JP2016157639A - Transparent electrode substrate and method for producing the same, electronic device and organic el device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent electrode substrate having higher transparency and conductivity, and in addition, preferably to provide a method for producing a transparent electrode substrate, high in utilization efficiency of materials and in time efficiency, capable of achieving a larger area, and capable of forming a conductive layer even to a substrate with a curved surface.SOLUTION: A transparent electrode substrate includes a substrate and a transparent electrode that includes a metal-containing conductive layer and an intermediate layer disposed between the conductive layer and the substrate. The intermediate layer is formed of one or more self-organized monomolecular films including a compound that has an aromatic hydrocarbon group or an aromatic heterocyclic group at one molecular end thereof and a hydrophilic group at the other molecular end.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transparent electrode substrate, a manufacturing method thereof, an electronic device, and an organic EL device.

  An organic EL element (also referred to as an organic electroluminescent element) using electroluminescence (hereinafter referred to as EL) of an organic material is a thin film type complete solid-state element capable of emitting light at a low voltage of several V to several tens V It 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.

  Therefore, by providing silver (Ag) having a high electrical conductivity as a conductive layer, and providing an intermediate layer made of a nitrogen-containing organic compound having a lone pair not involved in aromaticity under the conductive layer, There has been proposed a method for producing a transparent electrode in which a strong interaction is exerted between a nitrogen-containing organic compound and silver to achieve both excellent light transmittance and conductivity (see, for example, Patent Documents 3 and 4). .

JP 2002-015623 A Japanese Unexamined Patent Publication No. 2006-164961 International Publication No. 2013/105569 International Publication No. 2013/141097

  However, the transparent electrodes of Patent Documents 3 and 4 are desired to have higher transparency and conductivity. Moreover, the intermediate layer which comprises the transparent electrode of patent document 3 and 4 is mainly formed by the dry process (for example, vapor deposition method). Compared with the wet method, the dry method is advantageous in that it does not use a solvent, but the film formation rate is low, the material utilization efficiency is low, and it is difficult to form a thin film on a large-area substrate from the viewpoint of device constraints. It was disadvantageous. In addition, it is difficult to form a thin film on a substrate having a curved surface or a substrate having a complicated surface shape.

  The present invention has been made in view of such circumstances, and an object thereof is to provide a transparent electrode substrate having higher transparency and conductivity, an electronic device including the same, and an organic EL device. Preferably, the present invention provides a method for producing a transparent electrode substrate that has higher material utilization efficiency and time efficiency, can have a large area, and can be formed on a curved substrate.

（一般式（１）中、
Ｒは、置換又は無置換の含窒素芳香族複素環基を表し；
Ｌ^１は、炭素原子数が２以上のアルキレン基を表し、前記アルキレン基中の炭素原子の一部が酸素原子又は硫黄原子に置き換えられてもよく；
Ａ^１は、炭素原子、ケイ素原子、−Ｃ（＝Ｏ）−又は−ＮＨ−Ｃ（＝Ｏ）−を表し；
−ＯＢ^１、−ＯＢ^２及び−ＯＢ^３は、それぞれヒドロキシ基又はアルコキシ基を表し、かつ−ＯＢ^１、−ＯＢ^２及び−ＯＢ^３は、他分子又は基板表面のヒドロキシ基又はアルコキシ基と縮合していてもよく；
ｍ及びｎは、前記Ａ^１が炭素原子又はケイ素原子である場合はそれぞれ１を表し、−Ｃ（＝Ｏ）−又は−ＮＨ−Ｃ（＝Ｏ）−の場合はそれぞれ０を表す）
［５］ 前記一般式（１）で表される化合物は、下記一般式（２）で表される化合物である、［４］に記載の透明電極基板。

（一般式（２）中、
Ｘ^１〜Ｘ^５は、それぞれ炭素原子又は窒素原子を表し、かつＸ^１〜Ｘ^５の少なくとも一つは窒素原子を表し；
Ｒ^１〜Ｒ^５は、それぞれ水素原子又は置換基を表し；
Ｌ^２は、炭素原子数が２以上のアルキレン基を表し、前記アルキレン基中の炭素原子の一部が酸素原子又は硫黄原子に置き換えられてもよく；
Ａ^２は、炭素原子、ケイ素原子、−Ｃ（＝Ｏ）−又は−ＮＨ−Ｃ（＝Ｏ）−を表し；
−ＯＢ^４、−ＯＢ^５及び−ＯＢ^６は、それぞれヒドロキシ基又はアルコキシ基を表し、かつ−ＯＢ^４、−ＯＢ^５及び−ＯＢ^６は、他分子又は基板表面のヒドロキシ基又はアルコキシ基と縮合していてもよく；
ｍ及びｎは、前記Ａ^２が炭素原子又はケイ素原子である場合はそれぞれ１を表し、−Ｃ（＝Ｏ）−又は−ＮＨ−Ｃ（＝Ｏ）−の場合はそれぞれ０を表す）
［６］ 前記一般式（２）中のＡ^２が、炭素原子又はケイ素原子である、［５］に記載の透明電極基板。
［７］ 前記一般式（１）で表される化合物が、下記一般式（３）で表される化合物である、［４］〜［６］のいずれかに記載の透明電極基板。

（一般式（３）中、
Ｒ^６及びＲ^７は、それぞれ置換基を表し；
Ｌ^３は、炭素原子数が２以上のアルキレン基を表し、前記アルキレン基中の炭素原子の一部が酸素原子又は硫黄原子に置き換えられてもよく；
Ａ^３は、炭素原子、ケイ素原子、−Ｃ（＝Ｏ）−又は−ＮＨ−Ｃ（＝Ｏ）−を表し；
−ＯＢ^７、−ＯＢ^８及び−ＯＢ^９は、それぞれヒドロキシ基又はアルコキシ基を表し、かつ−ＯＢ^７、−ＯＢ^８及び−ＯＢ^９は、他分子又は基板表面のヒドロキシ基又はアルコキシ基と縮合していてもよく；
ｍ及びｎは、前記Ａ^３が炭素原子又はケイ素原子である場合はそれぞれ１を表し、−Ｃ（＝Ｏ）−又は−ＮＨ−Ｃ（＝Ｏ）−の場合はそれぞれ０を表す）
［８］ 前記一般式（３）中のＡ^３が、炭素原子又はケイ素原子である、［７］に記載の透明電極基板。
［９］ 前記一般式（３）中のＬ^３が、炭素原子数６以上の直鎖状アルキレン基である、［７］又は［８］に記載の透明電極基板。
［１０］ 前記基板が、ガラス、ポリエチレンテレフタラート又はポリメタクリル酸メチル樹脂を含む、［１］〜［９］のいずれかに記載の透明電極基板。
［１１］ 基板を、一般式（４）で表される化合物を含む溶液に浸漬して、前記基板上に前記化合物の自己組織化単分子膜を含む中間層を形成する工程と、前記中間層上に、導電性層を形成する工程とを含む、透明電極基板の製造方法。

（一般式（４）中、
Ｒは、置換又は無置換の含窒素芳香族複素環基を表し；
Ｌ^１は、炭素原子数が２以上のアルキレン基を表し、前記アルキレン基中の炭素原子の一部が酸素原子又は硫黄原子に置き換えられてもよく；
Ａ^１は、炭素原子、ケイ素原子、−Ｃ（＝Ｏ）−又は−ＮＨ−Ｃ（＝Ｏ）−を表し；
Ｙ^１、Ｙ^２及びＹ^３は、それぞれヒドロキシ基、アルコキシ基又はハロゲン原子を表し；
ｍ及びｎは、前記Ａ^１が炭素原子又はケイ素原子である場合はそれぞれ１を表し、−Ｃ（＝Ｏ）−又は−ＮＨ−Ｃ（＝Ｏ）−の場合はそれぞれ０を表す）
［１２］ ［１］〜［１０］のいずれかに記載の透明電極基板を含む、電子デバイス。
［１３］ 陰極及び陽極の一方が設けられた基板と、前記陰極及び前記陽極の他方と、前記陰極と前記陽極との間に配置された発光層とを含み、前記陰極及び陽極の一方が設けられた基板が、［１］〜［１０］のいずれかに記載の透明電極基板である、有機ＥＬデバイス。 [1] A substrate, a conductive layer containing a metal as a main component, and a transparent electrode including an intermediate layer disposed between the conductive layer and the substrate, wherein the intermediate layer is one molecule A transparent electrode substrate which is one or more self-assembled monolayers containing a compound containing an aromatic hydrocarbon group or an aromatic heterocyclic group at an end and a hydrophilic group at the other molecular end.
[2] The transparent electrode substrate according to [1], wherein the conductive layer contains as a main component one or more selected from the group consisting of gold, silver, and copper.
[3] The transparent electrode substrate according to [1] or [2], wherein the conductive layer contains silver as a main component.
[4] The transparent electrode substrate according to any one of [1] to [3], wherein the compound is a compound represented by the following general formula (1).

(In general formula (1),
R represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group;
L ¹ represents an alkylene group having 2 or more carbon atoms, and part of the carbon atoms in the alkylene group may be replaced with an oxygen atom or a sulfur atom;
A ¹ represents a carbon atom, a silicon atom, —C (═O) — or —NH—C (═O) —;
-OB ^1, -OB ² and -OB ³ each represent a hydroxy group or an alkoxy group, and ^-OB 1, -OB ² and -OB ³ is other molecules or substrate surface hydroxy group or an alkoxy group is fused May be;
m and n each represents 1 when A ¹ is a carbon atom or a silicon atom, and each represents 0 when —C (═O) — or —NH—C (═O) —.
[5] The transparent electrode substrate according to [4], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In general formula (2),
X ^{1 to} X ⁵ each represent a carbon atom or a nitrogen atom, and at least one of X ^{1 to} X ⁵ represents a nitrogen atom;
R ^{1 to} R ⁵ each represent a hydrogen atom or a substituent;
L ² represents an alkylene group having 2 or more carbon atoms, and part of the carbon atoms in the alkylene group may be replaced with an oxygen atom or a sulfur atom;
A ² represents a carbon atom, a silicon atom, —C (═O) — or —NH—C (═O) —;
-OB ^4, -OB ⁵ and -OB ⁶ each represent a hydroxy group or an alkoxy group, and ^-OB 4, -OB ⁵ and -OB ⁶ are other molecules or substrate surface hydroxy group or an alkoxy group is fused May be;
m and n each represent 1 when A ² is a carbon atom or a silicon atom, and each represents 0 when —C (═O) — or —NH—C (═O) —.
[6] The transparent electrode substrate according to [5], wherein A ² in the general formula (2) is a carbon atom or a silicon atom.
[7] The transparent electrode substrate according to any one of [4] to [6], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

(In general formula (3),
R ⁶ and R ⁷ each represent a substituent;
L ³ represents an alkylene group having 2 or more carbon atoms, and a part of the carbon atoms in the alkylene group may be replaced with an oxygen atom or a sulfur atom;
A ³ represents a carbon atom, a silicon atom, —C (═O) — or —NH—C (═O) —;
-OB ^7, -OB ⁸ and -OB ⁹ each represent a hydroxy group or an alkoxy group, and ^-OB 7, -OB ⁸ and -OB ⁹ are other molecules or substrate surface hydroxy group or an alkoxy group is fused May be;
m and n each represents 1 when A ³ is a carbon atom or a silicon atom, and each represents 0 when —C (═O) — or —NH—C (═O) —.
[8] The transparent electrode substrate according to [7], wherein A ³ in the general formula (3) is a carbon atom or a silicon atom.
[9] The transparent electrode substrate according to [7] or [8], wherein L ³ in the general formula (3) is a linear alkylene group having 6 or more carbon atoms.
[10] The transparent electrode substrate according to any one of [1] to [9], wherein the substrate includes glass, polyethylene terephthalate, or polymethyl methacrylate resin.
[11] A step of immersing the substrate in a solution containing the compound represented by the general formula (4) to form an intermediate layer including a self-assembled monolayer of the compound on the substrate; and the intermediate layer The manufacturing method of a transparent electrode substrate including the process of forming an electroconductive layer on the top.

(In general formula (4),
R represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group;
L ¹ represents an alkylene group having 2 or more carbon atoms, and part of the carbon atoms in the alkylene group may be replaced with an oxygen atom or a sulfur atom;
A ¹ represents a carbon atom, a silicon atom, —C (═O) — or —NH—C (═O) —;
Y ¹ , Y ² and Y ³ each represent a hydroxy group, an alkoxy group or a halogen atom;
m and n each represents 1 when A ¹ is a carbon atom or a silicon atom, and each represents 0 when —C (═O) — or —NH—C (═O) —.
[12] An electronic device comprising the transparent electrode substrate according to any one of [1] to [10].
[13] A substrate including one of a cathode and an anode, the other of the cathode and the anode, and a light emitting layer disposed between the cathode and the anode, wherein one of the cathode and the anode is provided An organic EL device, wherein the obtained substrate is the transparent electrode substrate according to any one of [1] to [10].

  ADVANTAGE OF THE INVENTION According to this invention, the transparent electrode which has high permeability | transmittance and electroconductivity, an electronic device including the same, and an organic EL device can be provided. Preferably, it is possible to provide a method for producing a transparent electrode substrate that has higher material utilization efficiency and time efficiency, can be increased in area, and can be formed on a curved substrate.

It is a schematic diagram which shows an example of a structure of a transparent electrode substrate. It is a figure which shows the preferable one aspect | mode of the compound which forms a self-assembled monolayer. It is a schematic diagram which shows an example of the self-assembled monolayer containing the compound of FIG. It is a schematic diagram which shows an example of the intermediate | middle layer comprised by the self-assembled monolayer of one layer. It is a schematic diagram which shows an example of the intermediate | middle layer comprised by a self-assembled monolayer of two or more layers. It is explanatory drawing which shows an example of the formation process of the intermediate | middle layer by a dip method. It is a schematic sectional drawing which shows the 1st example of the organic EL device containing the transparent electrode substrate of this invention. It is a schematic sectional drawing which shows the 2nd example of the organic EL device containing the transparent electrode substrate of this invention. It is a schematic sectional drawing which shows the 1st example of an illuminating device.

  As a result of intensive studies to solve the above problems, the present inventor, in a transparent electrode substrate including a substrate, an intermediate layer, and a conductive layer, the intermediate layer is designated as “an aromatic hydrocarbon group or By using one or more self-assembled monolayers (SAMs) containing a compound containing an aromatic heterocyclic group and a hydrophilic group at the other molecular end, high light transmittance and It was found that both high conductivity (low resistance value) can be achieved. Although this reason is not necessarily clear, it is estimated as follows.

  The self-assembled monomolecular film may have a structure in which the aromatic hydrocarbon group or the aromatic heterocyclic group of the compound is aligned so as to be adjacent to the conductive layer and the hydrophilic group is adjacent to the substrate. As a result, when the conductive layer is formed on the intermediate layer, the metal component of the conductive layer interacts with the aromatic hydrocarbon group or aromatic heterocyclic group of the above compound constituting the intermediate layer with high efficiency, Aggregation of metal components in the conductive layer can be suppressed. As a result, the conductive layer can be easily grown in a monodisperse type, and a conductive layer with high transmittance and low resistance can be formed.

  The self-assembled monolayer can be obtained by forming the compound preferably by a dip method (immersion method). As a result, the utilization efficiency and time efficiency of the material can be increased, and the area can be increased. Furthermore, a transparent electrode having a uniform thickness can be formed relatively easily on a substrate having a curved surface, a substrate having a complicated shape, and a substrate having high rigidity. The present invention has been made based on such findings.

1. Transparent electrode substrate The transparent electrode substrate includes a substrate and a transparent electrode. The transparent electrode includes a conductive layer and an intermediate layer disposed between the conductive layer and the substrate and adjacent to the conductive layer. The intermediate layer is one or more self-assembled monolayers containing a compound having an aromatic hydrocarbon group or an aromatic heterocyclic group at one molecular end and a hydrophilic group at the other molecular end. is there.

  FIG. 1 is a schematic diagram illustrating an example of a configuration of a transparent electrode substrate. As shown in FIG. 1, the transparent electrode substrate 10 includes a substrate 11 and a transparent electrode 1. The transparent electrode 1 includes a conductive layer 1b and an intermediate layer 1a provided between the conductive layer 1b and the substrate 11 and adjacent to the conductive layer 1b.

1-1. Substrate 11
Examples of the material constituting the substrate 11 include glass and plastic. The substrate 11 may be transparent or opaque. When the transparent electrode substrate 10 is used for an electronic device that extracts light from the substrate 11 side, the substrate 11 is preferably transparent. Examples of the material constituting the transparent substrate 11 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.

Examples of resin films 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, polyether Films of cycloolefin resins such as luimide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) and Appel (trade name, manufactured by Mitsui Chemicals) Is mentioned.

  The surface of the substrate may be subjected to physical treatment such as polishing as necessary from the viewpoint of imparting adhesion, durability and smoothness to the intermediate layer 1a, or a coating made of an inorganic or organic material. Alternatively, a hybrid coating obtained by combining these coatings may be formed.

Such coatings and hybrid coatings have a water vapor transmission rate (25 ± 0.5 ° C., relative humidity 90 ± 2%) measured by a method according to JIS K 7129-1992 of 0.01 g / m ² · 24 h or less. It is preferable that it is a barrier film. Furthermore, the oxygen permeability measured by a 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 · A high barrier film of 24 hours or less is preferable.

  The material constituting the barrier coating may be a material having a function of suppressing the intrusion of moisture, oxygen, and the like, and may be, for example, silicon oxide, silicon dioxide, silicon nitride, or the like. Furthermore, in order to improve the brittleness of the barrier coating, it is more preferable to have a laminated structure of a layer made of these inorganic materials (inorganic layer) and a layer made of an 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 barrier coating is, for example, a vacuum deposition method, a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, an ion plating method, a plasma polymerization method, an atmospheric pressure plasma polymerization method, a plasma CVD method, a laser CVD method. Alternatively, it may be formed by a thermal CVD method, a coating method, or the like. Among these, those formed by the atmospheric pressure plasma polymerization method described in JP-A-2004-68143 are particularly preferable. On the other hand, when the substrate 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.

  The substrate can usually have a film shape or a plate shape, but may have various shapes depending on the application. For example, at least a part of the substrate may have a curved surface shape or an uneven shape.

  The thickness of the substrate (in the case of a substrate having a non-uniform thickness, the minimum thickness of the substrate) depends on the application, but is, for example, about 1 to 10000 μm, preferably 10 to 1000 μm, and preferably 10 to 500 μm. More preferred.

1-2. Intermediate layer 1a
The intermediate layer 1a is composed of one or more self-assembled monolayers. The self-assembled monomolecular film includes a compound having an aromatic hydrocarbon group or an aromatic heterocyclic group at one molecular end and a hydrophilic group at the other molecular end.

  Examples of the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group of the above compound include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring and the like.

  The aromatic heterocyclic ring in the aromatic heterocyclic group of the above compound is preferably a nitrogen-containing aromatic heterocyclic ring in that high interaction with the metal contained in the conductive layer is easily obtained. A nitrogen-containing aromatic heterocyclic ring is an aromatic heterocyclic ring containing a nitrogen atom as a ring constituent atom. Examples thereof include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, an oxazole ring, a thiazole ring, an oxa Diazole ring, thiadiazole ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring and the like are included. Among these, two or more rings may be condensed.

  The aromatic hydrocarbon ring or aromatic heterocycle may further have a substituent. The total number of carbon atoms of the substituted or unsubstituted aromatic hydrocarbon ring group may be, for example, 6 to 20. The total number of carbon atoms of the substituted or unsubstituted aromatic heterocyclic group may be 3 to 20, for example.

  Examples of the substituent that the aromatic hydrocarbon ring or the aromatic heterocyclic ring may have include an aryl group (for example, a phenyl group), a heteroaryl group (for example, an imidazolyl group, a pyridinyl group, a benzopyridinyl group, etc.), an alkyl group (for example, a methyl group) Group, ethyl group, propyl group, isopropyl group), alkoxy group (for example, methoxy group), thiol group, amino group, halogen atom (for example, chlorine atom, fluorine atom) and the like.

  Among these, a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group is preferable from the viewpoint that high interaction with a metal contained in the conductive layer is easily obtained, and “a lone pair of electrons not involved in aromaticity is selected. A substituted or unsubstituted nitrogen-containing aromatic heterocyclic group containing “a nitrogen atom” as a ring constituent atom is more preferable.

  “A nitrogen atom having an unshared electron pair not involved in aromaticity” means a nitrogen atom having an unshared electron pair, and the unshared electron pair is a non-localized atom on a conjugated unsaturated ring structure (aromatic ring). This means that the activated π-electron system is not involved as an essential element for the expression of aromaticity. Details of the “nitrogen atom having an unshared electron pair not involved in aromaticity” are as described in paragraphs 0057 to 0079 of Japanese Patent Application No. 2014-213474. Since such nitrogen atoms have strong nucleophilicity and high coordination properties to metal atoms, they exhibit high interaction with the metal (preferably gold, silver or copper) constituting the conductive layer 1b. It is thought to be possible.

  Examples of nitrogen-containing aromatic heterocycles containing “a nitrogen atom having an unshared electron pair not involved in aromaticity” as a ring constituent atom include those other than the pyrrole ring among the nitrogen-containing aromatic heterocycles described above. included.

The hydrophilic group of the compound is a group having affinity for the substrate. Examples of such hydrophilic groups include -SiZ3 _-n (OR) _n , -CZ3 _-n (OR) _n , -NHC (= O) (OR) and -C (= O) (OR). Is included. R and Z each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 to 3. -OR may be condensed with a hydroxy group or alkoxy group of an adjacent other molecule or substrate.

  The aromatic hydrocarbon group or aromatic heterocyclic group of the above compound and the hydrophilic group are connected by a divalent organic group. Examples of the divalent organic group include an alkylene group having 2 or more carbon atoms and an alkenylene group.

The compound is preferably a compound represented by the following general formula (1).

  R in the general formula (1) represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group. The substituted or unsubstituted nitrogen-containing aromatic heterocyclic group has the same meaning as the aforementioned substituted or unsubstituted nitrogen-containing aromatic heterocyclic group, and the nitrogen-containing aromatic heterocyclic ring contained therein includes a pyridine ring, an imidazole ring or A triazine ring is preferred.

L ^{1 in the} general formula (1) represents an alkylene group having 2 or more carbon atoms. The alkylene group having 2 or more carbon atoms is preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 6 to 9 carbon atoms. The alkylene group may be linear or branched, but is preferably linear from the viewpoint of forming a self-assembled monolayer having a high density. Examples of the alkylene group having 2 or more carbon atoms include ethylene group, propylene group, butylene group, pentylene group, hexylene group and the like. Some of the carbon atoms in the alkylene group may be replaced with oxygen atoms or sulfur atoms. Examples of such alkylene groups include polyoxyalkylene groups (for example, polyethyleneoxy groups) and the like.

A ^{1 in the} general formula (1) represents a carbon atom, a silicon atom, —C (═O) — or —NH—C (═O) —. Among these, a carbon atom and a silicon atom are preferable from the viewpoint that affinity with a substrate is easily obtained.

^-OB 1, -OB ² and -OB ³ of the general formula (1) each represents a hydroxy group or an alkoxy group. —OB ¹ , —OB ^2, and —OB ³ may each be condensed with an adjacent other molecule or a hydroxy group or an alkoxy group on the substrate surface. m and n each represent 1 when A ¹ is a carbon atom or a silicon atom, and each represents 0 when —C (═O) — or —NH—C (═O) —.

The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).

X < ¹ > -X < ⁵ > of General formula (2) represents a carbon atom or a nitrogen atom, respectively. However, at least one of X ^{1 to} X ⁵ represents a nitrogen atom.

R < ¹ > -R < ⁵ > of General formula (2) represents a hydrogen atom or a substituent, respectively. A substituent is synonymous with the substituent which the above-mentioned aromatic hydrocarbon ring or aromatic heterocyclic ring may have. Among these, the substituent is preferably an aryl group or a heteroaryl group, more preferably a heteroaryl group from the viewpoint that high interaction with a metal contained in the conductive layer is easily obtained. A heteroaryl group containing a “nitrogen atom having an unshared electron pair not involved in aromaticity” (for example, an imidazolyl group or a pyridinyl group) is more preferable.

L ² , A ² , B ⁴ , B ⁵ , B ⁶ , m and n in the general formula (2) are L ¹ , A ¹ , B ¹ , B ² , B ³ , m and n in the general formula (1). Are synonymous with each other.

The compound represented by the general formula (1) is more preferably a compound represented by the following general formula (3).

R ⁶ and R ⁷ in the general formula (3) have the same meanings as R ^{1 to} R ^{5 in} the general formula (2), respectively. L ³ , A ³ , B ⁸ , B ⁹ , B ¹⁰ , m and n in the general formula (3) are L ¹ , A ¹ , B ¹ , B ² , B ³ , m and n in the general formula (1). Are synonymous with each other.

Examples of compounds containing an aromatic hydrocarbon group or aromatic heterocyclic group at one molecular end and a hydrophilic group at the other molecular end include the following compounds (1) to (28): It is.

FIG. 2 shows a preferred example of the compound constituting the self-assembled monolayer. The compound shown in FIG. 2 has a substituent (—Si (OB) ₃ ) having a high affinity for the substrate at one molecular end, and a substituent having a high affinity for the conductive layer at the other molecular end. (Triazine ring substituted with an imidazole ring) and a structure in which these substituents are bonded via a rod-like linear alkyl group.

  FIG. 3 is a schematic view showing an example of a self-assembled monolayer containing the compound shown in FIG. -Si-O in FIG. 3 is a substituent having a high affinity for the substrate. The oxygen atom of —Si—O is covalently bonded to a silicon atom in the compound, while being covalently or non-covalently bonded to a hydrogen atom, a carbon atom or a silicon atom derived from the substrate. These bonds are formed by the interaction (for example, chemisorption) of the compound constituting the self-assembled monolayer and the substrate. This interaction is particularly easily obtained when a substrate mainly composed of glass, polyethylene terephthalate and polymethyl methacrylate resin (PMMA) is used.

  The imidazole ring in FIG. 3 is a substituent having a high affinity for the conductive layer. The nitrogen atom of the imidazole ring interacts (for example, coordinate bond) with a metal atom (for example, silver atom) that is a main component of the conductive layer.

  Thus, the above compound has a substituent that interacts with the substrate at one molecular end and a substituent that interacts with the conductive layer at the other molecular end, so that the self-assembled monomolecule A film may be formed. Furthermore, the linear alkyl group which couple | bonds these substituents also makes it easy to form a self-assembled monolayer. That is, as shown in FIG. 3, when the compounds are regularly arranged, a hydrophobic effect due to the intermolecular force between adjacent alkyl groups is likely to be obtained. Thereby, the packing in the lateral direction is strengthened, and a self-assembled monolayer having a high density can be formed.

Whether or not the intermediate layer 1a is formed of a self-assembled monolayer can be confirmed by TEM observation of the cross section of the substrate on which the intermediate layer 1a is formed. In particular,
1) The substrate on which the intermediate layer 1a is formed is cut in the thickness direction of the substrate to obtain a sample having a thickness of 0.1 μm.
2) The cut surface of the obtained sample is imaged with a transmission electron microscope apparatus to obtain a TEM image. As the transmission electron microscope apparatus, JEM-2000FX (manufactured by JEOL Ltd.) can be used. The acceleration voltage may be about 1.0 kV, the observation magnification may be 100,000, and the observation field range may be 1.0 μm ² . When observed under such conditions, if it can be confirmed that the majority (for example, 60% or more) of the molecules of the above compound are regularly arranged, it can be determined to be a self-assembled monolayer. .

  The intermediate layer 1a may be composed of a single layer of self-assembled monolayer (see FIG. 4); or may be composed of two or more layers of self-assembled monolayer (see FIG. 5).

  The intermediate layer composed of one self-assembled monolayer can be an L film (Langmuir film) (see FIG. 4). In this case, since the length in the major axis direction of the compound molecules constituting the self-assembled monolayer film is the thickness of the intermediate layer, a functional thin film can be formed with the minimum number of molecules. . Therefore, it is excellent in that the utilization efficiency of the material can be increased. The intermediate layer composed of two or more self-assembled monolayers can be an LB film (Langmuir-Blodgett film) in which a plurality of self-assembled monolayers are stacked in the vertical direction (see FIG. 5).

  Although the thickness of the intermediate | middle layer 1a is based also on the characteristic calculated | required, it is preferable that it is 1-30 nm, for example, and it is more preferable that it is 5-10 nm.

  Other layers may be provided below the intermediate layer 1a, that is, between the intermediate layer 1a and the substrate 11, if necessary.

1-3. Conductive layer 1b
The conductive layer 1b is provided on the intermediate layer 1a and contains a metal as a main component. The metal constituting the conductive layer 1b preferably includes gold, silver, copper, or an alloy thereof, and more preferably includes silver or an alloy thereof.

  Examples of the alloy containing silver (Ag) include silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), and silver indium (AgIn).

  The fact that the conductive layer 1b contains a metal as a main component means that the constituent ratio of the metal is the highest among the components constituting the conductive layer 1b. That is, the content of the metal (preferably silver or an alloy thereof) in the conductive layer is preferably 60% by mass or more and 90% by mass or more with respect to the total amount of components constituting the conductive layer 1b. Is more preferable, and it is especially preferable that it is 98 mass% or more.

  The conductive layer 1b may be a single layer or multiple layers. For example, the conductive layer 1b may have a configuration in which layers containing gold, silver, copper, or an alloy thereof as a main component as necessary and having different compositions are divided into a plurality of layers.

  The thickness of the conductive layer 1b is preferably 5 to 20 nm, and more preferably 5 to 12 nm. When the thickness of the conductive layer 1b is 20 nm or less, the absorption component or the reflection component of the conductive layer 1b decreases, and the light transmittance of the transparent electrode can be sufficiently increased. When the thickness of the conductive layer 1b is 5 nm or more, the conductivity of the conductive layer 1b can be sufficiently increased.

  The upper part of the conductive layer 1b may be covered with a protective film, or another conductive layer may be further 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.

1-4. Physical properties of transparent electrode 1 The transparent electrode 1 has a high light transmittance and a low resistance value. Specifically, the light transmittance at a measurement light wavelength of 550 nm of the transparent electrode 1 is preferably 50% or more, and more preferably 70% or more.

The light transmittance of the transparent electrode 1 can be measured by the following procedure.
1) The light transmittance of the transparent electrode substrate at a measurement light wavelength of 550 nm is measured using a spectrophotometer (U-3300 manufactured by Hitachi High-Technologies Corporation).
2) As a reference, the light transmittance at a measurement light wavelength of 550 nm of a substrate not provided with a transparent electrode is measured in the same manner as described above.
3) The difference in light transmittance obtained in the above 1) and 2) is referred to as “light transmittance of transparent electrode”.

  The sheet resistance value of the transparent electrode 1 is preferably 20Ω / □ or less, and more preferably 10Ω / □ or less. The sheet resistance value (Ω / □) of the transparent electrode can be measured by a four-probe method constant current application method using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

  The thickness of the transparent electrode 1 is usually 6 to 50 nm, and more preferably 6 to 20 nm.

1-5. Action The transparent electrode substrate 10 includes a substrate 11 and a transparent electrode 1; the transparent electrode 1 includes an intermediate layer 1a and a conductive layer 1b. The intermediate layer 1a can be composed of one or more self-assembled monolayers as described above.

  Thereby, when forming the conductive layer 1b on the intermediate layer 1a, the metal atoms (preferably gold atoms, silver atoms or copper atoms) which are the main components of the conductive layer 1b constitute the intermediate layer 1a. It interacts with substituents that have an affinity for metal atoms in the compound. As a result, it is presumed that the diffusion distance of the metal atoms on the intermediate layer 1a is shortened, and the aggregation of the metal atoms at the specific location can be suppressed. Such an interaction is considered to be particularly effective when the metal atom is mainly composed of a gold atom or a silver atom or copper atom, particularly when the metal atom is mainly composed of a silver atom. As a result, the layer growth type (Frank−) in which the metal atoms as the main component of the conductive layer 1b form a two-dimensional nucleus on the intermediate layer 1a and form a two-dimensional single crystal layer around it. It is considered that the film is formed by the film growth of van der Merwe (FM type).

  That is, conventionally, an island-shaped growth type (Volume-Weber) in which metal atoms attached on the surface of the intermediate layer 1a are bonded while diffusing the surface to form a three-dimensional nucleus and grow into a three-dimensional island shape. : VW type), it is considered that the film was easily formed into an island shape. On the other hand, in the present invention, the "compound containing an aromatic hydrocarbon ring group or an aromatic heterocyclic group at one molecular end and a hydrophilic group at the other molecular end" constituting the intermediate layer 1a. Thus, it is assumed that island growth is suppressed and layer growth is promoted.

  In addition, since the intermediate layer 1a contains the above compound, the initial content can be maintained without the conductive layer 1b being detached even under forced deterioration conditions. Therefore, the transparent electrode is presumed to have a high transmittance and a low resistance value even under forced deterioration conditions.

  Therefore, even if it is thin, the conductive layer 1b having a uniform thickness can be obtained. As a result, it is presumed that a transparent electrode having high conductivity while having high light transmittance can be obtained. Furthermore, film formation by a wet method is possible, which is effective in that the range of manufacturing conditions is widened.

2. The manufacturing method of a transparent electrode substrate The manufacturing method of the transparent electrode substrate of this invention includes the process of forming 1) an intermediate | middle layer on a board | substrate, and 2) forming a conductive layer on an intermediate | middle layer.

Step 1) The intermediate layer can be formed by any method as long as it can be formed as the above-described self-assembled monolayer, for example, a coating method, an inkjet method, a spin coating method, a dip method, and the like. Or a dry method such as a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, or a CVD method. Among these, the wet method is preferable and the dip method is particularly preferable because it is easy to form a self-assembled monolayer.

  FIG. 6 is an explanatory diagram showing an example of a process for forming an intermediate layer by the dipping method. As shown in FIG. 6, the step of forming the intermediate layer by the dip method includes the steps (a) “one end of one molecule contains an aromatic hydrocarbon group or aromatic heterocyclic group and the other end of the molecule is hydrophilic. A step of preparing a solution containing a precursor of a compound containing a functional group, (b) a step of immersing the substrate in the solution and allowing it to stand for a certain period of time, and (c) a step of drying after removing the substrate. .

  In the step (a), the precursor of the above compound is dispersed or dissolved in an organic solvent to prepare a solution.

The precursor of the above compound includes hydrophilic groups “—SiZ _3-n (OR) _n , —CZ _3-n (OR) _n , —NHC (═O) (OR) and —C (= O) (oR) "a" _{-SiZ 3-n Y n, -CZ} 3-n Y n, can be a -NHC (= O) Y and -C (= O) Y 'and compounds. R and Z each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 to 3, and is preferably 3. Y represents a hydroxy group, an alkoxy group or a halogen atom. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, and examples thereof include a methoxy group and an ethoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom and an iodine atom. Such a precursor is preferably a compound represented by the general formula (4).

^R, L ^{1, A} 1, m and n in the general formula (4) is ^R respectively general formula (1), L ^{1, A} 1, respectively m and n synonymous. Y ¹ , Y ² and Y ³ each represent a hydroxy group, an alkoxy group or a halogen atom.

  The organic solvent is not particularly limited, but ethanol, n-propanol, 2-propanol, PGME (1-methoxy-2-propanol), methyl acetate, MEK (methyl ethyl ketone) from the viewpoint of high versatility and suppression of environmental load. And water is preferred.

  The content of the precursor in the solution can be about 0.1 to 5% by mass.

  In the step (b), the substrate is immersed in the prepared solution. From the viewpoint of facilitating the formation of a self-assembled monolayer, the immersion temperature is preferably a certain temperature or more, for example, preferably 10 to 100 ° C, and more preferably 20 to 80 ° C. . The immersion time is preferably 10 minutes to 10 hours, and more preferably 10 minutes to 2 hours.

  In the step (c), the substrate after immersion is taken out of the solution and dried. The drying method is not particularly limited. It may be naturally dried or dried by applying a drying air.

The dip method not only facilitates the formation of a self-assembled monomolecular film, but also excels in material utilization efficiency, time efficiency, and increase in area as compared with a vacuum deposition method, a spin coating method, and the like. Further, a transparent electrode having a uniform thickness can be formed on a substrate having a curved surface or a substrate having a complicated shape. From these viewpoints, the dipping method is compared with other methods (vacuum deposition method and spin coating method) for the case where an intermediate layer is formed on a 30 mm × 30 mm substrate with a constant material usage (about 1 g). (See Table 1).

  In the vacuum evaporation method, the material is filled in a vapor deposition boat and set inside the vapor deposition machine, while the substrate on which the film is to be formed is set, the pressure inside the vapor deposition machine is reduced to a desired vacuum level, and is stabilized at a desired vapor deposition rate. This is a film forming method in which the current is applied until the thickness reaches a desired thickness. There are advantages such as the simplicity of the operation method and the ability to form a film on a large number of substrates at once, but taking into account the preparation and decompression time, it takes a lot of time, and even a single film formation takes 2 hours or more. There are also disadvantages. For example, when a laboratory vapor deposition machine is used, only about 20 substrates can be set at a time due to restrictions on the size of the apparatus.

  The spin coating method is a method of creating a uniform thin film on the entire substrate by dropping a solution prepared in advance on a substrate set on a spin table and then rotating the spin table. Therefore, most of the dropped solution is scattered, and the amount formed in a thin film of several tens of nm is small. When preparing a solution to be dropped, assuming that a thin film that can function sufficiently can be formed at a concentration of 5 mg / ml, a solution of 200 ml can be prepared with 1 g of material. If the amount of solution required for one spin coat film formation is 1 ml, a total of 200 thin films can be formed. However, in order to form a film using 200 spin coats, it takes 3 hours or more. It takes a lot of time.

  On the other hand, in the dip method, an L film or an LB film can be easily formed and a monomolecular film is sufficient, and therefore the concentration of the solution to be prepared may be as low as about 1 mg / ml. That is, a 1 L solution can be prepared with as little as 1 g. Furthermore, the intermediate layer can be formed by simply immersing the substrate in this solution and allowing it to stand for about 30 minutes. Assuming that 100 substrates can be set in a container filled with 1 L of solution, 200 substrates can be produced in just one hour. Therefore, it is considered that the film formation method has higher time efficiency and material efficiency than the vacuum deposition method and the spin coating method. Furthermore, the prepared solution can be used repeatedly until all the dissolved thin film forming material is consumed, the area of the thin film can be increased as the amount of the solution increases, and the substrate has a curved surface. In view of the ability to form a thin film having a uniform thickness, it is considered that this is a film forming method excellent in production suitability.

Step 2) For forming the conductive layer, for example, a wet method such as a coating method, an ink jet method, a spin coating method, a dip method, or a dry method such as a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, or the like. Can be done by law. The vapor deposition method is preferable in that it is easy to form a thin and uniform thickness.

  On the substrate on which the conductive layer 1b is formed, an intermediate layer having high rinsing durability with respect to an organic solvent is provided. Therefore, a wet method may be used in terms of reduction in manufacturing cost. The organic solvent for rinsing the conductive layer formed by a wet method can be the same as the organic solvent used for rinsing the intermediate layer.

  When the conductive layer 1b is formed by a wet method, it is preferable to use a conductive ink mainly composed of gold, silver, or copper. In the present configuration in which high light transmittance is realized by reducing the thickness of the conductive layer, the conductive ink composed of nanoparticles having a small particle diameter of about 10 nanometers and the conductive composed of a complex are used. It is particularly preferable to use a reactive ink.

  However, since many of the commercially available conductive inks are mainly used for the production of electric circuits and light reflecting films, etc., these are usually used to produce thin films with excellent light transmittance. It is difficult. Therefore, it is necessary to devise a method of diluting the conductive ink with a solvent and optimizing thin film formation process conditions. As the solvent to be diluted, a conventionally known solvent such as an organic solvent or an aqueous solvent can be used without particular limitation as long as the effect of the transparent electrode substrate is not impaired. Further, the conductive layer 1b is formed on the intermediate layer 1a, so that a high-temperature annealing treatment (for example, a heating process at 100 ° C. or higher) after the formation of the conductive layer is performed as necessary. Good.

3. Use of transparent electrode substrate The transparent electrode substrate of the present invention can be used in various electronic devices. Examples of the electronic device include an organic EL device, an LED (Light Emitting Diode), a liquid crystal display device, a solar cell, a touch panel, and the like. In these electronic devices, the transparent electrode substrate of the present invention is used for an electrode member that requires light transmittance. The transparent electrode substrate of the present invention is preferably used for a transparent electrode substrate of an organic EL device.

  In other words, the organic EL device includes a substrate provided with one of a cathode and an anode, the other of the cathode and the anode, and a light emitting layer disposed between the cathode and the anode. The substrate provided with one of the cathode and the anode is the transparent electrode substrate of the present invention. Below, embodiment of the organic EL device containing the transparent electrode substrate of this invention is described.

3-1-1. First Example of Organic EL Device <Configuration of Organic EL Device>
FIG. 7: is a schematic sectional drawing which shows the 1st example of the organic EL device containing the transparent electrode substrate of this invention as an example of the electronic device of this invention.

  As shown in FIG. 7, the organic EL device 100 includes a transparent substrate (substrate) 13, a sealing material 17, and an organic EL element 7 disposed therebetween. The organic EL element 7 has a structure in which the transparent electrode 1, the organic functional layer 3, and the counter electrode 5a provided on the transparent substrate 13 are laminated in this order. In the organic EL device 100, the transparent substrate 13 provided with the transparent electrode 1 may be the transparent electrode substrate of the present invention.

  In the organic EL device 100 configured as described above, the organic functional layer 3 sandwiched between the transparent electrode 1 and the counter electrode 5a serves as a light emitting region. The organic EL device 100 is configured to extract the generated light (hereinafter referred to as emitted light h) from at least the transparent substrate 13 side.

  The layer structure of the organic EL device 100 is not limited to the example described below, and may be a general layer structure. In the organic EL device 100, the transparent electrode 1 functions as an anode (anode), and the counter electrode 5a functions as a cathode (cathode).

  The organic functional layer 3 includes at least a light emitting layer 3c. The organic functional layer 3 can be configured by laminating 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 in this order from the transparent electrode 1 side which is an anode. 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 the organic functional layer 3, for example, the electron injection layer 3e may be composed of an inorganic material.

  The organic functional layer 3 may include a hole blocking layer, an electron blocking layer, or the like at a necessary position as necessary. Further, 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 color light emitting layer is laminated via a non-light emitting auxiliary layer. The auxiliary layer may function as a hole blocking layer or an electron blocking layer.

  The counter electrode 5a may also have a laminated structure with other layers as necessary. For the purpose of reducing the resistance of the transparent electrode 1, an auxiliary electrode 15 may be provided in contact with the conductive layer 1b of the transparent electrode 1.

  In the organic EL device 100, the organic EL element 7 is sealed with a sealing material 17 for the purpose of preventing deterioration of the organic functional layer 3. The sealing material 17 is fixed to the transparent substrate 13 side with an adhesive 19. On the transparent substrate 13, the terminal portion of the transparent electrode 1 and the terminal portion of the counter electrode 5 a are provided so as to be insulated from each other by the organic functional layer 3 and exposed from the sealing material 17.

  Hereinafter, the detail of the main layers which comprise the organic EL device 100 is demonstrated.

(Transparent substrate 13)
The transparent substrate 13 is a member corresponding to the substrate 11 of FIG. As such a transparent substrate 13, the transparent substrate 11 which has a light transmittance among the above-mentioned substrates 11 is used.

(Transparent electrode 1 (anode))
The transparent electrode 1 has an intermediate layer 1a provided on the transparent substrate 13 and a conductive layer 1b in this order. In FIG. 7, the transparent electrode 1, particularly the conductive layer 1b, functions as an anode.

(Counter electrode 5a (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 sheet resistance value as the counter electrode 5a is preferably several hundred Ω / □ or less, and the thickness is usually selected within the range of 5 nm to 5 μm, preferably 5 to 200 nm. In addition, when this organic EL device 100 is what takes out the emitted light h also from the counter electrode 5a side, it is a counter electrode by the conductive material with favorable light transmittance selected from the electrically conductive materials mentioned above. 5a should just be comprised.

(Light emitting layer 3c)
The light emitting layer 3c contains a light emitting material. The light emitting material preferably contains a phosphorescent light emitting dopant (phosphorescent light emitting material, phosphorescent light emitting compound, phosphorescent compound). The light emitting layer 3c may contain a plurality of light emitting materials, for example, may contain a phosphorescent light emitting dopant (phosphorescent compound) and a fluorescent dopant (fluorescent light emitting material, fluorescent compound); It is preferable that the compound (light emitting host) and the light emitting material (light emitting dopant) are included to make the light emitting layer 3c emit light more.

  The light emitting layer 3c is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer 3d and holes injected from the hole transport layer 3b, and the light emitting portion is a layer of the light emitting layer 3c. Even within, it may be an interface between the light emitting layer 3c and an adjacent layer. Such a light emitting layer 3c is not particularly limited in its configuration as long as the contained light emitting material satisfies the requirements for light emission. 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 1 to 100 nm, and more preferably 1 to 30 nm because a lower driving voltage can be obtained. The sum total of the thickness of the light emitting layer 3c is a thickness including the auxiliary layer when a non-light emitting auxiliary layer exists between the light emitting layers 3c.

  When the light emitting layer 3c is comprised with a several light emitting layer, it is preferable that the thickness of each light emitting layer is 1-50 nm, and it is more preferable that it is 1-20 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.

(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, and a compound having a phosphorescence quantum yield of less than 0.01 is more preferable. . Moreover, it is preferable that the volume ratio of the host compound in the light emitting layer 3c layer is 50% or more.

  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 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 is a value determined by a method based on JIS K 7121-2012 using DSC (Differential Scanning Colorimetry).

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. 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-3632.
No. 27, No. 2002-231453, No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-260861, No. 2002-280183. No. 2002, No. 2002-299060, No. 2002-302516, No. 2002-305083, No. 2002-305084, No. 2002-308837, US Patent Application Publication No. 2003/0175553, US Patent Application Publication No. 2006/0280965, US Patent Application Publication No. 2005/0112407, US Patent Application Publication No. 2009/0017330, US Patent Application Publication No. 2009/0030202, US Patent Published application 2005/0238919 Pat, International Publication No. 2001
No. 0/03234, International Publication No. 2009/021126, International Publication No. 2008/056746, International Publication No. 2004/093207, International Publication No. 2005/089025, International Publication No. 2007/063796, International Publication No. 2007. No. 063754, International Publication No. 2004/107822, International Publication No. 2005/030900, International Publication No. 2006/114966, International Publication No. 2009/086028, International Publication No. 2009/003898, International Publication No. 2012/023947. No., JP 2008-074939 A, JP 2007-254297 A, European Patent No. 2034538, and the like.

(Luminescent material)
(1) Phosphorescence emission dopant As a luminescent material contained in the light emitting layer 3c, 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.). 01 or more compounds, preferably phosphorescence quantum yield of 0.1 or more compounds.

  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.

  Two or more phosphorescent dopants may be contained in at least one light emitting layer 3c, and the content of the phosphorescent dopant in the light emitting layer 3c may vary in the thickness direction of the light emitting layer 3c. The content of the phosphorescent light emitting 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.

Specific examples of known phosphorescent dopants include compounds described in the following documents. Nature, 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. , 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. , 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Application Publication No. 2006/835469, US Patent Application Publication No. 2006. No. 0202194, U.S. Patent Application Publication No. 2007/0087321, U.S. Patent Application Publication No. 2005/0244673, Inorg. Chem. , 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. , 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. , 34, 592 (2005), Chem. Commun. , 2906 (2005), Inorg. Chem. , 42, 1248 (2003), International Publication No. 2009/050290, International Publication No. 2002/015645, International Publication No. 2009/000673, US Patent Application Publication No. 2002/0034656, and US Pat. No. 7,332,232. United States Patent Application Publication No. 2009/0108737, United States Patent Application Publication No. 2009/0039776, United States Patent No. 6921915, United States Patent No. 6,687,266, United States Patent Application Publication No. 2007/0190359. No., US Patent Application Publication No. 2006/0008670, US Patent Application Publication No. 2009/0165846, US Patent Application Publication No. 2008/0015355, US Pat. No. 7,250,226, US Patent No. 7396598 Writing, U.S. Patent Application Publication No. 2006/0263635, U.S. Patent Application Publication No. 2003/0138657, U.S. Patent Application Publication No. 2003/0152802, U.S. Patent No. 7090928, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. , 18, 5119 (2006), Inorg. Chem. 46, 4308 (2007), Organometallics, 23, 3745 (2004), Appl. Phys. Lett. , 74, 1361 (1999), International Publication No. 2002/002714, International Publication No. 2006/009024, International Publication No. 2006/056418, International Publication No. 2005/019373, International Publication No. 2005/123873, International Publication. No. 2005/123873, International Publication No. 2007/004380, International Publication No. 2006/082742, US Patent Application Publication No. 2006/0251923, US Patent Application Publication No. 2005/0260441, US Pat. No. 7,393,599. No. 7, U.S. Pat. No. 7,534,505, U.S. Pat. No. 7,445,855, U.S. Patent Application Publication No. 2007/0190359, U.S. Patent Application Publication No. 2008/0297033, U.S. Pat. No. 7,338,722. Letter, United States Published Patent Application No. 2002/0134984, U.S. Pat. No. 7,279,704, U.S. Patent Application Publication No. 2006/098120, U.S. Patent Application Publication No. 2006/103874, International Publication No. 2005/076380. International Publication No. 2010/032663, International Publication No. 2008/140115, International Publication No. 2007/052431, International Publication No. 2011/134013, International Publication No. 2011/157339, International Publication No. 2010/086089, International Publication No. Publication No. 2009/113646, International Publication No. 2012/020327, International Publication No. 2011/051404, International Publication No. 2011/004639, International Publication No. 2011/073149, US Patent Application Publication No. 2012/228583 , Rice Japanese Patent Application Publication No. 2012/212126, Japanese Patent Application Laid-Open No. 2012-069737, Japanese Patent Application Laid-Open No. 2011-181303, Japanese Patent Application Laid-Open No. 2009-114086, Japanese Patent Application Laid-Open No. 2003-81988, Japanese Patent Application Laid-Open No. 2002-302671. Japanese Patent Laid-Open No. 2002-363552.
Among these, a preferable phosphorescent dopant includes an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode among a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferable.

(2) Fluorescent dopant The fluorescent dopant contained in the light emitting layer 3c is a compound that can emit light from an excited singlet, and is not particularly limited as long as it is a compound that emits light from an excited singlet. As fluorescent dopants, coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes , Polythiophene dyes, rare earth complex phosphors, and the like. In recent years, light emitting dopants utilizing delayed fluorescence have been developed, and these may be used.
Specific examples of the luminescent dopant using delayed fluorescence include, for example, the compounds described in International Publication No. 2011/156793, Japanese Patent Application Laid-Open No. 2011-213643, Japanese Patent Application Laid-Open No. 2010-93181, and the like. Is not limited to these.

(Injection layer: hole injection layer 3a, electron injection layer 3e)
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 2) Chapter 2 “Electrode Material” (pages 123 to 166) of “S.

  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 desirably a very thin film, and the thickness thereof is preferably in the range of 1 nm to 10 μm although it depends on the material.

(Hole transport layer 3b)
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 Triphenylamine units disclosed in Japanese is coupled to the three starburst 4,4 ', 4 "- tris [
N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) and the like.

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.

  Although there is no restriction | limiting in particular about the 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 3d)
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.

From the cathode, 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 the layer portion adjacent to the light emitting layer 3c in the electron transport layer 3d having a multilayer structure. What is necessary is just to have the function to transmit the injected electron 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 the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group are also used as the material for the electron transport layer 3d. 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 (Alq3), 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), and the like, and the central metals of these metal complexes are In, Mg, A metal complex replaced with Cu, Ca, Sn, Ga, or Pb can also be used as the material of the electron transport layer 3d.

  In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the material for the electron transport layer 3d. Further, a distyrylpyrazine derivative that is also used as the material of the light emitting layer 3c can be used as the material of the electron transport layer 3d, and n-type-Si, n-type as in the case of the hole injection layer 3a and the hole transport layer 3b. 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 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. The thickness of the hole blocking layer is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

  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.

(Auxiliary electrode 15)
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. 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 17)
The sealing material 17 is a plate-shaped or film-shaped sealing member that covers the organic EL element 7. The sealing material 17 may be fixed to the transparent substrate 13 side by the adhesive 19 or may be a sealing 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 are exposed. Further, an electrode may be provided on the sealing material 17 so that the terminal portions of the transparent electrode 1 and the counter electrode 5a are electrically connected to this electrode.

  Examples of the plate-like (film-like) sealing material 17 include a glass substrate, a polymer substrate, a metal substrate, and the like, and these substrate materials may be used in the form of a thinner film. 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 polymer substrate or metal substrate can be preferably used as the sealing material. The polymer substrate made into a film has a oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ ml / m ² · 24 h · atm or less, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)%) measured in (1) is 1 × 10 ⁻³ g / m ² · 24 h or less.

  These substrates may be processed into a concave plate shape and used as the sealing material 17. In this case, the substrate is subjected to processing such as sand blasting 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 is for sealing the organic EL element 7 sandwiched between the sealing material 17 and the transparent substrate 13. Used as a sealant. 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 7 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), 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, barium perchlorate) , Magnesium perchlorate, etc.), and anhydrous salts are preferably used as sulfates, metal halides and perchloric acids.

  On the other hand, when a sealing film is used as the sealing material 17, the sealing film is provided on the transparent substrate 13 with the organic functional layer 3 completely covered and the terminal portions of the transparent electrode 1 and the counter electrode 5a exposed. It is done. 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 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)
The organic EL device may further include a protective film as necessary. That is, the protective film and the transparent substrate 13 may be provided so as to sandwich the organic EL element 7 and the sealing material 17. This protective film or protective plate is for mechanically protecting the organic EL element 7. In particular, when the sealing material 17 is a sealing film, it is preferable to provide such a protective film or a protective plate because mechanical protection for the organic EL element 7 is not sufficient.

  As the protective film or protective plate, a glass plate, a polymer plate, a polymer film thinner than this, a metal plate, a metal film thinner than this, 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 manufacturing organic EL device>
An example of a method for manufacturing the organic EL device 100 shown in FIG. 7 will be described.
First, the above-described intermediate layer 1a is formed on the transparent substrate 13 by a wet method, preferably a dip method. As described above, the thickness of the intermediate layer 1a can be 1 to 30 nm, preferably 1 to 10 nm.

  Next, the conductive layer 1b mainly composed of silver (or an alloy containing silver) is formed on the intermediate layer 1a by a wet method or a dry method. As described above, the thickness of the conductive layer 1b is 5 to 20 nm, preferably 8 to 12 nm. Thereby, the transparent electrode 1 used as an anode is produced.

  After the formation of the intermediate layer 1a or after the formation of the conductive layer 1b, an auxiliary electrode 15 may be further formed as necessary. The auxiliary electrode 15 can be formed by a vapor deposition method, a sputtering method, a printing method, an ink jet method, an aerosol jet method, or the like.

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 with Pa, a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −50 to 300 ° C., and a layer thickness of 0.1 to 5 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 7 is obtained. Then, the sealing material 17 which covers at least the organic functional layer 3 is provided in a state in which the terminal portions of the transparent electrode 1 and the counter electrode 5a of the organic EL element 7 are exposed. Thereby, the organic EL device 100 can be obtained.

  In the production of such an organic EL device 100, it is preferable that the organic functional layer 3 to the counter electrode 5a are produced consistently by a single vacuum. However, the transparent substrate 13 may be taken out from the vacuum atmosphere and a different film forming method may be applied. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  When a DC voltage is applied to the organic EL device 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.

<Operation of organic EL device>
The organic EL device 100 includes the transparent electrode substrate 10 of the present invention having high light transmittance and conductivity as an anode substrate, and is provided with an organic functional layer 3 and a counter electrode 5a serving as a cathode on the upper portion. The For this reason, a high voltage is applied by applying a sufficient voltage between the transparent electrode 1 and the counter electrode 5a to realize high luminance light emission, and improving the extraction efficiency of the emitted light h from the transparent electrode 1 side. It is possible to plan. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.

3-1-2. Second Example of Organic EL Device <Configuration of Organic EL Device>
FIG. 8: is a schematic sectional drawing which shows the 2nd example of the organic EL device containing the transparent electrode substrate of this invention as an example of the electronic device of this invention. The organic EL device 200 of the second example shown in FIG. 8 is configured in substantially the same manner as the organic EL device 100 of the first example shown in FIG. 8 except that the transparent electrode substrate 10 is used as the cathode substrate. 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 device 200 in the second example will be described.

  As shown in FIG. 8, in the organic EL device 200, the transparent substrate 13 provided with the transparent electrode 1 can be the above-described transparent electrode substrate, as in the first example. For this reason, the organic EL device 200 is configured to extract the emitted light h from at least the transparent substrate 13 side. However, the transparent electrode 1 in FIG. 8 functions as a cathode (cathode), and the counter electrode 5b functions as an anode. The layer structure of the organic EL device 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.

  The organic functional layer 3 is formed by laminating an electron injection layer 3e / electron transport layer 3d / light emitting layer 3c / hole transport layer 3b / hole injection layer 3a in this order on the transparent electrode 1 functioning as a cathode. sell.

  In addition to these layers, the organic functional layer 3 may further include other layers as necessary, as in the first example. In such a configuration, the organic functional layer 3 sandwiched between the transparent electrode 1 and the counter electrode 5b is the light emitting region as in the first example.

The counter electrode 5b used as the anode is made 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 can be produced by forming a thin film of these conductive materials by a method such as vapor deposition or sputtering.

  The sheet resistance value of the counter electrode 5b functioning as the anode is preferably several hundred Ω / □ or less. The thickness of the counter electrode 5b is usually 5 nm to 5 μm, and more preferably 5 to 200 nm. In addition, when this organic EL device 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.

  Furthermore, for the purpose of preventing deterioration of the organic functional layer 3, at least the organic functional layer 3 is sealed with a sealing material 17 as in the first example.

  Of the main layers constituting the organic EL device 200 described above, the detailed configuration of the components other than the counter electrode 5b used as the anode is the same as that of the first example.

<Operation of organic EL device>
In the organic EL device 200 described above, the transparent electrode substrate 10 of the present invention having high light transmittance and conductivity is used as a cathode substrate, and the organic functional layer 3 and the counter electrode 5b serving as an anode are laminated thereon. Can be configured. Therefore, 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, and the extraction efficiency of the emitted light h from the transparent electrode 1 is improved. By doing so, it is possible to increase the brightness. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.

3-2. Use of Organic EL Device The organic EL device of the present invention can function as a surface light emitter, and therefore can be used as various light sources. Examples of light-emitting light sources include lighting devices for home lighting and interior lighting, backlights for clocks and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, optical communications Examples include a light source of a processing machine and a light source of a photosensor. 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.

  Moreover, the organic EL device of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection apparatus 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 having different emission colors.

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

  The organic EL device of the present invention used as a lighting device may have a design in which each organic EL device having the above-described configuration has a resonator structure. Applications of organic EL devices configured to have a resonator structure include light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, light sources for optical sensors, etc. It is not limited. Moreover, you may use for the said use by making a laser oscillation.

  In addition, the material used for an organic EL element 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. As a combination of a plurality of emission colors, those containing the three emission maximum wavelengths of the three primary colors of red, green and blue may be used, or two emission using the complementary colors such as blue and yellow, blue green and orange, etc. It may contain a maximum wavelength.

  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.

  There is no restriction | limiting in particular as a luminescent 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 adapt to the wavelength range corresponding to CF (color filter) characteristic. Any one of the above-described metal complexes and known light-emitting materials may be selected and combined for whitening. By using such a white organic EL element, it is possible to produce a lighting device that emits substantially white light.

3-2-1. First Example of Illuminating Device FIG. 9 is a schematic cross-sectional view of an illuminating device in which a plurality of organic EL elements are arranged to increase the light emitting surface area. As shown in FIG. 9, the lighting device 300 includes a transparent substrate 13, a support substrate 23 (sealing material), and a plurality of organic EL elements 7 and 7 arrayed (tiled) therebetween. Including. The organic EL elements 7 and 7 have the transparent electrode 1, the organic functional layer 3, and the counter electrode 5b in this order from the transparent substrate 13 side. Hereinafter, detailed description of the same components as those in the first example will be omitted.

  The transparent substrate 13 provided with the transparent electrode 1 can be the aforementioned transparent electrode substrate.

  The support substrate 23 may also serve as the sealing material 17. Then, the organic EL elements 7 and 7 are sandwiched between the support substrate 23 and the transparent substrate 13 and are tiled. Thereby, the illuminating device 300 which has the structure which enlarged the light emission surface can be obtained. An adhesive 19 may be filled between the support substrate 23 and the transparent substrate 13, thereby sealing the organic EL elements 7 and 7. In addition, the edge part of the transparent electrode 1 which is an anode, and the edge part of the counter electrode 5a which is a cathode are exposed around the illuminating device 300. FIG. However, in FIG. 9, only the exposed part of the counter electrode 5a is shown.

  The organic EL element 7 includes the transparent electrode 1, the organic functional layer 3, and the counter electrode 5a in this order. The organic functional layer 3 can be configured by sequentially laminating 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 from the transparent electrode 1 side.

  In the illuminating device 300 having such a configuration, the center of each organic EL element 7 is a light emitting area A, and a non-light emitting area B is formed between the two organic EL elements 7 and 7. 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.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

1. Production and evaluation of transparent electrode substrate (1)
<Preparation of transparent electrode substrate 101>
An alkali-free glass substrate (thickness 1000 μm) was attached to a substrate holder of a commercially available vacuum deposition apparatus. In addition, the comparative compound (1) (also referred to as the comparison (1)) is put in a tantalum resistance heating board and attached to the first vacuum chamber of the vacuum evaporation apparatus, and silver (Ag) is put in the resistance heating board made of tungsten. And installed in the second vacuum chamber.

In this state, first, the first vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, then the resistance heating board containing the comparative compound (1) was heated, and the deposition rate was 0.1 nm / sec to 0.2 nm / sec. An intermediate layer having a thickness of 10 nm was formed on the substrate.

Next, the substrate on which the intermediate layer is formed is transferred into the second vacuum chamber, and after the pressure in the second vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, the resistance heating board containing silver (Ag) is heated and the deposition rate is increased. A conductive layer having a thickness of 10 nm and an area of 5 cm × 5 cm was formed on the intermediate layer at a rate of 0.1 nm / second to 0.2 nm / second. Thereby, the transparent electrode substrate 101 was produced.

<Preparation of transparent electrode substrate 102>
Comparative compound (1) was dissolved in PGME (1-methoxy-2-propanol) to prepare a solution having a concentration of 0.5% by mass. This solution was applied on a non-alkali glass substrate by a spin coating method, and then the coating film was heated and dried at 100 ° C. for 1 hour to form an intermediate layer having a thickness of 10 nm.
A transparent electrode substrate 102 having a thickness of 10 nm was produced in the same manner as the production of the transparent electrode substrate 101 except that the obtained intermediate layer was used.

<Preparation of transparent electrode substrate 103>
Comparative compound (1) was dissolved in PGME (1-methoxy-2-propanol) to prepare a solution having a concentration of 0.5% by mass. A substrate made of alkali-free glass was immersed (dip) in this solution at 40 ° C. for 30 minutes, and then heated and dried at 100 ° C. for 1 hour to form an intermediate layer having a thickness of 10 nm.
A conductive layer having a thickness of 10 nm was formed in the same manner as in the production of the transparent electrode substrate 101 except that the obtained intermediate layer was used, and the transparent electrode substrate 103 was produced.

<Preparation of transparent electrode substrate 104>
A transparent electrode substrate 104 was produced in the same manner as in the production of the transparent electrode substrate 102 except that the constituent material of the intermediate layer was changed to the compound (1). As a precursor of the compound (1) used for the preparation of the intermediate layer forming solution, a compound in which all of —O at the molecular terminals of the compound (1) were —OCH ₃ was used.

<Preparation of transparent electrode substrate 105>
A precursor of compound (1) (a compound in which all of —O at the molecular terminals of compound (1) is —OCH ₃ ) was dissolved in PGME (1-methoxy-2-propanol), and the concentration was 0.5% by mass. A solution of was prepared. A substrate made of alkali-free glass was immersed (dip) in this solution at 40 ° C. for 30 minutes, and then heated and dried at 100 ° C. for 1 hour to form a 10 nm thick intermediate layer containing compound (1). .

The substrate on which the intermediate layer was formed was attached to a substrate holder of a commercially available vacuum deposition apparatus, and zinc (Zn) was placed in a tantalum resistance heating board and attached to the second vacuum chamber of the vacuum deposition apparatus. Then, after reducing the pressure of the second vacuum tank to 4 × 10 ⁻⁴ Pa, the resistance heating board containing zinc (Zn) is heated, and the deposition rate is 0.1 nm / sec to 0.2 nm / sec. A conductive layer having a thickness of 10 nm and an area of 5 cm × 5 cm was formed on the transparent electrode substrate 105.

<Preparation of transparent electrode substrates 106 to 107>
Transparent electrode substrates 106 to 107 were produced in the same manner except that the constituent material of the conductive layer was changed as shown in Table 2 in the production of the transparent electrode substrate 105.

<Preparation of Transparent Electrode Substrates 108-115>
In the production of the transparent electrode substrate 107, transparent electrode substrates 108 to 115 were produced in the same manner except that the constituent material of the intermediate layer was changed to the compounds shown in Table 2. As the precursor of the compound shown in Table 2 used for the preparation of the solution for forming the intermediate layer, a compound in which all of —O at the molecular terminals of the compound shown in Table 2 were —OCH ₃ was used.

<Preparation of Transparent Electrode Substrates 116-119>
In the production of the transparent electrode substrates 114 and 115, transparent electrode substrates 116 to 119 were produced in the same manner except that the types of the substrates were changed as shown in Table 2. The polyethylene terephthalate in the table is a polyethylene terephthalate film having a thickness of 500 μm; the PMMA is a polymethyl methacrylate film having a thickness of 500 μm.

<Preparation of transparent electrode substrates 120-121>
As a conductive layer material, a solution was prepared by diluting 1.0 ml of inkjet ink made of complex silver (manufactured by Ink Tec Co., Ltd., TEC-IJ-010) 10 times with ethanol.
After applying 0.1 ml of this diluted solution on the intermediate layer used for the production of the transparent electrode substrates 114 and 115 by a spin coating method, baking was performed at 120 ° C. for 30 minutes to form a conductive layer made of silver having a thickness of 10 nm. Formed. Thereby, the transparent electrode substrates 120 and 121 in which the intermediate layer and the conductive layer were sequentially laminated on the substrate were obtained.

<Evaluation of transparent electrode substrate>
The light transmittance, sheet resistance value, and sheet resistance value change (durability) under high temperature storage of the obtained transparent electrode substrates 101 to 121 were measured by the following methods. These results are shown in Table 2.

(1) Measurement of light transmittance The light transmittance (%) at a measurement light wavelength of 550 nm of the obtained transparent electrode substrate was measured using a spectrophotometer (U-3300 manufactured by Hitachi High-Technologies Corporation). The substrate of each transparent electrode was used as a reference.

(2) Measurement of sheet resistance value The sheet resistance value (Ω / □) of the obtained transparent electrode substrate was measured using a resistivity meter (MCP-T610, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Measured with

(3) Measurement of change in sheet resistance value under high temperature storage The obtained transparent electrode substrate was stored in an atmosphere at a temperature of 80 ° C / 90% relative humidity, and the change in sheet resistance value was measured. Specifically, the sheet resistance values before the start of the test and after the lapse of 120 hours were compared, the change was evaluated, and the results are shown in Table 2.
The sheet resistance value was measured using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and the sheet resistance value (Ω / □) was measured by a four-point probe constant current application method, and the change in resistance value from the initial sheet Was calculated. The change in sheet resistance value of each transparent electrode under high temperature storage is shown as a relative value with the change in sheet resistance value of the transparent electrode substrate 108 being 100, indicating that the smaller the value, the smaller the change and the better the durability. ing.

  Further, the transparent electrode substrates 103, 104, and 107 were subjected to cross-sectional TEM observation to confirm whether the intermediate layer was a self-assembled monolayer.

(4) Cross-sectional TEM observation The transparent electrode substrate was cut in the thickness direction of the substrate to obtain a sample having a thickness of 0.1 μm. Using the transmission electron microscope apparatus JEM-2000FX (manufactured by JEOL Ltd.), the acceleration voltage was set to 1.0 kV, the observation magnification was set to 100,000 times, and the observation visual field range was set to 1. for the cut surface of the obtained sample. Observed as 0 μm ² .

  As shown in Table 2, the transparent electrode substrates 101 to 104 cannot achieve both high light transmittance and low sheet resistance; whereas the transparent electrode substrates 105 to 121 have high light transmittance and low sheet resistance. Are shown to be compatible. In addition, the intermediate layers of the transparent electrode substrates 101, 103, and 104 are not self-assembled monolayers; whereas the intermediate layer of the transparent electrode substrate 107 is confirmed to be a self-assembled monolayer. It was.

  The reason why the transparent electrode substrates 105 to 121 can achieve both high light transmittance and low sheet resistance is considered that the intermediate layer of the transparent electrode substrates 105 to 121 is a self-assembled monolayer.

  The contrast of the transparent electrode substrates 105 to 107 indicates that the light transmittance is high and the resistance is low when the conductive layer is mainly composed of silver (Ag).

  Comparison between the transparent electrode substrate 107 and 108 to 115 indicates that high light transmittance and low resistance are easily obtained when the constituent material of the intermediate layer contains a nitrogen-containing aromatic heterocycle. Further, the comparison of the transparent electrode substrates 108 to 115 shows that when the constituent material of the intermediate layer includes a triazine ring among nitrogen-containing aromatic heterocycles, higher light transmittance and lower resistance are easily obtained.

  The contrast between the transparent electrode substrates 114 to 119 shows that good high light transmittance and low resistance can be obtained using not only alkali-free glass substrates but also PMMA and polyethylene terephthalate substrates.

  The comparison between the transparent electrode substrates 114 to 115 and 120 to 121 shows that even when the conductive layer is formed by the spin coating method, the same effect as the vacuum deposition method can be obtained.

2. Production and evaluation of transparent electrode substrate (2)
<Preparation of transparent electrode substrate 201>
A substrate made of non-alkali glass having a curved surface (minimum thickness of 1000 μm) was attached to a substrate holder of a commercially available vacuum deposition apparatus. In addition, the comparative compound (3) (also referred to as the comparison (3)) is put in a resistance heating board made of tantalum and attached to the first vacuum chamber of the vacuum evaporation apparatus, and silver (Ag) is put in the resistance heating board made of tungsten. And installed in the second vacuum chamber.

In this state, first, the first vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, then the resistance heating board containing the comparative compound (3) was heated, and the deposition rate was 0.1 nm / second to 0.2 nm / second. An intermediate layer having a thickness of 10 nm was formed on the substrate.

Next, the substrate on which the intermediate layer is formed is transferred into the second vacuum chamber, and after the pressure in the second vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, the resistance heating board containing silver (Ag) is heated and the deposition rate is increased. A conductive layer having a thickness of 10 nm and an area of 5 cm × 5 cm was formed on the intermediate layer at a rate of 0.1 nm / second to 0.2 nm / second, thereby producing a transparent electrode substrate 201.

<Preparation of transparent electrode substrate 202>
Comparative compound (3) was dissolved in PGME (1-methoxy-2-propanol) to prepare a solution having a concentration of 1.0% by mass. This solution was applied onto a non-alkali glass substrate having a curved surface by a spin coating method, and then heated and dried at 100 ° C. for 1 hour to form an intermediate layer having a thickness of 10 nm.
A conductive layer having a thickness of 10 nm was formed in the same manner as in the production of the transparent electrode substrate 201 except that the obtained intermediate layer was used, and a transparent electrode substrate 202 was produced.

<Preparation of transparent electrode substrate 203>
Comparative compound (3) was dissolved in PGME (1-methoxy-2-propanol) to prepare a solution having a concentration of 1.0% by mass. An alkali-free glass substrate was immersed (dip) in this solution at 30 ° C. for 40 minutes, and then heated and dried at 100 ° C. for 1 hour to form an intermediate layer having a thickness of 10 nm.
A conductive layer having a thickness of 10 nm was formed in the same manner as the production of the transparent electrode substrate 201 except that the obtained intermediate layer was used, and a transparent electrode substrate 203 was produced.

<Preparation of transparent electrode substrate 204>
A transparent electrode substrate 204 was produced in the same manner except that the constituent material of the intermediate layer was changed to the compound (3) in the production of the transparent electrode substrate 202. As a precursor of the compound (3) used for the preparation of the intermediate layer forming solution, a compound in which all of —O at the molecular terminals of the compound (3) were —OCH ₃ was used.

<Preparation of transparent electrode substrate 205>
A precursor of the compound (3) (a compound in which all of —O at the molecular end of the compound (3) is —OCH ₃ ) is dissolved in PGME (1-methoxy-2-propanol), and the concentration is 1.0 mass. % Dipping solution was prepared. A substrate made of alkali-free glass was immersed (dip) in this solution at 30 ° C. for 40 minutes and then heated and dried at 100 ° C. for 1 hour to form a 10 nm-thick intermediate layer containing compound (3). .
The obtained substrate on which the intermediate layer was formed was attached to a substrate holder of a commercially available vacuum deposition apparatus, and zinc (Zn) was placed in a resistance heating board made of tantalum and attached to the second vacuum chamber of the vacuum deposition apparatus. Then, after reducing the pressure of the second vacuum tank to 4 × 10 ⁻⁴ Pa, the resistance heating board containing zinc (Zn) is heated, and the deposition rate is 0.1 nm / sec to 0.2 nm / sec. A conductive layer having a thickness of 10 nm and an area of 5 cm × 5 cm was formed on the transparent electrode substrate 205.

<Preparation of transparent electrode substrates 206 to 207>
Transparent electrode substrates 206 to 207 were prepared in the same manner except that the constituent material of the conductive layer was changed as shown in Table 3 in the production of the transparent electrode substrate 205.

<Preparation of transparent electrode substrates 208 to 213>
Transparent electrode substrates 208 to 213 were prepared in the same manner except that the constituent material of the intermediate layer was changed to the compounds shown in Table 3 in the production of the transparent electrode substrate 207. As a precursor of the compound shown in Table 3 used for preparing the solution for forming the intermediate layer, a compound in which all of —O at the molecular end of the compound shown in Table 3 was —OCH ₃ was used.

<Evaluation of transparent electrode substrate>
The light transmittance, sheet resistance value, and sheet resistance value change (durability) under high temperature storage of the obtained transparent electrode substrates 201 to 213 were measured in the same manner as described above. These results are shown in Table 3.

  As shown in Table 3, the transparent electrode substrates 205 to 212 can form a transparent electrode having a uniform thickness even on a non-alkali glass substrate having a curved surface, and have higher light transmission than the transparent electrode substrates 201 to 204. It is shown that both the rate and the low sheet resistance can be achieved.

  The contrast of the transparent electrode substrates 204 to 206 indicates that the light transmittance is high and the resistance is low, particularly when the conductive layer is mainly composed of silver (Ag).

Comparison between the transparent electrode substrate 207 and 208 to 213 indicates that high light transmittance and low resistance are easily obtained when the constituent material of the intermediate layer contains a nitrogen-containing aromatic heterocyclic ring. Further, the comparison of the transparent electrode substrates 208 to 213 indicates that when the constituent material of the intermediate layer includes a triazine ring among nitrogen-containing aromatic heterocycles, higher light transmittance and lower resistance are easily obtained. From the comparison between the transparent electrode substrates 212 and 213, the constituent material of the intermediate layer is a linear alkylene group in which L ^{3 in the} general formula (3) has 6 or more carbon atoms (may be substituted with an oxygen atom) It is shown that higher light transmittance and lower resistance are easily obtained.

3. Production / Evaluation of Organic EL Device A double-sided light-emitting organic EL device using a transparent electrode substrate as an anode substrate was produced with reference to FIG.

<Preparation of organic EL device 301>
An alkali-free glass substrate (thickness 1000 μm) was attached to a substrate holder of a commercially available vacuum deposition apparatus. In addition, the comparative compound (2) (also referred to as the comparison (2)) is placed in a tantalum resistance heating board and attached to the first vacuum chamber of the vacuum evaporation apparatus, and silver (Ag) is placed in the resistance heating board made of tungsten. And installed in the second vacuum chamber.

In this state, first, the first vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, then the resistance heating board containing the comparative compound (2) was heated, and the deposition rate was 0.1 nm / sec to 0.2 nm / sec. An intermediate layer having a thickness of 15 nm was formed on the substrate.
Next, the substrate on which the intermediate layer is formed is transferred into the second vacuum chamber, and after the pressure in the second vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, the resistance heating board containing silver (Ag) is heated and the deposition rate is increased. A conductive layer having a thickness of 12 nm and an area of 5 cm × 5 cm was formed on the intermediate layer at a rate of 0.1 nm / second to 0.2 nm / second. Thereby, a transparent electrode substrate was produced.

The obtained transparent electrode substrate was attached to a substrate holder of a commercially available vacuum deposition apparatus, and a deposition mask was disposed on the surface of the transparent electrode. 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. The heating boat used was made of tungsten resistance heating material. Next, the inside of the vapor deposition chamber of the vacuum vapor deposition apparatus was depressurized to a degree of vacuum of 4 × 10 ⁻⁴ Pa, a heating boat containing each material was sequentially energized and heated, and each layer was formed as follows.

First, as a hole injecting and transporting material, a heating boat containing α-NPD is energized and heated, and a hole injecting and transporting layer serving as both the hole injecting layer 3a and the hole transporting layer 3b is formed on the transparent electrode 1. A film was formed on the conductive layer 1b. At this time, the deposition rate was 0.1 to 0.2 nm / second, and the thickness was 20 nm.

  Next, a heating boat containing the host material mCP (N, N-dicarbazolyl-3,5-benzene) and a phosphorescent dopant Ir (ppy) 3 (tris (2-phenylpyridine) iridium (III)) were contained. The heating boat was energized independently, and the light emitting layer 3c containing the host material mCP and the phosphorescent light emitting dopant Ir (ppy) 3 was formed on the hole injecting and transporting layer 31. At this time, the energization amount of the heating boat was adjusted so that the deposition rate was the host material mCP: phosphorescent dopant Ir (ppy) 3 = 100: 6. The thickness was 30 nm.

Next, as an electron transport material, a heating boat containing ET-6 shown below and a heating boat containing potassium fluoride are energized independently, and an electron transport layer 3d containing ET-6 and potassium fluoride is supplied. Was deposited on the light emitting layer. At this time, the energization amount of the heating boat was adjusted so that the deposition rate was ET-6: potassium fluoride = 75: 25. The thickness was 30 nm.

  Next, as an electron injection material, a heating boat containing potassium fluoride was energized and heated, and an electron injection layer 3e made of potassium fluoride was formed on the electron transport layer 3d. At this time, the deposition rate was 0.01 to 0.02 nm / second, and the 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. Then, 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 thickness of 150 nm was formed as a cathode. Thus, the organic EL element 7 was formed on the transparent substrate 13.

  Thereafter, the organic EL element 7 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 7. ). 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 7. Stopped.

  In the formation of the organic EL element 7, 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 serving as the anode and the counter electrode 5a serving as the cathode are insulated by the organic functional layer 3 from the hole transport injection layer to the electron injection layer 3e, and a terminal portion is provided on the periphery of the transparent substrate 13. It was formed in the drawn shape.

As described above, an organic EL device 301 in which the organic EL element 7 was provided on the transparent substrate 13 and sealed with the sealing material 17 and the adhesive 19 was produced.
In the organic EL device 301, the emitted light h of each color generated in the light emitting layer 3c is extracted from both the transparent electrode 1 side (transparent substrate 13 side) and the counter electrode 5a side (sealing material 17 side).

<Preparation of organic EL device 302>
Comparative compound (2) was dissolved in PGME (1-methoxy-2-propanol) to prepare a solution having a concentration of 1.2% by mass. This solution was applied onto a non-alkali glass substrate by spin coating, and then dried by heating at 100 ° C. for 1 hour to form an intermediate layer having a thickness of 15 nm.
A transparent electrode substrate and an organic EL device 302 including the same were prepared in the same manner as the organic EL device 301 except that the obtained intermediate layer was used.

<Preparation of organic EL device 303>
Comparative compound (2) was dissolved in PGME (1-methoxy-2-propanol) to prepare a solution having a concentration of 1.2% by mass. A substrate made of alkali-free glass was immersed (dip) in this solution at 70 ° C. for 30 minutes, and then heated and dried at 100 ° C. for 1 hour to form an intermediate layer having a thickness of 15 nm.
A transparent electrode substrate and an organic EL device 303 including the same were produced in the same manner as the production of the organic EL device 301 except that the obtained intermediate layer was used.

<Preparation of organic EL device 304>
A precursor of the compound (4) (a compound in which all of —O at the molecular terminal of the compound (4) is —OCH ₃ ) was dissolved in PGME (1-methoxy-2-propanol), and the concentration was 1.2% by mass. A solution of was prepared. This solution was applied onto a non-alkali glass substrate by spin coating, and then heated and dried at 100 ° C. for 1 hour to form a 15 nm-thick intermediate layer containing the compound (4).
A transparent electrode substrate and an organic EL device 304 including the same were prepared in the same manner as the organic EL device 301 except that the obtained intermediate layer was used.

<Preparation of organic EL device 305>
A precursor of the compound (4) (a compound in which all of —O at the molecular terminal of the compound (4) is —OCH ₃ ) was dissolved in PGME (1-methoxy-2-propanol), and the concentration was 1.2% by mass. A solution of was prepared. In this solution, a non-alkali glass substrate was immersed (dip) at 70 ° C. for 30 minutes, and then heated and dried at 100 ° C. for 1 hour to form a 15 nm-thick intermediate layer containing the compound (4). .
The substrate on which the intermediate layer was formed was attached to a substrate holder of a commercially available vacuum deposition apparatus, and zinc (Zn) was placed in a tantalum resistance heating board and attached to the second vacuum chamber of the vacuum deposition apparatus. Then, after reducing the pressure of the second vacuum tank to 4 × 10 ⁻⁴ Pa, the resistance heating board containing nickel (Ni) is heated, and the deposition rate is 0.1 nm / sec to 0.2 nm / sec. A conductive layer having a thickness of 12 nm and an area of 5 cm × 5 cm was formed on the transparent electrode substrate.
An organic EL device 305 was produced in the same manner as the organic EL device 301 except that the obtained transparent electrode substrate was used.

<Production of organic EL devices 306 and 307>
A transparent electrode substrate was produced in the same manner as in the production of the organic EL device 305 except that the constituent material of the conductive layer was changed as shown in Table 4.
Organic EL devices 306 and 307 were prepared in the same manner as the organic EL device 301 except that the obtained transparent electrode substrate was used.

<Preparation of organic EL devices 308 to 317>
In the production of the organic EL device 307, a transparent electrode substrate was produced in the same manner except that the constituent material of the intermediate layer was changed to the compounds shown in Table 4. As a precursor of the compound shown in Table 4 used for the preparation of the intermediate layer forming solution, a compound in which all of —O at the molecular terminals of the compound shown in Table 4 were —OCH ₃ was used.
Organic EL devices 308 to 317 were prepared in the same manner as the organic EL device 301 except that the obtained transparent electrode substrate was used.

<Preparation of organic EL devices 318 to 321>
Transparent electrode substrates were produced in the same manner except that the types of substrates were changed as shown in Table 3 in the production of the organic EL devices 316 and 317.
Organic EL devices 318 to 321 were produced in the same manner as the production of the organic EL device 301 except that the obtained transparent electrode substrate was used.

<Preparation of organic EL devices 322 to 323>
As the conductive layer ink, a solution was prepared by diluting 1.0 ml of an inkjet ink made of complex silver (manufactured by Ink Tec Co., Ltd., TEC-IJ-010) 10 times with ethanol.
0.1 ml of this diluted solution is applied on the intermediate layer used in the production of the transparent electrodes 316 and 317 by spin coating, and then baked at 120 ° C. for 30 minutes to form a conductive layer made of silver having a thickness of 10 nm. did. Thereby, a transparent electrode substrate in which an intermediate layer and a conductive layer were sequentially laminated on the substrate was obtained.
Organic EL devices 322 and 323 were produced in the same manner as the production of the organic EL device 301 except that the obtained transparent electrode substrate was used.

<Evaluation of organic EL devices>
The light transmittance, drive voltage, and external quantum efficiency change (durability) under high temperature storage of the produced organic EL devices 301 to 323 were measured by the following methods. These evaluation results are shown in Table 4.

(1) Measurement of light transmittance The light transmittance (%) at a measurement light wavelength of 550 nm of each of the produced organic EL devices was measured using a spectrophotometer (U-3300 manufactured by Hitachi High-Technologies Corporation). The transparent electrode substrate of each light-emitting panel was used as a reference.

(2) Measurement of driving voltage The front luminance on the transparent electrode 1 side (namely, the transparent substrate 13 side) and the front luminance on the counter electrode 5a side (namely, the sealing material 17 side) of each of the organic EL devices produced above. Each was measured, and the voltage when the sum was 1000 cd / m ² was measured as the drive voltage (V). The measurement of luminance was performed using a spectral radiance meter CS-1000 (manufactured by Konica Minolta). It represents that it is so preferable that the numerical value of the obtained drive voltage is small.

(3) Measurement of change in external quantum efficiency (EQE) under high temperature storage Each organic EL element of the organic EL device produced above was allowed to emit light at 75 ° C. under a constant current condition of ^2.5 mA / cm ^2. The emission luminance immediately after the start and the emission luminance after 200 hours from the start were measured using a spectral radiance meter CS-2000 (manufactured by Konica Minolta). Relative light emission luminance after 200 hours from the light emission luminance immediately after the start of light emission was obtained, and this was used as a measure of external quantum efficiency (EQE). The smaller the value, the smaller the change in emission luminance and the better the external quantum efficiency.

  As shown in Table 4, the organic EL devices 301 to 304 cannot achieve both high light transmittance and low driving voltage, and most of them do not emit light; whereas the organic EL devices 305 to 321 have high light transmittance. And a low driving voltage can be achieved, and high light emission is shown even under high temperature storage. This is probably because the transparent electrodes of the organic EL devices 301 to 304 have an intermediate layer formed of a self-assembled monomolecular film, so that both high light transmittance and low resistance can be achieved.

  The comparison between the organic EL devices 305 to 307 indicates that the light transmittance is particularly high and the driving voltage is low particularly when the conductive layer is mainly composed of silver (Ag).

The comparison between the organic EL devices 307 and 308 to 317 indicates that a higher light transmittance and a lower driving voltage are more easily obtained when the constituent material of the intermediate layer of the transparent electrode contains a nitrogen-containing aromatic heterocycle. In addition, the comparison between the organic EL devices 308 to 317 indicates that when the constituent material of the intermediate layer includes a triazine ring among nitrogen-containing aromatic heterocycles, higher light transmittance and lower drive voltage are easily obtained. . Correlation of the organic EL devices 311 and 312, and 315 and from the comparison 316, the material of the intermediate layer, is more ^{A 3} of ^{A 2} or of the general formula (2) (3) is a silicon atom, -C It is shown that a higher light transmittance and a lower driving voltage can be easily obtained than in the case of (= O)-.

  The comparison of the organic EL devices 316 to 321 shows that good high light transmittance and low driving voltage can be obtained using not only alkali-free glass substrates but also PMMA and polyethylene terephthalate substrates.

  The comparison between the organic EL devices 316 to 317 and 322 to 323 shows that even when the conductive layer of the transparent electrode is formed by the spin coating method, the same effect as that obtained by the vacuum deposition method can be obtained.

  According to the present invention, it is possible to provide a transparent electrode substrate having higher transparency and conductivity, an electronic device including the transparent electrode substrate, and an organic EL device. Furthermore, it is possible to provide a method for manufacturing a transparent electrode substrate that has high material utilization efficiency and time efficiency, can have a large area, and can form a conductive layer on a curved substrate.

DESCRIPTION OF SYMBOLS 1 Transparent electrode 1a Intermediate | middle layer 1b Conductive 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 Counter electrode 7 Organic EL element 11 Substrate 13 Transparent substrate ( substrate)
13a Light extraction surface 15 Auxiliary electrode 17 Sealing material 19 Adhesive 23 Support substrate 100, 200 Organic EL device 300 Lighting device A Light emitting region B Non-light emitting region h Light emitting light

Claims (13)

A substrate,
A transparent layer including a conductive layer containing a metal as a main component and an intermediate layer disposed between the conductive layer and the substrate;
The intermediate layer is one or more self-assembled monolayers containing a compound containing an aromatic hydrocarbon group or an aromatic heterocyclic group at one molecular end and a hydrophilic group at the other molecular end. A transparent electrode substrate.   The transparent electrode substrate according to claim 1, wherein the conductive layer contains, as a main component, one or more selected from the group consisting of gold, silver, and copper.   The transparent electrode substrate according to claim 1, wherein the conductive layer contains silver as a main component. The said compound is a transparent electrode substrate as described in any one of Claims 1-3 which is a compound represented by following General formula (1).

(In general formula (1),
R represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group;
L ¹ represents an alkylene group having 2 or more carbon atoms, and part of the carbon atoms in the alkylene group may be replaced with an oxygen atom or a sulfur atom;
A ¹ represents a carbon atom, a silicon atom, —C (═O) — or —NH—C (═O) —;
-OB ^1, -OB ² and -OB ³ each represent a hydroxy group or an alkoxy group, and ^-OB 1, -OB ² and -OB ³ is other molecules or substrate surface hydroxy group or an alkoxy group is fused May be;
m and n each represents 1 when A ¹ is a carbon atom or a silicon atom, and each represents 0 when —C (═O) — or —NH—C (═O) —. The transparent electrode substrate according to claim 4, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In general formula (2),
X ^{1 to} X ⁵ each represent a carbon atom or a nitrogen atom, and at least one of X ^{1 to} X ⁵ represents a nitrogen atom;
R ^{1 to} R ⁵ each represent a hydrogen atom or a substituent;
L ² represents an alkylene group having 2 or more carbon atoms, and part of the carbon atoms in the alkylene group may be replaced with an oxygen atom or a sulfur atom;
A ² represents a carbon atom, a silicon atom, —C (═O) — or —NH—C (═O) —;
-OB ^4, -OB ⁵ and -OB ⁶ each represent a hydroxy group or an alkoxy group, and ^-OB 4, -OB ⁵ and -OB ⁶ are other molecules or substrate surface hydroxy group or an alkoxy group is fused May be;
m and n each represent 1 when A ² is a carbon atom or a silicon atom, and each represents 0 when —C (═O) — or —NH—C (═O) —. The transparent electrode substrate according to claim 5, wherein A ² in the general formula (2) is a carbon atom or a silicon atom. The transparent electrode substrate according to claim 4, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

(In general formula (3),
R ⁶ and R ⁷ each represent a substituent;
L ³ represents an alkylene group having 2 or more carbon atoms, and a part of the carbon atoms in the alkylene group may be replaced with an oxygen atom or a sulfur atom;
A ³ represents a carbon atom, a silicon atom, —C (═O) — or —NH—C (═O) —;
-OB ^7, -OB ⁸ and -OB ⁹ each represent a hydroxy group or an alkoxy group, and ^-OB 7, -OB ⁸ and -OB ⁹ are other molecules or substrate surface hydroxy group or an alkoxy group is fused May be;
m and n each represents 1 when A ³ is a carbon atom or a silicon atom, and each represents 0 when —C (═O) — or —NH—C (═O) —. The transparent electrode substrate according to claim 7, wherein A ³ in the general formula (3) is a carbon atom or a silicon atom. The transparent electrode substrate according to claim 7 or 8, wherein L ³ in the general formula (3) is a linear alkylene group having 6 or more carbon atoms.   The transparent electrode substrate according to any one of claims 1 to 9, wherein the substrate comprises glass, polyethylene terephthalate or polymethyl methacrylate resin. Immersing the substrate in a solution containing the compound represented by the general formula (4) to form an intermediate layer including a self-assembled monolayer of the compound on the substrate;
Forming a conductive layer on the intermediate layer.

(In general formula (4),
R represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group;
L ¹ represents an alkylene group having 2 or more carbon atoms, and part of the carbon atoms in the alkylene group may be replaced with an oxygen atom or a sulfur atom;
A ¹ represents a carbon atom, a silicon atom, —C (═O) — or —NH—C (═O) —;
Y ¹ , Y ² and Y ³ each represent a hydroxy group, an alkoxy group or a halogen atom;
m and n each represents 1 when A ¹ is a carbon atom or a silicon atom, and each represents 0 when —C (═O) — or —NH—C (═O) —.   The electronic device containing the transparent electrode substrate as described in any one of Claims 1-10. A substrate provided with one of a cathode and an anode, the other of the cathode and the anode, and a light emitting layer disposed between the cathode and the anode,
The organic EL device in which the substrate provided with one of the cathode and the anode is the transparent electrode substrate according to any one of claims 1 to 10.

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