TW202204367A - 矽前驅物和使用其製造含矽薄膜的方法及電子設備 - Google Patents
矽前驅物和使用其製造含矽薄膜的方法及電子設備 Download PDFInfo
- Publication number
- TW202204367A TW202204367A TW110115677A TW110115677A TW202204367A TW 202204367 A TW202204367 A TW 202204367A TW 110115677 A TW110115677 A TW 110115677A TW 110115677 A TW110115677 A TW 110115677A TW 202204367 A TW202204367 A TW 202204367A
- Authority
- TW
- Taiwan
- Prior art keywords
- thin film
- group
- silicon
- precursor
- films
- Prior art date
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 20
- 229910052710 silicon Inorganic materials 0.000 title abstract description 20
- 239000010703 silicon Substances 0.000 title abstract description 20
- 239000012686 silicon precursor Substances 0.000 title abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 29
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000007740 vapor deposition Methods 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 56
- 239000002243 precursor Substances 0.000 claims description 47
- 230000008569 process Effects 0.000 claims description 40
- 238000000151 deposition Methods 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000004065 semiconductor Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 7
- 230000003746 surface roughness Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000001272 nitrous oxide Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 125000004429 atom Chemical group 0.000 claims 1
- 230000008021 deposition Effects 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 229910052814 silicon oxide Inorganic materials 0.000 description 18
- 238000002347 injection Methods 0.000 description 11
- 239000007924 injection Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000004626 scanning electron microscopy Methods 0.000 description 10
- 238000010926 purge Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- BOEIIBPRMGQTJR-UHFFFAOYSA-N n-propan-2-yl-n-trichlorosilylpropan-2-amine Chemical compound CC(C)N(C(C)C)[Si](Cl)(Cl)Cl BOEIIBPRMGQTJR-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WZUCGJVWOLJJAN-UHFFFAOYSA-N diethylaminosilicon Chemical compound CCN([Si])CC WZUCGJVWOLJJAN-UHFFFAOYSA-N 0.000 description 2
- AWFPGKLDLMAPMK-UHFFFAOYSA-N dimethylaminosilicon Chemical compound CN(C)[Si] AWFPGKLDLMAPMK-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VYIRVGYSUZPNLF-UHFFFAOYSA-N n-(tert-butylamino)silyl-2-methylpropan-2-amine Chemical compound CC(C)(C)N[SiH2]NC(C)(C)C VYIRVGYSUZPNLF-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GIRKRMUMWJFNRI-UHFFFAOYSA-N tris(dimethylamino)silicon Chemical compound CN(C)[Si](N(C)C)N(C)C GIRKRMUMWJFNRI-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WTWRNRJJRBQKDA-UHFFFAOYSA-N CCCC[SiH2]N Chemical compound CCCC[SiH2]N WTWRNRJJRBQKDA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YGPLDDRYUUWKJG-UHFFFAOYSA-N Cl[Si](NC(C)C)(Cl)Cl Chemical compound Cl[Si](NC(C)C)(Cl)Cl YGPLDDRYUUWKJG-UHFFFAOYSA-N 0.000 description 1
- BIVNKSDKIFWKFA-UHFFFAOYSA-N N-propan-2-yl-N-silylpropan-2-amine Chemical compound CC(C)N([SiH3])C(C)C BIVNKSDKIFWKFA-UHFFFAOYSA-N 0.000 description 1
- UOERHRIFSQUTET-UHFFFAOYSA-N N-propyl-N-silylpropan-1-amine Chemical compound CCCN([SiH3])CCC UOERHRIFSQUTET-UHFFFAOYSA-N 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OWKFQWAGPHVFRF-UHFFFAOYSA-N n-(diethylaminosilyl)-n-ethylethanamine Chemical compound CCN(CC)[SiH2]N(CC)CC OWKFQWAGPHVFRF-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
- C23C16/402—Silicon dioxide
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Abstract
本發明涉及可通過氣相沉積被沉積作為薄膜的氣相沉積化合物,並且具體地,涉及適用於原子層沉積(ALD)或化學氣相沉積(CVD)且可以以高速沉積,特別地通過高溫ALD的矽前驅物以及使用其製造含矽薄膜的方法及電子設備。
Description
本發明主張於 2020 年 5 月 8 日提交之韓國專利申請號10-2020-0054948的優先權和權益,為了所有目的該申請案之內容為本文之基礎且以全文引用方式併入本文中。
本發明涉及可通過氣相沉積被沉積作為薄膜的氣相沉積化合物,並且更特別地,涉及適用於原子層沉積(Atomic layer deposition,ALD)或化學氣相沉積(Chemical vapor deposition,CVD)和可用於製造具有優良品質的薄膜,特別地在高工藝溫度的新穎矽前驅物(silicon precursor),以及使用其製造含矽薄膜的方法及電子設備。
含矽薄膜用作半導體技術(比如包括RAM(記憶體和邏輯晶片)的微電子設備、平板顯示器比如薄膜電晶體(Thin-Film Transistor,TFT)和太陽能熱應用)中的半導體基材、擴散掩模、氧化屏障和介電膜。
特別地,隨著半導體設備的集成密度增加,已經需要具有各種性能的含矽薄膜,並且已增加其縱橫比。因此,出現了問題,因為使用常規前驅物沉積含矽薄膜未滿足所需性能。
當使用常規前驅物在高度集成的半導體設備上沉積薄膜時,會出現問題,因為難以實現薄膜的優良階梯覆蓋(step coverage)和控制其厚度,而且薄膜中含有雜質。
因此,為了沉積高品質的含矽薄膜,除了常規矽前驅物比如矽烷、二矽烷和鹵代矽烷外,還研究和開發了各種矽前驅物,比如氨基矽烷。
廣泛使用的氨基矽烷前驅物通常包括丁基氨基矽烷(butyl aminosilane,BAS)、雙(叔丁基氨基)矽烷(bis(tertiary butylamino)silane,BTBAS)、二甲基氨基矽烷(dimethyl aminosilane,DMAS)、雙(叔甲基氨基)矽烷(bis(tertiary methylamino)silane,BDMAS)、三(二甲基氨基)矽烷(tris(dimethylamino)silane,3-DMAS)、二乙基氨基矽烷(diethyl aminosilane,DEAS)、雙(二乙基氨基) 矽烷(bis(diethylamino)silane,BDEAS)、二丙基氨基矽烷(dipropyl aminosilane,DPAS)和二異丙基氨基矽烷(diisopropyl aminosilane,DIPAS)。
對於製造含矽薄膜,廣泛使用原子層沉積(ALD)或化學氣相沉積(CVD)。
特別地,使用 ALD 來形成含矽薄膜具有優勢,因為薄膜的厚度均勻性和物理性能可被改善,從而引起半導體設備的特性改善。由於該優勢,使用ALD 最近大大增加。然而,由於 CVD 和 ALD 具有不同反應機制,適合應用於CVD的前驅物,當應用于ALD時,可能不會被製造成具有期望品質的薄膜。出於該原因,適用於CVD和ALD二者的前驅物已被越來越多地研究和開發。
同時,與使用前驅物比如三(二甲基氨基)矽烷(3-DMAS)(其是氨基矽烷前驅物之一)有關的專利包括美國專利號5593741。然而,即使當3-DMAS用作前驅物時,仍然無法在高工藝溫度下獲得高品質的薄膜。另外,甚至當使用 以鹵素元素取代的矽前驅物時,其在低溫沉積中也是有效的,但在高工藝溫度仍然無法獲得高品質的薄膜。
[相關技術文獻]
[專利文獻]
(專利文獻1) 韓國專利公開第2011-0017404號。
(專利文獻2) 美國專利號第5593741號。
本發明旨在提供適用於原子層沉積(ALD)或化學氣相沉積(CVD)的新穎矽化合物。
特別地,本發明的目的是提供包括新穎矽化合物的矽前驅物,由於其可能應用於 600°C 或更高的高工藝溫度,可確保在高溫的 ALD 行為,可形成具有低雜質濃度的氧化矽膜(特別地未檢測到雜質比如 Cl、C 和 N),可確保優良的階梯覆蓋特性和表面特性(粗糙度等),並且因此具有優良的界面特性,同時具有優良的耐腐蝕性;以及使用其製造含矽薄膜的方法。
然而,本發明的目的不限於以上提到的目的,本領域的技術人員將從以下描述中清楚地理解本文未提到的其他目的。
本發明的一個方面提供了製造薄膜的方法,方法包括將包括由下式 1 表示的化合物的氣相沉積前驅物引入腔室中的步驟:
[式1] SiX1n
(NR1
R2
)(
4-n)
其中n是1至3範圍的整數,X1
是選自由Cl、Br和I組成的群組中的任何一種,並且 R1
和 R2
各自獨立地是氫、具有 1 至 4 個碳原子的取代的或未取代的、直鏈或支鏈的、飽和或不飽和的烴基或其異構物。
本發明的另一方面提供了製造薄膜的方法,其中 R1
和 R2
各自獨立地包括選自由氫、甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、 叔丁基和其異構物組成的群組中的任何一種。
本發明的仍另一方面提供了製造薄膜的方法,其中,在式 1 中,n 是3,並且R1
和R2
各自獨立地是異丙基。
本發明的還另一方面提供了製造薄膜的方法,其中方法通過選自原子層沉積(ALD)和化學氣相沉積(CVD)之中的方法進行。
本發明的仍還另一方面提供了製造薄膜的方法,其中方法進一步包括注入選自由氧(O2
)、水(H2
O)、臭氧(O3
)、氧(O2
)和氫(H2
)的混合物、氮(N2
)、氨(NH3
)、一氧化二氮(N2
O)和過氧化氫(H2
O2
)組成的群組中的任何一種或多種反應氣體的步驟。
本發明的進一步方面提供了製造薄膜的方法,其中方法進一步包括在600°C或更高的工藝溫度進行沉積的步驟。
本發明的另一進一步方面提供了通過根據本發明的製造方法製造的並且具有0.2nm或更小的表面粗糙度和2.5 g/cm3
或更大的密度的薄膜。
本發明的仍另一進一步發明提供了包括根據本發明製造的薄膜的電子設備,電子設備為選自由半導體設備、顯示裝置和太陽能電池組成的群組中的任何一種。
下文,將參照附圖詳細描述本發明的實施方式和實施例,以便本領域的技術人員可以容易地進行本發明。然而,本發明可以以各種不同形式呈現,並且不限於本文和附圖所述的實施方式和實施例。在附圖中,為了清楚地描述本發明,與描述無關的部分被省略了。
本發明的一個方面提供了製造薄膜的方法,方法包括將包括由下式 1 表示的化合物的氣相沉積前驅物引入腔室中的步驟:
[式1] SiX1n
(NR1
R2
)(4-n)
其中n是1至3範圍的整數,X1
是選自由Cl、Br和I組成的群組中的任何一種,並且 R1
和 R2
各自獨立地是氫、具有 1 至 4 個碳原子的取代的或 未取代的、直鏈或支鏈的、飽和或不飽和的烴基或其異構物。
優選地,R1
和R2
可以各自獨立地是選自由氫、甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基和其異構物組成的群組中的任何一種。
更優選地,在式 1 中,n 可以是 3 但不限於此,和R1
和 R2
可各自獨立地是異丙基但不限於此。
將氣相沉積前驅物引入腔室的步驟可包括但不限於物理吸附步驟、化學吸附步驟以及物理和化學吸附步驟。
在本發明的一個實施方式中,氣相沉積可包括但不限於原子層沉積(ALD)或化學氣相沉積(CVD),並且化學氣相沉積可包括但不限於金屬有 機化學氣相沉積(metal organic chemical vapor deposition,MOCVD)或低-壓力化學氣相沉積(low-pressure chemical vapor deposition,LPCVD)。
在本發明的一個實施方式中,製造薄膜的方法可進一步包括注入選自由氧(O2
)、水(H2
O)、臭氧(O3
)、氧(O2
)和氫(H2
)的混合物、氮(N2
)、氨(NH3
)、一氧化二氮(N2
O)和過氧化氫(H2
O2
)組成的群組中的任何一種或多種反應氣體的步驟。
另外,根據薄膜所需特性也可使用各種含氧反應物、含氮反應物或含碳反應物,但是本發明的範圍不限於此。
在本發明的一個實施方式中,製造薄膜的方法可在高溫進行。前驅物可在300°C至800°C,優選地600°C至800°C的工藝溫度沉積。
當在600°C或更高的高工藝溫度使用常規矽前驅物時,難以控制薄膜厚度,並且未提供具有期望特性的高品質薄膜。然而,本發明的新穎矽前驅物即使在600°C或更高也是熱穩定的,並且因此即使在高溫工藝中可提供具 有優良品質的薄膜。
本發明的另一方面提供了通過製造薄膜的方法製造的並且具有0.2 nm或更小的表面粗糙度和2.5 g/cm3
或更大,優選地2.55 g/cm3
或更大的密度的高純度非晶氧化矽膜。取決於反應物的選擇,薄膜可以作為各種薄膜比如氧化物膜、氮化物膜、碳化物膜、碳氮化物膜和氧氮化物膜提供。另外, 由於其表面特性和密度,期望薄膜具有優良介面特性和耐腐蝕性。
本發明的仍另一方面提供了包括根據本發明製造的薄膜的多層薄膜。
本發明的還另一方面提供了包括根據本發明製造的薄膜的電子設備。電子設備可以是選自由半導體設備、顯示裝置和太陽能電池組成的群組中的任何一種。特別地,薄膜作為 3D-NAND 記憶體設備的隧道氧化物膜可展示優良特性。
下文,本發明將參考實施例更詳細描述,但是本發明的範圍不限於這些實施例。
[
實施例
1]
二異丙基氨基三氯矽烷
(
C6
H
14
Cl3
NSi
)
的產生
將SiCl4
(1.0 eq.(當量))放置入燒瓶中,以戊烷(12 eq.)稀釋,並且然後在0°C保持的水浴中冷卻。在攪拌所得溶液的同時,將在戊烷(6 eq.)中稀釋的二異丙胺(2.87 eq.)緩慢添加入溶液中。在完成添加後,在室溫攪拌混合物15 小時。在完成反應後,過濾反應混合物,並且在大氣壓煮沸濾液溶液以去除溶劑。獲得的液體在減壓下純化以獲得無色透明液體。
在以下反應方案和化學結構式中顯示合成二異丙基氨基三氯矽烷的反應方案和二異丙基氨基三氯矽烷的化學結構,並且如在圖1中顯示的通過1
H-NMR確認二異丙基氨基三氯矽烷的化學結構。
另外,獲得的化合物具有234.63 g/mol的分子量,在室溫以無色液體狀態,並且具有205°C的沸點。化合物可容易地通過高蒸汽壓引入工藝腔室,並且在短時間內可提供足夠量的前驅物。
[
製造實施例
1
至
3]
以上實施例 1 中產生的化合物使用原子層沉積(ALD)系統沉積,因此製造氧化矽膜。該實驗中使用的基材是裸 Si 晶片。在沉積之前,裸 Si 晶片依次在丙酮、乙醇和DI水中各自超音波(ultrasonically)處理10分鐘,並且然後裸Si晶片上的天然氧化物通過浸泡在10% HF溶液(HF:H2
O =1:9)中10秒被去除。
具體地,進行原子層沉積多個週期,各自由以下順序步驟組成:注入實施例1的矽前驅物X秒;用Ar吹掃前驅物10秒;注入反應氣體5秒;和用Ar吹掃反應氣體10秒。
在注入實施例1的矽前驅物X秒的步驟中,X設置為1至12秒,以200 sccm的流速注入用於前驅物的載氣氬(Ar),和在600°C至850°C範圍的工藝溫度進行前驅物的沉積。
將所有容器加熱至 40°C 的溫度,以 2,000 sccm 的流速注入用於吹掃的Ar。
另外,氫(H2
)氣體和氧(O2
)氣體(H2
+ O2
)的混合物用作反應氣體。在600°C (製造實施例1-1至1-5),700°C (製造實施例2-1至2-5)和750°C (製造實施例3-1至3-5)的工藝溫度製造氧化矽薄膜。
對於反應氣體的注入,將氧(O2
)和氫(H2
)分別以1,000 sccm和325 sccm 流速供應入反應腔室。
分別在以下表1至3和圖2中顯示製造實施例1至3的沉積工藝條件和沉積結果。
如在圖2中顯示,觀察到即使在600°C或更高的更高溫度,通過沉積實施例1的矽前驅物化合物形成薄膜。因此,確認實施例1的矽前驅物化合物和通過沉積其形成的氧化矽膜甚至在高溫具有優良的熱穩定性。
另外,來自在850°C的工藝溫度進行的沉積實驗的結果,可確認由於實施例1的前驅物化合物的熱分解,ALD工藝不可在850°C或更高的工藝溫度應用。
[
表
1]
在
600
°
C
的工藝溫度使用實施例
1
的前驅物化合物和反應氣體
(
H
2
+ O2
)
沉
積的結果。
製造實 施例 | 前驅物的注入時間(秒) | 前驅物 的吹掃時間(秒) | 反應氣體的注入時間(秒) | 反應氣體的 吹 掃 時間(秒) | 周 期的 數量 | 厚度(Å) | 沉積速率(Å/週期) |
1-1 | 1 | 10 | 5 | 10 | 100 | 0.7 | 0 |
1-2 | 3 | 10 | 5 | 10 | 100 | 1.05 | 0 |
1-3 | 6 | 10 | 5 | 10 | 100 | 17.4 | 0.17 |
1-4 | 9 | 10 | 5 | 10 | 100 | 28 | 0.28 |
1-5 | 12 | 10 | 5 | 10 | 100 | 26.8 | 0.27 |
以上表1顯示在600°C的工藝溫度進行的沉積的結果。其確認,隨著前驅物的注入時間從 1 秒增加到 12 秒,沉積速率逐漸增加,並且在 9 秒左右觀察到自限性反應。
[
表
2]
在
700
°
C
的工藝溫度使用實施例
1
的前驅物化合物和反應氣體
(
H
2
+ O2
)
沉
積的結果
製造實 施例 | 前驅物的注入時間(秒) | 前驅物 的吹掃時間(秒) | 反應氣體的注入時間(秒) | 反應氣體的 吹 掃 時間(秒) | 周 期的 數量 | 厚度(Å) | 沉積速率(Å/週期) |
2-1 | 1 | 10 | 5 | 10 | 100 | 84 | 0.84 |
2-2 | 3 | 10 | 5 | 10 | 100 | 111 | 1.11 |
2-3 | 6 | 10 | 5 | 10 | 100 | 138 | 1.38 |
2-4 | 9 | 10 | 5 | 10 | 100 | 157 | 1.57 |
2-5 | 12 | 10 | 5 | 10 | 100 | 157 | 1.57 |
以上表2顯示在700°C的工藝溫度進行的沉積的結果。其確認,隨著前驅物的注入時間從1秒增加到12秒,沉積速率從0.84增加到1.57 Å /週期, 並且在9秒左右觀察到自限性反應。
[
表
3]
在
750
°
C
的工藝溫度使用實施例
1
的前驅物化合物和反應氣體
(
H
2
+ O2
)
沉
積的結果
製造實 施例 | 前驅物的注入時間(秒) | 前驅物 的吹掃時間(秒) | 反應氣體的注入時間(秒) | 反應氣體的 吹 掃 時間(秒) | 周 期的 數量 | 厚度(Å) | 沉積速率(Å/週期) |
3-1 | 1 | 10 | 5 | 10 | 100 | 137 | 1.37 |
3-2 | 3 | 10 | 5 | 10 | 100 | 168 | 1.68 |
3-3 | 6 | 10 | 5 | 10 | 100 | 218 | 2.18 |
3-4 | 9 | 10 | 5 | 10 | 100 | 249 | 2.49 |
3-5 | 12 | 10 | 5 | 10 | 100 | 254 | 2.54 |
以上表3顯示在750°C的工藝溫度進行的沉積的結果。其確認,隨著前驅物的注入時間從1秒增加到12秒,沉積速率從1.37增加到2.54 Å /週期, 並且在9秒左右觀察到自限性反應。
來自以上表1至3和圖2中的沉積結果,其確認,隨著前驅物的注入時間增加,沉積速率增加,並且在除了工藝溫度的相同工藝條件下進行的沉積實驗中,沉積速率隨著工藝溫度增加而增加。
[
實驗性實施例
1]
由實施例
1
的前驅物製造的氧化矽膜
(Si
O2
)
的組成分析
通過XPS分析,分析通過分別在600°C和750°C的工藝溫度沉積實施例1的前驅物和氧和氫的混合物(H2 + O2
)製造的氧化矽膜的組成,並且在圖3中顯示分析的結果。
如圖3中顯示,來自在600°C (圖3a)和750°C (圖3b)的工藝溫度製造的所有薄膜的 XPS 分析的結果,其可確認,沒有檢測到雜質比如碳(C)、氯(Cl)和氮(N),提示形成的矽薄膜具有優良品質且不含有雜質。
[
實驗性實施例
2]
由實施例
1
的前驅物製造的氧化矽膜
(
SiO2
)
的表面特性
通過使用原子力顯微鏡(AFM)和掃描電子顯微鏡(SEM)觀察測量分別在600°C和750°C的工藝溫度通過沉積實施例1的前驅物和氧和氫的混合物(H2 + O2
)製造的氧化矽膜的表面粗糙度(Ra),並且在圖 4 中顯示測量的結果。
如圖4中顯示,測量表面粗糙度(Ra)為0.097 nm至0.134 nm範圍,指示氧化矽膜皆具有低粗糙度(1.5 Å或更小)。另外,其可確認,隨著工藝溫度增加粗糙度增加(圖4a (工藝溫度:600°C,和Ra:0.097 nm)和圖4b (工藝溫度:750°C,和Ra:0.134 nm))。
該低表面粗糙度也可通過SEM確認。
[
實驗性實施例
3]
由實施例
1
的前驅物製造的氧化矽膜
(
SiO2
)
的密度特性
通過 XRR 分析來分析分別在 600°C 和 750°C 的工藝溫度通過沉積實施例1的前驅物和氧和氫的混合物(H2 + O2
)製造的氧化矽膜的密度,並且在圖5顯示分析的結果。
由圖5中的分析結果,確認,在600°C的工藝溫度,密度是2.574 g/cm3
(圖5a),和在750°C的工藝溫度,密度是2.581 g/cm3
(圖5b)。
如以上分析,可確認,製造的薄膜的密度都接近 SiO2
堆積(bulk)薄膜的密度(2.68 g/cm3
),指示形成的薄膜具有優良品質和優良的耐腐蝕性。
[
實驗性實施例
4]
由實施例
1
的前驅物製造的氧化矽膜
(
SiO2
)
的乾式刻蝕特性
通過橢圓計和掃描電子顯微鏡(SEM)分析分別在 600°C 和 750°C 的工藝溫度通過沉積實施例1的前驅物和氧和氫的混合物(H2
+ O2
)製造的氧化矽膜的乾式刻蝕特性,並且在圖6中顯示SEM分析的結果。
在完成沉積之後在刻蝕(As-dep)之前通過橢圓計和SEM測量的薄膜的 厚度分別是30.6 nm和31 nm。
在沉積的薄膜在室溫通過浸漬在氫氟酸的溶液(HF,以1:200在蒸餾水中稀釋)中刻蝕15分鐘之後,薄膜的厚度通過橢圓計和SEM測量。結果,測量厚度分別為10.3 nm和8 nm。即,通過橢圓計和SEM測量的厚度值分別對應於1.35和1.53的刻蝕速率。
如上述,確認本發明的新穎矽前驅物即使在600°C或更高的高工藝溫度也是熱穩定的,並且因此可應用於高溫ALD,並且新穎矽前驅物使用低薄膜生長速率和均勻沉積速率使精確的厚度控制成為可能,並且具有優良的密度和刻蝕特性。另外,確認具有優良品質的矽薄膜通過沉積本發明的新穎矽前驅物形成。
由於這些優良的特性,期望高品質矽薄膜在未來用作 3D-NAND 存儲器設備的隧道氧化物膜。另外,該高品質矽薄膜可在包括奈米設備和奈米結構的製造、半導體設備、顯示裝置和太陽能電池的各種應用中使用。另外,高品質矽薄膜可用作非記憶體半導體設備的製造中的介電膜等。
如以上所述,根據本發明的新穎矽前驅物即使在600°C或更高的高溫具有不會被熱分解的性質,特別地應用於高溫ALD,具有均勻沉積速率以便使精確的厚度控制成為可能,並且具有優良的階梯覆蓋特性。
另外,具有優良品質的含矽薄膜可通過沉積根據本發明的新穎矽前驅物製造。
由於這些優良的特性,期望高品質含矽薄膜在未來用作 3D-NAND 存儲器設備的隧道氧化物膜和間隙填充。另外,該高品質含矽薄膜可在包括納米設備和納米結構製造、半導體設備、顯示裝置和太陽能電池的各種應用中使用。另外,高品質的含矽薄膜也可作為非記憶體半導體設備的介電 膜使用。
這些物理特性提供了適用於原子層沉積(ALD)和化學氣相沉積(CVD)的前驅物,並且期望該前驅物通過使其沉積的製造薄膜的工藝被應用作為半導體設備的介電材料。
應該理解,本發明的範圍由所附的權利要求而不是詳細描述來限定,並且衍生自權利要求的含義和範圍的所有變化形式或更改形式以及其等效概念均落入本發明的範圍內。
圖1顯示實施例1的前驅物的核磁共振(NMR)分析的結果。
圖2是顯示當在600°C、700°C和750°C的每個工藝溫度使用實施例1的前驅物進行沉積時,沉積速率(Å/週期)作為實施例1的前驅物的注入時間的函數的圖(製造實施例1至3)。
圖3描繪了顯示X-射線光電子能譜(XPS)結果的圖,進行所述X-射線光電子能譜以測量通過分別在600°C(圖3a)和750°C(圖3b)的工藝溫度沉積實施例1的前驅物製造的氧化矽膜的組成(實驗性實施例1)。
圖4描繪了通過分別在600°C(圖4a)和750°C(圖4b)的工藝溫度沉積實施例 1 的前驅物製造的氧化矽膜的原子力顯微鏡(AFM)和掃描電子顯微鏡(SEM)圖像,和顯示了通過 SEM 分析氧化矽膜的表面狀態(包括表面粗糙度(Ra))的結果(實驗性實施例2)。
圖5顯示了通過分別在600°C(圖5a)和750°C的工藝溫度(圖5b)沉積實施例1的前驅物製造的氧化矽膜的X-射線反射(XRR)的結果,和顯示通過XRR測量的氧化矽膜的密度值(實驗性實施例3)。
圖 6 顯示掃描電子顯微鏡(SEM)的結果,進行所述掃描電子顯微鏡(SEM)以測量通過沉積實施例 1 的前驅物製造的氧化矽膜在刻蝕之前(圖 6a) 和刻蝕之後(圖6b)的厚度(實驗性實施例4)。
Claims (9)
- 一種製造薄膜的方法,所述方法包括將包括由下式1表示的化合物的氣相沉積前驅物引入腔室中的步驟: [式1] SiX1n (NR1 R2 )(4-n) 在式1中, n是1至3範圍的整數, X1 是選自由Cl、Br和I組成的群組中的任何一種,和 R1 和R2 各自獨立地是氫、具有1至4個碳原子的取代的或未取代的、 直鏈或支鏈的、飽和或不飽和的烴基或其異構物。
- 如請求項1所述的製造薄膜的方法,其中R1 和R2 各自獨立地包括選自由 氫、甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基和其異構物組成的群組中的任何一種。
- 如請求項1所述的製造薄膜的方法,其中,在式1中,n是3,並且R1 和R2 各自獨立地是異丙基。
- 如請求項1至3的任一項所述的製造薄膜的方法,其包括原子層沉積(ALD) 或化學氣相沉積(CVD)。
- 如請求項1所述的製造薄膜的方法,其進一步包括注入選自由氧(O2 )、水(H2 O)、臭氧(O3 )、氧(O2 )和氫(H2 )的混合物、氮(N2 )、氨(NH3 )、一氧化二氮(N2 O)和過氧化氫(H2 O2 )組成的群組中的任何一種或多種反應氣體的步驟。
- 如請求項1所述的製造薄膜的方法,其進一步包括在600°C或更高的工藝溫度進行沉積的步驟。
- 一種薄膜,其通過請求項1所述的製造薄膜的方法製造,並且該薄膜具有 0.2nm 或更小的表面粗糙度,以及該薄膜具有2.5g/cm3 或更大的密度。
- 一種電子設備,包含如請求項7所述的薄膜。
- 如請求項8所述的電子設備,其中該電子設備是選自由半導體設備、顯示裝置和太陽能電池組成的群組中的任何一種。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2020-0054948 | 2020-05-08 | ||
KR1020200054948A KR102364476B1 (ko) | 2020-05-08 | 2020-05-08 | 실리콘 전구체 및 이를 이용한 실리콘 함유 박막의 제조방법 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW202204367A true TW202204367A (zh) | 2022-02-01 |
TWI828980B TWI828980B (zh) | 2024-01-11 |
Family
ID=78378019
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW110115677A TWI828980B (zh) | 2020-05-08 | 2021-04-29 | 製造氧化矽薄膜的方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20210348026A1 (zh) |
JP (1) | JP7196228B2 (zh) |
KR (1) | KR102364476B1 (zh) |
CN (1) | CN113621941B (zh) |
TW (1) | TWI828980B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117642525A (zh) * | 2021-07-16 | 2024-03-01 | Up化学株式会社 | 硅前体化合物、包含其的用于形成含硅膜的组合物以及使用用于形成含硅膜的组合物来形成膜的方法 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4572841A (en) * | 1984-12-28 | 1986-02-25 | Rca Corporation | Low temperature method of deposition silicon dioxide |
JP2684942B2 (ja) | 1992-11-30 | 1997-12-03 | 日本電気株式会社 | 化学気相成長法と化学気相成長装置および多層配線の製造方法 |
US6984591B1 (en) * | 2000-04-20 | 2006-01-10 | International Business Machines Corporation | Precursor source mixtures |
JP4954448B2 (ja) * | 2003-04-05 | 2012-06-13 | ローム・アンド・ハース・エレクトロニック・マテリアルズ,エル.エル.シー. | 有機金属化合物 |
US8119210B2 (en) * | 2004-05-21 | 2012-02-21 | Applied Materials, Inc. | Formation of a silicon oxynitride layer on a high-k dielectric material |
CN1834288A (zh) * | 2006-04-07 | 2006-09-20 | 中国科学院上海硅酸盐研究所 | 一种低温化学气相沉积制备氮化硅薄膜的方法 |
US7943531B2 (en) | 2007-10-22 | 2011-05-17 | Applied Materials, Inc. | Methods for forming a silicon oxide layer over a substrate |
JP5102393B2 (ja) | 2008-06-03 | 2012-12-19 | エア プロダクツ アンド ケミカルズ インコーポレイテッド | ケイ素含有フィルムの低温堆積 |
JP2010041038A (ja) * | 2008-06-27 | 2010-02-18 | Asm America Inc | 重要な用途のための二酸化ケイ素の低温熱でのald |
JP2010103484A (ja) | 2008-09-29 | 2010-05-06 | Adeka Corp | 半導体デバイス、その製造装置及び製造方法 |
JP5829196B2 (ja) | 2011-10-28 | 2015-12-09 | 東京エレクトロン株式会社 | シリコン酸化物膜の成膜方法 |
US9460912B2 (en) * | 2012-04-12 | 2016-10-04 | Air Products And Chemicals, Inc. | High temperature atomic layer deposition of silicon oxide thin films |
GB201207448D0 (en) * | 2012-04-26 | 2012-06-13 | Spts Technologies Ltd | Method of depositing silicon dioxide films |
JP5925673B2 (ja) * | 2012-12-27 | 2016-05-25 | 東京エレクトロン株式会社 | シリコン膜の成膜方法および成膜装置 |
JP6030455B2 (ja) * | 2013-01-16 | 2016-11-24 | 東京エレクトロン株式会社 | シリコン酸化物膜の成膜方法 |
US10109492B2 (en) * | 2013-02-25 | 2018-10-23 | Globalfoundries Inc. | Method of forming a high quality interfacial layer for a semiconductor device by performing a low temperature ALD process |
US9824881B2 (en) | 2013-03-14 | 2017-11-21 | Asm Ip Holding B.V. | Si precursors for deposition of SiN at low temperatures |
MX2016012607A (es) * | 2014-03-27 | 2016-12-14 | Teijin Ltd | Sustrato polimerico con capa de recubrimiento dura y metodo de manufacturacion para tal sustrato polimerico. |
US10053775B2 (en) * | 2015-12-30 | 2018-08-21 | L'air Liquide, Societé Anonyme Pour L'etude Et L'exploitation Des Procédés Georges Claude | Methods of using amino(bromo)silane precursors for ALD/CVD silicon-containing film applications |
US10283348B2 (en) * | 2016-01-20 | 2019-05-07 | Versum Materials Us, Llc | High temperature atomic layer deposition of silicon-containing films |
JP6832776B2 (ja) * | 2017-03-30 | 2021-02-24 | 東京エレクトロン株式会社 | 選択成長方法 |
-
2020
- 2020-05-08 KR KR1020200054948A patent/KR102364476B1/ko active IP Right Grant
-
2021
- 2021-04-29 TW TW110115677A patent/TWI828980B/zh active
- 2021-05-06 JP JP2021078482A patent/JP7196228B2/ja active Active
- 2021-05-07 US US17/314,784 patent/US20210348026A1/en active Pending
- 2021-05-08 CN CN202110501185.4A patent/CN113621941B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
US20210348026A1 (en) | 2021-11-11 |
JP7196228B2 (ja) | 2022-12-26 |
CN113621941B (zh) | 2023-12-01 |
JP2021177550A (ja) | 2021-11-11 |
KR20210136551A (ko) | 2021-11-17 |
KR102364476B1 (ko) | 2022-02-18 |
CN113621941A (zh) | 2021-11-09 |
TWI828980B (zh) | 2024-01-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI557259B (zh) | 用於沉積氧化矽膜的組合物及方法 | |
KR101308572B1 (ko) | 실리콘을 함유하는 박막 증착을 위한 실리콘 전구체 제조 방법 | |
JP7436054B2 (ja) | シリコン前駆体化合物、製造方法、及びこれを利用するシリコン含有膜の形成方法 | |
CN109585264B (zh) | 一种氮化硅薄膜的可流动化学气相沉积方法 | |
TWI828980B (zh) | 製造氧化矽薄膜的方法 | |
TWI817139B (zh) | 氣相沉積前驅物化合物及使用方法 | |
CN114929937B (zh) | 硅前体化合物、包含该硅前体化合物的用于形成含硅膜的组合物以及用于形成含硅膜的方法 | |
JP7164789B2 (ja) | 550℃以上の温度でALDを使用してSi含有膜を堆積させるための前駆体及びプロセス | |
TW202142545A (zh) | 用於製造含矽薄膜之前驅物及方法 | |
KR101934773B1 (ko) | 저온에서의 실리콘-함유 박막 형성방법 | |
JP6941181B2 (ja) | シリコン前駆体およびこれを用いたシリコン含有薄膜の製造方法 | |
EP3680245A1 (en) | Silicon precursor and method for manufacturing silicon-containing thin film using same | |
TWI776109B (zh) | 在550°C或更高的溫度下使用ALD沈積含Si膜之先質及製程 | |
US20240222114A1 (en) | Method of forming a conformal and continuous crystalline silicon nanosheet with improved electrical properties at low doping levels | |
KR102491073B1 (ko) | 실리콘 전구체 화합물, 이를 포함하는 실리콘-함유 막 형성용 조성물, 및 실리콘-함유 막 형성용 조성물을 이용한 막 형성 방법 | |
JP2008007471A (ja) | 有機金属化学蒸着法用原料及び該原料を用いたシリコン含有膜の製造方法 | |
TWI791586B (zh) | 含Ge之Co膜形成材料、含Ge之Co膜及其成膜方法 | |
TW202311273A (zh) | 矽前驅物 | |
JP2024526692A (ja) | ケイ素含有膜を形成するための方法、及び、その方法によって形成されるケイ素含有膜 | |
TW202432867A (zh) | 形成在低摻雜水平下具有改善的電特性的保形且連續結晶矽奈米片之方法 | |
TW202128720A (zh) | 化合物、前驅物、薄膜及其製備方法與電子裝置 | |
KR20130049787A (ko) | 실리콘을 함유하는 박막 증착을 위한 실리콘 전구체 |