TWI683037B - 於製造一半導體裝置時用於選擇性移除矽氮化物的蝕刻溶液 - Google Patents
於製造一半導體裝置時用於選擇性移除矽氮化物的蝕刻溶液 Download PDFInfo
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- TWI683037B TWI683037B TW107119087A TW107119087A TWI683037B TW I683037 B TWI683037 B TW I683037B TW 107119087 A TW107119087 A TW 107119087A TW 107119087 A TW107119087 A TW 107119087A TW I683037 B TWI683037 B TW I683037B
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- Prior art keywords
- alcohol
- ether
- etching solution
- glycol
- silicon nitride
- Prior art date
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- 238000005530 etching Methods 0.000 title claims abstract description 69
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 31
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000004065 semiconductor Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 23
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 14
- 238000004377 microelectronic Methods 0.000 claims abstract description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 39
- -1 alkoxy alcohol Chemical compound 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- CSZZMFWKAQEMPB-UHFFFAOYSA-N 1-methoxybutan-2-ol Chemical compound CCC(O)COC CSZZMFWKAQEMPB-UHFFFAOYSA-N 0.000 claims description 2
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- LJVNVNLFZQFJHU-UHFFFAOYSA-N 2-(2-phenylmethoxyethoxy)ethanol Chemical compound OCCOCCOCC1=CC=CC=C1 LJVNVNLFZQFJHU-UHFFFAOYSA-N 0.000 claims description 2
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 claims description 2
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 2
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 claims description 2
- FMVOPJLFZGSYOS-UHFFFAOYSA-N 2-[2-(2-ethoxypropoxy)propoxy]propan-1-ol Chemical compound CCOC(C)COC(C)COC(C)CO FMVOPJLFZGSYOS-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- DEDUBNVYPMOFDR-UHFFFAOYSA-N 2-ethoxypropan-1-ol Chemical compound CCOC(C)CO DEDUBNVYPMOFDR-UHFFFAOYSA-N 0.000 claims description 2
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 claims description 2
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 claims description 2
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 2
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 claims description 2
- 229940088601 alpha-terpineol Drugs 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003827 glycol group Chemical group 0.000 claims 2
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- ZHZCYWWNFQUZOR-UHFFFAOYSA-N pent-4-en-2-ol Chemical compound CC(O)CC=C ZHZCYWWNFQUZOR-UHFFFAOYSA-N 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 83
- 239000000463 material Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 20
- 229910004298 SiO 2 Inorganic materials 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
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- 230000004888 barrier function Effects 0.000 description 4
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- 239000002245 particle Substances 0.000 description 4
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- 239000000654 additive Substances 0.000 description 3
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- 239000012964 benzotriazole Substances 0.000 description 3
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Images
Classifications
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- 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
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/66—Chemical treatment, e.g. leaching, acid or alkali treatment
- C03C25/68—Chemical treatment, e.g. leaching, acid or alkali treatment by etching
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- 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
-
- 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
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- 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
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- 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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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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- H—ELECTRICITY
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
- H01L21/461—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/465—Chemical or electrical treatment, e.g. electrolytic etching
Abstract
於本文中描述出一種包含水、磷酸溶液(水性)及含羥基溶劑的蝕刻溶液。此組成物有用地用於一上面具有矽氮化物與氧化矽的微電子裝置,在其製造期間來選擇性移除此等材料。
Description
本申請案在35 U.S.C.§ 119(e)下主張2017年6月5日提出的美國臨時專利申請案案號62/515,351之優先權,其全文以參考之方式併入本文。
本發明係關於一種使用在半導體裝置之製造的水性磷酸蝕刻溶液。更特別是,本發明提供一種水性磷酸蝕刻溶液,其對在矽氮化物-氧化矽複合半導體裝置中之矽氮化物膜的蝕刻選擇性增加超過二氧化矽膜。
矽氮化物廣泛使用在半導體工業中作為阻障物或頂層以防止污染物擴散進半導體裝置中。其亦使用在矽的局部氧化(LOCOS)方法中作為選擇性氧化阻障物,以允許在需要的區域中發生氧化而提供電晶體分隔。矽氮化物基本
上具惰性、緻密及難以蝕刻。可使用氫氟酸及經緩衝的氧化物蝕刻劑,但是其蝕刻速率通常甚至在高溫下亦慢且光阻經常因極端的蝕刻條件而受相反影響。另一個問題為當在蝕刻溶液中使用磷酸時,磷酸會蝕刻二氧化矽與矽氮化物二者。當需要選擇性蝕刻矽氮化物時,此共蝕刻係不想要。例如,美國專利案號5,472,562教導將一可溶的矽化合物加入至磷酸、氫氟酸及硝酸之蝕刻溶液將輔助矽氮化物相關於矽及二氧化矽的蝕刻選擇性。但是,額外的氫氟酸及硝酸之存在係不想要,且在許多情況中,其對半導體製程有害。在技藝中所揭示出的其它方法提供一種已加入矽來修改該組成物之蝕刻特徵的剝除組成物。典型來說,此可藉由將含固體矽材料諸如矽晶圓加入至已加熱的磷酸溶液而達成。此方法係不想要,因為需要一段時間來消化矽晶圓且於該蝕刻溶液中存在有未溶解的粒子。再者,加熱方法會伴隨著自己一套要關心的事物,諸如需要特別的設備來包括蒸氣。因此,在技藝中仍然有需要一種對SiN的選擇性超過高於SiO2之經改良的蝕刻溶液。
在一個態樣中,本發明提供一種合適於從微電子裝置中選擇性移除矽氮化物超過氧化矽之蝕刻溶液,其包含:水、磷酸溶液(水性)及含羥基溶劑,其係一可與水溶混(或可溶於水)的溶劑。該蝕刻溶液可選擇性包含一界面活性劑,例如,非離子界面活性劑。
在另一個態樣中,本發明提供一種選擇性提高在包含矽氮化物與二氧化矽的複合半導體裝置中之矽氮化物相對於二氧化矽的蝕刻速率之方法,該方法其步驟包括:讓該包含矽氮化物及二氧化矽的複合半導體裝置與一包含磷酸及含羥基溶劑之水性組成物接觸;及在至少部分移除該矽氮化物後,沖洗該複合半導體裝置,其中該矽氮化物對氧化矽的蝕刻選擇性係約50至約500或較高,或約200至約500。
本發明之具體實例可單獨或彼此組合著使用。
圖1闡明一包含不同溶劑型式之組成物的Si3N4及SiO2蝕刻速率圖;圖2闡明一圖1之組成物的Si3N4/SiO2蝕刻選擇性圖;圖3闡明包含不同溶劑型式的組成物之Si3N4及SiO2蝕刻速率圖;圖4闡明一圖3之組成物的Si3N4/SiO2蝕刻選擇性圖;圖5闡明包含不同溶劑型式的組成物之Si3N4及SiO2蝕刻速率圖;及圖6闡明一圖5之組成物的Si3N4/SiO2蝕刻選擇性圖。
於本文中所引用,包括公告、專利申請案及專利的全部參考資料藉此以參考方式併入本文,至如若每篇參考各別及特別指示出以參考方式併入本文及其全文係於本文中提出般相同的程度。
在描述出本發明的上下文中(特別在下列申請專利範圍的上下文中),除非其它方面於本文中有指示出或上下文有明確矛盾,否則用語「一」及「一種」及「該」及類似指涉之使用欲推斷為涵蓋單數及複數二者。除非其它方面有提到,否則用語「包含(comprising)」、「具有(having)」、「包括(including)」及「包括(containing)」欲推斷為開放式用語(即,意謂著「包括但不限於」)。除非其它方面於本文中有指示出,否則於本文中所列舉的值範圍全然意欲提供作為各別指出落在該範圍內的每個分別值之速記方法,及每個分別值係併入本專利說明書中如若其各別於本文中敘述般。除非其它方面於本文中有指示出或其它方面上下文有明確矛盾,否則於本文中所描述的全部方法皆可以任何合適的順序進行。除非其它方面有主張,否則於本文中所提供的任何及全部實施例或範例性文字(例如,「諸如」)之使用全然意欲較好闡明本發明及不引起本發明範圍之限制。在本專利說明書中並無文字應該推斷為指示出任何未主張的元素作為實行本發明之基本。在本專利說明書及申請專利範圍中的用語「包含」之使用包括更狹窄的用字「實質上由...組成」及「由...組成」。
於本文中描述出本發明的較佳具體實例,包括已由發明家知曉用來進行本發明的最好模式。可由一般熟悉此技藝之人士在讀取前述說明後明瞭那些較佳具體實例的變化。本發明家預計熟練人士可如適當地使用此變化,及本發明家意欲與如於本文所特別描述不同般來實行本發明。此外,本發明包括在到此為止所附加如由管轄法律所准許的申請專利範圍中所敘述之主題的全部改質及同等物。再者,除非其它方面於本文中有指示出或其它方面上下文有明確矛盾,否則本發明包括上述元素在其全部可能的變化內之任何組合。
本發明普遍關於一種有用地用於一上面具有矽氮化物及氧化矽的微電子裝置之組成物,其在該裝置的製造期間,對此等材料之矽氮化物的移除選擇性超過氧化矽。
為了參照容易,「微電子裝置」與經製造使用於微電子、積體電路或電腦晶片應用的半導體基材、平板顯示器、相位變化記憶體裝置、太陽能面板及其它產品包括太陽能基板、光電伏特計及微電機系統(MEMS)相應。該太陽能基板包括但不限於矽、非晶矽、多晶矽、單晶矽、CdTe、硒化銦銅、硫化銦銅及砷化鎵在鎵上。該太陽能基板可經摻雜或未摻雜。要瞭解的是,用語「微電子裝置」不意謂著以任何方式限制及包括最終將變成微電子裝置或微電子組合之任何基材。
如於本文中所定義,「低k介電材料」與使
用在積層的微電子裝置中作為介電材料之任何材料相應,其中該材料具有介電常數小於約3.5。較佳的是,該低k介電材料包括低極性材料,諸如含矽有機聚合物、含矽的雜合有機/無機材料、有機矽酸鹽玻璃(OSG)、TEOS、氟化的矽酸鹽玻璃(FSG)、二氧化矽及摻雜碳的氧化物(CDO)玻璃。要瞭解的是,該低k介電材料可具有不同密度及不同多孔洞性。
如於本文中所定義,用語「阻障材料」與在技藝中使用來密封金屬線例如銅互相連接,以最小化該金屬例如銅擴散進介電材料中的任何材料相應。較佳的阻障層材料包括鉭、鈦、釕、鉿及其它耐火性金屬及其氮化物及矽化物。
「實質上無」於本文中係定義為少於0.001重量%。「實質上無」亦包括0.000重量%。用語「無」意謂著0.000重量%。
如於本文中所使用,「約」意欲與所描述的值之±5%相應。
在該組成物的特定組分係參照包括零下限的重量百分比範圍進行討論之全部此等組成物中,將要了解的是,於該組成物的多個特定具體實例中,此等組分可存在或缺乏,及在此等組分係存在的例子中,它們可以低如0.001重量百分比之濃度呈現,以使用此等組分的組成物之總重量為基準。
在此態樣的寬廣實行中,本開發之蝕刻溶液
包含水、磷酸及含羥基溶劑、基本上由其組成或由其組成。
在某些具體實例中,於本文中所揭示的蝕刻溶液組成物係調配成實質上無下列化學化合物之至少一種:過氧化氫及其它過氧化物、銨離子、氟化物離子及研磨材料。
在其它具體實例中,於本文中所揭示出的蝕刻溶液組成物係調配成無下列化學化合物之至少一種:過氧化氫及其它過氧化物、銨離子、氟化物離子及研磨材料。本發明之組成物可無下列化學化合物之至少一種:硫酸、氫氟酸、六氟矽酸、氟化銨、鹽酸、硝酸。在本發明之某些組成物中,唯一存在於該組成物中的無機陰離子係磷酸離子。
水
本開發的蝕刻組成物係水性基底,因此,包含水。在本發明中,水以多種方式作用,諸如例如,溶解該組成物之一或多種組分、作為該等組分之載劑、作為移除殘餘物之輔助、作為該組成物之黏度改質劑及作為稀釋劑。較佳的是,在該清潔組成物中所使用的水係去離子化(DI)水。
對大部分應用來說,咸信在該組成物中的水之重量百分比其開始及結束點將以選自於下列數字之群的範圍呈現:0.5、1、5、10、15、20、25、30、40及60。可使用在該組成物中的水範圍之實施例包括例如約0.5%
至約60重量%,或1%至約60重量%的水,或約0.5%至約40重量%,或約1%至約25重量%,或約1%至約20重量%,或約1%至約15重量%,或約5%至約20重量%,或5至約15重量%的水。本發明的又其它較佳具體實例可包括達成其它原料之想要的重量百分比的水量。
磷酸
本發明之蝕刻組成物包含磷酸。該磷酸主要作用為蝕刻矽氮化物。可使用商業等級磷酸。典型來說,該可商業購得的磷酸可以80%至85%水溶液獲得,但是,於本文中所描述及主張的磷酸量係以純淨溶液為基準。在較佳的具體實例中,使用電子等級磷酸溶液,其中此電子等級溶液典型具有粒子計數低於100粒子/毫升,及其中該粒子尺寸係少於或等於0.5微米及金屬離子係以每升低每百萬份至每億份程度存在於該酸中。並無將其它酸諸如氫氟酸、硝酸或其混合物加入至本發明之溶液。
對大部分應用來說,咸信所包含的磷酸量將係該組成物之約40%至約99重量%,或約50%至約95重量%,或約60%至約90重量%,或70%至約90重量%,或80%至約90重量%,或具有開始及結束點係選自於40、50、60、70、80、90、95及99之任何其它重量%範圍,以該組成物的總重量為基準。
含羥基溶劑
本發明之蝕刻組成物包含一含羥基溶劑。該含羥基溶劑主要作用為保護氧化矽,如此優先及選擇性蝕刻矽氮化物。在本發明中所使用的溶劑可係水可溶混。
該含羥基溶劑的種類包括但不限於烷烴雙醇及多元醇(包括但不限於伸烷基二醇)、二醇、烷氧基醇(包括但不限於二醇單醚)、飽和脂肪族單羥基醇、不飽和非芳香族單羥基醇、及包括環結構的低分子量醇。
該可溶於水的烷烴雙醇及多元醇諸如(C2-C20)烷二醇及(C3-C20)烷烴三醇之實施例包括但不限於2-甲基-1,3-丙二醇、1,3-丙二醇、2,2-二甲基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、1,2-丁二醇、2,3-丁二醇及。
該可溶於水的伸烷基二醇之實施例包括但不限於乙二醇、丙二醇、二甘醇、二丙二醇、三甘醇及四甘醇。
該可溶於水的烷氧基醇之實施例包括但不限於3-甲氧基-3-甲基-1-丁醇、3-甲氧基-1-丁醇、1-甲氧基-2-丁醇及可溶於水的二醇單醚。
該可溶於水的二醇單醚之實施例包括但不限於乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單正丙基醚、乙二醇單異丙基醚、乙二醇單正丁基醚、二甘醇單甲基醚、二甘醇單乙基醚、二甘醇單丁基醚、三甘醇單甲基醚、三甘醇單乙基醚、三甘醇單丁基醚、1-甲氧基-2-丙醇、2-甲氧基-1-丙醇、1-乙氧基-2-丙醇、2-乙氧基-1-丙醇、
丙二醇單正丙基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單正丙基醚、三丙二醇單乙基醚、三丙二醇單甲基醚及乙二醇單苄基醚、二甘醇單苄基醚。
該可溶於水的飽和脂肪族單羥基醇之實施例包括但不限於甲醇、乙醇、正丙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、三級丁醇、2-戊醇、三級戊醇及1-己醇。
該可溶於水的不飽和非芳香族單羥基醇之實施例包括但不限於烯丙醇、炔丙醇、2-丁烯基醇、3-丁烯基醇及4-戊烯-2-醇。
該包括環結構之可溶於水的低分子量醇之實施例包括但不限於α-萜品醇、四氫糠基醇、糠醇及1,3-環戊二醇。
對大部分應用來說,咸信在該組成物中之含羥基溶劑的重量百分比可在具有開始及結束點係選自於下列列出的重量百分比之範圍內:0.5、1、5、7、12、15、20、30、35、40、50、59.5。此溶劑範圍的實施例包括該組成物之約0.5%至約59.5重量%;或約1%至約50重量%;或約1%至約40重量%;或約0.5%至約30重量%;或約1%至約30重量%;或約5%至約30重量%;或約5%至約15重量%;或約7%至約12重量%。
界面活性劑(選擇性)
本發明之組成物選擇性包含至少一種界面活性劑。使用在本文描述的組成物中之界面活性劑包括但
不限於兩性鹽、陽離子界面活性劑、陰離子界面活性劑、兩性離子界面活性劑、非離子界面活性劑及其組合,包括但不限於雙(2-乙基己基)磷酸酯、全氟庚酸、全氟癸酸、三氟甲烷磺酸、膦醯醋酸、十二碳烯基琥珀酸、磷酸氫雙十八烷基酯、磷酸二氫十八烷基酯、十二烷胺、十二碳烯基琥珀酸單二乙醇醯胺、月桂酸、棕櫚酸、油酸、杜松酸、12羥基硬脂酸、磷酸十二烷基酯。
所預期的非離子界面活性劑包括但不限於聚氧基伸乙基月桂基醚(Emalmin NL-100(Sanyo)、Brij 30、Brij 98、Brij 35)、十二碳烯基琥珀酸單二乙醇醯胺(DSDA,Sanyo)、乙二胺四(乙氧基化物-嵌段-丙氧基化物)四醇(Tetronic 90R4)、聚乙二醇類(例如,PEG 400)、聚丙二醇類、聚伸乙基或聚伸丙基二醇醚類、以環氧乙烷及環氧丙烷為主的嵌段共聚物(Newpole PE-68(Sanyo)、Pluronic L31、Pluronic 31R1、Pluronic L61、Pluronic F-127)、聚氧基伸丙基蔗糖醚(SN008S,Sanyo)、三級辛基苯氧基聚乙氧基乙醇(Triton X100)、10-乙氧基-9,9-二甲基癸烷-1-胺(Triton®CF-32)、聚氧基伸乙基(9)壬基苯基醚、分枝的(IGEPAL CO-250)、聚氧基伸乙基(40)壬基苯基醚、分枝的(IGEPAL CO-890)、聚氧基伸乙基山梨糖醇六油酸酯、聚氧基伸乙基山梨糖醇四油酸酯、聚乙二醇脫水山梨糖醇單油酸酯(Tween 80)、單油酸脫水山梨糖醇酯(Span 80)、Tween 80與Span 80之組合、醇烷氧基化物(例如,Plurafac RA-20)、烷基-多糖苷、全氟丁酸乙酯、
1,1,3,3,5,5-六甲基-1,5-雙[2-(5-降ㄝ烯-2-基)乙基]三矽氧烷、單體十八烷基矽烷衍生物諸如SIS6952.0(Siliclad,Gelest)、經矽氧烷修改的聚矽氮烷諸如PP1-SG10 Siliclad Glide 10(Gelest)、聚矽氧-聚醚共聚物諸如Silwet L-77(Setre Chemical Company)、Silwet ECO Spreader(Momentive)、及乙氧基化的氟界面活性劑(ZONYL®FSO-100、ZONYL®FSN-100)。
所預期的陽離子界面活性劑包括但不限於溴化鯨蠟基三甲基銨(CTAB)、十七烷氟辛烷磺酸、四乙基銨、氯化硬脂基三甲基銨(Econol TMS-28,Sanyo)、溴化4-(4-二乙基胺基苯基偶氮)-1-(4-硝基苄基)吡錠、氯化鯨蠟基吡錠單水合物、氯化苄烷銨、氯化苄乙氧銨、氯化苄基二甲基十二烷基銨、氯化苄基二甲基十六烷基銨、溴化十六烷基三甲基銨、氯化二甲基雙十八烷基銨、氯化十二烷基三甲基銨、對-甲苯磺酸十六烷基三甲基銨、溴化雙十二烷基二甲基銨、氯化二(氫化獸脂)二甲基銨、溴化四庚基銨、溴化四(癸基)銨、Aliquat®336及奧芬溴銨(oxyphenonium bromide)、胍鹽酸(C(NH2)3Cl)或三氟甲基磺酸鹽諸如三氟甲烷磺酸四丁基銨、氯化二甲基雙十八烷基銨、溴化二甲基雙十六烷基銨及氯化二(氫化獸脂)二甲基銨(例如,Arquad 2HT-75,Akzo Nobel)。
所預期的陰離子界面活性劑包括但不限於聚丙烯酸銨(例如,DARVAN 821A)、在水中經修改的聚丙烯酸(例如,SOKALAN CP10S)、磷酸鹽聚醚酯(例如,
Triton H-55)、癸基膦酸、十二烷基膦酸(DDPA)、十四烷基膦酸、十六烷基膦酸、十八烷基膦酸、十二烷基苯磺酸、聚(丙烯酸鈉鹽)、聚氧基伸乙基月桂基醚鈉、二己基磺基琥珀酸鈉、磺化琥珀酸二環己基酯鈉鹽、7-乙基-2-甲基-4-十一烷基硫酸鈉(Tergitol 4)、SODOSIL RM02及磷酸鹽氟界面活性劑,諸如Zonyl FSJ及ZONYL®UR。
該兩性離子界面活性劑包括但不限於炔系雙醇或經修改的炔系雙醇(例如,SURFONYL®504)、椰油醯胺基丙基甜菜鹼、環氧乙烷烷基胺(AOA-8,Sanyo)、N,N-二甲基十二烷基胺N-氧化物、椰油胺基丙酸鈉(LebonApl-D,Sanyo)、3-(N,N-二甲基肉荳蔻基銨基)丙烷磺酸鹽及(3-(4-庚基)苯基-3-羥丙基)二甲基銨基丙烷磺酸鹽。較佳的是,該至少一種界面活性劑包含十二烷基苯磺酸、十二烷基膦酸、十二烷基磷酸鹽、Triton X-100、SOKALAN CP10S、PEG 400及PLURONIC F-127。
當存在時,該界面活性劑的量範圍可在約0.001重量%至約1重量%內,較佳為約0.1重量%至約1重量%,以該濃縮物的總重量為基準。任擇地,咸信對某些應用來說,若存在時,所包含的一或多種界面活性劑係該組成物之約0.1重量%至約15重量%,或該組成物之約0.1重量%至約10重量%,或約0.5重量%至約5重量%,或約0.1重量%至約1重量%,或約0.5重量%至約5重量%。在任擇的具體實例中,以該組成物的總重量為基準,該界面活性劑於該組成物中的重量百分比可在具有開始及結束點係
選自於下列之任何範圍內:0.1、0.5、1、5、10及15。
在某些具體實例中,本發明之組成物將無或實質上無任何或全部上述列出的界面活性劑。
腐蝕抑制劑(選擇性)
本發明之組成物選擇性包含至少一種腐蝕抑制劑。該腐蝕抑制劑提供與曝露在欲蝕刻的基材表面上之任何金屬特別是銅或非金屬反應,以讓該表面成鈍態及防止在清潔期間過量蝕刻。
可使用在技藝中已知用於類似應用的任何腐蝕抑制劑。該腐蝕抑制劑之實施例包括芳香族羥基化合物、炔系醇、含羧基有機化合物及其酐、及三唑化合物。
範例性芳香族羥基化合物包括酚、甲酚、二甲苯酚、焦兒茶酚、間苯二酚、氫醌、焦棓酚、1,2,4-苯三醇、水楊基醇、對-羥基苄基醇、鄰-羥基苄基醇、對-羥基苯乙基醇、對-胺基酚、鄰-胺基酚、二胺基酚、胺基間苯二酚、對-羥基苯甲酸、鄰-羥基苯甲酸、2,4-二羥基苯甲酸、2,5-二羥基苯甲酸、3,4-二羥基苯甲酸及3,5-二羥基苯甲酸。
範例性炔系醇包括2-丁炔-1,4-二醇、3,5-二甲基-1-己炔-3-醇、2-甲基-3-丁炔-2-醇、3-甲基-1-戊炔-3-醇、3,6-二甲基-4-辛炔-3,6-二醇、2,4,7,9-四甲基-5-癸炔-4,7-二醇及2,5-二甲基-3-己炔-2,5-二醇。
範例性含羧基有機化合物及其酐包括蟻
酸、醋酸、丙酸、丁酸、異丁酸、草酸、丙二酸、琥珀酸、戊二酸、馬來酸、反丁烯二酸、苯甲酸、酞酸、1,2,3-苯三羧酸、羥乙酸、乳酸、馬來酸、醋酸酐及水楊酸。
範例性三唑化合物包括苯并三唑、鄰-甲苯基三唑、間-甲苯基三唑、對-甲苯基三唑、羧基苯并三唑、1-羥基苯并三唑、硝基苯并三唑及二羥基丙基苯并三唑。
在範例性具體實例中,該腐蝕抑制劑包括下列之一或多種:苯并三唑、羧基苯并三唑、胺基-苯并三唑、D-果糖、三級丁基兒茶酚、L-抗壞血酸、香草精、水楊酸、二乙基羥胺及聚(伸乙基亞胺)。
在其它具體實例中,該腐蝕抑制劑係三唑及係苯并三唑、鄰-甲苯基三唑、間-甲苯基三唑及對-甲苯基三唑之至少一種。
對大部分應用來說,咸信若存在時,所包含的腐蝕抑制劑將係該組成物之約0.1重量%至約15重量%,較佳為包含該組成物之約0.1重量%至約10重量%,較佳的是,約0.5重量%至約5重量%,及最佳為,約0.1重量%至約1重量%,或約0.5重量%至約5重量%。
在某些具體實例中,本發明之組成物將無或實質上無任何或全部上述列出的腐蝕抑制劑。
其它選擇性原料
本發明之蝕刻組成物亦可包括一或多種下列添加劑:螯合劑、化學改質劑、染料、滅菌劑及其它添加劑。可將
該添加劑加入至它們不會相反影響該組成物之性能的程度。
可使用在該蝕刻組成物中的另一種選擇性原料係金屬螯合劑,其可作用以增加該組成物將金屬保留在溶液中及提高金屬殘餘物溶解的能力。對此目的有用的螯合劑之典型實施例有下列有機酸及其異構物及鹽:乙二胺四醋酸(EDTA)、丁二胺四醋酸、(1,2-伸環己基二胺)四醋酸(CyDTA)、二伸乙基三胺五醋酸(DETPA)、乙二胺四丙酸、(羥乙基)乙二胺三醋酸(HEDTA)、N,N,N’,N’-乙二胺四(伸甲基膦)酸(EDTMP)、三伸乙基四胺六醋酸(TTHA)、1,3-二胺基-2-羥基丙烷-N,N,N’,N’-四醋酸(DHPTA)、甲基亞胺基二醋酸、丙二胺四醋酸、硝基三醋酸(NTA)、檸檬酸、酒石酸、葡萄糖酸、糖質酸、甘油酸、草酸、酞酸、馬來酸、扁桃酸、丙二酸、乳酸、水楊酸、沒食子酸丙酯、焦棓酚、8-羥基喹啉及半胱胺酸。較佳的螯合劑有胺基羧酸,諸如EDTA、CyDTA;及胺基膦酸,諸如EDTMP。
咸信該螯合劑若存在時,其在該組成物中的量將係約0.1重量%至約10重量%,較佳的量為該組成物之約0.5重量%至約5重量%。
在某些具體實例中,本發明之組成物將無或實質上無任何或全部上述列出的螯合劑加入至該組成物。
可在該清潔組成物中包括習知量之其它通常已知的組分,諸如染料、滅菌劑等等,例如,其量最高
總共係該組成物之約5重量%。
可在該清潔組成物中包括習知量之其它通常已知的組分,諸如染料、滅菌劑等等,例如,其量最高總共係該組成物之約5重量%。
本發明之蝕刻溶液組成物典型藉由在室溫下於容器中一起混合該等組分來製備,直到全部固體已溶解在該水性基底媒質中。
方法
在另一個態樣中,有提供一種用以選擇性提高在包含矽氮化物及二氧化矽的複合半導體裝置中之矽氮化物相對於二氧化矽的蝕刻速率之方法,其係藉由以一包含磷酸及含羥基溶劑、實質上由其組成或由其組成之組成物來蝕刻該複合半導體裝置。該方法包含下列步驟:讓該包含矽氮化物及二氧化矽之複合半導體裝置與一包含磷酸及含羥基溶劑、實質上由其組成或由其組成之組成物接觸;及在至少部分移除矽氮化物後,沖洗該複合半導體裝置。亦可在該方法中包括額外的乾燥步驟。「至少部分移除」意謂著移除至少50%的該材料,較佳為移除至少70%。最佳的是,使用本開發之組成物移除至少80%。
可藉由任何合適的方法進行該接觸步驟,諸如例如,沈浸、噴灑或經由單晶圓方法。該組成物在該接觸步驟期間的溫度較佳為約100至200℃及更佳為約150至180℃。
在較佳具體實例中,使用本發明之組成物所觀察到的蝕刻選擇性係約50至500或更大,更佳為約100至500及最佳為約125至500。
在該接觸步驟後係一選擇性沖洗步驟。可藉由任何合適的方法進行該沖洗步驟,例如,使用去離子水,藉由沈浸或噴灑技術來沖洗該基材。在較佳具體實例中,可使用去離子水與有機溶劑,諸如例如,異丙醇之混合物進行該沖洗步驟。
在該接觸步驟及選擇性沖洗步驟後係一選擇性乾燥步驟,其係藉由任何合適的方法進行,例如,異丙醇(IPA)蒸氣乾燥、熱或藉由向心力。
藉由下列討論的闡明性實施例更完全地顯示出特徵及優點。
用以製備該清潔組成物的一般程序
在250毫升燒杯中,以1”塗佈鐵弗龍的攪拌棒來混合組分以製備係本實施例的目標之全部組成物。典型來說,加入至該燒杯的第一材料係去離子化(DI)水。典型加入磷酸,其次接著該含羥基溶劑。
基材的組成物
在本實施例中所使用的20毫米乘以20毫米測試試樣每個皆係在矽基材上包含一層矽氮化物Si3N4。比
較例係在矽基材上包含一層氧化矽SiO2。
加工條件
在250毫升燒杯中,使用設定在400rpm的½”圓鐵弗龍攪拌棒,使用100克蝕刻組成物進行蝕刻測試。在加熱板上,將該蝕刻組成物加熱至溫度約160℃。將該測試試樣沈浸在該組成物中約20分鐘,同時攪拌。
然後,以DI水浴或噴灑來沖洗該等斷片3分鐘,隨後使用經過濾的氮來乾燥。藉由橢圓偏振光譜(MG-1000,Nano-View Co.,Ltd.,南韓)測量在蝕刻前及後之厚度變化來估計矽氮化物及氧化矽的蝕刻速率。Si3N4的典型開始層厚度係4395埃及SiO2係229埃。
實施例組1
製備四個水性蝕刻組成物,每個各別包含60重量%磷酸及30體積%的(1)DMSO(33重量%)、(2)環丁碸(37.8重量%)、(3)丙二醇(PG)(31.2重量%)及(4)二丙二醇甲基醚(PGME)(28.5重量%)。該組成物的剩餘部分為水。如上所述般但是沒有溶劑(「n.a」)製得一組成物。該組成物係85重量%磷酸及剩餘部分係水。
參照圖1及圖2,加入DMSO會減低Si3N4及SiO2二者之蝕刻速率而沒有改變選擇性。加入環丁碸進一步減低SiO2之蝕刻速率且選擇性增加至54。加入包含-OH基團的PG及DPGME大大抑制SiO2之蝕刻速率且選擇性
各別大增加至104及137。但是,當加入PG及DPGME時,該蝕刻劑會在加熱後變黏。
實施例組2
在此實施例組中,改變溶劑量。製備四個水性蝕刻組成物,各者各別包含60重量%磷酸及任一的10%或30體積%的(1)丙二醇(PG)(11重量%,10體積%)(33重量%,30體積%),及(2)二丙二醇甲基醚(PGME)(9.5重量%,10體積%)及(28.5重量%,30體積%)。該組成物的剩餘部分係水。如上述般但是沒有溶劑(「n.a」)製得一組成物,即該組成物為85重量%磷酸及剩餘部分的水。
參照圖3及圖4,加入10體積%的SiO2蝕刻減少係比30體積%的少。因為Si3N4之蝕刻未明顯影響,其蝕刻選擇性仍然高於僅有85重量%的H3PO4,但是更低於加入30體積%的PG及DPGME。雖然在該組成物中所使用的溶劑量減少至10體積%,該蝕刻劑溶液仍然在加熱後變黏。
實施例組3
至於另一個比較點,因為PG在10體積%(10.4重量%)下比DPGME更有效地降低SiO2的蝕刻速率,於PG存在下加入HF來確定蝕刻速率是否將增加。
參照圖5及圖6,於PG存在下,內含HF的組成物之蝕刻選擇性從15.4增加至19.7,其不如此有效。但是,整體來說,將HF加入至該PG/H3PO4蝕刻組成物,當
該HF係以該組成物之10體積%(10.4重量%)呈現時,其選擇性從56大大減少至19,及當以30體積%(31.2重量%)呈現時,從104減少至20。
前述說明主要意欲用於闡明的目的。雖然本發明已經顯示及描述出其相關的典型具體實例,應該要由熟習該項技術者了解的是,可在其形式及細節中製得前述及多種其它改變、省略及加入而沒有離開本發明之精神及範圍。
Claims (16)
- 一種合適於從微電子裝置中選擇性移除矽氮化物超過氧化矽之蝕刻溶液,其包含:0.5%至60%水,以該蝕刻溶液的總重量為基準;40%至90%磷酸;及0.5%至低於50%含羥基溶劑,以該蝕刻溶液的總重量為基準,其中該含羥基溶劑係選自於由下列組成之群:烷烴二醇或多元醇、二醇、烷氧基醇、飽和脂肪族單羥醇、不飽和非芳香族單羥醇及包括環結構的醇。
- 如請求項1之蝕刻溶液,其中該含羥基溶劑係烷烴二醇或多元醇及選自於由下列組成之群:2-甲基-1,3-丙二醇、1,3-丙二醇、2,2-二甲基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、1,2-丁二醇、2,3-丁二醇及酉品。
- 如請求項1之蝕刻溶液,其中該含羥基溶劑係二醇及選自於由下列組成之群:乙二醇、丙二醇、二甘醇、二丙二醇、三甘醇及四甘醇。
- 如請求項1之蝕刻溶液,其中該含羥基溶劑係烷氧基醇及選自於由下列組成之群:3-甲氧基-3-甲基-1-丁醇、3-甲氧基-1-丁醇、1-甲氧基-2-丁醇及二醇單醚。
- 如請求項1之蝕刻溶液,其中該含羥基溶劑係飽和脂肪族單羥醇及選自於由下列組成之群:甲醇、乙醇、正丙基醇、異丙醇、1-丁醇、2-丁醇、異丁醇、三級丁醇、2-戊醇、三級戊醇及1-己醇。
- 如請求項1之蝕刻溶液,其中該含羥基溶劑係不飽和非芳香族單羥醇及選自於由下列組成之群:烯丙醇、炔丙醇、2-丁烯基醇、3-丁烯基醇及4-戊烯-2-醇。
- 如請求項4之蝕刻溶液,其中該含羥基溶劑係二醇單醚及選自於由下列組成之群:乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單正丙基醚、乙二醇單異丙基醚、乙二醇單正丁基醚、二甘醇單甲基醚、二甘醇單乙基醚、二甘醇單丁基醚、三甘醇單甲基醚、三甘醇單乙基醚、三甘醇單丁基醚、1-甲氧基-2-丙醇、2-甲氧基-1-丙醇、1-乙氧基-2-丙醇、2-乙氧基-1-丙醇、丙二醇單正丙基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單正丙基醚、三丙二醇單乙基醚、三丙二醇單甲基醚、及乙二醇單苄基醚、及二甘醇單苄基醚。
- 如請求項1之蝕刻溶液,其中該含羥基溶劑係包括環結構的醇及選自於由下列組成之群:α-萜品醇、四氫糠基醇、糠醇及1,3-環戊二醇。
- 如請求項1之蝕刻溶液,其中該含羥基溶劑係以該蝕刻溶液的約1%至約40重量%之量呈現。
- 如請求項1之蝕刻溶液,其中該含羥基溶劑係二丙二醇單乙基醚(DPGME)。
- 如請求項10之蝕刻溶液,其中該二丙二醇單乙基醚(DPGME)係以該蝕刻溶液的約1重量%至約50重量%之量呈現。
- 一種選擇性提高在包含矽氮化物與二氧化 矽的複合半導體裝置中之矽氮化物相對於二氧化矽的蝕刻速率之方法,該方法其步驟包括:讓該包含矽氮化物及二氧化矽的複合半導體裝置與如請求項1至11中任一項所述的蝕刻溶液接觸;及在至少部分移除矽氮化物後,沖洗該複合半導體裝置,其中該矽氮化物對氧化矽之蝕刻選擇性係約50至約500。
- 如請求項12之方法,更包含乾燥該半導體裝置的步驟。
- 如請求項12之方法,其中該矽氮化物對氧化矽的蝕刻選擇性係約100至約500。
- 如請求項12之方法,其中該矽氮化物對氧化矽的蝕刻選擇性係約125至約500。
- 如請求項12之方法,其中該接觸步驟係在溫度約100℃至約200℃下進行。
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