WO2020262418A1 - 電荷輸送性ワニス - Google Patents

電荷輸送性ワニス Download PDF

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WO2020262418A1
WO2020262418A1 PCT/JP2020/024702 JP2020024702W WO2020262418A1 WO 2020262418 A1 WO2020262418 A1 WO 2020262418A1 JP 2020024702 W JP2020024702 W JP 2020024702W WO 2020262418 A1 WO2020262418 A1 WO 2020262418A1
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group
charge
transporting
organic
thin film
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PCT/JP2020/024702
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English (en)
French (fr)
Japanese (ja)
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倉田　陽介
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日産化学株式会社
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Priority to KR1020227001763A priority Critical patent/KR20220027970A/ko
Priority to CN202080045353.7A priority patent/CN114008808A/zh
Priority to JP2021527666A priority patent/JP7491311B2/ja
Publication of WO2020262418A1 publication Critical patent/WO2020262418A1/ja

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Definitions

  • the present invention relates to a charge transporting varnish.
  • the method for forming an organic functional layer such as a hole injection layer used in an organic electroluminescence (EL) device is roughly classified into a dry process represented by a vapor deposition method and a wet process represented by a spin coating method. Comparing each of these processes, the wet process can efficiently produce a thin film having a large area and high flatness. Therefore, at present, the area of organic EL displays is being increased, and a hole injection layer that can be formed by a wet process is desired.
  • the applicant has applied a charge transporting material that can be applied to various wet processes and provides a thin film capable of realizing excellent EL device characteristics when applied to a hole injection layer of an organic EL device.
  • we have been developing compounds with good solubility in organic solvents used for them see, for example, Patent Documents 1 to 3).
  • the charge-transporting thin film for organic EL elements has been in the visible region because the coloring of the charge-transporting thin film used for the organic EL element reduces the color purity and color reproducibility of the organic EL element. It is desired to have high transparency and high transparency (see, for example, Patent Document 6).
  • the applicant has already found a material for a wet process that suppresses coloring in the visible region and provides a charge-transporting thin film having excellent transparency (see, for example, Patent Documents 6 and 7), but of an organic EL display.
  • a partition wall (bank) is generally provided so as to surround the layer forming region, and the partition wall is opened.
  • Organic functional ink is applied to the inside of the part.
  • the ink applied in the opening may crawl up on the side surface of the partition wall, and the thickness of the peripheral portion of the coating film in contact with the side surface of the partition wall may be thicker than that of the central portion of the coating film, so-called crawling phenomenon may occur. ..
  • crawling phenomenon occurs, the plurality of organic functional layers formed between the electrodes do not function in the order of stacking, causing a situation in which a leak current path is formed.
  • Patent Documents 8 and 9 propose means for suppressing the crawling phenomenon, but in response to the recent situation in which the development of organic EL displays using a wet process is further accelerated, the suppression of such a crawling phenomenon is suppressed.
  • the demand for technology related to is increasing.
  • the present invention has been made in view of the above circumstances, and is a charge that suppresses the creeping phenomenon, provides a thin film having a high refractive index and high transparency, and provides a charge transporting thin film suitable as a functional layer of an organic EL element. It is intended to provide a transportable varnish.
  • the present inventor is obtained from a charge transport varnish containing zirconia particles surface-modified with a surface treatment agent, a monodisperse charge transport organic compound, and an organic solvent.
  • the thin film exhibits high charge transportability, high transparency (low k value) and high refractive index (high n value), and when the varnish is applied into the partition wall by a wet process, the varnish creeping up is extremely suppressed.
  • the present invention has been completed by finding that a thin film can be produced.
  • the present invention provides the following charge transporting varnish.
  • a charge-transporting varnish containing (A) zirconia particles surface-modified with a surface treatment agent, (B) a monodisperse charge-transporting organic compound, and (C) an organic solvent.
  • a charge-transporting varnish having an average particle size of 2 to 100 nm for zirconia particles surface-modified with the surface treatment agent.
  • the charge-transporting varnish of the present invention By using the charge-transporting varnish of the present invention, it is possible to produce a charge-transporting thin film in which the varnish creeps up (so-called pile-up) is extremely suppressed even when it is applied into the partition wall by a wet process. Further, the charge-transporting thin film obtained from the charge-transporting varnish of the present invention is excellent in flatness and charge-transporting property, and has high transparency and high refractive index. Therefore, the charge-transporting thin film obtained from the charge-transporting varnish of the present invention can be suitably used as a thin film for electronic devices such as organic EL devices.
  • FIG. 1 It is a figure which shows the shape of the charge transport thin film in the partition wall of the substrate with a charge transport thin film obtained in Example 4.
  • FIG. 1 shows the shape of the charge transport thin film in the partition wall of the substrate with a charge transport thin film obtained in Example 4.
  • the charge-transporting varnish of the present invention includes (A) zirconia particles surface-modified with a surface treatment agent (hereinafter, also referred to as surface-modified zirconia particles), (B) a monodisperse charge-transporting organic compound, and (C). It contains an organic solvent.
  • a surface treatment agent hereinafter, also referred to as surface-modified zirconia particles
  • B a monodisperse charge-transporting organic compound
  • C contains an organic solvent.
  • the surface-modified zirconia (ZrO 2 ) particles of the component (A) are obtained by surface-treating the nuclear particles made of zirconia with a surface treatment agent.
  • the surface treatment agent include n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane, and 2- [methoxy (polyethyleneoxy) propyl].
  • Alcohols such as; glycol ethers such as triethylene glycol monomethyl ether; carboxylic acids such as octanoic acid, acetic acid, propionic acid, 2- [2- (2-methoxyethoxy) ethoxy] acetic acid, oleic acid, stearic acid, benzoic acid and the like. Can be mentioned.
  • the average particle size of the nuclear particles is preferably 1 to 90 nm, more preferably 2 to 45 nm, and even more preferably 3 to 18 nm.
  • Examples of the method for measuring the average particle size of the nuclear particles include a method using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • Various methods for measuring the average particle size using TEM are known, and one example thereof is a method based on the equivalent circle diameter. This is a method of obtaining the equivalent circle diameter of each particle by processing the projected image of the particles obtained by using TEM with image processing software, and obtaining the average particle diameter as the number average of the equivalent circle diameters. ..
  • the equivalent circle diameter also called the Haywood diameter, is the diameter of a circle that has the same area as the projected image of the particles.
  • the projected image is typically processed using image processing software created by the manufacturer and distributor of the TEM, which is provided with the TEM.
  • the surface-modified zirconia particles preferably have an average particle diameter of 2 to 100 nm, more preferably 3 to 50 nm, and even more preferably 5 to 20 nm.
  • the average particle size of the surface-modified zirconia particles is a particle size (median diameter D 50 ) at which the cumulative frequency distribution in the volume-based particle size distribution measurement by the dynamic light scattering method is 50%.
  • the surface-modified zirconia particles commercially available products or those surface-treated thereof can be used, and specific examples thereof include EP zirconium oxide, SPZ zirconium oxide, and UEP manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.
  • Nanouse registered trademark
  • ZR-40BL Dispersed liquids of surface-modified zirconia particles such as ZR-30AL, ZSL-10A manufactured by Daiichi Rare Element Chemical Industry Co., Ltd., ZSL-10T, ZSL-20N, and ZSL00014, or surface-treated ones thereof.
  • the surface-modified zirconia particles may be produced by a known method.
  • the content of the surface-modified zirconia particles of the component (A) is usually about 1 to 98% by mass, preferably about 5 to 90% by mass, and more preferably about 10 to 80% by mass in the solid content.
  • the solid content means a component other than the solvent among the components contained in the varnish.
  • the charge-transporting organic compound for example, those used in the field of organic EL and the like can be used.
  • arylamine derivatives aniline derivatives
  • oligoaniline derivatives N, N'-diarylbenzidine derivatives, N, N, N', N'-tetraarylbenzidine derivatives, oligothiophene derivatives, and thienothiophene derivatives.
  • Thionophen derivatives such as thienobenzothiophene derivatives
  • various charge-transporting organic compounds such as pyrrole derivatives such as oligopyrrole.
  • arylamine derivatives and thiophene derivatives are preferable.
  • Examples of the charge-transporting organic compound include JP-A-2002-151272, International Publication No. 2004/105446, International Publication No. 2005/043962, International Publication No. 2008/032617, International Publication No. 2008/032616, and International Publication No. 2013/0426223, International Publication 2014/141998, International Publication No. 2014/185208, International Publication No. 2015/050253, International Publication No. 2015/137391, International Publication No. 2015/137395, International Publication No. 2015 / 146912, International Publication No. 2015/146965, International Publication No. 2016/190326, International Publication No. 2016/136544, International Publication No. 2016/204079, etc. can be used.
  • the charge-transporting organic compound needs to be monodisperse (that is, the molecular weight distribution is 1).
  • the molecular weight of the charge-transporting organic compound is usually about 200 to 9,000 from the viewpoint of preparing a uniform varnish that gives a thin film having high flatness, but 300 from the viewpoint of obtaining a thin film having more excellent charge-transporting property.
  • the above is preferable, 400 or more is more preferable, and from the viewpoint of preparing a uniform varnish that gives a thin film having high flatness with better reproducibility, 8,000 or less is preferable, 7,000 or less is more preferable, and 6,000 or less is preferable. Even more preferably, 5,000 or less is even more preferable.
  • the charge transporting organic compound a monodisperse charge transporting organic compound may be used alone, or two or more different monodisperse charge transporting organic compounds may be used in combination, but the creeping phenomenon From the viewpoint of suppressing reproducibility, the monodisperse charge-transporting organic compound used is preferably 1 to 3 types, and more preferably 1 or 2 types from the viewpoint of facilitating varnish preparation. More preferably, it is one kind.
  • Ph is a phenyl group and DPA is a diphenylamino group.
  • the content of the charge-transporting organic compound in the solid content is usually about 2 to 99% by mass, preferably about 10 to 95% by mass, and more preferably about 20 to 90% by mass.
  • Organic solvent is not particularly limited as long as it can dissolve or disperse each of the above-mentioned components and each of the optional components described below, but it is preferable to use a low-polarity solvent in terms of excellent process compatibility.
  • a low-polarity solvent is defined as a solvent having a relative permittivity of less than 7 at a frequency of 100 kHz
  • a high-polarity solvent is defined as a solvent having a relative permittivity of 7 or more at a frequency of 100 kHz.
  • low polar solvent examples include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as toluene, xylene, tetraline, cyclohexylbenzene and decylbenzene; 1-octanol, 1-nonanol, 1-decanol and the like.
  • Alibo alcohol solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, etc.
  • Solvents Methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis (2-ethylhexyl) phthalate, dimethyl phthalate, diisopropyl malate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether
  • ester solvents such as acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.
  • Examples of the highly polar solvent include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutylamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone.
  • Ketone solvent such as ethyl methyl ketone, isophorone, cyclohexanone; Cyano solvent such as acetonitrile and 3-methoxypropionitrile; Ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, Polyhydric alcohol solvents such as 2,3-butanediol; diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyl Monohydric alcohol solvents other than aliphatic alcohols such as oxyethanol, 3-phenoxybenzyl alcohol and tetrahydrofurfuryl alcohol; sulfoxide solvents such as dimethyl sulfoxide and the like can be mentioned.
  • Ketone solvent such as ethyl methyl ketone, isophor
  • the amount of the organic solvent used is such that the solid content concentration in the varnish of the present invention is usually about 0.1 to 20% by mass from the viewpoint of ensuring a sufficient film thickness while suppressing the precipitation of the charge-transporting organic compound.
  • the amount is preferably 0.5 to 10% by mass.
  • the organic solvent may be used alone or in combination of two or more.
  • the charge-transporting varnish of the present invention can also contain water as a solvent, but the water content is preferably higher than that of the solvent contained in the varnish from the viewpoint of obtaining an organic EL element having excellent durability with good reproducibility. From the viewpoint of obtaining a charge-transporting thin film having 3% by mass or less and suppressed pile-up with good reproducibility, it is preferable to use only an organic solvent as the solvent.
  • “only the organic solvent” means that only the organic solvent is used as the solvent, and even the existence of "water” contained in a trace amount in the organic solvent used, the solid content, etc. is denied. It's not something to do.
  • the charge-transporting varnish of the present invention may contain a dopant for the purpose of improving the charge-transporting property of the thin film obtained from the charge-transporting varnish of the present invention.
  • the dopant is not particularly limited as long as it is soluble in at least one solvent used for varnish, and either an inorganic dopant or an organic dopant can be used.
  • the dopant first develops its function as a dopant by removing a part of the molecule due to an external stimulus such as heating during firing. It may be a substance that becomes improved, for example, an aryl sulfonic acid ester compound protected by a group in which a sulfonic acid group is easily eliminated.
  • Heteropolyacid is preferable as the inorganic dopant, and specific examples thereof include phosphomolybdic acid, silicate molybdic acid, phosphotungstic acid, phosphotungstic acid, and silicate tungstic acid.
  • the heteropolyacid has a structure in which a hetero atom is located at the center of a molecule, which is typically represented by a Keggin type chemical structure represented by the following formula (HPA1) or a Dawson type chemical structure represented by the following formula (HPA2). It is a polyacid formed by condensing isopolyacid, which is an oxygen acid such as vanadium (V), molybdenum (Mo), and tungsten (W), and oxygen acid of a different element. Examples of such dissimilar element oxygen acids include oxygen acids of silicon (Si), phosphorus (P), and arsenic (As).
  • heteropolyacid examples include phosphomolybdic acid, silicate molybdic acid, phosphotungstic acid, silicate tungstic acid, and phosphotungstic acid. These may be used individually by 1 type or in combination of 2 or more type.
  • the heteropolyacid used in the present invention is available as a commercially available product, and can also be synthesized by a known method. In particular, when one kind of heteropolyacid is used, phosphotungstic acid or phosphomolybdic acid is preferable as the one kind of heteropolyacid, and phosphotungstic acid is most suitable.
  • one of the two or more kinds of heteropolyacids is preferably phosphotungstic acid or phosphomolybdic acid, and more preferably phosphotungstic acid.
  • the heteropolyacid in quantitative analysis such as elemental analysis, even if the number of elements of the heteropolyacid is large or small from the structure represented by the general formula, the heteropolyacid is obtained as a commercially available product or a known synthesis method. As long as it is properly synthesized according to the above, it can be used in the present invention.
  • phosphotungsic acid is generally represented by the chemical formulas H 3 (PW 12 O 40 ) and nH 2 O
  • phosphomolybdic acid is generally represented by the chemical formulas H 3 (PMo 12 O 40 ) and nH 2 O.
  • P (phosphorus), O (oxygen) or W (tungsten) or Mo (molybdenum) in this formula is large or small, it is obtained as a commercial product, or As long as it is appropriately synthesized according to a known synthesis method, it can be used in the present invention.
  • the mass of the heteropolyacid defined in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in the synthetic product or the commercially available product, but the form available as the commercially available product and the known synthesis. In a form that can be isolated by the method, it means the total mass in a state containing hydrated water and other impurities.
  • organic dopant examples include aryl sulfonic acid, aryl sulfonic acid ester, an ionic compound composed of a predetermined anion and its counter cation, a tetracyanoquinodimethane derivative, a benzoquinone derivative and the like.
  • the aryl sulfonic acid compound is preferably represented by the following formula (A) or (B) from the viewpoint of the transparency of the thin film obtained from the charge transporting varnish of the present invention.
  • a 1 is -O- or -S-, but -O- is preferable.
  • a 2 is a naphthalene ring or an anthracene ring, but a naphthalene ring is preferable.
  • a 3 is a 2- to tetravalent perfluorobiphenyl group.
  • p 1 is the number of bonds between A 1 and A 3, and is an integer satisfying 2 ⁇ p 1 ⁇ 4, but A 3 is a divalent group derived from perfluorobiphenyl and p 1 Is preferably 2.
  • p 2 is the number of sulfonic acid groups bonded to A 2 , and is an integer satisfying 1 ⁇ p 2 ⁇ 4, but 2 is preferable.
  • a 4 to A 8 are independently hydrogen atom, halogen atom, cyano group, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms or 2 to 2 carbon atoms, respectively. There are 20 halogenated alkenyl groups, but at least 3 of A 4 to A 8 are halogen atoms.
  • q is the number of sulfonic acid groups bonded to the naphthalene ring and is an integer satisfying 1 ⁇ q ⁇ 4, but 2 to 4 is preferable, and 2 is more preferable.
  • alkyl halide group having 1 to 20 carbon atoms examples include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, and a 3,3,3-trifluoropropyl group, 2,2, 3,3,3-Pentafluoropropyl group, perfluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3, Examples thereof include 4,4,4-heptafluorobutyl group and perfluorobutyl group.
  • halogenated alkenyl group having 2 to 20 carbon atoms examples include a perfluoroethenyl group, a 1-perfluoropropenyl group, a perfluoroallyl group, a perfluorobutenyl group and the like.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group having 1 to 20 carbon atoms include the same ones as mentioned in the description of R A and R B of formula (6).
  • a 4 to A 8 include a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 10 carbon atoms, or an alkenyl halide having 2 to 10 carbon atoms.
  • a group it is preferable that at least three fluorine atoms of a 4 - a 8, a hydrogen atom, a fluorine atom, fluorinated cyano group, an alkyl group having 1 to 5 carbon atoms, 5 It is more preferably an alkyl group or a fluorinated alkenyl group having 2 to 5 carbon atoms, and at least 3 of A 4 to A 8 are fluorine atoms, and a hydrogen atom, a fluorine atom, a cyano group, and 1 to 1 carbon atoms.
  • the perfluoroalkyl group of 5 or the perfluoroalkenyl group having 1 to 5 carbon atoms is, and A 4 , A 5 and A 8 are fluorine atoms.
  • the perfluoroalkyl group is a group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms
  • the perfluoroalkyl group is a group in which all the hydrogen atoms of the alkenyl group are substituted with fluorine atoms.
  • Suitable aryl sulfonic acids include, but are not limited to, those shown below.
  • the aryl sulfonic acid ester compound As the aryl sulfonic acid ester compound, the aryl sulfonic acid ester compound disclosed in International Publication No. 2017/217455, International Publication No. 2017/217457, from the viewpoint of the transparency of the thin film obtained from the charge transport varnish of the present invention. Examples thereof include the aryl sulfonic acid ester compound disclosed in No. 2, the aryl sulfonic acid ester compound described in Japanese Patent Application No. 2017-243631 and the like.
  • the aryl sulfonic acid ester compound is preferably represented by the following formulas (C) to (E).
  • a 11 is an m-valent group derived from perfluorobiphenyl (ie, a group obtained by removing m fluorine atoms from perfluorobiphenyl).
  • a 12 is —O— or —S—, but —O— is preferred.
  • a 13 is a (n + 1) -valent group derived from naphthalene or anthracene (that is, a group obtained by removing (n + 1) hydrogen atoms from naphthalene or anthracene), but a group derived from naphthalene is preferable. ..
  • R s1 to R s4 are independently hydrogen atoms or linear or branched alkyl groups having 1 to 6 carbon atoms, and R s5 is optionally substituted carbon. It is a monovalent hydrocarbon group of numbers 2 to 20.
  • Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. , N-Hexyl group and the like. Of these, an alkyl group having 1 to 3 carbon atoms is preferable.
  • the monovalent hydrocarbon group having 2 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl.
  • Examples include an alkyl group such as a group, a sec-butyl group and a tert-butyl group; and an aryl group such as a phenyl group, a naphthyl group and a phenanthryl group.
  • R s1 to R s4 it is preferable that R s1 or R s3 is a linear alkyl group having 1 to 3 carbon atoms and the rest are hydrogen atoms. Further, it is preferable that R s1 is a linear alkyl group having 1 to 3 carbon atoms and R s2 to R s4 are hydrogen atoms. As the linear alkyl group having 1 to 3 carbon atoms, a methyl group is preferable. Further, as R s5 , a linear alkyl group or a phenyl group having 2 to 4 carbon atoms is preferable.
  • n is an integer satisfying 1 ⁇ n ⁇ 4, but 2 is preferable.
  • a 14 is an m-valent hydrocarbon group having 6 to 20 carbon atoms containing one or more aromatic rings which may be substituted.
  • the hydrocarbon group is a group obtained by removing m hydrogen atoms from a hydrocarbon having one or more aromatic rings and having 6 to 20 carbon atoms.
  • Examples of the hydrocarbon include benzene, toluene, xylene, ethylbenzene, biphenyl, naphthalene, anthracene, phenanthrene and the like.
  • a part or all of the hydrogen atom of the hydrocarbon group may be further substituted with a substituent, and such substituents include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a nitro.
  • Group cyano group, hydroxy group, amino group, silanol group, thiol group, carboxy group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, ester group, thioester group, amide group, monovalent hydrocarbon group, organo Examples thereof include an oxy group, an organoamino group, an organosilyl group, an organothio group, an acyl group and a sulfo group. Of these, as A 14 , a group derived from benzene, biphenyl, or the like is preferable.
  • a 15 is —O— or —S—, but —O— is preferred.
  • a 16 is a (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms.
  • the aromatic hydrocarbon group is a group obtained by removing (n + 1) hydrogen atoms from the aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms.
  • the aromatic hydrocarbon compound include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like. Of these, as A 16 , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.
  • R s6 and R s7 are independently hydrogen atoms or linear or branched monovalent aliphatic hydrocarbon groups.
  • R s8 is a linear or branched monovalent aliphatic hydrocarbon group.
  • the total number of carbon atoms of R s6 , R s7 and R s8 is 6 or more.
  • the upper limit of the total number of carbon atoms of R s6 , R s7 and R s8 is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.
  • linear or branched monovalent aliphatic hydrocarbon group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-.
  • Alkyl group having 1 to 20 carbon atoms such as butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group; vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1- Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as a methyl-2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group and a hexenyl group.
  • R s6 A hydrogen atom is preferable as R s6
  • R s7 and R s8 an alkyl group having 1 to 6 carbon atoms is preferable as R s7 and R s8 .
  • R s7 and R s8 may be the same or different.
  • m is an integer satisfying 1 ⁇ m ⁇ 4, but 2 is preferable.
  • n is an integer satisfying 1 ⁇ n ⁇ 4, but 2 is preferable.
  • R s9 to R s13 independently represent a hydrogen atom, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. It is a halogenated alkenyl group having 2 to 10 carbon atoms.
  • the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl.
  • the alkyl halide group having 1 to 10 carbon atoms is not particularly limited as long as it is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms are substituted with halogen atoms.
  • the alkyl halide group may be linear, branched or cyclic, and specific examples thereof include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, 1,1,2,2, 2-Pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl Group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1 , 2,2,3,3,4,4,4-nonafluorobutyl group and the like.
  • the halogenated alkenyl group having 2 to 10 carbon atoms is not particularly limited as long as it is a group in which a part or all of the hydrogen atoms of the alkenyl group having 2 to 10 carbon atoms are substituted with halogen atoms.
  • Specific examples thereof include a perfluorovinyl group, a perfluoro-1-propenyl group, a perfluoro-2-propenyl group, a perfluoro-1-butenyl group, a perfluoro-2-butenyl group, and a perfluoro-3-butenyl group. And so on.
  • R s9 a nitro group, a cyano group, an alkyl halide group having 1 to 10 carbon atoms, an alkenyl halide group having 2 to 10 carbon atoms and the like are preferable, and a nitro group, a cyano group and 1 to 10 carbon atoms are preferable.
  • the alkyl halide group of 4 and the alkenyl halide group having 2 to 4 carbon atoms are more preferable, and the nitro group, the cyano group, the trifluoromethyl group, the perfluoropropenyl group and the like are even more preferable.
  • R s10 to R s13 a halogen atom is preferable, and a fluorine atom is more preferable.
  • a 17 is —O—, —S— or —NH—, but —O— is preferred.
  • a 18 is a (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms.
  • the aromatic hydrocarbon group is a group obtained by removing (n + 1) hydrogen atoms from the aromatic ring of an aromatic hydrocarbon compound having 6 to 20 carbon atoms.
  • the aromatic hydrocarbon compound include benzene, toluene, xylene, biphenyl, naphthalene, anthracene, pyrene and the like. Of these, as A 18 , a group derived from naphthalene or anthracene is preferable, and a group derived from naphthalene is more preferable.
  • R s14 to R s17 are independently hydrogen atoms or linear or branched monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms.
  • the monovalent aliphatic hydrocarbon group may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group.
  • R s18 is a linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or ⁇ OR s19 .
  • R s19 is a monovalent hydrocarbon group having 2 to 20 carbon atoms which may be substituted.
  • Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R s18 include those similar to those described in the description of R s14 to R s17 .
  • R s18 is a monovalent aliphatic hydrocarbon group
  • R s18 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Is even more preferable.
  • the monovalent hydrocarbon group having 2 to 20 carbon atoms represented by R s19 includes an aryl group such as a phenyl group, a naphthyl group and a phenanthryl group in addition to the above-mentioned monovalent aliphatic hydrocarbon groups other than the methyl group. And so on. Of these, as R s19 , a linear alkyl group or a phenyl group having 2 to 4 carbon atoms is preferable. Examples of the substituent that the monovalent hydrocarbon group may have include a fluorine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, and a cyano group.
  • n is an integer satisfying 1 ⁇ n ⁇ 4, but 2 is preferable.
  • Suitable aryl sulfonic acid ester compounds include, but are not limited to, those shown below.
  • the ionic compound represented by the following formula (F) is preferable from the viewpoint of the transparency of the thin film obtained from the charge transporting varnish of the present invention.
  • E is a Group 13 element of the long periodic table
  • Ar 1 to Ar 4 are independently aryl groups having 6 to 20 carbon atoms or heteroaryl groups having 2 to 20 carbon atoms.
  • a group such as a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, an acyl group having 2 to 12 carbon atoms such as a cyano group, a nitro group or an acetyl group, or a halogen having 1 to 10 carbon atoms such as a trifluoromethyl group. It may be substituted with an alkylated group.
  • a boron atom, an aluminum atom, and a gallium atom are preferable, and a boron atom is more preferable.
  • the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group and a 2-phenanthryl group. Examples thereof include a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.
  • heteroaryl group having 2 to 20 carbon atoms examples include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group and 3-.
  • Isooxazolyl group 4-isoxazolyl group, 5-isooxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, 4- Examples thereof include an imidazolyl group, a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group.
  • M + is an onium ion.
  • the onium ion include iodonium ion, sulfonium ion, ammonium ion, phosphonium ion and the like, and iodonium ion represented by the following formula (G) is particularly preferable.
  • R 1 and R 2 independently have an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, and 6 to 20 carbon atoms, respectively.
  • tetracyanoquinodimethane derivative examples include 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2,5-difluoro.
  • benzoquinone derivative examples include tetrachloro-1,4-benzoquinone (chloranil), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and the like.
  • aryl sulfonic acid compounds and aryl sulfonic acid ester compounds are preferable because they have a large effect of suppressing the creep-up phenomenon.
  • the charge-transporting varnish of the present invention contains a dopant
  • the content thereof varies depending on the type of dopant, the desired charge-transporting property, and the like, and therefore cannot be unconditionally defined.
  • the dopant for the charge-transporting organic compound (H) (H) is usually about 0.01 to 50 in terms of molar ratio, preferably about 0.1 to 10, and more preferably 1.
  • the amount is about 0 to 5.0.
  • the charge-transporting varnish of the present invention may further contain an organic silane compound for the purpose of adjusting the film physical characteristics of the obtained charge-transporting thin film.
  • organic silane compound examples include a dialkoxysilane compound, a trialkoxysilane compound, and a tetraalkoxysilane compound.
  • a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable.
  • the organic silane compound may be used alone or in combination of two or more.
  • the content thereof is usually about 0.1 to 50% by mass in the solid content, but the flatness of the obtained thin film is improved and the decrease in charge transportability is suppressed. In consideration of such a balance, it is preferably about 0.5 to 40% by mass, more preferably about 0.8 to 30% by mass, and even more preferably about 1 to 20% by mass.
  • the charge-transporting varnish of the present invention may contain an amine compound from the viewpoint of dissolving a charge-transporting organic compound or a dopant in an organic solvent to obtain a highly uniform varnish, and the content thereof is usually in the solid content. It is about 0.1 to 50% by mass.
  • the method for preparing the charge-transporting varnish is not particularly limited, and examples thereof include a method of adding a charge-transporting organic compound, surface-modified zirconia particles, and if necessary, a dopant or the like to the organic solvent in any order or at the same time.
  • a charge-transporting organic compound, surface-modified zirconia particles, and if necessary, a dopant or the like may be dissolved or dispersed in one organic solvent, and another organic solvent may be added thereto.
  • a charge-transporting organic compound, surface-modified zirconia particles, and, if necessary, a dopant and the like may be dissolved or dispersed sequentially or simultaneously in a mixed solvent of a plurality of organic solvents.
  • a charge transporting varnish may be prepared using a dispersion of surface-modified zirconia particles.
  • the mixing order is not particularly limited, but a mixture is prepared by mixing components other than the surface-modified zirconia particles (charge-transporting organic compound, etc.) with an organic solvent, and the surface-modified zirconia particles prepared in advance in the mixture are prepared. Examples thereof include a method of adding a dispersion and a method of adding a mixture thereof to a prepared dispersion of surface-modified zirconia particles.
  • an additional organic solvent may be added at the end, or a part of the components relatively easily soluble in the organic solvent may be added at the end without being included in the mixture.
  • a dispersion containing surface-modified zirconia particles in a good dispersed state or a good dissolved state and a mixture containing other components are prepared. It is preferable to prepare separately, mix the two, and then stir well. It should be noted that surface-modified zirconia particles, charge-transporting organic compounds, etc. may aggregate or precipitate when mixed depending on the type and amount of the organic solvent mixed together.
  • the charge transporting varnish it may be appropriately heated as long as the components do not decompose or deteriorate.
  • the charge-transporting varnish of the present invention is a submicrometer-order filter after dissolving a charge-transporting organic compound and, if necessary, a dopant or the like in an organic solvent from the viewpoint of obtaining a thin film having higher flatness with good reproducibility. It is desirable to filter using such as.
  • the viscosity of the charge-transporting varnish of the present invention is usually 1 to 50 mPa ⁇ s at 25 ° C.
  • the surface tension of the charge-transporting varnish of the present invention is usually 20 to 50 mN / m at 25 ° C.
  • the viscosity is a value measured by a TVE-25 type viscometer manufactured by Toki Sangyo Co., Ltd.
  • the surface tension is a value measured by an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.
  • the viscosity and surface tension of the varnish can be adjusted by changing the types of solvents described above, their ratios, the solid content concentration, and the like in consideration of various factors such as a desired film thickness.
  • the charge-transporting organic substance monodisperse in the charge-transporting varnish of the present invention.
  • the compound and, if contained, the dopant and the like are uniformly dissolved in the organic solvent, and the zirconia particles surface-modified with the surface treatment agent are uniformly dispersed in the organic solvent.
  • the charge-transporting thin film of the present invention can be formed by applying the charge-transporting varnish of the present invention on a substrate and firing it.
  • varnish coating method examples include, but are not limited to, the dip method, spin coating method, transfer printing method, roll coating method, brush coating, inkjet method, spray method, slit coating method, and the like. It is preferable to adjust the viscosity and surface tension of the varnish according to the coating method.
  • the firing atmosphere of the charge-transporting varnish after coating is not particularly limited, and it is possible to obtain a thin film having a uniform film-forming surface and high charge-transporting property not only in the air atmosphere but also in an inert gas such as nitrogen or in a vacuum. it can. Depending on the type of dopant used together, a thin film having higher charge transportability may be obtained with good reproducibility by firing the varnish in an air atmosphere.
  • the firing temperature is usually set appropriately within the range of about 100 to 260 ° C. in consideration of the intended use of the obtained thin film, the degree of charge transportability applied to the obtained thin film, the type of solvent, the boiling point, and the like.
  • a temperature change of two or more steps may be applied for the purpose of exhibiting higher uniform film forming property or allowing the reaction to proceed on the substrate, and heating may be performed by, for example, a hot plate or the like. It may be carried out using an appropriate device such as an oven.
  • the thickness of the charge transporting thin film is not particularly limited, but when used as a functional layer between the anode and the light emitting layer such as a hole injection layer, a hole transport layer, or a hole injection transport layer of an organic EL element, 5
  • the lower limit is preferably 10 nm, more preferably 20 nm, still more preferably 30 nm, still more preferably 40 nm, and even more preferably, from the viewpoint of obtaining a charge-transporting thin film having excellent flatness with good reproducibility.
  • Is 45 nm and the upper limit thereof is preferably 250 nm, more preferably 200 nm, even more preferably 150 nm, still more preferably 100 nm, and even more preferably 75 nm from the viewpoint of obtaining a thin film having excellent transparency with good reproducibility. .. If the particle size of the surface-modified zirconia particles is larger than the film thickness, a thin film having excellent flatness cannot be obtained. Therefore, the particle size of the surface-modified zirconia particles to be used is determined in consideration of the desired film thickness. Usually, the average particle diameter (nm) of the surface-modified zirconia particles is 3 nm or more smaller than the thickness (nm) of the charge-transporting thin film. Examples of the method of changing the film thickness include a method of changing the solid content concentration in the varnish and a method of changing the amount of liquid on the substrate at the time of coating.
  • the charge-transporting thin film of the present invention exhibits a refractive index (n) of 1.67 or more and an extinction coefficient (k) of 0.040 or less on average in the wavelength region of 400 to 800 nm, but in some embodiments. It exhibits a refractive index of 1.69 or higher, in some other embodiments a refractive index of 1.72 or higher, and in yet another embodiment a refractive index of 1.73 or higher. Further, in one embodiment, the extinction coefficient is 0.030 or less, in another aspect, the extinction coefficient is 0.025 or less, and in yet another aspect, the extinction coefficient is 0.020 or less.
  • the charge-transporting thin film of the present invention can be formed by the method described above, but by using the charge-transporting varnish of the present invention, the charge-transporting thin film can be suitably formed in the partition wall of the substrate with a partition wall.
  • the substrate with a partition wall is not particularly limited as long as it is a substrate on which a predetermined pattern is formed by a known photolithography method or the like. Normally, there are a plurality of openings defined by the partition wall on the substrate. Usually, the size of the opening is 100 to 210 ⁇ m on the long side, 40 ⁇ m ⁇ 100 ⁇ m on the short side, and the bank taper angle is 20 to 80 °.
  • the material of the substrate is not particularly limited, but is a transparent electrode material typified by indium tin oxide (ITO) and indium zinc oxide (IZO) used as an anode material of an electronic element; aluminum, gold, Metal anode materials composed of metals typified by silver, copper, indium, etc. or alloys thereof; polymer anode materials such as polythiophene derivatives and polyaniline derivatives having high charge transport properties, etc., are subjected to flattening treatment. Is preferable.
  • the charge transporting varnish of the present invention is applied to the inside of the partition wall of the substrate with a partition wall by an inkjet method, then depressurized, and further heated if necessary to remove the solvent from the charge transporting varnish coated inside the partition wall.
  • a charge-transporting thin film can be produced to produce a substrate with a charge-transporting thin film, and further, by laminating other functional films on the charge-transporting thin film, an electronic element such as an organic EL element can be formed. Can be manufactured.
  • the atmosphere at the time of coating with the inkjet is not particularly limited, and may be any of an air atmosphere, an atmosphere of an inert gas such as nitrogen, and a reduced pressure.
  • the degree of decompression (vacuum degree) at the time of depressurization is not particularly limited as long as the solvent of the varnish evaporates, but is usually 1,000 Pa or less, preferably 100 Pa or less, more preferably 50 Pa or less, still more preferably 25 Pa or less, and further. It is preferably 10 Pa or less.
  • the depressurizing time is also not particularly limited as long as the solvent evaporates, but is usually about 0.1 to 60 minutes, preferably about 1 to 30 minutes.
  • the conditions for firing (heating) are the same as the above-mentioned conditions.
  • the pile-up index described later is usually a high value of 84% or more, preferably 87% or more, more preferably 90% or more, even more preferably 93% or more, still more preferably 96% or more, and pile. Up can be suppressed.
  • the pile-up index is when the partition wall (bank) width is A ( ⁇ m) and the film thickness range of + 10% from the film thickness of the charge-transporting thin film at the center of the partition wall (bank) is B ( ⁇ m). It can be derived from the formula (B / A) ⁇ 100 (%).
  • the organic EL device of the present invention has a pair of electrodes, and has a functional layer made of the charge-transporting thin film of the present invention between these electrodes.
  • Typical configurations of the organic EL element include, but are not limited to, the following (a) to (f).
  • an electron block layer or the like may be provided between the light emitting layer and the anode, and a hole block layer or the like may be provided between the light emitting layer and the cathode.
  • the hole injection layer, the hole transport layer or the hole injection transport layer may have a function as an electron block layer or the like, and the electron injection layer, the electron transport layer or the electron injection transport layer may serve as a hole block layer or the like. It may also have the functions of.
  • an arbitrary functional layer can be provided between the layers.
  • Electron / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (b) anode / hole injection layer / hole transport layer / light emitting layer / electron injection transport layer / Cathode (c) anode / hole injection transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (d) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (e) anode / positive Hole injection layer / hole transport layer / light emitting layer / cathode (f) Electron / hole injection transport layer / light emitting layer / cathode
  • the "hole injection layer”, “hole transport layer” and “hole injection transport layer” are layers formed between the light emitting layer and the anode, and transport holes from the anode to the light emitting layer. It has a function. When only one layer of hole transporting material is provided between the light emitting layer and the anode, it is a “hole injection transport layer”, and a layer of hole transporting material between the light emitting layer and the anode. When two or more layers are provided, the layer close to the anode is the “hole injection layer”, and the other layers are the “hole transport layers”.
  • the hole injection (transport) layer a thin film having excellent not only hole acceptability from the anode but also hole injection property into the hole transport (emission) layer is used.
  • the "electron injection layer”, “electron transport layer” and “electron transport layer” are layers formed between the light emitting layer and the cathode and have a function of transporting electrons from the cathode to the light emitting layer. Is. When only one layer of electron transporting material is provided between the light emitting layer and the cathode, it is an “electron injection transporting layer”, and two layers of electron transporting material are provided between the light emitting layer and the cathode. When the above is provided, the layer close to the cathode is the “electron injection layer”, and the other layers are the “electron transport layer”.
  • the "light emitting layer” is an organic layer having a light emitting function, and includes a host material and a dopant material when a doping system is adopted.
  • the host material mainly has a function of promoting the recombination of electrons and holes and confining the excitons in the light emitting layer, and the dopant material efficiently emits excitons obtained by the recombination. Has a function.
  • the host material mainly has a function of confining excitons generated by the dopant in the light emitting layer.
  • the charge transporting thin film of the present invention can be suitably used as a functional layer provided between the anode and the light emitting layer in an organic EL device, and can be used as a hole injection layer, a hole transport layer, or a hole injection transport layer. It can be used more preferably, and can be used even more preferably as a hole injection layer.
  • the materials and manufacturing methods used when manufacturing an organic EL device using the charge transporting varnish of the present invention include, but are not limited to, the following.
  • An example of a method for producing an organic EL device having a hole injection layer made of a charge transporting thin film obtained from the charge transporting varnish of the present invention is as follows. It is preferable that the electrode is preliminarily subjected to surface treatment such as cleaning with alcohol, pure water or the like, UV ozone treatment, oxygen-plasma treatment or the like within a range that does not adversely affect the electrode.
  • a hole injection layer is formed on the anode substrate by the above method using the charge transporting varnish of the present invention. This is introduced into a vacuum vapor deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer / hole block layer, an electron injection layer, and a cathode metal are sequentially vapor-deposited.
  • a composition for forming a hole transport layer containing a hole transport polymer and a composition for forming a light emitting layer containing a light emitting polymer are used instead of forming the hole transport layer and the light emitting layer by vapor deposition in the method. These layers are formed by a wet process using. If necessary, an electron block layer may be provided between the light emitting layer and the hole transport layer.
  • anode material examples include transparent electrodes typified by ITO and IZO, metals typified by aluminum, and metal anodes composed of alloys thereof, and those subjected to flattening treatment are preferable.
  • Polythiophene derivatives and polyaniline derivatives having high charge transport properties can also be used.
  • other metals constituting the metal anode include, but are not limited to, gold, silver, copper, indium, and alloys thereof.
  • Examples of the material for forming the hole transport layer include (triphenylamine) dimer derivative, [(triphenylamine) dimer] spirodimer, and N, N'-bis (naphthalen-1-yl) -N, N'-.
  • Examples of the material forming the light emitting layer include a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo [h] quinoline, a bisstyrylbenzene derivative, a bisstyryl arylene derivative, and (2-hydroxyphenyl).
  • a metal complex such as an aluminum complex of 8-hydroxyquinoline, a metal complex of 10-hydroxybenzo [h] quinoline, a bisstyrylbenzene derivative, a bisstyryl arylene derivative, and (2-hydroxyphenyl).
  • Low molecular weight luminescent materials such as benzothiazole metal complexes and silol derivatives; poly (p-phenylene vinylene), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene], poly (3- Alkylthiophene), a system in which a light emitting material and an electron transfer material are mixed with a polymer compound such as polyvinylcarbazole, and the like, but are not limited thereto.
  • the light emitting layer When the light emitting layer is formed by vapor deposition, it may be co-deposited with a light emitting dopant, and the light emitting dopant may be a metal such as tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ). Examples thereof include, but are not limited to, a complex, a naphthacene derivative such as rubrene, a quinacridone derivative, and a condensed polycyclic aromatic ring such as perylene.
  • Examples of the material for forming the electron transport layer / whole block layer include, but are not limited to, an oxydiazole derivative, a triazole derivative, a phenanthroline derivative, a phenylquinoxaline derivative, a benzimidazole derivative, and a pyrimidine derivative.
  • Examples of the material forming the electron injection layer include metal oxides such as lithium oxide (Li 2 O), magnesium oxide (Mg O), and alumina (Al 2 O 3 ), lithium fluoride (LiF), and sodium fluoride (NaF). ), But is not limited to these.
  • cathode material examples include, but are not limited to, aluminum, magnesium-silver alloy, aluminum-lithium alloy, and the like.
  • Examples of the material for forming the electron block layer include, but are not limited to, tris (phenylpyrazole) iridium and the like.
  • hole-transporting polymer examples include poly [(9,9-dihexylfluorenyl-2,7-diyl) -co- (N, N'-bis ⁇ p-butylphenyl ⁇ -1,4-diamino).
  • Phenylene poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (N, N'-bis ⁇ p-butylphenyl ⁇ -1,1'-biphenylene-4,4- Diamine)], poly [(9,9-bis ⁇ 1'-penten-5'-yl ⁇ fluorenyl-2,7-diyl) -co- (N, N'-bis ⁇ p-butylphenyl ⁇ -1, 4-Diaminophenylene)], poly [N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl) -benzidine] -endcapped with polysilsesquioxane, poly [(9,, 9-didioctylfluorenyl-2,7-diyl) -co- (4,4'-(N- (p-butylphenyl)) diphenylamine)] and the like
  • luminescent polymer examples include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF) and poly (2-methoxy-5- (2'-ethylhexoxy) -1,4-phenylene vinylene) (MEH).
  • PDAF poly (9,9-dialkylfluorene)
  • MEH poly (2-methoxy-5- (2'-ethylhexoxy) -1,4-phenylene vinylene)
  • -PPV polyphenylene vinylene derivatives
  • PAT poly (3-alkylthiophene)
  • PVCz polyvinylcarbazole
  • the materials forming the anode and cathode and the layer formed between them differ depending on whether the element having the bottom emission structure or the top emission structure is manufactured. Therefore, the material is appropriately selected in consideration of this point. ..
  • a transparent anode is used on the substrate side to extract light from the substrate side
  • a reflective anode made of metal is used and the direction is opposite to that of the substrate.
  • Light is extracted from a certain transparent electrode (cathode) side. Therefore, for example, regarding the anode material, a transparent anode such as ITO is used when manufacturing an element having a bottom emission structure, and a reflective anode such as Al / Nd is used when manufacturing an element having a top emission structure.
  • the organic EL device of the present invention may be sealed together with a water catching agent or the like, if necessary, in accordance with a conventional method in order to prevent deterioration of characteristics.
  • the charge transporting thin film of the present invention can be used as a functional layer of an organic EL element, but in addition, an organic photoelectric conversion element, an organic thin film solar cell, an organic perovskite photoelectric conversion element, an organic integrated circuit, and an organic Electric field effect transistors, organic thin films, organic light emitting transistors, organic optical testers, organic photoreceivers, organic electric field extinguishing devices, light emitting electronic chemical batteries, quantum dot light emitting diodes, quantum lasers, organic laser diodes, organic Plasmon light emitting devices, etc. It can also be used as a functional layer of an electronic device.
  • the equipment used is as follows. (1) MALDI-TOF-MS: Bruker's autoflex III smart beam (2) 1 1 H-NMR: JNM-ECP300 FT NMR SYSTEM manufactured by JEOL Ltd. (3) Substrate cleaning: Substrate cleaning equipment manufactured by Choshu Sangyo Co., Ltd. (decompression plasma method) (4) Varnish application: Spin coater MS-A100 manufactured by Mikasa Co., Ltd. (5) Film thickness measurement and surface shape measurement: Fine shape measuring machine surf coder ET-4000A manufactured by Kosaka Laboratory Co., Ltd. (6) Manufacture of element: Multi-function vapor deposition equipment system C-E2L1G1-N manufactured by Choshu Sangyo Co., Ltd.
  • Measurement of element current density Multi-channel IVL measuring device manufactured by EHC Co., Ltd.
  • MMA Methyl methacrylate
  • HEMA 2-Hydroxyethyl methacrylate
  • HPMA 4-Hydroxyphenyl methacrylate
  • HPMA-QD Condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate with 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride
  • Compound CHMI N-cyclohexylmaleimide
  • PFHMA 2- (perfluorohexyl) ethyl methacrylate
  • MAA AIBN methacrylate: ⁇ , ⁇ '-azobisisobutyronitrile
  • QD1 ⁇ , ⁇ , ⁇ '-tris (4) -Hydroxyphenyl
  • GT-401 Tetrabutanetetracarboxylate (Tetrabutantetracarboxylate) 3,4-Epoxycyclohexylmethyl) modified ⁇ -caprolactone (trade name: Epolide GT-401, manufactured by Daicel Co., Ltd.)
  • PGME Propylene glycol monomethyl ether
  • PGMEA Propylene glycol monomethyl ether acetate
  • CHN Cyclohexanone
  • TMAH Tetramethylammonium hydroxide
  • TBSCl tert-butyldimethylchlorosilane
  • THF tetrahydrofuran
  • Pdba) 2 Bis (dibenzylideneacetone) Palladium (0) [(t-Bu) 3 PH]
  • BF 4 Tritert-butylphosphnium tetrafluoroborate
  • t-BuONa tert-sodium butoxy TBAF: tetrabutylammonium fluor
  • the number average molecular weight (Mn) and weight average molecular weight (Mw) of the acrylic polymers P1 and P2 were measured by gel permeation chromatography (GPC) under the following conditions.
  • GPC gel permeation chromatography
  • ⁇ Chromatograph GPC device LC-20AD manufactured by Shimadzu Corporation -Column: Shodex KF-804L and 803L (manufactured by Showa Denko KK) and TSK-GEL (manufactured by Tosoh Corporation) are connected in series.
  • the thin film was immersed in a 1.0 mass% TMAH aqueous solution for 120 seconds for development, and then the thin film was washed with running water for 20 seconds using ultrapure water. Next, the thin film on which this rectangular pattern was formed was post-baked (230 ° C., 30 minutes) and cured to prepare a substrate with a partition wall.
  • the visible region average refractive index n and the visible region average extinction coefficient k were measured at a wavelength of 400 to 800 nm. The results are shown in Table 1.
  • the thin film obtained from the charge-transporting varnish of the present invention showed a higher refractive index and a lower extinction coefficient than the thin film of the comparative example containing no particles.
  • a single-layer device was produced by forming an aluminum film at 0.2 nm / sec at 80 nm on the ITO substrate on which the thin film was formed, using a vapor deposition apparatus (vacuum degree 1.0 ⁇ 10 -5 Pa). did.
  • the elements were sealed with a sealing substrate and then their characteristics were evaluated. Sealing was performed by the following procedure. In a nitrogen atmosphere with an oxygen concentration of 2 ppm or less and a dew point of -76 ° C or less, the elements are placed between the sealing substrates, and the sealing substrates are bonded with an adhesive (Morresco Moisture Cut WB90US (P) manufactured by MORESCO Corporation).
  • a water trapping agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was housed in the sealing substrate together with the element.
  • the bonded substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ / cm 2 ) and then annealed at 80 ° C. for 1 hour to cure the adhesive.
  • a substrate with a charge-transporting thin film was obtained.
  • the charge-transporting thin film was discharged so that the film thickness near the center of the opening was 60 to 80 nm.
  • the shape of the surface of the charge-transporting thin film was measured with respect to the substrate with the charge-transporting thin film obtained in Example 4. The results are shown in FIG. In addition, the pile-up index was calculated for the prepared charge-transporting thin film.
  • the pile-up index is (B) when the partition wall (bank) width is A ( ⁇ m) and the film thickness range of + 10% from the film thickness of the charge-transporting thin film at the center of the partition wall (bank) is B ( ⁇ m). It was calculated as / A) ⁇ 100 (%).
  • Table 3 In Example 4, the pile-up index was calculated with the short side as the partition width.
  • the charge-transporting thin film shows good flatness and the pile-up index is 98. It showed a high value exceeding%.

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PCT/JP2020/024702 2019-06-26 2020-06-24 電荷輸送性ワニス WO2020262418A1 (ja)

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KR20230164092A (ko) 2021-03-31 2023-12-01 닛산 가가쿠 가부시키가이샤 전하 수송성 바니시

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