CN101541701B - 制备低电阻率、掺杂氧化锌涂层玻璃物件的方法及由此制成的涂层玻璃物件 - Google Patents
制备低电阻率、掺杂氧化锌涂层玻璃物件的方法及由此制成的涂层玻璃物件 Download PDFInfo
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- CN101541701B CN101541701B CN2007800393530A CN200780039353A CN101541701B CN 101541701 B CN101541701 B CN 101541701B CN 2007800393530 A CN2007800393530 A CN 2007800393530A CN 200780039353 A CN200780039353 A CN 200780039353A CN 101541701 B CN101541701 B CN 101541701B
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- zinc oxide
- gallium
- resistivity
- glass article
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 39
- 239000011521 glass Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000000376 reactant Substances 0.000 claims abstract description 19
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052738 indium Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract 3
- 238000000576 coating method Methods 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 44
- 238000000151 deposition Methods 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 15
- -1 Aluminum compound Chemical class 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 7
- 150000003752 zinc compounds Chemical class 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 6
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000002259 gallium compounds Chemical class 0.000 claims 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 2
- 125000005594 diketone group Chemical group 0.000 claims 2
- IGOGAEYHSPSTHS-UHFFFAOYSA-N dimethylgallium Chemical compound C[Ga]C IGOGAEYHSPSTHS-UHFFFAOYSA-N 0.000 claims 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 abstract description 12
- 239000011701 zinc Substances 0.000 abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011737 fluorine Substances 0.000 abstract description 9
- 229910052725 zinc Inorganic materials 0.000 abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 239000012159 carrier gas Substances 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- 229960001296 zinc oxide Drugs 0.000 description 24
- 239000008246 gaseous mixture Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 11
- 239000006200 vaporizer Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000005388 borosilicate glass Substances 0.000 description 6
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- KPPVNWGJXFMGAM-UUILKARUSA-N (e)-2-methyl-1-(6-methyl-3,4-dihydro-2h-quinolin-1-yl)but-2-en-1-one Chemical compound CC1=CC=C2N(C(=O)C(/C)=C/C)CCCC2=C1 KPPVNWGJXFMGAM-UUILKARUSA-N 0.000 description 1
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 description 1
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 description 1
- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 description 1
- YBMDPYAEZDJWNY-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octafluorocyclopentene Chemical compound FC1=C(F)C(F)(F)C(F)(F)C1(F)F YBMDPYAEZDJWNY-UHFFFAOYSA-N 0.000 description 1
- LVFXLZRISXUAIL-UHFFFAOYSA-N 2,2,3,4,4,4-hexafluorobutan-1-ol Chemical class OCC(F)(F)C(F)C(F)(F)F LVFXLZRISXUAIL-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- PRDFNJUWGIQQBW-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-yne Chemical compound FC(F)(F)C#C PRDFNJUWGIQQBW-UHFFFAOYSA-N 0.000 description 1
- QQFGOTHONVYTNR-UHFFFAOYSA-N CC1OC1.F.F.F.F.F.F Chemical compound CC1OC1.F.F.F.F.F.F QQFGOTHONVYTNR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229960003132 halothane Drugs 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- WBCLXFIDEDJGCC-UHFFFAOYSA-N hexafluoro-2-butyne Chemical compound FC(F)(F)C#CC(F)(F)F WBCLXFIDEDJGCC-UHFFFAOYSA-N 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 description 1
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
-
- 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
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- 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
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/216—ZnO
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
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- C03C2217/229—Non-specific enumeration
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/24—Doped oxides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/24—Doped oxides
- C03C2217/241—Doped oxides with halides
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明描述并要求保护一种制备低电阻率、掺杂氧化锌涂层玻璃物件的大气化学气相沉积方法,通过将一个或多个气体反应物流,特别是含锌化合物、含氟化合物、含氧化合物,和至少一种包含硼、铝、镓和铟其中一种或多种的化合物引到热玻璃衬底的表面上而制成。
Description
发明背景
本发明涉及将氧化锌涂层沉积在透明衬底上的方法。更具体地,本发明涉及将氧化锌涂层沉积在玻璃衬底上的化学气相沉积方法,所述涂层被改良成为具有所需组合特性的氧化锌涂层。
掺杂氧化锌涂层的沉积,已报道于专利文献。例如,美国专利5,306,522描述了涂布衬底的工艺,特别是包括防护表面(shieldedsurfaces)的衬底,涂有含氧化锌的涂层。所述工艺包括:使衬底与氧化锌前体接触,优选使涂有前体的衬底维持在一定条件下以平衡涂层,然后将前体氧化以形成含氧化锌的涂层。也描述了用于各种应用的通过所述工艺涂成的衬底。
与上述美国专利5,306,522相关的美国专利5,407,743,包括特别与用所述工艺制成的氧化锌涂层物件相关的其它信息。
此外,用溶胶-凝胶法(sol-gel method)制备F-、Al-掺杂的ZnO薄膜,见述于Castanedo-Perez等人的Solar Energy Materials & SolarCells(太阳能材料与太阳能电池)2004,82,35。
对耐用、涂层玻璃产品的需求日益增加。期望获得氧化锌涂层的玻璃产品,其具有高可见光透光率(transmittance)、低发射率(emissivity)特性和/或太阳能控制(solar control)特性、高电导率/低薄层电阻(sheetresistance),且生产的成本效率高。
发明概述
本发明涉及制备低电阻率、掺杂氧化锌涂层玻璃物件的大气压力化学气相沉积方法,其包括在例如浮法玻璃熔炉中加热玻璃衬底,将包括含锌化合物、含氟化合物、含氧化合物和至少一种包含硼、铝、镓和铟中至少一种的化合物的一个或多个气体反应物流,引到加热后的玻璃衬底表面上,在其上沉积掺杂氧化锌涂层。
附图简述
图1是本发明中六氟丙烯(HFP)对沉积速率影响的图示。
图2是本发明中六氟丙烯(HFP)对电阻率影响的图示。
图3是本发明中六氟丙烯(HFP)对迁移率影响的图示。
发明详述
虽然氧化锌涂层和沉积方法是周知的,但是在浮法玻璃生产线上的玻璃制造工艺中,以商业化可行的生长速率制造热解氧化锌涂层的成本有效的方法,之前并不为人所知。此外,至今未能将这种在线(on-line)制成的氧化锌涂层用一种或多种掺杂化合物掺杂,制成具有所需组合特性的涂层。本发明克服了制造这种掺杂氧化锌薄膜的先前障碍。
虽然可以将任何适当的大气压力化学气相沉积法用于本发明,但是优选Atofina Chemicals,Inc.的美国专利6,268,019中所公开的沉积方法。该′019专利通过其整体引用而并入本文。′019专利的方法显示能够以商业上有利的生长速率,例如大于5纳米/秒,沉积各类金属氧化物薄膜。′019专利的沉积方法还有一个优点是能够改变反应物原料的混合时间,进而,在这种情况下可调整氧化锌涂层的特性。特别地,本发明证实了使用多种前体化合物的好处,这些好处将在本文中作更详细的论述。
这种掺杂氧化锌涂层玻璃产品可用作建筑窗应用中的低发射率和/或太阳能控制层。这种透明传导性氧化物的其它可能应用包括:光电装置、固态发光(solid-state lighting)(LED和OLED)、感应加热、平板显示器、触摸板屏幕和可用于RFID标签和集成电路中的透明薄膜晶体管(TFT)。
适当的含锌化合物包括,但不限于通式R1R2Zn、R1R2ZnL或R1R2Zn-[R3R4N(CHR5)n(CH2)m(CHR6)nNR7R8]的化合物,其中R1-8可以是相同或不同的烷基或芳基,例如甲基、乙基、异丙基、正丙基、正丁基、仲丁基、苯基或取代苯基,而且可以包含一个或多个含氟取代基,R5和R6可以是H或烷基或芳基,L是基于氧的、商品化的中性配体,例如甲基四氢呋喃、四氢呋喃、呋喃、二乙基或二丁基醚、甲基叔丁基醚或二氧六环,且n可以是0或1,而且如果n是0,m可以是1至6,而如果n是1,m可以是0至6。
适当的含氟化合物包括,但不限于:二氟甲烷、1,1-二氟乙烷、1,1,1,2-四氟乙烷、1,1,1,2,2-五氟乙烷、1,1,1-三氟乙烷、1,1,1,3,3-五氟丙烷、氟乙烯、1,1-二氟乙烯、1,1,1,2,3,3,3-七氟丙烷、1,1,1,2,2,3,3-七氟丙烷、六氟丙烯、3,3,3-三氟丙烯、全氟环戊烯、全氟丁二烯、1,1,1,3,3,3-六氟-2-丙醇、1,1,1,3,3,3-六氟-2-甲基-2-丙醇、六氟环氧丙烷、2,2,3,4,4,4-六氟-1-丁醇、1,1,2,2,3,4-六氟-3,4-二(三氟甲基)环丁烷、六氟-2-丁炔、六氟丙酮、六氟戊二酸酐、三氟乙酸酐、三氟乙酰氯、2,2,2-三氟乙醇、1,1,1-三氟丙酮、三氟甲烷、1,1,1-三氟-2-丙醇、3,3,3-三氟丙酸、3,3,3-三氟丙炔、三氟胺、氟化氢、三氟乙酸、1,1,1,3,3-五氟丁烷,1,1,1,2,3,4,4,5,5,5-十氟戊烷。
适当的含氧化合物包括,但不限于:有机乙酸酯,例如乙酸叔丁酯(t-BuOAc)、乙酸乙酯(EtOAc),醇(包括全氟化的衍生物),氧和水,而优选H2O。
适当的含13族金属的前体包括通式R9 3ML或R9 (3-n)M(R10C(O)CR11C(O)R12)n的那些,其中M=B,Al,Ga,In或Tl其中之一,R9为烷基或芳基或卤素或烃氧化物基(alkoxide group),且可以相同或不同,R10-12可以相同或不同且为H、烷基或芳基(包括环状以及部分和全氟化的衍生物),L是基于氧的、商品化的中性配体,例如甲基四氢呋喃、四氢呋喃、呋喃、二乙基或二丁基醚、甲基叔丁基醚或二氧六环,n=0至3,且z=0至2。Me2Ga(acac)(acac=乙酰丙酮根)、Me2Ga(hfac)(hfac=六氟乙酰丙酮根,F3CC(O)CHC(O)CF3)和Et2Al(acac)是优选的13族化合物。
惰性载气,例如氮、氦等也可用作本发明气体反应物流的组分。
可用适当的方法制成加热后的玻璃衬底,但是优选用众所周知的浮法玻璃工艺制成的连续的玻璃带(ribbon),该工艺见述于美国专利3,356,474、3,433,612、3,531,274和3,790,361,它们全都通过整体引用而并入本文。
以下非限制实施例阐述本发明的某些方面。
实施例
实施例1至6中所用的APCVD仪器类似于美国专利6268019B1中所述的仪器。该仪器的关键特征是能够通过分别向涂层喷嘴加蒸汽来控制气体反应物的混合时间。在这些试验中涂层喷嘴由同心管组成:通过压缩装置(compression fitting)将3/8″管加入1″管中,可调整混合区的长度,外部的1.5″管与排风机相连,可移除副产物和未反应的蒸汽。由这个喷嘴构造所产生的薄膜为圆形,直径约为1.5″。
为了描述性目的,6个实施例的沉积变量不同,但是静态沉积条件类似:实施例1对应于与含铝前体结合的氧化锌沉积,实施例2对应于与含氟前体结合的氧化锌沉积,而实施例3对应于与含氟和铝前体结合的氧化锌沉积。对于每个实施例,所有前体的体积输送速率相同。实施例4描述了与镓前体结合的ZnO沉积,而实施例5描述了与镓和氟前体结合的ZnO沉积。实施例6描述了与氟和铝结合的沉积,如实施例3一样,但是使用不同的锌源,即Et2Zn·TMPDA(TMPDA=N,N,N′,N′-四甲基-1,3-丙烷二胺)。对于实施例1至6,沉积在静态玻璃衬底上进行,反应物浓度的计算是基于当所有流合并后存在的浓度。
实施例1:
在镍加热块上加热硼硅酸盐玻璃(1.1毫米厚)至430℃(用接触热电偶在衬底表面处测量)。通过涂层喷嘴的初级(primary)化学品给料口,加入于180℃温度下0.08摩尔%Et2Zn·TEEDA(TEEDA=N,N,N′,N′-四乙基乙二胺)和0.015摩尔%Et2Al(acac)(acac=乙酰丙酮根)在30升/分钟氮载气中的气体混合物。在分开的给料中,向涂布机内管加入0.40摩尔%水蒸汽(在蒸发器1中蒸发)在2.2升/分钟氮载气中的气体混合物。
调整内给料管使混合区长度为15厘米。选择氮载气流使两种给料的速度大致相等。在这些条件下,涂布机喷嘴出口处的面速度约为100厘米/秒,与约为150毫秒的反应物混合时间相关。
在Zn和Al前体流即将开始之前,将水蒸汽混合物预先给予(pre-dosed)衬底5秒钟。样品的沉积时间为45秒,得到厚度约310纳米的薄膜。用4点探针测得薄膜的薄层电阻为53ohm/sq。
实施例2:
在镍加热块上加热硼硅酸盐玻璃(1.1毫米厚)至430℃(用接触热电偶在衬底表面处测量)。通过涂层喷嘴的初级化学品给料口,加入于180℃温度下0.08摩尔%Et2Zn·TEEDA在30升/分钟氮载气中的气体混合物。在分开的给料中,加入0.48摩尔%水蒸汽(在蒸发器1中蒸发)和0.82摩尔%六氟丙烯(紧接在蒸发器之后经校准过的旋转式流量计引入气体流中)在2.2升/分钟氮载气中的气体混合物。
调整内给料管使混合区长度为15厘米。选择氮载气流使两种给料的速度大致相等。在这些条件下,涂布机喷嘴出口处的面速度约为100厘米/秒,与约为150毫秒的反应物混合时间相关。在Zn前体即将开始流向衬底之前,将水蒸汽和六氟丙烯气体混合物预先给予(pre-dosed)衬底5秒钟。样品的沉积时间为45秒,得到厚度约340纳米的薄膜。用4点探针测得薄膜的薄层电阻为138ohm/sq。
实施例3:
在镍加热块上加热硼硅酸盐玻璃(1.1毫米厚)至430℃(用接触热电偶在衬底表面处测量)。通过涂层喷嘴的初级化学品给料口,加入于180℃温度下0.08摩尔%Et2Zn·TEEDA和0.015摩尔%Et2Al(acac)在30升/分钟氮载气中的气体混合物。在分开的给料中,加入0.48摩尔%水蒸汽(在蒸发器1中蒸发)和0.82摩尔%六氟丙烯(紧接在蒸发器之后经校准过的旋转式流量计引入气体流中)在2.2升/分钟氮载气中的气体混合物。
调整内给料管使混合区长度为15厘米。选择氮载气流使两种给料的速度大致相等。在这些条件下,涂布机喷嘴出口处的面速度约为100厘米/秒,与约为150毫秒的反应物混合时间相关。
在Zn和Al前体即将开始流向衬底之前,将水蒸汽和六氟丙烯气体混合物预先给予(pre-dosed)衬底5秒钟。样品的沉积时间为45秒,得到厚度约290纳米的薄膜。用4点探针测得薄膜的薄层电阻为21ohm/sq。
如在上述实施例中所看到的,与铝和氟前体单独存在的其它样品相比较,沉积过程中氟和铝前体同时存在的实施例3中观察到导电率显著增加。
实施例4:
在镍加热块上加热硼硅酸盐玻璃(1.1毫米厚)至430℃(用接触热电偶在衬底表面处测量)。通过涂层喷嘴的初级化学品给料口,加入于180℃温度下0.08摩尔%Et2Zn·TEEDA和0.003摩尔%Me2Ga(hfac)在30升/分钟氮载气中的气体混合物。在分开的给料中,向涂布机内管中加入0.48摩尔%水蒸汽(在蒸发器1中蒸发)在2.2升/分钟氮载气中的气体混合物。
调整内给料管使混合区长度为15厘米。选择氮载气流使两种给料的速度大致相等。在这些条件下,涂布机喷嘴出口处的面速度约为100厘米/秒,与约为150毫秒的反应物混合时间相关。
在Zn和Ga前体即将开始流动之前,将水蒸汽气体混合物预先给予(pre-dosed)衬底5秒钟。样品的沉积时间为45秒,得到厚度约333纳米的薄膜。用4点探针测得薄膜的薄层电阻为23ohm/sq。
实施例5:
在镍加热块上加热硼硅酸盐玻璃(1.1毫米厚)至约430℃(用接触热电偶在衬底表面处测量)。通过涂层喷嘴的初级化学品给料口,加入于180℃温度下0.08摩尔%Et2Zn·TEEDA和0.003摩尔%Me2Ga(hfac)在30升/分钟氮载气中的气体混合物。在分开的给料中,加入0.48摩尔%水蒸汽(在蒸发器1中蒸发)和0.81摩尔%六氟丙烯(紧接在蒸发器之后经校准过的旋转式流量计引入气体流中)在2.2升/分钟氮载气中的气体混合物。
调整内给料管使混合区长度为15厘米。选择氮载气流使两种给料的速度大致相等。在这些条件下,涂布机喷嘴出口处的面速度约为100厘米/秒,与约为150毫秒的反应物混合时间相关。
在Zn和Ga前体即将开始流向衬底之前,将水蒸汽和六氟丙烯气体混合物预先给予(pre-dosed)衬底5秒钟。样品的沉积时间为45秒,得到厚度约340纳米的薄膜。用4点探针测得薄膜的薄层电阻为17ohm/sq。
实施例6:
在镍加热块上加热钠钙二氧化硅玻璃(Sodalime silica glass)(0.7毫米厚)至约430℃(用接触热电偶在衬底表面处测量)。通过涂层喷嘴的初级化学品给料口,加入于180℃温度下0.08摩尔%Et2Zn·TMPDA(TMPDA=N,N,N′,N′-四甲基-1,3-丙二胺)和0.003摩尔%Et2Al(acac)在30升/分钟氮载气中的气体混合物。在分开的给料中,加入0.48摩尔%水蒸汽(在蒸发器1中蒸发)和0.81摩尔%六氟丙烯(紧接在蒸发器之后经校准过的旋转式流量计引入气体流中)在2.2升/分钟氮载气中的气体混合物。
调整内给料管使混合区长度为15厘米。选择氮载气流使两种给料的速度大致相等。在这些条件下,涂布机喷嘴出口处的面速度约为100厘米/秒,与约为150毫秒的反应物混合时间相关。
在Zn和Al前体即将开始流向衬底之前,将水蒸汽和六氟丙烯气体混合物预先给予(pre-dosed)衬底5秒钟。样品的沉积时间为40秒,得到厚度约320纳米的薄膜。用4点探针测得薄膜的薄层电阻为18ohm/sq。
实施例7:静态模式涂层法
在170℃下,将0.43摩尔%Me2ZnTMPDA在10slpm氮载气中的气体混合物,加到初级给料管中。将第一掺杂剂从不锈钢喷口(bubbler)引到初级给料管中。喷***Me2Ga(acac),温度为34.5℃。Ga-前体被预热至60℃的430sccm流速的氮气吸收(pick up)。将197sccm的(2.5摩尔%)第二掺杂剂(六氟丙烯(HFP))加入初级给料中。
在二级给料管中,于170℃下加入1.25摩尔%H2O和3.26摩尔%2-丁醇在5slpm氮气中的气体混合物。将二级给料与初级流同时加到混合室里。混合室的长度为l1/4英寸,相当于初级和二级给料流之间的混合时间为278毫秒。用于沉积的衬底为厚度为0.7毫米的硼硅酸盐玻璃。在设于550℃的电阻加热镍块上加热衬底。这些薄膜在静态模式下的沉积时间为55秒钟,所得ZnO薄膜的厚度为565纳米,沉积速率为12纳米/秒。这些薄膜用BYK HazeGuard Plus混浊度测量仪测得的混浊度平均为0.5%。电阻率、迁移率和电子密度分别为2.2×10-4ohm-cm、23cm2/Vs和1.22×1021cm-3。
实施例8至9:使用备选的动态沉积方法
通过动态涂层工艺进行涂层试验,使3或4毫米厚的玻璃预热衬底,以24英寸/分钟的速度紧靠金属涂布机头的下方移动,引导气体化学混合物与600℃的热玻璃衬底接触,随后立即取出。
将下述气体混合物在化学品传输车中进行预混,并通过加热的传输管加到涂布机头内。根据化学品流动条件和试验实际尺寸,反应物混合时间经计算在到达加热玻璃之前超过1秒钟。涂层沉积时间,定义为玻璃在有效化学沉积区域下通过的时间,约为15秒。上述涂层工艺条件应用于下面的实施例8和9。
实施例8:来自DEZ/IPA/N2(DEZ=二乙基锌;IPA=异丙醇)化学的氧化锌
涂层条件设置如下
气体 | 喷口温度℃ | 流slm |
DEZ | 85 | 0.289 |
N2载气 | 0.75 | |
IPA | 58 | 0.304 |
N2载气 | 0.6 | |
N2 | 12 | |
总计 | 13.943 |
所得的氧化锌涂层约390纳米厚,测得的薄层电阻为1.7kohm/sq。来自XPS的组分分析表明,涂层中锌与氧原子比值约为1∶1。
实施例9:来自DEZ/IPA/DEAC/HFP/N2(DEAC=Et2AlCl)化学的氧化锌
涂层条件设置如下
气体 | 喷口温度℃ | 流slm |
DEZ | 85 | 0.289 |
N2载气 | 0.75 | |
DEAC | 80 | 0.001 |
N2载气 | 0.1 | |
IPA | 58 | 0.304 |
N2载气 | 0.6 | |
HFP | 0.2 | |
N2 | 10 | |
总计 | 12.244 |
由Zn,Al和F预混输料得到的薄膜约360纳米厚,4点探针测得的薄层电阻为35ohm/sq。向气体流中加入F和Al,导致较低的薄层电阻。
表1
实施例 | 涂层厚度(nm) | 薄层电阻(ohms/sq) | 薄膜生长速度(A/sec) |
1 | 310 | 53 | 69 |
2 | 340 | 138 | 76 |
3 | 290 | 21 | 64 |
4 | 333 | 23 | 74 |
5 | 340 | 17 | 76 |
6 | 320 | 18 | 80 |
7 | 565 | 3.9 | 120 |
8 | 390 | 1700 | 260 |
9 | 360 | 35 | 240 |
表1数据表明,与仅有镓存在的实施例4和仅有氟存在的实施例2相比较,沉积过程中氟和镓前体同时存在的实施例5和7,观察到薄层电阻显著下降(或电导率增加)。实施例3、6和9证明,与仅使用Al(实施例1)或仅使用F(实施例2)相比较,在同时使用Al和F时,可以获得类似的有益效果。
通过改变HFP流速,注意到,使用高的HFP流速会显著降低涂层沉积速度,而使用低的HFP流速(例如实施例8中所用的)会改善所得涂层的均匀性。基于实施例7,改变HFP的流速可产生图1至3的绘图。基于这些绘图中的数据,可以理解的是,性能益处必须与成相反趋势(reciprocal trending)的沉积速度相平衡。
图1显示HFP对沉积速度的影响,图2显示HFP对电阻率的影响,而图3显示HFP对迁移率的影响。
尽管已参考各种具体实施例和实施方式对本发明进行了描述,但是应该明白,本发明不限于此,且可在下列权利要求书的范围内变化性实施。
Claims (15)
1.一种低电阻率、掺杂氧化锌涂层玻璃物件的制备方法,其包括:
提供具有待沉积涂层于其上的表面的移动的热玻璃衬底;和
将气体反应物引到衬底表面上,在其上沉积掺杂氧化锌涂层,该气体反应物包括含锌化合物、至少一种含氟化合物、至少一种含氧化合物,和至少一种包含选自硼、铝、镓和铟的13族元素的化合物。
2.权利要求1的方法,其中沉积是在化学气相沉积过程中进行。
3.权利要求2的方法,其中化学气相沉积过程是在大气压力下进行。
4.一种制备低电阻率、掺杂氧化锌涂层玻璃物件的大气压力化学气相沉积方法,其包括:
提供具有待沉积涂层于其上的表面的移动的热玻璃衬底,表面温度为400℃或更高;和
将气体反应物引到表面上,在其上沉积掺杂氧化锌涂层,该气体反应物包括含锌化合物、含氟化合物、含氧化合物和至少一种包含选自硼、铝、镓和铟的13族元素的化合物。
5.权利要求4的方法,其中含铝化合物包括式R15 (3-n)AlR16 nLz的铝化合物,其中R15为烷基或芳基或卤素或烃氧化物基,R16为H、烷基、芳基、卤素或式(R17C(O)CR18C(O)R19)的二酮根,其中R17-19可以相同或不同,且为H、烷基或芳基(包括部分或全氟化的衍生物),n=0至3,其中L为含氧的供体配体而z=0至2。
6.权利要求5的方法,其中含铝化合物包括乙酰丙酮根合二乙基铝。
7.权利要求5的方法,其中含铝化合物包括氯化二乙基铝。
8.权利要求4的方法,其中含镓化合物包括式R15 (3-n)GaR16 nLz的镓化合物,其中R15为烷基或芳基或卤素或烃氧化物基,R16为H、烷基、芳基、卤素或式(R17C(O)CR18C(O)R19)的二酮根,其中R17-19可以相同或不同,且为H、烷基或芳基(包括部分或全氟化的衍生物),n=0至3,其中L为含氧的供体配体而z=0至2。
9.权利要求8的方法,其中含镓化合物包括乙酰丙酮根合二甲基镓。
10.权利要求8的方法,其中含镓化合物包括六氟乙酰丙酮根合二甲基镓。
11.权利要求4的方法,其中含氧化合物为水。
12.权利要求4的方法,其中氧源是醇和水的混合物,其中溶液中水的浓度为0摩尔%至25摩尔%。
13.权利要求12的方法,其中醇为2-丁醇。
14.一种制备低电阻率、掺杂氧化锌涂层物件的大气压力化学气相沉积方法,其包括:
提供具有待沉积涂层于其上的表面的移动的热介电衬底材料,表面温度为400℃或更高;和
将气体反应物引到待沉积掺杂氧化锌涂层于其上的表面,该气体反应物包括含锌化合物、含氧化合物、含氟化合物和至少一种包含硼、铝、镓和铟其中一种或多种的化合物,使含锌化合物、含氧化合物、含氟化合物和至少一种包含至少一种13族元素的化合物在一起混合足够短的时间,以至少5纳米/秒的沉积速率形成掺杂氧化锌涂层。
15.一种包含具有低电阻率、掺杂氧化锌涂层沉积于其上的玻璃衬底的玻璃物件,掺杂氧化锌涂层来自气体前体混合物在400℃或更高温度下的反应,气体前体混合物包括含锌化合物、含氟化合物、含氧化合物和至少一种包含选自硼、镓和铟的13族元素的化合物。
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