WO2019230682A1 - Dispositif électronique et son procédé de production - Google Patents

Dispositif électronique et son procédé de production Download PDF

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Publication number
WO2019230682A1
WO2019230682A1 PCT/JP2019/021001 JP2019021001W WO2019230682A1 WO 2019230682 A1 WO2019230682 A1 WO 2019230682A1 JP 2019021001 W JP2019021001 W JP 2019021001W WO 2019230682 A1 WO2019230682 A1 WO 2019230682A1
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layer
group
electronic device
organic
intermediate layer
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PCT/JP2019/021001
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English (en)
Japanese (ja)
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幸宏 牧島
井　宏元
宏 石代
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コニカミノルタ株式会社
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Priority to CN201980036162.1A priority Critical patent/CN112205076A/zh
Priority to JP2020522195A priority patent/JPWO2019230682A1/ja
Publication of WO2019230682A1 publication Critical patent/WO2019230682A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • 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
    • 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
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • 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 an electronic device and a manufacturing method thereof. More specifically, an electronic device comprising at least an organic functional layer and a sealing layer, wherein penetration of the solvent used in forming the sealing layer into the organic functional layer is suppressed, and the organic functional layer and the sealing layer
  • the present invention relates to an electronic device having excellent adhesion and a method for manufacturing the same.
  • organic electroluminescence elements hereinafter referred to as organic EL elements
  • solar cells using organic photoelectric conversion elements and organic thin-film transistors
  • organic thin-film transistors are made flexible by curved smartphones and next-generation lighting and signage that can be made free-form. It has become a very important theme for the spread of solar cells and thin-film transistors that are popular, lightweight and excellent in processability.
  • a sealing technique for protecting an organic EL element from moisture and oxygen in the outside air can be said to be a liver technique for producing an organic EL element. Unlike methods such as can sealing, the technical difficulty is high.
  • a sealing technique a gas barrier film, a metal foil, or the like in which a dense inorganic layer is formed on a base material by a CVD (Chemical Vapor Deposition) method is attached to an organic functional layer of an organic EL element using an adhesive.
  • CVD Chemical Vapor Deposition
  • the CVD method and the pasting operation have various problems such as high equipment / material costs, poor productivity, unsuitable for mass ordering, and cannot change specifications, performance, Cost and productivity could not be satisfied.
  • PHPS perhydropolysilazane
  • Patent Documents 1 to 3 a method of directly applying perhydropolysilazane (hereinafter referred to as PHPS), which is a silicon compound, onto an organic EL element.
  • PHPS perhydropolysilazane
  • the solvent penetrates into the organic EL element and the organic functional layer is destroyed, so that there is a problem that a light emitting functional failure (for example, a dark spot) of the organic EL element occurs. .
  • Patent Document 4 discloses a technique for forming a sealing layer made of an inorganic oxide on an organic EL element by coating film formation and a technique for an elution preventing layer for preventing solvent penetration into the organic EL element at the time of coating. Yes. However, the patent document does not disclose a specific embodiment using the elution prevention layer, and it is estimated from the materials used for the sealing layer and the elution prevention layer. It is thought that it is inferior to adhesiveness.
  • the present invention has been made in view of the above-described problems and circumstances, and a solution to the problem is an electronic device including at least an organic functional layer and a sealing layer, and an organic function of a solvent used when the sealing layer is formed It is an object of the present invention to provide an electronic device in which penetration into a layer is suppressed, a light emitting functional disorder (for example, a dark spot) is prevented, and excellent adhesion between an organic functional layer and a sealing layer, and a method for manufacturing the electronic device.
  • a light emitting functional disorder for example, a dark spot
  • the present inventor is an electronic device including at least an organic functional layer and a sealing layer in the process of examining the cause of the above-described problem, and the sealing layer includes polysilazane and its modification. And an intermediate layer containing a specific polymer is disposed between the organic functional layer and the sealing layer, so that the solvent penetrates into the electronic device when the sealing layer is formed. It has been found that an electronic device and a method for producing the same can be obtained in which adhesion is suppressed and adhesion between the electronic device and the sealing layer is excellent.
  • An electronic device comprising at least an organic functional layer and a sealing layer,
  • the sealing layer contains polysilazane and a modified product thereof, and an intermediate layer containing a light or thermosetting polymer is disposed between the organic functional layer and the sealing layer.
  • electronic devices comprising at least an organic functional layer and a sealing layer,
  • the sealing layer contains polysilazane and a modified product thereof, and an intermediate layer containing a light or thermosetting polymer is disposed between the organic functional layer and the sealing layer.
  • the intermediate layer contains a siloxane resin, an acrylic resin, or an epoxy resin.
  • a contact angle with respect to pure water at a temperature of 23 ° C. is within a range of 20 to 100 ° on the surface of the modified layer on the sealing layer side.
  • Item 7 The electronic device according to Item 5 or 6, wherein the thickness of the modified layer is in the range of 1 to 70 nm.
  • the organic metal oxide layer containing an organic metal oxide having a structure represented by the following general formula (A) is provided between the intermediate layer and the sealing layer.
  • the electronic device according to any one of the items up to.
  • R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group.
  • R represents fluorine as a substituent. It may be a carbon chain containing atoms, M represents a metal atom, OR 1 represents a fluorinated alkoxy group, x represents a valence of the metal atom, and y represents an arbitrary integer between 1 and x. Represents the degree of polycondensation.
  • the metal atom represented by M is selected from Si, Ti, Zr, Mg, Ca, Sr, Bi, Hf, Nb, Zn, Al, Pt, Ag, and Au.
  • Item 10 The electronic device according to Item 8 or 9, wherein the organometallic oxide layer is formed of a coating film subjected to at least sol-gel transition.
  • a modified layer is formed on the surface of the intermediate layer by a process of performing ultraviolet irradiation treatment, flash baking treatment, atmospheric pressure plasma treatment, plasma ion implantation treatment, or heat treatment on the intermediate layer, and 14.
  • Item 15 The method for manufacturing an electronic device according to Item 13 or 14, wherein the intermediate layer is formed by an inkjet printing method.
  • Item 16 The method for manufacturing an electronic device according to any one of Items 13 to 15, wherein the sealing layer is formed by an inkjet printing method, and then vacuum ultraviolet irradiation treatment is performed.
  • an electronic device having at least an organic functional layer and a sealing layer, the penetration of the solvent used at the time of forming the sealing layer into the organic functional layer is suppressed, and the light emitting functional disorder (for example, dark).
  • the light emitting functional disorder for example, dark It is possible to provide an electronic device that can prevent (spot) and has excellent adhesion between the organic functional layer and the sealing layer, and a method for manufacturing the electronic device.
  • the present invention includes laminating an intermediate layer containing a light or thermosetting polymer on an organic functional layer, a sealing layer containing polysilazane and a modified product thereof, and the intermediate layer is a siloxane-based resin. Containing an upper polysilazane and a modified product thereof by modifying the surface of the intermediate layer by ultraviolet irradiation treatment, flash firing treatment, atmospheric pressure plasma treatment, plasma ion implantation treatment, heat treatment, or the like.
  • the sealing layer that has the same type of modified body greatly improves the adhesion, and the dense modified body can exhibit an excellent effect of preventing solvent penetration from the sealing layer It is. With these effects, it is possible to completely prevent damage to the organic functional layer due to solvent permeation during the formation of the sealing layer and provide an electronic device having strong adhesion between the organic functional layer and the sealing layer. It is guessed.
  • FIG. 1 Schematic diagram showing the configuration of the electronic device of the present invention (organic EL element specification) Schematic showing an example of an ink jet printing system that is an example of a wet forming system
  • Example of inkjet head structure applicable to inkjet printing system Bottom view of inkjet head Sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element of a bulk heterojunction type Sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem type bulk heterojunction layer
  • the figure which shows the structural example of a structure of an organic thin-film transistor The figure which shows another structural example of a structure of an organic thin-film transistor
  • the figure which shows another structural example of a structure of an organic thin-film transistor The figure which shows another structural example of a structure of an organic thin-film transistor
  • the figure which shows another structural example of a structure of an organic thin-film transistor The figure which shows another structural example of a structure of an organic thin-film transistor
  • the electronic device of the present invention is an electronic device having at least an organic functional layer and a sealing layer, the sealing layer containing polysilazane and a modified body thereof, and the organic functional layer and the sealing An intermediate layer containing a light or thermosetting polymer is disposed between the layers.
  • a feature of the present invention is a laminated sealing technique of an intermediate layer capable of preventing permeation of a solvent from PHPS by a coating process, and a sealing layer containing PHPS and a modified body thereof. Since this method does not use the conventional CVD or bonding operation, the reduction in apparatus / material costs and productivity are significantly improved.
  • the coating method for example, from organic EL element production to sealing is consistently applied
  • the delivery time can be much shorter than before.
  • the use efficiency of the material can be improved and the electronic device can be made free-form.
  • the light or thermosetting polymer is a solvent-free polymer, so that there is no permeation of the solvent from the intermediate layer to the organic functional layer. From the viewpoint of suppressing damage to the organic functional layer, it is preferable.
  • the intermediate layer contains a siloxane-based resin, an acrylic resin, or an epoxy-based resin, and particularly contains a siloxane-based resin, so that the adhesion with the sealing layer containing PHPS and its modified body is improved. From the viewpoint of improvement, it is preferable.
  • a modified layer on the sealing layer side surface of the intermediate layer of the present invention from the viewpoint of preventing penetration of the solvent of PHPS, and water at a temperature of 23 ° C. on the sealing layer side surface of the modified layer. It is a preferred embodiment that the contact angle with respect to is in the range of 20 to 100 °, since this effect is more manifested. Further, it is preferable that the thickness of the modified layer is in the range of 1 to 70 nm from the viewpoint of preventing the penetration of the solvent and improving the adhesion between the intermediate layer and the sealing layer.
  • an organometallic oxide layer having an equivalent function may be disposed as an alternative to the modified layer according to the present invention.
  • it is preferably an organometallic oxide layer containing an organometallic oxide having a structure represented by the general formula (A), and a coating film is formed by a sol-gel method.
  • the layer is preferably a metal alkoxide in which the organometallic oxide is coordinate-substituted with hydroalcohol.
  • Metal alkoxide not only promotes reforming and improves adhesion during lamination due to the catalytic effect on the intermediate layer and sealing layer, but also has atmospheric stability characteristics by being coordinated with fluorinated alcohol. Therefore, it is preferable because of excellent production suitability.
  • a gas barrier film is further bonded onto the sealing layer via an adhesive.
  • the electronic device of the present invention is a preferred embodiment, which is an organic electroluminescence element, a solar cell using an organic photoelectric conversion element, or an organic thin film transistor. .
  • An electronic device manufacturing method for manufacturing an electronic device of the present invention includes a step of forming the intermediate layer on an organic functional layer, an ultraviolet irradiation treatment, flash firing treatment, atmospheric pressure plasma treatment, plasma ion implantation treatment on the intermediate layer, Alternatively, the method includes a step of performing a heat treatment and a step of stacking and forming the sealing layer on the intermediate layer.
  • a modified layer is formed on the surface of the intermediate layer by a step of performing ultraviolet irradiation treatment, flash firing treatment, atmospheric pressure plasma treatment, plasma ion implantation treatment, or heat treatment on the intermediate layer, and the modified layer Setting the contact angle to water at a temperature of 23 ° C. within the range of 20 to 100 ° on the surface suppresses permeation of the solvent into the organic functional layer during the formation of the sealing layer, and the organic functional layer and the sealing layer From the viewpoint of providing an electronic device having excellent adhesion and stress relaxation properties, it is a preferable production method.
  • Examples of means for generating ultraviolet rays include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV light lasers.
  • the intermediate layer can be formed by an inkjet printing method and a dispenser method, so that it is possible to shorten the delivery time and selectively seal only a portion where light emission is desired.
  • This is a preferable manufacturing method from the viewpoint of adapting electronic devices to freeform.
  • the inkjet printing method is particularly preferable in that a precise coating pattern can be drawn.
  • sealing layer by an inkjet printing method and a dispenser method, and then performing a vacuum ultraviolet irradiation treatment has a dense silicon-containing layer and forms a sealing layer having high barrier properties Therefore, this is a preferred production method.
  • ⁇ 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 electronic device of the present invention is an electronic device having at least an organic functional layer and a sealing layer, the sealing layer containing polysilazane and a modified body thereof, and the organic functional layer and the sealing An intermediate layer containing a light or thermosetting polymer is disposed between the layers.
  • the “light or thermosetting polymer” in the present invention is a layer formed by polymerization or crosslinking of a polymerizable monomer or polymerizable oligomer, or a polymerizable polymer by light such as ultraviolet rays or heating.
  • a polymer is a layer formed by polymerization or crosslinking of a polymerizable monomer or polymerizable oligomer, or a polymerizable polymer by light such as ultraviolet rays or heating.
  • FIG. 1 is a schematic diagram showing a configuration of an electronic device of the present invention.
  • the structure is shown about the example applied to an organic EL element (organic EL element) as an example of the electronic device of this invention.
  • organic EL element organic EL element
  • this is an example, and the present invention is not limited to this.
  • a gas barrier layer 1 is formed on the surface of a flexible substrate F, and a first electrode: an anode 2, an organic functional layer group 3 including a light emitting layer, and a second electrode: a cathode 4 are stacked thereon.
  • the peripheral part of the body is sealed with the intermediate layer 5 and the sealing layer 6 according to the present invention to constitute the organic EL element EL.
  • other functional layers may be appropriately disposed between the respective layers, and a gas barrier film may be laminated on the sealing layer 6) via an adhesive.
  • each element of the organic EL element will be described as an example of the electronic device of the present invention along the configuration.
  • Organic EL element there are no particular limitations on the substrate that can be used for the organic EL element (hereinafter also referred to as a base, support substrate, base material, support, etc.), and a glass substrate, a plastic substrate, or the like is used. It may be transparent or opaque, but a plastic substrate is preferred from the viewpoint of flexibility.
  • a resin film used as a base material of a plastic substrate For example, polyesters, such as a polyethylene terephthalate (PET) and a polyethylene naphthalate (PEN), or a polyimide (PI) etc. can be mentioned.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PI polyimide
  • a gas barrier film on which a gas barrier layer (also referred to as a “water vapor sealing layer”) that suppresses intrusion of water vapor, oxygen, or the like is provided on the resin film.
  • a gas barrier layer also referred to as a “water vapor sealing layer”
  • the material constituting the gas barrier layer is not particularly limited, and a film such as an inorganic film, an organic film, or a hybrid of both may be formed.
  • the gas barrier layer has a water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by a method according to JIS K 7129-1992, 0.01 g / (m 2 ⁇ 24h)
  • the following gas barrier film is preferable, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 ⁇ 10 ⁇ 3 mL / (m 2 ⁇ 24h ⁇ atm).
  • a high gas barrier film having a water vapor permeability of 1 ⁇ 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less is preferable.
  • the material constituting the gas barrier layer is not particularly limited as long as it is a material having a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • a material having a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen.
  • Inorganic materials, organic materials, hybrid materials of the both, or the like can be used.
  • Metal oxide, metal oxynitride or metal nitride includes silicon oxide, titanium oxide, indium oxide, tin oxide, metal oxide such as indium tin oxide (ITO), aluminum oxide, metal nitride such as silicon nitride And metal oxynitrides such as silicon oxynitride and titanium oxynitride.
  • the formation of the gas barrier layer is not particularly limited.
  • an inorganic material is sputtered (for example, magnetron cathode sputtering, flat plate magnetron sputtering, bipolar) AC flat plate magnetron sputtering, reactive AC sputtering, etc.), vapor deposition (for example, resistance heating vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma assisted vapor deposition), thermal CVD method, catalyst Layers by chemical vapor deposition (Cat-CVD), capacitively coupled plasma CVD (CCP-CVD), photo-CVD, plasma CVD (PE-CVD), epitaxial growth, chemical vapor deposition such as atomic layer deposition, etc. Preferably formed.
  • an inorganic gas barrier layer is formed.
  • the inorganic gas barrier layer can also be formed by a metallization technique such as metal plating on a resin base material or adhesion of a metal foil and a resin base material.
  • the inorganic gas barrier layer may include an organic layer containing an organic polymer. That is, the inorganic gas barrier layer may be a laminate of an inorganic layer containing an inorganic material and an organic layer.
  • the organic layer can be polymerized using, for example, an electron beam device, a UV light source, a discharge device, or other suitable device, for example, by applying an organic monomer or oligomer to a resin substrate to form a layer. And it can form by bridge
  • Examples of the method for applying the organic monomer or organic oligomer include roll coating (for example, gravure roll coating) and spray coating (for example, electrostatic spray coating).
  • bonding the gas barrier film having the gas barrier layer on the sealing layer according to the present invention via an adhesive is a preferable embodiment from the viewpoint of further improving the sealing effect. is there.
  • the adhesive examples include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. Can do. Moreover, heat
  • the organic functional layer in the present invention includes a light emitting layer, various charge transport layers, and the like.
  • Intermediate layer is characterized in that an intermediate layer containing a light or thermosetting polymer is disposed between the organic functional layer and the sealing layer.
  • the light or thermosetting polymer is preferably a solventless polymer.
  • the “solvent-free polymer” as used herein refers to a polymer that does not contain a solvent, and is preferably liquid from the viewpoint of processability. Since it is a solvent-free type, deterioration due to permeation of the solvent from the intermediate layer can be suppressed with respect to the organic functional layer located in the lower layer when forming the intermediate layer.
  • the intermediate layer preferably contains a siloxane resin, an acrylic resin, or an epoxy resin, and particularly preferably contains a siloxane resin.
  • the intermediate layer may be formed by vapor deposition of an organic material insoluble in a solvent or the like, but is preferably formed by coating.
  • a material to be formed by coating it is preferable to use a photocurable or thermosetting solventless monomer, and a solventless photocurable silicone monomer is particularly preferable.
  • a solid thin film is formed by photocuring and / or heat curing to form an intermediate layer.
  • a getter agent that absorbs moisture and oxygen may be mixed.
  • the intermediate layer is formed between the electrode according to the present invention and the sealing layer with the solvent-free monomer liquid or the coating liquid with a partly diluted solvent added for viscosity adjustment, but the formation method is particularly limited. Not a spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating method, bar coating method, die coating method, dispensing method, printing method including inkjet printing method, etc. It is preferable to apply by a wet forming method such as a patterning method. Among these, the inkjet printing method described later is preferable.
  • the thickness of the intermediate layer is 10 nm to 100 ⁇ m, more preferably 0.1 to 1 ⁇ m, as a dry film, and it is effective for stress relaxation, solvent penetration prevention from the sealing layer, and flatness. It is preferable in expressing.
  • the acrylic resin contained in the intermediate layer is preferably a polymer of a (meth) acrylic acid ester monomer, and examples of the (meth) acrylic acid ester monomer Acrylate monomers such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, and phenyl acrylate; Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexylme Acrylate, stearyl methacryl
  • the epoxy resin contained in the intermediate layer includes bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; alicyclic epoxy resins; phenol novolac type epoxy resins, cresol novolac type epoxy resins and the like.
  • Novolac type epoxy resin triphenolalkane type epoxy resin such as triphenolmethane type epoxy resin and triphenolpropane type epoxy resin
  • phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, stilbene type epoxy resin, naphthalene type epoxy resin, biphenyl Type epoxy resin, cyclopentadiene type epoxy resin and the like it is preferable to use a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin from the viewpoint of expressing the effects of the present invention.
  • the intermediate layer according to the present invention preferably contains a siloxane-based resin from the viewpoint of adhesion between the polysilazane contained in the sealing layer and its modified body, in addition to the expression of the solvent penetration preventing function.
  • a siloxane-based resin polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, or the like can be used.
  • a siloxane containing a fluorine atom can also be suitably used.
  • the siloxane-based resin used for the intermediate layer according to the present invention may be a low molecular weight material or a high molecular weight material. Particularly preferred are oligomers and polymers, and specific examples include polysiloxane derivatives such as polysiloxane compounds, polydimethylsiloxane compounds, and polydimethylsiloxane copolymers. Moreover, what combined these compounds may be used.
  • the compound having a polysiloxane skeleton has a structure represented by the following general formula (I), and changes the number of repetitions n (one or more) in the general formula (I) and the type of the organic modification part. Therefore, the effect of preventing solvent penetration can be arbitrarily controlled.
  • n or the organically modified part in the general formula (I) for example, a structure represented by the following general formula (II) (x and y are one or more numbers representing the number of repetitions, m is An integer of 1 or more), and the silicone skeleton can be modified by adding a side chain.
  • R ⁇ 1 > in general formula (II) a methyl group, an ethyl group, a decyl group etc. are mentioned, for example.
  • R 2 include a polyether group, a polyester group, and an aralkyl group.
  • a compound having a structure represented by the following general formula (III) (m is an integer of 1 or more) can also be used, and the silicone chain is composed of several Si—O bonds and corresponds to R 3 . It has an average of one polyether chain and the like.
  • control of the contact angle with water and compatibility with the formation of the modified layer Can be arbitrarily adjusted.
  • polysiloxane compounds examples include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -glycid.
  • a partially hydrolyzed product of a silane compound having a group, an organosilica sol in which fine particles of silicic anhydride are stably dispersed in an organic solvent, or the above-mentioned silane compound having radical polymerizability added to the organosilica sol Can be mentioned.
  • Polydimethylsiloxane compound Polydimethylsiloxane compounds include polydimethylsiloxane, alkyl-modified polydimethylsiloxane, carboxy-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, fluorine-modified polydimethylsiloxane, and (meth) acrylate-modified polydimethylsiloxane. (For example, GUV-235 manufactured by Toagosei Co., Ltd.).
  • the polydimethylsiloxane copolymer may be any of a block copolymer, a graft copolymer, and a random copolymer, but a block copolymer and a graft copolymer are preferable.
  • the intermediate layer according to the present invention is a step of performing ultraviolet irradiation treatment, flash firing treatment, atmospheric pressure plasma treatment, plasma ion implantation treatment, or heat treatment on the surface of the sealing layer after wet coating by an inkjet printing method or the like described later.
  • a known method can be used as a method for measuring the contact angle.
  • the contact angle between a standard liquid (pure water is preferred) and the substrate surface was measured in accordance with a method defined in JIS R3257.
  • the measurement conditions are a temperature of 23 ⁇ 5 ° C., a humidity of 50 ⁇ 10%, a drop amount of standard liquid dropped from 1 to 4 ⁇ L, and a time from dropping the standard liquid to measuring the contact angle is within 1 minute.
  • a specific operation procedure at a temperature of 23 ° C., about 1.5 ⁇ L of pure water as the standard liquid was dropped on the sample, and the sample was obtained using a solid-liquid interface analyzer (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.). Measure the above five locations and obtain the average contact angle from the average of the measured values. The time to contact angle measurement is measured within 1 minute after dropping the standard liquid.
  • the layer thickness of the modified layer is preferably in the range of 1 to 70 nm in order to exhibit the effects of stress relaxation, solvent penetration prevention from the sealing layer, and planarization.
  • a more preferable layer thickness is in the range of 10 to 50 nm.
  • the modification treatment of the intermediate layer in the present invention refers to a reaction for converting at least a part of the siloxane-based resin into silicon oxide, and the “modified layer” is an average of the carbon component ratio of the unmodified layer.
  • the layer thickness of the modified layer can be determined by elemental analysis in the layer thickness direction by the following XPS analysis method.
  • the XPS analysis method referred to here is a method of analyzing the constituent elements of the sample and their electronic states by irradiating the sample with X-rays and measuring the energy of the generated photoelectrons.
  • the element concentration distribution curve (hereinafter referred to as “depth profile”) in the thickness direction of the intermediate layer according to the present invention is an element concentration of silicon, oxygen, and carbon, measured by X-ray photoelectron spectroscopy, argon (Ar), etc.
  • the surface composition analysis can be performed sequentially while exposing the inside from the surface of the intermediate layer.
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic concentration ratio (unit: at%) of the element and the horizontal axis as the etching time (sputtering time).
  • the etching time generally correlates with the distance from the surface of the intermediate layer in the thickness direction of the intermediate layer in the layer thickness direction.
  • the distance from the surface of the intermediate layer in the thickness direction of the layer the distance from the surface of the intermediate layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement can be adopted. .
  • a rare gas ion sputtering method using argon (Ar) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / sec. It is preferable to use (equivalent value of SiO 2 thermal oxide film).
  • ⁇ Analyzer QUANTERA SXM manufactured by ULVAC-PHI
  • X-ray source Monochromatic Al-K ⁇ ⁇ Sputtering ion: Ar (3 keV)
  • Depth profile Repeated measurement at a predetermined thickness interval with a SiO 2 equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).
  • Quantification The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Data processing uses MultiPak manufactured by ULVAC-PHI.
  • a preferable method for modifying the surface of the intermediate layer according to the present invention is an ultraviolet irradiation treatment.
  • a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, an excimer lamp, or a UV light laser can be used as the ultraviolet ray generating means.
  • vacuum ultraviolet irradiation treatment is mentioned as one method of the said ultraviolet irradiation processing.
  • the illumination intensity of the vacuum ultraviolet rays in the coated surface of a siloxane-based resin film is subjected in the range of 30 ⁇ 200mW / cm 2, in the range of 50 ⁇ 160mW / cm 2 More preferred.
  • it is 30 mW / cm 2 or more there is no concern that the reforming efficiency is lowered, and when it is 200 mW / cm 2 or less, the coating film is not ablated and the substrate is not damaged.
  • Irradiation energy amount of the VUV in siloxane-based resin layer coated surface is preferably in the range of 200 ⁇ 10000mJ / cm 2, and more preferably in the range of 500 ⁇ 5000mJ / cm 2. Within this range, there are no cracks or thermal deformation of the substrate.
  • oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a low state. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably in the range of 0.001 to 2.0% by volume, more preferably in the range of 0.005 to 0.5% by volume, and still more preferably 0.1 to 0%. .5% by volume.
  • the gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably dry nitrogen gas from the viewpoint of cost.
  • the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.
  • the intermediate layer containing a siloxane resin or the like may be a single layer, but may have a laminated structure of two or more layers from the viewpoint of enhancing the effect.
  • a laminated structure for example, a laminated structure having different types of silicon-containing polymers such as polysiloxane / polysilazane may be used. By changing the type, it is possible to control adhesion in addition to the solvent penetration preventing function.
  • the modification process of the intermediate layer can also be performed by a xenon flash process (flash firing process) using a xenon lamp.
  • a xenon flash process flash firing process
  • a discharge tube of the flash lamp used in the flash firing process a discharge tube of xenon, helium, neon, argon or the like can be used, but a xenon lamp is preferably used.
  • the preferable spectral band of the flash lamp is preferably in the range of 240 to 2000 nm. Within this range, there is little damage such as thermal deformation of the substrate due to flash firing.
  • the light irradiation conditions of the flash lamp are arbitrary, but the total light irradiation energy is preferably in the range of 0.1 to 50 J / cm 2 , and preferably in the range of 0.5 to 10 J / cm 2. More preferred.
  • the light irradiation time is preferably in the range of 10 ⁇ sec to 100 msec, and more preferably in the range of 100 ⁇ sec to 10 msec. Further, the number of times of light irradiation may be one time or a plurality of times, and it is preferably performed within the range of 1 to 50 times.
  • the light irradiation device of the flash lamp may be any device that satisfies the above irradiation energy and irradiation time.
  • the flash firing can also be performed in an inert gas atmosphere such as nitrogen, argon, helium, etc., if the atmosphere is within the range of the concentration of the oxygen-containing substance.
  • an inert gas atmosphere such as nitrogen, argon, helium, etc.
  • the xenon flash device include “instant heating / high temperature firing flash lamp annealing” manufactured by USHIO.
  • a method by plasma CVD treatment at or near atmospheric pressure can be given as a preferred example.
  • the reforming treatment of the intermediate layer can be performed using an atmospheric pressure plasma discharge treatment apparatus having a configuration described in Japanese Patent Application Laid-Open No. 2004-68143.
  • modification treatment of the intermediate layer can also be performed by plasma ion implantation treatment.
  • the plasma ion implantation apparatus basically includes a vacuum chamber, a microwave power source, a magnet coil, and a direct current application device (pulse power source).
  • the vacuum chamber is a container for placing an object on which an intermediate layer coating film is formed at a predetermined position inside the chamber and for performing ion implantation on the coating film.
  • the DC application device is a DC power supply, and is a pulse power supply for applying a high voltage pulse to the workpiece.
  • the microwave power source plasma discharge electrode
  • the magnet coil by driving the microwave power source (plasma discharge electrode) and the magnet coil, the plasma of the gas introduced from the gas inlet around the conductor and the object to be processed is generated. Occur.
  • the driving of the microwave power source and the magnet coil is stopped, and the DC application device is driven, and a high voltage pulse (negative voltage) is passed through the high voltage introduction terminal and the conductor. Will be applied.
  • the ionic species is not particularly limited.
  • ions of rare gases such as argon, helium, neon, krypton, xenon; ions of fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, etc .; methane, ethane, propane, butane, pentane, hexane, etc.
  • alkane gases such as ethylene, propylene, butene and pentene ions
  • alkadiene gases such as pentadiene and butadiene
  • alkyne gases such as acetylene and methylacetylene
  • benzene Ions of aromatic hydrocarbon gases such as toluene, xylene, indene, naphthalene and phenanthrene
  • ions of cycloalkane gases such as cyclopropane and cyclohexane
  • ions of cycloalkene gases such as cyclopentene and cyclohexene
  • gold Silver, copper, Ion silane (SiH 4) or an organic silicon compound
  • At least one kind selected from the group consisting of hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, and krypton is obtained because it can be more easily injected and an excellent reforming treatment can be obtained. Ions are preferred.
  • the pressure in the vacuum chamber during ion implantation that is, the plasma ion implantation pressure to a value within the range of 0.01 to 1 Pa.
  • the applied voltage (high voltage pulse / negative voltage) when plasma ions are implanted is preferably set to a value in the range of ⁇ 1 to ⁇ 50 kV.
  • a value in the range of ⁇ 1 to ⁇ 15 kV is more preferable, and a value in the range of ⁇ 5 to ⁇ 8 kV is more preferable.
  • the plasma ion implantation apparatus (RF power supply: manufactured by JEOL Ltd., RF56000, high voltage pulse power supply: Kurita Seisakusho Co., Ltd., PV-3-HSHV-0835) is used for the intermediate layer.
  • the reforming process can be performed.
  • the modification treatment of the intermediate layer can also be performed by heat treatment, and is preferably performed by appropriately setting the temperature in combination with the above various treatments.
  • a method such as a heating oven or an infrared heater can be used.
  • an organometallic oxide layer having an equivalent function may be disposed as an alternative to the modified layer.
  • it is preferably an organometallic oxide layer containing an organometallic oxide having a structure represented by the general formula (A), and a coating film is formed by a sol-gel method.
  • the layer is preferably a metal alkoxide in which the organometallic oxide is coordinate-substituted with a fluorinated alcohol.
  • Metal alkoxide not only promotes reforming and improves adhesion during lamination due to the catalytic effect on the intermediate layer and sealing layer, but also has atmospheric stability characteristics by being coordinated with fluorinated alcohol. Therefore, it is preferable because of excellent production suitability.
  • the organometallic oxide used is an organometallic oxide monomer or polycondensate obtained by alcoholic decomposition of a metal alkoxide in the presence of an excess of alcohol to replace the alcohol. At that time, by using a long-chain alcohol in which a fluorine atom is substituted at the ⁇ -position of the hydroxy group, an organometallic oxide containing a fluorinated alkoxide is obtained.
  • the organometallic oxide can promote a sol-gel reaction and form a polycondensate by irradiating with sintering or ultraviolet rays.
  • the hydrolysis rate is reduced by reducing the frequency factor of water present around the metal in the metal alkoxide by the water repellent effect of fluorine.
  • the three-dimensional polymerization reaction can be suppressed, and a uniform and dense organometallic oxide layer containing a desired organometallic oxide can be formed.
  • the organometallic oxide contained in the organometallic oxide layer according to the present invention is a compound exemplified in the following reaction scheme I.
  • “M” in the “OM” part further has a substituent, but is omitted.
  • the organometallic oxide layer formed by polycondensation of the organometallic oxide by sintering or ultraviolet irradiation is hydrolyzed by water vapor (H 2 O), which is a gas component from outside the system, according to the following reaction scheme II. Decomposes and releases fluorinated alcohol (R'-OH), contributing to atmospheric stabilization.
  • H 2 O water vapor
  • R'-OH fluorinated alcohol
  • the organometallic oxide layer according to the present invention preferably contains an organometallic oxide having a structure represented by the following general formula (A) as a main component.
  • the “main component” is preferably 70% by mass or more of the organometallic oxide that releases at least a water-repellent substance or a hydrophobic substance, more preferably, of the total mass of the organometallic oxide layer. It means 80% by mass or more, particularly preferably 90% by mass or more.
  • R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group.
  • R represents fluorine as a substituent. It may be a carbon chain containing atoms, M represents a metal atom, OR 1 represents a fluorinated alkoxy group, x represents a valence of the metal atom, and y represents an arbitrary integer between 1 and x. Represents the degree of polycondensation.
  • the fluorine ratio of the organometallic oxide layer according to the present invention satisfies the following formula (a).
  • the measurement significance of the formula (a) quantifies that an organometallic oxide layer produced by the sol-gel method requires a certain amount or more of fluorine atoms.
  • F and C in the above formula (a) represent the concentration of fluorine atom and carbon atom, respectively.
  • a preferable range of the formula (a) is a range of 0.2 ⁇ F / (C + F) ⁇ 0.6.
  • the fluorine ratio is determined by applying a sol-gel solution used for forming an organometallic oxide layer on a silicon wafer to produce a thin film, and then applying the thin film to an SEM / EDS (Energy Dispersive X-ray Spectroscopy: energy dispersive X-ray).
  • SEM / EDS Electromagnetic X-ray Spectroscopy: energy dispersive X-ray
  • concentration of fluorine atoms and carbon atoms can be determined by elemental analysis using an analytical device.
  • An example of the SEM / EDS apparatus is JSM-IT100 (manufactured by JEOL Ltd.).
  • SEM / EDS analysis has the feature that it can detect elements with high speed, high sensitivity and accuracy.
  • the organometallic oxide according to the present invention is not particularly limited as long as it can be produced using a sol-gel method.
  • the metal silicon introduced in “Science of Sol-Gel Method” P13, P20 , Lithium, sodium, copper, magnesium, calcium, bismuth, hafnium, niobium, strontium, barium, zinc, boron, aluminum, gallium, yttrium, silicon, germanium, lead, phosphorus, antimony, vanadium, tantalum, tungsten, lanthanum, neodymium
  • metal oxides containing one or more metals selected from titanium, zirconium, platinum, silver, and gold are examples of metal oxides selected from titanium, zirconium, platinum, silver, and gold.
  • the metal atom represented by M is silicon (Si), titanium (Ti), zirconium (Zr), magnesium (Mg), calcium (Ca), strontium (Sr), bismuth (Bi), hafnium ( Hf), niobium (Nb), zinc (Zn), aluminum (Al), platinum (Pt), silver (Ag), and gold (Au) are preferably selected from the viewpoint of obtaining the effects of the present invention.
  • OR 1 represents a fluorinated alkoxy group.
  • R 1 represents an alkyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group substituted with at least one fluorine atom. Specific examples of each substituent will be described later.
  • R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group. Or what substituted at least one part of hydrogen of each group with the halogen may be used. Moreover, a polymer may be sufficient.
  • Alkyl groups are substituted or unsubstituted, and specific examples include methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl.
  • the alkenyl group is substituted or unsubstituted, and specific examples include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like, and preferably those having 8 or more carbon atoms. These oligomers and polymers may also be used.
  • the aryl group is substituted or unsubstituted, and specific examples include phenyl group, tolyl group, 4-cyanophenyl group, biphenyl group, o, m, p-terphenyl group, naphthyl group, anthranyl group, phenanthrenyl group, There are a fluorenyl group, a 9-phenylanthranyl group, a 9,10-diphenylanthranyl group, a pyrenyl group, and the like, preferably those having 8 or more carbon atoms. These oligomers and polymers may also be used.
  • substituted or unsubstituted alkoxy group examples include a methoxy group, an n-butoxy group, a tert-butoxy group, a trichloromethoxy group, and a trifluoromethoxy group, and preferably those having 8 or more carbon atoms. These oligomers and polymers may also be used.
  • substituted or unsubstituted cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, a norbonane group, an adamantane group, a 4-methylcyclohexyl group, a 4-cyanocyclohexyl group, and preferably those having 8 or more carbon atoms. Good. These oligomers and polymers may also be used.
  • substituted or unsubstituted heterocyclic group examples include pyrrole group, pyrroline group, pyrazole group, pyrazoline group, imidazole group, triazole group, pyridine group, pyridazine group, pyrimidine group, pyrazine group, triazine group, indole group, Benzimidazole group, purine group, quinoline group, isoquinoline group, sinoline group, quinoxaline group, benzoquinoline group, fluorenone group, dicyanofluorenone group, carbazole group, oxazole group, oxadiazole group, thiazole group, thiadiazole group, benzoxazole group Benzothiazole group, benzotriazole group, bisbenzoxazole group, bisbenzothiazole group, bisbenzimidazole group and the like. These oligomers and polymers may also be used.
  • substituted or unsubstituted acyl group examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group Group, malonyl group, succinyl group, glutaryl group, adipoyl group, pimeloyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, elidoyl group, maleoyl group , Fumaroyl group, citraconoyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthal
  • the metal alkoxide, metal carboxylate, and fluorinated alcohol (R′-OH) are converted to the organometallic oxide according to the present invention by the following reaction scheme III.
  • (R′—OH) is exemplified by the following structures F-1 to F-16.
  • Examples of the metal alkoxide or metal carboxylate according to the present invention include compounds represented by the following M (OR) n or M (OCOR) n, and the organometallic oxide according to the present invention includes the above (R′—OH: F In combination with -1 to F-16), compounds having the structures of the following Exemplified Compound Nos. 1 to 135 (see Exemplified Compounds I, II and III below) are obtained.
  • the organometallic oxide according to the present invention is not limited to this.
  • the method for producing an organometallic oxide for producing an organometallic oxide according to the present invention is characterized by producing using a mixed liquid of a metal alkoxide and a fluorinated alcohol.
  • reaction scheme IV of Exemplified Compound No. 1 As an example of the reaction, the reaction scheme IV of Exemplified Compound No. 1 and the structure of the organometallic oxide when applied to the organometallic oxide layer are shown below.
  • Ti in the “O—Ti” part further has a substituent, but is omitted.
  • a fluorinated alcohol is added to a metal alkoxide or metal carboxylate, and the mixture is stirred and mixed. Then, water and a catalyst are added as necessary and reacted at a predetermined temperature.
  • a method can be mentioned.
  • a substance that can be a catalyst for the hydrolysis / polymerization reaction as shown below may be added.
  • What is used as a catalyst for hydrolysis / polymerization reaction of sol-gel reaction is "Functional thin film fabrication technology by the latest sol-gel method” (by Hirashima Satoshi, General Technology Center, P29) and "Sol-Gel It is a catalyst used in a general sol-gel reaction described in “Science of Law” (Sakuo Sakuo, Agne Jofusha, P154).
  • inorganic and organic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, tartaric acid, and toluenesulfonic acid
  • alkali metals such as ammonium hydroxide, potassium hydroxide, and sodium hydroxide Quaternary ammonium hydroxide such as hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, triethylamine, tributylamine, morpholine, pyridine, piperidine, ethylenediamine, diethylenetriamine, ethanolamine, diethanolamine , Amines such as triethanolamine, aminosilanes such as 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminoprop
  • the amount of the catalyst used is preferably 2 molar equivalents or less, more preferably 1 molar equivalent or less, per 1 mol of the metal alkoxide or metal carboxylate used as the organic metal oxide raw material.
  • the preferable amount of water added is 40 molar equivalents or less, more preferably 10 molar equivalents or less with respect to 1 mol of the metal alkoxide or metal carboxylate as the raw material of the organometallic oxide. More preferably, it is 5 molar equivalents or less.
  • the preferred reaction concentration, temperature, and time of the sol-gel reaction cannot be generally described because the type and molecular weight of the metal alkoxide or metal carboxylate used and the respective conditions are related to each other. That is, when the molecular weight of the alkoxide or metal carboxylate is high, or when the reaction concentration is high, if the reaction temperature is set high or the reaction time is too long, the reaction product is accompanied by hydrolysis and polycondensation reaction. There is a possibility that the molecular weight of the polymer increases, resulting in high viscosity or gelation. Accordingly, the usual preferable reaction concentration is generally 1 to 50% in terms of the mass% concentration of solid content in the solution, and more preferably 5 to 30%. Although depending on the reaction time, the reaction temperature is usually 0 to 150 ° C., preferably 1 to 100 ° C., more preferably 20 to 60 ° C., and the reaction time is preferably about 1 to 50 hours.
  • the organocondensate polycondensate forms an organometallic oxide layer, which absorbs moisture and produces the following oligomers according to the following reaction scheme V, contributing to the improvement of atmospheric stability.
  • organometallic oxide layer which absorbs moisture and produces the following oligomers according to the following reaction scheme V, contributing to the improvement of atmospheric stability.
  • OR 'in the layer there is a portion remaining as OR 'in the layer, but not so much as to affect the adhesion.
  • Ti in the “O—Ti” part further has a substituent, but is omitted.
  • the organometallic oxide layer according to the present invention is prepared by preparing a coating solution containing the organometallic oxide of the present invention, coating the substrate and sintering or irradiating it with ultraviolet rays to form a film while polycondensing. Can be formed.
  • organic solvent examples include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, or Ethers such as aliphatic ethers or alicyclic ethers can be used as appropriate.
  • hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, or Ethers such as aliphatic ethers or alicyclic ethers can be used as appropriate.
  • the concentration of the organometallic oxide according to the present invention in the coating solution varies depending on the target thickness and the pot life of the coating solution, but is preferably about 0.2 to 35% by mass. It is also preferable to add a catalyst for promoting polymerization to the coating solution.
  • the prepared coating liquid includes spray coating, spin coating, blade coating, dip coating, dip coating, casting, roll coating, bar coating, die coating, and other coating methods, inkjet printing methods, and dispenser methods.
  • a wet forming method such as a patterning method such as a printing method can be used, and it can be used depending on the material.
  • the inkjet printing method is preferable.
  • the ink jet printing method is not particularly limited, and a known method can be adopted.
  • the on-demand method or the continuous method may be used as the method for discharging the coating liquid from the ink jet head by the ink jet printing method.
  • On-demand inkjet heads are available in electro-mechanical conversion methods such as single cavity type, double cavity type, bender type, piston type, shear mode type and shared wall type, or thermal inkjet type and bubble jet (registered trademark). ) Any type of electrical-thermal conversion system or the like may be used.
  • ultraviolet light In order to fix the organometallic oxide layer after coating, it is preferable to use plasma, ozone, or ultraviolet light that can be polymerized at low temperatures. Among these, ultraviolet light is preferred for improving the smoothness of the thin film surface. preferable.
  • Examples of the means for generating ultraviolet rays in the ultraviolet treatment include metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV light lasers as described above.
  • UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used.
  • the base material on which the organic metal oxide layer is formed is a long film, it is carried out by continuously irradiating ultraviolet rays in the drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. Can do.
  • the time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the base material used and the composition and concentration of the desiccant-containing coating solution.
  • the energy coated surface receives is preferably 1.0 J / cm 2 or more, and more preferably 1.5 J / cm 2 or more.
  • it is preferably 14.0J / cm 2 or less, more preferably 12.0J / cm 2 or less, is 10.0J / cm 2 or less It is particularly preferred.
  • the oxygen concentration at the time of irradiation with ultraviolet rays is preferably 300 to 10,000 volume ppm (1 volume%), more preferably 500 to 5000 volume ppm. By adjusting to such an oxygen concentration range, it is possible to prevent the organometallic oxide layer from becoming excessively oxygen and to prevent deterioration of moisture absorption.
  • the gas other than oxygen at the time of ultraviolet irradiation it is preferable to use a dry inert gas, and it is particularly preferable to use a dry nitrogen gas from the viewpoint of cost.
  • the sealing layer according to the present invention is a layer formed by applying a modification treatment to a layer obtained by applying a coating liquid containing at least polysilazane (hereinafter, the sealing layer is referred to as a polysilazane layer). May be.)
  • the thickness of the sealing layer after drying is preferably within a range of 5 to 1000 nm, more preferably within a range of 10 to 800 nm, and particularly preferably within a range of 50 to 500 nm. From the viewpoint of achieving compatibility, it is preferable.
  • Polysilazane is a polymer having a silicon-nitrogen bond, such as SiO 2 , Si 3 N 4 having a bond such as Si—N, Si—H, or N—H, and ceramics such as both intermediate solid solutions SiO x N y. It is a precursor inorganic polymer.
  • polysilazane preferably has a partial structure represented by the following general formula (1).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. .
  • R 1 , R 2 and R 3 may be the same or different.
  • examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms.
  • the aryl group include aryl groups having 6 to 30 carbon atoms.
  • non-condensed hydrocarbon group such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc.
  • non-condensed hydrocarbon group such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, nap
  • the (trialkoxysilyl) alkyl group includes an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specific examples include 3- (triethoxysilyl) propyl group and 3- (trimethoxysilyl) propyl group.
  • the substituent optionally present in R 1 to R 3 is not particularly limited, and examples thereof include an alkyl group, a halogen atom, a hydroxy group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO 3 H), a carboxy group (—COOH), a nitro group (—NO 2 ) and the like.
  • the optionally present substituent is not the same as R 1 to R 3 to be substituted. For example, when R 1 to R 3 are alkyl groups, they are not further substituted with alkyl groups.
  • R 1 , R 2 and R 3 are preferably hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, phenyl, vinyl, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.
  • n is an integer, and it is preferable that the polysilazane having the structure represented by the general formula (1) has a number average molecular weight of 150 to 150,000 g / mol.
  • one of preferred embodiments is perhydropolysilazane in which all of R 1 , R 2 and R 3 are hydrogen atoms.
  • Polysilazane is commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a coating solution for forming a gas barrier layer.
  • Examples of commercially available polysilazane solutions include AQUAMICA (registered trademark) NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, and NP110 manufactured by AZ Electronic Materials Co., Ltd. NP140, SP140 and the like.
  • the content of polysilazane in the sealing layer before the modification treatment may be 100% by mass when the total mass of the sealing layer is 100% by mass.
  • the content of polysilazane in the layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass or less. Is more preferably 70% by mass or more and 95% by mass or less.
  • the sealing layer forming coating solution preferably contains an aluminum compound from the viewpoint of improving the heat resistance of the sealing layer.
  • the aluminum compound include aluminum trimethoxide and aluminum triethoxide.
  • Specific examples of commercially available products include AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate diisopropylate) and the like.
  • the content in the coating liquid for forming the sealing layer is preferably 0.1 to 10% by mass, and more preferably 1 to 5% by mass.
  • a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with a polysilazane having a main skeleton composed of a unit represented by the general formula (1) for example, JP-A-5-238827
  • a glycidol-added polysilazane obtained by reacting glycidol for example, see JP-A-6-122852
  • an alcohol-added polysilazane obtained by reacting an alcohol for example, JP-A No. Hei.
  • a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (for example, see JP-A-6-299118), and a metal-containing acetylacetonate complex.
  • Obtained acetylacetonate complex-added polysila Down e.g., JP-A-6-306329 JP reference.
  • Fine metal particles of the metal particles added polysilazane obtained by adding e.g., JP-A-7-196986 JP reference.
  • the intermediate layer and the sealing layer are preferably produced by a wet forming method or an ink jet printing method.
  • wet forming methods other than the ink jet printing method applicable to the present invention include spin coating methods, casting methods, screen printing methods, die coating methods, blade coating methods, roll coating methods, spray coating methods, curtain coating methods, LB methods ( Langmuir-Blodgett method), dispenser, and the like. From the viewpoint of obtaining a uniform thin film and high productivity, a die coating method, a roll coating method, a spray coating method, and the like are preferable.
  • Discharge methods include electro-mechanical conversion methods (eg, single cavity type, double cavity type, bender type, piston type, shear mode type, shared wall type, etc.), and electro-thermal conversion methods (eg, thermal Specific examples include an ink jet type, a bubble jet (registered trademark) type, an electrostatic suction type (for example, an electric field control type, a slit jet type, etc.), and a discharge type (for example, a spark jet type).
  • any discharge method may be used.
  • a serial head method, a line head method, or the like can be used without limitation.
  • the volume of ink droplets ejected from the inkjet head is preferably in the range of 0.5 to 100 pL.
  • the range of 2 to 20 pL is more preferable from the viewpoint of less application unevenness of the formation layer and high printing speed.
  • the volume of the ink droplet can be appropriately adjusted to a desired condition by adjusting the applied voltage or the like.
  • Printing methods based on the ink jet printing method include a one-pass printing method and a multi-pass printing method.
  • the one-pass printing method is a method in which a plurality of inkjet heads are fixedly arranged in a predetermined printing area and printed by one head scan.
  • the multi-pass printing method (also referred to as a serial printing method) is a method for printing a predetermined printing area by a plurality of head scans.
  • a wide head in which nozzles are arranged in parallel over the width of a desired coating pattern.
  • a wide head having at least the width of each coating pattern may be used.
  • FIG. 2 is a schematic view showing an example of a method for forming an intermediate layer or a sealing layer using an inkjet printing method of a one-pass printing method.
  • FIG. 2 shows a gas barrier layer, a first electrode, an organic functional layer group, and a second electrode, which are formed on a flexible base material F and constitute an organic EL element, using an ink jet printer equipped with an ink jet head 30.
  • An example of a method for forming a plurality of independent organic EL elements EL by sequentially ejecting ink containing each forming material of the intermediate layer or the sealing layer is shown.
  • the ink containing the intermediate layer or the sealing layer forming material is sequentially ejected as ink droplets by the ink jet head 30 to form the organic EL element EL. Form.
  • the inkjet head 30 applicable to the manufacturing method of the present invention is not particularly limited.
  • the inkjet head 30 includes a diaphragm having a piezoelectric element in the ink pressure chamber, and ink is changed by the pressure change in the ink pressure chamber by the diaphragm.
  • a shear mode type (piezo-type) head that discharges the liquid may be used, or a heat generating element may be used, and the ink liquid is discharged from the nozzle by a sudden volume change due to film boiling of the ink liquid due to the heat energy from the heat generating element. It may be a thermal type head.
  • the ink jet head 30 is connected to an ink supply mechanism for ejecting ink.
  • the ink liquid is supplied by the tank 38A.
  • the tank liquid level is made constant so that the ink liquid pressure in the ink jet head 30 is always kept constant.
  • the ink liquid is overflowed from the tank 38A and returned to the tank 38B under a natural flow.
  • the ink liquid is supplied from the tank 38B to the tank 38A by the pump 31, and is controlled so that the liquid level of the tank 38A is stably constant according to the ejection conditions.
  • the ink liquid is returned from the pump 31 to the tank 38A through the filter 32.
  • the filter medium having an absolute filtration accuracy or semi-absolute filtration accuracy of 0.05 to 50 ⁇ m at least once.
  • the ink liquid from the tank 36 and the cleaning solvent from the tank 37 can be forcibly supplied to the inkjet head 30 by the pump 39.
  • tank pumps may be divided into a plurality of parts for the ink jet head 30, pipe branches may be used, or a combination thereof may be used. In FIG. 2, a pipe branch 13 is used.
  • the ink liquid is forcibly sent from the tank 36 to the ink jet 30 by the pump 39, and the ink liquid is extracted from the air vent pipe described below to the waste liquid tank 34. May be sent.
  • FIG. 3 is a schematic external view showing an example of the structure of an inkjet head applicable to the inkjet printing method.
  • FIG. 3A is a schematic perspective view showing an inkjet head 30 applicable to the present invention
  • FIG. 3B is a bottom view of the inkjet head 30.
  • An inkjet head 30 applicable to the present invention is mounted on an inkjet printer (not shown), a head chip that ejects ink from a nozzle, a wiring board on which the head chip is disposed, and the wiring board. And a drive circuit board connected via a flexible board, a manifold for introducing ink into the channel of the head chip via a filter, a casing 56 containing the manifold inside, and a bottom opening of the casing 56 A cap receiving plate 57 attached so as to close, first and second joints 81a and 81b attached to the first ink port and the second ink port of the manifold, and a third attached to the third ink port of the manifold. A joint 82 and a cover member 59 attached to the housing 56 are provided. Further, attachment holes 68 for attaching the casing 56 to the printer main body are formed. Reference numerals 641, 651, 661, and 671 denote recessed portions for attachment.
  • the cap receiving plate 57 shown in FIG. 3B is formed in a substantially rectangular plate shape whose outer shape is long in the left-right direction, corresponding to the shape of the cap receiving plate mounting portion 62, and a plurality of nozzles are formed in the substantially central portion. In order to expose the arranged nozzle plate 61, a nozzle opening 71 that is long in the left-right direction is provided.
  • FIG. 2 described in JP 2012-140017 A can be referred to.
  • FIG. 3 shows a representative example of an ink jet head.
  • JP 2012-140017 A JP 2013-010227 A, JP 2014-058171 A, and JP 2014-097664 A. Gazette, JP-A-2015-14279, JP-A-2015-142980, JP-A-2016-002675, JP-A-2016-002682, JP-A-2016-107401, JP-A-2017-109476,
  • An ink jet head having a configuration described in Japanese Patent Application Laid-Open No. 2017-177626 can be appropriately selected and applied.
  • the sealing layer according to the present invention includes polysilazane and a modified product thereof, and can be obtained, for example, by modifying polysilazane in the polysilazane-containing sealing layer formed by the inkjet printing method.
  • the modification treatment refers to a reaction that converts part or all of polysilazane into silicon oxide or silicon oxynitride.
  • the reforming treatment is preferably performed by the vacuum ultraviolet irradiation treatment described in the above-described method for modifying the intermediate layer.
  • Si—H bonds and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation with vacuum ultraviolet irradiation and the like. It is considered that they are recombined as N (a dangling bond of Si may be formed). That is, it is cured as a SiN 2 composition without being oxidized. In this case, the polymer main chain is not broken. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. The cut H is released out of the membrane as H 2 .
  • Si—O—Si Bonds by Hydrolysis / Dehydration Condensation Si—N bonds in perhydropolysilazane are hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH.
  • Two Si—OH are dehydrated and condensed to form a Si—O—Si bond and harden. This is a reaction that occurs even in the air, but during vacuum ultraviolet irradiation in an inert atmosphere, water vapor generated from the base material by the heat of irradiation is considered to be the main moisture source.
  • Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO 2.1 to 2.3 is obtained.
  • Adjustment of the composition of silicon oxynitride in the layer obtained by subjecting the polysilazane-containing layer to vacuum ultraviolet irradiation can be performed by appropriately controlling the oxidation state by appropriately combining the oxidation mechanisms (1) to (4) described above. .
  • the modification of polysilazane is limited by the ultraviolet intensity of the lamp, irradiation time, temperature conditions during irradiation, etc. in normal production, and even if the reactions (1) to (4) above occur, the polysilazane in the layer Therefore, it is difficult to convert all of the polysilazane. Therefore, in the modification process of polysilazane on a production basis, unmodified polysilazane often remains within a range of several percent.
  • conditions such as illuminance, irradiation energy amount, selection of light source, oxygen concentration at the time of irradiation, and heat treatment are the conditions of the above-mentioned intermediate layer of vacuum ultraviolet irradiation. Conditions can be used as appropriate.
  • the sealing layer and the intermediate layer according to the present invention are preferably applied as a sealing layer of the organic photoelectric conversion element.
  • the intermediate layer and the sealing layer of the present invention are omitted, but the entire element is covered with the intermediate layer and the sealing layer as in the above-described organic EL element.
  • FIG. 4 is a cross-sectional view showing an example of a solar cell having a single configuration (a configuration having one bulk heterojunction layer) composed of a bulk heterojunction type organic photoelectric conversion element.
  • a bulk heterojunction type organic photoelectric conversion element 200 includes a transparent electrode (anode) 202, a hole transport layer 207, a bulk heterojunction layer photoelectric conversion unit 204, an electron transport layer (or an electron transport layer) on one surface of a substrate 201. Also referred to as a buffer layer, 208) and a counter electrode (cathode) 203 are sequentially stacked.
  • the substrate 201 is a member that holds the transparent electrode 202, the photoelectric conversion unit 204, and the counter electrode 203 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 201 side, the substrate 201 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. A transparent member is preferred.
  • the substrate 201 for example, a glass substrate or a resin substrate is used.
  • the substrate 201 is not essential.
  • the bulk heterojunction organic photoelectric conversion element 200 may be configured by forming the transparent electrode 202 and the counter electrode 203 on both surfaces of the photoelectric conversion unit 204.
  • the photoelectric conversion unit 204 is a layer that converts light energy into electrical energy, and includes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed.
  • the p-type semiconductor material functions relatively as an electron donor (donor)
  • the n-type semiconductor material functions relatively as an electron acceptor (acceptor).
  • the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”.
  • an electron acceptor which don't just donate or accept electrons like an electrode, but donates or accepts electrons by photoreaction.
  • FIG. 4 light incident from the transparent electrode 202 through the substrate 201 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the photoelectric conversion unit 204, and electrons move from the electron donor to the electron acceptor. Thus, a hole-electron pair (charge separation state) is formed.
  • the generated electric charge is caused by an internal electric field, for example, when the work functions of the transparent electrode 202 and the counter electrode 203 are different, the electrons pass between the electron acceptors and the holes are electron donors due to the potential difference between the transparent electrode 202 and the counter electrode 203.
  • the photocurrent is detected by passing through different electrodes.
  • the transport direction of electrons and holes can be controlled.
  • a hole blocking layer such as a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, or a smoothing layer may be included.
  • tandem configuration (a configuration having a plurality of bulk heterojunction layers) in which such photoelectric conversion elements are stacked may be used for the purpose of further improving the sunlight utilization rate (photoelectric conversion efficiency).
  • FIG. 5 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element having a tandem bulk heterojunction layer.
  • the transparent electrode 202 and the first photoelectric conversion unit 209 are sequentially stacked on the substrate 201, the charge recombination layer (intermediate electrode) 205 is stacked, and then the second photoelectric conversion unit 206, Next, by stacking the counter electrode 203, a tandem structure can be obtained.
  • Examples of materials that can be used for the layer as described above include n-type semiconductor materials and p-type semiconductor materials described in paragraphs 0045 to 0113 of JP-A-2015-149483.
  • the electrodes constituting the organic photoelectric conversion element it is preferable to use the anode and the cathode described in the above-mentioned organic EL element.
  • the organic photoelectric conversion element positive charges and negative charges generated in the bulk heterojunction layer are respectively extracted from the transparent electrode and the counter electrode via the p-type organic semiconductor material and the n-type organic semiconductor material, respectively. It functions as a battery.
  • Each electrode is required to have characteristics suitable for carriers passing through the electrode.
  • the organic photoelectric conversion element has a hole transport layer / electron block layer in between the bulk heterojunction layer and the transparent electrode because it is possible to more efficiently extract charges generated in the bulk heterojunction layer. It is preferable.
  • PEDOT such as Clevios manufactured by Heraeus, polyaniline and its doped material, cyan compounds described in WO2006 / 019270, and the like can be used.
  • the organic photoelectric conversion device can extract charges generated in the bulk heterojunction layer more efficiently by forming an electron transport layer, hole blocking layer, and buffer layer between the bulk heterojunction layer and the counter electrode. Therefore, it is preferable to have these layers.
  • the organic photoelectric conversion element may have various optical function layers for the purpose of more efficiently receiving sunlight.
  • the optical functional layer for example, a light condensing layer such as an antireflection film or a microlens array, or a light diffusing layer that can scatter the light reflected by the counter electrode and enter the bulk heterojunction layer again can be provided. Good.
  • FIG. 6 is a schematic sectional view showing the configuration of the organic thin film transistor.
  • the sealing layer and the intermediate layer according to the present invention are preferably applied as a sealing layer of an organic thin film transistor.
  • the intermediate layer and the sealing layer according to the present invention are omitted, the entire element is covered with the intermediate layer and the sealing layer in the same manner as the organic EL element described above.
  • a source electrode 302 and a drain electrode 303 are formed on a support 306 by a metal foil or the like, and 6,13-bistriisopropyl is used as an organic semiconductor material described in the reissue table 2009/101862 between both electrodes.
  • a field effect transistor is formed by forming a charge transfer thin film (organic semiconductor layer) 301 made of silylethynylpentacene, forming an insulating layer 305 thereon, and further forming a gate electrode 304 thereon.
  • FIG. 6B shows the organic semiconductor layer 301 formed between the electrodes in FIG. 6A so as to cover the entire surface of the electrode and the support using a coating method or the like.
  • FIG. 6C shows a structure in which an organic semiconductor layer 301 is first formed on a support 306 by using a coating method or the like, and then a source electrode 302, a drain electrode 303, an insulating layer 305, and a gate electrode 304 are formed.
  • the gate electrode 304 after forming the gate electrode 304 with a metal foil or the like over the support 306, the insulating layer 305 is formed, and the source electrode 302 and the drain electrode 303 are formed with the metal foil or the like on the insulating layer 305. Then, an organic semiconductor layer 301 formed of the light emitting composition of the present invention is formed.
  • Example 1 Using the following solventless polymer as the material of the intermediate layer, ⁇ UV curable fluorine resin Defensor OP-3801 (manufactured by DIC) The above UV curable resin was spin-coated on a silicon wafer with a layer thickness of 200 nm and irradiated with UV: 365 nm for 1 minute, and subjected to the modification treatment of the intermediate layer surface described in Table I A measurement sample was obtained.
  • the reforming treatment conditions are as follows.
  • Flash firing process Using a xenon flash lamp 2400WS (made by COMET) equipped with a short wavelength cut filter of 250 nm or less, an oxygen concentration of 0.002% by volume and a water vapor concentration of 0.002% by volume (oxygen-containing substance concentration of 0.004% by volume). Under the atmosphere, flash processing was performed by irradiating flash light having a total light irradiation energy of 2 J / cm 2 with an irradiation time of 2 milliseconds.
  • Plasma ion implantation process Using a plasma ion implantation apparatus (RF power supply: manufactured by JEOL Ltd., RF56000, high voltage pulse power supply: Kurita Seisakusho Co., Ltd., PV-3-HSHV-0835), 2J was applied to the surface of the obtained intermediate layer. Plasma ion implantation was performed under the conditions of / cm 2 .
  • RF power supply manufactured by JEOL Ltd., RF56000
  • high voltage pulse power supply Kurita Seisakusho Co., Ltd., PV-3-HSHV-0835
  • the carbon component ratio at the intermediate layer surface depth of 0 to 70 nm is 12 at% on average, and the carbon component ratio at the surface depth of 70 to 200 nm is 30 at% on average, with a thickness of 70 nm from the intermediate layer surface. It was found that it was modified. In the present invention, it is defined as a modified layer that the carbon component ratio is lower than that of a normal layer. Since the carbon component is decomposed and volatilized by high energy irradiation, it is generally said that the lower the carbon component, the denser the film.
  • the flash firing treatment and the plasma ion implantation treatment were modified, but the degree of modification was weak.
  • ⁇ Measurement of contact angle> The contact angle of pure water on the surface of the intermediate layer was measured using a contact angle meter (trade name DropMaster DM100, manufactured by Kyowa Interface Science Co., Ltd.) in an atmosphere of 23 ° C. and 55% RH based on JIS-R3257. Then, 1 ⁇ L of pure water was dropped and the contact angle after 1 minute was measured. In addition, the measurement measured 10 points
  • Example 2 The sample was spin-coated on the silicon wafer in the same manner as in Example 1 so that the intermediate layer had a thickness of 200 nm, irradiated with UV: 365 nm for 1 minute, and subjected to each surface modification treatment.
  • a coating solution containing PHPS is spin-coated on the intermediate layer to a thickness of 500 nm, dried on a hot plate at 80 ° C. for 1 minute, and then subjected to a VUV surface modification treatment under conditions of 6 J / cm 2 and sealed. Layered.
  • the coating solution containing PHPS includes a dibutyl ether solution containing 20% by mass of PHPS (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl- Mix with a 20% by weight dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) containing 1,6-diaminohexane (TMDAH) at a ratio of 4: 1 (mass ratio) and further dry.
  • a coating solution was prepared by appropriately diluting with dibutyl ether solution containing 20% by mass of PHPS (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl- Mix with a 20% by weight dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) containing 1,6-
  • the cellophane tape was strongly pressure-bonded to the grid area, and the end of the tape was peeled off at an angle of 45 °, and the condition of the grid pattern between the intermediate layer and the PHPS layer was evaluated by comparison with the standard diagram (FIG. 7). did.
  • Example 3 (Production of organic EL element) A glass substrate on which 100 nm of ITO (indium tin oxide) was formed as an anode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas and UV ozone cleaned, and fixed to a substrate holder of a vacuum deposition apparatus.
  • ITO indium tin oxide
  • HAT-CN (1, 4, 5, 8, 9, 12-hexaazatriphenylenehexacarbonitrile) was deposited to a thickness of 10 nm to provide a hole injection transport layer.
  • ⁇ -NPD 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • MCP (1,3-bis (N-carbazolyl) benzene) as the host material and FIrpic (Bis [2- (4,6-difluorophenyl) pyridinato-C2, N] (picolinato) iridium (III)) as the luminescent compound
  • FIrpic Bis [2- (4,6-difluorophenyl) pyridinato-C2, N] (picolinato) iridium (III)
  • BCP 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • the intermediate layer was formed by spin coating on the cathode with a layer thickness of 200 nm, irradiated with UV: 365 nm for 1 minute, subjected to each surface modification treatment of Example 1, and then Example 2 Similarly to the above, a coating solution containing PHPS as a sealing layer was formed by spin coating on the intermediate layer with a layer thickness of 500 nm.
  • the non-light-emitting surface of the organic EL element is covered with a glass case, and a glass substrate having a thickness of 300 ⁇ m is used as a sealing substrate, and an epoxy-based photocurable adhesive (LUX The track LC0629B) was applied, and this was overlaid on the cathode and brought into close contact with the transparent support substrate, irradiated with UV from the glass substrate side, cured, and sealed in a glass can. This is to block the influence of humidity and gas from the outside on the intermediate layer and the sealing layer of the organic EL element produced as described above, and to clarify the effect of forming the intermediate layer and the sealing layer according to the present invention.
  • a gas barrier film was laminated on the sealing layer instead of sealing the glass can.
  • a gas barrier film (denoted as a barrier film in the table) was prepared and used in the following procedure.
  • Gas barrier film An inorganic gas barrier layer made of SiO x is formed on the entire surface of a polyethylene naphthalate film (manufactured by Teijin Film Solutions Co., Ltd.) using an atmospheric pressure plasma discharge treatment apparatus having a structure described in Japanese Patent Application Laid-Open No. 2004-68143. It formed so that it might become 500 nm. Thus, a flexible gas barrier film having a gas barrier property with an oxygen permeability of 0.001 mL / (m 2 ⁇ 24 h ⁇ atm) or less and a water vapor permeability of 0.001 g / (m 2 ⁇ 24 h) or less was produced. .
  • thermosetting liquid adhesive epoxy resin
  • a thermosetting liquid adhesive epoxy resin having a thickness of 25 ⁇ m was formed as a sealing resin layer on one side of the gas barrier film. Then, the gas barrier film provided with this sealing resin layer was superposed on the intermediate layer or the element coated with the PHPS coating solution. At this time, the sealing resin layer forming surface of the gas barrier film was continuously overlaid on the sealing surface side of the organic EL element so that the ends of the anode and cathode extraction portions were exposed.
  • the sample to which the gas barrier film was bonded was placed in a decompression apparatus, and pressed at 90 ° C. under a decompression condition of 0.1 MPa and held for 5 minutes. Subsequently, the sample was returned to the atmospheric pressure environment and further heated at 90 ° C. for 30 minutes to cure the adhesive.
  • the sealing process is performed under atmospheric pressure and in a nitrogen atmosphere with a water content of 1 ppm or less in accordance with JIS B 9920.
  • the measured cleanliness is class 100, the dew point temperature is ⁇ 80 ° C. or less, and the oxygen concentration is 0.8 volume. It was carried out at atmospheric pressure below ppm.
  • ⁇ Evaluation> The light emission state after being left for 1 week at 60 ° C. and 90% RH was observed, and the sealing performance was evaluated. Specifically, a part of the light emitting portion of the organic EL element was photographed with a 100 ⁇ optical microscope (Mortex Co., Ltd. MS-804, lens MP-ZE25-200). Next, the captured image was cut out in a 2 mm square, and the presence or absence of dark spots was observed for each image. From the observation results, the ratio of the dark spot generation area to the light emission area was determined, and the dark spot resistance was evaluated according to the following criteria.
  • the area where dark spots are generated is less than 0.1% 4: The area where dark spots are generated is 0.1% or more and less than 1.0% 3: The area where dark spots are generated is 1.0 % And less than 3.0% 2: Dark spot generation area is 3.0% and less than 6.0% 1: Dark spot generation area is 6.0% and more
  • VUV applied to the intermediate layer was the most effective for preventing solvent penetration of the upper layer (see Examples Nos. 102 to 107 and 109).
  • the one provided with the intermediate layer acts as a cushion layer (stress relaxation layer) and has an effect of suppressing damage to the organic EL element (No. 108 as a reference example and Examples). No. 109).
  • Example 4 In the same manner as in Example 3, an organic EL element was produced.
  • OP-3801 was spin-coated with a thickness of 200 nm on the cathode as an intermediate layer and dried to form an intermediate layer. Drying conditions were 120 ° C. and 20 minutes.
  • a coating solution containing PHPS as a sealing layer is spin-coated on the intermediate layer with a layer thickness of 500 nm, and a hot plate at 80 ° C. For 1 minute.
  • the area where dark spots are generated is less than 0.1% 4: The area where dark spots are generated is 0.1% or more and less than 1.0% 3: The area where dark spots are generated is 1.0 % And less than 3.0% 2: Dark spot generation area is 3.0% and less than 6.0% 1: Dark spot generation area is 6.0% and more
  • Example 5 In the same manner as in Example 3, an organic EL element was produced.
  • OP-3801 was spin-coated with a thickness of 200 nm on the cathode as an intermediate layer and dried to form an intermediate layer. Drying conditions were 120 ° C. and 20 minutes.
  • a coating solution containing PHPS as a sealing layer is spin-coated on the intermediate layer with a layer thickness of 500 nm, and a hot plate at 80 ° C. For 1 minute.
  • ⁇ Evaluation> The light emitting state after being left for 4 days at 60 ° C. and 90% RH was observed, and the sealing performance was evaluated. Specifically, a part of the light emitting portion of the organic EL element was photographed with a 100 ⁇ optical microscope (Mortex Co., Ltd. MS-804, lens MP-ZE25-200). Next, the captured image was cut out in a 2 mm square, and the presence or absence of dark spots was observed for each image. From the observation results, the ratio of the dark spot generation area to the light emission area was determined, and the dark spot resistance was evaluated according to the following criteria.
  • the area where dark spots are generated is less than 0.1% 4: The area where dark spots are generated is 0.1% or more and less than 1.0% 3: The area where dark spots are generated is 1.0 % And less than 3.0% 2: Dark spot generation area is 3.0% and less than 6.0% 1: Dark spot generation area is 6.0% and more
  • Example 6 the sealing property of the lighting device (and element) that emits blue fluorescent light, which was manufactured by the inkjet printing method, was confirmed.
  • ITO indium tin oxide
  • the base material on which the hole injection layer is formed is transferred to a nitrogen atmosphere using nitrogen gas (grade G1), and is applied by an inkjet printing method using a coating liquid for forming a hole transport layer having the following composition. And dried at 150 ° C. for 30 minutes to form a hole transport layer having a layer thickness of 30 nm.
  • nitrogen gas grade G1
  • ⁇ Light emitting layer forming coating solution> Host compound H-4 9 parts by weight Metal complex CD-2 1 part by weight Fluorescent material F-1 0.1 part by weight Normal butyl acetate 2000 parts by weight (formation of block layer)
  • the base material on which the light emitting layer was formed was applied by an ink jet printing method using a coating solution for forming a block layer having the following composition, and dried at 80 ° C. for 30 minutes to form a block layer having a layer thickness of 10 nm.
  • IPA Isopropyl alcohol
  • the substrate on which the block layer is formed is applied by an ink jet printing method using an electron transport layer forming coating solution having the following composition, and dried at 80 ° C. for 30 minutes to form an electron transport layer having a layer thickness of 30 nm. did.
  • ⁇ Coating liquid for electron transport layer formation > ET-1 6 parts by mass 2,2,3,3-tetrafluoro-1-propanol 2000 parts by mass (formation of electron injection layer and cathode) Subsequently, the substrate was attached to a vacuum deposition apparatus without being exposed to the atmosphere. Moreover, what put sodium fluoride and potassium fluoride in the resistance heating boat made from molybdenum was attached to the vacuum evaporation system, and the vacuum tank was pressure-reduced to 4x10 ⁇ -5 > Pa. Thereafter, the boat was energized and heated, and sodium fluoride was deposited on the electron transport layer at 0.02 nm / second to form a thin film having a thickness of 1 nm. Similarly, potassium fluoride was vapor-deposited on the sodium fluoride thin film at 0.02 nm / second to form an electron injection layer having a layer thickness of 1.5 nm.
  • OP-3801 was spin-coated with a thickness of 200 nm on the cathode as an intermediate layer and dried to form an intermediate layer. Drying conditions were 120 ° C. and 20 minutes.
  • a coating solution containing PHPS as a sealing layer is spin-coated on the intermediate layer with a layer thickness of 500 nm, and a hot plate at 80 ° C. For 1 minute, and then irradiated with 6 J / cm 2 of VUV.
  • the organic EL device with the intermediate layer and the sealing layer laminated has a greater resistance to dark spots when left at 60 ° C. and 90% RH for one week than the organic EL device without the intermediate layer. It was improved.
  • a lighting device manufactured by the inkjet printing method can obtain high sealing performance by the intermediate layer and the sealing layer formed by the coating film formation according to the present invention.
  • Example 7 On the cathode of the organic EL device produced in Example 6, the above-mentioned OP-3801 was spin-coated as an intermediate layer with a layer thickness of 200 nm, and irradiated with UV: 365 nm for 1 minute and dried to form an intermediate layer.
  • the drying condition was 120 ° C. for 20 minutes, and the reforming treatment was performed with and without irradiation at 1 J / cm 2 of the cumulative amount of vacuum ultraviolet light (VUV) as shown in Table VI.
  • VUV vacuum ultraviolet light
  • the modification process is performed with or without irradiation with an integrated amount of ultraviolet (UV) light of 2 J / cm 2. did.
  • a coating solution containing PHPS is spin-coated on the organometallic oxide layer with a layer thickness of 500 nm, heated on a hot plate at 80 ° C. for 1 minute, and then subjected to 6 V of vacuum ultraviolet (VUV). / Cm 2 irradiation to perform the modification treatment, the organic EL element No. 401 to 403 were produced.
  • TFPO Exemplified Compound F-1
  • Si (OEt) 4 tetraethoxide silane
  • Example 8 An organic thin-film solar cell (organic photoelectric conversion element) was produced using the intermediate layer and the sealing layer formed by the coating film formation of the present invention.
  • a glass substrate on which 100 nm of ITO (Indium Tin Oxide) was formed as an anode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas and UV ozone cleaned, and fixed to a substrate holder of a vacuum deposition apparatus.
  • ITO Indium Tin Oxide
  • CuPC copper phthalocyanine
  • anthra 9, 1, 2-c, d, e: 10, 5, 6-c are formed on the anode.
  • a bulk heterojunction layer was provided in thickness.
  • OP-3801 as an intermediate layer was applied and formed on the cathode at a layer thickness of 200 nm by an ink jet printing method, and dried to form an intermediate layer. Drying conditions were 120 ° C. and 20 minutes.
  • a coating solution containing PHPS as a sealing layer is formed by spin coating on the intermediate layer with a layer thickness of 500 nm, and a hot plate at 80 ° C. After heating for 1 minute, VUV was irradiated at 6 J / cm 2 to produce an organic photoelectric conversion element.
  • Example 9 An organic thin film transistor was produced using the intermediate layer and the sealing layer formed by the coating film formation of the present invention.
  • a source electrode 302 and a drain electrode 303 are formed on a support 306 with a metal foil or the like, and 6,13-bistriisopropyl is used as an organic semiconductor material described in Table 2009/101862 between both electrodes.
  • An organic semiconductor layer having a thickness of about 30 nm is formed as a charge transfer thin film (organic semiconductor layer) 301 made of silylethynylpentacene, an insulating layer 305 is formed thereon, and a gate electrode 304 is further formed thereon to form an organic thin film transistor Was made.
  • OP-3801 was spin-coated with a thickness of 200 nm as an intermediate layer on the insulating layer 305 and the gate electrode 304, and dried to form an intermediate layer. Drying conditions were 120 ° C. and 20 minutes.
  • a coating solution containing PHPS as a sealing layer is formed by spin coating on the intermediate layer with a layer thickness of 500 nm, and a hot plate at 80 ° C. After heating for 1 minute, VUV was irradiated at 6 J / cm 2 to produce an organic thin film transistor.
  • the electronic device of the present invention is an electronic device in which penetration of a solvent used for forming a sealing layer into an organic functional layer is suppressed, a light emitting functional failure is prevented, and adhesion between the organic functional layer and the sealing layer is excellent. Therefore, it is suitable for an electronic device having a sealing layer such as an organic EL element, a solar battery having an organic photoelectric conversion element, and an organic thin film transistor.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Electromagnetism (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Thin Film Transistor (AREA)
  • Photovoltaic Devices (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

La présente invention aborde le problème consistant à fournir : un dispositif électronique qui est pourvu d'au moins une couche fonctionnelle organique et d'une couche d'étanchéité, et qui ne subit par de perméation d'un solvant qui est utilisé pendant la formation de la couche d'étanchéité dans la couche fonctionnelle organique, ce qui permet d'empêcher un dysfonctionnement d'émission de lumière (par exemple des taches sombres), et qui présente une excellente adhérence entre la couche fonctionnelle organique et la couche d'étanchéité ; et un procédé de production de ce dispositif électronique. Un dispositif électronique selon la présente invention est pourvu d'au moins une couche fonctionnelle organique et d'une couche d'étanchéité, et est caractérisé en ce que : la couche d'étanchéité contient un polysilazane et une forme modifiée de celui-ci ; et une couche intermédiaire qui contient un polymère photodurcissable ou thermodurcissable est disposée entre la couche fonctionnelle organique et la couche d'étanchéité.
PCT/JP2019/021001 2018-05-31 2019-05-28 Dispositif électronique et son procédé de production WO2019230682A1 (fr)

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CN113327734A (zh) * 2021-05-13 2021-08-31 佛山华骏特瓷科技有限公司 一种电阻片制备方法
WO2023008234A1 (fr) * 2021-07-30 2023-02-02 日本ゼオン株式会社 Structure de dispositif et son procédé de fabrication
JP7457513B2 (ja) 2020-02-03 2024-03-28 リンテック株式会社 保護膜形成フィルム、保護膜形成用複合シートおよび装置の製造方法

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JP2002222691A (ja) * 2000-07-24 2002-08-09 Tdk Corp 発光素子
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JP2015221757A (ja) * 2014-05-22 2015-12-10 双葉電子工業株式会社 化合物、乾燥剤、封止構造及び有機ｅｌ素子
JP2015225785A (ja) * 2014-05-28 2015-12-14 国立大学法人山形大学 有機エレクトロルミネッセンス素子の封止方法
WO2016147959A1 (fr) * 2015-03-18 2016-09-22 コニカミノルタ株式会社 Film étanche au gaz
WO2018037791A1 (fr) * 2016-08-24 2018-03-01 コニカミノルタ株式会社 Dispositif d'émission à électroluminescence organique

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Publication number Priority date Publication date Assignee Title
JP2002222691A (ja) * 2000-07-24 2002-08-09 Tdk Corp 発光素子
US20040234813A1 (en) * 2003-05-20 2004-11-25 Lee Jong-Hyuk Organic electroluminescent device and method of manuatacturing the same
JP2015221757A (ja) * 2014-05-22 2015-12-10 双葉電子工業株式会社 化合物、乾燥剤、封止構造及び有機ｅｌ素子
JP2015225785A (ja) * 2014-05-28 2015-12-14 国立大学法人山形大学 有機エレクトロルミネッセンス素子の封止方法
WO2016147959A1 (fr) * 2015-03-18 2016-09-22 コニカミノルタ株式会社 Film étanche au gaz
WO2018037791A1 (fr) * 2016-08-24 2018-03-01 コニカミノルタ株式会社 Dispositif d'émission à électroluminescence organique

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7457513B2 (ja) 2020-02-03 2024-03-28 リンテック株式会社 保護膜形成フィルム、保護膜形成用複合シートおよび装置の製造方法
CN113327734A (zh) * 2021-05-13 2021-08-31 佛山华骏特瓷科技有限公司 一种电阻片制备方法
CN113327734B (zh) * 2021-05-13 2022-05-06 佛山华骏特瓷科技有限公司 一种电阻片制备方法
WO2023008234A1 (fr) * 2021-07-30 2023-02-02 日本ゼオン株式会社 Structure de dispositif et son procédé de fabrication

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