TWI495744B - A method of manufacturing a laminated film - Google Patents
A method of manufacturing a laminated film Download PDFInfo
- Publication number
- TWI495744B TWI495744B TW099137018A TW99137018A TWI495744B TW I495744 B TWI495744 B TW I495744B TW 099137018 A TW099137018 A TW 099137018A TW 99137018 A TW99137018 A TW 99137018A TW I495744 B TWI495744 B TW I495744B
- Authority
- TW
- Taiwan
- Prior art keywords
- film
- producing
- transparent conductive
- laminated film
- barrier
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 230000004888 barrier function Effects 0.000 claims description 89
- 229920005989 resin Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 60
- 239000007789 gas Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 20
- 238000007733 ion plating Methods 0.000 claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000005240 physical vapour deposition Methods 0.000 claims description 7
- 239000011135 tin Substances 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229920005672 polyolefin resin Polymers 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- QCSXNSFTJPBQOI-UHFFFAOYSA-N [Zn+2].[O-2].[Zn+2].[In+3] Chemical compound [Zn+2].[O-2].[Zn+2].[In+3] QCSXNSFTJPBQOI-UHFFFAOYSA-N 0.000 claims description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 303
- 230000015572 biosynthetic process Effects 0.000 description 38
- 239000000758 substrate Substances 0.000 description 16
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 238000005401 electroluminescence Methods 0.000 description 7
- -1 polyethylene terephthalate Polymers 0.000 description 7
- 239000012495 reaction gas Substances 0.000 description 7
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 6
- 239000011112 polyethylene naphthalate Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- YTPFRRRNIYVFFE-UHFFFAOYSA-N 2,2,3,3,5,5-hexamethyl-1,4-dioxane Chemical compound CC1(C)COC(C)(C)C(C)(C)O1 YTPFRRRNIYVFFE-UHFFFAOYSA-N 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000004549 pulsed laser deposition Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical compound C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 description 1
- QTDAXPXRSUIMFH-UHFFFAOYSA-N 1,1,1,2-tetramethoxydecane Chemical compound COC(C(OC)(OC)OC)CCCCCCCC QTDAXPXRSUIMFH-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ACYKYDRFAMWELS-UHFFFAOYSA-N 2,2,3,3,5-pentamethyl-1,4-dioxane Chemical compound CC1COC(C)(C)C(C)(C)O1 ACYKYDRFAMWELS-UHFFFAOYSA-N 0.000 description 1
- NONFFUDNIJCNAN-UHFFFAOYSA-N 2,2,3-trimethyl-1,4-dioxane Chemical compound CC1OCCOC1(C)C NONFFUDNIJCNAN-UHFFFAOYSA-N 0.000 description 1
- BWEUYKNMLNSHIJ-UHFFFAOYSA-N 2,2,3-trimethyldecane Chemical compound CCCCCCCC(C)C(C)(C)C BWEUYKNMLNSHIJ-UHFFFAOYSA-N 0.000 description 1
- QDKSGHXRHXVMPF-UHFFFAOYSA-N 2,2-dimethylundecane Chemical compound CCCCCCCCCC(C)(C)C QDKSGHXRHXVMPF-UHFFFAOYSA-N 0.000 description 1
- GRNVJCVESFLAJP-UHFFFAOYSA-N 2,3,5,6-tetramethyl-1,4-dioxane Chemical compound CC1OC(C)C(C)OC1C GRNVJCVESFLAJP-UHFFFAOYSA-N 0.000 description 1
- AWBIJARKDOFDAN-UHFFFAOYSA-N 2,5-dimethyl-1,4-dioxane Chemical compound CC1COC(C)CO1 AWBIJARKDOFDAN-UHFFFAOYSA-N 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- LBIHNTAFJVHBLJ-UHFFFAOYSA-N 3-(triethoxymethyl)undec-1-ene Chemical compound C(=C)C(C(OCC)(OCC)OCC)CCCCCCCC LBIHNTAFJVHBLJ-UHFFFAOYSA-N 0.000 description 1
- RPDFRSKJKOQCIT-UHFFFAOYSA-N 3-ethyldodecane Chemical compound CCCCCCCCCC(CC)CC RPDFRSKJKOQCIT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- JZHKIUBMQMDQRG-UHFFFAOYSA-N C(=C)C(C(OC)(OC)OC)CCCCCCCC Chemical compound C(=C)C(C(OC)(OC)OC)CCCCCCCC JZHKIUBMQMDQRG-UHFFFAOYSA-N 0.000 description 1
- RDISCVBNNQSUDT-UHFFFAOYSA-N C(C)(C)(C)C(C=C)CCCCCCC Chemical compound C(C)(C)(C)C(C=C)CCCCCCC RDISCVBNNQSUDT-UHFFFAOYSA-N 0.000 description 1
- JSGRIFNBTXDZQU-UHFFFAOYSA-N C1(=CC=CC=C1)C(C(OC)(OC)OC)CCCCCCCC Chemical compound C1(=CC=CC=C1)C(C(OC)(OC)OC)CCCCCCCC JSGRIFNBTXDZQU-UHFFFAOYSA-N 0.000 description 1
- PZKBIVOXIFYDRI-UHFFFAOYSA-N CC(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound CC(C(OCC)(OCC)OCC)CCCCCCCC PZKBIVOXIFYDRI-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical group [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UZILCZKGXMQEQR-UHFFFAOYSA-N decyl-Benzene Chemical compound CCCCCCCCCCC1=CC=CC=C1 UZILCZKGXMQEQR-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000004022 organic phosphonium compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 101150002764 purA gene Proteins 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
-
- 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
- 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
- C23C16/503—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 using dc or ac discharges
-
- 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
- C23C16/54—Apparatus specially adapted for continuous coating
- C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Description
本發明係關於一種藉由於樹脂膜上形成障壁膜及透明導電膜而製造積層膜之方法。
近年來,有機EL(electro luminescence,電致發光)元件作為自發光元件而受到矚目。有機EL元件係於基板上以電極夾持有機化合物之發光層之構成,且係對電極間供給電流時會發光之元件。由於發光層為有機化合物,故而藉由使用樹脂膜作為基板,而可製作可撓性之有機EL元件,但因發光層或陰極會由於氧氣或水分而容易劣化,故而有必要於樹脂膜上設置障壁膜,儘可能阻斷經由樹脂膜而侵入之水分或氧氣。
作為如上所述之有機EL元件之構件,對以樹脂膜作為基板,且包含障壁膜及成為一側電極之透明導電膜之積層膜進行了各種研究。並且,作為障壁膜之形成法,研究有電子束法、濺鍍法、電漿CVD(chemical vapor deposition,化學氣相沈積)法、離子電鍍法等,作為透明導電膜之形成法,研究有濺鍍法、離子電鍍法等物理氣相沈積(PVD,physical vapor deposition)法(例如參照日本專利特開2008-235165號公報(段落0002、段落0050))。然而,上述先前之積層膜存在若彎曲,則障壁性容易降低,導電性亦容易降低之問題。再者,CVD為「化學氣相沈積」之簡稱。
本發明之目的在於提供一種可製造以樹脂膜作為基板,包含障壁膜及透明導電膜,並且即便彎曲,障壁性難以降低,導電性亦難以降低之積層膜的方法。
本發明者等人進行銳意研究,結果發現,藉由採用特定之電漿CVD法作為障壁膜之形成法,可達成上述目的,從而完成本發明。
即,本發明提供一種積層膜之製造方法,其特徵在於:其係藉由於樹脂膜上形成障壁膜及透明導電膜而製造積層膜者,且上述障壁膜係藉由輥間放電電漿CVD法而形成。
成為積層膜之基板之樹脂膜較佳為無色透明,作為構成樹脂膜之樹脂例如可列舉:聚對苯二甲酸乙二酯(PET,Polyethylene terephthalate)、聚萘二甲酸乙二酯(PEN,Polyethylene naphthalate)等聚酯樹脂,聚乙烯(PE,polyethylene)、聚丙烯(PP,polypropylene)、環狀聚烯烴等聚烯烴樹脂,聚醯胺樹脂,聚碳酸酯樹脂,聚苯乙烯樹脂,聚乙烯醇樹脂,乙烯-醋酸乙烯酯共聚物之皂化物,聚丙烯腈樹脂,縮醛樹脂,聚醯亞胺樹脂,聚醚硫醚(PES,polyether sulfide),根據需要亦可將該等2種以上加以組合使用。根據透明性、耐熱性、線膨脹性等必要之特性,較佳為選自聚酯樹脂、聚烯烴樹脂,更佳為PET、PEN、環狀聚烯烴。
至於樹脂膜之厚度,考慮製造積層膜時之穩定性等而適當設定,但由於即便於真空中,樹脂膜之搬送亦較為容易,故而較佳為5~500 μm。進而,於藉由本發明所採用之輥間放電電漿CVD法形成障壁膜時,因通過樹脂膜而進行放電,故而樹脂膜之厚度更佳為50~200 μm,尤佳為50~100 μm。
再者,就樹脂膜與障壁膜之密接性之觀點而言,亦可對樹脂膜實施用於清潔其表面之表面活性處理。作為此種表面活性處理,例如可列舉電暈處理、電漿處理、火焰處理。
本發明中使用輥間放電電漿CVD法作為於樹脂膜上形成障壁膜之方法。藉此可獲得即便彎曲,障壁性亦難以降低之積層膜。先前之積層膜一旦彎曲,便容易於障壁膜上產生龜裂,而障壁性容易降低,但根據本發明,可獲得即便彎曲,亦難以於障壁膜上產生龜裂,障壁性難以降低之積層膜。
此處,CVD法為於物質表面形成薄膜之方法之一。電漿CVD法為其中之一,係藉由交流將含有原料物質之氣體電漿化,藉此原料物質自由基化、及/或離子化,並且原料物質堆積於樹脂膜等基板上之成膜方法。該電漿CVD法較佳為低壓電漿CVD法。此處,所謂低壓,係指放電氣體被激發之放電空間區域之壓力,及使激發之放電氣體與形成薄膜之氣體接觸而形成薄膜之區域的壓力,通常為0.1~10 Pa。並且,於輥間放電電漿CVD法中,使複數個成膜輥間之空間產生電漿放電。
於輥間放電電漿CVD法之典型性例中,以4~5 cm之間隔設置兩個內置不旋轉之磁鐵的水冷旋轉筒。於該兩個輥間形成磁場,對磁鐵與輥間施加中頻。導入氣體後即於兩個輥間形成極為明亮之高密度之電漿。藉由其間之磁場與電場,而將電子關入間隙之中心附近,形成高密度之電漿(密度>1012
/cm3
)。
該電漿源可藉由數Pa左右之低壓力而動作,中性粒子或離子之溫度較低,為室溫附近。另一方面,由於電子之溫度較高,故生成較多自由基或離子。又,防止高溫之二次電子於磁場之作用下流入樹脂膜,因此,可於將樹脂膜之溫度抑制在較低水平之狀態下輸入較高之電力,而達成高速成膜。膜之堆積主要僅於樹脂膜表面發生,由於電極被樹脂膜覆蓋而難以受污染,故而可實現較長時間之穩定成膜。
此處,根據低壓方式,可防止CVD法中之氣相反應、即微粒之產生。又,下一個步驟之透明導電膜之成膜為需要更低壓之環境之物理性成膜法,故而障壁膜與透明導電膜之成膜步驟間之成膜環境之壓力差較少。即,與於壓力較高之環境形成障壁膜的先前方法相比,無需用於調整壓力之裝置,裝置成本大幅降低。
障壁膜較佳為含有矽、氧及碳,亦較佳為進而含有氮。矽、氧及碳於障壁膜中之各濃度可固定,但例如碳及氧之濃度亦可於膜厚方向上發生變化。又,該元素濃度可藉由XPS(X-ray Photoelectron Spectrum,X-射線光電子光譜)分析裝置而測定。
至於障壁膜之厚度,最佳條件根據所使用之材料種類或構成而不同,可適當選擇,較佳為1~5000 nm。若障壁膜過薄,則無法獲得均勻之膜,且難以獲得對於水分等氣體之較高之障壁性,又,若障壁膜過厚,則難以使樹脂膜保持可撓性。又,障壁膜較佳為於使電氣元件之光學資訊透射之構成中光學性損失較少之透明。
作為於樹脂膜上形成透明導電膜之方法,由於可獲得低電阻之透明導電膜,故而較佳為使用物理氣相沈積(PVD)法,作為其例可舉出真空蒸鍍法、電子束蒸鍍法、濺鍍法、離子電鍍法、鐳射剝離法(脈衝雷射沈積(Pulsed Laser Deposition),PLD法),但就成膜速度、成膜面積之廣度、成膜面之均勻性、蝕刻特性等之觀點而言,較佳為離子電鍍法、濺鍍法。又,作為離子電鍍法,就即便彎曲,導電性亦難以降低,成膜速度較快,陰極不暴露於氣體環境而壽命較長,可長時間連續穩定成膜而言,較佳為使用壓力梯度型電漿槍(稱為浦本槍)之離子電鍍法。
透明導電膜較佳為含有選自由銦(In)、錫(Sn)、鋅(Zn)及鈦(Ti)所組成群中之至少一種元素。尤佳為選自由氧化銦錫(ITO)、氧化鋅錫(ZTO)、氧化銦鋅(IZO)、氧化銦鎵(IGO)、氧化銦鋅錫(IZTO)、氧化銦鎵鋅(IGZO)、摻鋁氧化鋅(AZO)、摻鎵氧化鋅(GZO)、摻銻氧化錫(ATO)、摻氟氧化錫(FTO)、摻鈮氧化鈦(NTO)、摻鉭氧化鈦(TTO)及摻釩氧化鈦(VTO)所組成群中之至少一種氧化物之膜。
至於在樹脂膜上形成障壁膜及透明導電膜,例如可於樹脂膜之一面形成障壁膜後,於障壁膜上形成透明導電膜,亦可於樹脂膜之一面形成障壁膜後,於另一面形成透明導電膜,還可於樹脂膜之一面形成透明導電膜後,於另一面形成障壁膜,又可於樹脂膜之兩面形成障壁膜後,於一側障壁膜上形成透明導電膜,所得之積層膜之層構成根據用途等進行適當設定,但本發明之積層膜之製造方法尤其於如下情形時可有利地採用:在樹脂膜之一面形成障壁膜後,於障壁膜上形成透明導電膜而製造包含透明導電膜/障壁膜/樹脂膜之層構成之積層膜。
於樹脂膜之一面形成障壁膜後,於障壁膜上形成透明導電膜之情形時,具體可採用下述(1)~(3)之態樣。
(1):抽出輥狀之樹脂膜,一面連續地搬送,一面形成障壁膜,將所得之附有障壁膜之膜捲取成輥狀。繼而,抽出該輥狀之附有障壁膜之膜,切割成片狀後,形成透明導電膜,而獲得積層膜。該態樣係以輥-輥(roll-to-roll)方式進行障壁膜之形成,以單片方式進行透明導電膜之形成。
(2):抽出輥狀之樹脂膜,一面連續地搬送,一面形成障壁膜,將所獲得之附有障壁膜之膜捲取成輥狀。繼而,抽出該輥狀之附有障壁膜之膜,一面連續地搬送,一面形成透明導電膜,獲得積層膜並捲取成輥狀。該態樣係以輥-輥方式分別連續地進行障壁膜之形成與透明導電膜之形成。
(3):自輥狀之樹脂膜抽出樹脂膜,一面連續地搬送,一面形成障壁膜,繼而形成透明導電膜,將所得之積層膜捲取成輥狀。該態樣係以輥-輥方式一併連續地進行障壁膜之形成與透明導電膜之形成。
再者,形成透明導電膜之前,亦可根據需要於障壁膜上形成其他層,例如專利文獻1中所提出,可形成平坦化膜,但於本發明中,就削減裝置成本之觀點而言,較佳為不於透明導電膜上形成其他層,而直接形成透明導電膜。
圖1如上述(1)或(2)之態樣般,係表示適於以輥-輥方式藉由輥間放電電漿CVD法形成障壁膜之情形的裝置之一例之示意圖。該裝置包括送出輥11、搬送輥21、22、23、24、成膜輥31、32、氣體供給管41、電漿產生裝置51、磁場產生裝置61、62、及捲取輥71。又,該裝置中,於真空腔室內至少配置有成膜輥31、32、氣體供給管41、電漿產生裝置51、及磁場產生裝置61、62,可調整真空腔室內之壓力。進而,於該裝置中,可藉由電漿電源51而於成膜輥31與成膜輥32之間之空間產生電漿。又,於該裝置中,於成膜輥31、32以即便輥旋轉相對於成膜輥31與成膜輥32間之空間亦保持固定位置關係之方式,分別安裝磁場產生裝置61、62。根據該裝置,可於成膜輥31上於樹脂膜100之表面上堆積障壁膜成分,進而可於成膜輥32上堆積障壁膜成分,故而可於樹脂膜100之表面上效率佳地形成障壁膜。
作為送出輥11及搬送輥21、22、23、24,可使用適當公知之輥。又,作為捲取輥71,可使用適當公知之輥。進而,作為成膜輥31、32,雖可使用適當公知之輥,但成膜輥31、32之直徑較佳為5~100 cm。又,作為氣體供給管41,可適當使用能以特定速度供給或排出原料氣體等者。進而,作為電漿產生裝置51,可使用適當公知之電漿產生裝置。又,作為磁場產生裝置61、62,可使用適當公知之磁場產生裝置。進而,作為樹脂膜100,可使用預先使障壁膜形成者。如上所述,藉由使用預先使障壁膜形成者作為樹脂膜100,可增加障壁膜之厚度。
使用該裝置,適當調整例如原料氣體之種類、電漿產生裝置之電極輥之電力、真空腔室內之壓力、成膜輥之直徑及膜之搬送速度,藉此可於樹脂膜100上形成障壁膜。即,將原料氣體等成膜氣體供給至真空腔室內,並產生電漿放電,藉此,上述原料氣體因電漿而分解,藉由電漿CVD法於樹脂膜100之表面上形成障壁膜。繼而,樹脂膜100藉由成膜輥31、32而分別搬送,藉此以輥-對-輥方式於樹脂膜100之表面上形成障壁膜。
原料氣體可根據所形成之障壁膜之材質適當選擇並使用。作為原料氣體,例如可使用含有矽之有機矽化合物。作為此種有機矽化合物,例如可例舉:六甲基二矽氧烷、1,1,3,3-四甲基二矽氧烷、乙烯基三甲基矽烷、甲基三甲基矽烷、六甲基二矽烷、甲基矽烷、二甲基矽烷、三甲基矽烷、二乙基矽烷、丙基矽烷、苯基矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、四甲氧基矽烷、四乙氧基矽烷、苯基三甲氧基矽烷、甲基三乙氧基矽烷、八甲基環四矽氧烷、二甲基二矽氮烷、三甲基二矽氮烷、四甲基二矽氮烷、五甲基二矽氮烷、六甲基二矽氮烷。就化合物之操作性或所得之障壁膜之阻氣性等之觀點而言,該等有機矽化合物之中,較佳為六甲基二矽氧烷、1,1,3,3-四甲基二矽氧烷。又,該等有機矽化合物既可單獨使用1種,亦可將2種以上加以組合使用。
作為上述成膜氣體,除上述原料氣體以外,亦可使用反應氣體。作為此種反應氣體,可適當選擇使用與上述原料氣體反應而成為氧化物、氮化物等無機化合物之氣體。作為用於形成氧化物之反應氣體,例如可使用氧氣或臭氧。又,作為用於形成氮化物之反應氣體,例如可使用氮氣或氨氣。該等反應氣體既可單獨使用1種,亦可將2種以上加以組合使用,例如於形成氮氧化物之情形時,可將用於形成氧化物之反應氣體與用於形成氮化物之反應氣體加以組合使用。
作為上述成膜氣體,為了將上述原料氣體供給至真空腔室內,根據需要亦可使用載氣。進而,作為上述成膜氣體,為了產生電漿放電,根據需要亦可使用放電用氣體。作為此種載氣及放電用氣體,可適當使用公知者,例如可使用氦氣、氬氣、氖氣、氙氣等稀有氣體;氫氣。
以真空腔室內之壓力表示之該真空腔室內之真空度可根據原料氣體之種類等適當調整,較佳為0.5~50 Pa。又,電漿產生裝置之電極輥之電力可根據原料氣體之種類或真空腔室內之壓力等適當調整,但較佳為0.1~10 kW。
樹脂膜100之搬送速度(線速度)可根據原料氣體之種類或真空腔室內之壓力等適當調整,較佳為0.25~100 m/min,更佳為0.5~20 m/min。若線速度未滿上述下限,則有易於膜上產生因熱引起之皺紋之傾向,另一方面,若超過上述上限,則有所形成之障壁膜之厚度變薄之傾向。
以上說明之藉由本發明之製造方法而獲得之積層膜,係以樹脂膜作為基板,可用作可撓性製品之構件,又,具有障壁膜及透明導電膜,即便彎曲,障壁性難以降低,導電性亦難以降低,故而可較佳地用作以有機EL元件為代表之可撓的必需有障壁性及導電性之各種製品之構件。
實施例
以下表示本發明之實施例。以下所示之實施例係用於說明本發明之較佳之例示,本發明並不限定於該等例。
使用圖1所示之製造裝置於樹脂膜上形成障壁膜。即,首先,將成為基材之樹脂膜100(雙軸延伸聚萘二甲酸乙二酯膜(PEN膜)、厚度:100 μm、寬度:350 mm、帝人杜邦薄膜(Teijin Dupont Films)(股)製造、商品名「Teonex Q65FA」)之卷體裝載至送出輥11。將自該卷體抽出之樹脂膜100依次經由搬送輥21、成膜輥31、搬送輥22及23、成膜輥32、及搬送輥24,而捲繞於捲取輥71。繼而,一面搬送樹脂膜100,一面於成膜輥31與成膜輥32之間施加磁場,並將電力分別供給至成膜輥31與成膜輥32,於成膜輥31與成膜輥32之間放電而產生電漿,將成膜氣體(作為原料氣體之六甲基二矽氧烷(HMDSO)與作為反應氣體之氧氣(亦發揮作為放電氣體之作用)之混合氣體)供給至此種放電區域,於下述條件下藉由電漿CVD法形成薄膜,獲得於樹脂膜100上形成障壁膜之積層膜A。
原料氣體之供給量:50 sccm(Standard Cubic Centimeter per Minute,標準立方公分/分)(0℃、1大氣壓基準)
氧氣之供給量:500 sccm(0℃、1大氣壓基準)
真空腔室內之真空度:3 Pa
由電漿產生用電源之施加電力:0.8 kW
電漿產生用電源之頻率:70 kHz
膜之搬送速度:0.5 m/min。
所獲得之障壁膜之厚度為370 nm。又,所獲得之積層膜A於溫度40℃、低濕度側之濕度為0% RH、高濕度側之濕度為90% RH之條件下的水蒸氣滲透率為3.1×10-4
g/(m2
‧day),於溫度40℃、低濕度側之濕度為10% RH、高濕度側之濕度為100% RH之條件下的水蒸氣滲透率為未滿檢測極限(0.02 g/(m2
‧day))之值。進而確認,於曲率半徑8 mm之條件下彎曲後,於溫度40℃、低濕度側之濕度為10% RH、高濕度側之濕度為100% RH之條件下的水蒸氣滲透率為未滿檢測極限之值,且即便於彎曲所獲得之積層膜A之情形時,亦可充分抑制阻氣性之降低。
又,於下述條件下對所獲得之積層膜A進行XPS深度剖析(depth profile)測定,並研究組成分佈。
蝕刻離子種類:氬(Ar+
)
蝕刻速率(SiO2
熱氧化膜換算值):0.05 nm/sec
蝕刻間隔(SiO2
換算值):10 nm
X射線光電子分光裝置:Thermo Fisher Scientific公司製造、機種名「VG Theta Probe」
照射X射線:單晶分光AlKα
X射線之點之形狀及尺寸:長徑800 μm及短徑400 μm之橢圓形。
根據XPS深度剖析測定之組成分佈可確認,上述障壁膜為含有矽、氧及碳之組成的膜。
於上述積層膜A之障壁膜上,使用明淨金屬製造之ITO(In:Sn=95:5、高密度品、純度99.99%、粒徑3~5 mm)作為靶,藉由壓力梯度型電漿槍之離子電鍍成膜裝置(中外爐工業製造:SUPLaDUO、CVP-4111)於以下成膜條件下形成透明導電膜,獲得積層膜B。
放電電力:5.0 kW
基板溫度:室溫
Ar氣體流量:20 sccm(0℃、1大氣壓基準)
O2
氣體流量:13.7 sccm(0℃、1大氣壓基準)
成膜壓力:0.06 Pa
預放電時間:180 s
成膜時間:62 s
藉由經FIB(focused ion beam,聚焦離子束)加工之TEM(Transmission Electron Microscopy,穿透式電子顯微鏡像)求出透明導電膜之厚度為150 nm。又,使用霧度計(滋賀試驗機製造:HGM-2DP)對所獲得之積層膜B測定總光線透射率與霧度,總光線透射率為80.8%,霧度為0.6%。使用電阻率計(三菱化學製造:Loresta-GP、MCP-T610)求出透明導電膜之薄片電阻為42.7 Ω/□,比電阻為6.4×10-4
Ωcm。進而使用原子力顯微鏡AFM(atomic force microscope)(SII製造:SPI3800N)測定之透明導電膜之表面粗糙度Ra為2.34 nm。
使用實施例1中所獲得之積層膜A,於積層膜A之障壁膜上,使用明淨金屬製造之ITO(In:Sn=95:5、高密度品、純度99.99%、粒徑3~5 mm)作為靶,藉由壓力梯度型電漿槍之離子電鍍成膜裝置(中外爐工業製造:SUPLaDUO、CVP-4111)於以下成膜條件下形成透明導電膜,獲得積層膜C。
放電電力:5.0 kW
基板溫度:180℃
Ar氣體流量:20 sccm(0℃、1大氣壓基準)
O2
氣體流量:13.7 sccm(0℃、1大氣壓基準)
成膜壓力:0.06 Pa
預放電時間:180 s
成膜時間:62 s
以與實施例1相同之方式進行測定之透明導電膜之膜厚、積層膜C之總光線透射率與霧度、透明導電膜之薄片電阻與比電阻及透明導電膜之表面粗糙度分別為100 nm、81.2%與0.6%、18 Ω/□與1.8×10-4
Ωcm及2.37 nm。
使用實施例1中所獲得之積層膜A,於積層膜A之障壁膜上,使用ZTO(Zn2
SnO4
、氧化鋅錫)作為靶,藉由壓力梯度型電漿槍之離子電鍍成膜裝置(中外爐工業製造:SUPLaDUO、CVP-4111)於以下成膜條件下形成透明導電膜,獲得積層膜D。
再者,作為ZTO靶,係使用將氧化鋅粉末(高純度化學研究所製造、4N)與氧化錫粉末(高純度化學研究所製造、4N)以鋅:錫=2:1(莫耳比)之方式稱量、混合、燒結而製作燒結體,並將其以成為離子電鍍之靶之方式粉碎成粒徑3~5 mm左右者。
放電電力:11.2 kW
基板加熱溫度:室溫
Ar氣體流量:20 sccm(0℃、1大氣壓基準)
O2
氣體流量:0 sccm(0℃、1大氣壓基準)
成膜壓力:0.06 Pa
預放電時間:26 s
成膜時間:33 s
以與實施例1相同之方式進行測定之透明導電膜之膜厚、積層膜D之總光線透射率與霧度、透明導電膜之薄片電阻與比電阻及透明導電膜之表面粗糙度分別為100 nm、81.2%與0.6%、65 Ω/口與6.5×10-3
Ωcm及1.93 nm。
使用實施例1中所獲得之積層膜A,於積層膜A之障壁膜上,使用ZTO(Zn2
SnO4
、氧化鋅錫)作為靶,藉由壓力梯度型電漿槍之離子電鍍成膜裝置(中外爐工業製造:SUPLaDUO、CVP-4111)於以下成膜條件下形成透明導電膜,獲得積層膜E。
再者,作為ZTO靶,係使用將氧化鋅粉末(高純度化學研究所製造、4N)與氧化錫粉末(高純度化學研究所製造、4N)以鋅:錫=2:1(莫耳比)之方式進行稱量、混合、燒結而製作燒結體,並將其以成為離子電鍍之靶之方式粉碎成粒徑3~5 mm左右者。
放電電力:11.2 kW
基板加熱溫度:180℃
Ar氣體流量:20 sccm(0℃、1大氣壓基準)
O2
氣體流量:0 sccm(0℃、1大氣壓基準)
成膜壓力:0.06 Pa
預放電時間:26 s
成膜時間:33 s
以與實施例1相同之方式進行測定之透明導電膜之膜厚、積層膜E之總光線透射率與霧度、透明導電膜之薄片電阻與比電阻及透明導電膜之表面粗糙度分別為100 nm、82.3%與0.7%、40 Ω/□與4.0×10-3
Ωcm及1.92 nm。
以將矽作為靶藉由反應濺鍍法進行氧化矽膜之成膜代替實施例1之藉由電漿CVD法而成膜,於實施例1所使用之基材(PEN膜)獲得積層膜F。以與實施例1相同之方式進行氧化矽膜之XPS深度剖析測定,確認氧化矽膜為含有矽及氧之膜,但不含碳。
所獲得之氧化矽膜之厚度為100 nm。又,所獲得之積層膜F於溫度40℃、低濕度側之濕度10% RH、高濕度側之濕度100% RH之條件下的水蒸氣滲透率為1.3 g/(m2
‧day),與基材之PEN之水蒸氣滲透率之1.3 g/(m2
‧day)相同,未確認氧化矽膜之障壁性。
使用所獲得之積層膜F,於積層膜F之氧化矽膜上,使用ITO藉由濺鍍法形成透明導電膜,獲得積層膜G。
以與實施例1相同之方式求得之透明導電膜之膜厚為150 nm,可見光之透射率為79%。所獲得之積層膜G缺乏障壁性,不適合作為有機EL等之可撓性基板。
根據本發明,可獲得一種積層膜,其係以樹脂膜作為基板,包含障壁膜及透明導電膜,且即便彎曲,障壁性難以降低,導電性亦難以降低。
11...送出輥
21、22、23、24...搬送輥
31、32...成膜輥
41...氣體供給管
51...電漿產生裝置
61、62...磁場產生裝置
71...捲取輥
100...樹脂膜
圖1係表示適於藉由輥間放電電漿CVD法形成障壁膜之裝置之一例的示意圖。
11...送出輥
21、22、23、24...搬送輥
31、32...成膜輥
41...氣體供給管
51...電漿產生裝置
61、62...磁場產生裝置
71...捲取輥
100...樹脂膜
Claims (12)
- 一種積層膜之製造方法,其特徵在於:其係藉由於樹脂膜上形成障壁膜及透明導電膜而製造積層膜者,且上述障壁膜係藉由內置於磁場產生裝置之兩個成膜輥做為電極放電,並導入氣體後使上述輥間產生電漿,以於經由上述輥搬送之樹脂膜表面上進行成膜之方法而形成。
- 如請求項1之積層膜之製造方法,其中上述樹脂膜為聚酯樹脂膜或聚烯烴樹脂膜。
- 如請求項1之積層膜之製造方法,其中上述障壁膜為含有矽、氧及碳之膜。
- 如請求項2之積層膜之製造方法,其中上述障壁膜為含有矽、氧及碳之膜。
- 如請求項1至4中任一項之積層膜之製造方法,其中藉由物理氣相沈積法形成上述透明導電膜。
- 如請求項5之積層膜之製造方法,其中上述物理氣相沈積法為離子電鍍法。
- 如請求項6之積層膜之製造方法,其中上述離子電鍍法為使用壓力梯度型電漿槍之離子電鍍法。
- 如請求項5之積層膜之製造方法,其中上述物理氣相沈積法為濺鍍法。
- 如請求項1至4中任一項之積層膜之製造方法,其中上述透明導電膜為含有選自由銦、錫、鋅及鈦所組成群中之至少1種元素之膜。
- 如請求項1至4中任一項之積層膜之製造方法,其中上述 透明導電膜為選自由氧化銦錫、氧化鋅錫、氧化銦鋅、氧化銦鎵、氧化銦鋅錫、氧化銦鎵鋅、摻鋁氧化鋅、摻鎵氧化鋅、摻銻氧化錫、摻氟氧化錫、摻鈮氧化鈦(NTO)、摻鉭氧化鈦(TTO)及摻釩氧化鈦(VTO)所組成群中之至少1種氧化物之膜。
- 如請求項1至4中任一項之積層膜之製造方法,其中於上述樹脂膜上形成上述障壁膜後,於上述障壁膜上形成上述透明導電膜。
- 如請求項11之積層膜之製造方法,其中於上述障壁膜上直接形成上述透明導電膜。
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TW099137018A TWI495744B (zh) | 2009-10-30 | 2010-10-28 | A method of manufacturing a laminated film |
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EP (1) | EP2495738A4 (zh) |
JP (1) | JP5601153B2 (zh) |
KR (1) | KR101697806B1 (zh) |
CN (1) | CN102598158B (zh) |
TW (1) | TWI495744B (zh) |
WO (1) | WO2011052764A1 (zh) |
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TW201319296A (zh) * | 2011-06-21 | 2013-05-16 | Sumitomo Chemical Co | 層合薄膜之檢查方法及層合薄膜之製造方法 |
JP5803488B2 (ja) * | 2011-09-22 | 2015-11-04 | 凸版印刷株式会社 | 原子層堆積法によるフレキシブル基板への成膜方法及び成膜装置 |
JP6495174B2 (ja) | 2012-12-06 | 2019-04-03 | ステムバイオス テクノロジーズ,インコーポレイテッド | Lgr5+体性幹細胞 |
US9502681B2 (en) | 2012-12-19 | 2016-11-22 | Universal Display Corporation | System and method for a flexible display encapsulation |
JP2014189890A (ja) * | 2013-03-28 | 2014-10-06 | Kobe Steel Ltd | 成膜装置及び成膜方法 |
WO2014178254A1 (ja) * | 2013-04-30 | 2014-11-06 | コニカミノルタ株式会社 | 封止フィルム、その製造方法及び封止フィルムで封止された機能素子 |
CN105210158B (zh) * | 2013-05-23 | 2017-07-11 | 琳得科株式会社 | 导电膜和具有导电膜的电子设备 |
MX2016001247A (es) | 2013-07-30 | 2016-08-17 | Musculoskeletal Transplant Foundation | Matrices derivadas de tejido suave acelular y metodos para preparar las mismas. |
WO2015029732A1 (ja) * | 2013-08-27 | 2015-03-05 | コニカミノルタ株式会社 | ガスバリアフィルムおよびガスバリアフィルムの製造方法 |
JP6409258B2 (ja) * | 2013-09-03 | 2018-10-24 | Jnc株式会社 | ガスバリアフィルム積層体とそれを用いた電子部品 |
CN103628042B (zh) * | 2013-12-10 | 2016-04-27 | 浙江正泰太阳能科技有限公司 | 一种改善晶硅电池镀膜质量的方法 |
JP6478086B2 (ja) * | 2014-05-30 | 2019-03-06 | パナソニックIpマネジメント株式会社 | 電子デバイス及びその製造方法 |
JP6587384B2 (ja) * | 2014-11-14 | 2019-10-09 | 東レエンジニアリング株式会社 | 封止膜の形成方法および封止膜 |
US10912864B2 (en) | 2015-07-24 | 2021-02-09 | Musculoskeletal Transplant Foundation | Acellular soft tissue-derived matrices and methods for preparing same |
US11052175B2 (en) | 2015-08-19 | 2021-07-06 | Musculoskeletal Transplant Foundation | Cartilage-derived implants and methods of making and using same |
WO2017085984A1 (ja) * | 2015-11-19 | 2017-05-26 | コニカミノルタ株式会社 | プラズマcvd成膜装置 |
WO2018003274A1 (ja) * | 2016-06-28 | 2018-01-04 | コニカミノルタ株式会社 | ガスバリア性フィルムの製造方法 |
JP7198607B2 (ja) * | 2017-08-25 | 2023-01-04 | 住友化学株式会社 | 積層フィルム |
JP6589033B2 (ja) * | 2017-11-10 | 2019-10-09 | 住友化学株式会社 | 表示装置 |
KR20210029186A (ko) * | 2018-07-05 | 2021-03-15 | 바스프 코팅스 게엠베하 | 투명 전도성 필름 |
GB201815842D0 (en) * | 2018-09-28 | 2018-11-14 | Power Roll Ltd | Method of processing substrate for an energy storage device |
CN112992408A (zh) * | 2021-01-28 | 2021-06-18 | 中国乐凯集团有限公司 | 柔性复合透明导电膜及其制备方法和器件 |
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- 2010-10-26 KR KR1020127010602A patent/KR101697806B1/ko active IP Right Grant
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- 2010-10-26 WO PCT/JP2010/069394 patent/WO2011052764A1/ja active Application Filing
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EP1921180A1 (en) * | 2005-08-31 | 2008-05-14 | Konica Minolta Holdings, Inc. | Plasma discharge processing device and production method of gas barrier film |
JP2009023331A (ja) * | 2007-03-23 | 2009-02-05 | Dainippon Printing Co Ltd | ガスバリア性シート |
Also Published As
Publication number | Publication date |
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CN102598158A (zh) | 2012-07-18 |
KR20120091121A (ko) | 2012-08-17 |
WO2011052764A1 (ja) | 2011-05-05 |
KR101697806B1 (ko) | 2017-01-18 |
EP2495738A4 (en) | 2013-11-13 |
CN102598158B (zh) | 2016-11-02 |
JP2011116124A (ja) | 2011-06-16 |
EP2495738A1 (en) | 2012-09-05 |
TW201131003A (en) | 2011-09-16 |
JP5601153B2 (ja) | 2014-10-08 |
US20120269988A1 (en) | 2012-10-25 |
US9011985B2 (en) | 2015-04-21 |
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