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Wet Etching and Cleaning - Surface

Wet Etching and Cleaning - Surface

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11/20/2012

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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

NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing

Raghavan

1

Outline
• Etching and cleaning solutions/processes • Particle adhesion theory • Surface charge and chemistry • Contamination

NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing

Raghavan

2

Etching and Cleaning Solutions • HF Solutions – Dilute HF (DHF) solutions .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 NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 3 .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) .

NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan Temperature 4 . Etch Rate (Å/min) 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.Etch Rate of SiO2 Etch Rate (Å/min) at constant temp. Etch rate also directly increases with increasing temperature. as well as higher ratios of NH4F buffer in BHF solutions.

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 NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 5 .

Etching and Cleaning Solutions (cont’d) • SC-2 (Standard Clean 2) – HCl (73%). 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 NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 6 . H2O2 (30%).

nonionic surfactant (<2%). 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%). and chelating/complexing agents • Could possibly be used with H2O2 to replace SC1 and SC2 sequence NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 7 .Alkaline Cleaning Solutions • SC-1 (Standard Clean 1) – NH4OH (28%). pH regulators for a range of 8-10.

Surfactants • Alkyl phenoxy polyethylene oxide alcohol – – – – Nonionic compounds Alkyl group: 8 .9 carbons 9 . 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) NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 8 .10 ethylene oxide groups Examples: NCW 601A (Wako Chemicals).

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 NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 9 .

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.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. Fe) NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 10 .g.g.

X<1) are being actively investigated NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 11 .Problems with SC1 Clean • Some metals (e. Al) are insoluble in this oxidizing.g. 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.

electrostatic repulsion between the removed particle and the oxide surface will prevent particle redeposition.3 nm/min at 70 ºC. NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 12 . most surfaces are negatively charged.Particle Removal During SC1 Clean • H2O2 promotes the formation of an oxide • NH4OH slowly etches the oxide – In a 1:1:5 SC1. Hence. At the alkaline pH value of SC1 solution. the oxide etch rate is ~0.

0 Particle Removal Efficiency 1:1:5 NH4OH:H2O2:H2O The efficiency curve is steeper with a higher concentration of NH4OH in the SC1 solution. Immersion Time 0 NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 13 . Immersion Time SC1 solutions w/ varying NH4OH concentration 1.Particle Removal Efficiency vs.

Piranha/SPM – 4:1 H2SO4 (40%):H2O2 (30%) @ 90 C for 15 min – Removes organic contaminants • Step 2 . etc. Ni.DI water rinse • Step 3 .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.) NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 14 . Cu.Standard Clean for Silicon • Step 1 . Ag.DHF – HF (2%) for 30 sec • Step 4 .

SC-2 – 1:1:5 HCl (30%):H2O2 (30%):H2O at 70 C for 10 min – dissolves alkali ions and hydroxides of Al3+.Spin rinse dry NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 15 . Fe3+.Standard Clean for Silicon (cont’d) • Step 6 .DI water rinse • Step 7 . Mg3+ – desorbs by complexing residual metals • Step 8 .DI water rinse • Step 9 .

particle deposition is favorable NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 16 .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 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 NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 17 .

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 NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 18 .

Bulk SiO2 -Si-O. H+ OHBasic Solutions (high pH) H+ OHAqueous Solution -O-Si-OH2+ Bulk Solid -O-Si-OH2+ -O-Si-OH Solution Bulk Solid -O-Si-O-O-Si-O-O-Si-OH Solution NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 19 . Acidic Solutions (low pH) -Si-O. -O-Si.........Surface Charge Development on SiO2 Immersed in Aqueous Solutions -O-Si.

5 surf PZC 5.Point of Zero Charge (PZC) of Materials • PZC = the solution pH value at which the surface bears no net charge. Acidic oxides have a lower PZC than basic oxides. surf = 0 20 (microcoulombs/cm2) Material SiO2 TiO2 Al2O3 Si Ny lon pHPZC 2-2.e. i.charge at a given pH depends on the nature of the metal-oxygen bond and the acid/base character of the surface MOH groups. NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 20 .5-6 ~9 ~4 ~6 0 pH -20 Development of + or .

Ψ o = 0.059 (PZC-pH) volts NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing 21 .-ζ + .Liquid Zeta Potential (ζ ): • Potential in the double layer at a short distance (typically the diameter of a hydrated counter ion) from the solid surface • Experimentally measurable through electrokinetic techniques • Decreases (more negative) with increasing pH Raghavan 0 Surface Potential (Ψ o ): • Not experimentally measurable • Oxides immersed in aqueous soln’s.Surface Potential (Ψ o) and Zeta Potential (ζ ) +--+ Solid Ψo +-++.

Zeta Potential Electrophoretic Method ν ∈ζ = E Kη E   = 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 NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 22 .

dielectric constant. and conductivity of solution. and k are viscosity.  .  Es/P is the slope of the streaming potential vs. which is related to zeta potential k ∆E ζ = +4πη ∈ ∆P s  . pressure drop. Raghavan NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing 23 .Zeta Potential from Streaming Potential LIQUID IN P (+) and (-) charges LIQUID OUT V • Generation of an electrical potential due to the flow of liquid past a charged surface • Potential generated = streaming potential (Estr ).

6” wafers Electrode LIQ IN LIQ OUT Electrode Block Cell Channel LIQ IN LIQ OUT NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 24 .Streaming Potential Cell Schematic Sketch .

Zeta Potential vs.Activation Etch 0 Zeta Potential. mV (-) pH NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 25 . pH Oxide Wafer .

Contamination Mechanisms • Liquid film draining (liquid/air interface) A A Hydrophilic L (OR) L Hydrophobic • Bulk deposition from liquids • Contaminant pick-up from air NSF/SRC Engineering Research Center for Environmentally Benign Semiconductor Manufacturing Raghavan 26 .

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