JP2014213558A - Transparent electrode, electronic device, and organic electroluminescence element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent electrode which has both sufficient electric conductivity and sufficient optical transparency, and also is excellent in durability.SOLUTION: A transparent electrode (1) comprises an electrically conductive layer (1b) and at least one intermediate layer (1a) provided adjacent to the electrically conductive layer (1b). The electrically conductive layer (1b) comprises silver as the main component, and the intermediate layer (1a) contains a one, two, three, or four coordinate metal complex.

Description

  The present invention relates to a transparent electrode, an electronic device, and an organic electroluminescence element. More specifically, the present invention relates to a transparent electrode that has both conductivity and light transmittance, and is excellent in durability, and an electronic device and an organic electroluminescence element including the transparent electrode.

  An organic EL element (also referred to as an organic electroluminescence element) using organic electroluminescence (hereinafter referred to as EL) is a thin-film type that can emit light at a low voltage of several volts to several tens of volts. It is a solid element 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 configuration in which a light emitting layer made of an organic material is disposed between two electrodes, and emitted light generated in the light emitting layer passes through the electrode and is extracted outside. For this reason, at least one of the two electrodes is configured as a transparent electrode.

As the transparent electrode, an oxide semiconductor material such as indium tin oxide (SnO ₂ -In ₂ O ₃ : Indium Tin Oxide: ITO) is generally used. Studies aiming at resistance have also been made (see, for example, Patent Documents 1 and 2). However, since ITO uses rare metal indium, the material cost is high, and it is necessary to anneal at about 300 ° C. after film formation in order to reduce resistance.

Then, the technique (for example, refer patent document 3) which aimed at coexistence of the transmittance | permeability and electroconductivity by comprising a thin film using the alloy of silver (Ag) and magnesium (Mg) with high electrical conductivity. Short wavelength by constructing a thin film using an alloy of silver and aluminum, a technique for constructing a thin film using zinc (Zn) and tin (Sn), which are inexpensive and easily available, as raw materials A technique (for example, see Patent Document 5) that transmits light in a region has been proposed.
However, the resistance value of the electrode disclosed in Patent Document 3 is at most about 100Ω / □, which is insufficient as the conductivity of the electrode. In addition, since magnesium is easily oxidized, there is a problem that deterioration with time is remarkable. there were.
In the electrode disclosed in Patent Document 4, a ZnO-based thin film containing Zn, which does not provide a sufficient resistance value, reacts with water and its performance is likely to fluctuate. An SnO _2- based thin film containing Sn is There were problems such as difficulty in etching.
The resistance value of the electrode disclosed in Patent Document 5 is at most 128 Ω / □, and it cannot be said that the electrode is a transparent electrode having sufficient conductivity and light transmittance.

On the other hand, an organic EL element in which silver is deposited as a cathode with a film thickness of 15 nm is disclosed (for example, see Patent Document 6).
However, in the silver film disclosed in Patent Document 6, when the film is thinned, it is difficult to maintain electrode characteristics because silver easily migrates, and development of a new technique is desired.

JP 2002-015623 A Japanese Unexamined Patent Publication No. 2006-164961 JP 2006-344497 A JP 2007-031786 A JP 2009-151963 A US Patent Application Publication No. 2011/0260148

  The present invention has been made in view of the above-described problems and circumstances, and a solution to the problem is a transparent electrode having both sufficient conductivity and light transmission, and excellent durability, and an electronic device including the transparent electrode And providing an organic electroluminescent device.

  As a result of studying the cause of the above problem and the like in order to solve the above problems, the present inventor has a conductive layer and at least one intermediate layer provided adjacent to the conductive layer. However, it is composed of silver as a main component, and the intermediate layer contains one-coordinate, two-coordinate, three-coordinate or four-coordinate metal complex, so that it has excellent conductivity and light. The present inventors have found that a transparent electrode having both good transmittance and excellent durability can be realized, and the present invention has been achieved.

  That is, the said subject which concerns on this invention is solved by the following means.

1. In a transparent electrode comprising a conductive layer and at least one intermediate layer provided adjacent to the conductive layer,
The conductive layer is composed mainly of silver,
The said intermediate | middle layer contains the metal complex which is either 1 coordination, 2 coordination, 3 coordination, and 4 coordination, The transparent electrode characterized by the above-mentioned.

  2. 2. The transparent electrode according to item 1, wherein the metal complex is a compound having a ligand of an organic compound.

  3. Item 3. The transparent electrode according to Item 1 or 2, wherein the charge in the entire molecule of the metal complex is neutral.

  4). The metal complex has a transition metal atom, and the coordination atom in the ligand of the metal complex is any one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a carbene carbon atom. The transparent electrode according to any one of items 1 to 3 above.

  5. 5. The transparent electrode according to item 4, wherein the metal complex is a compound having a structure represented by any one of the following general formulas (1) to (5).

  In the general formulas (1) to (5), M represents a transition metal atom, and forms a covalent bond and a coordinate bond with the polydentate ligand. Multidentate ligands may combine with each other to form tridentate or tetradentate ligands. L represents an auxiliary ligand and forms a covalent bond or a coordinate bond with M. n represents an integer of 0 to 2. When n is 1, L may be a monodentate ligand or a polydentate ligand, and when n is 2, L may be the same or different, but the charge in the whole molecule Is neutral.

  6). 6. The transparent electrode according to item 5, wherein the metal complex represented by the general formula (1) is a compound having a structure represented by the following general formula (1-1).

In general formula (1-1), M represents a transition metal atom. R ₁ and R ₂ each independently represents a substituent. L ₁ and L ₂ represent a ligand that forms a covalent bond or a coordinate bond with M, and may bond to each other to form a bidentate ligand.

  7). 6. The transparent electrode according to item 5, wherein the metal complex represented by the general formula (2) is a compound having a structure represented by the following general formula (2-1).

In general formula (2-1), M represents a transition metal atom. R ₃ and R ₄ each independently represents a substituent. R _{5 to} R ₁₂ each independently represent a substituent and may be bonded to each other to form a ring.

  8). 6. The transparent electrode according to item 5, wherein the metal complex represented by the general formula (3) is a compound having a structure represented by the following general formula (3-1).

In general formula (3-1), M represents a transition metal atom. X _{1 to} X ₄ each independently represent —CR ₂₁ or a nitrogen atom, and R ₂₁ represents a hydrogen atom or a substituent. R _{13 to} R ₂₀ each independently represent a substituent and may be bonded to each other to form a ring.

  9. 6. The transparent electrode according to item 5, wherein the metal complex represented by the general formula (4) is a compound having a structure represented by the following general formula (4-1).

In general formula (4-1), M represents a transition metal atom. R _{22 to} R ₂₅ each independently represent a substituent. Ring A represents a 5-membered or 6-membered aromatic heterocyclic ring formed together with a nitrogen atom and a carbon atom, and may further have a substituent, and these substituents are bonded to each other to form a ring. May be. L ₃ and L ₄ represent a ligand that forms a covalent bond or a coordinate bond with M, and may bond to each other to form a bidentate ligand.

  10. 6. The transparent electrode according to item 5, wherein the metal complex represented by the general formula (5) is a compound having a structure represented by the following general formula (5-1).

In general formula (5-1), M represents a transition metal atom. R _{26 to} R ₂₉ each independently represent a substituent, and may be bonded to each other to form a ring. X ₅ and X ₆ each independently represent —CR ₃₀ or a nitrogen atom, and R ₃₀ represents a hydrogen atom or a substituent. R ₃₁ represents a hydrogen atom or a substituent. L ₅ and L ₆ each represent a ligand that forms a covalent bond or a coordinate bond with M, and may bond to each other to form a bidentate ligand.

  11. The transition metal atom is any one selected from Co (II), Ni (II), Cu (II), Pd (II), Pt (II) and Au (III). The transparent electrode according to any one of Items 4 to 10.

  12 The transparent electrode according to item 11, wherein the transition metal atom is any one selected from Cu (II), Pd (II), Pt (II) and Au (III).

  13. 13. The transparent electrode according to item 12, wherein the transition metal atom is any one selected from Pd (II), Pt (II) and Au (III).

  14 14. The transparent electrode according to item 13, wherein the transition metal atom is Au (III).

15. The intermediate layer is composed of two layers of a first intermediate layer and a second intermediate layer in order from the conductive layer side,
The first intermediate layer is a layer containing the metal complex;
The second intermediate layer is a layer containing an aromatic heterocyclic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity;
15. The transparent electrode according to any one of items 1 to 14, wherein a thickness of the first intermediate layer is in a range of 0.5 to 10 nm.

  16. The conductive layer is formed by a wet method using a conductive ink containing silver as a main component and containing an organic solvent, according to any one of items 1 to 15, The transparent electrode as described.

  17. An electronic device comprising the transparent electrode according to any one of items 1 to 16.

  18. An organic electroluminescence device comprising the transparent electrode according to any one of items 1 to 16.

  By the above-mentioned means of the present invention, it is possible to provide a transparent electrode having sufficient conductivity and light transmittance and having excellent durability, an electronic device having the transparent electrode, and an organic electroluminescence element.

  The expression mechanism and action mechanism of the effect of the present invention are not clear, but are presumed as follows.

In the transparent electrode of the present invention, a conductive layer composed mainly of silver is provided on the intermediate layer, and the intermediate layer is a metal having any one of 1 to 4 coordinates. It is the structure that the complex is contained.
In a low-coordination metal complex of 1-coordinate to 4-coordinate, the periphery of the central metal is not crowded by the ligand and is often exposed. As a general example, FIG. Examples thereof include metal complexes having planarity as shown in a). In the planar metal complex, since the surface of the central metal in the vertical axis direction is exposed, as shown in FIG. 9B, this space is used as a coordination site, and a new ligand is axially coordinated with the central metal, It is known to form complexes.
On the other hand, in a metal complex having a coordination number of five or more coordinations, the periphery of the central metal is crowded with a plurality of or bulky ligands, so that as shown in FIG. Has a three-dimensional structure, and there are few exposed portions of the central metal surface.

That is, a low-coordination metal complex of 1-coordinate to 4-coordinate has sufficient space around the central metal for interaction with silver which is the main component of the conductive layer. . Thereby, when forming a conductive layer on the upper part of the intermediate layer, the silver atoms constituting the conductive layer interact with the central metal of the metal complex contained in the intermediate layer, and on the surface of the intermediate layer. The diffusion distance of silver atoms was reduced, and the aggregation of silver at specific locations could be suppressed.
On the other hand, in the case of a metal complex having a coordination number of five or more, since there is little space for interaction with silver, the interaction with silver is reduced and aggregation of silver can be suppressed. Therefore, it is considered that the film quality is deteriorated.

That is, the silver atom first forms a two-dimensional nucleus on the surface of the intermediate layer containing the silver affinity compound having an atom having an affinity for the silver atom, and forms a two-dimensional single crystal layer around it. The film is formed by the layer growth type (Frank-van der Merwe: FM type) film growth.
In general, an island-like growth type (Volume-Weber) in which silver atoms adhering to the surface of the intermediate layer are combined while diffusing on the surface to form a three-dimensional nucleus and grow into a three-dimensional island shape. It is considered that the film is easily formed in an island shape by the film growth in the VW type.
However, in the present invention, when the island-like growth is suppressed and the layer-like growth is promoted by the metal complex having any one of 1-coordinate to 4-coordinate that is a silver affinity compound contained in the intermediate layer. Inferred.
Accordingly, it is possible to obtain a conductive layer having a uniform film thickness even though the film thickness is small. As a result, while maintaining light transmittance with a thinner film thickness, conductivity can be ensured, and furthermore, a transparent electrode excellent in durability can be obtained.

  In addition, the whole structure (coordination mode) of a metal complex is determined by the coordination number of the ligand and center metal which are comprised. Therefore, a desired metal complex having a sufficient space for causing an interaction with silver can be formed by appropriately selecting these types and combinations.

Schematic sectional view showing an example of the configuration of the transparent electrode of the present invention Schematic sectional view showing a first example of an organic EL device using the transparent electrode of the present invention Schematic sectional view showing a second example of an organic EL device using the transparent electrode of the present invention Schematic sectional view showing a third example of an organic EL element using the transparent electrode of the present invention Schematic cross-sectional view of an illuminating device having a light-emitting surface enlarged using an organic EL element having a transparent electrode of the present invention Schematic sectional view showing an example of the configuration of the transparent electrode of the present invention Schematic cross-sectional view of a light-emitting panel equipped with an organic EL device produced in the examples Schematic cross-sectional view of a light-emitting panel equipped with an organic EL device produced in the examples Schematic diagram showing the coordination mode of metal complexes

  The transparent electrode of the present invention comprises a conductive layer and at least one intermediate layer provided adjacent to the conductive layer, and the conductive layer is composed mainly of silver, It is characterized by containing a metal complex that is one-coordinate, two-coordinated, three-coordinated or tetracoordinated. This feature is a technical feature common to the inventions according to claims 1 to 18.

  As an embodiment of the present invention, it is preferable that the metal complex contained in the intermediate layer is a compound having a ligand of an organic compound from the viewpoint that various metal complexes can be formed.

  As an embodiment of the present invention, it is preferable that the charge in the whole molecule of the metal complex contained in the intermediate layer is neutral from the viewpoint of film formation by vacuum deposition.

  As an embodiment of the present invention, it is preferable that the metal complex contained in the intermediate layer is a compound having a transition metal atom, since the atomic radius is large and the effect of easily interacting with silver is obtained. . Furthermore, it is more preferable that the coordination atom in the ligand of the metal complex is any one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a carbene carbon atom.

  As an embodiment of the present invention, the metal complex contained in the intermediate layer is preferably a compound having a structure represented by the general formulas (1) to (5). ), (2-1), (3-1), (4-1) and (5-1), the ligand itself has high planarity, and as a result The entire metal complex is also preferable because it has high planarity.

  As an embodiment of the present invention, from the viewpoint of easily forming a planar metal complex, the transition metal atom which is the central metal of the metal complex contained in the intermediate layer is Co (II), Ni (II), Cu (II ), Pd (II), Pt (II) and Au (III), preferably Cu (II), Pd (II), Pt (II) and Au (III). More preferably, any one selected from the group consisting of Pd (II), Pt (II) and Au (III) is more preferable, and Au (III) is more preferable. Most preferred.

As an embodiment of the present invention, the intermediate layer is composed of two layers of a first intermediate layer and a second intermediate layer in order from the conductive layer side, and the first intermediate layer is a layer containing a metal complex, The second intermediate layer is a layer containing an aromatic heterocyclic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity, and the thickness of the first intermediate layer is in the range of 0.5 to 10 nm. It is preferable to be within.
When the intermediate layer is composed of two layers, the first intermediate layer and the second intermediate layer, the first intermediate layer has a thin thickness of 0.5 to 10 nm, so that it is a complete continuous film. There may be a portion where the conductive layer is in contact with the second intermediate layer. As a result, the silver of the conductive layer interacts with both the nitrogen atom contained in the second intermediate layer and the central metal of the metal complex contained in the first intermediate layer, thereby further suppressing the aggregation of silver. An effect can be obtained.

  As an embodiment of the present invention, it is preferable that the conductive layer is formed by a wet method using a conductive ink containing silver as a main component and containing an organic solvent, because the manufacturing cost can be reduced. .

  Moreover, the transparent electrode of this invention can be comprised suitably for an electronic device and an organic electroluminescent element.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" showing a numerical range is used by the meaning containing the numerical value described before and behind that as a lower limit and an upper limit.

[First Embodiment]
<< 1. Transparent electrode >>
<Configuration of transparent electrode>
As shown in FIG. 1, the transparent electrode 1 has a two-layer structure in which an intermediate layer 1a and a conductive layer 1b are stacked on the intermediate layer 1a. 1a and conductive layer 1b are provided in this order. The intermediate layer 1a is a layer that is configured to contain a metal complex that is any one of 1-coordinate to 4-coordinate, and the conductive layer 1b is a layer that is mainly composed of silver. .
The main component of the conductive layer 1b is a component having the highest component ratio among the components constituting the conductive layer 1b. The composition ratio of silver in the conductive layer 1b is preferably 60% by mass or more, more preferably 90% by mass or more, and particularly preferably 98% by mass or more.
Moreover, the transparency of the transparent electrode 1 means that the light transmittance at a wavelength of 550 nm is 50% or more.

  Next, a detailed structure is demonstrated in order of the base material 11 with which the transparent electrode 1 of such a laminated structure is provided, the intermediate | middle layer 1a which comprises the transparent electrode 1, and the electroconductive layer 1b.

(Base material)
Examples of the substrate 11 on which the transparent electrode 1 of the present invention is formed include, but are not limited to, glass and plastic. Moreover, the base material 11 may be transparent or opaque. When the transparent electrode 1 of the present invention is used in an electronic device that extracts light from the substrate 11 side, the substrate 11 is preferably transparent. Examples of the transparent substrate 11 that is preferably used include glass, quartz, and a transparent resin film.

  Examples of the glass 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 obtained by combining these films may be formed.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Is mentioned.

As described above, a film made of an inorganic material or an organic material, or a hybrid film combining these films may be formed on the surface of the resin film. Such a coating and a hybrid coating have a water vapor transmission rate (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 · 24h) The following barrier film (also referred to as a barrier film or the like) is preferable. Furthermore, the oxygen permeability measured by the method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, and the water vapor permeability is 1 × 10 ⁻⁵ g / ( m ² · 24h) or less is preferable.

  The material for forming the barrier film as described above may be any material that has a function of suppressing intrusion of factors that cause deterioration of electronic devices such as moisture and oxygen and organic EL elements. Silicon, silicon nitride, or the like can be used. Furthermore, in order to improve the brittleness of the barrier film, it is more preferable to have a laminated structure of a layer made of these inorganic materials (inorganic layer) and a layer made of organic material (organic layer). Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

  The method for producing the barrier film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method described in JP-A-2004-68143 is particularly preferable.

  On the other hand, when the base material 11 is made of an opaque material, for example, a metal substrate such as aluminum or stainless steel, a film, an opaque resin substrate, a ceramic substrate, or the like can be used.

(Middle layer)
The intermediate layer 1a according to the present invention is a layer configured by using a metal complex having any one of 1-coordinate to 4-coordinate.
The ligand of the metal complex is preferably an organic compound.
Moreover, it is preferable that the electric charge in the whole molecule | numerator of a metal complex is neutral. That is, it is preferable that the metal complex has a structure composed of only the central metal and the ligand without having a counter anion (counter ion), and the charge is neutral (the charge amount is 0).

The ligand of the metal complex according to the present invention is preferably a chelate ligand having a plurality of coordination sites. The chelate-type ligand itself has a highly planar structure, and can form a metal complex having planarity more easily. In addition, the chelate-type ligand is coordinated in a multidentate manner with respect to the central metal, so that the bond is strong and stable.
Therefore, it is preferable to use at least one chelate-type ligand, and more preferable to use only a chelate-type ligand from the viewpoint of forming a more stable metal complex with higher planarity.

  As the chelate-type ligand, it can be appropriately selected from conventionally known ligands. Among them, acetylacetonate-type ligands, salen-type coordinations are particularly preferable from the viewpoint of forming complexes with various central metals. It is preferable that they are a child, a porphyrin-type ligand, a phthalocyanine-type ligand, a phenylpyridine-type ligand, a phenylimidazole-type ligand, and a phenylimidazolecarbene-type ligand.

On the other hand, the selection of the central metal is also an important factor for forming a planar metal complex.
For example, in the case of a tetracoordinate metal complex, there are two types, a regular tetrahedron type and a planar square type. Although both are embodiments in which the effects of the present invention are manifested, it is clear that the latter planar square shape is preferable in that the periphery of the central metal is more exposed.

This way the formation is a flat square type metal complex, the electrons meet the d orbital of the outermost shell of the central metal number (d ⁿ of electron configuration.) And periodicity (horizontal axis in the periodic table) Need to be considered. When the central metal is in the d ⁷ , d ⁸ and d ⁹ electron configuration, more preferably in the d ⁸ electron configuration, it tends to be a planar quadrilateral shape, and the higher the transition metal atom is, the more likely it is a planar quadrilateral shape.

  For the above reasons, there are not many kinds of central metals that can form a metal complex that is a planar quadrilateral shape and consists only of a chelate-type ligand. In the present invention, the central metal is any one selected from Co (II), Ni (II), Cu (II), Pd (II), Pt (II) and Au (III). Is preferred.

Co (II) is ^{d 7} electron configuration, Ni (II) is a ^{d 8} electronic configuration, it is possible to form a square-planar type.
Pd (II) and Pt (II) is, d ⁸ is an electronic arrangement, and the fifth row respectively, a high transition metal atom of the sixth column cycle, to form a square-planar type complex, more preferable.

  Moreover, the interaction between the central metal of the metal complex and the silver atoms of the conductive layer described later is mainly a metal-metal bond. One index that predicts the affinity between different metal species is a phase diagram, and the realization and properties of the alloy are predicted, but metals in the same family (columns in the periodic table) with similar chemical properties Generally high affinity. Therefore, it is speculated that the transition metal atoms having a high affinity with silver and easily forming a metal-metal bond are copper and gold, which are the same Group 11.

In view of the above, Cu (II), it is possible to form a square planar type with d ⁹ electronic configuration, and a strong interaction with the silver atoms in the group 11, more preferably.

Au (III) is a d ⁸ electronic configuration, the sixth column to form a square-planar type complex for a high transition metal atom of the periodic, and a strong interaction with the silver atoms in the group 11, the most preferred .

  Hereinafter, the metal complex which has a structure represented by General Formula (1)-(5) used for the intermediate | middle layer 1a which concerns on this invention is demonstrated.

(Metal complex having a structure represented by general formulas (1) to (5))
The metal complex contained in the intermediate layer 1a is preferably a metal complex having a structure represented by the following general formulas (1) to (5).

  In the general formulas (1) to (5), M represents a transition metal atom, and forms a covalent bond and a coordinate bond with the polydentate ligand. Multidentate ligands may combine with each other to form tridentate or tetradentate ligands. L represents an auxiliary ligand, and forms a covalent bond or a coordinate bond with M. n represents an integer of 0 to 2. When n is 1, L may be a monodentate ligand or a polydentate ligand, and when n is 2, L may be the same or different, but the charge of the whole molecule Is neutral.

  In the general formulas (1) to (5), the transition metal atom represented by M is not particularly limited, but Co (II), Ni (II), Cu (II), Pd (II) Pt (II) or Au (III) is preferred, Cu (II), Pd (II), Pt (II) or Au (III) is more preferred, and Pd (II), Pt (II) Or Au (III) is more preferable, and Au (III) is most preferable.

  The metal complex having a structure represented by the general formula (1) is preferably a metal complex having a structure represented by the following general formula (1-1).

In general formula (1-1), M represents a transition metal atom. R ₁ and R ₂ each independently represents a substituent. L ₁ and L ₂ represent a ligand that forms a covalent bond or a coordinate bond with M, and may bond to each other to form a bidentate ligand.

  M in the general formula (1-1) has the same meaning as M in the general formulas (1) to (5).

In the general formula (1), examples of the substituent represented by R ₁ and R ₂ include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group). Group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group) , Propargyl group, etc.), aromatic hydrocarbon group (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, biphenyl Enilyl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group) Group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of carbolinyl group is replaced by nitrogen atom), phthalazinyl group, etc.), heterocyclic group (for example, pyrrolidyl group, imidazolidyl group) , Morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group) Group, cyclohexyloxy group Etc.), aryloxy groups (for example, phenoxy group, naphthyloxy group, etc.), alkylthio groups (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group ( For example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group) , Dodecyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group, naphthyloxycarbonyl group etc.), sulfamoyl group (eg aminosulfonyl group, methylamino) Sulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.) An acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group) Etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group) Dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexyl) Carbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, Pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecyla Minocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group) , Phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group) Naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonate) Group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, Amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, piperidyl group (also called piperidinyl group), 2,2,6,6-tetramethylpiperidinyl group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, Pentafluoroethyl group, pen Fluorophenyl group), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphate group (for example, A dihexyl phosphoryl group), a phosphite group (for example, a diphenylphosphinyl group), a phosphono group, and the like.

  The metal complex having a structure represented by the general formula (2) is preferably a metal complex having a structure represented by the following general formula (2-1).

In general formula (2-1), M represents a transition metal atom. R ₃ and R ₄ each independently represents a substituent. R _{5 to} R ₁₂ each independently represent a substituent and may be bonded to each other to form a ring.

  M in the general formula (2-1) has the same meaning as M in the general formulas (1) to (5).

In the general formula (2-1), examples of the substituent represented by R ₃ and R ₄ include the same substituents as those represented by R ₁ and R ₂ in the general formulas (1) to (5). It is done.

In the general formula (2-1), examples of the substituent represented by R _{5 to} R ₁₂ include the same substituents represented by R ₁ and R ₂ in the general formulas (1) to (5). It is done.

  The metal complex having a structure represented by the general formula (3) is preferably a metal complex having a structure represented by the following general formula (3-1).

In general formula (3-1), M represents a transition metal atom. X _{1 to} X ₄ each independently represent —CR ₂₁ or a nitrogen atom, and R ₂₁ represents a hydrogen atom or a substituent. R _{13 to} R ₂₀ each independently represent a substituent and may be bonded to each other to form a ring.

  M in the general formula (3-1) has the same meaning as M in the general formulas (1) to (5).

In General Formula (3-1), examples of the substituent represented by R ₂₁ include the same substituents represented by R ₁ and R ₂ in General Formulas (1) to (5).

In the general formula (3-1), examples of the substituent represented by R _{13 to} R ₂₀ include the same substituents as those represented by R ₁ and R ₂ in the general formulas (1) to (5). It is done.

  The metal complex having a structure represented by the general formula (4) is preferably a metal complex having a structure represented by the following general formula (4-1).

In general formula (4-1), M represents a transition metal atom. R _{22 to} R ₂₅ each independently represent a substituent. Ring A represents a 5-membered or 6-membered aromatic heterocyclic ring formed together with a nitrogen atom and a carbon atom, and may further have a substituent, and these substituents are bonded to each other to form a ring. May be. L ₃ and L ₄ represent a ligand that forms a covalent bond or a coordinate bond with M, and may bond to each other to form a bidentate ligand.

  M in the general formula (4-1) has the same meaning as M in the general formulas (1) to (5).

In General Formula (4-1), examples of the substituent represented by R _{22 to} R ₂₅ include the same substituents as those represented by R ₁ and R ₂ in General Formulas (1) to (5). It is done.

  The metal complex having a structure represented by the general formula (5) is preferably a metal complex having a structure represented by the following general formula (5-1).

In general formula (5-1), M represents a transition metal atom. R _{26 to} R ₂₉ each independently represent a substituent, and may be bonded to each other to form a ring. X ₅ and X ₆ each independently represent —CR ₃₀ or a nitrogen atom, and R ₃₀ represents a hydrogen atom or a substituent. R ₃₁ represents a hydrogen atom or a substituent. L ₅ and L ₆ each represent a ligand that forms a covalent bond or a coordinate bond with M, and may bond to each other to form a bidentate ligand.

  M in the general formula (5-1) has the same meaning as M in the general formulas (1) to (5).

In the general formula (5-1), examples of the substituent represented by R _{26 to} R ₂₉ include the same substituents represented by R ₁ and R ₂ in the general formulas (1) to (5). It is done.

In the general formula (5-1), examples of the substituent represented by R ₃₀ and R ₃₁ are the same as the substituents represented by R ₁ and R ₂ in the general formulas (1) to (5). It is done.

  Although the specific example (Exemplary compound (1)-(258)) of the metal complex contained in the intermediate | middle layer 1a based on this invention is shown below, it is not limited to these.

  The metal complex that can be used for the intermediate layer 1a can be synthesized by a conventionally known method.

  When such an intermediate layer 1a is formed on the substrate 11, 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. (Resistance heating, EB method, etc.), a method using a dry process such as a sputtering method, a CVD method, or the like.

  The layer thickness of the intermediate layer 1a is preferably in the range of 5.0 to 40 nm.

(Conductive layer)
The conductive layer 1b according to the present invention is a layer composed mainly of silver and formed on the intermediate layer 1a.
The conductive layer 1b may have a configuration in which a layer mainly composed 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 20 nm, and more preferably in the range of 5 to 12 nm.
When the layer thickness is less than 20 nm, the absorption component or reflection component of the layer is reduced, and the transmittance of the transparent electrode 1 is improved, which is preferable. Further, it is preferable that the layer thickness is thicker than 5 nm because the conductivity of the layer becomes sufficient.

  In addition, in the transparent electrode 1 having a laminated structure including the intermediate layer 1a and the conductive layer 1b formed thereon, the upper part of the conductive layer 1b may be covered with a protective film, Another conductive layer may be laminated. In this case, it is preferable that the protective film and another conductive layer have light transmittance so that the light transmittance of the transparent electrode 1 is not impaired. Moreover, it is good also as a structure which provided the layer as needed also under the intermediate | middle layer 1a, ie, between the intermediate | middle layer 1a and the base material 11. FIG.

  The conductive layer 1b may be made of an alloy containing silver (Ag). Examples of such an alloy include silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver, and the like. Palladium copper (AgPdCu), silver indium (AgIn), etc. are mentioned.

As a method for forming the conductive layer 1b, a wet process such as a coating method, an inkjet method, a coating method, or a dip method, a dry method such as a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, or the like is used. Examples include a method using a process.
In particular, it is preferable to form the conductive layer 1b by a wet method using a conductive ink containing silver as a main component and containing an organic solvent. As an organic solvent, a conventionally well-known thing can be especially used without a restriction | limiting, unless the effect of the transparent electrode 1 of this invention is inhibited.

  Further, 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. Although it is characterized by having, it may have been subjected to high-temperature annealing treatment after film formation, if necessary.

<Effect of transparent electrode>
The transparent electrode 1 having the above-described configuration is a conductive layer composed mainly of silver on an intermediate layer 1a configured using a metal complex that is one-coordinate to four-coordinated. 1b is provided. As a result, when the conductive layer 1b is formed on the intermediate layer 1a, the silver atoms constituting the conductive layer 1b interact with the central metal of the metal complex constituting the intermediate layer 1a. The diffusion distance on the surface of the intermediate layer 1a is reduced and silver aggregation is suppressed.

Here, in the formation of a conductive layer generally composed of silver as a main component, an island-like growth type (Volume-Weber: VW type) thin film is grown, so that silver particles are isolated in an island shape. When the film thickness is small, it is difficult to obtain conductivity, and the sheet resistance value is increased.
Therefore, it is necessary to increase the film thickness in order to ensure conductivity. However, if the film thickness is increased, the light transmittance is lowered, which is not suitable as a transparent electrode.

  However, according to the transparent electrode 1 of the configuration of the present invention, since aggregation of silver is suppressed on the intermediate layer 1a as described above, in the film formation of the conductive layer 1b composed mainly of silver, the layered A thin film grows in a growth type (Frank-van der Merwe: FM type).

  In addition, the transparency of the transparent electrode 1 of the present invention means that the light transmittance at a wavelength of 550 nm is 50% or more. However, each of the materials used as the intermediate layer 1a is a conductive material mainly composed of silver. Compared with the conductive layer 1b, a film having sufficiently good light transmittance is formed. On the other hand, 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 is possible to achieve a balance with improvement in performance.

<< 2. Applications of transparent electrodes >>
The transparent electrode 1 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. As electrode members that require light transmission in these electronic devices, the above-mentioned transparent The electrode 1 can be used.
Below, embodiment of the organic EL element using the transparent electrode 1 of this invention is described as an example of a use.

≪3. First example of organic EL element >>
<Configuration of organic EL element>
FIG. 2 is a schematic cross-sectional view showing a first example of an organic EL element using the transparent electrode 1 described above as an example of the electronic device of the present invention.
Below, the structure of an organic EL element is demonstrated based on this figure.

  As shown in FIG. 2, the organic EL element 100 is provided on a transparent substrate (base material) 13, and an organic functional layer 3 configured using the transparent electrode 1, an organic material, and the like in order from the transparent substrate 13 side. And the counter electrode 5a are laminated in this order. In the organic EL element 100, the transparent electrode 1 of the present invention described above is used as the transparent electrode 1. For this reason, 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.

  Further, the layer structure of the organic EL element 100 is not limited to the example described below, and may be a general layer structure. Here, 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). In this case, for example, the organic functional layer 3 has a structure in which a hole injection layer 3a / a hole transport layer 3b / a light emitting layer 3c / an electron transport layer 3d / an electron injection layer 3e are stacked in this order from the transparent electrode 1 side which is an anode. Although illustrated, it is essential to have at least the light emitting layer 3c composed of an organic material. The hole injection layer 3a and the hole transport layer 3b may be provided as a hole transport injection layer. The electron transport layer 3d and the electron injection layer 3e may be provided as an electron transport injection layer. Of these organic functional layers 3, for example, the electron injection layer 3e may be made of an inorganic material.

  In addition to these layers, the organic functional layer 3 may have a hole blocking layer, an electron blocking layer, or the like laminated as necessary. Furthermore, the light emitting layer 3c may have a structure in which each color light emitting layer that generates light emitted 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. Furthermore, the counter electrode 5a as a cathode may also have a laminated structure as necessary. In such a configuration, only a portion where the organic 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.

  In the layer configuration as described above, the auxiliary electrode 15 may be 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.

  The organic EL element 100 having the above configuration is sealed with a sealing material 17 described later on the transparent substrate 13 for the purpose of preventing deterioration of the organic functional layer 3 configured using an organic material or the like. ing. The sealing material 17 is fixed to the transparent substrate 13 side with an adhesive 19. However, it is assumed that 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 sealing material 17 in a state of being insulated from each other by the organic functional layer 3.

  Hereinafter, the details of the main layers for constituting the organic EL element 100 described above will be described in terms of the transparent substrate 13, the transparent electrode 1, the counter electrode 5a, the light emitting layer 3c of the organic functional layer 3, the other layers of the organic functional layer 3, and the auxiliary. The electrode 15 and the sealing material 17 will be described in this order.

(Transparent substrate)
The transparent substrate 13 is the base material 11 on which the transparent electrode 1 of the present invention described above is provided, and the transparent base material 11 having light transmittance among the base materials 11 described above is used.

(Transparent electrode (anode))
The transparent electrode 1 is the transparent electrode 1 of the present invention described above, and has a configuration in which an intermediate layer 1a and a conductive layer 1b are sequentially formed from the transparent substrate 13 side. Here, in particular, the transparent electrode 1 functions as an anode, and the conductive layer 1b is a substantial anode.

(Counter electrode (cathode))
The counter electrode 5a is an electrode film that functions as a cathode for supplying electrons to the organic functional layer 3, and is made of a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof. 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 a thin film of these conductive materials by a method such as vapor deposition or sputtering.
Further, the sheet resistance value as the counter electrode 5a is preferably several hundred Ω / □ or less, and the film thickness is usually selected within a range of 5 nm to 5 μm, preferably 5 to 200 nm.

  In addition, when this organic EL element 100 takes out the emitted light h also from the counter electrode 5a side, the counter electrode is made of a conductive material having a good light transmission property selected from the above-described conductive materials. 5a should just be comprised.

(Light emitting layer)
The light emitting layer 3c contains a light emitting material, and among them, it is preferable that a phosphorescent dopant (phosphorescent material, phosphorescent compound, phosphorescent 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 the light emitting layer 3c. Even within the layer, it may be the interface between the light emitting layer 3c and the adjacent layer.

  There is no restriction | limiting in particular in the structure as such a light emitting layer 3c, if the light emitting material contained satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting auxiliary layer (not shown) 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 because a lower driving voltage can be obtained. In addition, 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.

  In the case of the light emitting layer 3c having a configuration in which a plurality of layers are laminated, the thickness of each light emitting layer is preferably adjusted within a range of 1 to 50 nm, and more preferably adjusted within a range of 1 to 20 nm. When the plurality of stacked light emitting layers correspond to the respective emission colors of blue, green, and red, 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 using a known thin film forming method such as a vacuum evaporation method, a spin coating method, a casting method, an LB method, or an ink jet method, for example, by using a light emitting material or a host compound described later. Can be formed.

  The light emitting layer 3c may be configured by mixing a plurality of light emitting materials, and a phosphorescent light emitting dopant (phosphorescent compound) and a fluorescent dopant (fluorescent light emitting material, fluorescent compound) are mixed. It may be configured.

  As a structure of the light emitting layer 3c, it is preferable to contain a host compound (light emitting host) and a light emitting material (light emitting dopant) and to emit light from the light emitting material.

(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.

  As a host compound, a well-known host compound may be used independently, or multiple types may be used. By using 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. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

  The host compound used may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .

As the known host compound, a compound having a hole transporting ability and an electron transporting ability while preventing the emission of light from being increased in wavelength and having a high Tg (glass transition temperature) is preferable.
The glass transition temperature here is a value determined by a method based on JIS K 7121 using DSC (Differential Scanning Colorimetry).

  Although the specific example (H1-H79) of the host compound which can be used by this invention below is shown, it is not limited to these. Note that x and y in the host compound H68 and p, q and r in the host compound H69 represent the ratio of the random copolymer. The ratio can be, for example, x: y = 1: 10.

  As specific examples of known host compounds, compounds described in the following documents may be used. For example, Japanese Patent Application Laid-Open Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860 Gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette, 2002-338579 gazette. No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, No. 2002-231453. No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060. 2002-302516, 2002-305083, 2002-305084, 2002-308837, and the like.

(Luminescent material)
(1) Phosphorescence emission dopant As a luminescent material which can be used by this invention, a phosphorescence emission dopant is mentioned.

  A phosphorescent dopant 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 phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. The phosphorescence quantum yield in a solution can be measured using various solvents, but when using a phosphorescent dopant in the present invention, the above phosphorescence quantum yield (0.01 or more) is achieved in any solvent. It only has to be done.

There are two types of light emission principles of the phosphorescent dopant.
One is that recombination of carriers occurs on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent dopant to obtain light emission from the phosphorescent dopant. It is an energy transfer type.
The other is a carrier trap type in which the phosphorescent dopant becomes a carrier trap, and carrier recombination occurs on the phosphorescent dopant to emit light from the phosphorescent dopant. In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.

  The phosphorescent light emitting dopant can be appropriately selected from known materials used for the light emitting layer of a general organic EL device, and preferably contains a group 8-10 metal in the periodic table of elements. A complex compound, more preferably an iridium compound, an osmium compound, a platinum compound (platinum complex compound), or a rare earth complex, and most preferably an iridium compound.

  In the present invention, at least one light emitting layer 3c may contain two or more phosphorescent light emitting dopants, and the concentration ratio of the phosphorescent light emitting dopant in the light emitting layer 3c varies in the thickness direction of the light emitting layer 3c. It may be.

  The phosphorescent dopant is preferably 0.1% by volume or more and less than 30% by volume with respect to the total amount of the light emitting layer 3c.

(1.1) Phosphorescent dopant having a structure represented by the general formula (A) The phosphorescent dopant contained in the light emitting layer 3c is a compound having a structure represented by the following general formula (A). Is preferred.

  In addition, it is preferable that the phosphorescence emission dopant (it is also called a phosphorescence-emitting metal complex) which has a structure represented by general formula (A) is contained in the light emitting layer 3c of the organic EL element 100 as a light emission dopant. Although it is an aspect, you may contain in organic functional layers other than the light emitting layer 3c.

In general formula (A), 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, and j1 + j2 is 2 or 3. M ₁ represents a transition metal atom of Group 8 to Group 10 in the periodic table.

In the general formula (A), the aromatic hydrocarbon ring formed by A ₁ together with P—C includes 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, picene ring , Pyrene ring, pyranthrene ring, anthraanthrene ring and the like.
These rings may further have a substituent represented by R ₁ and R ₂ in the general formulas (1) to (5).

In the general formula (A), the aromatic heterocyclic ring A ₁ forms together with the P-C, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, Benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, azacarbazole A ring etc. are mentioned.
Here, the azacarbazole ring refers to one in which at least one carbon atom of the benzene ring constituting the carbazole ring is replaced with a nitrogen atom.
These rings may further have a substituent represented by R ₁ and R ₂ in the general formulas (1) to (5).

In the general formula (A), 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, a thiatriazole ring, Examples include a thiazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an imidazole ring, a pyrazole ring, and a triazole ring.
These rings may further have a substituent represented by R ₁ and R ₂ in the general formulas (1) to (5).

Examples of the bidentate ligand represented by P ₁ -L ₁ -P ₂ include phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone, and picolinic acid.

  In general formula (A), j2 represents an integer of 0 to 2, and j2 is preferably 0.

In the general formula (A), M ₁ is a transition metal atom of group 8 to group 10 (also simply referred to as a transition metal) in the periodic table, and iridium is particularly preferable.

(1.2) The phosphorescence emission dopant which has a structure represented by general formula (B) The phosphorescence emission dopant which has a structure represented by the said general formula (A) is represented by the following general formula (B). A phosphorescent dopant having a structure is preferable.

In general formula (B), 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. A ₃ represents -C (R ₀₁ ) = C (R ₀₂ )-, -N = C (R ₀₂ )-, -C (R ₀₁ ) = N- or -N = N-, and R ₀₁ and R ₀₂ Each represents a hydrogen atom or a substituent. 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, and j1 + j2 is 2 or 3. M ₁ represents a transition metal atom of Group 8 to Group 10 in the periodic table.

In the general formula (B), 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 a substituent represented by R ₁ and R ₂ in the general formulas (1) to (5).

Examples of the aromatic hydrocarbon ring group (also referred to as aromatic hydrocarbon group, aryl group, etc.) 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.
These groups may be unsubstituted or may have a substituent represented by R ₁ and R ₂ in the general formulas (1) to (5).

In the general formula (B), 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, ε-caprolactone ring, ε- Caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thiomorpholine Ring, thiomorpholine-1,1-dioxide And groups derived from a ring, a pyranose ring, a diazabicyclo [2,2,2] -octane ring, and the like.
These groups may be unsubstituted or may have a substituent represented by R ₁ and R ₂ in the general formulas (1) to (5).

Examples of the aromatic heterocyclic group include 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). Group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, 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, quinazo Group, phthalazinyl group, and the like.
These groups may be unsubstituted or may have a substituent represented by R ₁ and R ₂ in the general formulas (1) to (5).

  The group represented by Z is preferably an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

In the general formula (B), the aromatic hydrocarbon ring that A ₁ forms with P—C includes a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, and a 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, picene ring , Pyrene ring, pyranthrene ring, anthraanthrene ring and the like.
These groups may be unsubstituted or may have a substituent represented by R ₁ and R ₂ in the general formulas (1) to (5).

In the general formula (B), the aromatic heterocycle formed by A ₁ together with P—C includes a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a 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, carboline ring And azacarbazole ring.
Here, the azacarbazole ring refers to one in which at least one carbon atom of the benzene ring constituting the carbazole ring is replaced with a nitrogen atom.
These groups may be unsubstituted or may have a substituent represented by R ₁ and R ₂ in the general formulas (1) to (5).

_-C represented by _{A 3} in the general formula _{(B) (R 01) =} C (R 02) -, - N = C (R 02) -, - C (R 01) = In _{N-, R 01} and substituents represented by R ₀₂ has the general formula (1) is synonymous with the substituent to (5) represented by _{R 1} and _{R 2.}

In the general formula (B), 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. Is mentioned.

  In general formula (B), j2 represents an integer of 0 to 2, and j2 is preferably 0.

In the general formula (B), (also referred to simply as a transition metal) group 8-10 transition metal atom of the periodic table represented by M _1, the periodic In the formula (A), represented by M ₁ It is synonymous with the transition metal atom of 8th group-10th group in a table | surface.

(1.3) Compound having structure represented by general formula (C) The phosphorescent dopant having the structure represented by the general formula (B) has a structure represented by the following general formula (C). A phosphorescent dopant is preferred.

In general formula (C), 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 1 or 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. Z1 represents an atomic group necessary for forming a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle with C—C. Z2 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 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, and j1 + j2 is 2 or 3. M1 represents a group 8-10 group transition metal atom 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.

In the general formula (C), the substituents represented by R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ are synonymous with the substituents represented by R ₁ and R ₂ in the general formulas (1) to (5). is there.

In the general formula (C), examples of the 6-membered aromatic hydrocarbon ring formed by Z ₁ together with C—C include a benzene ring.
These rings may further have a substituent, and the substituent is the same as the substituent represented by R ₁ and R ₂ in the general formulas (1) to (5). Is mentioned.

In the general formula (C), examples of the 5-membered or 6-membered aromatic heterocycle formed by Z ₁ together with C—C include 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 the substituent is the same as the substituent represented by R ₁ and R ₂ in the general formulas (1) to (5). Is mentioned.

In the general formula (C), 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 the substituents represented by R ₁ and R ₂ in the general formulas (1) to (5). The same thing is mentioned.

Examples of the aromatic hydrocarbon ring group (also referred to as aromatic hydrocarbon group, aryl group, etc.) 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.
These groups may be unsubstituted or may have a substituent. Examples of such a substituent include the substituents represented by R ₁ and R ₂ in the general formulas (1) to (5). The same thing is mentioned.

In the general formula (C), 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, ε-caprolactone ring, ε -Caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thio Morpholine ring, thiomorpholine-1,1-dioxy De ring, pyranose ring, a diazabicyclo [2,2,2] - and the groups derived from the octane ring.
These groups may be unsubstituted or may have a substituent. Examples of such a substituent include the substituents represented by R ₁ and R ₂ in the general formulas (1) to (5). The same thing is mentioned.

Examples of the aromatic heterocyclic group include 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). Group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, 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, quinazo Group, phthalazinyl group, and the like.
These rings may be unsubstituted or may have a substituent. Examples of such a substituent include the substituents represented by R ₁ and R ₂ in the general formulas (1) to (5). The same thing is mentioned.

In the general formula (C), the ring formed by Z ₁ and Z ₂ is preferably a benzene ring.

In formula _(C), bidentate ligand represented by P 1 _-L 1 -P ₂ is In formula _(A), coordination of bidentate represented by P 1 _-L 1 -P ₂ Synonymous with rank.

In the formula (C), a transition metal atom of group 8-10 of the periodic table represented by _{M 1} are the compounds of formula (A), group 8-10 of the periodic table represented by _{M 1} It is synonymous with the transition metal atom.

  Further, the phosphorescent light emitting dopant can be appropriately selected from known materials used for the light emitting layer 3 c of the organic EL element 100.

  Specific examples (Pt-1 to Pt-3, A-1, Ir-1 to Ir-45) of the phosphorescent dopant according to the present invention are shown below, but the present invention is not limited thereto. In these compounds, m and n represent the number of repetitions.

  The phosphorescent dopant (also referred to as a phosphorescent metal complex or the like) is described 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, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) New Journal of Chemistry, Vol. 26, page 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and methods such as references described in these documents. It can be synthesized by applying.

(2) Fluorescent dopants Fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Examples thereof include dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

(Injection layer: hole injection layer, electron injection layer)
The injection layer is a layer provided between the electrode and the light emitting layer 3c in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and the forefront of its industrialization (November 30, 1998, NT. 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of the 2nd volume of “S. Co., Ltd.”, which includes a hole injection layer 3a and an electron injection layer 3e.

  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.

  The details of the hole injection layer 3a are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Specific examples thereof include phthalocyanine represented by copper phthalocyanine. Examples thereof include a layer, an oxide layer typified by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the electron injection layer 3e are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specifically represented by strontium, aluminum and the like. Examples thereof include a metal layer, an alkali metal halide layer typified by potassium fluoride, an alkaline earth metal compound layer typified by magnesium fluoride, and an oxide layer typified by molybdenum oxide. The electron injection layer 3e is preferably a very thin film, and the layer thickness is preferably in the range of 1 nm to 10 μm, although it depends on the material.

(Hole transport layer)
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. For example, 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.

  Although the above-mentioned thing can be used as a positive hole transport material, It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styryl amine compound, especially an aromatic tertiary amine compound.

  Representative examples of 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 (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-tolyl) Aminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminostilbenzene, N-phenylcarbazole, and also two fused aromatic rings described in US Pat. No. 5,061,569 In the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308688 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) in which three triphenylamine units described in the publication are linked in a starburst type Etc.

  Furthermore, 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. In addition, 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.

  JP-A-11-251067, J. Org. Huang et. al. , Applied Physics Letters, 80 (2002), p. A so-called p-type hole transport material as described in 139 can also be used. In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.

  The hole transport layer 3b is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. be able to. Although there is no restriction | limiting in particular about the layer thickness of the positive hole transport layer 3b, Usually, 5 nm-about 5 micrometers, Preferably it exists in the range of 5-200 nm. The hole transport layer 3b may have a single layer structure composed of one or more of the above materials.

  Also, the p-type can be enhanced by doping impurities into the material of the hole transport layer 3b. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  Thus, it is preferable to increase the p property of the hole transport layer 3b because an element with lower power consumption can be manufactured.

(Electron transport layer)
The electron transport layer 3d is made of a material having a function of transporting electrons, and in a broad sense, the electron injection layer 3e and the hole blocking layer are also included in the electron transport layer 3d. The electron transport layer 3d can be provided as a single layer structure or a multilayer structure of a plurality of layers.

  An electron transport material for the electron transport layer 3d having a single layer structure and an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer 3c in the electron transport layer 3d having a multilayer structure are injected from the cathode. What is necessary is just to have a function to transmit the emitted electrons to the light emitting layer 3c. As such a 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. Further, in the above oxadiazole derivative, a thiadiazole derivative in which an 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. Can do. Furthermore, 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.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (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 (Znq), etc., and the central metals of these metal complexes are In, Mg Metal complexes replaced by Cu, Ca, Sn, Ga, or Pb can also be used as the material for the electron transport layer 3d.

  In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with alkyl groups or sulfonic acid groups can be preferably used as the material for the electron transport layer 3d. Further, a distyrylpyrazine derivative that is also used as a material for the light emitting layer 3c can be used as a material for the electron transport layer 3d. An inorganic semiconductor such as -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. Although there is no restriction | limiting in particular about the layer thickness of 3 d of electron carrying layers, Usually, 5 nm-about 5 micrometers, Preferably it exists in the range of 5-200 nm. The electron transport layer 3d may have a single-layer structure made of one or more of the above materials.

  In addition, the electron transport layer 3d can be doped with impurities 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. Furthermore, it is preferable that the electron transport layer 3d contains potassium, a potassium compound, or the like. As the potassium compound, for example, potassium fluoride can be used. Thus, when the n property of the electron transport layer 3d is increased, an element with lower power consumption can be manufactured.

  Further, as 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 same applies to the electron transport layer 3d also serving as the electron injection layer 3e.

(Blocking layer: hole blocking layer, electron blocking layer)
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic functional layer 3 described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  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. Moreover, the structure of said electron carrying layer 3d can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer 3c.

On the other hand, 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 a function of transporting holes but has a very small ability to transport electrons, and improves the probability of recombination of electrons and holes by blocking electrons while transporting holes. be able to. Moreover, the structure of said positive hole transport layer 3b can be used as an electron blocking layer as needed.
The thickness of the hole blocking layer is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.

(Auxiliary electrode)
The auxiliary electrode 15 is 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 for forming the auxiliary electrode 15 is preferably a metal with low resistance such as gold, platinum, silver, copper, or aluminum. Since these metals have low light transmittance, a pattern is formed in a range not affected by extraction of the emitted light h from the light extraction surface 13a. Examples of a method for producing such an auxiliary electrode 15 include a vapor deposition method, a sputtering method, a printing method, an ink jet method, an aerosol jet method, and the like. The line width of the auxiliary electrode 15 is preferably 50 μm or less from the viewpoint of the aperture ratio for extracting light, and the thickness of the auxiliary electrode 15 is preferably 1 μm or more from the viewpoint of conductivity.

(Encapsulant)
The sealing material 17 covers the organic EL element 100 and may be a plate-like (film-like) sealing member that is fixed to the transparent substrate 13 side by the adhesive 19. It may be a stop film. Such a sealing material 17 is provided in a state of covering at least the organic functional layer 3 in a state in which the terminal portions of the transparent electrode 1 and the counter electrode 5a in the organic EL element 100 are exposed. 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.

  Specific examples of 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 thin film. Examples of the glass substrate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of 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.

  Among them, since the element can be thinned, a thin film-like polymer substrate or metal substrate can be preferably used as the sealing material.

Furthermore, the polymer substrate in the form of a film has an oxygen permeability of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less measured by a method according to JIS K 7126-1987, and JIS K 7129- The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to 1992 is 1 × 10 ⁻³ g / (m ² · 24 h) or less. It is preferable.

  Further, the above substrate material may be processed into a concave plate shape and used as the sealing material 17. In this case, the above-described substrate material is subjected to processing such as sandblasting and chemical etching to form a concave shape.

The 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. Specifically, such an adhesive 19 is a photocuring and thermosetting adhesive having a reactive vinyl group of an acrylic acid-based oligomer, a methacrylic acid-based oligomer, a moisture-curing type such as 2-cyanoacrylic acid ester, or the like. Can be mentioned.
In addition, epoxy-based heat and chemical curing type (two-component mixing), hot-melt type polyamide, polyester, polyolefin, and cationic curing type UV-curable epoxy resin adhesive can also be exemplified.

  In addition, the organic material which comprises the organic EL element 100 may deteriorate with heat processing. For this reason, the adhesive 19 is preferably one that can be adhesively cured from room temperature (25 ° C.) to 80 ° C. Further, a desiccant may be dispersed in the adhesive 19.

  Application | coating of the adhesive agent 19 to the adhesion part of the sealing material 17 and the transparent substrate 13 may use a commercially available dispenser, and may print like screen printing.

  In addition, when a gap is formed between the plate-shaped sealing material 17, the transparent substrate 13, and the adhesive 19, in this gap, in the gas phase and the liquid phase, 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.

  Examples of the hygroscopic compound 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). Etc.), 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), and anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.

  On the other hand, when a sealing film is used as the sealing material 17, the organic 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 configured using an inorganic material or an organic material. In particular, it is made of a material having a function of suppressing entry of a substance that causes deterioration of the organic functional layer 3 in the organic EL element 100 such as moisture and oxygen. As such a material, for example, inorganic materials such as silicon oxide, silicon dioxide, and silicon nitride are used. Furthermore, in order to improve the brittleness of the sealing film, 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 producing these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

(Protective film, protective plate)
A protective film or a protective plate may be provided so as to sandwich the organic EL element 100 and the sealing material 17 together with the transparent substrate 13. 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.

  As the protective film or protective plate as described above, 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. In particular, it is preferable to use a polymer film because it is lightweight and thin.

<Method for producing organic EL element>
Here, as an example, a method for manufacturing the organic EL element 100 shown in FIG. 2 will be described.

  First, on the transparent substrate 13, an intermediate layer 1a containing a metal complex of any one of coordination to tetracoordination is appropriately deposited by vapor deposition or the like so as to have a layer thickness of 1 μm or less, preferably 10 to 100 nm. It forms by the method of. Next, the conductive layer 1b containing silver (or an alloy containing silver) as a main component is appropriately deposited by an evaporation method or the like so as to have a layer thickness within a range of 5 to 20 nm, preferably within a range of 5 to 12 nm. The transparent electrode 1 which is formed on the intermediate layer 1a by the method and becomes an anode is produced.

Next, a hole injection layer 3a, a hole transport layer 3b, a light emitting layer 3c, an electron transport layer 3d, and an electron injection layer 3e are formed in this order on this, and the organic functional layer 3 is formed. 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. When employing a vapor deposition method for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C. and a degree of vacuum of 1 × 10 ⁻⁶ to 1 × 10 ^−2. It is desirable to appropriately select each condition within the ranges of Pa, vapor deposition rate of 0.01 to 50 nm / second, substrate temperature of −50 to 300 ° C., and layer thickness of 0.1 to 5 μm.

  After the organic functional layer 3 is formed as described above, the counter electrode 5a serving as a cathode is formed thereon by an appropriate film forming method such as a vapor deposition method or a sputtering method. At this time, the counter electrode 5 a is patterned in a shape in which a terminal portion is drawn from the upper side of the organic functional layer 3 to the periphery of the transparent substrate 13 while being kept insulated from the transparent electrode 1 by the organic functional layer 3. Thereby, the organic EL element 100 is obtained. Thereafter, the sealing material 17 that covers at least the organic functional layer 3 is provided in a state where the terminal portions of the transparent electrode 1 and the counter electrode 5a in the organic EL element 100 are exposed.

  As described above, a desired organic EL element is obtained on the transparent substrate 13. In the production of such an organic EL element 100, it is preferable that the organic functional layer 3 to the counter electrode 5a are consistently produced by a single evacuation. A film method may be applied. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  When a DC voltage is applied to the organic EL element 100 thus obtained, the transparent electrode 1 as an anode has a positive polarity, the counter electrode 5a as a cathode has a negative polarity, and a voltage of about 2 to 40V. Luminescence can be observed by applying. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

<Effect of organic EL element>
The organic EL element 100 described above has a configuration in which the transparent electrode 1 having both conductivity and light transmittance according to the present invention is used as an anode, and an organic functional layer 3 and a counter electrode 5a serving as a cathode are provided on the transparent electrode 1. is there. 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. Therefore, it is possible to increase the luminance. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.

<< 4. Second example of organic EL element >>
<Configuration of organic EL element>
FIG. 3 is a schematic cross-sectional view showing a second example of an organic EL element using the transparent electrode 1 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.
Hereinafter, a detailed description of the same components as those in the first example will be omitted, and a characteristic configuration of the organic EL element 200 in the second example will be described.

  As shown in FIG. 3, the organic EL element 200 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. ing. For this reason, the organic EL element 200 is configured to extract the emitted light h from at least the transparent substrate 13 side. However, the transparent electrode 1 is used as a cathode (cathode). For this reason, the counter electrode 5b is used as an 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.

  As an example of the case of the second example, an electron injection layer 3e / electron transport layer 3d / light emitting layer 3c / hole transport layer 3b / hole injection layer 3a are arranged in this order on the transparent electrode 1 functioning as a cathode. A stacked configuration is exemplified. However, it is essential to have at least the light emitting layer 3c made of an organic material.

  In addition to these layers, the organic functional layer 3 employs various configurations as necessary, as described in the first example. In such a configuration, only the portion where the organic functional layer 3 is sandwiched between the transparent electrode 1 and the counter electrode 5 b becomes the light emitting region in the organic EL element 200 as in the first example.

  In the layer structure as described above, 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.

Here, 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. Specific examples include metals such as gold (Au), oxide semiconductors such as copper iodide (CuI), ITO, ZnO, TiO ₂ , and SnO ₂ .

The counter electrode 5b configured as described above can be produced by forming a thin film of these conductive materials by a method such as vapor deposition or sputtering.
Further, the sheet resistance value as the counter electrode 5b is preferably several hundred Ω / □ or less, and the film thickness is usually selected within a range of 5 nm to 5 μm, preferably 5 to 200 nm.

  In addition, when 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 the deterioration of the organic functional layer 3.

  Of the main layers constituting the organic EL element 200 described above, the detailed structure of the constituent elements other than the counter electrode 5b used as the anode and the method for manufacturing the organic EL element 200 are the same as in the first example. For this reason, detailed description is omitted.

<Effect of organic EL element>
The organic EL element 200 described above has a configuration in which the transparent electrode 1 having both conductivity and light transmittance according to the present invention is used as a cathode, and the organic functional layer 3 and the counter electrode 5b serving as an anode are provided on the transparent electrode 1. is there. 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.

≪5. Third example of organic EL element >>
<Configuration of organic EL element>
FIG. 4 is a schematic cross-sectional view showing a third example of the organic EL element using the transparent electrode 1 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 shown in FIG. 2 in that the counter electrode 5c is provided on the substrate 131 side, and the organic functional layer 3 and It is in the place which laminated | stacked the transparent electrode 1 in this order.
Hereinafter, 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 organic functional layer 3, and the transparent electrode 1 serving as a cathode are laminated in this order from the substrate 131 side. . Among these, the transparent electrode 1 of the present invention described above is used as the transparent electrode 1. For this reason, 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.

  As an example of the case of the third example, a configuration in which a hole injection layer 3a / a hole transport layer 3b / a light emitting layer 3c / an electron transport layer 3d are stacked in this order on the counter electrode 5c functioning as an anode is illustrated. Is done. 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.

  In particular, the characteristic configuration of the organic EL element 300 of 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 transporting layer 3d having electron injecting properties, and a conductive layer 1b provided thereon. Is.

  Such an electron transport layer 3d is configured by using the material constituting the intermediate layer 1a of the transparent electrode 2 described above.

  In addition to these layers, the organic functional layer 3 adopts various configurations as necessary, as described in the first example. However, the electron transport also serving as the intermediate layer 1a of the transparent electrode 2 is used. No electron injection layer or hole blocking layer is provided between the layer 3d and the conductive layer 1b of the transparent electrode 1. In the configuration as described above, only the portion where the organic functional layer 3 is sandwiched between the transparent electrode 2 and the counter electrode 5c becomes the light emitting region in the organic EL element 300, as in the first example.

  In the layer structure as described above, 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.

Furthermore, the counter electrode 5c used as the anode is composed of a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof. Specific examples include metals such as gold (Au), oxide semiconductors such as copper iodide (CuI), ITO, ZnO, TiO ₂ , and SnO ₂ .

The counter electrode 5c configured as described above can be produced by forming a thin film of these conductive materials by a method such as vapor deposition or sputtering.
Further, the sheet resistance value as the counter electrode 5c is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 5 nm to 5 μm, preferably 5 to 200 nm.

  In addition, when this organic EL element 300 is comprised so that the emitted light h can be taken out also from the counter electrode 5c side, as a material which comprises the counter electrode 5c, light transmittance is favorable among the electrically conductive materials mentioned above. A suitable conductive material is selected and used. In this case, the substrate 131 is the same as the transparent substrate 13 described in the first example, and the surface facing the outside of the substrate 131 is the light extraction surface 131a.

<Effect of organic EL element>
In the organic EL element 300 described above, the electron transport layer 3d having the electron injecting property constituting the uppermost part of the organic functional layer 3 is used as the intermediate layer 1a, and the conductive layer 1b is provided on the intermediate layer 1a. The transparent electrode 1 composed of the 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. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance. Further, when the counter electrode 5c is light transmissive, the emitted light h can be extracted from the counter electrode 5c.

  In the third example described above, the intermediate layer 1a of the transparent electrode 2 has been described as also serving as the electron transport layer 3d having electron injection properties. However, the present example is not limited to this, and the intermediate layer 1a may also serve as an electron transport layer 3d that does not have electron injection properties, or the intermediate layer 1a may serve as an electron injection layer instead of an electron transport layer. In addition, 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.

  Further, when 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 5c on the substrate 131 side is used as a cathode, The transparent electrode 1 may be an anode. In this case, the organic functional layer 3 is, for example, in order from the counter electrode (cathode) 5c side on the substrate 131, for example, an electron injection layer 3e / electron transport layer 3d / light emitting layer 3c / hole transport layer 3b / hole injection layer 3a. Are stacked. And the transparent electrode 1 which consists of a laminated structure of the ultra-thin intermediate | middle layer 1a and the electroconductive layer 1b is provided in this upper part as an anode.

≪6. Applications of organic EL elements >>
Since the organic EL elements having the above-described configurations are surface light emitters as described above, they can be used as various light emission sources. For example, lighting devices such as home lighting and interior lighting, backlights for watches and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, Examples include a light source of an optical sensor. In particular, it can be effectively used for a backlight of a liquid crystal display device combined with a color filter and a light source for illumination.

  Further, 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). In this case, with the recent increase in the size of lighting devices and displays, 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 driving 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. In addition, 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.

  Hereinafter, a lighting device will be described as an example of the application, and then a lighting device in which the light emitting surface is enlarged by tiling will be described.

≪7. Lighting device-1 >>
The lighting device according to the present invention can include the organic EL element.

  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.

  In addition, the material used for the organic EL element of this invention is applicable to the organic EL element (white organic EL element) which produces substantially white light emission. For example, a plurality of luminescent colors can be simultaneously emitted by a plurality of luminescent materials, and white light emission can be obtained by mixing colors. 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.

  In addition, 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 each emitting light are individually arranged in parallel in an array 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 deposition can be performed on one side by vapor deposition, casting, spin coating, ink jet, printing, etc., and productivity is also improved. To do.

  Moreover, there is no restriction | limiting in particular as a light emitting material used for the light emitting layer of such a white organic EL element, For example, if it is a backlight in a liquid crystal display element, it will fit in the wavelength range corresponding to CF (color filter) characteristic. As described above, any one of the above-described metal complexes and known light-emitting materials may be selected and combined to be whitened.

  If the white organic EL element demonstrated above is used, it is possible to produce the illuminating device which produces substantially white light emission.

≪8. Lighting device-2 >>
FIG. 5 is a schematic cross-sectional view of an illuminating device having a large light emitting surface using a plurality of organic EL elements having the above-described configurations.
As shown in FIG. 5, the illuminating device 21 has a light emitting surface having a large area by arranging a plurality of light emitting panels 22 including the organic EL elements 100 on the transparent substrate 13 on the support substrate 23 (tiling). This is a structured. The support substrate 23 may also serve as the sealing material 17, 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. In addition, 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. However, only the exposed part of the counter electrode 5a is shown in FIG.
In FIG. 5, as the organic functional layer 3 constituting the organic EL element 100, the hole injection layer 3a / the hole transport layer 3b / the light emitting layer 3c / the electron transport layer 3d / the electron injection layer 3e are formed on the transparent electrode 1. A configuration in which the layers are sequentially stacked is shown as an example.

  In the lighting device 21 having such a configuration, the center of 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. For this reason, 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. As the light extraction member, a light collecting sheet or a light diffusion sheet can be used.

[Second Embodiment]
The second embodiment is different from the first embodiment mainly in the following points.

<Configuration of transparent electrode>
As shown in FIG. 6, the transparent electrode 2 has a three-layer structure in which a two-layer intermediate layer 2a and a conductive layer 1b are stacked on the intermediate layer 2a. The intermediate layer 2a includes a first intermediate layer 2a1 and a second intermediate layer 2a2. For example, the transparent electrode 2 is provided on the base 11 in the order of the second intermediate layer 2a2, the first intermediate layer 2a1, and the conductive layer 1b.
The first intermediate layer 2a1 is the same as the intermediate layer 1a in the first embodiment, and is a layer that is configured to contain a metal complex of any one of 1-coordinate to 4-coordinate. The 2nd intermediate | middle layer 2a2 is a layer comprised by containing the aromatic heterocyclic compound which has a nitrogen atom with an unshared electron pair which does not participate in aromaticity.

In the present invention, the “nitrogen atom having an unshared electron pair not involved in aromaticity” is a nitrogen atom having an unshared electron pair, and the unshared electron pair is an aromatic of an unsaturated cyclic compound. A nitrogen atom that is not directly involved in sex. That is, a non-localized π electron system on a conjugated unsaturated ring structure (aromatic ring) has a nitrogen atom in which a lone pair is not involved as an essential element for aromatic expression in the chemical structural formula Say.
Here, “aromaticity” means that in a conjugated (resonant) unsaturated ring structure in which atoms having π electrons are arranged in a ring, the number of electrons contained in a delocalized π electron system on the ring is Satisfying 4n + 2 (n = 0 or a natural number) (so-called Huckel rule).
For example, a nitrogen atom of pyridine, a nitrogen atom of an amino group as a substituent, and the like correspond to “a nitrogen atom having an unshared electron pair not involved in aromaticity” according to the present invention.

(Middle layer)
The intermediate layer 2a includes a first intermediate layer 2a1 configured to contain a metal complex having any one of 1-coordinate to 4-coordinate, and a nitrogen atom having an unshared electron pair not involved in aromaticity. And the second intermediate layer 2a2 that is configured to contain the aromatic heterocyclic compound that is included.

The first intermediate layer 2a1 is the same as the intermediate layer 1a according to the first embodiment, but from the viewpoint of suppressing aggregation of silver contained in the conductive layer 1b together with the second intermediate layer 2a2, the layer thickness is It is preferable to be in the range of 0.5 to 10 nm.
The layer thickness of the second intermediate layer 2a2 is preferably in the range of 20 to 100 nm.

The 2nd intermediate | middle layer 2a2 is a layer comprised by containing the aromatic heterocyclic compound which has a nitrogen atom with an unshared electron pair which does not participate in aromaticity.
As the method for forming the second intermediate layer 2a2, as in the first intermediate layer 2a1, 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 (resistance heating, EB method, etc.) And a method using a dry process such as a sputtering method and a CVD method.

  The aromatic heterocyclic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity contained in the second intermediate layer 2a2 can be appropriately selected from conventionally known compounds, A compound having a structure represented by the following general formulas (I) to (IV) is preferable.

(Compound having the structure represented by the general formula (I))
The compound contained in the second intermediate layer 2a2 is preferably a compound having a structure represented by the following general formula (I).

In the general formula (I), X represents NR ₁ , an oxygen atom or a sulfur atom. E _{1 to} E ₈ each independently represent CR ₂ or a nitrogen atom, and at least one represents a nitrogen atom. R ₁ and R ₂ each independently represents a hydrogen atom or a substituent.

In the general formula (I), examples of the substituent represented by R ₁ and R ₂ include the same substituents represented by R ₁ and R ₂ in the general formulas (1) to (5).

(Compound having the structure represented by the general formula (II))
The compound having a structure represented by the general formula (I) is preferably a compound having a structure represented by the following general formula (II).

In General Formula (II), E _{9 to} E ₁₅ each independently represent CR ₄ . R ₃ and R ₄ each independently represents a hydrogen atom or a substituent.

In the general formula (II), examples of the substituent represented by R ₃ and R ₄ include the same substituents represented by R ₁ and R ₂ in the general formulas (1) to (5). Can do.

(Compound having a structure represented by the general formula (III))
The compound having the structure represented by the general formula (I) is preferably a compound having a structure represented by the following general formula (III).

In the general formula _{(III), E} 16 ~E ₂₂ each independently represent a CR _5. R ₅ represents a hydrogen atom or a substituent.

In the general formula (III), examples of the substituent represented by R ₅ include the same substituents represented by R ₁ and R ₂ in the general formulas (1) to (5).

(Compound having a structure represented by the general formula (IV))
The compound having a structure represented by the general formula (I) is preferably a compound having a structure represented by the following general formula (IV).

In the general formula _{(IV), E} 23 ~E ₂₈ each independently represent a CR _7. R ₆ and R ₇ each independently represents a hydrogen atom or a substituent.

In the general formula (IV), examples of the substituent represented by R ₆ and R ₇ include the same substituents represented by R ₁ and R ₂ in the above general formulas (1) to (5). Can do.

  Although the specific example (N-1 to N-65) of the organic compound contained in the 2nd intermediate | middle layer 2a2 which concerns on this invention below is shown, it is not limited to these.

The organic compound according to the present invention can be easily synthesized according to a conventionally known synthesis method.
Hereinafter, although an example of the synthesis | combining method of the organic compound contained in 2nd intermediate | middle layer 2a2 is shown, this invention is not limited to this.

(Synthesis Example: Synthesis of N-47)

(1) Synthesis of Intermediate 1 In a 300 ml eggplant flask, 2,8-diiododibenzofuran (10 g, 0.024 mol), δ-carboline (2.2 eq.), K ₃ PO ₄ (6 eq.), Cu ₂ O DMSO (50 ml) solution containing (0.4 eq.) And dipyvalyl methane (1 eq.) Was added, and the mixture was refluxed at 150 ° C. for 16 hours under a nitrogen atmosphere.
Thereafter, the temperature was returned to room temperature (25 ° C.), and the solution was transferred to a separating funnel for extraction. Ethyl acetate and saturated brine were added to separate the organic phase and the aqueous phase, and then the organic phase was taken out and evaporated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain a white solid of Intermediate 1 (6.5 g, yield 55%).

(2) Synthesis of Intermediate 2 A solution of Intermediate 1 (6.5 g, 0.013 mol) in DCM (200 ml) was added to a 300 ml eggplant flask and cooled to −40 ° C. in a nitrogen atmosphere. Br ₂ (1.1 eq.) Was added dropwise to the flask and stirred for 16 hours while gradually returning to room temperature (25 ° C.).
Thereafter, the solution was transferred to a separatory funnel and extracted. Ethyl acetate and saturated brine were added to separate the organic phase and the aqueous phase, and then the organic phase was taken out and evaporated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain a white solid of Intermediate 2 (2.0 g, yield 27%).

(3) Synthesis of N-47 In a 100 ml eggplant flask, Intermediate 2 (2.0 g, 0.0035 mol), δ-carboline (1.1 eq.), K ₃ PO ₄ (3 eq.), Cu ₂ O (0 DMSO (25 ml) containing .2 eq.) And dipyvalyl methane (0.5 eq.) Was added, and the mixture was refluxed at 150 ° C. for 16 hours under a nitrogen atmosphere.
Thereafter, the temperature was returned to room temperature (25 ° C.), and the solution was transferred to a separating funnel for extraction. Ethyl acetate and saturated brine were added to separate the organic phase and the aqueous phase, and then the organic phase was taken out and evaporated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain a white solid of N-47 (3.0 g, yield 76%).

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

[Example 1]
<< Preparation of transparent electrode >>
As described below, the transparent electrodes 101 to 122 were produced so that the area of the conductive region was 5 cm × 5 cm. The transparent electrodes 101 to 104 were prepared as transparent electrodes having a single layer structure composed of only a conductive layer, and the transparent electrodes 105 to 122 were prepared as transparent electrodes having a laminated structure of an intermediate layer and a conductive layer.

(1) Production of transparent electrode 101 First, a transparent non-alkali glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus and attached to a vacuum chamber of the vacuum deposition apparatus. Moreover, the resistance heating boat made from tungsten was filled with silver (Ag), and was attached in the said vacuum chamber. Next, after depressurizing the vacuum tank to 4 × 10 ⁻⁴ Pa, the resistance heating boat is energized and heated, and the layer thickness is 5 nm on the substrate within the range of the deposition rate of 0.1 to 0.2 nm / second. A conductive layer made of silver was formed to produce a transparent electrode 101 having a single-layer structure.

(2) Production of transparent electrodes 102 to 104 Transparent electrodes 102 to 104 were produced in the same manner as the production of the transparent electrode 101 except that the thickness of the conductive layer was changed to 8 nm, 10 nm, and 15 nm, respectively.

(3) Production of transparent electrode 105 A transparent non-alkali glass base material was fixed to a base material holder of a commercially available vacuum deposition apparatus, and the following comparative compound (1) was filled in a resistance heating boat made of tantalum. The substrate holder and the heating boat were attached to the first vacuum chamber of the vacuum deposition apparatus. Moreover, the resistance heating boat made from tungsten was filled with silver, and it attached in the 2nd vacuum chamber.

In this state, first, the first vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing the comparative compound (1) was energized and heated, and the deposition rate was 0.1 to 0.2 nm / second. In this range, an intermediate layer made of the comparative compound (1) having a layer thickness of 25 nm was provided on the substrate.

Next, the base material formed up to the intermediate layer is transferred to the second vacuum chamber while being vacuumed, 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. Then, a conductive layer made of silver having a layer thickness of 8 nm was formed within the range of the deposition rate of 0.1 to 0.2 nm / second, and a transparent electrode 105 having a laminated structure of an intermediate layer and a conductive layer was produced.

(4) Production of transparent electrodes 106 and 107 In production of the transparent electrode 105, the transparent electrodes 106 and 107 were prepared in the same manner except that the constituent materials of the intermediate layer were changed to the comparative compounds (2) and (3) shown below, respectively. Was made.

(5) Production of transparent electrode 108 In production of the transparent electrode 105, the transparent electrode 108 was prepared in the same manner except that the constituent material of the intermediate layer was changed to the exemplified compound (11) and the thickness of the conductive layer was changed to 5 nm. Was made.

(6) Production of transparent electrodes 109 to 111 Transparent electrodes 109 to 111 were produced in the same manner as the production of the transparent electrode 108 except that the thickness of the conductive layer was changed to 8 nm, 10 nm, and 20 nm, respectively.

(7) Production of transparent electrodes 112 to 119 Transparent electrodes 112 to 119 were produced in the same manner as the production of the transparent electrode 109 except that the constituent material of the intermediate layer was changed to the exemplified compounds shown in Table 1.

(8) Production of transparent electrodes 120 to 122 Transparent electrodes 120 to 122 were produced in the same manner as the production of the transparent electrodes 117 to 119 except that the base material was changed from a non-alkali glass to a PET (polyethylene terephthalate) film.

<< Evaluation of transparent electrode >>
About the produced transparent electrodes 101-122, according to the following method, the light transmittance, the sheet resistance value, and durability (electrode lifetime) were measured.

(1) Measurement of light transmittance For each of the produced transparent electrodes, a light transmittance (%) at a wavelength of 550 nm is measured using a spectrophotometer (U-3300, manufactured by Hitachi, Ltd.) with reference to the base material of each transparent electrode. did.
The measurement results are shown in Table 1.

(2) Measurement of sheet resistance value For each of the produced transparent electrodes, a sheet resistance value (Ω / □) was measured by a 4-terminal 4-probe method constant current application method using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation). did.
The measurement results are shown in Table 1.

(3) Measurement of electrode life A current of 10 A was continuously supplied to each of the produced transparent electrodes under the atmosphere, and the time required for the sheet resistance value to be twice the initial value was measured.
The measurement results are shown in Table 1.
The electrode life is indicated by a relative value where the electrode life of the transparent electrode 106 is 100.

(4) Summary As is apparent from Table 1, the present invention is such that a conductive layer mainly composed of silver (Ag) is provided on an intermediate layer using a metal complex having any one of 1-coordination to 4-coordination. Each of the transparent electrodes 108 to 122 has a light transmittance of 51% or more and a sheet resistance value of 17.9 Ω / □ or less. On the other hand, some of the transparent electrodes 101 to 107 of the comparative example had a light transmittance of less than 51% and a sheet resistance value exceeded 17.9 Ω / □.
Moreover, it turns out that the transparent electrodes 108-122 of this invention are excellent also in durability (electrode lifetime) compared with the transparent electrodes 101-107 of a comparative example.

  From the above, it was confirmed that the transparent electrode of the present invention has high light transmittance and conductivity, and is further excellent in durability.

[Example 2]
<< Preparation of transparent electrode >>
In the same manner as in Example 1, the transparent electrodes 201 to 223 were prepared so that the area of the conductive region was 5 cm × 5 cm. The transparent electrodes 201 to 204 were prepared as transparent electrodes having a single layer structure made of only a conductive layer, and the transparent electrodes 205 to 223 were prepared as transparent electrodes having a laminated structure of an intermediate layer and a conductive layer.

(1) Production of transparent electrode 201 First, a transparent non-alkali glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus and attached to a vacuum chamber of the vacuum deposition apparatus. Moreover, the resistance heating boat made from tungsten was filled with silver (Ag), and was attached in the said vacuum chamber. Next, after depressurizing the vacuum tank to 4 × 10 ⁻⁴ Pa, the resistance heating boat is energized and heated, and the layer thickness is 5 nm on the substrate within the range of the deposition rate of 0.1 to 0.2 nm / second. A conductive layer made of silver was formed to produce a transparent electrode 201 having a single layer structure.

(2) Production of transparent electrodes 202 to 204 Transparent electrodes 202 to 204 were produced in the same manner as the production of the transparent electrode 201 except that the thickness of the conductive layer was changed to 8 nm, 10 nm, and 15 nm, respectively.

(3) Production of transparent electrode 205 A thin film was formed by spin coating using a toluene solution of comparative compound (1) on a transparent non-alkali glass substrate. An intermediate layer made of the comparative compound (1) having a film thickness of 25 nm was provided by heating and drying at 150 ° C. for 1 hour.
On this intermediate layer, a conductive layer made of silver having a layer thickness of 8 nm was deposited by a method similar to that for the transparent electrode 201 to produce a transparent electrode 205.

(4) Production of transparent electrodes 206 and 207 Transparent electrodes 206 and 207 were produced in the same manner as in production of transparent electrode 205 except that the constituent material of the intermediate layer was changed to comparative compounds (2) and (3), respectively. .

(5) Preparation of transparent electrode 208 In the preparation of the transparent electrode 205, the transparent electrode 208 was prepared in the same manner except that the constituent material of the intermediate layer was changed to the exemplified compound (3) and the thickness of the conductive layer was changed to 5 nm. Was made.

(6) Production of transparent electrodes 209 to 211 Transparent electrodes 209 to 211 were produced in the same manner as the production of the transparent electrode 208 except that the thickness of the conductive layer was changed to 8 nm, 10 nm, and 20 nm, respectively.

(7) Production of transparent electrodes 212 to 220 Transparent electrodes 212 to 220 were produced in the same manner as the production of the transparent electrode 209 except that the constituent material of the intermediate layer was changed to the exemplified compounds shown in Table 2.

(8) Production of transparent electrodes 221 to 223 Transparent electrodes 221 to 223 were produced in the same manner as the production of the transparent electrodes 218 to 220 except that the base material was changed from a non-alkali glass to a PET (polyethylene terephthalate) film.

<< Evaluation of transparent electrode >>
About the produced transparent electrodes 201-223, according to the following method, the light transmittance, the sheet resistance value, and durability (electrode lifetime) were measured.

(1) Measurement of light transmittance and sheet resistance value About each produced transparent electrode, it carried out similarly to Example 1, and measured the light transmittance (%) and sheet resistance value (ohm / square).
The measurement results are shown in Table 2.

(2) Measurement of electrode life A current of 8 A was continuously supplied to each of the produced transparent electrodes in the air, and the time required for the sheet resistance value to be twice the initial value was measured.
The measurement results are shown in Table 2.
The electrode life is indicated by a relative value where the electrode life of the transparent electrode 206 is 100.

(4) Summary As is apparent from Table 2, the present invention is such that a conductive layer mainly composed of silver (Ag) is provided on an intermediate layer using a metal complex having any one of 1-coordination to 4-coordination. Each of the transparent electrodes 208 to 223 has a light transmittance of 50% or more and a sheet resistance value of 19.0Ω / □ or less. On the other hand, some of the transparent electrodes 201 to 207 of the comparative example had a light transmittance of less than 50% and a sheet resistance value exceeded 19.0Ω / □.
Moreover, it turns out that the transparent electrodes 208-223 of this invention are excellent also in durability (electrode lifetime) compared with the transparent electrodes 201-207 of a comparative example.

  From the above, it was confirmed that the transparent electrode of the present invention has high light transmittance and conductivity, and is further excellent in durability.

[Example 3]
<< Preparation of transparent electrode >>
As in Example 1, the transparent electrodes 301 to 318 were prepared so that the area of the conductive region was 5 cm × 5 cm. The transparent electrodes 301 and 302 were produced as a single-layer transparent electrode consisting only of a conductive layer, and the transparent electrodes 303 to 318 were produced as a transparent electrode having a laminated structure of an intermediate layer and a conductive layer.

(1) Production of Transparent Electrode 301 On a transparent non-alkali glass substrate, 0.1 mL of inkjet ink made of complex silver as a conductive layer material (TEC-IJ-010, manufactured by Ink Tec Co., Ltd.) After coating and patterning by a spin coating method, baking was performed at 130 ° C. for 5 minutes to form a conductive layer made of silver having a layer thickness of 12 nm, and a transparent electrode 301 having a single layer structure was manufactured.

(2) Production of Transparent Electrode 302 A transparent electrode 302 was produced in the same manner as the production of the transparent electrode 301 except that the thickness of the conductive layer was changed to 20 nm.

(3) Production of transparent electrode 303 A thin film was formed by spin coating on a non-alkali glass substrate using a toluene solution of the comparative compound (1). An intermediate layer made of the comparative compound (1) having a layer thickness of 40 nm was provided by heating and drying at 150 ° C. for 1 hour.

  On this intermediate layer, 0.1 mL of inkjet ink (TEC-IJ-010, manufactured by Ink Tec Co., Ltd.) made of complex silver as a conductive layer material was applied and patterned by a spin coating method, and then 5 ° C. at 130 ° C. After baking for a minute, a conductive layer made of silver having a layer thickness of 12 nm was formed, and a transparent electrode 303 having a laminated structure of an intermediate layer and a conductive layer was produced.

(4) Production of transparent electrodes 304 to 315 Transparent electrodes 304 to 315 were produced in the same manner except that the constituent materials of the intermediate layer were changed to the compounds shown in Table 3 in the production of the transparent electrode 303. Note that the thickness of the conductive layer of the transparent electrode 307 was set to 20 nm.

(5) Production of transparent electrodes 316 to 318 Transparent electrodes 316 to 318 were produced in the same manner except that the base material was changed from non-alkali glass to PET (polyethylene terephthalate) film.

<< Evaluation of transparent electrode >>
(1) Measurement of light transmittance, sheet resistance value and electrode life For each transparent electrode produced, the light transmittance (%), sheet resistance value (Ω / □) and electrode life were measured in the same manner as in Example 1. did. The electrode life is shown as a relative value with the electrode life of the transparent electrode 304 as 100.
Table 3 shows the measurement results.

(2) Summary As is apparent from Table 3, the present invention is such that a conductive layer mainly composed of silver (Ag) is provided on an intermediate layer using a metal complex having any one of 1-coordination to 4-coordination. Each of the transparent electrodes 306 to 318 has a light transmittance of 51% or more and a sheet resistance value of 17.9 Ω / □ or less. On the other hand, some of the transparent electrodes 301 to 305 of the comparative example had a light transmittance of less than 51% and a sheet resistance value exceeded 19.0Ω / □.
Moreover, it turns out that the transparent electrodes 306-318 of this invention are excellent also in durability (electrode lifetime) compared with the transparent electrodes 301-305 of a comparative example.

  From the above, it was confirmed that the transparent electrode of the present invention has high light transmittance and conductivity, and is further excellent in durability.

[Example 4]
<Production of light emitting panel>
Double-sided light emitting panels 401 to 423 using the transparent electrode of the present invention as an anode were manufactured. Hereinafter, a manufacturing procedure will be described with reference to FIG.

(1) Production of Light-Emitting Panel 401 First, the transparent substrate 101 produced in Example 1, that is, the transparent substrate 13 on which the transparent electrode 1 having only the conductive layer 1b is formed is used as a substrate holder of a commercially available vacuum deposition apparatus. It fixed and the vapor deposition mask was opposingly arranged by the formation surface side of the transparent electrode 1. FIG. Moreover, each material which comprises the organic functional layer 3 was filled in each heating boat in a vacuum evaporation apparatus in the optimal quantity for film-forming of each layer. In addition, what was produced with the resistance heating material made from tungsten was used for the heating boat.

Next, the inside of the vapor deposition chamber of the vacuum vapor deposition apparatus was depressurized to a vacuum degree of 4 × 10 ⁻⁴ Pa, and each layer was formed as follows by sequentially energizing and heating the heating boat containing each material.

  First, a hole-injecting injection layer 31 that serves as both a hole-injecting layer and a hole-transporting layer made of α-NPD is heated by energizing a heating boat containing α-NPD shown below as a hole-transporting injecting material. Was formed on the conductive layer 1 b constituting the transparent electrode 1. At this time, the deposition rate was 0.1 to 0.2 nm / second, and the layer thickness was 20 nm.

  Next, the heating boat containing the host material H4 and the heating boat containing the phosphorescent dopant Ir-4 are energized independently, and the light emitting layer 3c composed of the host material H4 and the phosphorescent dopant Ir-4. Was formed on the hole transport injection layer 31. At this time, the energization of the heating boat was adjusted so that the deposition rate was host material H4: phosphorescent dopant Ir-4 = 100: 6. The layer thickness was 30 nm.

  Next, 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. At this time, the deposition rate was 0.1 to 0.2 nm / second, and the layer thickness was 10 nm.

  Thereafter, a heating boat containing ET-6 shown below as an electron transporting material and a heating boat containing potassium fluoride were energized independently, and an electron transporting layer 3d made of ET-6 and potassium fluoride. Was formed on the hole blocking layer 33. At this time, the energization of the heating boat was adjusted so that the deposition rate was ET-6: potassium fluoride = 75: 25. The layer thickness was 30 nm.

  Next, 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. At this time, the deposition rate was 0.01 to 0.02 nm / second, and the layer thickness was 1 nm.

  Thereafter, 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. Next, in the processing chamber, a film was formed at a film forming rate of 0.3 to 0.5 nm / second, and a light-transmitting counter electrode 5a made of ITO having a film thickness of 150 nm was formed as a cathode. As described above, the organic EL element 400 was formed on the transparent substrate 13.

  Thereafter, the organic EL element 400 is covered with a sealing material 17 made of a glass substrate having a thickness of 300 μm, 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. ). As the adhesive 19, 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.

  In forming the organic EL element 400, an evaporation mask is used for forming each layer, and the central 4.5 cm × 4.5 cm of the 5 cm × 5 cm transparent substrate 13 is defined as the light emitting region A, and the entire circumference of the light emitting region A is formed. A non-light emitting region B having a width of 0.25 cm was provided. Further, the transparent electrode 1 as the anode and the counter electrode 5a as the cathode are insulated from each other by the organic functional layer 3 from the hole transport injection layer 31 to the electron injection layer 3e, and a terminal portion is formed on the periphery of the transparent substrate 13. Was formed in a drawn shape.

As described above, the light emitting panel 401 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 manufactured.
In the light emitting panel 401, the emitted light 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.

(2) Production of light-emitting panels 402 to 404 Light-emitting panels 402 to 404 were produced in the same manner except that the thickness of the conductive layer 1b was changed to 8.5 nm, 10 nm, and 15 nm, respectively. .

(3) Production of Light Emitting Panel 405 A light emitting panel 405 was produced in the same manner as the light emitting panel 401 except that the transparent electrode 1 was produced as follows.

  A transparent non-alkali glass base material 13 is fixed to a base material holder of a commercially available vacuum deposition apparatus, a comparative compound (1) is filled in a resistance heating boat made of tantalum, and these substrate holders and the heating boat are vacuum-deposited. Attached to the first vacuum chamber of the apparatus. Moreover, the resistance heating boat made from tungsten was filled with silver, and it attached in the 2nd vacuum chamber.

In this state, first, the first vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing the comparative compound (1) was energized and heated, and the deposition rate was 0.1 to 0.2 nm / second. In this range, an intermediate layer 1a made of the comparative compound (1) having a layer thickness of 20 nm was provided on the base material 13.

Next, the base material 13 formed up to the intermediate layer 1a is transferred to the second vacuum chamber while being vacuumed, and after the pressure of the second vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, a heating boat containing silver is energized. Heating is performed to form a conductive layer 1b made of silver having a layer thickness of 8.5 nm within a deposition rate range of 0.1 to 0.2 nm / second, and has a laminated structure of the intermediate layer 1a and the conductive layer 1b. A transparent electrode 1 was produced.

(4) Production of light-emitting panels 406 to 408 Light-emitting panels 406 to 408 were produced in the same manner except that the constituent material of the intermediate layer 1a was changed to ET-1 to ET-3 shown below. did.

(5) Production of light-emitting panel 409 In the production of light-emitting panel 405, the light-emitting panel was similarly manufactured except that the constituent material of intermediate layer 1a was changed to exemplary compound (24) and the thickness of the conductive layer was changed to 5 nm. 409 was produced.

(6) Production of light-emitting panels 410 to 412 Light-emitting panels 410 to 412 were produced in the same manner except that the thickness of the conductive layer 1b was changed to 8.5 nm, 15 nm, and 20 nm in the production of the light-emitting panel 409. .

(7) Production of light emitting panels 413 to 420 Light emitting panels 413 to 420 were produced in the same manner as the light emitting panel 410 except that the constituent material of the intermediate layer 1a was changed to the exemplified compounds shown in Table 4.

(8) Production of light-emitting panels 421 to 423 Light-emitting panels 421 to 423 were produced in the same manner as the light-emitting panels 418 to 420 except that the base material 13 was changed from non-alkali glass to a PET (polyethylene terephthalate) film. .

<Evaluation of luminous panel>
About the produced light emission panels 401-423, according to the following method, the light transmittance, the drive voltage, and durability (luminance half life) were measured.

(1) Measurement of light transmittance About each produced light emitting panel, the light transmittance (%) in wavelength 550nm is used for the base material of the transparent electrode of each light emitting panel using a spectrophotometer (Hitachi Ltd. U-3300). ) Was measured.
Table 4 shows the measurement results.

(2) Measurement of drive voltage For each of the produced light-emitting panels, front luminance on 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) of each light-emitting panel. Was measured, and the voltage when the sum was 1000 cd / m ² was measured as the drive voltage (V). For the measurement of luminance, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used. It represents that it is so preferable that the numerical value of the obtained drive voltage is small.
Table 4 shows the measurement results.

(3) Measurement of Luminance Half Life The time (τ1 / 2) required for each manufactured light-emitting panel to continue to pass a current of 10 A under the atmosphere and to be half the initial luminance was measured.
Table 4 shows the measurement results.
Note that the luminance half-life is shown as a relative value where the luminance half-life of the light-emitting panel 408 is 100.

(4) Summary As is clear from Table 4, each of the light emitting panels 409 to 423 of the present invention using the transparent electrode of the present invention as the anode of an organic EL element has a light transmittance of 53% or more and is driven. The voltage is suppressed to 4.3V or less. On the other hand, the light emitting panels 401 to 408 using the transparent electrode of the comparative example as the anode of the organic EL element have a light transmittance of less than 53% and do not emit light even when a voltage is applied, or emit light. Even in some cases, the drive voltage exceeded 4.3V.
Moreover, it turns out that the light emission panels 409-423 of this invention are excellent also in durability (luminance half life) compared with the light emission panels 401-408 of a comparative example.

  Accordingly, it was confirmed that the light-emitting panel using the transparent electrode of the present invention can emit light with high luminance at a low driving voltage. In addition, it was confirmed that the driving voltage for obtaining the predetermined luminance can be reduced and the light emission life can be improved.

[Example 5]
<Production of light emitting panel>
Double-sided light emitting panels 501 to 523 using the transparent electrode of the present invention as an anode were manufactured. Hereinafter, a manufacturing procedure will be described with reference to FIG.

(1) Production of Light-Emitting Panel 501 First, the transparent substrate 101 produced in Example 1, that is, the transparent substrate 13 on which the transparent electrode 2 having only the conductive layer 1b is formed, is fixed to a substrate holder of a commercially available vacuum deposition apparatus. Then, a vapor deposition mask was disposed opposite to the surface on which the transparent electrode 2 was formed. Moreover, each material which comprises the organic functional layer 3 was filled in each heating boat in a vacuum evaporation apparatus in the optimal quantity for film-forming of each layer. In addition, what was produced with the resistance heating material made from tungsten was used for the heating boat.

Next, the inside of the vapor deposition chamber of the vacuum vapor deposition apparatus was depressurized to a vacuum degree of 4 × 10 ⁻⁴ Pa, and each layer was formed as follows by sequentially energizing and heating the heating boat containing each material.

  First, a heating boat containing α-NPD as a hole transport injection material is energized and heated, and a hole transport injection layer 31 serving as both a hole injection layer and a hole transport layer made of α-NPD is transparent. A film was formed on the conductive layer 1 b constituting the electrode 2. At this time, the deposition rate was 0.1 to 0.2 nm / second, and the layer thickness was 20 nm.

  Next, the heating boat containing the host material H4 and the heating boat containing the phosphorescent dopant Ir-4 are energized independently, and the light emitting layer 3c composed of the host material H4 and the phosphorescent dopant Ir-4. Was formed on the hole transport injection layer 31. At this time, the energization of the heating boat was adjusted so that the deposition rate was host material H4: phosphorescent dopant Ir-4 = 100: 6. The layer thickness was 30 nm.

  Next, a heating boat containing BAlq 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. At this time, the deposition rate was 0.1 to 0.2 nm / second, and the layer thickness was 10 nm.

  Thereafter, a heating boat containing ET-6 as an electron transporting material and a heating boat containing potassium fluoride were energized independently, and an electron transporting layer 3d made of ET-6 and potassium fluoride was positively connected. A film was formed on the hole blocking layer 33. At this time, the energization of the heating boat was adjusted so that the deposition rate was ET-6: potassium fluoride = 75: 25. The layer thickness was 30 nm.

  Next, 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. At this time, the deposition rate was 0.01 to 0.02 nm / second, and the layer thickness was 1 nm.

  Thereafter, 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. Next, in the processing chamber, a film was formed at a film forming rate of 0.3 to 0.5 nm / second, and a light-transmitting counter electrode 5a made of ITO having a film thickness of 150 nm was formed as a cathode. Thus, the organic EL element 500 was formed on the transparent substrate 13.

  Thereafter, the organic EL element 500 is covered with a sealing material 17 made of a glass substrate having a thickness of 300 μm, 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 500. ). As the adhesive 19, 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 500. Stopped.

  In forming the organic EL element 500, 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 2 as the anode and the counter electrode 5a as the cathode are insulated from each other by the organic functional layer 3 from the hole transport injection layer 31 to the electron injection layer 3e. Was formed in a drawn shape.

As described above, the light emitting panel 501 in which the organic EL element 500 was provided on the transparent substrate 13 and sealed with the sealing material 17 and the adhesive 19 was manufactured.
In the light emitting panel 501, the emitted light h of each color generated in the light emitting layer 3c is extracted from both the transparent electrode 2 side, that is, the transparent substrate 13 side, and the counter electrode 5a side, that is, the sealing material 17 side.

(2) Production of light-emitting panels 502 to 504 Light-emitting panels 502 to 504 were produced in the same manner except that the thickness of the conductive layer 1b was changed to 8 nm, 10 nm, and 15 nm, respectively.

(3) Production of Light Emitting Panel 505 A light emitting panel 505 was produced in the same manner as the light emitting panel 501, except that the transparent electrode 2 was produced as follows.

  A transparent non-alkali glass base material 13 is fixed to a base material holder of a commercially available vacuum deposition apparatus, ET-3 and a comparative compound (1) are filled in a resistance heating boat made of tantalum, and these substrate holders are heated. The boat was attached to the first vacuum chamber of the vacuum deposition apparatus. Moreover, the resistance heating boat made from tungsten was filled with silver, and it attached in the 2nd vacuum chamber.

Next, the first vacuum chamber of the vacuum evaporation apparatus was depressurized to a vacuum degree of 4 × 10 ⁻⁴ Pa, and each layer was formed as follows by sequentially energizing and heating the heating boat containing each material.

  First, the second intermediate layer made of ET-3 having a layer thickness of 20 nm on the substrate 13 within a range of the deposition rate of 0.1 to 0.2 nm / second is heated by energizing a heating boat containing ET-3. Layer 2a2 was provided.

  Next, the heating boat containing the comparative compound (1) is energized and heated, and the comparative compound (1) having a layer thickness of 5 nm is formed on the base material within a deposition rate range of 0.1 to 0.2 nm / second. A first intermediate layer 2a1 was provided.

Next, the base material 13 formed up to the first intermediate layer 2a1 is transferred to the second vacuum chamber while maintaining a vacuum, and after the pressure of the second vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, the heated boat containing silver is energized. Then, the conductive layer 1b made of silver having a layer thickness of 8 nm is formed within the range of the deposition rate of 0.1 to 0.2 nm / second, and the second intermediate layer 2a2, the first intermediate layer 2a1 and the conductive layer are formed. A transparent electrode 2 having a laminated structure of the layer 1b was produced.

(4) Production of Light-Emitting Panels 506 to 520 Table 5 shows the constituent materials of the first intermediate layer 2a1 and the second intermediate layer 2a2 and the layer thicknesses of the first intermediate layer and the conductive layer in the production of the light-emitting panel 505. Luminescent panels 506 to 520 were produced in the same manner except that the compound was changed.

(5) Production of light-emitting panels 521 to 523 Light-emitting panels 521 to 523 were produced in the same manner except that the base material 13 was changed from non-alkali glass to PET (polyethylene terephthalate) film. .

<Evaluation of luminous panel>
About the produced light emission panels 501-523, the light transmittance, the drive voltage, and durability (luminance half life) were measured in accordance with the following method.

(1) Measurement of light transmittance and driving voltage For each of the produced light emitting panels, the light transmittance (%) and the driving voltage (V) were measured in the same manner as in Example 4.
Table 5 shows the measurement results.

(2) Measurement of Luminance Half Life The manufactured light-emitting panel was continuously supplied with a current of 15 A in the atmosphere, and the time (τ1 / 2) required to reach half the initial luminance was measured.
Table 5 shows the measurement results.
Note that the luminance half-life is indicated by a relative value where the luminance half-life of the light-emitting panel 507 is 100.

(3) Summary As is clear from Table 5, the light-emitting panels 508 to 523 of the present invention using the transparent electrode of the present invention having two intermediate layers as the anode of the organic EL element each have a light transmittance of 51. % And the drive voltage is suppressed to 4.1 V or less. On the other hand, the light emitting panels 501 to 507 using the transparent electrode of the comparative example as the anode of the organic EL element have a light transmittance of less than 51% and do not emit light even when a voltage is applied, or emit light. Even in some cases, the drive voltage exceeded 4.1V.
Moreover, it turns out that the light emission panels 508-523 of this invention are excellent also in durability (luminance half life) compared with the light emission panels 501-507 of a comparative example.

  Accordingly, it was confirmed that the light-emitting panel using the transparent electrode of the present invention can emit light with high luminance at a low driving voltage. In addition, it was confirmed that the driving voltage for obtaining the predetermined luminance can be reduced and the light emission life can be improved.

1 transparent electrode 1a intermediate layer 1b conductive layer 2 transparent electrode 2a intermediate layer 2a1 first intermediate layer 2a2 second intermediate layer 3 organic functional layer 3a hole injection layer 3b hole transport layer 3c light emitting layer 3d electron transport layer 3e electron injection Layer 5a, 5b, 5c Counter electrode 11 Base material 13, 131 Transparent substrate (base material)
13a, 131a Light extraction surface 15 Auxiliary electrode 17 Sealant 19 Adhesive 21 Illumination device 22 Light emitting panel 23 Support substrate 31 Hole transport injection layer 33 Hole blocking layer 100, 200, 300, 400, 500 Organic EL element A Light emission Area B Non-light emitting area h Emitted light

Claims (18)

In a transparent electrode comprising a conductive layer and at least one intermediate layer provided adjacent to the conductive layer,
The conductive layer is composed mainly of silver,
The said intermediate | middle layer contains the metal complex which is either 1 coordination, 2 coordination, 3 coordination, and 4 coordination, The transparent electrode characterized by the above-mentioned.   The transparent electrode according to claim 1, wherein the metal complex is a compound having a ligand of an organic compound.   The transparent electrode according to claim 1, wherein the charge in the whole molecule of the metal complex is neutral.   The metal complex has a transition metal atom, and the coordination atom in the ligand of the metal complex is any one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a carbene carbon atom. The transparent electrode according to any one of claims 1 to 3. The transparent electrode according to claim 4, wherein the metal complex is a compound having a structure represented by any one of the following general formulas (1) to (5).

[In General Formulas (1) to (5), M represents a transition metal atom, and forms a covalent bond and a coordinate bond with a polydentate ligand. Multidentate ligands may combine with each other to form tridentate or tetradentate ligands. L represents an auxiliary ligand and forms a covalent bond or a coordinate bond with M. n represents an integer of 0 to 2. When n is 1, L may be a monodentate ligand or a polydentate ligand, and when n is 2, L may be the same or different, but the charge in the whole molecule Is neutral. ] The transparent electrode according to claim 5, wherein the metal complex having a structure represented by the general formula (1) is a compound having a structure represented by the following general formula (1-1).

[In General Formula (1-1), M represents a transition metal atom. R ₁ and R ₂ each independently represents a substituent. L ₁ and L ₂ represent a ligand that forms a covalent bond or a coordinate bond with M, and may bond to each other to form a bidentate ligand. ] The transparent electrode according to claim 5, wherein the metal complex having a structure represented by the general formula (2) is a compound having a structure represented by the following general formula (2-1).

[In General Formula (2-1), M represents a transition metal atom. R ₃ and R ₄ each independently represents a substituent. R _{5 to} R ₁₂ each independently represent a substituent and may be bonded to each other to form a ring. ] The transparent electrode according to claim 5, wherein the metal complex having a structure represented by the general formula (3) is a compound having a structure represented by the following general formula (3-1).

[In General Formula (3-1), M represents a transition metal atom. X _{1 to} X ₄ each independently represent —CR ₂₁ or a nitrogen atom, and R ₂₁ represents a hydrogen atom or a substituent. R _{13 to} R ₂₀ each independently represent a substituent and may be bonded to each other to form a ring. ] The transparent electrode according to claim 5, wherein the metal complex having a structure represented by the general formula (4) is a compound having a structure represented by the following general formula (4-1).

[In General Formula (4-1), M represents a transition metal atom. R _{22 to} R ₂₅ each independently represent a substituent. Ring A represents a 5-membered or 6-membered aromatic heterocyclic ring formed together with a nitrogen atom and a carbon atom, and may further have a substituent, and these substituents are bonded to each other to form a ring. May be. L ₃ and L ₄ represent a ligand that forms a covalent bond or a coordinate bond with M, and may bond to each other to form a bidentate ligand. ] The transparent electrode according to claim 5, wherein the metal complex having a structure represented by the general formula (5) is a compound having a structure represented by the following general formula (5-1).

[In General Formula (5-1), M represents a transition metal atom. R _{26 to} R ₂₉ each independently represent a substituent, and may be bonded to each other to form a ring. X ₅ and X ₆ each independently represent —CR ₃₀ or a nitrogen atom, and R ₃₀ represents a hydrogen atom or a substituent. R ₃₁ represents a hydrogen atom or a substituent. L ₅ and L ₆ each represent a ligand that forms a covalent bond or a coordinate bond with M, and may bond to each other to form a bidentate ligand. ]   The transition metal atom is any one selected from Co (II), Ni (II), Cu (II), Pd (II), Pt (II) and Au (III). The transparent electrode according to any one of claims 4 to 10.   The transparent electrode according to claim 11, wherein the transition metal atom is any one selected from Cu (II), Pd (II), Pt (II), and Au (III).   The transparent electrode according to claim 12, wherein the transition metal atom is any one selected from Pd (II), Pt (II), and Au (III).   The transparent electrode according to claim 13, wherein the transition metal atom is Au (III). The intermediate layer is composed of two layers of a first intermediate layer and a second intermediate layer in order from the conductive layer side,
The first intermediate layer is a layer containing the metal complex;
The second intermediate layer is a layer containing an aromatic heterocyclic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity;
15. The transparent electrode according to claim 1, wherein a thickness of the first intermediate layer is in a range of 0.5 to 10 nm.   16. The conductive layer according to any one of claims 1 to 15, wherein the conductive layer is formed by a wet method using a conductive ink containing silver as a main component and containing an organic solvent. The transparent electrode as described.   An electronic device comprising the transparent electrode according to any one of claims 1 to 16.   An organic electroluminescence device comprising the transparent electrode according to any one of claims 1 to 16.

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