WO2015163134A1 - ガラス積層体および電子デバイスの製造方法 - Google Patents
ガラス積層体および電子デバイスの製造方法 Download PDFInfo
- Publication number
- WO2015163134A1 WO2015163134A1 PCT/JP2015/060777 JP2015060777W WO2015163134A1 WO 2015163134 A1 WO2015163134 A1 WO 2015163134A1 JP 2015060777 W JP2015060777 W JP 2015060777W WO 2015163134 A1 WO2015163134 A1 WO 2015163134A1
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- WO
- WIPO (PCT)
- Prior art keywords
- inorganic layer
- glass
- glass substrate
- layer
- substrate
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 238000000034 method Methods 0.000 title description 87
- 239000000758 substrate Substances 0.000 claims abstract description 331
- 239000011521 glass Substances 0.000 claims abstract description 258
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 22
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- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
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- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 290
- 239000003513 alkali Substances 0.000 description 23
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- 229910004298 SiO 2 Inorganic materials 0.000 description 7
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
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- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 239000011651 chromium Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- -1 ZnF 2 Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000000465 moulding Methods 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000694440 Colpidium aqueous Species 0.000 description 1
- 229910016509 CuF 2 Inorganic materials 0.000 description 1
- 229910005269 GaF 3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- WNDSQRGJJHSKCQ-UHFFFAOYSA-N naphthalene-1,5-dicarbonitrile Chemical compound C1=CC=C2C(C#N)=CC=CC2=C1C#N WNDSQRGJJHSKCQ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
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- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
- B32B43/006—Delaminating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B40/00—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it
- C03B40/02—Preventing adhesion between glass and glass or between glass and the means used to shape it, hold it or support it by lubrication; Use of materials as release or lubricating compositions
- C03B40/033—Means for preventing adhesion between glass and glass
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a glass laminate and a method for manufacturing an electronic device.
- Patent Document 1 A method for separating a glass substrate from a laminate has been proposed.
- the present invention has been made in view of the above points, and an object of the present invention is to provide a glass laminate capable of easily peeling a glass substrate.
- a glass substrate can be easily peeled off by forming a specific inorganic layer on a support substrate, and the present invention has been completed. .
- the present invention provides the following (1) to (10).
- a support substrate, an inorganic layer, a fragile layer, and a glass substrate are provided in this order, the inorganic layer contains an F-containing inorganic layer containing F, and the fragile layer contains Al and Si.
- the F-containing inorganic layer contains at least one selected from the group consisting of metal fluorides and fluorine-doped metal oxides. .
- the metal fluoride is selected from the group consisting of alkali metals, alkaline earth metals, Sc, Y, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, In and lanthanoids
- the glass laminate according to (4) or (5) comprising at least one element.
- the glass laminate according to (4), wherein the fluorine-doped metal oxide is fluorine-doped tin oxide.
- An electronic device member is formed on the surface opposite to the inorganic layer side of the glass substrate provided in the glass laminate according to any one of (1) to (9) above, A member forming step for obtaining a laminate with members, a separation step for separating the inorganic layer and the support substrate from the laminate with members for an electronic device, and obtaining an electronic device having the glass substrate and the member for electronic devices;
- An electronic device manufacturing method comprising:
- a glass laminate capable of easily peeling a glass substrate can be provided.
- FIG. 1 is a schematic cross-sectional view showing a first aspect of the glass laminate of the present invention.
- FIG. 2 is a schematic cross-sectional view showing a second embodiment of the glass laminate of the present invention.
- 3A and 3B are schematic cross-sectional views sequentially showing each step in a preferred embodiment of the method for manufacturing an electronic device of the present invention.
- FIG. 1 is a schematic cross-sectional view showing a first aspect of the glass laminate of the present invention.
- the glass laminate 10 according to the first embodiment includes a support substrate 16 with an inorganic layer composed of a support substrate 12 and an inorganic layer 14, and a glass substrate 18.
- the support substrate 16 with an inorganic layer and the glass substrate 18 are laminated so as to be peelable, with (the surface of the glass substrate 18 on the inorganic layer 14 side) as a lamination surface. That is, the inorganic layer 14 has one surface fixed to the layer of the support substrate 12 and the other surface in contact with the first main surface 18 a of the glass substrate 18, and the interface between the inorganic layer 14 and the glass substrate 18. Are in close contact with each other. In other words, the inorganic layer 14 is easily peelable from the first main surface 18 a of the glass substrate 18.
- the glass laminated body 10 is used until the member formation process mentioned later. That is, the glass laminate 10 is used until a member for an electronic device such as a liquid crystal display device is formed on the second main surface 18b of the glass substrate 18 (the surface opposite to the inorganic layer 14 side of the glass substrate 18). Is done. Thereafter, the layer of the support substrate 16 with the inorganic layer is peeled off at the interface with the layer of the glass substrate 18, and the layer of the support substrate 16 with the inorganic layer does not become a member constituting the electronic device. A new glass substrate 18 is laminated on the separated support substrate 16 with the inorganic layer, and can be reused as a new glass laminate 10.
- peeling strength that is, stress required for peeling
- fixing means that the peeling strength is larger than the adhesion.
- the peel strength at the interface between the inorganic layer 14 and the support substrate 12 is greater than the peel strength at the interface between the inorganic layer 14 and the glass substrate 18 in the glass laminate 10.
- the peelable adhesion means that it can be peeled at the same time that it can be peeled without causing peeling of the fixed surface.
- the glass substrate 10 when the operation of separating the glass substrate 18 and the support substrate 12 is performed, the glass substrate 10 is peeled off at the closely contacted surface (interface between the inorganic layer 14 and the glass substrate 18) and fixed on the surface. It means not peeling. Therefore, when the operation of separating the glass laminate 10 into the glass substrate 18 and the support substrate 12 is performed, the glass laminate 10 is separated into two, the glass substrate 18 and the support substrate 16 with an inorganic layer.
- FIG. 2 is a schematic cross-sectional view showing a second embodiment of the glass laminate of the present invention.
- the glass laminated body 11 which is a 2nd aspect is equipped with the support substrate 12, the inorganic layer 14, the weak layer 26, and the glass substrate 18 in this order, and the inorganic layer 14 of the support substrate 16 with an inorganic layer is provided. Between the glass substrate 18 and the glass substrate 18.
- the glass laminated body 11 which has the weak layer 26 is obtained by exposing the glass laminated body 10 which is a 1st aspect to high temperature conditions (for example, 400 degreeC or more).
- the support substrate 16 with an inorganic layer and the glass substrate 18 constituting the glass laminate 10 (11) will be described in detail, and then the procedure for manufacturing the glass laminate 10 (11) will be described in detail. In the detailed description of this procedure, the fragile layer 26 constituting the glass laminate 11 is also described.
- the support substrate 16 with an inorganic layer includes a support substrate 12 and an inorganic layer 14 disposed (fixed) on the surface thereof.
- the inorganic layer 14 is arrange
- the support substrate 12 has a first main surface and a second main surface, cooperates with the inorganic layer 14 disposed on the first main surface, supports and reinforces the glass substrate 18, and a member to be described later It is a substrate that prevents the glass substrate 18 from being deformed, scratched or damaged during the production of the electronic device member in the forming step (the step of producing the electronic device member).
- a metal plate such as a glass plate, a plastic plate, or a stainless steel (SUS) plate is used as the support substrate 12.
- the support substrate 12 is preferably formed of a material having a small difference in linear expansion coefficient from the glass substrate 18, and more preferably formed of the same material as the glass substrate 18,
- the support substrate 12 is preferably a glass plate.
- the support substrate 12 is preferably a glass plate made of the same glass material as the glass substrate 18.
- the thickness of the support substrate 12 may be thicker or thinner than a glass substrate 18 described later.
- the thickness of the support substrate 12 is selected based on the thickness of the glass substrate 18, the thickness of the inorganic layer 14, and the thickness of the glass laminate 10 (11) described later.
- the thickness of the support substrate 12 is 0.4 mm.
- the thickness of the support substrate 12 is preferably 0.2 to 5.0 mm.
- the thickness of the glass plate is preferably 0.08 mm or more because it is easy to handle and difficult to break. Further, the thickness of the glass plate is preferably 1.0 mm or less because the rigidity is desired so that the glass plate is appropriately bent without being broken when it is peeled off after forming the electronic device member.
- the difference in average linear expansion coefficient between the support substrate 12 and the glass substrate 18 at 25 to 300 ° C. is preferably 500 ⁇ 10 ⁇ 7 / ° C. or less, more preferably It is 300 ⁇ 10 ⁇ 7 / ° C. or less, more preferably 200 ⁇ 10 ⁇ 7 / ° C. or less. If the difference is too large, the glass laminate 10 (11) may be warped severely during heating and cooling in the member forming step. When the material of the glass substrate 18 and the material of the support substrate 12 are the same, it can suppress that such a problem arises. In this specification, the average linear expansion coefficient can be measured according to JIS R3102 (1995).
- the inorganic layer 14 is a layer disposed (fixed) on the main surface of the support substrate 12 in the glass laminate 10 and in direct contact with the first main surface 18 a of the glass substrate 18.
- Such an inorganic layer 14 contains an F-containing inorganic layer containing F.
- the inorganic layer 14 may be composed of only the F-containing inorganic layer, or may be a plurality of layers containing inorganic layers other than the F-containing inorganic layer.
- the position other than the F-containing inorganic layer in the thickness direction of the inorganic layer 14 is not particularly limited, but may be the outermost layer in contact with the first main surface 18a of the glass substrate 18. preferable.
- the F-containing inorganic layer contained in the inorganic layer 14 preferably contains at least one selected from the group consisting of metal fluorides and fluorine-doped metal oxides.
- examples of the fluorine-doped metal oxide include fluorine-doped tin oxide, fluorine-doped zinc oxide, fluorine-doped titanium oxide, fluorine-doped aluminum oxide, fluorine-doped silicon oxide, and fluorine.
- Dope quartz etc. are mentioned, These may be used individually by 1 type and may be used together 2 or more types. Of these, fluorine-doped tin oxide is preferred.
- the inorganic layer 14 contains a metal fluoride
- the chemical stability of the metal fluoride contained in the inorganic layer 14 is high in that the peelability of the glass substrate 18 is more excellent.
- the melting point of the metal fluoride can be used. That is, the melting point of the metal fluoride is preferably 800 ° C. or higher, more preferably 900 ° C. or higher, and further preferably 1000 ° C. or higher.
- the inorganic layer 14 may contain two or more kinds of metal fluorides.
- the composition of the metal fluoride contained in the inorganic layer 14 is not particularly limited, but alkali metal, alkaline earth metal, Sc, Y, V, Cr, Mn, Fe, Co, and the like in that the peelability of the glass substrate 18 is more excellent. It is preferable to contain at least one selected from the group consisting of Ni, Cu, Zn, Al, Ga, In and lanthanoids.
- examples of the alkali metal include Li, Na, K, Rb, and Cs.
- examples of the alkaline earth metal include Mg, Ca, Sr, and Ba.
- the lanthanoid is from La to Lu, and examples thereof include La, Ce, Pr, Nd, Pm, and Sm.
- the number of OH groups on the surface of the inorganic layer 14 and the surface flatness can be adjusted, and the adhesion between the inorganic layer 14 and the glass substrate 18 can be controlled.
- a part of the metal fluoride contained in the inorganic layer 14 may be oxidized. That is, the inorganic layer 14 may contain oxygen atoms (oxygen element) (O).
- the adhesion amount between the inorganic layer 14 and the glass substrate 18 can be controlled by adjusting the number of OH groups and surface flatness on the surface of the inorganic layer 14 depending on the addition amount of metal fluoride and oxygen atoms.
- the metal fluoride in which the inorganic layer 14 contains a metal fluoride for example, RF, R′F 2 , ScF 3 , VF 3 , CrF 3 , MnF 2 , FeF 3 , CoF 2 , NiF 2 , CuF 2 , ZnF 2 , AlF 3 , GaF 3 , InF 3, LF 3 and the like.
- R represents an alkali metal
- R ′ represents an alkaline earth metal
- L represents a lanthanoid.
- the average linear expansion coefficient of the inorganic layer 14 is not particularly limited, but when a glass plate is used as the support substrate 12, the average linear expansion coefficient is preferably 10 ⁇ 10 ⁇ 7 to 200 ⁇ 10 ⁇ 7 / ° C. If it is this range, the difference of the average linear expansion coefficient with a glass plate will become small, and the position shift of the glass substrate 18 and the support substrate 16 with an inorganic layer in a high temperature environment can be suppressed more.
- the inorganic layer 14 preferably contains at least one selected from the group consisting of metal fluorides and fluorine-doped metal oxides as a main component.
- the main component means that the total content of the metal fluoride is 90% by mass or more with respect to the total amount of the inorganic layer 14, preferably 98% by mass or more, and 99% by mass or more. It is more preferable that it is 99.999 mass% or more.
- the thickness of the inorganic layer 14 is not particularly limited, but is preferably 5 to 5000 nm and more preferably 10 to 500 nm in terms of maintaining scratch resistance.
- the inorganic layer 14 is shown as a single layer in FIG. 1, but may be a laminate of two or more layers. In the case of two or more layers, each layer may have a different composition. In this case, “thickness of the inorganic layer” means the total thickness of all the layers.
- the inorganic layer 14 is usually provided on one entire main surface of the support substrate 12, but is provided on a part of the surface of the support substrate 12 as long as the effects of the present invention are not impaired. May be.
- the surface roughness (Ra) of the first major surface 14a of the inorganic layer 14 is preferably 2.0 nm or less, and more preferably 1.2 nm or less.
- the lower limit is not particularly limited but is preferably 0. If it is the said range, adhesiveness with the glass substrate 18 will become more favorable, the position shift of the glass substrate 18 etc. can be suppressed more, and the peelability of the glass substrate 18 is also more excellent.
- Ra is measured according to JIS B 0601 (revised 2001).
- the inorganic layer 14 simply contains the F-containing inorganic layer, the laminateability (ease of lamination) when the glass substrate 18 is laminated on the inorganic layer 14 may be inferior. That is, even if the inorganic layer 14 and the glass substrate 18 are stacked, they do not naturally adhere to each other, but they may not adhere even when mechanically pressed, or may be easily peeled off. Therefore, in the inorganic layer 14, the water contact angle of the first main surface 14a on which the glass substrate 18 is laminated is preferably 0 to 40 °. Thereby, the lamination property of the inorganic layer 14 and the glass substrate 18 is excellent. The water contact angle is measured using a commercially available contact angle meter according to JIS R 3257: 1999.
- a method for forming the inorganic layer 14 on the support substrate 12 for example, a PVD (Physical Vapor Deposition) method such as an evaporation method; a CVD (Chemical Vapor Deposition) method such as a thermal CVD method or a plasma CVD method;
- a PVD Physical Vapor Deposition
- CVD Chemical Vapor Deposition
- thermal CVD thermal CVD
- plasma CVD plasma CVD
- the process which controls the water contact angle of the 1st main surface 14a of the inorganic layer 14 it is preferable to perform the process which controls the water contact angle of the 1st main surface 14a of the inorganic layer 14 to 0-40 degrees.
- treatment include hydrophilic treatment, and specific examples thereof include alkali treatment, plasma treatment, UV treatment, and the like, and alkali treatment is preferred.
- Examples of the alkali treatment include a treatment in which an alkali treatment liquid is brought into contact with the first main surface 14a of the inorganic layer 14.
- the alkali treatment liquid used for the alkali treatment for example, a solution containing a base such as sodium hydroxide, potassium hydroxide, or ammonia is preferable.
- the pH of the alkaline treatment liquid is more than 7, and preferably 8-14.
- Examples of the alkali treatment method include a method of spraying the alkali treatment liquid onto the first main surface 14a of the inorganic layer 14 using a spray or the like, and a method of immersing the support substrate 16 with the inorganic layer in the alkali treatment liquid. . After the alkali treatment, it is preferable to rinse with pure water and dry the first main surface 14a of the inorganic layer 14 with an air knife or the like.
- the inorganic layer 14 and the glass substrate 18 Stackability may be inferior. For this reason, it is preferable to laminate the glass substrate 18 in as short a time as possible after performing a process of controlling the water contact angle of the first main surface 14a of the inorganic layer 14 to 0 to 40 °.
- the time from the above treatment to the lamination is not particularly limited, but is preferably within 1 hour, more preferably within 30 minutes.
- foreign matters such as dust in the atmosphere may be adsorbed on the surface and the lamination property may be deteriorated.
- the surface of the inorganic layer 14 may be cut as necessary.
- examples of such treatment include polishing and ion sputtering.
- the glass substrate 18 a glass plate containing at least SiO 2 and Al 2 O 3 on an oxide basis is used. That is, the glass substrate 18 contains at least Si (silicon element) and Al (aluminum element).
- the glass plate contains, for example, SiO 2 as a main component (most component), and further contains Al 2 O 3 , B 2 O 3 , MgO, CaO, SrO, BaO, etc. as other components. A glass plate is mentioned.
- Al 2 O 3 is preferable as the next most component after SiO 2 . That is, in the glass substrate 18, except for O (oxygen element), it is preferable that the first element having the largest content is Si and the second element having the second largest content after the first element is Al. .
- Examples of the glass plate used for the glass substrate 18 include a non-alkali glass plate, and specific examples thereof include SiO 2 : 54 to 73% in terms of oxide-based mass percentage, Al 2 O 3 : 10 to 23%, B 2 O 3 : 0 to 13.0%, MgO: 0 to 12%, CaO: 0 to 15%, SrO: 0 to 16%, BaO: 0 to 15%, and MgO + CaO + SrO + BaO : Alkali-free glass plate containing 8 to 26%.
- the type of the glass substrate 18 may be a general one as long as the above-described conditions are satisfied, and examples thereof include a glass substrate for a display device such as an LCD or an OLED.
- the glass substrate 18 is excellent in chemical resistance and moisture permeation resistance and has a low heat shrinkage rate.
- As an index of the heat shrinkage rate a linear expansion coefficient defined in JIS R 3102 (revised in 1995) is used.
- the glass substrate 18 is obtained by melting a glass raw material and molding the molten glass into a plate shape.
- a molding method may be a general one, and for example, a float method, a fusion method, a slot down draw method, a full call method, a rubber method, or the like is used.
- a glass substrate having a particularly small thickness can be obtained by heating a glass once formed into a plate shape to a moldable temperature, and stretching it by means of stretching or the like to make it thin (redraw method).
- the glass of the glass substrate 18 satisfies the above-described conditions, in addition to the non-alkali borosilicate glass described above, for example, borosilicate glass, soda lime glass, high silica glass, and other silicon oxides as main components. It is also possible to use oxide-based glass or the like. As the oxide-based glass, a glass having a silicon oxide content of 40 to 90% by mass in terms of oxide is preferable.
- a glass substrate for a liquid crystal panel is made of glass (non-alkali glass) that does not substantially contain an alkali metal component because the elution of an alkali metal component easily affects the liquid crystal (however, usually an alkaline earth metal) Ingredients are included).
- the glass of the glass substrate 18 is appropriately selected based on the type of device to be applied and its manufacturing process.
- the thickness of the glass substrate 18 is not particularly limited, but is, for example, 0.8 mm or less, preferably 0.3 mm or less, more preferably 0.8 mm or less, from the viewpoint of reducing the thickness and / or weight of the glass substrate 18. It is 15 mm or less. If it exceeds 0.8 mm, the glass substrate 18 may not be able to meet the demand for thinning and / or lightening. In the case of 0.3 mm or less, it is possible to give good flexibility to the glass substrate 18. In the case of 0.15 mm or less, the glass substrate 18 can be wound into a roll. Moreover, the thickness of the glass substrate 18 is preferably 0.03 mm or more because the glass substrate 18 is easy to manufacture and the glass substrate 18 is easy to handle.
- the glass substrate 18 may be composed of two or more layers.
- the material forming each layer may be the same material or different materials.
- the thickness of the glass substrate means the total thickness of all the layers.
- the first major surface 14 a of the inorganic layer 14 and the first major surface 18 a of the glass substrate 18 are in direct contact.
- the inorganic thin film layer is not provided on the first main surface 18a (the surface on the inorganic layer 14 side) of the glass substrate 18, and in particular, the inorganic thin film layer made of metal fluoride is not provided. preferable.
- the adhesion between the glass substrate with the metal fluoride layer and the support substrate with the inorganic layer is deteriorated after the high temperature treatment, It peels spontaneously and cannot be used as a glass laminate.
- the glass substrate spontaneously peels off after the high-temperature treatment and the act of peeling cannot be performed artificially it is treated as inferior in the present invention.
- the manufacturing method in particular of the glass laminated body 10 is not restrict
- the surfaces of the inorganic layer 14 and the glass substrate 18 that are in contact with each other are sufficiently washed and laminated in a clean environment. Is preferred.
- the obtained glass laminate 10 (see FIG. 1) is subjected to a treatment under a high temperature condition of, for example, 400 ° C. or higher, so that the glass laminate 11 after the high temperature treatment having the fragile layer 26, that is, the support substrate. 12, the glass laminated body 11 (refer FIG. 2) which has the inorganic layer 14, the weak layer 26, and the glass substrate 18 in this order is obtained.
- a high temperature condition for example, 400 ° C. or higher
- the fragile layer 26 will be described in detail.
- water adsorbed water
- the first main surface 14a that is the exposed surface of the inorganic layer 14 of the support substrate 16 with the inorganic layer. It is considered that OH groups are generated.
- the glass substrate 18 is obtained by stacking the glass substrate 18 on the first main surface 14a of the inorganic layer 14 as described above, the obtained glass laminate 10 is exposed to a high temperature condition, whereby the first layer of the inorganic layer 14 is obtained.
- adsorbed water H 2 O
- the inorganic layer 14 contains, for example, an F-containing inorganic layer containing magnesium fluoride (MgF 2 )
- MgF 2 magnesium fluoride
- the fragile layer 26 is formed in the region of the glass substrate 18 on the first main surface 18a side (region on the inorganic layer 14 side).
- the fragile layer 26 is a layer derived from the glass substrate 18, but due to the volatilization of H 2 SiF 6 , Si that constitutes the layer is lost and becomes fragile, and is easily cohesive. For this reason, in the separation step described later, cohesive failure occurs in the fragile layer 26, and the glass substrate 18 can be easily peeled off.
- the fragile layer 26 is a layer derived from the glass substrate 18, the composition or the like basically depends on the glass substrate 18, but, like the glass substrate 18, contains at least Si and Al. Further, except for O (oxygen element), it is preferable that the first element having the largest content is Si and the second element having the second largest content after the first element is Al.
- the fragile layer 26 is a layer formed by volatilizing Si of the glass substrate 18, the amount of Si in the layer is relatively smaller than that of the glass substrate 18. Therefore, the atomic ratio of Al to Si (Al / Si) in the layer is smaller in the glass substrate 18 than in the fragile layer 26. More specifically, the ratio (Y / X) of the atomic ratio Y (Al / Si) of Al and Si in the fragile layer 26 to the atomic ratio X (Al / Si) of Al and Si in the glass substrate 18. Is 1.2 or more, and 1.3 or more is preferable and 1.5 or more is more preferable in that the effect of the present invention is more excellent. The upper limit is not particularly limited, but is usually 4.0 or less in many cases. The atomic ratio can be measured by, for example, an X-ray photoelectron spectroscopy (XPS) method.
- XPS X-ray photoelectron spectroscopy
- the thickness of the fragile layer 26 is not particularly limited, but is preferably 30 nm or more, and more preferably 50 nm or more, from the viewpoint that the effect of the present invention is more excellent.
- the upper limit is not particularly limited, but is usually 500 nm or less.
- the glass laminate 10 (11) can be used for various applications, for example, manufacturing electronic parts such as display panel, PV, thin film secondary battery, and semiconductor wafer having a circuit formed on the surface, which will be described later. The use to do is mentioned. In this application, the glass laminate 10 is often exposed (for example, for 10 minutes or more) under high temperature conditions (for example, 400 ° C. or more).
- the display device panel includes LCD, OLED, electronic paper, plasma display panel, field emission panel, quantum dot LED panel, MEMS (Micro Electro Mechanical Systems) shutter panel, and the like.
- FIG. 3A and 3B are schematic cross-sectional views sequentially showing each step in a preferred embodiment of the method for manufacturing an electronic device of the present invention.
- FIG. 3A shows a member forming step
- FIG. (B) shows a separation process. That is, the electronic device manufacturing method of the present invention includes a member forming step and a separating step.
- the materials used in each step and the procedure thereof will be described in detail with reference to FIGS. 3 (A) and 3 (B). First, a member formation process is explained in full detail.
- a member formation process is a process of forming the member for electronic devices on the glass substrate in a glass laminated body. More specifically, as shown in FIG. 3A, the electronic device member 20 is formed on the second main surface 18b of the glass substrate 18, and the laminated body 22 with the electronic device member is manufactured. First, the electronic device member 20 used in this step will be described in detail, and the procedure of the subsequent steps will be described in detail.
- the electronic device member 20 is a member that is formed on the second main surface 18b of the glass substrate 18 and constitutes at least a part of the electronic device. More specifically, examples of the electronic device member 20 include a member used for an electronic component such as a display panel, a solar cell, a thin film secondary battery, or a semiconductor wafer having a circuit formed on the surface thereof. Examples of the display device panel include a liquid crystal panel, an organic EL panel, a plasma display panel, a field emission panel, and the like.
- a silicon type includes a transparent electrode such as tin oxide of a positive electrode, a silicon layer represented by p layer / i layer / n layer, a metal of a negative electrode, and the like. And various members corresponding to the dye-sensitized type, the quantum dot type, and the like.
- a transparent electrode such as a metal or a metal oxide of a positive electrode and a negative electrode, a lithium compound of an electrolyte layer, a metal of a current collecting layer, a resin as a sealing layer, etc.
- various members corresponding to nickel hydrogen type, polymer type, ceramic electrolyte type and the like can be mentioned.
- metal of conductive part, silicon oxide and silicon nitride of insulating part, etc. other various sensors such as pressure sensor and acceleration sensor, rigid printed board, flexible printed board And various members corresponding to a rigid flexible printed circuit board.
- the manufacturing method of the laminated body 22 with the member for electronic devices mentioned above is not specifically limited, According to the kind of the structural member of the member for electronic devices, on the surface of the 2nd main surface 18b of the glass substrate 18 by a conventionally well-known method. Then, the electronic device member 20 is formed.
- the electronic device member 20 is not all of the members finally formed on the second main surface 18b of the glass substrate 18 (hereinafter referred to as “all members”), but a part of all members (hereinafter referred to as “parts”). May be referred to as a member.
- the glass substrate with partial members can be made into a glass substrate with all members (corresponding to an electronic device described later) in the subsequent steps.
- the member for electronic devices may be formed in the peeling surface (1st main surface) in the glass substrate with all the members.
- the laminated body with all members can be assembled, and then the supporting substrate 16 with inorganic layer (inorganic layer and supporting substrate) can be peeled from the laminated body with all members to manufacture an electronic device.
- an electronic device can also be manufactured by assembling an electronic device using two laminates with all members, and then peeling the two support substrates 16 with inorganic layers from the laminate with all members.
- a transparent electrode is formed on the surface on which the transparent electrode is further formed.
- Various layer formation and processing such as vapor deposition of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, etc., formation of a back electrode, and sealing using a sealing plate are performed. Specific examples of these layer formation and treatment include film formation treatment, vapor deposition treatment, sealing plate adhesion treatment, and the like.
- the TFT-LCD manufacturing method is formed by using a resist solution on the second main surface 18b of the glass substrate 18 of the glass laminate 10 by a general film forming method such as a CVD method or a sputtering method.
- a general film forming method such as a CVD method or a sputtering method.
- Forming a thin film transistor (TFT) by patterning a metal film, a metal oxide film, and the like, and forming a resist solution on the second main surface 18b of the glass substrate 18 of another glass laminate 10
- TFT thin film transistor
- It has various processes such as a CF forming process for forming a color filter (CF) and a bonding process for laminating a device substrate with TFT and a device substrate with CF.
- the TFT and CF are formed on the second main surface 18b of the glass substrate 18 by using a well-known photolithography technique, etching technique, or the like. At this time, a resist solution is used as a coating solution for pattern formation.
- a cleaning method known dry cleaning or wet cleaning can be used.
- a liquid crystal material is injected and laminated between the laminated body with TFT and the laminated body with CF.
- the method for injecting the liquid crystal material include a reduced pressure injection method and a drop injection method.
- the fragile layer 26 is formed between the inorganic layer 14 and the glass substrate 18 as shown in FIG. That is, the glass laminated body (laminated body 22 with an electronic device member) containing the support substrate 12, the inorganic layer 14, the weak layer 26, the glass substrate 18, and the electronic device member 20 is formed.
- the separation step includes the electronic device member 20 and the glass substrate 18 by separating the support substrate 16 with inorganic layer (inorganic layer and support substrate) from the laminate 22 with electronic device member obtained in the member forming step.
- This is a step of obtaining an electronic device 24 (a glass substrate with a member for electronic devices). That is, this is a step of separating the electronic device member-attached laminate 22 into the support substrate 16 with inorganic layer (inorganic layer and support substrate) and the electronic device 24.
- the fragile layer 26 is often separated into the support substrate 16 with an inorganic layer and the electronic device 24 due to cohesive failure.
- the method of separating into the support substrate 16 with an inorganic layer and the electronic device 24 is not particularly limited.
- a sharp blade-like object is inserted in the vicinity of the fragile layer 26 located between the inorganic layer 14 and the glass substrate 18 to give a trigger for peeling, and then a mixed fluid of water and compressed air is sprayed. Can be peeled off.
- the laminate 22 with electronic device members is placed on a surface plate so that the support substrate 12 is on the upper side and the electronic device member 20 side is on the lower side, and the electronic device member 20 side is vacuum-adsorbed on the surface plate. (In the case where support substrates are laminated on both sides, the steps are sequentially performed).
- the cutter is allowed to enter the vicinity of the fragile layer 26. Then, the support substrate 12 side is sucked by a plurality of vacuum suction pads, and the vacuum suction pads are raised in order from the vicinity of the place where the blade is inserted. If it does so, cohesive failure will occur in the weak layer 26 and the support substrate 16 with an inorganic layer can be peeled easily.
- the peeling strength when peeling the electronic device 24 is not particularly limited, but is preferably 2.0 N / 25 mm or less, and more preferably 1.2 N / 25 mm or less from an industrial point of view.
- the peel strength when peeling the electronic device 24 can be rephrased as peel strength when peeling the glass substrate 18. That is, when the glass substrate 18 is peeled from the glass laminate (including the electronic device member 20 as necessary) 11 including the support substrate 12, the inorganic layer 14, the fragile layer 26, and the glass substrate 18.
- the peel strength is preferably in the above range.
- peel strength can be calculated
- the electronic device 24 obtained by the above process is suitable for manufacturing a small display device used for a mobile terminal such as a mobile phone, a smartphone, or a tablet PC.
- the display device is mainly an LCD or an OLED, and the LCD includes a TN type, STN type, FE type, TFT type, MIM type, IPS type, VA type, and the like.
- the present invention can be applied to both passive drive type and active drive type display devices.
- a glass plate made of non-alkali borosilicate glass (length 100 mm, width 100 mm, plate thickness 0.2 mm, linear expansion coefficient 38 ⁇ 10 ⁇ 7 / ° C., manufactured by Asahi Glass Co., Ltd.)
- the name “AN100” was used as the support substrate.
- a glass plate made of non-alkali borosilicate glass (length 100 mm, width 100 mm, plate thickness 0.5 mm, linear expansion coefficient 38 ⁇ 10 ⁇ 7 / ° C., trade name “AN100” manufactured by Asahi Glass Co., Ltd.) It was used.
- the composition of the alkali-free borosilicate glass used as the glass substrate and the supporting substrate (expressed in terms of mass percentage based on oxide) is as follows. SiO 2 : 59.8% Al 2 O 3 : 17.2% B 2 O 3 : 7.9% MgO: 3.3% CaO: 4.0% SrO: 7.7% BaO: 0.1%
- Example 1 One main surface of the support substrate was cleaned with pure water and then cleaned with alkali.
- a vacuum deposition apparatus manufactured by Showa Vacuum Co., SEC-16CM was used for forming the inorganic layer.
- MgF 2 (magnesium fluoride) pellets were used as the vapor deposition source, and after exhausting to 10 ⁇ 5 Torr or less, film formation was performed at room temperature.
- the thickness of the inorganic layer was measured by a film thickness monitor using a crystal resonator as a film thickness sensor and a stylus type film thickness meter (hereinafter the same).
- An MgF 2 layer (corresponding to an inorganic layer) with a thickness of 30 nm was formed on the cleaned surface by a vapor deposition method to obtain a support substrate with an inorganic layer for the glass laminate A1.
- the surface roughness (Ra) of the first main surface of the inorganic layer of the obtained support substrate with an inorganic layer was 0.3 nm.
- the surface roughness (Ra) was measured in accordance with JIS B 0601 (revised in 2001) using AFM (model: L-trace (Nanoavi), manufactured by Hitachi High-Technologies Corporation) (hereinafter the same). ).
- the alkali treatment was performed with respect to the 1st main surface of the inorganic layer of the obtained support substrate with an inorganic layer. Specifically, first, the first main surface of the inorganic layer was shower washed with a 40 ° C. aqueous potassium hydroxide solution (potassium hydroxide 3 mass%, pH 12 or more). Next, the potassium hydroxide aqueous solution was sufficiently removed with pure water at 25 ° C. Thereafter, pure water was removed by air pressure. Thereby, the water contact angle of the 1st main surface of the inorganic layer was 4 degrees. The water contact angle was measured using a contact angle meter CA-X manufactured by Kyowa Interface Science Co., Ltd. according to JIS R 3257: 1999 (hereinafter the same).
- one main surface of the glass substrate was cleaned with pure water and then cleaned with alkali to be cleaned.
- the 1st main surface of the inorganic layer of the support substrate with an inorganic layer and the 1st main surface which cleaned the glass substrate were bonded together by vacuum press at room temperature, and glass laminated body A1 was obtained.
- the time from the alkali treatment to the lamination of the glass substrate was 5 minutes.
- the support substrate with an inorganic layer and the glass substrate were in close contact with each other without generating bubbles, had no distortion-like defects, and had good smoothness.
- the glass laminate A1 was heat-treated at 550 ° C. for 10 minutes in a nitrogen atmosphere. Thereby, the weak layer was formed between the inorganic layer and the glass substrate.
- the thickness of the fragile layer was 140 nm. The thickness of the fragile layer was measured using a scanning electron microscope (hereinafter the same).
- the peel strength (N / 25 mm) of the glass substrate was measured.
- a glass laminate A1 having a width of 25 mm and a length of 70 mm was prepared, and the glass substrate was peeled off using Autograph AG-20 / 50kNXDplus (Shimadzu Corporation).
- a stainless steel knife having a thickness of 0.1 mm is inserted in the vicinity of the fragile layer of the glass laminate A1 after the heat treatment to form a notch for separation, and then the glass substrate is completely fixed and the support substrate is pulled up.
- the strength was measured.
- the peeling speed was 30 mm / min.
- the point where the load was detected was set to 0, and the peel strength at a position where the load was lifted by 2.0 mm was taken as the measured value.
- the peel strength at that time was 0.18 N / 25 mm. From this result, it was confirmed that the peel strength at the interface between the inorganic layer and the support substrate layer was larger than the peel strength at the interface between the inorganic layer and the glass substrate.
- the fragile layer was coherently broken.
- adhesion of the fragile layer that was coherently broken was confirmed. Therefore, when the atomic ratio Y (Al / Si) between Al and Si in the fragile layer was measured for the fragile layer adhering to the first main surface of the inorganic layer, the value was 0.48. .
- the atomic ratio X (Al / Si) of Al and Si in the glass substrate was measured, the value was 0.19. Therefore, the ratio of the atomic ratio Y to the atomic ratio X (Y / X) was 2.53 (rounded to the second decimal place).
- the atomic ratio was measured using an X-ray photoelectron spectrometer (PHI5000 VersaProbe, manufactured by ULVAC-PHI) (hereinafter the same).
- Example 2 a CeF 3 (cerium fluoride) layer (Example 2) or a SnO 2 ⁇ F (fluorine-doped tin oxide) layer (Example 3) was prepared according to the following procedure. According to the same procedure as in Example 1, glass laminates A2 to A3 were produced.
- CeF 3 cerium fluoride
- SnO 2 ⁇ F fluorine-doped tin oxide
- the support substrate with an inorganic layer and the glass substrate were in close contact without generating bubbles, and there were no distortion defects and good smoothness.
- the glass laminates A2 to A3 were subjected to heat treatment according to the same procedure as in Example 1. Thereby, the weak layer was formed between the inorganic layer and the glass substrate.
- the glass substrate after the heat treatment was peeled in the same manner as in Example 1, it was peeled (separated) into the support substrate with an inorganic layer and the glass substrate. During the peeling, the fragile layer was coherently broken. On the first main surface of the inorganic layer in the peeled support substrate with an inorganic layer, adhesion of the fragile layer that was coherently broken was confirmed.
- Example 2 As in Example 1, the atomic ratio Y (Al / Si) of the fragile layer, the atomic ratio X (Al / Si) of the glass substrate, and the atomic ratio with respect to the atomic ratio X The ratio of Y (Y / X) was measured. Moreover, it carried out similarly to Example 1, and measured the peeling strength (unit: N / 25mm) at the time of peeling a glass substrate. The results are shown in Table 1 below.
- a glass laminate B1 was produced according to the same procedure as Example 1 except that CeO 2 (cerium oxide) was produced according to the following procedure.
- the support substrate with an inorganic layer and the glass substrate were in close contact with each other without generating bubbles, and there were no distortion-like defects and good smoothness.
- the glass laminate B1 is subjected to heat treatment according to the same procedure as in Example 1.
- the support substrate with an inorganic layer and the glass substrate partially generate bubbles. However, it was in close contact.
- formation of a fragile layer could not be confirmed between the inorganic layer and the glass substrate.
- the glass substrate B1 after the heat treatment was tried to peel off the glass substrate by inserting a knife according to the same procedure as in Example 1, but the glass substrate could not be peeled off.
- a glass laminate B2 was produced according to the same procedure as in Example 1 except that ITO (indium tin oxide layer) was produced according to the following procedure.
- ITO layer indium tin oxide layer
- a magnetron sputtering method heating temperature 300 ° C., film forming pressure 5 mTorr, power density 4.9 W / cm 2
- glass A support substrate with an inorganic layer for laminate B2 was obtained.
- the support substrate with an inorganic layer and the glass substrate were in close contact with each other without generating bubbles, there was no distortion defect, and the smoothness was good.
- the glass laminate B2 is subjected to heat treatment according to the same procedure as in Example 1.
- the support substrate with an inorganic layer and the glass substrate partially generate bubbles. However, it was in close contact.
- formation of a fragile layer could not be confirmed between the inorganic layer and the glass substrate.
- the glass substrate B2 after the heat treatment was tried to peel off the glass substrate by inserting a knife according to the same procedure as in Example 1, but the glass substrate could not be peeled off.
- Example 1 The results of Examples 1 to 3 and Comparative Examples 1 and 2 are summarized in Table 1 below.
- the peel strength at the interface between the inorganic layer and the support substrate is greater than the peel strength at the interface between the inorganic layer and the glass substrate, as a result of the above-described peeling of the glass substrate. confirmed.
- the “type” column of “inorganic layer” describes the type of inorganic layer disposed (fixed) on the support substrate, and the “melting point” column describes the melting point thereof. .
- Table 1 below in the column relating to the ratio (Y / X), “ ⁇ ” is described when formation of a fragile layer was not confirmed.
- the column “Lamination” in “Evaluation” describes the results when a glass laminate was produced. If the support substrate with an inorganic layer and the glass substrate are in close contact with each other without generating bubbles, and there is no distorted defect and smoothness is good, “ ⁇ ” is described as being excellent in laminating properties. In other cases, “x” is described.
- “Removability” column of “Evaluation” when the glass substrate could be peeled after the heat treatment, “ ⁇ ” was described as being excellent in peelability and could not be peeled off. In some cases, “x” was described as inferior in peelability.
- “—” is entered in the “peel strength” column of “evaluation” when the peel strength was not measured.
- Example 4 an OLED was produced using the glass laminate A1 produced in Example 1 before the heat treatment.
- the process of 400 degreeC or more is implemented as heat processing temperature in the following processes. More specifically, a molybdenum film was formed by sputtering on the second main surface of the glass substrate in the glass laminate A1, and a gate electrode was formed by etching using a photolithography method. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the glass substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering.
- a gate insulating film, a semiconductor element portion, and source / drain electrodes were formed by etching using a photolithography method.
- a passivation layer by further forming silicon nitride on the second main surface side of the glass substrate by plasma CVD
- indium tin oxide is formed by sputtering and photolithography is used.
- a pixel electrode was formed by etching.
- Aluminum was deposited, and a counter electrode was formed by etching using a photolithography method.Next, ultraviolet light was formed on the second main surface of the glass substrate on which the counter electrode was formed.
- Another glass substrate was bonded and sealed through a wire-curable adhesive layer, and the glass laminate obtained by the above procedure and having an organic EL structure on the glass substrate had an electronic device member. Corresponds to the laminate.
- Example 5 LCD was produced using the glass laminated body A1 manufactured in Example 1 before the heat treatment.
- the process of 400 degreeC or more is implemented as heat processing temperature in the following processes.
- Two glass laminates A1 are prepared. First, a molybdenum film is formed on the second main surface of the glass substrate of one glass laminate A1 by sputtering, and a gate electrode is formed by etching using photolithography. did. Next, silicon nitride, intrinsic amorphous silicon, and n-type amorphous silicon are formed in this order on the second main surface side of the glass substrate provided with the gate electrode by plasma CVD, and then molybdenum is formed by sputtering.
- a gate insulating film, a semiconductor element portion, and source / drain electrodes were formed by etching using a photolithography method.
- a passivation layer by further forming silicon nitride on the second main surface side of the glass substrate by plasma CVD
- indium tin oxide was formed by sputtering and photolithography was used.
- a pixel electrode was formed by etching.
- a polyimide resin liquid was applied on the second main surface of the glass substrate on which the pixel electrode was formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed.
- the obtained glass laminate is referred to as a glass laminate X1.
- a chromium film was formed by sputtering on the second main surface of the glass substrate in the other glass laminate A1, and a light-shielding layer was formed by etching using photolithography.
- a color resist was further applied by a die coating method to the second main surface side of the glass substrate provided with the light shielding layer, and a color filter layer was formed by a photolithography method and thermal curing.
- an indium tin oxide film was further formed on the second main surface side of the glass substrate by a sputtering method to form a counter electrode.
- an ultraviolet curable resin liquid was applied to the second main surface of the glass substrate provided with the counter electrode by a die coating method, and columnar spacers were formed by a photolithography method and heat curing.
- a polyimide resin solution was applied on the second main surface of the glass substrate on which the columnar spacers were formed by a roll coating method, an alignment layer was formed by thermosetting, and rubbing was performed.
- the sealing resin liquid is drawn in a frame shape on the second main surface side of the glass substrate by the dispenser method, and the liquid crystal is dropped in the frame by the dispenser method, the above-described glass laminate X1 is used.
- the 2nd main surface side of the glass substrate of a sheet of glass laminated body was bonded together, and the laminated body which has an LCD panel by ultraviolet curing and thermosetting was obtained.
- the laminate having the LCD panel is referred to as a laminate X2 with a panel.
- LCD panel B (corresponding to an electronic device) composed of a substrate on which a TFT array is formed and a substrate on which a color filter is formed is peeled off from the laminate X2 with a panel in the same manner as in Example 1 and the substrate with the inorganic layer is peeled off.
- an IC driver was connected to the manufactured LCD panel B and driven under normal temperature and normal pressure, no display unevenness was observed in the driving region.
- SYMBOLS 10 Glass laminated body 11 Glass laminated body 12 Support substrate 14 Inorganic layer 14a 1st main surface (surface on the opposite side to the support substrate side of an inorganic layer) 16 Support substrate with inorganic layer 18 Glass substrate 18a First main surface (surface on the inorganic layer side of glass substrate) 18b 2nd main surface (surface on the opposite side to the inorganic layer side of a glass substrate) 20 Electronic Device Member 22 Laminate with Electronic Device Member 24 Electronic Device (Glass Substrate with Electronic Device Member) 26 Vulnerable layer
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Laminated Bodies (AREA)
- Electroluminescent Light Sources (AREA)
- Joining Of Glass To Other Materials (AREA)
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KR1020167028992A KR20160146712A (ko) | 2014-04-25 | 2015-04-06 | 유리 적층체 및 전자 디바이스의 제조 방법 |
JP2016514846A JPWO2015163134A1 (ja) | 2014-04-25 | 2015-04-06 | ガラス積層体および電子デバイスの製造方法 |
CN201580022073.3A CN106232351A (zh) | 2014-04-25 | 2015-04-06 | 玻璃层叠体及电子器件的制造方法 |
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JP2018064088A (ja) * | 2016-08-31 | 2018-04-19 | 株式会社半導体エネルギー研究所 | 半導体装置の作製方法 |
US10014177B2 (en) | 2012-12-13 | 2018-07-03 | Corning Incorporated | Methods for processing electronic devices |
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US11097509B2 (en) | 2016-08-30 | 2021-08-24 | Corning Incorporated | Siloxane plasma polymers for sheet bonding |
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CN107857480A (zh) * | 2016-09-21 | 2018-03-30 | 旭硝子株式会社 | 玻璃板和玻璃基板的制造方法 |
US11999135B2 (en) | 2017-08-18 | 2024-06-04 | Corning Incorporated | Temporary bonding using polycationic polymers |
US11331692B2 (en) | 2017-12-15 | 2022-05-17 | Corning Incorporated | Methods for treating a substrate and method for making articles comprising bonded sheets |
Also Published As
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JPWO2015163134A1 (ja) | 2017-04-13 |
CN106232351A (zh) | 2016-12-14 |
KR20160146712A (ko) | 2016-12-21 |
TWI647099B (zh) | 2019-01-11 |
TW201605616A (zh) | 2016-02-16 |
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