CN113980747B - Cleaning agent for degreasing treatment of semiconductor material surface - Google Patents
Cleaning agent for degreasing treatment of semiconductor material surface Download PDFInfo
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- CN113980747B CN113980747B CN202111326662.4A CN202111326662A CN113980747B CN 113980747 B CN113980747 B CN 113980747B CN 202111326662 A CN202111326662 A CN 202111326662A CN 113980747 B CN113980747 B CN 113980747B
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- cleaning
- percent
- semiconductor material
- cleaning agent
- washing
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- 238000005238 degreasing Methods 0.000 title claims abstract description 48
- 239000004065 semiconductor Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 28
- 238000011282 treatment Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 19
- 239000003945 anionic surfactant Substances 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
- IFJOCHBDHXGFAA-UHFFFAOYSA-N CC([CH2-])=O.OCC(O)CO Chemical compound CC([CH2-])=O.OCC(O)CO IFJOCHBDHXGFAA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 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
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 8
- 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 8
- 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
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-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
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- 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
- 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
- 238000004140 cleaning Methods 0.000 abstract description 84
- 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
- BRCNMMGLEUILLG-UHFFFAOYSA-N 4,5,6-trihydroxyhexan-2-one Chemical compound CC(=O)CC(O)C(O)CO BRCNMMGLEUILLG-UHFFFAOYSA-N 0.000 abstract description 7
- 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
- 239000002904 solvent Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 77
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 65
- 229910052710 silicon Inorganic materials 0.000 description 47
- 239000010703 silicon Substances 0.000 description 47
- 239000007788 liquid Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 30
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- 239000000243 solution Substances 0.000 description 25
- 230000002378 acidificating effect Effects 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002253 acid Substances 0.000 description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 15
- 230000008569 process Effects 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 238000002791 soaking 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
- 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 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000006210 lotion Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 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
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000005227 alkyl sulfonate group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 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
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- LGNQGTFARHLQFB-UHFFFAOYSA-N 1-dodecyl-2-phenoxybenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OC1=CC=CC=C1 LGNQGTFARHLQFB-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920013813 TRITON H-66 Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching 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
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- CQBPOPVKDNHISM-UHFFFAOYSA-N propane-1,2,3-triol;propan-2-one Chemical compound CC(C)=O.OCC(O)CO CQBPOPVKDNHISM-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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 degreasing treatment of the surface of a semiconductor material, which consists of, by mass, 2.1% -3.3% of an oxyhydrogen compound, 1.5% -4.5% of carbonate, 2.1% -3.9% of pyrophosphate, 1.8% -3% of potassium tripolyphosphate, 4.5% -6.3% of acetonylglycerol, 1.2% -3% of an anionic surfactant and 2.7% -5.4% of a nonionic surfactant, wherein a solvent is water. By proper component proportion, anionic surfactant and nonionic surfactant 1:1.8-1:3, the proportion is matched, and the saponification reaction is more effectively promoted to remove greasy dirt by combining with the acetonide glycerol, so that better effects of removing particles, removing static electricity and the like are achieved. The cleaning agent for degreasing the surface of the semiconductor material and the metal ion cleaning solution can be matched for cleaning to remove metal ions more effectively.
Description
Technical Field
The invention belongs to the technical field of semiconductor materials, and relates to a cleaning agent for degreasing treatment of the surface of a semiconductor material.
Background
In the process of manufacturing flat panel displays such as TFT liquid crystal, micro information processors, memories, and semiconductor devices such as CCD, silicon oxide (SiO 2 ) The substrate surface of glass or the like is patterned or thin-film formed with a size of submicron or 1/4 micron. Therefore, in each of these steps of manufacturing, it is an extremely important issue to remove minute contaminants on the substrate surface and to highly clean the substrate surface; the same equipment consumables also need to be highly cleaned, particles in the semiconductor engineering are taken as important control objects, and products used in the engineering are required to be cleaned by a cleaning process to remove factors influencing the particles. But follow withThe development of very large scale integrated circuits, the continuous improvement of integration level and the continuous reduction of line width have higher and higher requirements on the cleanliness and surface state of the silicon wafer surface. With the increasing demand, not only removal of contamination on the surface of a silicon wafer but also surface chemical state, oxide film thickness, surface roughness, and the like, which are caused during cleaning, are also important parameters for obtaining a high-quality semiconductor device. At present, the failure of electronic components due to poor cleaning has exceeded more than half of the total loss in integrated circuit fabrication. The cleaning method is mainly applied at present and is improved and evolved based on RCA cleaning technology proposed by Werner in 1970. The method is to soak and clean the silicon wafer in a strong acid mixing mode, and remove particles, partial organic matters and partial metals on the surface of the silicon wafer by using APM, 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, has poor stability in the use process, has low service life and quick invalidation of solution cleaning capability. 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 process is used in a large scale, the damage to the environment is serious. Furthermore, it has been found that SC1 solutions are reported to be effective in removing surface particulates from semiconductor silicon, but at the same time introduce additional sources of foreign metal impurities such as iron, zinc, aluminum, and the like. The SC1 solution, while substantially eliminating particles having a surface size of silicon greater than 0.5 μm, instead increases the deposition of particles having a particle size of less than 0.5 μm. There is a great need for improvements in cleaning processes for semiconductor materials. The cleanliness of the surface of the silicon wafer plays an important role in the production of electronic devices and improving the performance, reliability and stability of products. Therefore, in order to meet the increasing requirements of the surface quality of electronic devices, development of a cleaning process method and related cleaning agents with simple operation, less cleaning steps, small amount of chemical reagents, low concentration of cleaning liquid and environmental friendliness are needed.
Disclosure of Invention
In view of the above, the invention aims to provide a simple cleaning agent for degreasing the surface of a semiconductor material, which has the advantages of simple raw materials, low use concentration, low industrial cost and no environmental pollutants.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. the cleaning agent for degreasing treatment of the surface of the semiconductor material comprises the following components in percentage by mass: 2.1 to 3.3 percent of oxyhydrogen 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 acetonide 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 degreasing the surface of the semiconductor material, the mass ratio of the anionic surfactant to the nonionic surfactant is 1:1.8-1:3.
further, the anionic surfactant is a sulfonic acid type anionic surfactant in the cleaning agent for degreasing the surface of the semiconductor material.
Further, the anionic surfactant is sodium dodecyl diphenyl ether disulfonate, sodium dodecyl benzene sulfonate, sodium fatty alcohol isethionate, sodium secondary alkyl sulfonate and alpha-alkenyl sulfonate.
Further, in the cleaning agent for degreasing the surface of the semiconductor material, the nonionic surfactant is H-66 and vinyl ether nonionic surfactant.
Further, the vinyl ether nonionic surfactant is selected from the group consisting of isomeric decaol polyoxyethylene ether, nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, laurinol polyoxyethylene ether and fatty amine polyoxyethylene ether.
Further, in the cleaning agent for degreasing treatment of the surface of the semiconductor material, the cleaning agent comprises the following components in percentage by mass: 2.6 to 3 percent of oxyhydrogen 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 acetonide, 1.4 to 1.8 percent of anionic surfactant, 2.7 to 5.4 percent of nonionic surfactant and the balance of water.
Further, in the cleaning agent for degreasing treatment of 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 the semiconductor material, wherein the semiconductor material is a silicon material, a quartz material or a ceramic material.
2. Use of the surface degreasing cleaning agent according to any one of the above in semiconductor material processing.
Further, the semiconductor material is a silicon material, a quartz material, or a ceramic material.
The invention has the beneficial effects that: the invention provides a cleaning agent suitable for surface degreasing treatment of semiconductor materials such as silicon, quartz, ceramic and the like, which 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, prolonged service life of the cleaning agent, small corrosiveness to silicon products and no increase of Ra of the products after cleaning. The invention reduces the chemical activity of unsaturated chemical bonds on the surface of a silicon wafer by combining the oxyhydrogen compound, carbonate, pyrophosphate, potassium tripolyphosphate, acetonide glycerol, anionic surfactant and nonionic surfactant, effectively removes the surface contamination of a semiconductor material such as a silicon polished wafer and improves the cleanliness of the semiconductor material. In particular with anionic and nonionic surfactants 1:1.8-1:3, the proportion is matched, and the saponification reaction is more effectively promoted to remove greasy dirt by combining with the acetonide glycerol, so that better effects of removing particles, removing static electricity and the like are achieved. The alkaline degreasing washing liquid and the metal ion cleaning solution can be used for cleaning in a matching way, so that metal ions adsorbed on the semiconductor material can be removed more effectively.
Drawings
In order to make the objects, technical solutions and advantageous effects of the present invention more clear, the present invention provides the following drawings for description:
FIG. 1 is an external view of 2 samples before and after degreasing and cleaning.
Fig. 2 is a view of a 1000-fold high definition digital microscope of a silicon wafer sample after degreasing and cleaning.
Fig. 3 shows different samples for the test: sample weights and Ra data before and after degreasing and cleaning of the etched silicon facet, the machined silicon surface, and the machined quartz surface.
FIG. 4 is a comparison of 1000-fold high definition digital microscope images of different samples before and after degreasing cleaning.
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-fold 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 samples before and after the quartz plate is cleaned with the acidic a rinse after etching.
Fig. 8 is a high definition digital microscope image of samples before and after cleaning the polished silicon surface with an acidic a rinse.
FIG. 9 is a microscopic view of the silicon working surface and quartz surface before and after the neutral wash treatment.
FIG. 10 is a high definition digital microscope image (2000X) of the etched silicon facets before and after washing with acidic B wash.
The etched silicon ring of fig. 11 has a pre-clean appearance with the marks as micro-areas.
FIG. 12 shows the microcosmic surface of a silicon ring after washing with an alkaline degreasing washing solution and after washing with pure water, compared with the microcosmic surface before washing.
FIG. 13 shows the microcosmic comparison of the microcosmic after washing of the silicon ring with the acidic A washing solution and then with pure water.
FIG. 14 shows the microcosmic surface of the silicon ring after washing with a neutral washing liquid and washing with pure water, compared with the microcosmic surface before washing.
FIG. 15 shows the microcosmic comparison of the microcosmic after washing of the silicon ring with acidic B washing solution and washing with pure water.
FIGS. 16 to 19 show the results of analysis and detection of the surface residual metal element after the respective treatments of the different samples.
FIG. 20 shows the results of analysis and detection of residual metal elements on the surface of the silicon ring after RCA cleaning.
Fig. 21 and 22 are high-definition microscopy images of the samples after RCA cleaning.
Fig. 23 and 24 are external views 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 polished quartz surface.
Detailed Description
For the purpose of making the objects, technical solutions and technical effects of the embodiments of the present invention more apparent, the technical solutions in the preferred embodiments of the present invention will be described in detail, with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art without the exercise of inventive faculty, are intended to be within the scope of the invention in connection with the embodiments herein. The experimental methods for which specific conditions are not specified in the examples are generally conducted under conventional conditions or under conditions recommended by the manufacturer.
Example 1
Alkaline degreasing washing liquid 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 acetonide, 1.8% of sodium dodecyl diphenyl ether disulfonate, 2% of H-662.5% (TRITON H-66 of Dow chemical), and the balance of water; all percentages are calculated as mass volume percentages and are the same as follows. Immersing a plurality of silicon product samples (etched quartz plate, silicon wafer, polished silicon wafer, silicon processing surface, quartz processing surface, P-type monocrystalline silicon, polysilicon and the like) into the alkaline degreasing washing liquid, soaking and washing by ultrasonic waves, controlling the temperature at 35-50 ℃, washing for about 15-20 minutes, and washing by deionized water. After washing, there was no oil and fat residue from the appearance of the product, and it was microscopically 1000X free of significant foreign matter. The ultrasonic frequency is 40-50Hz, preferably 45Hz. 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 the cleanliness degree and facilitates operation procedures.
In actual industrial production, each substance can be firstly configured according to the following proportion range, and then diluted to 30% of the original concentration for use, so that the preparation and storage of the original solution are convenient, and the industrial mass production is facilitated. An alkaline degreasing lotion stock solution is prepared as in the embodiment: 10% of potassium hydroxide, 12% of potassium carbonate, 7% of dipotassium dihydrogen pyrophosphate, 6.667% of potassium tripolyphosphate, 15% of acetonide, 6% of sodium dodecyl diphenyl ether disulfonate, 6.667% of 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, experiments prove that potassium hydroxide: 2.1% -3.3%, potassium carbonate: 1.5% -4.5%, dipotassium dihydrogen pyrophosphate: 2.1% -3.9%, potassium tripolyphosphate: 1.8% -3%, acetonylglycerol: 4.5 to 6.3 percent of dodecyl diphenyl ether disulfonate 1.2 to 3 percent of H-66:1.5% -3%, fatty amine polyoxyethylene ether: 1.2% -2.4%, and the balance is deionized water; in this range, the degreasing and cleaning effects are good. Wherein sodium dodecyl diphenyl ether disulfonate can also be replaced by sulfonic anionic surfactants such as sodium dodecyl benzene sulfonate, sodium fatty alcohol hydroxyethyl sulfonate, sodium secondary alkyl sulfonate, sodium alpha-alkenyl sulfonate, and the like, and the preferred sodium dodecyl diphenyl ether disulfonate. The nonionic surfactant is H-66 and vinyl ether nonionic surfactant, and the fatty amine polyoxyethylene ether can be replaced by nonionic surfactant such as isomeric polyoxyethylene lauryl ether (Basoff XP-50), polyoxyethylene nonylphenol ether, polyoxyethylene fatty alcohol ether, isomeric polyoxyethylene tridecyl ether, polyoxyethylene lauryl ether, etc., preferably fatty amine polyoxyethylene ether. In the invention, preferably, the anionic surfactant and the nonionic surfactant are matched in a ratio of 1:1.8-1:3, and the acetone-glycerol is combined to more effectively promote saponification reaction to remove greasy dirt, so that better effects of removing particles, removing 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
Alkaline degreasing washing liquid 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 acetonide, 1.6% of sodium dodecyl diphenyl ether disulfonate, 1.6% of H-662% of fatty amine polyoxyethylene ether and the balance of deionized water; several silicon product samples (same as example 1) were immersed in the alkaline degreasing washing solution, immersed in ultrasonic waves for washing at 35-50 c for about 15-20 minutes, and rinsed with deionized water after washing.
The samples after degreasing treatment in example 1 and example 2 were tested, and fig. 1 is an external view of 2 silicon wafer samples before and after degreasing cleaning, and the third row is a comparative view of the same condition cleaning of a certain degreasing liquid in the market, and the results are obviously better than those of the commercial products. FIG. 2 is a drawing of a 1000-fold high-definition digital microscope after degreasing and cleaning of a silicon wafer sample, wherein the weight and Ra of the sample are not obviously changed before and after cleaning, the microscopic corrosion is avoided, and the foreign matter removing effect is obvious before and after cleaning. Fig. 3 shows different samples for the test: the weight of the samples before and after degreasing cleaning of the silicon etched surface, the silicon processed surface and the quartz processed surface and the Ra data (roughness values of two different points are tested) have no obvious change, and fig. 4 is a comparison of 1000 times of high-definition digital microscope images before and after degreasing cleaning of different samples, and as can be seen from fig. 4, the foreign matter removal effect after cleaning is obvious, no corrosion phenomenon exists, and no damage is caused to the microscopic surface of the samples.
Fig. 5 is a comparison of the appearance of the silicon ring sample before and after degreasing and cleaning, and the physical image shows that the silicon ring sample has no dirt phenomenon after cleaning and has clean and smooth appearance. FIG. 6 is a comparison of 1000-fold high definition digital microscope images of a silicon ring sample before and after degreasing and cleaning, and also shows no corrosion or damage after cleaning (the black image in the figure is the marked position of the sample for positioning).
Example 3
The metal ion cleaning liquid suitable for the silicon, quartz and ceramic semiconductor materials comprises an acidic A cleaning liquid, a neutral cleaning liquid and an acidic B cleaning liquid, and can treat metal elements on the surface of a sample, wherein the metal elements comprise 30 metal elements required by the semiconductor industry, and particularly 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, zr.
Firstly, soaking and cleaning a sample by using an acidic A lotion at room temperature for about 15-20 minutes, and washing the sample by using deionized water after cleaning; then placing the mixture into neutral washing liquid, soaking and cleaning by ultrasonic wave, controlling the temperature at 35-50 ℃, cleaning for about 15-20 minutes, and washing by deionized water after cleaning; finally, the mixture is put into acid B washing liquid for soaking and washing, the temperature is controlled at room temperature, the washing is carried out for about 15-20 minutes, and deionized water is used for washing after the washing. Wherein, the acid A lotion is: 3.9% of ammonium fluoride, 2% of fluosilicic acid, H-951.2% (Mersolated H95, germany), 3.5% 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 acetonylglycerol, 3.8% of diethylene glycol mono-tert-butyl ether (CAS: 110-09-8) and the balance of deionized water; the acidic washing liquid B is: hydrochloric acid 3.7%, hydrogen peroxide 3%, LFG4414% (new development) and deionized water in balance.
The ultrasonic frequency is 40-50Hz, preferably 45Hz. 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 the cleanliness degree and facilitates operation procedures.
Through tests, the metal elements on the surface of the sample can be effectively removed within the following concentration ranges of the components: ammonium fluoride: 3.75% -4.35%, fluosilicic acid: 1.5% -2.1%, sulfuric acid: 3-4.5%, H-95:1.2% -2.4% and the balance deionized water. The neutral washing liquid is: acetone: 2% -3%, glycerol: 1.6% -2.8%, diethylene glycol: 3.6% -5%, acetonylglycerol: 4.2% -5.6%, diethylene glycol mono-tert-butyl ether: 3.4-4.4%, and the balance deionized water. The acidic washing liquid B is: hydrochloric acid 2.2-4.2%, hydrogen peroxide: 2.8-4%, LFG441:4-4.8%, and the balance deionized water.
In the actual industrial production, the materials can be firstly configured according to the following proportion range, and then diluted to the working concentration for use, so that the preparation and the storage of the raw solution are convenient, and the industrial batch production is facilitated. The concentration of each lotion mother liquor is as follows, acid A lotion: 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 liquid: acetone: 10% -15%, glycerol: 8% -14%, diethylene glycol: 18% -25%, acetonylglycerol: 21% -28%, diethylene glycol mono-tert-butyl ether: 17-22%, and the balance of deionized water; the solution was diluted to 20% mother liquor concentration for use. Acidic B wash: hydrochloric acid: 11-21%, hydrogen peroxide: 14-20%, LFG441, 20-24%, and the balance deionized water; the solution was diluted to 20% mother liquor concentration for use.
Example 4
The metal ion cleaning liquid is suitable for silicon, quartz and ceramic semiconductor materials, and comprises an acidic A cleaning liquid, a neutral cleaning liquid and an acidic B cleaning liquid. The cleaning method in this example is the same as in example 3, and the acidic A wash is: 4.3% of ammonium fluoride, 1.8% of fluosilicic acid, 4% of H-951.6% 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 acetonylglycerol, 4.1% of diethylene glycol mono-tert-butyl ether and the balance of deionized water. The acidic washing liquid B is: hydrochloric acid 3%, hydrogen peroxide 3.5%, LFG4414.8% and the balance deionized water.
Examples 3 and 4 the sample test patterns before and after washing with the acidic a washing solution are shown in fig. 7 and 8, fig. 7 is a high definition digital microscope image of the etched quartz piece, and fig. 8 is a high definition digital microscope image of the polished silicon surface. FIG. 9 is a microscopic view of the silicon working surface and quartz surface before and after the neutral wash treatment. FIG. 10 is a high definition digital microscope image (2000X) of the etched silicon facets before and after washing with acidic B wash.
Example 5
A cleaning method suitable for silicon, quartz and ceramic semiconductor materials comprises the following steps:
a. degreasing: preparing alkaline degreasing washing liquid according to the mass percentages of all 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 acetonide glycerol, 1.4% of sodium dodecyl diphenyl ether disulfonate, 1.7% of H-661.8% of fatty amine polyoxyethylene ether and the balance of deionized water; several samples of silicon product (as in example 1) were immersed in the alkaline degreasing rinse, rinsed by ultrasonic immersion at 35-50 c for about 15-20 minutes, rinsed with deionized water. After washing, there was no oil and fat residue from the appearance of the product, and no apparent foreign matter at 1000X and 1000X on a microscopic scale. The ultrasonic frequency is 40-50Hz, preferably 45Hz during ultrasonic cleaning.
b. Metal ion treatment: the metal elements on the surface of the sample are treated by an acid A washing liquid, a neutral washing liquid and an acid B washing liquid respectively, wherein the metal elements comprise 30 metal elements required by the semiconductor industry, and particularly 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, zr.
Soaking and cleaning the degreased sample with an acidic A washing solution at normal temperature for about 15-20 minutes, and washing with deionized water; then placing the mixture into neutral washing liquid, soaking and cleaning by ultrasonic wave, controlling the temperature at 35-50 ℃, cleaning for about 15-20 minutes, and washing by deionized water after cleaning; finally, the mixture is put into acid B washing liquid to be soaked and washed at room temperature for about 15 to 20 minutes, and the mixture is washed by deionized water after washing. Wherein, the acid A lotion is: 3.75% of ammonium fluoride, 2% of fluosilicic acid, 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 acetonylglycerol, 4.36% of diethylene glycol mono-tert-butyl ether and the balance of deionized water; the acidic washing liquid B is: hydrochloric acid 2.4%, hydrogen peroxide 3%, LFG4414.4% and the balance deionized water.
Example 6-example 9
A cleaning method suitable for silicon, quartz and ceramic semiconductor materials comprises the following steps:
in the specific method, the concentrations (unit%, mass and volume percentages) of the alkaline degreasing washing liquid, the acidic A washing liquid, the neutral washing liquid and the acidic B washing liquid are shown in Table 1, and the same procedure as in example 5 was repeated.
TABLE 1
Example 10
The effect of the silicon product before and after cleaning in the solution was verified, a microscopic region (as shown in fig. 11) was designated as an experimental object, and a comparative analysis of the silicon product 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 shows the microcosmic surface of a silicon ring after washing with an alkaline degreasing washing solution and after washing with pure water, compared with the microcosmic surface before washing. As shown in the figure, no obvious foreign matters exist after cleaning, and the cleaning is quite clean. FIG. 13 shows the microcosmic comparison of the microcosmic after washing of the silicon ring with the acidic A washing solution and then with pure water. As shown in the figure, the residual foreign matter after cleaning is further reduced. FIG. 14 shows the microcosmic surface of the silicon ring after washing with a neutral washing liquid and washing with pure water, compared with the microcosmic surface before washing. As shown in the figure, the amount of the acid A washing liquid is reduced after washing compared with the first washing. FIG. 15 shows the microcosmic comparison of the microcosmic after washing of the silicon ring with acidic B washing solution and washing with pure water. Microscopic display of the same location either reduces or lightens the color without additional foreign matter. The effects of the treatments of examples 6-9 are the same as those of the present example, and the drawings will not be repeated. Fig. 16 is a result of analysis and detection of residual metal elements on the surface of a silicon ring product after cleaning by the cleaning method for semiconductor materials according to the present invention, fig. 17 is a result of analysis and detection of residual metal elements on the surface of a quartz product after cleaning, and fig. 18 is a result of analysis and detection of residual metal elements on the surface of a silicon ring product after cleaning. Fig. 19 shows the analysis and detection result of the residual metal element on the surface of one of the products after cleaning in the development process of the invention, and the residual metal element such as B, ca, ni, mg, K, na, zn is relatively high.
Example 11
The existing main RCA cleaning method is used for soaking cleaning in a strong acid mixing mode, and the cleaning method is as follows:
SPM: h at SPM 2 SO 4 (volume fraction 98%) and H 2 O 2 (30%) are arranged in a ratio of 4:1.
2.HF(DHF)：HF∶H 2 O is 1:100-1:250, and can effectively remove natural oxide layers and partial metal ions on the surface of the silicon wafer.
3.APM(SC-1)：NH 4 OH：H 2 O 2 ：H 2 O=1:1:5, temperature 30-80 ℃.
4.HPM(SC-2)：HCl：H 2 O 2 ：H 2 O, the temperature is 65-85 ℃, and the O is used for removing partial metal contamination such as sodium, iron, magnesium and the like on the surface of the silicon wafer.
Fig. 20 is a result of analyzing and detecting residual metal elements on the surface of a silicon ring after RCA cleaning (sample No. SM10004, GT10013 and HN10036 are samples tested by other cleaning methods in the research process of the present invention), and fig. 21 and 22 are high-definition microscopic images of the sample after RCA cleaning, which show that there is a little obvious impurity residue. FIGS. 23 and 24 are external views of test samples of other cleaning agents and cleaning methods during the course of the study of the present invention, and the circled areas are marked with white marks, which are analyzed to cause corrosion patterns on the surface due to higher concentrations in the solution. Fig. 23 is a silicon product, and fig. 24 is a quartz polished surface.
Finally, it is noted that the above-mentioned preferred embodiments are only intended to illustrate rather than limit the invention, and that, although the invention has been described in detail by means of the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (5)
1. A cleaning agent for degreasing treatment of the surface of a semiconductor material, which is characterized by comprising the following components in percentage by mass: 2.1 to 3.3 percent of oxyhydrogen 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 acetonide glycerol, 1.2 to 3 percent of anionic surfactant, 2.7 to 5.4 percent of nonionic surfactant and the balance of water; the mass ratio of the anionic surfactant to the nonionic surfactant is 1:1.8-1:3, a step of; the anionic surfactant is sodium dodecyl diphenyl ether disulfonate; the nonionic surfactant is H-66 and fatty amine polyoxyethylene ether.
2. The cleaning agent for surface degreasing treatment of semiconductor material according to claim 1, wherein the cleaning agent comprises the following components in mass percent: 2.6 to 3 percent of oxyhydrogen 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 acetonide, 1.4 to 1.8 percent of anionic surfactant, 2.7 to 5.4 percent of nonionic surfactant and the balance of water.
3. The cleaning agent for degreasing treatment of semiconductor material surface according to claim 1, 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 pyrophosphate.
4. The cleaning agent for surface degreasing treatment of semiconductor material according to claim 1, wherein the semiconductor material is a silicon material, a quartz material or a ceramic material.
5. Use of a cleaning agent for surface degreasing treatment of semiconductor material according to any one of claims 1 to 4 in semiconductor material processing.
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