TW201741489A - 膜形成方法 - Google Patents
膜形成方法 Download PDFInfo
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- TW201741489A TW201741489A TW106115213A TW106115213A TW201741489A TW 201741489 A TW201741489 A TW 201741489A TW 106115213 A TW106115213 A TW 106115213A TW 106115213 A TW106115213 A TW 106115213A TW 201741489 A TW201741489 A TW 201741489A
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- Prior art keywords
- gas
- film
- material gas
- molecular species
- reaction chamber
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 title claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 230000007246 mechanism Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 71
- 239000002994 raw material Substances 0.000 claims description 48
- 238000003860 storage Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229910001868 water Inorganic materials 0.000 claims description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 238000009825 accumulation Methods 0.000 abstract description 5
- 230000006837 decompression Effects 0.000 abstract description 2
- 241000894007 species Species 0.000 abstract 10
- 239000007789 gas Substances 0.000 description 207
- 238000001179 sorption measurement Methods 0.000 description 12
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 239000012159 carrier gas Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- 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
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- 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]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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- 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
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- 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
- C23C16/452—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 by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
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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
- 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
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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
- 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
- C23C16/403—Oxides of aluminium, magnesium or beryllium
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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
- 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
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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
- 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
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- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
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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
- 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
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- 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
- C23C16/45557—Pulsed pressure or control pressure
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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
- H01L21/02104—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
- H01L21/02269—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 thermal evaporation
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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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02373—Group 14 semiconducting materials
- H01L21/02376—Carbon, e.g. diamond-like carbon
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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
- H01L21/04—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
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
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Abstract
本發明的目的係提供一種在室溫下高速地且被覆性優異地將化合物膜加以成膜之方法。本發明係關於一種膜形成方法,其係具備有積蓄機構、瞬間加熱部及反應室之膜形成裝置的膜形成方法,前述積蓄機構係各自積蓄第一原料氣體與第二原料氣體;前述瞬間加熱部係將前述第一原料氣體與前述第二原料氣體加熱;前述反應室係放置有溫度比前述瞬間加熱部之加熱溫度還低溫之基體,且前述膜形成方法係包含:使積蓄於積蓄機構的第一原料氣體與第二原料氣體通過瞬間加熱部,並生成第一氣體分子物種與第二氣體分子物種,且使該第一氣體分子物種與該第二氣體分子物種突出並供給至放置有基體且減壓後之具有一定容量的反應室,使得第一氣體分子物種的分壓與第二氣體分子物種的分壓急速上昇,而將第一氣體分子物種或第二氣體分子物種交互地重複引導至基體的表面,且使第一氣體分子物種或第二氣體分子物種反應,並於基體的表面形成化合物膜。
Description
本發明係關於一種膜形成裝置的膜形成方法。
一般來說,氣體分子的化學鍵結能多為3eV以上,僅將氣體高溫加熱,分子係不會分解。然而,一旦使加熱至高溫的氣體與含有觸媒效果的元素之金屬垂直碰撞,則可改變氣體分子的構造。同時,一旦於觸媒上將可進行化學反應的氣體加熱並與觸媒碰撞,則生成與原氣體相異的分子物種或相異形態的氣體(以下,將此稱為觸媒碰撞反應)。
舉例來說,於置入釕觸媒的容器內,一旦於釕觸媒上,使甲烷與水蒸氣瞬間加熱後之氣體與釕觸媒碰撞,則進行反應並生成氫氣H2
、二氧化碳CO2
、及一氧化碳CO。此反應係觸媒碰撞反應的一例。雖然將水加熱即形成水蒸氣,但此不僅是單純地將溫度變高,而被認為是因為分子結構從聚集後之聚集物(水分子簇)變化為單量體。生成之單量體氣體係化學性質變化,且其與通常的水相比,具有不同活性的化學性質。
為了將此觸媒碰撞反應於產業上利用,變得需要將氣體瞬間地加熱之裝置及使氣體於觸媒碰撞之便宜又小型的加熱裝置。
滿足上述要求的氣體加熱裝置已於文獻中被揭露(例如,參照專利文獻1、2、3、4、5)。因此,於後文將此等瞬間加熱裝置,於此處作為熱束加熱裝置(HB)。此HB的加熱原理係於高速下使氣體與高溫的壁碰撞,並進行高效率之壁與氣體的熱交換。
因此,在形成於熱交換器基體表面之狹窄氣體流路,將氣體高速化並使其與流路的壁垂直碰撞。該流路的壁係被電加熱,並藉由碰撞來進行熱交換。
同時,已揭示一種成膜裝置,其係使用HB加熱裝置將複數氣體加熱,且在保持著比其加熱溫度還低之溫度的玻璃或塑膠基體上,使被認為若基體升溫至其耐熱溫度以上之高溫則無法生長之材料加以成膜的成膜裝置(例如,參照專利文獻5)。
[先前技術文獻] [專利文獻] [專利文獻1]特開第2013-235945號公報 [專利文獻2]特開第2014-59080號公報 [專利文獻3]特開第2015-96792號公報 [專利文獻4]特開第2015-64132號公報 [專利文獻5]日本專利第5105620號公報
[發明所欲解決之課題] 然而,於專利文獻5的發明中,因為基體與碳製高溫熱交換構件的距離拉進,而有輻射熱會使塑膠或玻璃變形的課題。因此,於處理塑膠基體時,必須在更低溫度下製作來自原料氣體的化學活性反應氣體並將其引導至基體。
因此,本發明係為了解決上述課題,提供一種膜形成方法,其係使兩種類的原料氣體積蓄,以使分子物種的分壓突出並作成波峰的方式,將原料氣體瞬時加熱所生成之活性氣體分子物種交互地供給至放置於經減壓的反應室之室溫的試料表面,並形成化合物膜。
[用於解決課題之手段] 形態1;本發明的1或者其以上的實施形態係提議一種膜形成方法,其係具備有積蓄機構、瞬間加熱部及反應室之膜形成裝置的膜形成方法,前述積蓄機構係各自積蓄第一原料氣體與第二原料氣體;前述瞬間加熱部係將前述第一原料氣體與前述第二原料氣體加熱;前述反應室係放置有溫度比前述瞬間加熱部之加熱溫度還低溫之基體,且前述膜形成方法係包含:使積蓄於前述積蓄機構的前述第一原料氣體與前述第二原料氣體通過前述瞬間加熱部,並生成第一氣體分子物種與第二氣體分子物種,且使該第一氣體分子物種與該第二氣體分子物種突出並供給至放置有基體且經減壓之具有一定容量的前述反應室,使得前述第一氣體分子物種的分壓與前述第二氣體分子物種的分壓急速上昇,而將前述第一氣體分子物種或前述第二氣體分子物種交互地重複引導至前述基體的表面,且使前述第一氣體分子物種或前述第二氣體分子物種反應,並於前述基體的表面形成化合物膜。再者,此處的「積蓄機構」係指設置於積蓄容器與其導入口及導出口之控制原料氣體或氣體分子物種的流量之閥等機構要件、或電控制流量的元件,「使突出」係指藉由積蓄容器內氣體的1大氣壓容量與減壓反應室容量之比所定義的分壓變化,且指的是短時間內分壓的峰值。
形態2;本發明的1或者其以上的實施形態係提議了一種膜形成方法,其中,前述第一原料氣體係含有矽、鋁、鎵、鈦、鋅、銦中的至少一個元素,且前述第二原料氣體係水或水溶液或氨。
形態3;本發明的1或者其以上的實施形態係提議了一種膜形成方法,其中,配合使前述第一原料氣體或前述第二原料氣體突出並使分壓急速上昇之週期,將排氣遮斷或降低排氣速度,而使前述第一氣體分子物種的分壓或前述第二氣體分子物種的分壓上昇。
形態4;本發明的1或者其以上的實施形態係提議了一種膜形成方法,其中,前述瞬間加熱部流路的表面係由含有釕、鎳、鉑、鐵、鉻、鋁、鉭之元素中一個以上的金屬來形成。
形態5;本發明的1或者其以上的實施形態係提議了一種膜形成方法,其中,前述瞬間加熱部的加熱溫度係從室溫至700℃。
形態6;本發明的1或者其以上的實施形態係提議了一種膜形成方法,其中,前述基體係薄膜基體且在前述反應室內移動。
形態7;本發明的1或者其以上的實施形態係提議了一種膜形成方法,其中,於前述反應室內具備複數個前述基體。
形態8;本發明的1或者其以上的實施形態係提議了一種膜形成方法,其中,前述基體係矽晶圓。
形態9;本發明的1或者其以上的實施形態係提議了一種膜形成方法,其中,前述基體係塑膠容器。
形態10;本發明的1或者其以上的實施形態係提議了一種膜形成方法,其中,前述基體係有機EL裝置、或液晶裝置、或太陽能電池、或形成有構造圖案的裝置基板。
[發明的效果] 依據本發明的1或者其以上的實施形態,具有下述效果:將原料氣體導入氣體瞬間加熱裝置並將氣體瞬間加熱,且將產生之所欲的生成氣體分子物種引導至保持在低溫之反應室中的基體表面,並於將高溫材料成膜時,在高壓下將積蓄之生成氣體突出供給並使其膨脹冷卻的同時,使反應室的生成氣體分壓急速上昇並使其容易吸附於基體表面。
經冷卻的高分壓之分子物種係高密度吸附,吸附之各分子物種在表面互相結合,產生擬似液化而濕潤表面。若分子物種以使表面濕潤的程度吸附,能夠形成具有均一平滑表面的膜。若吸附密度增加,以一次吸附而能夠成長的膜厚度亦增加,因此得到相較於單純的原子層成長(被稱為原子層沉積(Atomic layer Deposition)的方法)還要高的成長速度之效果。
以下,針對本發明的實施形態,使用圖1至圖6進行說明。
<實施形態> 藉由將兩種原料氣體瞬間加熱並將產生之活性分子物種交互且重複地引導至基板,即使在室溫下亦能將高溫材料成膜。此時,若使基體之活性分子物種的吸附量增加,則能生成高密度的吸附層。以高密度吸附之可反應的兩種類活性分子物種層能夠反應並得到化合物的膜。此時,因為以高密度吸附,能得到較單純的原子層成長更高之成長速度。此係本實施形態的本質且為其特徵。
用於本實施形態膜形成方法的裝置係如圖1所示,其係由閥113、114、105、106、原料氣體積蓄容器101、102、瞬間加熱部107、108、反應室111、基體112、及排氣配管116來構成。
於以下,將原料氣體S1與原料氣體S2作為可反應的原料氣體,基於具體例,針對本實施形態的膜形成方法進行說明。
原料氣體S1係使用載氣將三甲基鋁(標記為TMA)起泡(Bubbling)而得之原料氣體,並將在原料氣體壓力P1下所控制之一定容量的原料氣體S1從閥V3(113)積蓄至原料氣體積蓄容器1(101)。原料氣體S2係使用載氣將水起泡而得之原料氣體,並將在原料氣體壓力P2(104)下所控制之一定容量的原料氣體S2從閥V4(114)積蓄至原料氣體積蓄容器2(102)。
原料氣體S1、原料氣體S2係在各自的壓力下,以一定的容量積蓄於原料氣體積蓄容器1(101)、原料氣體積蓄容器2(102)。透過閥V1(105)、閥V2(106),將原料氣體積蓄容器接續於作為原料氣體瞬間加熱部之HB氣體加熱部1(107)與HB氣體加熱部2(108)。圖未示之控制部根據程序的設定將閥V1(105)與閥V2(106)調成ON/OFF(開閉)。再者,因為HB氣體加熱部係被揭露於專利文獻1~5的技術,此處省略其詳細的說明。
將閥V1(105)調成ON(開),並開始噴出僅有原料氣體(TMA氣體)S1積蓄的部分。噴出之原料氣體(TMA氣體)S1係在HB氣體加熱部1(107)瞬間加熱,並將TMA單量體的HB生成氣體1突出供給至反應室111。此時,因為具有一定容量的反應室成為減壓,在高壓力下導入之氣體膨脹,並突出且被供給,故分壓上昇。接著,HB生成氣體1因為膨脹而被冷卻。
接著,將閥V2(106)調成ON(開)。噴出僅有水之原料氣體S2積蓄的部分,並在HB氣體加熱部2(108)被瞬間加熱,且使作為水單體量的HB生成氣體2突出並供給至反應室111。此時,因為反應室成為減壓,在高壓力下導入之氣體係膨脹且被冷卻。接著,作為水的單量體氣體之HB生成氣體2的分壓上昇。接著,HB生成氣體2因為膨脹而被冷卻。
將閥V1與閥V2交互地調成ON/OFF,重複原料氣體S1、原料氣體S2的突出供給循環。藉此,於基體112的表面,TMA與水的單量體分子物種係被膨脹供給並冷卻,且其分壓交互地上昇並吸附。藉由重複此交互吸附,氧化鋁膜成長。導入原料氣體S1、原料氣體S2時,還能夠另外準備載氣,並將其與原料氣體S1、原料氣體S2合流,而突出供給至反應室111。
藉由總是在一定的減壓條件下交互地導入,並使經有意加壓且積蓄之原料氣體S1、原料氣體S2瞬間且一鼓作氣地突出並供給至反應室,藉此,一瞬間引起高分壓的分子物種吸附,表面吸附密度變高。若表面吸附密度變高到一定程度以上,在表面引起液化並使表面平滑地濕潤。藉此,能夠期待表面之平滑膜的成長。假設即使存有垃圾等異物粒子,亦使其濕潤,並形成異物含於內部之表面吸附層,而將異物與表面被覆。藉此,即使存在異物,也能形成具有異物含於內部之表面平滑的膜。若重複減壓與突出供給且供給分子物種,亦輸送HB生成氣體並被覆於形成深孔或深邃影子的空間。因此,亦具有於如螺絲般組合之構造內側成膜的能力。
以上,將所述之氣體導入之1循環的程序概略地顯示於圖2。在t0時將閥V1(105)調成ON(開)並使原料氣體S1的HB生成氣體1突出且供給至反應室111。反應室111的壓力P3係瞬間上昇並到達壓力波峰PH1。於t1時,將閥V1(105)調成OFF(閉),停止原料氣體S1的供給。此時,因為閥V2(106)也是調成OFF(閉),壓力持續減少,殘留於反應室111的氣體被清除(purge)。清除係在圖未示的載氣下進行,亦可在僅有排氣下進行。
於t2時,反應室111的壓力成為PL1。在t2時,將閥V2(106)調成ON,並使原料氣體S2的HB生成氣體2突出且供給至反應室111。反應室111的壓力P3係瞬間上昇並到達壓力波峰PH2。於t3時,將閥V2(106)調成OFF(閉),而停止原料氣體S2的供給。此時,因為閥V1(105)也是調成OFF(閉),壓力持續減少。在t4時,反應室111內的氣體被清除,且壓力成為PL2。清除係在圖未示的載氣下進行,亦可在僅有排氣下進行。
此處,因為原料氣體的供給容量、載氣流量與反應室容量係因應排氣速度而變化,PH1、PH2、PL1、PL2係圖示相異的值。再者,此等係可調整成相同的值。同時,壓力變化的曲線係概略地顯示一例之曲線。因應作為原料氣體的積蓄機構之容器構造、氣體導入管的厚度與長度、及原料氣體壓力P1、P2的設定,壓力曲線係相異的。同時,為了重複前述的循環,將後述循環的原料氣體從閥V3(113)與閥V4(114)補給至原料氣體積蓄容器1、2(107、108)。補給條件的壓力、量及時機係能夠使用程序自由地設計。
原料氣體S1係含有矽、鋁、鎵、鈦、鋅、銦中的至少一個元素,且原料氣體S2係水或水溶液或氨。
再者,原料氣體S1係可為金屬有機化合物氣體,亦可為鹵化物的氣體。作為鋁的有機化合物之三甲基鋁在常溫下係液體。
在常溫下為液體的原料係使用載氣起泡成為原料氣體,或提高溫度成為原料氣體。因為矽、鎵、鈦、鋅、及銦的有機氣體係可能液化為液體,故使用起泡或加熱成為原料氣體。若水加熱至甚低的150℃,則成為被稱作過熱蒸汽的單分子氣體。為了不讓原料氣體在積蓄容器內液化,積蓄容器係因應必要而加熱。
單分子的水之分子小且浸透作用強。同時,因為單分子的水極化,其被認為以高密度吸附時呈現強氧化作用。亦可使用藥品的水溶液作為原料氣體。氟化氫或甲酸的水溶液係能夠一同導入單分子的水與藥品的成分之原料。
配合使原料氣體S1或原料氣體S2突出並使分壓急速上昇之週期,將排氣遮斷或降低排氣速度,而使第一氣體分子物種的分壓或第二氣體分子物種的分壓上昇。即使僅將排氣速度維持在低速,因分壓突出的效果顯著,故可將排氣配管116設計成固定且細的。或者,較佳係準備兩種類的排氣配管116來切換。亦可以控制排氣泵的旋轉數來控制排氣速度。於排氣配管116設置排氣檔板,藉此,可藉由導電控制來控制分子物種的分壓。只要是使用質量流量控制器並以動態地程序進行控制原料氣體S1與原料氣體S2之供給量的積蓄機構,亦可藉由未具備原料氣體積蓄容器101、102的構造與控制設計,進行分子物種分壓的突出供給調整。
瞬間加熱部107、108流路的表面係由含有釕、鎳、鉑、鐵、鉻、鋁、鉭等元素中一個以上的金屬來形成。
瞬間加熱部的加熱溫度係從室溫至700℃。加熱溫度在150度以上則水產生過熱蒸汽的分子物種。氨在550℃以上放出氫並產生經氫與氮化合的活性分子物種。因此,就瞬間加熱部107、108的溫度而言,從室溫至700℃的範圍中選擇即可。成為900℃以上時,於瞬間加熱部107、108係不鏽鋼的情況下,其表面與氫、水、及氨原料氣體反應,而變得無法長時間維持材料組織,並不適合實際應用。
作為變形例,亦可考慮基體112係薄膜基體且在前述反應室111內移動的形態。圖3係顯示基體112為薄膜基體時的裝置概要之圖。薄膜基體312係從供給滾筒301被供給且在反應室111內移動,並於回收滾筒302捲取回收。此處,薄膜基體312可為塑膠,亦可為PET薄膜。
如圖4所示,基體112可為複數個。此時,突出供給至反應室111的HB生成氣體1、2環繞著被配置於複數個基體112的背後之基體112,且與基體112係單一物體的情況幾乎同樣地形成膜。
基體112可為矽晶圓,且亦可為塑膠容器。同時,反應室111其自身可為係作為基體的容器。再者,基體112係有機EL裝置、或液晶裝置、或太陽能電池、或形成有構造圖案的裝置基板。此等裝置係因氧化或吸溼而劣化。為了防止劣化,必須以使氧及水無法通過之膜成長的薄膜狀基體來被覆。然而,薄膜狀基體係不具有耐熱性。因此,藉由可在室溫下膜成長的本方法可不使水通過,例如,使鋁膜成長即可。
如以上所說明般,根據本實施形態,能夠在反應室得到活性分子物種的高分壓。因此,預先在容器中積蓄一大氣壓壓力的原料氣體。使此原料氣體通過HB氣體加熱部並瞬間加熱,使其變化成活性化學分子物種,且突出供給至減壓的反應室。經突出供給之分子物種係膨脹且溫度下降,同時,在反應室內的分子物種分壓急速提高,以高密度吸附於放置在室溫下的基體表面。藉由高密度吸附,各分子物種互相結合,使表面成為濕潤的程度。因為成為在單分子吸附中無法到達之量的吸附分子數目,能夠期待較原子層成長ALD(Atomic layer Deposition)更快的成長速度。
同時,能夠設計各種類的化合物膜。矽、鋁、鎵、鈦、鋅、銦的有機氣體係可工業供給的材料。若將此等的金屬與氧或氮化合,能夠形成此等金屬的氧化物或氮化物之膜。氨在550℃以上放出氫並開始分解。若在HB氣體加熱部加熱並將其與觸媒金屬碰撞,在更低溫下引起其分解。因此,能夠使活性氨的分子物種與含有上述金屬的分子物種反應並形成氮化物的膜。同時,水在100℃下係其自身的多聚物。然而,在HB加熱部加熱至150℃以上的過熱蒸汽係成為含有單量體成分的活性分子物種。因此,變得可形成上述金屬的氧化物膜。以上係元素組合的一例。藉由組合氣體瞬間加熱部的溫度與原料氣體的元素,能夠設計形成化合物的膜。
同時,使分子物種分壓上昇係容易的。於使排氣速度成為低速時,僅將排氣配管設計成細的即能夠充分。可準備寬、細兩種類的排氣配管來切換。因為亦可控制排氣泵的旋轉數來控制排氣速度,能夠使用程序並配合時機來對應。或者,於排氣配管設置排氣檔板,並能夠藉由導電控制來控制分子物種的分壓。
同時,能夠選擇形成原料氣體瞬間加熱部之流路表面的金屬。藉由使用對於氣體分解有催化作用之釕、鎳、鉑等構成表面,或藉由使此等金屬與置於流路中的氣體碰撞接觸,能夠在更低溫下將原料氣體分解並生成活性分子物種。根據溫度區域,鋁及鉭係成為防腐蝕的材料。因為鐵、鉻、鎳係不鏽鋼的主成分,故能夠使用耐腐蝕性的不鏽鋼。
同時,原料氣體瞬間加熱部的加熱溫度係可在室溫至700℃的範圍內選擇。由水製作過熱蒸汽時,使用150℃以上係有效的。從超過600℃來看,因為產生氫之烴分解亦成為可能,故能夠設計將烴作為原料氣體來產生分子物種,並從此分子物種形成可能的膜。
同時,長的薄膜基體係能夠相對於與生成氣體接觸之反應室相對地連續移動。因為薄膜係能夠彎曲,能夠在反應室內以鋸齒狀的方式移動。薄膜的代表係聚對苯二甲酸乙二酯(PET)。若能夠於具有100℃以下耐熱性的薄膜上形成高溫材料的氧化鋁或矽氮化物之膜,則藉由形成有裝置之薄膜將此薄膜被覆,能夠達到防止水份通過之阻隔膜的效果。阻隔膜係具有提高裝置可靠性的效果。若裝置形成於連續的薄膜上,則能夠使阻隔膜連續並成長。因為一般高溫材料係陶瓷所以堅硬。能夠使沒有傷痕之堅硬膜成長於薄膜的表面。
同時,能夠處理多數的基體。基體可為晶圓、容器、管子、及印刷基板。再者,於欲在由塑膠粒子、玻璃粒子及藥品粒子等而成之粒子基體表面成膜的情況下亦係有效的。尺寸亦可從mm單位至nm單位。藉由將可反應的分子物種交互地在突出分壓下供給至填充有如此之粒子基體的筒,使得於粒子上形成膜成為可能。
同時,使得於層積有不能提高溫度之材料的矽晶圓上成膜變得可能。有使用光阻材料於矽晶圓上形成微細構造的情形。或者,有形成溫度有限制之材料的情形。於有必要在具有如此之材料構造的矽晶圓基體成膜時,因為本成膜方法係室溫成長,能夠克服課題。
同時,亦具有將形成有以光阻製作之流路的矽基板利用於含有血液或細胞之液體成分分析的要求。於如此時,若在光阻上形成氧化鋁膜,則能夠得到化學穩定的流路。如此之室溫成長的要求係回應本發明的效果。
同時,雖然於光阻的圖案上進行成長具有乾式蝕刻耐性之作為遮罩(mask)材料的氧化矽膜,但因為於此使用被稱為電漿CVD的方法而成為昂貴的製程。在本發明中,因為係不使用電漿處理而僅使用熱的成膜方法,能夠實現便宜的製程。
同時,使在塑膠容器上成膜變得可能。因為塑膠容器便宜且輕,適合放置食品及藥品。於此容器中,必須具有防止內容物被外部而來之大氣水分及氧侵入的功能。同時,必須具有防止內容物成分散溢至外部大氣的功能。舉例來說,本成膜方法若使用被覆有氧化鋁膜的容器,則能滿足此功能。若是使分子物種分壓突出並調整之於多數容器基體內部使高密度吸附分子物種的本成膜方法,則因為能夠一次在多數個容器基體成膜,故可以便宜地來製作。
接著,能夠在形成有有機EL裝置、或液晶裝置、或太陽能電池之裝置基體上成膜。作為有機EL代表的顯示裝置係因為氧化或吸溼而劣化。此係成為保證壽命之實用化的妨礙。因此,具有下述課題:直接將大面積基板維持在低溫,無法將具有耐溼性之材料的保護薄膜於形成有裝置之基體表面成膜。現在,雖然氧化矽膜的真空濺鍍係唯一的方法,但製造價格高,且其成為大型有機EL顯示器實用化的阻礙。同時,太陽能電池亦需確保長期可靠性因而提升了製造成本。根據本實施形態,具有解決此等課題的效果。
<實施例1> 以下,使用圖1,針對使作為化合物膜之氧化鋁膜成長於基體表面的實施例進行說明。
在本實施例中,使用以氬氣起泡之三甲基鋁(TMA)與氬氣載氣的混合氣體作為原料氣體S1。就原料氣體S2而言,使用以氬氣起泡之水與氬氣載氣的混合氣體。
藉由供給程序,在原料氣體S1與原料氣體S2之朝向反應室內的供給中,各自的供給時間都沒有重疊。打開閥V3(113)、閥V4(114),將各自的原料氣體積蓄於原料氣體積蓄容器1、2(101、102)。容器內的原料氣體壓力P1與原料氣體壓力P2係一大氣壓。原料氣體積蓄容器1、2的容積約30cc。
原料氣體積蓄容器1、2(101、102)係透過閥V1(105)、閥V2(106),與作為原料氣體加熱裝置之HB氣體加熱部1(107)及HB氣體加熱部2(108)接續。此處,HB氣體加熱部1、2(107、108)的設定加熱溫度係160℃。
在圖2所示之時間t0的時間點,將閥V1調成ON(開),僅噴出原料氣體S1(TMA氣體)積蓄於原料氣體積蓄容器1(101)的部分,並在HB氣體加熱部1(107)瞬間加熱,且將TMA單量體之HB生成氣體1突出供給至反應室111。
藉由排氣Ex的平衡而使反應室111成為減壓0.01大氣壓。因此,積蓄於原料氣體積蓄容器1(101)之氣體在一大氣壓下被突出供給,且其分壓急速上昇並膨脹。HB生成氣體1因為膨脹而被冷卻。反應室111的容量係800cc。若於此將相對於一大氣壓原料氣體供給容量30cc之反應室111的容量比定義為分壓變化指數,則其係約0.038。此指數係顯現本技術之變化分壓之特徵的指數。
時間t0與時間t1間的時間間隔T01係1秒。在時間t1的時間點,閥V1(105)與閥V2(106)兩者關閉,且反應室111的壓力下降。此狀態持續至時間t2。時間t1與時間t2間的時間間隔T12係9秒。
在時間t2的時間點,將閥V2(106)調成ON(開)。僅噴出由水而成之原料氣體S2積蓄於原料氣體積蓄容器2(102)的部分並使其流出,並在HB氣體加熱部2(108)瞬間加熱,且將水單量體之HB生成氣體2突出供給至反應室111。因為反應室111成為減壓,在高壓下導入之HB生成氣體急速膨脹。HB生成氣體2因為此膨脹而被冷卻。閥V2(106)打開的時間係從時間t2持續至時間t3,在此之間的時間間隔T23係1秒。反應室111的容量係800cc。因為一大氣壓原料氣體的供給容量係同樣為30cc,分壓變化指數係0.038。
在時間t3的時間點,閥V1(105)與閥V2(106)兩者關閉,且反應室111的壓力下降持續至時間t4。時間t3至時間t4為止的時間間隔T34係9秒。
在閥V1(105)關閉的時間進行原料氣體1朝向原料氣體積蓄容器1(101)的補給積蓄。在閥V2(106)關閉的時間進行原料氣體2朝向原料氣體積蓄容器2(102)的補給積蓄。
一邊進行原料氣體朝向原料氣體積蓄容器1、2(101、102)的補給,一邊依據如圖2所示之時間表,將閥V1(105)與閥V2(106)開閉,重複將HB生成氣體突出供給至反應室111的循環。一個循環的時間係1秒+9秒+1秒+9秒 = 20秒。重複75次。75次的循環,也就是說,在25分鐘下觀察到成長有約100nm之氧化鋁膜的剖面TEM。
放置作為基體112之製作有光阻孔圖案的矽晶圓501。觀察其剖面之SEM圖像(電子顯微鏡圖像)。將其示意圖顯示於圖5。具有80nm直徑的孔之表面1(504)係平坦的。具有150nm直徑的孔之表面2(505)係平滑地凹陷。
此形狀與普通的CVD不同。就像是液體固化之剖面形狀。因為無法測量及原位觀察,雖然為推測,但此形狀係被暗示為TMA或水的單量體吸附並成長為液體狀之物理現象。一般認為此係實現高密度的分子物種吸附並在表面液化。
<實施例2> 就這樣將成長條件固定與實施例1相同,放置作為基體112之聚對苯二甲酸乙二酯(PET)。製作成膜之膜與基體PET薄膜的層積構造。進行此層積構造的氦(He)通過試驗。以一大氣壓之He填滿薄膜的單側,並以四極桿的質量分析計(quadrupole mass analyzer)來測定於相反側洩逸出之He分壓的方法進行通過試驗。
於未成膜有此氧化鋁膜之PET薄膜單體的情況下,He在兩分鐘左右時通過。然而,層積有此氧化鋁之PET薄膜構造與1mm厚的玻璃板相同,即使經過10分鐘He也不會通過。因此,吾人明白其具有防止對於比He分子尺寸還大之水、二氧化碳、及氧通過的特性。同時,將此層積構造薄膜浸漬於50℃的水並放置一天後,於分析鋁的溶出時,確認到未溶出。此係暗示該氧化鋁的組成係化學計量的。
<實施例3> 使反應室111的容積成為50L,在與實施例1相同的氣體供給條件下成膜。計算之分壓變化指數係0.0006。
放置作為基體112之製作有光阻之孔圖案的矽晶圓501。觀察其剖面之SEM圖像(電子顯微鏡圖像)。具有80nm直徑的孔之表面係平坦的。此與實施例1相同。然而,具有150nm直徑的孔之表面係如圖6所示,膜沿著孔壁(保形的(Conformal))成長。此係與實施例1不同。分壓變化指數係作為顯示成長條件差異之特徵的指數。
若比較實施例1與實施例3,相較於分壓變化指數係0.0006的情況,分壓變化指數係0.038的條件係能夠被評價為使表面平坦的效果更高。
以上,雖然基於本發明的實施形態,並參照圖面進行詳述,但具體的構成並不限於該等實施形態,只要是沒有逸脫本發明要旨的範圍之設計等亦包含在內。
101‧‧‧原料氣體積蓄容器1
102‧‧‧原料氣體積蓄容器2
105‧‧‧閥V1
106‧‧‧閥V2
107‧‧‧瞬間加熱部1(HB氣體加熱部1)
108‧‧‧瞬間加熱部2(HB氣體加熱部2)
111‧‧‧反應室
112‧‧‧基體
113‧‧‧閥V3
114‧‧‧閥V4
116‧‧‧排氣配管
201‧‧‧壓力曲線
301‧‧‧供給滾筒
302‧‧‧回收滾筒
303‧‧‧滾筒室
312‧‧‧薄膜基體
412‧‧‧複數基體
501‧‧‧矽晶圓基體
502‧‧‧光阻
503‧‧‧氧化鋁膜
504‧‧‧表面1
505‧‧‧表面2
S1‧‧‧原料氣體
S2‧‧‧原料氣體
Ex‧‧‧排氣
102‧‧‧原料氣體積蓄容器2
105‧‧‧閥V1
106‧‧‧閥V2
107‧‧‧瞬間加熱部1(HB氣體加熱部1)
108‧‧‧瞬間加熱部2(HB氣體加熱部2)
111‧‧‧反應室
112‧‧‧基體
113‧‧‧閥V3
114‧‧‧閥V4
116‧‧‧排氣配管
201‧‧‧壓力曲線
301‧‧‧供給滾筒
302‧‧‧回收滾筒
303‧‧‧滾筒室
312‧‧‧薄膜基體
412‧‧‧複數基體
501‧‧‧矽晶圓基體
502‧‧‧光阻
503‧‧‧氧化鋁膜
504‧‧‧表面1
505‧‧‧表面2
S1‧‧‧原料氣體
S2‧‧‧原料氣體
Ex‧‧‧排氣
[圖1] 係用於本發明實施形態中膜形成方法的裝置之概略構成圖。 [圖2] 係顯示用於本發明實施形態中膜形成方法的分壓突出調製時間表之圖。 [圖3] 係本發明實施形態膜形成方法中藉由滾筒將基體供給時的裝置之概略構成圖。 [圖4] 係用於本發明實施形態膜形成方法中,於複數基體上形成膜時的裝置之概略構成圖。 [圖5] 係顯示用於本發明實施形態膜形成方法中所形成鋁膜的嵌埋特性之示意圖。 [圖6] 係顯示用於本發明實施形態膜形成方法中所形成鋁膜的嵌埋特性之示意圖。
101‧‧‧原料氣體積蓄容器1
102‧‧‧原料氣體積蓄容器2
105‧‧‧閥V1
106‧‧‧閥V2
107‧‧‧瞬間加熱部1(HB氣體加熱部1)
108‧‧‧瞬間加熱部2(HB氣體加熱部2)
111‧‧‧反應室
112‧‧‧基體
113‧‧‧閥V3
114‧‧‧閥V4
116‧‧‧排氣配管
S1‧‧‧原料氣體
S2‧‧‧原料氣體
Ex‧‧‧排氣
Claims (10)
- 一種膜形成方法,其係具備有積蓄機構、瞬間加熱部及反應室之膜形成裝置的膜形成方法,前述積蓄機構係各自積蓄第一原料氣體與第二原料氣體;前述瞬間加熱部係將前述第一原料氣體與前述第二原料氣體加熱;前述反應室係放置有溫度比前述瞬間加熱部之加熱溫度還低溫之基體,且前述膜形成方法係包含: 使積蓄於前述積蓄機構的前述第一原料氣體與前述第二原料氣體通過前述瞬間加熱部,並生成第一氣體分子物種與第二氣體分子物種,且使該第一氣體分子物種與該第二氣體分子物種突出並供給至放置有前述基體且經減壓之具有一定容量的前述反應室,使得前述第一氣體分子物種的分壓與前述第二氣體分子物種的分壓急速上昇,而將前述第一氣體分子物種或前述第二氣體分子物種交互地重複引導至前述基體的表面,且使前述第一氣體分子物種或前述第二氣體分子物種反應,並於前述基體的表面形成化合物膜。
- 如請求項1所述之膜形成方法,其中,前述第一原料氣體係含有矽、鋁、鎵、鈦、鋅、銦中的至少一個元素,且前述第二原料氣體係水或水溶液或氨。
- 如請求項1或2所述之膜形成方法,其中,配合使前述第一原料氣體或前述第二原料氣體突出並使分壓急速上昇之週期,將排氣遮斷或降低排氣速度,而使前述第一氣體分子物種的分壓或前述第二氣體分子物種的分壓上昇。
- 如請求項1~3中任一項所述之膜形成方法,其中,前述瞬間加熱部之流路的表面係由含有釕、鎳、鉑、鐵、鉻、鋁、鉭之元素中一個以上的金屬來形成。
- 如請求項1~4中任一項所述之膜形成方法,其中,前述瞬間加熱部的加熱溫度係從室溫至700℃。
- 如請求項1~5中任一項所述之膜形成方法,其中,前述基體係薄膜基體且在前述反應室內移動。
- 如請求項1~5中任一項所述之膜形成方法,其中,於前述反應室內具備複數個前述基體。
- 如請求項1~5、7中任一項所述之膜形成方法,其中,前述基體係矽晶圓。
- 如請求項1~5、7中任一項所述之膜形成方法,其中,前述基體係塑膠容器。
- 如請求項1~5、7中任一項所述之膜形成方法,其中,前述基體係有機EL裝置、或液晶裝置、或太陽能電池、或形成有構造圖案的裝置基板。
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