TWI827764B - 矽蝕刻液 - Google Patents
矽蝕刻液 Download PDFInfo
- Publication number
- TWI827764B TWI827764B TW108145725A TW108145725A TWI827764B TW I827764 B TWI827764 B TW I827764B TW 108145725 A TW108145725 A TW 108145725A TW 108145725 A TW108145725 A TW 108145725A TW I827764 B TWI827764 B TW I827764B
- Authority
- TW
- Taiwan
- Prior art keywords
- etching
- silicon
- group
- hydrogen atom
- hydroxyl group
- Prior art date
Links
- 238000005530 etching Methods 0.000 title claims abstract description 139
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 73
- 239000010703 silicon Substances 0.000 title claims abstract description 73
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims abstract description 17
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- -1 phenol compound Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002989 phenols Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 abstract description 43
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000000908 ammonium hydroxide Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract 1
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 abstract 1
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 18
- 239000000654 additive Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 229910052814 silicon oxide Inorganic materials 0.000 description 11
- 235000012431 wafers Nutrition 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 238000001039 wet etching Methods 0.000 description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 3
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- MGGVALXERJRIRO-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-2-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-1H-pyrazol-5-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)O MGGVALXERJRIRO-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- KNDAEDDIIQYRHY-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(piperazin-1-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCNCC1 KNDAEDDIIQYRHY-UHFFFAOYSA-N 0.000 description 1
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 1
- BPGIOCZAQDIBPI-UHFFFAOYSA-N 2-ethoxyethanamine Chemical compound CCOCCN BPGIOCZAQDIBPI-UHFFFAOYSA-N 0.000 description 1
- OMNGOGILVBLKAS-UHFFFAOYSA-N 2-methoxyphenol Chemical compound COC1=CC=CC=C1O.COC1=CC=CC=C1O OMNGOGILVBLKAS-UHFFFAOYSA-N 0.000 description 1
- QASBCTGZKABPKX-UHFFFAOYSA-N 4-(methylsulfanyl)phenol Chemical compound CSC1=CC=C(O)C=C1 QASBCTGZKABPKX-UHFFFAOYSA-N 0.000 description 1
- LKVFCSWBKOVHAH-UHFFFAOYSA-N 4-Ethoxyphenol Chemical compound CCOC1=CC=C(O)C=C1 LKVFCSWBKOVHAH-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVSWSHNHAMOAAE-UHFFFAOYSA-N C(C)OC1=CC=C(C=C1)O.C(C)OC1=CC=C(O)C=C1 Chemical compound C(C)OC1=CC=C(C=C1)O.C(C)OC1=CC=C(O)C=C1 BVSWSHNHAMOAAE-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 125000004001 thioalkyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
- H01L21/30608—Anisotropic liquid etching
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Emergency Medicine (AREA)
- Weting (AREA)
Abstract
本發明的課題係在於提供可提升對矽的蝕刻速度,且在蝕刻中不會在蝕刻面形成附著物,並且以即使長時間、連續使用,亦不會降低蝕刻速度的TMAH等的四級銨化合物作為主劑的蝕刻液為目標。
本發明的矽蝕刻液,其特徵在於包含:以下式(1)所示的酚化合物、四級銨化合物、及水,pH 12.5以上,
式中、R1
為氫原子、羥基、烷基、烷氧基或胺基,R2
為氫原子、羥基、烷氧基或胺基。R1
與R2
不會同時為氫原子,R1
為氫原子時,R2
不是羥基,而R1
為烷基或羥基時,R2
不是氫原子。
Description
本發明係關於使用在製造各種矽元件時的表面加工、蝕刻步驟的矽蝕刻液。
矽,利用其優良的機械特性、及低電阻、且與其他的金屬比較相對較穩定而對於後處理的限制較少等電氣特性而應用於各式各樣的領域。利用機械特性,應用在閥、噴嘴、印表機用噴頭;以及用於進行檢測流量、壓力及加速度等的各種物理量的半導體傳感器(例如半導體壓力傳感器的隔膜或半導體加速度傳感器的懸臂等)等。此外,利用電氣特性,應用在作為金屬線路的一部分、閘極電極等的材料的各種裝置。如此的各種矽元件,按照用途要求高積體化、細微化、高靈敏度化、高機能化。用於滿足該等要求在製造該等矽元件使用細微加工技術。
在矽的表面加工、蝕刻上,作為濕式蝕刻有使用氟硝酸的等向性矽蝕刻、及使用KOH、聯胺、四甲基氫氧化銨(以下,簡稱為TMAH。)等的一般的鹼性藥品的水溶液的異向性蝕刻(參照專利文獻1及2)。
使用氟硝酸的蝕刻,由於不分矽的結晶方位,可等向性蝕刻,故可對單晶矽、多晶矽、非晶矽均勻地蝕刻。但是,對矽與矽氧化膜沒有蝕刻選擇比,此外,對遮罩容易有底切(undercut)、側向蝕刻等課題。再者,在此所謂蝕刻選擇比,係對目標物質的蝕刻性,與對其他構件的蝕刻性的比。只蝕刻目標物質,而不蝕刻其他構件時,稱作「蝕刻選擇比高」。因此,所謂「沒有矽與矽氧化膜的蝕刻選擇比」,係指矽與矽氧化膜均會被同樣地蝕刻。
在鹼性蝕刻,由於依照矽的結晶方位有蝕刻速度差100倍性質,故可利用該蝕刻異向性對單晶矽製造具有複雜的3維結構的矽元件。例如,藉由將欲迴避蝕刻的部分以矽氧化膜或矽氮化膜等遮罩的矽晶圓,投到導入蝕刻液的蝕刻槽,將矽晶圓的不需要的部分溶解,可製造矽元件。雖然對於多晶矽、非晶矽無法利用結晶異向性這個性質,利用對矽與矽氧化膜的蝕刻選擇比高的性質,在各種半導體製程使用鹼性蝕刻。其中毒性低且處理容易的KOH、TMAH可以單獨良好地使用。
該等之中,TMAH,相較於使用KOH的情形,對矽氧化膜的蝕刻速度大致低1階,故具有作為遮罩材料,可使用較矽氮化膜廉價的矽氧化膜的長處(參照非專利文獻1)。TMAH具有如此的長處的反面,由於相較於KOH對矽的蝕刻速度較慢,故有生產效率變低的缺點。因此,作為提高TMAH對矽的蝕刻速度的方法,有添加特定添加劑的方法的提案(參照專利文獻3及4)。例如,在專利文獻3,藉由添加選自由羥基胺類、次亞磷酸鹽類、還原醣類、抗壞血酸及焦兒茶酚(brenzcatechin)、以及該等的衍生物之至少1種所組成的還原性化合物提高蝕刻速度。此外,在專利文獻4,藉由添加選自由鐵、氯化鐵(III),氫氧化鐵(II),氫氧化鎳(II)、鎳、羥基胺、二甲基胺、N,N-二乙基羥基胺、乙二胺、異丙醇胺、苄基胺、2-乙氧基乙基胺、氟化銨、碘化銨、硫代硫酸銨、硫代氰酸銨、抗壞血酸、L-半胱胺酸(L-cysteine)、吡啶、喹啉酚、草酸、兒茶酚(catechol)、氫醌(hydroquinone)、苯醌(benzoquinone)及胍碳酸鹽(guanidine carbonate)所組成之群之至少1種化合物圖謀提升蝕刻速度。
[先前技術文獻]
[專利文獻]
專利文獻1︰日本特開平9-213676號公報
專利文獻2︰日本特開平11-233482號公報
專利文獻3︰日本特開2006-054363號公報
專利文獻4︰日本特開2006-186329號公報
[非專利文獻]
非專利文獻1︰傳感器與材料(Sensors and Materials),田畑等,2001年,第13卷,第5號,273-283頁
[發明所欲解決的課題]
本發明者們,為調查以專利文獻3及4所述的TMAH等的四級銨化合物作為主劑的蝕刻液的實用性,進行蝕刻液的連續使用性評價。結果發現,根據添加的添加劑種類,其性能不同而發生幾個問題。即,(1)使用添加羥基胺等的胺類的蝕刻液時,將蝕刻液長時間,連續使用,則會發生蝕刻速度下降的問題;(2)添加鐵、鎳等金屬或其鹽等,將該等金屬溶解的蝕刻液,雖然蝕刻速度會提升,但是金屬會附著在蝕刻中被蝕刻的矽基板的傾斜部(矽(111)面),而會發生在蝕刻之後,需要去除如此的附著物的步驟的問題。因此,發現具有優良效果的添加劑是有意義。
因此,本發明係以提供,可提升對矽的蝕刻速度,且在蝕刻中不會在蝕刻面形成附著物,並且以即使長時間、連續使用,亦不會降低蝕刻速度的TMAH等的四級銨化合物作為主劑的蝕刻液為目標。
[用於解決課題的手段]
上述附著物的問題,由於係使用金屬系添加劑時的特有的問題,故藉由使用金屬系以外的添加劑,可以避免。此外,上述蝕刻速度下降的問題,恐怕是起因於添加劑的穩定性,添加劑在系統內的舉動,由於與各式各樣的因素交互作用,故難以籠統地判定。
本發明者,研究各式各樣的化合物的添加效果,結果發現蝕刻液添加特定的化合物時,可提升矽的蝕刻速度,且不會形成附著物,可抑制因連續使用的蝕刻速度下降,而達至完成本發明。
即,本發明係關於一種矽蝕刻液,其特徵在於:包含:以下式(1) 所示的酚化合物、四級銨化合物、及水,pH12.5以上。
[化1](1)
式中、R1
為氫原子、羥基、烷基、烷氧基或胺基,R2
為氫原子、羥基、烷氧基或胺基。R1
與R2
不會同時為氫原子,R1
為氫原子時,R2
不是羥基,而R1
為烷基或羥基時R2
不是氫原子。
四級銨化合物的濃度為1~50質量%,式(1)所示酚化合物的濃度以0.05~20質量%為佳。
此外,本發明的其他態樣係一種矽元件的製造方法,其為包含將矽晶圓、多晶矽膜、非晶矽膜蝕刻的步驟的矽元件的製造方法,其特徵在於:使用上述矽蝕刻液進行蝕刻。
[發明的效果]
藉由使用本發明的蝕刻液,可高速進行矽的濕蝕刻。且即使長時間,連續使用,蝕刻速度並不會下降。再者,由於不使用金屬系的添加劑,故不會在被蝕刻的矽基板的傾斜部形成附著物,在蝕刻後無需進行去除金屬附著物的步驟。
本發明的蝕刻液,包含四級銨化合物的水溶液。在此,作為四級銨化合物,可無特別限制地使用由先前的四級銨化合物水溶液所組成的蝕刻液的四甲基氫氧化銨(TMAH)、四乙基氫氧化銨、或四丁基氫氧化銨。該等四級銨化合物,可以1種單獨使用,亦可混合使用複數不同種類。該等四級銨化合物之中,由矽的蝕刻速度高等理由,使用TMAH最佳。此外,四級銨化合物的濃度,與先前的蝕刻液並無特別不同的點,以蝕刻液全體的質量作為基準為1~50質量%,較佳的是3~30質量%的範圍,進一步較佳的是3~25質量%的範圍。在1~50質量%的範圍,則不會發生結晶析出,而能夠得到優良的蝕刻效果。
本發明的蝕刻液,其特徵在於:含有特定量的下式(1)所示酚化合物。藉由含有該酚化合物,可以提升對矽的蝕刻速度。
[化2]
在上述式(1),R1
為氫原子、羥基、烷基、烷氧基或胺基,R2
為氫原子、羥基、烷氧基或胺基。R1
與R2
不會同時為氫原子,R1
為氫原子時,R2
不是羥基,R1
為烷基或羥基時,R2
不是氫原子。
在R1
、R2
,烷基、烷氧基,分別以碳數1~3的為佳,以碳數1~2的更為佳。
作為R1
,以氫原子、烷氧基或烷基為佳,作為R2
,以羥基、烷氧基或胺基為佳。再者,R1
為氫原子時,R2
以烷氧基或胺基為佳,R1
為烷氧基或烷基時,R2
以羥基特別為佳。
具體表示在本發明可特別良好地使用的上述式(1)所示的酚化合物,可舉出鄰甲氧基酚(o-methoxyphenol)、對甲氧基酚、對乙氧基酚(p-ethoxyphenol)、鄰胺基酚(o-aminophenol)、對胺基酚、甲基氫醌(methylhydroquinone)、甲氧基氫醌(methoxyhydroquinone)等。該等之中,以對甲氧基酚、對胺基酚、甲基氫醌、甲氧基氫醌特別為佳。該等酚化合物,可以1種單獨使用,亦可混合使用複數不同種類。
在本發明的蝕刻液的上述式(1)所示酚化合物的較佳含量,因酚化合物的種類不同而不同,但一般而言,酚化合物的質量總和占蝕刻液全體質量的比例,以0.05~20質量%的量為佳,以0.1~10質量%更為佳,以1~5質量%特別為佳。此時,調整酚化合物及四級銨化合物的含量,使蝕刻液的pH為12.5以上。較佳的是pH 13以上。酚化合物的含量,在0.05~20質量%的範圍內,且蝕刻液的pH為12.5以上時,能夠得到提升矽的蝕刻速度的優良效果。上述式(1)所示酚化合物的濃度,比0.05質量%低時,難以得到所期望的效果,比20質量%高時,會降低蝕刻速度的提升效果。此外,蝕刻液的pH低於12.5時,有時會降低蝕刻速度。
本發明的蝕刻液,可容易地藉由對既定濃度的四級銨化合物水溶液添加既定量上述酚化合物,使之溶解而調製。此時亦可不直接將酚化合物添加,而預先調整既定濃度的酚化合物的水溶液,而將此添加。
本發明的蝕刻液,含有上述酚化合物及四級銨化合物,餘部通常是水,但在不阻礙本發明的目標的範圍內,亦可調配先前使用於蝕刻液的添加劑,或溶解矽。此外,為提升潤濕性,亦可添加界面活性劑,例如亦可使用陽離子系、非離子系、陰離子系的任一界面活性劑。或者,亦可添加用於防止添加劑分解的分解抑制劑;防止使用於矽的細微加工的矽以外的構件的損傷,或用於控制矽的蝕刻速度的添加劑或有機溶劑。有機溶劑,因添加而會變色,或變性的不佳,但只要是可以提升或維持蝕刻性,則並無限制。如此的其他的添加劑,可對蝕刻液全體質量以10質量%以下的比例包含。
本發明的蝕刻液,具有四級銨化合物水溶液系蝕刻液的特長,即毒性低、處理容易、且作為遮罩材料可使用廉價的矽氧化膜的長處。再者,本發明的蝕刻液,與先前的四級銨化合物水溶液系蝕刻液相比,在同一條件下蝕刻時,可提升矽的蝕刻速度,且具有可防止附著物,抑制因連續使用的蝕刻速度下降的特長。因此,本發明的蝕刻液,可良好地使用於作為,藉由矽的濕式蝕刻技術,製造應用於閥、噴嘴、印表機用噴頭、以及用於檢測流量、壓力及加速度等的各種物理量的半導體傳感器(例如半導體壓力傳感器的隔膜或半導體加速度傳感器的懸臂等)的加工、及作為金屬線路的一部分、閘極電極等的材料的各種裝置的多晶矽、非晶矽的蝕刻等的各種矽元件時的蝕刻液
使用本發明的蝕刻液製造矽元件時,只要使用本發明的蝕刻液進行矽的濕式蝕刻即可。此時的方法,與使用先前的蝕刻液的情形並無特別不同的點,例如可更良好地藉由將作為被蝕刻物的「將矽晶圓的必要部分以矽氧化膜或矽氮化膜等遮蔽的矽晶圓」投到導入蝕刻液的蝕刻槽,利用與蝕刻液的化學反應,使矽晶圓的不需要的部分溶解而進行。
蝕刻時的蝕刻液的溫度,考量所期望的蝕刻速度、蝕刻後的矽的形狀或表面狀態、生產性等,以20~95℃的範圍適當決定即可,以40~95℃的範圍為佳。
矽的濕蝕刻,可為僅將被蝕刻物浸漬在蝕刻液即可,惟亦可採用對被蝕刻物施加一定的電位的電化學蝕刻法。
作為在本發明的蝕刻處理對象物,可舉出矽單晶、多晶矽、或非晶矽,亦可在對象物中包含不是蝕刻處理對象的非對象物的矽氧化膜或矽氮化膜等、鋁等金屬。例如,可舉出在矽單晶上層積矽氧化膜或矽氮化膜,甚至是層積金屬膜並製作圖案形狀者;或進一步在其上成膜、塗佈多晶矽或抗蝕劑(resist)者;鋁等的金屬部分以保護膜覆蓋,而矽被形成圖案的結構體等。
實施例
以下,將本發明以實施例更詳細地說明,惟本發明不應限定於該等實施例。
實施例1~8
在容量60(ml)的氟樹脂製容器,導入將表1所示的各種添加物質溶解2質量%的5質量%TMAH水溶液20(ml)之後,使用水浴將液溫加熱到80℃。
液溫達到80℃之後,將1cm×2cm的矽晶圓的小片浸漬在上述蝕刻液20秒,測定矽的蝕刻速度。再者,該矽晶圓,係在矽晶圓上使用批次式熱氧化爐形成氧化膜,在其上面採用低壓CVD法,將多晶矽成膜1μm(±10%)。蝕刻速度,係將使用低壓CVD法成膜的多晶矽的蝕刻前與蝕刻結束時的膜厚,以反射分光膜厚計(FILMETRICS公司製F20膜厚測定系統)測定,將其差除以蝕刻時間而求得。此外,各蝕刻液的pH,係使用pH計(堀場製造所製桌上型pH計F-73)與pH電極(堀場製造所製Flat ISFET pH電極0040-10D),測定液溫為23~24℃時的值。將其結果示於表1。
此外,以FE-SEM(日本電子製JSM-7800F Prime)觀察被蝕刻的矽表面,結果由於沒有使用金屬系添加劑,故沒有看到附著物的形成。
實施例9~28
將TMAH的濃度、添加物質的種類及量變更為如表1所示以外,以與實施例1同樣地求得蝕刻速度。將其結果示於表1。
[表1]
TMAH濃度 (質量%) | 添加物質 | 添加量 (質量%) | 蝕刻速度 (μm/分) | pH | |
實施例1 | 5 | 對乙氧基酚 | 2 | 1.1 | 13.6 |
實施例2 | 5 | 鄰甲氧基酚 | 2 | 0.9 | 13.5 |
實施例3 | 5 | 鄰胺基酚 | 2 | 1.0 | 13.5 |
實施例4 | 5 | 1,2,4-苯三酚 (1,2,4-benzenetriol) | 2 | 1.0 | 13.4 |
實施例5 | 5 | 甲基氫醌 | 2 | 1.2 | 13.3 |
實施例6 | 5 | 甲氧基氫醌 | 2 | 1.5 | 13.4 |
實施例7 | 5 | 對甲氧基酚 | 2 | 1.6 | 13.5 |
實施例8 | 5 | 對胺基酚 | 2 | 1.5 | 13.5 |
實施例9 | 5 | 甲氧基氫醌 | 0.5 | 1.4 | 13.6 |
實施例10 | 5 | 甲氧基氫醌 | 1 | 1.6 | 13.5 |
實施例11 | 5 | 甲氧基氫醌 | 3 | 0.9 | 13.2 |
實施例12 | 10 | 甲氧基氫醌 | 1 | 1.5 | 13.9 |
實施例13 | 10 | 甲氧基氫醌 | 3 | 1.6 | 13.7 |
實施例14 | 10 | 甲氧基氫醌 | 5 | 1.3 | 13.7 |
實施例15 | 5 | 對甲氧基酚 | 0.5 | 1.5 | 13.6 |
實施例16 | 5 | 對甲氧基酚 | 1 | 1.6 | 13.6 |
實施例17 | 5 | 對甲氧基酚 | 3 | 1.6 | 13.5 |
實施例18 | 5 | 對甲氧基酚 | 5 | 1.4 | 13.3 |
實施例19 | 10 | 對甲氧基酚 | 1 | 1.4 | 13.9 |
實施例20 | 10 | 對甲氧基酚 | 3 | 1.4 | 13.9 |
實施例21 | 10 | 對甲氧基酚 | 4 | 1.4 | 13.8 |
實施例22 | 10 | 對甲氧基酚 | 5 | 1.5 | 13.8 |
實施例23 | 10 | 對甲氧基酚 | 10 | 1.4 | 13.7 |
實施例24 | 10 | 對胺基酚 | 1 | 1.4 | 13.9 |
實施例25 | 10 | 對胺基酚 | 3 | 1.4 | 13.8 |
實施例26 | 10 | 對胺基酚 | 4 | 1.6 | 13.7 |
實施例27 | 10 | 對胺基酚 | 5 | 1.5 | 13.7 |
實施例28 | 10 | 對胺基酚 | 10 | 1.1 | 13.6 |
實施例29、30
為調查預設長時間、連續使用的熱穩定性試驗的蝕刻速度有無下降,在實施例6、8,預先以液溫80℃加熱24小時之後進行蝕刻以外,以與實施例1同樣的方法調查蝕刻速度。將其結果示於表2。
[表2]
TMAH濃度 (質量%) | 添加物質 | 添加量 (質量%) | 蝕刻速度 (μm/分) | |
實施例29 | 5 | 甲氧基氫醌 | 2 | 1.5 (1.5;實施例6) |
實施例30 | 5 | 對胺基酚 | 2 | 1.6 (1.5;實施例8) |
比較例1~11
將TMAH的濃度、添加物質的種類及量變更為如表3所示以外,以與實施例1同樣地求得蝕刻速度。將其結果示於表3。
[表3]
TMAH濃度 (質量%) | 添加物質 | 添加量 (質量%) | 蝕刻速度 (μm/分) | pH | |
比較例1 | 5 | - | - | 0.8 | 13.6 |
比較例2 | 10 | - | - | 0.8 | 14.0 |
比較例3 | 5 | 間甲氧基酚 | 2 | 0.8 | 13.6 |
比較例4 | 5 | 對第三丁基酚 | 2 | 0.3 | 13.6 |
比較例5 | 5 | 4-(甲基硫代)酚 (4-(methylthio) phenol) | 2 | 0.8 | 13.5 |
比較例6 | 5 | 2,4-二甲苯酚 (24-xylenol) | 2 | 0.7 | 13.5 |
比較例7 | 5 | 鄰苯甲酚 | 2 | 0.6 | 13.5 |
比較例8 | 5 | 間苯甲酚 | 2 | 0.7 | 13.5 |
比較例9 | 5 | 對苯甲酚 | 2 | 0.8 | 13.6 |
比較例10 | 5 | 甲氧基氫醌 | 5 | 0.4 | 12.1 |
比較例11 | 10 | 甲氧基氫醌 | 10 | 0.3 | 12.3 |
如表1所示,使用添加式(1)所表示的酚化合物的pH 12.5以上的5質量%TMAH水溶液及10質量%TMAH水溶液所組成的蝕刻液時,矽的蝕刻速度最低為0.9μm/分,最高為1.6μm/分。從比較例1、2所示,5質量%TMAH水溶液及10質量%TMAH水溶液的矽的蝕刻速度為0.8μm/分,可知藉由添加式(1)所示的酚化合物的蝕刻速度為1.1~2倍。
另一方面,如比較例4~6、9所示,式(1)中的R2
不是氫原子、羥基、烷氧基或胺基,而為烷基或硫代烷基時,可知並未看到矽的蝕刻速度的提升,有的反而蝕刻速度變慢。如比較例7所示,R1
為烷基,R2
為氫原子時,亦可知並未看到矽的蝕刻速度的提升,有的反而蝕刻速度變慢。
此外,如比較例10、11所示,蝕刻液的pH低於12.5,則可知並未看到矽的蝕刻速度的提升,反而有蝕刻速度變慢。
如實施例2、3、7、8所示,可知以式(1)所示的酚化合物的取代基在對位時(實施例7、8),矽的蝕刻速度較鄰位的情形(實施例2、3)大大的提升。另一方面,如比較例3、8所示,以式(1)所示的酚化合物的取代基為間位時,沒有提升矽的蝕刻速度的效果。
如實施例29、30所表示,使用預先以液溫80℃加熱處理24小時後的蝕刻液時的矽的蝕刻速度為1.5μm/分及1.6μm/分。如實施例6、8所示,沒有長時間加熱的蝕刻液的矽的蝕刻速度均為1.5μm/分,可知蝕刻速度並不會因長時間加熱而下降,熱穩定性優良。
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