CN109054838A - 用于在半导体器件的制造过程中选择性除去氮化硅的蚀刻溶液 - Google Patents
用于在半导体器件的制造过程中选择性除去氮化硅的蚀刻溶液 Download PDFInfo
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- CN109054838A CN109054838A CN201810570790.5A CN201810570790A CN109054838A CN 109054838 A CN109054838 A CN 109054838A CN 201810570790 A CN201810570790 A CN 201810570790A CN 109054838 A CN109054838 A CN 109054838A
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- Prior art keywords
- glycol
- alcohol
- ether
- weight
- silicon nitride
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- 238000005530 etching Methods 0.000 title claims abstract description 49
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 37
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000004065 semiconductor Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 76
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 29
- 238000004377 microelectronic Methods 0.000 claims abstract description 11
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 45
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- -1 Alkoxyl alcohol Chemical compound 0.000 claims description 33
- 235000019441 ethanol Nutrition 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- BTANRVKWQNVYAZ-UHFFFAOYSA-N 2-butanol Substances CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 6
- 229940093476 ethylene glycol Drugs 0.000 claims description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 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
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 229940083957 1,2-butanediol Drugs 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-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
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical group OCC(C)CO QWGRWMMWNDWRQN-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
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 claims description 2
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical group COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 claims description 2
- 229910003978 SiClx Inorganic materials 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
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-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
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 2
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 claims 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 4
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 22
- 229910052681 coesite Inorganic materials 0.000 description 13
- 229910052906 cristobalite Inorganic materials 0.000 description 13
- 229910052682 stishovite Inorganic materials 0.000 description 13
- 229910052905 tridymite Inorganic materials 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
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- 239000003112 inhibitor Substances 0.000 description 9
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical group OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- WGYZMNBUZFHYRX-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-ol Chemical compound COCC(C)OCC(C)O WGYZMNBUZFHYRX-UHFFFAOYSA-N 0.000 description 4
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- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 3
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- 125000000217 alkyl group Chemical group 0.000 description 3
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- 229910052708 sodium Inorganic materials 0.000 description 3
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
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- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
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- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- WVFDILODTFJAPA-UHFFFAOYSA-M sodium;1,4-dihexoxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CCCCCCOC(=O)CC(S([O-])(=O)=O)C(=O)OCCCCCC WVFDILODTFJAPA-UHFFFAOYSA-M 0.000 description 1
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- 239000005720 sucrose Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- BVQJQTMSTANITJ-UHFFFAOYSA-N tetradecylphosphonic acid Chemical compound CCCCCCCCCCCCCCP(O)(O)=O BVQJQTMSTANITJ-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
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- JOFWLTCLBGQGBO-UHFFFAOYSA-N triazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1Cl JOFWLTCLBGQGBO-UHFFFAOYSA-N 0.000 description 1
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
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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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02046—Dry cleaning only
-
- 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
-
- 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
- H01L21/3105—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
-
- 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
- H01L21/34—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 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Weting (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
本文描述的是包含水,磷酸溶液(水性的)和含羟基溶剂的蚀刻溶液。这样的组合物可用于在微电子器件制造过程中从其上具有氮化硅和氧化硅的微电子器件相对于氧化硅选择性除去氮化硅。
Description
相关申请的交叉引用
本申请根据35U.S.C.§119(e)要求于2017年6月5日提交的美国临时专利申请号62/515,351的优先权,其全部内容通过引用并入本文。
背景技术
本发明涉及用于半导体器件制造的水性磷酸蚀刻溶液。更具体地,本发明提供了水性磷酸蚀刻溶液,其表现出氮化硅-氧化硅复合半导体器件中的氮化硅膜相对于二氧化硅膜的增加的蚀刻选择性。
氮化硅在半导体工业中被广泛用作屏障层或顶层以防止污染物扩散到半导体器件中。它也被用作硅的局部氧化(LOCOS)工艺中的选择性氧化屏障,以允许在需要的区域中发生氧化以提供晶体管隔离。氮化硅是基本上惰性的、致密的且难以蚀刻的。可以使用氢氟酸和缓冲氧化物蚀刻剂,但蚀刻速率即使在高温下也通常缓慢,并且光致抗蚀剂经常受到极端蚀刻条件的不利影响。另一个问题是当在蚀刻溶液中使用磷酸时,磷酸蚀刻二氧化硅和氮化硅两者。当需要氮化硅的选择性蚀刻时,这种共蚀刻是不期望的。例如,美国专利号5,472,562教导了向磷酸、氢氟酸和硝酸的蚀刻溶液中加入可溶性硅化合物将有助于相对于硅和二氧化硅的氮化硅蚀刻的选择性。然而,额外的氢氟酸和硝酸的存在是不期望的,并且在许多情况下对半导体工艺是有害的。本领域公开的其它工艺提供了剥离组合物,其具有被添加以改变组合物的蚀刻特性的硅。通常,这可以通过向加热的磷酸溶液添加诸如硅晶片的固体含硅材料来实现。由于消化硅晶片所需的时间长度和未溶解的颗粒在蚀刻溶液中的存在,这种工艺是不期望的。而且,加热的工艺伴随发生其自身的一组问题,例如需要特殊设备来容纳蒸气。因此,本领域仍然需要相对于SiO2具有对SiN的高选择性的改进的蚀刻溶液。
发明内容
在一个方面,本发明提供了适用于从微电子器件相对于氧化硅选择性除去氮化硅的蚀刻溶液,该蚀刻溶液包含:水;磷酸溶液(水性的);和含羟基溶剂,其可以是水混溶性(或水溶性)溶剂。蚀刻溶液可以任选地包含表面活性剂,例如非离子表面活性剂。
另一方面,本发明提供了在包含氮化硅和二氧化硅的复合半导体器件上选择性地提高氮化硅相对于二氧化硅的蚀刻速率的方法,所述方法包括以下步骤:使所述包含氮化硅和二氧化硅的复合半导体器件与包含磷酸和含羟基溶剂的水性组合物接触;以及在所述氮化硅被至少部分地除去之后清洗所述复合半导体器件,其中氮化硅相对于二氧化硅的蚀刻选择性为约50至约500或更高或者约200至约500。
本发明的实施方式可以单独或彼此组合使用。
附图说明
图1是说明包含不同类型的溶剂的组合物的Si3N4和SiO2蚀刻速率的图;
图2是说明对于图1的组合物的蚀刻选择性Si3N4/SiO2的图;
图3是说明包含不同类型的溶剂的组合物的Si3N4和SiO2蚀刻速率的图;
图4是说明对于图3的组合物的蚀刻选择性Si3N4/SiO2的图;
图5是说明包含不同类型的溶剂的组合物的Si3N4和SiO2蚀刻速率的图;和
图6是说明对于图5的组合物的蚀刻选择性Si3N4/SiO2的图。
具体实施方式
本文引用的所有参考文献(包括出版物、专利申请和专利)通过引用并入本文,如同每篇参考文献被单独且具体地指出通过引用并入本文并且在本文中全文阐述一样。
除非本文中另有说明或与上下文明显矛盾,否则在描述本发明的上下文中(特别是在下文的权利要求的上下文中)使用术语“一个/一种(a/an)”和“该/所述(the)”以及类似的指称被解释为涵盖单数和复数两者。除非另有说明,否则术语“包含”、“具有”、“包括”和“含有”被解释为开放式术语(即,意指“包括但不限于”)。除非本文另外指出,否则本文中数值范围的记载仅仅意在作为单独提及落入该范围内的每个单独数值的简写方法,并且每个单独数值被引入到说明书中,如同其在本文中单独记载一样。除非本文另有指示或者与上下文明显矛盾,否则本文描述的所有方法可以以任何合适的顺序执行。除非另外声明,否则本文提供的任何和所有实例或示例性语言(例如,“如”)的使用仅旨在更好地说明本发明,并且不对本发明的范围施加限制。说明书中的任何语言都不应被解释为表明任何未要求保护的要素对于本发明的实施是必要的。在说明书和权利要求书中使用术语“包含”包括更窄的语言“基本上由......组成”和“由...组成”。
本文描述了本发明的优选实施方式,包括发明人已知用于实施本发明的最佳模式。在阅读前面的描述之后,那些优选实施方式的变化对于本领域的普通技术人员可以变得显而易见。本发明人期望技术人员适当地采用这样的变化,并且本发明人想要本发明以不同于本文具体描述的方式来实施。因此,本发明包括可适用的法律所允许的所附权利要求书中记载的主题的所有修改方式和等同方式。此外,除非本文另有说明或者与上下文明显矛盾,否则本发明涵盖上述要素在其所有可能变化中的任何组合。
本发明一般地涉及可用于在微电子器件制造过程中从其上具有氮化硅和氧化硅的微电子器件相对于氧化硅选择性除去氮化硅的组合物。
为了便于说明,“微电子器件”对应于半导体衬底、平板显示器、相变存储器件、太阳能电池板和包括太阳能衬底、光伏器件和微机电系统(MEMS)的其他产品,其经制造以用于微电子,集成电路或计算机芯片应用。太阳能衬底包括但不限于硅、非晶硅、多晶硅、单晶硅、CdTe、硒化铜铟、硫化铜铟和镓上砷化镓。太阳能衬底可以是掺杂的或不掺杂的。应理解,术语“微电子器件”并不意味着以任何方式进行限制,并且包括最终将成为微电子器件或微电子组件的任何衬底。
如本文所定义,“低k介电材料”对应于用作层状微电子器件中的介电材料的任何材料,其中该材料具有小于约3.5的介电常数。优选地,低k介电材料包括低极性材料,例如含硅有机聚合物、含硅杂化有机/无机材料、有机硅酸盐玻璃(OSG)、TEOS、氟化硅酸盐玻璃(FSG)、二氧化硅和碳掺杂氧化物(CDO)玻璃。应认识到,低k介电材料可以具有不同的密度和不同的孔隙率。
如本文所定义的,术语“屏障材料”对应于本领域中用于密封金属线(例如铜互连)以最小化所述金属(例如铜)扩散到介电材料中的任何材料。优选的屏障层材料包括钽、钛、钌、铪和其他难熔金属以及它们的氮化物和硅化物。
“基本上不含”在本文中定义为小于0.001重量%。“基本上不含”还包括0.000重量%。术语“不含”是指0.000重量%。
如本文所使用的,“约”旨在对应于所陈述值的±5%。
在所有这样的组合物中(其中根据包括零下限的重量百分比范围讨论组合物的特定组分),应理解,这样的组分可以存在或不存在于组合物的各种具体实施方式中,且在存在这样的组分的情况下,基于其中使用这样的组分的组合物的总重量,它们可以以低至0.001重量%的浓度存在。
在该方面的广泛实践中,本发明的蚀刻溶液包含水、磷酸和含羟基溶剂;基本上由水、磷酸和含羟基溶剂组成;或由水、磷酸和含羟基溶剂组成。
在一些实施方式中,将本文公开的蚀刻溶液组合物配制为基本上不含以下化学化合物中的至少一种:过氧化氢和其他过氧化物、铵离子、氟离子和磨料。
在其他实施方式中,将本文公开的蚀刻溶液组合物配制为不含以下化学化合物中的至少一种:过氧化氢和其他过氧化物、铵离子、氟离子和磨料。本发明的组合物可以不含下列化学化合物中的至少一种:硫酸、氢氟酸、六氟硅酸、氟化铵、盐酸,硝酸。在本发明的一些组合物中,组合物中存在的唯一无机阴离子是磷酸根离子(phosphoric ion)。
水
本发明的蚀刻组合物是水基的,且因此包含水。在本发明中,水以各种方式起作用,例如溶解组合物的一种或多种组分、作为组分的载体、作为残余物去除中的助剂、作为组合物的粘度调节剂和作为稀释剂。优选地,清洁组合物中使用的水是去离子(DI)水。
据信对于大多数应用,组合物中水的重量百分比将存在于具有选自下组数字的起点和终点的范围内:0.5、1、5、10、15、20、25、30、40和60。可用于组合物的水的范围的实例包括例如约0.5重量%至约60重量%,或约1重量%至约60重量%的水;或约0.5重量%至约40重量%,或约1重量%至约25重量%,或约1重量%至约20重量%,或约1重量%至约15重量%,或约5重量%至约20重量%,或5至约15重量%的水。本发明的又一些优选实施方式可以包括获得其他成分的期望重量百分比的量的水。
磷酸
本发明的蚀刻组合物包含磷酸。磷酸主要起到蚀刻氮化硅的作用。可以使用商品级磷酸。通常,可商购的磷酸可以作为80%至85%的水溶液获得;然而,本文所述和要求保护的磷酸的量是基于纯溶液。在优选实施方式中,使用电子级磷酸溶液,其中这样的电子级溶液通常具有低于100个颗粒/ml的颗粒计数,并且其中颗粒的尺寸小于或等于0.5微米,并且金属离子以每升低百万分率至十亿分率的水平存在于酸中。没有其他酸例如氢氟酸、硝酸或其混合物被加入到本发明的溶液中。
据信对于大多数应用,基于组合物的总重量,磷酸的量将占组合物的约40重量%至约99重量%,或约50重量%至约95重量%,或约60重量%至约90重量%,或70重量%至约90重量%,或80重量%至约90重量%或具有选自以下的起点和终点的任何其他重量%范围:40、50、60、70、80、90、95和99。
含羟基溶剂
本发明的蚀刻组合物包含含羟基溶剂。含羟基溶剂主要起到保护氧化硅的作用,使得氮化硅被优先和选择性地蚀刻。用于本发明的溶剂可以是水混溶性的。
含羟基溶剂的种类包括但不限于烷二醇和多元醇(包括但不限于亚烷基二醇)、二醇(glycols)、烷氧基醇(包括但不限于二醇单醚)、饱和脂肪族一元醇、不饱和非芳香族一元醇和含环结构的低分子量醇。
水溶性烷二醇和多元醇如(C2-C20)烷二醇和(C3-C20)烷三醇的实例包括但不限于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-丁二醇和频哪醇。
水溶性亚烷基二醇的实例包括但不限于乙二醇、丙二醇、二乙二醇、二丙二醇、三乙二醇和四乙二醇。
水溶性烷氧基醇的实例包括但不限于3-甲氧基-3-甲基-1-丁醇、3-甲氧基-1-丁醇、1-甲氧基-2-丁醇和水溶性二醇单醚。
水溶性二醇单醚的实例包括但不限于乙二醇单甲醚、乙二醇单乙醚、乙二醇单正丙醚、乙二醇单异丙醚、乙二醇单正丁醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、三乙二醇单甲醚、三乙二醇单乙醚、三乙二醇单丁醚、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、丙二醇单正丙醚、二丙二醇单甲醚、二丙二醇单乙醚、二丙二醇单正丙醚、三丙二醇单乙醚、三丙二醇单甲醚和乙二醇单苄基醚、二乙二醇单苄基醚。
水溶性饱和脂肪族一元醇的实例包括但不限于甲醇、乙醇、正丙醇、异丙醇、1-丁醇、2-丁醇、异丁醇、叔丁醇、2-戊醇、叔戊醇和1-己醇。
水溶性不饱和非芳香族一元醇的实例包括但不限于烯丙醇、炔丙醇、2-丁烯醇、3-丁烯醇和4-戊烯-2-醇。
含环结构的水溶性低分子量醇的实例包括但不限于α-萜品醇、四氢糠醇、糠醇和1,3-环戊二醇。
据信对于大多数应用,组合物中含羟基溶剂的重量百分比可以在具有选自以下重量百分比列表的起点和终点的范围内:0.5、1、5、7、12、15、20、30、35、40、50、59.5。这样的溶剂范围的实例包括组合物的约0.5重量%至约59.5重量%,或约1重量%至约50重量%,或约1重量%至约40重量%,或约0.5重量%至约30重量%,或约1重量%至约30重量%,或约5重量%至约30重量%,或约5重量%至约15重量%,或约7重量%至约12重量%。
表面活性剂(任选的)
本发明的组合物任选地包含至少一种表面活性剂。用于本文所述组合物的表面活性剂包括但不限于两性盐、阳离子表面活性剂、阴离子表面活性剂、两性离子表面活性剂、非离子表面活性剂及其组合,包括但不限于双(2-乙基己基)磷酸盐、全氟庚酸、全氟癸酸、三氟甲磺酸、膦酰基乙酸、十二烯基琥珀酸、双十八烷基磷酸氢盐、十八烷基磷酸二氢盐、十二烷基胺、十二烯基琥珀酸单二乙醇酰胺、月桂酸、棕榈酸、油酸、桧酸、12-羟基硬脂酸、十二烷基磷酸盐。
设想的非离子表面活性剂包括但不限于聚氧乙烯月桂醚(Emalmin NL-100(Sanyo)、Brij 30,Brij 98,Brij 35)、十二烯基琥珀酸单二乙醇酰胺(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(例如PEG400)、聚丙二醇、聚乙二醇或聚丙二醇醚、基于环氧乙烷和环氧丙烷的嵌段共聚物(Newpole PE-68(Sanyo)、Pluronic L31、Pluronic 31R1、Pluronic L61、Pluronic F-127)、聚氧丙烯蔗糖醚(SN008S,Sanyo)、叔辛基苯氧基聚乙氧基乙醇(Triton X100)、10-乙氧基-9,9-二甲基癸-1-胺(CF-32)、支链聚氧乙烯(9)壬基苯醚(IGEPAL CO-250)、支链聚氧乙烯(40)壬基苯醚(IGEPAL CO-890)、聚氧乙烯山梨糖醇六油酸酯、聚氧乙烯山梨糖醇四油酸酯、聚乙二醇脱水山梨糖醇单油酸酯(Tween 80)、脱水山梨糖醇单油酸酯(Span 80)、Tween80和Span 80的组合、醇烷氧基化物(例如Plurafac RA-20)、烷基聚葡糖苷、全氟丁酸乙酯、1,1,3,3,5,5-六甲基-1,5-双[2-(5-降冰片烯-2-基)乙基]三硅氧烷、单体十八烷基硅烷衍生物例如SIS6952.0(Siliclad,Gelest)、硅氧烷改性的聚硅氮烷例如PP1-SG10SilicladGlide 10(Gelest)、硅氧烷-聚醚共聚物例如Silwet L-77(Setre Chemical Company)、Silwet ECO Spreader(Momentive)和乙氧基化含氟表面活性剂(FSO-100,FSN-100)。
设想的阳离子表面活性剂包括但不限于鲸蜡基三甲基溴化铵(CTAB)、十七烷氟辛烷磺酸、四乙基铵、硬脂基三甲基氯化铵(Econol TMS-28,Sanyo)、溴化4-(4-二乙基氨基苯基偶氮基)-1-(4-硝基苄基)吡啶、氯化鲸蜡基吡啶一水合物、苯扎氯铵、苄索氯铵、苄基二甲基十二烷基氯化铵、苄基二甲基十六烷基氯化铵、十六烷基三甲基溴化铵、二甲基双十八烷基氯化铵、十二烷基三甲基氯化铵、十六烷基三甲基铵对甲苯磺酸盐、双十二烷基二甲基溴化铵、二(氢化牛脂基)二甲基氯化铵、四庚基溴化铵、四(癸基)溴化铵、336和奥芬溴铵、胍盐酸盐(C(NH2)3Cl)或三氟甲磺酸盐如四丁基铵三氟甲磺酸盐、二甲基双十八烷基氯化铵、二甲基双十六烷基溴化铵和二(氢化牛脂基)二甲基氯化铵(例如Arquad 2HT-75,Akzo Nobel)。
设想的阴离子表面活性剂包括但不限于聚丙烯酸铵(例如DARVAN 821A)、水中的改性聚丙烯酸(例如SOKALAN CP10S)、磷酸聚醚酯(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(丙烯酸钠盐)、聚氧乙烯月桂醚钠、二己基磺基琥珀酸钠、二环己基磺基琥珀酸钠盐、7-乙基-2-甲基-4-十一烷基硫酸钠(Tergitol 4)、SODOSIL RM02和磷酸含氟表面活性剂例如Zonyl FSJ和UR。
两性离子表面活性剂包括但不限于炔属二醇或改性炔属二醇(例如504)、椰油酰胺丙基甜菜碱、环氧乙烷烷基胺(AOA-8,Sanyo)、N,N-二甲基十二烷基胺N-氧化物、椰油氨基丙酸钠(sodium cocaminpropinate)(LebonApl-D,Sanyo)、3-(N,N-二甲基肉豆蔻基铵基)丙磺酸盐和(3-(4-庚基)苯基-3-羟丙基)二甲基铵基丙磺酸盐。优选地,该至少一种表面活性剂包含十二烷基苯磺酸、十二烷基膦酸、十二烷基磷酸盐、TRITON X-100、SOKALAN CP10S、PEG 400和PLURONIC F-127。
当存在时,基于浓缩物的总重量,表面活性剂的量可以在约0.001重量%至约1重量%,优选约0.1重量%至约1重量%的范围内。或者,据信对于一些应用,如果存在的话,该一种或多种表面活性剂将占组合物的约0.1重量%至约15重量%;或约0.1重量%至约10重量%,或约0.5重量%至约5重量%,或约0.1重量%至约1重量%,或组合物的约0.5重量%至约5重量%。在替代实施方式中,基于组合物的总重量,组合物中表面活性剂的重量百分比可以在具有选自以下的起点和终点的任何范围内:0.1、0.5、1、5、10和15。
在一些实施方式中,本发明的组合物将不含或基本上不含任何或全部上文列出的表面活性剂。
腐蚀抑制剂(任选的)
本发明的组合物任选地包含至少一种腐蚀抑制剂。腐蚀抑制剂用于与暴露在经受蚀刻的衬底表面上的任何金属(特别是铜)或非金属反应,以使表面钝化并阻止在清洁过程中过度蚀刻。
可以使用本领域已知用于类似应用的任何腐蚀抑制剂。腐蚀抑制剂的实例包括芳香族羟基化合物、炔属醇、含羧基有机化合物及其酸酐,和三唑化合物。
示例性芳香族羟基化合物包括苯酚、甲酚、二甲苯酚、邻苯二酚、间苯二酚、氢醌、连苯三酚、1,2,4-苯三酚、水杨醇、对羟基苄醇、邻羟基苄醇、对羟基苯乙醇、对氨基苯酚、间氨基苯酚、二氨基苯酚、氨基间苯二酚、对羟基苯甲酸、邻羟基苯甲酸、2,4-二羟基苯甲酸、2-5-二羟基苯甲酸、3,4-二羟基苯甲酸和3,5-二羟基苯甲酸。
示例性炔属醇包括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-4,7-二醇和2,5-二甲基-3-己炔-2,5-二醇。
示例性的含羧基有机化合物及其酸酐包括甲酸、乙酸、丙酸、丁酸、异丁酸、草酸、丙二酸、琥珀酸、戊二酸、马来酸、富马酸、苯甲酸、邻苯二甲酸、1,2,3-苯三甲酸、乙醇酸、乳酸、马来酸、乙酸酐和水杨酸。
示例性三唑化合物包括苯并三唑、邻甲苯基三唑、间甲苯基三唑、对甲苯基三唑、羧基苯并三唑、1-羟基苯并三唑、硝基苯并三唑和二羟基丙基苯并三唑。
在示例性实施方式中,腐蚀抑制剂包括苯并三唑、羧基苯并三唑、氨基苯并三唑、D-果糖、叔丁基邻苯二酚、L-抗坏血酸、香草醛、水杨酸、二乙基羟基胺和聚(乙烯亚胺)中的一种或多种。
在其他实施方式中,腐蚀抑制剂是三唑并且是苯并三唑、邻甲苯基三唑、间甲苯基三唑和对甲苯基三唑中的至少一种。
据信对于大多数应用,如果存在的话,腐蚀抑制剂将占组合物的约0.1重量%至约15重量%;优选其占组合物的约0.1重量%至约10重量%,优选约0.5重量%至约5重量%,最优选组合物的约0.1重量%至约1重量%或约0.5重量%至约5重量%。
在一些实施方式中,本发明的组合物不含或基本上不含任何或全部上文列出的腐蚀抑制剂。
其他任选成分
本发明的蚀刻组合物还可以包含下列添加剂中的一种或多种:螯合剂、化学改性剂、染料、杀生物剂和其他添加剂。可以将添加剂添加至它们不会不利地影响组合物的性能的程度。
可用于蚀刻组合物中的另一种任选成分是金属螯合剂;它可以起到增加组合物在溶液中保留金属的能力并增强金属残留物的溶解的作用。可用于此目的的螯合剂的典型实例是以下有机酸及其异构体和盐:乙二胺四乙酸(EDTA)、丁二胺四乙酸、(1,2-环己二胺)四乙酸(CyDTA)、二亚乙基三胺五乙酸(DETPA)、乙二胺四丙酸、(羟基乙基)乙二胺三乙酸(HEDTA)、N,N,N’,N’-乙二胺四(亚甲基膦)酸(EDTMP)、三亚乙基四胺六乙酸(TTHA)、1,3-二氨基-2-羟基丙烷-N,N,N’,N’-四乙酸(DHPTA)、甲基亚氨基二乙酸、丙二胺四乙酸、硝基三乙酸(NTA)、柠檬酸、酒石酸、葡糖酸、糖酸、甘油酸、草酸、邻苯二甲酸、马来酸、扁桃酸、丙二酸、乳酸、水杨酸、没食子酸丙酯、连苯三酚、8-羟基喹啉和半胱氨酸。优选的螯合剂是氨基羧酸如EDTA、CyDTA和氨基膦酸如EDTMP。
据信螯合剂(如果存在的话)将以组合物的约0.1重量%至约10重量%的量、优选约0.5重量%至约5重量%的量存在于组合物中。
在一些实施方式中,本发明的组合物不含或基本上不含添加到组合物中的任何或全部上文列出的螯合剂。
其它通常已知的组分例如染料、杀生物剂等可以以常规量包含在清洁组合物中,例如至多组合物的总计约5重量%的量。
其它通常已知的组分例如染料、杀生物剂等可以以常规量包含在清洁组合物中,例如至多组合物的总计约5重量%的量。
本发明的蚀刻溶液组合物通常通过将组分在容器中在室温下一起混合直至所有固体已溶解在水基介质中而制备。
方法
在另一方面,提供了用于通过在包含磷酸和含羟基溶剂、基本上由磷酸和含羟基溶剂组成或由磷酸和含羟基溶剂组成的组合物中蚀刻包含氮化硅和二氧化硅的复合半导体器件而选择性地增加所述复合半导体器件中氮化硅相对于二氧化硅的蚀刻速率的方法。该方法包括以下步骤:使所述包含氮化硅和二氧化硅的复合半导体器件与所述包含磷酸和含羟基溶剂、基本上由磷酸和含羟基溶剂组成或由磷酸和含羟基溶剂组成的组合物接触;以及在氮化硅被至少部分除去之后清洗所述复合半导体器件。该方法中还可以包括额外的干燥步骤。“至少部分除去”是指除去至少50%的材料,优选除去至少70%。最优选地,使用本发明的组合物除去至少80%。
接触步骤可以通过任何合适的方式进行,例如浸渍、喷雾或经由单晶片工艺。接触步骤过程中组合物的温度优选为约100℃至200℃,更优选约150℃至180℃。
在优选的实施方式中,用本发明的组合物观察到的蚀刻选择性为约50至500或更多,更优选约100至500,最优选约125至500。
接触步骤之后是任选的清洗步骤。清洗步骤可以通过任何合适的方式进行,例如通过浸渍或喷雾技术用去离子水清洗衬底。在优选的实施方式中,清洗步骤可以使用去离子水和有机溶剂例如异丙醇的混合物进行。
在接触步骤和任选的清洗步骤之后是任选的干燥步骤,该干燥步骤通过任何合适的方式进行,例如异丙醇(IPA)蒸气干燥、加热或通过离心力。
特征和优点更全面地通过下文讨论的说明性实施例显示。
实施例
用于制备清洁组合物的一般程序
作为本实施例的主体的所有组合物通过用1”Teflon涂布搅拌棒将组分在250mL烧杯中混合而制备。通常,加入烧杯的第一种材料是去离子(DI)水。通常先加入磷酸,然后加入含羟基溶剂。
衬底的组成
在本实施例中使用的每个测试20mm×20mm试样包含在硅衬底上的氮化硅Si3N4层。比较例包含在硅衬底上的氧化硅SiO2层。
处理条件
蚀刻测试使用100g蚀刻组合物在具有设定为400rpm的1/2”圆形Teflon搅拌棒的250ml烧杯中进行。在热板上将蚀刻组合物加热至约160℃的温度。将测试样品在搅拌下浸入组合物中约20分钟。
然后将片段在DI水浴或喷雾中清洗3分钟,随后使用过滤的氮气干燥。氮化硅和氧化硅的蚀刻速率根据蚀刻前后厚度的变化估计,并且通过椭圆偏振光谱法(MG-1000,Nano-View Co.,Ltd.,韩国)测量。典型起始层厚度对于Si3N4为而对于SiO2为
实施例组1
制备四种水性蚀刻组合物,各自包含60重量%的磷酸和30体积%的分别(1)DMSO(33重量%)、(2)环丁砜(37.8重量%)、(3)丙二醇(PG)(31.2重量%)和(4)二丙二醇甲醚(PGME)(28.5重量%)。组合物其余为水。如上所述制备一种组合物,但没有溶剂(“n.a”)。该组合物为85重量%磷酸,其余为水。
参照图1和图2,添加DMSO降低了Si3N4和SiO2两者的蚀刻速率,而没有改变选择性。添加环丁砜进一步降低了SiO2的蚀刻速率,选择性增加到54。添加各自包含-OH基团的PG和DPGME极大地抑制了SiO2的蚀刻速率,选择性分别大幅提高至104和137。但是,当添加PG和DPGME时,蚀刻剂在加热后变成粘性的。
实施例组2
在该实例组中,溶剂的量是变化的。制备四种水性蚀刻组合物,各自包含60重量%(30体积%)的溶剂;和76.5重量%(10体积%)的磷酸;和10或30体积%的分别(1)丙二醇(PG)(11重量%(10体积%),33重量%(30体积%))和(2)二丙二醇甲醚(PGME)(9.5重量%(10体积%)和28.5重量%(30体积%))。组合物其余为水。如上所述制备一种组合物,但没有溶剂(“n.a”)。
参照图3和图4,添加10体积%与添加30体积%相比,SiO2的蚀刻减少更少。由于Si3N4的蚀刻没有受到显著影响,所以蚀刻选择性仍然高于仅85重量%H3PO4,但远低于添加30体积%PG和DPGME。尽管组合物中使用的溶剂的量减少至10体积%,但是蚀刻剂溶液在加热时仍然变成粘性的。
实施例组3
作为另一个比较点,由于PG在10体积%(10.4重量%)时比DPGME更有效地降低SiO2蚀刻速率,因此添加HF以确定在PG存在下蚀刻速率是否会增加。
参照图5和图6,在PG存在下,含HF组合物的蚀刻选择性从15.4增加到19.7,这不是那么有效的。然而,总体上,向PG/H3PO4蚀刻组合物添加HF,在HF以组合物的10体积%(10.4重量%)存在时,将选择性从56极大地降低至19,在HF以组合物的30体积%(31.2重量%)存在时,选择性从104极大地降低至20。
前面的描述主要是出于说明的目的。虽然已经就本发明的示例性实施方式示出和描述本发明,但本领域技术人员应理解,可以在其形式和细节中进行前述和各种其他变化、省略和增加,而不脱离本发明的精神和范围。
Claims (17)
1.一种适用于从微电子器件相对于氧化硅选择性除去氮化硅的蚀刻溶液,所述蚀刻溶液包含:
水;
磷酸;和
含羟基溶剂。
2.根据权利要求1所述的蚀刻溶液,其中所述含羟基溶剂选自烷二醇或多元醇、二醇、烷氧基醇、饱和脂肪族一元醇、不饱和非芳香族一元醇和含环结构的醇。
3.根据权利要求1或2所述的蚀刻溶液,其中所述含羟基溶剂是所述烷二醇或多元醇并且选自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-丁二醇和频哪醇。
4.根据前述权利要求任一项所述的蚀刻溶液,其中所述含羟基溶剂是所述二醇并且选自乙二醇、丙二醇、二乙二醇、二丙二醇、三乙二醇和四乙二醇。
5.根据前述权利要求任一项所述的蚀刻溶液,其中所述含羟基溶剂是所述烷氧基醇并且选自3-甲氧基-3-甲基-1-丁醇、3-甲氧基-1-丁醇、1-甲氧基-2-丁醇和二醇单醚。
6.根据前述权利要求任一项所述的蚀刻溶液,其中所述含羟基溶剂是所述饱和脂肪族一元醇并且选自甲醇、乙醇、正丙醇、异丙醇、1-丁醇、2-丁醇、异丁醇、叔丁醇、2-戊醇、叔戊醇和1-己醇。
7.根据前述权利要求任一项所述的蚀刻溶液,其中所述含羟基溶剂是所述不饱和非芳香族一元醇并且选自烯丙醇、炔丙醇、2-丁烯醇、3-丁烯醇和4-戊烯-2-醇。
8.根据前述权利要求任一项所述的蚀刻溶液,其中所述含羟基溶剂是所述二醇单醚并且选自乙二醇单甲醚、乙二醇单乙醚、乙二醇单正丙醚、乙二醇单异丙醚、乙二醇单正丁醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、三乙二醇单甲醚、三乙二醇单乙醚、三乙二醇单丁醚、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、丙二醇单正丙醚、二丙二醇单甲醚、二丙二醇单乙醚、二丙二醇单正丙醚、三丙二醇单乙醚、三丙二醇单甲醚和乙二醇单苄基醚,和二乙二醇单苄基醚。
9.根据前述权利要求任一项所述的蚀刻溶液,其中所述含羟基溶剂是所述含环结构的醇并且选自α-萜品醇、四氢糠醇、糠醇和1,3-环戊二醇。
10.根据前述权利要求任一项所述的蚀刻溶液,其中所述含羟基溶剂以所述组合物的约0.5重量%至约59.5重量%的量存在。
11.根据前述权利要求任一项所述的蚀刻溶液,其中所述含羟基溶剂是二丙二醇单乙醚(DPGME)。
12.根据权利要求11所述的蚀刻溶液,其中所述二丙二醇单乙醚(DPGME)以约1重量%至约50重量%的量存在。
13.一种在包含氮化硅和二氧化硅的复合半导体器件上选择性提高氮化硅相对于二氧化硅的蚀刻速率的方法,所述方法包括以下步骤:
使所述包含氮化硅和二氧化硅的复合半导体器件与权利要求1-12任一项所述的蚀刻溶液接触;和
在所述氮化硅被至少部分地除去之后,清洗所述复合半导体器件,其中氮化硅相对于氧化硅的蚀刻选择性为约50至约500。
14.根据权利要求13所述的方法,其还包括干燥所述半导体器件的步骤。
15.根据权利要求13或14所述的方法,其中氮化硅相对于氧化硅的蚀刻选择性为约100至约500。
16.根据权利要求13-15任一项所述的方法,其中氮化硅相对于氧化硅的蚀刻选择性为约125至约500。
17.根据权利要求13-16任一项所述的方法,其中所述接触步骤在约100℃至约200℃的温度下进行。
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