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  • 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
• • H—ELECTRICITY
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  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
  • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
  • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
  • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
  • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
  • H10K85/114—Poly-phenylenevinylene; Derivatives thereof
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  • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
  • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
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  • H10K85/30—Coordination compounds
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  • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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  • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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  • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
  • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes

Definitions

• the present invention relates to a charge transport material and a charge transport varnish, and more specifically to a charge transport material and a charge transport varnish containing a heteropoly acid compound.
• Non-patent Document 1 Applied Physics Letters, USA, 1996, 69, p. 2160-21612. Further, it has been reported that a drive voltage can be lowered by forming a thin film by vacuum-depositing a metal oxide and using it as a hole injection layer (Non-Patent Document 2: Journal of Physics D). : Applied Physics D (Applied Physics), UK, 1996, 29, pp. 2750-2753).
• PLED organic electroluminescence
• Patent Document 1 Japanese Patent Laid-Open No. 3-273877
• Non-Patent Document 3 Nature, UK, 1992, 357, 477-47
• Non-patent Document 4 Applied Physics Letters, USA, 1998, 72, pp. 2660-2661. It has been reported that the same effect as the OLED element can be obtained by using the thin film as the hole transport layer.
• Patent Document 4 International Publication No. 2004/043117 Pamphlet
• Patent Document 5 International Publication No. 2005/107335 Pamphlet
• Non-patent Document 5 Applied Physics Letters, USA, 2007, Vol. 91, p.253504, Non-Patent Document 6: Applied Physics Letters, USA, 2008, Vol. 93, p. 043308), there is no example of a coating-type material having an oxidizing property with respect to a hole transport material. Development of new materials is required.
• the present invention has been made in view of such circumstances, and includes a charge transporting material including a substance having both high solubility in an organic solvent and charge transporting property, and further oxidizing property to a hole transporting material, and It is an object to provide a charge transporting varnish containing a charge transporting material.
• heteropolyacid compounds such as phosphomolybdic acid have high solubility and charge transportability in organic solvents, and further oxidation properties to hole transport materials. And when the charge transporting thin film containing the heteropoly acid compound is used as a hole injection layer of an OLED element, the driving voltage can be lowered and the element life can be improved. Completed the invention.
• a heteropolyacid compound such as phosphomolybdic acid typically has a Keggin-type chemical structure represented by Chemical Formula 1 or a Dawson-type chemical structure represented by Chemical Formula 2, that is, a structure in which a heteroatom is located at the center of the molecule. .
• this compound Due to these special chemical structures, there are significant differences in solubility and oxidation-reduction characteristics from isopolyacids and simple metal oxides composed only of metal oxygen acids.
• this compound has been well known as a polymerization catalyst or a color reagent for organic compounds, but there are few examples in which the compound itself is used as a charge transporting substance.
• the present inventors have found that this heteropolyacid compound functions as an effective hole injection layer by forming a layer with an ultrathin film in an organic EL device.
• a charge transport material comprising a heteropolyacid compound as a charge transport material, 2. 1 charge transporting material, wherein the heteropolyacid compound is phosphomolybdic acid, 3.
• a charge transporting varnish comprising 1 or 2 of a charge transporting material and an organic solvent, wherein the heteropolyacid compound is uniformly dissolved in the organic solvent; 4).
• a charge transporting thin film comprising one or two charge transporting materials; 7).
• An organic electroluminescent device comprising 6 or 7 charge transporting thin films; 9. The charge transporting thin film provides 8 electroluminescent elements constituting a hole injection layer.
• the charge transporting material of the present invention and the heteropolyacid compound contained in the varnish have good solubility in an organic solvent used for the preparation of a general charge transporting varnish. By dissolving in, it exhibits excellent solubility in various organic solvents including low surface tension solvents. Therefore, a low-polarity organic solvent-based charge transporting varnish can be prepared using a part or almost all of the low surface tension solvent.
• Such a low-polarity organic solvent-based charge transporting varnish can be applied not only by an inkjet coating apparatus in which solvent resistance is a problem, but also has a problem of solvent resistance such as an insulating film and partition walls on the substrate. Even when a structure exists, it can be used.
• an amorphous solid thin film having high flatness can be produced without any problem.
• the heteropolyacid compound exhibits good charge transportability by itself, the thin film obtained using only the heteropolyacid compound as the charge transport material and without using the dopant substance or other charge transport substance is good. Excellent charge transport property.
• this thin film as a hole injection layer, the driving voltage of the organic EL element can be lowered and the life of the element can be extended.
• heteropoly acid compounds generally have a high refractive index, an improvement in light extraction efficiency can be expected by an effective optical design.
• this thin film can be applied not only to an organic EL element but also to a buffer layer or a hole transport layer of a solar cell, a fuel cell electrode, a capacitor electrode protective film, and an antistatic film.
• the charge transport material according to the present invention includes a heteropolyacid compound as a charge transport material.
• the charge transportability is synonymous with conductivity, and means any one of hole transportability, electron transportability, and both charge transportability of holes and electrons.
• the heteropolyacid compound is a polyacid formed by condensing an isopolyacid that is an oxygen acid such as vanadium (V), molybdenum (Mo), or tungsten (W) and an oxyacid of a different element.
• oxygen acids of different elements mainly include oxygen acids such as silicon (Si), phosphorus (P), and arsenic (As).
• heteropolyacid compound examples include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, and phosphotungstomolybdic acid.
• high solubility in organic solvents, charge transportability In addition, phosphomolybdic acid, phosphotungstic acid, and phosphotungstomolybdic acid are preferred, and phosphomolybdic acid is particularly preferred from the viewpoints of lowering driving voltage and improving life when used in an organic EL device.
• These heteropolyacid compounds are available as commercial products.
• phosphomolybdic acid Phosphobomobic acid hydrate, or 12 Polybodo (VI) phosphoric acid n-hydrate, an illustrative formula: H 3 (PMo 12 O 40 ) ⁇ NH 2 O) is available from Kanto Chemical Co., Inc., Wako Pure Chemical Industries, Ltd., Sigma-Aldrich Japan Co., Ltd. and the like.
• the charge transporting varnish according to the present invention includes the heteropolyacid compound (charge transporting substance) described above and an organic solvent, and the heteropolyacid compound is uniformly dissolved in the organic solvent.
• the heteropolyacid compound that is the charge transport material of the present invention improvement in film flatness during coating and subsequent baking processes, improvement in organic EL characteristics, and suppression of solid precipitation of charge transport varnish
• a solid material suitable for each purpose may be used in combination.
• the organic solvent used when preparing the charge transporting varnish a good solvent having the ability to dissolve the heteropolyacid compound can be used.
• the good solvent means a solvent that can dissolve the heteropolyacid compound well.
• the heteropolyacid compound has high solubility in a highly polar solvent
• the good solvent is desirably highly polar.
• the boiling point at normal pressure is preferably 50 to 300 ° C.
• the heteropolyacid compound can be completely dissolved to form a uniform solution and can be removed in the film formation process.
• Examples of such a good solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N-cyclohexyl-2- Pyrrolidinone, cyclohexanol, ethylene glycol, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol , Propylene glycol, hexylene glycol, o-cresol, m-cresol, p-cresol, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone Cyclohexan
• a high viscosity solvent and / or a low surface tension solvent can be used together with the good solvent.
• the good solvent, the high-viscosity solvent, and the low surface tension solvent may each have properties of each other.
• a high-viscosity solvent gives a viscosity suitable for spraying and coating in various coating devices to form a uniform wet film. During firing, it causes solvent volatilization while suppressing the aggregation of the wet film and the occurrence of irregularities. It means a solvent capable of forming a thin film having uniform film thickness uniformity.
• high-viscosity solvent examples include those having a viscosity of 10 to 200 mPa ⁇ s, particularly 50 to 150 mPa ⁇ s at 25 ° C., and specifically, those having a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure.
• High viscosity solvents cyclohexanol, ethylene glycol, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4 -Butanediol, propylene glycol, hexylene glycol, o-cresol, m-cresol, p-cresol and the like are preferred.
• the proportion of use is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the entire solvent in the varnish.
• a low surface tension solvent can be used together with the good solvent.
• a low surface tension solvent means improved coating properties to the substrate by reducing surface tension, imparting volatility, imparting physical properties suitable for spraying or coating in various coating devices, and reducing corrosivity to coating devices. It means the solvent that makes it possible.
• Examples of such a low surface tension solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, p-xylene, o-xylene, and styrene; n-pentane, n-hexane, n-heptane, and n-octane.
• ethyl acetate isopropyl acetate, n-propyl acetate, i-butyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl caproate, acetic acid -Esters such as 2-methylpentyl, n-ethyl lactate, n-butyl lactate; ethylene glycol dimethyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Glycol esters or glycol ethers such as ethyl ether and diethylene glycol monoethyl ether acetate; diethyl ether, di-n-propyl ether, di-i-propyl ether
• the use ratio thereof is not particularly limited.
• the viscosity is improved and the surface tension is increased. It is possible to impart new preferable physical properties such as reduction, imparting volatility, improving paintability to the substrate surface, coating, and improving sprayability.
• the polarity of the obtained varnish being lowered, it becomes possible to use a coating apparatus, a substrate or the like in which solvent resistance is a problem, and the application range is expanded.
• the ratio of the good solvent and the low surface tension solvent is preferably about 9: 1 to 1: 9, more preferably about 1: 1 to 1: 4 in terms of mass ratio. preferable.
• the boiling point of the good solvent is desirably equal to or higher than that of other solvents.
• the method for preparing the charge transporting varnish is not particularly limited and can be prepared by mixing the heteropolyacid compound and various solvents in an arbitrary order.
• the heteropolyacid compound described above is once a good solvent. Since it has the property that precipitation does not easily occur even if a low surface tension solvent having a lower polarity is added, a solution in which a heteropolyacid compound is dissolved in a good solvent and a low surface tension solvent are used. It is preferable to prepare by mixing. When such a method is used, the ratio of the low surface tension solvent in the charge transporting varnish can be increased.
• the content of the heteropolyacid in the charge transport varnish is not particularly limited, but is usually about 0.01 to 50% by mass, and considering that a thin film of 0.1 to 200 nm is formed, 0.1 to 10% by mass is preferable, and 0.5 to 5% by mass is more preferable.
• the viscosity of the charge transporting varnish is not particularly limited. However, considering that a thin film having a thickness of 0.1 to 200 nm is prepared with high film thickness uniformity by a spin coating method, an ink jet method or a spray coating method, 25 1 to 100 mPa ⁇ s is preferred at 0 ° C., more preferably 3 to 30 mPa ⁇ s, even more preferably 5 to 20 mPa ⁇ s.
• a charge transporting thin film can be formed on a substrate by applying the charge transporting varnish described above on the substrate and evaporating the solvent.
• the method for applying the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an ink jet method, a spray method, and a slit coating method.
• the method for evaporating the solvent is not particularly limited.
• the solvent may be evaporated in a suitable atmosphere, that is, in an inert gas such as air or nitrogen, in a vacuum, or the like using a hot plate or an oven. Thereby, a thin film having a uniform film formation surface can be obtained.
• the firing temperature is not particularly limited as long as the solvent can be evaporated, but it is preferably performed at 40 to 250 ° C. In this case, two or more stages of temperature changes may be applied for the purpose of developing higher uniform film forming properties or allowing the reaction to proceed on the substrate.
• the thickness of the charge transporting thin film is not particularly limited, but when used as a charge injection layer in an organic EL device, it is preferably 0.1 to 200 nm, more preferably 0.5 to 50 nm, and further preferably 1.0 to 15 nm. preferable.
• As a method of changing the film thickness there are a method of changing the solid content concentration in the varnish, or changing the amount of the solution on the substrate at the time of application.
• Examples of materials used and methods for producing an OLED element using the charge transporting varnish of the present invention include the following, but are not limited thereto.
• the electrode substrate to be used is preferably cleaned in advance by liquid cleaning with detergent, alcohol, pure water or the like.
• the anode substrate is subjected to surface treatment such as ozone treatment or oxygen-plasma treatment immediately before use. Is preferred.
• the surface treatment may not be performed.
• a hole transporting varnish for an OLED element
• the hole transporting varnish is applied onto the anode substrate, evaporated and baked by the above method, and a hole transporting thin film is formed on the electrode to form a hole injection layer or a hole transport layer.
• This is introduced into a vacuum deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode metal are sequentially deposited to form an OLED element.
• an element may be manufactured by removing any one layer or a plurality of layers as necessary.
• a carrier block layer may be provided between arbitrary layers.
• anode material examples include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and those subjected to planarization treatment are preferable.
• ITO indium tin oxide
• IZO indium zinc oxide
• Polythiophene derivatives and polyaniline derivatives having high charge transporting properties can also be used.
• TPD triphenylamine dimer derivative
• ⁇ -NPD ⁇ -naphthyldiphenylamine dimer
• Spiro-TAD spiro-dimer
• Triarylamines such as 4,4 ′, 4 ′′ -tris [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA), 4,4 ′, 4 ′′ -tris [1-naphthyl (phenyl) ) Amino] triphenylamine (1-TNATA) and other starburst amines, 5,5 ′′ -bis- ⁇ 4- [bis (4-methylphenyl) amino] phenyl ⁇ -2,2 ′: 5 ′,
• the hole transport material having reducibility with respect to the heteropolyacid compound used in the present invention is preferable from the viewpoint of lowering the driving voltage in the organic EL device characteristics.
• a layer containing these compounds is used as a hole injection layer containing the heteropolyacid compound. It is preferable to use it as a hole transport layer adjacent to.
• Materials for forming the light emitting layer include tris (8-quinolinolato) aluminum (III) (Alq 3 ), bis (8-quinolinolato) zinc (II) (Znq 2 ), bis (2-methyl-8-quinolinolato) ( p-phenylphenolate) aluminum (III) (BAlq) and 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVBi), and the like.
• the light emitting layer may be formed by co-evaporation.
• Examples of the electron transport material include Alq 3 , BAlq, DPVBi, (2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole) (PBD), triazole derivatives ( TAZ), bathocuproine (BCP), silole derivatives and the like.
• luminescent dopant examples include quinacridone, rubrene, coumarin 540, 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM), tris (2-phenylpyridine) iridium ( III) (Ir (ppy) 3 ), (1,10-phenanthroline) -tris (4,4,4-trifluoro-1- (2-thienyl) -butane-1,3-dionate) europium (III) ( Eu (TTA) 3 phen) and the like.
• Examples of the material for forming the carrier block layer include PBD, TAZ, and BCP.
• Materials for forming the electron injection layer include lithium oxide (Li 2 O), magnesium oxide (MgO), alumina (Al 2 O 3 ), lithium fluoride (LiF), magnesium fluoride (MgF 2 ), and strontium fluoride. (SrF 2 ), Liq, Li (acac), lithium acetate, lithium benzoate and the like.
• Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium and the like.
• an electron transport varnish for an OLED element when using an electron transport varnish for an OLED element, the following method can be mentioned.
• An electron transporting varnish is applied onto a cathode substrate to produce an electron transporting thin film, which is introduced into a vacuum deposition apparatus, and using the same materials as described above, an electron transporting layer, a light emitting layer, and a hole transporting layer After forming the hole injection layer, the anode material is deposited by a method such as sputtering to obtain an OLED element.
• the manufacturing method of the PLED element using the charge transportable varnish of this invention is not specifically limited, The following methods are mentioned.
• the charge transporting varnish of the present invention is formed by forming a light emitting charge transporting polymer layer instead of performing vacuum deposition operation of the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer.
• a PLED element including a charge transporting thin film formed by the above can be produced.
• the charge transporting varnish (hole transporting varnish) of the present invention is applied to prepare a hole transporting thin film by the above-described method, and a luminescent charge transporting property is high on the upper part.
• a molecular layer is formed, and a cathode electrode is further deposited to form a PLED element.
• An interlayer may be provided between the hole transporting thin film and the light emitting polymer layer in order to improve light emission efficiency and device lifetime.
• the charge transporting varnish (electron transporting varnish) of the present invention is applied on the cathode substrate to prepare an electron transporting thin film by the above-described method, and the light emitting charge transporting polymer layer and the hole are formed thereon.
• a transport layer is sequentially formed, and an anode electrode is formed by a method such as sputtering, vapor deposition, or spin coating to obtain a PLED element.
• An interlayer may be provided between the hole transporting thin film and the light emitting polymer layer in order to improve light emission efficiency and device lifetime.
• the cathode and anode material to be used the same substances as those used in the production of the OLED element can be used, and the same cleaning treatment and surface treatment can be performed.
• a method for forming the light emitting charge transporting polymer layer a solvent is added to the light emitting charge transporting polymer material or a material obtained by adding a light emitting dopant to the material, and the solution is dissolved or evenly dispersed to inject holes.
• An example is a method in which a film is formed by evaporation of a solvent after application to an electrode substrate on which a layer is formed.
• Examples of the light-emitting charge transporting polymer material include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylene vinylene, and the like. And polyphenylene vinylene derivatives such as (MEH-PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).
• polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylene vinylene, and the like.
• polyphenylene vinylene derivatives such as (MEH-PPV)
• polythiophene derivatives such as poly (3-alkylthiophene) (PAT)
• PVCz polyvinylcarbazol
• Examples of the solvent include toluene, xylene, chloroform, and the like.
• Examples of the dissolution or uniform dispersion method include methods such as stirring, heating and stirring, and ultrasonic dispersion.
• the application method is not particularly limited, and examples thereof include an inkjet method, a spray method, a dip method, a spin coating method, a slit coating method, a transfer printing method, a roll coating method, and a brush coating method. Application is preferably performed under an inert gas such as nitrogen or argon.
• Examples of the solvent evaporation method include a method of heating in an oven or a hot plate under an inert gas or in a vacuum.
• the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.
• the solid content concentration described below was computed without subtracting the moisture content with the weighed value. In the weighing, pretreatment such as water removal was not performed, and the purchased compound was used as it was.
• the obtained solution was filtered using a PTFE filter having a pore size of 0.2 ⁇ m to obtain a light brown transparent charge transporting varnish (solid content concentration 3.3 mass%, viscosity 11 mPa ⁇ s, 25 ° C.).
• the obtained varnish was applied by spin coating on an ITO substrate that had been subjected to ozone cleaning for 30 minutes, and baked at 220 ° C. for 30 minutes in the air on a hot plate to form a charge transporting thin film.
• the thin film obtained was a uniform amorphous solid.
• Example 2 To 0.30 g of phosphotungstic acid (manufactured by Nippon Shin Metals Co., Ltd., H 3 PW 12 O 40 ⁇ n hydrate), 2.93 g of DMI, which is a good solvent, was added and dissolved in a nitrogen atmosphere. To this solution, 1.47 g of propylene glycol and 4.40 g of cyclohexanol melted by heating to 40 ° C. were added and allowed to cool to room temperature to obtain a light brown transparent solution.
• the obtained solution was filtered using a PTFE filter having a pore size of 0.2 ⁇ m to obtain a light brown transparent charge transporting varnish (solid content concentration 3.3 mass%, viscosity 11 mPa ⁇ s, 25 ° C.).
• the obtained varnish was applied by spin coating on an ITO substrate that had been subjected to ozone cleaning for 30 minutes, and baked at 220 ° C. for 30 minutes in the air on a hot plate to form a charge transporting thin film.
• the thin film obtained was a uniform amorphous solid.
• Example 3 To 0.30 g of lintongue molybdate (manufactured by Nippon Shin Metals Co., Ltd., H 3 PW 6 Mo 6 O 40 ⁇ n hydrate), 2.93 g of DMI, which is a good solvent, was added and dissolved in a nitrogen atmosphere. To this solution, 1.47 g of propylene glycol and 4.40 g of cyclohexanol melted by heating to 40 ° C. were added and allowed to cool to room temperature to obtain a light brown transparent solution.
• the obtained solution was filtered using a PTFE filter having a pore size of 0.2 ⁇ m to obtain a light brown transparent charge transporting varnish (solid content concentration 3.3 mass%, viscosity 11 mPa ⁇ s, 25 ° C.).
• the obtained varnish was applied by spin coating on an ITO substrate that had been subjected to ozone cleaning for 30 minutes, and baked at 220 ° C. for 30 minutes in the air on a hot plate to form a charge transporting thin film.
• the thin film obtained was a uniform amorphous solid.
• Examples 4 to 7 The following experiment was conducted to conduct the conductivity measurement. In order to avoid the influence of the solvent, DMAc was used as the same solvent. In the conductivity measurement, the resistance value of the sample thin film itself needs to sufficiently exceed the resistance of the measuring element, and it is necessary to form a thick film. Therefore, a high concentration varnish was prepared.
• Phosphomolybdic acid H 3 PMo 12 O 40 ⁇ n hydrate
• phosphotungstic acid H 3 PW 12 O 40 ⁇ n hydrate
• phosphotungsto molybdic acid H 3 PW 6 Mo 6 O 40 ⁇ nhydrate
• silicotungstic acid manufactured by Nippon Shin Metals Co., Ltd., H 4 SiW 12 O 40 ⁇ n hydrate
• Each of the obtained varnishes was applied on an ITO substrate that had been cleaned with ozone for 30 minutes by a spin coating method (1500 rpm-20 seconds) and baked on an hot plate at 220 ° C. for 30 minutes in the atmosphere to form a charge transporting thin film. Formed.
• the thin film obtained was a uniform amorphous solid.
• PEDOT / PSS manufactured by HC Starck, grade name CH8000 was applied on the ITO substrate by a spin coating method, and baked on the hot plate at 100 ° C. for 60 minutes in the air to form a charge transporting thin film.
• the thin film obtained was a uniform amorphous solid.
• each of the obtained substrates was introduced into a vacuum deposition apparatus, and a sandwich type element (ITO / sample / Al (150 nm)) in which Al was deposited to a thickness of 150 nm by a deposition mask. ) was used to measure the electrical conductivity (electrode area 0.2 mm 2 , current density 100 mA / cm 2 ).
• the viscosity is about 10 mPa ⁇ s, which is suitable for film formation by a spin coating method and an ink-jet method, and the film thickness should be sufficient for the hole injection layer. It can be seen that it can be satisfied.
• all the compounds of the present invention have a small electric field dependency of conductivity, good charge transport property at a slight voltage, and high conductivity sufficient as a hole injection layer material (generally 10 ⁇ 7 S). / Cm or more is required).
• the Ip value is preferably a value close to or deeper than that of the hole transport material, that is, about 5.4 eV or a deeper value. Met.
• Example 4 the refractive index at wavelengths of 450 nm and 650 nm was measured for the thin film obtained in Example 4 (measuring device: M-2000, manufactured by JA Woollam Japan), which was 1.95 and 1.89, respectively.
• the phosphomolybdic acid thin film showed a high refractive index value.
• Example 8 Production of OLED element
• the spin rotation number was changed to form a hole transporting thin film having two kinds of film thickness on the ITO substrate, and then this substrate was introduced into a vacuum deposition apparatus.
• NPD, Alq 3 , LiF, and Al were sequentially deposited to produce an OLED element.
• the film thicknesses were 40 nm, 60 nm, 0.8 nm, and 150 nm, respectively, and the vapor deposition operation was performed after the pressure became 2 ⁇ 10 ⁇ 4 Pa or less.
• the deposition rate was 0.1 to 0.2 nm / s for ⁇ -NPD and Alq 3 , 0.01 to 0.02 nm / s for LiF, and 0.2 to 0.4 nm / s for Al.
• the transfer operation between the vapor deposition operations was performed in a vacuum.
• Example 6 An OLED element was produced using the same method as in Example 8 except that PEDOT / PSS (manufactured by HC Starck, grade name AI4083) was used as the hole injection layer. Table 2 shows the element characteristics obtained in Example 8 and Comparative Examples 5 and 6. In addition, the characteristic of the OLED element was measured using the organic electroluminescent luminous efficiency measuring apparatus (EL1003, Precise Gauge Co., Ltd. product).
• PEDOT / PSS manufactured by HC Starck, grade name AI4083
• the device of Example 8 has stable characteristics even at 10 mm square. It can be seen that the initial characteristics (voltage and current efficiency) and lifetime are equal or equal to or greater at a film thickness of 10 nm.
• triphenylamine-containing materials such as triphenylamine-containing materials are mostly used for the hole transport layer laminated adjacent to the hole injection layer.
• the following experiment was conducted. Since triphenylamine-containing compounds are similar in physical properties to other triarylamine-containing compounds used as hole transport layer materials, this makes it possible to evaluate the oxidation properties of triarylamine-based hole transport layer materials in general. . Having an oxidizing property with respect to the hole transport layer material means that carriers can be generated electrostatically in a part of the hole transport layer, thereby reducing the driving voltage in the organic EL element. It can be reduced.
• the hole injection layer containing phosphomolybdic acid forms a doping layer by oxidizing the contact interface with a hole transport layer made of a hole transport material containing triphenylamine or an analogous skeleton thereof. This suggests the possibility of contributing to a decrease in the driving voltage of the organic EL element.

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