WO2010067861A1 - 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
WO2010067861A1
WO2010067861A1 PCT/JP2009/070751 JP2009070751W WO2010067861A1 WO 2010067861 A1 WO2010067861 A1 WO 2010067861A1 JP 2009070751 W JP2009070751 W JP 2009070751W WO 2010067861 A1 WO2010067861 A1 WO 2010067861A1
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layer
electrode layer
organic electroluminescent
electroluminescent element
auxiliary electrode
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PCT/JP2009/070751
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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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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8051—Anodes
    • H10K59/80516—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8052—Cathodes
    • H10K59/80521—Cathodes characterised by their shape
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8052—Cathodes
    • H10K59/80522—Cathodes combined with auxiliary electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/17—Passive-matrix OLED displays

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 discloses a first auxiliary electrode having a frame shape disposed on the surface of the first electrode and electrically connected to the first electrode
  • an organic electroluminescence element including a second auxiliary electrode that is arranged in a frame of the auxiliary electrode and is configured by a thin wire electrode that is electrically connected to the first auxiliary electrode
  • Patent Document 2 proposes an electroluminescent element in which a transparent electrode made of a single ITO film is formed on a glass substrate and a network-like low-resistance conductive layer made of Al is laminated thereon. ing.
  • Patent Document 3 discloses an organic material in which the anode is a three-layer structure of a conductive metal oxide, a highly conductive material and a conductive metal oxide, or a two-layer structure of a conductive metal oxide and a highly conductive material. Electroluminescent elements have been proposed.
  • JP 2008-034362 A Japanese Patent Laid-Open No. 10-199680 Japanese Patent Laid-Open No. 10-308285
  • a frame-shaped first auxiliary electrode disposed on the surface of the first electrode and electrically connected to the first electrode, and disposed within the frame of the first auxiliary electrode, and electrically connected to the first auxiliary electrode
  • An organic electroluminescent element provided with a second auxiliary electrode constituted by connected thin wire electrodes is opaque because the first auxiliary electrode and the second auxiliary electrode are made of a metal material. Therefore, in order to increase the light extraction efficiency, it is necessary to increase the aperture ratio. However, even if the aperture ratio is increased, the first auxiliary electrode and the second auxiliary electrode block light transmission, so that there is a problem that the light emission efficiency is lowered.
  • This problem also applies to an electroluminescent element in which a transparent electrode made of a single ITO film is formed on a glass substrate and a network-like low-resistance conductive layer made of Al is laminated thereon.
  • An organic electroluminescence element having a three-layer structure of a conductive metal oxide, a highly conductive material and a conductive metal oxide, or a two-layer structure of a conductive metal oxide and a highly conductive material is used as an anode.
  • the thickness of the layer In order to maintain the transparency of the conductive material, it is necessary to make the thickness of the layer as very thin as 100 to 1000 angstroms. However, in this case, there is a problem that the conductivity is not sufficient.
  • an object of the present invention is to provide an organic electroluminescence device having high luminance efficiency with little luminance unevenness even when surface emission is performed in a large area. 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 element of the present invention includes an electrode layer formed and in contact with at least one of the first electrode layer, the second electrode layer, and the first electrode layer and the second electrode layer.
  • An auxiliary electrode layer having higher electrical conductivity, a dielectric layer formed between the first electrode layer and the second electrode layer, a recess formed at least through the dielectric layer, and a recess A light emitting portion that is formed in contact with the inner surface and emits light by supplying a current, wherein at least one of the first electrode layer and the second electrode layer transmits light emitted from the light emitting portion, and at least a concave portion
  • the width is 10 ⁇ m or less.
  • the auxiliary electrode layer preferably has a thickness of 50 nm to 1000 nm.
  • the auxiliary electrode layer can be formed between the first electrode layer and the dielectric layer, or the auxiliary electrode layer can be formed between the second electrode layer and the dielectric layer.
  • the light emitting unit can be disposed through a dielectric layer.
  • the auxiliary electrode layer can also be formed at the bottom of the recess.
  • at least one of the first electrode layer and the second electrode layer can have a resistivity of 1 ⁇ 10 3 ⁇ ⁇ cm to 5 ⁇ 10 8 ⁇ ⁇ cm, and has a wavelength of 450 nm to 600 nm. It preferably has a transmittance of 50% or more for light.
  • the recess is preferably formed so that the aperture ratio is 5% to 80%, and the recess has a substantially cylindrical shape penetrating the auxiliary electrode layer, the dielectric layer, and the second electrode layer, or is mutually connected. It is preferable to form a substantially parallel groove shape.
  • the light emitting part preferably contains a phosphorescent material.
  • the display device of the present invention includes the organic electroluminescent element described above.
  • 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. 1 is a partial cross-sectional view illustrating a first example of an organic electroluminescent element to which the present exemplary embodiment is applied.
  • An organic electroluminescent element 10 shown in FIG. 1 is formed on a substrate 11 as an anode layer 12 as a first electrode layer for injecting holes, and in electrical contact with the anode layer 12. 12, an auxiliary electrode layer 13 for suppressing a voltage drop at 12, an insulating dielectric layer 14, and a cathode layer 15 as a second electrode layer for injecting electrons are sequentially stacked.
  • the light-emitting material has a recess 16 formed through the auxiliary electrode layer 13, the dielectric layer 14, and the cathode layer 15, and is formed in contact with the inner surface of the recess 16 and emits light by applying a voltage. It has the light emission part 17 which becomes. In the light emitting portion 17, 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 substrate 11 serves as a support for forming the anode layer 12, the auxiliary electrode 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 substrate 11 is not limited to a material transparent to visible light, and an opaque material can be used. Specifically, in addition to the above materials, copper (Cu), silver (Ag), gold (Au), platinum (Pt), tungsten (W), titanium (Ti), tantalum (Ta), silicon (Si) Alternatively, niobium (Nb) alone, an alloy thereof, or a material made of stainless steel or the like can be used.
  • the thickness of the substrate 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 anode layer 12 applies voltage between the cathode layer 15 and injects holes into the light emitting portion 17.
  • the anode layer 12 is formed as a continuous film that is not penetrated by the recess 16. That is, it does not have a through-hole formed by the recess 16 and is formed as a so-called solid film.
  • the organic electroluminescent element 10 when used as a lighting device, it is preferable to emit light with a high luminance of 1000 cd / cm 2 or more. Further, it is more preferable to emit light at 5000 cd / cm 2 or more.
  • the current density may be 10 mA / cm 2 or more. Under this driving condition, luminance unevenness on the light emitting surface is more likely to occur, and in order to prevent this luminance unevenness, it is necessary to use an electrode material having a low surface resistance as an electrode. Note that the luminance unevenness referred to here generally means a case where the luminance difference in the light emitting surface is 10% or more.
  • the anode layer has a surface resistance of 5 ⁇ . / ⁇ or less, preferably having a resistivity of 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less.
  • a transparent metal oxide such as ITO (Indium Tin Oxide) or IZO (Indium-Zinc Oxide) is usually used as a material in order to extract light from the anode layer side.
  • a film thickness of 50 nm to 500 nm is usually required.
  • a light emitting region is divided into a plurality of pixels. The width of this pixel is generally about 50 ⁇ m.
  • the sheet resistance is 8 ⁇ 10 5 ⁇ / ⁇ or less and the resistivity is less than 8 ⁇ 10 2 ⁇ ⁇ cm.
  • auxiliary electrode layer made of a metal material having a resistivity of 1 ⁇ 10 ⁇ 5 ⁇ ⁇ cm or more on the outer periphery of the pixel, it is possible to emit light over the entire surface with a light emitting area of 20 mm ⁇ 20 mm square or more.
  • a material having a low resistivity can be used as the anode layer. Therefore, it is necessary to use a limited material among metals, highly conductive metal oxides, and the like. Moreover, since it is necessary to increase the film thickness in order to reduce the electric resistance, it is limited to the use of a highly transparent material.
  • an auxiliary electrode layer 13 having a low resistivity is provided with respect to the anode layer 12, and the width of the opening of the recess 16 that is a light emitting region is set to 10 ⁇ m or less.
  • a material having a higher resistivity than the conventional material can be used as the anode layer 12 and the selectivity of the material is increased.
  • a resist having a resistivity of 1 ⁇ 10 3 ⁇ ⁇ cm or more can be used.
  • the anode layer 12 can be made thinner. Therefore, a material having low light transmittance can be used as the anode layer 12.
  • a metal oxide can be used for the anode layer 12.
  • a metal oxide can be used for the anode layer 12.
  • the material containing the metal oxide of this is mentioned.
  • DLC diamond-like carbon
  • conductive polymer single crystal silicon (Si), single crystal germanium, inorganic semiconductors such as GeAs, organic semiconductor compounds, etc.
  • Si single crystal silicon
  • germanium inorganic semiconductors such as GeAs, organic semiconductor compounds, etc.
  • the anode layer 12 needs to be manufactured so as to transmit light emitted from the light emitting portion 17 when it is desired to extract the light from the substrate 11 side.
  • the anode layer 12 preferably has a transmittance of 50% or more for visible light having a wavelength of 450 nm to 600 nm. Further, this transmittance is more preferably 80% or more, and particularly preferably 90% or more.
  • the film thickness of the anode layer 12 is usually about 0.5 nm to 500 nm. However, when light is extracted from the anode layer 12, the film thickness may be thick as long as the light transmittance satisfies the above conditions. Furthermore, it is preferable that the surface smoothness of the anode layer 12 is high in order to perform uniform light emission within a defined light emitting region.
  • surface roughness Ra is used as an index of surface smoothness, Ra is preferably 5 nm or less, and more preferably 2 nm or less. When Ra is 5 nm or more, abnormal discharge such as current flowing locally from the protruding portion on the surface may occur, which may cause a short circuit.
  • the auxiliary electrode layer 13 is a layer for reducing the surface resistance and suppressing the voltage drop even when a material having a high resistivity is used for the anode layer 12.
  • it is a layer for preventing local heat generation and short circuit due to luminance unevenness, charge concentration, and the like. That is, when a material having a high resistivity is used as the anode layer 12, a voltage drop occurs and the injection of holes into the anode layer 12 is likely to be hindered. In this case, unevenness in the hole injection distribution at each location in the organic electroluminescent element 10 occurs, and in particular, when the area of the light emitting region is made large, uneven luminance easily occurs.
  • the auxiliary electrode layer 13 does not need to be disposed on the entire light emitting surface. That is, since the auxiliary electrode layer 13 only assists the flow of the current of the anode layer 12, the present embodiment has a sufficient effect even when partially arranged. Specifically, it may be arranged in a certain pattern (strip shape, lattice shape, random shape).
  • the pattern for creating the auxiliary electrode layer 13 may be matched with the pattern in which the concave portion 16 is created, and the pattern in which the auxiliary electrode layer 13 is created at a position corresponding to the concave portion 16 and the case where the auxiliary electrode layer 13 is not created may be alternately repeated. .
  • the material used for the auxiliary electrode layer 13 is not particularly limited as long as it has a higher electrical conductivity (a lower resistivity) than the anode layer 12.
  • the auxiliary electrode layer 13 is not positioned on the extraction path of the light emitted from the light emitting unit 17, not only a transparent material but also an opaque material can be used.
  • metal materials such as aluminum (Al), silver (Ag), chromium (Cr), gold (Au), copper (Cu), tantalum (Ta), or alloys thereof are preferably used.
  • aluminum (Al), silver (Ag), chromium (Cr), copper (Cu), or alloys thereof are more preferable from the viewpoint of high electrical conductivity and ease of material handling.
  • the thickness of the auxiliary electrode layer 13 from the viewpoint of lowering the resistivity of the anode layer 12 for the purpose of providing the auxiliary electrode layer 13, increasing the film thickness is an effective means.
  • the thickness is 50 nm to 1000 nm because of the problem of manufacturing accuracy of the recess 16 described later.
  • the auxiliary electrode layer 13 is in electrical contact with the anode layer 12.
  • “electrically contacting” is not only the case where the auxiliary electrode layer 13 and the anode layer 12 are in direct contact and electrically conducting, but also electrically conducting, for example, via a predetermined thin film layer. This includes cases where The reason why the thin film layer is used in this way is that the adhesion between the material constituting the auxiliary electrode layer 13 and the material constituting the anode layer 12 may be poor or a chemical reaction may occur due to direct contact.
  • Materials used for the thin film layer include oxides, fluorides and nitrides of alkali metals such as lithium (Li), sodium (Na) and potassium (K); calcium (Ca), strontium (Sr), barium ( Ba) and other alkaline earth metal oxides, fluorides and nitrides; aluminum (Al), titanium (Ti), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), gallium ( Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), silver (Ag), indium (In), tin (Sn), tantalum (Ta), tungsten (W) and other metal oxides, fluorine And silicon compounds such as SiN 4 and SiO 2 ; organic compounds such as fluorinated polymers.
  • alkali metals such as lithium (Li), sodium (Na) and potassium (K); calcium (Ca), strontium (Sr), barium ( Ba) and other alkaline earth metal
  • the resistivity of the material used as the thin film layer is not particularly limited.
  • the film thickness when the resistivity is 1 ⁇ 10 ⁇ 1 ⁇ ⁇ cm or more, it is preferable to reduce the thickness in order to facilitate electrical conduction between the anode layer 12 and the auxiliary electrode layer 13.
  • the film thickness of the thin film layer is preferably 10 nm or less, and more preferably 5 nm or less.
  • the dielectric layer 14 is formed between the anode layer 12 and the cathode layer 15, separates and insulates the anode layer 12 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 resistivity is required to be 1 ⁇ 10 8 ⁇ ⁇ cm or more, preferably 1 ⁇ 10 12 ⁇ ⁇ cm or more.
  • 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.
  • 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 12 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 driving voltage is 5 V
  • the anode layer 12 and the anode layer 12 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 applies a voltage between the anode layer 12 and injects electrons into the light emitting portion 17.
  • the material used for the cathode layer 15 is not particularly limited as long as it has electrical conductivity. However, a material having a low work function and being chemically stable is preferable.
  • 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 to the inner surface and taking out light from the light emitting portion 17, and in this embodiment, the anode layer 12 which is the first electrode layer does not penetrate, The auxiliary electrode layer 13, the dielectric layer 14, and the cathode layer 15 as the second electrode layer are formed so as to penetrate.
  • the light emitted from the light emitting portion 17 by providing the concave portion 16 in this manner propagates through the concave portion 16 and can be extracted in both directions on the substrate 11 side and the cathode layer 15 side.
  • the recess 16 is formed through the auxiliary electrode layer 13, the dielectric layer 14, and the cathode layer 15, the anode layer 12 as the first electrode layer is an electrode that transmits light. Even when the cathode layer 15 as the second electrode layer is formed of an opaque material, light can be extracted from the substrate 11 side.
  • 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 recess 16 sandwiched between the auxiliary electrode layers 13 and the like serves as a light extraction region.
  • the width of the recess 16 is preferably as narrow as possible. In this case, the distance between the auxiliary electrode layer 13 and the central portion of the recess 16 can be made very close. Therefore, even if a material having a high resistivity is used for the anode layer 12, for example, the voltage drop due to the electrode resistance of the anode layer 12 is small even in the portion of the anode layer 12 located at the center of the recess 16. Therefore, phenomena such as luminance unevenness can be suppressed.
  • the light extraction efficiency is constant regardless of the size of the aperture ratio, which is the ratio of the area occupied by the light extraction region by the recess 16 to the area of the light emission region of the organic electroluminescent element 10. is there.
  • Increasing the aperture ratio increases the amount of light that can be extracted.
  • the aperture ratio is increased too much, the effect of the auxiliary electrode layer 13 is sufficiently increased by increasing the electrical resistance due to the thinning of the width of the auxiliary electrode layer 13. Prone to being unable to demonstrate.
  • heat storage tends to be induced during high-luminance emission. Therefore, the light emitting material forming the light emitting portion 17 may be deteriorated and lead to luminance unevenness. Therefore, it may be better to lower the aperture ratio to some extent.
  • the aperture ratio is preferably 5% to 80%, more preferably 10% to 60%.
  • 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.
  • 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 12 and the cathode layer 15, for example.
  • the cathode layer 15 is penetrated by the recess 16 and the upper portion 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 recess 16 is formed so as to penetrate the auxiliary electrode layer 13, the dielectric layer 14, and the cathode layer 15.
  • the light emitting part 17 it is sufficient that at least the dielectric layer 14 penetrates through the recess 16, and the other layers may or may not penetrate.
  • FIG. 3 is a partial cross-sectional view illustrating a second example of an organic electroluminescent element to which the present embodiment is applied, and is a diagram illustrating a case of further penetrating the anode layer 12 that is the first electrode layer. is there.
  • the organic electroluminescent element 20 shown in FIG. 3 further has a recess 16 penetrating through the anode layer 12 as the first electrode layer with respect to the organic electroluminescent element 10 shown in FIG. By doing in this way, it is possible to extract light from the substrate 11 side even if an opaque material such as a metal material is used as the anode layer 12.
  • the auxiliary electrode layer 13 is in electrical contact with the anode layer 12.
  • the auxiliary electrode layer 13 may be formed in contact with the cathode layer 15.
  • FIG. 4 is a partial cross-sectional view illustrating a third example of an organic electroluminescent element to which the present exemplary embodiment is applied.
  • the auxiliary electrode layer 13 is formed in electrical contact with the cathode layer 15.
  • FIG. The organic electroluminescent element 30 shown in FIG. 4 does not form the auxiliary electrode layer 13 in electrical contact with the anode layer 12 but is electrically connected to the cathode layer 15 with respect to the organic electroluminescent element 20 shown in FIG. It is formed in contact with. That is, the anode layer 12, the dielectric layer 14, the auxiliary electrode layer 13, and the cathode layer 15 are formed on the substrate 11 in this order.
  • the surface resistance is reduced by providing a layer having higher electrical conductivity than the cathode layer 15 as the auxiliary electrode layer 13.
  • a voltage drop is less likely to occur, and electrons can be more easily injected into the cathode layer 15.
  • luminance unevenness of the organic electroluminescent element 30 is less likely to occur.
  • the auxiliary electrode layer 13 that is in electrical contact with the anode layer 12 is not necessarily required by using a material having high electrical conductivity such as a metal material as the anode layer 12.
  • FIG. 5 is a partial cross-sectional view illustrating a fourth example of an organic electroluminescent element to which the present exemplary embodiment is applied.
  • the concave portion 16 is filled with the light emitting portion 17 and the second concave portion 18 is not formed in the organic electroluminescent element 30 shown in FIG.
  • the cathode layer 15 is formed in a so-called solid film shape so as to be laminated on the dielectric layer 14. That is, it is formed as a continuous film that does not have a hole that penetrates through the recess 16 and is not penetrated by the recess 16.
  • the recess 16 penetrates the anode layer 12, the auxiliary electrode layer 13, and the dielectric layer 14 as the first electrode layer, but does not penetrate the cathode layer 15 as the second electrode layer.
  • the cathode layer 15 By forming the cathode layer 15 in this way, the recess 16 is covered. Even if 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 and Similarly, 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 an electrode that transmits light. It is not possible.
  • the cathode layer 15 preferably has the same configuration as the anode layer 12 described in detail in FIG.
  • the light emitting portion 17 is formed so as not to form the second concave portion 18 and fills the entire concave portion 16, but the second concave portion 18 is formed. May be.
  • the organic electroluminescent element 40b shown in FIG. 6 is a partial cross-sectional view illustrating a fifth example of the organic electroluminescent element to which the present exemplary embodiment is applied.
  • the organic electroluminescent device 40b is different from the organic electroluminescent device 40a shown in FIG. 5 in that the concave portion 16 is not completely filled with the light emitting portion 17 and the second concave portion 18 is formed, and the cathode layer 15 is formed thereon. is doing.
  • the organic electroluminescent element 40c shown in FIG. 7 is the fragmentary sectional view explaining the 6th example of the organic electroluminescent element to which this Embodiment is applied.
  • the light emitting portion 17 is developed not only inside the recess 16 but also on the upper surface of the auxiliary electrode layer 13 with respect to the organic electroluminescent element 40b shown in FIG.
  • the upper surface of the cathode layer 15 may not be made flat like the organic electroluminescent element 40b shown in FIG.
  • the cathode layer 15 and the auxiliary electrode layer 13 electrically contact each other, after the light emitting portion 17 is formed and before the cathode layer 15 is formed, This can be achieved by bringing the surface into contact with a highly smooth flat surface, the side surface of a bar, or the like. Specifically, a plate surface made of electropolished stainless steel, quartz glass, or the like, or a side surface of a cylindrical rod is pressed against the surface of the light emitting unit 17. Since the light emitting portion 17 on the auxiliary electrode layer 13 is exposed on the outermost surface and extremely thin, a part thereof is lost by this operation, and as a result, a part of the auxiliary electrode layer 13 is exposed. It will be.
  • FIG. 8 is a partial cross-sectional view illustrating a seventh example of the organic electroluminescent element to which the exemplary embodiment is applied.
  • the anode layer 12 is formed at the bottom of the concave portion 16, and the light emitting portion 17 is formed so as to be laminated on the anode layer 12.
  • the anode layer 12 and the auxiliary electrode layer 13 are formed so as to be laminated.
  • the side surfaces of the anode layer 12 and the auxiliary electrode layer 13 may be used as in the present embodiment, even if they are not laminated. Even if the sides are in contact with each other, the resistivity of the anode layer 12 can be reduced.
  • the anode layer 12 and the auxiliary electrode layer 13 need only be in electrical contact in some form, and the shapes and positions of the anode layer 12 and auxiliary electrode layer 13 are not particularly limited. However, the anode layer 12 is preferably not in contact with the cathode layer 15 which is a counter electrode.
  • FIG. 9 is a partial cross-sectional view illustrating an eighth example of an organic electroluminescent element to which the present exemplary embodiment is applied.
  • the organic electroluminescent element 60 shown in FIG. 9 has the function of the auxiliary electrode layer 13 on the substrate 11 and is in electrical contact with the anode layer 12. Therefore, the organic electroluminescent element 60 can be manufactured by laminating three layers of the anode layer 12, the dielectric layer 14, and the cathode layer 15 on the substrate 11 having the function of the auxiliary electrode layer 13. That is, since the layer structure is reduced, the number of manufacturing steps can be reduced when the organic electroluminescent device 60 is manufactured, and the thickness of the organic electroluminescent device 60 can be easily reduced.
  • an inorganic semiconductor such as a silicon single crystal substrate can be used as a material of the substrate 11 having the function of the auxiliary electrode layer 13, for example.
  • an inorganic semiconductor such as a silicon single crystal substrate can be used as a material of the substrate 11 having the function of the auxiliary electrode layer 13.
  • the light emitted from the light emitting unit 17 can be extracted from the cathode layer 15 side.
  • the anode layer 12 and the auxiliary electrode layer 13 or the cathode layer 15 and the auxiliary electrode layer 13 have the same shape (for example, the structure shown in FIGS. 3 to 7), the anode layer 12 and the auxiliary electrode layer 13 or The cathode layer 15 and the auxiliary electrode layer 13 can be a mixed layer that changes continuously.
  • the advantage of providing such a mixed layer is that, for example, when materials having poor adhesion to each other are selected as materials used for the anode layer 12 and the auxiliary electrode layer 13 or the cathode layer 15 and the auxiliary electrode layer 13, the adhesion between the two is sufficient. This is because there is a problem that both of them are peeled off. That is, by using a mixed layer, it is possible to sufficiently bond the two. For example, when the anode layer 12 and the auxiliary electrode layer 13 are formed by sputtering, in order to form such a mixed layer, the operation of alternately forming the anode layer 12 and the auxiliary electrode layer 13 is repeated a plurality of times. Do.
  • the sputtering apparatus is adjusted so that the anode layer 12 and the auxiliary electrode layer 13 can each be deposited in C minutes (that is, the total A + B nm can be laminated in a total of C minutes). Under these conditions, only the component of the anode layer 12 is formed on the substrate 11 for the first C / 11 minutes. Then, the component of the anode layer 12 is formed for the first 0.9 ⁇ C / 11 minutes of the next C / 11 minutes, and the component of the auxiliary electrode layer 13 is formed for the remaining 0.1 ⁇ C / 11 minutes.
  • the component of the anode layer 12 is formed for the first 0.8 ⁇ C / 11 minutes, and the component of the auxiliary electrode layer 13 is formed for the remaining 0.2 ⁇ C / 11 minutes.
  • the composition is changed pseudo-continuously from the component of the anode layer 12 to the component of the auxiliary electrode layer 13, and only the component of the auxiliary electrode layer 13 is formed for the last C / 11 minutes.
  • the anode layer 12 is formed on the lower side when the substrate 11 side is the lower side.
  • the case where the cathode layer 15 is formed on the upper side with the body layer 14 sandwiched therebetween has been described as an example.
  • the present invention is not limited to this, and the anode layer 12 and the cathode layer 15 may be replaced. That is, when the substrate 11 side is the lower side, the cathode layer 15 may be formed on the lower side, and the anode layer 12 may be formed on the upper side with the dielectric layer 14 interposed therebetween.
  • the light emitting region is subdivided and the light emitting portion emits light with higher luminance (for example, 1000 cd / m 2 or more), so that the entire organic electroluminescence device has a high luminance surface. It can be viewed as a light emitter.
  • FIG. 10 is a first example illustrating a case where the light emitting region of the organic electroluminescent element is subdivided.
  • the organic electroluminescent element 10e shown in FIG. 10 the organic electroluminescent element 10e is viewed obliquely from above.
  • the organic electroluminescent element 10e has the same structure as the organic electroluminescent element 10 described in FIG. 1, and the anode layer 12 is formed on the substrate 11 in a solid film shape.
  • the anode layer 12 there is a light emitting region 90 composed of the auxiliary electrode layer 13, the dielectric layer 14, the cathode layer 15, and the light emitting portion 17 (see FIG. 1) formed in contact with the inner surface of the recess 16.
  • the light emitting region 90 is subdivided, and in the organic electroluminescent element 10e, the light emitting region 90 is separated by a lattice-like non-light emitting region 91 at a predetermined interval. Due to the non-light emitting area 91, the light emitting area 90 has a rectangular shape and is arranged in a grid pattern.
  • the width (W) of the substantially cylindrical recess 16 formed in the light emitting region 90 is preferably 10 ⁇ m or less, preferably 3 ⁇ m or less. Is more preferable and 1 ⁇ m or less is most preferable.
  • a material having a resistivity of 5 ⁇ 10 6 ⁇ ⁇ cm or less can be used as the anode layer 12, and a material having a resistivity of 5 ⁇ 10 4 ⁇ ⁇ cm or less is more preferable.
  • the width (W) of the recess 16 is more preferably 5 ⁇ m or less.
  • a material having a resistivity of 1 ⁇ 10 7 ⁇ ⁇ cm or less can be used as the anode layer 12, and the resistivity is 5 It is more preferable to use a material of ⁇ 10 5 ⁇ ⁇ cm or less.
  • the width (W) of the recess 16 is preferably 1 ⁇ m or less.
  • the width (W) of the recess 16 refers to the distance (shortest distance) on the short axis side from the end of the recess 16 to the other end.
  • the light emitting regions 90 are arranged in a rectangular lattice pattern.
  • the present invention is not limited to this.
  • the light emitting regions 90 are circular, oval, square, or the like. Other shapes may be used.
  • the light emitting region is composed of the anode layer 12, the auxiliary electrode layer 13, the dielectric layer 14, the cathode layer 15, and the light emitting portion 17 formed in contact with the inner surface of the recess 16. It suffices if it includes at least the concave portion 16 and the light emitting portion 17, and the other layers may be formed so as to protrude from the non-light emitting region 91.
  • FIG. 11 is a second example illustrating the case where the light emitting regions of the organic electroluminescent element are arranged in a fragmented manner.
  • the light emitting region 90 of the organic electroluminescent element 10f shown in FIG. 11 has a groove shape in which the concave portions 16 are substantially parallel to the organic electroluminescent element 10e shown in FIG.
  • the light emitting area 90 has a strip shape, and is similarly disposed so as to sandwich the non-light emitting area 91 having a strip shape.
  • the width (W) of the concave portion 16 in the organic electroluminescent element 10f is a groove width in the case of the present embodiment, and is preferably 10 ⁇ m or less like the organic electroluminescent element 10e shown in FIG.
  • FIG. 12A to 12F are diagrams illustrating a method for manufacturing the organic electroluminescent element 10 to which the present exemplary embodiment is applied.
  • the anode layer 12, the auxiliary electrode layer 13, the dielectric layer 14, and the cathode layer 15 are formed in this order on the substrate 11 (FIG. 12A).
  • resistance heating vapor deposition, electron beam vapor deposition, sputtering, ion plating, or the like can be used.
  • a coating film forming method that is, a method in which a target material is dissolved in a solvent and applied to a substrate and drying
  • a spin coating method a dip coating method, an ink jet method, a printing method, a spray method
  • a film using a method such as a dispenser method.
  • the cathode buffer layer can also be formed by the same method.
  • the auxiliary electrode layer 13 is patterned, the patterning can be performed after the auxiliary electrode layer 13 is formed and before the dielectric layer 14 is formed. Specifically, the patterning can be performed by a lithography method using a resist, a printing method such as screen printing or letterpress printing, an ink jet method using an ink jet, or the like.
  • the performance of the overcoated layer (adhesion with the anode layer 12, surface smoothness, reduction of the hole injection barrier, etc.) can be improved.
  • Surface treatment includes sputtering treatment, corona treatment, UV ozone irradiation treatment, oxygen plasma treatment, etc. as well as high-frequency plasma treatment.
  • anode buffer layer (not shown) instead of or in addition to the surface treatment of the anode layer 12.
  • 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 12 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 concave portion 16 is formed so as to penetrate each layer formed in the step of FIG. 12A.
  • 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. 12B).
  • the exposed portion of the cathode layer 15 is removed by etching, and a recess 16 is formed so as to penetrate each layer formed in the step of FIG. 12A (FIG. 12E).
  • etching either dry etching or wet etching can be used.
  • the 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. 12 (f)).
  • 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, it becomes easy to prevent oxidation of the upper cathode layer 15. 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.
  • the concave portion 16 is formed by a lithography method using a resist, but the concave portion 16 can be formed by other methods.
  • the processing depth can be increased by increasing the output of the laser, and the diameter of the hole can be reduced by narrowing the focal point of the laser beam.
  • the laser output is adjusted, and processing is performed so that the pattern 72 is formed up to the position where the auxiliary electrode layer 13 is processed.
  • This method using laser light has an advantage that the steps of resist coating, exposure, development, and etching can be omitted as compared with the previous lithography method.
  • the auxiliary electrode layer 13, the dielectric layer 14, and the cathode layer 15 removed by the laser light irradiation adhere to the surface after processing and are contaminated, or when the auxiliary electrode layer 13 is patterned. There is a problem that cannot be used.
  • the manufacturing method of the organic electroluminescent element 10 mentioned above is an example, and is not restricted to this.
  • a predetermined pattern 72 corresponding to the recess 16 is formed in the auxiliary electrode layer 13.
  • the pattern 72 can be formed by any one of a lithography method and a method of irradiating laser light in the same manner as described above.
  • a dielectric layer 14 and a cathode layer 15 are formed so as to overlap therewith.
  • a resist layer 71 is applied and exposed in the same manner as in the previous manufacturing method.
  • this manufacturing method compared to the previous manufacturing method is that only the auxiliary electrode layer 13 is removed even when direct patterning is performed by laser light, and thus there is an advantage that the previous contamination hardly occurs.
  • this manufacturing method has an advantage that an organic electroluminescent element having a structure in which the auxiliary electrode layer 13 is covered with the dielectric layer 14 can be manufactured as will be described in detail with reference to FIG.
  • the auxiliary electrode layer 13 having a recess 16, an unpatterned (solid) anode layer 12, and a dielectric layer having a recess 16. 14 can be easily manufactured.
  • the anode layer 12 and the dielectric layer 14 are formed in advance on the auxiliary electrode layer 13 in which the recess 16 is formed, the anode layer 12 is separated by this manufacturing method so as to overlap the pattern of the auxiliary electrode layer 13.
  • the recess 16 can be formed only in the dielectric layer 14.
  • this manufacturing method has a problem in that the number of steps is increased because etching using a resist needs to be performed twice.
  • FIG. 13 is a diagram illustrating an example of a display device using the organic electroluminescent element in this embodiment.
  • the display device 200 shown in FIG. 13 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 an organic electroluminescent element. 214, a sealing plate 216, and a sealing material 218.
  • the display device substrate 202 for example, a transparent substrate such as a rectangular glass substrate 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.
  • the anode auxiliary wiring 206 functions as a terminal for connecting to the external wiring on the end side of the display device substrate 202, and the anode auxiliary wiring 206 is connected from a driving circuit (not shown) provided outside. A current can be supplied to the anode wiring 204 through the wiring.
  • the anode auxiliary wiring 206 is made of a metal film having a thickness of 500 nm to 600 nm, for example.
  • 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 substrate 11, the anode layer 12, the auxiliary electrode 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.
  • a plurality of cathode partitions 212 are formed on the insulating film 210 along a direction perpendicular to the anode wiring 204.
  • the cathode partition 212 plays a role in spatially separating the plurality of cathode wirings 208 so that the wirings of the cathode wirings 208 are not electrically connected to each other. Accordingly, the cathode wiring 208 is disposed between the adjacent cathode partition walls 212.
  • a cathode partition with a height of 2 to 3 ⁇ m and a width of 10 ⁇ m can be used.
  • the display device substrate 202 is bonded 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. 14 is a diagram illustrating an example of a lighting device including the organic electroluminescent element in the present embodiment.
  • a lighting device 300 shown in FIG. 14 is installed adjacent to the organic electroluminescent element 10 and the substrate 11 (see FIG. 1) of the organic electroluminescent element 10 and connected to the anode layer 12 (see FIG. 1).
  • the lighting circuit 301 has a DC power supply (not shown) and a control circuit (not shown) inside, and supplies a current between the anode layer 12 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 20 shown in FIG. 3 was produced by the following method. Specifically, an ITO (Indium Tin Oxide) film having a thickness of 150 nm is first formed on a glass substrate (100 mm square, thickness 0.7 mm) made of quartz glass by using a sputtering apparatus (E-401s manufactured by Canon Anelva Co., Ltd.). A silver (Ag) layer was deposited to 100 nm, a silicon dioxide (SiO 2 ) layer was deposited to 200 nm, and an aluminum (Al) layer was deposited to 100 nm.
  • the glass substrate corresponds to the substrate 11.
  • the ITO film corresponds to the anode layer 12, the silver layer corresponds to the auxiliary electrode layer 13, the silicon dioxide layer corresponds to the dielectric layer 14, and the aluminum layer corresponds to the cathode layer 15.
  • a photoresist (AZ 1500 made by AZ Electronic Materials Co., Ltd.) was formed to a thickness of about 1 ⁇ m by spin coating.
  • a photomask having quartz (plate thickness of 3 mm) as a base material and circular patterns (outlined) having a diameter of 4 ⁇ m arranged in a close-packed manner with respective intervals of 4 ⁇ m was prepared, and a stepper exposure apparatus (manufactured by Nikon, Using model NSR-1505i6), exposure was performed at 1/5 scale.
  • 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
  • each layer was sequentially processed by dry etching using a reactive ion etching apparatus (RIE-200iP manufactured by Samco Corporation).
  • RIE-200iP reactive ion etching apparatus manufactured by Samco Corporation.
  • an aluminum layer as the cathode layer 15, a silicon dioxide layer as the dielectric layer 14, a silver layer as the auxiliary electrode layer 13, and a recess 16 penetrating the ITO film as the anode layer 12 are formed. It was.
  • the resist residue was removed by pouring a resist removing solution (N methylpyrrolidone) over the substrate.
  • 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.
  • the organic electroluminescent element 20 was able to be manufactured by the above process.
  • Example 2a An organic electroluminescent element was produced in the same manner as in Example 1 except that the structure of the organic electroluminescent element was changed to that shown in FIG.
  • the organic electroluminescent element shown in FIG. 15 has an anode layer 12 (ITO film), an auxiliary electrode layer 13 (silver layer), and a dielectric layer 14 (silicon dioxide layer) stacked in this order on a substrate 11 (glass substrate).
  • Concave portions 16 are formed in the three layers.
  • the light emitting material fills the concave portion 16 and also expands on the upper surface of the dielectric layer 14 to form the light emitting portion 17 having the extending portion 17a.
  • the cathode layer 15 (aluminum layer) is formed on the light emitting portion 17 in a solid film shape and in a planar shape.
  • An organic electroluminescent device having such a structure can be manufactured as follows. First, an ITO film, a silver layer, and a silicon dioxide layer are sequentially laminated on a glass substrate. Next, the recess 16 is formed so as to penetrate these layers. Then, after the light emitting portion 17 is formed, an aluminum layer is formed. In this case, the manufacturing conditions in each step are the same as in Example 1. In the case of this embodiment, after the light emitting portion 17 is formed, a 2.0 nm-thick sodium (Na) film is formed as a cathode buffer layer by a vacuum evaporation apparatus, and then an aluminum layer is formed.
  • Na sodium
  • Example 2b Compared to Example 2a, the film thickness of the silver layer as the auxiliary electrode layer 13 was changed to 200 nm, and the organic layer was etched in the same manner as in Example 2a except that the reaction time was changed to 14 minutes as the etching condition for the silver layer. An electroluminescent element was produced.
  • Example 2c In contrast to Example 2a, the film thickness of the silver layer as the auxiliary electrode layer 13 was changed to 1000 nm, and the etching conditions for the silver layer were the same as in Example 2a except that the reaction time was changed to 50 minutes. An electroluminescent element was produced.
  • Example 2d An organic electroluminescent element was produced in the same manner as in Example 1 except that the silver layer as the auxiliary electrode layer 13 was changed to a chromium (Cr) layer with respect to Example 2a.
  • the chrome layer etching conditions are the same as the ITO film etching conditions.
  • Example 3 An organic electroluminescent element was produced in the same manner as in Example 1 except that the structure of the organic electroluminescent element was changed to that shown in FIG.
  • the organic electroluminescent element of the present embodiment was manufactured by the method described in FIG. The manufacturing conditions in each step are the same as in Example 1.
  • Example 4 An organic electroluminescent element was produced in the same manner as in Example 2a, except that the structure of the organic electroluminescent element was changed to that shown in FIG. 16 with respect to Example 2a.
  • an anode layer 12 ITO film
  • an auxiliary electrode layer 13 silver layer
  • a dielectric layer 14 silicon dioxide layer
  • a recess 16 is formed in the auxiliary electrode layer 13 and the dielectric layer 14.
  • the light emitting material fills the concave portion 16 and also expands on the upper surface of the dielectric layer 14 to form the light emitting portion 17 having the extending portion 17a.
  • the cathode layer 15 (aluminum layer) is formed in a solid film shape on the light emitting portion 17.
  • the organic electroluminescent element having such a structure can be manufactured as follows. First, an ITO film, a silver layer, and a silicon dioxide layer are sequentially laminated on a glass substrate. Next, the recess 16 is formed so as to penetrate the ITO film and the silver layer. Then, after the light emitting portion 17 is formed, an aluminum layer is formed. In this case, the manufacturing conditions in each step are the same as in Example 1. In the case of this embodiment, after the light emitting portion 17 is formed, a 2.0 nm-thick sodium (Na) film is formed as a cathode buffer layer by a vacuum evaporation apparatus, and then an aluminum layer is formed.
  • Na 2.0 nm-thick sodium
  • Example 5 An organic electroluminescent element was produced in the same manner as in Example 3, except that the structure of the organic electroluminescent element was changed to that shown in FIG.
  • the difference between the organic electroluminescent device shown in FIG. 17 and the organic electroluminescent device shown in FIG. 1 is that the auxiliary electrode layer 13 is covered with a dielectric layer 14, and the auxiliary electrode layer 13 and the light emitting portion 17 are made of the dielectric layer 14. It is a point arranged via.
  • the auxiliary electrode layer 13 is covered with the dielectric layer 14 in this manner, the current flowing from the auxiliary electrode layer 13 to the light emitting unit 17 can be reduced.
  • the thickness of the dielectric layer 14 covering the auxiliary electrode layer 13 is preferably 1 nm or more, more preferably 5 nm or more, and most preferably 10 nm or more.
  • the auxiliary electrode layer 13 is patterned so as to have the shape shown in FIG. 17 by a method such as photolithography using a resist. Then, the dielectric layer 14 and the cathode layer 15 are formed on the auxiliary electrode layer 13. Then, a resist is applied again, and ultraviolet rays for modifying the resist are irradiated from the substrate 11 side and developed. As a result, a pattern corresponding to the recess 16 is formed. In this pattern, the opening needs to be made smaller than the pattern when the auxiliary electrode layer 13 is formed.
  • the exposure time can be shortened to 1 / 2T to 3 / 4T with respect to the ultraviolet exposure time T for forming the resist pattern of the auxiliary electrode layer 13. That is, the amount of exposure light is the strongest in a portion away from the pattern of the auxiliary electrode layer 13, that is, near the center of the recess 16, because an interference effect of light occurs when passing through the pattern of the auxiliary electrode layer 13. From here, the amount of light decreases toward the portion overlapping the auxiliary electrode layer 13. Therefore, as the exposure time is shortened, only a narrow range centered on the center of the recess 16 is exposed. The longer the irradiation time, the wider the exposure.
  • the exposure time for forming a pattern having the same shape as the pattern of the auxiliary electrode layer 13 is made shorter than the exposure time to cover the pattern of the auxiliary electrode layer 13 so as to cover the pattern of the auxiliary electrode layer 13 or the cathode.
  • a pattern of layer 15 can be formed.
  • the recessed part 16 can be formed by removing the dielectric material layer 14 and the cathode layer 15 of the location corresponding to the recessed part 16 with an etching method.
  • Example 6 An organic electroluminescent element was produced in the same manner as in Example 4 except that the structure of the organic electroluminescent element was changed to that shown in FIG.
  • the difference between the organic electroluminescent device shown in FIG. 18 and the mechanical electroluminescent device shown in FIG. 16 is that the auxiliary electrode layer 13 is covered with the dielectric layer 14, and the auxiliary electrode layer 13 and the light emitting portion 17 are made of the dielectric layer 14. It is a point arranged via. In this way, the auxiliary electrode layer 13 can be covered with the dielectric layer 14 by a method similar to the method shown in the fifth embodiment.
  • Example 7 An organic electroluminescent element was produced in the same manner as in Example 2a, except that the structure of the organic electroluminescent element was changed to that shown in FIG. In order to manufacture the organic electroluminescent element 40c shown in FIG. 7, it is necessary to reverse the order in which the auxiliary electrode layer 13 and the dielectric layer 14 are laminated. In addition, since the auxiliary electrode layer 13 and the cathode layer 15 are isolated via the extending portion 17a of the light emitting portion 17, a process of bringing them into electrical contact is added.
  • the surface of the light emitting layer 17 is electropolished with a stainless steel plate (plate thickness: 1 mm, size: 100 mm ⁇ ). Were stacked three times from the top and then removed three times.
  • Example 8 An organic electroluminescent element was produced in the same manner as in Example 4 except that the structure of the organic electroluminescent element was changed to that shown in FIG.
  • the organic electroluminescent element shown in FIG. 19 is different from the organic electroluminescent element shown in FIG. 16 in that the order of stacking the auxiliary electrode layer 13 and the dielectric layer 14 is reversed. Therefore, in order to manufacture the organic electroluminescent element shown in FIG. 19, it is necessary to reverse the order in which the auxiliary electrode layer 13 and the dielectric layer 14 are laminated. In addition, since the auxiliary electrode layer 13 and the cathode layer 15 are isolated via the extending portion 17a of the light emitting portion 17, a process of bringing them into electrical contact is added.
  • the surface of the light emitting layer 17 is electropolished with a stainless steel plate (plate thickness: 1 mm, size: 100 mm ⁇ ). Were stacked three times from the top and then removed three times.
  • Example 9 An organic electroluminescent element was produced in the same manner as in Example 4 except that the structure of the organic electroluminescent element was changed to that shown in FIG.
  • the organic electroluminescent element shown in FIG. 20 is different from the organic electroluminescent element shown in FIG. 16 in that an auxiliary electrode layer 13 is formed on both surfaces with a dielectric layer 14 interposed therebetween. Therefore, it is necessary to add a process for forming the auxiliary electrode layer 13 on the dielectric layer 14.
  • Example 10 An organic electroluminescent element was produced in the same manner as in Example 4 except that the structure of the organic electroluminescent element was changed to that shown in FIG.
  • an auxiliary electrode layer 13 (silver layer), an anode layer 12 (ITO film), and a dielectric layer 14 (silicon dioxide layer) are laminated on a substrate 11 (glass substrate).
  • the recess 16 is first formed in the auxiliary electrode layer 13, and the inside of the recess 16 is filled with the anode layer 12.
  • a concave portion 16 is also formed in the dielectric layer 14, and the inside of the concave portion 16 is filled with a light emitting material and also spreads on the upper surface of the dielectric layer 14 to form a light emitting portion 17 having an extending portion 17 a.
  • the cathode layer 15 (aluminum layer) is formed in a solid film shape on the light emitting portion 17.
  • the difference between the organic electroluminescent device shown in FIG. 21 and the organic electroluminescent device shown in FIG. 16 is that the order in which the anode layer 12 and the auxiliary electrode layer 13 are laminated is reversed.
  • the auxiliary electrode layer 13 and the light emitting portion 17 are covered with the anode layer 12.
  • the auxiliary electrode layer 13 When the auxiliary electrode layer 13 is covered with the anode layer 12 in this way, the current flowing from the auxiliary electrode layer 13 to the light emitting unit 17 can be reduced. When a current flows from the auxiliary electrode layer 13 to the light emitting portion 17, this amount becomes a current loss, which may reduce the light emission efficiency.
  • the method described in the description of FIG. 12 can be used.
  • Example 11 Compared to Example 2a, the structure of the organic electroluminescent element was changed to that shown in FIG. 9, and an organic electroluminescent element was produced in the same manner as in Example 1 except that the cathode layer 15 was changed to an ITO film of 150 nm. .
  • a copper substrate 100 mm ⁇ , thickness 0.7 mm
  • the substrate 11 also serves as the auxiliary electrode layer 13.
  • the substrate 11 since the substrate 11 is opaque and the cathode layer 15 is transparent, the light emitted from the light emitting portion 17 is extracted from the cathode layer 15 side.
  • Example 12 An organic electroluminescent element was produced in the same manner as in Example 2a, except that the structure of the organic electroluminescent element was changed to that shown in FIG.
  • a mixed layer 19 and a dielectric layer 14 are laminated on a substrate 11 (glass substrate).
  • the recess 16 is formed in the dielectric layer 14 and the mixed layer 19, and the inside of the recess 16 is filled with the light emitting material, and also spreads on the upper surface of the dielectric layer 14 to have the extending portion 17a.
  • the cathode layer 15 (aluminum layer) is formed in a solid film shape on the light emitting portion 17.
  • the mixed layer 19 is a film in which ITO films and thin silver layers are alternately stacked.
  • the operation of alternately forming ITO and silver is repeated a plurality of times.
  • the sputtering apparatus is adjusted so that the ITO film 150 nm and the silver layer 100 nm can each be formed in 5.5 minutes (that is, both can be laminated in a total of 11 minutes). Under these conditions, the first 1 minute is silver only, the next 1 minute is silver for the first 0.9 minute, the remaining 0.1 minute is ITO, the next 1 minute is silver for the first 0.8 minute, The next 0.2 minutes will be ITO.
  • the silver film formation time is shortened by 0.1 minute every minute, and the ITO film formation time is increased by 0.1 minute. Then, the composition is changed from silver to ITO in a quasi-continuous manner, and only ITO is formed for the last minute. Thereby, the mixed layer 19 whose composition changes continuously can be formed.
  • Example 13 In contrast to Example 2d, an organic electroluminescent element was produced in the same manner as in Example 1 except that the structure of the organic electroluminescent element was that the auxiliary electrode layer 13 was patterned in a lattice pattern.
  • the lattice-shaped auxiliary electrode layer 13 was formed by the following method: (1) After forming the anode layer 12 and then the auxiliary electrode layer 13 (chrome 100 nm) on the substrate 11, the method shown in Example 1 Apply resist.
  • Comparative Examples 1 to 13 organic electroluminescent elements were produced in the same manner as in Examples 1, 2a, and 3 to 13 except that the auxiliary electrode layer 13 was not formed.
  • the above value can be used as an index of luminance unevenness.
  • an organic electroluminescent element having a light emitting surface 400 of 50 mm ⁇ on a 100 mm substrate 11 was produced.
  • a positive voltage and a negative voltage are applied from positions 430 and 440 2 mm to the left and right of the one vertex 410, respectively.
  • the luminance value of a circular portion having a diameter of 0.5 mm is obtained by centering a point 450 on a straight line (indicated by a dotted line) connecting the vertex 410 and the diagonal vertex 420 and at a distance of 10 mm from the vertex 410. Let it be luminance A.
  • luminance B a luminance value of a circular portion having a diameter of 0.5 mm around the point 460 on the straight line and at a distance of 10 mm from the diagonal vertex 420 is defined as luminance B.
  • the average luminance of the light emitting surface is defined as (A + B) / 2
  • the luminance unevenness F can be expressed by the following equation (1).
  • F is a numerical value in the range of 0 ⁇ F ⁇ 1, and the closer to 1, the less the luminance unevenness and the better.
  • a luminance meter manufactured by Topcon Corporation, BM-9, viewing angle 0.2 degree
  • the voltage applied to the organic electroluminescent element was adjusted so that the luminance at the location where the luminance A was measured was about 2000 cd / m 2 .
  • Table 1 shows the results of evaluation of luminance unevenness.
  • Table 2 shows the values of sheet resistance.
  • ITO-Ag is the value of the sheet resistance of the mixed layer 19 of Example 12.
  • Examples 1 to 13 have less luminance unevenness. That is, luminance unevenness is reduced by providing the auxiliary electrode layer 13. Further, when Examples 2a to 2d are respectively compared, it can be seen that the luminance unevenness is smaller when the silver layer as the auxiliary electrode layer 13 is thicker. The luminance unevenness can be suppressed by using a chrome layer in addition to the silver layer as the auxiliary electrode layer 13. When Examples 5 and 6 are compared with Examples 3 and 4, in Examples 5 and 6, the auxiliary electrode layer 13 and the light emitting layer 17 are isolated, thereby suppressing the current consumed unnecessarily without contributing to light emission.
  • the auxiliary electrode layer 13 is partially provided as in Example 13, it can be seen that there is an effect of reducing luminance unevenness.
  • ITO which is a transparent electrode
  • aluminum is used as the cathode layer 15
  • the former has a high surface resistance of 20 ohms. Therefore, in the organic light-emitting element in which the auxiliary electrode layer 13 is not provided, luminance unevenness is caused.
  • the aluminum of the cathode layer 15 has a lower surface resistance than the ITO of the anode layer 12 and thus is less than the anode layer 12, but causes luminance unevenness.
  • a silver layer or the like as the auxiliary electrode layer 13 in the structure of the organic electroluminescent element, it is considered that the surface resistance of the anode layer 12 and the cathode layer 15 is reduced and the luminance unevenness is reduced.
  • (A)-(d) is a figure explaining the other form of the shape of the light emission part. It is the fragmentary sectional view explaining the 2nd example of the organic electroluminescent element to which this Embodiment is applied, and is the figure explaining the case where it penetrates further through the anode layer which is a 1st electrode layer. It is the fragmentary sectional view explaining the 3rd example of the organic electroluminescent element to which this Embodiment is applied, and is the figure explaining the case where an auxiliary electrode layer is formed in electrical contact with a cathode layer.
  • (A)-(f) 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 fragmentary sectional view explaining the 9th example of the organic electroluminescent element to which this Embodiment is applied. It is a fragmentary sectional view explaining the 10th example of the organic electroluminescent element to which this Embodiment is applied.

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  • Electroluminescent Light Sources (AREA)

Abstract

L’invention concerne un élément électroluminescent organique avec une faible variation de luminance et un fort rendement d’émission de lumière, même avec une émission de lumière de surface utilisant une aire importante. L’élément électroluminescent organique (10) est équipé d’une couche d’anode (12), d’une couche de cathode (15), d’une couche d’électrode auxiliaire (13) qui est formée en contact électrique avec la couche d’anode (12) et dont la conductivité électrique est supérieure à celle de la couche d’anode (12), une couche diélectrique (14) qui est formée entre la couche d’anode (12) et la couche de cathode (15), une partie concave (16) dont la largeur est inférieure ou égale à 10 µm et formée pour traverser au moins la couche diélectrique (14), et une partie émettrice de lumière (17) qui est formée en contact avec la surface intérieure de la partie concave (16) et émet de la lumière lorsqu’elle est alimentée en courant. La couche d’anode (12) transmet la lumière émise par la partie émettrice de lumière (17).
PCT/JP2009/070751 2008-12-12 2009-12-11 Élément électroluminescent organique, dispositif d’affichage et dispositif d’éclairage WO2010067861A1 (fr)

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WO2014077627A1 (fr) 2012-11-16 2014-05-22 주식회사 엘지화학 Élément électroluminescent organique et procédé permettant de fabriquer ce dernier
US9831298B2 (en) 2014-03-14 2017-11-28 Lg Display Co., Ltd. Organic light-emitting device

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