JPWO2020054441A1 - フレキシブルデバイス用基板 - Google Patents
フレキシブルデバイス用基板 Download PDFInfo
- Publication number
- JPWO2020054441A1 JPWO2020054441A1 JP2020546847A JP2020546847A JPWO2020054441A1 JP WO2020054441 A1 JPWO2020054441 A1 JP WO2020054441A1 JP 2020546847 A JP2020546847 A JP 2020546847A JP 2020546847 A JP2020546847 A JP 2020546847A JP WO2020054441 A1 JPWO2020054441 A1 JP WO2020054441A1
- Authority
- JP
- Japan
- Prior art keywords
- oxide film
- substrate
- glass
- stainless steel
- base material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 claims abstract description 134
- 239000000758 substrate Substances 0.000 claims abstract description 69
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 65
- 239000010935 stainless steel Substances 0.000 claims abstract description 60
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 21
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010292 electrical insulation Methods 0.000 claims abstract description 6
- 239000011651 chromium Substances 0.000 claims description 20
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 6
- 238000005452 bending Methods 0.000 abstract description 15
- 230000004888 barrier function Effects 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 7
- 238000003908 quality control method Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 104
- 239000010408 film Substances 0.000 description 63
- 238000010304 firing Methods 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 238000004804 winding Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 5
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- 239000011888 foil Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
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- 229920005989 resin Polymers 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
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- 239000000377 silicon dioxide Substances 0.000 description 3
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
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- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
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- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910015371 AuCu Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
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- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
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- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 239000002270 dispersing agent Substances 0.000 description 1
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
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- 230000005496 eutectics Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
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- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
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- -1 polypropylene carbonate Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
-
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
-
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
-
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
-
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Abstract
Description
下記特許文献1には、プラスチックフィルム基材上に、透明導電層、有機発光媒体層、陰極層を順次積層し、接着層を介して金属箔が積層された有機EL素子の構造が提案されているが、かかるプラスチックフィルム基材は水分バリア性や耐熱性の点で満足するものではない。
また下記特許文献2には、ステンレス基材上にポリイミド樹脂から成る平坦化層を設けたフレキシブルデバイス用基板が提案されているが、ポリイミド樹脂の吸水性が高いことから、やはり水分バリア性の点で満足するものではない。
更に下記特許文献3には、ステンレス基材上にシリカ系ガラスを製膜したフレキシブル太陽電池基板が提案されているが、シリカ系ガラスは一般にステンレスに比べて熱膨張係数が小さく、ステンレス基材に対する密着性に欠けると共に、シリカ系ガラスは曲げ加工や衝撃に弱いという問題を有している。
また金属基材として発錆のおそれのないステンレススチール基材を用いた場合、ステンレススチール基材とガラス層の間に充分な密着性が得られないことから、曲げ耐性に劣り、ガラス層が割れて剥離するというような問題がある。
上記フレキシブルデバイス用基板は、ステンレススチール基材を用いることにより発錆のおそれが有効に防止されていると共に、ステンレス基材表面にニッケルめっき層を形成することにより、ステンレススチール基材とガラス層の密着性が顕著に向上し、優れた曲げ耐性を有していることから、フレキシブルデバイス用基板として用いた場合でもガラス層の剥離などが起こらない、充分なフレキシブル性を有している。
従って本発明の目的は、耐錆性、水分バリア性、ガラス層の密着性、曲げ耐性及びガラス層表面の表面平滑性に優れている共に、製造や品質管理等も容易なフレキシブルデバイス用基板を提供することである。
本発明のフレキシブルデバイス用基板においては、
1.前記酸化物膜の厚みが30nm以上であること、
2.前記酸化物膜の厚みが80nm以上であること、
3.前記酸化物膜と前記ガラス層との界面から、酸化物膜の厚み方向に20nm地点におけるクロム濃度が30atomic%以上であること、
4.前記酸化物膜と前記ガラス層との界面から、酸化物膜の厚み方向に20nm地点におけるクロム濃度が50atomic%以上であること、
5.前記ビスマス系ガラスが、Bi2O3,ZnO,B2O3を含有すること、
が好適である。
本発明のフレキシブルデバイス用基板用基材においては、前記酸化物膜の厚みが80nm以上であることが特に好適である。
またステンレススチール基材表面にニッケルめっき層を形成する必要がないことから、製造工程が少なく、しかもガラス層を形成するまでの品質管理も容易になるため、生産性に優れている。
更にまた、密な構造で水分の透過を完全に防ぐことが可能なガラス層を有していることから、水分バリア性にも優れており、有機EL関連用の基板として有効に使用できる。
本発明のフレキシブルデバイス用基板においては、ステンレススチール基材表面に酸化物膜を形成してなるフレキシブルデバイス用基板用基材に、この基材の酸化物膜表面にガラス層を形成することにより、酸化物膜とガラスとが反応して密着層が形成され、ステンレススチール基材とガラス層の密着性を顕著に向上することが可能になる。その結果、前述したとおり、曲げ耐性が向上し、ガラス層の剥離を生じることなく、ロールツーロールの工程にも対応可能になる。
本発明のフレキシブルデバイス用基板において、ステンレススチール基材上に形成される酸化物膜は、酸化物膜中に存在するクロム濃度が高いことから、酸化物膜とガラスが反応して密着層が形成され、ステンレススチール基材とガラス層の密着性が向上されると考えられる。
本発明のフレキシブルデバイス用基板に用いられるステンレススチール基材としては、従来公知のステンレススチールをすべて使用することができるが、特にフェライト系ステンレススチールを好適に使用できる。また熱膨張係数が9.9×10−6〜21×10−6/℃、特に10×10−6〜14×10−6/℃の範囲にあるものを使用することが好ましい。
ステンレススチール基材の厚みは、10〜200μm、特に25〜100μmの範囲にあることが好適であり、これにより充分なフレキシブル性を得ることができる。
本発明のフレキシブルデバイス用基板において、ステンレススチール基材表面に形成される酸化物膜は、ステンレススチール基材表面を大気中などの酸素含有雰囲気下で焼成することにより形成され、ステンレススチール基材から拡散した鉄、クロム及びその他の添加元素の酸化物から成っている。
すなわち、本発明のフレキシブルデバイス用基板においては、ステンレススチール基材表面に酸化物膜が形成されていることにより、ガラス層とステンレススチール基材表面を密着(相互拡散)させる過程でガラス層中に存在する酸素が奪われず、また奪われたとしてもその度合いが小さいことから、ガラス層中の酸素が欠損することがない。そのため、ガラス層とステンレススチール基材との界面で組成のズレを生じる度合いが、酸化物膜が形成されていない場合(すなわち、ステンレススチール基材表面を酸素含有雰囲気下で焼成していない場合)に比して小さく、密着性が低下することが有効に抑制されている。
このように、クロムリッチな酸化物膜が形成されていることにより、ガラス層とステンレススチール基材との密着性が顕著に向上される。すなわち、クロム酸化物は非常に緻密であるのに対して、鉄酸化物はクロム酸化物に比して脆弱である。このため、ステンレススチール基材表面(酸化物膜を含む)のクロム濃度が高くなることにより、脆弱な鉄酸化物が形成される確率が低くなり、ステンレススチール基材とガラス層との密着性が向上される。
尚、酸化物膜の厚みが厚いほど、酸化物膜中に含有されるクロム量も多くなることからステンレススチール基材とガラス層の密着性が向上し、曲げ耐性も向上するが、酸化物膜の厚みが2000nmを超えると、酸化物膜が脆化して曲げ耐性が低下することから、酸化物膜の厚みは2000nm以下、特に1500nm以下であることが好ましい。
本発明のフレキシブルデバイス用基板は、上述した酸化物膜上に、絶縁層として、優れた水分バリア性及びステンレススチール基材との優れた密着性を有するビスマス系ガラスからなるガラス層が形成されている。
本発明においては、ビスマス系ガラスとして、Bi2O3,ZnO,B2O3を含有するビスマス系ガラスを好適に使用することができる。すなわち、主成分たるBi2O3と共に、ZnO及びB2O3を必須の成分として含有し、これらの成分が共晶点近傍の組成範囲にあることにより、結晶化しにくいガラスネットワーク構造を形成でき、上述した酸化物膜との組み合わせと相俟って、ガラス表面にはじきの発生が有効に抑制されたフレキシブルデバイス用基板を提供することが可能になる。
またビスマス系ガラスは、上記必須成分に加えて、更にCuO及び/又はNiOを含有することが好適であり、CuOを2重量%以下、NiOを2重量%以下の量で配合することにより、ガラスの溶融性が向上される。
更にビスマス系ガラスは、上記必須成分に加えて、Y2O3、ZrO2、La2O3、CeO2、TiO2、CoO,Fe2O3の何れかを1.5重量%以下の量で含有してもよく、これにより、ガラスの耐久性を向上することができるが、これらの成分の配合量が多くなるとかえってガラスの耐久性を低下させるおそれがある。尚、これらの成分は、複数種を組み合わせで使用することも可能であるが、その場合には、合計量が1.5重量%以下であることが好ましい。
本発明のフレキシブルデバイス用基板は、フレキシブルデバイス用基板用基材の製造工程であるステンレススチール基材の少なくとも一方の表面に酸化物膜を形成する酸化物膜形成工程、及び前記酸化物膜上にビスマス系ガラス層を形成するガラス層形成工程、を含む製造方法により製造することができる。
本発明のフレキシブルデバイス用基板及び該基板の製造に用いられるフレキシブルデバイス用基板用基材の製造方法においては、ステンレススチール基材を酸素含有雰囲気中で焼成することにより、ステンレススチール基材表面に酸化物膜を形成することができる。
焼成条件は、前述した酸化物膜が形成される限り、特に限定されないが、焼成温度が200〜1300℃、好ましくは1000〜1250℃、より好ましくは1000〜1100℃の温度であることが望ましい。上記範囲よりも焼成温度が低い場合には、上記範囲にある場合に比して酸化物膜を効率よく形成することができず、その一方上記範囲よりも焼成温度が高い場合には、ステンレススチール基材の厚みにもよるが、ステンレススチール基材がゆがむおそれがある。
焼成時間は、酸素含有雰囲気の酸素濃度、焼成温度によって適宜変更することができるが、大気中で上記温度範囲で焼成する場合には、10〜500秒間焼成することが好適である。
酸化物膜は、前述したとおり、30nm以上、好ましくは80nm以上であり、2000nm以下、好ましくは1500nm以下の範囲となるように形成されることが望ましい。
次いで、酸化物膜上に、ビスマス系ガラス層を形成する。
ガラス層の形成工程は、この手順に限定されないが、大まかに言って、ガラス粉体とビヒクルを混合・分散してガラスペーストを調製し、このガラスペーストを酸化物膜上に塗工・乾燥した後、焼成することにより形成することができる。
ガラスペーストは、上述したビスマス系ガラスから成るガラスフリットを粉砕して得られるガラス粉体とビヒクルを混合・分散することにより得られる。
ガラス粉体は、上述したガラス原料を混合し、800〜1200℃の温度で加熱して溶融、急冷してガラスフリットを得た後、これを粉砕することにより得られる。粉砕方法としては、JET粉砕、ラピッドミル粉砕、ボールミル粉砕等従来公知の方法を挙げることができる。
ガラス粉体は平均粒径が20μm以下、好ましくは1〜10μm、より好ましくは1〜5μmの範囲にあることが、平滑なガラス表面を得る上で好ましく、このような微細な粉体を得るためには、上記粉砕方法の中でもJET粉砕によることが好適である。
混合・分散の方法は、撹拌翼を備えた回転式の混合機やビーズミル、ペイントシェイカー、ロールミル、メノウ乳鉢、超音波等による分散方法を例示できるが、好適には、ビーズミル、ペイントシェイカー、ロールミルによって、混合・分散することが望ましい。
また、ガラスペーストには、必要に応じて、公知の増粘剤、分散剤等を公知の処方に従って添加することもできる。
ガラスペーストは、上述したガラス粉体を30〜80重量%、バインダを0〜10重量%(ゼロを含まない)、溶媒を10〜70重量%の量で含有することが好適である。上記範囲よりもガラス粉体の量が少ない場合には、ペースト粘度が低くなり、所望厚みのガラス層の形成が難しくなり、その一方上記範囲よりもガラス粉体の量が多い場合には、ペースト粘度が高くなりすぎて塗工性に劣るようになる。また上記範囲よりもバインダの量が少ない場合には、塗工性に劣るようになり、その一方上記範囲よりもバインダの量が多いと、焼成後に未分解物が残留するおそれがある。更に上記範囲よりも溶媒の量が少ない場合には、ペースト粘度が高くなりすぎて塗工性に劣るようになり、その一方上記範囲よりも溶媒の量が多いと、ペースト粘度が低くなりすぎ、所望厚みのガラス層の形成が困難になる。
バインダとしては、これに限定されないが、メチルセルロース、エチルセルロース、カルボキシメチルセルロース、オキシエチルセルロース、ベンジルセルロース、プロピルセルロース、ニトロセルロース等のセルロース系樹脂;メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、2−ヒドロキシエチルメタクリレート、ブチルアクリレート、2−ヒドロキシエチルアクリレート等のアクリル系モノマーの1種以上を重合して得られるアクリル系樹脂等の有機樹脂;ポリプロピレンカーボネート等の脂肪族ポリオレフィン系カーボネート樹脂を例示することができる。
また溶剤は用いるバインダによって適宜選択され、これに限定されないが、セルロース系樹脂の場合は、水、ターピネオール、ブチルカルビトールアセテート、エチルカルビトールアセテート等;アクリル系樹脂の場合は、メチルエチルケトン、ターピネオール、ブチルカルビトールアセテート、エチルカルビトールアセテート等;脂肪族ポリオレフィン系カーボネートの場合は、炭酸プロピレン、トリアセチン等;の溶媒を用いることができる。
調製されたガラスペーストを、ガラスペーストの粘度に対応した塗工方法で酸化物膜上に塗工する。塗工方法としては、これに限定されないが、例えばバーコーター、ダイコーター、ロールコーター、グラビアコーター、スクリーン印刷、オフセット印刷、アプリケーター等によって塗工することができる。
塗工されたガラスペーストは、80〜180℃の温度で乾燥する。乾燥後、必要により、脱バインダ処理を行う。脱バインダ処理は、180〜450℃の温度で10分以上加熱することが好ましい。
乾燥後、必要により脱バインダ処理に賦された塗工面を、550〜900℃、好適には650〜900℃の温度で、10〜300秒間、焼成することによりガラス層が形成される。上記範囲よりも焼成温度が低い場合には、上記範囲にある場合に比して溶融が不十分になるおそれがあり、一方上記範囲よりも焼成温度が高い場合には、上記範囲にある場合に比してガラス表面に影響を与えるおそれがある。
図2は、図1に示した本発明のフレキシブルデバイス用基板を用いた、有機ELデバイス用基板の一例の断面構造を示す図である。
全体を1で示すフレキシブルデバイス用基板は、両面に酸化物膜11a,11bが形成されたステンレススチール基材10の一方の酸化物膜11aの表面にガラス層12が形成されている。
全体を3で示す有機ELデバイス用基板は、上記フレキシブルデバイス用基板1のガラス層12上に形成された電極層(Ag、Al)20、電極層20の上に形成された有機薄膜発光層21、有機薄膜発光層21の上に形成された透明電極層22、を少なくとも有している。図2に示す具体例では、透明電極層22の上に透明封止層23、透明封止材24が更に積層されていると共に、酸化物膜11bの上に耐食性層25が積層されている。
このような下地層としては、ニッケル(Ni)、酸化インジウム錫(ITO)、銀(Ag)、金(Au)、銅(Cu)、マグネシウム−銀(MgAg)、金−銅(AuCu)、銀−銅(AgCu)、酸化亜鉛(ZnO)、コバルト(Co)、パラジウム(Pd)等の金属又は金属酸化物等をスパッタリング法、蒸着法、CVD法等従来公知の方法によって形成することができるが、特にスパッタで成膜することが好適である。
この下地層は、有機EL基板に使用されるアルミニウム(Al)、銀(Ag)、金(Au)やこれらの合金等から成るすべての電極層に対して優れた密着性を発現できるが、特にアルミニウム(Al)、銀(Ag)から成る電極層を形成する場合には、下地層は上記金属又は酸化金属等の中でもニッケル、酸化インジウム錫から成ることが好適である。
下地層の厚みは、5〜100nmの範囲にあることが好ましい。
ステンレススチール基材として、厚さ0.05mmの以下の4種を使用した。
SUS430MA:フェライト系ステンレス箔(日本金属株式会社製)
JFE443CT:フェライト系ステンレス箔(JFEスチール株式会社製)
NCA−1:フェライト系ステンレス箔(日新製鋼株式会社製)
SUS430:フェライト系ステンレス箔(日新製鋼株式会社製)
表2に示す条件で、ステンレススチール基材の表面を20秒間熱処理を行った。
脱脂工程:各試料の表面をアルコールに浸したガーゼで拭き取り、脱脂した。
塗膜形成工程:有機溶剤とバインダとを混合したビヒクルを用意し、ビヒクルと、表1に記載された組成のビスマス系ガラス粉体とを重量比が25:75になるように乳鉢で混合し、セラミック製ロールミルにて分散処理を行ない、塗膜形成用ガラスペーストを作製した。バーコーターで焼成後の膜厚が10μmになるようにガラスペーストを塗布した。その後、電気炉を用いて、乾燥(温度:150℃、時間:3分)、脱バインダ(温度:330℃、時間:20分)、焼成(温度:850℃、時間:30秒)を行い、ガラス層を形成した。
(1)酸化物膜の厚み
実施例及び比較例により得られたフレキシブルデバイス用基板用基材の酸化物膜の厚みをフィールドエミッションオージェマイクロプローブ(AES:日本電子社製、品番;JAMP−9500F)を用いて測定した。
直径(φ)が30mm、20mm、10mmのステンレス製の丸棒に、実施例及び比較例で得られたフレキシブルデバイス用基板を、ガラス層が外側、あるいはガラス層が内側になるようにそれぞれ巻きつけて、剥離、クラック発生の有無を目視にて観察した。結果を表2に示す。
尚、評価基準は以下の通りである。
巻き付け試験による剥離、クラック発生の有無(目視観察)
◎:ガラス/基材界面からの剥離なし、クラックなし
○:ガラス/基材界面からの剥離なし、クラックあり(程度極小)
△:ガラス/基材界面からの剥離なし、クラックあり(程度小)
×:ガラス/基材界面からの剥離あり、クラックあり
◎:ガラス層外側巻付けのφ20の評価が◎であって、ガラス層内側巻付けのすべての評価が◎のもの
○:ガラス層外側巻付けのφ30の評価が◎且つφ20の評価が○であって、ガラス層内側巻付けのすべての評価が◎のもの
△:ガラス層外側巻付けのφ30の評価が◎且つφ20の評価が△であって、ガラス層内側巻付けのすべての評価が◎のもの
△△:ガラス層外側巻付けのφ30の評価が○或いは△であって、ガラス層内側巻付けのすべてが◎のもの
△△△:ガラス層外側巻付けのすべての評価が×であって、ガラス層内側巻付けのφ30及びφ20が◎又はすべての評価が◎のもの
×:ガラス層外側巻付けのすべての評価が×であって、ガラス層内側巻付けのφ30の評価のみが◎のもの
実施例2,4,9〜14,21,24,25,27と比較例1〜4により得られたフレキシブルデバイス用基板用基材について、ガラス層と酸化物膜の界面から酸化物膜の厚み方向に20nm地点のクロム(Cr)量、鉄(Fe)量をX線光電子分光(XPS)分析により測定し、下記の式からクロム濃度を算出した。結果を表2に示す。
Cr濃度(atomic%)=Cr/(Cr+Fe)×100
Claims (8)
- ステンレススチール基材と、該ステンレススチール基材の表面に形成された酸化物膜と、該酸化物膜の表面に電気絶縁性を有するビスマス系ガラスが層状に形成されたガラス層とを有することを特徴とするフレキシブルデバイス用基板。
- 前記酸化物膜の厚みが30nm以上である請求項1記載のフレキシブルデバイス用基板。
- 前記酸化物膜の厚みが80nm以上である請求項1記載のフレキシブルデバイス用基板。
- 前記酸化物膜と前記ガラス層との界面から、酸化物膜の厚み方向に20nm地点におけるクロム濃度が30atomic%以上である請求項1〜3の何れかに記載のフレキシブルデバイス用基板。
- 前記酸化物膜と前記ガラス層との界面から、酸化物膜の厚み方向に20nm地点におけるクロム濃度が50atomic%以上である請求項1〜3の何れかに記載のフレキシブルデバイス用基板。
- 前記ビスマス系ガラスが、Bi2O3,ZnO,B2O3を含有する請求項1〜5の何れかに記載のフレキシブルデバイス用基板。
- ステンレススチール基材と、該ステンレススチール基材の表面に形成された酸化物膜から成り、前記酸化物膜の厚みが30nm以上であることを特徴とするフレキシブルデバイス用基板用基材。
- 前記酸化物膜の厚みが80nm以上である請求項7記載のフレキシブルデバイス用基板用基材。
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