WO2012063766A1 - 表示装置およびその製造方法 - Google Patents

表示装置およびその製造方法 Download PDF

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Publication number
WO2012063766A1
WO2012063766A1 PCT/JP2011/075566 JP2011075566W WO2012063766A1 WO 2012063766 A1 WO2012063766 A1 WO 2012063766A1 JP 2011075566 W JP2011075566 W JP 2011075566W WO 2012063766 A1 WO2012063766 A1 WO 2012063766A1
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Prior art keywords
electrode
partition wall
base
organic
partition
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PCT/JP2011/075566
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English (en)
French (fr)
Japanese (ja)
Inventor
優 梶谷
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住友化学株式会社
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Priority to KR1020137011892A priority Critical patent/KR101867637B1/ko
Priority to CN2011800540930A priority patent/CN103210699A/zh
Publication of WO2012063766A1 publication Critical patent/WO2012063766A1/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
    • H10K59/10—OLED displays
    • H10K59/17—Passive-matrix OLED displays
    • H10K59/173—Passive-matrix OLED displays comprising banks or shadow masks
    • 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
    • H10K59/8051—Anodes
    • H10K59/80515—Anodes characterised by their shape
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures
    • 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
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks

Definitions

  • the present invention relates to a display device and a manufacturing method thereof.
  • organic electroluminescence element hereinafter sometimes referred to as “organic EL element”
  • organic EL element organic electroluminescence element
  • a large number of organic EL elements corresponding to pixels are arranged on a predetermined base.
  • a partition for defining a predetermined partition is provided on the base, and a large number of organic EL elements are arranged in alignment with the regions partitioned by the partition.
  • Each organic EL element is formed by laminating a first electrode, an organic layer, and a second electrode in this order from the base side.
  • the above-mentioned organic layer can be formed by, for example, a coating method.
  • a method for forming the organic layer will be described with reference to FIG.
  • FIG. 8A first, a base 12 on which a first electrode 16 and a partition wall 13 are formed in advance is prepared. Next, the ink 17 containing the material which becomes the organic layer 18 is supplied to the region 15 surrounded by the partition wall 13 in the base 12. The supplied ink 17 is accommodated in a region (concave portion) 15 surrounded by the partition wall 13 (see FIG. 8B). And the organic layer 18 is formed when the solvent of the ink 17 vaporizes (refer FIG. 8C).
  • the partition wall 13 When the partition wall 13 is lyophilic with respect to the ink 17, the supplied ink may flow down to the adjacent recess along the surface of the partition wall 13.
  • a partition wall 13 having a certain degree of liquid repellency with respect to the ink is provided on the base 12.
  • the partition wall 13 exhibits liquid repellency
  • the ink supplied to the recess 15 evaporates while being repelled by the partition wall 13 and becomes a thin film, so that a light emitting layer with a non-uniform film thickness may be formed.
  • the portion of the organic layer 18 that contacts the partition wall 13 (that is, the peripheral portion of the organic layer 18) may be thinner than the thickness of the central portion.
  • the electrical resistance of the peripheral part of the organic layer is lower than that of the central part.
  • the peripheral edge of the light emitting layer 18 is thinner than the desired film thickness, the peripheral edge of the light emitting layer 18 may not emit light as intended.
  • a spacer 19 is provided between the partition wall 13 and the first electrode 16, and a fine gap is provided between the end of the partition wall and the first electrode (see FIG. 9).
  • the above-described conventional technique has a problem that the configuration of the display device is complicated because a spacer is required to form the gap.
  • an object of the present invention is to provide a display device having a simple structure capable of forming an organic layer having a uniform film thickness in a region surrounded by partition walls.
  • a display device including a base, a partition that defines a predetermined section on the base, and a plurality of organic electroluminescence elements respectively provided in the section defined by the partition.
  • Each organic electroluminescence element includes at least one first electrode, at least one organic layer, and at least one second electrode stacked in this order from the base side
  • the partition wall has an end in contact with the first electrode
  • the first electrode has a remaining portion excluding a portion covered by the end portion of the partition wall and a peripheral portion of the remaining portion, as viewed from one side in the thickness direction of the base, and an end portion of the partition wall and the first electrode.
  • a display device having a dent recessed toward the base from the interface with one electrode.
  • a display device including a base, a partition that defines a predetermined section on the base, and a plurality of organic electroluminescence elements respectively provided in the section defined by the partition.
  • Each organic electroluminescence element is a method of manufacturing a display device including at least one first electrode, at least one organic layer, and at least one second electrode stacked in this order from the base side, Preparing a base on which at least one first electrode is provided; and Patterning partition walls so that the end portions thereof are in contact with the first electrode; Forming a recess in the surface of the remaining portion of the first electrode except the portion covered by the end of the partition wall and the peripheral portion of the remaining portion; Forming at least one organic layer on the first electrode; Forming at least one second electrode on the organic layer.
  • the recess is formed by wet etching.
  • a display device having a simple structure capable of forming an organic layer having a uniform film thickness in a region surrounded by partition walls is provided.
  • FIG. 1 is a diagram schematically showing an enlarged part of a display device 1 according to an embodiment of the present invention.
  • FIG. 2 is an enlarged plan view schematically showing a part of the display device 1 according to the embodiment of the present invention.
  • FIG. 3A is a view for explaining a method for manufacturing a display device according to an embodiment of the present invention.
  • FIG. 3B is a view for explaining the method for manufacturing the display device according to the embodiment of the present invention.
  • FIG. 3C is a view for explaining the method for manufacturing the display device according to the embodiment of the present invention.
  • FIG. 4A is a view for explaining a method for manufacturing a display device according to an embodiment of the present invention.
  • FIG. 4B is a view for explaining the method for manufacturing the display device according to the embodiment of the present invention.
  • FIG. 4C is a view for explaining the method for manufacturing the display device according to the embodiment of the present invention.
  • FIG. 5A is a diagram for explaining a method for manufacturing a display device according to an embodiment of the present invention.
  • FIG. 5B is a view for explaining the method for manufacturing the display device according to the embodiment of the present invention.
  • FIG. 5C is a view for explaining the method for manufacturing the display device according to the embodiment of the present invention.
  • FIG. 6 is a plan view schematically showing an enlarged part of the display device 1 according to an embodiment of the present invention.
  • FIG. 7 is a diagram schematically showing an enlarged part of the display device 1 according to an embodiment of the present invention.
  • FIG. 8A is a diagram for explaining a method of manufacturing the display device.
  • FIG. 8B is a diagram for explaining a method for manufacturing the display device.
  • FIG. 8C is a diagram for explaining a method for manufacturing the display device.
  • FIG. 9 is a diagram for explaining a method of manufacturing a
  • a display device includes a base, a partition that defines a preset section on the base, and a plurality of organic EL elements provided in the section defined by the partition.
  • Each organic EL element includes at least one first electrode, at least one organic layer, and at least one second electrode stacked in this order from the base side, and the partition wall includes an end thereof.
  • a portion is in contact with the first electrode, and the first electrode has a remaining portion excluding a portion covered with an end of the partition wall as viewed from one side in the thickness direction of the base, and the remaining portion.
  • a recess is provided that is recessed toward the base side from the interface between the end of the partition wall and the first electrode.
  • Display devices mainly include active matrix drive type devices and passive matrix drive type devices. Although the present invention can be applied to both types of display devices, in this embodiment, a display device applied to an active matrix drive type display device will be described as an example.
  • FIG. 1 is a cross-sectional view schematically showing an enlarged part of the display device 1 of the present embodiment.
  • FIG. 2 is a plan view schematically showing an enlarged part of the display device 1 of the present embodiment.
  • the display device 1 mainly includes a base 2, partition walls 3 that define preset sections on the base 2, and a plurality of organic EL elements 4 that are respectively provided in sections defined by the partition walls 3. It is comprised including.
  • the partition wall 3 is formed on the base 2 in, for example, a lattice shape or a stripe shape.
  • FIG. 2 shows a display device 1 provided with a grid-like partition wall 3 as one embodiment. In the figure, the hatched area corresponds to the partition wall 3.
  • the concave portion 5 corresponds to a section defined by the partition wall 3.
  • the partition wall 3 of this embodiment is provided in a lattice shape. Therefore, when viewed from one side in the thickness direction Z of the base 2 (hereinafter sometimes referred to as “in plan view”), the plurality of recesses 5 are arranged in a matrix. That is, the recesses 5 are provided with a predetermined interval in the row direction X and aligned in the column direction Y with a predetermined interval.
  • the shape of each recess 5 in plan view is not particularly limited.
  • the recess 5 may be formed in a shape such as a substantially rectangular shape, a substantially oval shape, or an oval shape in plan view.
  • a substantially rectangular recess 5 is provided in plan view.
  • the row direction X and the column direction Y are directions perpendicular to the thickness direction Z of the base and are perpendicular to each other.
  • the partition wall 3 of this embodiment has a so-called forward taper shape. That is, the partition wall 3 of this embodiment is formed in a tapered shape as the distance from the base 2 increases.
  • the cross-sectional shape is a partial region in the vicinity of the base of the partition 3 (the surface of the base The height of the region from is equivalent to the thickness of the peripheral portion of the first electrode 6), and is formed in a tapered shape as the distance from the base is increased.
  • a partition wall having a substantially isosceles trapezoidal shape that is, an isosceles trapezoidal shape excluding a part of the vicinity of the base
  • the upper base is compared with the lower base on the base side.
  • the lower base is wider than the upper base.
  • the section of the partition wall actually formed does not necessarily have a trapezoidal shape, and the straight part and corners of the trapezoidal shape may be rounded and may be formed in a so-called kamaboko shape (dome shape).
  • the partition wall 3 is mainly provided in a region excluding a region where the organic EL element is provided.
  • the partition 3 is mainly provided in a region excluding a region where the first electrode 6 described later is provided, but the end 3 a is also formed on the peripheral portion of the first electrode 6 so as to overlap the first electrode 6. It is formed. Further, a predetermined gap 31 is formed between the end 3 a of the partition wall 3 and the first electrode 6. Note that the end 3 a of the partition wall 3 does not have to be formed so as to cover the entire peripheral edge of the first electrode 6.
  • the partition wall may be formed so that the opposite ends of the four sides of the first electrode 6 are covered by the end portions of the partition wall.
  • the end 3 a of the partition wall 3 is formed so as to cover the entire peripheral edge of the first electrode 6.
  • the width of the peripheral edge portion of the first electrode 6 covered by the end portion 3a of the partition wall 3 is usually 20 nm or more, and preferably 20 nm to 1 ⁇ m (here, the first electrode covered by the end portion of the partition wall).
  • the width of the peripheral edge means the width of the peripheral edge when viewed from one side in the thickness direction of the base, for example, in the form of FIG.
  • the row direction X is followed. (It means the width.)
  • the organic EL element 4 is provided in a section defined by the partition 3 (that is, the recess 5).
  • each organic EL element 4 is provided in each recess 5.
  • the organic EL elements 4 are arranged in a matrix like the recesses 5 and are arranged on the base 2 with a predetermined interval in the row direction X and with a predetermined interval in the column direction Y. Is provided.
  • three types of organic EL elements 4 are provided. That is, (1) a red organic EL element 4R that emits red light, (2) a green organic EL element 4G that emits green light, and (3) a blue organic EL element 4B that emits blue light are provided. These three types of organic EL elements 4R, 4G, and 4B are arranged in an aligned manner by, for example, repeating the following rows (I), (II), and (III) in the column direction Y in this order. (See FIG. 2). (I) Rows in which the red organic EL elements 4R are arranged at predetermined intervals in the row direction X. (II) Rows in which the green organic EL elements 4G are arranged at predetermined intervals in the row direction X. (III) A row in which the blue organic EL elements 4B are arranged at predetermined intervals in the row direction X.
  • an organic EL element that emits white light may be further provided.
  • a monochrome display device may be realized by providing only one type of organic EL element.
  • the organic EL element 4 includes at least one first electrode, at least one organic layer, and at least one second electrode stacked in this order from the base 2 side.
  • a layer containing an organic substance is referred to as an organic layer.
  • the organic EL element 4 includes at least one light emitting layer as an organic layer.
  • the organic EL element may further include an organic layer or an inorganic layer different from the light emitting layer, if necessary, in addition to the single light emitting layer.
  • a hole injection layer, a hole transport layer, an electron block layer, an electron transport layer, an electron injection layer, and the like may be provided between the first electrode 6 and the second electrode 10. Two or more light emitting layers may be provided between the first electrode 6 and the second electrode 10.
  • the organic EL element 4 includes a first electrode 6 and a second electrode 10 as a pair of electrodes including an anode and a cathode.
  • One of the first electrode 6 and the second electrode 10 is provided as an anode, and the other electrode is provided as a cathode.
  • first electrode 6 that functions as an anode
  • first organic layer 7 that functions as a hole injection layer
  • second organic layer 9 that functions as a light emitting layer
  • second electrode 10 that functions as a cathode.
  • the organic EL element 4 configured by being stacked on the base 2 in this order will be described.
  • the red organic EL element 4R includes a red light emitting layer 9 that emits red light.
  • the green organic EL element 4G includes a green light emitting layer 9 that emits green light.
  • the blue organic EL element 4B includes a blue light emitting layer 9 that emits blue light.
  • the first electrode 6 is provided for each organic EL element 4. That is, the same number of first electrodes 6 as the organic EL elements 4 are provided on the base 2.
  • the first electrodes 6 are provided corresponding to the arrangement of the organic EL elements 4 and are arranged in a matrix like the organic EL elements 4.
  • the partition wall 3 of the present embodiment is formed in a lattice shape mainly in a region excluding the first electrode 6, but is further formed so that the end 3 a covers the peripheral edge of the first electrode 6 (see FIG. 1).
  • the first electrode 6 has a remaining portion 6a excluding a portion covered with the end portion 3a of the partition wall as viewed from one side in the thickness direction of the base 2, and a peripheral portion of the remaining portion (that is, in the vicinity of the remaining portion).
  • the outer region (6b) has a recess that is recessed toward the base 2 from the interface 11 between the end 3a of the partition wall and the first electrode 6. By forming such a depression, a predetermined gap 31 is formed between the end 3 a of the partition wall 3 and the first electrode 6.
  • this hollow is provided over the remaining part 6a except the part covered with the edge part 3a of the said partition, and the peripheral part 6b of this remaining part, and it is one for every 1st electrode 6. It may be provided one by one.
  • the first organic layer 7 functioning as a hole injection layer is provided on the first electrode 6 in the recess 5.
  • the first organic layer 7 is provided with a different material or film thickness depending on the type of the organic EL element, if necessary. In addition, from a viewpoint of the simplicity of the formation process of the 1st organic layer 7, you may form all the 1st organic layers 7 with the same material and the same film thickness.
  • the first organic layer 7 is formed so that the end thereof is filled in the gap 31 between the partition wall 3 and the first electrode 6.
  • the second organic layer 9 functioning as a light emitting layer is provided on the first organic layer 7 in the recess 5.
  • the light emitting layer is provided according to the type of the organic EL element. That is, the red light emitting layer 9 is provided in the recess 5 in which the red organic EL element 4R is provided.
  • the green light emitting layer 9 is provided in the recess 5 in which the green organic EL element 4G is provided.
  • the blue light emitting layer 9 is provided in the recess 5 in which the blue organic EL element 4B is provided.
  • the second organic layer 9 is formed so that the end thereof is filled in the gap 31 between the partition wall 3 and the first electrode 6.
  • the second electrode 10 is formed on the entire display area where the organic EL element 4 is provided. That is, the second electrode 10 is formed not only on the second organic layer 9 but also on the partition 3, continuously formed over a plurality of organic EL elements, and provided as a common electrode for all the organic EL elements 4. It is done.
  • a step of preparing a base on which at least one first electrode is provided, and patterning a partition so that an end thereof is in contact with the first electrode A step of forming a depression in the surface of the remaining portion of the first electrode excluding the portion covered by the end of the partition wall and the peripheral portion of the remaining portion; and at least on the first electrode
  • the method includes a step of forming one organic layer and a step of forming at least one second electrode on the organic layer.
  • a base on which at least one first electrode is provided is prepared.
  • the first electrode 6 is formed on the base 2 (see FIG. 3A).
  • the base 2 on which the first electrode 6 is previously formed may be prepared by obtaining from the market a base on which the first electrode 6 is previously formed.
  • a substrate on which circuits for individually driving a plurality of organic EL elements are formed in advance may be used as the base 2.
  • a substrate on which a TFT (Thin Film Transistor) and a capacitor are formed in advance may be used as a base.
  • a plurality of first electrodes 6 are formed in a matrix on the base 2.
  • the first electrode 6 may be patterned by forming a conductive thin film on one surface of the base 2 and patterning it in a matrix by a photolithography method.
  • a mask having an opening formed in a predetermined portion is disposed on the base 2, and the first electrode 6 is selectively deposited on the predetermined portion on the base 2 through this mask. The pattern may be formed. The material of the first electrode 6 will be described later.
  • Step of forming partition walls In this step, the partition wall is patterned so that the end thereof is in contact with the first electrode.
  • an ink containing a photosensitive resin is applied on the base to form a partition wall forming film 8. Examples of the ink application method include spin coating and slit coating.
  • pre-baking is performed by heating the base 2 at a temperature of 80 ° C. to 110 ° C. for 60 seconds to 180 seconds to remove the solvent (see FIG. 3B).
  • the photosensitive resin includes a positive type resin and a negative type resin, and any resin may be used in this step.
  • a positive photosensitive resin light is irradiated to the remaining part of the partition forming film 8 except the part where the partition 3 is to be formed.
  • a negative photosensitive resin light is irradiated to a part of the partition forming film 8 where the partition 3 is to be formed.
  • a negative photosensitive resin is used in this step, a case where a negative photosensitive resin is used will be described with reference to FIG. 3C. As shown in FIG.
  • a photomask 21 is arranged on the substrate on which the partition wall forming film 8 is formed, and light is irradiated through the photomask 21, whereby the partition wall forming film 8 mainly includes the partition wall. 3 is irradiated with light.
  • the light applied to the partition wall forming film 8 is schematically indicated by an arrow symbol.
  • the exposed barrier rib forming film 8 is developed. Thereby, the partition 3 is patterned (see FIG. 4A). After development, post-bake as necessary.
  • the partition wall 3 is cured by performing post-baking by heating the base at a temperature of 200 ° C. to 230 ° C. for 15 to 60 minutes.
  • the photosensitive resin used for forming the partition includes a negative type and a positive type.
  • the portion irradiated with light is insolubilized in the developer and remains.
  • a binder resin In general, a binder resin, a crosslinking agent, a photoreaction initiator, a solvent, and other additives are blended in the ink containing the photosensitive resin.
  • the binder resin is polymerized in advance. Examples thereof include a non-polymerizable binder resin that does not have self-polymerizability and a polymerizable binder resin into which a substituent having polymerizability is introduced.
  • the binder resin has a weight average molecular weight in the range of 5,000 to 400,000 determined by gel permeation chromatography (GPC) using polystyrene as a standard.
  • the binder resin examples include phenol resin, novolac resin, melamine resin, acrylic resin, epoxy resin, and polyester resin.
  • the binder resin either a homopolymer or a copolymer obtained by combining two or more monomers may be used.
  • the binder resin is usually 5% to 90% in mass fraction with respect to the total solid content of the ink containing the photosensitive resin.
  • the crosslinking agent is a compound that can be polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator by light irradiation, and examples thereof include a compound having a polymerizable carbon-carbon unsaturated bond.
  • the crosslinking agent may be a monofunctional compound having one polymerizable carbon-carbon unsaturated bond in the molecule, or a bifunctional or trifunctional compound having two or more polymerizable carbon-carbon unsaturated bonds.
  • the above polyfunctional compounds may be used.
  • the crosslinking agent is usually 0.1 parts by mass or more and 70 parts by mass or less when the total amount of the binder resin and the crosslinking agent is 100 parts by mass.
  • the photoreaction initiator is usually 1 part by mass or more and 30 parts by mass or less when the total amount of the binder resin and the crosslinking agent is 100 parts by mass.
  • the irradiated portion is solubilized in the developer.
  • the positive photosensitive resin is generally constituted by combining a resin and a compound that becomes hydrophilic by a photoreaction.
  • the positive photosensitive resin a combination of a resin having chemical resistance and adhesion such as novolac resin, polyhydroxystyrene, acrylic resin, methacrylic resin, polyimide, and a photodegradable compound may be used. .
  • Examples of the additive that may be blended in the ink containing the photosensitive resin include a material that imparts liquid repellency to the partition walls.
  • Examples of the material imparting liquid repellency (liquid repellent) that may be used in this step include fluorine-containing compounds and silicone-containing compounds. Preferably, it is a fluorine-containing compound that exhibits excellent liquid repellency even with respect to organic solvents.
  • the fluorine-containing compound examples include compounds having a linear or branched fluoroalkyl group and / or fluoropolyether group having 1 to 8 carbon atoms.
  • the fluorine-containing compound is preferably a polymer having a crosslinkable group, and more preferably a polymer having a fluoroalkyl group and / or fluoropolyether group having 4 to 6 carbon atoms and having a crosslinkable group.
  • the fluorine-containing compound preferably has a soluble function in the developer.
  • the fluorine-containing compound is not limited to a polymer and may be a low molecular compound as long as it can impart liquid repellency to the partition wall surface after the partition wall is formed.
  • the crosslinkable group imparts a crosslinkable function to the fluorine-containing compound, and examples thereof include an ethylenically unsaturated bond group, an epoxy group, and a hydroxyl group.
  • the type of the crosslinkable group is not limited to the above as long as it has a function of crosslinking with the photosensitive resin used for forming the partition wall.
  • liquid repellent for example, MegaFac RS-101, RS-102, RS-105, RS-401, RS-402, RS-501, RS-502, RS-718 (above, manufactured by DIC), OPTOOL DAC , Optoace HP series (manufactured by Daikin Industries, Ltd.), perfluoro (meth) acrylate, perfluorodi (meth) acrylate, and the like.
  • the above liquid repellents may be used alone or in combination of two or more.
  • the liquid repellent is usually 0.1 to 3 parts by mass with respect to the total solid content of the ink containing the photosensitive resin.
  • Examples of the developer used for development include an aqueous potassium chloride solution and an aqueous tetramethylammonium hydroxide (TMAH) solution.
  • TMAH tetramethylammonium hydroxide
  • the shape of the partition 3 and the arrangement thereof are appropriately set according to the specifications of the display device such as the number of pixels and the resolution, the ease of manufacturing, and the like.
  • the width of the partition wall 3 in the row direction X or the column direction Y is about 5 ⁇ m to 50 ⁇ m
  • the height of the partition wall 3 is about 0.5 ⁇ m to 5 ⁇ m
  • the partition walls 3 adjacent to each other in the row direction X or the column direction Y That is, the width of the recess 5 in the row direction X or the column direction Y is about 10 ⁇ m to 200 ⁇ m.
  • the width of the first electrode 6 in the row direction X or the column direction Y is about 10 ⁇ m to 200 ⁇ m, respectively.
  • Step of forming a recess in the first electrode In this step, a depression is formed on the surface of the remaining portion of the first electrode 6 excluding the portion covered with the end 3a of the partition wall 3 and the peripheral portion of the remaining portion (see FIG. 4B). That is, in this process, when viewed from one side in the thickness direction of the base 2, the partition wall 3 is formed on the remaining portion 6 a excluding the portion covered by the end portion 3 a of the partition wall 3 and the peripheral portion 6 b of the remaining portion. A recess that is recessed toward the base 2 side from the interface 11 between the end 3a of the first electrode 6 and the first electrode 6 is formed (see FIG. 1).
  • the partition 3 on the first electrode 6 is used as a mask, and isotropic etching is performed on the first electrode 6 to form a depression on the surface of the first electrode 6 and also used as a mask.
  • the undercut of the partition 3 can be undercut.
  • Etching includes a wet etching method and a dry etching method, but the wet etching method is preferable.
  • the partition walls 3 may also be etched, or reaction products may be deposited on the surface.
  • the wet etching method it is easier to selectively etch the first electrode 6 than the partition walls 3, and without removing the partition walls 3 on the peripheral portions of the remaining portions, the peripheral portions of the remaining portions. It is preferable because a depression can be formed in the surface. By performing the etching in this manner, a so-called undercut can be made under the end portion 3a of the partition wall 3.
  • etching can be performed using a mixed solution of hydrochloric acid and ferric chloride solution or a mixed solution of hydrochloric acid and nitric acid.
  • etching IZO Indium Zinc Oxide
  • it can etch using the mixed solution of phosphoric acid, nitric acid, and acetic acid.
  • Examples of the dry etching method include a method in which a material is exposed to a reactive gas (reactive gas etching) and a reactive ion etching in which gas is ionized and radicalized by plasma to perform etching.
  • Examples of the fluorine-based gas used in the dry etching method include CF 4 , CHF 3 , CH 2 F 2 , C 3 F 8 , C 4 F 6 , and C 4 F 8 .
  • the remaining portion excluding the portion covered by the end of the partition wall and the peripheral portion of the remaining portion (that is, the outer region in the vicinity of the remaining portion) A depression can be formed on the surface.
  • this hollow is provided over the surface of the remaining part except the part covered by the edge part of the said partition, and the peripheral part of this remaining part, and it provides one for every 1st electrode 6. It's okay.
  • partition wall forming film 8 may be post-baked twice, and the etching may be performed between the first post-bake and the second post-bake.
  • the first temperature for performing the first post-baking is preferably lower than the second temperature.
  • the second temperature is a temperature at which the partition 3 can be reliably cured, and the first temperature is lower than a temperature at which the partition 3 can be reliably cured.
  • the first post-baking is performed by heating at 110 ° C. for 3 minutes. When the first post-bake is performed under such conditions, the partition wall 3 having low adhesion to the first electrode 6 is formed.
  • the etchant easily penetrates into the interface between the first electrode 6 and the partition wall 3, and the partition wall 3 even in the case of isotropic etching. Underneath, the etching proceeds easily in the lateral direction, and a wider undercut can be formed.
  • the partition walls 3 can be reliably cured by performing post-baking at the second temperature after etching under normal post-baking conditions. As a result, the partition wall 3 having strong adhesion to the base and the first electrode can be formed.
  • the first post-bake conditions are preferably a first temperature of 100 ° C. to 120 ° C. and a heating time of 2 minutes to 10 minutes, and the second post-bake conditions are such that the second temperature is It is preferable that the heating time is 200 to 230 ° C. and the heating time is 15 to 60 minutes.
  • the depth LD of the depression is preferably 20 nm to 300 nm.
  • the width of the peripheral portion of the depression of the first electrode 6 in plan view is usually 20 nm.
  • the width of the peripheral edge means the width of the peripheral edge when viewed from one side in the thickness direction of the base.
  • the entire peripheral edge of the first electrode is In the form of FIG. 2 covered by the end portions of the partition walls, the width along the row direction X and the width along the column direction Y means the two opposite sides of the four sides of the first electrode are the end portions of the partition walls. In the form of FIG. 6 covered by the line, it means the width along the row direction X.
  • At least one organic layer is formed on the first electrode.
  • at least one organic layer is formed by a coating method.
  • the first organic layer 7 and the second organic layer 9 are formed by a coating method.
  • the ink 22 containing the material to be the first organic layer 7 is supplied to the region (recessed portion 5) surrounded by the partition walls 3 (see FIG. 4C).
  • the ink is appropriately supplied by an optimum method in consideration of conditions such as the shape of the partition wall 3, the simplicity of the film forming process, and the film forming property.
  • the ink may be supplied by, for example, an inkjet printing method, a nozzle coating method, a relief printing method, an intaglio printing method, or the like.
  • the first organic layer 7 is formed by solidifying the supplied ink 22 (see FIG. 5A).
  • the ink may be solidified by, for example, natural drying, heat drying, or vacuum drying.
  • the material constituting the organic layer may be polymerized by heating the thin film or irradiating the thin film with light after supplying the ink. Good.
  • second organic layer another organic layer (hereinafter referred to as “second organic layer”) is formed on this organic layer (hereinafter sometimes referred to as “first organic layer”).
  • first organic layer can be hardly solubilized with respect to the ink used when forming the above.
  • the ink 22 supplied to the region (concave portion 5) surrounded by the partition wall 3 is sucked into the gap 31 between the end 3a of the partition wall 3 and the first electrode 6 by capillary action, and the solvent is evaporated. Thin film.
  • the ink can be prevented from being repelled by the partition wall 3, even if the partition wall 3 has liquid repellency, the first organic layer 7 in the vicinity of the partition wall 3 has a central portion. As compared with the case, it is possible to prevent thinning. Thereby, the flat first organic layer 7 can be formed.
  • a second organic layer 9 that functions as a light emitting layer is formed.
  • the second organic layer 9 can be formed in the same manner as the first organic layer 7. That is, three types of ink are supplied to the area surrounded by the partition wall 3, the ink containing the material that becomes the red light emitting layer 9, the ink containing the material that becomes the green light emitting layer 9, and the ink containing the material that becomes the blue light emitting layer 9.
  • Each light emitting layer 9 can be formed by solidifying them.
  • a flat second organic layer 9 can be formed.
  • Step of forming the second electrode In this step, at least one second electrode is formed on the organic layer.
  • the second electrode 10 is formed on the entire display area where the organic EL element 4 is provided. That is, the second electrode 10 is formed not only on the second organic layer 9 but also on the partition 3 and continuously formed over a plurality of organic EL elements. By forming the second electrode in this way, the second electrode 10 that functions as an electrode common to all the organic EL elements 4 is provided.
  • a flat organic layer can be formed by forming a recess in the first electrode 6 and providing the gap 31 between the end 3 of the partition wall 3 and the first electrode 6.
  • the gap 31 is provided between the end 3 of the partition wall 3 and the first electrode 6 by providing a spacer.
  • the partition wall is formed only by forming a recess in the first electrode 6. 3 can be formed between the end portion 3 and the first electrode 6, and a flat organic layer can be formed with a simple device configuration without adding a device configuration.
  • FIG. 6 is a plan view schematically showing an enlarged part of the display device of this embodiment provided with stripe-shaped partition walls. In the figure, the hatched area corresponds to the partition wall 3.
  • FIG. 7 shows a cross-sectional shape of a display device in which the display device is cut along a plane perpendicular to the row direction X. The cross-sectional shape of the display device obtained by cutting the display device along a plane perpendicular to the column direction Y is the same as FIG.
  • the display device of the present embodiment has substantially the same configuration as the display device of the above-described embodiment, only the different parts will be described below, and the corresponding parts will be denoted by the same reference numerals and redundant description will be given. May be omitted.
  • the partition walls are composed of, for example, a plurality of partition members extending in the column direction Y.
  • the partition members are arranged at predetermined intervals in the row direction X.
  • the striped recess is defined by the striped partition and the base.
  • the organic EL elements 4 are arranged at predetermined intervals in the column direction Y in the respective recesses extending in the column direction Y.
  • the first electrodes 6 are arranged in a matrix similar to the above-described embodiment.
  • the partition 3 is formed so that the end 3a covers one end of the first electrode 6 in the row direction X and the other end (see FIG. 1). As shown in FIG. 7, in the present embodiment, the end portion in the column direction Y of the first electrode 6 is not covered with the partition walls.
  • each of the first organic layer 7 and the second organic layer 9 is formed so as to extend to each recess extending in the column direction Y, and is formed so as to be continuous over a plurality of organic EL elements. .
  • the first electrode 6 is a remaining portion excluding the portion covered with the end of the partition wall when viewed from one side in the thickness direction of the base 2. 6a and a peripheral portion 6b of the remaining portion have a recess recessed closer to the base than the interface 11 between the end 3a of the partition wall and the first electrode 6. By forming such a depression, a predetermined gap 31 is formed between the end 3 a of the partition wall 3 and the first electrode 6. Accordingly, a flat organic layer can be formed as in the above-described embodiment.
  • the organic EL element has at least one light emitting layer as an organic layer.
  • the organic EL element may have, for example, a hole injection layer, a hole transport layer, an electron block layer, a hole block layer, an electron transport layer, and an electron injection layer between a pair of electrodes.
  • anode / light emitting layer / cathode b) anode / hole injection layer / light emitting layer / cathode c) anode / hole injection layer / light emitting layer / electron injection layer / cathode d) anode / hole injection layer / light emitting layer / Electron transport layer / electron injection layer / cathode e) anode / hole injection layer / hole transport layer / light emitting layer / cathode f) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode g ) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode h) Anode / light emitting layer / electron injection layer / cathode i) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cath
  • the organic EL element of this embodiment may have two or more light emitting layers.
  • the configuration of the organic EL element having two light emitting layers is as follows.
  • the layer structure shown in j) below can be given.
  • the two (structural unit A) layer structures may be the same or different.
  • the charge generation layer is a layer that generates holes and electrons by applying an electric field. Examples of the charge generation layer include a thin film made of vanadium oxide, indium tin oxide (abbreviated as ITO), indium zinc oxide (abbreviated as IZO), molybdenum oxide, or the like.
  • examples of the configuration of the organic EL element having three or more light emitting layers include the layer configuration shown in the following k). . k) anode / (structural unit B) x / (structural unit A) / cathode
  • x represents an integer of 2 or more
  • (structural unit B) x is a stack in which the structural unit B is stacked in x stages. Represents the body.
  • a plurality of (structural units B) may have the same or different layer structure.
  • an organic EL element in which a plurality of light emitting layers are directly laminated may be configured without providing a charge generation layer.
  • a base that is not chemically changed in the process of manufacturing the organic EL element is suitably used.
  • the base material include glass, plastic, polymer film, silicon plate, and laminates thereof.
  • an electrode exhibiting optical transparency is used for the anode.
  • the electrode exhibiting light transmittance a thin film made of a material such as metal oxide, metal sulfide, and metal can be used, and an electrode having high electrical conductivity and light transmittance is preferably used.
  • a thin film made of indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (abbreviated as IZO), gold, platinum, silver, copper, or the like is used.
  • ITO, IZO Or a thin film made of tin oxide is preferably used.
  • the anode may have a stacked structure in which two or more layers are stacked.
  • Examples of the method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
  • an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.
  • a material for the cathode is preferably a material having a low work function, easy electron injection into the light emitting layer, and high electrical conductivity.
  • the cathode material is preferably a material having a high reflectance with respect to visible light in order to reflect light emitted from the light emitting layer to the anode side by the cathode.
  • Examples of such cathode materials include metals, alloys, graphite, and graphite intercalation compounds.
  • the metal include alkali metals, alkaline earth metals, transition metals, and metals of Group 13 of the periodic table.
  • Specific examples include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium.
  • the alloy include an alloy of two or more of the metals; and one or more of the metals, gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin.
  • the cathode may be a transparent electrode.
  • Examples of the material thereof include conductive metal oxides such as indium oxide, zinc oxide, tin oxide, ITO, and IZO; polyaniline or a derivative thereof, polythiophene or a derivative thereof, and the like. Examples thereof include conductive organic substances.
  • the cathode may have a stacked structure in which two or more layers are stacked. An electron injection layer may be used as the cathode.
  • Examples of the method for producing the cathode include a vacuum deposition method and an ion plating method.
  • the film thickness of the anode or cathode is appropriately set in consideration of the required characteristics and the simplicity of the film forming process, and is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, and more preferably 50 nm to 500 nm. .
  • the hole injection material constituting the hole injection layer examples include oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide; phenylamine compounds; starburst amine compounds; phthalocyanine compounds; amorphous carbon Polyaniline; and polythiophene derivatives.
  • Examples of the method for forming the hole injection layer include film formation from a solution containing a hole injection material.
  • a hole injection layer may be formed by coating a film containing a hole injection material by a predetermined coating method and solidifying the solution.
  • the film thickness of the hole injection layer is appropriately set in consideration of required characteristics and process simplicity, and is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
  • Hole transport layer examples of the hole transport material constituting the hole transport layer include polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amines in side chains or main chains, pyrazoline derivatives, arylamine derivatives, stilbene derivatives. , Triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, or poly (2,5-thienylene vinylene) Or the derivative
  • guide_body etc. can be mentioned.
  • the film thickness of the hole transport layer is set in consideration of the required characteristics and the simplicity of the film forming process, and is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm. .
  • the light emitting layer usually contains an organic substance that mainly emits fluorescence and / or phosphorescence.
  • the light emitting layer may further include a dopant that assists the organic matter.
  • the dopant is added, for example, in order to improve the luminous efficiency and change the emission wavelength.
  • the organic substance which comprises a light emitting layer may be a low molecular compound or a high molecular compound, and when forming a light emitting layer by the apply
  • the polymer compound has a polystyrene-equivalent number average molecular weight of, for example, about 10 3 to 10 8 .
  • Examples of the light emitting material constituting the light emitting layer include the following dye materials, metal complex materials, polymer materials, and dopant materials.
  • dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds. Pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, oxadiazole dimers, pyrazoline dimers, quinacridone derivatives, coumarin derivatives, and the like.
  • Metal complex materials examples include central metals such as rare earth metals (eg, Tb, Eu, Dy), Al, Zn, Be, Ir, Pt, oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structures, and the like.
  • the metal complex which has these ligands can be mentioned.
  • metal complexes include metal complexes that emit light from triplet excited states such as iridium complexes and platinum complexes, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazolyl zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes. , Porphyrin zinc complex, phenanthroline europium complex, and the like.
  • Polymer material examples include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and the above-mentioned dye materials and metal complex light emitting materials. Can be mentioned.
  • the thickness of the light emitting layer is usually about 2 nm to 200 nm.
  • Electrode transport material constituting the electron transport layer
  • known materials can be used, for example, oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyano Anthraquinodimethane or derivative thereof, fluorenone derivative, diphenyldicyanoethylene or derivative thereof, diphenoquinone derivative, or metal complex of 8-hydroxyquinoline or derivative thereof, polyquinoline or derivative thereof, polyquinoxaline or derivative thereof, polyfluorene or derivative thereof, etc. Can be mentioned.
  • the film thickness of the electron transport layer is appropriately set in consideration of the required characteristics and the simplicity of the film forming process, and is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm. .
  • the electron injecting material constituting the electron injecting layer an optimum material is appropriately selected according to the type of the light emitting layer.
  • the electron injection material include alkali metals; alkaline earth metals; alloys containing one or more of alkali metals and alkaline earth metals; oxides, halides, carbonates of alkali metals or alkaline earth metals; and A mixture of these substances can be mentioned.
  • the alkali metal and its oxide, halide, and carbonate include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium oxide, sodium fluoride, potassium oxide, potassium fluoride, and oxidation.
  • the electron injection layer may have a stacked structure in which two or more layers are stacked, and examples thereof include LiF / Ca.
  • the thickness of the electron injection layer is preferably about 1 nm to 1 ⁇ m.
  • Examples of the method for forming each organic layer include a coating method such as a nozzle printing method, an ink jet printing method, a relief printing method, an intaglio printing method, and a vacuum deposition method.
  • an organic layer is formed by coating and forming an ink containing an organic EL material to be each organic layer and solidifying the ink.
  • the ink solvent used in the coating method include chlorine solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, and ketones such as acetone and methyl ethyl ketone.
  • ester solvents such as solvent, ethyl acetate, butyl acetate and ethyl cellosolve acetate, and water.
  • a TFT substrate on which a first electrode made of an ITO thin film having a thickness of 200 nm is formed is prepared (see FIG. 3A).
  • a photosensitive resin solution (Photo Nice SL-1904, manufactured by Toray Industries, Inc.) is applied to the surface of the TFT substrate by a spin coater, and heated at 110 ° C. for 120 seconds on a hot plate for pre-baking. By this pre-baking, the solvent of the photosensitive resin solution is evaporated to form a photosensitive resin thin film (see FIG. 3B).
  • the proximity exposure machine is used to expose the photosensitive resin thin film through a predetermined mask (see FIG. 3C).
  • the exposure amount is 100 mJ / cm 2 .
  • development is performed for 90 seconds with a developer (SD-1 (TMAH 2.38 wt%) solution manufactured by Tokuyama Corporation) to form a forward tapered partition (see FIG. 4A).
  • SD-1 TMAH 2.38 wt%) solution manufactured by Tokuyama Corporation
  • This partition is heated at 230 ° C. for 20 minutes to cure the resin.
  • a partition having a thickness of 1.0 ⁇ m is formed by this post-baking.
  • the substrate is introduced into a vacuum chamber, CF4 plasma surface treatment is performed, and liquid repellency is imparted to the partition wall surface.
  • ink is applied to the pixels surrounded by the partition walls using an ink jet apparatus (Litrex142P manufactured by ULVAC).
  • a poly (ethylenedioxythiophene) (PEDOT) / polystyrene sulfonic acid (PSS) aqueous dispersion having a solid content concentration of 1.5% (AI 4083, manufactured by Bayer) is used.
  • PEDOT poly(ethylenedioxythiophene)
  • PSS polystyrene sulfonic acid
  • AI 4083 manufactured by Bayer
  • the portion is filled so as to be sucked into the portion (that is, the gap between the end portion of the partition wall and the first electrode), and spreads uniformly throughout the pixels surrounded by the partition wall (see FIG. 4C).
  • This substrate is baked at 200 ° C. to form a hole injection layer having a uniform film thickness of 50 nm (see FIG. 5A).
  • a polymer light emitting material that emits red light is mixed with an organic solvent so that its concentration is 0.8 wt% to prepare red ink.
  • a polymer light emitting material that emits green light is mixed with an organic solvent so that the concentration thereof is 0.8 wt% to prepare a green ink.
  • a blue light ink is prepared by mixing a polymer light emitting material that emits blue light with an organic solvent so that its concentration is 0.8 wt%.
  • the ink Since the ink is repelled by the partition wall having a large contact angle with the ink, it is prevented from overflowing to the adjacent area through this top surface and is accommodated in the pixel.
  • the ink accommodated in the pixel is filled so as to be sucked into the portion where the undercut is formed below the end of the partition wall, and spreads uniformly in the corners of the pixel surrounded by the partition wall.
  • a Ca layer having a thickness of 20 nm and an Al layer having a thickness of 150 nm are sequentially formed on the light emitting layer by a vacuum vapor deposition method to form a second electrode (cathode).
  • a second electrode cathode
  • substrate with which the organic EL element was formed, and the glass substrate for sealing are bonded together, and it seals, and produces a display apparatus.
  • the organic EL element manufactured in this way emits light uniformly in the display region and also emits light uniformly in each pixel.

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  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
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KR101483669B1 (ko) 2013-11-20 2015-01-16 주식회사 사운들리 저전력 음파 수신 방법 및 이를 이용한 모바일 기기
JP6844620B2 (ja) * 2016-06-07 2021-03-17 ソニー株式会社 表示装置
CN111357392A (zh) * 2017-11-28 2020-06-30 堺显示器制品株式会社 有机el发光元件及其制造方法
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KR20200124372A (ko) 2019-04-23 2020-11-03 삼성디스플레이 주식회사 컬러제어부재 및 이를 적용한 표시장치
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