WO2014065215A1 - Électrode transparente, dispositif électronique, et élément électroluminescent organique - Google Patents

Électrode transparente, dispositif électronique, et élément électroluminescent organique Download PDF

Info

Publication number
WO2014065215A1
WO2014065215A1 PCT/JP2013/078343 JP2013078343W WO2014065215A1 WO 2014065215 A1 WO2014065215 A1 WO 2014065215A1 JP 2013078343 W JP2013078343 W JP 2013078343W WO 2014065215 A1 WO2014065215 A1 WO 2014065215A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
ring
transparent electrode
compound
organic
Prior art date
Application number
PCT/JP2013/078343
Other languages
English (en)
Japanese (ja)
Inventor
秀謙 尾関
貴之 飯島
和央 吉田
健 波木井
Original Assignee
コニカミノルタ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタ株式会社 filed Critical コニカミノルタ株式会社
Priority to JP2014543271A priority Critical patent/JP6187471B2/ja
Publication of WO2014065215A1 publication Critical patent/WO2014065215A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/56—One oxygen atom and one sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/36—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/76—Sulfur atoms attached to a second hetero atom
    • C07D277/78—Sulfur atoms attached to a second hetero atom to a second sulphur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • H10K59/80517—Multilayers, e.g. transparent multilayers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures
    • H10K2102/3023—Direction of light emission
    • H10K2102/3031—Two-side emission, e.g. transparent OLEDs [TOLED]

Definitions

  • the present invention relates to a transparent electrode, an electronic device, and an organic electroluminescence element, and more particularly, to a transparent electrode having both conductivity and light transmittance, and an electronic device and an organic electroluminescence element including the transparent electrode.
  • organic electroluminescence element (hereinafter also referred to as “organic EL element” or “organic electroluminescence element”) using an organic material electroluminescence (hereinafter abbreviated as “EL”) is several V to several It is a thin-film type completely solid element that can emit light at a low voltage of about 10 V, and has many excellent features such as high brightness, high luminous efficiency, thinness, and light weight. For this reason, it has been attracting attention in recent years as surface light emitters such as backlights for various displays, display boards such as signboards and emergency lights, and illumination light sources.
  • Such an organic EL element has a structure in which a light emitting layer made of an organic material is sandwiched between two electrodes, and emitted light generated in the light emitting layer is transmitted through the electrode and taken out to the outside. For this reason, at least one of the two electrodes is configured as a transparent electrode.
  • an oxide semiconductor material such as indium tin oxide (SnO 2 —In 2 O 3 : Indium Tin Oxide, hereinafter abbreviated as ITO) is generally used.
  • ITO indium tin oxide
  • Japanese Patent Laid-Open No. 2002-15623 and Japanese Patent Laid-Open No. 2006-16961 have examined materials aiming at low resistance by laminating silver.
  • ITO uses an indium element which is a rare metal, the material cost is high, and it is necessary to anneal at about 300 ° C. after film formation in order to reduce resistance.
  • Patent Document 1 there is a technique for forming a thin film using an alloy of silver (Ag) and magnesium (Mg) having high electrical conductivity, and a technique for forming a thin film using a cheap and easily available metal material instead of indium. It has been proposed (see, for example, Patent Document 1 and Patent Document 2).
  • Patent Document 1 by using an alloy of silver and magnesium as an electrode material, it is possible to obtain desired conductivity under thin film conditions as compared with an electrode formed by silver alone. It is said that both can be achieved.
  • the resistance value of the electrode obtained by the method described in Patent Document 1 is at most about 100 ⁇ / ⁇ , which is insufficient as the conductivity of the transparent electrode.
  • magnesium has a characteristic that it is easily oxidized. For this reason, there is a problem that the performance deteriorates when stored for a long period of time in a high temperature and high humidity environment, and specifically, the variation width of the resistance value of the transparent electrode is likely to increase.
  • a transparent conductive film using a metal material such as zinc (Zn) or tin (Sn) that is inexpensive and easily available as a raw material instead of indium (In) Is disclosed.
  • the resistance value does not sufficiently decrease with these alternative metals, and in addition, the ZnO-based transparent conductive film containing zinc has a characteristic that its performance tends to fluctuate by reacting with water. Further, it has been found that the SnO 2 -based transparent conductive film containing tin has a problem that it is difficult to process by etching.
  • an organic electroluminescence element using a thin film having a layer thickness of about 15 nm and a highly transmissive silver film as a cathode is disclosed (for example, see Patent Document 3).
  • Patent Document 3 since the formed silver film is still a thick film as an electrode, the light transmittance (transparency) as a transparent electrode is not sufficient, and migration (atomic It is easy to cause movement.
  • the present invention has been made in view of the above problems, and a solution to the problem is that it has sufficient conductivity and light transmittance, has a low sheet resistance value, and is durable (sheet resistance stability).
  • a solution to the problem is that it has sufficient conductivity and light transmittance, has a low sheet resistance value, and is durable (sheet resistance stability).
  • an excellent transparent electrode and an electronic device and an organic electroluminescent element that have the transparent electrode, have sufficient conductivity and light transmittance, have low driving voltage, and have excellent durability (dark spot resistance). That is.
  • the present inventor has a configuration having a conductive layer and an intermediate layer provided adjacent to the conductive layer, and as a transparent electrode, the light transmittance at a wavelength of 550 nm and A sheet resistance value is within a specific range, the intermediate layer contains two or more organic compounds, and a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity as the first organic compound, A transparent material comprising 50% by mass or more and less than 99.5% by mass of the total mass of the two or more organic compounds, and the conductive layer is composed mainly of silver.
  • the electrode has sufficient conductivity and light transmittance, has a low sheet resistance value, has excellent durability (sheet resistance stability), and has the transparent electrode, sufficient conductivity And light transmission, with low driving voltage, Found that it is possible to realize an electronic device and an organic electroluminescence device excellent in durability (dark spot resistance), a completed the invention.
  • a transparent electrode having a conductive layer and an intermediate layer provided adjacent to the conductive layer,
  • the transparent electrode has a light transmittance of 50% or more at a wavelength of 550 nm and a sheet resistance value of 20 ⁇ / ⁇ or less
  • the intermediate layer contains two or more organic compounds, and a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity as the first organic compound is a total mass of the two or more organic compounds.
  • a transparent electrode, wherein the conductive layer is composed mainly of silver.
  • the total content of the first organic compound and the second highest organic compound is 99.5% by mass or more, and the first organic compound
  • the transparent electrode according to item 2, wherein the content of is in the range of 50 to 90% by mass.
  • the total content of the first organic compound, the second highest organic compound, and the third highest organic compound is 99.5% by mass or more. And the total content of the organic compound having the second highest content and the organic compound having the third highest content is 10% by mass or more and less than 49.5% by mass.
  • the organic compound other than the first organic compound among the two or more organic compounds is an organic compound having a halogen atom, wherein the organic compound has a halogen atom.
  • Transparent electrode is an organic compound having a halogen atom, wherein the organic compound has a halogen atom.
  • the organic compound containing a sulfur atom having an unshared electron pair is at least one selected from compounds having structures represented by the following general formulas (S1) to (S4).
  • Formula (S1): R 1 —SR 2 Formula (S2): R 3 -SSR 4 Formula (S3): R 5 -SH Formula (S4): S C (R 6 ) -SH [Wherein R 1 to R 6 each represents a substituent. ] 13.
  • the organic compound other than the first organic compound is an asymmetric compound having a nitrogen atom having an unshared electron pair not involved in aromaticity.
  • the transparent electrode according to any one of Items 12 to 12.
  • An electronic device comprising the transparent electrode according to any one of items 1 to 13.
  • An organic electroluminescence device comprising the transparent electrode according to any one of items 1 to 13.
  • a transparent electrode having sufficient conductivity and light transmittance, having a low sheet resistance value and excellent in durability (sheet resistance stability), the transparent electrode, and sufficient It is possible to provide an electronic device and an organic electroluminescent element that have conductivity and light transmittance, are low in driving voltage, and are excellent in durability (dark spot resistance).
  • the transparent electrode of the present invention has a conductive layer containing silver as a main component above the intermediate layer, and the intermediate layer has an aromatic property as the first organic compound.
  • the second organic compound has a compound having a nitrogen atom having an unshared electron pair that does not participate in the compound (hereinafter also referred to as a silver affinity compound), and the second organic compound has a small content with respect to the first organic compound.
  • the third organic compound is allowed to coexist.
  • the silver atoms constituting the conductive layer are aromatic, which is the first organic compound contained in the intermediate layer.
  • the diffusion distance of silver atoms on the surface of the intermediate layer is reduced, and aggregation of silver atoms at specific locations can be suppressed. it can.
  • the silver affinity compound is a compound having a nitrogen atom having an unshared electron pair that does not participate in aromaticity
  • the nitrogen atom having an unshared electron pair is an atom having an affinity for a silver atom.
  • the second organic compound and further the third organic compound are allowed to coexist in a smaller content than the first organic compound together with the compound having a nitrogen atom having an unshared electron pair not involved in aromaticity.
  • a synergy effect is exhibited and the amorphous property of the intermediate layer containing a compound having a nitrogen atom having an unshared electron pair is increased, so that the film density, uniformity and durability of the intermediate layer are further improved, and the upper layer is improved.
  • the conductive layer composed mainly of silver is thin, uniform, and effectively suppresses variations in sheet resistance as a transparent electrode when stored in a high-temperature, high-humidity environment. Was able to.
  • the difference in glass transition point (Tg) between the first organic compound and the second organic compound is preferably within 30 ° C.
  • An intermediate layer formed by mixing compounds having a Tg difference of 30 ° C. or less has a small fluctuation with respect to the external temperature, and can be a transparent electrode excellent in durability (sheet resistance stability).
  • the silver atom has 2 on the surface of the intermediate layer containing a compound having a nitrogen atom having an unshared electron pair that does not participate in aromaticity having an affinity for the silver atom and the second or third organic compound.
  • the film is formed by single-layer growth type (Frank-van der Merwe: FM type) film formation in which a two-dimensional single crystal layer is formed around a dimensional nucleus.
  • the silver atoms attached on the surface of the intermediate layer are bonded while diffusing on the surface to form three-dimensional nuclei and grow into three-dimensional islands (Volume- In the present invention, a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity, which is considered to be easily formed into an island shape by film growth with (Weber: VW type). Thus, it is assumed that island-like growth in this manner is prevented and single layer growth is promoted.
  • Schematic sectional view showing an example of the configuration of the transparent electrode of the present invention Schematic sectional view showing an example of another configuration of the transparent electrode of the present invention
  • Schematic sectional view showing a third example of an organic EL device comprising the transparent electrode of the present invention The schematic sectional drawing which shows an example of the illuminating device which enlarged the light emission surface using the organic EL element which comprised the transparent electrode of this invention.
  • the transparent electrode of the present invention is a transparent electrode having a conductive layer and an intermediate layer provided adjacent to the conductive layer, and the transparent electrode has a light transmittance of 50% or more at a wavelength of 550 nm,
  • the sheet resistance value is 20 ⁇ / ⁇ or less
  • the intermediate layer contains two or more organic compounds
  • the first organic compound has a nitrogen atom having an unshared electron pair not involved in aromaticity.
  • the conductive layer is composed mainly of silver.
  • the content of the organic compound having the second highest content of two or more organic compounds is set to 0. 2)
  • the total content of the first organic compound and the second highest organic compound among the two or more organic compounds is 99.% by mass or more and less than 50% by mass. 5% by mass or more, and the content of the first organic compound is in the range of 50 to 90% by mass, or 3) of the two or more organic compounds, the first organic compound,
  • the total content of the organic compound having the second highest content and the organic compound having the third highest content is 99.5% by mass or more, and the organic compound having the second highest content and the third.
  • the total content of organic compounds with a high content is 10% by mass
  • the amorphous property of the intermediate layer is further improved, and further excellent suppression of the fluctuation range of the sheet resistance value and suppression of variation of the sheet resistance value can be obtained. It is preferable from the viewpoint.
  • the compound having a nitrogen atom having an unshared electron pair not involved in aromaticity has an azacarbazole ring, a pyridine ring, or a ⁇ , ⁇ '-diazacarbazole ring or ⁇ - It is preferable to have a carboline ring from the viewpoint of obtaining further excellent conductivity, light transmittance, and durability.
  • the other organic compound used in combination with the first organic compound is preferably an organic compound having a halogen atom, and further, the halogen atom contained in the organic compound having a halogen atom is bromine. Further excellent conductivity, light transmittance and durability can be obtained when the compound is an atom or iodine atom, or the organic compound having a halogen atom is a compound having a structure represented by the general formula (1). It is preferable from the viewpoint that
  • the other organic compound used in combination with the first organic compound is preferably an organic compound containing a sulfur atom having an unshared electron pair, and further, a sulfur atom having an unshared electron pair.
  • the organic compound containing is at least one selected from compounds having a structure represented by the general formulas (S1) to (S4), so that further excellent conductivity, light transmittance and durability can be obtained. It is preferable from a viewpoint which can be obtained.
  • the other organic compound used in combination with the first organic compound is an asymmetric compound having a nitrogen atom having an unshared electron pair not involved in aromaticity, and further excellent conductivity. From the viewpoint of obtaining light transmittance and durability.
  • the electronic device of the present invention is characterized by including the transparent electrode of the present invention.
  • the organic electroluminescent element of this invention has comprised the transparent electrode of this invention, It is characterized by the above-mentioned.
  • ⁇ is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
  • Transparent electrode >> 1A and 1B are schematic cross-sectional views each showing an example of the configuration of the transparent electrode of the present invention.
  • the transparent electrode 1 of the present invention shown in FIG. 1A is characterized in that the light transmittance at a wavelength of 550 nm is 50% or more and the sheet resistance value is 20 ⁇ / ⁇ or less, and the structure is intermediate.
  • the layer 1a has a two-layer structure in which a conductive layer 1b is stacked on the intermediate layer 1a.
  • the intermediate layer 1 a and the conductive layer 1 b are provided in this order on the base 11.
  • the intermediate layer 1a according to the present invention contains two or more kinds of organic compounds, and the first organic compound contains a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity as the two or more kinds.
  • the conductive layer 1b according to the present invention which is a layer containing 50% by mass or more and less than 99.5% by mass of the total mass of the organic compound, is composed mainly of silver. It is the layer currently made.
  • the main component of the conductive layer 1b means that the silver content in the conductive layer 1b is 60% by mass or more, and preferably the silver content is 80% by mass or more. More preferably, the silver content is 90% by mass or more, and particularly preferably the silver content is 98% by mass or more.
  • transparent as used in the transparent electrode 1 of the present invention means that the light transmittance measured at a wavelength of 550 nm is 50% or more, preferably 70% or more, and more preferably 80% or more.
  • the transparent electrode 1 of the present invention has an intermediate layer 1a and a conductive layer 1b on a substrate 11, and a second layer on the conductive layer 1b. It is also a preferred embodiment that the intermediate layer 1c is laminated and the conductive layer 1b is sandwiched between the intermediate layer 1a and the intermediate layer 1c.
  • the upper portion of the conductive layer 1b is further covered with a protective layer.
  • a protective layer It may be a configuration, or a configuration in which the second conductive layer is laminated.
  • both the protective layer and the second conductive layer have high light transmittance so as not to impair the light transmittance of the transparent electrode 1.
  • Examples of the base material 11 used to hold the transparent electrode 1 of the present invention include, but are not limited to, glass and plastic. Moreover, although the base material 11 may be transparent or opaque, when the transparent electrode 1 of this invention is used for the electronic device which takes out light from the base material 11 side, the base material 11 is transparent. It is preferable that Examples of the transparent substrate 11 that is preferably used include glass, quartz, and a resin film.
  • the glass examples include silica glass, soda lime silica glass, lead glass, borosilicate glass, and alkali-free glass. From the viewpoints of adhesion to the intermediate layer 1a, durability, and smoothness, the surface of these glass materials may be subjected to physical treatment such as polishing, if necessary, and from inorganic or organic substances. Or a hybrid film formed by combining these films may be used.
  • polyesters such as polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (abbreviation: TAC), cellulose acetate butyrate, Cellulose acetates such as cellulose acetate propionate (abbreviation: CAP), cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, poly Methylpentene, polyetherketone, polyimide, polyethersulfone (abbreviation: PES), polypheny Sulfide, polysulfones, polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyary
  • a coating made of an inorganic material or an organic material (hereinafter also referred to as “barrier film”) or a hybrid coating combining these coatings may be formed.
  • Such coatings and hybrid coatings have a water vapor permeability (25 ⁇ 0.5 ° C., relative humidity 90 ⁇ 2% RH) measured by a method according to JIS-K-7129-1992 of 0.01 g / (m (2 ⁇ 24 hours) or less is preferable.
  • the oxygen permeability measured by a method according to JIS-K-7126-1987 is 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 hours ⁇ atm) or less
  • the water vapor permeability is 1 ⁇ 10 ⁇ 5 g. / (M 2 ⁇ 24 hours) or less is preferable.
  • the material for forming the barrier film as described above may be any material having a function of suppressing the intrusion of factors that cause deterioration of electronic devices such as moisture and oxygen and organic EL elements, such as silicon dioxide, Silicon nitride or the like can be used. Furthermore, in order to improve the brittleness of the barrier film, it is more preferable to have a laminated structure of these inorganic layers and layers (organic layers) made of an organic material. Although there is no restriction
  • the method for producing the barrier film is not particularly limited.
  • vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A polymerization method, a plasma CVD method (CVD: Chemical Vapor Deposition), a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but the atmospheric pressure plasma weight described in JP-A-2004-68143 can be used. A legal method is particularly preferred.
  • the base 11 is made of an opaque material, for example, a metal substrate such as aluminum or stainless steel, a film or an opaque resin substrate, a ceramic substrate, or the like can be used.
  • the intermediate layer 1a according to the present invention contains two or more kinds of organic compounds, and the first organic compound contains a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity as the two or more kinds. It is a layer comprised by containing in the range of 50 mass% or more and less than 99.5 mass% of the total mass of an organic compound.
  • the content of the organic compound having the second highest content is 2% by mass or more and less than 50% by mass among the two or more organic compounds contained in the intermediate layer. Is a preferable configuration.
  • the first organic compound is a compound having a nitrogen atom having an unshared electron pair that does not participate in aromaticity.
  • the total content of the organic compound having the second highest content is 99.5% by mass or more, and the first organic compound has a nitrogen atom having an unshared electron pair not involved in aromaticity. It is preferable that the content of the compound is in the range of 50 to 90% by mass.
  • the first organic compound, the second highest organic compound, and the third highest organic compound among the two or more organic compounds contained in the intermediate layer The total content of the organic compound having the second highest content and the third highest organic compound is 10% by mass or more and 49.5% by mass. It is a preferable structure that it is less than%.
  • the first organic compound has a nitrogen atom having a non-shared electron pair that does not participate in aromaticity, and the first organic compound has a structure different from that of the first organic compound and does not participate in other aromaticity.
  • a compound having a nitrogen atom having an electron pair can also be used as the second organic compound or the third organic compound.
  • the compound having a nitrogen atom having an unshared electron pair that is not involved in aromaticity with the highest content is the first organic compound, and the second organic compound, 3 in order of the higher content. It is defined as the second organic compound.
  • the organic compound other than the first organic compound contained in the intermediate layer is an organic compound having a halogen atom, a sulfur atom having an unshared electron pair, or unshared not involving aromaticity.
  • An asymmetric compound having a nitrogen atom having an electron pair is preferred.
  • the method for forming the film includes a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, or a vapor deposition method.
  • a method using a dry process such as resistance heating, EB method (electron beam method), sputtering method, CVD method, or the like.
  • the vapor deposition method is preferably applied.
  • the intermediate layer 1a includes, as the first organic compound, a compound having a nitrogen atom having an unshared electron pair that does not participate in aromaticity, and an all organic material constituting the intermediate layer. It is contained within the range of 50% by mass or more and less than 99.5% by mass of the compound.
  • the “nitrogen atom having an unshared electron pair not involved in aromaticity” is a nitrogen atom having an unshared electron pair, and the unshared electron pair becomes an aromatic property of the unsaturated cyclic compound.
  • a nitrogen atom that is not directly involved as an essential element That is, a non-localized ⁇ electron system on a conjugated unsaturated ring structure (aromatic ring) has a nitrogen atom in which a lone pair is not involved as an essential element for aromatic expression in the chemical structural formula Say.
  • Nitrogen atom is a Group 15 element and has 5 electrons in the outermost shell. Of these, three unpaired electrons are used for covalent bonds with other atoms, and the remaining two become a pair of unshared electron pairs, so that the number of bonds of nitrogen atoms is usually three.
  • an amino group (—NR 1 R 2 ), an amide group (—C ( ⁇ O) NR 1 R 2 ), a nitro group (—NO 2 ), a cyano group (—CN), a diazo group (—N 2 ), An azide group (—N 3 ), a urea bond (—NR 1 C ⁇ ONR 2 —), an isothiocyanate group (—N ⁇ C ⁇ S), a thioamide group (—C ( ⁇ S) NR 1 R 2 ) and the like.
  • R 1 and R 2 each represent a substituent.
  • the resonance formula of a nitro group (—NO 2 ) can be expressed as follows. Strictly speaking, the unshared electron pair of the nitrogen atom in the nitro group is used for the resonance structure with the oxygen atom, but in the present invention, it is defined that the nitrogen atom of the nitro group also has an unshared electron pair.
  • a nitrogen atom can also create a fourth bond by utilizing an unshared electron pair.
  • TBAC tetrabutylammonium chloride
  • Tris (2-phenylpyridine) iridium (III) (abbreviation: Ir (ppy) 3 ) is a neutral metal complex in which an iridium atom and a nitrogen atom are coordinated. Although these compounds have a nitrogen atom, the lone pair of electrons is used for ionic bond and coordinate bond, respectively. Is not applicable.
  • the present invention is to effectively utilize unshared electron pairs of nitrogen atoms that are not used for bonding.
  • the left side shows the structure of tetrabutylammonium chloride (abbreviation: TBAC), and the right side shows the structure of tris (2-phenylpyridine) iridium (III) (abbreviation: Ir (ppy) 3 ).
  • nitrogen atoms are common as heteroatoms that can constitute an aromatic ring, and can contribute to the expression of aromaticity.
  • nitrogen-containing aromatic ring examples include a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, and a tetrazole ring.
  • the nitrogen atom of the pyridine ring corresponds to the “nitrogen atom having an unshared electron pair not involved in aromaticity” according to the present invention.
  • the molecular orbital of the pyridine ring is shown below.
  • a pyrrole ring As shown below, one of the carbon atoms constituting the five-membered ring is substituted with a nitrogen atom, but the number of ⁇ electrons is six and satisfies the Hückel rule.
  • a nitrogen-containing aromatic ring Since the nitrogen atom of the pyrrole ring is also bonded to a hydrogen atom, an unshared electron pair is mobilized to the 6 ⁇ electron system.
  • the nitrogen atom of the pyrrole ring has an unshared electron pair, it has been utilized as an essential element for the expression of aromaticity, and therefore the “unshared electron pair not involved in aromaticity” of the present invention. Does not correspond to "nitrogen atom having".
  • the molecular orbital of the pyrrole ring is shown below.
  • the imidazole ring is a nitrogen-containing aromatic ring having a structure in which two nitrogen atoms are substituted at the 1- and 3-positions in a 5-membered ring, and also has 6 ⁇ electrons.
  • the nitrogen atom N 1 is a pyridine ring-type nitrogen atom in which only one unpaired electron is mobilized to the 6 ⁇ -electron system, and the unshared electron pair is not used for aromaticity expression.
  • the nitrogen atom N 2 is a pyrrole-ring nitrogen atom that mobilizes an unshared electron pair to the 6 ⁇ electron system.
  • the nitrogen atom N 1 of the imidazole ring corresponds to the “nitrogen atom having an unshared electron pair not involved in aromaticity” in the present invention.
  • the molecular orbital of the imidazole ring is shown below.
  • ⁇ -carboline is an azacarbazole compound in which a benzene ring skeleton, a pyrrole ring skeleton, and a pyridine ring skeleton are condensed in this order.
  • the nitrogen atom N 3 of the pyridine ring mobilizes only one unpaired electron
  • the nitrogen atom N 4 of the pyrrole ring mobilizes an unshared electron pair to the ⁇ -electron system, respectively, to form a ring.
  • the total number of ⁇ electrons is 14 aromatic rings.
  • the nitrogen atom N 3 of the pyridine ring corresponds to the “nitrogen atom having an unshared electron pair not involved in aromaticity” according to the present invention, but the nitrogen of the pyrrole ring The atom N 4 does not fall under this.
  • the “nitrogen atom having an unshared electron pair not involved in aromaticity” defined in the present invention expresses a strong interaction between the unshared electron pair and silver which is the main component of the conductive layer. Is important for.
  • a nitrogen atom is preferably a nitrogen atom in the nitrogen-containing aromatic ring from the viewpoint of stability and durability.
  • the compound having a nitrogen atom having an unshared electron pair not involved in aromaticity as long as it has a structure having a nitrogen atom having an unshared electron pair not involved in aromaticity in the molecule, although it is not limited, it is preferably a compound having an aromatic heterocycle in the molecule, a compound having an azacarbazole ring in the molecule, or ⁇ , ⁇ '-diazacarbazole ring or ⁇ -A compound having a carboline ring is preferred.
  • Specific examples of the compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention include an aromatic heterocyclic compound represented by the following general formula (1A).
  • the aromatic heterocyclic compound represented by the general formula (1A) is an aromatic heterocyclic compound represented by any of the following general formula (1B), general formula (1C), or general formula (1D). It is preferable. Further, an aromatic heterocyclic compound represented by the following general formula (1E) or general formula (1F) is also preferable as a nitrogen atom-containing compound having an unshared electron pair not involved in the aromaticity contained in the intermediate layer. Can be used.
  • E 101 to E 108 each represent C (R 12 ) or a nitrogen atom, and at least one of E 101 to E 108 is a nitrogen atom.
  • R ⁇ 11 > in General formula (1A) and said R ⁇ 12 > respectively represent a hydrogen atom or a substituent.
  • substituents examples include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group).
  • alkyl group for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group.
  • a cycloalkyl group for example, cyclopentyl group, cyclohexyl group, etc.
  • an alkenyl group for example, vinyl group, allyl group, etc.
  • an alkynyl group for example, ethynyl group, propargyl group, etc.
  • an aromatic hydrocarbon ring group also called aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl Group, pyrenyl group, biphenylyl group), aromatic heterocyclic group (eg For example, furyl, thienyl, pyridyl, pyridazinyl, pyr
  • substituents may be further substituted with the above substituents.
  • a plurality of these substituents may be bonded to each other to form a ring.
  • the general formula (1B) is also a form of the general formula (1A).
  • Y 21 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof.
  • E 201 to E 216 and E 221 to E 238 each represent C (R 21 ) or a nitrogen atom, and R 21 represents a hydrogen atom or a substituent.
  • R 21 represents a hydrogen atom or a substituent.
  • at least one of E 221 to E 229 and at least one of E 230 to E 238 represent a nitrogen atom.
  • k21 and k22 each represents an integer of 0 to 4, and k21 + k22 is an integer of 2 or more.
  • examples of the arylene group represented by Y 21 include o-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group, and biphenyl.
  • Diyl groups eg, [1,1′-biphenyl] -4,4′-diyl group, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.
  • terphenyldiyl group eg, [1,1′-biphenyl] -4,4′-diyl group, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.
  • terphenyldiyl group eg, [1,1′-biphenyl] -4,4′-diyl group, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.
  • terphenyldiyl group eg, [1,1′-biphenyl] -4,4′-diyl group, 3,3′-biphenyldiyl
  • examples of the heteroarylene group represented by Y 21 include a carbazole ring, a carboline ring, a diazacarbazole ring (also referred to as a monoazacarboline ring, one of carbon atoms constituting the carboline ring). From the group consisting of a triazole ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a quinoxaline ring, a thiophene ring, an oxadiazole ring, a dibenzofuran ring, a dibenzothiophene ring, and an indole ring. Examples are derived divalent groups and the like.
  • the divalent linking group comprising an arylene group, a heteroarylene group or a combination thereof represented by Y 21 , a condensed aromatic heterocyclic ring formed by condensing three or more rings among heteroarylene groups
  • the group derived from a condensed aromatic heterocycle formed by condensation of three or more rings is preferably a group derived from a dibenzofuran ring or a dibenzothiophene ring. Preferred are the groups
  • E 201 to E 208 and 6 or more of E 209 to E 216 are each represented by C (R 21 ).
  • At least one of E 225 to E 229 and at least one of E 234 to E 238 are nitrogen atoms.
  • any one of E 225 to E 229 and any one of E 234 to E 238 are preferably nitrogen atoms.
  • E 221 to E 224 and E 230 to E 233 are each represented by C (R 21 ).
  • E 203 is represented by C (R 21 ) and R 21 represents a linking site
  • E 211 is also represented by C (R 21 ).
  • R 21 preferably represents a linking moiety.
  • E 225 and E 234 are preferably nitrogen atoms, and E 221 to E 224 and E 230 to E 233 are each preferably represented by C (R 21 ).
  • the general formula (1C) is also a form of the general formula (1A).
  • E 301 to E 312 each represent C (R 31 ), and R 31 represents a hydrogen atom or a substituent.
  • Y 31 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof.
  • the general formula (1D) is also a form of the general formula (1A).
  • E 401 to E 414 each represent C (R 41 ), and R 41 represents a hydrogen atom or a substituent.
  • Ar 41 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring.
  • k41 represents an integer of 3 or more.
  • Ar 41 represents an aromatic hydrocarbon ring
  • examples of the aromatic hydrocarbon ring include a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, and pyrene.
  • These rings may further have the substituents exemplified as R 11 and R 12 in the general formula (1A).
  • Ar 41 represents an aromatic heterocyclic ring
  • examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, Pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring Carbazole ring, azacarbazole ring and the like.
  • the azacarbazole ring refers to one in which at least one carbon atom of the benzene ring constituting the carbazole ring is replaced with a nitrogen atom. These rings may further have the substituents exemplified as R 11 and R 12 in the general formula (1A).
  • At least one of E 501 and E 502 is a nitrogen atom
  • at least one of E 511 to E 515 is a nitrogen atom
  • one of E 521 to E 525 At least one is a nitrogen atom.
  • R 51 represents a substituent.
  • R 51 represents a substituent
  • examples of the substituent include the substituents exemplified as R 11 and R 12 in the general formula (1A).
  • E 601 to E 612 each represent C (R 61 ) or a nitrogen atom, and R 61 represents a hydrogen atom or a substituent.
  • Ar 61 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring.
  • R 61 of C (R 61) represented by each of E 601 ⁇ E 612 is a substituent
  • examples of the substituent, R 11 in the general formula (1A) The substituents exemplified as R 12 apply in the same manner.
  • the substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring represented by Ar 61 may be the same as Ar 41 in the general formula (1D).
  • No. 1-No. 37 is a specific example of a compound having a structure represented by general formula (1A) to general formula (1F).
  • the compound having a nitrogen atom having an unshared electron pair not involved in the aromaticity according to the present invention which is contained in the intermediate layer 1a according to the present invention, is represented by the general formulas (1A) to (1F) below. Specific examples other than the compound having a structure are shown below, but are not limited thereto.
  • x and y represent the ratio of a random copolymer, respectively.
  • the compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention can be easily synthesized according to a conventionally known synthesis method.
  • the organic compound other than the first organic compound is preferably an organic compound having a halogen atom.
  • the organic compound having a halogen atom according to the present invention is a compound containing at least a halogen atom and a carbon atom, and the structure thereof is not particularly limited, but the halogenated aryl compound represented by the following general formula (1) Is preferred.
  • Ar represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • X represents a halogen atom, and m is an integer of 1 to 5.
  • L represents a direct bond or a divalent linking group, and n represents 0 or 1.
  • R represents a hydrogen atom or a substituted ring group.
  • k represents an integer of 1 to 5.
  • examples of the aromatic hydrocarbon ring group represented by Ar include a phenyl group, a p-chlorophenyl group, a mesityl group, and tolyl.
  • Examples of the aromatic heterocyclic group represented by Ar include a pyridyl group, a pyrimidinyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a benzimidazolyl group, a pyrazolyl group, a pyrazinyl group, and a triazolyl group (for example, 1,2, Examples include 4-triazol-1-yl group and 1,2,3-triazol-1-yl group.
  • Ar is preferably an aromatic hydrocarbon ring group, more preferably a phenyl group.
  • halogen atom represented by X examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • a chlorine atom, a bromine atom or an iodine atom is preferable, and a more preferable example is , Bromine atom or iodine atom.
  • M represents an integer of 1 to 5, preferably 1 or 2.
  • L represents a direct bond or a divalent linking group.
  • the divalent linking group include an alkylene group (eg, methylene group, ethylene group, trimethylene group, propylene group), a cycloalkylene group (eg, 1,2-cyclobutanediyl group, 1,2-cyclopentanediyl group, 1,3-cyclopentanediyl group, 1,2-cyclohexanediyl group, 1,3-cyclohexanediyl group, 1,4-cyclohexanediyl group, 1,2-cycloheptanediyl group, 1,3-cycloheptanediyl group 1,4-cycloheptanediyl group, etc.), arylene groups (for example, o-phenylene group, m-phenylene group, p-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 1,3 -Nap
  • the divalent linking group represented by L is preferably an alkylene group, and more preferably a methylene group.
  • N represents 0 or 1, but is preferably 0.
  • R represents a hydrogen atom or a substituent.
  • substituents include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group).
  • cycloalkyl group eg, cyclopentyl group, cyclohexyl group, etc.
  • alkenyl group eg, vinyl group, allyl group, etc.
  • alkynyl group eg, ethynyl group, propargyl group, etc.
  • aromatic hydrocarbon ring group Also referred to as aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, Indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic complex A group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imi
  • K represents an integer from 1 to 5.
  • the halogenated aryl compound represented by the general formula (1) is a compound further having a structure formed from seven phenyl groups represented by the following general formula (2) as a mother nucleus. Is preferred.
  • X represents a halogen atom
  • m1 to m3 are each an integer of 0 to 5.
  • m1 + m2 + m3 is at least 1 or more.
  • L represents a direct bond or a divalent linking group, and n1 to n3 each represents 0 or 1.
  • halogen atom represented by X examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • a chlorine atom, a bromine atom or an iodine atom is preferable, and a bromine atom is more preferable.
  • it is an iodine atom.
  • L represents a direct bond or a divalent linking group and is synonymous with L in the general formula (1).
  • halogenated aryl compound represented by the general formula (1) according to the present invention are shown below, but the present invention is not limited to these exemplified compounds.
  • the halogenated aryl compound represented by the general formula (1) according to the present invention can be easily synthesized according to a conventionally known synthesis method.
  • the halogen atom ratio defined by the following formula (1) is within the range of 0.30 to 0.65. It is preferable from the viewpoint that the objective effect of the present invention can be expressed more.
  • the organic compound other than the first organic compound is preferably an organic compound containing a sulfur atom having an unshared electron pair.
  • the organic compound containing a sulfur atom having an unshared electron pair according to the present invention is preferably at least one selected from compounds having structures represented by the following general formulas (S1) to (S4).
  • Formula (S1): R 1 —SR 2 Formula (S2): R 3 -SSR 4 Formula (S3): R 5 -SH Formula (S4): S C (R 6 ) -SH
  • R 1 to R 6 each represents a substituent.
  • Examples of the substituent represented by R 1 to R 6 include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, Tridecyl group, tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl group etc.) , Aromatic hydrocarbon groups (also referred to as aromatic carbocyclic groups, aryl groups, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group
  • Oxy group a Alkyloxy group (for example, phenoxy group, naphthyloxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group) Group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group) Group), aryloxycarbonyl group (eg, phenyloxycarbonyl
  • the compound having a structure represented by the general formula (3) includes a compound having a structure in which a hydrogen atom is desorbed and ionized.
  • the following is a compound other than the first organic compound that can be used in combination with a compound having a nitrogen atom having an unshared electron pair that is not involved in aromaticity, which is the first organic compound, in the intermediate layer according to the present invention.
  • a compound having a nitrogen atom having an unshared electron pair that is not involved in aromaticity
  • Specific examples of the organic compound containing a sulfur atom having an unshared electron pair are shown, but the invention is not limited thereto.
  • the organic compound containing a sulfur atom having an unshared electron pair according to the present invention can be easily synthesized according to a conventionally known synthesis method.
  • the first organic compound which has a nitrogen atom having a non-shared electron pair that does not participate in aromaticity, has a similar structure but does not participate in aromaticity. It is preferable to use an asymmetric compound having a nitrogen atom having a pair as an organic compound other than the first organic compound.
  • asymmetric compound means that the chemical structure of the compound does not have a line symmetry axis and a rotation axis. However, rotamers are not distinguished and are regarded as the same compound.
  • the comparative compounds (target compounds) shown below, ET-1 and ET-2 have a line symmetry axis at the center, and the left and right sides of the symmetry axis have mirror symmetry and line symmetry.
  • ET-3 overlaps itself and has three-fold rotational symmetry when rotated 120 degrees around the center of the molecule.
  • the asymmetric compound according to the present invention does not have an axis of line symmetry, and since it cannot overlap with itself even if it rotates about the center of the molecule, it has an axis of rotational symmetry. It is a structural feature that it is not.
  • an intermediate layer It is considered that the uniformity and the film density are improved, and as a result, the conductive layer composed mainly of silver formed in the upper layer is thin and uniform.
  • the content of nitrogen atom not involved in aromaticity defined by the following formula (2) is 0 It is preferably 40% or more.
  • Nitrogen atom content (number of nitrogen atoms having unshared electron pairs not involved in aromaticity / molecular weight of asymmetric compound) ⁇ 100 (%)
  • the nitrogen atom content defined in the present invention is more preferably 0.80% or more, and the upper limit value is preferably 1.50% or less.
  • Examples of the asymmetric compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention include a group of compounds having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the invention exemplified above. Among them, a compound having a nitrogen atom having an unshared electron pair not having aromaticity and having an asymmetric structure corresponding to the above definition can be used.
  • the conductive layer 1b according to the present invention is a layer composed mainly of silver and is formed on the intermediate layer 1a.
  • Examples of the method for forming the conductive layer 1b according to the present invention include a method using a wet process such as a coating method, an inkjet method, a coating method, a dipping method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, and the like. And a method using a dry process such as a CVD method.
  • the vapor deposition method is preferably applied.
  • the conductive layer 1b is formed on the intermediate layer 1a, so that the conductive layer 1b is sufficiently conductive even without a high-temperature annealing process (for example, a heating process at 150 ° C. or higher) after the formation of the conductive layer.
  • a high-temperature annealing process for example, a heating process at 150 ° C. or higher
  • high-temperature annealing may be performed after the film formation.
  • the layer composed mainly of silver in the present invention means that the silver content in the conductive layer 1b is 60% by mass or more, and preferably the silver content is 80%. More preferably, the silver content is 90% by mass or more, and particularly preferably the silver content is 98% by mass or more.
  • the conductive layer 1b may be formed of silver alone or an alloy containing silver (Ag).
  • alloys include silver / magnesium (Ag / Mg), silver / copper (Ag / Cu), silver / palladium (Ag / Pd), silver / palladium / copper (Ag / Pd / Cu), silver -Indium (Ag.In) etc. are mentioned.
  • the conductive layer 1b according to the present invention may have a configuration in which a layer composed mainly of silver is divided into a plurality of layers as necessary.
  • the conductive layer 1b preferably has a layer thickness in the range of 5 to 8 nm.
  • a layer thickness of 8 nm or less is more preferable because the absorption component or reflection component of the layer is reduced and the transmittance of the transparent electrode is improved.
  • a layer thickness of 5 nm or more is preferable because the layer has sufficient conductivity.
  • the transparent electrode 1 of the present invention is composed mainly of silver on the intermediate layer 1a configured to contain a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity.
  • the conductive layer 1b is provided.
  • the nitrogen having the unshared electron pair in which the silver atoms constituting the conductive layer 1b are not involved in the aromaticity constituting the intermediate layer 1a By interacting with atoms, the diffusion distance of silver atoms on the surface of the intermediate layer 1a is reduced, and the formation of silver aggregates can be suppressed.
  • the film grows in an island-like growth type (Volume-Weber: VW type), so that silver particles are isolated in an island shape.
  • VW type island-like growth type
  • the layer thickness needs to be increased to some extent.
  • the layer thickness is increased, the light transmittance is lowered, which is not suitable as a transparent electrode.
  • the transparent electrode 1 having the configuration defined in the present invention, the interaction between the nitrogen atom and silver on the intermediate layer 1a containing the compound having a nitrogen atom having an unshared electron pair not involved in aromaticity. As a result, the aggregation of silver is suppressed, so that in the formation of the conductive layer 1b composed mainly of silver, the film grows in a single-layer growth type (Frank-van der Merwe: FM type). .
  • transparent in the transparent electrode 1 means that the light transmittance at a wavelength of 550 nm is 50% or more.
  • the above-described materials used as the intermediate layer 1a are mainly made of silver. Compared to the conductive layer 1b as a component, it is a good film having sufficient light transmittance.
  • the conductivity of the transparent electrode 1 is ensured mainly by the conductive layer 1b. Therefore, as described above, the conductive layer 1b composed mainly of silver has a thinner layer to ensure conductivity, thereby improving the conductivity and light transmission of the transparent electrode 1. It was possible to achieve a balance with improvement in performance.
  • the transparent electrode 1 of the present invention having the above-described configuration can be used for various electronic devices.
  • Examples of electronic devices include organic EL elements, LEDs (light emitting diodes), liquid crystal elements, solar cells, touch panels, etc.
  • the present invention is used as an electrode member that requires light transmission.
  • the transparent electrode 1 can be used.
  • FIG. 2 is a schematic cross-sectional view showing a first example of an organic EL element including the transparent electrode 1 of the present invention as an example of the electronic device of the present invention.
  • an example of the configuration of the organic EL element will be described with reference to FIG.
  • An organic EL element 100 shown in FIG. 2 is provided on a transparent substrate (base material) 13, and in order from the transparent substrate 13 side, a light emitting functional layer group 3 configured using the transparent electrode 1, an organic material, and the like, The counter electrode 5a is laminated in this order.
  • the transparent electrode 1 of the present invention described above is used as the transparent electrode 1.
  • the organic EL element 100 is configured to extract the emitted light L generated from the emission point h from at least the transparent substrate 13 side.
  • the layer structure of the organic EL element 100 will be described, but the present invention is not limited to these exemplified configuration examples, and a general layer structure may be used.
  • FIG. 2 shows a configuration in which the transparent electrode 1 functions as an anode (that is, an anode) and the counter electrode 5a functions as a cathode (that is, a cathode).
  • the hole injection layer 3a / hole transport layer 3b / light emitting layer 3c / electron transport layer 3d / electron injection are sequentially arranged from the transparent electrode 1 side which is an anode.
  • the layer 3e is stacked.
  • it is an indispensable condition for the organic EL element to provide at least the light emitting layer 3c composed of an organic material.
  • the hole injection layer 3a and the hole transport layer 3b may be provided as a hole transport / injection layer.
  • the electron transport layer 3d and the electron injection layer 3e may be provided as an electron transport / injection layer.
  • the electron injection layer 3e may be made of an inorganic material.
  • the light emitting functional layer group 3 may be laminated at a necessary place as necessary, such as a hole blocking layer and an electron blocking layer, in addition to the constituent layers exemplified above.
  • the light emitting layer 3c may have a structure in which each color light emitting layer that generates emitted light in each wavelength region is laminated, and each of these color light emitting layers is laminated via a non-light emitting auxiliary layer.
  • the auxiliary layer may function as a hole blocking layer or an electron blocking layer.
  • the counter electrode 5a which is a cathode, may have a laminated structure as necessary. In such a configuration, only the portion where the light emitting functional layer group 3 is sandwiched between the transparent electrode 1 and the counter electrode 5 a becomes a light emitting region in the organic EL element 100.
  • the auxiliary electrode 15 as shown in FIG. 2 is provided in contact with the conductive layer 1 b of the transparent electrode 1 for the purpose of reducing the resistance of the transparent electrode 1. May be.
  • the organic EL element 100 having the above-described configuration is formed on the transparent substrate 13 with a sealing material 17 to be described later for the purpose of preventing deterioration of the light emitting functional layer group 3 configured mainly using an organic material or the like.
  • the sealing structure is formed.
  • the sealing material 17 is fixed to the transparent substrate 13 side with an adhesive 19.
  • the terminal portions of the transparent electrode 1 and the counter electrode 5a are provided on the transparent substrate 13 in a state of being exposed from the sealing material 17 while maintaining insulation from each other by the light emitting functional layer group 3.
  • the details of the main layers for constituting the organic EL element 100 shown in FIG. 2 are as follows: the transparent substrate 13, the transparent electrode 1, the counter electrode 5 a, the light emitting layer 3 c of the light emitting functional layer group 3, and the light emitting functional layer group 3.
  • Other functional layers, the auxiliary electrode 15, and the sealing material 17 will be described in this order.
  • the transparent substrate 13 is the base material 11 on which the transparent electrode 1 of the present invention described above is provided, and the transparent base material 11 having light transmittance among the base materials 11 described above is used.
  • the transparent electrode 1 (anode: anode) is the transparent electrode 1 of the present invention already described in detail, and contains, in order from the transparent substrate 13 side, a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity.
  • the intermediate layer 1a and the conductive layer 1b containing silver as a main component are sequentially formed.
  • the transparent electrode 1 functions as an anode (anode), and the conductive layer 1b is a substantial anode.
  • the counter electrode 5a (cathode: cathode) is an electrode film that functions as a cathode (cathode) for supplying electrons to the light emitting functional layer group 3, and is, for example, a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof.
  • Etc. aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TiO 2 , An oxide semiconductor such as SnO 2 can be given.
  • the counter electrode 5a can be produced by forming these conductive materials into a thin film by a method such as vapor deposition or sputtering.
  • the sheet resistance as the counter electrode 5a is preferably several hundred ⁇ / ⁇ or less, and the layer thickness is usually selected in the range of 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the organic EL element 100 In the case where the organic EL element 100 sometimes takes out the emitted light L from the counter electrode 5a side, it can be countered by selecting a conductive material having a good light transmission property from among the conductive materials described above. What is necessary is just to comprise the electrode 5a.
  • the light emitting layer 3c constituting the light emitting functional layer of the organic EL device of the present invention contains a light emitting material. Among them, it is preferable that a phosphorescent light emitting compound is contained as the light emitting material.
  • the light emitting layer 3c is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer 3d and holes injected from the hole transport layer 3b, and the light emitting portion is a light emitting layer. Even in the layer 3c, it may be an interface between the light emitting layer 3c and the adjacent layer.
  • the light emitting layer 3c is not particularly limited in its configuration as long as the light emitting material contained satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting auxiliary layer between the light emitting layers 3c.
  • the total thickness of the light emitting layer 3c is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm from the viewpoint of obtaining a lower driving voltage.
  • the sum total of the layer thickness of the light emitting layer 3c is a layer thickness also including the said auxiliary layer, when a nonluminous auxiliary layer exists between the light emitting layers 3c.
  • the thickness of each light emitting layer is preferably adjusted within the range of 1 to 50 nm, and more preferably adjusted within the range of 1 to 20 nm.
  • the plurality of stacked light emitting layers correspond to blue, green, and red light emission colors, there is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.
  • the light emitting layer 3c configured as described above is formed by forming a light emitting material or a host compound, which will be described later, according to a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, and an ink jet method. Can be formed.
  • a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, and an ink jet method. Can be formed.
  • the light emitting layer 3c may be configured by mixing a plurality of light emitting materials, and a phosphorescent light emitting material and a fluorescent light emitting material (hereinafter also referred to as “fluorescent dopant” or “fluorescent compound”). And may be configured.
  • the structure of the light emitting layer 3c contains a host compound (hereinafter also referred to as “light emitting host”) and a light emitting material (hereinafter also referred to as “light emitting dopant compound”, “light emitting dopant” or “dopant compound”), and emits light. It is preferable to make the material emit light.
  • a host compound hereinafter also referred to as “light emitting host”
  • a light emitting material hereinafter also referred to as “light emitting dopant compound”, “light emitting dopant” or “dopant compound”
  • ⁇ Host compound> As the host compound contained in the light emitting layer 3c, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in the light emitting layer 3c.
  • the host compound a known host compound may be used alone, or a plurality of types may be used. By using a plurality of types of host compounds, the charge transfer rate can be adjusted, and the organic EL element can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.
  • the host compound used may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .
  • Tg glass transition temperature
  • H1 to H79 Specific examples (H1 to H79) of host compounds that can be used in the present invention are shown below, but are not limited thereto.
  • x, y, p, q, and r described in the host compounds H68 to H71 each represent a ratio of the random copolymer.
  • N represents the degree of polymerization.
  • Light emitting material examples include phosphorescent compounds (hereinafter also referred to as “phosphorescent compounds” and “phosphorescent materials”).
  • a phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C.
  • a preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.
  • the phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of the Fourth Edition Experimental Chemistry Course 7.
  • the phosphorescence quantum yield in the solution can be measured using various solvents, but when using a phosphorescent compound in the present invention, the phosphorescence quantum yield is 0.01 or more in any solvent. Should be achieved.
  • the light emission principle of the phosphorescent compound There are two methods for the light emission principle of the phosphorescent compound.
  • One method is that recombination of carriers occurs on a host compound to which carriers are transported, and an excited state of the host compound is generated, and this energy is transferred to the phosphorescent compound, thereby transferring the energy from the phosphorescent compound. It is an energy transfer type that obtains luminescence.
  • Another method is a carrier trap type in which a phosphorescent compound becomes a carrier trap, carrier recombination occurs on the phosphorescent compound, and light emission from the phosphorescent compound is obtained. In either case, the condition is that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.
  • the phosphorescent compound can be appropriately selected and used from known compounds used in the light emitting layer of a general organic EL device.
  • a group 8-10 metal in the periodic table of elements is used. It is a complex compound to be contained, more preferably an iridium compound, an osmium compound, a platinum compound (platinum complex compound), or a rare earth complex, and most preferably an iridium compound.
  • At least one light emitting layer 3c may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light emitting layer 3c is the thickness direction of the light emitting layer 3c. It may be an aspect that changes.
  • the content of the phosphorescent compound is preferably in the range of 0.1 to 30% by volume with respect to the total volume of the light emitting layer 3c.
  • the light emitting layer 3c according to the present invention contains a compound having a structure represented by the following general formula (A) as a phosphorescent compound. It is preferable.
  • the phosphorescent compound represented by the following general formula (A) (also referred to as a phosphorescent metal complex) is preferably contained in the light emitting layer 3c of the organic EL element 100 as a light emitting dopant. However, it may be contained in the light emitting functional layer group 3 other than the light emitting layer 3c.
  • P and Q each represent a carbon atom or a nitrogen atom.
  • a 1 represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with P—C.
  • a 2 represents an atomic group that forms an aromatic heterocycle with QN.
  • P 1 -L 1 -P 2 represents a bidentate ligand, and P 1 and P 2 each independently represent a carbon atom, a nitrogen atom or an oxygen atom.
  • L 1 represents an atomic group that forms a bidentate ligand together with P 1 and P 2 .
  • j1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 is 2 or 3.
  • M 1 represents a group 8-10 transition metal element in the periodic table.
  • P and Q each represent a carbon atom or a nitrogen atom.
  • examples of the aromatic hydrocarbon ring that A 1 forms with P—C include, for example, a benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, Naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, Examples include a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring.
  • These rings may further have a substituent.
  • substituents include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group).
  • examples of the aromatic heterocycle formed by A 1 together with PC include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, Triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring And azacarbazole ring.
  • the azacarbazole ring means one in which at least one carbon atom of the benzene ring constituting the carbazole ring is replaced with a nitrogen atom.
  • examples of the aromatic heterocycle formed by A 2 together with QN include an oxazole ring, an oxadiazole ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, a thiadiazole ring, and a thiatriazole ring.
  • P 1 -L 1 -P 2 represents a bidentate ligand
  • P 1 and P 2 each independently represent a carbon atom, a nitrogen atom or an oxygen atom
  • L 1 represents an atomic group forming a bidentate ligand together with P 1 and P 2 .
  • Examples of the bidentate ligand represented by P 1 -L 1 -P 2 include phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone, picolinic acid, and the like.
  • j1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 represents 2 or 3
  • j2 is preferably 0.
  • a transition metal element of Group 8 to Group 10 (also simply referred to as a transition metal) in the periodic table is used, and among these, iridium is preferable.
  • Z represents a hydrocarbon ring group or a heterocyclic group.
  • P and Q each represent a carbon atom or a nitrogen atom.
  • a 1 represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with P—C.
  • P 1 -L 1 -P 2 represents a bidentate ligand.
  • P 1 and P 2 each independently represent a carbon atom, a nitrogen atom, or an oxygen atom.
  • L 1 represents an atomic group that forms a bidentate ligand together with P 1 and P 2 .
  • j1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 is 2 or 3.
  • M 1 represents a group 8-10 transition metal element in the periodic table.
  • examples of the hydrocarbon ring group represented by Z include a non-aromatic hydrocarbon ring group and an aromatic hydrocarbon ring group, and examples of the non-aromatic hydrocarbon ring group include a cyclopropyl group. , Cyclopentyl group, cyclohexyl group and the like. These groups may be unsubstituted or may have the same substituents that the ring represented by A 1 in the general formula (A) may have.
  • aromatic hydrocarbon ring group examples include, for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl. Group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like.
  • examples of the heterocyclic group represented by Z include a non-aromatic heterocyclic group and an aromatic heterocyclic group.
  • examples of the non-aromatic heterocyclic group include an epoxy ring and an aziridine group. Ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ⁇ -caprolactone ring, ⁇ - Caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring
  • aromatic heterocyclic group examples include a pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl).
  • oxazolyl group 1,2,3-triazol-1-yl group, etc.
  • benzoxazolyl group thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group , Benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl Group, pyridazinyl group, triazinyl group, Nazoriniru group, phthalazinyl group, and the like.
  • the group represented by Z is an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • examples of the aromatic hydrocarbon ring that A 1 forms with PC include a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, Naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, Examples include a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring.
  • These rings may further have a substituent, and examples of such a substituent are the same as the substituent that the ring represented by A 1 in the general formula (A) may have. Things.
  • examples of the aromatic heterocycle formed by A 1 together with PC include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine.
  • the azacarbazole ring means one in which at least one carbon atom of the benzene ring constituting the carbazole ring is replaced with a nitrogen atom.
  • These rings may further have a substituent, and examples of such a substituent are the same as the substituent that the ring represented by A 1 in the general formula (A) may have. Things.
  • R 01 and the substituent represented by R 02 has the same meaning as the substituent which the ring represented by A 1 in the general formula (A) may have.
  • examples of the bidentate ligand represented by P 1 -L 1 -P 2 include phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone, and picoline. An acid etc. are mentioned.
  • J1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 represents 2 or 3
  • j2 is preferably 0.
  • transition metal element of group 8 to group 10 in the periodic table of elements represented by M 1 (also simply referred to as transition metal) is the element represented by M 1 in the general formula (A). Synonymous with Group 8-10 transition metal elements in the periodic table.
  • R 03 represents a substituent.
  • R 04 represents a hydrogen atom or a substituent, and a plurality of R 04 may be bonded to each other to form a ring.
  • n01 represents an integer of 1 to 4.
  • R 05 represents a hydrogen atom or a substituent, and a plurality of R 05 may be bonded to each other to form a ring.
  • n02 represents an integer of 1 to 2.
  • R 06 represents a hydrogen atom or a substituent, and may combine with each other to form a ring.
  • n03 represents an integer of 1 to 4.
  • Z 1 represents an atomic group necessary for forming a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle with C—C.
  • Z 2 represents an atomic group necessary for forming a hydrocarbon ring group or a heterocyclic group.
  • P 1 -L 1 -P 2 represents a bidentate ligand, and P 1 and P 2 each independently represent a carbon atom, a nitrogen atom or an oxygen atom.
  • L 1 represents an atomic group forming a bidentate ligand together with P 1 and P 2 .
  • j1 represents an integer of 1 to 3
  • j2 represents an integer of 0 to 2
  • j1 + j2 is 2 or 3.
  • M 1 represents a group 8-10 transition metal element in the periodic table.
  • R 03 and R 06 , R 04 and R 06, and R 05 and R 06 may be bonded to each other to form a ring.
  • each of the substituents represented by R 03 , R 04 , R 05 and R 06 may be substituted by the ring represented by A 1 in the general formula (A). Synonymous with group.
  • examples of the 6-membered aromatic hydrocarbon ring formed by Z 1 together with C—C include a benzene ring.
  • These rings may further have a substituent, and such a substituent is the same as the substituent which the ring represented by A 1 in the general formula (A) may have. Things.
  • examples of the 5-membered or 6-membered aromatic heterocycle formed by Z 1 together with C—C include, for example, an oxazole ring, an oxadiazole ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, Examples include thiadiazole ring, thiatriazole ring, isothiazole ring, thiophene ring, furan ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, triazole ring and the like.
  • These rings may further have a substituent, and such a substituent is the same as the substituent which the ring represented by A 1 in the general formula (A) may have. Things.
  • examples of the hydrocarbon ring group represented by Z 2 include a non-aromatic hydrocarbon ring group and an aromatic hydrocarbon ring group, and examples of the non-aromatic hydrocarbon ring group include cyclopropyl. Group, cyclopentyl group, cyclohexyl group and the like. These groups may be unsubstituted or may have a substituent. Examples of such a substituent include a substituent that the ring represented by A 1 in General Formula (A) may have. The same thing as a group is mentioned.
  • aromatic hydrocarbon ring group examples include, for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl.
  • phenyl group p-chlorophenyl group
  • mesityl group tolyl group
  • xylyl group naphthyl group
  • anthryl group azulenyl.
  • acenaphthenyl group fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like.
  • These groups may be unsubstituted or may have a substituent. Examples of such a substituent include a substituent that the ring represented by A 1 in General Formula (A) may have. The same thing as a group is mentioned.
  • examples of the heterocyclic group represented by Z 2 include a non-aromatic heterocyclic group and an aromatic heterocyclic group.
  • examples of the non-aromatic heterocyclic group include an epoxy ring, Aziridine ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ⁇ -caprolactone ring, ⁇ -Caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran
  • aromatic heterocyclic group examples include a pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl).
  • oxazolyl group 1,2,3-triazol-1-yl group, etc.
  • benzoxazolyl group thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group , Benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl Group, pyridazinyl group, triazinyl group, Nazoriniru group, phthalazinyl group, and the like.
  • the group formed by Z 1 and Z 2 is preferably a benzene ring.
  • bidentate ligand represented by P 1 -L 1 -P 2 the In formula (A), the bidentate represented by P 1 -L 1 -P 2 Synonymous with ligand.
  • transition metal elements group 8-10 of the periodic table represented by M 1 is, in the general formula (A), group 8 in the periodic table represented by M 1 ⁇ 10 It is synonymous with the group transition metal element.
  • the phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer 3c of the organic EL element 100.
  • the phosphorescent compound according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex system). Compound) and rare earth complexes, and most preferred is an iridium compound.
  • Pt-1 to Pt-3, A-1, Ir-1 to Ir-45 Specific examples (Pt-1 to Pt-3, A-1, Ir-1 to Ir-45) of the phosphorescent compound according to the present invention are shown below, but the present invention is not limited to these.
  • m and n each represent the number of repetitions.
  • fluorescent light emitting materials include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, Examples thereof include stilbene dyes, polythiophene dyes, and rare earth complex phosphors.
  • the injection layer is a layer provided between the electrode and the light emitting layer 3c in order to lower the driving voltage and improve the light emission luminance.
  • the organic EL element and its industrialization front line June 30, 1998, NTT
  • the details are described in Volume 2, Chapter 2, “Electrode Materials” (pages 123 to 166) of “Part 2” of S Co., Ltd., and there are a hole injection layer 3a and an electron injection layer 3e as injection layers. .
  • the injection layer can be provided as necessary.
  • the hole injection layer 3a may be present between the anode and the light emitting layer 3c or the hole transport layer 3b, and the electron injection layer 3e may be present between the cathode and the light emitting layer 3c or the electron transport layer 3d. Good.
  • hole injection layer 3a The details of the hole injection layer 3a are described in, for example, JP-A-9-45479, JP-A-9-260062, and JP-A-8-288069, and a specific example is represented by copper phthalocyanine.
  • a specific example is represented by copper phthalocyanine.
  • examples thereof include a phthalocyanine layer, an oxide layer typified by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
  • the details of the electron injection layer 3e are described, for example, in JP-A-6-325871, JP-A-9-17574, and JP-A-10-74586, and are specifically represented by strontium, aluminum and the like.
  • Metal layers alkali metal halide layers typified by potassium fluoride, alkaline earth metal compound layers typified by magnesium fluoride, oxide layers typified by molybdenum oxide, and the like.
  • the electron injection layer 3e is a very thin film, and although depending on the material, the layer thickness is preferably in the range of 1 nm to 10 ⁇ m.
  • the hole transport layer 3b is made of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer 3a and the electron blocking layer are also included in the hole transport layer 3b.
  • the hole transport layer 3b can be provided as a single layer or a plurality of layers.
  • the hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • triazole derivatives oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives
  • Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • hole transport material those described above can be used, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
  • aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (abbreviation: TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1 -Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-di-p -Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p
  • polymer materials in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
  • a so-called p-type hole transport material as described in 139 can also be used. In the present invention, these materials are preferably used from the viewpoint of obtaining a light-emitting element with higher efficiency.
  • the hole transport material may be a known material such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, an LB method (Langmuir Brodget, Langmuir Brodgett method), and the like.
  • the thin film can be formed by the method.
  • the layer thickness of the hole transport layer 3b is not particularly limited, but is usually in the range of about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the hole transport layer 3b may have a single layer structure composed of one or more of the above materials.
  • the p property can be increased by doping the material of the hole transport layer 3b with an impurity.
  • impurity examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
  • the electron transport layer 3d is made of a material having a function of transporting electrons. In a broad sense, the electron injection layer 3e and the hole blocking layer are also included in the electron transport layer 3d.
  • the electron transport layer 3d can be provided as a single layer structure or a multilayer structure of a plurality of layers.
  • an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer 3c is an electron injected from the cathode.
  • an electron transport material also serving as a hole blocking material
  • any one of conventionally known compounds can be selected and used. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group are also used as the material for the electron transport layer 3d.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (abbreviation: Alq 3 ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8- Quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (abbreviation: Znq), etc., and the central metal of these metal complexes
  • a metal complex in which In, Mg, Cu, Ca, Sn, Ga, or Pb is replaced can also be used as the material of the electron transport layer 3d.
  • metal-free or metal phthalocyanine or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the material for the electron transport layer 3d.
  • a distyrylpyrazine derivative exemplified also as the material of the light emitting layer 3c can be used as the material of the electron transport layer 3d.
  • n-type Si, n An inorganic semiconductor such as type-SiC can also be used as the material of the electron transport layer 3d.
  • the electron transport layer 3d can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.
  • the thickness of the electron transport layer 3d is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the electron transport layer 3d may have a single layer structure composed of one or more of the above materials.
  • the electron transport layer 3d can be doped with an impurity to increase the n property.
  • examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
  • the electron transport layer 3d contains potassium, a potassium compound, or the like.
  • the potassium compound for example, potassium fluoride can be used.
  • the material (electron transporting compound) of the electron transport layer 3d the same material as that of the intermediate layer 1a described above may be used.
  • the electron transport layer 3d also serving as the electron injection layer 3e, and the same material as that constituting the intermediate layer 1a described above may be used.
  • the blocking layer is a layer provided as necessary in addition to the constituent layers of the light emitting functional layer group 3 described above. For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237.
  • the hole blocking layer has the function of the electron transport layer 3d in a broad sense.
  • the hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved.
  • the structure of the electron carrying layer 3d mentioned later can be used as a hole-blocking layer as needed.
  • the hole blocking layer is preferably provided adjacent to the light emitting layer 3c.
  • the electron blocking layer has the function of the hole transport layer 3b in a broad sense.
  • the electron blocking layer is made of a material that has the ability to transport holes and has a very small ability to transport electrons. By blocking holes while transporting holes, the probability of recombination of electrons and holes is improved. Can be made.
  • the structure of the positive hole transport layer 3b mentioned later can be used as an electron blocking layer as needed.
  • the layer thickness of the hole blocking layer applied to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.
  • the auxiliary electrode 15 is an electrode provided for the purpose of reducing the resistance of the transparent electrode 1, and is provided in contact with the conductive layer 1 b of the transparent electrode 1.
  • the material forming the auxiliary electrode 15 is preferably a metal having low resistance such as gold, platinum, silver, copper, or aluminum. Since many of these metals have low light transmittance, they are formed in a pattern as shown in FIG. 2 within a range not affected by extraction of the emitted light L from the light extraction surface 13a.
  • Examples of the method for forming the auxiliary electrode 15 include a vapor deposition method, a sputtering method, a printing method, an ink jet method, and an aerosol jet method.
  • the line width of the auxiliary electrode 15 is preferably 50 ⁇ m or less from the viewpoint of the aperture ratio of the light extraction region, and the thickness of the auxiliary electrode 15 is preferably 1 ⁇ m or more from the viewpoint of conductivity.
  • the sealing material 17 covers the organic EL element 100 and may be a plate-shaped (film-shaped) sealing member that is fixed to the transparent substrate 13 by the adhesive 19. It may be a sealing film. Such a sealing material 17 is provided in a state of covering at least the light emitting functional layer group 3 in a state in which the terminal portions of the transparent electrode 1 and the counter electrode 5a in the organic EL element 100 are exposed. Moreover, an electrode may be provided on the sealing material 17 so that the transparent electrode 1 of the organic EL element 100 and the terminal portions of the counter electrode 5a are electrically connected to this electrode.
  • the plate-like (film-like) sealing material 17 include a glass substrate, a polymer substrate, a metal substrate, and the like, and these substrate materials may be used in the form of a thinner film.
  • the glass substrate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal substrate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • a thin film-like polymer substrate or metal substrate can be preferably used as the sealing material.
  • the polymer substrate in the form of a film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 ⁇ 10 ⁇ 3 ml / (m 2 ⁇ 24 h ⁇ atm) or less, and JIS K 7129-1992.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by a method in accordance with the above is 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less. It is preferable.
  • the above substrate material may be processed into a concave plate shape and used as the sealing material 17.
  • the above-described substrate member is subjected to processing such as sand blasting or chemical etching to form a concave shape.
  • An adhesive 19 for fixing the plate-shaped sealing material 17 to the transparent substrate 13 side seals the organic EL element 100 sandwiched between the sealing material 17 and the transparent substrate 13. It is used as a sealing agent.
  • Specific examples of such an adhesive 19 include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, moisture curing types such as 2-cyanoacrylates, and the like. Can be mentioned.
  • examples of the adhesive 19 include an epoxy-based thermal and chemical curing type (two-component mixing). Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • the adhesive 19 is preferably one that can be adhesively cured from room temperature to 80 ° C. Further, a desiccant may be dispersed in the adhesive 19.
  • Application of the adhesive 19 to the bonding portion between the sealing material 17 and the transparent substrate 13 may be performed using a commercially available dispenser or may be printed like screen printing.
  • an inert gas such as nitrogen or argon or a fluorine is used. It is preferable to inject an inert liquid such as activated hydrocarbon or silicon oil. A vacuum can also be used. Moreover, a hygroscopic compound can also be enclosed inside.
  • hygroscopic compound examples include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate).
  • metal oxides for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide
  • sulfates for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate.
  • metal halides eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.
  • perchloric acids eg perchloric acid Barium, magnesium perchlorate, and the like
  • anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.
  • the sealing material 17 when a sealing film is used as the sealing material 17, the light emitting functional layer group 3 in the organic EL element 100 is completely covered and the terminal portions of the transparent electrode 1 and the counter electrode 5a in the organic EL element 100 are exposed.
  • a sealing film is provided on the transparent substrate 13.
  • Such a sealing film is composed of an inorganic material or an organic material.
  • it is made of a material having a function of suppressing intrusion of a substance that causes deterioration of the light emitting functional layer group 3 in the organic EL element 100 such as moisture and oxygen.
  • a material for example, inorganic materials such as silicon oxide, silicon dioxide, and silicon nitride are used.
  • a laminated structure may be formed by using a film made of an organic material together with a film made of these inorganic materials.
  • the method for forming these films is not particularly limited.
  • vacuum deposition method sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma
  • a polymerization method a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
  • a protective film or a protective plate may be provided between the transparent substrate 13 and the organic EL element 100 and the sealing material 17.
  • This protective film or protective plate is for mechanically protecting the organic EL element 100, and in particular when the sealing material 17 is a sealing film, sufficient mechanical protection is provided for the organic EL element 100. Therefore, it is preferable to provide such a protective film or protective plate.
  • a glass plate, a polymer plate, a thinner polymer film, a metal plate, a thinner metal film, a polymer material film or a metal material film is applied.
  • a polymer film because it is light and thin.
  • an intermediate layer 1a containing two or more organic compounds according to the present invention is appropriately deposited on the transparent substrate 13 by a method such as vapor deposition so that the layer thickness is 1 ⁇ m or less, preferably in the range of 10 to 100 nm. Select and form.
  • a method such as vapor deposition is appropriately selected so that the conductive layer 1b composed of silver or an alloy containing silver as a main component has a layer thickness of 12 nm or less, preferably in the range of 4 to 9 nm.
  • a transparent electrode 1 formed on the intermediate layer 1a and serving as an anode is produced.
  • each layer constituting the light emitting functional layer group 3 includes a spin coat method, a cast method, an ink jet method, a vapor deposition method, a printing method, etc., but it is easy to obtain a homogeneous film and a pinhole is not easily generated. From this point, the vacuum evaporation method or the spin coating method is particularly preferable. Further, different film formation methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally the boat heating temperature is in the range of 50 to 450 ° C., and the degree of vacuum is 1 ⁇ 10 ⁇ 6 to 1 ⁇ .
  • Each condition is appropriately selected within a range of 10 ⁇ 2 Pa, a deposition rate of 0.01 to 50 nm / second, a substrate temperature of ⁇ 50 to 300 ° C., and a layer thickness of 0.1 to 5 ⁇ m. Is desirable.
  • the counter electrode 5a serving as a cathode is formed thereon by appropriately selecting a film forming method such as a vapor deposition method or a sputtering method.
  • the counter electrode 5a is patterned in a shape in which a terminal portion is drawn from the upper side of the light emitting functional layer group 3 to the periphery of the transparent substrate 13 while being kept insulated from the transparent electrode 1 by the light emitting functional layer group 3. .
  • the organic EL element 100 is obtained.
  • a sealing material 17 that covers at least the light emitting functional layer group 3 is provided in a state where the terminal portions of the transparent electrode 1 and the counter electrode 5a in the organic EL element 100 are exposed.
  • an organic EL element having a desired configuration can be produced on the transparent substrate 13.
  • a method of producing from the light emitting functional layer group 3 to the counter electrode 5a consistently by a single vacuum is preferable, but the transparent substrate 13 is taken out from the vacuum atmosphere in the middle, Different film forming methods may be applied. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.
  • the transparent electrode 1 as an anode has a positive polarity
  • the counter electrode 5a as a cathode has a negative polarity
  • the voltage is 2 to 40 V.
  • An alternating voltage may be applied.
  • the alternating current waveform to be applied may be arbitrary.
  • the organic EL element 100 having the configuration shown in FIG. 2 described above uses the transparent electrode 1 of the present invention having both conductivity and light transmission as an anode, and is opposed to the light emitting functional layer group 3 and the cathode above this. It is the structure which provided the electrode 5a. For this reason, the extraction efficiency of the emitted light L from the transparent electrode 1 side is improved while applying a sufficient voltage between the transparent electrode 1 and the counter electrode 5a to realize high luminance light emission in the organic EL element 100. Thus, it is possible to increase the luminance. Further, in order to obtain a desired luminance, it is possible to improve the light emission lifetime by reducing the drive voltage.
  • FIG. 3 is a schematic cross-sectional view showing a second example of the organic EL element using the transparent electrode described above as an example of the electronic device of the present invention.
  • the organic EL element 200 of the second example shown in FIG. 3 is different from the organic EL element 100 of the first example shown in FIG. 2 in that the transparent electrode 1 is used as a cathode.
  • the transparent electrode 1 is used as a cathode.
  • the organic EL element 200 shown in FIG. 3 is provided on the transparent substrate 13, and the transparent electrode 1 of the present invention described above is used as the transparent electrode 1 on the transparent substrate 13 as in the first example. Yes. For this reason, the organic EL element 200 is configured to extract the emitted light L from at least the transparent substrate 13 side.
  • the transparent electrode 1 is used as a cathode (cathode), and the counter electrode 5b is used as an anode (anode).
  • the layer structure of the organic EL element 200 configured as described above is not limited to the example described below, and may be a general layer structure as in the first example.
  • an electron injection layer 3e / electron transport layer 3d / light emitting layer 3c / hole transport layer 3b / hole injection layer 3a are formed on the transparent electrode 1 functioning as a cathode.
  • the light emitting functional layer group 3 laminated in order is illustrated. However, among these, it is an essential condition to have at least the light emitting layer 3c made of an organic material.
  • the light emitting functional layer group 3 can incorporate various functional layers as necessary, as described in the first example. In such a configuration, only the portion where the light emitting functional layer group 3 is sandwiched between the transparent electrode 1 and the counter electrode 5b becomes the light emitting region in the organic EL element 200, as in the first example.
  • the auxiliary electrode 15 may be provided in contact with the conductive layer 1b of the transparent electrode 1 for the purpose of reducing the resistance of the transparent electrode 1. Similar to the example.
  • the counter electrode 5b used as the anode is composed of a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof.
  • metals such as gold (Au), oxide semiconductors such as copper iodide (CuI), ITO, ZnO, TiO 2 , and SnO 2 .
  • the counter electrode 5b composed of the above materials can be formed by forming a thin film from these conductive materials by a method such as vapor deposition or sputtering. Further, the sheet resistance as the counter electrode 5b is preferably several hundred ⁇ / ⁇ or less, and the layer thickness is usually selected within the range of 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • this organic EL element 200 is comprised so that emitted light L can be taken out also from the counter electrode 5b side, as a material which comprises the counter electrode 5b, favorable light transmittance is mentioned among the electrically conductive materials mentioned above.
  • a suitable conductive material is selected and used.
  • the organic EL element 200 configured as described above is sealed with the sealing material 17 in the same manner as in the first example for the purpose of preventing deterioration of the light emitting functional layer group 3.
  • the detailed structure of the constituent elements other than the counter electrode 5b used as the anode and the method for producing the organic EL element 200 are the same as those in the first example. Therefore, detailed description is omitted.
  • the transparent electrode 1 of the present invention having both conductivity and light transmission is used as a cathode, and the light emitting functional layer group 3 and the counter electrode 5b serving as an anode are formed thereon. Is provided. For this reason, as in the first example, a sufficient voltage is applied between the transparent electrode 1 and the counter electrode 5b to realize high-luminance light emission in the organic EL element 200, and light emitted from the transparent electrode 1 side. It is possible to increase the luminance by improving the L extraction efficiency. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.
  • FIG. 4 is a schematic cross-sectional view showing a third example of the organic EL element using the above-described transparent electrode as an example of the electronic device of the present invention.
  • the organic EL element 300 of the third example shown in FIG. 4 is different from the organic EL element 100 of the first example described with reference to FIG. 2 in that a counter electrode 5c is provided on the substrate 131 side, and a light emitting functional layer is formed thereon.
  • the group 3 and the transparent electrode 1 are stacked in this order.
  • the detailed description of the same components as those in the first example will be omitted, and the characteristic configuration of the organic EL element 300 in the third example will be described.
  • the organic EL element 300 shown in FIG. 4 is provided on a substrate 131. From the substrate 131 side, the counter electrode 5c serving as an anode, the light emitting functional layer group 3, and the transparent electrode 1 serving as a cathode are laminated in this order. Yes. Among these, as the transparent electrode 1, the transparent electrode 1 of the present invention described above is used. For this reason, the organic EL element 300 is configured to extract the emitted light L from at least the transparent electrode 1 side opposite to the substrate 131.
  • the layer structure of the organic EL element 300 configured as described above is not limited to the example described below, and may be a general layer structure as in the first example.
  • a hole injection layer 3a / hole transport layer 3b / light emitting layer 3c / electron transport layer 3d are formed on the counter electrode 5c functioning as an anode.
  • stacked in order is illustrated. However, it is essential to have at least the light emitting layer 3c configured using an organic material.
  • the electron transport layer 3d also serves as the electron injection layer 3e, and is provided as an electron transport layer 3d having electron injection properties.
  • the characteristic configuration of the organic EL element 300 shown as the third example is that an electron transport layer 3d having electron injection properties is provided as the intermediate layer 1a in the transparent electrode 1. That is, in the third example, the transparent electrode 1 used as a cathode is composed of an intermediate layer 1a also serving as an electron transport layer 3d having electron injection properties, and a conductive layer 1b provided on the intermediate layer 1a. It is.
  • Such an electron transport layer 3d is configured by using the material constituting the intermediate layer 1a of the transparent electrode 1 described above.
  • the light emitting functional layer group 3 can employ various functional layers as necessary, as described in the first example.
  • An electron injection layer or a hole blocking layer is not provided between the electron transport layer 3d serving also as 1a and the conductive layer 1b of the transparent electrode 1.
  • the portion where the light emitting functional layer group 3 is sandwiched between the transparent electrode 1 and the counter electrode 5c becomes the light emitting region in the organic EL element 300, as in the first example.
  • the auxiliary electrode 15 may be provided in contact with the conductive layer 1b of the transparent electrode 1 for the purpose of reducing the resistance of the transparent electrode 1. The same as in the example.
  • the counter electrode 5c used as the anode is made of a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof.
  • metals such as gold (Au), oxide semiconductors such as copper iodide (CuI), ITO, ZnO, TiO 2 , and SnO 2 .
  • the counter electrode 5c made of the material as described above can be formed by forming a thin film from these conductive materials by a method such as vapor deposition or sputtering. Further, the sheet resistance as the counter electrode 5c is preferably several hundred ⁇ / ⁇ or less, and the layer thickness is usually selected within the range of 5 nm to 5 ⁇ m, preferably 5 nm to 200 nm.
  • the material constituting the counter electrode 5c is light among the above-described conductive materials.
  • a conductive material having good permeability is selected and used.
  • the substrate 131 is the same as the transparent substrate 13 described in the first example. In such a configuration, the surface facing the outside of the substrate 131 is also the light extraction surface 131a.
  • the electron transport layer 3d having the electron injecting property constituting the uppermost part of the light emitting functional layer group 3 is used as the intermediate layer 1a, and the conductive layer 1b is provided thereon.
  • the transparent electrode 1 composed of the intermediate layer 1a and the upper conductive layer 1b is provided as a cathode. Therefore, similarly to the first example and the second example, a sufficient voltage is applied between the transparent electrode 1 and the counter electrode 5c to realize high-luminance light emission in the organic EL element 300, while the transparent electrode 1 side. It is possible to increase the luminance by improving the extraction efficiency of the emitted light L from the light source.
  • the counter electrode 5c is made of a light-transmitting electrode material, the emitted light L can be extracted from the counter electrode 5c.
  • the intermediate layer 1a of the transparent electrode 1 has been described as also serving as the electron transport layer 3d having electron injection properties.
  • the configuration is limited to these examples.
  • the intermediate layer 1a may also serve as the electron transport layer 3d that does not have electron injection properties, or the intermediate layer 1a may serve as the electron injection layer instead of the electron transport layer. May be.
  • the intermediate layer 1a may be formed as an extremely thin film that does not affect the light emitting function of the organic EL element. In this case, the intermediate layer 1a has electron transport properties and electron injection properties. Not.
  • the intermediate layer 1a of the transparent electrode 1 is formed as an extremely thin film that does not affect the light emitting function of the organic EL element
  • the counter electrode on the substrate 131 side is used as a cathode
  • the light emitting functional layer group 3 The upper transparent electrode 1 may be an anode.
  • the light emitting functional layer group 3 includes, for example, an electron injection layer 3e / electron transport layer 3d / light emission layer 3c / hole transport layer 3b / hole injection layer in order from the counter electrode 5c (cathode) side on the substrate 131. 3a is laminated.
  • a transparent electrode 1 having a laminated structure of an extremely thin intermediate layer 1a and a conductive layer 1b is provided as an anode on the top.
  • the organic EL element which consists of each structure demonstrated with the said each figure is a surface light-emitting body as mentioned above, it can be applied as various light emission light sources.
  • lighting devices such as home lighting and interior lighting, backlights for watches and liquid crystal display devices, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, optical communication processors
  • Examples include, but are not limited to, a light source and a light source of an optical sensor.
  • the light source can be effectively used as a backlight of a liquid crystal display device combined with a color filter and an illumination light source.
  • the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a type for directly viewing a still image or a moving image. It may be used as a display device (display).
  • the light emitting surface may be enlarged by so-called tiling, in which light emitting panels provided with organic EL elements are joined together in a plane.
  • the drive method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method.
  • a color or full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.
  • a lighting device will be described as an example of the application, and then a lighting device having a light emitting surface enlarged by tiling will be described.
  • Lighting device-1 The lighting device according to the present invention can include the organic EL element of the present invention.
  • the organic EL element used in the lighting device according to the present invention may be designed such that each organic EL element having the above-described configuration has a resonator structure.
  • the purpose of use of the organic EL element configured to have a resonator structure includes a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processor, a light source of an optical sensor, etc. It is not limited to. Moreover, you may use for the said use by making a laser oscillation.
  • the material used for the organic EL element of the present invention can be applied to an organic EL element that emits substantially white light (also referred to as a white organic EL element).
  • a plurality of light emitting materials can simultaneously emit a plurality of light emission colors to obtain white light emission by color mixing.
  • the combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of red, green and blue, or two using the complementary colors such as blue and yellow, blue green and orange. The thing containing the light emission maximum wavelength may be used.
  • a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and excitation of light from the light emitting materials. Any combination with a pigment material that emits light as light may be used, but in a white organic EL element, a combination of a plurality of light-emitting dopants may be used.
  • Such a white organic EL element is different from a configuration in which organic EL elements emitting each color are individually arranged in parallel to obtain white light emission, and the organic EL element itself emits white light. For this reason, a mask is not required for film formation of most layers constituting the element, and for example, an electrode film can be formed on one side by vapor deposition, casting, spin coating, ink jet, printing, etc., and productivity is improved. To do.
  • any metal complex according to the present invention or a known light emitting material may be selected and combined to be whitened.
  • the white organic EL element described above it is possible to produce a lighting device that emits substantially white light.
  • FIG. 5 shows a schematic cross-sectional view of a lighting device in which a plurality of organic EL elements having the above-described configurations are used to increase the light emitting surface area.
  • the lighting device 21 shown in FIG. 5 has a large light emitting surface, for example, by arranging a plurality of light emitting panels 22 provided with the organic EL elements 100 on the transparent substrate 13 on the support substrate 23 (that is, tiling). It is the structure which made the area.
  • the support substrate 23 may also serve as a sealing material, and each light-emitting panel 22 is tied with the organic EL element 100 sandwiched between the support substrate 23 and the transparent substrate 13 of the light-emitting panel 22. Ring.
  • An adhesive 19 may be filled between the support substrate 23 and the transparent substrate 13, thereby sealing the organic EL element 100.
  • the edge part of the transparent electrode 1 which is an anode, and the counter electrode 5a which is a cathode are exposed around the light emission panel 22.
  • FIG. only the exposed portion of the counter electrode 5a is shown in the drawing.
  • the hole injection layer 3 a / hole transport layer 3 b / light emission layer 3 c / electron transport layer 3 d / electron injection are formed on the transparent electrode 1.
  • a configuration in which the layers 3e are sequentially stacked is shown as an example.
  • each light-emitting panel 22 is a light-emitting area A, and a non-light-emitting area B is generated between the light-emitting panels 22.
  • a light extraction member for increasing the light extraction amount from the non-light emitting region B may be provided in the non-light emitting region B of the light extraction surface 13a.
  • a light collecting sheet or a light diffusion sheet can be used as the light extraction member.
  • Example 1 Preparation of transparent electrode >> According to the method described below, the transparent electrodes 1 to 125 were produced so that the area of the conductive region was 5 cm ⁇ 5 cm.
  • the transparent electrodes 1 to 4 are prepared as single layer transparent electrodes, the transparent electrodes 5 to 109 and the transparent electrodes 118 to 125 are transparent electrodes having a laminated structure of an intermediate layer and a conductive layer.
  • a transparent electrode having a laminated structure of three layers of an intermediate layer, a conductive layer, and a second intermediate layer was produced.
  • a transparent electrode 1 of a comparative example having a single layer structure was produced according to the method shown below.
  • a transparent non-alkali glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, and this was attached to a vacuum tank of the vacuum deposition apparatus.
  • a resistance heating boat made of tungsten was filled with silver (Ag) and mounted in the vacuum chamber.
  • the resistance heating boat is energized and heated to form silver on the base material within a deposition rate range of 0.1 to 0.2 nm / second.
  • a transparent electrode 1 was produced by depositing a single film of a conductive layer having a thickness of 5 ⁇ m.
  • transparent electrodes 2 to 4 In the production of the transparent electrode 1, transparent electrodes 2 to 4 were produced in the same manner except that the thickness of the conductive layer was changed to 9 nm, 11 nm, and 15 nm, respectively.
  • transparent electrode 5 On the transparent base made of alkali-free glass, Alq 3 having the following structure was formed as an intermediate layer having a layer thickness of 22 nm by a sputtering method, and a conductive layer was formed on the transparent electrode 1 on top of this.
  • a transparent electrode 5 was produced by vapor deposition of a conductive layer made of silver (Ag) having a layer thickness of 9 nm by the same method (vacuum vapor deposition method) used in the above.
  • a transparent non-alkali glass base material is fixed to a base material holder of a commercially available vacuum deposition apparatus, ET-1 having the structure shown below is filled in a resistance heating boat made of tantalum, and the substrate holder and the heating boat are connected to each other. It attached to the 1st vacuum chamber of a vacuum evaporation system. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.
  • the heating boat containing ET-1 was heated by energization, and the substrate was deposited within a deposition rate range of 0.1 to 0.2 nm / second.
  • the intermediate layer made of ET-1 having a layer thickness of 22 nm was formed by vapor deposition on the top.
  • the base material on which the intermediate layer is formed is transferred to the second vacuum chamber while being in a vacuum state, and after the pressure of the second vacuum chamber is reduced to 4 ⁇ 10 ⁇ 4 Pa, the heating boat containing silver is energized and heated, A conductive layer made of silver having a layer thickness of 9 nm was deposited at a deposition rate of 0.1 to 0.2 nm / second to obtain a transparent electrode 6 in which an intermediate layer and a conductive layer made of silver were laminated thereon. .
  • Transparent electrodes 7 and 8 were produced in the same manner as in the production of the transparent electrode 6 except that ET-1 used for forming the intermediate layer was changed to ET-2 and ET-3, respectively.
  • a transparent non-alkali glass base material is fixed to a base material holder of a commercially available vacuum deposition apparatus, and the exemplified compound “No. 2” as the first organic compound and the exemplified compound as the second organic compound
  • Each of “121” was filled in a resistance heating boat made of tantalum, and these substrate holder and heating boat were attached to the first vacuum chamber of the vacuum deposition apparatus.
  • silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.
  • each tantalum resistance heating boat was heated by energization, and within the range of the deposition rate of 0.1 to 0.2 nm / second, the compound “ No. 2 ”:
  • the compound“ 121 ” was vapor-deposited on the substrate under the condition that the mass ratio (mass%) of the compound“ 121 ”was 99.7: 0.3, to form an intermediate layer 1a having a layer thickness of 22 nm.
  • the base material on which the intermediate layer 1a is formed is transferred to the second vacuum chamber in a vacuum state, and after the pressure of the second vacuum chamber is reduced to 4 ⁇ 10 ⁇ 4 Pa, the heating boat containing silver is energized and heated.
  • the conductive layer 1b made of silver having a layer thickness of 3.5 nm was deposited at a deposition rate of 0.1 to 0.2 nm / second, and the intermediate layer 1a and the conductive layer 1b made of silver were laminated thereon.
  • a transparent electrode 13 was obtained.
  • Transparent electrodes 14 and 15 were produced in the same manner as in the production of the transparent electrode 13 except that the second organic compound was changed to the exemplified compounds “compound (7)” and “2-6”, respectively.
  • a transparent non-alkali glass substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, and the compound “No. 2” exemplified as the first organic compound and the compound “2” exemplified as the second organic compound are used.
  • ⁇ 6 ”and the compound“ 121 ”shown as the third organic compound were respectively filled in a resistance heating boat made of tantalum, and these substrate holder and heating boat were attached to the first vacuum chamber of the vacuum evaporation apparatus.
  • silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.
  • each tantalum resistance heating boat was heated by energization, and within the range of the deposition rate of 0.1 to 0.2 nm / second, the compound “ No. 2 ”: Compound“ 2-6 ”: Compound“ 121 ”was vapor-deposited on the substrate under the condition that the mass ratio (mass%) was 85.0: 10.0: 5.0, and the layer thickness was 22 nm.
  • the intermediate layer 1a was formed.
  • the base material on which the intermediate layer 1a is formed is transferred to the second vacuum chamber in a vacuum state, and after the pressure of the second vacuum chamber is reduced to 4 ⁇ 10 ⁇ 4 Pa, the heating boat containing silver is energized and heated.
  • the conductive layer 1b made of silver having a layer thickness of 3.5 nm was deposited at a deposition rate of 0.1 to 0.2 nm / second, and the intermediate layer 1a and the conductive layer 1b made of silver were laminated thereon.
  • a transparent electrode 21 was obtained.
  • transparent electrodes 23 to 25 were produced in the same manner except that the thickness of the conductive layer 1b was changed to 5 nm, 12 nm, and 20 nm, respectively.
  • a light transmittance (%) at a wavelength of 550 nm was measured using a spectrophotometer (U-3300, manufactured by Hitachi, Ltd.) with reference to the base material used for producing each transparent electrode.
  • Change width of sheet resistance value ⁇
  • the change width of the sheet resistance value of each transparent electrode was expressed as a relative value with the change ratio of the transparent electrode 8 being 100.
  • the variation resistance of the sheet resistance value was evaluated according to the following criteria.
  • Variation width of sheet resistance value ⁇ (maximum value of sheet resistance value ⁇ minimum value of sheet resistance value) / average value of sheet resistance value ⁇ ⁇ 100 (%) ⁇ : Sheet resistance value variation width is less than 2.0% ⁇ : Sheet resistance value variation width is 2.0% or more and less than 5.0% ⁇ ⁇ : Sheet resistance value variation width , 5.0% or more and less than 10.0% ⁇ : variation width of sheet resistance value is 10.0% or more and less than 15.0% ⁇ : variation width of sheet resistance value is 15.0 % Or more and less than 30.0% XX: Variation width of sheet resistance value is 30.0% or more Tables 6 to 8 show the results obtained as described above.
  • the transparent electrodes 1 to 4 of Comparative Examples having no intermediate layer although the sheet resistance value decreases as the layer thickness of the conductive layer which is a silver layer is increased, the formation of the conductive layer Decrease in light transmittance due to silver aggregation (motor) at the time becomes remarkable, and it is impossible to achieve both light transmittance and sheet resistance value. Further, even in the transparent electrodes 5 to 8 using Alq 3 or ET-1 to ET-3 as the intermediate layer, the light transmittance was low and the sheet resistance value could not be lowered to a desired condition. In addition, the transparent electrodes 1 to 4 were not able to be measured because the sheet resistance value after forced deterioration was remarkably reduced.
  • the transparent electrodes 9 to 12 using an organic compound alone can obtain a certain degree of light transmittance and sheet resistance value, but the sheet resistance value fluctuates as durability after energization under fairly severe conditions. Resistance and variation resistance within the electrode surface of the sheet resistance value were somewhat inferior.
  • Example 2 ⁇ Production of light emitting panel> [Preparation of light-emitting panel 1] Using the transparent electrode 1 produced in Example 1 as an anode, a double-sided light emitting panel 1 having the configuration shown in FIG. 6 (but not having the intermediate layer 1a) was produced according to the following procedure.
  • the transparent substrate 13 having the transparent electrode 1 formed only with the conductive layer 1b produced in Example 1 is fixed to a substrate holder of a commercially available vacuum deposition apparatus, and the transparent electrode 1 (only the conductive layer 1b) is formed.
  • a vapor deposition mask was placed opposite to the surface side.
  • each material which comprises the light emission functional layer group 3 was filled with the optimal quantity for film-forming of each layer in each heating boat in a vacuum evaporation system.
  • a heating boat what was produced with the resistance heating material made from tungsten was used as a heating boat.
  • the inside of the vapor deposition chamber of the vacuum vapor deposition apparatus is depressurized to a vacuum degree of 4 ⁇ 10 ⁇ 4 Pa, and each layer constituting the light emitting functional layer group 3 shown below is heated by sequentially energizing a heating boat containing each material. Was deposited.
  • a hole-transporting / injecting layer that serves as both a hole-injecting layer and a hole-transporting layer made of ⁇ -NPD by energizing and heating a heating boat containing the following ⁇ -NPD as a hole-transporting injecting material 31 was formed on the conductive layer 1 b constituting the transparent electrode 1.
  • the vapor deposition rate was in the range of 0.1 to 0.2 nm / second, and the vapor deposition was performed under the condition that the layer thickness was 20 nm.
  • the heating boat containing Exemplified Compound H4 as the host compound and the heating boat containing Exemplified Compound Ir-4 as the phosphorescent compound were energized independently, respectively, and Exemplified Compound H4 as the host compound and Phosphorus
  • the deposition rate nm / sec
  • Exemplified Compound Ir-4 100: 6
  • the energization condition of the heating boat is adjusted as appropriate so that the thickness of the light emitting layer becomes 30 nm. I made it.
  • a heating boat containing BAlq shown below as a hole blocking material was energized and heated to form a hole blocking layer 33 made of BAlq on the light emitting layer 3c.
  • the deposition was performed under the condition that the deposition rate was 0.1 to 0.2 nm / second and the layer thickness was 10 nm.
  • a heating boat containing ET-4 shown below as an electron transporting material and a heating boat containing potassium fluoride were energized independently, and an electron transport layer composed of ET-4 and potassium fluoride. 3d was deposited on the hole blocking layer 33.
  • the energization conditions of the heating boat are adjusted as appropriate so that the layer thickness of the electron transport layer 3d is 30 nm. And deposited.
  • a heating boat containing potassium fluoride as an electron injection material was energized and heated to form an electron injection layer 3e made of potassium fluoride on the electron transport layer 3d.
  • the deposition was performed so that the layer thickness was 1 nm at a deposition rate of 0.01 to 0.02 nm / second.
  • the transparent substrate 13 formed up to the electron injection layer 3e was transferred from the vapor deposition chamber of the vacuum vapor deposition apparatus to the processing chamber of the sputtering apparatus to which an ITO target as a counter electrode material was attached while maintaining the vacuum state.
  • a light-transmitting counter electrode 5a made of ITO having a layer thickness of 150 nm was formed as a cathode at a film formation rate of 0.3 to 0.5 nm / second.
  • the organic EL element 400 was formed on the transparent substrate 13.
  • the organic EL element 400 is covered with a sealing material 17 made of a glass substrate having a thickness of 300 ⁇ m, and the adhesive 19 (sealing material) is interposed between the sealing material 17 and the transparent substrate 13 so as to surround the organic EL element 400.
  • a sealing material 17 made of a glass substrate having a thickness of 300 ⁇ m
  • the adhesive 19 (sealing material) is interposed between the sealing material 17 and the transparent substrate 13 so as to surround the organic EL element 400. ).
  • an epoxy photocurable adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) was used.
  • the adhesive 19 filled between the sealing material 17 and the transparent substrate 13 is irradiated with UV light from the glass substrate (sealing material 17) side to cure the adhesive 19 and seal the organic EL element 400. Stopped.
  • the organic EL element 400 In forming the organic EL element 400, an evaporation mask is used for forming each layer, and the central 4.5 cm ⁇ 4.5 cm of the 5 cm ⁇ 5 cm transparent substrate 13 is defined as the light emitting region A, and the entire circumference of the light emitting region A is formed. A non-light emitting region B having a width of 0.25 cm was provided. Further, the transparent electrode 1 as the anode and the counter electrode 5a as the cathode are insulated from each other by the light emitting functional layer group 3 from the hole transport / injection layer 31 to the electron injection layer 35, and on the periphery of the transparent substrate 13. The terminal portion was formed in a drawn shape.
  • the light-emitting panel 1 in which the organic EL element 400 was provided on the transparent substrate 13 and sealed with the sealing material 17 and the adhesive 19 was produced.
  • the light emission L of each color generated in the light emitting layer 3c is extracted from both the transparent electrode 1 side, that is, the transparent substrate 13 side, and the counter electrode 5a side, that is, the sealing material 17 side. It has become.
  • the light-emitting panels 1-125 produced above were evaluated for light transmittance, driving voltage, and durability according to the following methods.
  • the light transmittance (%) in wavelength 550nm was measured using the base material used for preparation of each transparent electrode using the spectrophotometer (Hitachi U-3300).
  • the front luminance is measured on both sides of the transparent electrode 1 side (that is, the transparent substrate 13 side) and the counter electrode 5a side (that is, the sealing material 17 side) of each of the produced light emitting panels, and the sum is 1000 cd / m 2.
  • V drive voltage
  • a spectral radiance meter CS-1000 manufactured by Konica Minolta was used. It represents that it is so preferable that the numerical value of the obtained drive voltage is small.
  • the display screen was divided into a total of 100 blocks of 10 ⁇ 10, and then light was emitted. The presence or absence of dark spots was confirmed, and the ratio of blocks where dark spots were generated was measured in%.
  • Evaluation was expressed as a relative value with the dark spot generation area ratio of the light emitting panel 8 being 100. The smaller the value, the better the durability (dark spot resistance).
  • the emission luminance variation resistance was evaluated according to the following criteria.
  • Variation width of light emission luminance ⁇ (maximum value of light emission luminance ⁇ minimum value of light emission luminance) / average value of light emission luminance ⁇ ⁇ 100 (%)
  • the light-emitting panels 1 to 8 using the transparent electrode of the comparative example as the anode of the organic EL element have a light transmittance of less than 56%, and do not emit light even when a voltage is applied. Or even if it emitted light, the drive voltage exceeded 3.8V.
  • the light emitting panels 9 to 12 using the transparent electrode using an organic compound alone a certain degree of light transmittance and driving voltage can be obtained, but the dark spot resistance after energization under fairly severe conditions, and The result was slightly inferior to the variation in emission luminance.
  • the light-emitting panel including the organic EL element of the present invention using the transparent electrode having the configuration defined in the present invention can emit high-intensity light at a low driving voltage, and is durable in harsh environments. It was confirmed to be excellent. In addition, it has been confirmed that this is expected to reduce the driving voltage for obtaining a predetermined luminance and improve the light emission lifetime.
  • the transparent electrode of the present invention has sufficient conductivity and light transmittance, has a low sheet resistance value, is excellent in durability, has sufficient conductivity and light transmittance, and has a low driving voltage.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention a pour objectif de fournir : une électrode transparente qui combine une conductivité et des propriétés de transmission de la lumière, qui possède une basse valeur de résistance de couche, et qui est excellente en termes de durabilité ; un dispositif électronique qui est muni de cette électrode transparente, qui possède une conductivité suffisante et des propriétés de transmission de la lumière, qui présente une faible tension d'excitation, et qui est excellent en termes de durabilité ; et un élément électroluminescent organique. L'électrode transparente de l'invention possède une couche conductrice, et une couche intermédiaire agencée de manière adjacente par rapport à la couche conductrice. Ladite électrode transparente est caractéristique en ce que sa transmittance pour une longueur d'onde à 550nm est supérieure ou égale à 50% ; sa valeur de résistance de couche est inférieure ou égale à 20Ω au carré ; ladite couche intermédiaire comprend au moins deux sortes de composés organiques, et comprend en tant que premier composé organique, un composé possédant des atomes d'azote ayant une paire d'électrons non partagée ne conférant pas d'aromaticité, dans une plage supérieure ou égale à 50% en masse de la masse totale desdits composés organiques d'au moins deux sortes et de moins de 99,5% en masse ; et ladite couche conductrice est configurée avec un argent pour composant principal.
PCT/JP2013/078343 2012-10-24 2013-10-18 Électrode transparente, dispositif électronique, et élément électroluminescent organique WO2014065215A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014543271A JP6187471B2 (ja) 2012-10-24 2013-10-18 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012234848 2012-10-24
JP2012-234848 2012-10-24

Publications (1)

Publication Number Publication Date
WO2014065215A1 true WO2014065215A1 (fr) 2014-05-01

Family

ID=50544595

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/078343 WO2014065215A1 (fr) 2012-10-24 2013-10-18 Électrode transparente, dispositif électronique, et élément électroluminescent organique

Country Status (2)

Country Link
JP (1) JP6187471B2 (fr)
WO (1) WO2014065215A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2014057796A1 (ja) * 2012-10-11 2016-09-05 コニカミノルタ株式会社 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007103174A (ja) * 2005-10-04 2007-04-19 Kuraray Co Ltd エレクトロルミネセンス素子およびその製造方法
JP2011077028A (ja) * 2009-09-04 2011-04-14 Hitachi Displays Ltd 有機ｅｌ表示装置
JP2011249089A (ja) * 2010-05-25 2011-12-08 Panasonic Corp 有機ｅｌ表示パネルとその製造方法、および有機ｅｌ表示装置
WO2013141097A1 (fr) * 2012-03-22 2013-09-26 コニカミノルタ株式会社 Électrode transparente, dispositif électronique et élément organique électroluminescent
WO2013161639A1 (fr) * 2012-04-23 2013-10-31 コニカミノルタ株式会社 Électrode transparente, procédé de fabrication d'électrode transparente, dispositif électronique et élément d'électroluminescence organique
WO2013161750A1 (fr) * 2012-04-25 2013-10-31 コニカミノルタ株式会社 Électrode transparente, dispositif électronique et élément électroluminescent organique

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008106015A (ja) * 2006-10-27 2008-05-08 Chemiprokasei Kaisha Ltd 新規なフェナントロリン誘導体、そのリチウム錯体、それを用いた電子輸送材料、電子注入材料および有機ｅｌ素子
JP5063992B2 (ja) * 2006-11-20 2012-10-31 ケミプロ化成株式会社 新規なジ（ピリジルフェニル）誘導体、それよりなる電子輸送材料およびそれを含む有機エレクトロルミネッセンス素子

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007103174A (ja) * 2005-10-04 2007-04-19 Kuraray Co Ltd エレクトロルミネセンス素子およびその製造方法
JP2011077028A (ja) * 2009-09-04 2011-04-14 Hitachi Displays Ltd 有機ｅｌ表示装置
JP2011249089A (ja) * 2010-05-25 2011-12-08 Panasonic Corp 有機ｅｌ表示パネルとその製造方法、および有機ｅｌ表示装置
WO2013141097A1 (fr) * 2012-03-22 2013-09-26 コニカミノルタ株式会社 Électrode transparente, dispositif électronique et élément organique électroluminescent
WO2013161639A1 (fr) * 2012-04-23 2013-10-31 コニカミノルタ株式会社 Électrode transparente, procédé de fabrication d'électrode transparente, dispositif électronique et élément d'électroluminescence organique
WO2013161750A1 (fr) * 2012-04-25 2013-10-31 コニカミノルタ株式会社 Électrode transparente, dispositif électronique et élément électroluminescent organique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2014057796A1 (ja) * 2012-10-11 2016-09-05 コニカミノルタ株式会社 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子

Also Published As

Publication number Publication date
JPWO2014065215A1 (ja) 2016-09-08
JP6187471B2 (ja) 2017-08-30

Similar Documents

Publication Publication Date Title
JP6287834B2 (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子
JP6015765B2 (ja) 透明電極、電子デバイスおよび有機エレクトロルミネッセンス素子
JP6020472B2 (ja) 透明電極、透明電極の製造方法、電子デバイス及び有機エレクトロルミネッセンス素子
JP6036804B2 (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子
JP6241193B2 (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子
JP6231009B2 (ja) 透明電極、電子デバイスおよび有機エレクトロルミネッセンス素子
JP6241189B2 (ja) 透明電極、透明電極の製造方法、電子デバイス及び有機エレクトロルミネッセンス素子
JP6112107B2 (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子
JP6142645B2 (ja) 透明電極、透明電極の製造方法、電子デバイス及び有機エレクトロルミネッセンス素子
JP5967047B2 (ja) 透明電極、透明電極の製造方法、電子デバイス及び有機エレクトロルミネッセンス素子
JP6295958B2 (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子
JP6432124B2 (ja) 透明電極、電子デバイスおよび有機エレクトロルミネッセンス素子
JP2016058205A (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子
JP6468186B2 (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子
JP6028668B2 (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子
JP6187471B2 (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子
JP6028806B2 (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子
JP6119521B2 (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子
JP6237638B2 (ja) 透明電極、電子デバイス及び有機エレクトロルミネッセンス素子

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13848359

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014543271

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13848359

Country of ref document: EP

Kind code of ref document: A1