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Wet Etching and Cleaning - Surface
Wet Etching and Cleaning - Surface
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
1
Outline
• Contamination
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
2
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
3
Etch Rate (Å/min)
at constant temp.
Etch Rate of SiO2
Temperature
0 Weight % HF 100 More NH4F Less NH4F
NH4F/HF Ratios
• 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
5
Etching and Cleaning Solutions (cont’d)
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
6
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
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
7
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
8
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
9
RCA Cleaning
Two-step wet cleaning process involving SC-1 and SC-2:
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
10
Problems with SC1 Clean
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
11
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.
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
12
Particle Removal Efficiency vs. Immersion Time
SC1 solutions w/ varying NH4OH concentration
1.0
1:1:5 NH4OH:H2O2:H2O
Particle Removal Efficiency
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
13
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
14
Standard Clean for Silicon (cont’d)
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
15
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)
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
16
Particle Deposition Model
• Parameters controlling deposition
– zeta potential of wafers
– size and zeta potential of particles
– ionic strength and temperature of solution
Diffusion
layer
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
17
Surface Charge and Surface Electricity
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
18
Surface Charge Development on SiO2
Immersed in Aqueous Solutions
-O-Si...
H+ Aqueous
Bulk
SiO2 -Si-O... Solution
OH-
-O-Si...
-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
19
Point of Zero Charge (PZC) of Materials
• PZC = the solution pH value at which the surface bears no net charge; i.e. surf = 0
20
Material pHPZC
(microcoulombs/cm2)
PZC
SiO2 2-2.5
TiO2 5.5-6
surf
0
pH
Al2O3 ~9
Si ~4
Ny lon ~6 -20
Cell
Block
Channel
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
24
Zeta Potential vs. pH
Oxide Wafer - Activation Etch
Zeta Potential, mV 0
(-)
pH
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
25
Contamination Mechanisms
A
A
Raghavan
NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing
26