WO2017090599A1 - Film à composition à gradient, et film de barrière contre les gaz et dispositif électronique le comprenant - Google Patents

Film à composition à gradient, et film de barrière contre les gaz et dispositif électronique le comprenant Download PDF

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Publication number
WO2017090599A1
WO2017090599A1 PCT/JP2016/084582 JP2016084582W WO2017090599A1 WO 2017090599 A1 WO2017090599 A1 WO 2017090599A1 JP 2016084582 W JP2016084582 W JP 2016084582W WO 2017090599 A1 WO2017090599 A1 WO 2017090599A1
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layer
transition metal
film
region
gradient composition
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PCT/JP2016/084582
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English (en)
Japanese (ja)
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森　孝博
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コニカミノルタ株式会社
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    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity

Definitions

  • the present invention relates to a gradient composition film, a gas barrier film and an electronic device including the gradient composition film, and more particularly relates to a gradient composition film having a high gas barrier property, a gas barrier film and an electronic device including the gradient composition film. .
  • organic electroluminescent element (hereinafter also referred to as “organic EL element”) using electroluminescence of organic material (hereinafter also referred to as “EL”) can emit light at a low voltage of several V to several tens V. It is a thin film type complete solid-state device and has many excellent features such as high brightness, high luminous efficiency, thinness, and light weight. For this reason, it is applied as a backlight for various displays, display boards such as signboards and emergency lights, and surface light emitters such as illumination light sources.
  • a flexible organic EL element using a resin base material having a thin and light gas barrier layer has attracted attention, and is applied as a light source having a curved surface and a high design property.
  • the gas barrier layer studied by this method is a multi-layer stack of layers having different compositions formed by chemical vapor deposition (CVD), and also has a recently required water vapor transmission rate (Water Vapor Transmission Rate).
  • CVD chemical vapor deposition
  • Water Vapor Transmission Rate water vapor transmission rate
  • the layer is thick, it was found that there is a concern that the gas barrier property may be deteriorated, for example, when the gas barrier layer is cracked repeatedly when bent with a small diameter. Accordingly, there has been a demand for a gas barrier layer capable of obtaining a very high gas barrier property with a thinner film thickness.
  • the present invention has been made in view of the above problems and situations, and a solution to the problem is to provide a gradient composition film having a high gas barrier property, a gas barrier film and an electronic device having the same. is there.
  • the present inventor has studied the cause of the above problems, and as a result, in the detected intensity curve obtained by EDS (energy dispersive X-ray analysis) line analysis that changes in the thickness direction from the surface, It has been found that a high gas barrier property can be obtained by detecting a metal and a non-transition metal at the same time, and having an inclined region in which the detection intensity of the transition metal increases and the detection intensity of the non-transition metal decreases.
  • a gradient composition film containing a transition metal and a non-transition metal wherein the detected intensity of the transition metal and non-transition metal obtained by EDS line analysis of the cross-section of the gradient composition film changes from the surface to the thickness direction.
  • the inclined region is provided in an intermediate region between an A region which is a region containing the transition metal as a main component of the metal and a B region which is a region containing the non-transition metal as a main component of the metal.
  • a gas barrier film comprising the gradient composition film according to any one of items 1 to 7.
  • An electronic device comprising the gas barrier film according to Item 8.
  • An electronic device comprising an organic electroluminescence element.
  • the region having the non-transition metal (M1) as the main component of the metal is the B region and the region having the transition metal (M2) as the main component of the metal is the A region
  • the B region and the A region are When laminated, the non-transition metal (M1) can be diffused into the A region
  • the transition metal (M2) can be diffused into the B region
  • a region where the non-transition metal (M1) and the transition metal (M2) coexist can be formed.
  • this region has a gradient composition in which the content ratio of the non-transition metal (M1) increases and the content ratio of the transition metal (M2) decreases at the same time in the thickness direction.
  • This phenomenon is caused by the fact that the bond between the non-transition metal (M1) and the transition metal (M2) is more likely to occur than the bond between the non-transition metals (M1) or the transition metal (M2).
  • a high-density structure including a direct bond between the non-transition metal (M1) and the transition metal (M2) is formed, and thus high gas barrier properties are obtained. It is thought that it was obtained.
  • the gradient region further contains oxygen.
  • the inclined region further contains oxygen and nitrogen from the viewpoint of improving gas barrier properties.
  • the gradient composition film of the present invention is a gradient composition film containing a transition metal and a non-transition metal, and the detected intensity of the transition metal and the non-transition metal obtained by EDS line analysis of a cross section of the gradient composition film.
  • the detected intensity of the transition metal and the non-transition metal obtained by EDS line analysis of a cross section of the gradient composition film.
  • the region A is a region containing the transition metal as the main component of the metal and the region containing the non-transition metal as the main component of the metal. It is preferable to have the inclined region in an intermediate region with respect to the B region.
  • the inclined region preferably further contains oxygen, and more preferably contains oxygen and nitrogen.
  • oxygen in the inclined region, a further gas barrier property improving effect can be obtained, and in particular, by containing oxygen and nitrogen, a remarkable gas barrier property improving effect can be obtained.
  • the non-transition metal is silicon because an effect of improving gas barrier properties and transparency can be obtained.
  • the transition metal is selected from niobium (Nb), tantalum (Ta), and vanadium (V) because the effects of improving gas barrier properties and improving high temperature and high humidity durability can be obtained.
  • the thickness of the inclined region is 5 nm or more because an effect of improving the gas barrier property can be obtained.
  • the gradient composition film of the present invention can be preferably provided in a gas barrier film.
  • the gas barrier film can be provided in an electronic device.
  • the electronic device may include an organic electroluminescence element.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the gradient composition film of the present invention is a gradient composition film containing a transition metal and a non-transition metal, and the detected intensity of the transition metal and the non-transition metal obtained by EDS line analysis of a cross section of the gradient composition film.
  • the detected intensity of the transition metal and the non-transition metal obtained by EDS line analysis of a cross section of the gradient composition film.
  • the gradient composition film is a gas barrier film having an inclined region in an intermediate region between the A region and the B region.
  • the gas barrier property of the gas barrier film comprising the gradient composition film of the present invention on the substrate is measured according to JIS K 7126 when measured with a gas barrier film having the gradient composition film formed on the resin substrate.
  • -Oxygen permeability measured by a method according to 1987 is 1 ⁇ 10 -3 cm 3 / (m 2 ⁇ 24h ⁇ atm) or less
  • water vapor permeability measured by a method according to JIS K 7129-1992 25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is preferably a high gas barrier property of 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) is 1 ⁇ 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less.
  • the layer thickness of the gas barrier layer is not particularly limited, but is preferably in the range of 5 to 1000 nm. If it is such a range, it will be excellent in high gas barrier performance, bending resistance, and cutting processability.
  • the gas barrier layer may be composed of two or more adjacent layers.
  • the “region” is a plane substantially perpendicular to the thickness direction of the gradient composition film (that is, a plane parallel to the outermost surface of the gradient composition film), and the gradient composition film has a constant or arbitrary thickness.
  • Constant means a compound constituting a specific region of the gradient composition film and a simple substance of metal or nonmetal.
  • Main component means a constituent component of the element having the highest detection intensity in the EDS line analysis applied to the present invention.
  • a region> The A region which is a transition metal-containing region refers to a region containing a transition metal as a main component of a metal.
  • the transition metal (M2) is not particularly limited, and any transition metal can be used alone or in combination.
  • the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and the transition metal includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y , Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta , W, Re, Os, Ir, Pt, and Au.
  • Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, and the like can be cited as transition metals (M2) that can provide good gas barrier properties.
  • M2 transition metals
  • Nb, Ta, and V, which are Group 5 elements, are likely to be bonded to the non-transition metal (M1) contained in the gradient composition film, and form a dense structure based on various examination results. Since it is considered easy, it can be preferably used.
  • the transition metal (M2) is a Group 5 element (particularly Nb) and the above-mentioned non-transition metal (M1) is Si, a significant gas barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 element (particularly Nb) is particularly likely to occur. Furthermore, from the viewpoint of optical properties, the transition metal (M2) is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.
  • the region A preferably further contains oxygen, and more preferably contains oxygen and nitrogen. Moreover, carbon and other elements may be contained.
  • Non-transition metal-containing region B region>
  • the B region which is a non-transition metal-containing region refers to a region containing a non-transition metal as a main component of a metal.
  • the non-transition metal is preferably a non-transition metal selected from Group 12 to Group 14 metals in the long-period periodic table.
  • the non-transition metal (M1) is not particularly limited, and any metal of Group 12 to Group 14 can be used alone or in combination. Examples thereof include Si, Al, Zn, In, and Sn. Can be mentioned. Especially, it is preferable that Si, Sn, or Zn is included as the non-transition metal (M1), Si is more preferable, and Si alone is particularly preferable.
  • the B region preferably further contains oxygen, and may further contain nitrogen or carbon. Moreover, you may contain other elements.
  • the B region preferably further contains oxygen, and particularly preferably contains oxygen and nitrogen. Moreover, carbon and other elements may be contained.
  • the gradient region is a transition metal and non-transition metal detection intensity obtained by EDS line analysis of the cross section of the gradient composition film, and the transition metal detection intensity increases when measured as a detection intensity curve that changes in the thickness direction. And the area
  • the thickness of the inclined region is preferably 5 nm or more from the viewpoint of obtaining good gas barrier properties, and within the range of 5 to 100 nm from the viewpoint of achieving both gas barrier properties and productivity. More preferably, it is more preferably in the range of 7 to 50 nm.
  • the inclined region preferably contains oxygen, and may further contain nitrogen or carbon. Moreover, you may contain other elements.
  • the gradient composition film having the above-described configuration exhibits a very high gas barrier property that can be applied as a gas barrier layer for an electronic device such as an organic EL element.
  • the gradient composition film of the present invention is a gradient composition film containing a transition metal and a non-transition metal, and the detected intensity of the transition metal and the non-transition metal obtained by EDS line analysis of a cross section of the gradient composition film.
  • EDS line analysis When measured as a detection intensity curve that changes in the thickness direction from the surface, there is a slope region in which the detection intensity of the transition metal increases and the detection intensity of the non-transition metal decreases.
  • EDS (Energy Dispersive X-ray Spectroscopy) line analysis has the feature that it can detect elements with high speed and high sensitivity with high accuracy.
  • a cross-sectional observation sample processed into a thin film having a thickness of about 60 nm by FIB processing is used as the sample.
  • the substrate on which the gradient composition film is formed it is preferable to use a sample in which the gradient composition film is formed on a highly rigid substrate.
  • an EDS line analysis of the sample cross section was performed using an atomic resolution analytical electron microscope: JEM-ARM200F (manufactured by JEOL) under the condition of acceleration voltage: 200.0 kV, and within the range including the gradient composition film of the gas barrier layer.
  • a detection intensity curve that changes in the thickness direction of the element is obtained.
  • the detection intensity curve is obtained by plotting the detection intensity of each element on the vertical axis and the distance in the thickness direction on the horizontal axis.
  • the interval between the measurement points in the thickness direction is preferably 2 nm or less.
  • a data obtained by removing a wavelength component having a wavelength of less than 5 nm from raw data of a measured detection intensity curve is used as a detection intensity curve.
  • Removal of wavelength components with a wavelength of less than 5 nm can be performed by using Fourier analysis (fast Fourier transform). Specifically, for example, calculation can be performed using Fourier analysis of an analysis tool which is a data analysis function of a commercially available spreadsheet software Excel (registered trademark) manufactured by Microsoft Corporation.
  • the element is detected in the thickness direction from the surface having a low transition metal content to the surface having a high transition metal content.
  • the increase or decrease of the detection intensity is performed in the detection intensity curve that has been subjected to the noise component removal process described above.
  • An increase or decrease means an increase exceeding a certain range, and a decrease means a decrease below the certain range.
  • the certain range refers to a region that continuously increases or decreases within a range of intensity of 20% or more with respect to the maximum detected intensity of each element.
  • FIG. 2A is a detection intensity curve before removing wavelength components of Si, Nb, and O having a wavelength of less than 5 nm plotted in the thickness direction
  • FIG. 2B is a detection intensity curve of removing wavelength components having a wavelength of less than 5 nm. is there.
  • the inclined region can be obtained as 13 nm as shown in FIG. 2B.
  • a gas barrier film By providing the gradient composition film of the present invention on a resin substrate, a gas barrier film can be obtained.
  • a resin substrate a general plastic film described later can be used.
  • the gradient composition film can be formed directly on the resin substrate. Moreover, after forming on inorganic base materials, such as glass, it can also peel-transfer on a plastic film, and can also form.
  • the plastic film used is not particularly limited in material, thickness and the like as long as it can hold an underlayer, a gas barrier layer, and the like, and can be appropriately selected according to the purpose of use.
  • Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide.
  • Resin Cellulose acylate resin, Polyurethane resin, Polyether ether ketone resin, Polycarbonate resin, Alicyclic polyolefin resin, Polyarylate resin, Polyether sulfone resin, Polysulfone resin, Cycloolefin copolymer, Fluorene ring modified polycarbonate resin, Alicyclic Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.
  • the thickness of the resin substrate is preferably about 5 to 500 ⁇ m, more preferably 15 to 250 ⁇ m.
  • transition metal (M2) examples include Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, and the like from the viewpoint of obtaining good gas barrier properties as described above.
  • Nb, Ta, and V which are Group 5 elements, can be preferably used because they are likely to be bonded to the non-transition metal (M1) contained in the gradient composition film.
  • the formation of the layer containing the transition metal (M2) is not particularly limited.
  • using a conventionally known vapor deposition method using an existing thin film deposition technique efficiently forms the inclined region. It is preferable from the viewpoint.
  • the vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assist vapor deposition, plasma CVD (chemical vapor deposition), and ALD. Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more.
  • the target application method is appropriately selected according to the target type, and any of DC (direct current) sputtering, DC pulse sputtering, AC sputtering, and RF (high frequency) sputtering may be used.
  • a reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used.
  • a metal oxide film can be formed at a high film formation speed, which is preferable.
  • the inert gas used for the process gas He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used.
  • oxygen, nitrogen, and carbon can be contained in the A region by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas.
  • the film formation conditions in the sputtering method include the degree of vacuum, magnetic force, applied power, discharge current, discharge voltage, process gas supply amount, time, and the like. These depend on the sputtering apparatus, film material, layer thickness, etc. It can be appropriately selected depending on the case.
  • the sputtering method may be multi-source simultaneous sputtering using a plurality of sputtering targets including a transition metal (M2) alone or its oxide.
  • a transition metal (M2) alone or its oxide.
  • the film forming conditions for carrying out the co-evaporation method include the ratio of the transition metal (M2) and oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas during the film forming, and the film forming process.
  • One or two or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation are exemplified, and these film formation conditions (preferably oxygen content)
  • the composition can be controlled by adjusting the pressure.
  • the method for forming the B region containing the non-transition metal (M1) is not particularly limited, and for example, a vapor deposition method can be used by a known method.
  • the vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assisted vapor deposition, plasma CVD (chemical vapor deposition), and ALD. Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method.
  • PVD physical vapor deposition
  • a method of forming by a wet coating method using a polysilazane-containing coating solution containing Si as a non-transition metal is also a preferable method.
  • the “polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond in the structure, and is composed of Si—N, Si—H, NH, etc., SiO 2 , Si 3 N 4 and intermediate solid solutions of both. It is a ceramic precursor inorganic polymer such as SiO x N y .
  • polysilazane polysilazane which is modified to silicon oxide, silicon nitride, and / or silicon oxynitride at a relatively low temperature as described in JP-A-8-112879 can be preferably used.
  • polysilazane those having the following structure are preferably used.
  • R 1 , R 2 and R 3 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.
  • R 1 , R 2 and R 3 may each be the same or different.
  • PHPS perhydropolysilazane
  • the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to the base substrate is improved and the polysilazane which is hard and brittle It is possible to impart toughness to the ceramic film produced by the above, and there is an advantage that generation of cracks can be suppressed even when the film thickness is increased.
  • these perhydropolysilazane and organopolysilazane may be selected as appropriate and may be used in combination.
  • Perhydropolysilazane is presumed to have a structure in which a linear structure and a ring structure centered on a 6- and / or 8-membered ring coexist.
  • the molecular weight of polysilazane is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and is a liquid or solid substance, and varies depending on the molecular weight.
  • polysilazane compounds are commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as a polysilazane compound-containing coating solution as it is.
  • polysilazanes that are ceramicized at a low temperature include silicon alkoxide-added polysilazanes obtained by reacting the above polysilazanes with silicon alkoxides (Japanese Patent Laid-Open No. 5-238827), and glycidol-added polysilazanes obtained by reacting glycidol (specially No. 6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (Japanese Patent Laid-Open No. 6-240208), and a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (Japanese Patent Laid-Open No. 6-299118). No.
  • acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (JP-A-7- 1969 6 No.), and the like.
  • Coating liquid containing polysilazane As an organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane.
  • organic solvents include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers. Can be used.
  • organic solvents such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran.
  • organic solvents may be selected according to the purpose such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed.
  • the concentration of polysilazane in the coating liquid containing polysilazane varies depending on the film thickness of the target first gas barrier layer and the pot life of the coating liquid, but is preferably about 0.2 to 35% by mass.
  • an amine or metal catalyst can be added to the coating liquid containing polysilazane in order to promote modification to silicon oxide, silicon nitride, and / or silicon oxynitride.
  • a polysilazane solution containing a catalyst such as NAX120-20, NN120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140 manufactured by AZ Electronic Materials Co., Ltd. as a commercial product is used. be able to.
  • these commercial items may be used independently and may be used in mixture of 2 or more types.
  • the addition amount of the catalyst is adjusted to 2% by mass or less with respect to polysilazane in order to avoid excessive silanol formation by the catalyst, decrease in film density, increase in film defects, and the like. It is preferable.
  • the coating liquid containing polysilazane can contain an inorganic precursor compound in addition to polysilazane.
  • the inorganic precursor compound other than polysilazane is not particularly limited as long as a coating liquid can be prepared.
  • compounds other than polysilazane described in paragraphs “0110” to “0114” of JP2011-143577A can be appropriately employed.
  • An organometallic compound of a metal element other than Si can be added to the coating liquid containing polysilazane.
  • an organometallic compound of a metal element other than Si By adding an organometallic compound of a metal element other than Si, the replacement of N atom and O atom of polysilazane is promoted in the coating and drying process, and the coating composition can be changed to a stable composition close to SiO 2 after drying. it can.
  • metal elements other than Si include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), Magnesium (Mg), tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), Examples include potassium (K), calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), and the like.
  • Al, B, Ti and Zr are preferable, and among them, an organometallic compound containing Al is preferable.
  • Examples of the aluminum compound applicable to the present invention include aluminum isopoloxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, aluminum tri-n- Examples include butyrate, aluminum tri-sec-butylate, aluminum ethyl acetoacetate / diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer, etc. be able to.
  • Specific commercial products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate / diisopropylate), ALCH-TR (aluminum trisethyl acetoate).
  • the temperature is preferably raised to 30 to 100 ° C. and maintained for 1 minute to 24 hours with stirring.
  • the content of the additive metal element in the polysilazane-containing layer constituting the gas barrier film according to the present invention is preferably 0.05 to 10 mol%, more preferably 100 mol% of silicon (Si). Is 0.5 to 5 mol%.
  • the ratio of the non-transition metal (M1) and oxygen in the deposition raw material, the ratio of the inert gas and the reactive gas during the deposition, Inclination by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation Regions can be formed.
  • a film forming raw material type (polysilazane type or the like) containing the non-transition metal (M1), a catalyst type, a catalyst content, a coating film thickness, and a drying temperature.
  • the inclined region can be formed by adjusting one or more conditions selected from the group consisting of time, reforming method, and reforming conditions.
  • the A region is formed by the above-described vapor deposition method
  • the ratio of the transition metal (M2) and oxygen in the deposition material for example, the ratio of the inert gas and the reactive gas during the deposition
  • An inclined region by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation Can be formed.
  • the formation conditions of the method for forming the A region and the B region can be appropriately adjusted and controlled.
  • a desired thickness can be obtained by controlling the deposition time.
  • the gradient composition film of the present invention is formed as a layer to be peeled through a peeling layer on a substrate such as glass as in the peeling method described in JP-A-2015-173249, and then the layer to be peeled is formed of a plastic. It can also be transferred to a film and function as a gas barrier film. Moreover, it can transfer to electronic devices, such as an organic electroluminescent (EL) element, and can also function as a sealing layer.
  • EL organic electroluminescent
  • Such a method of forming a gradient composition film makes it easy to manage the cleanliness of the process of forming a thin gas barrier layer or sealing layer in a light, thin, or flexible electronic device. It is preferable from the viewpoint of improving the yield.
  • the first step of forming a release layer on the substrate, the first layer in contact with the release layer on the release layer, and the release target including the gradient composition film of the present invention It is preferable to form the gradient composition film as a layer to be peeled by a peeling method having a second step of forming a layer and a third step of separating the peeling layer and the layer to be peeled.
  • a step of forming a starting point of peeling may be provided between the second step and the third step.
  • a peeling layer 103 with a thickness of less than 10 nm is formed over a manufacturing substrate 101, and then, as a second step, a layer to be peeled 105 is formed on the peeling layer 103 (FIG. 1A).
  • a layer to be peeled 105 is formed on the peeling layer 103 (FIG. 1A).
  • an example in which an island-shaped release layer is formed is shown, but the present invention is not limited thereto.
  • the layer to be peeled 105 may be formed in an island shape.
  • the layer to be peeled 105 when the layer to be peeled 105 is peeled from the manufacturing substrate 101, peeling occurs in the interface between the manufacturing substrate 101 and the peeling layer 103, the interface between the peeling layer 103 and the layer to be peeled 105, or the peeling layer 103.
  • Select material In this embodiment, the case where separation occurs at the interface between the separation layer 105 and the separation layer 103 is illustrated; however, the present invention is not limited to this depending on the combination of materials used for the separation layer 103 and the separation layer 105. Note that in the case where the layer to be peeled 105 has a stacked structure, a layer in contact with the peeling layer 103 is particularly referred to as a first layer.
  • the thickness of the peeling layer 103 is, for example, less than 10 nm, preferably 8 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less.
  • the thickness of the release layer 103 may be, for example, 0.1 nm or more, preferably 0.5 nm or more, more preferably 1 nm or more.
  • a thicker release layer 103 is preferable because a uniform film can be formed.
  • the thickness of the release layer 103 is preferably 1 nm or more and 8 nm or less. In this embodiment, a tungsten film with a thickness of 5 nm is used.
  • the thickness of the release layer 103 is desirably as described above over the entire layer.
  • the peeling layer 103 may have a region with the above thickness at least in part.
  • the release layer 103 may have a region with the above-described thickness in a region of 50% or more of the release layer, more preferably in a region of 90% or more of the release layer. That is, in one embodiment of the present invention, part of the peeling layer 103 may have a region with a thickness of less than 0.1 mm or a region with a thickness of 10 nm or more.
  • the manufacturing substrate 101 a substrate having heat resistance that can withstand at least a processing temperature in the manufacturing process is used.
  • a glass substrate, a quartz substrate, a sapphire substrate, a semiconductor substrate, a ceramic substrate, a metal substrate, a resin substrate, a plastic substrate, or the like can be used.
  • a large glass substrate is preferably used as the manufacturing substrate 101 in order to improve mass productivity.
  • the third generation 550 mm ⁇ 650 mm
  • the third generation 600 mm ⁇ 720 mm, or 620 mm ⁇ 750 mm
  • the fourth generation (680 mm ⁇ 880 mm, or 730 mm ⁇ 920 mm)
  • the fifth generation (1100 mm ⁇ 1300 mm
  • 6th generation (1500 mm ⁇ 1850 mm
  • 7th generation (1870 mm ⁇ 2200 mm
  • 8th generation (2200 mm ⁇ 2400 mm
  • 9th generation 2400 mm ⁇ 2800 mm, 2450 mm ⁇ 3050 mm
  • 10th generation 2950 mm ⁇ 3400 mm
  • a glass substrate or a glass substrate larger than this can be used.
  • an insulating film such as a silicon oxide film, a silicon oxynitride film, a silicon nitride film, or a silicon nitride oxide film is formed as a base film between the manufacturing substrate 101 and the separation layer 103. It is preferable because contamination from the glass substrate can be prevented.
  • the separation layer 103 includes an element selected from tungsten (W), molybdenum (Mo), titanium, tantalum, niobium, nickel, cobalt, zirconium, zinc, ruthenium, rhodium, palladium, osmium, iridium, and silicon, and the element.
  • An alloy material or a compound material containing the element can be used.
  • the crystal structure of the layer containing silicon may be any of amorphous, microcrystalline, and polycrystalline.
  • a metal oxide such as aluminum oxide, gallium oxide, zinc oxide, titanium dioxide, indium oxide, indium tin oxide, indium zinc oxide, or In—Ga—Zn oxide may be used. It is preferable to use a refractory metal material such as tungsten, titanium, or molybdenum for the separation layer 103 because the degree of freedom in the formation process of the separation layer 105 is increased.
  • the peeling layer 103 is formed by, for example, sputtering, CVD (Chemical Vapor Deposition) (plasma CVD, thermal CVD, MOCVD (Metal Organic CVD), etc.), ALD (Atomic Layer Deposition), coating (spin coating, (Including a droplet discharge method, a dispensing method, and the like), a printing method, a vapor deposition method, and the like.
  • CVD Chemical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • MOCVD Metal Organic CVD
  • ALD Atomic Layer Deposition
  • coating spin coating, (Including a droplet discharge method, a dispensing method, and the like), a printing method, a vapor deposition method, and the like.
  • the separation layer 103 has a single-layer structure, it is preferable to form a tungsten film, a molybdenum film, or a film containing a mixture of tungsten and molybdenum.
  • a film containing tungsten oxide or oxynitride, a film containing molybdenum oxide or oxynitride, or a film containing an oxide or oxynitride of a mixture of tungsten and molybdenum may be formed.
  • the mixture of tungsten and molybdenum corresponds to, for example, an alloy of tungsten and molybdenum.
  • the surface of a film containing tungsten is subjected to thermal oxidation treatment, oxygen plasma treatment, nitrous oxide (N 2 O) plasma treatment, treatment with a solution having strong oxidizing power such as ozone water, and the like to form tungsten oxide.
  • a containing film may be formed.
  • Plasma treatment and heat treatment may be performed in oxygen, nitrogen, nitrous oxide alone, or a mixed gas atmosphere of the gas and other gases.
  • tungsten film with a thickness of less than 10 nm by using a tungsten film with a thickness of less than 10 nm, it is possible to easily perform separation with a small separation force in the third step, so that the plasma treatment or the heat treatment is not performed. Good. This is preferable because it can simplify the peeling process and the manufacturing process of the apparatus.
  • a gas barrier layer including the gradient composition film of the present invention in contact with the peeling layer 103 is produced. Furthermore, a functional element may be fabricated on the gas barrier layer including the gradient composition film.
  • FIG. 1B corresponds to a cross-sectional view taken along the alternate long and short dash line A1-A2 in FIG. 1C.
  • 1C is a plan view seen from the substrate 109 (not shown) side.
  • the bonding layer 107 is preferably disposed so as to overlap with the peeling layer 103 and the peeled layer 105. 1B and 1C, the end portion of the bonding layer 107 is preferably not positioned outside the end portion of the release layer 103.
  • a starting point of peeling is formed by irradiation with laser light (step of forming a starting point of peeling) (FIGS. 1B and 1D).
  • the laser light is applied to a region where the cured bonding layer 107, the layer to be peeled 105, and the peeling layer 103 overlap (see arrow P1 in FIG. 1B).
  • the laser light may be irradiated from either side of the substrate, but it is preferable to irradiate from the side of the manufacturing substrate 101 provided with the release layer 103 in order to suppress the scattered light from being irradiated to the functional element or the like. .
  • a material that transmits the laser light is used for the substrate on the laser light irradiation side.
  • At least the first layer (the layer included in the layer to be peeled 105 and in contact with the peeling layer 103) is cracked (to cause film cracking or cracking), thereby removing a part of the first layer, A starting point can be formed (see the area enclosed by the dotted line in FIG. 1D).
  • the first layer not only the first layer but also other layers of the layer to be peeled 105, the peeling layer 103, and part of the bonding layer 107 may be removed.
  • the formation method of the starting point of peeling is not ask
  • the force for separating the layer to be peeled 105 and the peeling layer 103 is concentrated on the starting point of peeling, so that the starting point of peeling is formed near the end rather than the central part of the cured bonding layer 107.
  • a starting point of peeling in the form of a solid line or a broken line by continuously or intermittently irradiating a laser beam in the vicinity of the end of the bonding layer 107 because the peeling becomes easy.
  • laser used to form the starting point of peeling there is no particular limitation on the laser used to form the starting point of peeling.
  • a continuous wave laser or a pulsed laser can be used.
  • Laser light irradiation conditions frequencies, power density, energy density, beam profile, and the like are appropriately controlled in consideration of the thickness, material, and the like of the manufacturing substrate 101 and the separation layer 103.
  • the layer to be peeled 105 and the manufacturing substrate 101 are separated from the starting point of the peeling (FIGS. 1E and 1F).
  • the layer 105 to be peeled can be transferred from the manufacturing substrate 101 to the substrate 109.
  • the manufacturing substrate 101 may be fixed to an adsorption stage, and the layer to be peeled 105 may be peeled from the manufacturing substrate 101.
  • the substrate 109 may be fixed to the suction stage and the manufacturing substrate 101 may be peeled from the substrate 109.
  • the bonding layer 107 formed outside the separation starting point remains on at least one of the manufacturing substrate 101 and the substrate 109.
  • 1E and 1F show examples that remain on both sides, but the present invention is not limited to this.
  • the layer to be peeled 105 and the manufacturing substrate 101 may be separated from the starting point of peeling by a physical force (a process of peeling with a human hand or a jig, a process of separating while rotating a roller, or the like).
  • the manufacturing substrate 101 and the layer to be peeled 105 may be separated by infiltrating a liquid such as water into the interface between the peeling layer 103 and the layer to be peeled 105.
  • the liquid can be easily separated by permeating between the peeling layer 103 and the peeled layer 105 by capillary action.
  • static electricity generated at the time of peeling can be prevented from adversely affecting the functional elements included in the layer to be peeled 105 (such as a semiconductor element being destroyed by static electricity).
  • the liquid may be sprayed in the form of mist or steam.
  • pure water, an organic solvent, or the like can be used, and a neutral, alkaline, or acidic aqueous solution, an aqueous solution in which a salt is dissolved, or the like may be used.
  • the bonding layer 107 that does not contribute to adhesion between the layer to be peeled 105 and the substrate 109 remaining on the substrate 109 after the separation may be removed. By removing, it is possible to suppress adverse effects on the functional elements in the subsequent steps (mixing of impurities, etc.), which is preferable. For example, unnecessary resin can be removed by wiping, washing, or the like.
  • a peeling starting point is formed by laser light irradiation, and the peeling layer 103 and the layer to be peeled 105 are easily peeled, and then peeling is performed. Thereby, the yield of a peeling process can be improved.
  • the gas barrier film of the present invention exhibits excellent gas barrier properties and transparency, and is used for electronic devices such as photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various applications such as a barrier film and an electronic device using the same.
  • a gas barrier film having a gas barrier layer formed by the transfer method as described above also has excellent bending resistance. For this reason, it can be preferably used also for an electronic device imparted with bending resistance.
  • Examples of the electronic device body used in the electronic device of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. be able to. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.
  • organic EL element organic electroluminescence element
  • LCD liquid crystal display element
  • PV solar cell
  • An organic EL element that is a representative example of an electronic device to which the gradient composition film of the present invention is applied includes, for example, an anode, a first organic functional layer group, a light emitting layer, a second organic functional layer group, and a cathode on a transparent substrate. It is configured by stacking.
  • the first organic functional layer group includes, for example, a hole injection layer, a hole transport layer, an electron blocking layer, and the like
  • the second organic functional layer group includes, for example, a hole blocking layer, an electron transport layer, and an electron injection layer. Etc.
  • Each of the first organic functional layer group and the second organic functional layer group may be composed of only one layer, or the first organic functional layer group and the second organic functional layer group may not be provided.
  • Anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode ii) Anode / hole injection transport layer / light emitting layer / hole blocking layer / electron injection transport layer / cathode (iii) Anode / Hole injection transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron injection transport layer / Cathode (iv) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (v) Anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / Electron transport layer / electron injection layer / cathode (vi) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode
  • the element may have a non-light emitting intermediate layer.
  • Example 1 ⁇ Preparation of release layer-formed substrate >> A silicon oxynitride film having a thickness of about 200 nm was formed as a base film on a non-alkali glass plate (thickness 0.7 mm) having a size of 50 mm ⁇ 50 mm.
  • the silicon oxynitride film was formed by plasma CVD under the conditions of silane gas and N 2 O gas flow rates of 10 sccm and 1200 sccm, power supply power 30 W, pressure 22 Pa, and substrate temperature 330 ° C.
  • a tungsten film was formed as a release layer on the base film.
  • the thickness of the tungsten film was 30 nm.
  • the tungsten film was formed by sputtering under the conditions of an Ar gas flow rate of 100 sccm, a power supply power of 60 kW, a pressure of 2 Pa, and a substrate temperature of 100 ° C.
  • N 2 O plasma treatment nitrous oxide (N 2 O) plasma treatment was performed.
  • the flow rate of N 2 O gas was 100 sccm, source power 500 W, pressure 100 Pa, a substrate temperature of 330 ° C., was carried out under conditions of 240 seconds.
  • a film-forming time was set to a thickness of 150 nm on the release layer of the produced release layer-forming substrate by sputtering to form a silicon oxide layer as the first layer (B region).
  • a magnetron sputtering apparatus manufactured by Canon Anelva: Model EB1100
  • a commercially available polycrystalline silicon target was used as the target.
  • Film formation by RF method was performed using Ar and O 2 as process gases.
  • the sputtering power source power was 5.0 W / cm 2 and the film forming pressure was 0.4 Pa.
  • a film formation time was set on the silicon oxide layer so as to have a thickness of 30 nm, and a niobium oxide layer was formed.
  • a commercially available oxygen-deficient niobium oxide target (Nb 12 O 29 ) was used as the target.
  • the process gas used and Ar and O 2 the O 2 partial pressure of 12%, a film was formed by DC method.
  • the sputtering power source power was 5.0 W / cm 2 and the film forming pressure was 0.4 Pa. In this way, Sample 1 was obtained.
  • a dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) ))
  • a dibutyl ether solution (NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.) containing 20% by mass of perhydropolysilazane in a ratio of 4: 1 (mass ratio), and further for adjusting the dry film thickness Dilution with dibutyl ether prepared a coating solution having a solid content of 5% by mass.
  • a coating solution was applied by spin coating so as to have a dry film thickness shown in Table 1 below, and dried at 80 ° C. for 2 minutes.
  • vacuum ultraviolet irradiation treatment was performed on the dried coating film using a vacuum ultraviolet irradiation apparatus having an Xe excimer lamp having a wavelength of 172 nm under the condition that the irradiation energy was 5 J / cm 2 .
  • the irradiation atmosphere was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume.
  • the stage temperature for installing the sample was set to 80 ° C.
  • a niobium oxide layer was formed on the polysilazane-containing layer in the same manner as in Sample 1, except that the film formation time was set to be 20 nm. In this way, Sample 2 was obtained.
  • Sample 3 was obtained in the same manner as Sample 2, except that the vacuum ultraviolet irradiation treatment was not performed.
  • Sample 4 was obtained in the same manner as Sample 3, except that the coating solution containing polysilazane was changed as follows.
  • a dibutyl ether solution of 20% by mass of perhydropolysilazane manufactured by AZ Electronic Materials Co., Ltd., NAX120-20
  • a liquid A diluted so as to be 5% by mass was prepared. The coating solution was adjusted in a glove box.
  • an aluminum compound liquid B was prepared by diluting aluminum ethyl acetoacetate diisopropylate with dibutyl ether so that the solid content concentration was 5 mass%.
  • Si and aluminum compound liquid B are mixed so that the Al / Si atomic ratio is 0.01, heated to 80 ° C. while stirring, held at 80 ° C. for 2 hours, and then to room temperature (25 ° C.). Slowly cooled. In this way, a coating solution having a solid content of 5% by mass was prepared.
  • Sample 5 was obtained in the same manner as Sample 1, except that the niobium oxide layer was not formed and the film formation time was set so that the thickness of the silicon oxide layer was 200 nm.
  • Sample 6 was obtained in the same manner as Sample 3, except that the niobium oxide layer was not formed.
  • Sample 7 was obtained in the same manner as Sample 3, except that the niobium oxide layer was changed to a silicon oxide layer.
  • the film formation time of the silicon oxide layer was set according to the method for preparing Sample 1 so that the thickness of the silicon oxide layer was 20 nm.
  • the thickness of each layer was obtained in advance by obtaining a calibration curve of the sputtering time and the thickness of the layer to be formed, and adjusting the sputtering film forming time to form the film to the thickness of each layer. .
  • Sample 8 was obtained in the same manner as Sample 1, except that the silicon oxide layer was not formed and the film formation time was set so that the thickness of the niobium oxide layer was 100 nm.
  • ⁇ Detection intensity curve of gradient composition film> An extremely thin section (thickness: about 60 nm) of the gradient composition film (gas barrier layer) on the glass substrate prepared above was prepared, and an acceleration voltage: 200.0 kV using an atomic resolution analysis electron microscope: ARM200F (manufactured by JEOL). The EDS line analysis was conducted under the following conditions. The measurement was performed at intervals of 2 nm or less in the thickness direction with respect to the total film thickness.
  • the detection intensity of each element was obtained as a detection intensity curve of each element changing from the surface in the thickness direction.
  • FIGS. 2A to 5B The detection intensity curves of Samples 1 to 4 are shown in FIGS. 2A to 5B.
  • Each figure attached with A is data before data processing measured by the above method, and each figure attached with B is measured at intervals of 2 nm or less in the thickness direction with respect to the figure attached with A. And it is the detection intensity curve which removed the wavelength component less than wavelength 5nm. From FIGS. A to 5B, it can be seen that Samples 1 to 4 have an inclined region of 5 nm or more. Although not shown in the figure, Samples 5 to 8 had no inclined region.
  • the surface of the second layer shows a portion where an inclined region exists in the measurement example at the left end in the figure. Also, the oxygen intensity in each figure marked with B is omitted.
  • Table 1 shows the above results and the composition of each sample.
  • thermosetting sheet-like adhesive epoxy resin
  • release film on both sides as a sealing resin layer
  • the glass plate on which the layer to be peeled of each sample including the prepared gradient composition film is formed is put in a glove box, and the Ca vapor-deposited surface of the Ca vapor-deposited glass plate and the sample to be peeled off using a vacuum laminating apparatus.
  • the laminate was bonded with a sheet-like adhesive from which the release film was removed so that the layers were opposed to each other. At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the Ca vapor-deposited glass plate down, and cured for 30 minutes.
  • the layer to be peeled including the gradient composition film was peeled off. Specifically, laser light was irradiated from the side of the glass plate on which the layer to be peeled was formed to form a starting point of peeling, and peeling was performed after the peeling layer and the layer to be peeled were easily peeled.
  • a 50 ⁇ m thick polyethylene terephthalate film (manufactured by Toray Industries Inc., Lumirror (registered trademark) (U403)) is used as a protective film on the surface of the layer to be peeled, and a 25 ⁇ m thick transparent adhesive sheet manufactured by Nitto Denko Corporation is used.
  • a 50 ⁇ m thick polyethylene terephthalate film manufactured by Toray Industries Inc., Lumirror (registered trademark) (U403)
  • a 25 ⁇ m thick transparent adhesive sheet manufactured by Nitto Denko Corporation
  • the gas barrier film provided with the gradient composition films 1 to 4 of the present invention has a very excellent gas barrier property that can be applied as a substrate of an organic electroluminescence element or a sealing film. I understand that. In particular, it can be seen that the gas barrier film having the gradient composition films 2 to 4 containing oxygen and nitrogen in the inclined region has remarkably excellent gas barrier properties.
  • the gradient composition film of the present invention has a high gas barrier property, and can be suitably applied to a gas barrier film and an electronic device having the gas barrier film.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Electroluminescent Light Sources (AREA)
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Abstract

L'invention vise à procurer un film à composition à gradient ayant des propriétés de barrière contre les gaz élevées, et un film de barrière contre les gaz et un dispositif électronique le comportant. À cet effet, l'invention porte sur un film à composition à gradient, lequel film comprend un métal de transition et un métal de non-transition, et lequel film à composition à gradient est caractérisé en ce qu'il a une région de gradient dans laquelle, quand les intensités détectées du métal de transition et du métal de non-transition, obtenues par analyse de ligne par spectroscopie à dispersion d'énergie de la section transversale du film à composition à gradient, sont mesurées sous la forme d'une courbe d'intensité détectée qui change à partir de la surface dans la direction de l'épaisseur, l'intensité détectée du métal de transition augmente et l'intensité détectée du métal de non-transition diminue.
PCT/JP2016/084582 2015-11-24 2016-11-22 Film à composition à gradient, et film de barrière contre les gaz et dispositif électronique le comprenant WO2017090599A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002004376A1 (fr) * 2000-07-12 2002-01-17 Nippon Sheet Glass Co., Ltd. Element photocatalytique
JP2005035128A (ja) * 2003-07-18 2005-02-10 Sumitomo Bakelite Co Ltd 透明ガスバリアフィルムおよびそれを用いた表示装置
JP2008275737A (ja) * 2007-04-26 2008-11-13 Toppan Printing Co Ltd 光学薄膜積層体
JP2016175372A (ja) * 2015-03-23 2016-10-06 コニカミノルタ株式会社 ガスバリア性フィルム

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002004376A1 (fr) * 2000-07-12 2002-01-17 Nippon Sheet Glass Co., Ltd. Element photocatalytique
JP2005035128A (ja) * 2003-07-18 2005-02-10 Sumitomo Bakelite Co Ltd 透明ガスバリアフィルムおよびそれを用いた表示装置
JP2008275737A (ja) * 2007-04-26 2008-11-13 Toppan Printing Co Ltd 光学薄膜積層体
JP2016175372A (ja) * 2015-03-23 2016-10-06 コニカミノルタ株式会社 ガスバリア性フィルム

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