WO2022025173A1 - 有機ｅｌ表示装置およびその製造方法 - Google Patents

有機ｅｌ表示装置およびその製造方法 Download PDF

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Publication number
WO2022025173A1
WO2022025173A1 PCT/JP2021/028066 JP2021028066W WO2022025173A1 WO 2022025173 A1 WO2022025173 A1 WO 2022025173A1 JP 2021028066 W JP2021028066 W JP 2021028066W WO 2022025173 A1 WO2022025173 A1 WO 2022025173A1
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organic
layer
auxiliary electrode
electrode
display device
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English (en)
French (fr)
Japanese (ja)
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新井猛
三好一登
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Toray Industries Inc
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Toray Industries Inc
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Priority to KR1020227042132A priority Critical patent/KR20230043787A/ko
Priority to JP2021544795A priority patent/JPWO2022025173A1/ja
Priority to CN202180048825.9A priority patent/CN115804246A/zh
Publication of WO2022025173A1 publication Critical patent/WO2022025173A1/ja
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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
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • 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
    • 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
    • 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
    • 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
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to an organic EL display device and a method for manufacturing the same.
  • Organic EL display devices are attracting attention as next-generation flat panel displays.
  • the organic EL is electroluminescence of an organic EL layer made of an organic compound provided between two electrodes.
  • a display device using an organic EL light emitting element is an organic EL display device.
  • Self-luminous organic EL display devices are capable of wide viewing angles, high-speed response, and high-contrast image display, and are also capable of being thinner, lighter, and more flexible, and have been actively researched and developed in recent years. It is being advanced.
  • Organic EL display devices are classified into a bottom emission method that extracts light to the substrate side and a top emission system that extracts light to the opposite surface of the substrate, depending on the light extraction method.
  • the top emission method can improve the area ratio of the display pixels, and can realize a display device having higher luminous efficiency.
  • the electrode on the substrate side is made into an island type and connected to the TFT, and the opposite side of the substrate is a transparent electrode as a common layer. A structure is often used.
  • auxiliary electrodes there is one that utilizes the region on the insulating layer, which is a pixel dividing layer that does not affect light emission, and a method of connecting the auxiliary electrode and the transparent electrode by making the auxiliary electrode an overhang structure (for example, a method (see Patent Document 1) and a method of connecting the electrodes by making the transparent electrode an island type (see, for example, Patent Document 2) have been proposed.
  • Patent Document 2 there is an additional requirement for patterning to make the transparent electrode an island type, and there is an advantage in the manufacturing process of the top emission method in which the transparent electrode can be formed as a common layer on the entire display area in which the display pixels are arranged. Will be damaged.
  • the organic EL display device including the formation of an auxiliary electrode can be manufactured by a simple method, the number of defects of the transparent electrode can be reduced, and the sheet resistance can be reduced. It is an object of the present invention to provide a display device and a manufacturing method thereof.
  • a first aspect of the organic EL display device of the present invention comprises a substrate and a reflective electrode, an insulating layer, an auxiliary electrode, an organic EL layer, and a transparent electrode on the substrate.
  • An auxiliary electrode, an organic EL layer, and a transparent electrode are provided on the insulating layer in this order.
  • the organic EL layer has one or more layers selected from the group consisting of a hole transport layer, a light emitting layer, and an electron transport layer.
  • the maximum height (Rz) in the surface roughness of the auxiliary electrode on the side in contact with the organic EL layer is 30 nm or more and 500 nm or less.
  • the substrate, the organic EL layer, and the transparent electrode are provided in this order, and the reflective electrode is patterned on the substrate and formed in the voids of the reflective electrode.
  • the reflective electrode is patterned on the substrate and formed in the voids of the reflective electrode.
  • the method for manufacturing the organic EL display device of the present invention includes a step of forming a reflective electrode patterned on a substrate, a step of forming an insulating layer in a gap of the reflective electrode, and an auxiliary electrode on the insulating layer.
  • a step of forming the auxiliary electrode, a step of applying a roughening treatment to the auxiliary electrode, a step of forming an organic EL layer covering the entire display area, and a step of forming a transparent electrode covering the entire display area are included in this order.
  • the organic EL display device of the present invention can manufacture an organic EL display device including the formation of an auxiliary electrode by a simple method, can reduce the number of defects of the transparent electrode, and can reduce the sheet resistance. can.
  • the organic EL display device of the present invention is a top-emission organic EL display device having a plurality of display pixels formed on a matrix.
  • a passive drive type that divides the electrodes into columns and rows and emits light only the display pixels sandwiched between the electrodes
  • an active drive type that switches by providing several TFTs in each display pixel. It is separated, but is not particularly limited.
  • a first aspect of the organic EL display device of the present invention comprises a substrate and a reflective electrode, an insulating layer, an auxiliary electrode, an organic EL layer, and a transparent electrode on the substrate.
  • An auxiliary electrode, an organic EL layer, and a transparent electrode are provided on the insulating layer in this order.
  • the organic EL layer has one or more layers selected from the group consisting of a hole transport layer, a light emitting layer, and an electron transport layer.
  • the maximum height (Rz) in the surface roughness of the auxiliary electrode on the side in contact with the organic EL layer is 30 nm or more and 500 nm or less.
  • the second aspect of the organic EL display device of the present invention has a substrate, an organic EL layer, and a transparent electrode in this order, a reflective electrode patterned on the substrate, and an insulating layer formed in the voids of the reflective electrode. And there is an auxiliary electrode on the insulating layer, the organic EL layer and the transparent electrode cover the entire display area, and the maximum height (Rz) in the surface roughness of the auxiliary electrode on the side in contact with the organic EL layer is 30 nm or more and 500 nm or less.
  • the display area refers to an area in which display pixels for display are arranged.
  • FIG. 1 shows a schematic cross-sectional view of a top emission type organic EL display device which is an example of the organic EL display device of the present invention.
  • the top-emission organic EL display device of FIG. 1 has a reflective electrode 2 on a substrate 1.
  • the substrate 1 is made of a base material 13.
  • the insulating layer 3 is provided in the void of the reflective electrode 2, and the auxiliary electrode 4 is further provided on the insulating layer. It has an organic EL layer 5 and a transparent electrode 6 on it. Since the organic EL layer 5 is sandwiched between the reflective electrode 2 and the transparent electrode 6, the light emitted from the organic EL layer 5 is taken out on the opposite surface of the substrate.
  • the substrate may be composed of only the base material described later, or may be a base material provided with wiring, a TFT, or the like.
  • Wiring is often connected to an external device via an FPC (Flexible Printed Circuit) for driving.
  • FPC Flexible Printed Circuit
  • a camera sensors such as ID and fingerprint reading and illuminance, and a pattern antenna for communication and power supply may be provided.
  • the above-mentioned wiring, TFTs, sensors, pattern antennas, etc. formed on the substrate, and the flattening layer described later, which are below the reflective electrode (on the substrate side), are the substrate. Be a part.
  • a flattening layer By providing the flattening layer, it is possible to cover unevenness such as wiring and TFT before forming the reflective electrode and flatten the substrate.
  • the range called the display pixel is a range regulated by the portion where the reflective electrodes and the transparent electrodes arranged opposite to each other intersect and overlap, and further, the insulating layer in the gap of the reflective electrode.
  • the shape of the display pixel may be, for example, rectangular or circular, and can be easily changed depending on the shape of the insulating layer.
  • full-color display can be displayed by arranging organic EL elements having emission peak wavelengths in the red, green, and blue regions, or by manufacturing a white organic EL element on the entire surface and using it separately in combination with a color filter. It will be possible.
  • the peak wavelength of the displayed light in the red region is in the range of 560 to 700 nm
  • the green region is in the range of 500 to 560 nm
  • the blue region is in the range of 420 to 500 nm.
  • the organic EL element is vulnerable to oxygen and moisture, it is preferable to provide a sealing layer and a desiccant on the surface side of the device to ensure light emission reliability.
  • members according to the usage environment and purpose, such as a color filter for improving display quality, a polarizing layer for preventing external light reflection, and an ultraviolet absorbing layer for improving weather resistance reliability.
  • a touch panel is required depending on the application, it is also possible to stack or mount a touch sensor. In particular, when a touch sensor is provided, it is preferable to provide a cover glass or a hard coat film having excellent scratch resistance on the outermost surface side.
  • FIG. 3 shows a schematic cross-sectional view of a general top emission type organic EL display device.
  • the top-emission organic EL display device of FIG. 3 has a drive circuit 7 on a base material 13.
  • the flattening layer 8 is machined on it, but a hole for connecting to the drive circuit 7 is provided.
  • the reflective electrode 2 is formed on the substrate thus obtained, and the connection with the drive circuit 7 is achieved by the holes provided in advance.
  • the insulating layer 3 is provided in the void of the reflective electrode 2, and the auxiliary electrode 4 is further provided on the insulating layer. It has an organic EL layer 5 and a transparent electrode 6 on it.
  • the organic EL layer 5 Since the organic EL layer 5 is sandwiched between the reflective electrode 2 and the transparent electrode 6, the light emitted from the organic EL layer 5 is taken out on the opposite surface of the substrate. Further, a sealing layer 9, a polarizing layer 10, and an ultraviolet absorbing layer 11 are provided. The order of the sealing layer 9, the polarizing layer 10, and the ultraviolet absorbing layer 11 is not limited to this, and can be appropriately replaced or omitted.
  • Base material a material such as metal, glass, or a resin film, which is preferable for supporting a display device or transporting a post-process, can be appropriately selected. Especially when it is necessary to have translucency, glass or a resin film is used.
  • soda lime glass non-alkali glass, or the like can be used.
  • the thickness of the glass may be sufficient to maintain the mechanical strength.
  • non-alkali glass is preferable because it is preferable that the amount of elution ions from the glass is small, but soda lime glass having a barrier coat such as SiO 2 can also be used.
  • the resin film material preferably contains a resin film material selected from polybenzoxazole, polyamideimide, polyimide, polyamide and poly (p-xylylene) because of its excellent translucency.
  • the base material may contain the materials of these resin films alone, or may contain a plurality of kinds in combination.
  • the base material is formed of a polyimide resin
  • a solution containing polyamic acid (including a partially imidized polyamic acid) or a soluble polyimide, which is a precursor of polyimide is applied to a support substrate. It can also be formed by firing.
  • a gas barrier layer may be appropriately provided as a structure of the base material.
  • a display device having high emission reliability can be obtained by laminating and using an inorganic thin film.
  • the first aspect of the organic EL display device of the present invention has a reflective electrode on a substrate.
  • the reflective electrode is patterned on the substrate.
  • the reflective electrode refers to an electrode having a reflectance of 80% or more.
  • the reflectance is preferably 90% or more in order to efficiently extract light emission.
  • the reflectance of the reflective electrode in the present invention refers to the reflectance at a wavelength of 550 nm.
  • the reflectance of the reflective electrode can be measured by a spectrophotometer for the electrode formed on the substrate.
  • the reflective electrode a material having a certain thickness or more, exhibiting high reflectance with respect to visible light, and exhibiting low electrical resistance is preferable. Therefore, as an example of the material of the reflective electrode, a metal or an alloy containing Ag, Al, Cr, Mo or Ni as a main component is preferable. Further, from the viewpoint of wet etching and cleaning, weather resistance in storage and use environment, and reflectance, which are subsequent steps, Ag or an Ag alloy containing Ag as a main component is more preferable as the material of the reflective electrode. As the Ag alloy, AgPdCu alloy, AgTiCu alloy, AgIn alloy, AgZn alloy, AgZnBi alloy and the like containing Ag as a main component can be used.
  • Al or an Al alloy containing Al as a main component is also a good material for a reflective electrode for top emission.
  • AlNi alloy, AlCr alloy, AlTi alloy and AlNd alloy are preferable.
  • an AlNi alloy containing 0.1 to 2 atomic% of Ni has a high reflectance comparable to that of pure Al, and is low even when the AlNi alloy is directly connected to an oxide conductive material such as ITO or IZO. It is preferable because contact resistance can be realized.
  • the principal component in the present invention refers to the metal contained most in the object as the number of atoms.
  • the reflective electrode has a multi-layer structure in order to achieve both complex characteristics.
  • the work function adjusting layer can be selected from known materials, but ITO, IZO, AZO, GZO, ATO, WO X , MoO X and the like, which have high transmittance and low resistivity, are preferable.
  • ITO that can be used in common with the underlying layer is particularly preferable.
  • the resistance of the reflective electrode is not limited as long as a sufficient current can be supplied to emit light from the light emitting element, but it is desirable that the resistance is small from the viewpoint of power consumption of the light emitting element.
  • the resistance of the reflective electrode is preferably 10 ohms or less as the sheet resistance, and more preferably 5 ohms or less.
  • the lower limit is not particularly limited, but is usually about 1 ohm as the sheet resistance.
  • the thickness of the reflective electrode can be arbitrarily selected according to the characteristics such as reflectance and resistance value, but it is usually 100 to 1000 nm.
  • a known method can be used as the method for forming the reflective electrode.
  • it can be formed by forming a film by a vacuum film forming method such as thin film deposition or sputtering, and patterning it using a photosensitive resist.
  • the first aspect of the organic EL display device of the present invention has an insulating layer on a substrate.
  • the insulating layer is formed in the voids of the reflective electrode.
  • the display pixels can be divided by forming an insulating layer in the voids of the reflective electrode. That is, by patterning the insulating layer in the voids of the reflective electrode, the exposed portion of the reflective electrode is limited, and only the opening portion functions as a display pixel. Further, by covering the peripheral edge of the island-type reflective electrode with the insulating layer, it is possible to prevent a short circuit occurring at the edge of the reflective electrode and disconnection of the transparent electrode, and it is possible to improve the reliability of the display device.
  • the insulating layer is formed at a place other than the void of the reflective electrode, if necessary.
  • the insulating layer is not limited to either an organic insulating layer or an inorganic insulating layer, but it is preferable to include a cured film of the photosensitive resin composition from the viewpoint of processability.
  • the photosensitive resin composition preferably contains (A) an alkali-soluble resin, (B) a photosensitive agent and (C) an organic solvent, and may further contain (D) a coloring material.
  • A) an alkali-soluble resin and (B) a photosensitive agent in combination as the photosensitive resin composition pattern processing using photosensitive can be performed.
  • C) an organic solvent it can be made into a varnish state, and the coatability may be improved.
  • the photosensitive resin composition contains the coloring material (D), so that the insulating layer can be blackened.
  • the photosensitive resin composition may further contain other components.
  • a known method can be used as the method for forming the insulating layer.
  • the wet coating method is preferable because a thin film can be uniformly formed on a large-sized substrate.
  • the wet coating method include a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method and the like.
  • the thickness of the insulating layer is usually 0.3 ⁇ m to 10 ⁇ m, but is not particularly limited as long as it is sufficient to cover the unevenness of the reflective electrode. Further, since the structure covering the transparent electrode is also supported in the subsequent process and the strength of the display device is affected, it is also effective to design the display device in a stepped shape as appropriate. Further, the insulating layer must be patterned, and the residue of the removed portion may be directly linked to defects such as short circuits and black spots. Further, depending on the shape of the edge of the insulating layer, it may cause disconnection of the transparent electrode, so a gentle forward taper shape is preferable.
  • Alkali-soluble in the present invention means that a solution of a resin dissolved in ⁇ -butyrolactone is applied onto a silicon wafer and prebaked at 120 ° C. for 4 minutes to form a prebaked film having a thickness of 10 ⁇ m ⁇ 0.5 ⁇ m. After immersing the membrane in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ⁇ 1 ° C. for 1 minute and then rinsing with pure water, the dissolution rate obtained from the film thickness reduction is 50 nm / min or more. Say.
  • the alkali-soluble resin preferably has an aromatic carboxylic acid structure from the viewpoint of improving heat resistance.
  • the aromatic carboxylic acid structure means a carboxylic acid structure directly covalently bonded to the aromatic ring.
  • Examples of the material of the alkali-soluble resin (A) include polyamide resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, acrylic resin, epoxy resin, cardo resin, and precursors of these resins.
  • the material of the alkali-soluble resin (A) may be a mixture of two or more of these resins and precursors of these resins.
  • the photosensitive resin composition contains a polyimide resin, a polyimide precursor, a polybenzoxazole resin, and / or a polybenzoxazole precursor from the viewpoint of achieving both heat resistance and chemical resistance.
  • a polyimide resin a polyimide precursor, a polybenzoxazole resin, and / or a polybenzoxazole precursor from the viewpoint of achieving both heat resistance and chemical resistance.
  • High chemical resistance is preferable because the film loss when the auxiliary electrode on the insulating layer is processed by wet etching is small. Since the film loss is small, there is no undercut structure at the end of the auxiliary electrode, and disconnection of the transparent electrode is less likely to occur. Further, since the amount of outgas is small under high temperature conditions, a polyimide precursor is particularly preferable. Further, a polyimide precursor having an amic acid structure is more preferable from the viewpoint of improving alkali solubility.
  • the auxiliary electrode is on the insulating layer.
  • any material having conductivity can be used without particular limitation, but it is important that the surface roughness on the side finally in contact with the organic EL layer can be increased as described later.
  • the atomic force microscope (AFM) used for measuring the surface roughness in the present invention generally measures from vertically above the substrate of the organic EL display device placed on a horizontal surface. Therefore, in the present invention, the "surface roughness of the auxiliary electrode on the side in contact with the organic EL layer" is defined as the surface of the auxiliary electrode in contact with the organic EL layer that can be measured by AFM, that is, substantially parallel to the substrate. Refers to the surface roughness of a smooth surface.
  • the end portion of the auxiliary electrode has a forward taper shape.
  • the forward taper shape refers to a state in which the angle formed by the tangent at the interface between the insulating layer and the auxiliary electrode and the tangent at 50% of the thickness of the auxiliary electrode at the end of the auxiliary electrode is less than 90 degrees.
  • the reflection electrode 2 is provided on the substrate 1.
  • the substrate 1 is made of a base material 13.
  • the insulating layer 3 is provided in the void of the reflective electrode 2, and the auxiliary electrode 4 is further provided on the insulating layer.
  • the angle formed by the tangent at the interface between the insulating layer and the auxiliary electrode and the tangent at the end of the auxiliary electrode at 50% of the thickness of the auxiliary electrode (point A) is defined as the taper angle (B).
  • the taper shape can be adjusted according to the etching conditions, and can be confirmed by observing the cross section of the substrate.
  • the material used for the auxiliary electrode examples include one metal selected from Al, Au, Cr, Cu, Ni, Pt, Sn, Ti, Zn and the like, or an alloy containing two or more metals.
  • the auxiliary electrode contains at least one selected from the group consisting of Ag, Al, Cu, Mo, and Ni, and the main component of the auxiliary electrode is at least one of Ag, Al, Cu, Mo, and Ni. It is more preferable to have.
  • the main component of the auxiliary electrode is Ag. By using Ag as a main component, it is possible to easily obtain a desired shape, and finally, it is possible to effectively contribute to lowering the resistance of the transparent electrode.
  • the auxiliary electrode contains a cured film of a resin composition containing conductive fine particles.
  • the auxiliary electrode can be manufactured by a wet coating method in which coating is performed in an atmospheric pressure environment. Examples of the wet coating method include a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method and the like. Definitions and preferred embodiments of the conductive fine particles are as described below.
  • the resistance of the auxiliary electrode is not particularly limited as long as the characteristics are sufficient to reduce the resistance of the transparent electrode.
  • the resistance of the auxiliary electrode is preferably 10 ohms or less as the sheet resistance, and more preferably 5 ohms or less.
  • the lower limit is not particularly limited, but is usually about 1 ohm as the sheet resistance.
  • the thickness of the auxiliary electrode can be arbitrarily selected according to the characteristics such as reflectance and resistance value, but it is usually about 100 to 1000 nm.
  • the maximum height (Rz) of the surface roughness of the auxiliary electrode on the side in contact with the organic EL layer is 30 nm or more and 500 nm or less.
  • the "maximum height (Rz) in surface roughness” may be simply referred to as “maximum height (Rz)".
  • the maximum height (Rz) is less than 30 nm, the surface of the auxiliary electrode is equal to or less than the thickness of the organic EL layer, so that the transparent electrode and the auxiliary electrode can be connected when the transparent electrode is formed in a subsequent step. It disappears.
  • the maximum height (Rz) exceeds 500 nm, it may cause pinholes in the transparent electrode or lead to defects in the sealing layer described later.
  • the protrusions having the maximum height (Rz) in the above range are present at a frequency of one or more in 10 ⁇ m ⁇ . When it is present at a frequency of one or more, it is easy to exert a sufficient effect for lowering the resistance of the transparent electrode.
  • the maximum height (Rz) and the frequency of existence of such protrusions can be confirmed by observing the surface of the auxiliary electrode with an atomic force microscope (AFM) and acquiring the maximum height (Rz).
  • the maximum height (Rz) of the protrusion may be measured after the step of roughening the auxiliary electrode, which will be described later, or from the organic EL display device, the organic EL layer, the transparent electrode, the sealing layer, and the polarized light.
  • the measurement may be performed after removing the members on the upper part of the roughened surface of the auxiliary electrode such as the layer and the ultraviolet absorbing layer. After removing the upper member, the organic EL layer may remain in a part, but if it is further washed with a general organic solvent such as acetone or THF (tetrahydrofuran), the surface of the auxiliary electrode can be measured.
  • a general organic solvent such as acetone or THF (tetrahydrofuran)
  • the first aspect of the organic EL display device of the present invention has an organic EL layer on an insulating layer, and the organic EL layer is selected from the group consisting of a hole transport layer, a light emitting layer, and an electron transport layer. It has one or more layers.
  • the organic EL layer covers the entire display area.
  • an organic EL layer covering the entire display area is formed between the auxiliary electrode and the transparent electrode.
  • the organic EL display device of the present invention is characterized in that the auxiliary electrode and the transparent electrode can be electrically connected to each other even through the organic EL layer because the surface roughness of the auxiliary electrode is large.
  • the configuration of the organic EL layer in the present invention is not particularly limited, and for example, (1) hole transport layer / light emitting layer, (2) hole transport layer / light emitting layer / electron transport layer, and (3) light emitting layer / electron transport. It may be any of the layers.
  • the thickness of each layer is generally selected from 1 to 200 nm in consideration of the resistance value of each layer material and the influence on the extraction efficiency of EL light emission.
  • the thickness of the organic EL layer on the auxiliary electrode is preferably 30 nm or more and 500 nm or less. When the thickness of the organic EL layer on the auxiliary electrode is 30 nm or more, defects of the transparent electrode due to the surface roughness of the auxiliary electrode are less likely to occur, which further improves the reliability of the display device. On the other hand, when the thickness of the organic EL layer on the auxiliary electrode is 500 nm or less, it becomes easy to connect the auxiliary electrode and the transparent electrode.
  • the thickness of the organic EL layer on the auxiliary electrode is smaller than the maximum height (Rz) in the surface roughness of the auxiliary electrode.
  • the hole transport layer is formed, for example, by a method of laminating or mixing one or more kinds of hole transport materials, or a method of using a mixture of a hole transport material and a polymer binder. Further, an inorganic salt such as iron (III) chloride may be added to the hole transport material to form a hole transport layer.
  • the hole transporting material is not particularly limited as long as it is a compound that forms a thin film necessary for producing a light emitting device, can inject holes from an electrode serving as an anode, and can further transport holes.
  • the hole transport material are 4,4'-bis (N- (3-methylphenyl) -N-phenylamino) biphenyl, 4,4'-bis (N- (1-naphthyl) -N. -Phenylamino) biphenyl, 4,4', 4 "-tris (3-methylphenyl (phenyl) amino) triphenylamine derivatives such as triphenylamine, bis (N-allylcarbazole), bis (N-alkylcarbazole) Biscarbazole derivatives such as, pyrazoline derivatives, stylben compounds, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, phthalocyanine derivatives, porphyrin derivatives and other heterocyclic compounds, and in polymer systems, the above-mentioned monomers are used as side chains. Examples thereof include polycarbonate, styrene derivative, polythiophene, polyaniline,
  • the light emitting layer is a layer in which a light emitting material is excited by recombination energy due to collision of holes and electrons and emits light. It is a major feature of the organic EL display device that various multicolor emission is possible by selecting the material constituting this light emitting layer.
  • the light emitting layer may be a single layer or may be formed by laminating a plurality of layers, and each is formed of a light emitting material (host material, dopant material). Each light emitting layer may be composed of only one of the host material and the dopant material, or may be composed of a combination of one or more kinds of host materials and one or more kinds of dopant materials.
  • the light emitting layer is preferably composed of a combination of a host material and a dopant material.
  • the dopant material may be contained entirely or partially in the host material.
  • the content of the dopant material in the light emitting layer is preferably 30 parts by mass or less, more preferably 20 parts by mass or less with respect to 100 parts by mass of the host material, from the viewpoint of suppressing the concentration quenching phenomenon.
  • the light emitting layer can be formed, for example, by a method of co-depositing a host material and a doping material, a method of premixing a host material and a doping material, and then vapor deposition.
  • Examples of the dopant material constituting the light emitting material include fused ring derivatives such as anthracene and pyrene, metal complex compounds such as tris (8-quinolinolate) aluminum, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, and tetraphenyl.
  • Examples thereof include a butadiene derivative, a dibenzofuran derivative, a carbazole derivative, an indrocarbazole derivative, and a polyphenylene vinylene derivative.
  • the dopant materials used when the light emitting layer emits triplet include iridium (Ir), ruthenium (Ru), palladium (Pd), platinum (Pt), osmium (Os) and rhenium (Re). ),
  • a metal complex compound containing at least one metal selected from the group consisting of) is preferable.
  • the ligand constituting the metal complex compound can be appropriately selected from the required emission color, the performance of the organic EL display device, and the relationship with the host compound. Above all, it is preferable that the ligand has a nitrogen-containing aromatic heterocycle such as a phenylpyridine skeleton, a phenylquinoline skeleton, and a carbene skeleton.
  • the metal complex compound include, specifically, tris (2-phenylpyridyl) iridium complex bis (2-phenylpyridyl) (acetylacetonate) iridium complex, tetraethylporphyrin platinum complex and the like. Two or more of these may be used.
  • Examples of the host material constituting the luminescent material include compounds having a fused aryl ring such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, and indene. Two or more of these may be used.
  • Host materials used when the light emitting layer emits triple term light include metal chelated oxynoid compounds, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, indolocarbazole derivatives, triazine derivatives, triphenylene derivatives and the like. It is preferably used. Among them, a compound having an anthracene skeleton or a pyrene skeleton is more preferable because high-efficiency light emission can be easily obtained.
  • the electron transport layer is a layer that transports electrons injected from the cathode to the light emitting layer. It is desired that the electron transport layer has high electron injection efficiency and efficiently transports the injected electrons. Therefore, it is preferable that the electron transport layer is a substance having high electron affinity and electron mobility, excellent stability, and less likely to generate trap impurities during production and use. In particular, when the electron transport layer is thick, a compound having a molecular weight of 400 or more is preferable because a compound having a low molecular weight tends to cause crystallization or deterioration.
  • the electron transport layer When considering the transport balance between holes and electrons, if the electron transport layer mainly plays a role of efficiently blocking the holes from the anode from flowing to the cathode side without recombination, the electron transport. Even if the electron transport layer is made of a material having a low capacity, the effect of improving the light emission efficiency is the same as that of the material having a high electron transport capacity. Therefore, the electron transport layer in the present invention has holes.
  • a hole blocking layer that can efficiently block the movement of electrons is also included as a synonym.
  • the electron transport layer may be a single layer or a plurality of layers may be laminated.
  • Examples of the electron transport material constituting the electron transport layer include condensed polycyclic aromatic derivatives such as naphthalene and anthracene. Two or more of these may be used. Among these, a compound having a heteroaryl ring structure containing electron-accepting nitrogen is preferable because the driving voltage can be further reduced and high-efficiency light emission can be obtained.
  • the electron-accepting nitrogen referred to here represents a nitrogen atom forming a multiple bond with an adjacent atom. Due to the high electronegativity of the nitrogen atom, such multiple bonds have electron-accepting properties. Therefore, the aromatic heterocycle containing electron-accepting nitrogen has a high electron affinity.
  • the electron transporting material having electron-accepting nitrogen can easily receive electrons from the cathode, so that the driving voltage can be further reduced. In addition, the supply of electrons to the light emitting layer is increased, and the recombination probability is increased, so that the luminous efficiency is improved.
  • heteroaryl ring containing electron-accepting nitrogen examples include a triazine ring and a pyridine ring.
  • examples of the compounds having these heteroaryl ring structures include triazole derivatives such as N-naphthyl-2,5-diphenyl-1,3,4-triazole, and 2,5-bis (6'-(2', 2 "-"-. Bipyridyl))-1,1-dimethyl-3,4-diphenylsilol and other bipyridine derivatives, 1,3-bis (4'-(2,2': 6'2 "-terpyridinyl)) benzene and other bipyridine derivatives , Is preferably used from the viewpoint of electron transport ability. Two or more of these may be used.
  • the electron transport material may be used alone, but two or more of the electron transport materials may be mixed and used, or one or more of the other electron transport materials may be mixed with the electron transport material and used.
  • the electron transport layer may contain a donor compound.
  • the donor compound is a compound that facilitates electron injection from the cathode or the electron injection layer into the electron transport layer by improving the electron injection barrier, and further improves the electrical conductivity of the electron transport layer.
  • Examples of the donor compound include an alkali metal, an inorganic salt of an alkali metal, a complex of an alkali metal and an organic substance, an alkaline earth metal, an inorganic salt of an alkaline earth metal, or a complex of an alkaline earth metal and an organic substance. Be done.
  • the donor compound is easy to vaporize in vacuum and is excellent in handling
  • a complex with an inorganic salt or an organic substance is preferable to a simple substance of metal, and since it is easy to handle in the atmosphere and the addition concentration is easily adjusted, the organic substance is easy to handle. Complexes with are more preferred.
  • the first aspect of the organic EL display device of the present invention has a transparent electrode on an insulating layer.
  • the transparent electrode covers the entire display area.
  • the transparent electrode refers to an electrode having a light transmittance of 30% or more at a wavelength of 550 nm.
  • the light transmittance in the present invention can be measured by a spectrophotometer for an electrode formed on a transparent glass substrate.
  • Examples of the material for forming the transparent electrode in the present invention include transparent conductive oxides and metals.
  • ITO, IZO, AZO, GZO, ATO and the like are preferable, and when used as a cathode, Li, Mg, Ag, Al and the like are preferable.
  • the transparent electrode it is difficult to make the transparent electrode thick due to the requirement of light transmittance regardless of which material is used, and the resistance value of the electrode becomes large.
  • a transparent electrode is provided as a common layer on the entire surface of the display area, if the resistance value of the electrode is large, not only the power consumption increases but also display abnormalities such as uneven brightness occur.
  • the present invention since it is possible to secure a good electrical connection with the auxiliary electrode provided on the insulating layer, it is possible to achieve low resistance of the transparent electrode and avoid display abnormality.
  • wiring or TFT as a drive circuit may be provided as included in the substrate.
  • the patterned island type reflective electrode is often connected to a TFT formed in advance as a part of the substrate.
  • the semiconductor layer of the TFT is oxidized with p-Si, an oxide represented by a-Si (amorphous silicon), p-Si (polycrystalline silicon), microcrystal silicon, In-Ga-Zn-O, etc.
  • p-Si an oxide represented by a-Si (amorphous silicon), p-Si (polycrystalline silicon), microcrystal silicon, In-Ga-Zn-O, etc.
  • LTPO Low Semiconductor Polysilicon Oxide
  • TFTs using a-Si have low mobility, which is an index showing the ease of movement of electrons, but the manufacturing process is relatively short, and they can be manufactured on large substrates, so they can be used for small to large displays. Can be widely used.
  • a TFT using p-Si has high mobility and can form a driver circuit or the like on a glass substrate.
  • the p-SiTFT has a longer manufacturing process than the a-SiTFT, and it is difficult to manufacture a large substrate. Therefore, it is preferable to use the p-SiTFT mainly for small and medium-sized displays.
  • p-Si in the p-Si TFT can be generally formed by irradiating laser light with a-Si as a starting film and instantaneously melting and crystallization.
  • the threshold value of the TFT characteristics may be controlled by doping the Si film with impurities.
  • TFTs can be roughly classified into bottom gate type and top gate type from the structural aspect. It is preferable to use a bottom gate type for a-SiTFT and a top gate type for p-SiTFT.
  • the electrode on the drain side and the electrode on the source side are connected to the semiconductor layer, and the gate electrode is provided above the semiconductor layer.
  • the gate electrode is arranged in the lowermost layer, the semiconductor layer / insulating film is in the upper layer thereof, and the source electrode and the drain electrode are formed in the upper layer.
  • an inverted triangle is formed, and a structure also called an "inverted stagger structure" may be used.
  • the TFT is formed on the substrate by repeating the element processes of thin film formation, patterning, etching, and cleaning several times.
  • a method for forming the TFT for example, a known method can be used.
  • the organic EL display device of the present invention preferably has a flattening layer.
  • a flattening layer By providing the flattening layer, it is possible to cover and flatten the unevenness, especially when wiring or TFT is provided as a substrate as in the active matrix type.
  • the reflective electrode is provided on the flattening layer. Therefore, in the organic EL display device of the present invention, the reflective electrode and the driving wiring are connected to each other through the contact hole formed in the flattening layer. It is preferable to connect.
  • the flattening layer is not limited to either an organic flattening layer or an inorganic flattening layer.
  • the flattening layer preferably contains a cured film of the photosensitive resin composition. Since the flattening layer can uniformly form a thin film on a large-sized substrate, it can be applied by a wet coating method such as a spin coating method, a slit coating method, a dip coating method, a spray coating method, or a printing method. can.
  • the photosensitive resin composition preferably contains (A) an alkali-soluble resin, (B) a photosensitive agent and (C) an organic solvent, and may further contain (D) a coloring material.
  • A) an alkali-soluble resin and (B) a photosensitive agent in combination as the photosensitive resin composition pattern processing using photosensitive can be performed.
  • C) an organic solvent it can be made into a varnish state, and the coatability may be improved.
  • the photosensitive resin composition contains the coloring material (D), the flattening layer can be blackened.
  • the photosensitive resin composition may further contain other components.
  • the material of the alkali-soluble resin (A) examples include polyamide resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, acrylic resin, epoxy resin, cardo resin, and precursors of these resins.
  • the material of the alkali-soluble resin (A) may be a mixture of two or more of these resins and precursors of these resins.
  • the photosensitive resin composition appropriately contains (D) a coloring material.
  • the thickness of the flattening layer is not particularly limited as long as it is sufficient to cover the unevenness.
  • the organic EL display device of the present invention it is preferable to form a transparent electrode and then seal it with a sealing layer. This is because the organic EL element is said to be vulnerable to oxygen and moisture. In order to obtain a display device with high emission reliability, it is preferable to perform sealing in an atmosphere with as little oxygen and moisture as possible. It is preferable to select a member having a high gas barrier property as the member used for the sealing layer.
  • the moisture permeability of the sealing layer is preferably 20 g / m 2 , day, atm or less.
  • the oxygen permeability of the sealing layer is preferably 20 cc / m 2 , day, atm or less.
  • Moisture permeability can be measured by a method according to JIS K 7129 (2019).
  • the oxygen permeability can be measured by a method according to JIS K 7126 (2006).
  • the material constituting the sealing layer for example, glass, a resin film, a gas barrier film, or the like can be appropriately selected as in the case of the base material.
  • the gas barrier film include materials such as SiO 2 (silicon oxide), SiN (silicon nitride), and SiON (silicon oxynitride).
  • a layer made of a resin material such as an acrylic resin or a silicone resin may be provided on a layer such as glass, a resin film, or a gas barrier film to form a multilayer structure for the sealing layer.
  • the sealing layer is light transmissive.
  • the light transmittance at a wavelength of 550 nm is preferably 30% or more, more preferably 50% or more, still more preferably 70% or more.
  • the light transmittance in the present invention can be measured with a spectrophotometer for the sealing layer formed on the transparent glass substrate.
  • an adhesive having a high gas barrier property as the adhesive used when adhesion with the sealing layer is required.
  • an adhesive having a high gas barrier property such as a two-component epoxy adhesive (XNR, Nagase ChemteX Co., Ltd.) and a sealing material for organic devices (Moisture Cut, MORESCO Co., Ltd.). You can choose from the ones you have. Further, for example, the frit glass can be bonded by a method of melting with a laser.
  • the desiccant is not particularly limited as long as it has a high water adsorption performance. Specific examples thereof include barium oxide and calcium oxide.
  • the organic EL display device of the present invention preferably further has a polarizing layer.
  • a polarizing layer include a polarizing layer in which a ⁇ / 4 retardation layer and a linearly polarizing layer are laminated to suppress reflection of light incident from the outside.
  • the linearly polarizing layer for example, a film obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretching it is often used.
  • the material constituting the ⁇ / 4 retardation plate is not particularly limited, but a polyimide resin is preferable because it has high heat resistance.
  • the organic EL display device of the present invention preferably further has an ultraviolet absorbing layer.
  • an ultraviolet absorbing layer By having an ultraviolet absorbing layer, weather resistance reliability can be improved.
  • the organic EL display device of the present invention is used outdoors, it is effective to have an ultraviolet absorbing layer because it absorbs ultraviolet rays contained in sunlight.
  • the ultraviolet absorbing layer a layer that absorbs light having a wavelength of 320 nm or less is preferable, a layer that absorbs light having a wavelength of 360 nm or less is more preferable, and a layer that absorbs light having a wavelength of 420 nm or less is further preferable.
  • the ultraviolet absorbing layer has a high transmittance in a region having a wavelength of 420 nm or more.
  • the ultraviolet absorbing layer preferably contains a resin.
  • resins include polyimide resin, polyamide resin, polyamideimide resin, polycarbonate resin, polyester resin, polyether sulfone resin, polyarylate resin, polyolefin resin, polyethylene terephthalate resin, polymethylmethacrylate resin, polysulfone resin, polyethylene resin, and poly.
  • examples thereof include vinyl chloride resin, alicyclic olefin polymer resin, acrylic polymer resin, cellulose ester resin and the like.
  • the ultraviolet absorbing layer may contain two or more of the above resins. Among these resins, polyimide resins and polyamide resins are preferable because they have high heat resistance, chemical resistance, and flexibility.
  • the ultraviolet absorbing layer may contain an ultraviolet absorbing agent.
  • the ultraviolet absorber include benzophenone compounds, oxybenzophenone compounds, benzotriazole compounds, sultylate compounds, salicylic acid ester compounds, acrylic nitrile compounds, cyanoacrylate compounds, hindered amine compounds, triazine compounds, and nickel complex salts. Examples thereof include compounds, ultrafine titanium oxide, metal complex salt compounds, and high molecular weight ultraviolet absorbers.
  • Examples of the polymer ultraviolet absorber include those obtained by copolymerizing the reactive ultraviolet absorber RUVA-93 manufactured by Otsuka Chemical Co., Ltd. with an acrylic monomer.
  • the ultraviolet absorbing layer may contain two or more of these ultraviolet absorbers.
  • the ultraviolet absorber is preferably a benzotriazole-based compound or a benzophenone-based compound because of its excellent transparency, and a benzotriazole-based compound is more preferable.
  • the method for manufacturing an organic EL display device of the present invention includes a step of forming a patterned reflective electrode on a substrate, a step of forming an insulating layer in a gap of the reflective electrode, and a step of forming an auxiliary electrode on the insulating layer.
  • a step of roughening the auxiliary electrode, a step of forming an organic EL layer covering the entire display area, and a step of forming a transparent electrode covering the entire display area are included in this order.
  • a drive circuit on the glass substrate.
  • it is formed by using a known method such as "gate electrode forming step”, “gate insulating film forming step”, “Si film forming step”, “source and drain electrode forming step”. Can be done.
  • the flattening layer is formed into a film by, for example, a slit coating method.
  • processing is performed to provide a contact hole for the purpose of connecting to the reflective electrode.
  • processing for example, if the material used as the flattening layer is photosensitive, photolithography processing can be performed, and if it is non-photosensitive, general etching processing using a resist material as a mask can be used.
  • the method for manufacturing an organic EL device of the present invention includes a step of forming a patterned reflective electrode on a substrate. In this step, a reflective electrode is formed, and the reflective electrode is left in an island shape so as to correspond to the display pixel.
  • the method for manufacturing an organic EL device of the present invention includes a step of forming an insulating layer in the voids of the reflective electrode.
  • a step of forming an insulating layer in the voids of the reflective electrode include a step of providing an opening on the reflective electrode by photolithography after applying the photosensitive resin to the entire surface.
  • the method for manufacturing an organic EL device of the present invention includes a step of forming an auxiliary electrode on an insulating layer.
  • a known method can be used as the method for forming the auxiliary electrode.
  • it can be formed by forming a film by physical vapor deposition by a vacuum film forming method such as thin film deposition or sputtering, and patterning it using a photosensitive resist.
  • a vacuum film forming method such as thin film deposition or sputtering
  • it is possible to generate coarse particles generated from a solid evaporation source called droplets to increase the surface roughness.
  • sputtering if there is a negative bias voltage in addition to the positive bias voltage, the smoothing of the film progresses due to the etching effect, so DC sputtering consisting of only the positive bias voltage is preferable.
  • High-power DC sputtering is particularly preferable because the film formation speed is high and the productivity is high. Specifically, it is preferable to form a film at DC 500 W or more, preferably DC 1000 W or more.
  • the step of forming the auxiliary electrode on the insulating layer is the step of forming the auxiliary electrode by the coating method.
  • the coating method include inkjet and printing.
  • An auxiliary electrode can be formed by forming a conductive resin composition into a film by a coating method and drying and curing it by heating.
  • the conductive resin composition is a thermosetting conductive resin composition containing a conductive powder and a thermosetting resin.
  • the conductive powder is a powder containing at least one selected from the group consisting of Ag, Al, Cu, Mo, and Ni, and its average particle size (D50) is 0.1 to 20 ⁇ m.
  • the average particle size (D50) can be measured by the laser diffraction method. Specifically, 0.3 g of the conductive powder sample is weighed in a 50 ml beaker, 30 ml of isopropyl alcohol is added, and then treated with an ultrasonic cleaner (USM-1 manufactured by AS ONE Co., Ltd.) for 5 minutes to disperse. It can be measured by using a microtrack particle size distribution measuring device (9320-HRA X-100 manufactured by Nikkiso Co., Ltd.).
  • thermosetting conductive resin composition copper or silver powder as the conductive powder contained in the composition, or silver-coated copper obtained by coating the surface of a copper-based powder (copper or copper alloy powder) with silver.
  • a thermosetting conductive resin composition examples include a configuration in which a based powder is used and an epoxy resin and / or a blocked polyisocyanate compound is used as the thermosetting resin.
  • the conductive fine particles are fine particles containing one or more selected from the group consisting of Ag, Al, Cu, Mo, and Ni, and the particle size of the fine particles is 10 nm or more and less than 100 nm.
  • the particle size of the conductive fine particles is measured by a laser diffraction method.
  • the step of forming the auxiliary electrode by the coating method is the step of forming the auxiliary electrode by applying the resin composition containing the conductive fine particles.
  • the resin composition containing the conductive fine particles is a photosensitive resin composition. Since it is a photosensitive resin composition, the patterning process tends to be simplified. In particular, in order to form an ultrafine pattern having a particle size of 5 ⁇ m or less, it is preferable to use conductive fine particles having a particle size of 50 nm or less.
  • the conductive fine particles include surface-coated conductive fine particles.
  • the conductive fine particles By coating the surface, it is possible to prevent the fusion of the conductive fine particles even when the fusion of the conductive fine particles proceeds even at around room temperature.
  • a method for surface coating of conductive fine particles a vapor phase reaction method or coating of an organic substance in a liquid phase is common.
  • the conductive fine particles surface-coated with an organic substance silver fine particles surface-coated with an amine compound and the like are known.
  • the conductive fine particles include conductive fine particles whose surface is coated with a simple substance of carbon and / or a carbon compound.
  • a gas phase reaction method is preferable, and a thermal plasma method is more preferable from the viewpoint of high productivity.
  • the method for generating thermal plasma include arc discharge, high frequency plasma, hybrid plasma and the like. Of these, high-frequency plasma is preferable because impurities are less likely to be mixed from the electrodes.
  • a resist layer is first provided on an auxiliary electrode, and then the resist layer is exposed and developed to form a resist pattern. Then, the portion of the auxiliary electrode that is not covered by the resist pattern is removed by etching.
  • etching method for example, wet etching is used.
  • wet etching in general, in order to completely remove the portion of the auxiliary electrode that is not covered by the resist pattern, the etching time is the time required for so-called just etching, that is, etching the auxiliary electrode by the thickness thereof (hereinafter, just). Etching time) is set to be longer.
  • photosensitive resist examples include AZ (Shipley), KAR (Kodak), FPPR (Fuji Yakuhin Kogyo), OFPR (Tokyo Ohka) and the like as commercially available products.
  • the method for manufacturing an organic EL display device of the present invention includes a step of roughening an auxiliary electrode. By performing the roughening treatment, the surface roughness of the auxiliary electrode can be increased.
  • the opportunity for roughening treatment is not particularly limited as long as it is before the formation of the organic EL layer.
  • the roughening treatment may be performed in combination with the etching step for the purpose of patterning the auxiliary electrode, or may be performed in combination with the cleaning step before forming the organic EL layer.
  • the roughening treatment method is not particularly limited, such as mechanical polishing using an abrasive, shot blasting or wet blasting by injecting an abrasive, plasma processing, dry etching processing such as RIE, and the like.
  • the surface roughness can be adjusted by selecting the etching solution and processing temperature for wet etching, and by setting the etching gas and output for dry etching.
  • the conditions for increasing the size may be appropriately selected, but since the organic EL element is vulnerable to oxygen and moisture, it is preferable not to leave moisture in the substrate.
  • dehydration treatment such as heating or depressurization may be combined.
  • the dry etching step is preferable for the reason of suppressing the absorption of moisture to the substrate, and the plasma treatment is more preferable for the roughening treatment from the viewpoint of processing controllability.
  • oxygen oxygen, nitrogen, hydrogen, and argon
  • nitrogen nitrogen
  • hydrogen argon
  • the method for manufacturing an organic EL display device of the present invention it is preferable to have a step of performing a heat treatment at 180 to 260 ° C. before the step of forming the organic EL layer described later.
  • heat treatment By heat treatment, dehydration of the substrate progresses, and a highly reliable display device can be obtained.
  • the surface roughness of the insulating layer is increased by the roughening treatment, it is possible to cause reflow and smooth the surface.
  • by adjusting the heat treatment temperature to correspond to the cure temperature of the insulating layer, it is possible to smooth only the surface of the insulating layer without affecting the surface roughness of the auxiliary electrode.
  • an organic EL display device of the present invention there may be a step of performing cleaning before the step of forming the organic EL layer described later.
  • it is effective to perform wet or dry cleaning because contamination in the previous process such as photolithography processing often remains on the surface of the reflective electrode.
  • wet cleaning it is possible to select from immersion, ultrasonic cleaning, boiling cleaning and the like using an organic solvent, a surfactant, water, an acid solution, an alkaline solution and the like.
  • dry cleaning it is possible to select from glow discharge treatment, plasma discharge treatment, UV / ozone treatment and the like.
  • dry cleaning using an oxygen atmosphere can also promote oxidation of the reflective electrodes and adjust the work function.
  • the oxygen defect existing on the outermost surface of the reflective electrode can be oxidized by the generated radical species or ionic species to increase the work function.
  • the work function of the reflective electrode By adjusting the work function of the reflective electrode, the carrier injection efficiency from the reflective electrode into the adjacent organic EL layer becomes high, and as a result, the characteristics as a display device such as luminous efficiency and reliability are easily improved.
  • the method for manufacturing an organic EL device of the present invention includes a step of forming an organic EL layer that covers the entire display area.
  • Each layer such as the hole transport layer, the light emitting layer, and the electron transport layer constituting the organic EL layer can be formed by a known method, and can be formed by, for example, a mask vapor deposition method or an inkjet method.
  • the mask vapor deposition method is a method in which an organic compound is vapor-deposited and patterned using a thin-film deposition mask. Can be mentioned. In order to obtain a highly accurate vapor deposition pattern, it is important to attach a highly flat vapor deposition mask to the substrate. Generally, a technique for applying tension to the vapor deposition mask or a magnet placed on the back surface of the substrate is used for the vapor deposition mask. It is possible to use a technique of bringing the film into close contact with the substrate.
  • Examples of the manufacturing method of the vapor deposition mask include etching method, mechanical polishing, sandblasting method, sintering method, laser processing method, utilization of photosensitive resin, electroforming method, etc., but if a fine pattern is required, It is preferable to use an etching method or an electroforming method having excellent processing accuracy.
  • the mask vapor deposition method and the inkjet method are more difficult as the pattern becomes finer, so for example, it is required to adopt the light emitting layer that determines the emission color to the minimum necessary.
  • it is required to adopt the light emitting layer that determines the emission color to the minimum necessary.
  • it is permitted to form a film on the entire surface, and the productivity of the display device is improved.
  • the method for manufacturing an organic EL display device of the present invention includes a step of forming a transparent electrode that covers the entire display area. After forming the organic EL layer, a transparent electrode is formed.
  • a known method can be used as the forming method, but the vacuum vapor deposition method is preferable because it is easy to avoid deterioration and damage of the organic EL layer as a base.
  • the transparent electrode can secure a good electrical connection with the auxiliary electrode provided on the insulating layer, it is possible to achieve low resistance of the transparent electrode and avoid display abnormality.
  • the organic EL display device of FIG. 3 After the step of forming the transparent electrode, the sealing layer, the polarizing layer, and the ultraviolet absorbing layer are laminated and formed in this order. As described above, the organic EL display device of FIG. 3 is completed.
  • ⁇ Measurement of film thickness of auxiliary electrode, taper observation, surface roughness> The film thickness of the auxiliary electrodes in each Example and Comparative Example was measured from the step of the patterning portion using a surface roughness measuring machine (Surfcom 1400D manufactured by Tokyo Seimitsu Co., Ltd.). The state of the taper was observed by observing the cross section of the cut substrate with a scanning electron microscope (SEM, S-3000N manufactured by Hitachi High-Technologies Corporation). For the surface roughness, the maximum height (Rz) was adopted from the observation results using an atomic force microscope (AFM, Division Icon, Bruker). The observation conditions were RTESS-300 probe, tapping mode, scan size 10 ⁇ m ⁇ , scan rate 1 Hz, and 256 sample lines.
  • AFM atomic force microscope
  • the sheet resistance of the auxiliary electrodes used in each example and comparative example is the electricity between the opposite sides of the electrode having a film thickness of 500 nm formed on a glass substrate (OA-10; manufactured by Nippon Electric Glass Co., Ltd.) of 5 cm ⁇ . The resistance value was measured. A source meter (Keithley Instruments Co., Ltd. 2400) was used for the measurement. The results are summarized in Table 1.
  • the thickness displayed on the crystal oscillation type film thickness monitor was used as the thickness.
  • the crystal oscillation type film thickness monitor was calibrated in advance using an atomic force microscope (AFM, Bruker's Dimension Icon).
  • a sputtering apparatus (SH-450 manufactured by ULVAC, Inc.) was used for film formation of the auxiliary electrodes in each Example and Comparative Example. Each film formation condition is shown in Table 2.
  • the silver-coated aluminum powder use an aluminum powder with a silver-coated amount of 20% by mass and an average particle size (D50) of 6 ⁇ m, an epoxy resin (Mitsubishi Chemical Corporation jER825), and a curing agent (boron trifluoride monomethylamine).
  • the conductive resin composition prepared in the above was used.
  • 90 parts by mass of silver-coated aluminum powder, 9.5 parts by mass of epoxy resin as a thermosetting component, and 0.5 parts by mass of a curing agent were mixed and kneaded with a three-roll mill. Then, butyl diglycol acetate was added as a solvent to adjust the viscosity to 100 Pa ⁇ s (1 rpm).
  • the viscosity of the conductive resin composition was measured using a DV-III viscometer (manufactured by Brookfield). CP-52 was used as the cone at the time of measurement, and the viscosity at room temperature of 23 ° C. at 1 rpm was measured.
  • the average particle size (D50) was measured by laser diffraction. Specifically, 0.3 g of a spherical powder sample was weighed in a 50 ml beaker, 30 ml of isopropyl alcohol was added, and then treated with an ultrasonic washer (USM-1 manufactured by AS ONE Co., Ltd.) for 5 minutes to disperse the particles.
  • the average particle size (D50) was measured using a microtrack particle size distribution measuring device (microtrack particle size distribution measuring device 9320-HRAX-100 manufactured by Nikkiso Co., Ltd.).
  • the conductive resin composition thus obtained was slit-coated on the substrate, and the substrate was heated and cured in a hot air dryer at 180 ° C. for 60 minutes.
  • silver fine particles 80 g of silver fine particles NB-01 (manufactured by NaBond), 4.06 g of dispersant DISPERBYK140 (manufactured by Big Chemie Japan Co., Ltd.), and 196.1 g of solvent PGMEA are homogenized at 1200 rpm and 30. A mixed solution was obtained by subjecting the mixture to minutes. Further, the mixed solution was dispersed using a mill-type disperser filled with zirconia beads to obtain a silver particle dispersion.
  • a photosensitive conductive resin composition was prepared by adding 30.5 g of a solvent (PGMEA) to a mixture of 1.30 g of acrylate PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.) and stirring the mixture.
  • the photosensitive conductive resin composition thus obtained was applied onto a substrate using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.).
  • VPC-1100 manufactured by ULVAC Kiko Co., Ltd.
  • ULVAC Kiko Co., Ltd. a thin-film deposition device
  • an aqueous phosphoric acid solution prepared by dissolving 0.442 g of phosphoric acid in 27.71 g of water was added dropwise over 10 minutes. After completion of the dropping, the mixture was stirred at 40 ° C. for 30 minutes to hydrolyze the silane compound. After completion of hydrolysis, a solution in which 9.84 g (7.5 mol%) of TMSSucA was dissolved in 8.22 g of PGMEA was added. Then, the bath temperature was set to 70 ° C. and the mixture was stirred for 1 hour, and then the bath temperature was subsequently raised to 115 ° C.
  • the resin solution obtained by heating and stirring for 2 hours was cooled in an ice bath, and then 2% by mass of each of the anion exchange resin and the cation exchange resin was added to the resin solution and stirred for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were filtered off to obtain a polysiloxane solution (PS-1).
  • PS-1 polysiloxane had a Mw of 4,000 and a carboxylic acid equivalent of 910.
  • PGMEA was dissolved in 59.47 g, GMA in 14.22 g (20 mol%), DBA in 0.676 g (1 mol%), and 4-MOP in 0.186 g (0.3 mol%).
  • the solution was added and stirred at 90 ° C. for 4 hours to obtain an acrylic resin solution (AC-1).
  • the obtained acrylic resin had a Mw of 15,000, a carboxylic acid equivalent of 490, and a double bond equivalent of 730.
  • PI-1 polyimide
  • Examples 1 to 19 The procedure for measuring the sheet resistance of the transparent electrode in each Example and Comparative Example will be described with reference to FIGS. 4A to 4F.
  • the combinations of the insulating layer material and the auxiliary electrode material are collectively shown in Table 3.
  • Comparative Example 1 is an example without an auxiliary electrode.
  • AgPdCu 100 nm was formed by sputtering on a 5 cm ⁇ glass substrate 1 (A in FIG. 4) as a reflective electrode 2, and wet-etched to 4.5 ⁇ 5 cm so as to leave 2.5 mm at each end. Patterned in (B in FIG. 4). Then, a 4.6 ⁇ 5 cm insulating layer 3 was formed so as to fill the voids of the reflective electrode 2 (C in FIG. 4). At this time, in order to prevent a short circuit or disconnection later, 0.5 mm above each reflective electrode 2 is formed to overlap the insulating layer 3. Further, the auxiliary electrode 4 was formed on the entire surface of the substrate by the method shown in Table 2 with a film thickness of 500 nm.
  • Ar was used as the gas for sputtering, and the gas pressure at the start of film formation was 0.1 Pa. Further, when the pressure increase was confirmed during the film formation, it was judged that the heat resistance of the insulating layer was insufficient, and it was described as B in "Vacuum degree during sputtering" in Table 2. Those in which the pressure increase during the film formation could not be confirmed were described as A because they had sufficient heat resistance.
  • Example 14 the auxiliary electrode material, which is a photosensitive conductive resin composition, was patterned by a photolithography method.
  • Table 4 the results of confirmation of the presence or absence of undercut by cross-sectional observation are also shown in Table 4. It was determined that the cause of the undercut was insufficient etchant resistance of the insulating layer.
  • Comparative Example 1 is an example in which there is no auxiliary electrode and no roughening treatment
  • Comparative Examples 2 to 6 are examples in the case where there is an auxiliary electrode and there is no roughening treatment.
  • an organic compound (HT-1) represented by the following chemical formula was deposited as the organic EL layer 5 on the entire surface of the substrate with the thickness shown in Table 6 (E in FIG. 4).
  • the film thickness of the thin-film deposition film is a display value on the crystal oscillation type film thickness monitor.
  • the electric resistance value between the opposite sides of the transparent electrode is measured as a sheet resistance using a tester 12, and if the resistance value is 10 ohms or less, which is sufficiently small, the characteristic is due to the electric connection with the auxiliary electrode.
  • the resistance value is more than 10 ohms and 30 ohms or less is the characteristic (B)
  • the resistance value is more than 30 ohms and 100 ohms or less is the characteristic (C)
  • the resistance value is more than 100 ohms.
  • D characteristic
  • Example 15 it was confirmed that the transparent electrode was partially broken at the end of the auxiliary electrode.
  • the results of defect observation after leaving for 24 hours are also shown in "Defects" in Table 6. A was defined as no defect in the transparent electrode, B was defined as partially defective, and C was defined as having a defect on the entire surface.
  • Substrate 2 Reflective electrode 3 Insulation layer 4 Auxiliary electrode 5 Organic EL layer 6 Transparent electrode 7 Drive circuit 8 Flattening layer 9 Sealing layer 10 Polarizing layer 11 Ultraviolet absorption layer 12 Tester 13 Base material

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Publication number Priority date Publication date Assignee Title
US20240049543A1 (en) * 2020-12-24 2024-02-08 Semiconductor Energy Laboratory Co., Ltd. Display device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005149800A (ja) * 2003-11-12 2005-06-09 Sony Corp 表示装置およびその製造方法
JP2015158981A (ja) * 2014-02-21 2015-09-03 パナソニックＩｐマネジメント株式会社 有機エレクトロルミネッセンス素子及び照明装置
WO2015151391A1 (ja) * 2014-03-31 2015-10-08 パナソニックＩｐマネジメント株式会社 有機エレクトロルミネッセンス素子、その製造方法及び照明装置

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4434411B2 (ja) 2000-02-16 2010-03-17 出光興産株式会社 アクティブ駆動型有機ｅｌ発光装置およびその製造方法
JP4483245B2 (ja) * 2003-09-19 2010-06-16 ソニー株式会社 有機発光素子およびその製造方法ならびに表示装置
JP2008078038A (ja) * 2006-09-22 2008-04-03 Fuji Electric Holdings Co Ltd 有機ｅｌディスプレイパネルおよびその製造方法
JP2010040211A (ja) * 2008-07-31 2010-02-18 Sumitomo Chemical Co Ltd 有機エレクトロルミネッセンス素子、その製造方法、照明装置、面状光源、および表示装置
WO2010070798A1 (ja) * 2008-12-18 2010-06-24 パナソニック株式会社 有機エレクトロルミネッセンス表示装置及びその製造方法
WO2012124258A1 (en) * 2011-03-11 2012-09-20 Semiconductor Energy Laboratory Co., Ltd. Light-emitting element, light-emitting device, and manufacturing method of light-emitting element
KR101976065B1 (ko) * 2011-05-11 2019-05-09 삼성디스플레이 주식회사 유기발광표시장치 및 이의 제조방법
KR102059962B1 (ko) * 2013-05-22 2019-12-30 삼성디스플레이 주식회사 유기 발광 표시 장치 및 그 제조방법
JP2015005434A (ja) * 2013-06-21 2015-01-08 大日本印刷株式会社 トップエミッション型有機エレクトロルミネッセンス表示装置の製造方法、およびトップエミッション型有機エレクトロルミネッセンス表示装置
KR102439307B1 (ko) 2018-01-29 2022-09-02 삼성디스플레이 주식회사 유기발광표시장치 및 그 제조방법
CN109585699B (zh) * 2018-12-05 2020-12-29 合肥鑫晟光电科技有限公司 Oled显示面板及其制造方法、显示装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005149800A (ja) * 2003-11-12 2005-06-09 Sony Corp 表示装置およびその製造方法
JP2015158981A (ja) * 2014-02-21 2015-09-03 パナソニックＩｐマネジメント株式会社 有機エレクトロルミネッセンス素子及び照明装置
WO2015151391A1 (ja) * 2014-03-31 2015-10-08 パナソニックＩｐマネジメント株式会社 有機エレクトロルミネッセンス素子、その製造方法及び照明装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240049543A1 (en) * 2020-12-24 2024-02-08 Semiconductor Energy Laboratory Co., Ltd. Display device

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