WO2020262112A1 - Dispositif électroluminescent organique, et procédé de fabrication de celui-ci - Google Patents

Dispositif électroluminescent organique, et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2020262112A1
WO2020262112A1 PCT/JP2020/023584 JP2020023584W WO2020262112A1 WO 2020262112 A1 WO2020262112 A1 WO 2020262112A1 JP 2020023584 W JP2020023584 W JP 2020023584W WO 2020262112 A1 WO2020262112 A1 WO 2020262112A1
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organic layer
bank
organic
light emitting
emitting region
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PCT/JP2020/023584
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English (en)
Japanese (ja)
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昭雄 海保
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住友化学株式会社
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    • 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
    • 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
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • 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
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/816—Multilayers, e.g. transparent multilayers

Definitions

  • the present invention relates to an organic EL device and a method for manufacturing the same.
  • An organic EL (electroluminescence) device is a device including a light emitting element utilizing electric field emission of an organic compound.
  • Patent Document 1 describes an electroluminescence device in which a liquid-repellent partition wall (bank) is provided on a substrate and a functional layer is formed in a region partitioned by the partition wall. ..
  • An object of the present invention is to provide an organic EL device having a light emitting region in which unevenness of light emitting brightness is reduced.
  • the present invention provides the following organic EL device and a method for manufacturing the organic EL device.
  • An organic EL device having a light emitting region. With the board A bank having a thickness and a width arranged on the substrate so as to surround the light emitting region, Organic layer structure and Including The organic layer structure is used, the number and partial (A) disposed in the light emitting region, a portion (B) which is disposed on the bank have a length L B in the width direction of the bank, the And When the maximum film thickness in the portion (A) is T AS and the central film thickness in the portion (A) is T AC , the organic layer structure portion has the following formula: T AS / T AC ⁇ 1.1 An organic EL device that includes a portion that meets the requirements.
  • the partial maximum film thickness T BS in (B) is greater than the central thickness T AC in the portion (A), an organic EL device described in [1].
  • the L B is 2.5mm or more, [1] to [3] The organic EL device according to any one of.
  • the organic layer structure portion includes a first organic layer and a second organic layer arranged on the first organic layer.
  • the first organic layer is perforated and partial (A1) which is disposed in the light emitting region, a portion (B1) which has a length L B1 in the width direction of the bank is placed on the bank, the And
  • the second organic layer is perforated and partial (A2) which is disposed in the light emitting region, a portion (B2) which have a length L B2 in the width direction of the bank is placed on the bank, the And Wherein L B2 is greater equal to or than with the L B1, an organic EL device described in [5].
  • the organic layer structure includes a portion (A) disposed in the light emitting region, so as to have a portion (B) which is disposed on the bank have a length L B in the width direction of the bank
  • T AS the maximum film thickness in the portion (A)
  • T AC the central film thickness in the portion (A) is T AC
  • the following formula: T AS / T AC ⁇ 1.1 A method for manufacturing an organic EL device, which is formed so as to include a portion that satisfies the above conditions.
  • the organic layer structure has a maximum thickness T BS in the portion (B) is formed to be larger than the central thickness T AC in the portion (A), organic according to [10] A method for manufacturing an EL device.
  • the organic layer structure section, said L B is formed to be above 2.5 mm, [10] or [11] The method for producing an organic EL device according to.
  • the step of forming the organic layer structure portion is A step of applying a coating liquid for forming a first organic layer on a substrate on which the bank is formed to form a first coating film, and The step of drying the first coating film to form the first organic layer, and A step of applying a coating liquid for forming a second organic layer on the first organic layer to form a second coating film, and A step of drying the second coating film to form a second organic layer, and Including Wherein the first organic layer has a portion (A1) which is disposed in the light emitting region, a portion (B1) which is disposed on the bank has a length L B1 in the width direction of the bank, the Formed like The second organic layer has a portion (A2) arranged in the emission region, a portion (B2) which is disposed on the bank have a length L B2 in the width direction of the bank, the as such, and the L B2 is formed to be larger equal to or than even with the L B1, a method of manufacturing an organic EL device described in [13].
  • the step of controlling the liquid repellency includes the step of making the contact angle of at least the upper surface of the bank with respect to the coating liquid for forming the first organic layer less than 10 degrees, according to [10] to [14].
  • the method for manufacturing an organic EL device according to any one.
  • the organic EL device according to the present invention includes a substrate, a bank arranged on the substrate, and an organic layer structure portion.
  • the bank defines the light emitting region of the organic EL device, and is arranged on the substrate so as to surround the light emitting region.
  • the light emitting region of the organic EL device means an area surrounded by the bank among the two-dimensional areas that emit light when a voltage is applied.
  • the organic EL device may have only one light emitting region or may have two or more light emitting regions. For example, two or more light emitting regions may be arranged in a two-dimensional array (or matrix shape) on the substrate.
  • the spacing between the light emitting regions in each column, the spacing between the light emitting regions in each row, the arrangement example of the light emitting regions, the number of light emitting regions, and the like are appropriately set according to the specifications of the organic EL device and the like.
  • the organic EL device may be a top emission type device or a bottom emission type device.
  • the light emitting region of the organic EL device is provided with a light emitting portion which is a structural part for generating light.
  • the light emitting portion includes at least a first electrode (for example, an anode), an organic layer structure portion, and a second electrode (for example, a cathode) in this order from the substrate side.
  • the organic layer structure portion is composed of an organic layer, and may include one layer or two or more organic layers.
  • the organic layer structure is a layer that contributes to light emission of the organic EL device.
  • FIG. 1 is a schematic plan view showing an example of a banked substrate that the organic EL device according to the present invention can have.
  • the banked substrate 10 shown in FIG. 1 has a substrate 11, a first electrode 12 (for example, an anode), and a bank 13.
  • the substrate 11 is a support that supports the first electrode 12 and the bank 13, and is, for example, a plate-shaped transparent member having translucency with respect to visible light (light having a wavelength of 400 nm to 800 nm).
  • the thickness of the substrate 11 is, for example, 30 ⁇ m or more and 1100 ⁇ m or less.
  • the substrate 11 may be, for example, a rigid substrate such as a glass substrate or a silicon substrate, or a flexible substrate such as a plastic substrate or a polymer film. By using a flexible substrate, the organic EL device can have flexibility.
  • a circuit for driving the light emitting unit may be formed in advance on the substrate 11.
  • a TFT Thin Film Transistor
  • a capacitor or the like may be formed in advance on the substrate 11.
  • the first electrode 12 is, for example, an anode.
  • the first electrode 12 may be a cathode and the second electrode may be an anode.
  • the plan view shape of the first electrode 12 shape seen from the thickness direction of the substrate 11
  • a quadrangle such as a rectangle or a square, another polygon, and a quadrangle or another polygon have rounded corners. Examples include the attached shape.
  • the plan view shape of the first electrode 12 may be circular or elliptical.
  • the plan-view shape of the first electrode 12 may be a quadrangle or another polygon in which at least one side is arcuate (for example, arcuate).
  • the plan view means that the layer or the like is viewed from the thickness direction.
  • the first electrode 12 a thin film made of a metal oxide, a metal sulfide, a metal or the like can be used, and specifically, indium oxide, zinc oxide, tin oxide, indium tin oxide (Indium Tin Oxide: abbreviated as ITO). ), Indium Zinc Oxide (abbreviated as IZO), a thin film made of gold, platinum, silver, copper or the like is used.
  • ITO Indium Tin Oxide
  • IZO Indium Zinc Oxide
  • the organic EL device emits light from the substrate 11 side, the first electrode 12 exhibiting light transmission is used.
  • the thickness of the first electrode 12 can be appropriately determined in consideration of light transmission, electrical conductivity, and the like.
  • the thickness of the first electrode 12 is, for example, 10 nm or more and 10 ⁇ m or less, preferably 20 nm or more and 1 ⁇ m or less, and more preferably 50 nm or more and 500 nm or less.
  • a layer composed of an insulating layer or the like may be provided between the first electrode 12 and the substrate 11.
  • a layer composed of an insulating layer or the like can also be regarded as a part of the substrate 11.
  • the bank 13 is a partition wall having a thickness and a width for defining a light emitting region 14 of an organic EL device, in other words, a partition wall having a thickness and a width arranged so as to surround the light emitting region 14. is there.
  • the bank 13 is arranged on the substrate 11, more specifically, on the first electrode 12 formed on the substrate 11. At this time, from the viewpoint of preventing a short circuit between the first electrode 12 and the second electrode, the bank 13 is arranged so as to be arranged directly above at least a part of the peripheral edge portion of the first electrode 12, as shown in FIG. It is preferable to do so.
  • the bank 13 is provided on the substrate 11 in a pattern having an opening in order to partition a preset light emitting region 14 on the surface of the substrate 11.
  • the plan view shape of the bank 13 has a square frame shape, but is not limited to this, and the opening shape and the outer shape of the bank 13 (both are plan view shapes). Is appropriately selected according to the desired shape of the light emitting region 14, the shape of the substrate 11 (both are planar views), and the like.
  • the opening shape (that is, the shape of the light emitting region 14) of the bank 13 usually has an area of 1 mm 2 or more, preferably 5 mm 2 or more, and usually 1 m 2 or less.
  • the opening shape of the bank 13 (that is, the shape of the light emitting region 14) is a square shape such as a square or a rectangle as shown in FIG. 1, and the length of at least one side thereof is It may be 1 mm or more, and the length of two or more sides or all sides may be 1 mm or more. The length of the side may be 5 mm or more, 10 mm or more, and further 20 mm or more.
  • the opening shape of the bank 13 is a square shape, the length of one side is usually 1000 mm or less.
  • the bank 13 can be composed of, for example, one or more kinds of resin compositions.
  • the bank 13 has a viewpoint that the light emitting region 14 can be suitably defined (partitioned) by the bank, and a bank. From the viewpoint of preventing the organic layer from getting wet and spreading outside of 13, at least the upper surface thereof (the surface opposite to the substrate 11) has liquid repellency, and more preferably the upper surface thereof and the upper surface thereof and the surface opposite to the substrate 11 have liquid repellency. Its side surface has liquid repellency.
  • the fact that at least the upper surface of the bank 13 has liquid repellency suppresses uneven shrinkage of the coating film in the drying step of heating the coating film formed so as to be in contact with at least the upper surface of the bank 13 to form an organic layer. It is also advantageous to do.
  • the liquid repellency in the present specification is the liquid repellency to the coating liquid for forming an organic layer used in the coating method.
  • the organic layer in "liquid repellency to a coating liquid for forming an organic layer” is usually the organic layer first formed on the first electrode 12 (the organic layer closest to the first electrode 12), that is, the first organic layer. Is.
  • a layer made of a thermoplastic resin composition containing a liquid-repellent agent a layer made of a cured product of a photosensitive resin composition containing a liquid-repellent agent, or a thermosetting containing a liquid-repellent agent.
  • a bank such as a layer made of a cured product of a thermosetting resin composition, a layer made of a thermoplastic resin, a layer made of a cured product of a photosensitive resin composition, or a layer made of a cured product of a thermosetting resin composition. Examples include banks that have been subjected to liquid repellent treatment.
  • liquid repellent treatment examples include a treatment of applying a liquid repellent agent containing a fluororesin or the like, a treatment of irradiating the coated surface with active energy rays such as ultraviolet rays after the application of the liquid repellent treatment, and the like.
  • the liquid repellency of at least the upper surface of the bank 13 may be controlled by UV ozone treatment.
  • a layer made of a thermoplastic resin composition containing a liquid repellent a layer made of a cured product of a photosensitive resin composition containing a liquid repellent, or a layer made of a cured product of a thermosetting resin composition containing a liquid repellent.
  • the above liquid repellent treatment may be further applied.
  • the contact angle of the upper surface of the bank 13 with the coating liquid is preferably less than 10 degrees. It is more preferably less than or equal to the degree, and further preferably less than 8 degrees.
  • the contact angle of the side surface of the bank 13 with respect to the coating liquid is preferably less than 10 degrees, more preferably 9 degrees or less, and further preferably less than 8 degrees. The contact angle is measured according to the method described in [Example] described later.
  • the bank 13 may have a single-layer structure or a multi-layer structure in which two or more layers are laminated in the thickness direction.
  • the bank 13 preferably has a single-layer structure because the bank 13 is easier to prepare.
  • the cross-sectional shape of the bank 13 is not particularly limited, and for example, the side surface desired for the light emitting region 14 of the bank 13 may be orthogonal to the surface of the substrate 11 or may be inclined so as to form an acute angle. (Forward taper type).
  • the thickness (height) of the bank 13 is, for example, about 0.3 ⁇ m or more and 10 ⁇ m or less, preferably 0.5 ⁇ m or more and 5 ⁇ m or less.
  • the width of the bank 13 (W shown in FIG. 1) is, for example, about 0.5 mm or more and 20 mm or less, preferably 1 mm or more and 10 mm or less.
  • the outer shape (planar view shape) of the bank 13 is a square shape, the length of one side thereof is, for example, about 0.5 mm or more and 1000 mm or less, preferably about 1 mm or more and 1000 mm or less.
  • the banked substrate 10 can be manufactured, for example, by forming the first electrode 12 on the light emitting region 14 preset on the substrate 11 and then forming the bank 13.
  • the bank 13 can be formed by using, for example, a coating method. Specifically, the coating film containing the material of the bank 13 is applied to the substrate 11 on which the first electrode 12 is formed, the coating film is dried, and if necessary, the coating film is cured. Can be formed by patterning in a predetermined shape. Examples of the coating method include a spin coating method and a slit coating method.
  • the solvent of the coating liquid containing the material of bank 13 may be any solvent that can dissolve the material of bank 13.
  • the bank 13 is a direct drawing method in which a coating film patterned by, for example, an inkjet coating method, a screen printing method, a gravure printing method, a flexographic printing method, a dispenser coating method, a nozzle coating method, or the like is formed, and a curing treatment is performed as necessary. It can also be formed by.
  • a light emitting portion is provided in the light emitting region of the organic EL device, and the light emitting portion includes at least a first electrode (for example, an anode), an organic layer structure portion, and a second light emitting portion. Includes electrodes (eg, cathodes).
  • the organic layer structure portion is composed of an organic layer between the first electrode and the second electrode, and may include one layer or two or more organic layers, and usually two or more organic layers are included.
  • the first organic layer means an organic layer first formed on the first electrode 12 (the organic layer closest to the first electrode 12).
  • the first organic layer is preferably a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer or an electron injection layer, more preferably a hole injection layer or a light emitting layer, and further preferably a hole injection. It is a layer.
  • the light emitting unit further has at least a light emitting layer as an organic layer other than the first organic layer.
  • the light emitting portion may have only the first organic layer as the organic layer, but it is preferable that the first organic layer further contains another organic layer.
  • the hole injection layer is an organic layer having a function of improving the hole injection efficiency from the anode (for example, the first electrode 12) to the light emitting layer.
  • a known hole injection material can be used as the material of the hole injection layer.
  • the hole injection material include oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide and aluminum oxide; phenylamine compounds; starburst amine compounds; phthalocyanine compounds; amorphous carbon; polyaniline; polyethylene dioxythiophene (PEDOT). Polythiophene derivatives such as.
  • the light emitting layer is an organic layer having a function of emitting light having a predetermined wavelength.
  • the light emitting layer is usually formed mainly of an organic substance that emits fluorescence and / or phosphorescence, or a dopant that assists the organic substance. Dopants are added, for example, to improve luminous efficiency and change the emission wavelength.
  • the organic substance contained in the light emitting layer may be a low molecular weight compound or a high molecular weight compound. Examples of the light emitting material constituting the light emitting layer include the following pigment-based materials, metal complex-based materials, polymer-based materials, and dopant materials.
  • dye-based luminescent material examples include cyclopendamine or a derivative thereof, tetraphenylbutadiene or a derivative thereof, triphenylamine or a derivative thereof, oxadiazole or a derivative thereof, pyrazoloquinolin or a derivative thereof, distyrylbenzene or a derivative thereof.
  • Examples of the light emitting material of the metal complex system include rare earth metals such as Tb, Eu, and Dy, or Al, Zn, Be, Pt, and Ir as the central metal, and oxadiazole, thiadiazole, phenylpyridine, and phenylbenzo. Examples thereof include metal complexes having an imidazole, quinoline structure or the like as a ligand. Examples of the metal complex include a metal complex that emits light from a triple-term excited state such as an iridium complex and a platinum complex, an aluminum quinolinol complex, a benzoquinolinol berylium complex, a benzoxazolyl zinc complex, a benzothiazole zinc complex, and an azomethylzinc complex. , Porphyrin zinc complex, phenanthroline europium complex and the like.
  • polymer-based luminescent material examples include polyparaphenylene vinylene or its derivative, polythiophene or its derivative, polyparaphenylene or its derivative, polysilane or its derivative, polyacetylene or its derivative, polyfluorene or its derivative, polyvinylcarbazole or the like.
  • the above-mentioned dye material a material obtained by polymerizing a metal complex material, and the like can be mentioned.
  • red light-emitting material includes, for example, coumarin or a derivative thereof, a thiophene ring compound, a polymer thereof, polyparaphenylene vinylene or a derivative thereof. , Polythiophene or a derivative thereof, polyfluorene or a derivative thereof, and the like.
  • red light emitting material examples include materials disclosed in Japanese Patent Application Laid-Open No. 2011-105701.
  • green light emitting material examples include quinacridone or a derivative thereof, coumarin or a derivative thereof, and a polymer thereof, polyparaphenylene vinylene or a derivative thereof, polyfluorene or a derivative thereof. Derivatives and the like can be mentioned.
  • examples of the green light emitting material include materials disclosed in Japanese Patent Application Laid-Open No. 2012-0363888.
  • blue light emitting material examples include distyrylarylene or a derivative thereof, oxadiazole or a derivative thereof, a polymer thereof, polyvinylcarbazole or a derivative thereof, and polypara. Examples thereof include phenylene or a derivative thereof, polyfluorene or a derivative thereof. Examples of the blue light emitting material include materials disclosed in Japanese Patent Application Laid-Open No. 2012-144722.
  • Examples of the dopant material include perylene or its derivative, coumarin or its derivative, rubrene or its derivative, quinacridone or its derivative, squalium or its derivative, porphyrin or its derivative, styryl dye, tetracene or its derivative, pyrazolone or its derivative, Examples thereof include decacyclene or a derivative thereof, phenoxazone or a derivative thereof.
  • the optimum value of the thickness of the light emitting layer differs depending on the material used, and is appropriately determined in consideration of the required characteristics and the ease of forming the layer.
  • the thickness of the light emitting layer is, for example, 1 nm or more and 1 ⁇ m or less, preferably 2 nm or more and 500 nm or less, and more preferably 5 nm or more and 200 nm or less.
  • the electron injection layer is a layer having a function of improving the electron injection efficiency from the cathode to the light emitting layer.
  • a known electron injection material can be used for the electron injection layer.
  • the thickness of the electron injection layer varies depending on the material used and the like, but is, for example, 1 nm or more and 50 nm or less.
  • the organic layer structure portion is an element forming the light emitting portion, and is basically within the light emitting region 14 (opening of the bank 13) defined by the bank 13.
  • the present invention is characterized in that the organic layer structure portion has a portion (A) arranged in the light emitting region 14 and a portion (B) arranged on the bank 13. To do.
  • FIG. 2 is a schematic cross-sectional view showing a partially enlarged view of the periphery of the bank in an example of the organic EL device according to the present invention.
  • the organic layer structure portion 1 has a portion (A) arranged in the light emitting region 14 and a portion (B) arranged on the bank 13.
  • Portions organic layer structure 1 is extending over the bank 13 beyond the light-emitting region 14, i.e. the length of the portion (B), a length in the width W direction of the bank 13, the length L B There, L B is greater than zero, preferably less than the width W of the bank 13.
  • the organic layer structure portion 1 When the organic layer structure portion 1 is formed by a coating method or the like, the organic layer structure portion 1 has a portion having the largest thickness in the vicinity of the light emitting region 14 side end portion of the bank 13.
  • the maximum film thickness in the portion (A) of the organic layer structure portion 1 is referred to as " TAS ".
  • the position where the portion (A) has the maximum film thickness T AS usually exists in a range from a position of about 100 ⁇ m from the light emitting region 14 side end of the bank 13 to a position of about 1000 ⁇ m from the light emitting region 14 side end. ..
  • the central film thickness in the portion (A) of the organic layer structure portion 1 is referred to as “ TAC ”.
  • the central film thickness TAC means the film thickness at the center point of the portion (A). So as to have a portion (B), i.e., by the end to form an organic layer structure 1 so as to be located on the bank 13, closer to the ratio T AS / T AC and T AS and T AC 1 This makes it possible to reduce unevenness in emission brightness within the emission region 14. From the viewpoint of reducing unevenness of emission brightness, the ratio T AS / T AC is 1.0 or more and 1.1 or less, preferably 1.0 or more and 1.05 or less, and more preferably 1.0. ..
  • a coating method using a coating liquid for forming the organic layer constituting the organic layer structure portion 1 is preferable, and more preferably, inkjet printing. It is a law.
  • the length L B is preferably not 2.5mm or more, and more preferably 3mm or more.
  • the maximum film thickness in the portion (B) of the organic layer structure portion 1 is referred to as “ TBS ”.
  • TBS the maximum thickness in the organic layer structure 1 of part (B) is preferably greater than the center thickness T AC at the portion (A).
  • Such a thickness relationship can be realized by adopting a coating method for forming the organic layer structure portion 1 and then adjusting the concentration, viscosity, coating film drying method, and the like of the coating liquid. Satisfying the thickness relationship is advantageous in providing an organic EL device having a light emitting region in which unevenness of light emission brightness is reduced.
  • the central film thickness T AC in the portion (A) of the organic layer structure portion 1, the maximum film thickness T AS in the portion (A), and the maximum film thickness T BS in the portion (B) carefully cut the prepared organic EL device.
  • An image is acquired of the exposed cross section using a scanning transmission electron microscope, and one point arbitrarily selected from this image is actually measured according to the above definition.
  • Part (B) of the length L B (same for L B1, L B2 and L B3 which will be described later), for forming organic layer structure 1 (or organic layer) is measured using a precision length measuring machine ..
  • Value of the center thickness T AC of the organic layer structure first portion (A) is, for example, 10nm or more 10 ⁇ m or less, preferably 50nm or more 5 ⁇ m or less.
  • the first organic layer is an organic layer constituting the organic layer structure, and when the organic layer structure is composed of two or more organic layers, the first of these organic layers is the first. It is an organic layer arranged near the electrode 12.
  • the first organic layer has a portion (A1) arranged in the light emitting region 14 and a portion (B1) arranged on the bank 13 from the viewpoint of reducing unevenness of the emission brightness in the light emitting region 14. Is preferable.
  • the length of the portion (B1) in which the first organic layer extends beyond the light emitting region 14 to the top of the bank 13 is the length of the bank 13 in the width W direction, and is the length LB1 .
  • LB1 is greater than zero and preferably less than the width W of bank 13.
  • the first organic layer having the portion (B1) From the viewpoint of reducing uneven emission brightness over as wide a region as possible within the light emitting region 14, it is preferable that as many ends of the first organic layer as possible are located on the bank 13, and all of the first organic layer. More preferably, the ends are located on the bank 13.
  • a coating method using a coating liquid for forming the first organic layer is preferable, and an inkjet printing method is more preferable.
  • the value of the central film thickness in the portion (A1) of the first organic layer is not particularly limited as long as the function of the first organic layer is exhibited, and may be a thickness corresponding to the function.
  • the optimum value of the central film thickness may differ depending on the material of the first organic layer.
  • its central film thickness is, for example, 1 nm or more and 1 ⁇ m or less, preferably 2 nm or more and 500 nm or less, and more preferably 5 nm or more and 200 nm or less.
  • the first organic layer when the first organic layer is a light emitting layer, its central film thickness is, for example, 1 nm or more and 2 ⁇ m or less, preferably 5 nm or more and 500 nm or less, and more preferably 10 nm or more and 200 nm or less.
  • its central film thickness is, for example, 1 nm or more and 50 nm or less.
  • the organic layer structure portion 1 formed in the light emitting region 14 can include organic layers other than the first organic layer.
  • Examples of the organic layer other than the first organic layer include the second organic layer and the second organic layer provided adjacent to the first organic layer (the side opposite to the first electrode 12 side in the first organic layer).
  • Examples thereof include a third organic layer provided adjacent to (the side of the second organic layer opposite to the first electrode 12 side).
  • the organic layer structure portion 1 may include four or more organic layers.
  • Examples of the layer structure of the organic layer structure portion having only the first organic layer as the organic layer and the layer structure of the organic layer structure portion including the first organic layer and other organic layers other than the first organic layer include, for example.
  • the following layer structure can be mentioned.
  • (A) 1st electrode / light emitting layer / 2nd electrode (b) 1st electrode / hole injection layer / light emitting layer / 2nd electrode (c) 1st electrode / hole injection layer / light emitting layer / electron injection layer / 2nd electrode (d) 1st electrode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / 2nd electrode (e) 1st electrode / hole injection layer / hole transport layer / light emitting layer / first 2 electrode (f) 1st electrode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / 2nd electrode (g) 1st electrode / hole injection layer / hole transport layer / light emitting layer / electron Transport layer
  • the hole transport layer is a layer having a function of improving hole injection from the anode, the hole injection layer, or the like into the light emitting layer.
  • a known hole transporting material can be used as the material of the hole transporting layer.
  • the material of the hole transport layer include polyvinylcarbazole or its derivative, polysilane or its derivative, polysiloxane or its derivative having an aromatic amine in the side chain or main chain, pyrazoline or its derivative, arylamine or its derivative, and the like.
  • Stilben or its derivatives triphenyldiamine or its derivatives, polyaniline or its derivatives, polythiophene or its derivatives, polyarylamine or its derivatives, polypyrrole or its derivatives, poly (p-phenylene vinylene) or its derivatives, and poly (2, 5-Thienylene binylene) or a derivative thereof and the like can be mentioned. Further, the hole transport material disclosed in JP2012-144722A can also be mentioned.
  • the central film thickness of the second organic layer (the film thickness at the center of the second organic layer) varies depending on the material used and the like, but is, for example, 1 nm or more and 1 ⁇ m or less. It is preferably 2 nm or more and 500 nm or less, and more preferably 5 nm or more and 200 nm or less. The same applies when the third organic layer is a hole transport layer.
  • the electron transport layer is a layer having a function of improving electron injection from a cathode, an electron injection layer, or the like.
  • a known electron transport material can be used for the electron transport layer.
  • the central film thickness of the second organic layer (the film thickness at the center of the second organic layer) varies depending on the material used and the like, but is, for example, 1 nm or more and 1 ⁇ m or less. It is preferably 2 nm or more and 500 nm or less, and more preferably 5 nm or more and 200 nm or less. The same applies when the third organic layer is an electron transport layer.
  • FIG. 3 is a schematic cross-sectional view showing a partially enlarged view of the periphery of the bank in another example of the organic EL device according to the present invention.
  • the organic EL device shown in FIG. 3 includes an organic layer structure portion 1 having a two-layer structure of a first organic layer 1a and a second organic layer 1b.
  • the organic layer structure 1 includes the first organic layer 1a and the second organic layer 1b arranged on the first organic layer 1a
  • the second organic layer 1b preferably has a portion (A2) arranged in the light emitting region 14 and a portion (B2) arranged on the bank 13. From the viewpoint of reducing the above amount.
  • the length of the portion where the second organic layer 1b extends beyond the light emitting region 14 to the top of the bank 13, that is, the portion (B2) is the length in the width W direction of the bank 13, and the length L B2 .
  • LB2 is greater than zero and preferably less than the width W of bank 13.
  • the length L B2 of the portion (B2) of the second organic layer 1b is the same as the length L B1 of the portion (B1) of the first organic layer 1a. Or larger than that.
  • the length L B2 portion (B2) of the second organic layer 1b is the same as the length L B of the portion of the organic layer structure 1 shown in FIG. 2 (B) is there.
  • the organic layer structure 1 further includes a third organic layer arranged on the second organic layer 1b.
  • the third organic layer has a portion (A3) arranged in the light emitting region 14 and a portion (B3) arranged on the bank 13.
  • the length of the portion where the third organic layer extends beyond the light emitting region 14 to the top of the bank 13, that is, the portion (B3) is the length in the width W direction of the bank 13, and is the length LB3 .
  • LB3 is greater than zero and preferably less than the width W of bank 13.
  • the length L B3 of the portion of the third organic layer (B3) is either the same as the length L B2 portion (B2) of the second organic layer 1b Or it is preferably larger than that.
  • the third organic layer As many ends of the third organic layer as possible are located on the bank 13, and all of the third organic layer. More preferably, the ends are located on the bank 13.
  • the film thickness and length of each organic layer constituting the organic layer structure portion 1 can be measured in the same manner as the various film thicknesses and lengths of the organic layer structure portion 1.
  • the second electrode is, for example, a cathode.
  • the cathode is provided on one or more organic layers contained in the light emitting portion.
  • As the material of the cathode a material having a small work function, easy electron injection into the light emitting layer, and high electric conductivity is preferable.
  • the organic EL device extracts light from the anode side, the light emitted from the light emitting layer is reflected by the cathode toward the anode side, so that a material having a high visible light reflectance is preferable as the material of the cathode.
  • the cathode for example, an alkali metal, an alkaline earth metal, a transition metal, a group 13 metal of the periodic table, or the like can be used.
  • a transparent conductive cathode made of a conductive metal oxide, a conductive organic substance, or the like can also be used.
  • the thickness of the cathode is appropriately set in consideration of electrical conductivity and durability.
  • the thickness of the cathode is, for example, 10 nm or more and 10 ⁇ m or less, preferably 20 nm or more and 1 ⁇ m or less, and more preferably 50 nm or more and 500 nm or less.
  • a cathode may be provided for each light emitting region, or a cathode common to all light emitting regions 14 across the bank 13. May be provided.
  • a sealing substrate is usually provided on the second electrode of the organic EL device.
  • the organic EL device may include, for example, other known elements included in the organic EL lighting device and the organic EL display.
  • the method for manufacturing an organic EL device includes the following steps.
  • a step of forming a bank 13 having a thickness and a width on the substrate 11 (bank forming step) for defining a light emitting region 14.
  • a step of controlling the liquid repellency of the upper surface of the bank 13 (liquid repellency control step)
  • a step of forming an organic layer structure portion on a substrate 11 on which a bank 13 is formed by a coating method (organic layer structure portion forming step).
  • the manufacturing method according to the present invention is suitable as a method for manufacturing the organic EL device according to the present invention.
  • the organic layer structure forming step usually includes the step of forming the first organic layer 1a described above.
  • the first organic layer 1a can be formed by the following steps. A step of applying a coating liquid for forming a first organic layer to form a first coating film (first coating step), and a step of drying the first coating film to form a first organic layer 1a (first drying). Process).
  • the production method further includes the following steps after the first drying step.
  • Step of forming (second drying step).
  • the manufacturing method further includes the following steps after the second drying step.
  • the bank forming step is usually a step of producing a banked substrate 10 as shown in FIG. 1, for example.
  • the above description is cited for the substrate 11, the first electrode 12, and the bank 13 constituting the banked substrate 10, and the method for manufacturing the banked substrate 10.
  • the liquid repellency control step is a step of adjusting the liquid repellency of at least the upper surface of the bank 13.
  • a layer made of a thermoplastic resin composition containing a liquid repellent As a method for adjusting (controlling) the liquid repellency of at least the upper surface of the bank 13, a layer made of a thermoplastic resin composition containing a liquid repellent, a layer made of a cured product of a photosensitive resin composition containing a liquid repellent, or repellent.
  • a method of applying a liquid repellent treatment to at least the upper surface of the bank 13 can be mentioned.
  • the liquid repellent control step is a part of the bank forming step.
  • the liquid repellent treatment in the latter case include a treatment of applying a liquid repellent agent containing a fluororesin and the like, and a treatment of irradiating the coated surface with active energy rays such as ultraviolet rays after the application of the liquid repellent agent.
  • the liquid repellency of at least the upper surface of the bank 13 may be controlled by UV ozone treatment.
  • a layer made of a thermoplastic resin composition containing a liquid repellent On at least the upper surface of a layer made of a thermoplastic resin composition containing a liquid repellent, a layer made of a cured product of a photosensitive resin composition containing a liquid repellent, or a layer made of a cured product of a thermosetting resin composition containing a liquid repellent.
  • the above liquid repellent treatment may be further applied.
  • the liquid repellent control step is performed by the contact angle of the upper surface of the bank 13 with respect to the coating liquid ( ⁇ organic EL device).
  • >) Is preferably less than 10 degrees, more preferably 9 degrees or less, and even more preferably less than 8 degrees in the step of adjusting the liquid repellency of the upper surface of the bank 13.
  • the contact angle of the side surface of the bank 13 with respect to the coating liquid is preferably less than 10 degrees, more preferably 9 degrees or less, and further preferably less than 8 degrees.
  • the liquid repellency of the side surface of the bank 13 is adjusted so as to be.
  • the contact angle is usually the contact angle with respect to the coating liquid for forming the first organic layer.
  • the organic layer structure part 1 can be formed by a coating method in which the coating film is dried after the coating liquid is applied.
  • the coating method of the coating liquid include an inkjet printing method.
  • other known coating methods for example, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, spray, as long as the coating method can form a layer in the opening of the bank 13.
  • a coating method, a screen printing method, a flexographic printing method, an offset printing method, or a nozzle printing method may be used.
  • the solvent contained in the coating liquid is not particularly limited as long as it can dissolve the functional material contained in the coating liquid, and is, for example, a chloride solvent such as chloroform, methylene chloride or dichloroethane; an ether solvent such as tetrahydrofuran or butyl cellosolve; toluene.
  • a chloride solvent such as chloroform, methylene chloride or dichloroethane
  • an ether solvent such as tetrahydrofuran or butyl cellosolve
  • toluene toluene.
  • Aromatic hydrocarbon solvents such as xylene, cyclohexylbenzene; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, ethyl cell solve acetate, butyl lactate; methanol, ethanol, propanol, 2-ethyl Examples thereof include an alcohol solvent such as hexanol. Only one type of solvent may be used, or two or more types may be used in combination.
  • the method for drying the coating film is not particularly limited as long as the first coating film can be dried, and examples thereof include vacuum drying and heat drying.
  • the organic layer structure part 1 may be composed of two or more organic layers. In this case, two or more organic layers are formed by repeating the above-mentioned coating and drying.
  • the organic layer structure 1 has a portion (A) disposed within the light emitting region 14, and a portion (B) which is disposed on the bank 13 have a length L B in the width W direction of the bank 13 It is carried out as.
  • the length L B is greater than zero, preferably less than the width W of the bank 13.
  • the ratio T AS / T AC is 1.0 or more and 1.1 or less, preferably 1.0 or more and 1.05 or less, and more preferably 1.0. ..
  • the length L B is preferably not 2.5mm or more, and more preferably 3mm or more.
  • the organic layer structure portion 1 is preferably formed so that as many ends as possible are located on the bank 13, and all the ends. It is more preferable that the portion is formed so as to be located on the bank 13.
  • the organic layer structure 1, part (B) maximum film thickness T BS is preferably formed to be larger than the central thickness T AC at the portion (A) in the.
  • Such a thickness relationship can be realized by adjusting the concentration, viscosity, coating film drying method, etc. of the coating liquid in the coating method using the coating liquid. Satisfying the thickness relationship is advantageous in providing an organic EL device having a light emitting region in which unevenness of light emission brightness is reduced.
  • a coating liquid for forming the first organic layer is applied to the opening (light emitting region 14) of the bank 13.
  • the first organic layer 1a can be formed by forming one coating film (first coating step) and then drying the first coating film (first drying step).
  • the coating liquid for forming the first organic layer may be a coating liquid containing a hole injection material, a coating liquid containing a light emitting material, a coating liquid containing an electron injection material, or the like. Examples of the coating method of the coating liquid and the drying method of the coating film are as described above.
  • the first coating step includes the portion (A1) in which the first organic layer 1a obtained through the first drying step is arranged in the light emitting region 14.
  • the bank 13 has a length LB1 in the width W direction and has a portion (B1) arranged on the bank 13.
  • the length LB1 is greater than zero and preferably less than the width W of the bank 13.
  • a coating liquid for forming a second organic layer is applied onto the first organic layer 1a to form a second coating film (second coating step).
  • the second organic layer 1b can then be formed by drying the second coating film (second drying step).
  • the coating liquid for forming the second organic layer may be a coating liquid containing a hole transport material, a coating liquid containing a light emitting material, a coating liquid containing an electron transport material, a coating liquid containing an electron injection material, or the like. Examples of the solvent contained in the coating liquid for forming the second organic layer, the coating method of the coating liquid, and the drying method of the coating film are as described above.
  • the second coating step includes the portion (A2) in which the second organic layer 1b obtained through the second drying step is arranged in the light emitting region 14.
  • the bank 13 has a length LB2 in the width W direction and has a portion (B2) arranged on the bank 13.
  • the length LB2 is greater than zero and preferably less than the width W of the bank 13.
  • the length L B2 of the portion (B2) of the second organic layer 1b is the same as the length L B1 of the portion (B) of the first organic layer 1a. Or larger than that.
  • a coating liquid for forming a third organic layer is applied onto the second organic layer 1b to form a third coating film (third coating step), and then the third coating film is dried (third drying step). ), A third organic layer can be formed.
  • the coating liquid for forming the third organic layer is a coating liquid containing a light emitting material, a coating liquid containing an electron transport material, a coating liquid containing an electron injection material, a coating liquid containing a hole transport material, and a coating liquid containing a hole injection material. It can be a liquid or the like. Examples of the solvent contained in the coating liquid for forming the third organic layer, the coating method of the coating liquid, and the drying method of the coating film are as described above.
  • the third coating step includes a portion (A3) in which the third organic layer obtained through the third drying step is arranged in the light emitting region 14. It is preferable that the bank 13 has a length LB3 in the width W direction and has a portion (B3) arranged on the bank 13. The length LB3 is greater than zero and preferably less than the width W of the bank 13.
  • the length L B3 of the portion of the third organic layer (B3) is either the same as the length L B2 portion (B2) of the second organic layer 1b Or it is preferably larger than that.
  • the fourth and subsequent organic layers can be formed in the same manner as the first to third organic layers.
  • An organic EL device can be obtained by performing a step of forming a second electrode (for example, a cathode) after forming a desired one or more organic layers.
  • a second electrode for example, a cathode
  • Examples of the method for forming the second electrode include a vapor deposition method and a coating method similar to those for the first electrode 12.
  • [B] Film thickness and length of layer portion The central film thickness and maximum film thickness of the organic layer structure were measured according to the above definitions. Specifically, an image was acquired of a cross section exposed by carefully cutting the produced organic EL device using a scanning transmission electron microscope, and one point arbitrarily selected from this image was centered according to the above definition. The film thickness and the maximum film thickness were measured. The length of the layer portions such as L B was measured using a precision length measuring machine. L B shown in Table 1 below, L B1, the value of L B2, L B3 and L B4, the average of the measurements at the central position of each side of the formed in a square shape organic layer structure or the organic layer (Average of 4 points).
  • a banked substrate 10 having the configuration shown in FIG. 1 was prepared.
  • the outer shape of the substrate 11 was a square having a side length of about 50 mm.
  • the material of the substrate 11 is glass.
  • the outer shape of the bank 13 was a square having a side length of about 34 mm, the opening shape of the bank 13 was a square having a side length of about 22 mm, and the width W of the bank 13 was about 6 mm.
  • the bank 13 is a layer (single layer structure) formed by curing a photosensitive resin composition containing a liquid repellent, and after forming the layer, the surfaces (upper surface and side surfaces) are subjected to UV ozone treatment to obtain a first layer.
  • the contact angles of the upper surface and the side surface of the bank 13 with respect to the coating liquid for forming the organic layer were reduced to about 8 degrees.
  • the bank 13 is aligned so as to be arranged directly above a part of the peripheral edge portion of the first electrode 12 (anode).
  • a first organic layer 1a (hole injection layer) was formed in the light emitting region 14 (opening of the bank 13) of the banked substrate 10 by the following procedure.
  • a coating liquid for forming a first organic layer containing a hole injection material was prepared.
  • a first coating film was formed in the light emitting region 14 by an inkjet printing method using this coating liquid, and then the first coating film was dried on a hot plate to form a first organic layer 1a.
  • the length L B1 portion (B1) of the first organic layer 1a shown in Table 1. All the ends of the first organic layer 1a in this experimental example were located on the bank 13.
  • the second organic layer 1b (hole transport layer) was formed on the first organic layer 1a by the following procedure.
  • a coating liquid for forming a second organic layer containing a hole transport material was prepared.
  • a second coating film was formed on the first organic layer 1a by an inkjet printing method using this coating liquid, and then the second coating film was dried on a hot plate to form a second organic layer 1b.
  • the length L B2 of the portion (B2) of the second organic layer 1b is shown in Table 1. All the ends of the second organic layer 1b in this experimental example were located on the bank 13.
  • a third organic layer (light emitting layer) was formed on the second organic layer 1b by the following procedure.
  • a coating liquid for forming a third organic layer containing a luminescent material was prepared.
  • a third coating film was formed on the second organic layer 1b by an inkjet printing method using this coating liquid, and then the third coating film was dried on a hot plate to form a third organic layer.
  • the length L B3 of the portion (B3) of the third organic layer is shown in Table 1. All the ends of the third organic layer in this experimental example were located on the bank 13.
  • a fourth organic layer (electron transport layer) was formed on the third organic layer.
  • a coating liquid for forming a fourth organic layer containing an electron transport material was prepared.
  • a fourth coating film was formed on the third organic layer by an inkjet printing method using this coating liquid, and then the fourth coating film was dried on a hot plate to form a fourth organic layer.
  • an electron injection layer (inorganic layer) and a cathode were formed on the fourth organic layer by a vapor deposition method and sealed in a nitrogen atmosphere to obtain an organic EL device.
  • the length L B4 of the portion (B4) of the fourth organic layer is shown in Table 1.
  • 1 Organic layer structure 1a 1st organic layer, 1b 2nd organic layer, 10 Banked substrate, 11 substrate, 12 1st electrode, 13 bank, 14 light emitting region.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention fournit un dispositif électroluminescent organique qui possède une région de luminescence dans laquelle les irrégularité de brillance de luminescence sont réduites.　Plus précisément, l'invention fournit un dispositif électroluminescent organique qui possède une région de luminescence, qui contient un substrat, un banc possédant une épaisseur et une largeur disposé sur ledit substrat de manière à entourer la région de luminescence, et une partie structure de couches organiques, et dans lequel la partie structure de couches organiques possède une portion (A) disposée à l'intérieur de la région de luminescence, et une portion (B) possédant une longueur (ＬＢ) dans la direction largeur du banc et disposée sur le banc. Lorsque l'épaisseur de film maximale au niveau de la portion (A) est représentée par ＴＡＳ, et que l'épaisseur de film central dans la portion (A) est représentée par ＴＡＣ, alors la partie structure de couches organiques contient une portion satisfaisant la formule ＴＡＳ／ＴＡＣ≦１,１.
PCT/JP2020/023584 2019-06-27 2020-06-16 Dispositif électroluminescent organique, et procédé de fabrication de celui-ci WO2020262112A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070190673A1 (en) * 2006-02-11 2007-08-16 Ko Ick-Hwan Organic light emitting diode and method of manufacturing the same
WO2009038171A1 (fr) * 2007-09-21 2009-03-26 Toppan Printing Co., Ltd. Affichage électroluminescent organique et son procédé de fabrication
WO2009084209A1 (fr) * 2007-12-28 2009-07-09 Panasonic Corporation Dispositif électroluminescent organique, panneau d'affichage électroluminescent organique, et procédé de fabrication du dispositif électroluminescent organique
WO2010038356A1 (fr) * 2008-09-30 2010-04-08 パナソニック株式会社 Dispositif électroluminescent organique et son procédé de fabrication
WO2013190636A1 (fr) * 2012-06-19 2013-12-27 パイオニア株式会社 Panneau électroluminescent organique
US20170005149A1 (en) * 2015-06-30 2017-01-05 Lg Display Co., Ltd. Organic Light Emitting Diode Display Device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070190673A1 (en) * 2006-02-11 2007-08-16 Ko Ick-Hwan Organic light emitting diode and method of manufacturing the same
WO2009038171A1 (fr) * 2007-09-21 2009-03-26 Toppan Printing Co., Ltd. Affichage électroluminescent organique et son procédé de fabrication
WO2009084209A1 (fr) * 2007-12-28 2009-07-09 Panasonic Corporation Dispositif électroluminescent organique, panneau d'affichage électroluminescent organique, et procédé de fabrication du dispositif électroluminescent organique
WO2010038356A1 (fr) * 2008-09-30 2010-04-08 パナソニック株式会社 Dispositif électroluminescent organique et son procédé de fabrication
WO2013190636A1 (fr) * 2012-06-19 2013-12-27 パイオニア株式会社 Panneau électroluminescent organique
US20170005149A1 (en) * 2015-06-30 2017-01-05 Lg Display Co., Ltd. Organic Light Emitting Diode Display Device

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