WO2022163199A1 - Élément électroluminescent organique, son procédé de production, dispositif d'éclairage le comportant, dispositif d'affichage et modèle imprimé - Google Patents

Élément électroluminescent organique, son procédé de production, dispositif d'éclairage le comportant, dispositif d'affichage et modèle imprimé Download PDF

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WO2022163199A1
WO2022163199A1 PCT/JP2021/046667 JP2021046667W WO2022163199A1 WO 2022163199 A1 WO2022163199 A1 WO 2022163199A1 JP 2021046667 W JP2021046667 W JP 2021046667W WO 2022163199 A1 WO2022163199 A1 WO 2022163199A1
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light
organic
emitting layer
layer
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和博 及川
倫生 泉
秀雄 ▲高▼
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コニカミノルタ株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]

Definitions

  • the present invention relates to an organic electroluminescence element, a method for manufacturing the same, and a lighting device, a display device, and a printed product having the same. More specifically, it relates to an organic electroluminescence element or the like that has high luminous efficiency, has a long life, can suppress deterioration in performance during manufacturing in the atmosphere, and can be manufactured at low cost.
  • An organic electroluminescent device (or diode; also referred to as an "organic EL element”) has a structure in which a layer containing a light-emitting compound is sandwiched between a cathode and an anode. It is a device that utilizes the recombination of the holes injected from the cathode and the electrons injected from the cathode to generate excitons, and the emission of light (electromagnetic waves) when the excitons are deactivated.
  • organic electroluminescence elements As the attractiveness of organic electroluminescence elements as surface light sources increases, there is a need for organic EL elements with performance that satisfies all of higher efficiency, longer life, and lower cost.
  • the vapor deposition method has a problem of high manufacturing cost due to the low efficiency of manufacturing equipment and materials used to achieve a high degree of vacuum.
  • the vapor deposition method has a limit on the number of materials to be mixed, and it is necessary to layer the layers while separating the functions by changing the material for each layer.
  • Non-Patent Document 1 discloses an example of an organic EL display device in which a multi-color pixel is realized by injecting a polymer light-emitting material into an insulating bank by inkjet printing.
  • the above-mentioned manufacturing method of the display device represented by the organic EL display device requires pre-formation of the bank and advanced alignment technology. did not meet expectations.
  • Non-Patent Document 2 discloses an organic EL device in which dots of 200 ⁇ m are patterned by an inkjet printing method without prior formation of banks.
  • PMMA polymethyl methacrylate
  • a host compound and a light-emitting material are printed using inkjet printing on the image area of the receiving layer.
  • the conductive luminescent material is injected and mixed with the insulating non-image area formed only by the receiving layer.
  • a phosphorescent compound such as Ir(ppy) 3 , which can be expected to have an external quantum efficiency of about 20%, is usually used, but the external quantum efficiency of the light-emitting part remains at about 3.1%. Further improvements were needed.
  • the present invention has been made in view of the above problems and circumstances, and the problem to be solved is that the luminous efficiency is high, the life is long, and the deterioration of performance during manufacturing in the atmosphere can be suppressed, and the cost is low. It is an object of the present invention to provide an organic electroluminescence element that can be manufactured by the method, a method for manufacturing the same, and an illumination device, a display device, and a printed product having the same.
  • the present inventors have investigated the causes of the above problems and found that the charge-transporting host compound, the luminescent dopant, the polymer, etc. contained in the light-emitting layer can improve the hole mobility and the electron mobility.
  • the inventors have found that the above object can be achieved by controlling the difference between the common logarithms, and have completed the present invention. That is, the above problems related to the present invention are solved by the following means.
  • An organic electroluminescence element having an image display portion sandwiched between an anode and a cathode facing each other on at least a substrate, wherein the image display section is composed of a luminescent image display section and a non-luminescent image display section,
  • the light-emitting image display section has at least a light-emitting layer adjacent to an electrode, a charge injection layer, or a charge transport layer,
  • the light-emitting layer contains at least a polymer having a conductivity of 1 [S/m] or less, a charge-transporting host compound, and a light-emitting dopant, and
  • An organic electroluminescence device wherein the absolute value of the difference between the common logarithms of hole mobility and electron mobility in the light-emitting layer is 4.5 or less.
  • a method for producing an organic electroluminescence device for producing the organic electroluminescence device according to any one of items 1 to 13, A method for producing an organic electroluminescence device, comprising a step of forming the light-emitting layer by an inkjet printing method.
  • Item 14 The method for producing an organic electroluminescence element according to Item 14, comprising a step of forming the light-emitting layer by an inkjet printing method in the atmosphere.
  • a lighting device comprising the organic electroluminescence element according to any one of items 1 to 13.
  • a display device comprising the organic electroluminescence element according to any one of items 1 to 13.
  • a printed modeled article comprising the organic electroluminescence element according to any one of items 1 to 13.
  • an organic electroluminescent element that has high luminous efficiency, has a long life, can suppress performance deterioration during manufacturing in the atmosphere, and can be manufactured at low cost, and a method for manufacturing the same. and a lighting device, a display device, and a printed product having the same.
  • the difference between the common logarithms of hole mobility and electron mobility in the light-emitting layer is controlled to a specific value or less by using a charge-transporting host compound, a light-emitting dopant, a polymer, or the like contained in the light-emitting layer. It is presumed that the problem was solved.
  • the following explanation considers the manifestation mechanism of the effect obtained by controlling the difference between the hole mobility and the electron mobility, and is not necessarily clear. Therefore, the expression mechanism of the effect of the present invention is not limited to the speculated mechanism below.
  • the polymer When an ordinary insulating polymer such as polymethyl methacrylate (PMMA) is used in the light-emitting layer of an organic EL element, the polymer mainly disperses or agglomerates in the layer, suppressing current flow. or the route (conductive path) is blocked. In addition, the charge-transporting host compound and the light-emitting dopant aggregate in the form of being extruded into the polymer, causing a decrease in conductivity, interfacial recombination, and a decrease in recombination probability.
  • PMMA polymethyl methacrylate
  • polymer having a conductivity of 1 [S/m] or less (hereinafter also simply referred to as "polymer”) is localized at the interface between adjacent layers, thereby exhibiting carrier balance and various block properties. It has been suggested.
  • the above polymer has the effect of dispersing the host compound and the dopant, and has the effect of suppressing the trapping of charge carriers traveling between these molecules at the grain boundary, and the effect of suppressing the trapping of these carriers. It is possible to achieve compatibility with the carrier block effect that suppresses penetration of the light-emitting layer.
  • the light-emitting material is oxidized during operation and becomes a light emission quencher (also referred to as a "quencher"), and the polymer has a high probability of occurrence. It has the highest effect of suppressing recombination at the light-emitting layer interface. In particular, the effect is significant when the absolute value of the difference between the common logarithms of hole mobility and electron mobility is 4.5 or less, localized near the interface between the light-emitting layer and the adjacent layer.
  • the effect of the present invention is likely to be exhibited when the light-emitting layer is formed by a droplet discharge method such as inkjet.
  • a droplet discharge method such as inkjet.
  • the effect of the active gas in the film formation atmosphere is more pronounced than when the film is formed by vapor deposition or spin coating, and the effect of lowering the luminous efficiency and shortening the life is reduced.
  • the film is formed by vapor deposition or spin coating, and the effect of lowering the luminous efficiency and shortening the life is reduced.
  • it still emits light without performance degradation in such cases. Therefore, manufacturing costs for inert gas and vacuum equipment can also be reduced.
  • Schematic cross-sectional view of the organic EL element of the present invention Conceptual diagram showing that light-emitting image display units are arranged in dots.
  • Sectional view showing an example of a partition (bank) Conceptual diagram showing a method for fabricating an organic EL element using an inkjet recording method
  • the organic electroluminescence element of the present invention is an organic electroluminescence element having, on at least a substrate, an image display portion sandwiched between an anode and a cathode facing each other, wherein the image display portion comprises a light-emitting image display portion and a non-light-emitting portion.
  • the light-emitting image display portion has at least a light-emitting layer adjacent to an electrode, a charge injection layer, or a charge transport layer, and the light-emitting layer has an electrical conductivity of at least 1 [S/m] or less.
  • This feature is a technical feature common to or corresponding to each of the following embodiments (forms).
  • the absolute value of the difference between the common logarithm of the hole mobility and the electron mobility of the light emitting layer is 3.5 or less, and the conductivity is at least 1 [S / m] or less. It is preferable from the viewpoint of maximizing the blocking function of the polymer, improving the recombination probability and driving life, and suppressing the influence during production in the atmosphere. More preferably, it is 2.5 or less.
  • the mass ratio of the polymer is in the range of 5 to 80% by mass when the total mass of the light-emitting layer is 100.
  • the polymer prefferably be a polymer containing a benzene ring, because it is easy to obtain the effects of increasing the film density and dispersing the carrier transport material and dopant.
  • the polymer containing the benzene ring is a non-conjugated polymer from the viewpoint of carrier blocking.
  • a layer it is preferable in terms of retaining the charge in the emitted light and increasing the recombination probability.
  • the non-conjugated polymer contains a benzene ring as a side chain in terms of the effects of increasing the density and dispersing the carrier transport material and the dopant.
  • the non-conjugated polymer is polystyrene from the viewpoint of suppressing recombination at the interface on both electrode sides.
  • the non-conjugated polymer is a polystyrene derivative from the viewpoint of suppressing recombination at the interface on both electrode sides.
  • the polystyrene derivative is polyvinyl phenol from the viewpoint of suppressing recombination at the interface on both electrode sides.
  • the non-conjugated polymer is a mixture of components with different stereoregularities in that the amount of polymer localized at the interface can be controlled and the carrier balance can be adjusted.
  • the light-emitting layer prefferably be directly adjacent to the charge injection layer or the electrode in terms of controlling the mobility of charge carriers.
  • the method for producing an organic electroluminescence element of the present invention is characterized by being a method of a mode having a step of forming the light-emitting layer by an inkjet printing method. Moreover, it is more preferable to have a step of forming the light-emitting layer by an inkjet printing method in the atmosphere.
  • the organic electroluminescence device of the present invention has various characteristics as described above, it can be suitably used for lighting devices, display devices, and printed objects.
  • An organic electroluminescence device (hereinafter referred to as an "organic EL device") of the present invention is an organic electroluminescence device having, on at least a substrate, an image display portion sandwiched between an anode and a cathode facing each other, wherein the image
  • the display section is composed of a light-emitting image display section and a non-light-emitting image display section, the light-emitting image display section has at least a light-emitting layer adjacent to an electrode, a charge injection layer, or a charge transport layer, and the light-emitting layer comprises at least
  • the light-emitting layer contains a polymer having a conductivity of 1 [S/m] or less, a charge-transporting host compound, and a light-emitting dopant, and the absolute value of the difference between the common logarithms of hole mobility and electron mobility of the light-emitting layer is , 4.5 or less.
  • the absolute value of the difference between the common logarithm of the hole mobility and the electron mobility of the light-emitting layer is 3.5 or less, making the most of the blocking function of the polymer and recombination It is preferable from the viewpoint of improving the probability and driving life and suppressing the influence during manufacturing in the atmosphere. More preferably, it is 2.5 or less.
  • conductivity also referred to as “electrical conductivity” or “electrical conductivity” refers to a value that is an indicator of how easily electricity can pass, and the reciprocal of electrical resistivity is the SI system The unit is S/m (siemens per meter).
  • Electron and hole mobility refers to a measure of the ease with which charge carriers, ie, electrons and holes, can move through a material in response to an electric field.
  • a method for measuring and evaluating the mobility of electrons and holes for example, a method of determining from the current-voltage characteristics of the space charge limited current, or a method of irradiating a predetermined element with pulsed light and moving the carriers from the time it takes to travel between the electrodes
  • There is an evaluation method by the Time-Of-Fight method for obtaining mobility or an evaluation method by impedance spectroscopy for obtaining mobility from the transit time effect when an AC voltage is applied to an organic EL element.
  • the electron and hole mobilities are measured as follows. That is, as a sample for measurement, an organic EL device composed of a laminate sandwiching a light-emitting layer containing at least an electron-transporting compound or a hole-transporting compound to be measured between an anode and a cathode is prepared. Next, calculate the electron mobility and hole mobility based on the graph obtained by plotting the measured values of the current density-voltage characteristics (“JV characteristics”) of each organic EL element produced and the following theoretical formula. do.
  • JV characteristics current density-voltage characteristics
  • Non-Patent Document MA Lampert, P. Mark, Current injection in solids Academic, New York, 1970
  • International Publication No. 2019/039174 You can refer to it. Concrete examples will be described in the description of the examples below.
  • the graph of the current density-voltage characteristics has a pattern similar to that of the space charge limited current. Furthermore, the absolute value of the difference between those common logarithms is calculated.
  • J (9/8) ⁇ 0 ⁇ (V 2 /L 3 )
  • ⁇ the dielectric constant of the organic thin film
  • ⁇ 0 the vacuum dielectric constant
  • ⁇ the carrier mobility
  • J the current density
  • V the applied voltage.
  • a graph of JV 2 is created by plotting the measured values of J and V 2 , and the slope of the tangent line to the quadratic curve Calculate the electron mobility ⁇ e and hole mobility ⁇ h of each organic EL device from a, and the difference between the common logarithmic values of each organic EL device (log [electron mobility] ⁇ log [hole mobility]), That is, the absolute value of log([electron mobility]/[hole mobility]), which is the common logarithm of the ratio of [electron mobility] to [hole mobility], is obtained.
  • the dielectric constant is 3, and it is assumed that it is not affected by the electric field. This is the mobility when Note that when attention is paid to the difference in mobility as in the present invention, there is no need to discuss the dielectric constant, so the discussion will be omitted.
  • the organic electroluminescence device of the present invention (hereinafter also referred to as “organic EL device”) has an image display portion sandwiched between an anode and a cathode facing each other on a substrate.
  • the image display section is composed of a light-emitting image display section having a light-emitting layer and a non-light-emitting image display section.
  • the light-emitting image display section may have a charge injection layer and a charge transport layer in addition to the light-emitting layer. A small number of layers is preferable, and the charge injection layer and the charge transport layer may be omitted.
  • the organic EL element of the present invention refers to an organic EL element in a broad sense including a non-luminous image display portion.
  • the organic EL device of the present invention can take various forms/configurations.
  • the method and format for extracting light is a bottom emission type that extracts light from the substrate side.
  • the image display part When viewed from the substrate side, an image is displayed, and the part where the image is displayed (including planar and three-dimensional structures) is called an "image display part".
  • the “luminescence image display section” of the image display section according to the present invention refers to individual dots themselves and aggregates thereof shown in FIG.
  • the light-emitting pixel is composed of a functional layer such as a "light-emitting layer” sandwiched between common electrodes.
  • the "light-emitting pixel” is a minimum element that expresses color information (color tone and gradation) by emitting light.
  • the "light-emitting pixels” are also referred to as “light-emitting dots", “dot light-emitting images”, or simply “dots”.
  • the light-emitting image display unit according to the present invention may be formed by dots or a solid pattern on a planar substrate, may be formed by a three-dimensional structure formed on the surface of a curved substrate, an elastic substrate, or the like, or may be formed by a sheet.
  • a bank material or a sealing material may be embedded in a three-dimensional structure other than the shape material.
  • the luminous pixels are partitioned by a partition structure that is a non-luminous image display portion, and the partition is preferably an insulating layer.
  • the light-emitting layer according to the present invention is formed in dots, it is desirable that patterning is possible.
  • a printing method using a mask having patterning openings may be used, but a non-contact method is preferable from the viewpoint of less damage to the non-light-emitting layer.
  • the dispenser method or the inkjet printing method is more preferable from the viewpoint of enabling high resolution.
  • the size of the dots is preferably within the range of 30 to 300 ⁇ m as a circle-equivalent particle size when measured based on an optical microscope photograph (plan view) taken from the main light-emitting surface side of the light-emitting layer.
  • FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element that constitutes a light-emitting image display section according to the present invention.
  • the organic EL element 10 includes a substrate 11, an anode 12, a hole injection layer 13, a hole transport layer 14, a light emitting layer 15, an electron transport layer 16, an electron injection layer 17 and a cathode 18 in this order.
  • the light-emitting layer 15 contains a common host compound, and the blue (B) light-emitting pixel 21, the green (G) light-emitting pixel 22 and the red (R) light-emitting pixel are arranged between the insulating layers (banks) 2.
  • the organic EL element 10 having 23 is obtained.
  • the layer from the hole injection layer to the electron injection layer is also called an "organic functional layer".
  • FIG. 2 is a conceptual diagram showing that narrowly-defined organic EL elements forming light-emitting pixels are arranged in dots in a light-emitting image display section according to the present invention. That is, FIG. 2 is a conceptual diagram (plan view) of the image display unit viewed from the viewing side. In FIG. 2, portions indicated by black dots are “luminous image display portions”, and other white portions are “non-luminous image display portions”.
  • the dots are preferably formed and arranged as minute pixels that cannot be visually recognized as dots when the image on the image display device is observed by a normal visual observation method.
  • portions other than dots are non-luminous image display portions.
  • a non-light-emitting image display portion does not contribute to light emission unless it has a light-emitting layer. That is, since it is non-luminous, in the light-emitting image display portion, an insulating layer may be used instead of the light-emitting layer, and other layer configurations may be the same.
  • the non-light-emitting image display portion does not need to have elements that contribute to the expression of light-emitting properties, but by using the same layer as the light-emitting image display portion for the layers other than the light-emitting layer, the non-light-emitting image display portion can be formed by uniform coating or the like. , easy to manufacture. Also, by using an insulating layer instead of the light-emitting layer, it is possible to prevent electrons and holes, ie charge carriers, from entering.
  • a charge injection layer according to the present invention refers to a hole injection layer and an electron injection layer
  • a charge transport layer refers to a hole transport layer and an electron transport layer.
  • Anode/light-emitting layer/cathode (2) Anode/hole-transporting layer/light-emitting layer/cathode (3) Anode/hole-transporting layer/light-emitting layer/electron-transporting layer/cathode (4) Anode/hole-transporting layer /light emitting layer/electron transport layer/electron injection layer/cathode (5) anode/hole injection layer/light emitting layer/electron transport layer/cathode (6) anode/hole injection layer/hole transport layer/light emitting layer/electron injection layer/cathode (7) anode/hole injection layer/light emitting layer/electron injection layer/cathode (8) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode (9) anode/ Hole injection layer/hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode
  • the light-emitting layer is directly adjacent to the charge injection layer or directly adjacent to the electrode from the viewpoint of controlling the mobility of charge carriers.
  • the light-emitting layer is a layer that provides a field for recombination of electrons and holes injected from an electrode or an adjacent layer to emit light via excitons.
  • the light-emitting layer is composed of a single layer or multiple layers. That is, the organic EL element is an element using an organic light-emitting material that emits light when a voltage is applied. By applying a voltage, electrons and holes recombine in the light-emitting layer, and the excitons (excitons) generated at this time are deactivated, and light (electromagnetic waves) emitted when returning to the ground state is used. It is.
  • the light-emitting layer according to the present invention includes at least a polymer having a conductivity of 1 [S/m] or less (also referred to as a "binder” or “host polymer”), a charge-transporting host compound (a "matrix material", or a “light-emitting host compound”).
  • the absolute value of the difference between the common logarithm of the hole mobility and the electron mobility of the light-emitting layer is 3.5 or less. It is preferable from the viewpoint of improving the bonding probability and driving life and suppressing the influence of manufacturing in the atmosphere. More preferably, it is 2.5 or less. From the viewpoint of controlling the mobility of holes and electrons, it is preferable that the mass ratio of the polymer is in the range of 5 to 80% when the total mass of the light-emitting layer is 100.
  • the polymer is localized at the electrode-side interface of the light-emitting layer.
  • an electrode is provided adjacent to the light emitting layer, other hole injection layer (anode buffer layer), hole transport layer, hole blocking layer (hole barrier layer), electron injection layer (cathode buffer layer), An electron-transporting layer, an electron-blocking layer (electron-blocking layer), and the like may be appropriately provided as layers constituting the organic EL element.
  • Each of these layers can be formed with known materials and methods as long as they satisfy the provisions of the present invention.
  • the light emitting layer is directly adjacent to the charge injection layer or directly adjacent to the electrode.
  • directly adjacent means that there is no functional layer between the light-emitting layer and the charge injection layer or electrode, and the layers are in direct contact with each other.
  • the "electrode-side interface of the light-emitting layer” refers to the interface of the light-emitting layer that is in contact with any functional layer including the anode or the cathode, which is on the electrode side of the light-emitting layer.
  • any functional layer including the anode or the cathode which is on the electrode side of the light-emitting layer.
  • Light emitting layer material Polymer materials used in the light-emitting layer can have various molecular weight distributions, depending on the physical properties of the ink and coating properties. Moreover, the material for the light-emitting layer that constitutes the light-emitting layer may be either a polymer or a low-molecular weight material. When the low-molecular-weight material is formed by coating, the dopant molecules are dispersed between the polymer chains to increase the luminous efficiency, which is preferable.
  • a compound with a molecular weight of 3000 or less may be used. By using a compound having a molecular weight of 3000 or less, the solubility in a solvent is improved. In addition, preferably, the molecular weight is 500 or more.
  • the molecular weights of the light-emitting dopant and the host compound used as light-emitting layer materials are not particularly limited. It is preferred to contain compounds that do not contain any radicals, alkenyl groups, alkynyl groups or arylalkyl groups.
  • the thickness of the light-emitting layer is not particularly limited, it is preferably 50 nm or more, more preferably 70 nm or more, from the viewpoint of the distance between the recombination region and the electron transport layer. Moreover, from the viewpoint of driving voltage, it is preferably 150 nm or less.
  • the method for forming the light-emitting layer is not particularly limited, but it is preferably formed by a wet method or the like because it contains a polymer. In this case, the manufacturing cost of the organic EL element can be reduced as compared with vacuum deposition or the like.
  • Wet methods include, for example, a spin coating method, a casting method, an inkjet printing method, a printing method, a die coating method, a blade coating method, a roll coating method, a dispenser method, a spray coating method, a curtain coating method, an LB method (Langmuir-Blodgett method, ) etc. can be used.
  • a method applicable to a roll-to-roll system such as a die coating method, a roll coating method, a dispenser method, and an inkjet printing method is preferable because a homogeneous thin film can be easily obtained and high productivity can be obtained.
  • the inkjet printing method will be described later.
  • the liquid medium for dissolving or dispersing the light emitting layer material includes, for example, alcohols such as isopropanol and tetrafluoropropanol, ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, chloroform, dichlorobenzene and the like.
  • Halogenated hydrocarbons aromatic hydrocarbons such as toluene, xylene, mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin and dodecane, organic solvents such as dimethylformamide (DMF) and dimethylsulfoxide (DMSO) can be used.
  • aromatic hydrocarbons such as toluene, xylene, mesitylene and cyclohexylbenzene
  • aliphatic hydrocarbons such as cyclohexane
  • decalin and dodecane organic solvents such as dimethylformamide (DMF) and dimethylsulfoxide (DMSO) can be used.
  • organic solvents such as dimethylformamide (DMF) and dimethylsulfoxide (DMSO)
  • dispersing the light-emitting layer material in a liquid medium it can be dispersed by a dispersion method such as ultrasonic waves, high-shear force dispersion, or media dispersion.
  • the method of forming the light-emitting layer can be formed either in the atmosphere or under an inert gas.
  • the atmosphere the adsorption of the adsorbed active gas on the surface of the light-emitting layer is saturated, and the degree of atmospheric degradation is evened out, so there is also the advantage of suppressing variations in chromaticity and uneven light emission.
  • the polymer contained in the light-emitting layer according to the invention is characterized by having an electrical conductivity of 1 [S/m] or less.
  • conductivity also referred to as “electrical conductivity” or “electrical conductivity” refers to a value that is an index representing how easily electricity can pass, and the reciprocal of electrical resistivity is the SI unit is expressed as S/m (Siemens per meter).
  • a conductivity of 1 S/m or less facilitates controlling the movement of injected electrons and holes, ie charge carriers. More preferably, it has relatively low conductivity or insulation, with a conductivity of 10 ⁇ 8 S/m or less.
  • the electrical conductivity exceeds 1 S/m, the rate of charge transfer through the polymer becomes more rate-determining than the charge transfer to the host compound or dopant, and the recombination probability decreases.
  • the polymer is a polymer containing a benzene ring, from the viewpoint of easily obtaining the effects of increasing the film density and dispersing the carrier transport material and the dopant.
  • the polymer containing the benzene ring is a non-conjugated polymer from the viewpoint of carrier blocking. is preferable from the viewpoint of increasing the recombination probability by retaining the charge in the emitted light.
  • the non-conjugated polymer contains a benzene ring as a side chain from the viewpoint of the effect of increasing the density and dispersing the carrier transport material and the dopant.
  • the non-conjugated polymer is polystyrene.
  • the non-conjugated polymer is more preferably a polystyrene derivative.
  • the effect of the present invention is remarkable for polymers containing benzene rings.
  • the light-emitting layer material interacts with the light-emitting layer material containing many ⁇ It easily encapsulates molecules and forms a phase-separated structure to easily obtain a trap suppressing effect and a carrier blocking effect.
  • the polystyrene derivative is polyvinylphenol from the viewpoint of suppression of recombination at the interface between both electrodes.
  • a polar group-added benzene ring in the side chain like polyvinylphenol (PVPh)
  • PVPh polyvinylphenol
  • hydrogen bonds between polymers are formed, and the formation of a phase separation structure is promoted by heating during drying.
  • the film is densely formed by ⁇ - ⁇ interactions and hydrogen bonding, the carrier transport sites formed by hosts and dopants through similar interaction networks are also densified.
  • the non-conjugated polymer is a mixture of components with different stereoregularities from the viewpoint of controlling the amount of polymer localized at the interface and adjusting the carrier balance.
  • the polymer of the light-emitting layer can be appropriately selected from known materials and used.
  • Polyalkylenes such as polyethylene, polypropylene, polyvinylidene fluoride, polyacrylonitrile, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polyphenyl ether, polyethylene ether ketone, polyphenylene sulfide, polyphenylene sulfone, polysulfone, polyether sulfone, polyarylate, polystyrene, Aromatic ring-containing polymers such as polyvinylphenol and derivatives of these polymers, cured resins such as phenolic resins and epoxy resins, and the like can be used. Among them, aromatic ring-containing polymers are preferable from the viewpoint of meshing with the electrode crystal lattice and interaction with adjacent layers.
  • Polymers used in the present invention are preferably aromatic ring-containing polymers having structures represented by the following general formulas (I) and (II).
  • polymers containing benzene rings are preferred.
  • the polymer containing the benzene ring is a non-conjugated polymer.
  • the non-conjugated polymer is a polymer containing benzene rings as side chains, such as polystyrene or polystyrene derivatives.
  • the aromatic ring-containing polymers having structures represented by the following general formulas (I) and (II) will be described in detail below.
  • A represents an aromatic ring
  • the aromatic ring includes an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Each of these may be a monocyclic ring or a condensed ring.
  • L represents a divalent linking group.
  • x and y represent an integer of 0 or 1 or more.
  • n represents the degree of polymerization and is 10 or more and 100,000 or less.
  • the aromatic ring represented by A includes an aromatic hydrocarbon ring and an aromatic heterocyclic ring, as described above. Each of these may be a monocyclic ring or a condensed ring. From the viewpoint of conductivity or insulation, the aromatic ring is preferably an aromatic hydrocarbon ring. From the viewpoint of solubility, the number of atoms constituting the aromatic ring of general formula (I) and general formula (II) excluding substituents is preferably 20 or less, more preferably 12 or less, and even more preferably 6 or less.
  • aromatic hydrocarbon rings examples include benzene ring, naphthalene ring, fluorene ring, anthracene ring, phenthrene ring, tetracene ring, pentacene ring, chrysene ring, pyrene ring, perylene ring, coronene ring, fluoranthene ring, dibenzoanthracene ring,
  • aromatic hydrocarbon rings include benzene ring, naphthalene ring, fluorene ring, anthracene ring, phenthrene ring, tetracene ring, pentacene ring, chrysene ring, pyrene ring, perylene ring, coronene ring, fluoranthene ring, dibenzoanthracene ring,
  • acene structures such as benzopyrene ring, preferably benzene ring and naphthalene
  • aromatic heterocyclic rings include pyridine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, acridine ring, thiophene ring, furan ring, pyrrole ring, benzofuran ring, benzothiophene ring, indole ring, imidazole ring and pyrazole ring.
  • oxazole ring isoxazole ring, thiazole ring, isothiazole ring, triazole ring, oxadiazole ring, thiadiazole ring, dioxazole ring, dithiazole ring, tetrazole ring, pentazole ring and the like.
  • the aromatic ring represented by A is preferably a benzene ring, and specific examples include the structure of the following general formula (III).
  • X and Y represent hydrogen or a bond with the repeating unit L or A in the general formula (I) and general formula (II).
  • R 1 to R 5 represent hydrogen or substituents, each independently hydrogen atom, deuterium atom, halogen atom, hydroxy group, carboxy group, sulfo group, alkoxycarbonyl group, haloformyl group, formyl group, acyl group, alkoxy group, mercapto group, cyano group, alkyl group, alkenyl group, alkynyl group, alkoxy group, amino group, carbamoyl group, silyl group, phosphine oxide group, imide group, aromatic imide ring group, aromatic hydrocarbon ring group, It represents an aromatic heterocyclic group, a non-aromatic hydrocarbon ring group, or a non-aromatic heterocyclic group, and may further have a substituent.
  • alkyl groups represented by R 1 to R 5 in general formula (I), general formula (II) and general formula (III) above include methyl group, ethyl group, propyl group, isopropyl group, (t ) butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, benzyl group and the like.
  • Alkenyl groups represented by R 1 to R 5 include, for example, those having one or more double bonds in the above alkyl group, more specifically vinyl group, allyl group, 1-propenyl group, iso propenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group and the like.
  • alkynyl groups represented by R 1 to R 5 include ethynyl group, acetylenyl group, 1-propynyl group, 2-propynyl group (propargyl group), 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 1-heptynyl group, 2-heptynyl group, 5-heptynyl group, 1-octynyl group, 3-octynyl group, 5-octynyl group and the like.
  • aromatic hydrocarbon ring groups (also referred to as aryl groups) represented by R 1 to R 5 include phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group and azulenyl. group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like.
  • aromatic heterocyclic groups represented by R 1 to R 5 include pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazinyl group and triazolyl group (e.g., 1, 2, 4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group , benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced
  • non-aromatic hydrocarbon ring groups represented by R 1 to R 5 include cycloalkyl groups (eg, cyclopentyl group, cyclohexyl group, etc.), cycloalkoxy groups (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), cycloalkylthio monovalent groups derived from groups (eg, cyclopentylthio group, cyclohexylthio group, etc.), tetrahydronaphthalene ring, 9,10-dihydroanthracene ring, biphenylene ring, etc.;
  • cycloalkyl groups eg, cyclopentyl group, cyclohexyl group, etc.
  • cycloalkoxy groups eg, cyclopentyloxy group, cyclohexyloxy group, etc.
  • cycloalkylthio monovalent groups derived from groups eg, cyclopent
  • non-aromatic hydrocarbon ring groups represented by R 1 to R 5 include epoxy ring, aziridine ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ⁇ -caprolactone ring, ⁇ -caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane ring,
  • alkoxy groups represented by R 1 to R 5 include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy and nonyloxy. group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group and the like.
  • Acyl groups represented by R 1 to R 5 include, for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group and phenylcarbonyl group. group, naphthylcarbonyl group, pyridylcarbonyl group, and the like.
  • amino groups represented by R 1 to R 5 include amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group and naphthylamino group. , 2-pyridylamino group and the like.
  • Silyl groups represented by R 1 to R 5 include, for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group and phenyldiethylsilyl group.
  • Phosphine oxide groups represented by R 1 to R 5 include, for example, diphenylphosphine oxide group, ditolylphosphine oxide group, dimethylphosphine oxide group, dinaphthylphosphine oxide group, 9,10-dihydro-9-oxa-10- A phosphaphenanthrene-10-oxide group and the like can be mentioned.
  • Substituents that the groups represented by R 1 to R 5 may further have include, for example, each independently alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, (t) butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, benzyl group, etc.), cycloalkyl group (e.g., cyclopentyl group, cyclohexyl group, etc.), alkenyl group (e.g., vinyl group, allyl group, etc.) , an alkynyl group (e.g., propargyl group, etc.), an aromatic hydrocarbon group (also called an aryl group, such as a phenyl group, p-chlorophenyl group, mesityl group, tolyl group, x
  • oxazolyl group benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group , a benzothienyl group, a dibenzothienyl group, an indolyl group, a carbazolyl group, a carbolinyl group, a diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced with a nitrogen atom), quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), halogen atoms (e.g., chlorine atom , bromine atom
  • aminocarbonyl group methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.
  • sulfinyl group e.g., methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group or arylsulfonyl group (e.g.
  • methylsulfonyl group ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.
  • amino groups e.g.
  • alkylsilyl group or arylsilyl group e.g., trimethylsilyl group, triethylsilyl group, (t) butyldimethyl silyl group, triisopropylsilyl group, (t) butyldiphenylsilyl group, triphenylsilyl group, trinaphthylsilyl group, 2-pyridylsilyl group, etc.
  • alkylphosphino group or arylphosphino group dimethylphosphino group, diethyl phosphino group, dicyclohexylphosphino group, methylphenylphosphino group, dipheny
  • L represents a divalent linking group, an alkylene group, an alkenylene group, a carbonyl group, an ether group, an imino group, an imide group, an amide group, an o-phenylene group. , m-phenylene group, p-phenylene group, sulfonyl group, sulfide group, thioester group, silyl group, phosphine oxide group, or divalent aromatic heterocyclic group, which may further have a substituent.
  • the alkylene group represented by L includes, for example, methylene group, ethylene group, trimethylene group, propylene group, butylene group, butane-1,2-diyl group, hexylene and the like.
  • the alkenylene group represented by L includes, for example, vinylene group, propenylene group, butenylene group, pentenylene group, 1-methylvinylene group, 1-methylpropenylene group, 2-methylpropenylene group, 1-methylpentenylene group, rene group, 3-methylpentenylene group, 1-ethylvinylene group, 1-ethylpropenylene group, 1-ethylbutenylene group, 3-ethylbutenylene group and the like.
  • Examples of the amide group represented by L include a methylcarbonylamino group, an ethylcarbonylamino group, a dimethylcarbonylamino group, a propylcarbonylamino group, a pentylcarbonylamino group, a cyclohexylcarbonylamino group, a 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group and the like.
  • divalent aromatic heterocyclic group represented by L includes , for example, aromatic Divalent groups derived from those mentioned as heterocyclic groups are included.
  • x and y represent 0 or an integer of 1 or more.
  • n represents the degree of polymerization and is 10 or more and 100,000 or less.
  • L and R 1 to R 5 may be the same or different.
  • devices using polymers represented by the following structural formulas (1) to (4) are described as comparative examples. This is because the absolute value of the difference between the common logarithms does not satisfy the numerical specification in the present invention. If the numerical specification is satisfied, it can be used in the present invention.
  • structural formula (5) is given as a comparative example to be described later.
  • n, x and y are integers
  • the degree of polymerization n is within the range of 10 to 100
  • the weight-average molecular weight of the polymer is preferably 1,000 or more from the viewpoint of suppressing the effects of crystallization and diffusion of low-molecular-weight components, and preferably has a molecular weight of 3,000,000 or less from the viewpoint of residual polymerization impurities. More preferably, it is 50,000 or more and 1,000,000 or less.
  • the weight average molecular weight here refers to the weight average molecular weight measured by gel permeation chromatography (GPC) using dimethylformamide as a solvent and converted to polystyrene. If it cannot be measured with dimethylformamide, use tetrahydrofuran. If it cannot be measured, use hexafluoroisopropanol. If it cannot be measured with hexafluoroisopropanol, use 2-chloronaphthalene.
  • GPC gel permeation chromatography
  • the polymer content is preferably in the range of 5 to 80% by weight.
  • the polymer is sufficiently present at the interface on the electrode side, so that movement of chemical species such as charge carriers and compounds can be restricted between the light-emitting layer and the adjacent layer or between the light-emitting layer and the electrode.
  • the charge carrier balance can be maintained, and the generation of factors that cause deterioration and quenching of the organic EL element can be suppressed.
  • the mass ratio of the polymer is more preferably within the range of 15-65% by mass, and still more preferably within the range of 20-60% by mass.
  • the polymer is preferably a polymer containing a benzene ring selected from the above structural formulas (1) to (30) (however, (except Structural Formula (11)).
  • the polymer contains a benzene ring selected from the above structural formulas (1) to (30) in the side chain (however, (except Structural Formula (11)).
  • Luminescent dopant As for the light emission method of the organic EL device, there are two types of light emission methods, one is “phosphorescence emission” in which light is emitted when returning from the triplet excited state to the ground state, and the other is returning from the singlet excited state to the ground state. There are two kinds of “fluorescence emission” that emits light when the light is emitted.
  • triplet excitons are generated with a probability of 75% and singlet excitons are generated with a probability of 25%. It is an excellent method for achieving high efficiency and low power consumption.
  • a fluorescent dopant also referred to as a fluorescent dopant or a fluorescent compound
  • a phosphorescent dopant phosphorescent dopant, phosphorescent compound Also called.
  • the concentration of the emissive dopant in the emissive layer can be arbitrarily determined based on the particular dopant used and device requirements.
  • the concentration of the light-emitting dopant may be uniform in the layer thickness direction of the light-emitting layer, or may have an arbitrary concentration distribution.
  • the light-emitting layer may contain a plurality of types of light-emitting dopants.
  • dopants having different structures may be used in combination, or a fluorescent dopant and a phosphorescent dopant may be used in combination. This makes it possible to obtain an arbitrary emission color.
  • the doping method of the luminescent dopant of the present invention it may be mixed with the host in advance as an ink and applied to form a film, or a host layer may be formed and then a dopant solution is applied to the luminescent layer.
  • a method of penetrating to the interface on the anode side may be used.
  • the distribution state of the polymer, host compound, and luminescent dopant in the light-emitting layer is measured perpendicular to the substrate by dynamic secondary ion mass spectrometry, static secondary ion mass spectrometry, or argon cluster ion beam X-ray photoelectron spectroscopy. It can be known by analyzing the composition of the light-emitting layer in the (depth) direction. Specifically, by analyzing the presence or absence of metal elements specific to phosphorescent materials, specific mass fragments, or heteroelements in organic compounds, the distribution of compounds in the light-emitting layer can be observed on the order of nanometers. can be done.
  • the phosphorescent dopant is a compound in which emission from excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25°C), and has a phosphorescence quantum yield of 0 at 25°C. .01 or higher.
  • the phosphorescent dopant used in the light-emitting layer preferably has a phosphorescence quantum yield of 0.1 or more.
  • the phosphorescence quantum yield can be measured by the method described in Experimental Chemistry Course 7, 4th Edition, Spectroscopy II, page 398 (1992 edition, Maruzen). Phosphorescence quantum yield in solution can be measured using various solvents.
  • the phosphorescence-emitting dopant used in the light-emitting layer should achieve the phosphorescence quantum yield (0.01 or more) in any solvent.
  • the phosphorescent dopant can be appropriately selected from known materials used in the light-emitting layer of organic EL devices and used. Specific examples of known phosphorescent dopants that can be used in the present invention include the compounds described in the following documents.
  • preferred phosphorescent dopants include organometallic complexes having Ir as a central metal. Complexes containing at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond, and metal-sulfur bond are more preferred.
  • the fluorescent dopant is a compound capable of emitting light from an excited singlet, and is not particularly limited as long as light emission from an excited singlet can be observed.
  • fluorescent dopants include anthracene derivatives, pyrene derivatives, chrysene derivatives, fluoranthene derivatives, perylene derivatives, fluorene derivatives, arylacetylene derivatives, styrylarylene derivatives, styrylamine derivatives, arylamine derivatives, boron complexes, coumarin derivatives, pyran derivatives, cyanine derivatives, croconium derivatives, squarium derivatives, oxobenzanthracene derivatives, fluorescein derivatives, rhodamine derivatives, pyrylium derivatives, perylene derivatives, polythiophene derivatives, rare earth complex compounds, and the like.
  • TTA delayed fluorescence compound
  • TTA Excited triplet-triplet annihilation
  • a luminescence method using delayed fluorescence has emerged to solve the problems of fluorescent compounds.
  • the TTA method originating from collisions between triplet excitons can be described by the following general formula. That is, conventionally, exciton energy is converted only to heat by non-radiative deactivation, but some of the triplet excitons have the advantage of being able to reverse intersystem crossover to singlet excitons that can contribute to light emission. In actual organic EL devices, it is possible to obtain an external extraction quantum efficiency approximately double that of conventional fluorescent light emitting devices.
  • T * +T * ⁇ S * +S (Wherein, T * represents a triplet exciton, S * represents a singlet exciton, and S represents a ground state molecule.)
  • T * represents a triplet exciton
  • S * represents a singlet exciton
  • S represents a ground state molecule.
  • the TADF method which is another high-efficiency fluorescence emission method, is a method that can solve the problems of TTA.
  • Fluorescent compounds have the advantage that they can be designed indefinitely as described above. That is, among molecularly designed compounds, there are compounds in which the energy level difference between the triplet excited state and the singlet excited state (hereinafter, appropriately abbreviated as " ⁇ EST ”) is extremely close. do.
  • examples of compounds that emit delayed fluorescence include International Publication No. 2011/156793, JP-A-2011-213643, and JP-A-2010. -93181, Japanese Patent No. 5366106, WO 2013/161437 and WO 2016/158540, etc., but the present invention is not limited thereto.
  • QD-OLED quantum dot-containing organic light-emitting device
  • QLED inorganic light emitting device
  • the contents described in JP-A-2015-156367 and JP-A-2018-078279 can be referred to.
  • the light-emitting layer according to the present invention may be a layer containing a perovskite compound.
  • perovskite compound means a compound having a perovskite structure.
  • the perovskite compound is preferably a perovskite compound in which an organic substance and an inorganic substance are constituent elements of the perovskite structure (a perovskite compound with an organic-inorganic hybrid structure).
  • the perovskite compound preferably has a structure represented by the following general formula (a) from the viewpoint of photoelectric conversion efficiency.
  • R represents an organic molecule.
  • M represents a metal atom.
  • X represents a halogen atom or a chalcogen atom.
  • R is an organic molecule, preferably a molecule represented by C1NmXn ( l , m and n all represent positive integers).
  • R is specifically methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, ethylmethylamine, methylpropylamine, butylmethylamine, methylpentylamine, hexylmethylamine, ethylpropylamine, ethylbutylamine, imidazole, azole, pyrrole, aziridine, azirine, azetidine, Azeto, imidazoline, carbazole and their ions (eg, methylammonium (CH 3 NH 3 ), etc.), phenethylammonium, and the like can be mentioned.
  • methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and their ions and phenethylammonium are preferred, and methylamine, ethylamine, propylamine and their ions are more preferred.
  • M is a metal atom such as lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum and europium. mentioned. These elements may be used alone, or two or more of them may be used in combination.
  • X is a halogen atom or a chalcogen atom such as chlorine, bromine, iodine, sulfur, selenium and the like. These elements may be used alone, or two or more of them may be used in combination. Among them, a halogen atom is preferable because the perovskite compound becomes soluble in an organic solvent by containing a halogen atom in the structure, and application to an inexpensive printing method or the like becomes possible. Furthermore, iodine is more preferable because it narrows the energy bandgap of the organic-inorganic perovskite compound.
  • luminescent dopants examples include the following.
  • the host compound is a compound that is mainly responsible for charge injection and transport in the light-emitting layer, and its own light emission is substantially not observed in the organic EL device.
  • the organic EL device of the present invention is characterized in that a plurality of light-emitting pixels have a common electrode and a common host compound, wherein the host compound is composed of a plurality of types of host compounds, and the plurality of light-emitting pixels It is preferable that the composition ratios of the plurality of types of host compounds are equal in the pixel. By using a plurality of types of host compounds, it is possible to adjust the movement of electric charges, and it is possible to improve the efficiency of the organic EL device.
  • the host compound used in the light-emitting layer compounds conventionally used in organic EL devices can be used.
  • it may be a low-molecular compound, a polymer compound having repeating units, or a compound having a reactive group such as a vinyl group or an epoxy group.
  • the host compound preferably has a high glass transition temperature (Tg).
  • Tg glass transition temperature
  • the host compound preferably has a Tg of 80° C. or higher, more preferably 100° C. or higher.
  • the "glass transition point (Tg)" is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).
  • the host compound must be able to exist stably in all active species states of cation radical state, anion radical state, and excited state, and not undergo chemical changes such as decomposition and addition reactions. It is preferred that the host molecules do not migrate at the angstrom level in the layer during the passage of current.
  • the host compound that can be used in the present invention is not particularly limited, and compounds that are conventionally used in organic EL devices can be used.
  • Representative examples are those having a basic skeleton such as carbazole derivatives, triarylamine derivatives, aromatic derivatives, nitrogen-containing heterocyclic compounds, thiophene derivatives, furan derivatives, oligoarylene compounds, etc., or carboline derivatives and diazacarbazole derivatives (here and the diazacarbazole derivative means that at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom.) and the like.
  • a known host compound that can be used in the present invention is preferably a compound that has hole-transporting ability and electron-transporting ability, prevents emission from becoming longer in wavelength, and has a high Tg as described above.
  • a conventionally known host compound may be used alone, or a plurality of types may be used in combination.
  • a plurality of types of host compounds it is possible to adjust the movement of electric charges, and to improve the efficiency of the organic EL device.
  • a plurality of conventionally known compounds it is possible to mix different luminescence, thereby obtaining an arbitrary luminescence color.
  • the host compound used in the present invention may be a low-molecular-weight compound, a high-molecular-weight compound having a repeating unit, or a low-molecular-weight compound (polymerizable host compound) having a polymerizable group such as a vinyl group or an epoxy group. Well, one or more of such compounds may be used.
  • the host compound of the present invention is preferably a host compound that dissolves in a non-halogen solvent, and more preferably an ester solvent. This is because the halogen solvent has the problem of dissolving the lower layer. Moreover, it is preferable that the molecular weight of the host compound is 1000 or less because it is easily dissolved.
  • the host compound used in the present invention is preferably a compound having a structure represented by the following general formula.
  • the light-emitting layer is preferably formed using a coating liquid containing a compound having a structure represented by the following general formula (1).
  • X represents O, S, or NR9.
  • R 9 is a hydrogen atom, deuterium atom, alkyl group, alkenyl group, alkynyl group, arylalkyl group, aromatic hydrocarbon ring group, aromatic heterocyclic group, non-aromatic hydrocarbon ring group, non-aromatic heterocyclic ring group or a substituent represented by the following general formula (2).
  • R 1 to R 8 each represent a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an acyl group, an amino group, a silyl group, a phosphine oxide group, and an aromatic hydrocarbon group. It represents a hydrogen ring group, an aromatic heterocyclic group, a non-aromatic hydrocarbon ring group, a non-aromatic heterocyclic group, or a substituent represented by the following general formula (2). At least one of R 1 to R 9 represents a substituent represented by general formula (2) below. R 1 to R 9 may be the same or different, and may have a substituent. ]
  • each L represents an alkylene group, an alkenylene group, an o-phenylene group, an m-phenylene group, a p-phenylene group, an amide group or a divalent aromatic heterocyclic group, and further substituted You may have a group.
  • n represents an integer of 1 to 8; When n represents an integer of 2 or more, 2 or more L's may be the same or different.
  • R is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon ring group, an aromatic heterocyclic group or a non-aromatic represents a group hydrocarbon ring group, which may further have a substituent.
  • m represents an integer of 1 to 3;
  • At least one of L and R represents an alkylene group or an alkyl group.
  • R 1 to R 9 in general formula (1) have the same meanings as R 1 to R 6 in general formulas (I) to (III).
  • the linking group represented by L in the general formula (2) has the same definition as L in the general formulas (I) and (II).
  • the alkyl group having 1 to 20 carbon atoms represented by R includes, for example, those listed as the alkyl groups represented by R 1 to R 9 in the general formula (1). , groups having 1 to 20 carbon atoms.
  • Examples of the fluorinated alkyl group having 1 to 20 carbon atoms represented by R include groups in which hydrogen atoms of the above alkyl groups having 1 to 20 carbon atoms are substituted with fluorine atoms.
  • Examples of the alkoxy group having 1 to 20 carbon atoms represented by R include those having 1 to 20 carbon atoms among the alkoxy groups represented by R 1 to R 8 in the above general formula (1). group.
  • the aromatic hydrocarbon ring group, aromatic heterocyclic group or non-aromatic hydrocarbon ring group represented by R includes, for example, aromatic hydrocarbon rings represented by R 1 to R 9 in the general formula (1) groups, aromatic heterocyclic groups or non-aromatic hydrocarbon ring groups.
  • the substituents that L and R may further have include, for example, the same substituents that R 1 to R 9 may have in general formula (1). is mentioned.
  • At least one L is preferably an alkylene group having 1 to 6 carbon atoms.
  • at least one R is preferably an alkyl group having 1 to 6 carbon atoms.
  • Charge carrier transport layer (also referred to as “charge transport layer”) refers to a layer containing a compound having a function of transporting charge carriers, that is, electrons or holes. .
  • charge carrier transport layer (“charge transport layer”) is divided into an “electron transport layer” and a “hole transport layer” for explanation.
  • Electron transport layer is made of a material having a function of transporting electrons among charge carriers, and in a broad sense, an electron injection layer is also included in the electron transport layer.
  • the electron transport layer can be provided as a single layer or multiple layers.
  • the electron transport layer is preferably formed using a coating liquid containing an electron transport material described below.
  • the coating liquid preferably contains the polar fluorinated solvent.
  • the solubility in the polar fluorinated solvent is preferably lower in the order of the material of the electron transport layer, the material of the insulating layer, and the material of the light emitting layer.
  • the electron transporting material used for the electron transporting layer should have the function of transmitting electrons injected from the cathode to the light emitting layer.
  • the material thereof any one can be selected and used from conventionally known compounds. Examples thereof include metal complexes such as fluorene derivatives, carbazole derivatives, azacarbazole derivatives, oxadiazole derivatives, triazole derivatives, silole derivatives, pyridine derivatives, pyrimidine derivatives and 8-quinolinol derivatives.
  • metal-free or metal phthalocyanines or those whose terminals are substituted with alkyl groups, sulfonic acid groups, etc., can also be preferably used as electron transport materials.
  • carbazole derivatives azacarbazole derivatives, pyridine derivatives and the like are preferred in the present invention, and azacarbazole derivatives are more preferred.
  • the electron transport layer can be formed by thinning the electron transport material by a known method such as a spin coating method, a casting method, a printing method including an inkjet printing method, or an LB method. It can be formed by a wet process using a coating liquid containing an electron transporting material and a fluorinated alcohol solvent.
  • the layer thickness of the electron-transporting layer is not particularly limited, but is usually in the range of about 5 nm to 5 ⁇ m, preferably in the range of 5 to 200 nm.
  • the electron-transporting layer may have a single-layer structure composed of one or more of the above materials.
  • an electron transport layer having a high n property doped with an impurity as a guest material can also be used.
  • Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, JP-A-2001-102175 and J. Am. Appl. Phys. , 95, 5773 (2004).
  • the electron transport layer in the invention preferably contains an alkali metal salt of an organic substance.
  • an organic substance formate, acetate, propionic acid, butyrate, valerate, caproate, enanthate, caprylate, oxalate, malonate, and succinate , benzoate, phthalate, isophthalate, terephthalate, salicylate, pyruvate, lactate, malate, adipate, mesylate, tosylate, benzenesulfonate.
  • ком ⁇ онент preferably formate, acetate, propionate, butyrate, valerate, caproate, enanthate, caprylate, oxalate, malonate, succinate, benzoate, more preferably is preferably an alkali metal salt of an aliphatic carboxylic acid such as formate, acetate, propionate and butyrate, and preferably the aliphatic carboxylic acid has 4 or less carbon atoms. Acetate is most preferred.
  • the type of alkali metal in the organic alkali metal salt is not particularly limited, but includes Na, K, Cs and Li, preferably K and Cs, more preferably Cs.
  • the alkali metal salts of organic substances include combinations of the above organic substances and alkali metals, preferably Li formate, K formate, Na formate, Cs formate, Li acetate, K acetate, Na acetate, Cs acetate, Li propionate, Sodium propionate, K propionate, Cs propionate, Li oxalate, Na oxalate, K oxalate, Cs oxalate, Li malonate, Na malonate, K malonate, Cs malonate, Li succinate, succinic acid Na, K succinate, Cs succinate, Li benzoate, Na benzoate, K benzoate and Cs benzoate, more preferably Li acetate, K acetate, Na acetate and Cs acetate, most preferably Cs acetate
  • the content of these dopants is preferably in the range of 1.5 to 35% by mass, more preferably in the range of 3 to 25% by mass, and most preferably in the range of 5 to It is within the range of 15% by mass.
  • the hole-transport layer is composed of a hole-transport material having a function of transporting holes among charge carriers, and is broadly referred to as a hole-injection layer, an electron A blocking layer is also included in the hole transport layer. Also, the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has either hole injection or transport or electron blocking properties, and may be either organic or inorganic.
  • triazole derivatives for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbenes. derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, thiophene oligomers, and the like.
  • hole transport material those mentioned above can be used, and porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds can be used, and aromatic tertiary amine compounds can be used in particular. preferable.
  • aromatic tertiary amine compounds and styrylamine compounds include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N'- Bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1 -bis(4-di-p-tolylaminophenyl)cyclohexane, N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis(4-di-p -tolylaminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-di
  • polymer materials in which these materials are introduced into the polymer chain or these materials are used as the main chain of the polymer can also be used.
  • Inorganic compounds such as p-type-Si and p-type-SiC can also be used as hole-injecting materials and hole-transporting materials.
  • Japanese Patent Application Laid-Open No. 11-251067, J. Am. Huang et. al. , Applied Physics Letters, 80 (2002), p. 139, so-called p-type hole transport materials can also be used. In the present invention, these materials are preferably used from the viewpoint of obtaining a light-emitting device with higher efficiency.
  • the hole-transporting layer is formed by applying the above-mentioned hole-transporting material by a known method such as a vacuum vapor deposition method, a spin coating method, a casting method, a printing method including an inkjet printing method, and an LB method (Langmuir Blodgett method). can be formed by thinning.
  • the layer thickness of the hole-transporting layer is not particularly limited, but is usually in the range of about 5 nm to 5 ⁇ m, preferably in the range of 5 to 200 nm.
  • the hole transport layer may have a single-layer structure composed of one or more of the above materials.
  • the p-property can be increased by doping the material of the hole transport layer with impurities.
  • impurities examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175 and J. Am. Appl. Phys. , 95, 5773 (2004).
  • Electron blocking layer has the function of a hole transport layer in a broad sense.
  • the electron-blocking layer is made of a material that has the function of transporting holes but has a significantly low ability to transport electrons. By blocking electrons while transporting holes, the probability of recombination between electrons and holes is improved. can be made Moreover, the structure of a hole transport layer can be used as an electron blocking layer as needed.
  • the layer thickness of the hole blocking layer is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
  • Charge carrier injection layer charge injection layer A “charge carrier injection layer (hereinafter also referred to as a “charge injection layer”)” is a compound having the function of injecting charge carriers, that is, electrons or holes. refers to a layer containing In the following description, the charge carrier injection layer (“charge injection layer”) is divided into “hole injection layer” and “hole injection layer”.
  • the charge injection layer is a layer for injecting charge carriers, that is, electrons or holes, provided between the electrode and the light emitting layer in order to reduce the driving voltage and improve the luminance of the emitted light.
  • charge carriers that is, electrons or holes
  • the details are described in "Organic EL element and its industrial front” (published by NTS on November 30, 1998), Part 2, Chapter 2, “Electrode materials” (pp. 123-166). , a hole-injection layer and an electron-injection layer.
  • An injection layer can be provided as needed.
  • a hole-injecting layer may be present between the anode and the light-emitting layer or the hole-transporting layer, and an electron-injecting layer may be present between the cathode and the light-emitting layer or the electron-transporting layer.
  • JP-A-9-45479 JP-A-9-260062, and JP-A-8-288069.
  • Examples include an oxide layer represented by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • the electron injection layer Details of the electron injection layer are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, etc. Specifically, a metal layer represented by strontium, aluminum, etc. , an alkali metal halide layer typified by potassium fluoride, an alkaline earth metal compound layer typified by magnesium fluoride, an oxide layer typified by molybdenum oxide, and the like.
  • the electron injection layer is desirably a very thin film, and although it depends on the constituent materials, the layer thickness is preferably in the range of 1 nm to 10 ⁇ m.
  • an electrode material having a large work function (4 eV or more), an alloy, an electrically conductive compound, or a mixture thereof is preferably used.
  • electrode materials include metals such as Au, conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , ZnO and IZO.
  • a material such as IDIXO (In 2 O 3 —ZnO) that is amorphous and capable of forming a transparent conductive film may also be used.
  • the anode may be formed by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering, and forming a pattern of a desired shape by photolithography. A pattern may be formed through a mask having a desired shape during vapor deposition or sputtering of the electrode material.
  • a wet film-forming method such as a printing method or a coating method may be used.
  • the transmittance is desirably greater than 10%, and the sheet resistance of the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually selected within the range of 10 to 1000 nm, preferably within the range of 10 to 200 nm.
  • Electroconductive compounds and mixtures thereof are used as electrode materials.
  • electrode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium/copper mixtures, magnesium/silver mixtures, magnesium/aluminum mixtures, magnesium/indium mixtures, aluminum/aluminum oxide (Al 2 O 3 ) mixtures, silver, indium, lithium/aluminum mixtures and rare earth metals;
  • a mixture of an electron injection metal and a second metal that has a higher work function and is more stable such as a magnesium/silver mixture, magnesium /aluminum mixtures, magnesium/indium mixtures, aluminum/aluminum oxide ( Al2O3 ) mixtures, lithium/aluminum mixtures, silver and aluminum, etc. are suitable.
  • the cathode can be produced by forming a thin film of these electrode substances by a method such as vapor deposition, sputtering, or lamination.
  • the sheet resistance of the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected within the range of 10 nm to 5 ⁇ m, preferably within the range of 50 to 200 nm.
  • the anode or the cathode of the organic EL element is transparent or semi-transparent because the luminance of the emitted light is improved.
  • a transparent or translucent cathode can be produced by forming the above-mentioned metal on the cathode with a film thickness in the range of 1 to 20 nm and then forming thereon the conductive transparent material mentioned in the explanation of the anode. By applying this, it is possible to fabricate a device in which both the anode and the cathode are transparent.
  • Non-luminous image display part The organic EL element of the present invention has an image display part composed of a "luminous image display part” and a “non-luminous image display part”. , a portion other than the “luminescent image display portion” that constitutes the image display portion. That is, the organic EL element of the present invention has a form in which a luminescence image display portion in which luminescence pixels are arranged in dots is provided between a plurality of non-luminescence image display portions included in the image display portion. is preferred.
  • partition walls functioning as an electrically insulating layer and ink containing a light-emitting material are permeated. It is preferable that the non-insulating ink-receiving layer portion functions as a partition wall (insulating layer).
  • insulating refers to a property in which electrons and holes are difficult to move, that is, it is difficult to conduct electricity. say nature. In other words, it refers to the property that the electrical conductivity is less than 10 ⁇ 5 S/m.
  • electric resistivity a value obtained under conditions conforming to JIS-K-6911 by a constant voltage application/leakage current measurement method using a double ring electrode is used.
  • a bank may be formed in advance, or after forming an insulating layer uniformly, a light-emitting layer is formed by ink-jetting separately, and spontaneously Banks may be formed, but the former method is preferred.
  • the organic EL device of the present invention it is a preferred form to form a bank as an insulating layer on the substrate surface.
  • the bank is formed on the periphery of the area to be coated with the liquid containing the material constituting the organic EL element on the substrate surface, and the applied liquid containing the material constituting the organic EL element is applied. It has the role of preventing outflow to the outside of the attached area and the role of providing electrical insulation.
  • FIG. 3 is a cross-sectional view showing an example of a substrate having banks.
  • the regions of the surface of the substrate 1 delimited by the banks 2 are bank depressions 2a, and the bank surfaces are bank projections 2b.
  • a light-emitting image display portion according to the present invention is formed in the concave portion 2a.
  • the height of the bank is not particularly limited as long as it is possible to prevent the applied ink from flowing out, but it is preferably in the range of 1.1 to 2.5 ⁇ m. A more preferable range is 1.5 to 2.5 ⁇ m.
  • Insulating Material A known material can be used as the material of the insulating layer (bank) according to the present invention, but the polysiloxane skeleton has at least one organic group other than an alkyl group. It is preferable to contain an organic-inorganic hybrid polymer. By having at least one organic group other than an alkyl group in the polysiloxane structure, it is possible to obtain a light-emitting image display portion having excellent solvent resistance and peeling resistance.
  • organic-inorganic hybrid polymer structure As the organic group other than the alkyl group of the organic-inorganic hybrid polymer used in the present invention, known substituents can be used without particular limitation. group, nitro group, nitroso group, azo group, diazo group, azide group, carbonyl group, phenyl group, hydroxy group, peroxy group, acyl group, acetyl group, aldehyde group, carboxy group, amide group, imide group, ester group, Oxime groups, thiol groups, sulfo groups, urea groups, isonitrile groups, allene groups, acryloyl groups, methacryloyl groups, epoxy groups, oxetane groups, isocyanate groups, and the like can be used. Among the above, an acryloyl group, an epoxy group, or an isocyanate group is preferred. Among them, an acryloyl group is particularly preferred.
  • polysiloxane structure examples include polysiloxanes (including polysilsesquioxanes) having Si—O—Si bonds.
  • polysiloxane can include [R 3 SiO 1/2 ], [R 2 SiO], [RSiO 3/2 ] and [SiO 2 ] as general structural units.
  • R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (eg, methyl group (Me), ethyl group, propyl group, etc.), an aryl group (eg, phenyl group (Ph), etc.), unsaturated alkyl group ( are independently selected from the group consisting of, for example, vinyl groups, etc.).
  • Examples of specific polysiloxane structures include [PhSiO 3/2 ], [MeSiO 3/2 ], [HSiO 3/2 ], [MePhSiO], [Ph 2 SiO], [PhViSiO], [ViSiO 3/2 ] (Vi represents a vinyl group), [MeHSiO], [MeViSiO], [Me 2 SiO] and [Me 3 SiO 1/2 ]. Mixtures and copolymers of polysiloxanes can also be used.
  • binder resin in addition to the organic-inorganic hybrid polymer used in the present invention, a binder resin may be used in the insulating layer within a range that does not impair the effects of the present invention.
  • binder resins include cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate; Polyvinyl alcohol derivatives such as polyester, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl benzal, norbornene-based polymers containing norbornene compounds, polymethyl methacrylate, polyethyl methacrylate, polypropyltyl methacrylate, polybutyl methacrylate, polymethyl Acrylic resins such as acrylates or copolymers of acrylic resins and other resins can be used, but the material is not particularly limited to these exemplified resin materials. Among these binder resins
  • insulating metal oxide As a material for the insulating layer, it is also preferable to contain an insulating metal oxide in the binder resin.
  • the insulating metal oxide is not particularly limited, alumina, zirconia, titania, silica, magnesia, or niobium is preferable from the viewpoint of chemical stability and physical stability.
  • metal oxides having a dielectric constant of 100 or more are preferable, and examples thereof include rutile-type titanium oxide (TiO 2 ), zirconium oxide (ZrO), niobium pentoxide (Nb 2 O 3 ), and titanic acid.
  • TiO 2 titanium oxide
  • ZrO zirconium oxide
  • Nb 2 O 3 niobium pentoxide
  • titanic acid barium (BaTiO 3 ), strontium titanate (SrTiO 3 ), lead titanate (PbTiO 3 ), barium zirconate titanate (BaTi 0.5 Zr 0.5 O 3 ), lead zirconate titanate (PbTi 0.5 ) . 5 Zr 0.5 O 3 ) or the like , or water thereof hydrates, and insulating solid solutions containing at least one of these in the composition.
  • the insulating layer may be patterned in advance on the non-image portion, or a method of forming a current flow path (conductive path) by injecting ink containing a soluble functional material into the insulating layer is used.
  • a method of forming a current flow path (conductive path) by injecting ink containing a soluble functional material into the insulating layer is used.
  • the insulating layer is formed by the following method.
  • a 0.5 mm glass substrate (Eagle XG manufactured by Corning) was washed with an alkali, and then a photosensitive polyimide containing 30% by mass of titanium oxide (manufactured by Merck) was applied by spin coating, and the temperature was kept at 60°C. is pre-baked for 120 seconds.
  • pattern exposure is performed by a photo process, development is performed with tetramethylammonium hydroxide (abbreviation: TMAH), and rinsing is performed with pure water to form banks having openings.
  • TMAH tetramethylammonium hydroxide
  • Polar fluorinated solvent A polar fluorinated solvent is preferably used for forming the insulating layer. A polar fluorinated solvent is also preferably used for forming an electron transport layer, which will be described later.
  • the polar fluorinated solvent refers to a solvent that contains fluorine atoms in the solvent molecule, has a dielectric constant of 3 or more, and has a solubility in water of 5 g/L or more at 25°C.
  • the boiling point of the polar fluorinated solvent is preferably within the range of 50 to 200°C.
  • the temperature is set to 50° C. or higher, it is possible to more reliably suppress the occurrence of unevenness due to heat of evaporation during drying of the coating film.
  • the temperature is set to 200° C. or less, the solvent can be dried quickly, the solvent content in the formed layer is reduced, so that the crystal growth in the layer can be suppressed more reliably, and the solvent escape route is rough. Therefore, the density is improved and the current efficiency can be increased. More preferably, it is within the range of 70 to 150°C.
  • the water content of the polar fluorinated solvent is preferably as low as possible because even a very small amount of water is a quencher of light emission, preferably 100 ppm or less, more preferably 20 ppm or less.
  • the content of impurities other than water in the polar fluorinated solvent is as low as 100 ppm, because even a very small amount can become a quencher of light emission, cause air bubbles, or cause deterioration of the film quality after drying.
  • the following is preferable, and 20 ppm or less is more preferable.
  • Impurities other than water include oxygen, inert gases such as nitrogen, argon and carbon dioxide, and inorganic compounds or metals brought in from catalysts, adsorbents and equipment used during preparation and purification.
  • Examples of the polar fluorinated solvent include fluorinated alcohols, fluorinated acrylates, fluorinated methacrylates, fluorinated esters, fluorinated ethers, fluorinated hydroxyalkylbenzenes, and fluorinated amines, and fluorinated alcohols, fluorinated esters, and fluorinated ethers. is more preferred, and fluorinated alcohol is even more preferred from the viewpoint of solubility and drying property.
  • the number of carbon atoms in the fluorinated alcohol is preferably 3 to 5 from the viewpoint of the boiling point and the solubility of the material.
  • the fluorine-substituted position is, for example, the position of hydrogen in the case of alcohol, and the fluorination rate is sufficient as long as it does not impair the solubility of the layer material, and is fluorinated to the extent that the lower layer material is not eluted. is desirable.
  • fluorinated alcohols examples include 1H,1H-pentafluoropropanol, 6-(perfluoroethyl)hexanol, 1H,1H-heptafluorobutanol, 2-(perfluorobutyl)ethanol (FBEO), 3-(perfluorobutyl ) propanol, 6-(perfluorobutyl) hexanol, 2-perfluoropropoxy-2,3,3,3-tetrafluoropropanol, 2-(perfluorohexyl) ethanol, 3-(perfluorohexyl) propanol, 6- (perfluorohexyl)hexanol, 1H,1H-(perfluorohexyl)hexanol, 6-(perfluoro-1-methylethyl)hexanol, 1H,1H,3H-tetrafluoropropanol (TFPO), 1H,1H,5H- o
  • fluorinated ethers examples include hexafluorodimethyl ether, perfluorodimethoxymethane, perfluorooxetane, perfluoro-1,3-dioxolane, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoro Propyl ether etc. are mentioned.
  • fluorinated esters examples include methyl perfluorobutyrate, ethyl perfluorobutyrate, methyl perfluoropropionate, methyl difluoroacetate, ethyl difluoroacetate, methyl-2-trifluoromethyl-3,3,3- and trifluoropropionate.
  • the content of the insulating compound is preferably within the range of 0.05 to 10% by mass, and the content of the polar fluorinated solvent is preferably within the range of 90 to 99.95% by mass in the coating liquid for forming the insulating layer.
  • the polar fluorinated solvent may be a mixed solvent of two or more polar fluorinated solvents, or a mixture of a polar fluorinated solvent and a solvent other than a polar fluorinated solvent, as long as it does not dissolve the light-emitting layer material.
  • a solvent may be used.
  • a mixed solvent of fluorinated alcohol and alcohol can be used.
  • the content of the polar fluorinated solvent is preferably 50% by mass or more.
  • Substrate The material of the substrate used in the organic EL device is not particularly limited, and preferable examples include glass, quartz, and resin films. Particularly preferred is a resin film that imparts flexibility to the organic EL element and can be embedded in a printed matter or the like.
  • resin films include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate (CAP ), cellulose esters such as cellulose acetate phthalate and cellulose nitrate, or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, Polyethersulfone (PES), polyphenylene sulfide, polysulfones, polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylates, Arton (trade name, manufactured by JSR Corporation) or APEL (trade name, manufactured by Mitsu
  • a gas barrier film may be formed on the surface of the resin film by a coating of an inorganic substance, an organic substance, or a hybrid coating of both.
  • the gas barrier film has a water vapor permeability (25 ⁇ 0.5°C, humidity (90 ⁇ 2)% RH) measured by a method conforming to JIS K 7129-1992 of 0.01 g/(m 2 24 h) or less. is preferably a gas barrier film.
  • the oxygen permeability measured by a method based on JIS K 7126-1987 is 1 ⁇ 10 -3 mL / (m 2 ⁇ 24 h ⁇ atm) or less, and the water vapor permeability is 1 ⁇ 10 -5 g / It is preferably a high gas barrier film of (m 2 ⁇ 24 h) or less.
  • any material can be used as long as it has a function of suppressing penetration of moisture, oxygen, and the like.
  • silicon oxide, silicon dioxide and silicon nitride can be used.
  • the order of lamination of the inorganic layer and the organic layer is not particularly limited, but it is preferable to alternately laminate the two layers a plurality of times.
  • the method for forming the gas barrier film is not particularly limited, and examples include vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, and atmospheric pressure plasma polymerization.
  • a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used.
  • atmospheric pressure plasma polymerization as described in JP-A-2004-68143 is preferred.
  • sealing means used for sealing the organic EL device of the present invention for example, a method of adhering a sealing member, an electrode, and a supporting substrate with an adhesive can be mentioned. .
  • the sealing member may be arranged so as to cover the display area of the organic EL element, and may be in the form of a concave plate or a flat plate. Moreover, transparency and electric insulation are not particularly limited.
  • glass plates glass plates, polymer plates/films, metal plates/films, and the like can be mentioned.
  • glass plates include soda-lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass and quartz.
  • polymer plate polycarbonate, acryl, polyethylene terephthalate, polyether sulfide, polysulfone, and the like can be used.
  • Metal plates include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium and tantalum.
  • a polymer film and a metal film can be preferably used because the organic EL element can be made thinner.
  • the polymer film preferably has an oxygen permeability of 10 ⁇ 3 g/(m 2 ⁇ 24 h) or less and a water vapor permeability of 10 ⁇ 3 g/(m 2 ⁇ 24 h) or less. Further, it is more preferable that both the water vapor permeability and the oxygen permeability are 10 ⁇ 5 g/(m 2 ⁇ 24 h) or less.
  • Sandblasting, chemical etching, or the like is used to process the sealing member into a concave shape.
  • adhesives include photocurable and thermosetting adhesives having reactive vinyl groups of acrylic acid-based oligomers and methacrylic acid-based oligomers, and moisture-curable adhesives such as 2-cyanoacrylic acid esters. be able to.
  • Thermal and chemical curing types such as epoxy systems can also be mentioned. Mention may also be made of hot-melt polyamides, polyesters and polyolefins. Further, a cationic curing type ultraviolet curing type epoxy resin adhesive can be mentioned.
  • a desiccant may be dispersed in the adhesive.
  • a commercially available dispenser may be used to apply the adhesive to the sealing portion, or printing such as screen printing may be used.
  • the electrode and the organic functional layer may be coated on the outside of the electrode on the side facing the supporting substrate with the organic functional layer interposed therebetween, and inorganic and organic layers may be formed in contact with the supporting substrate to form a sealing film.
  • the material for forming the film may be any material that has a function of suppressing the infiltration of substances that cause deterioration of the device, such as moisture and oxygen.
  • silicon oxide, silicon dioxide, silicon nitride, and the like can be used.
  • the method for forming these films is not particularly limited. A method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used.
  • An inert gas such as nitrogen or argon, or an inert liquid such as fluorocarbon or silicone oil may be injected into the gap between the sealing member and the display area of the organic EL element in the gas phase and the liquid phase.
  • a vacuum is also possible.
  • a hygroscopic compound can be sealed inside.
  • hygroscopic compounds include metal oxides (e.g. sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide, etc.), sulfates (e.g. sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.), Metal halides (e.g. calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide barium iodide, magnesium iodide, etc.) and perchlorates (e.g. barium perchlorate, magnesium perchlorate etc.), etc., and anhydrous salts are preferably used for sulfates, metal halides and perchlorates.
  • metal oxides e.g. sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide, etc.
  • sulfates e.g. sodium sulfate, calcium sulfate, magnesium s
  • a protective film or a protective plate may be provided on the outside of the sealing film or film for sealing on the side facing the support substrate with the organic functional layer interposed therebetween in order to increase the mechanical strength of the element.
  • the mechanical strength thereof is not necessarily high, so it is preferable to provide such a protective film or protective plate.
  • the same glass plate, polymer plate/film, metal plate/film, etc. used for the above sealing can be used. It is preferred to use polymer films.
  • the organic EL element emits light inside a layer with a higher refractive index than air (within a refractive index range of about 1.6 to 2.1). It is generally said that only light within the range of about 15 to 20% of the light can be extracted.
  • Methods for improving the efficiency of extracting light include, for example, forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (see, for example, US Pat. No. 4,774,435); A method of improving efficiency by imparting properties (for example, JP-A-63-314795), a method of forming a reflective surface on the side surface of an element (for example, JP-A-1-220394), a substrate and a light emitter A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between them (for example, JP-A-62-172691), a flat layer having a lower refractive index than the substrate between the substrate and the light emitter (for example, Japanese Patent Application Laid-Open No.
  • these methods can be used in combination with the organic EL device.
  • a method of forming a diffraction grating between the substrate and the outside world, including between or between any of the substrate and the light-emitting layer, can be preferably used.
  • the present invention can obtain an element with even higher luminance or excellent durability.
  • the low refractive index layer examples include airgel, porous silica, magnesium fluoride, and fluoropolymers. Since the refractive index of the transparent substrate is generally in the range of about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Moreover, it is preferable that it is 1.35 or less.
  • the thickness of the low refractive index medium is at least twice the wavelength in the medium. This is because when the thickness of the low-refractive-index medium is about the wavelength of light and reaches a thickness at which the electromagnetic wave seeped out by evanescence penetrates into the substrate, the effect of the low-refractive-index layer is weakened.
  • the method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving the light extraction efficiency.
  • This method utilizes the property that a diffraction grating can change the direction of light to a specific direction different from refraction by first-order diffraction, second-order diffraction, or so-called Bragg diffraction.
  • light that cannot go out due to total reflection between layers or the like is diffracted by introducing a diffraction grating in one of the layers or in the medium (inside the transparent substrate or in the transparent electrode), It's about getting the light out.
  • the diffraction grating to be introduced preferably has a two-dimensional periodic refractive index. This is because the light emitted from the light-emitting layer is randomly generated in all directions, so a general one-dimensional diffraction grating that has a periodic refractive index distribution in only one direction can only diffract light traveling in a specific direction. Therefore, the light extraction efficiency does not increase so much.
  • the position where the diffraction grating is introduced may be between any of the layers or in the medium (inside the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light-emitting layer where light is generated.
  • the period of the diffraction grating is preferably in the range of about 1/2 to 3 times the wavelength of light in the medium.
  • the arrangement of the diffraction gratings is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.
  • the organic EL element of the present invention is processed so as to provide a structure on the light extraction side of the support substrate (substrate), for example, a microlens array, or a so-called light condensing sheet.
  • the luminance in a specific direction can be increased by condensing light in a specific direction, for example, in the front direction with respect to the light emitting surface of the element.
  • square pyramids each having a side of 30 ⁇ m and an apex angle of 90° are arranged two-dimensionally on the light extraction side of the support substrate.
  • One side is preferably within the range of 10 to 100 ⁇ m. If it is smaller than this, the effect of diffraction will occur and coloring will occur.
  • the condensing sheet it is possible to use, for example, a material that has been put to practical use in the LED backlight of the liquid crystal display device.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3M Co., Ltd. can be used as such a sheet.
  • the shape of the prism sheet may be, for example, a substrate on which delta-shaped stripes with an apex angle of 90° and a pitch of 50 ⁇ m are formed. A shape or other shape may be used.
  • a light diffusing plate/film may be used together with the condensing sheet in order to control the light emission angle from the organic EL element.
  • a diffusion film (light up) manufactured by Kimoto Co., Ltd. can be used.
  • tandem-type organic EL element for example, US Pat. No. 6,337,492, US Pat. 6107734, US Patent No. 6337492, JP 2006-228712, JP 2006-24791, JP 2006-49393, JP 2006-49394, JP 2006-49396 JP, JP 2011-96679, JP 2005-340187, JP 4711424, JP 3496681, JP 3884564, JP 4213169, JP 2010-192719 , JP 2009-076929, JP 2008-078414, JP 2007-059848, JP 2003-272860, JP 2003-045676, International Publication No. 2005/009087 and International
  • the device configuration, constituent materials, and the like described in Japanese Unexamined Patent Publication No. 2005/094130 and the like can be mentioned, the present invention is not limited thereto.
  • the anode 12 is formed on the substrate 11 .
  • the insulating layer 2 is formed on the anode 12, and the hole injection layer 13 and the hole transport layer 14 are formed in this order in the concave portions of the insulating layer 2.
  • the light-emitting layer 15 is formed using the light-emitting layer forming coating solution.
  • an electron transport layer 16 is formed on the light emitting layer 15 using a coating solution for forming an electron transport layer.
  • an electron injection layer 17 and a cathode 18 are formed on the electron transport layer 16 .
  • Anode 12 and cathode 18 form a common electrode for the light emitting layer.
  • the light-emitting pixels include four colors (B, G, R, and W (white)), five colors (B, G, R, W (white), and LB).
  • (Mixed color of B and G) and O (Mixed color of G and R) are also preferable, and one or more types of configurations suitable for the image area can be selected from these emission colors.
  • each layer other than the light-emitting layer that constitutes the organic EL element 10 any method such as a wet method, vapor deposition, or sputtering may be used as described above. Also, the formation of the light-emitting layer and the electron transport layer is not limited to the wet method, and a method such as vapor deposition or sputtering may be used. However, from the viewpoint of cost, it is preferable to use a wet method for any of the layers constituting the organic EL element 10 .
  • the device after forming the cathode 18 is sealed (not shown).
  • the sealing means used for sealing the element known members and methods can be used.
  • any method such as a wet method, vapor deposition, and sputtering may be used as described above.
  • a wet method and particularly preferably to use an inkjet printing method, because deterioration in performance during manufacturing in the air is suppressed and costs are suppressed.
  • liquid media used in inkjet printing examples include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, isopropyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate, and halogenated carbons such as dichlorobenzene.
  • ketones such as methyl ethyl ketone and cyclohexanone
  • fatty acid esters such as ethyl acetate, isopropyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate
  • halogenated carbons such as dichlorobenzene.
  • a solvent having a boiling point within the range of 50 to 180° C. is preferably used.
  • a dispersion method it can be dispersed by a dispersion method such as ultrasonic wave, high shear force dispersion, media dispersion, or the like.
  • the solvent content contained in the organic EL element is within the range of 0.01 to 1 ⁇ g/cm 2 .
  • concentration 0.01 ⁇ g/cm 2 or less
  • the organic film becomes sparse, which causes a high voltage when the device is driven. resulting in low efficiency and a short drive life.
  • solvent contents can be determined by thermal desorption spectroscopy.
  • the luminescent layer according to the present invention is preferably formed by an inkjet printing method, particularly preferably by an inkjet printing method in the atmosphere.
  • an inkjet printing method particularly preferably by an inkjet printing method in the atmosphere.
  • the effect of the active gas in the film forming atmosphere is more pronounced than in the case of forming a film by vapor deposition or spin coating, resulting in a decrease in luminous efficiency and a short life.
  • the method of forming other layers constituting the organic EL element is not limited, and may be an inkjet printing method or other methods.
  • the inkjet head used in the inkjet printing method may be of an on-demand system or a continuous system.
  • an electro-mechanical conversion method eg, single cavity type, double cavity type, bender type, piston type, share mode type, shared wall type, etc.
  • an electro-thermal conversion method eg, thermal ink jet type
  • an electrostatic attraction method e.g., electric field control type, slit jet type, etc.
  • a discharge method e.g., spark jet type, etc.
  • a serial head method, a line head method, or the like can be used without limitation.
  • the volume of ink droplets ejected from the head is preferably in the range of 0.5 to 100 pL. It is more preferably in the range of 2 to 50 pL from the viewpoint of reducing coating unevenness and increasing the printing speed. Note that the volume of the ink droplet can be appropriately adjusted by adjusting the applied voltage or the like.
  • the print resolution is preferably within the range of 180 to 10,000 dpi (dots per inch), more preferably within the range of 360 to 2,880 dpi, and can be appropriately set in consideration of wet thickness, volume of ink droplets, and the like.
  • the wet thickness of the wet coating film at the time of inkjet coating can be appropriately set, preferably within the range of 1 to 100 ⁇ m, more preferably within the range of 1 to 30 ⁇ m, most preferably within the range of 1 to 30 ⁇ m. is within the range of 1 to 5 ⁇ m, the effect of the present invention is exhibited more remarkably.
  • the wet thickness can be calculated from the coating area, print resolution, and ink droplet volume.
  • Inkjet printing methods include a one-pass printing method and a multi-pass printing method.
  • the one-pass printing method is a method of printing a predetermined print area by one head scan.
  • the multi-pass printing method is a method of printing a predetermined print area by multiple head scans.
  • a wide head in which nozzles are arranged over a width equal to or greater than the width of the desired coating pattern.
  • a wide head that is at least as wide as the width of each coating pattern may be used.
  • FIG. 2 shows a conceptual diagram showing that the luminescent pixels 21 to 23 are arranged in dots when viewed from the direction perpendicular to the surface of the organic EL element 10 .
  • the position of each dot may be in a regular permutation or in a staggered arrangement. Among them, a staggered arrangement is more preferable.
  • FIG. 4A, 4B, and 4C are schematic diagrams showing an example of a single-pass system (line head system) inkjet recording apparatus applicable to the method for manufacturing an organic EL element of the present invention.
  • 100 is a line head type head unit that ejects inks of different hues (for example, inks containing compounds that emit red (R), green (G), and blue (B) colors). It is preferably composed of heads 102 to 104 and the nozzle pitch of each head is about 360 dpi.
  • the dpi referred to in the present invention represents the number of dots per 2.54 cm.
  • the substrates 1 are fed out in the direction of the arrow from the transport mechanism 101 in a state of being stacked in a roll.
  • FIG. 4B is a bottom view showing the arrangement of nozzles at the bottom of each head. As shown in FIG. 4B, the nozzles N of the head 102, the head 103, and the head 104 are staggered by half a pitch. With such a head structure, a more dense image can be formed.
  • FIG. 4C is a schematic diagram showing an example of a head unit configuration.
  • a head unit HU in which a plurality of heads H are arranged in a zigzag arrangement so as to cover the entire width of the substrate.
  • a coating liquid (ink) containing a luminescent dopant, a host compound, or the like that forms the luminescent layer of the organic EL element and a solvent is applied onto the substrate while the substrate is continuously conveyed, or
  • a coating liquid (ink) containing an organic functional material for forming an organic functional layer and a solvent is sequentially ejected as ink droplets onto a substrate to form a light-emitting layer and an organic functional layer.
  • An inkjet head having a configuration described in publications and the like can be appropriately selected and applied.
  • the organic EL element of the above-described embodiment is a surface or minute light emitter, it can be used as various light sources.
  • Lighting device For example, lighting devices such as home lighting and in-vehicle lighting, backlights for clocks and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copiers, light sources Light sources for communication processors, light sources for optical sensors, and the like.
  • the organic EL element of the present invention is a simple display device, it is possible to finely produce according to on-demand by a two-dimensional inkjet method or a three-dimensional inkjet method. It is possible to provide the original model and the like.
  • element No. 1 produced under an inert gas.
  • A element No. produced in the atmosphere.
  • B device No. manufactured for hole mobility measurement.
  • H element No. manufactured for electron mobility measurement. is marked with an E.
  • Mw is the weight average molecular weight of each commercial product
  • Mn is the number average molecular weight
  • Mv is the viscosity average molecular weight.
  • Polyethylene [Mw: ⁇ 4k, manufactured by Sigma-Aldrich] (3) Polychlorotrifluoroethylene [manufactured by Daikin Industries, Ltd., Polyflon (registered trademark) M-12]
  • Polyvinylidene fluoride [Mw: 410 to 575, manufactured by Piezotech, Piezotech (registered trademark) RT-TS]
  • Poly(3,4-ethylenedioxythiophene) [manufactured by Sigma-Aldrich, Aedtron C-NM] (6) Poly(2-vinylpyridine) [Mn: 152k, Mw: 159k, manufactured by Sigma-Aldrich]
  • Example 1 ⁇ Production of organic EL element under inert gas> ⁇ Production of Organic EL Element A (100 A)>> A bottom emission type organic EL element 100A was manufactured by laminating and sealing an anode/light-emitting layer/cathode on a substrate as follows.
  • an atmospheric pressure plasma discharge treatment apparatus having the configuration described in Japanese Patent Application Laid-Open No. 2004-68143 was used on the entire surface of a polyethylene naphthalate film (manufactured by Teijin DuPont, hereinafter abbreviated as PEN) on the anode forming side.
  • PEN polyethylene naphthalate film
  • an inorganic gas barrier layer made of silicon oxide (SiOx; 1 ⁇ x ⁇ 4) was formed to a layer thickness of 500 nm.
  • SiOx silicon oxide
  • ITO indium tin oxide
  • the coating solution was applied to the anode prepared above using a Konica Minolta inkjet head (MEMS head 1 pL) so as to form a square coating pattern of 100 ⁇ m on a side at four locations with an interval of 10 ⁇ m.
  • MEMS head 1 pL Konica Minolta inkjet head
  • Triethylene glycol monobutyl ether was used as the coating liquid.
  • the substrate coated with the coating liquid was subjected to a lyophilic treatment.
  • Argon gas was used as the discharge gas
  • oxygen gas was used as the reactive gas.
  • the power source used for plasma generation was PHF2-K manufactured by Heiden Laboratory, and a voltage of about 2 kV was applied to generate plasma.
  • the coating liquid was removed by cleaning the lyophilic substrate surface using a dry ice cleaner manufactured by Air Water. As a result, a substrate on which a pattern of lyophilic regions and lyophobic regions was formed was obtained.
  • the substrate on which the anode and bank were formed was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaned for 5 minutes.
  • a piezoelectric inkjet printer head manufactured by Konica Minolta which is a piezoelectric inkjet printer head having the structure shown in FIG. KM1024i" was injected onto a substrate at 40° C. under the condition that the layer thickness after drying was 50 nm, and then dried at 120° C. for 30 minutes to form a light-emitting layer.
  • the substrate was attached to the vacuum deposition apparatus.
  • a molybdenum resistance heating boat containing sodium fluoride and potassium fluoride was attached to a vacuum deposition apparatus, and the vacuum chamber was evacuated to 4 ⁇ 10 ⁇ 5 Pa. After that, the boat was energized and heated, and sodium fluoride was vapor-deposited on the light-emitting layer and bank at 0.02 nm/sec to form a thin film with a thickness of 1 nm. Similarly, potassium fluoride was vapor-deposited on the sodium fluoride thin film at 0.02 nm/sec to form an electron injection layer with a layer thickness of 1.5 nm.
  • sealing substrate was adhered to the laminate formed by the above steps using a commercially available roll laminator.
  • a 1.5 ⁇ m-thick adhesive was applied to a flexible 30 ⁇ m-thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.) using a two-liquid reactive urethane-based adhesive for dry lamination.
  • a layer was provided and a polyethylene terephthalate (PET) film having a thickness of 12 ⁇ m was laminated.
  • PET polyethylene terephthalate
  • thermosetting adhesive as a sealing adhesive was uniformly applied to a thickness of 20 ⁇ m along the bonding surface (glossy surface) of the aluminum foil of the sealing substrate using a dispenser. This was dried under a vacuum of 100 Pa or less for 12 hours. Furthermore, the sealing substrate is moved to a nitrogen atmosphere with a dew point temperature of ⁇ 80° C. or less and an oxygen concentration of 0.8 ppm, and dried for 12 hours or more, and the moisture content of the sealing adhesive is adjusted to 100 ppm or less. did.
  • thermosetting adhesive an epoxy-based adhesive mixed with the following (A) to (C) was used.
  • the above-mentioned sealing substrate was placed in close contact with the above-mentioned laminate, and was tightly sealed using a pressure roll under pressure conditions of a pressure roll temperature of 100°C, a pressure of 0.5 MPa, and an apparatus speed of 0.3 m/min.
  • an organic EL element 100A having the same configuration as the organic EL element having the configuration shown in FIG. 1 was manufactured.
  • NPB N,N'-bis(naphthalen-1-yl)N,N'-bis(phenyl)-benzidine
  • a device for hole mobility measurement also referred to as a “hole-only device” 100H was manufactured in the same manner, except for the above. Since NPB is a hole-transporting material, injection of electrons from the cathode does not occur, so it can be used for measuring hole mobility.
  • An electron mobility measuring device 100E was fabricated in the same manner as in the production of the organic EL device 100A, except that calcium was vapor-deposited to a thickness of 5 nm before forming the light-emitting layer. Calcium is an electron-injecting material and can be used for electron mobility measurement because it does not cause hole injection due to the large gap to the light-emitting layer HOMO.
  • Organic EL element 100B was produced in the same manner as in the production of organic EL element 100A under the inert gas, except that air (temperature 20° C.; humidity 50%) was used as the atmosphere for film formation of the light-emitting layer.
  • each organic EL device was manufactured in the same manner except that the type of polymer in the coating solution for forming the light-emitting layer in the formation of the light-emitting layer was changed as shown in Tables I and II.
  • Device B (101B-130B) was manufactured.
  • Organic EL devices A and B produced by the above method were evaluated as follows.
  • Organic EL devices H and E fabricated under an inert gas were used to calculate the absolute value of the difference between the common logarithms of hole mobility and electron mobility.
  • J (9/8) ⁇ 0 ⁇ (V 2 /L 3 )
  • J is the space charge limited current
  • ⁇ is the dielectric constant of the organic thin film
  • ⁇ 0 is the vacuum dielectric constant
  • J is the current density
  • V is the applied voltage.
  • the measured values J and V are plotted to plot J on the vertical axis and V on the horizontal axis.
  • the electron mobility ⁇ e and the hole mobility ⁇ h of each organic EL element are calculated from the slope a of the straight line, and the difference between the common logarithms of each organic EL element ( log[electron mobility ⁇ e ] ⁇ log[hole mobility ⁇ h ]) was obtained.
  • the organic EL devices of the present invention of Examples are superior to the organic EL devices of Comparative Examples in terms of luminous efficiency and driving life, and are capable of suppressing deterioration in performance during production in air. I understand.
  • an organic EL device having a light-emitting layer containing a polymer with a conductivity of 1 [S/m] or less is an organic EL device that does not.
  • the relative values of the EQE ratio and LT ratio under inert gas are high, and the decrease in these values is suppressed.
  • Example 2 ⁇ Production of organic EL element under inert gas> ⁇ Production of Organic EL Element A (200A)>>
  • the coating solution for forming the light-emitting layer in the formation of the light-emitting layer was changed as follows, and the solid content ratio (parts by mass) of the polymer, the host compound, and the light-emitting dopant was changed to
  • An organic EL device 200A was manufactured in the same manner except for the changes shown in Table III.
  • a hole mobility measuring device 200H was manufactured in the same manner as the organic EL device 100H.
  • each organic EL element B (201B) was manufactured in the same manner except that the type of polymer in the coating liquid for forming the light emitting layer in the formation of the light emitting layer was changed as shown in Table III. ⁇ 213B), H (201H-213H) and E (201E-213E) were prepared.
  • the organic EL devices of Examples of the present invention are superior to the organic EL devices of Comparative Examples in luminous efficiency and driving life, and It can be seen that both suppression of performance deterioration during manufacturing can be achieved.
  • Example 3 ⁇ Production of organic EL element under inert gas> ⁇ Production of organic EL elements A (300A and 301A), organic EL elements H (300B and 301B, for hole mobility measurement), and organic EL elements E (300B and 301B, for electron mobility measurement)>>>
  • the organic EL element 100A was produced in the same manner except that the coating solution for forming the light-emitting layer in the formation of the light-emitting layer was changed as follows and the conditions were changed to those described in Table IV.
  • EL elements A (300A and 301A), H (300H and 301H), and E (300H and 301H) were manufactured, respectively.
  • Organic EL elements B (300B and 301B) were manufactured in the same manner as in the manufacture of the organic EL elements 300A and 301A under the inert gas, except that air (50% humidity) was used as the atmosphere for film formation of the light-emitting layer.
  • the organic EL device of the present invention has excellent luminous efficiency and drive life due to the fact that the polymer is a mixture of components with different stereoregularities, and suppresses performance deterioration during manufacturing in the atmosphere. and can be further compatible.
  • Example 4 ⁇ Production of organic EL element under inert gas> ⁇ Production of Organic EL Element A (400A)>>
  • the coating solution for forming the light-emitting layer in the formation of the light-emitting layer was changed as follows, and the solid content ratio (parts by mass) of the polymer, host compound, and light-emitting dopant was changed as shown in Table V.
  • An organic EL device 400A was manufactured in the same manner except for the changes.
  • a hole mobility measuring device 400H was manufactured in the same manner as the organic EL device 100H.
  • Organic EL element 400B was produced in the same manner as in the production of organic EL element 400A under the inert gas, except that air (50% humidity) was used as the atmosphere for film formation of the light-emitting layer.
  • each organic EL element B (401B ⁇ 407B), H (401H-407H) and E (401E-407E) were prepared.
  • the problems of the present invention can be solved by controlling the difference between the hole mobility and the electron mobility with the charge-transporting host compound, the light-emitting dopant, the polymer, etc. contained in the light-emitting layer. That is, an organic electroluminescence element that has high luminous efficiency, has a long life, can suppress performance deterioration during manufacturing in the atmosphere, and can be manufactured at low cost, a method for manufacturing the same, a lighting device, and a display Equipment can be provided.
  • An organic electroluminescence element that has high luminous efficiency, has a long life, can suppress deterioration in performance during manufacturing in the atmosphere, and can be manufactured at low cost, a method for manufacturing the same, and a lighting device equipped with the same , a display device and a printed model can be provided.

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Abstract

La présente invention concerne : un élément électroluminescent organique qui peut être produit à faible coût, tout en ayant un rendement lumineux élevé et une longue durée de vie, et qui peut être supprimé dans la détérioration des performances pendant la production dans l'atmosphère ; un procédé de production de cet élément électroluminescent organique ; un dispositif d'éclairage ; un dispositif d'affichage ; et un modèle imprimé qui comprend cet élément électroluminescent organique, ce dispositif d'éclairage ou ce dispositif d'affichage.　L'invention concerne également un élément électroluminescent organique qui comprend, au moins sur un substrat, une partie d'affichage d'image qui est maintenue entre une électrode positive et une électrode négative se faisant face, et qui est caractérisée en ce que : la partie d'affichage d'image est composée d'une partie d'affichage d'image électroluminescente et d'une partie d'affichage d'image non électroluminescente ; la partie d'affichage d'image électroluminescente comprend au moins une électrode et une couche électroluminescente qui est adjacente à une couche d'injection de charge ou à une couche de transport de charge ; la couche électroluminescente contient un polymère qui a une conductivité électrique inférieure ou égale à 1 (S/m), un composé hôte de transport de charge et un dopant électroluminescent ; le rapport en masse du polymère se situe dans la plage de 5 à 80 si la masse totale de la couche électroluminescente est prise en tant que 100 ; et la valeur absolue de la différence entre les logarithmes communs de la mobilité des trous et la mobilité des électrons de la couche électroluminescente est inférieure ou égale à 4,5.
PCT/JP2021/046667 2021-01-29 2021-12-17 Élément électroluminescent organique, son procédé de production, dispositif d'éclairage le comportant, dispositif d'affichage et modèle imprimé WO2022163199A1 (fr)

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JP2020164518A (ja) * 2019-03-26 2020-10-08 大阪ガスケミカル株式会社 フルオレン化合物およびその製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117019578A (zh) * 2023-10-10 2023-11-10 芯体素(杭州)科技发展有限公司 微透镜基板及其制备方法、涂胶装置
CN117019578B (zh) * 2023-10-10 2024-01-09 芯体素(杭州)科技发展有限公司 微透镜基板及其制备方法、涂胶装置

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