight % of HF in

the etch solution, as well as higher ratios of NH4F buffer in BHF
solutions. Etch rate also directly increases with increasing
temperature.
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Etching and Cleaning Solutions (cont’d)

• Piranha
– H2SO4 (98%) and H2O2 (30%) in different ratios
– Used for removing organic contaminants and stripping
photoresists
• Phosphoric acid (80%)
– Silicon nitride etch
• Nitric acid and HF
– Silicon etch

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Etching and Cleaning Solutions (cont’d)

• SC-2 (Standard Clean 2)

– HCl (73%), H2O2 (30%), dionized water
– Originally developed at a ratio of 1:1:5
– Used for removing metallic contaminants
– Dilute chemistries (compositions with less HCl and
H2O2) are being actively considered

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Alkaline Cleaning Solutions
• SC-1 (Standard Clean 1)
– NH4OH (28%), H2O2 (30%) and dionized water
– Classic formulation is 1:1:5
– Typically used at 70 C
– Dilute formulations are becoming more popular

• Tetramethyl Ammonium Hydroxide (TMAH)

– Example: Baker Clean
• TMAH (<10%), nonionic surfactant (<2%), pH regulators for a range of
8-10, and chelating/complexing agents
• Could possibly be used with H2O2 to replace SC1 and SC2 sequence

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Surfactants
• Alkyl phenoxy polyethylene oxide alcohol
– Nonionic compounds
– Alkyl group: 8 - 9 carbons
– 9 - 10 ethylene oxide groups
– Examples: NCW 601A (Wako Chemicals), Triton X-100 (Union Carbide)
• Alkyl phenoxy polyglycidols
– Nonionic surfactants
– Example: Olin Hunt Surfactant (OHSR)
• Fluorinated alkyl sulfonates
– Anionic surfactants
– Typically 8 carbon chain
– Example: Fluorad FC-93 (3M)

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Surfactants (cont’d)

• Acetylenic alcohols
– Unsaturated triple bond in the structure
– Nonionic
– Example: Surfynol 61 (APCI)

• Betaines
– Zwitterionic in nature
– Used mostly in alkaline clean
– Example: Cocoamidopropyl betaine

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 RCA Cleaning
Two-step wet cleaning process involving SC-1 and SC-2:

1) 1:1:5 NH4OH-H2O2-H2O at ~70 C

• Oxidizing ammoniacal solution
• Ammonia complexes many multivalent metal ions (e.g. CU++)
• Treatment leaves a thin “chemical” oxide
• Without H2O2, Si will suffer strong attach by NH4OH

2) 1:1:5 HCl-H2O2-H2O at ~70 C

• HCl removes alkali and transition metals (e.g. Fe)

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Problems with SC1 Clean

• Some metals (e.g. Al) are insoluble in this oxidizing,

highly basic solution and tend to precipitate on the surface
of Si wafers
• High Fe contamination of the wafer surface after a SC1
clean
• Rough surface after cleaning
– SC1 solutions with lower ammonia content (X:1:5,
X<1) are being actively investigated

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Particle Removal During SC1 Clean
• H2O2 promotes the formation of an oxide
• NH4OH slowly etches the oxide
– In a 1:1:5 SC1, the oxide etch rate is ~0.3 nm/min at 70 ºC.

At the alkaline pH value of

SC1 solution, most surfaces
are negatively charged.
Hence, electrostatic
repulsion between the
removed particle and the
oxide surface will prevent
particle redeposition.

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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Particle Removal Efficiency vs. Immersion Time
SC1 solutions w/ varying NH4OH concentration

1.0

1:1:5 NH4OH:H2O2:H2O
Particle Removal Efficiency

The efficiency curve

is steeper with a
higher concentration
of NH4OH in the SC1
solution.
0
Immersion Time

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Standard Clean for Silicon

• Step 1 - Piranha/SPM
– 4:1 H2SO4 (40%):H2O2 (30%) @ 90 C for 15 min
– Removes organic contaminants
• Step 2 - DI water rinse
• Step 3 - DHF
– HF (2%) for 30 sec
• Step 4 - DI water rinse
• Step 5 (SC-1/APM)
– 1:1:5 NH4OH (29%):H2O2 (30%) H2O at 70 C for 10 min
– removes particulate contaminants
– desorbs trace metals (Au, Ag, Cu, Ni, etc.)

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Standard Clean for Silicon (cont’d)

• Step 6 - DI water rinse

• Step 7 - SC-2
– 1:1:5 HCl (30%):H2O2 (30%):H2O at 70 C for 10 min
– dissolves alkali ions and hydroxides of Al3+, Fe3+, Mg3+
– desorbs by complexing residual metals
• Step 8 - DI water rinse
• Step 9 - Spin rinse dry

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Adhesion of Particles to Surfaces
• Attractive Forces (AF)
– van der Waals forces (short range)
– Electrostatic (if the charge on the particles is opposite to the charge on
the surface (typically longer range)

• Repulsive Forces (RF)

– Electrostatic (charge on the particle has the same sign as that on the
surface)
– Steric forces (due to absorbed polymer layers on the surface of the
particles and wafer) (short range)

When AF > RF, particle deposition is favorable

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Particle Deposition Model
• Parameters controlling deposition
– zeta potential of wafers
– size and zeta potential of particles
– ionic strength and temperature of solution

• Transport of particles towards the wafer requires diffusion

through a surface boundary layer (particles move along the
flow in the solution and deposit by diffusion).
Substrate

Along the flow

Diffusion
layer
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Surface Charge and Surface Electricity

• Development of surface charge

– Adsorption of H+ and OH- ions (oxides)
– Selective adsorption of positive or negative ions
(hydrophobic materials)
– Ionization of surface groups (polymers such as nylon)
– Fixed charges in the matrix structure exposed due to
counter ion release
• example: positively charged modified filters used in DI water
purification

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Surface Charge Development on SiO2
Immersed in Aqueous Solutions
-O-Si...
H+ Aqueous
Bulk
SiO2 -Si-O... Solution
OH-
-O-Si...

Acidic Solutions -Si-O... Basic Solutions

(low pH) H+ OH- (high pH)

-O-Si-OH2+ -O-Si-O-
Bulk Bulk
Solid -O-Si-OH2+ Solution Solid -O-Si-O- Solution

-O-Si-OH -O-Si-OH

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Point of Zero Charge (PZC) of Materials
• PZC = the solution pH value at which the surface bears no net charge; i.e. surf = 0

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Material pHPZC

(microcoulombs/cm2)
PZC
SiO2 2-2.5
TiO2 5.5-6

surf
0
pH
Al2O3 ~9
Si ~4
Ny lon ~6 -20

Development of + or - charge at a given pH depends on the nature of

the metal-oxygen bond and the acid/base character of the surface MOH
groups. Acidic oxides have a lower PZC than basic oxides.
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Surface Potential (Ψ o) and Zeta Potential (ζ )
+--+
Solid +-+- + - Liquid
+- --
Ψo
ζ Zeta Potential (ζ ):
• Potential in the double layer at a
short distance (typically the
0 diameter of a hydrated counter ion)
from the solid surface
Surface Potential (Ψ o ):
• Experimentally measurable
• Not experimentally measurable through electrokinetic techniques
• Oxides immersed in aqueous • Decreases (more negative) with
soln’s, Ψ o = 0.059 (PZC-pH) volts increasing pH
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Zeta Potential
Electrophoretic Method
E
ν ∈ζ
=
E Kη


 = dielectric constant of liquid

 = viscosity of liquid
K = constant dependent on particle size >>
1/ or << 1/ 
(1/  is the electrical double layer thickness)
• Technique useful for particles suspended in
aqueous or non-aqueous media
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Zeta Potential from Streaming Potential
LIQUID IN LIQUID OUT
(+) and (-) charges
P

• Generation of an electrical potential due to the flow of

liquid past a charged surface
• Potential generated = streaming potential (Estr ), which is
related to zeta potential
 ,  , and k are viscosity, dielectric
k ∆E
ζ = +4πη
s
constant, and conductivity of solution;
∈ ∆P  Es/P is the slope of the streaming
potential vs. pressure drop.
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Streaming Potential Cell
Schematic Sketch - 6” wafers

Electrode LIQ IN LIQ OUT Electrode

Cell
Block

Channel

LIQ IN LIQ OUT

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NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Zeta Potential vs. pH
Oxide Wafer - Activation Etch
Zeta Potential, mV 0

(-)

pH

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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 Contamination Mechanisms

• Liquid film draining (liquid/air interface)

A
A

Hydrophilic (OR) Hydrophobic

L
L

• Bulk deposition from liquids

• Contaminant pick-up from air

Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
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