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WO2012018082A1 - Nanoparticules contenant un composé de métal de transition et leur processus de production, encre comportant des nanoparticules contenant chacune le composé de métal de transition dispersé et son processus de production, et dispositif équipé d'une couche de transport/injection de trous et son processus de production - Google Patents

Nanoparticules contenant un composé de métal de transition et leur processus de production, encre comportant des nanoparticules contenant chacune le composé de métal de transition dispersé et son processus de production, et dispositif équipé d'une couche de transport/injection de trous et son processus de production Download PDF

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Publication number
WO2012018082A1
WO2012018082A1 PCT/JP2011/067871 JP2011067871W WO2012018082A1 WO 2012018082 A1 WO2012018082 A1 WO 2012018082A1 JP 2011067871 W JP2011067871 W JP 2011067871W WO 2012018082 A1 WO2012018082 A1 WO 2012018082A1
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Prior art keywords
transition metal
group
organic
layer
metal compound
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English (en)
Japanese (ja)
Inventor
洋介 田口
匡哉 下河原
慎也 藤本
正隆 加納
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority to JP2012527769A priority Critical patent/JP5783179B2/ja
Publication of WO2012018082A1 publication Critical patent/WO2012018082A1/fr
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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
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer

Definitions

  • the element structure of the organic EL element is composed of a cathode / organic layer / anode.
  • This organic layer had a two-layer structure consisting of the light emitting layer / the hole injection layer in the initial organic EL element, but at present, the electron injection layer / electron is to obtain high luminous efficiency and long drive life.
  • Various multilayer structures have been proposed, such as a five-layer structure consisting of transport layer / light emitting layer / hole transport layer / hole injection layer.
  • the layers other than the light emitting layer such as the electron injection layer, the electron transport layer, the hole transport layer, and the hole injection layer have an effect of facilitating injection and transport of charges to the light emitting layer, or blocking by electron current and positive current It is said to have the effect of maintaining the balance of the hole current and the effect of suppressing the diffusion of light energy excitons.
  • Patent Document 6 describes that a charge injection layer is produced by screen printing using a slurry in which molybdenum oxide fine particles having an average particle diameter of 20 nm are dispersed in a solvent, but as in Patent Document 6, MoO 3 powder is used.
  • the lifetime of the organic EL element is the luminance half time when continuously driven by constant current driving or the like, and the longer the luminance half time, the longer the driving lifetime.
  • metal-containing nanoparticles having a particle diameter of 100 nm or less have been utilized in various fields such as, for example, abrasives, various functional fillers, additives of conductive paste, catalysts, etc., taking advantage of the characteristics.
  • metal oxide-containing nanoparticles are used, for example, in phosphors, catalysts, abrasives, transparent conductive films, and the like.
  • the present invention has been made in view of the above problems, and a first object thereof is to provide a novel metal compound-containing nanoparticle which can be stably dispersed in a solvent.
  • the second object of the present invention is a transition metal which is a material capable of forming a hole injecting and transporting layer which is stable even if an organic layer is formed adjacently by a solution coating method using a hydrophobic solvent. It is providing a compound containing nanoparticle.
  • the third object of the present invention is to provide a method for producing the transition metal compound-containing nanoparticles.
  • a fourth object of the present invention is to provide a transition metal compound-containing nanoparticle dispersed ink in which novel transition metal compound-containing nanoparticles are stably dispersed in a solvent.
  • nanoparticles are different from the case where molybdenum oxide or the like of the inorganic compound is used, and an organic containing a hydrophilic group on the nanoparticle surface Since the protective agent having a group is linked by a linking group, it has dispersibility in a hydrophilic solvent and also has high dispersion stability. In addition, it can be stably dispersed in a solvent while containing a specific transition metal compound such as one or more selected from the group consisting of transition metal carbon oxides, transition metal nitride oxides, and transition metal sulfide oxides. Therefore, as a novel nanoparticle, application is expected in various fields.
  • the nanoparticles according to the present invention can be formed into a thin film by a solution coating method using a hydrophilic solvent, they have great merits in the manufacturing process. From the hole injecting and transporting layer to the light emitting layer can be formed sequentially on the substrate having the liquid repellent bank only by the coating process. Therefore, as in the case of the molybdenum oxide of the inorganic compound, after the hole injection layer is deposited by highly precise mask deposition or the like, the hole transport layer and the light emitting layer are formed by solution coating, and the second electrode is further formed. There is the advantage that it is simpler and can produce devices at lower cost compared to processes such as evaporation.
  • the nanoparticles according to the present invention have high reactivity of the specific transition metal compound contained in the nanoparticles and easily form a charge transfer complex. Therefore, the nanoparticles according to the present invention are suitable for hole injection transport layer applications, and the devices provided with the hole injection transport layer containing nanoparticles according to the present invention are low voltage drive, high power efficiency, long. It is possible to realize a lifetime device. Furthermore, by selecting the type of protective agent for nanoparticles, it is easy to make the device multifunctional, such as imparting functionality such as charge transportability or adhesion.
  • the transition metal of the transition metal compound is at least one metal selected from the group consisting of molybdenum, tungsten, vanadium and rhenium. It is preferable from the point of lowering the efficiency and improving the device life.
  • Z 1 , Z 2 and Z 3 each independently represent a halogen atom or an alkoxy group, and R represents a hydrogen atom or a methyl group.
  • the protective agent is represented by the following general formula [I], having the functions of a hydrophilic group and a linking group, and aggregation of the nanoparticles. Is preferable in that a sufficient distance can be secured to prevent the General formula [I] X-Y-Z (In the general formula [I], X is a hydrophilic group, Y is a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms and / or an aromatic having 6 to 40 carbon atoms Group hydrocarbon group, Z represents a linking group)
  • the hydrophilic solvent preferably has a water solubility (20 ° C.) of 50 g / L or more.
  • the incompatibility between the transition metal compound-containing nanoparticle and the hydrophobic solvent used in the formation of the adjacent layer and the material of the adjacent layer can be ensured, and the amount of re-dissolution in the adjacent layer during lamination is reduced by the coating step. It can be done.
  • the method for producing a first transition metal compound-containing nanoparticle according to the present invention comprises the steps of: (A) carbonizing a transition metal and / or transition metal complex to form transition metal carbide; (B) protecting the transition metal carbide obtained in the step (A) with a protective agent having an organic group containing a linking group, and (C) oxidizing the transition metal carbide having an organic group obtained in the step (B) to obtain a transition metal carbide oxide having an organic group,
  • the protective agent is a protective agent having an organic group containing a linking group and a hydrophilic group, or the protective agent has an organic group containing a linking group and a hydrophobic group, and the hydrophobic It is characterized by including the process of replacing the protecting agent which has an organic group containing a nature group with the protecting agent which has an organic group containing a hydrophilic group.
  • the method for producing a second transition metal compound-containing nanoparticle according to the present invention comprises the steps of (a) protecting the transition metal and / or transition metal complex with a protective agent having an organic group containing a linking group, (B) carbonizing the transition metal or transition metal complex having an organic group obtained in the step (a) to obtain a transition metal carbide having an organic group; (C) oxidizing the transition metal carbide having an organic group obtained in step (b) to obtain a transition metal carbide oxide having an organic group,
  • the protective agent is a protective agent having an organic group containing a linking group and a hydrophilic group, or the protective agent has an organic group containing a linking group and a hydrophobic group, and the hydrophobic It is characterized by including the process of replacing the protecting agent which has an organic group containing a nature group with the protecting agent which has an organic group containing a hydrophilic group.
  • a step of carbonizing ( ⁇ ) transition metal and / or transition metal complex to form transition metal carbide ( ⁇ ) A step of oxidizing the transition metal carbide obtained in the step ( ⁇ ) into a transition metal carbide oxide, ( ⁇ ) A step of protecting the transition metal carbon oxide obtained in the step ( ⁇ ) with a protective agent having an organic group containing a linking group to obtain a transition metal carbon oxide having an organic group
  • the protective agent is a protective agent having an organic group containing a linking group and a hydrophilic group, or the protective agent has an organic group containing a linking group and a hydrophobic group, and the hydrophobic It is characterized by including the process of replacing the protecting agent which has an organic group containing a nature group with the protecting agent which has an organic group containing a hydrophilic group.
  • nanoparticles having dispersibility in a solvent and capable of being formed into a thin film or supported on the surface of a carrier can be obtained by a solution coating method.
  • performing the step of protecting with the protective agent in a solvent can stably perform the protecting step. preferable.
  • the step of forming the transition metal carbide may be carried out at 150 to 400 ° C. to make the particle diameter uniform and to make the unreacted transition metal It is preferable from the point of suppressing the formation of a complex.
  • performing the step of forming the transition metal carbide in an argon gas atmosphere maintains the dispersion stability in the reaction solution. It is preferable from the point of
  • the first transition metal compound-containing nanoparticle-dispersed ink according to the present invention is characterized by containing the transition metal compound-containing nanoparticle and a hydrophilic solvent.
  • the second transition metal compound-containing nanoparticle-dispersed ink according to the present invention contains at least one compound (U) selected from the group consisting of transition metal nitrides and transition metal sulfides, a linking group and a hydrophilic group.
  • U selected from the group consisting of transition metal nitrides and transition metal sulfides, a linking group and a hydrophilic group.
  • a protecting agent having an organic group and a hydrophilic solvent It is characterized by being used.
  • distribution ink is used suitably for forming the film
  • the method for producing a transition metal compound-containing nanoparticle-dispersed ink according to the present invention comprises: a transition metal complex containing an atom of carbon, nitrogen or sulfur, a protective agent having an organic group containing a linking group and a hydrophilic group, and a boiling point And heating the solution containing a hydrophilic solvent at 160 to 260 ° C. at 150 to 250 ° C., which is used to prepare the transition metal compound-containing nanoparticles of the present invention.
  • the device according to the present invention is a device having two or more electrodes facing each other on a substrate, and a hole injecting and transporting layer disposed between two electrodes of the two or more electrodes. It is characterized in that the hole injecting and transporting layer contains at least the transition metal compound-containing nanoparticle according to the present invention.
  • the device of the present invention is suitable for an embodiment including a charge transport layer containing a charge transport compound which can be dissolved and / or dispersed in a hydrophobic solvent adjacent to the hole injecting and transporting layer.
  • the hole injecting and transporting layer may contain two or more types of the transition metal compound-containing nanoparticles.
  • energy barriers between adjacent layers can be further reduced by enabling holes to move stepwise via two types of nanoparticles using nanoparticles with different work functions (HOMO), or
  • HOMO work functions
  • the device of the present invention is suitably used as an organic EL element containing an organic layer containing at least a light emitting layer.
  • the device according to the present invention is an organic transistor having a gate electrode, an insulating layer, a source electrode and a drain electrode, and an organic semiconductor layer on a substrate, wherein the transition metal compound is formed on at least a part of the surface of the source electrode and the drain electrode. It is suitably used also as an organic transistor which has a containing nanoparticle.
  • a first method of manufacturing a device according to the present invention is a method of manufacturing a device having two or more electrodes facing each other on a substrate, and a hole injecting and transporting layer disposed between two electrodes of the two or more electrodes. Forming a hole injecting and transporting layer on any of the layers on the electrode using the first transition metal compound-containing nanoparticle dispersed ink.
  • a second method of producing a device according to the present invention is a method of producing a device having two or more electrodes facing each other on a substrate, and a hole injecting and transporting layer disposed between two electrodes of the two or more electrodes. Forming a hole injecting and transporting layer on any layer on the electrode using the second transition metal compound-containing nanoparticle-dispersed ink; Oxidizing the compound (U).
  • the first and second device manufacturing methods of the present invention it is possible to provide a device capable of achieving long life while being able to form a hole injection transport layer by a solution coating method and having an easy manufacturing process. Is possible.
  • the step of oxidizing the compound (U) may be performed after the step of forming the hole injecting and transporting layer.
  • the compound (U ) May be performed after the step of preparing the transition metal compound-containing nanoparticle-dispersed ink, and before the step of forming the hole injecting and transporting layer.
  • the second method for producing a device according to the present invention it is preferable to use one of a heating means, a light irradiation means and a means for causing active oxygen in the step of oxidizing the compound (U).
  • a hydrophobic compound containing a hydrophobic solvent and a charge transport compound which can be dissolved and / or dispersed in a hydrophobic solvent is provided adjacent to the hole injecting and transporting layer. It is suitable for an embodiment including the step of forming a charge transport layer by applying a solution of a polarity.
  • the device is an organic EL element containing an organic layer containing at least a light emitting layer, a gate electrode, an insulating layer, a source electrode and a drain on a substrate It is suitable for the aspect which is an organic transistor which has an electrode and an organic-semiconductor layer, Comprising: The transition metal compound containing nanoparticle is provided in at least one part of the said source electrode and drain electrode surface.
  • the present invention can provide a novel transition metal compound-containing nanoparticle that can be stably dispersed in a hydrophilic solvent, and a novel transition metal compound-containing nanoparticle dispersed ink using the nanoparticle.
  • the transition metal compound-containing nanoparticles of the present invention have dispersibility in a solvent, and can be formed into a thin film or supported on the surface of a carrier by a solution coating method.
  • the transition metal compound-containing nanoparticle according to the present invention it is possible to form a hole injecting and transporting layer of a device capable of achieving long life while facilitating the manufacturing process.
  • the method for producing transition metal compound-containing nanoparticles of the present invention can easily produce such transition metal compound-containing nanoparticles.
  • the device of the present invention can achieve a long life while the manufacturing process is easy. According to the device manufacturing method of the present invention, it is possible to provide a device capable of achieving a long life while the manufacturing process is easy.
  • transition metal compound-containing nanoparticle according to the present invention and the method for producing the same, the transition metal compound-containing nanoparticle dispersed ink, the device and the method for producing the same will be described.
  • the transition metal compound-containing nanoparticle according to the present invention contains a hydrophilic group in at least one transition metal compound selected from the group consisting of transition metal carbon oxides, transition metal nitride oxides, and transition metal sulfide oxides.
  • a protective agent having an organic group is linked by a linking group, and is characterized by being dispersible in a hydrophilic solvent.
  • the transition metal compound-containing nanoparticle according to the present invention differs from particles formed simply by crushing the transition metal compound, in which the protective agent having an organic group containing a hydrophilic group is linked by a linking group on the nanoparticle surface There is. Since the protective agent includes a hydrophilic group and a linking group, when the protective agent is linked to the specific transition metal compound by the linking group, the hydrophilic group contained in the protective agent is the surface of the specific transition metal compound. Being disposed on the covered organic group, the surface of the nanoparticles becomes hydrophilic to have dispersibility in a hydrophilic solvent, and also has high dispersion stability.
  • nanoparticles can be dispersed in a hydrophilic solvent or not can be determined, for example, by adding 1 mg of nanoparticles to 1 mL of a hydrophilic solvent having a water solubility (20 ° C.) of 50 g / L or more, and room temperature (20 ° C. After 1 hour of ultrasonic wave irradiation, and if the dry weight of the precipitate becomes less than 0.1 mg after standing for 1 hour at 20 ° C., it is dispersible and the dry weight of the precipitate is 0.1 mg or more If it becomes, it will be judged that distribution is impossible.
  • a hydrophilic solvent having a water solubility (20 ° C.) of 50 g / L or more, and room temperature (20 ° C. After 1 hour of ultrasonic wave irradiation, and if the dry weight of the precipitate becomes less than 0.1 mg after standing for 1 hour at 20 ° C., it is dispersible and the dry weight of the precipitate is 0.1 mg or more If it
  • the hydrophilic solvent is a solvent that is compatible with water at a certain rate.
  • a hydrophilic solvent it can be used without particular limitation, as a standard that the solubility (20 ° C.) in water or water is 50 g / L or more.
  • the hydrophilic solvent is preferably a solvent that can be mixed with water in any proportion.
  • the hydrophilic solvent to be dispersed includes, for example, water, glycerin, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, propylene glycol, methyl diglycol, isopropyl glycol, butyl glycol, isobutyl glycol, methyl propylene diglycol, Propyl propylene glycol, butyl propylene glycol, diethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, ethylene glycol monoethyl ether, ethylene glycol Glycol monomethyl ether, cyclohexanone, mention may be made of diacetone alcohol.
  • the transition metal compound-containing nanoparticle according to the present invention contains a specific transition metal compound of one or more selected from the group consisting of transition metal carbon oxides, transition metal nitride oxides, and transition metal sulfide oxides.
  • the nanoparticles mean particles having a diameter of nm (nanometer) order, that is, less than 1 ⁇ m.
  • the nanoparticles according to the present invention may have a single structure or a composite structure, and may have a core-shell structure, an alloy, an island structure or the like.
  • the transition metal compound contained in the nanoparticles is at least one selected from the group consisting of transition metal carbide oxides, transition metal nitride oxides, and transition metal sulfide oxides. Other than these, borides, selenides, halides, complexes and the like may be contained.
  • transition metal carbon oxides transition metal nitride oxides or transition metal sulfide oxides
  • the value of ionization potential becomes optimum, or changes due to oxidation from unstable oxidation number +0 metal
  • the transition metal compound which is an oxide having a different oxidation number be contained in the nanoparticles.
  • transition metal atoms and compounds of various valences such as oxides and borides may be mixed according to the processing conditions.
  • the transition metal carbide oxide, transition metal nitride oxide, and transition metal sulfide oxide at least a part of each of the transition metal carbide, transition metal nitride, and transition metal sulfide may be oxidized.
  • the surface layer of about 1 nm is preferably oxidized.
  • the nanoparticles contain a specific metal compound such as transition metal carbide oxide, transition metal nitride oxide or transition metal sulfide oxide, they can be used for various applications as described later.
  • the metal elements of Groups 3 to 11 may be appropriately selected from the transition metal elements according to the application to be used.
  • molybdenum, tungsten, vanadium, rhenium and the like can be mentioned as the hole injecting and transporting layer application in the device from the charge injecting and transporting property of the above-mentioned metal compound.
  • molybdenum, vanadium, titanium, iron, cobalt, nickel, tungsten, palladium, platinum, gold and the like can be mentioned.
  • money, silver, copper, an indium, molybdenum etc. are raised as a wiring use.
  • ferroelectric applications include titanium and zirconium.
  • a transition metal of the transition metal compound at least one metal selected from the group consisting of molybdenum, tungsten, vanadium and rhenium has high reactivity, so it is easy to form a charge transfer complex, It is preferable from the point of reducing the drive voltage in the device and improving the device life.
  • Each element of tungsten, vanadium and rhenium is known to be oxidized in the same manner as molybdenum and to obtain hole injecting and transporting characteristics, in an oxide film forming method using a vacuum evaporation method.
  • vanadium is described in "J. PHYS. D: APPL. PHYS.” 41 (2008) 06 2003 (4 pp)
  • rhenium is described in "APPLIED PHYSICS LETTERS” 91 011113 (2007).
  • the transition metal carbide oxide, transition metal nitride oxide and transition metal sulfide oxide contained in the nanoparticles of the present invention are preferably contained in a total of 90 mol% or more in the transition metal compound. Furthermore, among these three transition metal compounds, it is preferable that 90 mol% or more of a single transition metal compound is contained, from the viewpoint of lowering the drive voltage and improving the device life in the device. It is more preferable to contain mol% or more.
  • the protective agent that protects the nanoparticles has a linking group and an organic group containing a hydrophilic group.
  • the protective agent is linked to the nanoparticle by the linking group, and the surface of the nanoparticle is covered and protected by the organic group containing the hydrophilic group, thereby making the nanoparticle surface hydrophilic which is dispersible in the solvent, the nanoparticle to the hydrophilic solvent Increase the dispersion stability of
  • the protective agent may be a low molecular weight compound or a high molecular weight compound.
  • the linking group is not particularly limited as long as it has a function of linking with a transition metal and / or a transition metal compound.
  • the linkage includes adsorption and coordination, but is preferably a chemical bond such as an ionic bond or a covalent bond.
  • the number of linking groups in the protective agent may be one or more in the molecule. However, when it is desired to obtain more uniform nanoparticles, it is preferable that the linking group and the hydrophilic group described later adopt different substituents, and that there is one linking group in one molecule of the protective agent.
  • the linking group contained in the protective agent is selected from functional groups represented by the following general formulas (1a) to (1o) from the viewpoint of the action of linking with a transition metal and / or a transition metal compound on nanoparticles. It is preferable that it is 1 or more types.
  • Z 1 , Z 2 and Z 3 each independently represent a halogen atom or an alkoxy group, and R represents a hydrogen atom or a methyl group.
  • hydrophilic group contained in the protective agent a substituent having an effect of making the nanoparticle surface hydrophilic is used while covering the nanoparticle surface with an organic group.
  • hydrophilic group include a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a thiol group, a silanol group, a sulfo group, a sulfonate, and an ammonium group.
  • the hydrophilic group at least one member selected from the group consisting of a hydroxyl group, a carbonyl group, an amino group, a thiol group, a sulfo group, a sulfonate and an ammonium group has an ability to connect to a transition metal compound It is preferable from the relatively weak point, and is further preferably one or more selected from the group consisting of a hydroxyl group, a carbonyl group, a thiol group, a sulfo group and a sulfonate.
  • the linking group and the hydrophilic group may be substituents of the same type, but at least a substituent performing the function of the linking group and a substituent performing the function of the hydrophilic group in one molecule Is included one by one.
  • the protecting agent has a plurality of linking groups, and there is a concern that the nanoparticles may be bound and aggregated via the linking group, so that the stable dispersibility can be obtained.
  • the linking group and the hydrophilic group be different.
  • the protective agent contains one or more hydrophilic groups that are difficult to bind to nanoparticles and one linking group that is easy to bind to nanoparticles.
  • the organic group contained in the protective agent may be any group containing carbon, and has 1 or more carbon atoms, preferably 1 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, still more preferably 4 to 25 carbon atoms.
  • Chain, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group, and / or aromatic hydrocarbon group having 6 to 40 carbon atoms, more preferably 12 to 34 carbon atoms, and / or 12 to 26 carbon atoms and / or hetero atoms A ring group etc. are mentioned.
  • carbon number of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and the substituent of a heterocyclic group is not included here as carbon number.
  • organic groups having no bulky structure such as a cyclic structure at the part directly bonded to the linking group can be densely protected without defects when the protective agent protects the surface via the linking group.
  • the protective agent contains an aromatic hydrocarbon and / or a heterocyclic ring as an organic group, it has charge transportability, and has an adjacent aromatic hydrocarbon and / or a heterocyclic ring.
  • the dispersion stability of the film can be improved by the improvement of the adhesion to the compound.
  • a linear or branched saturated or unsaturated aliphatic hydrocarbon group As a linear or branched saturated or unsaturated aliphatic hydrocarbon group, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, various pentylene groups, Various hexylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups and the like can be mentioned.
  • aromatic hydrocarbon and / or heterocycle examples include, for example, benzene, triphenylamine, fluorene, biphenyl, pyrene, anthracene, carbazole, phenylpyridine, trithiophene, phenyloxadiazole, phenyltriazole, benzimidazole And phenyl triazine, benzodiathiazine, phenyl quinoxaline, phenylene vinylene and phenyl silole, and combinations of these structures.
  • the protective agent preferably also has a charge transporting group.
  • the charge transporting group is a group which exhibits the property that the chemical structure group has drift mobility of electrons or holes, and as another definition, it is known that it can detect charge transporting performance such as time-of-flight method. It can be defined as a group from which a detection current resulting from charge transport can be obtained by the method of In the case where the charge transporting group can not exist alone, a compound obtained by adding a hydrogen atom to the charge transporting group may be a charge transporting compound.
  • charge transporting group examples include residues other than hydrogen atoms in hole transporting compounds (arylamine derivatives, carbazole derivatives, thiophene derivatives, fluorene derivatives, distyrylbenzene derivatives, etc.) as described later.
  • the protective agent is preferably represented by the following general formula [I] from the viewpoint of having each function of a hydrophilic group and a linking group and securing a sufficient distance to prevent aggregation of nanoparticles.
  • General formula [I] X-Y-Z (In the general formula [I], X is a hydrophilic group, Y is a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms and / or an aromatic having 6 to 40 carbon atoms Group hydrocarbon group, Z represents a linking group)
  • the protective agent which is a low molecular weight compound include, but are not limited to, thioglycolic acid, thioglycol, malonic acid, maleic acid, succinic acid, glutaric acid, glycolic acid, glycine, 4-hydroxythiophenol, 4-mercaptophenylacetic acid, biphenyl-4,4'-dicarboxylic acid, benzidine, 4- (4-aminophenyl) benzonitrile, 4,4'-diformyltriphenylamine, tris (4- Examples include formylphenyl) amine, N, N, N ', N'-tetrakis (4-aminophenyl) benzidine and the like.
  • the thickness of the protective agent covering the nanoparticle surface is small, so the transition metal-containing compound surface approaches and interacts with the adjacent layer compound. It is preferable because it can be expected that the transition metal-containing compound can easily contribute to the improvement of the hole injection property.
  • the lower limit of the molecular weight of the protective agent is not particularly limited, but may be 50 or more as a standard.
  • the protective agent is a polymer compound
  • a polymer compound containing two or more functional groups functioning as a linking group and a hydrophilic group in one molecule can be appropriately selected and used.
  • the polymer compound a polymer having a repeating unit is suitably used, and the weight average molecular weight is, for example, more than 1000 and about 50000 or less.
  • the weight average molecular weight here means the polystyrene conversion value by GPC (gel permeation chromatography).
  • polymer compound used as the protective agent include, but are not limited to, polyvinyl pyrrolidone, polyglycolide, poly (2-acrylamido-2-methyl-1-propanesulfonic acid), poly ( Acrylamide-acrylic acid) copolymer and the like.
  • the protective agent preferably has a solubility (20 ° C.) in the hydrophilic solvent of 10 g / L or more, more preferably 50 g / L or more, in order to make the nanoparticles dispersible in the hydrophilic solvent. .
  • a solubility (20 ° C.) in the hydrophilic solvent of 10 g / L or more, more preferably 50 g / L or more, in order to make the nanoparticles dispersible in the hydrophilic solvent.
  • a compound having an octanol-water partition coefficient logP of ⁇ 5 to 2 is preferable when adhesion to an adjacent organic layer is important.
  • the octanol-water partition coefficient logP is a parameter representing the balance of hydrophobicity / hydrophilicity.
  • logP is a value calculated using this software "Marvin Calibration Plugin".
  • the content ratio of the transition metal compound to the protective agent is appropriately selected depending on the application and is not particularly limited, but 10 to 40 parts by mass of the protective agent with respect to 100 parts by mass of the transition metal compound. Is preferred.
  • the average particle diameter of the nanoparticles of the present invention is not particularly limited, and may be, for example, 0.5 nm to 999 nm, and may be appropriately selected depending on the application.
  • the average particle size is preferably 0.5 nm to 50 nm, and more preferably 0.5 nm to 20 nm.
  • the thickness is more preferably 15 nm or less, and particularly preferably in the range of 1 nm to 10 nm. If the particle size is too small, production is difficult.
  • the average particle size is a number average particle size measured by a dynamic light scattering method, but in the state of being dispersed in the hole injecting and transporting layer, the average particle size is a transmission electron microscope (TEM) Obtained by selecting the region where it is confirmed that 20 or more nanoparticles are present from the image obtained by using, measuring the particle size of all the nanoparticles in this region, and calculating the average value. Value.
  • TEM transmission electron microscope
  • the nanoparticles according to the present invention have very high dispersion stability in a hydrophilic solvent, and one or more selected from the group consisting of transition metal carbon oxides, transition metal nitride oxides, and transition metal sulfide oxides. It is a novel nanoparticle containing a transition metal compound. Therefore, it can be suitably used in the form of an ink dispersed uniformly with high dispersion stability in a hydrophilic solvent.
  • the dispersion stability is very high in the solvent, it is possible to form a thin film of nm order high in stability and uniformity over time. Since the thin film is hydrophilic, even if an organic layer is formed adjacent to the thin film by a solution coating method using a hydrophobic solvent, the thin film is a stable film without re-dissolution. Conversely, on the other hand, on the organic layer formed by the solution coating method using a hydrophobic solvent, a layer containing the nanoparticles of the present invention is formed by a solution coating method using a hydrophilic solvent. Also, the organic layers can form thin films with high stability without re-dissolution. That is, it is possible to obtain a thin film laminate in which the hydrophobic organic thin film and the hydrophilic coating film containing the nanoparticles according to the present invention are adjacently laminated.
  • the nanoparticles when the highly hydrophobic nanoparticles are dispersed in a hydrophobic solvent and applied adjacent to the organic layer formed by the solution coating method using a hydrophobic solvent, the surface portion of the organic layer is By re-dissolving, the nanoparticles are embedded in the surface portion of the organic layer.
  • the nanoparticles according to the present invention expose the surface of the nanoparticles on the carrier 5 such as a hydrophobic organic layer. It can be made into the aspect supported in the state which it was made to make.
  • the carrier supporting the nanoparticles can be used without being particularly limited to the hydrophobic organic layer, and the nanoparticles according to the present invention are suitably used on a carrier surface by using the nanoparticle surface as a function. Can.
  • the nanoparticles according to the present invention can be used for various applications.
  • examples thereof include hole injection transport materials for devices, in particular devices, catalysts, additives such as friction modifiers used in lubricating oils, anti-wear agents, and antioxidants.
  • the nanoparticles according to the present invention are suitable as a device material in one aspect.
  • the specific transition metal compound is a specific transition metal compound-containing nanoparticle protected by a protective agent having an organic group containing a hydrophilic group
  • holes are injected by a solution coating method. While the transport layer can be formed and the manufacturing process is easy, the charge transfer complex can be formed to improve the hole injection property, and the organic layer can be formed adjacently by the solution coating method using a hydrophobic solvent.
  • It is particularly suitable as a material for forming a hole injecting and transporting layer because it provides a highly stable film. Since the dispersion stability is very high in a hydrophilic solvent, a highly uniform thin film of nm order can be formed. Since the thin film has high temporal stability and uniformity, it is difficult to short-circuit even when used in a device.
  • the nanoparticles according to the present invention can be formed into a thin film by a solution coating method using a hydrophilic solvent, they have great merits in the manufacturing process.
  • the hole injecting and transporting layer to the light emitting layer can be sequentially formed only on the coating process on the substrate having the liquid repellent bank. Therefore, as in the case of the molybdenum oxide of the inorganic compound, after the hole injection layer is deposited by highly precise mask deposition or the like, the hole transport layer and the light emitting layer are formed by solution coating, and the second electrode is further formed.
  • the advantage is simpler and can produce devices at lower cost compared to processes such as evaporation.
  • the nanoparticles according to the present invention have high reactivity of the specific transition metal compound contained in the nanoparticles and easily form a charge transfer complex. Therefore, the device provided with the hole injecting and transporting layer containing the nanoparticle according to the present invention can realize a low voltage drive, high power efficiency, and a long life device. Furthermore, by selecting the type of protective agent for nanoparticles, it is easy to make the device multifunctional, such as imparting functionality such as charge transportability or adhesion. Aspects of the device will be described in detail later.
  • the nanoparticles according to the present invention can also be used as a catalyst.
  • the transition metal compound in the nanoparticles is a transition metal carbide oxide, particularly molybdenum carbide oxide.
  • the carrier supporting the nanoparticles may be appropriately selected according to the reaction of the catalyst. For example, carbon nanotubes, carbon nanohorns, carbon nanofilaments, graphene, graphite, etc. And carbon materials having the conductivity of
  • the method for producing a first transition metal compound-containing nanoparticle according to the present invention comprises the steps of: (A) carbonizing a transition metal and / or transition metal complex to form transition metal carbide; (B) protecting the transition metal carbide obtained in the step (A) with a protective agent having an organic group containing a linking group, and (C) oxidizing the transition metal carbide having an organic group obtained in the step (B) to obtain a transition metal carbide oxide having an organic group,
  • the protective agent is a protective agent having an organic group containing a linking group and a hydrophilic group, or the protective agent has an organic group containing a linking group and a hydrophobic group, and the hydrophobic It is characterized by including the process of replacing the protecting agent which has an organic group containing a nature group with the protecting agent which has an organic group containing a hydrophilic group.
  • the method for producing a second transition metal compound-containing nanoparticle according to the present invention comprises the steps of (a) protecting the transition metal and / or transition metal complex with a protective agent having an organic group containing a linking group, (B) carbonizing the transition metal or transition metal complex having an organic group obtained in the step (a) to obtain a transition metal carbide having an organic group; (C) oxidizing the transition metal carbide having an organic group obtained in step (b) to obtain a transition metal carbide oxide having an organic group,
  • the protective agent is a protective agent having an organic group containing a linking group and a hydrophilic group, or the protective agent has an organic group containing a linking group and a hydrophobic group, and the hydrophobic It is characterized by including the process of replacing the protecting agent which has an organic group containing a nature group with the protecting agent which has an organic group containing a hydrophilic group.
  • a step of carbonizing ( ⁇ ) transition metal and / or transition metal complex to form transition metal carbide ( ⁇ ) A step of oxidizing the transition metal carbide obtained in the step ( ⁇ ) into a transition metal carbide oxide, ( ⁇ ) A step of protecting the transition metal carbon oxide obtained in the step ( ⁇ ) with a protective agent having an organic group containing a linking group to obtain a transition metal carbon oxide having an organic group
  • the protective agent is a protective agent having an organic group containing a linking group and a hydrophilic group, or the protective agent has an organic group containing a linking group and a hydrophobic group, and the hydrophobic It is characterized by including the process of replacing the protecting agent which has an organic group containing a nature group with the protecting agent which has an organic group containing a hydrophilic group.
  • FIG. 2 is a schematic view showing the order of the steps of the method for producing the first to third transition metal compound-containing nanoparticles according to the present invention.
  • FIG. 2 (i) shows an example of the method for producing the first transition metal compound-containing nanoparticle according to the present invention, wherein the transition metal and / or transition metal complex 10 is carbonized to form transition metal carbide 20, Next, the transition metal carbide is protected by linking the linking group of the protective agent 30 having an organic group containing a linking group to the surface of the transition metal carbide, and then the transition metal carbide is oxidized to form a transition metal carbide oxide 40. Compound-containing nanoparticles 1 are obtained.
  • the protective agent is a protective agent having an organic group containing a linking group and a hydrophilic group, or when the protective agent is a protective agent having an organic group containing a linking group and a hydrophobic group And further, replacing the protective agent having an organic group containing the hydrophobic group with a protective agent having an organic group containing a hydrophilic group (not shown), thereby forming the transition metal compound-containing nanoparticle 1 obtain.
  • the protective agent is a protective agent having an organic group containing a linking group and a hydrophobic group
  • the protective agent having an organic group containing the hydrophobic group is replaced with a protective agent having an organic group containing a hydrophilic group
  • the step of (C) may be performed before or after the oxidation step, but there is a concern that the surface state of the nanoparticles may change and the dispersibility may be reduced by the oxidation step, either simultaneously with (C) oxidation step or (C) A) after the oxidation step is preferred.
  • FIG. 2 shows an example of the method for producing the second transition metal compound-containing nanoparticle according to the present invention, and an organic group containing a linking group on the surface of the transition metal and / or the transition metal complex 10 Protected by linking the linking group of the protective agent 30 and then carbonizing the transition metal and / or transition metal complex 10 to form a protected transition metal carbide 20 (having an organic group containing a hydrophilic group) Then, the transition metal carbide is oxidized to obtain transition metal compound-containing nanoparticles 1 as a transition metal carbide oxide 40.
  • the protective agent is a protective agent having an organic group containing a linking group and a hydrophilic group, or when the protective agent is a protective agent having an organic group containing a linking group and a hydrophobic group And further, replacing the protective agent having an organic group containing the hydrophobic group with a protective agent having an organic group containing a hydrophilic group (not shown), thereby forming the transition metal compound-containing nanoparticle 1 obtain.
  • the protective agent is a protective agent having an organic group containing a linking group and a hydrophobic group
  • the protective agent having an organic group containing the hydrophobic group is replaced with a protective agent having an organic group containing a hydrophilic group
  • the step of (b) may be before or after the carbonization step and / or (c) the oxidation step, but the surface state of the nanoparticles is changed by the (b) carbonization step and / or (c) oxidation step, and the dispersibility is It is preferable that the reaction be performed simultaneously with the (c) oxidation step or after the (c) oxidation step, because there is a concern that the amount will decrease.
  • FIG. 2 shows an example of the method for producing the third transition metal compound-containing nanoparticle according to the present invention, wherein the transition metal and / or transition metal complex 10 is carbonized to form transition metal carbide 20, Then, the transition metal carbide is oxidized to form transition metal carbide oxide 40. Next, the surface of the transition metal carbide oxide 40 is protected by linking the linking group of the protective agent 30 having the organic group containing the linking group, and the transition metal compound-containing nanoparticle 1 is obtained.
  • the protective agent is a protective agent having an organic group containing a linking group and a hydrophilic group, or when the protective agent is a protective agent having an organic group containing a linking group and a hydrophobic group And further, replacing the protective agent having an organic group containing the hydrophobic group with a protective agent having an organic group containing a hydrophilic group (not shown), thereby forming the transition metal compound-containing nanoparticle 1 obtain.
  • a transition metal carbide can be obtained by adding a ligand containing a carbon atom such as hexacarbonyl or acetylacetonate and heating.
  • the transition metal complex may be a transition metal complex containing a carbon atom as a ligand, and is preferably a transition metal complex which is decomposed at a temperature as low as possible in a solvent.
  • transition metals such as molybdenum hexacarbonyl, tungsten hexacarbonyl, iron pentacarbonyl, cobalt carbonyl, cyclopentadienyl cobalt dicarbonyl and pentacarbonyl chlororhenium, vanadium acetylacetonate, titanium diisopropoxide bis (acetyl) (Acetonato), iron acetylacetonate, nickel acetylacetonate, palladium acetylacetonate, platinum acetylacetonate, silver acetylacetonate, copper acetylacetonate, acetylacetonate complexes of transition metals such as indium acetylacetonon
  • a method such as heating can be used, for example, when heating, the transition metal and / or transition metal complex can be carbonized by heating at 150 to 400 ° C. can do.
  • the heating in the carbonization step is preferred to be carried out in a solvent from the viewpoint of being able to uniformly carbonize the entire nanoparticles.
  • the transition metal carbide step is preferably performed under an argon gas atmosphere from the viewpoint of maintaining the dispersion stability in the reaction solution.
  • step (B) as the protective agent, those mentioned above for the nanoparticles can be used, and therefore the description thereof is omitted here.
  • the protection step of connecting the linking group of the protective agent having an organic group containing a linking group to the surface of transition metal carbide or the like is preferably performed in a solvent. Specifically, it is preferable to carry out heating and stirring in a solvent in which the protective agent is dispersed. At this time, as the solvent, a solvent having a boiling point of heating temperature + 10 ° C. or more is selected and used. It is preferable to carry out in the presence of a solvent having a boiling point of 200 ° C. or more from the viewpoint that protection with a protective agent can be carried out uniformly and stably in a high temperature environment.
  • heating means for example, heating means, light irradiation means, means for causing active oxygen to act, etc. may be mentioned, and these may be used in combination as appropriate.
  • the heating means may, for example, be a hot plate or an oven.
  • the heating temperature is preferably 50 to 250.degree.
  • An ultraviolet irradiation apparatus is mentioned as a light irradiation means.
  • means for causing active oxygen to act include a method of causing active oxygen to act by ultraviolet light, and a method of causing active oxygen to act by irradiating ultraviolet light to a photocatalyst such as titanium oxide.
  • the interaction between the nanoparticles and the interaction of the nanoparticles with the hole transportable compound are different depending on the heating temperature, the light irradiation amount and the active oxygen amount, so it is preferable to adjust appropriately.
  • oxidizing in order to oxidize transition metal carbide efficiently, it is preferable to carry out in oxygen presence.
  • the protecting agent in the protecting step is a protecting agent having an organic group containing a linking group and a hydrophobic group
  • the protecting agent having an organic group containing the hydrophobic group has an organic group containing a hydrophilic group
  • the step of exchanging for the protective agent is performed in a solvent in which nanoparticles protected with the protective agent having an organic group containing a hydrophobic group can be dispersed, and the protective agent having an organic group containing a hydrophilic group can be dissolved be able to.
  • the protective agent can be exchanged by stirring in a solvent such as chloroform at a temperature of normal temperature (20 ° C.) to about 60 ° C. for about 4 hours to 72 hours.
  • the time required for replacement can be further shortened.
  • the temperature to be heated in the replacement step can be increased by using a high boiling point solvent, and by increasing the temperature, the time required to replace the protective agent can be further shortened. Since aggregation of the nanoparticles is caused by the increase of the protective agent desorbed from the surface, it is preferable to carry out the temperature at the time of replacing the protective agent as low as possible in the temperature range where the protective agent can be exchanged.
  • methods of carbonizing, methods of oxidizing, and methods of protecting with a protective agent can use the respective methods of producing the first nanoparticles described above.
  • the step (A) of carbonizing the transition metal and / or transition metal complex and the step (B) of protecting with a protective agent may be performed simultaneously.
  • the method of producing nanoparticles is a method of producing nanoparticles in the case of containing transition metal carbide oxide as a transition metal compound, it contains transition metal nitride oxide or transition metal sulfide oxide as a transition metal compound.
  • the carbonization raw material added to the transition metal may be a nitriding raw material or a sulfide raw material, or the transition metal complex may be replaced with one containing a nitrogen atom or a sulfur atom, and the same method as described above can be performed.
  • sulfur As a sulfurization raw material added when sulfurizing a transition metal, for example, sulfur, dodecanethiol, benzenethiol and bistrimethylsilyl sulfur can be mentioned.
  • transition metal complex containing a nitrogen atom for example, tungsten pentacarbonyl-N-pentylithonitrile and triamine molybdenum tricarbonyl can be mentioned.
  • the first transition metal compound-containing nanoparticle-dispersed ink according to the present invention is characterized by containing the transition metal compound-containing nanoparticle and a hydrophilic solvent.
  • the first and second transition metal compound-containing nanoparticle-dispersed inks according to the present invention can be used for the above-mentioned applications while facilitating the manufacturing process, and provide, for example, a device capable of achieving long life. It is possible.
  • One or more compounds (U) selected from the group consisting of transition metal carbides, transition metal nitrides and transition metal sulfides contained in the second transition metal compound-containing nanoparticle dispersed ink are described in the above nanoparticles. Transition metal carbide oxides, transition metal nitride oxides and precursors of transition metal sulfide oxides, and their oxidation yields the corresponding oxides. In each of the compounds (U), at least a part of the transition metal and / or the transition metal complex may be carbonized, nitrided or sulfided.
  • transition metal carbide As a method of obtaining transition metal carbide, a conventionally known method can be used, and for example, the carbonization method of the transition metal described in the first method of producing nanoparticles can be used.
  • the carbonization raw material added to the transition metal is a nitriding raw material or a sulfided raw material
  • the transition metal complex may be replaced by one containing a nitrogen atom or a sulfur atom to carbonize the transition metal.
  • hydrophilic solvent As the hydrophilic solvent contained in the first and second transition metal compound-containing nanoparticle dispersion inks, in the first transition metal compound-containing nanoparticle dispersion ink, a transition metal compound-containing nanoparticle and a second transition metal
  • the compound-containing nanoparticle-dispersed ink is not particularly limited as long as the compound (U) and, if necessary, other components such as a protective agent and a hole-transporting compound described later dissolve and disperse well.
  • a hydrophilic solvent a hydrophilic solvent as described in the explanation of the nanoparticles can be used appropriately.
  • an ink for a hole injecting and transporting layer for forming a hole injecting and transporting layer which is used in a device described later
  • a positive electrode to be described later from the viewpoint of further improving the driving voltage of the hole injecting and transporting layer and the device life other than the above essential components.
  • a compound which is soluble in a hydrophilic solvent may be appropriately selected and contained.
  • the content of the hole transportable compound is 10 with respect to 100 parts by mass of the transition metal-containing nanoparticle. It is preferable that the content is about 10000 parts by mass because the hole injecting and transporting property is enhanced and the stability of the film is high to achieve a long life.
  • the hole injecting and transporting layer when the content of the hole transporting compound is too small, it is difficult to obtain the synergistic effect of mixing the hole transporting compound.
  • the content of the hole transportable compound is too large, it is difficult to obtain the effect of using the transition metal-containing nanoparticle.
  • examples of the curable functional group include acrylic functional groups such as acryloyl group and methacryloyl group, vinylene group, epoxy group and isocyanate group.
  • the curable resin may be a thermosetting resin or a photocurable resin, and examples thereof include epoxy resin, phenol resin, melamine resin, polyester resin, polyurethane resin, silicone resin and silane coupling agent. be able to.
  • the transition metal compound-containing nanoparticle dispersion ink generally contains, in a hydrophilic solvent, nanoparticles in the first transition metal compound-containing nanoparticle dispersion ink, and in the second transition metal compound-containing nanoparticle dispersion ink, the transition metal carbide.
  • hole transport in addition to essential components such as at least one compound (U) selected from the group consisting of transition metal nitrides and transition metal sulfides, a protective agent having an organic group including a linking group and a hydrophilic group It is prepared by mixing and dispersing optional components such as sex compounds according to a general preparation method. For mixing and dispersing, a paint shaker or a bead mill can be used.
  • the transition metal compound-containing nanoparticles are filtered out, or purified in one pot without transition metal compound-containing nanoparticles. It is a method of manufacturing a dispersed ink.
  • a second method for producing such a transition metal compound-containing nanoparticle-dispersed ink comprises a transition metal complex containing any atom of carbon, nitrogen or sulfur, a protecting agent having an organic group containing a linking group and a hydrophilic group, And a solution containing a hydrophilic solvent having a boiling point of 160 to 260.degree. C. is heated at 150 to 250.degree.
  • transition metal complex containing any atom of carbon, nitrogen or sulfur a transition metal complex containing an atom of carbon, nitrogen or sulfur as a ligand may be used, and the above-mentioned transition metal compound-containing nano The same ones as described in the particle production method can be used. Moreover, since the protective agent which has an organic group containing a coupling group and a hydrophilic group is the same as that of what was mentioned by the above-mentioned nanoparticle, explanation here is omitted.
  • a hydrophilic solvent having a boiling point of 160 to 260 ° C. can be used as a solvent for the ink as it is relatively easy to perform coating and drying.
  • the hydrophilic solvent having a boiling point of 160 to 260 ° C. include ethylene glycol, propylene glycol, methyl diglycol, butyl glycol, isobutyl glycol, methyl propylene diglycol, butyl propylene glycol, diethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol Dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, ethylene glycol monobutyl ether, diacetone alcohol and the like can be mentioned.
  • the step of carbonizing and the step of protecting with a protective agent are preferably performed under an argon gas atmosphere in order to maintain the dispersion stability in the reaction solution.
  • the heating temperature is preferably in the above temperature range and at least 10 ° C. lower than the boiling point of the hydrophilic solvent.
  • the device according to the present invention is a device having two or more electrodes facing each other on a substrate, and a hole injecting and transporting layer disposed between two electrodes of the two or more electrodes.
  • the hole injection transport layer contains at least the transition metal compound-containing nanoparticle according to the present invention.
  • the hole injecting and transporting layer contains the nanoparticles according to the present invention
  • hole injecting characteristics are improved by the characteristics of the transition metal compound contained, and stability over time and uniformity are achieved. Since the film has high conductivity, it is possible to achieve long life of the device.
  • the lifetime of the nanoparticles used in the device of the present invention can be improved by the reaction of transition metal carbon oxides, transition metal nitride oxides and transition metal compounds such as transition metal sulfide oxides contained in the nanoparticles.
  • the charge transfer complex is easily formed between nanoparticles or when a hole transporting compound is contained, because the nature is high.
  • the formation of the charge transfer complex is, for example, an aromatic ring observed in the vicinity of 6 to 10 ppm of the charge transport compound when the nanoparticles are mixed into a solution of the charge transport compound by 1 H NMR measurement. It is suggested that the phenomenon that the shape and chemical shift value of the proton signal derived from are changed compared with before mixing the nanoparticles is observed.
  • the nanoparticles according to the present invention have very high dispersion stability in a solvent, it is possible to form a nanometer-order thin film having high temporal stability and high uniformity. Since the thin film is hydrophilic, even if an organic layer is formed adjacent to the thin film by a solution coating method using a hydrophobic solvent, the thin film is a film having high stability without being redissolved. . Also, conversely, on the organic layer formed by the solution coating method using a hydrophobic solvent, adjacent to the organic layer formed by the solution coating method using a hydrophilic solvent in which the nanoparticles of the present invention are dispersed. Also, the organic layers can form thin films with high stability without re-dissolution.
  • the device of the present invention provided with a transport layer can realize a device with low voltage drive, high power efficiency, and particularly improved life.
  • the type of the protective agent for nanoparticles it is easy to achieve multifunctionality such as imparting functionality such as charge transportability or adhesion.
  • the device of the present invention is different from the case of using the transition metal oxide of the inorganic compound, and since the nanoparticles have very high dispersion stability in the solvent, the hole injection transport layer is formed by the solution coating method. Manufacturing process is easy because it is possible to form In the device of the present invention, since the hole injecting and transporting layer can be formed by a solution coating method, the hole injecting and transporting layer to the light emitting layer can be formed sequentially on the substrate having a liquid repellent bank only by the application process.
  • the hole injection layer is deposited by high-definition mask deposition or the like
  • the hole transport layer and the light emitting layer are formed by solution coating, and the second electrode is further formed.
  • the device according to the present invention is a device having two or more electrodes facing each other on a substrate, and a hole injecting and transporting layer disposed between the two electrodes.
  • the device according to the present invention includes an organic EL element, an organic transistor, a dye-sensitized solar cell, an organic thin film solar cell, an organic device including an organic semiconductor, a quantum dot light emitting element having a hole injecting and transporting layer, an oxide Also included are compound solar cells and the like.
  • FIG. 3 is a schematic cross-sectional view showing the basic layer configuration of the organic device according to the present invention.
  • the basic layer configuration of the device of the present invention comprises two opposing electrodes (61 and 62) on a substrate 50 and at least a hole injecting and transporting layer 70 disposed between the two electrodes (61 and 62). It has an organic layer 80.
  • the substrate 50 is a support for forming the layers constituting the device, and is not necessarily provided on the surface of the electrode 61, and may be provided on the outermost surface of the device.
  • the hole injecting and transporting layer 70 is a layer containing at least the above-mentioned nanoparticles and responsible for the injection and / or transport of holes from the electrode 61 to the organic layer 80.
  • the organic layer 80 is a layer that exerts various functions depending on the type of device by being subjected to hole injection transport, and may be composed of a single layer or multiple layers.
  • the organic layer is a layer serving as the center of the function of the device (hereinafter referred to as a functional layer) or an auxiliary of the functional layer.
  • the layer hereinafter referred to as an auxiliary layer) is included.
  • the hole transport layer further stacked on the surface of the hole injection transport layer corresponds to the auxiliary layer
  • the light emitting layer stacked on the surface of the hole transport layer corresponds to the functional layer .
  • the electrode 62 is provided where the organic layer 80 including the hole injecting and transporting layer 70 is present between the electrode 62 and the opposing electrode 61.
  • FIG. 4 is a schematic cross-sectional view showing an example of the layer configuration of the organic EL element which is an embodiment of the device according to the present invention.
  • the hole injecting and transporting layer 70 is laminated on the surface of the electrode 61, the hole transporting layer 90a as an auxiliary layer and the light emitting layer 100 as a functional layer are laminated on the surface of the hole injecting and transporting layer 70 It has a form that has been Thus, in the case where the hole injecting and transporting layer characteristic of the present invention is used at the position of the hole injecting layer, the hole injecting and transporting layer forms a charge transfer complex in addition to the improvement of the conductivity.
  • FIG. 5 is a schematic cross-sectional view showing another example of the layer configuration of the organic EL element which is an embodiment of the device according to the present invention.
  • the hole injection layer 90b is formed on the surface of the electrode 61 as an auxiliary layer
  • the hole injection transport layer 70 is laminated on the surface of the hole injection layer 90b
  • the light emitting layer 100 is stacked as a functional layer.
  • FIG. 6 is a schematic cross-sectional view showing another example of the layer configuration of the organic EL element which is an embodiment of the device according to the present invention.
  • the organic EL element of the present invention has a form in which the hole injecting and transporting layer 70 and the light emitting layer 100 as a functional layer are sequentially laminated on the surface of the electrode 61.
  • each of the hole injecting and transporting layer 70, the hole transporting layer 90a, and the hole injecting layer 90b may be composed of a plurality of layers instead of a single layer. .
  • the electrode 61 functions as an anode and the electrode 62 functions as a cathode.
  • the organic EL device when an electric field is applied between the anode and the cathode, holes are injected from the anode through the hole injecting and transporting layer 70 and the hole transporting layer 90a to the light emitting layer 100, and electrons are cathode
  • the holes and electrons injected inside the light emitting layer 100 are recombined to emit light to the outside of the device.
  • all layers present on at least one surface of the light emitting layer need to be transparent to light of at least a part of the visible wavelength range.
  • an electron transport layer and / or an electron injection layer may be provided between the light emitting layer and the electrode 62 (cathode) as required.
  • FIG. 7 is a schematic cross-sectional view showing an example of the layer configuration of an organic transistor which is another embodiment of the device according to the present invention.
  • the organic transistor is disposed on the substrate 50 between the electrode 63 (gate electrode), the opposing electrode 61 (source electrode) and the electrode 62 (drain electrode), and the electrode 63, the electrode 61, and the electrode 62.
  • An organic semiconductor layer 110 as an organic layer, and an insulating layer 120 interposed between the electrode 63 and the electrode 61 and between the electrode 63 and the electrode 61, and on the surface of the electrode 61 and the electrode 62, a hole injecting and transporting layer 70 are formed.
  • the organic transistor has a function of controlling the current between the source electrode and the drain electrode by controlling the charge accumulation in the gate electrode.
  • FIG. 8 is a schematic cross-sectional view showing an example of another layer configuration of the organic transistor which is an embodiment of the device according to the present invention.
  • the organic transistor is disposed on the substrate 50 between the electrode 63 (gate electrode), the opposing electrode 61 (source electrode) and the electrode 62 (drain electrode), and the electrode 63, the electrode 61, and the electrode 62.
  • the hole injecting and transporting layer 70 of the present invention is formed as an organic layer to form an organic semiconductor layer 110, and an insulating layer 120 interposed between the electrode 63 and the electrode 61 and between the electrode 63 and the electrode 62 is provided.
  • the hole injecting and transporting layer 70 is the organic semiconductor layer 110.
  • the hole injecting and transporting layer contains the nanoparticles according to the present invention, can be dispersed in a hydrophilic solvent, and the formed hole injecting and transporting layer becomes hydrophilic. Even if organic layers are formed adjacent to each other by a solution coating method using a hydrophobic solvent, the thin film becomes a stable film without re-dissolution. Therefore, the device of the present invention is suitable for an embodiment including a charge transport layer containing a charge transport compound which can be dissolved and / or dispersed in a hydrophobic solvent adjacent to the hole injection transport layer.
  • the layer configuration of the device of the present invention is not limited to the above-described example, and has substantially the same configuration as the technical idea described in the claims of the present invention, and the same function and effect. Anything that plays is included in the technical scope of the present invention.
  • each layer of the device according to the present invention will be described in detail.
  • the device of the present invention comprises at least a hole injecting and transporting layer.
  • the organic layer is a multilayer, the organic layer further assists the layer serving as the center of the device function and the functional layer in addition to the hole injecting and transporting layer.
  • auxiliary layers that play a role, those functional layers and auxiliary layers will be described in detail in the device examples described later.
  • the hole injecting and transporting layer in the device of the present invention contains at least the nanoparticles according to the present invention, and is preferably formed using the transition metal compound-containing nanoparticle dispersed ink.
  • the hole injecting and transporting layer in the device of the present invention includes not only a continuous layer which completely covers the lower layer surface but also an aspect in which it is a discontinuous layer formed in the form of scattered islands or nets.
  • the hole injecting and transporting layer in the device of the present invention may be composed only of nanoparticles, but may further contain other components. Among them, it is preferable to contain a hole transportable compound from the viewpoint of further reducing the driving voltage and improving the device life.
  • the hole injecting and transporting layer in the device of the present invention may be composed of one mixed layer containing nanoparticles and the hole transporting compound, or the mixture It may consist of a plurality of layers including a layer.
  • the hole injecting and transporting layer may be composed of a plurality of layers in which a layer containing nanoparticles and a layer containing a hole transporting compound are at least laminated.
  • the hole injecting and transporting layer may be a layer in which a layer containing nanoparticles, and a layer containing at least nanoparticles and a hole transporting compound are laminated.
  • the hole injecting and transporting layer of the present invention may contain two or more transition metal compound-containing nanoparticles.
  • the included transition metal and / or transition metal compound may contain two or more different transition metal compound-containing nanoparticles.
  • the energy barrier between the adjacent layers can be further reduced by enabling holes to move stepwise via two types of nanoparticles using nanoparticles with different work functions (HOMO), or
  • HOMO work functions
  • the hole injecting and transporting layer multifunctional by being able to select a plurality of types of protecting agents, for example, nanoparticles protected with a highly liquid repellent protecting agent and a high hole transporting protecting agent By including protected nanoparticles, there is an advantage that a hole injecting and transporting layer having two functions of high liquid repellency and high hole transporting property can be formed.
  • the contained transition metal and / or transition metal compound, and the protective agent may each contain two or more kinds of transition metal compound-containing nanoparticles.
  • the hole transporting compound can be appropriately used as long as it is a compound having a hole transporting property.
  • the hole transportability means that an overcurrent due to hole transport is observed by a known photocurrent method.
  • high molecular weight compounds are also suitably used as the hole transportable compound.
  • the hole transporting high molecular weight compound refers to a high molecular weight compound having a hole transporting property and having a weight average molecular weight of 2,000 or more according to the polystyrene conversion value of gel permeation chromatography (GPC).
  • the hole transporting compound is not particularly limited, and examples thereof include arylamine derivatives, anthracene derivatives, carbazole derivatives, thiophene derivatives, fluorene derivatives, distyrylbenzene derivatives and spiro compounds.
  • arylamine derivatives include N, N′-bis- (3-methylphenyl) -N, N′-bis- (phenyl) -benzidine (TPD), bis (N- (1-naphthyl-N-phenyl) ) Benzidine) ( ⁇ -NPD), 4,4 ′, 4 ′ ′-tris (3-methylphenylphenylamino) triphenylamine (MTDATA) and 4,4 ′, 4 ′ ′-tris (N- (2-naphthyl) And -N-phenylamino) triphenylamine (2-TNATA) and the like.
  • carbazole derivatives examples include 4,4-N, N′-dicarbazole-biphenyl (CBP) and the like.
  • fluorene derivatives examples include N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -9,9-dimethylfluorene (DMFL-TPD).
  • distyrylbenzene derivatives include 4- (di-p-tolylamino) -4 ′-[(di-p-tolylamino) styryl] stilbene (DPAVB) and the like.
  • spiro compound for example, 2,7-bis (N-naphthalen-1-yl-N-phenylamino) -9,9-spirobifluorene (Spiro-NPB) and 2,2 ′, 7,7′- And tetrakis (N, N-diphenylamino) -9,9'-spirobifluorene (Spiro-TAD).
  • the polymer which contains an arylamine derivative, an anthracene derivative, a carbazole derivative, a thiophene derivative, a fluorene derivative, a distyryl benzene derivative, a spiro compound etc. in a repeating unit can be mentioned, for example .
  • PC-TPD-DEG copoly [3,3'-hydroxy-tetraphenylbenzidine / diethylene glycol] carbonate
  • PC-TPD-DEG copoly [3,3'-hydroxy-tetraphenylbenzidine / diethylene glycol] carbonate
  • polymer containing anthracene derivative in the repeating unit poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (9,10-anthracene)] etc. may be mentioned. it can.
  • polymer which contains carbazole in a repeating unit polyvinyl carbazole (PVK) etc. can be mentioned.
  • PVK polyvinyl carbazole
  • Specific examples of the polymer containing a thiophene derivative in the repeating unit include poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (bithiophene)] and the like.
  • polymer containing a fluorene derivative in the repeating unit examples include poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4'-) represented by the following formula (1) (N- (4-sec-butylphenyl)) diphenylamine)] (TFB), poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- represented by the following formula (2) (N, N′-bis ⁇ 4-butylphenyl ⁇ -benzidine N, N ′- ⁇ 1,4-diphenylene ⁇ )], poly [(9,9-dioctylfluorenyl- represented by the following formula (3) 2,7-diyl)] (PFO) etc.
  • formula (1) N- (4-sec-butylphenyl)) diphenylamine)
  • TFB poly [(9,9-dioctylfluoreny
  • polymer containing the spiro compound in the repeating unit include poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (9,9′-spiro-bifluorene-2, 7-diyl)] and the like.
  • hole transportable polymer compounds may be used alone or in combination of two or more.
  • the average film thickness of the hole injecting and transporting layer can be appropriately determined depending on the purpose and the adjacent layer, but it is usually 0.1 to 1000 nm, preferably 1 to 500 nm.
  • the film thickness in the case of having a discontinuous layer such as an island is defined as a film thickness obtained by averaging the whole, and for example, the average film thickness can be obtained by measuring the entire film including the discontinuous layer with an ellipsometer. You can get a value.
  • the work function of the hole injecting and transporting layer is preferably 5.0 to 6.0 eV, more preferably 5.0 to 5.8 eV, from the viewpoint of hole injection efficiency.
  • the hole injecting and transporting layer of the present invention can be formed by a solution coating method.
  • the hole injecting and transporting layer of the present invention is easy to manufacture by being applied by a solution coating method and has a high yield because short circuits are unlikely to occur, and a charge transfer complex is formed to achieve long life. It is preferable from In this case, the hole injecting and transporting layer of the present invention is formed by a solution coating method using a solution (transition metal compound-containing nanoparticle dispersed ink) dispersed in a solvent in which at least the nanoparticles are well dispersed.
  • a solution in which nanoparticles and a hole transporting compound are mixed in a hydrophilic solvent in which both are well dissolved or dispersed is used. It may be formed by a solution coating method.
  • the nanoparticles and the hole transporting compound interact with each other in the solution to form a charge transfer complex. Since this becomes easy, it is possible to form a hole injecting and transporting layer excellent in the hole transporting property and the temporal stability of the film.
  • a layer containing a hole transporting compound may be stacked on a layer containing nanoparticles by a solution coating method.
  • the hole injecting and transporting layer may be a layer in which a layer containing at least nanoparticles and a hole transporting compound is laminated by a solution coating method on a layer containing nanoparticles. The solution coating method will be described below in the section of the device manufacturing method.
  • the substrate is to be a support of the device of the present invention, and may be, for example, a flexible material or a rigid material.
  • materials that can be used include glass, quartz, polyethylene, polypropylene, polyethylene terephthalate, polymethacrylate, polymethylmethacrylate, polymethylacrylate, polyester and polycarbonate.
  • the thickness of the substrate is not particularly limited, but is usually about 0.5 to 2.0 mm.
  • the device of the present invention has two or more opposing electrodes on a substrate.
  • the electrode is preferably formed of a metal or a metal oxide, and known materials can be appropriately adopted. Generally, it can be formed of a metal such as aluminum, gold, silver, nickel, palladium and platinum and a metal oxide such as an oxide of indium and / or tin.
  • the electrode is usually formed on a substrate by a sputtering method, a vacuum evaporation method or the like in many cases, but can also be formed by a wet method such as a coating method or a dip method.
  • the thickness of the electrodes varies depending on the transparency required for each electrode. When transparency is required, it is desirable that the light transmittance of the electrode in the visible light wavelength region is usually 60% or more, preferably 80% or more, and in this case, the thickness is usually 10 to 1000 nm, Preferably, it is about 20 to 500 nm.
  • a metal layer may be further provided on the electrode in order to improve the adhesion stability with the charge injection material.
  • the metal layer is a layer containing a metal, and is formed of the metal or metal oxide generally used for the electrode as described above.
  • the device of the present invention may optionally have a conventionally known electron injection layer and / or electron transport layer between the electron injection electrode and the organic layer.
  • One embodiment of the device of the present invention includes an organic EL element containing an organic layer containing at least the hole injecting and transporting layer of the present invention and the light emitting layer.
  • an organic EL element containing an organic layer containing at least the hole injecting and transporting layer of the present invention and the light emitting layer.
  • each layer constituting the organic EL element will be described in order with reference to FIGS.
  • the substrate 50 is a support of the organic EL element, and may be, for example, a flexible material or a hard material. Specifically, for example, those mentioned in the description of the substrate of the device can be used. In the case where light emitted from the light emitting layer 100 is transmitted through the substrate 50 side and taken out, at least the substrate 50 needs to be a transparent material.
  • the electrodes 61 and 62 differ in which electrode is required to be transparent or not.
  • the electrode 61 is transparent. It needs to be formed of a material, and when light is taken out from the electrode 62 side, the electrode 62 needs to be formed of a transparent material.
  • the electrode 61 provided on the light emitting layer side of the substrate 50 acts as an anode for injecting holes into the light emitting layer, and the electrode 62 provided on the light emitting layer side of the substrate 50 injects electrons into the light emitting layer 100.
  • the anode and the cathode are preferably formed of the metals or metal oxides listed in the description of the electrodes of the device.
  • the hole injecting and transporting layer 70, the hole transporting layer 90a, and the hole injecting layer 90b are appropriately formed between the light emitting layer 100 and the electrode 61 (anode), as shown in FIGS.
  • the hole transport layer 90a may be stacked on the hole injecting and transporting layer 70 according to the present invention, and the light emitting layer 100 may be stacked thereon, as shown in FIG.
  • the hole injecting and transporting layer 70 according to the present invention may be laminated on the injection layer 90b, and the light emitting layer 100 may be laminated thereon, or the electrode 61 according to the present invention as illustrated in FIG.
  • the hole injecting and transporting layer 70 may be stacked, and the light emitting layer 100 may be stacked thereon.
  • the positive hole transport material used for the positive hole transport layer 90a is not specifically limited. It is preferable to use the hole transporting compound described in the hole injecting and transporting layer according to the present invention. Above all, the adhesion stability of the interface between the hole injecting and transporting layer and the hole transporting layer is improved by using the same compound as the hole transporting compound used in the hole injecting and transporting layer 70 according to the present invention adjacent thereto. It is preferable from the point of contributing to long drive life.
  • the hole transport layer 90a can be formed using a hole transport material by the same method as the light emitting layer described later.
  • the thickness of the hole transport layer 90a is usually 0.1 to 1 ⁇ m, preferably 1 to 500 nm.
  • the hole injecting material used for the hole injecting layer 90b is not particularly limited, and The following compounds can be used. For example, oxides such as phenylamine type, star burst type amine type, phthalocyanine type, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide, amorphous carbon, polyaniline, polythiophene derivatives and the like can be mentioned.
  • the hole injection layer 90 b can be formed using a hole injection material by the same method as the light emitting layer 100 described later.
  • the thickness of the hole injection layer 90b is usually 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
  • the energy barrier for hole injection at each interface is as small as possible, and the energy barrier for the large hole injection between the electrode 61 and the light emitting layer 100 is complemented.
  • the material constituting the hole injecting and transporting layer 70 Select TFB (work function 5.4 eV) and nanoparticles with a work function of 5.0 to less than 5.4 eV as this and stack them in this order, and the value of the work function of each layer from the electrode 61 side toward the light emitting layer 100 is It is preferable to arrange so that it may take layer structure which becomes large in order.
  • the value of the work function or the HOMO is quoted from the measured value of photoelectron spectroscopy using a photoelectron spectrometer AC-1 (manufactured by Riken Keiki Co., Ltd.).
  • the large energy barrier of hole injection between the electrode 61 (work function 5.0 eV immediately after UV ozone cleaning) and the light emitting layer 100 (eg HOMO 5.7 eV) the value of HOMO is stepped
  • the light emitting layer 100 is formed of a light emitting material between the substrate 50 on which the electrode 61 is formed and the electrode 62, as shown in FIGS.
  • the material used for the light emitting layer of the present invention is not particularly limited as long as it is a material generally used as a light emitting material, and any of fluorescent materials and phosphorescent materials can be used. Specifically, materials such as dye-based light emitting materials and metal complex-based light emitting materials can be mentioned, and any of low molecular weight compounds and high molecular weight compounds can be used.
  • dye-based light emitting materials include arylamine derivatives, anthracene derivatives, (phenylanthracene derivatives), oxadiazole derivatives, oxazole derivatives, oligothiophene derivatives, carbazole derivatives, cyclopentadiene derivatives, silole derivatives, distyrylbenzene derivatives, Distyrylpyrazine derivative, distyrylarylene derivative, silole derivative, stilbene derivative, spiro compound, thiophene ring compound, tetraphenylbutadiene derivative, triazole derivative, triphenylamine derivative, trifnylamine derivative, pyrazoloquinoline derivative, hydrazone derivative, pyra Zorine dimers, pyridine ring compounds, fluorene derivatives, phenanthrolines, perinone derivatives, perylene derivatives and the like can be mentioned. In addition, compounds of these dimers, trimers, oligomers, and derivatives of two
  • metal complex light emitting materials examples include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethyl zinc complex, porphyrin zinc complex, europium complex, etc., or Al, Zn, Be at the central metal, etc.
  • metal complexes having a rare earth metal such as Tb, Eu, Dy, etc., and having, as a ligand, oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidal, quinoline structure and the like. These materials may be used alone or in combination of two or more.
  • the high molecular weight light emitting material materials in which the low molecular weight material is introduced into the molecule as a straight chain, a side chain or a functional group, a polymer, a dendrimer or the like can be used.
  • materials in which the low molecular weight material is introduced into the molecule as a straight chain, a side chain or a functional group, a polymer, a dendrimer or the like can be used.
  • polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyvinylcarbazole, polyfluorenone derivatives, polyfluorene derivatives and polyquinoxaline derivatives, copolymers thereof and the like can be mentioned.
  • a doping material may be added to the light emitting layer for the purpose of improving the light emission efficiency or changing the light emission wavelength.
  • these may be included as a light emitting group in the molecular structure.
  • doping materials for example, perylene derivatives, coumarin derivatives, rubrene derivatives, quinacdrine derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacyclene, phenoxazone, quinoxaline derivatives, carbazole derivatives and fluorene derivatives Can be mentioned.
  • transduced spiro group into these can also be used. These materials may be used alone or in combination of two or more.
  • any of a low molecular weight compound or a high molecular weight compound which emits fluorescence, and a low molecular weight compound or a high molecular weight compound which emits phosphorescence can be used as a material of the light emitting layer.
  • the hole injecting and transporting layer forms a charge transfer complex, and a hydrophobic solvent such as xylene used in the solution coating method
  • a hydrophobic solvent such as xylene used in the solution coating method
  • a polymer compound that emits fluorescence or a polymer compound that contains a low molecular compound that emits fluorescence, or a polymer compound that emits phosphorescence or a low molecular compound that emits phosphorescence can be suitably used.
  • the light emitting layer can be formed by a solution application method, a vapor deposition method, or a transfer method using a light emitting material.
  • a solution application method the same method as described in the item of the method of manufacturing a device described later can be used.
  • the evaporation method is, for example, in the case of a vacuum evaporation method, the material of the light emitting layer is put in a crucible installed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 -4 Pa by a suitable vacuum pump.
  • the crucible is heated to evaporate the material of the light emitting layer, and the light emitting layer 100 is placed on the laminate of the substrate 50 placed facing the crucible, the electrode 61, the hole injecting and transporting layer 70, and the hole transporting layer 90a. Let it form.
  • the transfer method is, for example, bonding a light emitting layer previously formed on a film by a solution coating method or a vapor deposition method to a hole injecting and transporting layer 70 provided on an electrode, and heating the light emitting layer 100 by a hole injecting and transporting layer 70. It is formed by transcribing onto.
  • the hole injecting and transporting layer side of the laminate in which the film, the light emitting layer 100, and the hole injecting and transporting layer 70 are laminated in this order may be transferred onto the electrode.
  • the thickness of the light emitting layer is usually about 1 to 500 nm, preferably about 20 to 1000 nm.
  • the present invention is advantageous in that the hole injecting and transporting layer is preferably formed by a solution coating method, so that the process cost can be reduced when the light emitting layer is also formed by a solution coating method.
  • FIG.7 Another embodiment of the device according to the invention is an organic transistor.
  • each layer which comprises an organic transistor is demonstrated using FIG.7 and FIG.8.
  • the hole injection transport layer 70 is formed on the surfaces of the electrode 61 (source electrode) and the electrode 62 (drain electrode), each electrode and the organic semiconductor layer The hole injecting and transporting ability between them is high, and the film stability of the hole injecting and transporting layer of the present invention is high, which contributes to the long drive life.
  • the hole injecting and transporting layer 70 of the present invention as shown in FIG. 8 may function as the organic semiconductor layer 110.
  • a hole injecting and transporting layer 70 is formed on the surfaces of the electrode 61 (source electrode) and the electrode 62 (drain electrode). You may form the positive hole injection transport layer 70 of this invention in which material differs in the formed positive hole injection transport layer.
  • a low molecular weight or high molecular weight organic semiconductor material of donor nature can be used as a material for forming the organic semiconductor layer.
  • the organic semiconductor materials include porphyrin derivatives, arylamine derivatives, polyacene derivatives, perylene derivatives, rubrene derivatives, coronene derivatives, perylenetetracarboxylic acid diimide derivatives, perylenetetracarboxylic acid dianhydride derivatives, polythiophene derivatives, polyparaphenylene derivatives, Polyparaphenylene vinylene derivative, polypyrrole derivative, polyaniline derivative, polyfluorene derivative, polythiophene vinylene derivative, polythiophene-heterocyclic aromatic copolymer and its derivative, ⁇ -6-thiophene, ⁇ -4-thiophene, oligoacene derivative of naphthalene, Oligothiophene derivatives, pyromellitic
  • metal phthalocyanines such as a phthalocyanine and copper phthalocyanine
  • arylamine derivative for example, m-TDATA
  • polyacene derivatives include naphthalene, anthracene, naphthacene and pentacene.
  • the organic transistor including the hole injecting and transporting layer of the present invention as shown in FIG. 7 is formed, as the compound constituting the organic semiconductor layer 110, it can be used in the hole injecting and transporting layer of the present invention
  • a hole transportable compound in particular a hole transportable polymer compound, improves the adhesion stability of the interface between the hole injecting and transporting layer 70 and the organic semiconductor layer 110 of the present invention, and extends the driving life. It is preferable from the point of contribution.
  • the carrier mobility of the organic semiconductor layer is preferably 10 -6 cm / Vs or more, particularly 10 -3 cm / Vs or more for an organic transistor, from the viewpoint of transistor characteristics.
  • the organic semiconductor layer can be formed by a solution coating method or a dry process, similarly to the light emitting layer of the organic EL element.
  • the substrate, the gate electrode, the source electrode, the drain electrode, and the insulating layer are not particularly limited, and can be formed using, for example, the following materials.
  • the substrate 50 is a support of the device of the present invention, and may be, for example, a flexible material or a rigid material.
  • the same substrate as the substrate of the organic EL element can be used.
  • the gate electrode, the source electrode, and the drain electrode are not particularly limited as long as they are conductive materials, but from the viewpoint of forming the hole injecting and transporting layer 70 using the transition metal compound-containing nanoparticle according to the present invention Or it is preferable that it is a metal oxide.
  • the same metal or metal oxide as the electrode in the above-mentioned organic EL element can be used, but platinum, gold, silver, copper, aluminum, indium, ITO and carbon are particularly preferable.
  • an inorganic oxide having a high dielectric constant is particularly preferable.
  • silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate examples thereof include barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate and yttrium trioxide.
  • Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.
  • organic compound polyimide, polyamide, polyester, polyacrylate, radical photopolymerization system, photocurable resin of cationic photopolymerization system, copolymer containing an acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, novolac resin and cyanoethyl pullulan , Polymer bodies, phosphazene compounds including elastomer bodies, and the like can be used.
  • the hole injection transport layer is also used for dye-sensitized solar cells, organic thin film solar cells, other organic devices such as organic semiconductors, quantum dot light emitting devices having a hole injection transport layer, oxide compound solar cells, etc. If it is set as the hole injection transport layer which concerns on the said invention, the other structure will not be specifically limited, It may be suitably the same as a well-known structure.
  • a first method of manufacturing a device according to the present invention is a method of manufacturing a device having two or more electrodes facing each other on a substrate, and a hole injecting and transporting layer disposed between two electrodes of the two or more electrodes. Forming a hole injecting and transporting layer on any of the layers on the electrode using the first transition metal compound-containing nanoparticle dispersed ink.
  • a second method of producing a device according to the present invention is a method of producing a device having two or more electrodes facing each other on a substrate, and a hole injecting and transporting layer disposed between two electrodes of the two or more electrodes. Forming a hole injecting and transporting layer on any layer on the electrode using the second transition metal compound-containing nanoparticle-dispersed ink; Oxidizing the compound (U).
  • the hole injecting and transporting layer containing nanoparticles is formed by the solution coating method using the first or second transition metal compound-containing nanoparticle dispersed ink as described above. Be done.
  • a deposition apparatus is not required at the time of formation of the hole injecting and transporting layer, and coating can be separately performed without using mask deposition and the like, productivity is high, and electrodes and holes are formed. It is possible to form a device with high adhesion stability between the interface of the injection and transport layer and the interface between the hole injection and transport layer and the organic layer.
  • the solution coating method is a method in which the first or second transition metal compound-containing nanoparticle dispersed ink is coated on an electrode or layer serving as a base and dried to form a hole injecting and transporting layer.
  • a liquid dropping method such as immersion method, spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating method, bar coating method, die coating method and ink jet method etc. may be mentioned.
  • spin coating is preferably used.
  • a liquid dropping method such as an ink jet method capable of depositing the hole injecting and transporting layer regioselectively on the substrate is preferably used.
  • the immersion method and the dip coating method are suitably used.
  • the second method for producing a device at least one compound selected from the group consisting of transition metal carbides, transition metal nitrides and transition metal sulfides contained in transition metal compound-containing nanoparticle dispersed ink
  • oxidizing (U) it is possible to form a layer containing a transition metal oxide having no solvent solubility using a solution coating method without using a vapor deposition method.
  • the compound (U) in the hole injecting and transporting layer into the corresponding transition metal carbide, transition metal nitride, or transition metal sulfide, the adjacent organic layer and the hole injecting and transporting layer are solution-coated with each other.
  • the step of oxidizing the compound (U) may be performed before the step of forming a hole injecting and transporting layer, or a hole injecting and transporting layer is formed. It may be performed after the process.
  • examples of the oxidation method include heating means, light irradiation means, means for causing active oxygen, and the like in the presence of oxygen, and these may be used in combination as appropriate.
  • the method may be the same as the method described in the above-described method of producing nanoparticles.
  • transition metal carbide, transition metal on any layer on the electrode, using the second transition metal compound-containing nanoparticle dispersed ink Forming a hole injecting and transporting layer containing at least one compound (U) selected from the group consisting of nitrides and transition metal sulfides and a protective agent, and the compound in the hole injecting and transporting layer
  • the production method may include the step of oxidizing U) to transition metal carbon oxides, transition metal nitride oxides or transition metal sulfide oxides, respectively. In this way, a hole injecting and transporting layer containing nanoparticles can be formed.
  • the transition metal carbide and transition contained in the second transition metal compound-containing nanoparticle dispersed ink before the step of forming the hole injecting and transporting layer A step of oxidizing one or more types of compounds (U) selected from the group consisting of metal nitrides and transition metal sulfides is performed to make the compounds (U) into nanoparticles.
  • the oxidized transition metal compound-containing nanoparticle dispersed ink is used to form a hole injection transport layer containing nanoparticles. After the formation of the layer, an oxidation step may be further performed.
  • the thickness of the layer or film is represented by the average film thickness.
  • the mixed solution is cooled to room temperature (24 ° C.), and the atmosphere is changed from an argon gas atmosphere to an air atmosphere to disperse polyvinyl pyrrolidone protected molybdenum carbide oxide-containing nanoparticles in a solvent; A substance-containing nanoparticle ink is obtained.
  • the mixture was brought to an argon gas atmosphere and heated to 280 ° C. with stirring, and the temperature was maintained for 1 hour. Thereafter, the mixture is cooled to room temperature (24 ° C.), and after changing from an argon gas atmosphere to the atmosphere, 20 g of ethanol is added, and then the precipitate is separated from the reaction solution by centrifugation, as shown below Purification by reprecipitation was performed according to the procedure. That is, the precipitate was mixed with 3 g of chloroform to form a dispersion, and 6 g of ethanol was dropped to this dispersion to obtain a purified precipitate.
  • the reprecipitated solution thus obtained is centrifuged, and the precipitate is separated from the reaction solution, and then dried to obtain a purified product of black n-hexadecylamine-protected molybdenum carbide oxide nanoparticles I got Next, 0.1 g of the synthesized n-hexadecylamine-protected molybdenum carbide oxide nanoparticles, 0.8 g of thioglycollic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 20 g of chloroform are weighed in a 50 ml eggplant flask, The mixture was heated to 50.degree. C. with stirring at and maintained at that temperature for 2 days.
  • the mixture was cooled to room temperature (24 ° C.), and the precipitate was separated from the reaction solution by centrifugation, and purification by reprecipitation was performed according to the following procedure. That is, the precipitate was mixed with 5 g of 2-propanol to make a dispersion, and 12 g of hexane was dropped to this dispersion to obtain a purified precipitate. Next, the reprecipitated solution was centrifuged, and the precipitate was separated from the reaction solution, and then dried to obtain thioglycolic acid-protected molybdenum carbide oxide nanoparticles. A molybdenum carbide oxide-containing nanoparticle ink was obtained by dispersing the molybdenum carbide oxide-containing nanoparticles thus obtained in a concentration of 0.5% by weight with respect to 2-propanol.
  • the measurement sample was prepared by dispersing the black powder of molybdenum carbide oxide nanoparticles protected with n-hexadecylamine, which is an intermediate obtained in Preparation Example 2, in air at a concentration of 0.4% by mass in cyclohexanone.
  • An ink was made. The ink was spin coated on a glass substrate with ITO in air to form a thin film. The thin film was dried in air at 200 ° C. for 30 minutes. The thickness of the thin film after drying was 10 nm.
  • the film thickness is determined by forming a layer formed of the material to be measured as a single layer on a cleaned ITO-attached glass substrate and forming a step with a cutter knife, and then measuring the height of the step with a probe microscope (S The measurement was performed in tapping mode using Nanopics 1000 manufactured by I. Nano Technology Co., Ltd.
  • the n-hexadecylamine-protected nanoparticles which are intermediates obtained in Production Example 2, are nanoparticles of molybdenum carbide oxide, and the surface layer It is inferred that the portion is a molybdenum carbide oxide having a valence of +6, and the inside has a shell structure that is a molybdenum carbide oxide having a valence of +4 from the surface layer.
  • Example 1 Preparation of Organic Diode
  • the organic diode element is formed by depositing an anode on a glass substrate, a layer containing transition metal compound-containing nanoparticles synthesized in Preparation Example 1 as a hole injecting and transporting layer, an organic semiconductor layer, and a cathode in this order.
  • the ITO-attached glass substrate was subjected to ultrasonic cleaning in the order of water, acetone and 2-propanol. Subsequently, the ITO was patterned by an etching method.
  • Example 2 Preparation of Organic Diode Example 1 is the same as Example 1 except that the transition metal compound-containing nanoparticle-containing ink prepared in Preparation Example 2 is used instead of the transition metal compound-containing nanoparticle-containing ink prepared in Preparation Example 1 Then, the organic diode of Example 2 was manufactured.
  • Comparative Example 1 Preparation of Organic Diode An organic diode of Example 2 was produced in the same manner as Example 1 except that the hole injecting and transporting layer containing the transition metal compound-containing nanoparticle was not formed in Example 1.
  • the atmosphere was changed from the vacuum to the atmosphere, and 0.8 g of molybdenum hexacarbonyl (manufactured by Kanto Chemical Co., Ltd.) was added.
  • the mixture was brought to an argon gas atmosphere and heated to 280 ° C. with stirring, and the temperature was maintained for 1 hour. Thereafter, the mixture is cooled to room temperature (24 ° C.), and after changing from an argon gas atmosphere to the atmosphere, 20 g of methanol is added, and then the precipitate is separated from the reaction solution by centrifugation, as shown below. Purification by reprecipitation was performed according to the procedure.
  • the precipitate was mixed with 3 g of chloroform to form a dispersion, and 6 g of methanol was dropped to this dispersion to obtain a purified precipitate.
  • the reprecipitated solution thus obtained is centrifuged, and the precipitate is separated from the reaction solution and then dried to obtain black tri-n-octyl phosphine oxide protected molybdenum carbide oxide nanoparticles.
  • the purified product was obtained.
  • Production Example 4 In the same manner as in Production Example 3, except that sodium 2-mercaptoethanesulfonate was used instead of sodium 3-mercapto-1-propanesulfonate in the production of the molybdenum carbide oxide-containing nanoparticles of Production Example 3. A sodium 2-mercaptoethane sulfonate protected molybdenum oxide-containing nanoparticle ink was prepared.
  • Production Example 6 The same procedure as in Production Example 3 was repeated, except that 6-amino-1-hexanol was used instead of sodium 3-mercapto-1-propanesulfonate in the production of the molybdenum carbide-containing oxide-containing nanoparticles of Production Example 3. A 6-amino-1-hexanol protected molybdenum oxide-containing nanoparticle ink was prepared.
  • the atmosphere was changed from the vacuum to the atmosphere, and 0.8 g of molybdenum hexacarbonyl (manufactured by Kanto Chemical Co., Ltd.) was added.
  • the mixture was brought to an argon gas atmosphere and heated to 180 ° C. with stirring, and the temperature was maintained for 2 hours.
  • the mixture is then cooled to room temperature (24.degree. C.) and black 12-amino-1-dodecanol protected molybdenum oxide nanoparticles are incorporated into 2-methyl-2,4-pentanediol.
  • a dispersed molybdenum oxide-containing nanoparticle ink was obtained.
  • Example 3 In the procedure described below, a laminate of a transparent anode on a glass substrate, a layer containing molybdenum carbide oxide-containing nanoparticles as a hole injecting and transporting layer, and a layer containing a hole transporting compound, a hole transporting layer
  • the light emitting layer, the hole blocking layer, the electron injection layer, and the cathode were formed in this order and stacked, and finally sealed, to fabricate an organic EL element. Except for the transparent anode and the hole injecting and transporting layer, work was performed in a nitrogen-substituted glove box having a water concentration of 0.1 ppm or less and an oxygen concentration of 0.1 ppm or less.
  • an ITO thin film (thickness: 150 nm) was used as a transparent anode.
  • the ITO-attached glass substrate manufactured by Sanyo Vacuum Industry Co., Ltd.
  • the patterned ITO substrate was subjected to ultrasonic cleaning in the order of a neutral detergent and ultrapure water, and subjected to UV ozone treatment.
  • the HOMO of ITO after UV ozone treatment was 5.0 eV.
  • the molybdenum carbide oxide-containing nanoparticles obtained in the above-mentioned Production Example 3 were dissolved in water at a concentration of 0.4% by mass to prepare an ink for a hole injecting and transporting layer.
  • the above-described ink for a hole injecting and transporting layer was applied by spin coating on the cleaned anode to form a hole injecting and transporting layer containing nanoparticles.
  • the hole injecting and transporting layer ink After the application of the hole injecting and transporting layer ink, it was dried at 200 ° C. for 30 minutes in the air using a hot plate to evaporate the solvent. The thickness of the hole injecting and transporting layer after drying was 10 nm.
  • a polyvinylcarbazole (PVK) thin film (thickness: 10 nm) manufactured by Aldrich was applied and formed as a hole transporting layer.
  • the weight average molecular weight of PVK is 1.1 million.
  • a solution of PVK dissolved in a solvent dichloroethane at a concentration of 0.5% by mass was filtered with a 0.2 ⁇ m filter and applied by spin coating to form a film. After application of the PVK solution, it was dried at 150 ° C. for 30 minutes using a hot plate to evaporate the solvent.
  • tris [2- (p-tolyl) pyridine] iridium (III) (Ir (mppy) 3 ) is contained as a light emitting dopant as a light emitting layer on the deposited hole transport layer
  • a mixed thin film containing 4'-bis (2,2-carbazol-9-yl) biphenyl (CBP) as a host was coated and formed.
  • a solution obtained by dissolving CBP at 1% by mass and Ir (mppy) 3 at a concentration of 0.05% by mass in toluene as a solvent was applied by spin coating to form a film. After application of the ink, it was dried at 100 ° C. for 30 minutes using a hot plate to evaporate the solvent. Next, a bis (2-methyl-8-quinolilato) (p-phenylphenolate) aluminum complex (BAlq) thin film was vapor deposited on the light emitting layer as a hole blocking layer. The BAlq thin film was formed to have a thickness of 15 nm by resistance heating in vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa).
  • Alq3 thin film was vapor deposited on the hole blocking layer as an electron transporting layer.
  • the Alq3 thin film was formed to have a thickness of 15 nm by resistance heating in vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa).
  • LiF (thickness: 0.5 nm) as an electron injection layer and Al (thickness: 100 nm) as a cathode were sequentially formed on the manufactured electron transport layer.
  • the film was formed by resistance heating evaporation in vacuum (pressure: 1 ⁇ 10 ⁇ 4 Pa).
  • sealing was performed using a non-alkali glass and a UV curable epoxy adhesive in a glove box, to fabricate an organic EL element of Example 3.
  • Example 4 In the production of the organic EL device of Example 3, the hole injection / transport layer was prepared except that the nanoparticles of Production Example 4 were used to form the hole injection / transport layer instead of using the nanoparticles of Production Example 3. The organic EL element of Example 4 was produced in the same manner as Example 3.
  • Example 5 In the production of the organic EL device of Example 3, the hole injection transport layer is carried out except that the nanoparticles of Production Example 5 are used to form the hole injection transport layer instead of using the nanoparticles of Production Example 3.
  • the organic EL element of Example 5 was produced in the same manner as Example 3.
  • Example 6 In the production of the organic EL device of Example 3, the hole injection transport layer is carried out except that the nanoparticles of Production Example 6 are used to form the hole injection transport layer instead of using the nanoparticles of Production Example 3.
  • the organic EL element of Example 6 was produced in the same manner as Example 3.
  • Example 7 In the manufacture of the organic EL device of Example 3, the hole injection and transport layer was carried out except that the nanoparticles of Production Example 7 were used to form the hole injection and transport layer instead of using the nanoparticles of Production Example 3.
  • the organic EL element of Example 7 was produced in the same manner as Example 3.
  • the organic EL devices fabricated in the above Examples 3 to 7 and Comparative Examples 2 to 3 were driven at 10 mA / cm 2 , and the emission luminance and the spectrum were measured by a spectroradiometer SR-2 manufactured by Topcon Corporation.
  • the organic EL elements produced in the above-described Examples and Comparative Examples all emitted green light from Ir (mppy) 3 .
  • the measurement results are shown in Table 2.
  • the current efficiency was calculated from the drive current and the luminance.
  • the life characteristics of the organic EL element were evaluated by observing how the luminance gradually decreased with time by constant current driving. Here, the time (hour) until the retention ratio deteriorates to 50% of the initial luminance of 1,000 cd / m 2 is defined as the life (LT 50).
  • the dispersibility of the ink is poor, the hole injecting and transporting layer tends to aggregate, and the device tends to short. Also in this dispersibility, it is understood that the molybdenum carbide oxide of the present invention is superior.
  • Example 3 in which the protective agent in the nanoparticles was changed was compared with the devices of Example 4, Example 5, Example 6, and Example 7, similar characteristics were obtained.
  • Example 8 The n-octyltrichlorosilane (OTS) treatment was performed on Si / SiO 2 , and Au was manufactured by a 30 nm vacuum evaporation method as a source-drain electrode. The channel length was 50 ⁇ m and the channel width was 1 mm. Subsequently, using the molybdenum carbon oxide-containing nanoparticle ink prepared in Production Example 2 by an inkjet method, a hole injecting and transporting layer containing a molybdenum carbon oxide was formed. After thin film formation, it was dried at 200 ° C. for 30 minutes in the atmosphere using a hot plate to evaporate the solvent.
  • OTS n-octyltrichlorosilane
  • the molybdenum nanoparticles prepared in Preparation Example 2 using a hydrophilic solvent could be formed only on the source and drain electrodes without wetting and spreading to the OTS-treated channel portion.
  • An organic thin film transistor was formed.
  • Comparative example 4 An organic thin film transistor of Comparative Example 4 was produced in the same manner as in Example 8 except that a hole injecting and transporting layer containing molybdenum carbide oxide nanoparticles was not formed in Example 8.
  • Example 8 As a result of comparing organic TFT characteristics of the organic thin film transistors (TFTs) obtained in Example 8 and Comparative Example 4, a hole injecting and transporting layer using the molybdenum carbide oxide-containing nanoparticles prepared in Production Example 2 was formed. In Example 8 in which the increase in the On current and the improvement in the FET mobility were confirmed.
  • transition metal compound-containing nanoparticle 5 supported carrier 10 transition metal and / or transition metal complex 20 transition metal carbide 30 protective agent 40 transition metal carbon oxide 50 substrate 61, 62, 63 electrode 70 hole injection transport layer 80 organic layer 90a Hole transport layer 90 b Hole injection layer 100 Light emitting layer 110 Organic semiconductor layer 120 Insulating layer

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Thin Film Transistor (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

L'invention concerne une nanoparticule innovante contenant un composé métallique qui peut être dispersée de manière stable dans un solvant. Cette nanoparticule contenant un composé de métal de transition est caractérisée en ce qu'elle est composée d'au moins un composé de métal de transition sélectionné parmi le groupe constitué d'un oxycarbure de métal de transition, d'un oxynitrure de métal de transition et d'un oxysulfure de métal de transition et d'un agent protecteur comportant un groupe organique hydrophile et lié au composé de métal de transition par un groupe liant, et est aussi caractérisée en ce qu'elle est dispersible dans un solvant hydrophile.
PCT/JP2011/067871 2010-08-06 2011-08-04 Nanoparticules contenant un composé de métal de transition et leur processus de production, encre comportant des nanoparticules contenant chacune le composé de métal de transition dispersé et son processus de production, et dispositif équipé d'une couche de transport/injection de trous et son processus de production Ceased WO2012018082A1 (fr)

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JP2013171968A (ja) * 2012-02-21 2013-09-02 Konica Minolta Inc 有機エレクトロルミネッセンス素子、照明装置および表示装置ならびに有機エレクトロルミネッセンス素子の製造方法
JP2016096123A (ja) * 2014-11-17 2016-05-26 大日本印刷株式会社 有機エレクトロルミネッセンス素子、及びその製造方法、並びに有機エレクトロルミネッセンス照明装置
WO2018051860A1 (fr) * 2016-09-16 2018-03-22 東レ株式会社 Procédé de fabrication d'un transistor à effet de champ et procédé de fabrication de dispositif de communication sans fil
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US11566316B2 (en) 2019-01-31 2023-01-31 Dai Nippon Printing Co., Ltd. Deposition mask group, manufacturing method of electronic device, and electronic device
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