CN113980747A - Cleaning agent for semiconductor material surface degreasing treatment - Google Patents
Cleaning agent for semiconductor material surface degreasing treatment Download PDFInfo
- Publication number
- CN113980747A CN113980747A CN202111326662.4A CN202111326662A CN113980747A CN 113980747 A CN113980747 A CN 113980747A CN 202111326662 A CN202111326662 A CN 202111326662A CN 113980747 A CN113980747 A CN 113980747A
- Authority
- CN
- China
- Prior art keywords
- percent
- semiconductor material
- cleaning agent
- cleaning
- degreasing treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005238 degreasing Methods 0.000 title claims abstract description 53
- 239000004065 semiconductor Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 45
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 21
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 17
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011591 potassium Substances 0.000 claims abstract description 11
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 11
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims abstract description 8
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 24
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000010453 quartz Substances 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- CQBPOPVKDNHISM-UHFFFAOYSA-N propane-1,2,3-triol;propan-2-one Chemical compound CC(C)=O.OCC(O)CO CQBPOPVKDNHISM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical group [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- CQAIPTBBCVQRMD-UHFFFAOYSA-L dipotassium;phosphono phosphate Chemical compound [K+].[K+].OP(O)(=O)OP([O-])([O-])=O CQAIPTBBCVQRMD-UHFFFAOYSA-L 0.000 claims description 7
- -1 hydroxide compound Chemical class 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 229940048084 pyrophosphate Drugs 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 125000005227 alkyl sulfonate group Chemical group 0.000 claims description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical group [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 229940087291 tridecyl alcohol Drugs 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 87
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 abstract description 8
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 abstract description 4
- 230000005611 electricity Effects 0.000 abstract description 3
- 238000007127 saponification reaction Methods 0.000 abstract description 3
- 230000003068 static effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 63
- 238000005406 washing Methods 0.000 description 62
- 229910052710 silicon Inorganic materials 0.000 description 46
- 239000010703 silicon Substances 0.000 description 46
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- 238000000034 method Methods 0.000 description 28
- 239000002253 acid Substances 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 230000002378 acidificating effect Effects 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 15
- 235000012431 wafers Nutrition 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 238000001000 micrograph Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- GICQWELXXKHZIN-UHFFFAOYSA-N 2-[2-[(2-methylpropan-2-yl)oxy]ethoxy]ethanol Chemical compound CC(C)(C)OCCOCCO GICQWELXXKHZIN-UHFFFAOYSA-N 0.000 description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 5
- 230000003749 cleanliness Effects 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QEOWFDYSNYCPRK-UHFFFAOYSA-N OCC[Na] Chemical compound OCC[Na] QEOWFDYSNYCPRK-UHFFFAOYSA-N 0.000 description 1
- 229920013813 TRITON H-66 Polymers 0.000 description 1
- 239000005842 Thiophanate-methyl Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- QGHREAKMXXNCOA-UHFFFAOYSA-N thiophanate-methyl Chemical group COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC QGHREAKMXXNCOA-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C11D1/83—Mixtures of non-ionic with anionic 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/2096—Heterocyclic 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
- C11D1/24—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds containing ester or ether groups directly attached to the nucleus
-
- 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
- C11D1/02—Anionic compounds
- C11D1/34—Derivatives of acids of phosphorus
-
- 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
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
The invention relates to a cleaning agent for semiconductor material surface degreasing treatment, which comprises, by mass, 2.1% -3.3% of hydroxide, 1.5% -4.5% of carbonate, 2.1% -3.9% of pyrophosphate, 1.8% -3% of potassium tripolyphosphate, 4.5% -6.3% of acetonide, 1.2% -3% of anionic surfactant and 2.7% -5.4% of nonionic surfactant, wherein a solvent is water. The preparation method comprises the following steps of (1) preparing a mixture by a proper component ratio and an anionic surfactant and a nonionic surfactant: 1.8-1:3, the combination of the acetone and the glycerol can more effectively promote the saponification reaction to remove oil stains, and achieve better effects of removing particles, static electricity and the like. The cleaning agent for degreasing the surface of the semiconductor material is matched with the metal ion cleaning solution for cleaning, so that the metal ions can be removed more effectively.
Description
Technical Field
The invention belongs to the technical field of semiconductor materials, and relates to a cleaning agent for degreasing the surface of a semiconductor material.
Background
In a flat panel display such as a TFT liquid crystal display, a micro information processor, a display device, a,In the manufacture of semiconductor devices such as memory and CCD, silicon and silicon oxide (SiO)2) And glass, etc. are patterned or formed into a thin film with a dimension of submicron to 1/4 μm. Therefore, in each step of these manufacturing processes, it is an extremely important subject to remove even minute contamination on the substrate surface and to highly clean the substrate surface; the same equipment consumables also need highly clean, and the product that uses in the engineering should clear away the factor that causes the influence to the particulate matter through cleaning process as key management and control object in the semiconductor engineering. With the development of very large scale integrated circuits, the integration level is continuously improved, the line width is continuously reduced, and the requirements on the cleanliness and the surface state of the silicon wafer surface are higher and higher. With the increasing demand, it is required to remove the contamination on the silicon wafer surface, and the surface chemical state, oxide film thickness, surface roughness, etc. caused during the cleaning process become the same important parameters in order to obtain a high quality semiconductor device. At present, electronic component failures due to poor cleaning have exceeded more than half of the total losses in integrated circuit manufacturing. At present, the main application cleaning method is improved and evolved on the basis of the RCA cleaning technology proposed by Werner in 1970. Soaking and cleaning are carried out in a strong acid mixing mode, and APM is used for removing particles, partial organic matters and partial metals on the surface of the silicon wafer, but the solution can increase the roughness of the surface of the silicon wafer. HPM and DHF are used for removing metal contamination on the surface of a silicon wafer, but HPM uses high-concentration strong acid, is easy to decompose and volatilize, and has poor stability in the using process, low service life and quick solution cleaning capability failure. Therefore, the currently used RCA cleaning process needs to use a lot of chemical reagents which are not friendly to the environment, and if the RCA cleaning process is used in a large scale, the damage to the environment is serious. Moreover, the SC1 solution is found to be effective in removing particles on the surface of semiconductor silicon, but brings about other foreign metal impurity contaminant sources, such as iron, zinc, aluminum and the like. The SC1 solution can substantially remove particles having a particle size greater than 0.5 μm from the surface of the silicon body, but rather increases the deposition of particles having a particle size less than 0.5 μm. There is therefore a great need for improvements in the cleaning processes for semiconductor materials. SiliconThe cleanliness of the sheet surface plays a crucial role in the production of electronic devices and in improving the performance, reliability and stability of the products. Therefore, in order to meet the increasing demands for surface quality of electronic devices, it is urgently needed to develop a cleaning process and a related cleaning agent which are simple in operation, less in cleaning steps, small in amount of used chemical reagents, low in cleaning liquid concentration and environment-friendly.
Disclosure of Invention
In view of the above, the present invention provides a simple cleaning agent for degreasing semiconductor material surface, which has the advantages of simple raw material, low use concentration, low industrial cost and no environmental pollution.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the cleaning agent for the surface degreasing treatment of the semiconductor material comprises the following components in percentage by mass: 2.1 to 3.3 percent of hydroxide compound, 1.5 to 4.5 percent of carbonate, 2.1 to 3.9 percent of pyrophosphate, 1.8 to 3 percent of potassium tripolyphosphate, 4.5 to 6.3 percent of acetone glycerol, 1.2 to 3 percent of anionic surfactant, 2.7 to 5.4 percent of nonionic surfactant and the balance of water.
Further, in the cleaning agent for semiconductor material surface degreasing treatment, the mass ratio of the anionic surfactant to the nonionic surfactant is 1:1.8-1: 3.
furthermore, in the cleaning agent for degreasing the surface of the semiconductor material, the anionic surfactant is a sulfonic acid anionic surfactant.
Further, the anionic surfactant is sodium dodecyl diphenyl ether disulfonate, sodium dodecyl benzene sulfonate, sodium fatty alcohol isethionate, secondary alkyl sulfonate and alpha-alkenyl sulfonate.
Further, the cleaning agent for semiconductor material surface degreasing treatment is characterized in that the nonionic surfactant is H-66 and vinyl ether nonionic surfactant.
Further, the vinyl ether nonionic surfactant is heterogeneous lauryl polyoxyethylene ether, nonyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, heterogeneous tridecanol polyoxyethylene ether, lauryl polyoxyethylene ether and fatty amine polyoxyethylene ether.
Further, the cleaning agent for the semiconductor material surface degreasing treatment comprises the following components in percentage by mass: 2.6 to 3 percent of hydroxide compound, 2.6 to 3.6 percent of carbonate, 2.1 to 3.5 percent of pyrophosphate, 2 to 2.6 percent of potassium tripolyphosphate, 4.5 to 5.5 percent of acetone glycerol, 1.4 to 1.8 percent of anionic surfactant, 2.7 to 5.4 percent of nonionic surfactant and the balance of water.
Furthermore, in the cleaning agent for degreasing the surface of the semiconductor material, the hydroxide compound is sodium hydroxide or potassium hydroxide, the carbonate is sodium carbonate or potassium carbonate, and the pyrophosphate is sodium pyrophosphate or potassium pyrophosphate or dipotassium dihydrogen pyrophosphate.
Further, the cleaning agent is used for degreasing the surface of a semiconductor material, wherein the semiconductor material is a silicon material, a quartz material or a ceramic material.
2. The cleaning agent for surface degreasing treatment is applied to processing of semiconductor materials.
Further, the semiconductor material is a silicon material, a quartz material or a ceramic material.
The invention has the beneficial effects that: the cleaning agent provided by the invention is suitable for surface degreasing treatment of semiconductor materials such as silicon, quartz, ceramics and the like, has the advantages of simple raw materials, low use concentration, low industrial cost, no environmental pollutants, good performance stability of the cleaning agent, no decomposition and volatilization, long service life of the cleaning agent, small corrosion to silicon products and no increase of Ra of the cleaned products. According to the invention, through the combination of the hydroxide compound, the carbonate, the pyrophosphate, the potassium tripolyphosphate, the acetonide, the anionic surfactant and the nonionic surfactant, the chemical activity of unsaturated chemical bonds on the surface of the silicon wafer is reduced, the surface contamination of semiconductor materials such as a silicon polished wafer is effectively removed, and the cleanliness of the semiconductor materials is improved. In particular with anionic and nonionic surfactants 1:1.8-1:3, the combination of the acetone and the glycerol can more effectively promote the saponification reaction to remove oil stains, and achieve better effects of removing particles, static electricity and the like. The alkaline degreasing washing liquid and the metal ion cleaning solution are matched for cleaning, so that metal ions adsorbed on a semiconductor material can be more effectively removed.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is an appearance diagram of 2 samples before and after degreasing and cleaning.
FIG. 2 is a 1000-fold high-definition digital microscope image of a silicon wafer sample after degreasing and cleaning.
Fig. 3 shows different samples for the test: sample weight and Ra data before and after degreasing cleaning of silicon etched surface, silicon processed surface, and quartz processed surface.
FIG. 4 is a comparison of 1000 times high-definition digital microscope images before and after degreasing and cleaning of different samples.
FIG. 5 is a comparison of the appearance of the silicon ring sample before and after degreasing and cleaning.
FIG. 6 is a comparison of 1000 times high-definition digital microscope images of a silicon ring sample before and after degreasing and cleaning.
FIG. 7 is a high definition digital microscope image of a sample before and after the quartz plate is cleaned with an acid A wash after etching.
FIG. 8 is a high definition digital microscope image of a sample before and after rinsing the silicon polished surface with an acid A rinse.
FIG. 9 is a microscopic view of a silicon processed surface and a quartz surface before and after a neutral washing liquid treatment.
FIG. 10 is a high definition digital microscope (2000X) of the silicon etched surface before and after washing with acidic B wash.
FIG. 11 shows the appearance of the etched silicon ring before cleaning, with microscopic regions marked.
FIG. 12 is a microscopic comparison of a silicon ring after being washed with an alkaline degreasing wash solution and then washed with pure water before being washed.
FIG. 13 is a comparison of the microstructure of a silicon ring after washing with an acid A wash solution and then with pure water before washing.
FIG. 14 is a comparison of the microstructure of a silicon ring after being washed with a neutral washing liquid and then washed with pure water before being washed.
FIG. 15 is a comparison of the microstructure of a silicon ring after washing with an acidic B washing solution and then with pure water before washing.
FIGS. 16-19 are the results of analysis and detection of residual metal elements on the surface of different samples after treatment.
Fig. 20 is a result of analyzing and detecting residual metal elements on the surface of the silicon ring after RCA cleaning.
Fig. 21 and 22 are high-definition microscope images of the samples after RCA cleaning.
FIGS. 23 and 24 are appearance diagrams of test samples of other cleaning methods in the course of the study of the present invention, FIG. 23 is a silicon product, and FIG. 24 is a quartz polishing surface.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention more clear, the technical solutions in the preferred embodiments of the present invention will be described in detail, in a complete and complete manner, with reference to the accompanying drawings. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. The experimental procedures, in which specific conditions are not specified in the examples, are generally carried out under conventional conditions or under conditions recommended by the manufacturers.
Example 1
The alkaline degreasing washing liquid is suitable for silicon, quartz and ceramic semiconductor materials:
3% of potassium hydroxide, 3.6% of potassium carbonate, 2.1% of dipotassium dihydrogen pyrophosphate, 2% of potassium tripolyphosphate, 4.5% of acetone glycerol, 1.8% of sodium dodecyl diphenyl ether disulfonate, H-662.5% (Tao's chemical TRITON H-66), 2% of fatty amine polyoxyethylene ether and the balance of water; all percentages are calculated as mass volume percentages, the same below. Immersing a plurality of silicon product samples (etched quartz wafers, silicon wafers, polished silicon wafers, silicon processing surfaces, quartz processing surfaces, P-type monocrystalline silicon, polycrystalline silicon and the like respectively) into the alkaline degreasing washing solution, soaking and washing by using ultrasonic waves, controlling the temperature at 35-50 ℃, washing for about 15-20 minutes, and washing by using deionized water after washing. After cleaning, no grease residue is seen from the appearance of the product, and no obvious foreign matter is seen at 1000X on a microscopic scale. The ultrasonic frequency is 40-50Hz, preferably 45 Hz. In the silicon product cleaning process, the efficient cleaning agent liquid plays an important key role in the cleaning technology process, and ultrasonic cleaning further assists in cleaning cleanliness and facilitates operation procedures.
In actual industrial production, the substances can be prepared according to the following proportion range, and the diluted solution is diluted to the original concentration of 30% for use, so that the original solution is convenient to prepare and store, and the industrial batch production is facilitated. In this example, a basic degreasing washing solution is prepared: 10% of potassium hydroxide, 12% of potassium carbonate, 7% of dipotassium dihydrogen pyrophosphate, 6.667% of potassium tripolyphosphate, 15% of acetone glycerol, 6% of sodium dodecyl diphenyl ether disulfonate, H-668.334%, 6.667% of fatty amine polyoxyethylene ether and the balance of deionized water.
In the alkaline degreasing washing liquid suitable for silicon, quartz and ceramic semiconductor materials, proved by experiments, the ratio of potassium hydroxide: 2.1% -3.3%, potassium carbonate: 1.5% -4.5%, dipotassium dihydrogen pyrophosphate: 2.1% -3.9%, potassium tripolyphosphate: 1.8% -3%, acetone glycerol: 4.5-6.3%, sodium dodecyl diphenyl ether disulfonate 1.2-3%, H-66: 1.5% -3%, fatty amine polyoxyethylene ether: 1.2 to 2.4 percent of deionized water; within the range, the degreasing and cleaning effects are better. Wherein the sodium dodecyl diphenyl ether disulfonate can also be replaced by sulfonic anionic surfactants such as sodium dodecyl benzene sulfonate, fatty alcohol hydroxyethyl sodium sulfonate, secondary alkyl sodium sulfonate, alpha-alkenyl sodium sulfonate and the like, and the preferred sodium dodecyl diphenyl ether disulfonate is sodium dodecyl diphenyl ether disulfonate. The nonionic surfactant is H-66 and vinyl ether nonionic surfactant, the fatty amine polyoxyethylene ether can be replaced by isomeric dodecyl alcohol polyoxyethylene ether (basf XP-50), nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether and other nonionic surfactants, and the preferable fatty amine polyoxyethylene ether is selected. In the invention, preferably, the anionic surfactant and the nonionic surfactant are matched in a ratio of 1:1.8-1:3, and are combined with the acetonide, so that the saponification reaction is effectively promoted to remove oil stains, and better effects of removing particles, static electricity and the like are achieved, and the ratio of the anionic surfactant to the nonionic surfactant is more preferably 1: 2.5.
Example 2
The alkaline degreasing washing liquid is suitable for silicon, quartz and ceramic semiconductor materials:
3% of potassium hydroxide, 4% of potassium carbonate, 3% of dipotassium dihydrogen pyrophosphate, 2.8% of potassium tripolyphosphate, 5.2% of acetone glycerol, 1.6% of sodium dodecyl diphenyl ether disulfonate, H-662%, 1.6% of fatty amine polyoxyethylene ether and the balance of deionized water; a plurality of silicon product samples (same as the example 1) are immersed into the alkaline degreasing washing solution, and are cleaned by ultrasonic soaking, the temperature is controlled to be 35-50 ℃, the cleaning time is about 15-20 minutes, and the silicon product samples are washed by deionized water after cleaning.
The samples after degreasing treatment in example 1 and example 2 are tested, fig. 1 is an appearance diagram before and after degreasing and cleaning 2 silicon wafer samples, and the third row is a comparative diagram for cleaning under the same conditions of a certain commercial degreasing solution, and as can be seen from the diagram, the effect is obviously better than that of a commercial product. FIG. 2 is a 1000-time high-definition digital microscope image of a silicon wafer sample after degreasing and cleaning, the weight and Ra of the sample before and after cleaning have no obvious change, the sample has no abnormal phenomena such as corrosion in a microscopic mode, and the foreign matter removal effect is obvious before and after cleaning. Fig. 3 shows different samples for the test: the sample weight and Ra data (testing the roughness values of two different points) before and after degreasing and cleaning of the silicon etched surface, the silicon processed surface and the quartz processed surface have no obvious change before and after cleaning, figure 4 is a 1000-time high-definition digital microscope image comparison before and after degreasing and cleaning of different samples, and as can be seen from figure 4, the foreign matter removal effect after cleaning is obvious, no corrosion phenomenon exists, and the sample is not damaged in a microscopic mode.
FIG. 5 is a comparison graph of the appearance of a silicon ring sample before and after degreasing and cleaning, and the physical graph shows that the sample after cleaning has no dirt phenomenon and has clean and smooth appearance. Fig. 6 is a comparison of 1000 times high-definition digital microscope images of a silicon ring sample before and after degreasing and cleaning, and no corrosion or damage is caused after cleaning (in the figure, the black shadow is the marked position of the sample so as to facilitate positioning).
Example 3
The metal ion cleaning solution suitable for silicon, quartz and ceramic semiconductor materials comprises an acidic A cleaning solution, a neutral cleaning solution and an acidic B cleaning solution, and can Be used for treating metal elements on the surface of a sample, wherein the metal elements comprise 30 metal elements required by the semiconductor industry, specifically Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cu, Ga, Ge, Fe, Pb, Li, Mg, Mn, Mo, Ni, K, Na, Sr, Sn, Ti, W, V, Zn and Zr.
Soaking and cleaning a sample by using an acid A lotion at room temperature for about 15-20 minutes, and washing by using deionized water after cleaning; then putting the mixture into neutral washing liquor, soaking and washing the mixture by using ultrasonic waves, controlling the temperature to be 35-50 ℃, washing the mixture for about 15-20 minutes, and washing the mixture by using deionized water; and finally, soaking and cleaning the mixture in an acid B cleaning solution, controlling the temperature at room temperature, cleaning for about 15-20 minutes, and washing the mixture by using deionized water after cleaning. Wherein the acid A lotion is: 3.9 percent of ammonium fluoride, 2 percent of fluosilicic acid, H-951.2 percent (Germany Lansheng MersolatH95), 3.5 percent of sulfuric acid and the balance of deionized water; the neutral washing liquid is: 2.25% of acetone, 2% of glycerol, 4.5% of diethylene glycol, 5% of acetone glycerol, 3.8% of diethylene glycol mono-tert-butyl ether (CAS: 110-09-8), and the balance of deionized water; the acidic B washing solution is: 3.7% of hydrochloric acid, 3% of hydrogen peroxide, 4414% of LFG (thiophanate methyl) and the balance of deionized water.
The ultrasonic frequency is 40-50Hz, preferably 45 Hz. In the silicon product cleaning process, the efficient cleaning agent liquid plays an important key role in the cleaning technology process, and ultrasonic cleaning further assists in cleaning cleanliness and facilitates operation procedures.
Tests show that the metal element and the acid A washing liquid on the surface of the sample can be effectively removed within the following component concentration ranges: ammonium fluoride: 3.75% -4.35%, fluosilicic acid: 1.5% -2.1%, sulfuric acid: 3-4.5%, H-95: 1.2 to 2.4 percent of the total weight of the water, and the balance of deionized water. The neutral washing liquid is: acetone: 2% -3%, glycerol: 1.6% -2.8%, diethylene glycol: 3.6% -5%, acetone glycerol: 4.2% -5.6%, diethylene glycol mono-tert-butyl ether: 3.4 to 4.4 percent, and the balance of deionized water. The acidic B washing solution is: 2.2-4.2% of hydrochloric acid, hydrogen peroxide: 2.8-4%, LFG441: 4-4.8 percent of the total weight of the water, and the balance of deionized water.
In the same way, in the actual industrial production, the substances can be prepared according to the following proportion range, and the diluted substances are diluted to the working concentration for use when in use, so that the original solution is convenient to prepare and store, and the industrial batch production is facilitated. The mother liquor of each washing solution is prepared into the following concentration, namely an acid A washing solution: 25% -29% of ammonium fluoride, and fluosilicic acid: 10% -14%, sulfuric acid: 20-30%, H-95: 8-16% and the balance of deionized water; the solution was diluted to a mother liquor concentration of 15% for use. Neutral washing liquor: acetone: 10% -15%, glycerol: 8% -14%, diethylene glycol: 18% -25%, acetonide: 21% -28%, diethylene glycol mono-tert-butyl ether: 17-22% and the balance of deionized water; the solution was diluted to 20% of the mother liquor and used. Acid B washing solution: hydrochloric acid: 11-21% and hydrogen peroxide: 14-20%, LFG441: 20-24%, and the balance of deionized water; the solution was diluted to 20% of the mother liquor and used.
Example 4
The metal ion cleaning solution suitable for silicon, quartz and ceramic semiconductor materials comprises an acidic A cleaning solution, a neutral cleaning solution and an acidic B cleaning solution. In this example, the washing procedure was the same as in example 3, and the acid A wash was: 4.3 percent of ammonium fluoride, 1.8 percent of fluosilicic acid, 4 percent of H-951.6 percent of sulfuric acid and the balance of deionized water. The neutral washing liquid is: 2.4% of acetone, 2.4% of glycerol, 3.8% of diethylene glycol, 4.67% of acetone ketal, 4.1% of diethylene glycol mono-tert-butyl ether and the balance of deionized water. The acidic B washing solution is: 3% of hydrochloric acid, 3.5% of hydrogen peroxide, 4414.8% of LFG and the balance of deionized water.
Examples 3 and 4 test images of samples before and after washing with acid wash a are shown in fig. 7 and 8, fig. 7 is a high definition digital microscope image of a quartz plate after etching, and fig. 8 is a high definition digital microscope image of a polished surface of silicon. FIG. 9 is a microscopic view of a silicon processed surface and a quartz surface before and after a neutral washing liquid treatment. FIG. 10 is a high definition digital microscope (2000X) of the silicon etched surface before and after washing with acidic B wash.
Example 5
The cleaning method is suitable for silicon, quartz and ceramic semiconductor materials and comprises the following steps:
a. degreasing treatment: preparing alkaline degreasing washing liquor according to the mass percent of the following substances:
2.6% of potassium hydroxide, 2.6% of potassium carbonate, 3.5% of dipotassium dihydrogen pyrophosphate, 2.6% of potassium tripolyphosphate, 5.5% of acetone glycerol, 1.4% of sodium dodecyl diphenyl ether disulfonate, H-661.8%, 1.7% of fatty amine polyoxyethylene ether and the balance of deionized water; several silicon product samples (same as the previous example 1) were immersed in the above-mentioned alkaline degreasing bath, cleaned by ultrasonic immersion at 35-50 ℃ for about 15-20 minutes, and rinsed with deionized water. After cleaning, no grease residues are seen from the appearance of the product, and no obvious foreign matters exist at microscopic 1000X and 1000X. The ultrasonic frequency for ultrasonic cleaning is 40-50Hz, preferably 45 Hz.
b. Metal ion treatment: and respectively treating metal elements on the surface of the sample with an acidic A washing solution, a neutral washing solution and an acidic B washing solution, wherein the metal elements comprise 30 metal elements required by the semiconductor industry, and specifically Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cu, Ga, Ge, Fe, Pb, Li, Mg, Mn, Mo, Ni, K, Na, Sr, Sn, Ti, W, V, Zn and Zr.
Soaking and cleaning the degreased sample at normal temperature by using an acid A cleaning solution for about 15-20 minutes, and washing by using deionized water after cleaning; then putting the mixture into neutral washing liquor, soaking and washing the mixture by using ultrasonic waves, controlling the temperature to be 35-50 ℃, washing the mixture for about 15-20 minutes, and washing the mixture by using deionized water; and finally, soaking and cleaning the mixture in an acid B cleaning solution at room temperature for about 15-20 minutes, and then washing the mixture cleanly by using deionized water. Wherein the acid A lotion is: 3.75% of ammonium fluoride, 2% of fluosilicic acid, 3.2% of H-951.8%, 3.2% of sulfuric acid and the balance of deionized water; the neutral washing liquid is: 2.5% of acetone, 2% of glycerol, 4.8% of diethylene glycol, 5.3% of acetone glycerol, 4.36% of diethylene glycol mono-tert-butyl ether and the balance of deionized water; the acidic B washing solution is: 2.4% of hydrochloric acid, 3% of hydrogen peroxide, 4414.4% of LFG and the balance of deionized water.
Example 6-example 9
The cleaning method is suitable for silicon, quartz and ceramic semiconductor materials and comprises the following steps:
the specific method is as shown in Table 1 except that the configuration concentrations (unit%, mass% by volume) of the alkaline degreasing solution, the acidic A solution, the neutral solution and the acidic B solution are the same as in example 5.
TABLE 1
Example 10
The effects of the silicon product before and after cleaning in the solution were verified, and a microscopic region (shown in fig. 11) was designated as an experimental object, and comparative analysis before and after cleaning was performed after the cleaning method of example 5 was performed, and the cleaning results are shown in fig. 12 to 15. FIG. 12 is a microscopic comparison of a silicon ring after being washed with an alkaline degreasing wash solution and then washed with pure water before being washed. As shown in the figure, no obvious foreign matters exist after cleaning, and the cleaning is very clean. FIG. 13 is a comparison of the microstructure of a silicon ring after washing with an acid A wash solution and then with pure water before washing. As shown in the figure, the amount of the remaining foreign matters after the cleaning is further reduced. FIG. 14 is a comparison of the microstructure of a silicon ring after being washed with a neutral washing liquid and then washed with pure water before being washed. As shown in the figure, the amount of the acid A washing solution after washing was still reduced compared to the first washing with the acid A washing solution. FIG. 15 is a comparison of the microstructure of a silicon ring after washing with an acidic B washing solution and then with pure water before washing. Microscopically displaying the same position, the foreign matters are reduced or the color is lightened, and the foreign matters are not additionally increased. The effects of the treatment of the examples 6 to 9 are the same as those of the present example, and the illustration in the drawings is not repeated. Fig. 16 is a result of analyzing and detecting residual metal elements on the surface of a silicon ring product after being cleaned by the cleaning method for semiconductor materials according to the present invention, fig. 17 is a result of analyzing and detecting residual metal elements on the surface of a quartz product after being cleaned, and fig. 18 is a result of analyzing and detecting residual metal elements on the surface of a silicon ring product after being cleaned. FIG. 19 shows the analysis and detection results of residual metal elements on the surface of one of the cleaned products in the development process of the present invention, and also shows relatively high residual metal elements such as B, Ca, Ni, Mg, K, Na, Zn, etc.
Example 11
The existing main RCA cleaning method is used, and soaking cleaning is carried out in a strong acid mixing mode, and the cleaning method comprises the following steps:
SPM: h from SPM2SO4(volume fraction 98%) and H2O2(30%) according to the ratio of 4: 1.
2.HF(DHF)：HF∶H2O is 1: 100-1: 250, and a natural oxide layer and part of metal ions on the surface of the silicon wafer can be effectively removed.
3.APM(SC-1)：NH4OH：H2O2：H2And O is 1:1:5, and the temperature is 30-80 ℃.
4.HPM(SC-2)：HCl：H2O2：H2And O, the temperature is 65-85 ℃, and the method is used for removing partial metal contamination of sodium, iron, magnesium and the like on the surface of the silicon wafer.
Fig. 20 shows the analysis and detection results of the residual metal elements on the surface of the silicon ring after RCA cleaning (sample No. SM10004, and GT10013 and HN10036 are other cleaning method test samples in the research process of the present invention), and fig. 21 and 22 show high-definition microscopic images of the sample after RCA cleaning, which shows that there are some obvious impurity residues. FIGS. 23 and 24 show the appearance of other cleaning agents and cleaning methods during the study of the present invention, wherein the circled area has a whitish mark, and is analyzed as corrosion on the surface due to the high concentration in the solution. FIG. 23 shows a silicon product and FIG. 24 shows a quartz polished surface.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. The cleaning agent for the surface degreasing treatment of the semiconductor material is characterized by comprising the following components in percentage by mass: 2.1 to 3.3 percent of hydroxide compound, 1.5 to 4.5 percent of carbonate, 2.1 to 3.9 percent of pyrophosphate, 1.8 to 3 percent of potassium tripolyphosphate, 4.5 to 6.3 percent of acetone glycerol, 1.2 to 3 percent of anionic surfactant, 2.7 to 5.4 percent of nonionic surfactant and the balance of water.
2. The cleaning agent for semiconductor material surface degreasing treatment, as recited in claim 1, wherein the mass ratio of the anionic surfactant to the nonionic surfactant is 1:1.8-1: 3.
3. the cleaning agent for degreasing treatment of semiconductor material surface as claimed in claim 1, wherein the anionic surfactant is sulfonic acid type anionic surfactant.
4. The cleaning agent for degreasing surface of semiconductor material as recited in claim 3, wherein the anionic surfactant is sodium dodecyl diphenyl ether disulfonate, sodium dodecyl benzene sulfonate, sodium fatty alcohol isethionate, sodium secondary alkyl sulfonate, sodium α -alkenyl sulfonate.
5. The cleaning agent for semiconductor material surface degreasing treatment, as recited in claim 1, wherein the nonionic surfactant is H-66 and vinyl ether nonionic surfactant.
6. The cleaning agent for semiconductor material surface degreasing treatment, as recited in claim 5, wherein the vinyl ether nonionic surfactant is isomeric dodecyl alcohol polyoxyethylene ether, nonyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, isomeric tridecyl alcohol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, or fatty amine polyoxyethylene ether.
7. The cleaning agent for degreasing treatment of the surface of the semiconductor material as claimed in any one of claims 1-6, wherein the cleaning agent comprises the following components in percentage by mass: 2.6 to 3 percent of hydroxide compound, 2.6 to 3.6 percent of carbonate, 2.1 to 3.5 percent of pyrophosphate, 2 to 2.6 percent of potassium tripolyphosphate, 4.5 to 5.5 percent of acetone glycerol, 1.4 to 1.8 percent of anionic surfactant, 2.7 to 5.4 percent of nonionic surfactant and the balance of water.
8. The cleaning agent for degreasing treatment of semiconductor material surface as claimed in claim 7, wherein the hydroxide compound is sodium hydroxide or potassium hydroxide, the carbonate is sodium carbonate or potassium carbonate, and the pyrophosphate is sodium pyrophosphate, potassium pyrophosphate or dipotassium dihydrogen pyrophosphate.
9. The cleaning agent for degreasing the surface of the semiconductor material as recited in claim 1, wherein the semiconductor material is a silicon material, a quartz material or a ceramic material.
10. Use of the cleaning agent for degreasing treatment of semiconductor material surface according to any one of claims 1-9 in semiconductor material processing.
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| CN115093903A (en) * | 2022-07-19 | 2022-09-23 | 广州天极电子科技股份有限公司 | Cleaning agent and application thereof, cleaning method of thin film circuit board substrate and preparation method of thin film circuit board |
| CN116103094A (en) * | 2022-12-15 | 2023-05-12 | 浙江传化化学品有限公司 | Efficient environment-friendly based heating box descaling agent for elasticizer and preparation method of efficient environment-friendly based heating box descaling agent |
| CN116606704A (en) * | 2023-05-16 | 2023-08-18 | 安徽应友光电科技有限公司 | Metal ion cleaning agent for semiconductor material |
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| CN116606704A (en) * | 2023-05-16 | 2023-08-18 | 安徽应友光电科技有限公司 | Metal ion cleaning agent for semiconductor material |
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