WO2011008658A1 - Materials and systems for advanced substrate cleaning - Google Patents
Materials and systems for advanced substrate cleaning Download PDFInfo
- Publication number
- WO2011008658A1 WO2011008658A1 PCT/US2010/041630 US2010041630W WO2011008658A1 WO 2011008658 A1 WO2011008658 A1 WO 2011008658A1 US 2010041630 W US2010041630 W US 2010041630W WO 2011008658 A1 WO2011008658 A1 WO 2011008658A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cleaning material
- cleaning
- substrate
- polymers
- patterned substrate
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 273
- 238000004140 cleaning Methods 0.000 title claims abstract description 116
- 239000000463 material Substances 0.000 title abstract description 35
- 239000011538 cleaning material Substances 0.000 claims abstract description 322
- 229920000642 polymer Polymers 0.000 claims abstract description 172
- 239000000356 contaminant Substances 0.000 claims abstract description 58
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 36
- 229920002125 Sokalan® Polymers 0.000 claims description 33
- 229920002401 polyacrylamide Polymers 0.000 claims description 28
- 239000004584 polyacrylic acid Substances 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000006172 buffering agent Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- 238000009736 wetting Methods 0.000 claims description 11
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 10
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical group [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920002873 Polyethylenimine Polymers 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
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- -1 polyethylene Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
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- 235000010981 methylcellulose Nutrition 0.000 claims description 4
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 claims description 4
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001817 Agar Polymers 0.000 claims description 2
- 229920000936 Agarose Polymers 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 102000008186 Collagen Human genes 0.000 claims description 2
- 108010035532 Collagen Proteins 0.000 claims description 2
- 108010068370 Glutens Proteins 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000008272 agar Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920001436 collagen Polymers 0.000 claims description 2
- 235000021312 gluten Nutrition 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 229920000669 heparin Polymers 0.000 claims description 2
- 229960002897 heparin Drugs 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
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- 235000018102 proteins Nutrition 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000000230 xanthan gum Substances 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 240000007472 Leucaena leucocephala Species 0.000 claims 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims 1
- 239000008279 sol Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 52
- 235000012431 wafers Nutrition 0.000 abstract description 37
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 39
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- 229910052581 Si3N4 Inorganic materials 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 16
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 16
- 239000002699 waste material Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 238000011109 contamination Methods 0.000 description 10
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- 230000007246 mechanism Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
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- 238000010586 diagram Methods 0.000 description 5
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- 238000009826 distribution Methods 0.000 description 4
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- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 230000005661 hydrophobic surface Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
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- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
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- 229920005591 polysilicon Polymers 0.000 description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
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- 230000005660 hydrophilic surface Effects 0.000 description 2
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- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
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- 239000010703 silicon Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
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- JVTIXNMXDLQEJE-UHFFFAOYSA-N 2-decanoyloxypropyl decanoate 2-octanoyloxypropyl octanoate Chemical compound C(CCCCCCC)(=O)OCC(C)OC(CCCCCCC)=O.C(=O)(CCCCCCCCC)OCC(C)OC(=O)CCCCCCCCC JVTIXNMXDLQEJE-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000008366 buffered solution Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
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- 239000001739 pinus spp. Substances 0.000 description 1
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- 238000011112 process operation Methods 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0014—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by incorporation in a layer which is removed with the contaminants
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/76—Synthetic resins containing no nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/268—Carbohydrates or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
- H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
- H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
- H01L21/67051—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing using mainly spraying means, e.g. nozzles
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- C11D2111/22—
Definitions
- wafers In the fabrication of semiconductor devices, such as integrated circuits, memory cells, and the like, a series of manufacturing operations are performed to define features on semiconductor wafers ("wafers").
- the wafers include integrated circuit devices in the form of multi-level structures defined on a silicon substrate.
- transistor devices with diffusion regions are formed.
- interconnect metallization lines and vias are patterned and electrically connected to the transistor devices to define a desired integrated circuit device. Patterned conductive layers are insulated from other conductive layers by dielectric materials.
- any material present in a manufacturing operation is a potential source of contamination.
- sources of contamination may include process gases, chemicals, deposition materials, and liquids, among others.
- the various contaminants may deposit on the wafer surface in particulate form. If the particulate contamination is not removed, the devices within the vicinity of the contamination will likely not operate as desired. Because the size of particulate contamination that would cause the failure of devices is on the order of the critical dimension size of features fabricated on the wafer (or greater), removal of small particulate contamination without damaging the features on the wafer can be quite difficult for advanced technology nodes with fine feature sizes.
- the embodiments of the present invention provide improved materials, apparatus, and methods for cleaning wafer surfaces, especially surfaces of patterned wafers (or substrates).
- the cleaning materials, apparatus, and methods discussed have advantages in cleaning patterned substrates with fine features without substantially damaging the features.
- the cleaning material includes polymers of one or more polymeric compounds dissolved in a solvent.
- the cleaning materials are in liquid phase, and deform around device features; therefore, the cleaning materials do not substantially damage the device features if at all.
- the polymers of the cleaning materials capture the contaminants on the substrate. In addition, the polymers entrap the contaminants preventing their return to the substrate surface.
- the cleaning materials can be used to clean different types of substrate surfaces, including hydrophilic, hydrophobic, and mixed hydrophobic and hydrophilic surfaces.
- the formulation windows and process windows for the cleaning materials are widened to allow a formulated cleaning material be used to clean different types of substrate surfaces.
- the cleaning apparatus can be designed to dispense and rinse cleaning materials with a range of viscosities.
- the polymers can be cross-linked.
- the extent of cross-link is relatively limited to avoid making the polymers too hard or rigid, which would prevent the polymers from being soluble in a solvent and being deformed around device features on the substrate surface.
- a cleaning material applied on a surface of a patterned substrate for defining integrated circuit devices to remove contaminants from the surface is provided.
- the cleaning material includes a solvent, and polymers of one or more polymeric compounds.
- the one or more polymeric compounds are dissolved in the solvent.
- the solubilized polymers have long polymer chains, which capture and entrap at least some of the contaminants from the surface of the patterned substrate for defining integrated circuit devices.
- the cleaning material is defined as a liquid phase.
- the viscosity of the cleaning material is between about 100 cP to about 10,000 cP measured at a reference shear rate less than about 100/s.
- the cleaning material deforms around device features on the surface of the patterned substrate when a force is applied on the cleaning material covering the patterned substrate.
- a cleaning material applied on a surface of a patterned substrate for defining integrated circuit devices to remove contaminants from the surface includes a solvent, and a buffering agent to change a potential of hydrogen (pH) value of the cleaning material, wherein the buffering agent and the solvent form a cleaning solution.
- the cleaning material also includes polymers of one or more polymeric compounds being dissolved in the cleaning solution.
- the cleaning material has the pH between about 7 and about 12.
- the solubilized polymers have long polymer chains to capture and entrap at least some of the contaminants from the surface of the patterned substrate for defining integrated circuit devices.
- the cleaning material is defined as a liquid phase.
- the viscosity of the cleaning material is between about 100 cP to about 10,000 cP measured at a reference shear rate.
- the cleaning material deforms around device features on the surface of the patterned substrate when a force is applied on the cleaning material covering the patterned substrate.
- the cleaning material further includes a surfactant to assist dispersing the polymers in the cleaning material and to assist wetting the surface of the patterned substrate.
- the cleaning material includes an ion-providing compound, which ionizes in the cleaning solution to adjust the viscosity of the cleaning material.
- Figure 1 shows a defect and device feature on a substrate, in accordance with one embodiment of the present invention.
- Figure 2A shows a diagram of 3 response curves related to applying a cleaning material on a patterned substrate, in accordance with one embodiment of the present invention.
- Figure 2B shows a diagram of 3 response curves related to applying a cleaning material on a patterned substrate.
- Figure 2C shows a diagram of 3 damage curves for different technology nodes and a force intensity curve of a cleaning material, in accordance with one embodiment of the present invention.
- Figure 3A shows a cleaning material containing polymers of a polymeric compound with large molecular weight dissolved in the cleaning solution, in accordance with one embodiment of the present invention.
- Figure 3B shows the cleaning material of Figure 3 A entrapping contaminants, in accordance with one embodiment of the present invention.
- Figure 3C shows the cleaning material of Figure 3A dispensed on a patterned wafer to clean contaminants from the substrate surface, in accordance with one embodiment of the present invention.
- Figure 3D shows the cleaning material of Figure 3A dispensed on a patterned wafer to clean contaminants from the substrate surface, in accordance with another embodiment of the present invention.
- Figure 3E shows the cleaning material of Figure 3A dispensed on a patterned wafer with trenches and vias to clean contaminants from the substrate surface, in accordance with one embodiment of the present invention.
- Figure 3F shows a cleaning material with gel-like polymer droplets emulsified in the cleaning solution, in accordance with one embodiment of the present invention.
- Figure 3G shows a cleaning material with gel-like polymer globs suspended in the cleaning solution, in accordance with one embodiment of the present invention.
- Figure 3H shows a foam cleaning material, in accordance with one embodiment of the present invention.
- Figure 4A shows particle removal efficiency (PRE) as a function of molecular weight for polyacrylic acid (PAA) and hydroxyethyl cellulose (HEC), in accordance with one embodiment of the present invention.
- FIG. 4B shows PRE as a function of molecular weight for polyacrylamide (PAM), in accordance with one embodiment of the present invention.
- FIG. 4C shows experimental results of using ammonium chloride to reduce viscosity of cleaning material made with polyacrylamide (PAM) polymers, in accordance with one embodiment of the present invention.
- Figure 4D shows viscosity data of cleaning materials with different pH values and different ionic strengths, in accordance one embodiment of the present invention.
- Figure 5A shows a system for cleaning contaminants from a substrate, in accordance with one embodiment of the present invention.
- Figure 5B shows a vertical cross-section view of the chamber with the substrate carrier located beneath the upper processing head and above the lower processing head, in accordance with one embodiment of the present invention.
- Figure 5C shows the upper processing head positioned above the substrate with the lower processing head positioned below the substrate opposite the upper processing head, in accordance with one embodiment of the present invention.
- Figure 5D shows a substrate cleaning system, in accordance with one embodiment of the present invention.
- Figure 6A shows a cleaning apparatus using the cleaning material containing polymers of a polymeric compound with large molecular weight to clean substrates and a rinsing apparatus to rinse off the cleaning material, in accordance with one embodiment of the present invention.
- Figure 6B shows a cleaning and rinsing apparatus using the cleaning material containing polymers of a polymeric compound with large molecular weight to clean substrates, in accordance with one embodiment of the present invention.
- Figure 7A shows a process flow of preparing a cleaning material containing polymers of one or more polymeric compounds with high molecular weights, in accordance with one embodiment of the present invention.
- Figure 7B shows a process flow using the cleaning material containing polymers of one or more polymeric compounds with high molecular weights to clean patterned substrates, in accordance with one embodiment of the present invention.
- a cleaning material includes polymers of one or more polymeric compounds dissolved in a solvent.
- the cleaning materials are in liquid phase, and deform around device features; therefore, the cleaning materials do not substantially damage the device features or reduce damage all together.
- the polymers of the cleaning materials capture the contaminants on the substrate.
- the polymers entrap the contaminants preventing their return to the substrate surface.
- the cleaning materials can be used to clean different types of substrate surfaces, including hydrophilic and hydrophobic surfaces.
- the formulation windows and process windows for the cleaning materials are widened to allow a formulated cleaning material be used to clean different types of substrate surfaces.
- the cleaning apparatus can be designed to dispense and rinse cleaning materials with a range of viscosities.
- the polymers form long polymer chains, which can also be cross-linked to form a network (or polymeric network).
- the long polymer chains and/or polymer network show superior capabilities of capturing and entrapping contaminants, in comparison to conventional cleaning materials.
- the cleaning material also contains a buffering agent to modify the pH of the cleaning material.
- the cleaning material further contains a surfactant to assist dispersing the polymers in the solvent and to assist wetting the surface of the patterned substrate.
- the cleaning material contains an ion-providing compound to modify the viscosity of the cleaning material.
- the embodiments described herein provide cleaning materials and cleaning methods that are effective in removing contaminants and do not damage the features on the patterned wafers, some of which may contain high aspect ratio features. While the embodiments provide specific examples related to semiconductor cleaning applications, these cleaning applications might be extended to any technology requiring the removal of contaminants from a substrate.
- Figure 1 shows a substrate 100 with a substrate body 101, in accordance with one embodiment of the present invention.
- substrate 101 On substrate 101 there is a device structure 102 and a particle 103 in the vicinity of surface 105.
- Particle 103 has an approximate diameter 107, which can be in the same order of magnitude as the width 104 of device structure 102.
- the width 104 of the device structure 102 is equal to or less than 65 nm.
- the widths of device structures, such as width 104 of device structure 102 are scaled continuously down with each technology node to fit more devices on the limited surface area of chips.
- the heights of the device structures, such as height 106 of device structure 102 in general do not scale down proportionally with the width of the device features due to concern of high resistivities.
- conductive structures such as polysilicon lines and metal interconnect
- narrowing the widths and heights of structures would increase the resistivity so much as to cause significant RC delay and generate too much heat for the conductive structures.
- device structures such as structure 102
- the aspect ratio of the device structure can be in the range of about 2 or greater.
- Force 112 is applied on particle 103 to assist in removing particle 103.
- Forces 111 and 112 are applied by cleaning material (not shown) on the substrate surface near device structure 102 to remove surface particulates, such as particle 103.
- forces 111 and 112 are very close in magnitude, since they are in the vicinity of each other.
- Forces 111, 112 applied on the substrate surface could be from any relative motion between the cleaning material and the substrate surface. For example, it can be from dispensing of cleaning material or rinsing of the cleaning material.
- the decreased width 104 of device structure 102 and the relatively high aspect ratio of device structure 102 make the device structure 102 prone to breakage under applied force 111 or accumulated energy under applied force 111.
- the damaged device structure 102 becomes a particle source to reduce yield.
- the damage device structure 102 also can become inoperable due to the damage.
- Figure 2A shows a diagram of 3 response curves related to applying a cleaning material on a patterned substrate, in accordance with one embodiment of the present invention.
- Curve 201 shows intensity versus energy (as a result of force) exerted by a cleaning material on the substrate surface. The intensity of cleaning energy exerted by the cleaning material peaks at E P .
- Curve 202 shows particle removal efficiency as a function of energy applied on the substrate by the cleaning material. The particle removal rate peaks at near E R . When the energy exerted by the cleaning material reaches E R , the cleaning material is most efficient at removing particles from the substrate surface.
- Curve 203 shows the amount of damages of device structures caused by the cleaning material as a function of energy applied on the substrate surface by the cleaning material.
- the device structures become damaged at Es, which is higher than the higher end, E N , of energy exerted by the cleaning material on the substrate. Since the device structure damage curve 203 is outside the energy distribution 201 of the cleaning material exerts on the pattern substrate, the device structures on the pattern substrate would not be damaged.
- the particle removal curve 202 shows that the cleaning material can remove particles (or contaminants) from the substrate surface without damaging structures on the substrate.
- Figure 2B shows a diagram of 3 response curves related to applying a cleaning material on a patterned substrate.
- Curve 201' shows intensity versus energy exerted by a cleaning material on a patterned substrate. The intensity exerted by the cleaning material peaks at E P '.
- Curve 202' shows particle removal rate versus energy applied on the substrate. The particle removal rate peaks at near E R '. When the energy exerted by the cleaning material reaches E R ', the cleaning material is most efficient at removing particles from the substrate surface.
- Curve 203' shows the amount of damages of device structures caused by the cleaning material as a function of energy applied on the substrate surface by the cleaning material.
- the device structures on the substrate become damaged at E 8 ', which is lower than the higher end, E N ', of energy distribution of energy exerted by the cleaning material. Since the device structure damage curve 203' is within the energy distribution 201' of the cleaning material exerts on the pattern substrate, the device structures on the pattern substrate would be damaged by the cleaning material to add particles (or defects).
- Conventional substrate cleaning apparatus and methods include brushes and pads utilizing mechanical forces in removing particulates from the substrate surface.
- the mechanical forces applied by the brushes and pads can damage the device structures.
- the harsh brushes and pads may also cause scratches on the substrate surface.
- Cleaning techniques such as megasonic cleaning and ultrasonic cleaning, utilizing cavitation bubbles and acoustic streaming to clean substrate can also damage fragile structures.
- Cleaning techniques using jets and sprays can cause erosion of films and can also damage fragile structures.
- Figure 2C shows a cleaning curve 201" for a conventional cleaning material applied by a conventional method, such as megasonic cleaning, in accordance with one embodiment of the present invention.
- the onset of damage starts at energy Esi for curve 203i for patterned wafers for 90 nm technology node.
- E S i is larger than the upper end E N " of energy distribution of the cleaning material on the patterned substrate. Therefore, there is no damage to the device structures.
- the conventional cleaning material of Figure 2C still works for 65 nm technology node, since the onset of damage starts at Es ⁇ , which is higher than E N ".
- Figure 3 A shows a liquid cleaning material 300, which contains polymers 310 with large molecular weight(s) dissolved in a solvent 305, in accordance with one embodiment of the present invention.
- the liquid cleaning material 300 is a gel.
- the liquid cleaning material 300 is a sol.
- the liquid cleaning material 300 is a liquid solution.
- the liquid cleaning material 300 when applied on a substrate with particles on the substrate surface, can remove particles on the substrate surface.
- the removed particles 320 are attached to the polymers 310, as shown in Figure 3B.
- the polymers have a large molecular weight(s). In one embodiment, the molecular weight(s) of the polymers is greater than about 10,000 g/mol.
- the polymers form long polymer chains to capture and trap the removed particles to prevent the particles from returning back to the substrate surface.
- the polymer chains form a polymeric network.
- the polymers 310 are either acidic or basic.
- the polymer 310 when dissolved in water, gives a solution with a hydrogen ion activity (pH) lower or greater than in pure water, i.e. a pH larger than or less than 7.0.
- the cleaning material 300 also contains a buffering agent that helps adjusting and maintaining the pH of the cleaning material.
- the polymers dissolved in the solvent can be a soft gel or become gel-like droplets suspended in the solvent.
- the contaminants on the substrate surface attach to the solvated polymers by ionic force, van der Waals force, electrostatic force, hydrophobic interaction, steric interaction, or chemical bonding when the polymer molecules come in vicinity of the contaminants.
- the polymers capture and entrap the contaminants.
- the polymers could form a network in the solvent 305.
- the polymers are dispersed in the liquid solvent 305.
- the liquid cleaning material 300 is gentle on the device structures on the substrate during cleaning process.
- the polymers 310 in the cleaning material 300 can slide around the device structures, such as structure 302, as shown in cleaning volume 330 of Figure 3C, without making a forceful impact on the device structure 302.
- hard brushes, and pads mentioned above would make unyielding contacts with the device structures and damage the device structures. Forces (or energy) generated by cavitation in megasonic cleaning and high-speed impact by liquid during jet spray can also damage the structure.
- more than one type of polymers can be dissolved in the solvent to formulate the cleaning material.
- the polymers in the cleaning material can include an "A" polymeric compound and a "B" polymeric compound.
- the polymers of one or more polymeric compounds with high molecular weights form long chains of polymers, with or without cross-linking to from a polymeric network.
- the polymers can be cross-linked.
- the extent of cross-link is relatively limited to avoid making the polymers too hard or rigid, which would prevent the polymers from being soluble in a solvent and being deformed around device features on the substrate surface.
- the polymers 310 come in contact with the contaminants, such as contaminants 320i, 320 ⁇ , 320m, 320rv on the patterned (or un-patterned) substrate surface and capture contaminants. After the contaminants are captured by the polymers, they become attached to the polymers and are suspended in the cleaning material.
- Figure 3C shows that contaminants 320m, and 320rv, which are attached to the polymer chain(s) 311 1 , and 31 In, respectively.
- Contaminants 32Oi and 32On are attached to other polymer chains.
- contaminants, 32O 1 , 32On, 320m, and 320rv can each be attached to multiple polymer chains, or be attached to a polymeric network.
- the contaminants attached to the polymers chains are removed from the substrate surface along with the polymer chains.
- FIG. 3C shows only one device structure 302.
- a number of device structures such as 302i, 302 ⁇ , 302m, and 302rv
- the liquid cleaning material 300 in the cleaning volume 330', is gentle on the device structures on the substrate during cleaning process.
- the polymers 310 in the cleaning material 300 slides around the device structures, 302i, 302 ⁇ , 302m, and 302rv, without making a forceful impact on the device structures.
- contaminants, 32O 1 , 320 ⁇ , 320m, and 320rv, of Figure 3C being attached to polymer chains, contaminants, 325i, 325 ⁇ , 325m, and 325rv, are also attached to polymers chains.
- FIG. 3E shows a substrate 301' with structures 302' that forms vias 315 and trenches 316, in accordance with one embodiment of the present invention.
- Contaminants 326i, 326 ⁇ , 326m, and 326rv can also be removed by cleaning material 300 by mechanisms discussed above in Figure 3C and 3D.
- the polymers of one or more polymeric compounds with large molecular weights are dispersed in the solvent.
- the polymeric compound with large molecular weight include, but not limited to, acrylic polymers such as polyacrylamide (PAM), and polyacrylic acid (PAA), such as Carbopol 940TM and Carbopol 941TM, poly- (N,N-dimethyl-acrylamide) (PDMAAm), poly-(N-isopropyl-acrylamide) (PIPAAm), polymethacrylic acid (PMAA), polymethacrylamide (PMAAm); polyimines and oxides, such as polyethylene imine (PEI), polyethylene oxide (PEO), polypropylene oxide (PPO) etc; vinyl polymers such as polyvinyl alcohol (PVA), polyethylene sulphonic acid (PESA), polyvinylamine (PVAm), polyvinyl-pyrrolidone (PVP), poly-4- vinyl pyridine (P4VP), etc; cellulose derivatives such as methyl
- polyacrylamide is an acrylate polymer (-CH 2 CHC ONH 2 -)n formed from acrylamide subunits.
- Polyvinyl alcohol is a polymer (-CH 2 CH0H-)m formed from vinyl alcohol subunits.
- the polymers of one or more polymeric compounds with large molecular weights either are soluble in an aqueous solution or are highly water-absorbent to form a soft gel in an aqueous solution.
- the molecular weights of the one or more polymeric compounds are greater than 10,000 g/mol. In another embodiment, the molecular weights of the one or more polymeric compounds are greater than 100,000 g/mol. In another embodiment, the molecular weights of the one or more polymeric compounds are between about 0.01M g/mol to about IOOM g/mol. In another embodiment, the molecular weights of the one or more polymeric compounds are between about 0.1M g/mol to about 5OM g/mol. In yet another embodiment, the molecular weights of the one or more polymeric compounds are between about IM g/mol to about 20M g/mol.
- the molecular weights of the one or more polymeric compounds are between about 15M g/mol to about 20M g/mol.
- the weight percentage of the polymers in the cleaning material is between about 0.001% to about 20%, in one embodiment. In another embodiment, the weight percentage is between about 0.001% to about 10%. In another embodiment, the weight percentage is between about 0.01% to about 10%. In yet another embodiment, the weight percentage is between about 0.05% to about 5%.
- the polymers can dissolve in the solvent, be dispersed completely in the solvent, form liquid droplets (emulsified) in the solvent, or form globs (or lumps) in the solvent.
- the polymers can be copolymers, which are derived from two or more monomeric species.
- the copolymers can include 90% of PAM and 10% of PAA made from monomers for PAM and PAA. Other concentrations of ingredients of copolymers are also possible.
- the polymers can be a mixture of two or more types of polymers.
- the polymers can be made by mixing two types of polymers, such as 90% of PAM and 10% of PAA, in the solvent. Using copolymers or a mixture of different polymers in the cleaning materials has the advantage of utilizing the different strengths of the different polymers to achieve best cleaning results.
- polymers of one or more polymeric compounds with large molecular weights are dissolved uniformly in the solvent.
- the solvent can be a non-polar liquid, such as turpentine, or a polar liquid, such as water (H 2 O).
- a polar liquid such as water (H 2 O).
- Other examples of solvent include isopropyl alcohol (IPA), dimethyl sulfoxide (DMSO), and dimethyl formamide (DMF).
- the solvent is a mixture of two or more liquids.
- the suitable solvent is a polar liquid, such as water (H 2 O).
- the polymers used in the cleaning materials can be acidic or basic.
- polymers containing acrylic acid unit are acidic and a mixture of PAA in water can give a pH value of about 3.
- Examples of basic polymer include polymers containing quaternary ammonium salts such as poly(diallyldimethylammonium chloride) or tertiary amines such as polyethyleneimine (PEI). 50 wt% PEI and water mixture can give a pH value of approximately 12.
- additives can be mixed in the cleaning material.
- Additive(s) can be mixed with the solvent to become a cleaning solution before the polymers are added.
- the additive can be a buffering agent, which can be a weak acid or a weak base, to adjust the potential of hydrogen (pH) value of the cleaning material.
- a weak acid to be used as a buffering agent is citric acid.
- a weak base to be used as a buffering agent is ammonium hydroxide (NH 4 OH).
- the pH values of the cleaning materials can be between about 1 to about 12.
- the cleaning material is basic.
- the pH values of cleaning materials for front-end applications are between about 7 to about 12, in one embodiment. In another embodiment, the pH values of cleaning materials for front-end applications are between about 7 to about 10.
- the cleaning solution is slightly basic, neutral, or acidic, in one embodiment. Copper in the backend interconnect is not compatible with a cleaning material containing ammonium hydroxide as a buffering agent. Ammonium hydroxide interacts with copper and dissolves copper.
- the pH values for backend applications are between about 1 to about 7, in one embodiment. In another embodiment, the pH values for backend applications are between about 1 to about 5.
- the pH values for backend applications are between about 1 to about 2. However, if the buffering agent is not ammonium hydroxide, the pH range for backend application can be widened. In one embodiment, the pH values for backend applications are between about 1 to about 12.
- the additives of the cleaning material include a surfactant, such as ammonium dodecyl sulfate (ADS), to assist dispersing the polymers in the cleaning solution.
- ADS ammonium dodecyl sulfate
- the surfactant also assists wetting of the cleaning material on the substrate surface. Wetting of the cleaning material on the substrate surface allows the cleaning material to come in close contact with the substrate surface and the particles on the substrate surface. Wetting improves cleaning efficiency.
- Other additives can also be added to improve surface wetting, viscosity, substrate cleaning, rinsing, and other related properties.
- buffered cleaning solution examples include a buffered ammonium hydroxide solution (BAS), which include basic and acidic buffering agents, such as 0.44 wt% of NH 4 OH and 0.4 wt% of citric acid, in the solution.
- BAS buffered ammonium hydroxide solution
- the buffered solution such as BAS
- a solution that contains 1 wt% of ADS, 0.44 wt% of NH3, and 0.4 wt% of citric acid is called solution "100". Both solution "100" and BAS have a pH value of about 10.
- FIGS. 3A-3E provide a liquid cleaning material 300 that has the polymers 310 with large molecular weight dispersed (or dissolved) uniformly in the cleaning solution 305.
- polymers with large molecular weight for this application are completely dissolved in the cleaning solution, which can be aqueous.
- the polymers are highly water-absorbent to form soft gel in an aqueous solution.
- Figure 3F shows an embodiment of a liquid cleaning material 300' with gel-like polymer droplets 340 emulsified in the cleaning solution 305'.
- the cleaning solution 305' also contains small and isolated polymer 306.
- a surfactant such as ADS, could be added to the cleaning solution to help the gel-like polymer droplets 340 disperse uniformly in the cleaning solution 305'.
- a surfactant such as ADS
- the gel-like polymer droplets 340 are soft and deform around device features on the substrate surface. Since the gel-like polymer droplets 340 deform around device features, they do not exert large energy (or force) on the device features to damage them.
- the diameters of the droplets are between about 0.1 ⁇ m to about 100 ⁇ m.
- the polymers of one or more polymeric compounds with large molecular weights dissolve in the cleaning solution to form gel-like polymer globs (or lumps) 350, which do not establish a distinct boundary with the cleaning solution 305", as shown in Figure 3G.
- the cleaning solution 305" also contains small and isolated polymers 306.
- the gel-like polymer globs 350 are soft and deform around device features on the substrate surface, and do not exert large amount of energy (or force) to the device features on the substrate surface, which would damage them.
- the diameters of the polymer globs are between about 0.1 ⁇ m to about 100 ⁇ m.
- the cleaning materials discussed above are all in the liquid phase.
- the cleaning material such as liquid cleaning materials 300, 300', and 300" discussed above, can be agitated to add a gas, such as N 2 , an inert gas, or a mixture of gases, such as air, to make the cleaning material into a foam, as shown in Figure 3H.
- the cleaning material 300* has air bubbles 360 dispersed in the cleaning solution 305.
- Polymers 310 are also dispersed in the cleaning solution 305.
- the polymers 310 in Figure 3H can be polymer droplets 340 or polymer globs 350, described in Figures 3F and 3G.
- the cleaning material 300* has a gas phase and a liquid phase.
- the cleaning material described above can be dispensed by many mechanisms on the substrate surface. As discussed above in Figures 2A and 2B, to avoid damaging device features on the patterned substrates, the energy applied by the cleaning material on the patterned surface needs to be below the minimum force E 8 or E 8 ' to avoid damaging the device features.
- the cleaning materials, such as cleaning materials 300, 300', 300", and 300*, discussed above are either in liquid phase or in gas/liquid phases. Liquid and foam can flow on the substrate surface and deform (or flow) around the device features on the substrate surface. Therefore, the cleaning material can be applied on the patterned substrate without exerting large force on the device features on the substrate surface.
- Viscosity of liquid cleaning materials can be measured in a range of shear rate, such as between about lxl ⁇ "6 /s to about lxlO 5 /s. In one embodiment, the viscosity of the liquid cleaning material can be measured at a reference shear rate less than about 100/s. In another embodiment, the viscosity can be measured at a reference shear rate less than about 10/s. In yet another embodiment, the viscosity can be measured at a reference shear rate less than about 1/s.
- the viscosity data in Table I are measured at strain rate of 500 s "1 .
- the rinse time measures the time it takes to rinse the cleaning material off the substrate surface.
- the PRE is measured by using particle monitor substrates, which are purposely deposited with silicon nitride particles with varying sizes. In this study, only particle sizes between 90 nm and 1 ⁇ m are measured. PRE is calculated by equation (1) listed below:
- PRE (Pre-clean counts - Post-clean counts)/Pre-clean counts X 100% •(1)
- Table I Comparison of cleaning materials with different concentration of Carbopol 941 TM PAA polymers
- the cleaning materials of Table I are made by mixing Carbopol 941TM PAA, which is commercially available, with BAS as described above.
- the Carbopol 941TM PAA used has a molecular weight of 1,250,000 (or 1.25M) g/mol.
- the results in Table I show that PRE increases with weight % of Carbopol 941TM PAA until about 0.5%. There is no significant difference in PRE between 0.5% and 1% of polymers.
- the results also show that the viscosity of the cleaning material increases with the weight percentage of the polymers.
- the rinse time it takes to rinse off the cleaning material increases with the viscosity of the cleaning material. Water is used to rinse the substrates.
- Table II compares the ability of different cleaning materials in entrapping or suspending particles in the cleaning materials. Silicon nitride particles are purposely added into the cleaning materials. After being added with silicon nitride particles, the cleaning materials are dispensed on clean substrates. The cleaning materials are then rinse off of the substrate, which is then measured for the number of particles (silicon nitride) remaining on the surface.
- Table II Comparison of particle counts with different cleaning materials added with silicon nitride particles.
- the first cleaning material "DIW” is only de-ionized water.
- the second cleaning material is DIW added with ammonium hydroxide to adjust the pH value to be greater than 10.
- the third cleaning material is solution "100", which is BAS added with 1 wt% of ADS. As mentioned above, the pH value of solution "100” is 10.
- the fourth cleaning material is 0.2 wt% of Carbopol 940TM PAA dissolved in "100" solution.
- the molecular weight of Carbopol 940TM PAA is 4M (or 4 million) g/mol.
- the fifth type is 0.5 wt% of PAM dissolved in solution "100".
- the molecular weight of PAM is 18M g/mol.
- the pH value of the fifth cleaning material is about 10.
- the five types of cleaning materials are mixed with two quantities of silicon nitride particles, IX, and 5OX.
- the number of silicon nitride particles of 5OX is fifty times the number of particles of IX.
- IX nitride particles represent the nitride particle weight % is 0.00048%
- 5OX nitride particle represent the nitride particle weight % is 0.024%.
- the molecular weight of polymers used in the cleaning material can affect the particle removal efficiency (PRE).
- Figure 4A shows a graph of PRE of greater than 90nm silicon nitride particles on a substrate by cleaning materials with 1% (weight %) of PAA in "100” and 1% (weight %) of hydroxyethyl cellulose (HEC) in "100” as a function of the molecular weight of these two polymers (PAA and HEC).
- the data in Figure 4 A show that PRE increases with molecular weight of HEC between 100,000 g/mol to IM (or 1,000,000) g/mol.
- Data in Figure 4A also show that PRE increases with molecular weight for PAA between 500,000 g/mol and IM g/mol.
- FIG. 4B shows a graph of PRE of greater than 90nm silicon nitride particles on a substrate by cleaning materials with 1% (weight %) of PAM in "100" as a function of the molecular weight of PAM.
- the data in Figure 4B show that increasing the PRE increases with molecular weight of PAM between 500,000 g/mol to 18M g/mol. Data in both graphs show the effects of molecular weight on PRE.
- the viscosity of the cleaning material would affect the rinsing time to remove the cleaning material from the substrate surface.
- Figure 4C shows the results of adding ammonium chloride (NH 4 Cl) to cleaning material with 0.2 wt% -1 wt% of PAM dissolved in de-ionized (DI) water.
- the PAM has a molecular weight of 18M g/mol.
- the added ammonium chloride ionizes in the cleaning solution to provide additional ions increasing the ionic strength of the cleaning material.
- the increased ionic strength reduces the viscosity of the cleaning material.
- 1.5 wt% of ammonium chloride is able to reduce the viscosity from about 100 cP (centipoises) to 60 cP for cleaning material with 1 wt% PAM.
- 1.5 wt% of ammonium chloride is also able to reduce the viscosity for cleaning material with 0.5 wt% PAM from about 50 cP to about 25 cP. These viscosities were measured at a shear rate of 500/s. Lowering the viscosity could lower the amount of time it takes to rinse the cleaning material from the substrate surface.
- viscosity also affects how the cleaning materials are dispensed on substrate surface. Cleaning materials with higher viscosities would need to be dispensed with larger openings in comparison to cleaning materials with lower viscosities. Rinse time for cleaning materials with higher viscosities can also be reduced by more rigorous rinsing.
- Table III compares PRE, pH values, and ionic strengths data for four formulations of cleaning materials.
- the polymers in all four cleaning materials are copolymers of acrylamide and acrylic acid. The copolymers are mixed in solution "100.”
- Ammonium hydroxide is used to adjust the pH values of the cleaning materials.
- Citric acid is used to modify the ionic strengths of the cleaning materials.
- the cleaning materials in Table III also include a small amount of surfactant, ammonium dodecyl sulfate, to improve solubility of polymers in the cleaning solution and improve wetting of the cleaning materials on substrate surfaces.
- the weight percentage of acrylic acid in the copolymers is less than about 50 %.
- Table III Comparison of data of PRE, pH, and ionic strength for 4 formulations of cleaning materials.
- the data in Table III show that the four different types of cleaning materials all have very good PRE.
- the pH values for the cleaning materials in Table III vary between about 7 to about 10.
- the ionic strengths for the cleaning materials vary from about 0.15X to about IX, where X is a set value.
- the viscosities of cleaning materials with 0.15X ionic strengths are more than 5 times the viscosities of cleaning materials with IX ionic strengths.
- the viscosity data of the cleaning materials on Table III are presented and discussed below in Figure 4D.
- the cleaning materials yield very good cleaning efficiencies over wide ranges of pH values, ionic strengths and viscosities. Such wide process windows are important, since during different process steps of device manufacturing substrate surfaces might be very different and requires wide process conditions.
- the wafers used in the study of Table III are made of silicon covered by a thin layer of native oxide.
- the surfaces of these wafers are hydrophilic.
- the cleaning materials have large formulation (or process) windows.
- Table IV shows data of particle adders on hydrophobic wafer surfaces after the wafers are treated with three different formulations of cleaning materials.
- the chemical compounds (or ingredients) used in formulating cleaning materials in Table IV are the same as those used in Table III.
- the wafers in the study of Table IV are exposed to the formulations and additional particle defects resulted from the exposure are measured by a commercial light scattering tool and classified as adders. The fewer the particle defects added the better the process will be.
- 95% CI represents 95% confidence interval. Numerous wafers are processed to obtain the data with 95% CL
- Table IV Comparison of data of particle adders, pH, and ionic strength for 3 formulations of cleaning materials.
- the data in Table IV show that for hydrophobic surfaces, cleaning materials with lower ionic strength and lower pH show better particle adder results.
- the results in Table III and Table IV show that different substrate surfaces may require different formulations of cleaning materials.
- the results also indicate that for some applications, low ionic strength could be needed to achieve good cleaning results. These applications may include processes where hydrophobic surfaces are encountered, such as photoresist, poly- silicon, low-k dielectric, or porous low-k dielectric, etc. Since lower ionic strength increase viscosity of cleaning materials, it would be necessary to have a cleaning system and method that work with the cleaning materials described above that have higher viscosity.
- Figure 4D shows viscosity data of the cleaning materials described above with different pH values and different ionic strengths, in accordance with one embodiment of the present invention.
- the data show that lower ionic strength results in higher viscosity.
- the viscosities of the cleaning materials are measured at 0.1/s shear rate. For example, viscosities measured at less than about 1/s ( ⁇ 1/s) are considered to be measured at low shear rates.
- IX normal ionic strength
- the viscosity increases with the pH value of the cleaning material.
- low ionic strength (0.15X) the viscosity decreases with the pH value.
- the range of low shear viscosity of the cleaning materials with polymers is between 10 cP to about 100,000 cP. In another embodiment, the range of low shear viscosity of the cleaning materials is between about 100 cP to about 10,000 cP.
- the process window of viscosities of the cleaning materials can be widened by making changes in equipment design and process conditions. For example, the dispense openings for the cleaning materials can be made larger to allow cleaning materials to be applied (or dispensed) on the substrates at reasonable rates.
- the apparatus for delivering and removing the rinse liquid can be designed to allow more rigorous rinsing to shorten the rinse time for cleaning materials with higher viscosities.
- FIG. 5A shows a system for cleaning contaminants from a substrate, in accordance with one embodiment of the present invention.
- the system includes a chamber 500 defined by enclosing walls 501.
- the chamber 500 includes an input module 519, a processing module 521, and an output module 523.
- a substrate carrier 503 and corresponding drive apparatus is defined to provide linear movement of a substrate 502 from the input module 519, through the processing module 521, to the output module 523, as indicated by arrow 507.
- a drive rail 505A and a guide rail 505B are defined to provide for controlled linear movement of the substrate carrier 503, such that the substrate 502 is maintained in a substantially horizontal orientation along a linear path defined by the drive rail5105A and guide rail 505B.
- the input module 519 includes a door assembly 513 through which the substrate 502 can be inserted into the chamber 500 by a substrate -handling device.
- the input module 519 also includes a substrate lifter 509 defined to move vertically through an open region of the substrate carrier 503, when the substrate carrier 503 is centered thereover in the input module 519.
- the substrate lifter 509 can be raised to receive the substrate 502 when inserted into the chamber 500 through the door assembly 513.
- the substrate lifter 509 can then be lowered to place the substrate 502 on the substrate carrier 503.
- the processing module 521 includes an upper processing head 517 disposed to process a top surface of the substrate 502 as the substrate carrier 503, with the substrate 502 positioned thereon, moves beneath the upper processing head 517.
- the processing module 521 also includes a lower processing head 518 (see Figure 5B) disposed below the linear travel path of the substrate carrier 503 opposite the upper processing head 517.
- the lower processing head 518 is defined and positioned to process a bottom surface of the substrate 502 as the substrate carrier 503 moves through the processing module 521.
- Each of the upper and lower processing heads 517 and 518 has a leading edge 541 and trailing edge 543, such that during a processing operation the substrate carrier 503 moves the substrate 502 along the linear path from the leading edge 541 toward the trailing edge 543.
- each of upper and lower processing heads 517 and 518 are defined to perform a multi-stage cleaning process on the top and bottom surfaces of the substrate 502, respectively.
- one or more additional processing heads may be used in conjunction with the upper processing head 517 above the linear travel path of the substrate carrier 503, and/or one or more additional processing heads may be used in conjunction with the lower processing head 518 below the linear travel path of the substrate carrier 503.
- processing heads defined to perform a drying process on the substrate 502 may be positioned behind the trailing edges of the upper and lower processing heads 517 and 518, respectively.
- the output module 515 includes a substrate lifter 511 defined to move vertically through the open region of the substrate carrier 503, when the substrate carrier 503 is centered thereover in the output module 511.
- the substrate lifter 511 can be raised to lift the substrate 502 from the substrate carrier 503 to a position for retrieval from the chamber 500.
- the output module 511 also includes a door assembly 515 through which the substrate 502 can be retrieved from the chamber 500 by a substrate-handling device.
- Figure 5B shows a vertical cross-section view of the chamber 500 with the substrate carrier 503 located beneath the upper processing head 517 and above the lower processing head 518, in accordance with one embodiment of the present invention.
- the upper processing head 517 is mounted to both the drive rail 505A and the guide rail 505B, such that a vertical position of the upper processing head 517 is indexed to both a vertical position of the drive rail 505A and a vertical position of the guide rail 505B, and is thereby indexed to a vertical position of the substrate carrier 503 and substrate 502 held thereon.
- the upper processing head 517 is defined to perform a cleaning process on the top surface of the substrate 502 as the substrate carrier 503 moves the substrate 502 thereunder.
- the lower processing head 518 is defined to perform a rinsing process on the bottom surface of the substrate 502 as the substrate carrier 503 moves the substrate 502 thereover.
- each of the upper and lower processing heads 517 and 518 within the processing module 521 can be defined to perform one or multiple substrate processing operations on the substrate 502.
- the upper and lower processing heads 517 and 518 within the processing module 521 are defined to span a diameter of the substrate 502, such that one pass of the substrate carrier 503 under/over the upper/lower processing heads 517/518 will process an entirety of the top/bottom surface of the substrate 102.
- FIG. 5C shows a cross-sectional view of the upper processing head 517 positioned above the substrate 502 with the lower processing head 518 positioned below the substrate 502 opposite the upper processing head 517, in accordance with one embodiment of the present invention.
- the upper processing head 517 includes a first topside module 517A operating to apply a cleaning material 56 IA through the cleaning material dispense port 529A to the substrate 502.
- the upper processing head 517 also includes a second topside module 517B operating to apply a cleaning material 561B through the cleaning material dispense port 529B to the substrate 502.
- the chemical components of the cleaning material 56 IA can be same or different from those of the cleaning material 561B.
- the cleaning material dispense ports 529A and 529B are long slits along the length of the upper processing head 517.
- rinsing material dispense port 541 A/54 IB supply rinsing material on the trailing side of the rinsing meniscus, while a first row of vacuum ports 547A/547B removes fluid on the leading side of the rinsing meniscus. Because the first row of vacuum ports 547A/547B is provided at the leading side of the rinsing meniscus, as opposed to being provided at both the leading and trailing sides, ports within the row of rinsing fluid supply ports 541 A/54 IB are angled downward toward the first row of vacuum ports 547A/547B.
- each of the first and second topside modules 517A/517B includes a second row of vacuum ports 549A/549B defined along a trailing side of the first row of vacuum ports 547A/547B.
- the second row of vacuum ports 549A/549B is defined to provide multi-phase suction of the cleaning material and the rinsing material from the substrate when present thereunder.
- the second row of vacuum ports 549A/549B can be controlled independently from the first row of vacuum ports 547A/547B.
- the ports of the second row of vacuum ports 549A/549B are defined as single phase liquid return ports and are configured to avoid disruption of the rinsing fluid meniscus stability.
- the first topside module 517A operates to flow the rinsing material through the topside rinsing meniscus 563A in a substantially uni-directional manner towards the cleaning material 56 IA and opposite a direction 560 of movement of the substrate 502.
- a flow rate of rinsing material through the topside rinsing meniscus 563A is set to prevent cleaning material leakage past the topside rinsing meniscus 563 A.
- the first topside module 517A leaves a uniform thin film of rinsing material 565 on the substrate 502.
- the second topside module 517B of the upper processing head 517 operates to apply cleaning material 56 IB to the substrate 502, and then expose the substrate 502 to a topside rinsing meniscus 563B.
- the second topside module 517B operates to flow the rinsing material through the topside rinsing meniscus 563B in a substantially uni-directional manner towards the cleaning material 56 IB and opposite the direction 560 of movement of the substrate 502.
- a flow rate of rinsing material through the topside rinsing meniscus 563B is set to prevent cleaning material leakage past the topside rinsing meniscus 563B.
- the second topside module 517B leaves a uniform thin film of rinsing material 567 on the substrate 502.
- the first bottomside module 518A of the lower processing head 518 operates to apply a bottomside rinsing meniscus 569A to the substrate 502 so as to balance a force applied to the substrate 502 by the topside rinsing meniscus 563A.
- the first bottomside module 518A operates to flow the rinsing material through the bottomside rinsing meniscus 569A in a substantially uni-directional manner opposite the direction 560 of movement of the substrate 502.
- the first bottomside module 518A leaves a uniform thin film of rinsing material 571 on the substrate 502.
- the second bottomside module 518B of the lower processing head 518 operates to apply a bottomside rinsing meniscus 569B to the substrate 502 so as to balance a force applied to the substrate 502 by the topside rinsing meniscus 563B.
- the second bottomside module 518B operates to flow the rinsing material through the bottomside rinsing meniscus 569B in a substantially uni-directional manner opposite the direction 560 of movement of the substrate 502.
- the second bottomside module 518B leaves a uniform thin film of rinsing material 573 on the substrate 502.
- Each of the first and second bottomside modules 518A/518B includes a respective row of rinsing material dispense ports 551 A/55 IB defined within the respective rinsing meniscus region 569A/569B.
- Each row of rinsing material dispense ports 551 A/55 IB is defined to dispense a rinsing material upward onto the substrate when present thereabove.
- the rinsing material is deionized water (DIW).
- DIW deionized water
- the rinsing material can be one of many different materials in liquid state, such as dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), dimethyl acetate (DMAC), a polar solvent easy mixable with DIW, an atomized liquid such as an atomized polar solvent (e.g., DIW), or any combination thereof.
- DMSO dimethyl sulfoxide
- DMF dimethyl formamide
- DMAC dimethyl acetate
- DIW dimethyl acetate
- a polar solvent easy mixable with DIW such as an atomized polar solvent (e.g., DIW)
- DIW atomized polar solvent
- FIG. 5D shows a cleaning system 550 with a substrate cleaning chamber 500', in accordance with one embodiment of the present invention.
- the substrate cleaning chamber 500' is similar to the chamber 500 described above.
- chamber 500' there is a substrate 502' held by a substrate carrier 503'.
- the substrate cleaning chamber 500' has an upper processing head 517' and a lower processing head 518'.
- the upper processing head 517' is held by an arm 581 and the lower processing head 518' is held by an arm 581'.
- the cleaning material with polymers is supplied to the upper processing head 517 via supply line 595.
- the rinsing material such as de-ionized water (DIW) is supplied to the upper processing head via supply line 597.
- DIW de-ionized water
- the cleaning waste is removed from the substrate 502' via waste line 596.
- the rinsing material is supplied to the lower processing head 518' via supply line 599.
- the rinsing waste is removed via waste line 598.
- the supply lines 595, 597, 599, and waste lines 596, 598 are coupled to a proximity head manifold 583.
- the proximity head manifold 583 is also coupled to a container 584 of the rinsing material, a container 585 for the cleaning material, and a waste container 586.
- the waste container 586 is further coupled to a vacuum pump 587.
- the proximity head manifold 583 is coupled to a proximity head controller 588, which is then controlled by a computer 590. An operator can make controlling command via the computer 590.
- the proximity head controller 588 is connected to the computer 590 via Internet 589.
- the ambient of the substrate cleaning chamber 500' can also be controlled.
- One or more types of gases can be supplied to chamber 500'.
- a gas tank 593 can be coupled to chamber 500'.
- the pressure of chamber 500' can also be maintained via a vacuum pump 594.
- the flow of gas from gas tank 593 and the vacuuming of chamber 500' can be controlled by a chamber manifold 592, which is coupled to an ambient controller 591.
- the ambient controller 591 can also be coupled to the computer 590.
- FIG. 6A shows a cleaning tank 680 containing cleaning material 681 and a rinsing tank 690 containing rinse liquid 691, in accordance with one embodiment of the present invention.
- Substrate 620' held by a substrate carrier 623, is first dipped into the cleaning material 481 of tank 680 to allow the cleaning material to be in contact with the contaminants on the substrate surface.
- Substrate 620' is lowered into and raised out of the cleaning material 681 in cleaning tank 680 by a mechanical mechanism (not shown).
- the substrate 620' held by a substrate carrier 626, is then dipped into the rinse liquid 691 of cleaning tank 690 to rinse off the cleaning material.
- a mechanical mechanism (not shown) is used to lower and raise the substrate into and out of the rinse tank 690.
- the cleaning material leaves the surface of substrate 620' in rinse tank (or rinsing tank) 690, the contaminants are removed from the substrate surface along with the cleaning material.
- Substrate 620' is lowered into the rinse liquid 691 in rinse tank 690 by a mechanical mechanism (not shown).
- the orientation of the substrate shown in Figure 6A is vertical, other orientation is also possible.
- the substrate can be submerged in the cleaning tank and/or the rinse tank in a horizontal orientation.
- Figure 6B shows another embodiment of a cleaning apparatus 699 for cleaning contaminants from the surface of the substrates.
- the cleaning apparatus has a cleaning tank 685 with a substrate support 683.
- Substrate 620* is placed on the substrate support 683, which rotates during the cleaning process.
- the cleaning apparatus 699 has a cleaning material dispensing head 697, which dispenses cleaning material on the surface of substrate 620*.
- the cleaning material dispensing head 697 (or a dispensing nozzle) is coupled to a storage tank 670 of cleaning material.
- the cleaning apparatus 699 also has a rinse liquid dispensing head 698 (or a dispensing nozzle), which sprays rinse liquid on the surface of the substrate 620".
- the rinse liquid dispensing head 698 is coupled to a storage tank 696 of the rinse liquid.
- the rotating substrate 620* allows the cleaning material and the rinse liquid to cover the entire substrate surface. The cleaning material is dispensed on the substrate surface before the rinse liquid is dispensed to remove the cleaning material from the substrate surface.
- the patterned substrate is dried by spinning (or rotating) the substrate at a relatively high speed. During the spinning, the substrate is secured by a device (or mechanism), which is not shown in Figure 6B.
- a surface tension reducing gas is applied on the surface of the patterned substrate to assist in removing the rinse and possibly residual cleaning material.
- the surface tension reducing gas includes a mixture of isopropyl alcohol (IPA) and nitrogen (N 2 ). Other surface tension reducing gases can also be used.
- the cleaning tank 685 can receive waste of the cleaning process.
- the waste of the cleaning process includes waste cleaning material and waste rinse liquid.
- the cleaning tank 685 has a drainage hold 603, which is connected to a waste line 604.
- Waste line 604 is coupled to a valve 605, which controls the draining of cleaning waste from the cleaning tank 685.
- the cleaning waste can be directed to a recycling processor 606 or a waste processor 607.
- the cleaning materials described above have special advantages in cleaning substrates with fine features (or topologies), such as polysilicon lines or metallic interconnects (with trenches and/or vias), on the substrate surface.
- the smallest width (or critical dimension) of these fine features can be 45 nm, 32 nm, 22 nm, 16 nm or less.
- FIG. 7A shows a process flow 700 of preparing a cleaning material containing one or more polymeric compounds with large molecular weights, in accordance with one embodiment of the present invention.
- one or more polymeric compounds is mixed with a solvent.
- the one or more polymeric compounds are in powder form and the amount is pre-measured. Before the mixing process, the amount of the one or more polymeric compounds is calculated and weighted. Similarly, the amount of solvent used in also measured.
- additives are mixed in with the mixture prepared at operation 701 to adjust the properties of the prepared cleaning material.
- the additives may include a buffering agent for adjusting the pH value of the cleaning material.
- the additives may also include an ion-providing compound for adjusting the viscosity of the cleaning material. Further, the additives may include a surfactant for improving the solubility of the polymeric compounds and/or to assist wetting the surface of the patterned substrate by the cleaning material. Other types of additives can also be included to adjust the properties of the cleaning material.
- the cleaning material can have a targeted pH value, a targeted viscosity, and other desired properties, such as solubilized polymers and good wetting characteristics.
- the operable pH range and viscosity range could be very wide.
- the mixing of the surfactant, buffering agent, and the ion-providing compound can occur in various sequential steps.
- the different ingredients used for preparing the cleaning material can be mixed in one single process step.
- Figure 7B shows a process flow 750 of cleaning a patterned substrate using a cleaning material containing one or more polymeric compounds with large molecular weights, in accordance with one embodiment of the present invention.
- the cleaning material is described above.
- the patterned substrate is place in a cleaning apparatus.
- the cleaning material is dispensed on the surface of the patterned substrate.
- a rinse liquid is dispensed on the surface of the patterned substrate to rinse off the cleaning material.
- the rinse liquid is described above. In one embodiment, after the rinse liquid is applied on the substrate surface, the rinse liquid, the cleaning material, and the contaminants on the substrate surface can be removed from the surface of the patterned substrate by vacuum.
- the cleaning materials, apparatus, and methods discussed above have advantages in cleaning patterned substrates with fine features without damaging the features.
- the cleaning materials are fluidic, either in liquid phase, or in liquid/gas phase (foam), and deform around device features; therefore, the cleaning materials do not damage the device features.
- the cleaning materials in the liquid phase can be in the form of a liquid, a sol, or a gel.
- the cleaning materials containing polymers with large molecular weight(s) capture the contaminants on the substrate.
- the cleaning materials entrap the contaminants and prevent the contaminants from returning to the substrate surface.
- the polymers form long polymer chains, which can also be cross-linked to form a network of polymers. The long polymer chains and/or polymer network show superior capabilities of capturing and entrapping contaminants, in comparison to conventional cleaning materials.
- the cleaning material is substantially free of non-deformable particles (or abrasive particles), before it is applied on the substrate surface to remove contaminants or particles from the substrate surface.
- Non-deformable particles are hard particles, such as particles in a slurry or sand, and can damage fine device features on the patterned substrate. During the substrate cleaning process, the cleaning material would collect contaminants or particles from the substrate surface. However, no non-deformable particles have been intentionally mixed in the cleaning material before the cleaning material is applied on the substrate surface for substrate cleaning.
- the discussion above is centered on cleaning contaminants from patterned wafers, the cleaning apparatus and methods can also be used to clean contaminants from un-patterned wafers.
- the exemplary patterns on the patterned wafers discussed above are protruding lines, such as polysilicon lines, metal lines, or dielectric lines.
- the concept of the present invention can apply to substrates with recessed features. For example, recess trenches or vias after CMP can form a pattern on the wafer and a most suitable design of cleaning head can be used to achieve the best contaminant removal efficiency.
- a substrate denotes without limitation, semiconductor wafers, hard drive disks, optical discs, glass substrates, flat panel display surfaces, and liquid crystal display surfaces, etc., which may become contaminated during manufacturing or handling operations. Depending on the actual substrate, a surface may become contaminated in different ways, and the acceptable level of contamination is defined in the particular industry in which the substrate is handled.
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US9926518B2 (en) | 2014-01-31 | 2018-03-27 | 3M Innovative Properties Company | Aqueous composition suitable for cleaning and protection comprising silica nanoparticles, copolymer of acrylamide and acrylic acid, nonionic and anionic surfactant |
US10273435B2 (en) | 2014-01-31 | 2019-04-30 | 3M Innovative Properties Company | Aqueous composition suitable for cleaning and protection comprising silica nanoparticles, copolymer of acrylamide and acrylic acid, nonionic and anionic surfactant |
US10414941B2 (en) | 2015-03-13 | 2019-09-17 | 3M Innovative Properties Company | Composition suitable for protection comprising copolymer and hydrophilic silane |
US10916435B2 (en) | 2016-03-30 | 2021-02-09 | Fujimi Incorporated | Surface treatment composition, method of producing surface treatment composition, method of treating surface, and method of producing semiconductor substrate |
US11135624B2 (en) | 2018-04-10 | 2021-10-05 | Semes Co., Ltd. | Method and apparatus for substrate cleaning |
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TWI487785B (en) | 2015-06-11 |
TW201132754A (en) | 2011-10-01 |
KR20120048562A (en) | 2012-05-15 |
CN102471726A (en) | 2012-05-23 |
SG177270A1 (en) | 2012-02-28 |
JP2012533649A (en) | 2012-12-27 |
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