WO2010032758A1 - Élément électroluminescent organique, dispositif d'affichage et dispositif d'éclairage - Google Patents

Élément électroluminescent organique, dispositif d'affichage et dispositif d'éclairage Download PDF

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Publication number
WO2010032758A1
WO2010032758A1 PCT/JP2009/066179 JP2009066179W WO2010032758A1 WO 2010032758 A1 WO2010032758 A1 WO 2010032758A1 JP 2009066179 W JP2009066179 W JP 2009066179W WO 2010032758 A1 WO2010032758 A1 WO 2010032758A1
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layer
organic electroluminescent
electroluminescent element
light emitting
heat dissipation
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PCT/JP2009/066179
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English (en)
Japanese (ja)
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勘治朗 迫
邦夫 近藤
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昭和電工株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • 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
    • H10K59/8794—Arrangements for heating and cooling
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine

Definitions

  • the present invention relates to, for example, an organic electroluminescent element used for a display device or a lighting device.
  • an organic electroluminescent element that emits light by forming a light emitting material made of an organic material in a layer and providing a pair of electrodes consisting of an anode and a cathode on the light emitting layer and applying a voltage. It attracts attention.
  • An organic electroluminescent element is produced by injecting holes and electrons from the anode and the cathode, respectively, by applying a voltage between the anode and the cathode, and the injected electrons and holes are combined in the light emitting layer. Uses energy to emit light. That is, the device utilizes a phenomenon in which light is generated when the light-emitting material of the light-emitting layer is excited by the energy of the coupling and returns from the excited state to the ground state again.
  • this organic electroluminescent element When this organic electroluminescent element is used as a display device, since an organic substance is used as a light-emitting material, it is easy to generate light with high color purity by selecting an organic substance, and thus a wide color reproduction range can be obtained. There is the feature that it is. In addition, since it is self-luminous, it has the characteristics of high response speed and wide viewing angle. Further, because of its structure, it is easy to reduce the thickness, so that it has an advantage that a thin display device can be manufactured. Furthermore, since it is possible to emit white light and it is surface light emission, an application in which an organic electroluminescent element is incorporated in a lighting device has been proposed.
  • Patent Document 1 includes a dielectric layer inserted between a hole injection electrode layer and an electron injection electrode layer, and at least the dielectric layer and the electrode layer Cavity light emitting electroluminescent devices have been proposed that extend through one and apply an electroluminescent coating material to an internal cavity surface comprising a hole injection electrode region, an electron injection electrode region, and a dielectric region.
  • Patent Document 2 discloses a metal nitride or metal carbide in an organic electroluminescence element in which a carrier transport layer and a light emitting layer using at least an organic material are laminated between a hole injection electrode and an electron injection electrode. There has been proposed an organic electroluminescence element characterized in that a heat dissipation layer is provided.
  • the cavity light-emitting electroluminescent device described in JP-T-2003-522371 has a sufficient countermeasure against the problem that the device is deteriorated due to heat generated during light emission and the durability is not necessarily guaranteed. Not a structure.
  • the device when the device is used for illumination or the like, it is necessary to emit light with a large area and high luminance, so that the amount of heat generated per unit area becomes very large. Therefore, it is necessary to take further measures against heat generation.
  • the metal nitride or metal carbide is an opaque material, and light transmission is blocked, resulting in a decrease in light emission efficiency.
  • an object of the present invention is to provide an organic electroluminescence device having high luminance efficiency with less luminance unevenness due to uneven heat generation. Another object is to provide a display device having high contrast and resolution and high luminous efficiency. Furthermore, another object is to provide an illuminating device with less luminance unevenness and high light emission efficiency.
  • the organic electroluminescent device of the present invention includes an electrode layer, a dielectric layer formed in contact with the electrode layer, a recess formed through at least the dielectric layer, and a light emitting unit formed on the inner surface of the recess.
  • a heat-dissipating layer that dissipates heat generated from the light-emitting portion, and the heat-dissipating layer forms an exposed portion further extended from the end portions of the electrode layer and the dielectric layer.
  • the exposed portion of the heat dissipation layer is preferably disposed so as to divide the light emitting region including the electrode layer, the dielectric layer, and the light emitting portion into a plurality of portions, and the exposed portion preferably has a lattice shape.
  • the heat dissipation layer preferably further functions as an electrode, and is preferably formed in accordance with the shape of the recess.
  • the recess preferably has a substantially cylindrical shape that penetrates the electrode layer, the dielectric layer, and the heat dissipation layer, and preferably has a groove shape that penetrates the electrode layer, the dielectric layer, and the heat dissipation layer and is substantially parallel to each other. .
  • the light emitting part preferably includes a phosphorescent material, and the phosphorescent material preferably has a molecular weight of 1,000 to 2,000,000 in terms of weight average molecular weight, and the phosphorescent material emits phosphorescence. More preferably, a phosphorescent unit and a carrier transporting unit for transporting carriers are provided in one molecule.
  • the electrode layer is preferably formed of an opaque material. And it has further a sealing member which seals the light emission area
  • the lighting device of the present invention is characterized by including the organic electroluminescent element described above.
  • an organic electroluminescent device having high luminance efficiency and less luminance unevenness due to uneven heat generation.
  • FIG. 15 is a cross-sectional view of the organic electroluminescence device shown in FIG. 14 taken along the line AA. It is the figure explaining the organic electroluminescent element which filled the inert liquid in the sealing plate.
  • FIG. 17 is a BB cross-sectional view of the organic electroluminescent element shown in FIG. It is a figure explaining the manufacturing method of the organic electroluminescent element to which this Embodiment is applied. It is a figure explaining an example of a display apparatus provided with the organic electroluminescent element in this Embodiment. It is a figure explaining an example of an illuminating device provided with the organic electroluminescent element in this Embodiment. It is a top view of an organic electroluminescent element.
  • FIG. 1 is a partial cross-sectional view illustrating a first example of an organic electroluminescent element to which the present exemplary embodiment is applied.
  • the organic electroluminescent device 10 shown in FIG. 1 has a structure in which a heat dissipation layer 12, an anode layer 13, an insulating dielectric layer 14, and a cathode layer 15 as an electrode layer are sequentially laminated on a substrate 11. take. Moreover, it has the recessed part 16 formed penetrating the thermal radiation layer 12, the anode layer 13, the dielectric material layer 14, and the cathode layer 15, and is formed in contact with the inner surface of the recessed part 16, and emits light by applying a voltage.
  • a light emitting unit 17 is included.
  • a light emitting material is applied to the inner surface of the recessed portion 16 without filling the entire recessed portion 16, thereby forming a second recessed portion 18.
  • the heat dissipation layer 12 forms an exposed portion 19 further extending from the end portions of the cathode layer 15 and the dielectric layer 14.
  • the substrate 11 serves as a support for forming the heat dissipation layer 12, the anode layer 13, the dielectric layer 14, the cathode layer 15, and the light emitting portion 17.
  • a material that satisfies the mechanical strength required for the organic electroluminescent element 10 is used for the substrate 11.
  • glass such as soda glass and non-alkali glass
  • transparent plastic such as acrylic resin, methacrylic resin, polycarbonate resin, polyester resin and nylon resin
  • silicon resin and the like are examples of the like.
  • the material of the base material 11 is not limited to a material transparent to visible light, and an opaque material can also be used. Specifically, in addition to the above materials, silicon (Si), copper (Cu), silver (Ag), gold (Au), platinum (Pt), tungsten (W), titanium (Ti), tantalum (Ta) Alternatively, niobium (Nb) alone, alloys thereof, or materials made of stainless steel can also be used.
  • the thickness of the base material 11 is preferably 0.1 mm to 10 mm, more preferably 0.25 mm to 2 mm, although it depends on the required mechanical strength.
  • the heat dissipation layer 12 is for absorbing heat generated by the light emitting portion 17 to emit light and dissipating heat.
  • the heat dissipation layer 12 is preferably formed in contact with the light emitting portion 17.
  • the heat absorbed by the heat radiating layer 12 conducts heat in the heat radiating layer 12 and generates heat conduction mainly on the base material 11 side, so that heat can be efficiently radiated from the base material 11.
  • luminance unevenness due to non-uniform heat generation can be made difficult to occur.
  • the heat dissipation layer 12 preferably has a thermal conductivity at room temperature of 10 W / (m ⁇ K) or more, and more preferably 15 W / (m ⁇ K) or more.
  • the thermal conductivity at room temperature is less than 10 W / (m ⁇ K)
  • materials that can be used for the heat dissipation layer 12 include metal nitrides having high thermal conductivity such as aluminum nitride and tantalum nitride; metal oxides such as alumina, sapphire, beryllium oxide, and magnesium oxide; diamond-like carbon (DLC: Diamond Like Carbon); single crystal silicon; polycrystalline silicon; amorphous silicon; silicon carbide.
  • DLC Diamond Like Carbon
  • a mixture of these may also be used.
  • a metal or metal alloy having excellent thermal conductivity can be used.
  • materials that are excellent in thermal conductivity but cannot be formed into a film by themselves because they are in powder form should be used after being mixed or dispersed in a resin and then formed into a film.
  • a carbon tube, particulate alumina, powder diamond, etc. mixed and dispersed in a polymer resin polystyrene, polyimide, polypropylene, polyethylene, polyethylene terephthalate, polymethacrylic acid, polycarbonate
  • a polymer resin polystyrene, polyimide, polypropylene, polyethylene, polyethylene terephthalate, polymethacrylic acid, polycarbonate
  • metal materials are particularly excellent in thermal conductivity.
  • aluminum (Al), copper (Cu), tantalum (Ta), gold (having a thermal conductivity of 150 W / (m ⁇ K) or more ( Au), silver (Ag), magnesium (Mg) and the like can be used particularly preferably.
  • the thickness of the heat dissipation layer 12 when the heat dissipation layer 12 is provided outside the anode layer 13 and the cathode layer 15 as in the organic electroluminescent device 10 shown in FIG. Is preferably in the range of 0.2 ⁇ m to 1000 ⁇ m, and more preferably in the range of 0.5 ⁇ m to 500 ⁇ m.
  • a thicker heat dissipation layer 12 has higher heat conduction and is preferable from the viewpoint of heat absorption and heat dissipation. However, if it is thicker than 1000 ⁇ m, the accuracy of manufacturing the recess 16 described later tends to be lowered.
  • the thickness is preferably 50 nm to 200 nm.
  • the heat dissipation layer 12 is 50 nm or less, the distance between the anode layer 13 and the cathode layer 15 becomes too narrow, and a short circuit is likely to occur between the anode layer 13 and the cathode layer 15, so that stable driving is difficult.
  • the work function of the heat dissipation layer 12 is as follows. It is preferable that the work function is higher. By doing so, it becomes easy to preferentially inject holes between the anode layer 13 and the light emitting portion 17, so that it is easy to prevent a short circuit from occurring.
  • the work function of the heat dissipation layer 12 is higher than the work function of the cathode layer 15. Preferably it is low. By doing so, it becomes easy to preferentially inject electrons between the cathode layer 15 and the light emitting portion 17, and thus it becomes easy to prevent a short circuit from occurring similarly. If the heat dissipation layer 12 is 200 nm or more, the drive voltage may be too high.
  • the heat radiation layer 12 forms an exposed portion 19 further extended from the end portions of the cathode layer 15 and the dielectric layer 14. Since the upper surface of the exposed portion 19 is in contact with air, heat can be radiated efficiently in the air. Therefore, the heat generated from the light emitting portion 17 and absorbed by the heat dissipation layer 12 can be radiated more efficiently due to the presence of the exposed portion 19.
  • the anode layer 13 applies voltage between the cathode layer 15 and injects holes into the light emitting portion 17.
  • the material used for the anode layer 13 is not particularly limited as long as it has electrical conductivity, but preferably has a sheet resistance of 1000 ⁇ or less in a temperature range of ⁇ 5 ° C. to 80 ° C. More preferably, it is 100 ⁇ or less. In addition, it is preferable that the electrical resistance does not change significantly with respect to the alkaline aqueous solution.
  • Metal oxides, metals, and alloys can be used as materials that satisfy such conditions.
  • examples of the metal oxide include ITO (indium tin oxide) and IZO (indium-zinc oxide).
  • the metal examples include stainless steel, copper (Cu), silver (Ag), gold (Au), platinum (Pt), tungsten (W), titanium (Ti), tantalum (Ta), niobium (Nb), and the like. .
  • An alloy containing these metals can also be used.
  • the thickness of the anode layer 13 is preferably 2 nm to 300 nm because high light transmittance is required when light is to be extracted from the substrate 11 side of the organic electroluminescent element 10. Further, when it is not necessary to extract light from the base material 11 side of the organic electroluminescent element 10, it can be formed with a thickness of 2 nm to 2 mm, for example.
  • the dielectric layer 14 is provided between the anode layer 13 and the cathode layer 15, and separates and insulates the anode layer 13 and the cathode layer 15 at a predetermined interval, and applies a voltage to the light emitting unit 17. It is. Therefore, the dielectric layer 14 needs to be a high resistivity material, and the electrical resistivity is required to be 10 8 ⁇ cm or more, preferably 10 12 ⁇ cm or more. Specific examples of the material include metal nitrides such as silicon nitride, boron nitride, and aluminum nitride; metal oxides such as silicon oxide and aluminum oxide, but other polymer compounds such as polyimide, polyvinylidene fluoride, and parylene. Can also be used.
  • the thickness of the dielectric layer 14 preferably does not exceed 1 ⁇ m in order to suppress the total thickness of the organic electroluminescent element 10. Further, the narrower the distance between the anode layer 13 and the cathode layer 15, the lower the voltage required for light emission, so the thinner the dielectric layer 14 is more preferable from this viewpoint. However, if the thickness is too thin, the dielectric strength may not be sufficient for the voltage for driving the organic electroluminescent element 10.
  • the dielectric strength is preferably such that the current density of the current flowing between the anode layer 13 and the cathode layer 15 is 0.1 mA / cm 2 or less when the light emitting portion 17 is not formed, and 0.01 mA. / Cm 2 or less is more preferable.
  • the anode layer 13 and the anode layer 13 are not formed in a state where the light emitting portion 17 is not formed. It is necessary to satisfy the above current density when a voltage of about 7 V is applied between the cathode layers 15.
  • the thickness of the dielectric layer 14 satisfying this is preferably 10 nm to 500 nm, more preferably 50 nm to 200 nm.
  • the cathode layer 15 is formed in contact with the dielectric layer 14, applies a voltage to the anode layer 13, and injects electrons into the light emitting unit 17.
  • the material used for the cathode layer 15 is not particularly limited as long as it has electrical conductivity like the anode layer 13, but preferably has a low work function and is chemically stable. .
  • the work function is preferably ⁇ 2.9 eV or less in view of chemical stability. Specifically, materials such as Al, MgAg alloy, Al and alkali metal alloys such as AlLi and AlCa can be exemplified.
  • the thickness of the cathode layer 15 is preferably 10 nm to 1 ⁇ m, more preferably 50 nm to 500 nm.
  • a cathode buffer layer (not shown) may be provided adjacent to the cathode layer 15 for the purpose of increasing the electron injection efficiency by lowering the electron injection barrier from the cathode layer 15 to the light emitting portion 17.
  • the cathode buffer layer is required to have a work function lower than that of the cathode layer 15, and a metal material is preferably used.
  • a metal material is preferably used.
  • alkali metals Na, K, Rb, Cs
  • alkaline earth metals Sr, Ba, Ca, Mg
  • rare earth metals Pr, Sm, Eu, Yb
  • fluorides or chlorides of these metals A simple substance selected from oxides or a mixture of two or more can be used.
  • the thickness of the cathode buffer layer is preferably from 0.05 nm to 50 nm, more preferably from 0.1 nm to 20 nm, and even more preferably from 0.5 nm to 10 nm.
  • the concave portion 16 is for applying the light emitting portion 17 on the inner surface and taking out light from the light emitting portion 17.
  • the concave portion 16 is an anode layer 13 that is a first electrode layer, and a cathode layer 15 that is a second electrode layer.
  • the dielectric layer 14 and the heat dissipation layer 12 are formed so as to penetrate.
  • the light emitted from the light emitting part 17 by providing the concave part 16 propagates through the concave part 16 and can be extracted in both directions of the base material 11 side and the cathode layer 15 side.
  • the recess 16 is formed so as to penetrate the heat dissipation layer 12, the anode layer 13, the dielectric layer 14, and the cathode layer 15, in the anode layer 13 and the second electrode layer which are the first electrode layers. Light can be extracted even when a certain cathode layer 15 is formed of an opaque material.
  • the shape of the concave portion 16 can be, for example, a substantially cylindrical shape, but is not limited thereto, and may be a shape that forms a groove shape that is substantially parallel to each other.
  • the diameter is preferably 0.1 ⁇ m to 20 ⁇ m, and the distance between centers is preferably 0.2 ⁇ m to 40 ⁇ m. More preferably, the diameter is 0.1 ⁇ m to 10 ⁇ m, and the center-to-center distance is 0.2 ⁇ m to 20 ⁇ m.
  • the center-to-center spacing can be set to 0.3 ⁇ m to 1 ⁇ m, for example.
  • the groove width is preferably 0.1 ⁇ m to 20 ⁇ m, and the interval between the groove centers is preferably 0.3 ⁇ m to 40 ⁇ m.
  • the anode layer 13 and the cathode layer 15 penetrates by forming the recess 16, so that light is emitted strongly at the edge portions of the anode layer 13 and the cathode layer 15.
  • the light emission intensity at the center tends to be weak.
  • the central portion of the recess 16 is likely to be in a non-lighting state, and as a result, the luminance per unit area of the organic electroluminescent element 10 is likely to decrease.
  • the light emitting portion 17 is a light emitting material that emits light when a voltage is applied. As described above, the light emitting portion 17 is applied to the inner surface of the recess 16 so as to form the second recess 18 by providing the light emitting material in contact with the recess 16. The In the light emitting unit 17, the holes injected from the anode layer 12 and the electrons injected from the cathode layer 15 are recombined to emit light.
  • the material of the light emitting portion 17 either a low molecular compound or a high molecular compound can be used.
  • a low molecular compound or a high molecular compound can be used as the material of the light emitting portion 17.
  • the luminescent low molecular weight compound and the luminescent high molecular weight compound described in Hiroshi Omori: Applied Physics, Vol. 70, No. 12, pp. 1419-1425 (2001) can be exemplified.
  • a material excellent in applicability is preferable. That is, in the structure of the organic electroluminescent element 10 in the present embodiment, in order for the light emitting portion 17 to emit light stably in the recess 16, the light emitting portion 17 is in uniform contact with the inner surface of the recess 16 and the film thickness is uniformly formed. It is preferable that the coverage is improved. If the light emitting portion 17 is formed without using a material having excellent coating properties, the light emitting portion 17 is not in contact with the entire recess 16 or the film thickness of the inner surface of the recess 16 is not uniform. For this reason, variations in the brightness of light emitted from the recess 16 are likely to occur.
  • the coating method it is easy to embed ink containing a light-emitting material in the concave portion 16, and thus it is possible to form a film with improved coverage even on a surface having irregularities.
  • materials having a weight average molecular weight of 1,000 to 2,000,000 are preferably used mainly for the purpose of improving coating properties.
  • coating property improvement additives such as a leveling agent and a defoaming agent, can also be added, and binder resin with few charge trap ability can also be added.
  • examples of the material having excellent coatability include, for example, an arylamine compound having a predetermined structure and a molecular weight of 1500 to 6000 as disclosed in JP-A-2007-86639, and JP-A 2000-034476.
  • examples thereof include the predetermined polymeric fluorescent substances.
  • a light-emitting polymer compound is preferable in terms of simplifying the manufacturing process of the organic electroluminescent element 10, and a phosphorescent compound is preferable in terms of high light emission efficiency. Therefore, a phosphorescent polymer compound is particularly preferable.
  • the addition amount of the low molecular light emitting material is preferably 30 wt% or less.
  • the light-emitting polymer compound can be classified into a conjugated light-emitting polymer compound and a non-conjugated light-emitting polymer compound, and among them, the non-conjugated light-emitting polymer compound is preferable.
  • the light-emitting material used in this embodiment is particularly preferably a phosphorescent non-conjugated polymer compound (a light-emitting material that is both a phosphorescent polymer and a non-conjugated light-emitting polymer compound).
  • the light emitting portion 17 in the organic electroluminescent device 10 of the present invention is preferably a phosphorescent polymer (in which a phosphorescent unit emitting phosphorescence and a carrier transporting unit transporting carriers are included in one molecule ( A phosphorescent material).
  • the phosphorescent polymer can be obtained by copolymerizing a phosphorescent compound having a polymerizable substituent and a carrier transporting compound having a polymerizable substituent.
  • the phosphorescent compound is a metal complex containing a metal element selected from iridium (Ir), platinum (Pt), and gold (Au), and among them, an iridium complex is preferable.
  • Examples of the polymerizable substituent in the phosphorescent compound include a urethane (meth) acrylate group such as a vinyl group, an acrylate group, a methacrylate group, and a methacryloyloxyethyl carbamate group, a styryl group and a derivative thereof, a vinylamide group and a derivative thereof, and the like.
  • a urethane (meth) acrylate group such as a vinyl group, an acrylate group, a methacrylate group, and a methacryloyloxyethyl carbamate group
  • a styryl group and a derivative thereof a vinylamide group and a derivative thereof, and the like.
  • vinyl group, methacrylate group, styryl group and derivatives thereof are preferable.
  • These substituents may be bonded to the metal complex via an organic group having 1 to 20 carbon atoms which may have a hetero atom.
  • a carrier transporting compound having a polymerizable substituent is a compound in which one or more hydrogen atoms in an organic compound having one or both of a hole transporting property and an electron transporting property are substituted with a polymerizable substituent. Can be mentioned.
  • the polymerizable substituent in the carrier transporting compound is a vinyl group.
  • the vinyl group is a urethane (meth) acrylate group such as an acrylate group, a methacrylate group, or a methacryloyloxyethyl carbamate group, a styryl group and its derivative, a vinylamide group and its derivative.
  • a compound substituted with a polymerizable substituent such as may be used.
  • These polymerizable substituents may be bonded via an organic group having 1 to 20 carbon atoms which may have a hetero atom.
  • the polymerization method of the phosphorescent compound having a polymerizable substituent and the carrier transporting compound having a polymerizable substituent may be any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization, but radical polymerization is preferred.
  • the molecular weight of the polymer is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000 in terms of weight average molecular weight.
  • the molecular weight here is a molecular weight in terms of polystyrene measured using a GPC (gel permeation chromatography) method.
  • the phosphorescent polymer may be a copolymer of one phosphorescent compound and one carrier transporting compound, one phosphorescent compound and two or more carrier transporting compounds, or two.
  • the above phosphorescent compound may be copolymerized with a carrier transporting compound.
  • the arrangement of the monomer in the phosphorescent polymer may be any of random copolymer, block copolymer, and alternating copolymer, the number of repeating units of the phosphorescent compound structure is m, and the repeating unit of the carrier transporting compound structure
  • the number is n (m, n is an integer of 1 or more)
  • the ratio of the number of repeating units of the phosphorescent compound structure to the total number of repeating units, that is, the value of m / (m + n) is 0.001 to 0.00. 5 is preferable, and 0.001 to 0.2 is more preferable.
  • JP-A Nos. 2003-342325, 2003-119179, 2003-113246, and 2003-206320 JP-A-2003-147021, JP-A-2003-171391, JP-A-2004-346212, JP-A-2005-97589, and JP-A-2007-305734.
  • the light emitting portion 17 of the organic electroluminescent element 10 in the present embodiment preferably includes the above-described phosphorescent compound, but a hole transporting compound or an electron transporting compound is used for the purpose of supplementing the carrier transporting property of the light emitting portion 17. It may be included.
  • the hole transporting compound used for these purposes for example, TPD (N, N′-dimethyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4′diamine) , ⁇ -NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), m-MTDATA (4,4 ′, 4 ′′ -tris (3-methylphenylphenylamino) And low molecular triphenylamine derivatives such as triphenylamine).
  • TPD N, N′-dimethyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4′diamine
  • ⁇ -NPD 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • m-MTDATA (4,4 ′, 4 ′′ -tris (3-
  • polyvinylcarbazole a triphenylamine derivative obtained by introducing a polymerizable functional group into a polymer; a polymer compound having a triphenylamine skeleton disclosed in JP-A-8-157575; polyparaphenylene vinylene, And polydialkylfluorene.
  • the electron transporting compound include low molecular weight materials such as quinolinol derivative metal complexes such as Alq3 (aluminum triskinolinolate), oxadiazole derivatives, triazole derivatives, imidazole derivatives, triazine derivatives, and triarylborane derivatives.
  • a polymer obtained by introducing a polymerizable functional group into the above low molecular electron transporting compound for example, a known electron transporting compound such as poly PBD disclosed in JP-A-10-1665 is exemplified. .
  • the light emitting portion 17 can be formed even when a light emitting low molecular weight compound is used as the light emitting material used for the light emitting portion 17 instead of the light emitting polymer compound described above.
  • the above-described light-emitting polymer compound can be added as a light-emitting material, and a hole-transporting compound or an electron-transporting compound can also be added.
  • the hole transporting compound in this case include, for example, TPD, ⁇ -NPD, m-MTDATA, phthalocyanine complex, DTDPFL, spiro-TPD, TPAC, PDA described in JP-A-2006-76901. Etc.
  • electron transport compound examples include BPhen, BCP, OXD-7, TAZ and the like described in JP-A-2006-76901.
  • a compound having a bipolar molecular structure having a hole transporting property and an electron transporting property in one molecule described in JP-A-2006-273792 can be used.
  • the light emitting portion 17 is in contact with the concave portion 16 to form the second concave portion 18 by providing the light emitting material, and although the bottom part of the 2nd recessed part 18 is formed so that it may be located in the location near the bottom part of the recessed part 16, it is not restricted to this.
  • FIGS. 2A to 2D are diagrams for explaining other forms of the shape of the light-emitting portion 17.
  • the depth of the second recess 18 is shallow, and the bottom of the second recess 18 is formed so as to be located closer to the top than the bottom of the recess 16. ing.
  • the second recess 18 is not formed, and the recess 16 is completely filled with the light emitting portion 17, and the upper surface of the light emitting portion 17 is the upper surface of the cathode layer 15. Is consistent with Furthermore, in the organic electroluminescent element 10c shown in FIG.
  • the second concave portion 18 is not formed, the concave portion 16 is completely filled with the light emitting portion 17, and the upper surface thereof has a convex shape.
  • the second recess 18 is formed, but the depth of the second recess 18 is shallow, and the bottom of the second recess 18 is the bottom of the recess 16.
  • the light emitting portion 17 is formed so as to be developed not only inside the concave portion 16 but also on the upper surface of the cathode layer 15.
  • the organic electroluminescent elements 10a, 10b, 10c, and 10d shown in FIGS. 2A to 2D the light emitted from the light emitting section 17 propagates inside the light emitting section 17, and the organic electroluminescent elements described above are used. 10, it can be taken out from both the substrate 11 side and the cathode layer 15 side.
  • the shape of the light-emitting portion 17 described in FIG. 1 and FIGS. 2A to 2D can be selected depending on the cross-sectional structures of the anode layer 13 and the cathode layer 15, for example.
  • the second recess 18 is preferably formed when the cathode layer 15 is penetrated by the recess 16 and the upper part is opened.
  • the cathode layer 15 is formed after the light emitting portion 17 is formed. Therefore, it is preferable to form the second recess 18 small or not because the coverage is improved when the cathode layer 15 is formed.
  • the heat dissipation layer 12 is provided between the base material 11 and the anode layer 13.
  • the present invention is not limited to this, and there is no particular limitation on the location.
  • FIG. 3 is a cross-sectional view illustrating a second example of an organic electroluminescent element to which the exemplary embodiment is applied.
  • a heat dissipation layer 12 is provided between the anode layer 13 and the dielectric layer 14 with respect to the organic electroluminescent element 10 shown in FIG. It is formed in contact with the layer 13. Also in the organic electroluminescent element 20, the heat dissipation layer 12 forms an exposed portion 19 further extending from the end portions of the cathode layer 15 and the dielectric layer 14.
  • the heat generated from the light emitting portion 17 is absorbed by the heat dissipation layer 12, and the heat transferred through the heat dissipation layer 12 is dissipated mainly from the substrate 11 side. And by having the exposed part 19 of the heat-radiating layer 12, heat can be radiated more efficiently.
  • the exposed portion 19 of the heat dissipation layer 12 is formed on the substrate 11 so as to be laminated, but the present invention is not limited thereto.
  • FIG. 4 is a cross-sectional view illustrating a third example of the organic electroluminescent element to which the exemplary embodiment is applied.
  • the organic electroluminescent element 30 shown in FIG. 4 employs a structure in which the anode layer 13 and the heat dissipation layer 12 further extend from the end portions of the cathode layer 15 and the dielectric layer 14. Therefore, the exposed portion 19 of the heat dissipation layer 12 is formed so as to be laminated on the anode layer 13. With such a structure, the heat dissipation layer 12 can be formed in a continuous form in the exposed portion 19 with respect to the organic electroluminescent element 30 described above.
  • the heat generated in the light emitting portion 17 and absorbed by the heat dissipation layer 12 is more likely to cause heat conduction in the exposed portion 19 of the heat dissipation layer 12, and heat can be radiated more efficiently in the exposed portion 19. .
  • the recess 16 includes the heat dissipation layer 12, the anode layer 13, the dielectric layer 14, and the cathode layer 15.
  • the present invention is not limited to this.
  • the light emitting portion 17 it is sufficient that at least the dielectric layer 14 penetrates through the recess 16.
  • the recess 16 desirably has a structure formed so as to penetrate at least one of the anode layer 13 and the cathode layer 15.
  • FIG. 5 is a cross-sectional view illustrating a fourth example of an organic electroluminescent element to which the present embodiment is applied, and the case where the concave portion 16 penetrates the anode layer 13 but does not penetrate the cathode layer 15 is described.
  • the light emitting part 17 is not applied to the inner surface of the recessed part 16 so as to form the second recessed part 18, the light emitted by the light emitting part 17 propagates inside the light emitting part 17, and the above-described organic electroluminescent element 10, Similarly to 20 and 30, it can be taken out from both the substrate 11 side and the cathode layer 15 side.
  • the cathode layer 15 is a solid film and covers the light emitting portion 17, light is extracted from the cathode layer 15 side unless the cathode layer 15 is transparent to visible light. It is not possible.
  • FIG. 6 is a cross-sectional view illustrating a fifth example of the organic electroluminescent element to which the exemplary embodiment is applied.
  • the recess 16 is formed through the heat dissipation layer 12, the anode layer 13, and the dielectric layer 14 with respect to the organic electroluminescent element 10 shown in FIG. 1.
  • the light emitting material is formed in a so-called solid film shape in which the light emitting portion 17 is formed by substantially filling the concave portion 16 and is laminated on the dielectric layer 14.
  • the cathode layer 15 is formed in a solid film shape so as to be further laminated on the light emitting material formed on the dielectric layer 14.
  • the exposed portion 19 of the heat dissipation layer 12 is formed so as to match the size of the base material 11 and its outer peripheral portion.
  • the exposed portion 19 may be formed to be smaller than the base material 11 as in the organic electroluminescent device 50 of the present embodiment.
  • FIG. 7 is a cross-sectional view illustrating a sixth example of the organic electroluminescent element to which the exemplary embodiment is applied.
  • the light emitting material is formed on the cathode layer 15 while the light emitting material substantially fills the concave portion 16 to form the light emitting portion 17 with respect to the organic electroluminescent device 10 shown in FIG. 1. In this way, it is formed in a so-called solid film shape.
  • the exposed portion 19 of the heat dissipation layer 12 is formed so that the exposed portion 19 is smaller than the base material 11 as in the organic electroluminescent element 50 described above.
  • FIG. 8 is a cross-sectional view illustrating a seventh example of the organic electroluminescent element to which the present exemplary embodiment is applied.
  • the recess 16 is formed without penetrating the heat dissipation layer 12 with respect to the organic electroluminescent element 50 shown in FIG. 6. Therefore, the heat dissipation layer 12 is formed on the substrate 11 in a solid film shape.
  • the light emitted by the light emitting unit 17 propagates through the light emitting unit 17 and can be extracted from both the base material 11 side and the cathode layer 15 side. is there.
  • the cathode layer 15 is a solid film and covers the light emitting portion 17, if the cathode layer 15 is not transparent to visible light, light is emitted from the cathode layer 15 side. It cannot be taken out.
  • the heat radiation layer 12 may be provided in several places.
  • the conventional sandwich composed of the anode layer, the light emitting portion, the cathode layer, etc., without providing the recesses 16 with respect to the position and number of the heat dissipation layers 12.
  • the degree of freedom is higher than that of the organic electroluminescent device having the structure. That is, in the organic electroluminescence device having a sandwich structure, the entire surface is a light emitting area, and therefore a heat dissipation layer can be inserted only on the back surface of the back electrode, and even when inserted, only a small area can be inserted from the viewpoint of light emission efficiency. Moreover, even if only a small area is inserted, the luminous efficiency is reduced.
  • the heat dissipation layer 12 can be provided in any region other than the portion where the recess 16 is provided. That is, the heat dissipation layer 12 can be formed in conformity with the shape of the recess, so that the effect of heat dissipation is high, and uneven generation of heat is generated in the organic electroluminescent element, thereby making it easy to prevent uneven brightness. And it becomes easy to raise luminous efficiency. Further, since a part of the heat dissipation layer 12 is in direct contact with the light emitting portion 17, it is possible to effectively dissipate heat from the light emitting portion 17.
  • the thermal radiation layer 12 there is no restriction
  • the anode layer 13 is formed on the lower side
  • the cathode layer 15 is formed on the upper side with the dielectric layer 14 sandwiched therebetween.
  • the structure is not limited to this, and the anode layer 13 and the cathode layer 15 may be replaced.
  • the cathode layer 15 may be formed on the lower side, and the anode layer 13 may be formed on the upper side with the dielectric layer 14 interposed therebetween.
  • the heat dissipation layer 12 can further function as an electrode. That is, the heat dissipation layer 12 has a good thermal conductivity, and by using an electrically conductive material, the heat dissipation layer 12 can have a single layer structure that also functions as the anode layer 13. In this case, for example, the layer structure is formed in the form of the base 11, the heat dissipation layer 12, the dielectric layer 14, and the cathode layer 15 from below.
  • FIG. 9 is a first example illustrating an exposed portion of a heat dissipation layer of an organic electroluminescent element to which the present exemplary embodiment is applied.
  • the organic electroluminescent element 10e shown in FIG. 9 the organic electroluminescent element 10e is viewed obliquely from above.
  • the organic electroluminescent element 10e has a structure similar to that of the organic electroluminescent element 10 described in FIG. 1, and a heat dissipation layer 12 (see FIG. 1) is formed on the substrate 11 so as to be laminated. Yes.
  • the heat dissipation layer 12 has an exposed portion 19 that extends from the light emitting region 60 including the other anode layer 13, dielectric layer 14, cathode layer 15, and light emitting portion 17 (see FIG. 1).
  • the exposed portion 19 is formed on the outer peripheral portion of the organic electroluminescent device 10e.
  • Light emitted from the light emitting unit 17 (see FIG. 1) is extracted from the recess 16.
  • the heat generated from the light emitting portion 17 and absorbed by the heat dissipation layer 12 can be dissipated from the base material 11 side, but conducts heat up to the exposed portion 19 and the organic electroluminescent element. Heat can be efficiently radiated in the outer peripheral portion of 10e.
  • FIG. 10 is a second example illustrating the exposed portion of the heat dissipation layer of the organic electroluminescent element to which the present exemplary embodiment is applied.
  • the organic electroluminescent element 10f shown in FIG. 10 the organic electroluminescent element 10f is viewed obliquely from above.
  • the organic electroluminescent element 10f has the same structure as the organic electroluminescent element 10 described with reference to FIG. 1, and a heat dissipation layer 12 (see FIG. 1) is formed on the substrate 11 so as to be laminated. Yes.
  • the heat dissipation layer 12 has an exposed portion 19 that extends from the light emitting region 60 including the other anode layer 13, dielectric layer 14, cathode layer 15, and light emitting portion 17 (see FIG. 1).
  • the exposed portion 19 is arranged so as to divide the light emitting region 60 into a plurality of parts.
  • the exposed portion 19 of the heat dissipation layer 12 is arranged in a lattice shape.
  • the exposed part 19 of the heat radiating layer 12 can be increased, and heat can be radiated more efficiently from the lattice-shaped exposed part 19.
  • the light emitting portion 17 is hardly deteriorated, and the luminance unevenness in the central portion is less likely to occur.
  • FIG. 11 is a third example illustrating the exposed portion of the heat dissipation layer of the organic electroluminescent element to which the present exemplary embodiment is applied.
  • the organic electroluminescent element 10g shown in FIG. 11 the organic electroluminescent element 10g is viewed obliquely from above.
  • the organic electroluminescent element 10g has the same structure as that of the organic electroluminescent element 10 described in FIG. 1, and a heat dissipation layer 12 (see FIG. 1) is formed on the substrate 11 so as to be laminated. Yes.
  • the heat dissipation layer 12 has an exposed portion 19 that extends from the light emitting region 60 including the other anode layer 13, dielectric layer 14, cathode layer 15, and light emitting portion 17 (see FIG. 1).
  • the exposed portion 19 is exposed in a rectangular hole surrounded by the light emitting region 60. By doing so, heat can be radiated more efficiently from the exposed portion 19, so that the light emitting portion 17 is hardly deteriorated and luminance unevenness is less likely to occur in the central portion.
  • FIG. 12 is a fourth example illustrating the exposed portion of the heat dissipation layer of the organic electroluminescent element to which the present exemplary embodiment is applied.
  • the organic electroluminescent element 10h shown in FIG. 12 the organic electroluminescent element 10h is viewed obliquely from above.
  • the organic electroluminescent element 10h has the same structure as that of the organic electroluminescent element 10 described in FIG. 1, and a heat dissipation layer 12 (see FIG. 1) is formed on the substrate 11 so as to be laminated. Yes.
  • the heat dissipation layer 12 has an exposed portion 19 that extends from the light emitting region 60 including the other anode layer 13, dielectric layer 14, cathode layer 15, and light emitting portion 17 (see FIG.
  • the exposed portion 19 is arranged so as to divide the light emitting region 60 into a plurality of portions.
  • the exposed portion 19 of the heat dissipation layer 12 is arranged to form a strip shape. Also by doing in this way, the exposed portion 19 of the heat dissipation layer 12 can be increased, and heat can be radiated more efficiently from the strip-shaped exposed portion 19. Therefore, the light emitting unit 17 is hardly deteriorated, and luminance unevenness in the central part is less likely to occur.
  • the shape in which the exposed portions 19 are arranged is not limited to the lattice shape or the strip shape, and may be another shape such as a circular shape, an elliptical shape, or a polygonal shape.
  • the exposed portions 19 By arranging the exposed portions 19 in a periodic pattern with such a shape, uniform heat radiation within the surface of the light emitting element can be promoted.
  • the width of the exposed portion 19 of the heat dissipation layer 12 is suppressed to 100 ⁇ m or less, so that it appears as if the surface of the human eye is emitting light. Therefore, by exposing the heat dissipation layer 12 in a strip shape or a lattice shape, it is possible to realize a surface emission mode with a large area while performing uniform heat dissipation.
  • the light emitting region 60 has a pattern
  • the total exposed portion area of the exposed portion 19 is preferably 10% or more, more preferably 20% or more with respect to the area occupied by the light emitting element.
  • FIG. 13 is a fifth example illustrating the exposed portion of the heat dissipation layer of the organic electroluminescent element to which the present exemplary embodiment is applied.
  • the organic electroluminescent element 10i shown in FIG. 13 the organic electroluminescent element 10i is viewed obliquely from above.
  • the organic electroluminescent element 10i has the same structure as the organic electroluminescent element 10 described with reference to FIG. 1, and a heat dissipation layer 12 (see FIG. 1) is formed on the substrate 11 in a stacked manner. Yes.
  • the heat dissipation layer 12 has an exposed portion 19 that extends from the light emitting region 60 including the other anode layer 13, dielectric layer 14, cathode layer 15, and light emitting portion 17 (see FIG. 1).
  • the light emitting region 60 is arranged with a predetermined pattern.
  • “580” can be displayed.
  • the exposed portion 19 is arranged so as to occupy a portion other than the pattern “580” which is the light emitting region 60. By doing in this way, heat can be efficiently radiated from the exposed portion 19.
  • a sealing layer as an example of a sealing member is formed by selectively laminating a binder layer having good thermal conductivity on at least a part of the exposed portion 19 on the exposed portion 19 of the heat radiating layer 12. You may take the method of contacting a plate.
  • 14 and 15 are diagrams illustrating an organic electroluminescent element in which a binder layer having a good thermal conductivity is laminated on a part of the exposed portion 19 and is brought into contact with the sealing plate. In the organic electroluminescent element 10j shown in FIG. 14, the organic electroluminescent element 10j is viewed obliquely from above. FIG.
  • the organic electroluminescent element 10j has a structure in which the organic electroluminescent element 10g shown in FIG.
  • a binder layer 62 is formed in contact with the sealing plate 61 and a part of the exposed portion 19 inside the sealing plate.
  • the binder layer 62 is preferably made of a material having excellent thermal conductivity, and the same material as the heat dissipation layer 12 described above can be used. Moreover, a heat conductive paste can also be used as the binder layer 62, and what is used in order to raise the heat conductivity between a to-be-radiated body and a heat radiator can be used. Specifically, powdered solids with excellent thermal conductivity such as aluminum nitride, alumina, copper, aluminum, silver, carbon nanotubes, graphite, etc. dispersed in resins such as silicone oil, epoxy, acrylic Is mentioned.
  • the sealing plate 61 is formed in contact with the base material 11 and seals the internal heat dissipation layer 12, the light emitting region 60, etc., but is not limited thereto.
  • it may be formed in contact with the heat dissipation layer 12 as in an organic electroluminescent element 10k shown in FIG.
  • a heat sink or the like may be further connected to the heat dissipation layer 12 to further increase the heat dissipation effect.
  • the sealing plate 61 is also preferably made of a material having excellent thermal conductivity, and can be made of metal or the like, for example. However, when light is to be extracted from the cathode layer 15 (see FIG. 1) side, it is necessary to be made of a material that is transparent to this light.
  • the thickness of the coating layer is preferably 0.5 ⁇ m or more in order to obtain an effective heat dissipation effect.
  • FIG. 16 and 17 are diagrams illustrating an organic electroluminescent element in which an inert liquid is filled in a sealing plate.
  • the organic electroluminescent element 10k shown in FIG. 16 the organic electroluminescent element 10k is viewed obliquely from above.
  • FIG. 17 is a BB sectional view of the organic electroluminescent element 10k shown in FIG.
  • the organic electroluminescent element 10k has a structure sealed using the sealing plate 61 in the same manner as the organic electroluminescent element 10j shown in FIG. 15, but the binder layer 62 is not formed.
  • the gap 63 between the sealing plate 61 and the light emitting region 60 is filled with an inert liquid made of perfluorocarbon.
  • the sealing plate instead of the above inert liquid, a method of filling the sealing plate with an inert gas having high thermal conductivity may be adopted.
  • the gas is filled in the same way as the inert liquid.
  • the inert gas needs to be excellent in heat conduction and inert so as not to cause oxidation / moisture deterioration with the material constituting the organic electroluminescent element.
  • helium or a gas containing helium as a main component is preferable.
  • the sealing plate 61 is formed in contact with the heat dissipation layer 12, and seals the internal heat dissipation layer 12, the light emitting region 60, etc., but is not limited to this. Instead, it may be formed in contact with the substrate 11 like the organic electroluminescent element 10j shown in FIG.
  • the base material 11 side is the lower side.
  • the case where the anode layer 13 is formed on the lower side and the cathode layer 15 is formed on the upper side with the dielectric layer 14 interposed therebetween has been described as an example.
  • the present invention is not limited to this.
  • a structure in which the layer 13 and the cathode layer 15 are interchanged may be used. That is, when the base material 11 side is the lower side, the cathode layer 15 may be formed on the lower side, and the anode layer 13 may be formed on the upper side with the dielectric layer 14 interposed therebetween.
  • FIG. 18 (a) to 18 (f) are diagrams illustrating a method of manufacturing the organic electroluminescent element 10 to which the present exemplary embodiment is applied.
  • the heat radiation layer 12, the anode layer 13, the dielectric layer 14, and the cathode layer 15 are formed on the base material 11 in this order (FIG. 18A).
  • resistance heating vapor deposition, electron beam vapor deposition, sputtering, ion plating, or the like can be used.
  • the anode layer 13, the dielectric layer 14, and the cathode layer 15 are formed in the exposed portion 19 by using a mask or the like in the step of forming each layer. You just don't have to.
  • the substrate on which the heat dissipation layer 12, the anode layer 13, the dielectric layer 14, and the cathode layer 15 are formed on the substrate 11 is selectively etched, and the anode layer 13, the dielectric layer 14, and the cathode layer 15 are partially etched.
  • the surface treatment of the anode layer 13 is performed, so that the performance of the overcoated layer (adhesion with the anode layer 13, surface smoothness, reduction of hole injection barrier, etc.) is improved.
  • Surface treatment includes sputtering treatment, corona treatment, UV ozone irradiation treatment, oxygen plasma treatment, etc. as well as high-frequency plasma treatment.
  • an effect similar to that of the surface treatment can be expected by forming an anode buffer layer (not shown) instead of or in addition to the surface treatment of the anode layer 13.
  • anode buffer layer is applied by a wet process, spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating
  • the film can be formed using a coating method such as a spray method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, or an inkjet printing method.
  • the compound that can be used in the film formation by the wet process is not particularly limited as long as the compound has good adhesion to the light-emitting compound contained in the anode layer 13 and the light-emitting portion 17.
  • Examples thereof include conductive polymers such as PEDOT, which is a mixture of poly (3,4) -ethylenedioxythiophene and polystyrene sulfonate, and PANI, which is a mixture of polyaniline and polystyrene sulfonate.
  • an organic solvent such as toluene or isopropyl alcohol may be added to these conductive polymers.
  • the conductive polymer containing 3rd components, such as surfactant may be sufficient.
  • the surfactant is, for example, selected from the group consisting of alkyl groups, alkylaryl groups, fluoroalkyl groups, alkylsiloxane groups, sulfates, sulfonates, carboxylates, amides, betaine structures, and quaternized ammonium groups.
  • Surfactants containing one group are used, but fluoride-based nonionic surfactants can also be used.
  • the anode buffer layer when the anode buffer layer is produced by a dry process, the anode buffer layer can be formed by using a plasma treatment or the like exemplified in Japanese Patent Application Laid-Open No. 2006-303412.
  • a method of forming a film of a single metal, a metal oxide, a metal nitride, or the like can be given.
  • Specific film forming methods include an electron beam evaporation method, a sputtering method, a chemical reaction method, a coating method, and a vacuum evaporation method. The method etc. can be used.
  • the recess 16 is formed so as to penetrate the heat dissipation layer 12, the anode layer 13, the dielectric layer 14, and the cathode layer 15.
  • a method using lithography can be used. In order to do this, first, a resist solution is applied on the cathode layer 15, and the excess resist solution is removed by spin coating or the like to form a resist layer 71 (FIG. 18B).
  • the exposed portion of the cathode layer 15 is removed by etching, and a recess 16 is formed so as to penetrate the heat dissipation layer 12, the anode layer 13, the dielectric layer 14, and the cathode layer 15 (FIG. 18E).
  • etching either dry etching or wet etching can be used.
  • shape of the recess 16 can be controlled by combining isotropic etching and anisotropic etching.
  • dry etching reactive ion etching (RIE) or inductively coupled plasma etching can be used.
  • RIE reactive ion etching
  • wet etching a method of immersing in dilute hydrochloric acid or dilute sulfuric acid can be used.
  • the remaining resist layer 71 is removed using a resist removing solution or the like, and the light emitting portion 17 is formed, whereby the organic electroluminescent element 10 can be manufactured (FIG. 18F).
  • the above-described coating method is used for forming the light emitting portion 17.
  • an ink in which a light emitting material constituting the light emitting unit 17 is dispersed in a predetermined solvent such as an organic solvent or water is applied.
  • various methods such as spin coating, spray coating, dip coating, ink jet, slit coating, dispenser, and printing can be used.
  • the ink is dried by heating or evacuating, and the light emitting material adheres to the inner surface of the recess 16 to form the light emitting portion 17.
  • the organic electroluminescent element 10 stably for a long period of time and to attach a protective layer or a protective cover (not shown) for protecting the organic electroluminescent element 10 from the outside.
  • a protective layer polymer compounds, metal oxides, metal fluorides, metal borides, silicon compounds such as silicon nitride and silicon oxide, and the like can be used. And these laminated bodies can also be used.
  • the protective cover a glass plate, a plastic plate whose surface has been subjected to low water permeability treatment, a metal, or the like can be used. It is preferable that the protective cover is sealed with a thermosetting resin or a photo-curing resin and bonded to the element substrate.
  • a spacer because a predetermined space can be maintained and the organic electroluminescent element 10 can be prevented from being damaged. If an inert gas such as nitrogen or argon is sealed in this space, the cathode layer 15 can be easily prevented from being oxidized. Moreover, when helium is used, heat dissipation is promoted, which is more preferable. Further, by installing a desiccant such as barium oxide in this space, it becomes easy to suppress the moisture adsorbed in the series of manufacturing steps from damaging the organic electroluminescent element 10.
  • FIG. 19 is a diagram illustrating an example of a display device using the organic electroluminescent element in this embodiment.
  • a display device 200 shown in FIG. 19 is a so-called passive matrix display device, and includes a display device substrate 202, an anode wiring 204, an anode auxiliary wiring 206, a cathode wiring 208, an insulating film 210, a cathode partition wall 212, and organic electroluminescence.
  • An element 214, a sealing plate 216, and a sealing material 218 are provided.
  • the display device substrate 202 for example, a transparent substrate made of rectangular glass or the like can be used.
  • the thickness of the display device substrate 202 is not particularly limited, but for example, a thickness of 0.1 to 1 mm can be used.
  • a plurality of anode wirings 204 are formed on the display device substrate 202.
  • the anode wirings 204 are arranged in parallel at a constant interval.
  • the anode wiring 204 is made of a transparent conductive film, and for example, ITO (Indium Tin Oxide) can be used.
  • the thickness of the anode wiring 204 can be set to 100 nm to 150 nm, for example.
  • An anode auxiliary wiring 206 is formed on the end of each anode wiring 204.
  • the anode auxiliary wiring 206 is electrically connected to the anode wiring 204.
  • a plurality of cathode wirings 208 are provided on the display device substrate 202.
  • the plurality of cathode wirings 208 are arranged so as to be parallel to each other and orthogonal to the anode wiring 204.
  • As the cathode wiring 208 Al or an Al alloy can be used.
  • the thickness of the cathode wiring 208 is, for example, 100 nm to 150 nm.
  • a cathode auxiliary wiring (not shown) is provided at the end of the cathode wiring 208 and is electrically connected to the cathode wiring 208. Therefore, current can flow between the cathode wiring 208 and the cathode auxiliary wiring.
  • An insulating film 210 is formed on the display device substrate 202 so as to cover the anode wiring 204.
  • the insulating film 210 is provided with a rectangular opening 220 so as to expose a part of the anode wiring 204.
  • the plurality of openings 220 are arranged in a matrix on the anode wiring 204.
  • an organic electroluminescent element 214 is provided between the anode wiring 204 and the cathode wiring 208 as described later. That is, each opening 220 is a pixel. Accordingly, a display area is formed corresponding to the opening 220.
  • the film thickness of the insulating film 210 can be, for example, 200 nm to 300 nm, and the size of the opening 220 can be, for example, 300 ⁇ m ⁇ 300 ⁇ m.
  • An organic electroluminescent element 214 is formed at a location corresponding to the position of the opening 220 on the anode wiring 204.
  • the organic electroluminescent element 214 since the anode wiring 204 is substituted for the base material 11, the heat radiation layer 12, the anode layer 13, the dielectric layer 14, the cathode layer 15, and the light emission are directly formed on the anode wiring 204.
  • a portion 17 (see FIG. 1) is formed.
  • the organic electroluminescent element 214 is sandwiched between the anode wiring 204 and the cathode wiring 208 in the opening 220.
  • the thickness of the organic electroluminescent element 214 can be set to, for example, 150 nm to 200 nm.
  • the display device base material 202 is bonded to each other through a sealing plate 216 and a sealing material 218. Thereby, the space in which the organic electroluminescent element 214 is provided can be sealed, and the organic electroluminescent element 214 can be prevented from being deteriorated by moisture in the air.
  • a sealing plate 216 for example, a glass substrate having a thickness of 0.7 mm to 1.1 mm can be used.
  • a current is supplied to the organic electroluminescent element 214 via the anode auxiliary wiring 206 and the cathode auxiliary wiring (not shown) by a driving device (not shown), and the light emitting unit 17 is caused to emit light. Can emit light.
  • An image can be displayed on the display device 200 by controlling light emission and non-light emission of the organic electroluminescence element 214 corresponding to the above-described pixel by the control device.
  • FIG. 20 is a diagram illustrating an example of a lighting device including the organic electroluminescent element according to this embodiment.
  • a lighting device 300 shown in FIG. 20 is installed adjacent to the organic electroluminescent element 10 and the base 11 (see FIG. 1) of the organic electroluminescent element 10 and connected to the anode layer 13 (see FIG. 1).
  • the terminal 302 connected to the base layer 11 (see FIG. 1) and connected to the cathode layer 15 (see FIG. 1) of the organic electroluminescent element 10, and the terminal 302 and the terminal 303. It comprises a lighting circuit 301 for driving the organic electroluminescent element 10.
  • the lighting circuit 301 has a DC power source (not shown) and a control circuit (not shown) inside, and supplies a current between the anode layer 13 and the cathode layer 15 of the organic electroluminescent element 10 through the terminal 302 and the terminal 303. And the organic electroluminescent element 10 is driven, the light emission part 17 (refer FIG. 1) is light-emitted, light is radiate
  • the light emitting unit 17 may be made of a light emitting material that emits white light, and the organic electroluminescent element 10 using a light emitting material that emits green light (G), blue light (B), and red light (R). A plurality of them may be provided, and the combined light may be white.
  • the lighting device 300 of the present embodiment when light is emitted with the diameter and interval of the recesses 16 (see FIG. 1) being reduced, it appears to the human eye to emit light.
  • E-2 iridium complex having a polymerizable substituent
  • E-54 hole transporting compound
  • E-66 Electron transporting compound
  • the reaction solution was dropped into acetone to cause precipitation, and the reprecipitation purification with dehydrated toluene-acetone was repeated three times to purify the phosphorescent polymer compound.
  • dehydrated toluene and acetone those obtained by further distilling a high-purity grade manufactured by Wako Pure Chemical Industries, Ltd. were used.
  • the solvent after the third reprecipitation purification was analyzed by high performance liquid chromatography, it was confirmed that no substance having absorption at 400 nm or more was detected in the solvent. That is, this means that the solvent contains almost no impurities, which means that the phosphorescent polymer compound has been sufficiently purified.
  • the purified phosphorescent polymer compound was vacuum dried at room temperature for 2 days. As a result, it was confirmed by high performance liquid chromatography (detection wavelength 254 nm) that the phosphorescent polymer compound (ELP) obtained had a purity exceeding 99.9%.
  • the organic electroluminescent element 50 shown in FIG. 6 was produced by the following method. Specifically, first, on a glass substrate (50 mm square, 1 mm thickness) made of quartz glass with a film thickness of 150 nm on the surface, a sputtering device (E-401s manufactured by Canon Anelva Co., Ltd.) was used to make alumina (Al 2 The O 3 ) layer was 150 nm, the ITO (Indium Tin Oxide) film was 150 nm, and the silicon dioxide (SiO 2 ) layer was 100 nm.
  • the glass substrate corresponds to the substrate 11.
  • the alumina (Al 2 O 3 ) layer corresponds to the heat dissipation layer 12
  • the ITO film corresponds to the anode layer 13
  • the silicon dioxide layer corresponds to the dielectric layer 14. At this time, an exposed portion 19 is formed.
  • a photoresist (AZ 1500 made by AZ Electronic Materials Co., Ltd.) was formed to a thickness of about 1 ⁇ m by spin coating. After exposure to ultraviolet, TMAH (Tetra methyl ammonium hydroxide: (CH3) 4 NOH) developed with 1.2% solution, the patterned resist layer. Thereafter, heat was applied at 130 ° C. for 10 minutes (post-baking treatment).
  • TMAH Tetra methyl ammonium hydroxide: (CH3) 4 NOH
  • the silicon dioxide layer was patterned by dry etching using a reactive ion etching apparatus (RIE-200iP manufactured by Samco Corporation).
  • RIE-200iP reactive ion etching apparatus
  • the resist residue was removed with a resist removing solution.
  • the recess 16 penetrating the dielectric layer 14, the anode layer 13, and the heat dissipation layer 12 was formed.
  • this recessed part 16 was a cylindrical shape with a diameter of 3 micrometers (um), and the distance between the edges of the recessed part 16 became 1 micrometer.
  • the glass substrate was washed by spraying pure water and dried using a spin dryer.
  • the solution A was applied by a spin coating method (rotation speed: 3000 rpm), and then allowed to stand at 120 ° C. for 1 hour in a nitrogen atmosphere and dried to form the light emitting portion 17.
  • LiF lithium fluoride
  • Al aluminum
  • Example 2 Compared to Example 1, an organic layer was formed in the same manner except that the alumina (Al 2 O 3 ) layer as the heat dissipation layer 12 was an aluminum nitride (AlN) layer and the ITO film as the anode layer 13 was a titanium (Ti) film. An electroluminescent element 50 was produced.
  • the alumina (Al 2 O 3 ) layer as the heat dissipation layer 12 was an aluminum nitride (AlN) layer and the ITO film as the anode layer 13 was a titanium (Ti) film.
  • An electroluminescent element 50 was produced.
  • the organic electroluminescent element 70 shown in FIG. 7 was produced by the following method. Specifically, first, aluminum nitride (AlN) is used on a glass substrate (50 mm square, 1 mm thickness) made of quartz glass having a thickness of 150 nm on the surface by using a sputtering apparatus (E-401s manufactured by Canon Anelva Co., Ltd.). ) Layer of 150 nm, titanium (Ti) film of 150 nm, silicon dioxide (SiO 2 ) layer of 100 nm, and aluminum (Al) layer of 150 nm.
  • the glass substrate corresponds to the substrate 11.
  • the aluminum nitride layer corresponds to the heat dissipation layer 12
  • the titanium film corresponds to the anode layer 13
  • the silicon dioxide layer corresponds to the dielectric layer 14
  • the aluminum (Al) layer corresponds to the cathode layer 15. At this time, an exposed portion 19 is formed.
  • a photoresist (AZ 1500 made by AZ Electronic Materials Co., Ltd.) was formed to a thickness of about 1 ⁇ m by spin coating. After exposure with ultraviolet rays, the resist layer was patterned by developing with a 1.2% solution of TMAH (Tetra methyl ammonium hydroxide: (CH 3 ) 4 NOH). Thereafter, heat was applied at 130 ° C. for 10 minutes (post-baking treatment).
  • TMAH Tetra methyl ammonium hydroxide: (CH 3 ) 4 NOH
  • the aluminum layer and the silicon dioxide layer were patterned by dry etching using a reactive ion etching apparatus (RIE-200iP manufactured by Samco Corporation).
  • RIE-200iP reactive ion etching apparatus
  • the resist residue was removed with a resist removing solution.
  • the concave portion 16 penetrating the cathode layer 15, the dielectric layer 14, the anode layer 13, and the heat dissipation layer 12 was formed.
  • this recessed part 16 was a cylindrical shape with a diameter of 3 micrometers (um), and the distance between the edges of the recessed part 16 became 1 micrometer.
  • the glass substrate was washed by spraying pure water and dried using a spin dryer.
  • organic electroluminescent element 70 manufactured in this way had a top view similar to that shown in FIG.
  • Example 4 As the organic electroluminescent element, the organic electroluminescent element 50 shown in FIG. 6 was produced. At this time, the exposed portion 19 divides the light emitting region 60 into a plurality of portions. And the exposed part 19 of the thermal radiation layer 12 was arrange
  • FIG. 21 (b) shows a top view of the organic electroluminescent element 50 thus fabricated.
  • the light emitting region 60 was manufactured as a whole with a size of 40 mm ⁇ 40 mm, but the lattice-shaped exposed portion 19 was provided in the light emitting region 60.
  • the grid-shaped exposed portions 19 had a width of 1 mm and were arranged in 2 rows ⁇ 2 columns. As a result, the light emitting area 60 is divided into nine.
  • Example 5 As the organic electroluminescent element, the organic electroluminescent element 80 shown in FIG. 8 was produced. Specifically, the step of patterning the alumina (Al 2 O 3 ) layer using a reactive ion etching apparatus was omitted from Example 1. As a result, the alumina (Al 2 O 3 ) layer that is the heat dissipation layer 12 is not removed and can remain as a solid film.
  • organic electroluminescent element 80 manufactured in this way had a top view similar to that shown in FIG.
  • Example 6 The organic electroluminescent element 50 produced in Example 1 was sealed using a sealing plate 61.
  • a sealing plate 61 one side of an aluminum plate having a plate thickness of 1 mm and an outer peripheral portion of 44 mm ⁇ 44 mm was prepared by leaving a portion having a width of 1 mm around the center portion and a center portion having a depth of 0.3 mm. was used.
  • an ultraviolet curable epoxy adhesive manufactured by Nagase Sangyo Co., Ltd.
  • silica beads having a diameter of about 10 ⁇ m as an adhesive
  • organic A sealing plate 61 was adhered to the exposed portion 19 of the electroluminescent element 50.
  • the adhesive was cured by irradiating from the organic electroluminescent element 50 side with ultraviolet rays (intensity 4 J / cm 2 ) using a high-pressure mercury lamp as a light source. Further, this was left for 1 hour in a constant temperature bath at 80 ° C. to complete the sealing.
  • the gap 63 was filled with argon (Ar) gas.
  • Ar argon
  • Example 7 The organic electroluminescent element 50 produced in Example 4 was sealed using a sealing plate 61.
  • the sealing plate 61 one side of an aluminum plate having a plate thickness of 1 mm and an outer peripheral portion of 44 mm ⁇ 44 mm is placed in a position that matches the portion with a width of 1 mm around and the exposed portion 19 that forms the lattice shape of the organic electroluminescent element 50.
  • a part produced by scoring the other part at a depth of 0.3 mm was used while leaving a part with a width of 0.5 mm.
  • the adhesive described above in Example 6 was applied to the peripheral portion of the sealing plate 61 having a width of 1 mm.
  • a heat conductive adhesive (EW2070 manufactured by Sumitomo 3M Co., Ltd.) was applied as an adhesive to a portion having a width of 0.5 mm corresponding to the exposed portion 19 forming the lattice shape of the organic electroluminescent element 50. And it sealed by the method similar to the method mentioned in Example 6.
  • Example 8 Compared to Example 6, the organic electroluminescent element 50 was made in the same manner as in Example 6 except that helium (He) gas having a thermal conductivity 10 times that of argon (Ar) gas was used for the gap 63. Sealing was performed using the sealing plate 61.
  • He helium
  • Ar argon
  • Example 1 An organic electroluminescent element was produced in the same manner as in Example 1 except that the exposed portion 19 was not provided for the organic electroluminescent element 50 of Example 1.
  • a top view of the organic electroluminescent element is shown in FIG. In FIG.21 (c), the light emission area
  • the organic electroluminescent element was allowed to emit light for a certain time with a constant voltage (7 V) applied, and the ratio of luminance decrease (deterioration ratio) at the center of the light emitting region 60 before and after this was used as an index.
  • the central portion of the light emitting region 60 was defined as follows. The center of gravity of the light emitting region 60 is used. Note that when the light emitting region 60 is divided by the exposed portion 19 as in the case of the fourth embodiment, the light emitting portion is divided because it does not emit light.
  • each pixel is isolated. However, these non-light emitting portions are ignored (assuming that light is emitted) and the center of gravity is determined. However, the exposed portion 19 around the light emitting region 60 is not counted as a light emitting portion.
  • the luminance was quantified using a luminance meter (Topcon Co., Ltd., BM-9, viewing angle 0.2 degree) with a circular measurement area with a diameter of approximately 0.5 mm. At this time, the luminance at the beginning of lighting of the organic electroluminescent element and the luminance after 24 hours from lighting were measured.
  • the luminance at the beginning of lighting was measured within 5 seconds after the organic electroluminescence device was energized.
  • the ratio of the luminance at the beginning of lighting to the luminance distribution 24 hours after lighting was used as an index of heat dissipation. That is, if the heat emitted from the organic light emitting device is accumulated in the light emitting region 60 as a result of the heat rise, deterioration is accelerated. Therefore, it can be determined that the larger the value of this ratio is, the lower the luminance decrease (deterioration) is and the higher the heat dissipation.
  • Example 1 and Example 6 are compared with Example 4 and Example 7, respectively, the reduction in luminance is smaller when the sealing plate 61 is provided and the heat dissipation is further enhanced by the sealing plate 61. That is, it can be seen that this can further suppress the heat increase of the organic electroluminescent element.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un élément électroluminescent organique (10) comprenant une couche d'électrode positive (13), une couche d'électrode négative (15), une couche diélectrique (14) formée en contact avec la couche d'électrode négative (15), un évidement (16) formé de façon à pénétrer la couche d'électrode positive (13), la couche diélectrique (14) et la couche d'électrode négative (15), une partie électroluminescente (17) formée sur la surface intérieure de l'évidement (16), et une couche de dissipation thermique (12) pour dissiper la chaleur générée dans la partie électroluminescente (17). L'élément électroluminescent organique (10) est caractérisé en ce que la couche de dissipation thermique (12) comporte une partie exposée (19) qui s'étend au-delà des extrémités de la couche d'électrode négative (15) et de la couche diélectrique (14). L'élément électroluminescent organique (10) présente une moindre irrégularité de luminance causée par une génération de chaleur non uniforme et un rendement lumineux élevé.
PCT/JP2009/066179 2008-09-17 2009-09-16 Élément électroluminescent organique, dispositif d'affichage et dispositif d'éclairage WO2010032758A1 (fr)

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