WO2017213262A1 - Élément électroluminescent organique, dispositif d'éclairage utilisant un élément électroluminescent organique, source de lumière planaire et dispositif d'affichage - Google Patents

Élément électroluminescent organique, dispositif d'éclairage utilisant un élément électroluminescent organique, source de lumière planaire et dispositif d'affichage Download PDF

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WO2017213262A1
WO2017213262A1 PCT/JP2017/021529 JP2017021529W WO2017213262A1 WO 2017213262 A1 WO2017213262 A1 WO 2017213262A1 JP 2017021529 W JP2017021529 W JP 2017021529W WO 2017213262 A1 WO2017213262 A1 WO 2017213262A1
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layer
organic
width
light
electrode
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English (en)
Japanese (ja)
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玲子 吉成
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凸版印刷株式会社
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal 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
    • H05B33/02—Details
    • 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
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • 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
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • 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]
    • 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
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • 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
    • H10K59/875—Arrangements for extracting light from the devices
    • H10K59/879—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses

Definitions

  • the present invention relates to an organic electroluminescence (EL) element with improved light extraction efficiency, an illumination device, a planar light source, and a display device.
  • EL organic electroluminescence
  • organic EL element utilizing an organic electroluminescence (EL) phenomenon (electroluminescence phenomenon of an organic material)
  • EL organic electroluminescence phenomenon of an organic material
  • Organic EL elements are attracting attention as next-generation light-emitting devices used in lighting devices, display devices, and the like.
  • the organic EL element has advantages such as surface emission, low temperature operation, cost reduction, weight reduction, and flexible element fabrication.
  • the organic EL element generally includes an organic EL layer including a light emitting layer containing an organic light emitting material, and an anode and a cathode sandwiching the organic EL layer. Furthermore, the organic EL layer may include an electron transport layer, an electron injection layer, a hole transport layer, a hole injection layer, and the like as necessary in addition to the light emitting layer.
  • the organic EL element has an anode made of a transparent conductive material such as ITO (Indium Tin Oxide), an organic EL layer including a light emitting layer, and a cathode made of metal on a transparent substrate such as a glass substrate.
  • a bottom emission type element that extracts light from the substrate side, or a top emission type element that includes a cathode, an organic EL layer, and an anode on the substrate in this order and extracts light from the side opposite to the substrate side. is there.
  • the organic EL element has advantages such as low viewing angle dependency, low power consumption, and extremely thin devices.
  • the organic EL element has a problem that the light extraction efficiency is low.
  • the light extraction efficiency is the ratio of the light energy emitted from the light extraction surface (for example, the substrate surface in the case of the bottom emission type) to the atmosphere with respect to the light energy emitted from the light emitting layer.
  • most of the light may be in a waveguide mode in which total reflection is repeated at the interface between a plurality of layers having different refractive indexes adjacent to the light emitting layer. In this guided mode, light is converted into heat while being guided between the layers, or the light moves through the layers to the side surface of the element and is emitted from the side surface. Such light guiding reduces the light extraction efficiency in the target direction.
  • the distance between the light emitting layer and the metal cathode is short. For this reason, a part of the near-field light from the light emitting layer is converted to surface plasmons on the surface of the cathode and lost. Such a loss also reduces the light extraction efficiency. Since the light extraction efficiency affects the brightness of a display equipped with an organic EL element, illumination, etc., various methods have been studied for the improvement.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-86353 discloses a light condensing layer composed of a light converging structure such as a microlens and a transparent resin covering the light converging structure.
  • a resin having a higher refractive index than the light condensing structure is used as the transparent resin.
  • Such a condensing layer is provided on the glass substrate to suppress total reflection occurring on the surface of the glass substrate, thereby improving the light extraction efficiency.
  • Patent Document 2 Japanese Patent No. 4762542 discloses a method of providing a one-dimensional or two-dimensional periodic fine structure on the surface of a metal layer (cathode).
  • the periodic microstructure functions as a diffraction grating.
  • the energy lost as surface plasmon on the cathode surface is extracted as light.
  • the light extraction efficiency is improved.
  • An object of the present invention is to provide an organic EL device that achieves both high light extraction efficiency and high uniformity of light emission. Furthermore, an object of this invention is to provide the illuminating device, planar light source, and display apparatus using this organic EL element.
  • the first aspect of the present invention relates to an organic EL element.
  • the organic EL element includes at least a light transmissive substrate, a light transmissive structure layer, a light transmissive first electrode, a functional layer including a light emitting layer, and a second electrode provided on the substrate.
  • the structural layer has a plurality of protrusions, and the plurality of protrusions has a distance between the tops of two adjacent protrusions of 10 ⁇ m or less, and is selected from the plurality of protrusions.
  • the width of the convex part (A) at the height (half height height) of the apparent height of one convex part (A) is defined as the convex width 1, and two convex parts adjacent to the convex part
  • the width at the half-height height of the two troughs between the part and the convex part (A) is the trough width 1 and the trough width 2, respectively, the following formula 1 is satisfied. .
  • the convex width 1 and the total convex width 1 are It is preferable to satisfy the following relationship.
  • the apparent height of the convex portion (A) is preferably 50 nm to 300 nm.
  • the total convex width 1 is preferably in the range of 300 nm to 3000 nm.
  • the ratio of the apparent height of the convex portion (A) to the total convex width 1, the (height) / (width) is in the range of 1/2 to 1/20. Is preferred.
  • the organic EL device of the present invention can further include a barrier layer between the light transmissive substrate and the structural layer.
  • the organic EL device of the present invention can further include a light extraction lens layer on the surface of the light transmissive substrate opposite to the surface on which the structural layer is provided.
  • the second aspect of the present invention relates to an organic EL element.
  • the organic EL element includes at least a light transmissive substrate, a light transmissive structure layer, a light transmissive first electrode, a functional layer including a light emitting layer, and a second electrode provided on the substrate.
  • the second electrode has a mountain-shaped wall having a network structure at least in the direction of the light-transmitting substrate, and a plurality of concave portions surrounded by the mountain-shaped wall, and the concave portion has a predetermined bottom surface.
  • the two concave portions adjacent to the concave portion are the concave portion 1 and the concave portion 2, and the center of gravity of the bottom surface of the concave portion 1 and the concave portion 2 is the center of gravity 1 and the center of gravity 2, respectively.
  • the distance between 1 and the center of gravity 2 is 10 ⁇ m or less.
  • the apparent depth of the recess is 50 nm to 300 nm.
  • the width of the recess is preferably in the range of 300 nm to 3000 nm.
  • the ratio of the apparent depth of the recess to the recess width, (depth) / (width) is preferably in the range of 1/3 to 1/20.
  • the organic EL device of the present invention can further include a barrier layer between the light transmissive substrate and the structural layer.
  • the organic EL device of the present invention can further include a light extraction lens layer on the surface of the light transmissive substrate opposite to the surface on which the structural layer is provided.
  • the present invention includes an illumination device, a planar light source, or a display device having at least a part of the organic EL element.
  • an organic EL element that achieves both high light extraction efficiency and high uniformity of light emission. Furthermore, by using this organic EL element, an illumination device, a planar light source, and a display device having excellent characteristics can be realized.
  • FIG. 1 is a cross-sectional view schematically showing an organic EL device according to an embodiment of the present invention.
  • FIG. 2 is a partially enlarged view of the organic EL element of the first embodiment.
  • FIG. 3 is a cross-sectional view schematically showing an organic EL device according to another embodiment of the first aspect of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing an organic EL device according to still another embodiment of the first aspect of the present invention.
  • FIG. 5 is a diagram for explaining the conditions of the convex portions included in the structural layer of the organic EL element according to the first embodiment of the present invention.
  • FIG. 6 is a diagram for explaining the conditions of the convex portions included in the structural layer of the organic EL element according to the first aspect of the present invention.
  • FIG. 7 is a diagram for explaining the conditions of the convex portions included in the structural layer of the organic EL element according to the first aspect of the present invention.
  • FIG. 8A is a perspective view showing an example of the shape of the structural layer of the organic EL element according to the first embodiment of the present invention.
  • FIG. 8B is a top view showing an example of the shape of the structural layer of the organic EL element according to the first aspect of the present invention.
  • FIG. 8C is a cross-sectional view showing an example of the shape of the structural layer of the organic EL element according to the first aspect of the present invention.
  • FIG. 9A is a perspective view showing another example of the shape of the structural layer of the organic EL element according to the first aspect of the present invention.
  • FIG. 9A is a perspective view showing another example of the shape of the structural layer of the organic EL element according to the first aspect of the present invention.
  • FIG. 9B is a top view showing another example of the shape of the structural layer of the organic EL element according to the first aspect of the present invention.
  • FIG. 9C is a cross-sectional view showing another example of the shape of the structural layer of the organic EL element according to the first aspect of the present invention.
  • FIG. 10 is a diagram showing an example (Example) in which the convex portions included in the structural layer of the organic EL element according to the first aspect of the present invention are regularly arranged.
  • FIG. 11 is a diagram showing the shape of the second electrode of the organic EL element according to the first aspect of the present invention.
  • FIG. 12 is a partially enlarged view of the organic EL element of the second embodiment.
  • FIG. 13 is a cross-sectional view schematically showing an organic EL element according to another embodiment of the second aspect of the present invention.
  • FIG. 14 is a cross-sectional view schematically showing an organic EL device according to still another embodiment of the second aspect of the present invention.
  • FIG. 15 is a diagram for explaining the conditions of the convex portions included in the structural layer of the organic EL element according to the second aspect of the present invention.
  • FIG. 16 is a diagram for explaining the conditions of the protrusions included in the structural layer of the organic EL element according to the second aspect of the present invention.
  • FIG. 17 is a diagram for explaining the conditions of the convex portions included in the structural layer of the organic EL element according to the second aspect of the present invention.
  • FIG. 15 is a diagram for explaining the conditions of the convex portions included in the structural layer of the organic EL element according to the second aspect of the present invention.
  • FIG. 16 is a diagram for explaining the conditions of the protrusions included in the structural layer of the organic
  • FIG. 18A is a diagram showing an example of the shape of the structural layer of the organic EL element according to the second aspect of the present invention, and is a perspective view of the structural layer.
  • FIG. 18B is a top view showing an example of the shape of the structural layer of the organic EL element according to the second aspect of the present invention.
  • FIG. 18C is a diagram showing an example of the shape of the structural layer of the organic EL element according to the second aspect of the present invention, and is a cross-sectional view of the structural layer.
  • FIG. 19A is a diagram showing an example of the shape of the second electrode of the organic EL element according to the second aspect of the present invention (a perspective view of the second electrode).
  • FIG. 19B is a diagram showing an example of the shape of the second electrode of the organic EL element according to the second aspect of the present invention, and is a top view of the second electrode.
  • FIG. 19C is a diagram showing an example of the shape of the second electrode of the organic EL element according to the second aspect of the present invention, and is a cross-sectional view of the second electrode.
  • FIG. 20 is a diagram for explaining the conditions of the concave portion and the mountain-shaped wall portion included in the second electrode of the organic EL element according to the second aspect of the present invention.
  • FIG. 21 is a schematic cross-sectional view showing an example when the organic EL element of the present invention is used in a lighting device and a surface light source.
  • FIG. 22 is a schematic cross-sectional view showing an example when the organic EL element of the present invention is used in a display device.
  • the present invention includes an organic EL element, and an illumination device, a planar light source, and a display device using the organic EL element.
  • the present invention is not limited to the first and second aspects of the organic EL element described below, and various changes or modifications can be made based on the knowledge of those skilled in the art. . Embodiments to which such changes or modifications are added are also included in the scope of the present invention.
  • the organic EL device includes at least a substrate, a structural layer, a first electrode, a functional layer including a light emitting layer, and a second electrode.
  • a specific structure of the organic EL element 100 of one embodiment is shown in FIG.
  • the organic EL device 100 of the present invention includes a light-transmitting substrate 102, a light-transmitting structural layer 104, a light-transmitting first electrode 106, a functional layer 108 including a light-emitting layer, and a second electrode 110 stacked in this order.
  • the organic EL element of the present invention is a bottom emission type organic EL element that extracts light from the substrate 102 side.
  • the organic EL element according to the first aspect of the present invention has a structural layer 104.
  • the structural layer 104 has a plurality of convex portions 202 on the surface on the first electrode 106 side toward the first electrode. Between the adjacent convex portions of the plurality of convex portions 202, there is a valley portion (in this specification, such a valley portion between the convex portions is also referred to as a “valley portion”) 204.
  • the convex portions 202 and the valley portions 204 are maintained in their shapes on the first electrode 106, the functional layer 108, and the second electrode 110 stacked on the structural layer 104.
  • the shape of the convex portion and the valley portion transferred from the structural layer 104 to the second electrode 110 can be maintained on both the substrate-side surface and the opposite surface of the second electrode 110.
  • the shape of the convex portion and the valley portion of the second electrode 110 may be formed only on the surface of the second electrode 110 on the substrate side.
  • the shape of the convex portion of the structural layer is transferred to the valley portion 206 on the surface of the second electrode on the substrate surface side, and the valley portion 204 of the structural layer is transferred to the convex portion 208 on the second electrode.
  • the second electrode 110 to which the shape of the convex portion and the valley portion is transferred can efficiently extract the light 210 emitted from the functional layer 108 as the light 212 to the substrate side. enable.
  • the first electrode 106 is an electrode that has optical transparency and serves as an anode.
  • the functional layer 108 includes a light emitting layer.
  • the second electrode 110 is an electrode serving as a counter electrode of the first electrode 106 and serves as a cathode.
  • the light transmissive property means a property transparent to light (light transmissive property).
  • the light-transmitting layer, electrode or substrate is preferably transparent particularly in the range from ultraviolet light to infrared light, and is transparent to light in the visible region. It is more preferable.
  • a condensing lens layer 302 and a light transmissive layer are formed on the surface of the light transmissive substrate 102 opposite to the structural layer 104.
  • a light extraction lens layer 310 including 304 may be further included.
  • the organic EL device includes a light-transmissive substrate 102, a barrier layer 402, a structural layer 104, a first electrode 106, a functional layer 108, and A second electrode 110 may be included.
  • the barrier layer 402 is a layer for preventing moisture harmful to the structural layer 104, the first and second electrodes 106 and 110, and the functional layer 108 from entering these layers. Therefore, the barrier layer 402 is preferably provided between the light transmissive substrate 102 and the structural layer 104.
  • the organic EL element of this embodiment may further include the above-described light extraction lens layer 310 (see FIG. 4).
  • a portion including at least the light transmissive substrate 102, the structural layer 104, and the first electrode 106 in FIG. 4 is also referred to as a light extraction substrate 120.
  • the light extraction lens layer 310 and the barrier layer 402 which are optional components can be included in the light extraction substrate 120.
  • the light transmissive substrate 102 is a plate-like member that transmits predetermined light (particularly preferably, light in the visible region).
  • the material is not particularly limited as long as it is conventionally used for organic EL elements such as glass and plastic.
  • the light transmissive substrate 102 is preferably a glass plate, a substrate made of a polymer, a resin film, or the like.
  • glass plate examples include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like.
  • Examples of the material of the substrate made of polymer include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like.
  • resin film materials include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefins such as polyethylene and polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, and cellulose acetate propionate.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polyolefins such as polyethylene and polypropylene
  • cellophane cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, and cellulose acetate propionate.
  • CAP cellulose acetates such as cellulose acetate phthalate (TAC), cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, poly Etherketone, polyimide, polyethersulfone (PES), polyphenylenesulfur I de, polysulfones, polyetherimide, polyether ketone imide, polyamide, fluorine resin, nylon, polymethyl methacrylate, acrylic or polyarylates, may be mentioned cycloolefin resin.
  • a resin film with a barrier layer in which a barrier layer described below is already provided on the surface of the resin film can also be used.
  • the barrier layer 402 is an optional component in the organic EL element of the present invention.
  • the barrier layer may be a hybrid film including an inorganic or organic film, or both.
  • the barrier layer has a water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) of 0.01 g / (m 2 ⁇ 24 h) when measured by a method according to JIS K 7129-1992. It preferably has the following barrier characteristics.
  • the barrier layer has an oxygen permeability of 1.0 ⁇ 10 ⁇ 3 cm 3 / (m 2 ⁇ 24 h ⁇ atm) or less when measured by a method according to JIS K 7126-1987, and has a water vapor permeability of It is preferably 1.0 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • the water vapor permeability is more preferably 1.0 ⁇ 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less.
  • the material of the barrier layer may be any material that has a function of suppressing entry of moisture, oxygen, and the like that cause deterioration of the organic EL element 100.
  • silicon oxide, silicon dioxide, silicon nitride, and the like can be given.
  • a barrier layer made of an inorganic material may be fragile. In order to improve this fragility, it is more preferable that the barrier layer has a multi-layer structure in which an inorganic material layer made of the above-described inorganic material and an organic material layer made of an organic material are laminated.
  • the order of stacking the inorganic material layer and the organic material layer is not particularly limited, but it is preferable to stack both layers alternately.
  • esters include (meth) acrylates that can be used alone or in combination with other multifunctional or monofunctional (meth) acrylates.
  • the method for forming the barrier layer is not particularly limited, and means usually used in this technical field may be used.
  • vacuum deposition method sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma polymerization method, plasma CVD (Chemical Vapor Deposition) method, laser A CVD method, a thermal CVD method, a coating method, or the like can be used.
  • a formation method by an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.
  • the organic EL element of the present invention has a structural layer 104.
  • the structural layer 104 has a plurality of convex portions 202 on the surface on the first electrode 106 side in the direction of the first electrode (see, for example, FIG. 2).
  • a valley portion 204 exists between adjacent convex portions of the plurality of convex portions 202.
  • the shapes of the convex portions 202 and the valley portions 204 are transferred and maintained on the first electrode 106, the functional layer 108, and the second electrode 110 stacked on the structural layer 104.
  • the convex portion provided in the structural layer 104 needs to satisfy a predetermined condition described below with reference to FIGS.
  • the distance between the tops of adjacent convex parts is within a predetermined range.
  • FIG. 5 shows the structural layer 104 in which a plurality of convex portions 502 are formed on the light transmissive substrate 102.
  • the distance between the tops of adjacent convex portions is 10 ⁇ m or less, preferably 10 ⁇ m to 3 ⁇ m, more preferably 5 to 3 ⁇ m. More preferably, the distance between the tops of adjacent convex portions of the convex portion 502 is 3 ⁇ m or less.
  • FIG. 6 shows a structural layer 104 having a convex portion 502 similar to FIG. A cross section in which the structural layer 104 is cut along a plane 602 passing through the vertices 702, 704, 706, 708, and 709 of the plurality of convex portions of such a structural layer is considered.
  • FIG. 7 shows the cross-sectional shape of the convex portion 502a (having the apex 702) and two adjacent convex portions 502b (having the apex 704) and 502c (having the apex 706). It is drawing which showed.
  • the convex portion 502a has a height 760 from the bottom side 104 a of the structural layer 104 to the top portion 702 thereof.
  • a valley portion 770 between the convex portion 502 a and the convex portion 502 b has a height 750 from the bottom side 104 a of the structural layer 104 to the bottom portion 710.
  • the valley portion 772 between the convex portion 502 a and the convex portion 502 c has a height 752 from the bottom side 104 a of the structural layer 104 to the bottom portion 712.
  • the average of the heights 750 and 752 of the two valleys 770 and 772 is taken to calculate the average height 754 of the valleys.
  • the average height 754 of the valley is subtracted from the height 760 to the vertex 702 of the convex portion 502a, and this value is set as the apparent height 762 of the convex portion 502a.
  • a half position of the apparent height 762 of the convex portion 502a is defined as a half-value height 764 of the convex portion 502a.
  • the width of the convex portion 502a (defined as convex width 1) 766 at the position of the half height height 764 of the convex portion 502a, and the half height height 764 of the convex portion 502a of the two valley portions 770 and 772
  • the widths 780 (valley width 1) and 782 (valley width 2) at the position are determined.
  • the convex width 1 is larger than a value obtained by adding the valley width 1 and the valley width 2 and dividing by 2. That is, it is desirable to satisfy the following (Formula 1).
  • Convex width 1 [valley width 1 + valley width 2] / 2 (Formula 1)
  • Convex width 1 Width of convex portion (502a) at position of half value (764) of convex portion (502a)
  • Valley width 1 Width of trough portion (770) at position of half value (764) of convex portion (502a)
  • Valley width 2 The width (782) of the valley portion (772) at the half value (764) position of the convex portion (502a).
  • Half value (764) of the convex portion (502a) Apparent height (762) of the convex portion (502a), and the average height (754) of two adjacent valleys of the convex portion (502a), Half of the value subtracted from the height (760) to the top (702) of the convex part (502a).
  • the required value of the above is, for example, to observe a desired region of the convex portion and valley portion of the structural layer in two dimensions using a scanning probe microscope AFM5400 (manufactured by Hitachi High-Tech Science Co., Ltd.). Can be obtained by: In this invention, after measuring an image about 10 places of a convex part and a trough part, 10 points
  • the region may be periodically arranged in the structural layer 104 or may be randomly arranged.
  • the region satisfying the above (Equation 1) is in the range of 50% to 100%, preferably 80% to 100% of the entire region of the structural layer.
  • a structural layer in which convex portions are regularly arranged is more preferable, and a structural layer in which regular convex portions are arranged in the entire structural layer is most preferable.
  • the convex portion 502a preferably further satisfies the following relationship.
  • the distance between the bottom 710 of the valley 770 and the bottom 712 of the valley 772 is defined as the full width 790 of the convex portion 502a (also referred to as the total convex width 1). It is preferable that the total convex width 1 and the convex width 1 of the convex portion 502a satisfy the following relationship (Equation 2).
  • the structural layer 104 is light transmissive.
  • the shape of the convex portion of the structural layer 104 is not particularly limited as long as the shape transferred to the second electrode 110 efficiently reflects the light emitted from the functional layer 108 toward the light transmissive substrate 102 side.
  • FIGS. 8A to 8C a hemispherical convex portion 502 as shown in FIGS. 8A to 8C can be given.
  • 8A is a perspective view schematically showing the structural layer 104 having a hemispherical convex portion 502
  • FIG. 8B is a plan view of the structural layer 104 seen from the direction in which the convex portion is formed
  • FIG. FIG. 8B is a sectional view taken along line VIIIC-VIIIC of 8B.
  • the protrusions 502 preferably have a regular arrangement as shown in FIGS. 8A to 8C.
  • the arrangement transferred to the second electrode 110 efficiently uses the light emitted from the functional layer 108.
  • the structural layer may have an arrangement in which a region having a regular arrangement exists in a part of the entire surface of the structural layer, such as the regions 810 and 812 surrounded by a dotted line in FIG. 8B. .
  • FIG. 9A to FIG. 9C show examples of other convex portions.
  • 9A is a perspective view showing an outline of the structural layer 104 having the convex portions 502
  • FIG. 9B is a plan view of the structural layer 104 seen from the direction in which the convex portions are formed
  • FIG. 9C is an IXC of FIG. 9B. -IXC sectional view.
  • the convex portion in this example has a mountain shape in which the top portion of the convex portion is a point and the bottom portion of the convex portion has a quadrangular shape. A cross-sectional view of this shape is as shown in FIG. 9C.
  • FIG. 10 shows an actual shape of a preferable convex portion of the present invention. This shape is the same as that shown in FIGS. 9A to 9C.
  • the bottom surface as shown in FIGS. 9A to 9C may have a polygonal shape such as a triangular shape, a pentagonal shape, or a hexagonal shape instead of a rectangular shape. In the present invention, those having a bottom shape close to a circle are particularly preferable.
  • the structural layer in which the convex portions are randomly formed does not satisfy the condition of the above (formula 1) and the condition of the distance adjacent to the convex portions. Therefore, the structural layer in which the convex portions are randomly formed does not become the structural layer 104 of the present invention having preferable convex portions.
  • the shape of the structural layer is transferred to the second electrode.
  • the transferred protrusions and valleys of the second electrode 110 can be formed on both the substrate-side surface of the second electrode 110 and the opposite surface.
  • the shape of the convex portion and the valley portion of the second electrode 110 may be formed only on the surface of the second electrode 110 on the substrate side.
  • the shape of the convex portion of the structural layer is transferred to the valley portion 206 on the surface of the second electrode on the substrate surface side, and the valley portion 204 of the structural layer is On the electrode, it is transferred to the convex portion 208.
  • the second electrode 110 to which the shape of the convex portion and the valley portion is transferred can efficiently extract the light 210 emitted from the functional layer 108 as the light 212 to the substrate side. enable.
  • the shape of the structural layer 104 transferred to the second electrode 110 suppresses plasmon absorption on the second electrode 110. Further, part of light emitted from the light emitting layer of the functional layer 108 is reflected by the second electrode toward the transmissive substrate 102, and light can be extracted effectively.
  • “reflection” of light on the second electrode means that the shape of the structural layer 104 transferred to the second electrode 110 suppresses plasmon absorption, so that light is transmitted to the light transmissive substrate side. This means that both the light is efficiently extracted and a part of light emitted from the light emitting layer of the functional layer 108 is reflected to the transmissive substrate 102 side by the second electrode.
  • the shape of the structural layer transferred to the second electrode 110 that reflects light from the functional layer including the light emitting layer and effectively extracts it.
  • the shape of the second electrode is a convex portion (which corresponds to a trough portion of the structural layer 104) and a trough portion (this is a convex portion of the structural layer 104) formed on the light transmissive substrate side of the second electrode. Corresponding to). Therefore, when the relationship of the above (Formula 1) is seen with respect to the second electrode, the convex portion and trough portion of the structural layer 104 may be read in reverse. In the organic EL element, the shape of the structural layer 104 is sufficiently reflected up to the second electrode.
  • the height (apparent height) of the convex portion of the structural layer 104 of the first aspect is preferably 50 nm or more and 300 nm or less.
  • the height of the plurality of convex portions is lower than 50 nm, the height of the convex portions is low, so that the effect of surface plasmon resonance cannot be obtained.
  • the height of the plurality of convex portions is higher than 300 nm, the height of the convex portions greatly exceeds the thickness of each layer such as the light emitting layer included in the functional layer, and the uniformity of the layer is significantly reduced. This causes uneven light emission and short-circuit (short circuit), leading to the occurrence of light emission failure.
  • the total width of the convex portions of the structural layer 104 is not less than 300 nm and not more than 3000 nm.
  • the width of the convex portion becomes smaller than the emission wavelength, and plasmon resonance becomes insufficient. For this reason, light is not re-emitted and the effect of sufficiently reducing plasmon absorption cannot be obtained.
  • the total width of the convex portion is larger than 3000 nm, the total width of the convex portion (total convex width 1) is larger than the wavelength of light emitted from the light emitting layer. Thereby, the light absorbed without causing plasmon resonance increases, and the effect of reducing plasmon absorption cannot be sufficiently obtained.
  • the ratio (height) / (width) of the height of the convex portion of the structural layer 104 (apparent height) to the total width of the convex portion (total convex width 1) is from 1/2. A range of 1/20 is preferable. If the ratio of the apparent height of the convex portion to the total width of the convex portion is greater than 1 ⁇ 2, the slope between the convex portion and the valley portion is not uniform when the structural layer 104 is formed, and uneven light emission or short ( Cause short circuit). This leads to a light emission failure of the organic EL element.
  • the ratio of the apparent height of the convex part to the total width of the convex part is smaller than 1/20, the slope of the slope between the convex part and the valley part becomes loose. Thereby, the traveling direction of the light re-emitted by plasmon resonance spreads in the lateral direction of the element. This phenomenon reduces light extracted through the light transmissive substrate 102. For this reason, the luminous efficiency cannot be improved.
  • the material constituting the structural layer 104 of the first aspect is preferably a light transmissive resin.
  • the light transmissive resin is, for example, low density or high density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-norbornene copolymer. , Ethylene-dimethanooctahydronaphthalene copolymer [ethylene-dmon (DMON) copolymer], polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin, etc.
  • DMON dimethyl methacrylate copolymer
  • Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate
  • Amide resins such as nylon-6, nylon-6,6, metaxylenediamine-adipic acid condensation polymer, polymethylmethacrylamide, etc .
  • Polymethylmeta Acrylic resins such as acrylate
  • Styrene-acrylonitrile resins such as polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, polyacrylonitrile
  • Hydrophobized cellulose resins such as cellulose triacetate and cellulose diacetate
  • Halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and polytetrafluoroethylene
  • hydrogen-bonding resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and cellulose derivatives
  • fine particles may be added to adjust the refractive index or give a light scattering effect.
  • Such fine particles may be particles composed of inorganic fine particles, organic fine particles, or a combination thereof.
  • the organic fine particles include acrylic polymers, styrene polymers, styrene-acrylic polymers and cross-linked products thereof, melamine-formalin condensates, polyurethane-based polymers, polyester-based polymers, silicone-based polymers, fluorine-based polymers, or copolymers thereof.
  • examples thereof include fine particles made of a coalescence or fine particles made of a combination thereof.
  • inorganic fine particles include clay compound particles such as smectite, kaolinite, and talc, fine particles made of inorganic oxides such as silica, titanium oxide, alumina, silica alumina, zirconia, zinc oxide, barium oxide, strontium oxide, or Examples include fine particles made of inorganic compounds such as calcium carbonate, barium carbonate, barium chloride, barium sulfate, barium nitrate, barium hydroxide, aluminum hydroxide, strontium carbonate, strontium chloride, strontium sulfate, strontium nitrate, strontium hydroxide, and glass. be able to.
  • first electrode 106 and the second electrode 110 according to the first aspect will be described.
  • description will be made assuming that the first electrode 106 is an anode and the second electrode 110 is a cathode.
  • the present invention is not limited to these examples.
  • the material of the anode that is the first electrode 106 is preferably, for example, a metal, an alloy, a metal oxide, a conductive compound, or a mixture thereof.
  • Examples of the material of the anode include tin oxide doped with (added to) antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and the like.
  • the anode may be a laminate, for example, a laminate of layers made of the above materials.
  • the material of the anode is preferably a conductive metal oxide, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.
  • the light transmittance of the anode be greater than 10%.
  • the sheet resistance of the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the anode depends on the material used for the anode, it is usually in the range of 10 nm to 1000 nm, preferably in the range of 10 nm to 200 nm.
  • the material of the second electrode 110 (cathode) of the first aspect for example, a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an electrically conductive alloy compound, and a mixture thereof are suitable.
  • the cathode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) mixture, Indium, lithium / aluminum mixtures, rare earth metals and the like can be mentioned.
  • the cathode material is a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this, for example, magnesium.
  • a silver / silver mixture a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like.
  • the sheet resistance of the cathode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the cathode is usually in the range of 10 nm to 5 ⁇ m, preferably in the range of 50 nm to 200 nm.
  • the functional layer 108 is a layer including a light emitting layer. This layer is provided between the first electrode 106 and the second electrode 110.
  • the first electrode 106, the functional layer 108, and the second electrode 110 can have various stacked structures.
  • the first electrode 106 is an anode and the second electrode 110 is a cathode. That is, all layers between the anode and the cathode are the functional layer 108.
  • the symbol “/” indicates that the layers sandwiching the symbol “/” are stacked adjacent to each other.
  • the configuration of the functional layer 108 and the stacked structure of the first electrode 106, the functional layer 108, and the second electrode 110 are not limited to the following layer configurations a) to p).
  • 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 / cathode e) Anode / hole injection layer / emission layer / electron transport layer / electron injection layer / cathode f) Anode / hole transport layer / emission layer / cathode g) Anode / hole transport layer / emission layer / Electron injection layer / cathode h) anode / hole transport layer / light emitting layer / electron transport layer / cathode i) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode j) anode / hole Injection layer / hole transport layer
  • each layer (light emitting layer, injection layer, transport layer) constituting the functional layer 108 will be described.
  • the light emitting layer is a layer that emits light by recombination of electrons and holes moving from the electrode, injection layer, or transport layer.
  • the portion that emits light may be in the layer of the light emitting layer, or may be the interface between the light emitting layer and the adjacent layer.
  • the total thickness of the light emitting layer is not particularly limited.
  • the film thickness is preferably 2 nm to 5 ⁇ m, more preferably 2 nm to 200 nm, and particularly preferably in the range of 10 nm to 20 nm. This is because the uniformity of the film and the unnecessary application of high voltage during light emission are prevented, and the stability of the emission color with respect to the drive current is improved.
  • the light emitting layer is at least one of a blue light emitting layer, a green light emitting layer, and a red light emitting layer.
  • the blue light emitting layer has a light emission maximum wavelength in the range of 430 nm to 480 nm
  • the green light emission layer has a light emission maximum wavelength in the range of 510 nm to 550 nm
  • the red light emission layer has a light emission maximum wavelength in the range of 600 nm to 640 nm.
  • a certain monochromatic light emitting layer is preferable.
  • the light emitting layer may be a layer in which a light emitting layer of at least three colors (blue light emitting layer, green light emitting layer, red light emitting layer) is laminated to form a white light emitting layer. Furthermore, when a plurality of light emitting layers are stacked, a non-light emitting intermediate layer may be provided between the light emitting layers.
  • the light emitting layer of the organic EL device of the first aspect of the present invention is preferably a white light emitting layer. That is, in the present invention, the case where the light emitting layer of the organic EL element is a white light emitting layer is particularly effective. It is preferable that the illumination device, the planar light source, and the display device of the present invention include a white light emitting layer. Therefore, it is preferable that the illuminating device, the planar light source, and the display device of the present invention have at least a part of an organic EL element whose light emitting layer is a white light emitting layer.
  • the light emitting layer contains a light emitting host compound and a light emitting dopant compound such as a phosphorescent dopant or a fluorescent dopant.
  • Examples of the luminescent host compound include those having a basic skeleton such as carbazole derivatives, triarylamine derivatives, aromatic derivatives, nitrogen-containing heterocyclic compounds, thiophene derivatives, furan derivatives, oligoarylene compounds, carboline derivatives, diaza And carbazole derivatives.
  • a basic skeleton such as carbazole derivatives, triarylamine derivatives, aromatic derivatives, nitrogen-containing heterocyclic compounds, thiophene derivatives, furan derivatives, oligoarylene compounds, carboline derivatives, diaza And carbazole derivatives.
  • fluorescent dopant compounds include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, Examples thereof include stilbene dyes, polythiophene dyes, and rare earth complex phosphors.
  • the injection layer is a layer provided between the electrode and the light emitting layer as necessary in order to lower the driving voltage, improve the light emission luminance, or the like.
  • the injection layer includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
  • the hole injection layer is provided between the anode and the light emitting layer (for example, the above-described layer configurations b), c), d), e)), or the anode and the hole transport layer. (For example, between the layer configurations j), k), l), and m)) described above.
  • the electron injection layer is provided between the cathode and the light emitting layer (for example, layer configurations (c), g), k), n)), or between the cathode and the electron transport layer (for example, a layer). Provided in configurations e), i), m), and p)).
  • a phthalocyanine buffer layer typified by copper phthalocyanine
  • an oxide buffer layer typified by vanadium oxide
  • an amorphous carbon buffer layer or a conductive polymer such as polyaniline (emeraldine) or polythiophene is used.
  • Polymer buffer layer and the like are examples of a phthalocyanine buffer layer typified by copper phthalocyanine, an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, or a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • Examples of the electron injection layer include a metal buffer layer typified by strontium and aluminum, an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, and aluminum oxide.
  • the hole injection layer and the electron injection layer are desirably very thin films.
  • the film thickness of these layers is preferably in the range of 0.1 nm to 5 ⁇ m.
  • the blocking layer is a layer provided on the functional layer as necessary.
  • the blocking layer includes a hole blocking layer and an electron blocking layer.
  • the hole blocking layer has the function of an electron transport layer in a broad sense.
  • the hole blocking layer is made of a hole blocking material having a function of transporting electrons and a very small ability to transport holes.
  • the hole blocking layer can improve the probability of recombination of electrons and holes by blocking the transport of holes while transporting electrons.
  • the electron transport layer described later can be used as a hole blocking layer as necessary.
  • the film thickness of the hole blocking layer is preferably 3 nm to 100 nm, and more preferably 5 nm to 30 nm.
  • the hole blocking layer preferably contains the carbazole derivative, carboline derivative, diazacarbazole derivative, or the like mentioned as the host compound.
  • the electron blocking layer has a function of a hole transport layer in a broad sense.
  • the electron blocking layer is made of a material having a function of transporting holes and a remarkably small ability to transport electrons.
  • the electron blocking layer can improve the probability of recombination of electrons and holes by blocking the transport of electrons while transporting holes.
  • the hole transport layer described later can be used as an electron blocking layer as necessary.
  • the thickness of the electron blocking layer is preferably 3 nm to 100 nm, and more preferably 5 nm to 30 nm.
  • the transport layer is a layer provided as necessary for transporting holes or electrons.
  • the transport layer includes a hole transport layer and an electron transport layer.
  • the hole transport layer is made of a hole transport material having a function of transporting holes.
  • the hole injection layer and the electron blocking layer described above are included in the hole transport layer in a broad sense.
  • the hole transport layer can be a single layer or a plurality of layers.
  • the hole transport material has any of the characteristics of hole injection or transport and electron barrier, and may be either organic or inorganic.
  • hole transport materials include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives. Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • the hole transport layer contains one or more of the above-described hole transport materials.
  • the hole transport layer is formed as a thin film from the above-described hole transport material by, for example, a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method.
  • the film thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 nm to 200 nm.
  • the electron transport layer is made of an electron transport material having a function of transporting electrons.
  • the electron injection layer and hole blocking layer described above are included in the electron transport layer in a broad sense.
  • the electron transport layer may be a single layer or a plurality of layers.
  • the electron transport layer is provided adjacent to the cathode side of the light emitting layer.
  • the electron transport material (also serving as a hole blocking material) used for the electron transport layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • the electron transport material can be selected from any conventionally known compounds. Examples of the electron transport material include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • a metal complex of 8-quinolinol derivative such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo) is used.
  • a metal complex in which the metal is replaced with In, Mg, Cu, Ca, Sn, Ga, or Pb can be used.
  • metal-free or metal phthalocyanine, or a material in which the terminal thereof is substituted with an alkyl group or a sulfonic acid group can also be suitably used.
  • the distyrylpyrazine derivatives exemplified as the material for the light emitting layer can also be used as the electron transporting material.
  • an inorganic semiconductor such as n-type-Si or n-type-SiC can also be used as the electron transport material.
  • the electron transport layer contains one or more materials among the electron transport materials described above. It is also possible to use an electron transport layer doped with impurities and having high n-type characteristics.
  • the electron transport layer is formed from the above-described electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.
  • the film thickness of the electron transport layer is not particularly limited, but is usually in the range of 5 nm to 5 ⁇ m, preferably in the range of 5 nm to 200 nm.
  • a light extraction lens layer 310 is optionally provided as a light scattering or condensing layer on the surface of the light transmissive substrate 102 opposite to the surface on which the structural layer 104 is provided (see FIGS. 3 and 4).
  • the light extraction lens layer 310 includes a light transmissive sheet 304 having light transmissive properties, and a lens layer 302 provided on the surface of the light transmissive sheet 304.
  • the lens layer 302 may be formed by molding the surface of the light transmissive sheet 304 into a microlens array.
  • a so-called condensing sheet may be used as the lens layer 302. With such a light extraction lens layer 310, light can be condensed in a specific direction, for example, the light extraction direction of the organic EL element (direction 112 in FIG. 1), and the luminance of light in the specific direction can be increased.
  • Examples of the resin material constituting the light extraction lens layer 310 include low density or high density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, and ethylene-octene copolymer.
  • Ethylene-norbornene copolymer ethylene-DMON copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, polyolefin resin such as ionomer resin; polyethylene terephthalate, poly Polyester resins such as butylene terephthalate and polyethylene naphthalate; nylon-6, nylon-6,6, metaxylenediamine-adipic acid condensation polymer; amide resins such as polymethylmethacrylamide; acrylic resins such as polymethylmethacrylate ; Po Styrene-acrylonitrile resins such as styrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, polyacrylonitrile; hydrophobic cellulose resins such as cellulose triacetate and cellulose diacetate; polyvinyl chloride, polyvinylidene chloride Hal
  • fine particles may be added to the resin material described above to further improve the light scattering effect.
  • the fine particles contained in the light extraction lens layer 310 may be particles made of inorganic fine particles, organic fine particles, or a combination thereof.
  • Such fine particles are, for example, acrylic polymers, styrene polymers, styrene-acrylic polymers and cross-linked products thereof, melamine-formalin condensates, polyurethane polymers, polyester polymers, silicone polymers, fluorine polymers, Or the microparticles
  • inorganic fine particles include clay compound particles such as smectite, kaolinite, and talc, fine particles made of inorganic oxides such as silica, titanium oxide, alumina, silica alumina, zirconia, zinc oxide, barium oxide, strontium oxide, or Examples include fine particles made of inorganic compounds such as calcium carbonate, barium carbonate, barium chloride, barium sulfate, barium nitrate, barium hydroxide, aluminum hydroxide, strontium carbonate, strontium chloride, strontium sulfate, strontium nitrate, strontium hydroxide, and glass. be able to.
  • the display area of the organic EL element 100 is preferably covered with a sealing member.
  • the sealing means include a method of bonding the sealing member, the electrode, and the support substrate with an adhesive.
  • the sealing member should just be arrange
  • the shape of the sealing member may be a concave plate shape or a flat plate shape. Further, the sealing member is not particularly required to have transparency or electrical insulation.
  • the sealing member examples include a glass plate, a polymer plate or a film, a metal plate or a film.
  • the glass plate include soda lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like.
  • the metal plate include a plate made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • Examples of the adhesive used for sealing include a photo-curing or thermosetting adhesive having a reactive vinyl group such as an acrylic acid oligomer and a methacrylic acid oligomer, and a moisture curing type such as 2-cyanoacrylate. Can be mentioned.
  • Examples of the adhesive include an epoxy-based thermosetting type or a chemical curing type (two-component mixing). Examples of other adhesives include hot melt polyamides, polyesters, and polyolefins.
  • a cationic curable ultraviolet curable epoxy resin adhesive can be used.
  • the organic EL element 100 may be deteriorated by heat treatment. For this reason, it is preferable to use a material that can be cured in a temperature range from room temperature to 80 ° C. as the adhesive.
  • an adhesive in which a desiccant is dispersed may be used.
  • coating of the adhesive agent to a sealing part may use a commercially available dispenser, and may perform it by printing like screen printing.
  • a gas phase or liquid phase inert substance into the gap between the sealing member and the display area of the organic EL element 100.
  • a gas phase or liquid phase inert substance for example, it is preferable to inject an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicone oil.
  • the gap between the sealing member and the display area of the organic EL element 100 can be evacuated.
  • a hygroscopic compound can also be enclosed inside the sealing member.
  • Hygroscopic compounds include, for example, metal oxides (eg, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide), sulfates (eg, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.) ), Metal halides (eg, calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.), perchloric acids (eg, barium perchlorate) Examples thereof include magnesium perchlorate and the like. Of these, anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.
  • metal oxides eg, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide
  • sulfates eg, sodium sulfate, calcium sulfate, magnesium sulf
  • the manufacturing method of the organic EL element of a 1st aspect includes the method for producing the organic EL device of the first aspect. This manufacturing method includes at least the following steps.
  • the width of the convex portion (A) at half height (half height) of the apparent height of one convex portion (A) selected from a plurality of convex portions is 5 ⁇ m or less.
  • the convex width 1 is defined as A process that satisfies, Convex width 1> [valley width 1 + valley width 2] / 2 (Formula 1) (C) forming a first electrode on the structural layer; (D) forming a functional layer on the first electrode; (E) A step of forming a second electrode on the functional layer.
  • Step (A) is a step of selecting an appropriate one from the light-transmitting substrate as described above, and performing cleaning and necessary pretreatment as necessary.
  • the cleaning and the necessary pretreatment are usually performed on the substrate of the organic EL element, and there is no particular limitation.
  • Step (B) is a step of forming a structural layer having a plurality of convex portions.
  • the substrate is pressed to transfer the desired convex shape to the light transmissive resin.
  • the obtained light-transmitting resin having a convex shape is photocured or thermoset to form a structural layer.
  • the structural layer can be formed by such a procedure.
  • the shape transfer substrate has a shape that is transferred in advance so as to satisfy the condition of the convex portion defined in the step (B).
  • Step (B) can be performed using a conventional pattern forming method such as a photolithography method in addition to the transfer method as described above.
  • Step (C) is a step of forming an anode that is a first electrode.
  • the anode may be, for example, (1) a wet method such as a printing method or a coating method, (2) a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or (3) a chemical method such as CVD or plasma CVD method. It can be formed on the substrate according to a method selected from known methods such as a method in consideration of suitability with the material constituting the anode. For example, when ITO is selected as the anode material, the anode can be formed by a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.
  • etching by photolithography or the like or physical etching by laser or the like can be used for patterning when forming the anode.
  • vacuum deposition, sputtering, or the like may be performed with the masks overlapped, and a lift-off method, a printing method, or the like may be employed.
  • Step (D) is a step of forming a functional layer including a light emitting layer.
  • the functional layer can be formed by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method.
  • Step (E) is a step of forming a cathode that is the second electrode.
  • a 2nd electrode can be formed by well-known methods, such as vapor deposition and sputtering, using the metal material etc. which can be utilized for the cathode mentioned above.
  • a thin film of a metal material can be formed over the entire surface on which the second electrode is formed, and the second electrode can be formed using a pattern formation method such as a photolithography method.
  • a step of forming a barrier layer may be further included between the step (A) and the step (B).
  • the barrier layer uses the above-described barrier layer materials, and includes vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weighting. It can be formed by a known method such as a legal method, a plasma CVD (Chemical Vapor Deposition) method, a laser CVD method, a thermal CVD method, or a coating method.
  • a plasma CVD Chemical Vapor Deposition
  • the manufacturing method of the organic EL element of the 1st aspect of this invention is the process of forming the light extraction lens layer 310 which has the condensing lens layer 302 and the light transmissive layer 304 following the said process (E). May be included.
  • the light extraction lens layer 310 can be formed by a method similar to the conventional method.
  • the structural layer 104 has a plurality of convex portions 202 on the surface on the first electrode 106 side toward the first electrode.
  • a valley portion 204 exists between adjacent convex portions of the plurality of convex portions 202.
  • each shape is transcribe
  • the shape of the second electrode first reflects light emitted from the light emitting layer of the functional layer efficiently toward the light transmissive substrate side.
  • the concave structure of the second electrode transferred from the convex portion of the structural layer improves the suppression of plasmon absorption. This makes it possible to efficiently extract the light emitted from the light emitting layer of the functional layer to the light transmissive substrate side.
  • the organic EL element of the second aspect of the present invention includes at least a substrate, a structural layer, a first electrode, a functional layer including a light emitting layer, and a second electrode.
  • the specific structure of the organic EL element 100 of one embodiment is as shown in FIG. 1 of the first aspect. Similar to the first embodiment, the organic EL element 100 according to the second embodiment of the present invention includes a light transmissive substrate 102, a light transmissive structure layer 104, a light transmissive first electrode 106, and a light emitting layer.
  • the functional layer 108 including the second electrode 110 is stacked in this order.
  • the organic EL element of the second aspect is a bottom emission type organic EL element that extracts light from the substrate 102 side.
  • the organic EL element of the second embodiment of the present invention has a structural layer 104.
  • the structural layer 104 has a plurality of convex portions 202 on the surface on the first electrode 106 side in the direction of the first electrode. Between the adjacent convex portions of the plurality of convex portions 202, there is a valley portion (in this specification, such a valley portion between the convex portions is also referred to as a “valley portion”) 204.
  • the convex portions 202 and the valley portions 204 are maintained in their shapes on the first electrode 106, the functional layer 108, and the second electrode 110 stacked on the structural layer 104.
  • the shape of the concave portion and the mountain-shaped portion transferred from the structural layer 104 to the second electrode 110 can be maintained on both the substrate-side surface of the second electrode 110 and the opposite surface.
  • the shape of the concave portion and the mountain-shaped portion of the second electrode 110 may be formed only on the surface of the second electrode 110 on the substrate side.
  • the shape of the convex portion of the structural layer is transferred to the concave portion (valley portion) 206 on the surface of the second electrode on the substrate surface side, and the trough portion 204 of the structural layer is peaked on the second electrode. Is transferred to a wall portion 208 (convex portion of the second electrode).
  • the second electrode 110 to which the shape of the convex portions and valley portions of the structural layer is transferred efficiently extracts the light 210 emitted from the functional layer 108 as the light 212 to the substrate side. Make it possible.
  • the top shape of the convex portion 202 of the structural layer 104 is a plane having a predetermined shape.
  • the first electrode 106 is an electrode that has optical transparency and serves as an anode.
  • the functional layer 108 includes a light emitting layer.
  • the second electrode 110 is an electrode serving as a counter electrode of the first electrode 106 and serves as a cathode.
  • the light transmissive property means a property transparent to light (light transmissive property).
  • the light-transmitting layer, electrode or substrate is preferably transparent particularly in the range from ultraviolet light to infrared light, and is transparent to light in the visible region. It is more preferable.
  • a condensing lens layer 302 and a light transmissive layer are formed on the surface of the light transmissive substrate 102 opposite to the structural layer 104.
  • a light extraction lens layer 310 including 304 may be further included.
  • an organic EL device includes a light-transmissive substrate 102, a barrier layer 402, a structural layer 104, a first electrode 106, a functional layer 108, and A second electrode 110 may be included.
  • the barrier layer 402 is a layer for preventing moisture harmful to the structural layer 104, the first and second electrodes 106 and 110, and the functional layer 108 from entering these layers. Therefore, the barrier layer 402 is preferably provided between the light transmissive substrate 102 and the structural layer 104.
  • the organic EL element of this embodiment may further include the above-described light extraction lens layer 310 (see FIG. 14).
  • a portion including at least the light transmissive substrate 102, the structural layer 104, and the first electrode 106 in FIG. 14 is also referred to as a light extraction substrate 120.
  • the light extraction lens layer 310 and the barrier layer 402 which are optional components can be included in the light extraction substrate 120.
  • each part constituting the organic EL element 100 of the second aspect will be described in detail.
  • the “light transmissive substrate” and the “barrier layer” in the second aspect are the same as those in the first aspect. Therefore, the configuration and materials of these layers are as described in the first embodiment.
  • the organic EL element according to the second aspect of the present invention has a structural layer 104.
  • the structural layer 104 has a plurality of convex portions 202 on the surface on the first electrode 106 side in the direction of the first electrode (see, for example, FIG. 12).
  • a valley portion 204 exists between adjacent convex portions of the plurality of convex portions 202.
  • the top of the convex portion is a plane having a predetermined shape (hereinafter, the top plane of the convex portion is also referred to as “top plane”).
  • the predetermined shape is a polygon such as a triangle, a quadrangle, a pentagon, a hexagon, or a circle.
  • the shapes of the convex portions 202 and the valley portions 204 are transferred and maintained on the first electrode 106, the functional layer 108, and the second electrode 110 stacked on the structural layer 104.
  • the convex part having a flat surface at the top and the valley part surrounding the convex part provided in the structural layer 104 must satisfy the predetermined conditions described below with reference to FIGS.
  • FIG. 15 shows the structural layer 104 in which a plurality of convex portions 1502 are formed on the light transmissive substrate 102.
  • the convex part of the structural layer 104 needs to be provided within a predetermined distance from the adjacent convex part.
  • the structural layer 104 has a convex portion 1502 having a square top surface as shown in FIG.
  • the center of gravity (reference number 1518) of the top plane of these convex portions is assumed to be at the position indicated by the black circle in FIG.
  • the distances 1510, 1512, 1514, 1516 between the centers of gravity of AA) and the convex part (AE) are 10 ⁇ m or less, preferably 10 ⁇ m to 3 ⁇ m, more preferably 5 to 3 ⁇ m. More preferably, the distance between two adjacent centroids of the convex portion 1502 is 3 ⁇ m or less. When the distance is larger than such an interval, the shape of the convex portion transferred to the second electrode 110 cannot efficiently reflect the light emitted from the functional layer 108 toward the light transmissive substrate 102 side.
  • FIG. 16 shows a structural layer 104 having a convex portion 1502 similar to FIG.
  • a plurality of convex portions of such a structural layer pass through substantially central portions 1702, 1704, 1706, and 1708 (in the example of FIGS. 15 and 16, these points correspond to the center of gravity 1518), and are on the top plane.
  • FIG. 17 is a drawing showing the cross-sectional shape of the convex portion 1502a and the two convex portions 1502b and 1502c adjacent thereto in such a cross section.
  • the convex portion 1502a has a height 1760 from the bottom side 104 a of the structural layer 104 to the top portion 1780 thereof.
  • a trough 1770 between the convex 1502a and the convex 1502b has a height 1750 from the bottom 104a of the structural layer 104 to the bottom 1710 thereof.
  • a trough 1772 between the convex portion 1502 a and the convex portion 1502 c has a height 1752 from the bottom side 104 a of the structural layer 104 to the bottom portion 1712.
  • the average of the heights 1750 and 1752 of the two valleys 1770 and 1772 is taken to calculate the average height 1754 of the valleys.
  • the average height 1754 of the valley is subtracted from the height 1760 to the top 1780 of the convex portion 1502a, and this value is defined as an apparent height 1762 of the convex portion 1502a.
  • a width 1792 of a plane also referred to as a micro-planar region in this specification
  • the width of the top corresponds to the length of the diagonal line of the square which is the shape of the top plane in the examples of FIGS.
  • top width refers to the portion of the top plane that has the longest width through the center of gravity of the top plane.
  • the distance between the bottom 1710 of the valley 1770 and the bottom 1712 of the valley 1772 is defined as the full width 1790 of the convex 1502a (also referred to as the full width of the convex).
  • the total width of the convex portion refers to a portion that extends through the “top width” and extends to the bottom 1710 of the valley 1770 and the bottom 1712 of the valley 1772.
  • the diagonal line of the square that is the top plane is extended and corresponds to the length to the valley on the extended line. It is preferable that the relationship of the following formula (Formula 4) is satisfied between the “top width” and the “full width of the convex portion”.
  • the above-described cross-sectional direction for measuring the relationship of (Equation 4) is a set of at least one convex portion having a microplanar region and two valley portions adjacent thereto.
  • the direction including the portion having the longest width of the shape of the top plane passing through the center of gravity of the microplanar region and the portion extending the portion having the longest width to the bottom of the two valleys adjacent to the convex portion select.
  • a cross section along the “full width of the convex portion” may be selected.
  • the shape of the convex portion is circular, the diameter direction passing through the center (center of gravity) of the circle may be selected.
  • disconnected is selected so that it may pass along the gravity center of the shape and the width
  • the required value of the above formula is obtained by, for example, using a scanning probe microscope AFM5400 (manufactured by Hitachi High-Tech Science Co., Ltd.) to observe the desired regions of the convex and valley portions of the structural layer in two dimensions. Can do.
  • AFM5400 manufactured by Hitachi High-Tech Science Co., Ltd.
  • pieces let the trough part between the arbitrary convex parts in an image and the convex part adjacent to this convex part be one point.
  • the microplanar region of the convex portion is measured using a scanning probe microscope AFM5400 (manufactured by Hitachi High-Tech Science Co., Ltd.) and the like, and the heights of the highest and lowest portions in the microplanar region of the convex portion are measured.
  • the difference is preferably 10% or less.
  • the region may be periodically arranged in the structural layer 104 or may be randomly arranged.
  • the region satisfying the above (Equation 4) is in the range of 50% to 100%, preferably 80% to 100% of the entire region of the structural layer 104.
  • a structural layer in which convex portions are regularly arranged is more preferable, and a structural layer in which regular convex portions are arranged in the entire structural layer is most preferable.
  • the structural layer 104 is light transmissive.
  • the shape of the convex portion of the structural layer 104 is not particularly limited as long as the shape transferred to the second electrode 110 efficiently reflects the light emitted from the functional layer 108 toward the light transmissive substrate 102 side.
  • FIGS. 18A to 18C the base of the convex portion is removed from the top of the quadrangular pyramid at a certain height.
  • the convex part of a shape can be mentioned.
  • 18A is a perspective view schematically showing the structural layer 104 having the convex portion 1502
  • FIG. 18B is a plan view of the structural layer 104 seen from the direction in which the convex portion is formed
  • FIG. 18C is an XVIIIC of FIG. 18B. -XVIIIC sectional view.
  • the convex portions 1502 preferably have a regular arrangement as shown in FIGS. 18A to 18C, but the arrangement transferred to the second electrode 110 is emitted from the functional layer 108.
  • the reflected light is efficiently reflected to the light-transmitting substrate 102 side.
  • a region having a regular arrangement such as regions 1810 and 1812 surrounded by a dotted line in FIG. 18B, may be arranged so as to exist on a part of the entire surface of the structural layer.
  • the bottom surface as shown in FIGS. 18A to 18C may have a polygonal shape such as a triangular shape, a pentagonal shape, or a hexagonal shape instead of a rectangular shape. In the present invention, those having a bottom shape close to a circle are particularly preferable.
  • the height (apparent height) of the convex portion of the structural layer 104 of the second aspect is preferably 50 nm or more and 300 nm or less.
  • the height of the plurality of convex portions is lower than 50 nm, the height of the convex portions is low, so that the effect of surface plasmon resonance cannot be obtained.
  • the height of the plurality of convex portions is higher than 300 nm, the height of the convex portions greatly exceeds the thickness of each layer such as the light emitting layer included in the functional layer, and the uniformity of the layer is significantly reduced. This causes uneven light emission and short-circuit (short circuit), leading to the occurrence of light emission failure.
  • the total width of the convex portions of the structural layer 104 of the second aspect is preferably 300 nm or more and 3000 nm or less.
  • the total width of the plurality of convex portions is smaller than 300 nm, the width of the convex portions becomes smaller than the emission wavelength, and plasmon resonance becomes insufficient. For this reason, light is not re-emitted and the effect of sufficiently reducing plasmon absorption cannot be obtained.
  • the total width of the convex portion is larger than 3000 nm, the total width of the convex portion is larger than the wavelength of light emitted from the light emitting layer. Thereby, the light absorbed without causing plasmon resonance increases, and the effect of reducing plasmon absorption cannot be sufficiently obtained.
  • the ratio of the height (apparent height) of the convex portion of the structural layer 104 to the total width of the convex portion, (height) / (width) is from 1/2 to 1.
  • the range is preferably / 20. If the ratio of the apparent height of the convex portion to the total width of the convex portion is greater than 1 ⁇ 2, the slope between the convex portion and the valley portion is not uniform when the structural layer 104 is formed, and uneven light emission or short ( Cause short circuit). This leads to a light emission failure of the organic EL element. If the ratio of the apparent height of the convex part to the total width of the convex part is smaller than 1/20, the slope of the slope between the convex part and the valley part becomes loose. Thereby, the traveling direction of the light re-emitted by plasmon resonance spreads in the lateral direction of the element. This phenomenon reduces light extracted through the light transmissive substrate 102. For this reason, the luminous efficiency cannot be improved.
  • the material constituting the structural layer 104 of the second aspect is preferably a light transmissive resin.
  • Examples of the light transmissive resin include the materials described in the first embodiment.
  • fine particles may be added to adjust the refractive index or give a light scattering effect.
  • Such fine particles may be particles composed of inorganic fine particles, organic fine particles, or a combination thereof.
  • examples of the organic fine particles and inorganic fine particles include those exemplified in the first embodiment.
  • first electrode 106 and the second electrode 110 according to the second aspect will be described.
  • description will be made assuming that the first electrode 106 is an anode and the second electrode 110 is a cathode.
  • the present invention is not limited to these examples.
  • First electrode anode
  • a material of the anode that is the first electrode 106 for example, a metal, an alloy, a metal oxide, a conductive compound, or a mixture thereof is suitable.
  • the material for the anode include the materials described in the first embodiment.
  • the anode material is preferably a conductive metal oxide, and ITO is particularly preferable from the viewpoint of productivity, high conductivity, transparency, and the like.
  • the light transmittance of the anode when light emitted from the anode side is taken out, it is desirable that the light transmittance of the anode be larger than 10%.
  • the sheet resistance of the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the anode depends on the material used for the anode, it is usually in the range of 10 nm to 1000 nm, preferably in the range of 10 nm to 200 nm.
  • the shape of the structural layer is transferred to the second electrode 110.
  • the transferred protrusions and valleys of the second electrode 110 can be formed on both the substrate-side surface of the second electrode 110 and the opposite surface.
  • the shape of the convex portion and the valley portion of the second electrode 110 may be formed only on the surface of the second electrode 110 on the substrate side.
  • FIG. 19A is a perspective view schematically showing the second electrode 110 having the concave portion 1902
  • FIG. 19B is a plan view of the second electrode 110 viewed from the direction in which the concave portion 1902 is formed (on the light transmitting substrate 102 side).
  • 19C is a cross-sectional view taken along the line XIXC-XIXC in FIG. 19B.
  • FIG. 20 is an enlarged view of the cross-sectional view of FIG. 19C. Note that the direction of the arrow 1050 in FIG. 20 indicates the light-transmitting substrate side.
  • the shape of the convex portion of the structural layer is transferred to the concave portion 1902 on the surface of the second electrode on the substrate surface side, and the trough portion of the structural layer is formed on the second electrode. It is transferred to a mountain-shaped wall portion 1904 having a mesh structure.
  • the second electrode 110 concave portion needs to be provided within a predetermined distance range as will be described below with the adjacent concave portion.
  • the second electrode 110 has a recess 1902 having a square-shaped recess bottom surface.
  • the center of gravity (reference number 1922) of the bottom surfaces of these recesses is assumed to be at the position indicated by the black circles in FIGS. 19A and 19B.
  • the distances 1910, 1912, 1914 and 1916 between the respective centroids are 10 ⁇ m or less, preferably 10 ⁇ m to 3 ⁇ m, more preferably 5 to 3 ⁇ m. More preferably, the distance between two adjacent centers of gravity of the recess 1902 is 3 ⁇ m or less. When the distance is larger than such an interval, the shape of the concave portion of the second electrode 110 cannot efficiently reflect the light emitted from the functional layer 108 toward the light transmissive substrate 102.
  • FIG. 19B consider a cross section in which the second electrode 110 is cut along the XIXC-XIXC plane so as to pass through the center of gravity 1922 of the plurality of recesses of the second electrode and through the diagonal line between the adjacent center of gravity and the recess.
  • FIG. 19C shows such a cross section
  • FIG. 20 is an enlarged view of FIG. 19C.
  • FIG. 20 shows the cross-sectional shape of the recess 1902a and the two recesses 1902b and 1902c adjacent to the recess 1902a.
  • the recess 1902a has two mountain-shaped walls 1904a and 1904b.
  • the distance between the top 1010 of the two mountain-shaped walls 1904a and the top 1012 of 1904b is defined as the recess width 1092.
  • the bottom 1080 of the recess 1902a has a bottom width 1094. Note that the width 1094 of the bottom surface of the recess corresponds to the length of the diagonal line of the square which is the shape of the bottom surface of the recess in the examples of FIGS. 19A to 19C and FIG.
  • the width of the bottom surface refers to a portion having the longest width of the shape of the bottom surface of the recess through the center of gravity of the bottom surface of the recess.
  • the recess width is the maximum distance between the tops of the mountain-shaped walls that pass through the “bottom width” and surround the recess having the bottom surface. That is, the width of the concave portion refers to a portion extending through the “bottom width” and extending the “bottom width” to the top portions 1010 and 1012 of the two mountain-shaped walls 1904a.
  • Equation 5 the following relationship (Equation 5) needs to be satisfied between the width 1094 of the bottom surface of the second electrode 110 and the recess width 1092.
  • the direction of the above-described cross-section for measuring the relationship of the above is that the center of gravity of the bottom of the recess is a set of at least one recess having a bottom and two adjacent mountain walls.
  • the direction including the portion having the longest width of the shape of the bottom surface of the concave portion and the portion obtained by extending the longest width portion to the two mountain-shaped walls adjacent to the concave portion is selected.
  • a cross section along the “recess width” may be selected.
  • the shape of the bottom surface of the recess is circular, the diameter direction passing through the center (center of gravity) of the circle may be selected.
  • the direction in which the recess is cut is selected so as to pass through the center of gravity of the shape and maximize the width of the polygon. More specifically, in the case of the bottom face of a regular polygon having an even number of sides, the diagonal direction is selected through the center (center of gravity) of the regular polygon. Further, in the case of a regular polygonal concave bottom having an odd number of sides, a direction passing through the center (center of gravity) of the regular polygon and passing through one vertex and the center of the opposite side is selected.
  • the required value of the above is, for example, using a scanning probe microscope AFM5400 (manufactured by Hitachi High-Tech Science Co., Ltd.) to observe the desired region of the concave portion of the second electrode and the mountain wall in two dimensions. Can be obtained.
  • AFM5400 manufactured by Hitachi High-Tech Science Co., Ltd.
  • pieces or more is made into the arbitrary recessed part in an image, and two mountain-shaped walls adjacent to this recessed part as an interval of 1 point. was used to determine the average.
  • the bottom surface of the recess is measured using a scanning probe microscope, AFM5400 (manufactured by Hitachi High-Tech Science Co., Ltd.) or the like, and the difference in height between the lowest and highest portions in the bottom surface of the recess is 10% or less. It is preferable.
  • the region may be periodically arranged by the second electrode 110 or may be randomly arranged.
  • the region satisfying the above (Formula 5) is in the range of 50% to 100%, preferably 80% to 100% of the entire region of the second electrode.
  • the second electrode in which the concave portions are regularly arranged is more preferable, and the second electrode in which the regular concave portions are arranged in the entire second electrode is most preferable.
  • FIGS. 19A to 19C a container-shaped recess having a square recess as shown in FIGS. 19A to 19C can be given.
  • 19A is a perspective view schematically showing the second electrode 110 having the recess 1902
  • FIG. 19B is a plan view of the second electrode 110 seen from the direction in which the recess is formed
  • FIG. 19C is the XIXC of FIG. 19B. -XIXC sectional view.
  • the recesses 1902 preferably have a regular arrangement as shown in FIGS. 19A to 19C.
  • the light emitted from the functional layer 108 can be efficiently transmitted to the light transmitting substrate 102 side.
  • a region having a regular arrangement such as regions 1918 and 1920 surrounded by a dotted line in FIG. 19B, may be arranged so as to exist on a part of the entire surface of the structural layer.
  • the concave shape on the surface of the second electrode as shown in FIGS. 19A to 19C described above may be a polygonal shape such as a triangular shape, a pentagonal shape, a hexagonal shape, etc. instead of a rectangular shape. In the present invention, those having a shape close to a circle are particularly preferable.
  • the fine structure on the surface of the second electrode 110 is obtained by transferring the shape of the structural layer 104 described above. Therefore, the shape of the concave portion and the mountain-shaped wall portion described above is determined by the structural layer 104. If the condition of (Expression 4) is satisfied, the condition of (Expression 5) is also satisfied.
  • the mountain-shaped wall 1904a has a height 1060 from the bottom 1080 of the recess 1902a.
  • the mountain-shaped wall 1904b has a height 1062 from the bottom 1080 of the recess 1902a.
  • the average of these heights 1060, 1062 is the apparent depth 1064 of the recess.
  • the apparent depth 1064 of the concave portion of the second electrode 110 is 50 nm or more and 300 nm or less.
  • the apparent depth 1064 of the plurality of concave portions is lower than 50 nm, the apparent depth 1064 of the concave portions is low, so that the effect of surface plasmon resonance cannot be obtained.
  • the apparent depth 1064 of the plurality of concave portions is higher than 300 nm, the apparent depth of the concave portions greatly exceeds the thickness of each layer such as the light emitting layer included in the functional layer, and the uniformity of the layer is significantly reduced. This causes uneven light emission and short-circuit (short circuit), leading to the occurrence of light emission failure.
  • the distance between the mountain-shaped walls of the second electrode 110 of the second aspect is preferably 300 nm or more and 3000 nm or less.
  • the recess width 1092 becomes smaller than the emission wavelength, and plasmon resonance becomes insufficient. For this reason, light is not re-emitted and the effect of sufficiently reducing plasmon absorption cannot be obtained.
  • the recess width 1092 is larger than 3000 nm, the recess width 1092 becomes larger than the emission wavelength. Thereby, the light absorbed without causing plasmon resonance increases, and the effect of reducing plasmon absorption cannot be sufficiently obtained.
  • the apparent depth of the recess and the ratio of 1064 to the recess width 1092 are preferably in the range of 1/2 to 1/20. . If the ratio of the apparent depth 1064 of the concave portion to the concave portion width 1092 is greater than 1/2, the slope of the mountain-shaped wall is not uniform when forming the second electrode, and uneven light emission or short-circuiting (short circuit) occurs. Cause. This leads to a light emission failure of the organic EL element. If the ratio of the apparent depth 1064 of the recess to the recess width 1092 is less than 1/20, the slope of the slope of the mountain-shaped wall becomes loose. Thereby, the traveling direction of the light re-emitted by plasmon resonance spreads in the lateral direction of the element. This phenomenon reduces light extracted through the light transmissive substrate 102. For this reason, the luminous efficiency cannot be improved.
  • the shape of the second electrode 110 suppresses plasmon absorption on the second electrode 110. Further, part of light emitted from the light emitting layer of the functional layer 108 is reflected by the second electrode toward the transmissive substrate 102, and light can be extracted effectively.
  • “reflection” of light at the second electrode means that light on the second electrode 110 is efficiently extracted to the light transmissive substrate side by suppressing plasmon absorption. And the meaning that both of the light emitted from the light emitting layer of the functional layer 108 is reflected by the second electrode toward the transmissive substrate 102 are included.
  • the cathode material As a material of the second electrode 110 (cathode) of the second aspect, for example, a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an electrically conductive alloy compound, and a mixture thereof are suitable.
  • the cathode material include the materials described in the first aspect.
  • the cathode material is a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this, for example, magnesium.
  • the sheet resistance of the cathode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the cathode is usually in the range of 10 nm to 5 ⁇ m, preferably in the range of 50 nm to 200 nm.
  • the functional layer 108 is a layer including a light emitting layer. This layer is provided between the first electrode 106 and the second electrode 110.
  • the first electrode 106, the functional layer 108, and the second electrode 110 can have various stacked structures.
  • the specific laminated structure of the first electrode 106, the functional layer 108, and the second electrode 110 in the second mode is as described above in the first mode.
  • Each layer (light emitting layer, injection layer, blocking layer, and transport layer) constituting the functional layer 108 is as described in the first embodiment.
  • a light extraction lens layer 310 is optionally provided as a light scattering or condensing layer on the surface opposite to the surface on which the structural layer 104 of the light transmissive substrate 102 is provided (FIGS. 13 and FIG. 13). 14).
  • the light extraction lens layer 310 includes a light transmissive sheet 304 having light transmissive properties, and a lens layer 302 provided on the surface of the light transmissive sheet 304.
  • the lens layer 302 may be formed by shaping the surface of the light transmissive sheet 304 into a microlens array shape, or a so-called condensing sheet may be used.
  • the light can be condensed in a specific direction, for example, the light extraction direction of the organic EL element (direction 112 in FIG. 1), and the luminance in the specific direction can be increased.
  • the resin material constituting the light extraction lens layer 310 is as described in the first aspect. *
  • the light scattering effect may be further improved by adding fine particles to the resin material described above.
  • the fine particles contained in the light extraction lens layer 310 may be particles made of inorganic fine particles, organic fine particles, or a combination thereof.
  • Such fine particles are as described in the first embodiment.
  • the display area of the organic EL element 100 is preferably covered with a sealing member.
  • the sealing means include a method of bonding the sealing member, the electrode, and the support substrate with an adhesive.
  • the sealing member should just be arrange
  • the shape of the sealing member may be a concave plate shape or a flat plate shape. Further, the sealing member is not particularly required to have transparency or electrical insulation.
  • the material of the sealing member is as described in the first aspect.
  • the adhesive used for sealing is as described in the first aspect.
  • the organic EL element 100 may be deteriorated by heat treatment. For this reason, it is preferable to use a material that can be adhesively cured in a temperature range from room temperature to 80 ° C. as the adhesive.
  • an adhesive in which a desiccant is dispersed may be used.
  • coating of the adhesive agent to a sealing part may use a commercially available dispenser, and may perform it by printing like screen printing.
  • a gas phase or liquid phase inert substance into the gap between the sealing member and the display area of the organic EL element 100.
  • a gas phase or liquid phase inert substance for example, it is preferable to inject an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicone oil.
  • the gap between the sealing member and the display area of the organic EL element 100 can be evacuated.
  • a hygroscopic compound can also be enclosed inside the sealing member.
  • the hygroscopic compound is as described in the first aspect.
  • This invention includes the manufacturing method of the organic EL element of the said 2nd aspect. This manufacturing method includes at least the following steps.
  • a step of forming a second electrode on the functional layer wherein the second electrode is formed on a mountain-shaped wall having a network structure at least in the direction of the light-transmitting substrate, and on the mountain-shaped wall A plurality of enclosed recesses, the recesses having a flat bottom surface having a predetermined bottom surface width, two recesses adjacent to the recesses are defined as a recess 1 and a recess 2, and the recesses 1 and 2 And the center of gravity of the bottom surface is defined as the center of gravity 1 and the center of gravity 2, respectively, the distance between the center of gravity 1 and the center of gravity 2 is 10 ⁇ m or less.
  • Step (A) is a step of selecting an appropriate one from the light-transmitting substrate as described above, and performing cleaning and necessary pretreatment as necessary.
  • the cleaning and the necessary pretreatment are usually performed on the substrate of the organic EL element, and there is no particular limitation.
  • Step (B) is a step of forming a structural layer having a plurality of convex portions.
  • the substrate is pressed to transfer the desired convex shape to the light transmissive resin.
  • the obtained light-transmitting resin having a convex shape is photocured or thermoset to form a structural layer.
  • the structural layer can be formed by such a procedure.
  • the shape transfer substrate has a shape that is transferred in advance so as to satisfy the condition of the convex portion defined in the step (B).
  • Step (B) can be performed using a conventional pattern forming method such as a photolithography method in addition to the transfer method as described above.
  • Step (C) is a step of forming an anode that is a first electrode.
  • the anode may be, for example, (1) a wet method such as a printing method or a coating method, (2) a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or (3) a chemical method such as CVD or plasma CVD method. It can be formed on the substrate according to a method selected from known methods such as a method in consideration of suitability with the material constituting the anode. For example, when ITO is selected as the anode material, the anode can be formed by a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.
  • etching by photolithography or the like or physical etching by laser or the like can be used for patterning when forming the anode.
  • the mask may be overlapped, and vacuum deposition, sputtering, or the like may be performed, and a lift-off method, a printing method, or the like may be employed.
  • Step (D) is a step of forming a functional layer including a light emitting layer.
  • the functional layer can be formed by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method.
  • Step (E) is a step of forming a cathode that is the second electrode.
  • a 2nd electrode can be formed by well-known methods, such as vapor deposition and sputtering, using the metal material etc. which can be utilized for the cathode mentioned above.
  • a thin film of a metal material can be formed over the entire surface on which the second electrode is formed, and the second electrode can be formed using a pattern formation method such as a photolithography method.
  • the second electrode formed in this step is a pattern in which a pattern having a fine structure as shown in FIGS. 19A to 19C, for example, is formed by transferring the structure of the protrusions and valleys formed by the structural layer. It becomes.
  • a step of forming a barrier layer may be further included between the step (A) and the step (B).
  • the barrier layer is formed by using the above-described barrier layer materials by vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma polymerization method, It can be obtained by a known method such as a plasma CVD (Chemical Vapor Deposition) method, a laser CVD method, a thermal CVD method, or a coating method.
  • a plasma CVD Chemical Vapor Deposition
  • the manufacturing method of the organic EL element of the 2nd aspect of this invention is the process of forming the light extraction lens layer 310 which has the condensing lens layer 302 and the light transmissive layer 304 following the said process (E). May be included.
  • the light extraction lens layer 310 can be formed by a method similar to the conventional method.
  • the structural layer 104 is formed on the surface on the first electrode 106 side so as to have a plurality of convex portions 202 in the direction of the first electrode.
  • a valley portion 204 exists between adjacent convex portions of the plurality of convex portions 202.
  • the shapes of the convex portions 202 and the valley portions 204 are transferred to the second electrode 110 as shown in FIGS. 19A to 19C.
  • the shape of the second electrode efficiently reflects light emitted from the light emitting layer of the functional layer toward the light transmissive substrate. This makes it possible to efficiently extract light emitted from the light emitting layer of the functional layer to the substrate side.
  • the present invention includes an illumination device, a planar light source, and a display device including the organic EL element.
  • the organic EL element of the present invention described above can be used as part of a lighting device and a planar light source.
  • a lighting device including a glass substrate, an anode, a functional layer, a cathode, a hygroscopic member, and a sealing glass from the light emission side
  • the organic EL element of the present invention can be used in a portion from the glass substrate to the cathode. More specifically, for example, as shown in FIG.
  • the organic EL element 100 of the present invention corresponds to the configuration from the glass substrate 102 to the second electrode 110.
  • the external connection terminal 114 is a member for connecting the second electrode 110 and the power source.
  • the external connection terminal 114 can be formed using a conductive material having a low water vapor transmission rate and a low oxygen transmission rate, such as a transparent conductive oxide.
  • the planar light source can also have the same configuration as the lighting device. Manufacture of such an illuminating device and a planar light source can be performed by adding an appropriate process to the manufacturing method of the organic EL element.
  • the organic EL element of the present invention can be used for a part of a display device such as a color display.
  • a display device including a color filter glass substrate (including a glass substrate and a color filter layer), a protective layer, an anode, a functional layer including a white organic EL light emitting layer, and a cathode can be exemplified.
  • the cathode portion may include a driving portion such as a silicon driving substrate.
  • the display device of the present invention includes a light-transmitting substrate 102, a color filter layer (eg, RGB color filter layer) 1302, a barrier layer 402, a structure from the light extraction direction.
  • An organic EL display including the layer 104, the first electrode (anode) 106, the functional layer 108, and the second electrode (cathode) 110 can be included.
  • Such a display element can be manufactured by inserting a known appropriate film forming step (for example, a spin coat method or a vapor deposition method in the case of a color filter layer) in addition to the manufacture of the organic EL element.
  • Example 1 The present example is an example of an organic EL element corresponding to the first aspect.
  • each convex portion of the structural layer 104 has a rectangular bottom surface (square) as shown in FIGS. 9A to 9C, and has a conical shape toward the top (maximum height) of the convex portion.
  • Have The plurality of convex portions were periodically arranged such that valley portions (that is, the bottom portion of the convex portions) between them were in a lattice shape.
  • the width and height between the respective convex portions are measured by using a scanning probe microscope, and after measuring the convex portion image at ten convex portions, the arbitrary convex portion in the convex portion image and the convex portion An interval of 10 or more points was measured with a valley between adjacent convex portions as an interval of one point, the average was obtained, and each value was obtained for obtaining the above (Equation 1) and (Equation 2).
  • Example 1-1 (Production of light extraction substrate) First, the light extraction substrate 120 in which the light transmissive substrate 102, the structural layer 104, and the light transmissive first electrode 106 are laminated in this order is manufactured.
  • a washed non-alkali glass plate having a thickness of 0.7 mm and a size of 30 mm ⁇ 40 mm was used for the light-transmitting substrate 102.
  • a layer of UV (ultraviolet) curable acrylic resin (Rioduras TYT manufactured by Toyo Ink Co., Ltd.) with a film thickness of 2 ⁇ m was formed as a first layer by a spin coater, and then a hot air oven Inside, it was heated at 100 ° C. for 1 minute to form a resin layer. Subsequently, a film plate having a fine concave pattern was pressed against the surface of the resin layer, and then exposed using a UV lamp (500 mJ / cm 2 ). Next, the film plate was peeled off to obtain a structural layer 104 having a convex pattern on the surface of the resin layer.
  • UV (ultraviolet) curable acrylic resin (Rioduras TYT manufactured by Toyo Ink Co., Ltd.) with a film thickness of 2 ⁇ m was formed as a first layer by a spin coater, and then a hot air oven Inside, it was heated at 100 ° C. for 1 minute
  • the apparent height is 100 nm
  • the total convex width is 500 nm
  • the convex width 1 is 300 nm
  • one valley width 1 of the valley portion sandwiching the convex portion is 1 Was 240 nm and the other valley width 2 was 160 nm.
  • the shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope.
  • an ITO layer which is a transparent electrode, is formed on the surface of the structural layer 104 as a light transmissive first electrode 106 (anode) by a sputtering method so as to have a film thickness of 100 nm, followed by patterning. It was.
  • the hole transport layer was formed with a thickness of 35 nm using 4,4 ′, 4 ′′ -tris (9-carbazole) triphenylamine.
  • the light-emitting layer includes a layer having a thickness of 15 nm using 4,4 ′, 4 ′′ -tris (9-carbazole) triphenylamine doped with a tris (2-phenylpyridinato) iridium (III) complex, and a tris [ It was formed with a 15 nm thick layer using 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene doped with 1-phenylisoquinoline-C2, N] iridium (III) complex.
  • the electron transport layer was formed with a thickness of 65 nm using 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene.
  • a lithium fluoride layer (thickness: 1.5 nm) was deposited as an electron injection layer on the surface of the organic layer.
  • the functional layer 108 including the light emitting layer was formed.
  • a metal electrode (aluminum, thickness: 50 nm) was formed on the surface of the functional layer 108 by a vapor deposition method.
  • the surface of the PET film (light transmissive layer 304 made of a light transmissive sheet) has a hemispherical microlens having a diameter of 5 ⁇ m and a condensing lens layer 302 having a 5 ⁇ m pitch apex angle 89 ° cross prism structure.
  • a light extraction lens layer 310 was formed.
  • the light extraction lens layer 310 was bonded to the light transmissive substrate 102 via an adhesive.
  • the side of the light transmissive layer 304 on which the condensing lens layer 302 is not provided is bonded to the light transmissive substrate 102, and the condensing lens layer side becomes a surface in contact with the outside. I did it.
  • the structural layer 104, the first electrode 106, the functional layer 108, and the second electrode 110 are laminated in this order on the light transmissive substrate 102 as shown in FIG.
  • an organic EL element 100 was obtained in which the light extraction lens layer 310 was provided on the surface opposite to the surface on which is provided.
  • Example 1-2 On the surface of the structural layer 104, a convex portion having an apparent height of 50 nm, a total convex width 1 of 400 nm, and a convex width 1 of 290 nm, and two valleys adjacent to the convex portion. A convex crest having a trough with one trough width 1 of 112 nm being 112 nm and the other trough width 2 being 108 nm was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 1-1.
  • Example 1-3 On the surface of the structural layer 104, a convex portion having an apparent height of 150 nm, a total convex width 1 of 300 nm, and a convex width 1 of 160 nm, and two valleys adjacent to the convex portion. A convex crest having a valley portion in which one valley width 1 of the portion is 135 nm and the other valley width 2 is 145 nm was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 1-1.
  • Example 1-4 On the surface of the structural layer 104, a convex portion having an apparent height of 300 nm, a total convex width 1 of 1500 nm, and a convex width 1 of 110 nm, and two valleys adjacent to the convex portion. A convex crest having a trough with one trough width 1 of 420 nm being 420 nm and the other trough width 2 being 380 nm was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 1-1.
  • Example 1-5 On the surface of the structural layer 104, a convex portion having an apparent height of 150 nm, a total convex width 1 of 3000 nm, and a convex width 1 of 1600 nm, and two valleys adjacent to the convex portion. A convex crest having a valley portion in which one valley width 1 is 1350 nm and the other valley width 2 is 1450 nm was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 1-1.
  • a UV curable acrylic resin (Rioduras TYT manufactured by Toyo Ink Co., Ltd.) is formed as a first layer on the light-transmitting substrate 102 with a film thickness of 2 ⁇ m using a spin coater, and is heated at 100 ° C. for 1 minute in a hot air oven. A resin layer was formed by heating. Thereafter, the light-transmitting substrate 102 having a resin layer was put in a box purged with N 2 and irradiated with light of 500 mJ / cm 2 with a UV lamp, so that the structural layer 104 with high smoothness was formed. Other than this, an organic EL element 100 was produced in the same manner as in Example 1-1.
  • ⁇ Comparative Example 1-2> On the surface of the structural layer 104, a convex portion having an apparent height of 330 nm, a total convex width 1 of 600 nm, and a convex width 1 of 300 nm, and two valleys adjacent to the convex portion. A convex crest having a valley portion in which one valley width 1 is 300 nm and another valley width 2 is 300 nm was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 1-1.
  • ⁇ Comparative Example 1-3> On the surface of the structural layer 104, a convex portion having an apparent height of 210 nm, a total convex width 1 of 400 nm, and a convex width 1 of 200 nm, and two valleys adjacent to the convex portion. A convex peak having a valley portion in which one valley width 1 of the portion is 180 nm and the other valley width 2 is 220 nm was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 1-1.
  • ⁇ Comparative Example 1-5> On the surface of the structural layer 104, a convex portion having an apparent height of 40 nm, a total convex width 1 of 880 nm, and a convex width 1 of 400 nm, and two valleys adjacent to the convex portion. A convex crest having a trough having one trough width 1 of 520 nm and another trough width 2 of 440 nm was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 1-1.
  • ⁇ Comparative Example 1-6> On the surface of the structural layer 104, a convex portion having an apparent height of 160 nm, a total convex width 1 of 280 nm, and a convex width 1 of 120 nm, and two valleys adjacent to the convex portion. A convex crest having a trough having one trough width 1 of 200 nm and another trough width 2 of 120 nm was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 1-1.
  • ⁇ Comparative Example 1-7> On the surface of the structural layer 104, a convex portion having an apparent height of 150 nm, a total convex width 1 of 3100 nm, and a convex width 1 of 1400 nm, and two valleys adjacent to the convex portion. A convex crest having a trough having one trough width 1 of 1600 nm and another trough width 2 of 1800 nm was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 1-1.
  • the light extraction efficiency was measured by measuring the organic EL elements of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-7 from a direct current (DC) power source with a current density of 20 mA / cm. A constant current of 2 was passed, the total emitted light was measured with an integrating sphere, and the light extraction efficiency ratio was determined based on the measurement results.
  • the light extraction efficiency ratio is based on the amount of total radiated light of Comparative Example 1-1 in which no convex portion is provided in the structural layer as a reference (1.00), and Examples 1-1 to 1-5 and Comparative Example 1 The ratio of the amount of total emitted light from 2 to 1-7.
  • the light extraction effect was set to 1.50 or more.
  • the short-circuit is confirmed by passing the above constant current through each organic EL element of Example 1-1 to Example 1-5 and Comparative Example 1-1 to Comparative Example 1-7 to raise the voltage.
  • an increase in current value was observed, it was evaluated as “no short” (good), and when no increase in current value was observed even when the voltage was increased, it was evaluated as “with short” (defective).
  • the determination is “ ⁇ ”, and when the light extraction porosity ratio is 1.5 or more and less than 1.6 and there is no short circuit, The judgment was “ ⁇ ”.
  • Example 1-1 to Example 1-5 were good without any short circuit.
  • Comparative Example 1-2 the light extraction efficiency ratio was 1.41, and a sufficient effect was not obtained. In addition, current leakage occurred over time from the start of measurement, and a short circuit occurred after measurement.
  • the convex portion becomes a shape that rises, and in the part of the valley between the convex portions, It is presumed that the functional layer was not uniformly formed on one electrode, and the functional layer in the valley portion was formed thinner than the functional layer in the peripheral portion. For this reason, the movement of the electric charge between the first electrode and the second electrode in the thinly formed functional layer portion is more dominant than the peripheral portion, and moves without contributing to light emission. It is presumed that carriers existed, and as a result, the luminous efficiency ratio decreased.
  • the thin functional layer as described above exists, it is estimated that a minute region that is energized between the two poles is generated as the voltage rises at that portion, the current flows excessively, and is short-circuited later to cause a light emission failure. .
  • the valley width 2 of the valley is larger than the protrusion width 1 of the protrusion of the structural layer, the slope of the concave shape formed on the functional layer side surface of the second electrode to which the shape of the protrusion is transferred. It is considered that the angle becomes loose, and the light re-emitted while suppressing plasmon absorption spreads in the lateral direction of the device.
  • the value of the convex width 1 of the convex portion of the structure layer is narrower than the valley width 2 of the valley portion, the concave portion of the second electrode to which the convex shape of the structural layer is transferred becomes narrow, and the light reflectance decreases. It is thought that happened. From these things, it is estimated that the light extraction efficiency ratio was not sufficiently obtained.
  • the width of the convex portion of the concavo-convex portion on the surface of the structural layer is considerably smaller than the emission wavelength, and re-emission of the light emission portion in the longer wavelength region in the emission spectrum was not obtained.
  • the convex width 1 of the convex portion of the structural layer is narrower than the valley width 1 and the valley width 2 of the valley portion, and as a result, the concave portion of the second electrode is narrowed, resulting in a decrease in reflectance. From these, it is presumed that the effect of improving the light extraction efficiency was not obtained.
  • Comparative Example 1-5 the light extraction efficiency was the same as in Comparative Example 1-1, and no effect was obtained. Moreover, no short circuit occurred.
  • the convex portion width 1 of the convex portion of the structural layer is the valley width 1 of the valley portion.
  • the valley width is narrower than 2, and the concave portion of the second electrode to which the shape of the convex portion of the structural layer is transferred becomes narrow, the reflectivity decreases, and the light extraction efficiency ratio is not sufficiently improved. Is done.
  • the concave portion of the second electrode to which the convex shape of the structural layer is transferred becomes narrow, and the light reflectance decreases. Probably happened. From these things, it is estimated that the light extraction efficiency ratio was not sufficiently obtained.
  • Comparative Example 1-7 the light extraction efficiency was the same as in Comparative Example 1, and no effect was obtained. Moreover, no short circuit occurred.
  • the convex width 1 of the convex portion on the surface of the structural layer is very large with respect to the apparent height of the convex portion, and the valley width 1 and the valley width 2 of the valley portion with respect to the convex width 1 of the convex portion. Due to the large shape, the concave shape of the second electrode to which the convex shape of the structural layer has been transferred becomes a gentle peak and valley shape, and the second electrode becomes almost flat as a whole, and the effect of suppressing plasmon absorption is obtained. It is presumed that this was because it was not.
  • the organic EL device includes a light-transmitting structural layer, a light-transmitting first electrode, a functional layer including a light-emitting layer, and a second electrode on a light-transmitting substrate.
  • the structural layer is provided with a convex portion having the relationship of (Expression 1).
  • Example 2 A present Example is an example of the organic EL element of a 2nd aspect.
  • each convex portion of the structural layer 104 has a trapezoidal shape, as shown in FIGS. 19A to 19C, where the bottom surface is rectangular (square) and the top of the convex portion has a flat shape.
  • the plurality of convex portions were periodically arranged such that valley portions (that is, the bottom portion of the convex portions) between them were in a lattice shape.
  • the width and height between the respective convex portions are measured by using a scanning probe microscope, and after measuring the convex portion image at ten convex portions, the arbitrary convex portion in the convex portion image and the convex portion An interval of 10 points or more was measured with a valley between adjacent convex portions as an interval of one point, and the average was obtained.
  • the fine structure on the structural layer 104 is inverted so that the light transmission of the second electrode is achieved. It was transferred to the surface on the conductive substrate side and satisfied the setting conditions of the fine structure on the second electrode of the present invention.
  • Example 2-1> (Production of light extraction substrate) First, the light extraction substrate 120 in which the light transmissive substrate 102, the structural layer 104, and the light transmissive first electrode 106 are laminated in this order is manufactured.
  • a washed non-alkali glass plate having a thickness of 0.7 mm and a size of 30 mm ⁇ 40 mm was used for the light-transmitting substrate 102.
  • a layer of UV (ultraviolet) curable acrylic resin (Rioduras TYT manufactured by Toyo Ink Co., Ltd.) with a film thickness of 2 ⁇ m was formed as a first layer by a spin coater, and then a hot air oven was heated at 100 ° C. for 1 minute to form a resin layer. Subsequently, a film plate having a fine concave pattern was pressed against the surface of the resin layer, and then exposed using a UV lamp (150 mJ / cm 2 ). Next, the film plate was peeled off to obtain a structural layer 104 having a convex pattern on the surface of the resin layer.
  • the convex part of was formed.
  • the shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope.
  • an ITO layer which is a transparent electrode, is formed on the surface of the structural layer 104 as a light transmissive first electrode 106 (anode) by a sputtering method so as to have a film thickness of 100 nm, followed by patterning. It was.
  • the hole transport layer was formed with a thickness of 35 nm using 4,4 ′, 4 ′′ -tris (9-carbazole) triphenylamine.
  • the light-emitting layer includes a layer having a thickness of 15 nm using 4,4 ′, 4 ′′ -tris (9-carbazole) triphenylamine doped with a tris (2-phenylpyridinato) iridium (III) complex, and a tris [ It was formed with a 15 nm thick layer using 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene doped with 1-phenylisoquinoline-C2, N] iridium (III) complex.
  • the electron transport layer was formed with a thickness of 65 nm using 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene.
  • a lithium fluoride layer (thickness: 1.5 nm) was deposited as an electron injection layer on the surface of the organic layer.
  • the functional layer 108 including the light emitting layer was formed.
  • a metal electrode (aluminum, thickness: 50 nm) was formed on the surface of the functional layer 108 by a vapor deposition method.
  • the surface of the PET film (light transmissive layer 304 made of a light transmissive sheet) has a hemispherical microlens having a diameter of 5 ⁇ m and a condensing lens layer 302 having a 5 ⁇ m pitch apex angle 89 ° cross prism structure.
  • a light extraction lens layer 310 was formed.
  • the light extraction lens layer 310 was bonded to the light transmissive substrate 102 via an adhesive.
  • the side of the light transmissive layer 304 on which the condensing lens layer 302 is not provided is bonded to the light transmissive substrate 102, and the condensing lens layer side becomes a surface in contact with the outside. I did it.
  • the structural layer 104, the first electrode 106, the functional layer 108, and the second electrode 110 are stacked in this order on the light transmissive substrate 102 as shown in FIG.
  • an organic EL element 100 was obtained in which the light extraction lens layer 310 was provided on the surface opposite to the surface on which is provided.
  • Example 2-2> A convex portion having an apparent height of 250 nm, a total width of 1250 nm, and a top width of 850 nm was formed on the surface of the structural layer 104.
  • the shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope.
  • an organic EL element 100 was produced in the same manner as in Example 2-1.
  • Example 2-3 On the surface of the structural layer 104, a convex portion having an apparent height of 50 nm, a total width of the convex portion of 1000 nm, and a top width of 800 nm was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 2-1.
  • Example 2-4 On the surface of the structural layer 104, a convex portion having an apparent height of 300 nm, a total width of the convex portion of 1000 nm, and a top width of 700 nm was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 2-1.
  • Example 2-6> A convex portion having an apparent height of 150 nm, a total width of 3000 nm, and a top width of 2500 nm was formed on the surface of the structural layer 104.
  • the shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope.
  • an organic EL element 100 was produced in the same manner as in Example 2-1.
  • Example 2-1 A UV curable acrylic resin (Rioduras TYT manufactured by Toyo Ink Co., Ltd.) is formed as a first layer on the light-transmitting substrate 102 with a film thickness of 2 ⁇ m using a spin coater, and 1 at 100 ° C. in a hot air oven. A resin layer was formed by heating for a minute. After that, the light-transmitting substrate 102 having a resin layer was put in an N 2 purged box, and 150 mJ / cm 2 of light was irradiated with a UV lamp to form a structural layer 104 with high smoothness. Other than this, an organic EL element 100 was produced in the same manner as in Example 2-1.
  • Example 2-3 A convex portion having an apparent height of 40 nm, a total width of 880 nm, and a top width of 400 nm was formed on the surface of the structural layer 104.
  • the shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope.
  • an organic EL element 100 was produced in the same manner as in Example 2-1.
  • Example 2-4 A convex portion having an apparent height of 150 nm, a total width of 3200 nm, and a top width of 1500 nm was formed on the surface of the structural layer 104.
  • the shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope.
  • an organic EL element 100 was produced in the same manner as in Example 2-1.
  • Example 2-5 On the surface of the structural layer 104, a convex portion having an apparent height of 160 nm, a total width of the convex portion of 280 nm, and a top width of 160 nm (proposed document 200 nm) was formed. The shape of the surface of the structural layer 104 was confirmed with a scanning probe microscope. Other than this, an organic EL element 100 was produced in the same manner as in Example 2-1.
  • the light extraction efficiency was measured by measuring the organic EL elements of Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-5 from a direct current (DC) power source at a current density of 20 mA / cm. A constant current of 2 was passed, the total emitted light was measured with an integrating sphere, and the light extraction efficiency ratio was determined based on the measurement results.
  • the light extraction efficiency ratio is based on the amount of total radiated light of Comparative Example 2-1 in which no convex portion is provided in the structural layer as a reference (1.00), and Examples 2-1 to 2-6 and Comparative Example 2- The ratio of the amount of total emitted light from 2 to 2-5.
  • the light extraction effect was set to 1.50 or more.
  • the short-circuit is confirmed by passing the above constant current through each organic EL element of Example 2-1 to Example 2-5 and Comparative Example 2-1 to Comparative Example 2-5 to increase the voltage.
  • an increase in current value was observed, it was evaluated as “no short” (good), and when no increase in current value was observed even when the voltage was increased, it was evaluated as “with short” (defective).
  • the determination is “ ⁇ ”, and when the light extraction porosity ratio is 1.5 or more and less than 1.6 and there is no short circuit, The judgment was “ ⁇ ”.
  • the concave structure transferred from the convex portion of the structural layer improves the suppression of plasmon absorption on the functional layer side surface of the second electrode by forming the convex portion in the structural layer, and It is estimated that the light reflectance on the two electrodes is high and the light extraction efficiency is improved.
  • Example 2-1 to Example 2-6 were good without any short circuit.
  • Comparative Example 2-2 the light extraction efficiency ratio was 1.46, and a sufficient effect was not obtained. In addition, current leakage occurred over time from the start of measurement, and a short circuit occurred after measurement.
  • the convex portion since the apparent height of the convex portion is high with respect to the entire width of the convex portion on the surface of the structural layer, the convex portion has a shape that stands up, and the height of the convex portion is the thickness of the functional layer.
  • the functional layer is not uniformly formed on the first electrode in a part of the valley between the convex portions, and the functional layer in the valley is thinner than the functional layer in the peripheral portion. Presumed to have been formed. For this reason, the movement of the electric charge between the first electrode and the second electrode in the thinly formed functional layer portion is more dominant than the peripheral portion, and moves without contributing to light emission.
  • Comparative Example 2-3 the light extraction efficiency ratio was the same as in Comparative Example 1, and a sufficient effect was not obtained. Moreover, no short circuit occurred.
  • Comparative Example 2-4 the light extraction efficiency ratio was the same as in Comparative Example 2-1, and a sufficient effect was not obtained. Moreover, no short circuit occurred.
  • the concave portion of the second electrode to which the convex shape of the structural layer is transferred is a gentle mountain-shaped concave portion
  • the effect of suppressing plasmon absorption could not be obtained because the overall shape was close to a flat surface.
  • the organic EL device of the present invention can suppress uneven light emission while maintaining good light extraction efficiency, and can realize good stability over time. For this reason, the organic EL element of the present invention is suitable for various uses such as a display, a planar light source, and a lighting device that require uniform light emission, and can contribute to energy saving.

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Abstract

La présente invention porte sur un élément électroluminescent (EL) organique, lequel comporte : un substrat transmettant de la lumière ; une couche fonctionnelle disposée sur ledit substrat et comprenant une couche structurale transmettant de la lumière, une première électrode transmettant de la lumière, et une couche électroluminescente ; et une seconde électrode. Dans l'élément EL organique, la forme de la couche structurale est transférée à la seconde électrode, et la seconde électrode, sur laquelle la forme de la couche structurale est transférée, permet d'extraire la lumière émise dans la couche fonctionnelle sous forme de lumière destinée au substrat. Dans un premier mode de la présente invention, la couche structurale présente une forme qui remplit une condition prescrite. En outre, dans un second mode de la présente invention, la seconde électrode, à laquelle la forme de la couche structurale est transférée, présente une forme qui remplit une condition prescrite.
PCT/JP2017/021529 2016-06-10 2017-06-09 Élément électroluminescent organique, dispositif d'éclairage utilisant un élément électroluminescent organique, source de lumière planaire et dispositif d'affichage WO2017213262A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2022246906A1 (fr) * 2021-05-28 2022-12-01 武汉华星光电半导体显示技术有限公司 Panneau d'affichage

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