WO2011027749A1 - Élément électroluminescent organique, procédé de fabrication d'éléments électroluminescents organiques, dispositif d'affichage et dispositif d'éclairage - Google Patents

Élément électroluminescent organique, procédé de fabrication d'éléments électroluminescents organiques, dispositif d'affichage et dispositif d'éclairage Download PDF

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WO2011027749A1
WO2011027749A1 PCT/JP2010/064847 JP2010064847W WO2011027749A1 WO 2011027749 A1 WO2011027749 A1 WO 2011027749A1 JP 2010064847 W JP2010064847 W JP 2010064847W WO 2011027749 A1 WO2011027749 A1 WO 2011027749A1
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layer
organic
light emitting
organic electroluminescent
hole transport
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PCT/JP2010/064847
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Japanese (ja)
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直之 林
雅之 三島
隆志 加藤
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富士フイルム株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers

Definitions

  • the present invention relates to an organic electroluminescent element, a method for manufacturing the organic electroluminescent element, a display device, and an illumination device.
  • organic electroluminescent elements such as organic electroluminescent elements (hereinafter also referred to as organic EL elements) and transistors using organic semiconductors.
  • the organic EL element is expected to develop as a lighting application as a solid light-emitting large-area full-color display element or an inexpensive large-area surface light source.
  • an organic electroluminescent element is composed of an organic layer including a light emitting layer and a pair of counter electrodes sandwiching the organic layer. When a voltage is applied to such an organic electroluminescence device, electrons are injected from the cathode and holes are injected from the anode into the organic layer. The electrons and holes recombine in the light emitting layer, and light is emitted by releasing energy as light when the energy level returns from the conduction band to the valence band.
  • an organic electroluminescent device as a method of forming a thin film which is an organic layer provided between a pair of electrodes, vacuum deposition is used as a vapor deposition method, spin coating method, printing method, ink jet method is used as a wet method. Yes.
  • the vapor deposition method is a method of forming a thin film on a substrate in a vacuum, and such an organic electroluminescent element (hereinafter also referred to as a vapor deposition type organic EL element) manufactured by using vapor deposition is used for a mobile phone, It has been put to practical use as a light emission source for displays such as televisions.
  • the vapor deposition process in the production of the vapor deposition type organic EL element has a large equipment cost for the vapor deposition apparatus and an energy cost when vapor depositing the material, and it is required to further reduce the production cost of the organic electroluminescent element. .
  • the wet method it is possible to use high molecular organic compounds that are difficult to form in a dry process such as vapor deposition.
  • the film formation method is simpler than vapor deposition, etc. Is not necessary, and there are advantages such as being suitable for durability such as bending resistance and film strength when used for flexible displays, etc., especially for large area and high definition. This is a technique suitable for a large screen organic EL display.
  • Patent Documents 1 and 2 disclose an organic electroluminescent element (hereinafter, also referred to as a coating-type organic EL element) in which a layer constituting the organic EL element is manufactured using a coating method.
  • Patent Document 3 discloses an element in which at least one organic layer includes an organic layer formed by a wet process using two or more organic compounds including at least one organic compound subjected to sublimation purification.
  • Patent Document 4 discloses a non-aqueous coating dispersion for an organic electroluminescence element that has good dispersion stability by incorporating a dispersion stabilizer in the coating dispersion.
  • an organic EL device having a high external extraction quantum efficiency and a long emission lifetime, which is formed using the coating dispersion or the non-aqueous coating dispersion is disclosed.
  • the coating type organic EL element has a problem that the luminous efficiency and durability are low. Impurities are considered to be a cause of deterioration in luminous efficiency and element durability in the coating type EL element. For this reason, there are cases where the coating method is adopted for polymer materials that cannot be deposited by vapor deposition, but low molecular weight materials that can be deposited by vapor deposition have a vapor deposition method that provides higher device performance. In general, it was used to form a film.
  • Japanese Unexamined Patent Publication No. 2004-160388 Japanese Unexamined Patent Publication No. 2007-42314 Japanese Unexamined Patent Publication No. 2008-66759 Japanese Unexamined Patent Publication No. 2007-165231
  • An object of the present invention is to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide an organic electroluminescent device that is excellent in luminous efficiency and durability, has a low driving voltage, and can reduce manufacturing costs. Another object of the present invention is to provide a method for producing an organic electroluminescent device that can produce an organic electroluminescent device having excellent luminous efficiency and durability and low driving voltage at a low production cost. Furthermore, an object of this invention is to provide the display apparatus and illuminating device which comprise the said organic electroluminescent element.
  • An organic electroluminescent device having a light emitting layer and at least one layer adjacent to the light emitting layer between a pair of electrodes
  • An organic electroluminescent device wherein the at least one layer adjacent to the light emitting layer is formed by a spray method using a liquid containing two or more low molecular weight compounds having a molecular weight of 1500 or less.
  • the two or more kinds of low molecular weight compounds having a molecular weight of 1500 or less are two kinds of compounds of the first low molecular weight compound and the second low molecular weight compound, and the mixing ratio thereof is 20:80 to 80:20 by mass ratio.
  • the organic electroluminescence device as described in any one of [1] to [3], wherein the two or more kinds of low molecular weight compounds having a molecular weight of 1500 or less are two or more kinds of hole transport materials.
  • [5] [4] The organic electroluminescence device as described in [4], wherein the difference in ionization potential between the two or more hole transport materials is 0.1 eV or more and 0.6 eV or less.
  • [8] The organic electroluminescence device according to [7], wherein the electron transport layer is formed of a liquid containing two or more kinds of electron transport materials.
  • Each of the said light emitting layer and the layer adjacent to the said light emitting layer is formed with the said spray method, The manufacturing method of the organic electroluminescent element as described in [10] characterized by the above-mentioned.
  • [12] [1] to [9] The organic electroluminescence device according to [9] or the display device comprising the organic electroluminescence device obtained from the method for producing an organic electroluminescence device according to any one of [10] or [11] .
  • the layer adjacent to the light emitting layer is formed by a spray method using a liquid containing two or more kinds of low molecular weight compounds having a molecular weight of 1500 or less, so that it has excellent thermal stability, light emitting efficiency and durability, and is driven.
  • An organic electroluminescent device having a low voltage and capable of reducing manufacturing costs can be provided.
  • the display apparatus and illuminating device which comprise the said organic electroluminescent element can be provided.
  • the organic EL device of the present invention is an organic electroluminescent device having a light emitting layer and at least one layer adjacent to the light emitting layer between a pair of electrodes, The at least one layer adjacent to the light emitting layer is formed by a spray method using a liquid containing two or more kinds of low molecular compounds having a molecular weight of 1500 or less.
  • the low molecular weight compound in the present invention refers to a compound having an unsaturated bond (so-called polymerizable monomer) by cleaving the unsaturated bond using an initiator and growing the bond in a chain manner. It is not a so-called polymer or oligomer obtained, but a compound having a constant molecular weight of 1500 or less (a compound having substantially no molecular weight distribution). The molecular weight is usually 100 or more.
  • the material forming the layer adjacent to the light emitting layer does not contain impurities derived from compounds such as a polymerization initiator, a polymerization terminator and a chain transfer agent used for polymer synthesis and oligomer synthesis.
  • impurities derived from compounds such as a polymerization initiator, a polymerization terminator and a chain transfer agent used for polymer synthesis and oligomer synthesis.
  • the low molecular weight compound having a molecular weight of 1500 or less is more preferably purified by a known purification method. Thereby, it can avoid more reliably that an impurity degrades the function of each layer.
  • Known purification methods include a sublimation purification method, a recrystallization purification method, a column purification method, and the like.
  • a polymer or oligomer when the repeating unit has an unintended structure due to reaction or the like, it is very difficult to purify such a polymer or oligomer by purification. It is preferably a molecular compound.
  • the number of low molecular compounds having a molecular weight of 1500 or less is 2 or more, preferably 2 to 4, more preferably 2 to 3, and still more preferably 2.
  • the mixing ratio of the first low molecular weight compound and the second low molecular weight compound is preferably 20:80 to 80:20, and 30:70 to 70: 30 is more preferable.
  • the organic EL element of the present invention having the above configuration can reduce the driving voltage.
  • the material constituting the layer is formed by spraying a solution in which a solvent is dissolved or dispersed in the solvent, it is not necessary to employ a vapor deposition process as described above, and the manufacturing cost of the organic EL element is reduced. it can.
  • FIG. 1 shows an example of the configuration of an organic EL element according to the present invention.
  • an organic layer is sandwiched between an anode 3 and a cathode 9 on a support substrate 2. More specifically, the organic layer includes, for example, a hole injection layer 4 on the anode, a hole transport layer 5 on the hole injection layer 4, a light emitting layer 6 on the hole transport layer 5, It consists of a hole blocking layer 7 on the light emitting layer 6 and an electron transporting layer 8 on the hole blocking layer 7.
  • the content of the solid content with respect to the total amount of the liquid is not particularly limited, but is usually 0.0001% by mass to 10% by mass, but considering the adoption of the spray method, it is 0.0001% by mass to 1% by mass. Preferably there is.
  • At least one layer adjacent to the light emitting layer is preferably a hole transport layer.
  • the solvent of the liquid may be the same organic solvent.
  • this makes it possible to obtain an organic EL element excellent in luminous efficiency and durability, in particular, because the bonding at the interface between the layers becomes better.
  • At least one of the light emitting layer and the layer adjacent to the light emitting layer is formed by applying the above liquid by a spray method.
  • the organic solvent of the liquid may be damaged by dissolving the other organic layer to an unintended degree. Since this can be reduced more reliably, it is possible to obtain an organic EL element that is more reliably excellent in luminous efficiency, durability, and color reproducibility.
  • the spray method can easily reduce the amount of solvent used and can be easily dried as compared with other coating methods, and thus can further reduce the manufacturing cost.
  • the spray method is suitable for forming a multilayer thin film because the layer can be formed without damaging the lower layer of the layer formed by the spray method.
  • the step of applying the liquid by the spray method is, in other words, the step of applying the aerosol to form a layer by injecting the aerosol in which the liquid particles are suspended in a gas (carrier gas) onto a predetermined surface.
  • a gas carrier gas
  • the form of the aerosol is not particularly limited, but the particle size of the liquid particles is usually 0.01 to 100 ⁇ m, more preferably 0.01 to 10 ⁇ m.
  • the gas include air, nitrogen, and argon. Any known spray device can be used for the spray method.
  • the flow rate of the aerosol carrier gas is preferably 0.1 L / min to 100 L / min, and more preferably 0.1 L / min to 10 L / min.
  • the spraying time of the aerosol conforms to the thickness to be obtained from each layer and is not particularly limited.
  • the layer formed by the spray method is preferably dried for a certain period after the layer formation by the spray method is completed, particularly when another layer is provided on the layer.
  • the drying method depends on the type of organic solvent used, but the temperature is preferably 20 to 200 ° C., and the drying time is preferably 1 minute to 10 hours.
  • the drying is preferably vacuum drying.
  • the application method of the other layers is not particularly limited.
  • it can be performed by spin coating, air knife coating, bar coating, blade coating, slide coating, curtain coating, spray method, casting method, dipping method, ink jet method and the like.
  • the material for the anode is normally a material having high resistance to organic solvents as described later.
  • any of the liquid coating methods exemplified above can be suitably used.
  • the spray method when adopting the spray method for the light-emitting layer and the electron transport layer, the spray method can also be used for the hole transport layer, so that the coating method can be unified. Cost can be reduced. Therefore, a form in which each of the light emitting layer and the layer adjacent to the light emitting layer is formed by applying the liquid by a spray method is more preferable, and each of the hole transport layer, the light emitting layer, and the electron transport layer is the liquid. The form formed by coating by a spray method is most preferable.
  • the layer configuration of the organic layer has been described with reference to FIG. 1 as described above, but is not particularly limited and can be appropriately selected according to the application and purpose of the organic EL element. Moreover, there is no restriction
  • Anode / hole transport layer / light emitting layer / electron transport layer / cathode (2) Anode / hole transport layer / light emitting layer / block layer / electron transport layer / cathode (3) Anode / hole transport layer / light emission Layer / block layer / electron transport layer / electron injection layer / cathode (4) anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / cathode (5) anode / hole injection layer / Hole transport layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode
  • the layer adjacent to the light emitting layer is formed by applying a liquid in which the material constituting the layer is dissolved or dispersed in a solvent.
  • the transport layer is preferably formed by a coating method
  • the hole transport layer and the electron transport layer are more preferably formed by a coating method
  • the light-emitting layer, the hole transport layer and the electron transport layer are formed by a coating method. More preferably, it is formed.
  • a material constituting each layer in each of a plurality of continuous layers including a hole transport layer, a light emitting layer, and an electron transport layer (however, the plurality of layers constitute a part or all of the organic layer). Is more preferably formed by applying a solution dissolved or dispersed in a solvent.
  • another layer constituting the organic layer (a block layer in the case of the above layer configuration (2)) is provided between the hole transport layer and the light-emitting layer and / or between the light-emitting layer and the electron transport layer.
  • the plurality of layers in the case of the layer configuration (2), the hole transport layer, the light-emitting layer, the block layer, and the electron transport layer) may be interposed, and any of the layers is formed by a vapor deposition method.
  • the organic EL that has excellent luminous efficiency and durability and can reduce the driving voltage A device tends to be obtained.
  • organic layer In addition to a light emitting layer, it has a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole block layer, an electron block layer, an exciton block layer, etc. It may be. Each of these layers may have other functions.
  • the present invention is a method for producing an organic electroluminescent device having a light emitting layer and a layer adjacent to at least one light emitting layer between a pair of electrodes,
  • the present invention also relates to a method for manufacturing an organic electroluminescent element, wherein the layer adjacent to the at least one light emitting layer is formed by a spray method using a liquid containing two or more compounds having a molecular weight of 1500 or less.
  • the organic solvent include the organic solvents. More preferably, at least one layer adjacent to the light emitting layer is formed by a spray method, and each of the light emitting layer and at least one layer adjacent to the light emitting layer is formed by a spray method. .
  • the hole transport layer and the electron transport layer are more preferably formed by a spray method, and the light emitting layer, the hole transport layer and the electron transport layer are more preferably formed by a spray method.
  • at least one of a hole transport layer, the light emitting layer, and the electron transport layer is formed by applying the liquid by a spray method, and each of the hole transport layer, the light emitting layer, and the electron transport layer is formed by: More preferably, the liquid is formed by coating by a spray method.
  • the organic layer included in the organic electroluminescent element of the present invention can be formed by any of the methods described below. Thereby, in forming the organic layer by spray coating, impurities (hydrocarbon, amine, particles) in the carrier gas (inert gas) and impurities such as particles / oil in the pipe can be removed.
  • an organic layer by depositing an aerosol obtained by mixing a carrier gas composed of an inert gas and a coating solution having an oxygen concentration of 100 ppm or less and a moisture content of 100 ppm or less on a substrate.
  • the inert gas is filtered.
  • a known gas such as argon, nitrogen, or helium can be used, and argon or nitrogen is preferably used.
  • the number of particles larger than 0.2 ⁇ m is less than one per 100 ⁇ m ⁇ 100 ⁇ m in the organic layer formed by depositing the aerosol on the substrate.
  • the organic layer formed by the above method is preferably dried or annealed in an inert gas atmosphere having an oxygen concentration of 100 ppm or less and a dew point of ⁇ 30 ° C. or less. Furthermore, it is preferable to deposit an organic layer by depositing it on an insoluble organic layer with respect to the coating solution.
  • the substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic compound layer.
  • Specific examples include zirconia stabilized yttrium (YSZ), inorganic materials such as glass, polyesters such as polyethylene terephthalate, polybutylene phthalate, polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, polycycloolefin. , Norbornene resins, and organic materials such as poly (chlorotrifluoroethylene).
  • YSZ zirconia stabilized yttrium
  • inorganic materials such as glass
  • polyesters such as polyethylene terephthalate, polybutylene phthalate, polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, polycycloolefin.
  • Norbornene resins and organic materials such as poly (ch
  • soda-lime glass it is preferable to use what gave barrier coatings, such as a silica.
  • barrier coatings such as a silica.
  • an organic material it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.
  • the shape, structure, size and the like of the substrate are not particularly limited and can be appropriately selected according to the use, purpose, etc. of the light emitting element.
  • the shape of the substrate is preferably a plate shape.
  • the structure of the substrate may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members.
  • the substrate may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the organic light emitting layer.
  • the substrate can be provided with a moisture permeation preventing layer (gas barrier layer) on the front surface or the back surface.
  • a moisture permeation preventive layer gas barrier layer
  • inorganic materials such as silicon nitride and silicon oxide are preferably used.
  • the moisture permeation preventing layer (gas barrier layer) can be formed by, for example, a high frequency sputtering method.
  • a thermoplastic substrate is used, a hard coat layer, an undercoat layer, or the like may be further provided as necessary.
  • the anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials.
  • the anode is usually provided as a transparent anode.
  • Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof.
  • Specific examples of the anode material include conductive metals such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.
  • Metals such as oxides, gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene, polypyrrole, etc.
  • conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.
  • the anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.
  • the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light emitting device, but it is preferably formed on the substrate.
  • the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof.
  • the patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method.
  • the thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 ⁇ m, and preferably 50 nm to 20 ⁇ m.
  • the resistance value of the anode is preferably 10 3 ⁇ / ⁇ or less, and more preferably 10 2 ⁇ / ⁇ or less.
  • the anode When the anode is transparent, it may be colorless and transparent or colored and transparent.
  • the transmittance In order to take out light emission from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more.
  • transparent anode is described in detail in Yutaka Sawada's “New Development of Transparent Electrode Film” published by CMC (1999), and the matters described here can be applied to the present invention.
  • a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.
  • the cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials.
  • Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium. -Rare earth metals such as silver alloys, indium and ytterbium. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.
  • alkali metals eg, Li, Na, K, Cs, etc.
  • alkaline earth metals eg, Mg, Ca, etc.
  • gold silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium.
  • -Rare earth metals such as silver alloys, indium and ytterbium. These may be used alone,
  • the material constituting the cathode is preferably an alkali metal or an alkaline earth metal from the viewpoint of electron injection, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
  • the material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01% by mass to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy). Etc.).
  • the method for forming the cathode is not particularly limited, and can be performed according to a known method.
  • the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like.
  • Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.
  • the cathode formation position is not particularly limited, and may be formed on the entire organic compound layer or a part thereof.
  • a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic compound layer in a thickness of 0.1 nm to 5 nm.
  • This dielectric layer can also be regarded as a kind of electron injection layer.
  • the dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.
  • the thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 ⁇ m, and preferably 50 nm to 1 ⁇ m. Further, the cathode may be transparent or opaque.
  • the transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 nm to 10 nm and further laminating a transparent conductive material such as ITO or IZO.
  • the organic layer in the present invention will be described.
  • the organic layer of the organic EL device of the present invention includes a hole transport layer, a light emitting layer, and an electron transport layer.
  • a hole transport layer As layers other than the above-mentioned layers (hole transport layer, light emitting layer and electron transport layer) constituting the organic layer, as described above, each layer such as a block layer, a hole injection layer, and an electron injection layer Is mentioned.
  • the light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines holes and electrons. It is a layer which has the function to provide and to emit light.
  • the light emitting layer in the present invention is a thin film containing an amorphous organic semiconductor.
  • the light emitting layer may be composed of only a light emitting material, but preferably has a mixed layer of a host material and a light emitting material (also referred to as a light emitting dopant).
  • the light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, but is preferably a phosphorescent light emitting material.
  • the host material is preferably a charge transport material.
  • the host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed.
  • the light emitting layer may include a material that does not have charge transporting properties and does not emit light.
  • the light emitting layer can contain two or more kinds of light emitting materials in order to improve color purity or to broaden the light emission wavelength region. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.
  • the phosphorescent material include complexes containing a transition metal atom or a lanthanoid atom.
  • the transition metal atom is not particularly limited, but preferably includes ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, gold, silver, copper, and platinum, and more preferably rhenium, iridium. And platinum, more preferably iridium and platinum.
  • lanthanoid atoms examples include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, and lutesium.
  • neodymium, europium, and gadolinium are preferable.
  • the specific ligand is preferably a halogen ligand (preferably a chlorine ligand) or an aromatic carbocyclic ligand (for example, preferably 5 to 30 carbon atoms, more preferably 6 to 6 carbon atoms).
  • a nitrogen-containing heterocyclic ligand for example, preferably Has 5 to 30 carbon atoms, more preferably 6 to 30 carbon atoms, still more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and phenylpyridine, benzoquinoline, quinolinol, bipyridyl, or phenanthroline.
  • diketone ligand for example, acetylacetone
  • carboxylic acid ligand for example, preferably 2 to 30 carbon atoms, more preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, such as an acetic acid ligand
  • an alcoholate ligand for example, preferably 1-30 carbon atoms, more preferably 1-20 carbon atoms, still more preferable.
  • trimethylsilyloxy ligand dimethyl-tert-butylsilyloxy ligand, triphenylsilyloxy ligand, etc.
  • carbon monoxide ligand isonitrile ligand
  • cyano ligand phosphorus coordination
  • 3 to 40 carbon atoms more preferably 3 to 30 carbon atoms, still more preferably 3 to 20 carbon atoms, and particularly preferably 6 to 20 carbon atoms.
  • Fin ligands, etc. thiolato ligands (preferably 1-30 carbon atoms, more preferably 1-20 carbon atoms, still more preferably 6-20 carbon atoms, such as phenylthiolato ligand), phosphor A fin oxide ligand (preferably having 3 to 30 carbon atoms, more preferably 8 to 30 carbon atoms, still more preferably 18 to 30 carbon atoms, such as a triphenylphosphine oxide ligand), and more preferably , A nitrogen-containing heterocyclic ligand.
  • the complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.
  • the light-emitting material include, for example, US6303238B1, US6097147, WO00 / 57676, WO00 / 70655, WO01 / 08230, WO01 / 39234A2, WO01 / 41512A1, WO02 / 02714A2, WO02 / 15645A1, and WO02 / 44189A1.
  • more preferable luminescent materials include Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb complex. , Gd complex, Dy complex, and Ce complex.
  • an Ir complex, a Pt complex, or a Re complex among which an Ir complex or a Pt complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond. Or Re complexes are preferred.
  • an Ir complex, a Pt complex, or a Re complex containing a tridentate or higher polydentate ligand is particularly preferable.
  • fluorescent light emitting material generally, benzoxazole, benzimidazole, benzothiazole, styrylbenzene, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin, pyran, perinone, oxadiazole, aldazine, pyralidine, cyclopentadiene, bis Of styrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compounds, condensed polycyclic aromatic compounds (such as anthracene, phenanthroline, pyrene, perylene, rubrene, or pentacene), 8-quinolinol Examples thereof include various metal complexes represented by metal complexes, pyromethene complexes and rare earth complexes, organosilanes, organosilanes, organos
  • specific examples of the light emitting material include specific compounds exemplified in paragraphs [0054] to [0064] of JP2009-16579A, and paragraphs [0059] to [0068] of JP2008-218972A.
  • Specific examples of the compound and the light-emitting material 1 used in Examples described later can be given, but are not limited to these because they are appropriately selected.
  • the light emitting material in the light emitting layer is generally contained in the light emitting layer in an amount of 0.1% by mass to 50% by mass with respect to the total mass of the compound forming the light emitting layer. From the viewpoint of durability and external quantum efficiency.
  • the content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass.
  • the thickness of the light emitting layer is not particularly limited, but is usually preferably 2 nm to 500 nm, and more preferably 3 nm to 200 nm, and more preferably 5 nm to 100 nm from the viewpoint of external quantum efficiency. More preferably.
  • a hole-transporting host material excellent in hole-transporting property (sometimes referred to as a hole-transporting host) and an electron-transporting host material excellent in electron-transporting property (electron-transporting property) May be described as a host).
  • ⁇ Hole-transporting host examples include the following materials. Pyrrole, indole, carbazole, azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone , Stilbene, silazane, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, organic silanes, carbon films, and derivatives thereof. Preferred are indole derivatives, carbazole derivatives, aromatic tertiary amine compounds, and thiophene derivatives, and more preferred are those having a carbazole group in the molecule.
  • the electron transporting host in the light emitting layer used in the present invention preferably has an electron affinity Ea of 2.5 eV or more and 3.5 eV or less from the viewpoint of improving durability and lowering driving voltage. More preferably, it is 0.4 eV or less, and further preferably 2.8 eV or more and 3.3 eV or less. Further, from the viewpoint of improving durability and reducing driving voltage, the ionization potential Ip is preferably 5.7 eV or more and 7.5 eV or less, more preferably 5.8 eV or more and 7.0 eV or less, and 5.9 eV or more. More preferably, it is 6.5 eV or less.
  • Such an electron transporting host include the following materials. Pyridine, pyrimidine, triazine, imidazole, pyrazole, triazole, oxazole, oxadiazol, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, Fluorine-substituted aromatic compounds, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanines, and derivatives thereof (which may form condensed rings with other rings), metal complexes and metals of 8-quinolinol derivatives Examples thereof include various metal complexes represented by metal complexes having phthalocyanine, benzoxazole or benzothiazol as a ligand.
  • the electron transporting host include metal complexes, azole derivatives (benzimidazole derivatives, imidazopyridine derivatives, etc.), and azine derivatives (pyridine derivatives, pyrimidine derivatives, triazine derivatives, etc.).
  • metal complex compounds are preferred.
  • the metal complex compound (A) is more preferably a metal complex having a ligand having at least one nitrogen atom, oxygen atom or sulfur atom coordinated to the metal.
  • the metal ion in the metal complex is not particularly limited, but is preferably beryllium ion, magnesium ion, aluminum ion, gallium ion, zinc ion, indium ion, tin ion, platinum ion, or palladium ion, more preferably beryllium ion, Aluminum ion, gallium ion, zinc ion, platinum ion, or palladium ion, and more preferably aluminum ion, zinc ion, or palladium ion.
  • ligands contained in the metal complex There are various known ligands contained in the metal complex. For example, “Photochemistry ⁇ ⁇ ⁇ and Photophysics ofCoordination Compounds”, Springer-Verlag, H.C. Examples include ligands described in Yersin, published in 1987, “Organometallic Chemistry: Fundamentals and Applications”, Hankabo, Yamamoto Akio, published in 1982, and the like.
  • the ligand is preferably a nitrogen-containing heterocyclic ligand (preferably having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 3 to 15 carbon atoms).
  • it may be a bidentate or higher ligand, preferably a bidentate or higher and a hexadentate or lower ligand, or a bidentate or higher and lower 6 or lower ligand and a monodentate mixed ligand. preferable.
  • the ligand examples include an azine ligand (for example, pyridine ligand, bipyridyl ligand, terpyridine ligand, etc.), a hydroxyphenylazole ligand (for example, hydroxyphenylbenzimidazole coordination). And a hydroxyphenylbenzoxazole ligand, a hydroxyphenylimidazole ligand, a hydroxyphenylimidazopyridine ligand, etc.), an alkoxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 carbon atom).
  • azine ligand for example, pyridine ligand, bipyridyl ligand, terpyridine ligand, etc.
  • a hydroxyphenylazole ligand for example, hydroxyphenylbenzimidazole coordination
  • alkoxy ligand preferably having 1 to 30 carbon atoms, more preferably 1 carbon atom.
  • aryloxy ligands preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example phenyl Carboxymethyl, 1-naphthyloxy, 2-naphthyloxy, 2,4,6-trimethylphenyl oxy, and 4-biphenyloxy and the like.
  • Heteroaryloxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, and quinolyloxy.
  • An alkylthio ligand preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio
  • arylthio ligands Preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, and particularly preferably having 6 to 12 carbon atoms, such as phenylthio
  • heteroarylthio ligand preferably having 1 carbon atom
  • siloxy ligands preferably having 1 to 30 carbon atoms, more preferably 3 to 25 carbon atoms. Particularly preferably 6 to 20 carbon atoms, such as a triphenylsiloxy group, a triethoxysiloxy group, and a triisopropylsiloxy group), an aromatic hydrocarbon anion ligand (preferably having 6 carbon atoms).
  • an aromatic heterocyclic anion ligand preferably Has 1 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, and particularly preferably 2 to 20 carbon atoms.
  • An indolenine anion ligand and the like.
  • it is a nitrogen-containing heterocyclic ligand, aryloxy ligand, heteroaryloxy group, or siloxy ligand, more preferably a nitrogen-containing heterocyclic ligand, aryloxy ligand, siloxy ligand , An aromatic hydrocarbon anion ligand, or an aromatic heterocyclic anion ligand.
  • Examples of the metal complex electron transporting host are described in, for example, Japanese Patent Application Laid-Open No. 2002-235076, Japanese Patent Application Laid-Open No. 2004-214179, Japanese Patent Application Laid-Open No. 2004-221106, Japanese Patent Application Laid-Open No. 2004-221068, Japanese Patent Application Laid-Open No. 2004-221683, and Japanese Patent Application Laid-Open No. 2004-327313 The compound of this is mentioned.
  • the content of the host material in the present invention is not particularly limited, but from the viewpoint of light emission efficiency and driving voltage, it is 15% by mass or more and 95% by mass or less based on the total compound mass forming the light emitting layer. Preferably there is.
  • the host material used in the present invention preferably has a glass transition point of 50 ° C. or higher and 150 ° C. or lower. More preferably, the glass transition point is 60 ° C. or higher and 150 ° C. or lower. If the glass transition point of the host material is less than 50 ° C., it is not preferable in terms of the heat resistance of the device, and if it exceeds 150 ° C., it is not preferable in that heat treatment after film formation becomes difficult.
  • specific examples of the host material in the present invention include the specific compounds exemplified in paragraphs [0079] to [0083] of JP-A-2009-16579, and the host material 1 used in the examples described later. However, it is not limited to these.
  • the hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side.
  • at least one layer adjacent to the light emitting layer is preferably a hole transport layer, and two or more kinds of low molecular weight compounds having a molecular weight of 1500 or less are two or more kinds of hole transport materials. preferable.
  • the difference in ionization potential between the two or more hole transport materials is preferably 0.1 eV or more and 0.6 eV or less, and more preferably 0.2 eV or more and 0.5 eV or less.
  • a material such as PEDOT / PSS, an arylamine polymer, or a starburst amine type is generally used as the hole injection layer, but these have a low ionization potential. For this reason, the hole injection barrier from the anode such as ITO is small, but the hole injection barrier to the light emitting layer is large, which causes an increase in driving voltage and deterioration in durability.
  • the two or more hole transport materials preferably contain an arylamine derivative or a carbazole derivative, and preferably contain an arylamine derivative and a carbazole derivative. This is because these materials have a
  • the electron-accepting dopant can be contained in the hole injection layer or the hole transport layer of the organic EL device of the present invention.
  • an inorganic compound or an organic compound can be used as long as it has an electron-accepting property and oxidizes an organic compound.
  • examples of the inorganic compound include metal halides such as ferric chloride, aluminum chloride, gallium chloride, indium chloride, and antimony pentachloride, and metal oxides such as vanadium pentoxide and molybdenum trioxide.
  • a compound having a nitro group, halogen, cyano group, trifluoromethyl group or the like as a substituent a quinone compound, an acid anhydride compound, fullerene, or the like can be preferably used.
  • JP2004-342614, JP2005-72012, JP20051666667 The compounds described in JP-A-2005-209643 and the like can be preferably used.
  • electron accepting dopants may be used alone or in combination of two or more.
  • the amount of the electron-accepting dopant used varies depending on the type of material, but is preferably 0.01% by mass to 50% by mass with respect to the hole transport layer material, and is 0.05% by mass to 20% by mass. It is more preferable that the content be 0.1% by mass to 10% by mass.
  • the thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
  • the thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
  • the thickness of the hole injection layer is preferably from 0.1 nm to 200 nm, more preferably from 0.5 nm to 100 nm, and even more preferably from 1 nm to 100 nm.
  • the hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .
  • the electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side.
  • at least one layer adjacent to the light emitting layer is an electron transport layer.
  • the electron carrying layer was formed with the liquid containing 2 or more types of electron carrying materials. By mixing two or more compounds, it is possible to provide a coating type electron injection layer excellent in electron injection from the cathode and electron injection into the light emitting layer.
  • the difference in electron affinity between two or more electron transport materials is preferably 0.1 eV or more and 0.6 eV or less, and more preferably 0.2 eV or more and 0.5 eV or less.
  • the electron injection layer or the electron transport layer of the organic EL device of the present invention can contain an electron donating dopant.
  • the electron donating dopant introduced into the electron injecting layer or the electron transporting layer only needs to have an electron donating property and a property of reducing an organic compound, such as an alkali metal such as Li or an alkaline earth metal such as Mg. Transition metals including rare earth metals and reducing organic compounds are preferably used.
  • a metal having a work function of 4.2 eV or less can be preferably used. Specifically, Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, Cs, La, Sm, Gd , And Yb.
  • Examples of the reducing organic compound include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds.
  • materials described in JP-A-6-212153, JP-A-2000-196140, JP-A-2003-68468, JP-A-2003-229278, JP-A-2004-342614, and the like can be used.
  • electron donating dopants may be used alone or in combination of two or more.
  • the amount of the electron-donating dopant used varies depending on the type of material, but is preferably 0.1% by mass to 99% by mass, and 1.0% by mass to 80% by mass with respect to the electron transport layer material. Is more preferable, and 2.0 mass% to 70 mass% is particularly preferable.
  • the thicknesses of the electron injection layer and the electron transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
  • the thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
  • the thickness of the electron injection layer is preferably from 0.1 nm to 200 nm, more preferably from 0.2 nm to 100 nm, and even more preferably from 0.5 nm to 50 nm.
  • the electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
  • the hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side.
  • a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side.
  • the compound constituting the hole blocking layer include aluminum complexes such as bis (2-methyl-8-quinolinolato) (phenolate) aluminum, triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10 -Phenanthroline derivatives such as phenanthroline, etc.
  • the thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
  • the hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
  • the electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side.
  • an electron blocking layer can be provided as the organic compound layer adjacent to the light emitting layer on the anode side.
  • the thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
  • the hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
  • the material constituting the organic layer of the organic electroluminescent element it is preferable to use a purified material, and it is more preferable that at least one material is a material purified by a zone melt method.
  • the zone melt method is difficult to purify by sublimation, easily decomposes, easily purifies a material having a high sublimation temperature, or a relatively high molecular weight.
  • a material suitable for the wet film forming method has high amorphousness and is difficult to be purified by sublimation. When purification is performed by sublimation, device performance may be lowered.
  • a device with high performance can be realized by combining purification by the zone melt method and wet film formation.
  • at least one or more materials are materials purified by a zone melt method, and an organic electroluminescent element produced by a wet film forming method (preferably a spray coating method) is more preferable.
  • a material that can be efficiently subjected to zone melt purification can be formed cleanly (smoothly) without any disturbance at the interface of the formed layer. This is because zone melt purification has a lower purification temperature than sublimation purification. The coating process temperature is usually closer to that of zone melt purification.
  • a material that can efficiently perform zone melt purification can form a film with less disorder in the coating process. When there is little disorder of the arrangement of the film, it is expected to improve the light emission efficiency and durability of the produced organic electroluminescence device.
  • the Tg of the material is preferably in the range of 100 ° C to 400 ° C.
  • the material is preferably a charge injection material, a charge transport material, a host material, or a light emitting material, and more preferably a carbazole derivative, an arylamine derivative, or a metal complex.
  • the entire organic EL element may be protected by a protective layer.
  • a material contained in the protective layer any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device.
  • Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO 2 , Al 2 O 3 , GeO, NiO, CaO, BaO, and Fe 2 O.
  • metal oxides such as Y 2 O 3 , TiO 2 , metal nitrides such as SiN x , SiN x O y , metal fluorides such as MgF 2 , LiF, AlF 3 , CaF 2 , polyethylene, polypropylene, polymethyl Monomer mixture containing methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer Copolymer obtained by copolymerization, cyclic in the copolymer main chain
  • fluorine-containing copolymer having a structure, a water-absorbing substance having a water absorption of 1% or more, and a moisture-proof substance having a water absorption of 0.1% or less.
  • the method for forming the protective layer is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.
  • the organic EL device of the present invention may be sealed using a sealing container. Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the light emitting element.
  • a moisture absorber For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, and magnesium oxide.
  • the inert liquid is not particularly limited, and examples thereof include paraffins, liquid paraffins, fluorinated solvents such as perfluoroalkane, perfluoroamine, and perfluoroether, chlorinated solvents, and silicone oils. Can be mentioned.
  • the sealing adhesive used in the present invention has a function of preventing intrusion of moisture and oxygen from the end portion.
  • the same material as that used for the resin sealing layer can be used.
  • epoxy adhesives are preferable from the viewpoint of moisture prevention, and among them, a photocurable adhesive or a thermosetting adhesive is preferable.
  • the filler added to the sealant is preferably an inorganic material such as SiO 2 , SiO (silicon oxide), SiON (silicon oxynitride) or SiN (silicon nitride).
  • SiO 2 silicon oxide
  • SiON silicon oxynitride
  • SiN silicon nitride
  • XNR5516 manufactured by Nagase Chemtech Co., Ltd. can be cited as a photo-curable epoxy adhesive.
  • the coating thickness of the sealing adhesive is preferably 1 ⁇ m or more and 1 mm or less. If it is thinner than this, the sealing adhesive cannot be applied uniformly, which is not preferable. On the other hand, if it is thicker than this, the route through which moisture invades becomes wide, which is not preferable.
  • the organic EL device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. be able to.
  • a direct current which may include an alternating current component as necessary
  • a direct current between the anode and the cathode usually 2 to 15 volts
  • a direct current between the anode and the cathode usually 2 to 15 volts
  • a direct current between the anode and the cathode usually 2 to 15 volts
  • the light emitting element of the present invention can improve the light extraction efficiency by various known devices. For example, by processing the substrate surface shape (for example, forming a fine concavo-convex pattern), controlling the refractive index of the substrate / ITO layer / organic layer, controlling the film thickness of the substrate / ITO layer / organic layer, etc. It is possible to improve light extraction efficiency and external quantum efficiency.
  • the light-emitting element of the present invention may be a so-called top emission method in which light emission is extracted from the anode side.
  • the organic EL element in the present invention may have a resonator structure.
  • a multilayer film mirror made of a plurality of laminated films having different refractive indexes, a transparent or translucent electrode, a light emitting layer, and a metal electrode are superimposed on a transparent substrate.
  • the light generated in the light emitting layer resonates repeatedly with the multilayer mirror and the metal electrode as a reflection plate.
  • a transparent or translucent electrode and a metal electrode each function as a reflecting plate on a transparent substrate, and light generated in the light emitting layer repeats reflection and resonates between them.
  • the optical path length determined from the effective refractive index of the two reflectors and the refractive index and thickness of each layer between the reflectors is adjusted to an optimum value to obtain the desired resonant wavelength. Is done.
  • the calculation formula in the case of the first embodiment is described in JP-A-9-180883.
  • the calculation formula in the case of the second embodiment is described in Japanese Patent Application Laid-Open No. 2004-127795.
  • a method for making an organic EL display of a full color type includes three primary colors (blue (B) and green). (G), red light (R)), a three-color light emitting method in which organic EL elements that emit light corresponding to red (R) are arranged on a substrate, and white light emitted by a white light emitting organic EL element into three primary colors through a color filter. And a color conversion method in which blue light emission by an organic EL element for blue light emission is converted into red (R) and green (G) through a fluorescent dye layer are known.
  • the planar light source of a desired luminescent color can be obtained by using combining the organic EL element of the different luminescent color obtained by the said method.
  • a white light-emitting light source that combines blue and yellow light-emitting elements a white light-emitting light source that combines blue, green, and red light-emitting elements.
  • the organic EL device and manufacturing method of the present invention are used in a wide range of fields including digital still camera displays, mobile phone displays, personal digital assistants (PDAs), computer displays, automobile information displays, TV monitors, or general lighting. Applied.
  • FIG. 2 is a cross-sectional view schematically showing an example of the display device according to the embodiment of the present invention.
  • the display device 20 according to the embodiment of the present invention includes a transparent substrate (support substrate) 2, an organic EL element 10, a sealing container 16, and the like.
  • the organic EL element 10 is configured by sequentially laminating an anode (first electrode) 3, an organic layer 11, and a cathode (second electrode) 9 on a substrate 2.
  • a protective layer 12 is laminated on the cathode 9, and a sealing container 16 is provided on the protective layer 12 with an adhesive layer 14 interposed therebetween.
  • the adhesive layer 14 is preferably a layer made of the sealing adhesive described above.
  • FIG. 3 is a cross-sectional view schematically showing an example of a lighting device according to an embodiment of the present invention.
  • the illumination device 40 according to the embodiment of the present invention includes the organic EL element 10 and the light scattering member 30 described above. More specifically, the lighting device 40 is configured such that the substrate 2 of the organic EL element 10 and the light scattering member 30 are in contact with each other.
  • the light scattering member 30 is not particularly limited as long as it can scatter light.
  • the light scattering member 30 is a member in which fine particles 32 are dispersed on a transparent substrate 31.
  • a glass substrate can be preferably cited.
  • the fine particles 32 transparent resin fine particles can be preferably exemplified.
  • the glass substrate and the transparent resin fine particles known ones can be used. In such an illuminating device 40, when light emitted from the organic EL element 10 is incident on the light incident surface 30A of the light scattering member 30, the incident light is scattered by the light scattering member 30, and the scattered light is emitted from the light emitting surface 30B. It is emitted as illumination light.
  • a deoxygenation treatment by nitrogen bubbling was performed in a nitrogen-substituted glove box (dew point -68 degrees, oxygen concentration 10 ppm), and a filter (pore size 0.2 ⁇ m, PTFE membrane filter) treatment was performed to prepare a coating solution.
  • a spray coating machine installed in a glove box (dew point ⁇ 45 ° C., oxygen concentration 50 ppm) is supplied with nitrogen (purity 99.9%, dew point ⁇ 40 ° C. or less) as a supply source, and gas filter: SFB100-02 (SMC shares) Connected via company product name).
  • Example 1 A glass substrate (manufactured by Geomat Co., Ltd., surface resistance 10 ⁇ / ⁇ , size: 0.5 mm thickness, 2.5 cm square) having a vapor deposition layer of indium tin oxide (abbreviated as ITO) is placed in a cleaning container, and in 2-propanol After ultrasonic cleaning with, UV-ozone treatment was performed for 30 minutes.
  • the following layers were sequentially provided on the transparent anode by a spray method.
  • the aerosol carrier gas was nitrogen gas, and the amount of carrier gas was 1 L / min. Further, the particle diameter of the liquid particles in the aerosol was set to 1 ⁇ m.
  • Light-emitting layer (40 nm): A xylene solution (solid content concentration: 0.6% by mass) containing the host material 1: CDBP and the light-emitting material 1: compound A at a mass ratio of 95: 5 is obtained by a spray method. After coating on the hole transport layer in such an amount that the resulting light emitting layer had a thickness of 40 nm, vacuum drying was performed at 100 ° C. for 1 hour. In addition, as the host material 1 and the light emitting material 1, those purified by sublimation purification were used.
  • Electron transport layer (30 nm) The substrate was attached to a vacuum deposition apparatus without being exposed to the atmosphere. Further, a molybdenum resistance heating boat containing BAlq was attached to a vacuum deposition apparatus, and the vacuum chamber was depressurized to 4 ⁇ 10 ⁇ 4 Pa. Thereafter, the boat was energized and heated to deposit BAlq on the light emitting layer at a deposition rate of 0.2 nm / second to form an electron transport layer having a thickness of 30 nm.
  • Electron injection layer (1 nm) LiF was deposited on the electron transport layer in an amount such that the thickness of the resulting electron injection layer was 1 nm by vacuum evaporation.
  • the prepared laminate was put in a glove box substituted with argon gas and sealed with a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516 manufactured by Nagase Chemtech Co., Ltd.). 1 organic EL element was produced.
  • Example 2 and 3 and Comparative Examples 1 and 2 In Example 1, the same procedure as in Example 1 was performed except that the mass ratio of the hole transport material 1 and the hole transport material 2 in the hole transport layer was changed to the ratio shown in Table 1. Organic EL elements of 2, 3 and Comparative Examples 1 and 2 were formed.
  • Example 3 the organic EL element of the comparative example 3 was formed by performing the same procedure as Example 1 except having replaced the hole transport layer with the following hole transport layers.
  • Hole transport layer (50 nm) The substrate was attached to a vacuum deposition apparatus without being exposed to the atmosphere. Moreover, the hole transport material 1 and the hole transport material 2 were installed in the molybdenum resistance heating boat, respectively. After depressurizing the vacuum chamber to 4 ⁇ 10 ⁇ 5 Pa, the boat is energized and heated to adjust the deposition rate so that the mass ratio of the hole transport material 1 and the hole transport material 2 is 50:50.
  • the hole transport layer having a film thickness of 50 nm was formed by vapor deposition on the substrate.
  • Example 4 the organic EL element of the comparative example 4 was formed by performing the same procedure as Example 1 except having replaced the positive hole transport layer with the following positive hole transport layers.
  • the hole transport material 1 and the hole transport material 2 those purified by sublimation purification were used.
  • ⁇ Luminous efficiency> A DC voltage was applied to the light-emitting element of the organic EL element produced using a source measure unit type 2400 manufactured by KEITHLEY, and light was emitted at a luminance of 1000 cd / m 2 .
  • the emission spectrum and the amount of light were measured using a luminance meter SR-3 manufactured by Topcon Corporation, and the external quantum efficiency was calculated from the emission spectrum, the amount of light and the current at the time of measurement.
  • ⁇ Drive voltage> A DC voltage was applied to the light emitting element using the source measure unit 2400 made by KEITHLEY for the produced organic EL element, and the voltage reaching the light emission luminance of 1000 cd / m 2 was evaluated as the driving voltage.
  • Example 4 the hole transporting material was changed to the hole transporting material 3 and the hole transporting material 4 listed in Table 2, and the same procedure as in Example 1 was performed except that the ratio in Table 2 was changed.
  • Organic EL elements of Examples 4 to 6 and Comparative Example were formed. Difference in ionization potential between the hole transport material 3 and the hole transport material 4: ⁇ Ip was 0.3 eV. In addition, about brightness half time.
  • the value of Comparative Example 5 was set as 1.0, and each was described as a relative value.
  • Comparative Example 7 In Comparative Example 3, the same procedure as in Comparative Example 3 was performed except that the hole transporting material was changed to the hole transporting material 3 and the hole transporting material 4 shown in Table 2, so that the organic EL element of Comparative Example 7 was used. Formed.
  • Comparative Example 8 In Comparative Example 4, the same procedure as in Comparative Example 4 was performed except that the hole transporting material was changed to the hole transporting material 3 and the hole transporting material 4 shown in Table 2, so that the organic EL device of Comparative Example 8 was used. Formed.
  • Example 7 In Example 1, the same procedure as in Example 1 was performed except that the hole transport material 1 and the hole transport material 2 were replaced with the following hole transport material 1 and hole transport material 5, whereby An organic EL element was formed. Difference in ionization potential between hole transport material 1 and hole transport material 5: ⁇ Ip was 0.2 eV.
  • Example 8 In Example 1, the same procedure as in Example 1 was performed except that the hole transport material 1 and the hole transport material 2 were replaced with the following hole transport material 1 and hole transport material 6, whereby Example 8 An organic EL element was formed. Difference in ionization potential between the hole transport material 1 and the hole transport material 6: ⁇ Ip was 0.1 eV.
  • Example 9 In Example 1, the same procedure as in Example 1 was performed except that the hole transport material 1 and the hole transport material 2 were replaced with the following hole transport material 1 and hole transport material 7, whereby Example 9 An organic EL element was formed. Difference in ionization potential between hole transport material 1 and hole transport material 7: ⁇ Ip was 0.6 eV. Note that the luminance half-life times of (Examples 7 to 9) were described as relative values, with the value of Comparative Example 1 being 1.0.
  • Example 9 In Example 1, the hole transport material 1 and the hole transport material 2 of the hole transport layer were changed to the following hole transport material 1 and hole transport material 8 (PTPDES 2: manufactured by Chemipro Kasei Co., Ltd., mass average molecular weight: 15,000).
  • the organic EL element of Comparative Example 9 was formed by performing the same procedure as in Example 1 except that the change was made. Difference in ionization potential between hole transport material 1 and hole transport material 8: ⁇ Ip was 0.1 eV.
  • the value of the comparative example 1 was set to 1.0, and was described by the relative value, respectively.
  • Example 10 In Example 1, the hole transport material 1 and the hole transport material 2 of the hole transport layer were changed to the following hole transport material 2 and hole transport material 8 (PTPDES 2: manufactured by Chemipro Kasei Co., Ltd., mass average molecular weight: 15,000).
  • the organic EL element of the comparative example 10 was formed by performing the same procedure as Example 1 except having changed. Difference in ionization potential between the hole transport material 2 and the hole transport material 8: ⁇ Ip was 0.5 eV.
  • the value of the comparative example 1 was set to 1.0, and was described by the relative value, respectively.
  • Example 10 In Example 1, the hole transport layer, the light emitting layer, and the electron transport layer were replaced with the following hole transport layer, light emitting layer, and electron transport layer, and the same procedure as in Example 1 was performed.
  • the organic EL device of Example 10 was formed. Difference in electron affinity between the electron transport material 1 and the electron transport material 2: ⁇ Ea was 0.4 eV.
  • Hole transport layer 50 nm: An aqueous solution of a PEDOT-PSS solution ((polyethylenedioxythiophene-polystyrene sulfonic acid dope) / (AI4083 manufactured by Bayer, mass average molecular weight: 100,000)) by a spray method. (Solid content concentration: 1% by mass) was applied onto the transparent anode in such an amount that the resulting hole transport layer had a thickness of 50 nm, and then vacuum dried at 150 ° C. for 5 hours.
  • PEDOT-PSS solution polyethylenedioxythiophene-polystyrene sulfonic acid dope
  • AI4083 manufactured by Bayer, mass average molecular weight: 100,000
  • Light-emitting layer (40 nm): A xylene solution (solid content concentration: 1% by mass) containing the following host 2 and light-emitting material 2 at a mass ratio of 95: 5 is obtained by a spray method. After coating on the hole transport layer in such an amount, vacuum drying was performed at 100 ° C. for 1 hour. In addition, as the host 2 and the light emitting material 2, those purified by sublimation purification were used.
  • Example 10 the same procedure as in Example 10 was performed except that the mass ratio of the electron transport material 1 and the electron transport material 2 in the electron transport layer was changed to the ratio shown in Table 6, so that Examples 11 and 12 were performed. And the organic EL elements of Comparative Examples 11 to 12 were formed.
  • Example 10 the organic EL element of the comparative example 13 was formed by performing the same procedure as Example 10 except having replaced the electron carrying layer with the following electron carrying layers.
  • Example 14 the organic EL element of the comparative example 14 was formed by performing the same procedure as Example 10 except having replaced the electron carrying layer with the following electron carrying layers.
  • the electron transport material 1 and the electron transport material 2 used what was refine
  • Example 13 In Example 10, the same procedure as in Example 10 was performed, except that the electron transport material 1 and the electron transport material 2 of the electron transport layer were replaced with the electron transport material 2 and the electron transport material 3 of the following electron transport layer.
  • the organic EL device of Example 13 was formed. Difference in electron affinity between the electron transport material 2 and the electron transport material 3: ⁇ Ea was 0.2 eV.
  • Example 14 In Example 10, the same procedure as in Example 10 was performed except that the electron transport material 1 and the electron transport material 2 of the electron transport layer were replaced with the electron transport material 1 and the electron transport material 3 of the following electron transport layer.
  • the organic EL element of Example 14 was formed. Difference in electron affinity between the electron transport material 1 and the electron transport material 3: ⁇ Ea was 0.6 eV.
  • Example 15 In Example 10, the same procedure as in Example 10 was performed except that the electron transport material 1 and the electron transport material 2 of the electron transport layer were replaced with the electron transport material 3 and the electron transport material 4 of the following electron transport layer, The organic EL element of Example 15 was formed. Difference in electron affinity between the electron transport material 3 and the electron transport material 4: ⁇ Ea was 0.1 eV. In addition, about the luminance half time of (Examples 13 to 15). Relative comparison was performed using Comparative Example 11 as a reference.
  • Example 15 In Example 10, the same procedure as in Example 10 was performed except that the electron transport material 1 and the electron transport material 2 of the electron transport layer were replaced with only the electron transport material 3 of the electron transport layer. An organic EL element was formed.
  • Example 16 In Example 10, the same procedure as in Example 10 was performed except that the electron transport material 1 and the electron transport material 2 in the electron transport layer were replaced with only the electron transport material 4 in the electron transport layer. An organic EL element was formed. Regarding the luminance half-life of (Comparative Examples 15 to 16). Relative comparison was performed using Comparative Example 11 as a reference.
  • Example 16 Thermal stability test
  • the organic EL elements of Examples 1, 2, and 3 and the organic EL elements of Comparative Examples 1 and 2 were each heat-treated at 110 ° C. for 24 hours, and the light emission efficiency and driving voltage before and after that were evaluated. The results are shown in Table 9.
  • Example 201 Purification by zone melt method 10 g of the following compound 201-1 is put into a 10 mm diameter Pyrex (registered trademark) tube, and vacuum sealed at 10 Pa using an oil rotary pump.
  • a transparent support substrate was obtained by depositing ITO to a thickness of 150 nm on a 25 mm ⁇ 25 mm ⁇ 0.7 mm glass substrate. This transparent support substrate was etched and washed. On this ITO glass substrate, a coating solution in which 2 parts by mass of PTPDES-2 (manufactured by Chemipro Kasei) and 98 parts by mass of cyclohexanone were spin-coated and dried to form a hole injection layer (film) Thickness about 40 nm). On top of this, a film was formed by spray coating using the hole transport layer coating solution 201 to form a hole transport layer (film thickness of about 20 nm). Drying was performed under vacuum at 120 ° C.
  • the layer adjacent to the light emitting layer is formed by a spray method using a liquid containing two or more kinds of low molecular weight compounds having a molecular weight of 1500 or less.
  • An organic electroluminescent device having a low voltage and capable of reducing manufacturing costs can be provided.
  • the display apparatus and illuminating device which comprise the said organic electroluminescent element can be provided.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

L'invention porte sur un élément électroluminescent organique qui présente une excellente efficacité lumineuse et une excellente endurance, dont la tension d'attaque est faible et dont le coût de fabrication peut être réduit. L'invention porte également sur un procédé de fabrication de l'élément électroluminescent organique décrit, et sur un dispositif d'affichage et un dispositif d'éclairage munis dudit élément électroluminescent organique. L'élément électroluminescent organique décrit comprend, entre deux électrodes, une couche électroluminescente et au moins une couche de transport de trous adjacente à la couche électroluminescente. Ladite ou lesdites couches de transport de trous adjacentes à la couche électroluminescente sont formées par pulvérisation d'un liquide qui contient au moins deux composés à faible poids moléculaire différents ayant des poids moléculaires de 1 500 ou moins.
PCT/JP2010/064847 2009-09-01 2010-08-31 Élément électroluminescent organique, procédé de fabrication d'éléments électroluminescents organiques, dispositif d'affichage et dispositif d'éclairage WO2011027749A1 (fr)

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AU2017275531A1 (en) * 2016-05-31 2018-10-11 Philip Morris Products S.A. Fluid permeable heater assembly for aerosol-generating systems
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