WO2014057796A1 - Électrode transparente, dispositif électronique et élément électroluminescent organique - Google Patents

Électrode transparente, dispositif électronique et élément électroluminescent organique Download PDF

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WO2014057796A1
WO2014057796A1 PCT/JP2013/075647 JP2013075647W WO2014057796A1 WO 2014057796 A1 WO2014057796 A1 WO 2014057796A1 JP 2013075647 W JP2013075647 W JP 2013075647W WO 2014057796 A1 WO2014057796 A1 WO 2014057796A1
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group
layer
ring
transparent electrode
organic
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PCT/JP2013/075647
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English (en)
Japanese (ja)
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秀謙 尾関
貴之 飯島
和央 吉田
健 波木井
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コニカミノルタ株式会社
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Priority to JP2014540792A priority Critical patent/JP6028806B2/ja
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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

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 using the transparent electrode.
  • Organic electroluminescent elements (hereinafter also referred to as “organic EL elements” and “organic electroluminescent elements”) using organic electroluminescence (hereinafter abbreviated as EL) are several V to several tens V. It is a thin-film type complete solid-state device capable of emitting light at a low voltage, 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 Laid-Open Patent Publication Nos. 2002-15623 and 2006-164961 discuss materials that aim to reduce resistance by laminating ITO and silver.
  • ITO uses an indium element which is a rare metal, the cost as a material is high, and in order to reduce the resistance, it is necessary to perform an annealing process at about 300 ° C. after film formation.
  • 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.
  • Patent Document 2 discloses a transparent conductive film using a metal material such as zinc (Zn) or tin (Sn) which is inexpensive and easily available instead of indium (In) as a raw material.
  • Zn zinc
  • Sn tin
  • 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. It has also been found that SnO 2 -based transparent conductive films containing tin have a problem that processing by etching is difficult.
  • an organic electroluminescence element in which a silver film having a high transparency and a thin film with a layer thickness of 15 nm is used as a cathode (see, for example, Patent Document 3).
  • a silver film having a high transparency and a thin film with a layer thickness of 15 nm is used as a cathode.
  • the formed silver film is still thick as an electrode, the light transmittance (transparency) as a transparent electrode is not sufficient, and migration (movement of atoms) ).
  • the silver film is made thinner, it becomes difficult to maintain the conductivity and the like, and therefore development of a technique that achieves both light transmittance and conductivity is eagerly desired.
  • the present invention has been made in view of the above problems, and the problem to be solved is a transparent electrode having sufficient conductivity and light transmittance and excellent in durability (light transmittance stability), and the transparent It is to provide an electronic device and an organic electroluminescence element including an electrode.
  • the inventor has a configuration in which an intermediate layer and a conductive layer provided adjacent to the intermediate layer are stacked, and the intermediate layer contains an organic compound having a halogen atom.
  • the conductive layer is composed of silver as a main component, and can achieve both excellent conductivity and light transmittance by a transparent electrode having a high light transmittance and a low sheet resistance value that have not been conventionally used. And it discovered that the transparent electrode excellent in durability was realizable, and came to this invention.
  • a transparent electrode having an intermediate layer and a conductive layer provided adjacent to the intermediate layer,
  • the light transmittance at a wavelength of 550 nm is 50% or more and the sheet resistance value is 20 ⁇ / ⁇ or less
  • the intermediate layer contains an organic compound having a halogen atom
  • the conductive layer is composed mainly of silver.
  • X represents a halogen atom
  • m1 to m3 each represents 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.
  • the transparent electrode according to item.
  • An electronic device comprising the transparent electrode according to any one of items 1 to 5.
  • An organic electroluminescence device comprising the transparent electrode according to any one of items 1 to 5.
  • a transparent electrode having sufficient electrical conductivity and light transmittance and having excellent durability (light transmittance stability), high light transmittance, driving at a low voltage, and durability It is possible to provide an electronic device and an organic electroluminescence element excellent in the above.
  • a conductive layer containing silver as a main component is provided above the intermediate layer, and the intermediate layer has atoms having an affinity for silver atoms.
  • This is a configuration in which a compound (hereinafter referred to as a “silver affinity compound”) is contained.
  • the silver atoms constituting the conductive layer interact with the silver affinity compound contained in the intermediate layer, and on the surface of the intermediate layer. This reduces the diffusion distance of silver atoms in and reduces the aggregation of silver at specific locations.
  • the silver atoms first form a two-dimensional nucleus on the surface of the intermediate layer containing a compound having an atom having an affinity for silver atoms, and form a two-dimensional single crystal layer around it.
  • the film is formed by growth-type (Frank-van der Merwe: FM type) film growth.
  • 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- It is considered that the island-like film is easily formed by the film growth using the Weber (VW type). However, in the present invention, such an island-like growth is prevented by the silver affinity compound contained in the intermediate layer, and the layer-like is formed. It is assumed that growth will be promoted.
  • a conductive layer having a uniform layer thickness can be obtained while being a thin film.
  • a transparent electrode in which conductivity was ensured while maintaining light transmittance with a thinner layer thickness could be realized.
  • 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 first example of an organic EL element to which the transparent electrode of the present invention is applied Schematic sectional view showing a second example of an organic EL element to which the transparent electrode of the present invention is applied
  • the schematic sectional drawing which shows an example of the illuminating device which enlarged the light emission surface using the organic EL element provided with the transparent electrode of this invention.
  • the transparent electrode of the present invention is a transparent electrode having an intermediate layer and a conductive layer provided adjacent to the intermediate layer, having a light transmittance of 50% or more at a wavelength of 550 nm and a sheet resistance of 20 ⁇ / ⁇ , the intermediate layer contains an organic compound having a halogen atom, the conductive layer is composed mainly of silver, and has both sufficient conductivity and light transmission, And the transparent electrode excellent in durability (light transmittance stability) is realizable.
  • This feature is a technical feature common to the inventions according to claims 1 to 7.
  • the halogen atom contained in the organic compound is a bromine atom or an iodine atom, from the viewpoint of further manifesting the intended effect of the present invention.
  • the organic compound having a halogen atom contained in the intermediate layer is preferably a halogenated aryl compound having a structure represented by the general formula (1). Furthermore, the compound having a structure represented by the general formula (1) is preferably a halogenated aryl compound having a structure represented by the general formula (2).
  • the layer configuration of the transparent electrode of the present invention is as follows. It is preferable that after the intermediate layer and the conductive layer are laminated on the substrate, a second intermediate layer is further formed on the conductive layer, and the conductive layer is sandwiched between the two intermediate layers. one of. Thereby, the electroconductivity and durability of the transparent electrode which has silver as a main component can be improved.
  • 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 shown in FIG. 1A has a two-layer structure in which an intermediate layer 1a is provided and a conductive layer 1b is laminated on the intermediate layer 1a.
  • the layers 1b are provided in this order.
  • the intermediate layer 1a according to the present invention is a layer containing an organic compound having a halogen atom, and the conductive layer 1b according to the present invention laminated thereon is composed mainly of silver. It is characterized by being a layer.
  • 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.
  • 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 transparent electrode 1 having a laminated structure including the intermediate layer 1a and the conductive layer 1b formed thereon the upper portion of the conductive layer 1b is further covered with a protective layer.
  • the structure may be a structure 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 transparent 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, or from an inorganic or organic material. Or a hybrid film in which these films are combined may be formed.
  • 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 barrier film 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, and 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.
  • silicon dioxide, Silicon nitride or the like can be used.
  • the method for producing the barrier film is not particularly limited.
  • 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 is a layer formed using a halogen compound having a halogen atom.
  • the film forming method 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. Examples thereof include a method using a dry process such as resistance heating, EB method (electron beam method), sputtering method, CVD method, or the like. Of these, the vapor deposition method is preferably applied.
  • the intermediate layer 1a contains 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.
  • a compound in which the halogenated aryl compound represented by the general formula (1) further has a structure formed from seven phenyl groups represented by the following general formula (2) as a mother nucleus is preferable.
  • 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 more preferable one is , Bromine atom or 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 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 has a configuration in which the conductive layer 1b composed mainly of silver is provided on the intermediate layer 1a configured to contain an organic compound having a halogen atom. It is.
  • the conductive layer 1b is formed on the intermediate layer 1a, the silver atoms constituting the conductive layer 1b interact with the halogen atoms constituting the intermediate layer 1a, so that the silver atom intermediate layer 1a is formed.
  • the diffusion distance on the surface is reduced, and the formation of silver aggregates can be suppressed.
  • the conductive layer 1b composed of silver as a main component
  • a thin film is grown in a nucleus growth type (Volume-Weber: VW type), so that silver particles are easily isolated in an island shape.
  • VW type nucleus growth type
  • the layer thickness is thin, it is difficult to obtain conductivity, and the sheet resistance value is increased. Therefore, in order to ensure conductivity, it is necessary to increase the layer thickness to some extent. However, if the layer thickness is increased, the light transmittance is lowered, which is not suitable as a transparent electrode.
  • the transparent electrode 1 having a configuration defined in the present invention, silver aggregation is suppressed on the intermediate layer 1a containing an organic compound having a halogen atom due to the interaction between the halogen atom and silver.
  • a thin film is grown by 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.
  • each of the above materials used as the intermediate layer 1a is 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 cross-sectional configuration diagram 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.
  • 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 3 configured using the transparent electrode 1, an organic material, and the like, and 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 generated light (hereinafter referred to as emission light h) from at least the transparent substrate 13 side.
  • the layer structure of the organic EL element 100 will be described.
  • the present invention is not limited to these exemplified configuration examples, and may have a general layer structure.
  • 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 / the hole transport layer 3b / the light emitting layer 3c / the electron transport layer 3d / the electron injection layer are sequentially formed from the transparent electrode 1 side as the anode. 3e is laminated.
  • 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 3 may be laminated at a necessary place, if necessary, such as a hole blocking layer or 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 a portion where the light emitting functional layer 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 provided with a sealing material 17 to be described later on the transparent substrate 13 for the purpose of preventing deterioration of the light emitting functional layer 3 mainly composed of an organic material or the like. And a 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 so as to be exposed from the encapsulant 17 while being insulated from each other by the light emitting functional layer 3.
  • the details of the main layers for constituting the organic EL element 100 shown in FIG. 2 are described in detail with respect to 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 3, The functional layer, 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 is provided.
  • the transparent base material 11 having light transmittance is used.
  • the transparent electrode is the transparent electrode 1 of the present invention that has already been described in detail, and in order from the transparent substrate 13 side, an intermediate layer 1a containing an organic compound having a halogen atom and a conductive material mainly composed of silver.
  • the layer 1b is 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 3, and includes, for example, a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof. It is composed of Specifically, 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. Further, the sheet resistance as the counter electrode 5a is preferably several hundred ⁇ / ⁇ or less, and the layer thickness is usually selected within a range of 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the organic EL element 100 sometimes takes out the emitted light h from the counter electrode 5a side, by selecting a conductive material having good light transmittance among the conductive materials described above, What is necessary is just to comprise the counter electrode 5a.
  • the light emitting layer 3c constituting the organic EL element 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 included 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 provide 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 is configured by mixing a phosphorescent light emitting material and a fluorescent light emitting material (hereinafter also referred to as a fluorescent dopant or a fluorescent compound). It may be.
  • the structure of the light emitting layer 3 c includes 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” or “dopant compound”), and causes the light emitting material to emit light. It is preferable.
  • a host compound hereinafter also referred to as “light emitting host”
  • a light emitting material hereinafter also referred to as “light emitting dopant compound” 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.
  • a known host compound may be used alone, or a plurality of types may be used.
  • a plurality of types of host compounds it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient.
  • 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.). Although defined as being a compound of 01 or more, a preferable phosphorescence quantum yield is 0.1 or more.
  • 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 from known compounds used for the light-emitting layer of a general organic EL device, but preferably contains a group 8 to 10 metal in the periodic table of elements. More preferred are iridium compounds, more preferably iridium compounds, osmium compounds, platinum compounds (platinum complex compounds), and rare earth complexes, and most preferred are iridium compounds.
  • 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 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 P2.
  • 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 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 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 such a substituent is the same as the substituent which 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 that 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 heterocyclic ring together 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 is a substituent which the ring represented by A 1 in the general formula (A) may have. Synonymous with group.
  • examples of the 6-membered aromatic hydrocarbon ring formed by Z 1 together with C—C include a benzene ring.
  • 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 that 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.
  • phosphorescent metal complex The above phosphorescent compound (hereinafter also referred to as “phosphorescent metal complex”) is disclosed in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, pp. 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, pages 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, pages 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and the methods described in references in these documents should be applied. Can be synthesized.
  • 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 (the hole injection layer 3a and the electron injection layer 3e) 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 details are described in Volume 2, Chapter 2, “Electrode Materials” (pages 123 to 166) of Volume 2 of the Forefront (November 30, 1998 issued by NTS).
  • 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.
  • JP-A-9-45479 JP-A-9-260062, JP-A-8-288069 and the like.
  • a phthalocyanine layer typified by copper phthalocyanine
  • 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 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 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 transport layer 3e and a hole blocking layer (not shown) 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 constituting the intermediate layer 1a described above may be used.
  • the electron transport layer 3d that also serves as the electron injection layer 3e the same material as that of the intermediate layer 1a described above may be used.
  • the blocking layer (hole blocking layer and electron blocking layer) is a layer provided as necessary in addition to the constituent layers of the light emitting functional layer 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. Hole blocking (hole block) layer and the like.
  • 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 the range not affected by extraction of the emitted light h 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 so as to cover at least the light emitting functional layer 3 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. In addition, an electrode may be provided on the sealing material 17 so that the transparent electrode 1 and the terminal portion of the counter electrode 5a of the organic EL element 100 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. 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 substrate material as described above 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 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 3 in the organic EL element 100 such as moisture and oxygen.
  • a material for example, an inorganic material such as silicon oxide, silicon dioxide, or silicon nitride is 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.
  • the intermediate layer 1a containing an organic compound having a halogen atom is formed on the transparent substrate 13 by appropriately selecting a method such as a vapor deposition method so that the layer thickness is 1 ⁇ m or less, preferably in the range of 10 to 100 nm. To do.
  • 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.
  • the hole injection layer 3a, the hole transport layer 3b, the light emitting layer 3c, the electron transport layer 3d, and the electron injection layer 3e are formed in this order on the transparent electrode 1 to form the light emitting functional layer 3.
  • the film formation of each of these layers includes spin coating, casting, ink jet, vapor deposition, and printing, but vacuum vapor deposition is easy because a homogeneous film is easily obtained and pinholes are difficult to generate.
  • the method or spin coating method is particularly preferred. 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. It 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 5 a is patterned in a shape in which a terminal portion is drawn from the upper side of the light emitting functional layer 3 to the periphery of the transparent substrate 13 while maintaining the insulating state with respect to the transparent electrode 1 by the light emitting functional layer 3.
  • the organic EL element 100 is obtained.
  • a sealing material 17 that covers at least the light emitting functional layer 3 is provided 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.
  • an organic EL element having a desired configuration can be produced on the transparent substrate 13.
  • the transparent substrate 13 is taken out from the vacuum atmosphere in the middle and is different.
  • a film forming method 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 a counter electrode serving as a light emitting functional layer 3 and a cathode on the top. 5a. For this reason, the extraction efficiency of the emitted light h 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 cross-sectional configuration diagram illustrating 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 h 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 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 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 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.
  • the sheet resistance as the counter electrode 5b 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.
  • this organic EL element 200 is comprised so that emitted light h 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 having the above configuration 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 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 organic EL element 200 shown in FIG. 3 described above uses the transparent electrode 1 of the present invention having both conductivity and light transmission as a cathode, and a light emitting functional layer 3 and a counter electrode 5b serving as an anode are formed thereon. This is a configuration 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 extraction efficiency of h. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.
  • FIG. 4 is a cross-sectional view showing a third 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 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. 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, and the counter electrode 5c serving as an anode, the light emitting functional layer 3, and the transparent electrode 1 serving as a cathode are laminated in this order from the substrate 131 side. .
  • the transparent electrode 1 the transparent electrode 1 of the present invention described above is used.
  • the organic EL element 300 is configured to extract the emitted light h 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 3 can employ various functional layers as necessary, as described in the first example, but the intermediate layer 1a of the transparent electrode 1 can be used.
  • the electron injection layer and the hole blocking layer are not provided between the electron transport layer 3d serving also as the conductive layer 1b and the conductive layer 1b of the transparent electrode 1.
  • the portion where the light emitting functional layer 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.
  • the sheet resistance as the counter electrode 5c is preferably several hundred ⁇ / ⁇ or less, and the layer thickness is usually selected in the range of 5 nm to 5 ⁇ m, preferably 5 nm to 200 nm.
  • the material constituting the counter electrode 5c may be light among the conductive materials described above.
  • 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 transporting layer 3d having the electron injecting property constituting the uppermost part of the light emitting functional layer 3 is used as the intermediate layer 1a, and the conductive layer 1b is provided thereon.
  • the transparent electrode 1 comprising 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 h from the light source.
  • the counter electrode 5c is made of a light-transmissive electrode material, the emitted light h 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 the electron injection property, 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 3 may be an anode.
  • the light emitting functional layer 3 is formed in order from the counter electrode 5c (cathode) side on the substrate 131, for example, electron injection layer 3e / electron transport layer 3d / light emitting layer 3c / hole transport layer 3b / hole injection layer 3a.
  • 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 cross-sectional configuration diagram 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 light emission functional layer 3 which comprises the organic EL element 100 on the transparent electrode 1, hole injection layer 3a / hole transport layer 3b / light emission layer 3c / electron transport layer 3d / electron injection layer
  • a configuration in which 3e is sequentially laminated 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 51 were prepared 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 40 and the transparent electrodes 49 to 51 are transparent electrodes having a laminated structure of an intermediate layer and a conductive layer.
  • a transparent electrode having a three-layer structure 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 layer thickness of 5 ⁇ m.
  • Transparent electrodes 2 to 4 were prepared in the same manner except that the thickness of the conductive layer was changed to 8 nm, 10 nm, and 15 nm, respectively, in the production of the transparent electrode 1.
  • 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 25 nm by a sputtering method. On top of this, a conductive layer was formed in the production of the transparent electrode 1. A transparent electrode 5 was produced by depositing a conductive layer made of silver (Ag) having a layer thickness of 8 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 25 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 with a layer thickness of 8 nm is 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 are laminated on top of this. It was.
  • a transparent non-alkali glass base material is fixed to a base material holder of a commercially available vacuum deposition apparatus, and the exemplary compound (1) of the present invention is filled in a resistance heating boat made of tantalum. 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 the exemplary compound (1) was heated by energization, and the deposition rate was within a range of 0.1 to 0.2 nm / second. It vapor-deposited on the base material and the intermediate
  • 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 is 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 are stacked on the intermediate layer 1a.
  • a transparent electrode 9 was obtained.
  • Transparent electrodes 10 to 13 were produced in the same manner except that the thickness of the silver layer of the conductive layer 1b was changed to 5 nm, 8 nm, 10 nm, and 20 nm in the production of the transparent electrode 9.
  • the intermediate layer 1a and the conductive layer 1b are formed on the base material in the same manner, and then further on the conductive layer 1b.
  • the second intermediate layer 1c is formed by the same method as the intermediate layer 1a, and the conductive layer 1b shown in FIG. 1B is sandwiched between the two intermediate layers 1a and 1c.
  • Transparent electrodes 41 to 48 were prepared.
  • transparent electrodes 49 to 51 In the production of the transparent electrodes 18 to 20, transparent electrodes 49 to 51 were produced in the same manner except that the base material was changed from non-alkali glass to a PET (polyethylene terephthalate) film.
  • 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 ratio of transmittance (initial transmittance ⁇ transmittance after 150 hours) / initial transmittance ⁇ 100
  • the change ratio of the transmittance of each transparent electrode was expressed as a relative value with the change ratio of the transparent electrode 8 being 100.
  • the transparent layer of the present invention in which a conductive layer mainly composed of silver (Ag) is provided on an intermediate layer formed using an organic compound having a halogen atom.
  • Each of the electrodes 9 to 44 has a light transmittance of 51% or more and a sheet resistance value of 20 ⁇ / ⁇ or less. This is because by forming the intermediate layer using an organic compound having a halogen atom, aggregation of the silver film formed thereon and generation of mottle can be suppressed, and a silver film having a certain thickness is formed. Even if formed, aggregation of silver was suppressed, and both high light transmittance and low sheet resistance value could be achieved.
  • 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.
  • 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 3 was filled in each heating boat in a vacuum evaporation system in the optimal quantity for film-forming of each layer.
  • a heating boat what was produced with the resistance heating material made from tungsten was used.
  • 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 3 shown below is heated by sequentially energizing and heating a heating boat containing each material. A film was formed.
  • 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 film was formed at a film forming speed of 0.3 to 0.5 nm / second, using a light transmissive counter electrode 5a made of ITO having a layer thickness of 150 nm as a cathode.
  • 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.
  • 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.
  • the transparent electrode 1 serving as the anode and the counter electrode 5a serving as the cathode are insulated from each other by the light emitting functional layer 3 from the hole transport / injection layer 31 to the electron injection layer 35. The part 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 h 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 to 51 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 Optics was used. It represents that it is so preferable that the numerical value of the obtained drive voltage is small.
  • Change ratio of transmittance (initial transmittance ⁇ transmittance after 150 hours) / initial transmittance ⁇ 100
  • the change ratio of the transmittance of each light-emitting panel was displayed as a relative value with the change ratio of the light-emitting panel 8 being 100.
  • each of the light-emitting panels 9 to 51 of the present invention using the transparent electrode 1 of the present invention as the anode of the organic EL element has a light transmittance of 56% or more, and The drive voltage is suppressed to 4.1 V or less.
  • 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 4.1V.
  • 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 is capable of high-luminance light emission at a low driving voltage and excellent in durability. confirmed. 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 transmissivity, and has a transparent electrode excellent in durability (light transmittance stability), the transparent electrode, and is used for an electronic device and an organic electroluminescence element. It can be suitably used as a transparent electrode.

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  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention traite le problème de la fourniture d'une électrode transparente qui associe une conductivité suffisante à des propriétés de transmission de la lumière et a une excellente durabilité (stabilité de transmittance), d'un dispositif électronique pourvu de l'électrode transparente, et d'un élément électroluminescent organique. Cette électrode transparente comprend une couche intermédiaire et une couche conductrice disposée de sorte à être attenante à la couche intermédiaire, et est caractérisée en ce que l'électrode transparente a une transmittance égale ou supérieure à 50 % à une longueur d'onde de 550 nm et une résistivité de couche égale ou inférieure à 20 Ω/□, la couche intermédiaire comprend un composé organique qui a un atome d'halogène, et la couche conductrice est constituée d'argent comme constituant principal.
PCT/JP2013/075647 2012-10-11 2013-09-24 Électrode transparente, dispositif électronique et élément électroluminescent organique WO2014057796A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
JP2015220415A (ja) * 2014-05-21 2015-12-07 コニカミノルタ株式会社 有機電界発光素子および有機電界発光素子の製造方法

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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
WO2012008281A1 (fr) * 2010-07-13 2012-01-19 東レ株式会社 Elément électroluminescent
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

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WO2014065215A1 (fr) * 2012-10-24 2014-05-01 コニカミノルタ株式会社 Électrode transparente, dispositif électronique, et élément électroluminescent organique
JP5967047B2 (ja) * 2012-10-24 2016-08-10 コニカミノルタ株式会社 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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2012008281A1 (fr) * 2010-07-13 2012-01-19 東レ株式会社 Elément électroluminescent
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
JP2015220415A (ja) * 2014-05-21 2015-12-07 コニカミノルタ株式会社 有機電界発光素子および有機電界発光素子の製造方法

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