JP6241189B2 - Transparent electrode, method for producing transparent electrode, electronic device, and organic electroluminescence element - Google Patents

Description

  The present invention relates to a transparent electrode, a method for producing a transparent electrode, an electronic device, and an organic electroluminescent element, and in particular, a transparent electrode having both conductivity and light transmittance, a method for producing the transparent electrode, and the transparent electrode. The present invention relates to an electronic device and an organic electroluminescence element.

  An organic electroluminescence element (also referred to as “organic EL element” or “organic electroluminescence element”) using an organic material electroluminescence (hereinafter abbreviated as EL) is about several V to several tens V. It is a thin-film type complete solid-state device capable of emitting light at a low voltage, and has many excellent features such as high brightness, high luminous efficiency, thinness, and light weight. For this reason, it has been attracting attention in recent years as surface light emitters such as backlights for various displays, display boards such as signs 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 sandwiched 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 a constituent material of the transparent electrode, an oxide semiconductor material such as indium tin oxide (SnO ₂ -In ₂ O ₃ : Indium Tin Oxide, hereinafter abbreviated as ITO) is generally used. For example, Japanese Patent Application Laid-Open Nos. 2002-15623 and 2006-164961 have examined materials aiming at lowering resistance by laminating silver. However, since ITO uses indium which is a rare metal, the material cost is high, and it is necessary to anneal the film at about 300 ° C. after film formation in order to reduce the resistance.

  Therefore, there is a technique for forming a thin film using an alloy of silver (Ag) and magnesium (Mg) having high electrical conductivity, and a technique for forming a thin film using a cheap and easily available metal material instead of indium. It has been proposed (see, for example, Patent Documents 1 and 2).

  In the invention described in Patent Document 1, by using an alloy of silver and magnesium as an electrode material, it is possible to obtain desired conductivity under thin film conditions as compared with an electrode formed by silver alone. It is said that both can be achieved. However, the resistance value of the electrode obtained by the method described in Patent Document 1 is at most about 100Ω / □, which is insufficient as the conductivity of the transparent electrode. In addition, magnesium has a characteristic that it is easily oxidized. Therefore, there is a problem that the performance is likely to deteriorate with time.

Patent Document 2 discloses a transparent conductive film using a metal material such as zinc (Zn) or tin (Sn) which is inexpensive and easily available as a raw material instead of indium (In). However, the resistance value does not decrease sufficiently with these alternative metals, and in addition, the ZnO-based transparent conductive film containing zinc has a characteristic that its performance tends to fluctuate by reacting with water. It has also been found that SnO ₂ -based transparent conductive films containing tin have a problem that processing by etching is difficult.

  On the other hand, an organic electroluminescence element using a thin film having a layer thickness of about 15 nm and having a highly transmissive silver layer deposited as a cathode is disclosed (for example, see Patent Document 3). However, the silver layer formed by the method proposed in Patent Document 3 causes silver migration (atom movement), and a thin silver layer having a thickness of about 15 nm has low conductivity and transmits light. Development of technology that achieves both compatibility and conductivity is eagerly desired.

JP 2006-344497 A JP 2007-031786 A US Patent Application Publication No. 2011/0260148

  The present invention has been made in view of the above problems, and a solution to the problem is a transparent electrode having both sufficient conductivity and light transmittance and excellent durability (light transmittance stability), and the transparent An electrode manufacturing method, an electronic device and an organic electroluminescence element that have high light transmittance, can be driven at a low voltage, and have excellent durability.

  As a result of diligent investigation in view of the above problems, the present inventor has a configuration in which an intermediate layer and a conductive layer provided adjacent to the intermediate layer are stacked, the intermediate layer containing a silver compound, The conductive layer is composed mainly of silver, and with a transparent electrode with a high light transmittance and a low sheet resistance value that has never existed before, it is possible to achieve both excellent conductivity and light transmittance and is durable. As a result, the inventors have found that a transparent electrode having excellent properties can be realized, and have reached the present invention.

  That is, the said subject of this invention is solved by the following means.

1. A transparent electrode having an intermediate layer and a conductive layer provided adjacent to the intermediate layer, having a light transmittance of 50% or more at a wavelength of 550 nm and a sheet resistance value of 20Ω / □ or less. The intermediate layer contains a silver compound, the conductive layer contains silver as a main component, and the silver compound is a compound represented by the following general formula (1) electrode.
General formula (1) Ag-Y (-R) _n
(In the formula, Y represents a chlorine atom, a bromine atom, an iodine atom, a sulfur atom or OC (═O). R represents an organic substituent. N represents 0 or 1.)

2 . In the above general formula (1), Y is bromine atom or iodine atom, a transparent electrode according to paragraph 1, characterized in that n represents 0.

3 . The conductive layer, an intermediate layer provided adjacent to the conductive layer, and a base layer provided adjacent to the intermediate layer are sequentially stacked,
3. The transparent electrode according to item 1 or 2, wherein the underlayer contains a compound represented by the following general formula (2).
Formula (2) R ₁ —Y (—R) _n
(In the formula, Y represents a chlorine atom, a bromine atom, an iodine atom, a sulfur atom, SS or OC (═O). When Y is a chlorine atom, a bromine atom or an iodine atom, n represents 0, and R _1. Represents a substituent, and when Y represents a sulfur atom, SS or OC (═O), n represents 1, R represents a substituent, and R ₁ represents a hydrogen atom or a substituent.

4 . The intermediate layer and the base layer form one intermediate base layer,
4. The transparent electrode according to item 3 , wherein the intermediate underlayer contains both the compound represented by the general formula (1) and the compound represented by the general formula (2).

5 . A method for producing a transparent electrode having a conductive layer containing silver as a main component,
A step of forming a layer containing at least one of a silver compound and a compound that reacts with silver derived from the conductive layer to form the silver compound;
Have a, and forming the conductive layer,
An intermediate layer containing the silver compound represented by the following general formula (1) is formed in the process of forming the conductive layer on an underlayer containing the compound represented by the following general formula (2) A method for producing a transparent electrode, comprising:
General formula (1) Ag-Y (-R) _n
(In the formula, Y represents an atom or group that forms a bond with one silver atom. R represents an organic substituent. N represents 0 or 1.)
Formula (2) R ₁ —Y (—R) _n
(In the formula, Y represents a chlorine atom, a bromine atom, an iodine atom, a sulfur atom, SS or OC (═O). When Y is a chlorine atom, a bromine atom or an iodine atom, n represents 0, and R _1. Represents a substituent, and when Y represents a sulfur atom, SS or OC (═O), n represents 1, R represents a substituent, and R ₁ represents a hydrogen atom or a substituent.

6 . In the said General formula (2), Y represents a bromine atom or an iodine atom, The manufacturing method of the transparent electrode of Claim 5 characterized by the above-mentioned.

7 . The method for producing a transparent electrode according to item 6, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).
General formula (3) Ar-X
(In the formula, Ar represents an aromatic group, and X represents a bromine atom or an iodine atom.)

8 . An electronic device comprising the transparent electrode according to any one of items 1 to 4 .

9 . An organic electroluminescence device comprising the transparent electrode according to any one of items 1 to 4 .

  According to the present invention, a transparent electrode having sufficient conductivity and light transmittance and excellent in durability (light transmittance stability), a method for producing the transparent electrode, and a high light transmittance, low voltage It is possible to provide an electronic device and an organic electroluminescence element that can be driven by the above-mentioned and excellent in durability.

  Although the expression mechanism and action mechanism of the effect of the present invention are not clarified, it is presumed as follows.

  That is, in the transparent electrode of the present invention, a conductive layer containing silver as a main component is provided on the upper part of the intermediate layer, and the intermediate layer contains a silver compound having affinity for silver atoms. It is the composition of being contained.

  Thereby, when forming a conductive layer on the upper part of the intermediate layer, the silver atoms constituting the conductive layer interact with the silver compound contained in the intermediate layer, and on the surface of the intermediate layer. The diffusion distance of silver atoms is reduced, and the aggregation of silver at specific points is suppressed.

  That is, silver atoms first form a two-dimensional nucleus on the surface of an intermediate layer containing silver atoms and a silver compound, and a two-dimensional single crystal layer is formed around the two-dimensional nucleus (Frank-van). der Merwe (FM type) film growth.

  In general, an island-shaped growth type (Volume-Weber) in which silver atoms attached on the surface of the intermediate layer 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 is easily formed into islands, but in the present invention, the silver compound contained in the intermediate layer suppresses the island-like growth in this manner, and the layer growth Is presumed to be promoted.

  It is known that the island-shaped silver layer having a layer thickness of several nanometers to several tens of nanometers promotes light absorption by surface plasmons. However, in a silver layer grown in the same average layer thickness as the island-shaped silver layer, light absorption by surface plasmons is reduced. For the above reason, it is presumed that the light transmittance of the transparent electrode of the present invention is increased due to the low light absorption of the conductive layer by the surface plasmon.

  Therefore, the conductive layer of the transparent electrode of the present invention has a uniform layer thickness even though it has the same average layer thickness or less than the conventionally known conductive layer. It has excellent characteristics and has a feature that light absorption is remarkably small. As a result, the transparent electrode of the present invention can be a transparent electrode having high light transmittance while retaining excellent conductivity.

Schematic sectional view showing an example of the configuration of a transparent electrode substrate having a transparent electrode of the present invention Schematic sectional view showing a first example of an organic EL element to which the transparent electrode of the present invention is applied Schematic sectional view showing a second example of an organic EL element to which the transparent electrode of the present invention is applied Schematic sectional view showing a third example of an organic EL element to which the transparent electrode of the present invention is applied. The schematic sectional drawing which shows an example of the illuminating device which enlarged the light emission surface using the organic EL element provided with the transparent electrode of this invention. Schematic sectional view showing a light-emitting panel provided with an organic EL element produced in the example

The transparent electrode of the present invention is a transparent electrode having an intermediate layer and a conductive layer provided adjacent to the intermediate layer, and has a light transmittance of 50% or more at a wavelength of 550 nm and a sheet resistance of 20Ω. The intermediate layer contains a silver compound, the conductive layer contains silver as a main component, and the silver compound is a compound represented by the general formula (1). Thus, it is possible to realize a transparent electrode having sufficient conductivity and light transmittance and excellent durability (light transmittance stability). This feature is a technical feature common to the inventions according to the first to ninth terms.

The embodiments of the present invention, in the general formula (1), wherein Y is bromine atom or iodine atom, it is good preferable that n represents 0.

  The conductive layer, an intermediate layer provided adjacent to the conductive layer, and a base layer provided adjacent to the intermediate layer are sequentially stacked, and the base layer is It is preferable to contain the compound represented by the general formula (2). As a result, the silver compound represented by the general formula (1) is generated by the reaction of the silver contained in the conductive layer with the compound represented by the general formula (2), and is contained in the conductive layer. It is thought that it can suppress the aggregation of silver.

  Further, the intermediate layer and the underlayer form one intermediate underlayer, and the intermediate underlayer is a compound represented by the general formula (1) and a compound represented by the general formula (2). It is preferable that both are contained. Even when a single intermediate base layer without a boundary is formed between the intermediate layer and the base layer, the aggregation of silver can be suppressed as in the case where the intermediate layer and the base layer are formed separately. . In addition, the cost can be reduced by forming with one layer.

The method for producing a transparent electrode for producing the transparent electrode of the present invention is a method for producing a transparent electrode having a conductive layer containing silver as a main component, which reacts with a silver compound and silver derived from the conductive layer. among the compounds which form the silver compound Te, a step of forming a layer containing at least one, have a, and forming the conductive layer, the above formula (2) compound in the process of forming the conductive layer on the base layer containing, and forming an intermediate layer containing a silver compound represented by the general formula (1). Further, in the process of forming the conductive layer, the compound represented by the general formula (2) is a compound represented by the general formula (3). From the viewpoint of obtaining a conductive layer having a sufficient thickness.

  The transparent electrode of the present invention is suitably provided in an electronic device. Especially, the transparent electrode of this invention is comprised suitably for an organic electroluminescent element.

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

<< 1. Transparent electrode >>
FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a transparent electrode substrate having a transparent electrode of the present invention.

  A transparent electrode 1 shown in FIG. 1 (a) has a two-layer structure in which an intermediate layer 1a is provided and a conductive layer 1b is laminated on the intermediate layer 1a. A transparent electrode 1 composed of a layer 1a and a conductive layer 1b is provided to form a transparent electrode substrate. The intermediate layer 1a according to the present invention is a layer containing a silver compound, and the conductive layer 1b according to the present invention laminated thereon is a layer composed mainly of silver. It is characterized by being.

  In the present application, the “main component of the conductive layer” means a component having the highest component ratio among the components constituting the conductive layer. The conductive layer according to the present invention is mainly composed of silver, and the composition ratio is preferably 60% by mass or more. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, Most preferably, it is 98 mass% or more.

  The term “transparent” as used in the transparent electrode 1 of the present invention means that the light transmittance measured at a wavelength of 550 nm is 50% or more.

  Moreover, as a layer structure of the transparent electrode substrate, as shown in FIG. 1B, the transparent electrode 1 of the present invention comprising the intermediate layer 1a and the conductive layer 1b is provided on the base material 11, and In another preferred embodiment, the second intermediate layer 1c is stacked on the conductive layer 1b, and the conductive layer 1b is sandwiched between the intermediate layer 1a and the intermediate layer 1c.

  In the present invention, in the transparent electrode 1 having a laminated structure including the intermediate layer 1a and the conductive layer 1b formed thereon, the upper portion of the conductive layer 1b is further covered with a protective layer. It may be a configuration, or a configuration in which the second conductive layer is laminated. In this case, it is preferable that both the protective layer and the second conductive layer have high light transmittance so as not to impair the light transmittance of the transparent electrode 1.

Moreover, it is good also as a structure which provided the functional layer as needed under the intermediate | middle layer 1a, ie, between the intermediate | middle layer 1a, and the base material 11. FIG.
For example, as shown in FIG. 1C, the base layer 1d may be sandwiched between the base material 11 and the intermediate layer 1a, and the conductive layer 1b is preferably provided on the intermediate layer 1a. .

  Next, further detailed structural requirements will be described in the order of the base material 11 used to hold the transparent electrode 1 having such a laminated structure, the intermediate layer 1a and the conductive layer 1b constituting the transparent electrode 1.

〔Base material〕
Examples of the base material 11 used to hold the transparent electrode 1 of the present invention include, but are not limited to, glass and plastic. Moreover, although the base material 11 may be transparent or opaque, when the transparent electrode 1 of this invention is used for the electronic device which takes out light from the base material 11 side, the base material 11 is transparent. Examples of the transparent base material 11 that is preferably used include glass, quartz, and resin films.

  Examples of the glass include silica glass, soda-lime silica glass, lead glass, borosilicate glass, and alkali-free glass. From the viewpoints of adhesion to the intermediate layer 1a, durability, and smoothness, the surface of these glass materials may be subjected to physical treatment such as polishing, if necessary, and from inorganic or organic substances. Or a hybrid film formed by combining these films may be used.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefins such as polyethylene and polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, and cellulose acetate. Cellulose esters such as propionate (CAP), cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, poly Ether ketone, polyimide, polyether sulfone (PES), polyphenylene sulfi , Polysulfones, Polyetherimide, Polyetherketoneimide, Polyamide, Fluororesin, Nylon, Polymethylmethacrylate, Acrylic or Polyarylate, Arton (trade name; manufactured by JSR) or Appel (trade name; manufactured by Mitsui Chemicals) And the like.

The surface of the resin film may have a structure in which a film made of an inorganic material or an organic material (also referred to as a barrier film) or a hybrid film formed by combining these films is formed. Such coatings and hybrid coatings have a water vapor permeability (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS-K-7129-1992 of 0.01 g / (m ⁽² · 24 hours) or less barrier film is preferable. Furthermore, the oxygen permeability measured by a method according to JIS-K-7126-1987 is 1 × 10 ⁻³ ml / (m ² · 24 hours · atm) or less, and the water vapor permeability is 1 × 10 ⁻⁵ g. / (M ² · 24 hours) or less is preferable.

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

  The method for producing the barrier film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma. A polymerization method, a plasma CVD method (CVD: Chemical Vapor Deposition), a laser CVD method, a thermal CVD method, a coating method, or the like can be used, and atmospheric pressure plasma weight described in JP-A-2004-68143 is used. A legal method is particularly preferred.

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

[Middle layer]
The intermediate layer 1a according to the present invention is a layer configured using a silver compound. When such an intermediate layer 1a is formed on the substrate 11, the film forming method includes a method using a wet process (coating method) such as an ink jet method, a coating method, a dip method, or a sputtering method. And a method using a dry process (evaporation method) such as a CVD method and the like. Of these, the vapor deposition method is preferably applied.

The intermediate layer 1a preferably has a thickness in the range of 1 to 100 nm, and more preferably in the range of 5 to 30 nm. Within this range, the effect can be obtained with any film thickness.
When the film thickness is less than 100 nm, the absorption component of the layer is reduced and the transmittance of the transparent electrode is improved, which is preferable. Further, it is preferable that the film thickness is thicker than 1 nm because a uniform and continuous intermediate layer is formed.

(Silver compound)
In the transparent electrode 1 of the present invention, the intermediate layer 1a contains a silver compound. Examples of the silver compound include inorganic silver compounds and organic silver compounds.

  The structure of the silver compound according to the present invention is not particularly limited, but a compound represented by the following general formula (1) is preferable.

  Hereinafter, the silver compound represented by the general formula (1) that can be suitably used in the present invention will be described.

General formula (1) Ag-Y (-R) _n
In the above general formula (1), Y represents a group that forms a salt with monovalent silver, and R represents an organic substituent. n represents 0 or 1.

  In the general formula (1), the group represented by Y is preferably a chlorine atom, a bromine atom, an iodine atom, a sulfur atom, or OC (═O). The organic substituent represented by R may be bonded to another silver atom.

  When Y represents a chlorine atom, a bromine atom or an iodine atom, n is 0, and when Y represents a sulfur atom or OC (═O), n is 1.

  Examples of the organic substituent represented by R include an alkyl group, a cycloalkyl group, an alkynyl group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, and a non-aromatic heterocyclic group.

  Examples of the alkyl group represented by R include methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, A hexadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, a docosyl group, a tricosyl group, etc. can be mentioned, Preferably they are a methyl group, an ethyl group, and a propyl group.

  Examples of the cycloalkyl group represented by R include a cyclopentyl group and a cyclohexyl group.

  Examples of the alkynyl group represented by R include ethynyl group, propargyl group, butynyl group and the like.

  Examples of the aromatic hydrocarbon ring group represented by R (also referred to as an aryl group or an aromatic hydrocarbon group) include, for example, a phenyl group, a p-chlorophenyl group, a mesityl group, a tolyl group, a xylyl group, and a naphthyl group. , Anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, and the like, preferably a phenyl group, a naphthyl group, and an anthryl group.

  Examples of the aromatic heterocyclic group represented by R include a pyridyl group, a pyrimidinyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a benzimidazolyl group, a pyrazolyl group, a pyrazinyl group, and a triazolyl group (for example, 1,2,4- Triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl Group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) Quinoxalinyl group, pyridazinyl group, tria Group, quinazolinyl group, and a phthalazinyl group, preferably, a pyridyl group, an imidazolyl group, a triazinyl group.

  Examples of the non-aromatic heterocyclic group represented by R include a pyrrolidyl group, an imidazolidyl group, a morpholyl group, and an oxazolidyl group.

  The alkyl group, aryl group, heteroaryl group, alkylene group, arylene group and heteroarylene group may be further substituted with a substituent. Examples of the substituent include the alkyl group, aryl group, heteroaryl group, alkylene group, arylene group, and heteroarylene group.

  In the present invention, preferably, R is an aryl group or an arylene group, and the aryl group or arylene group may be further substituted with an aryl group.

  The organic substituent represented by the above R may further have a substituent. Examples of the substituent that the substituent represented by R can have include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg ethynyl group, propargyl etc.) Group), aromatic hydrocarbon ring group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group , Acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, Phenylyl group, etc.), aromatic heterocyclic groups (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazole- 1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, Dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) ), Quinoxalinyl group, pyridazinyl group, tria Nyl group, quinazolinyl group, phthalazinyl group, etc.), non-aromatic heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyl) Oxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (For example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (for example, phenyl Thio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxy) Carbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecyl) Aminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethyl group) Rubonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy Group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propyl) Carbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group Dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group) Octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentyl) Ureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminourei Group), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.) ), Alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group) , Naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopente) Ruamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc., cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group) Group, triphenylsilyl group, phenyldiethylsilyl group, etc.), halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) and the like.

  Among these substituents, preferred is an aromatic hydrocarbon ring group, further having a plurality of aromatic hydrocarbon ring groups, and a structure in which these aromatic hydrocarbon ring groups are further bonded to a silver atom. Is also preferable.

  Specific examples of the silver compound represented by the general formula (1) according to the present invention are shown below, but the present invention is not limited to these exemplified compounds.

  The silver compound represented by the general formula (1) according to the present invention can be easily synthesized according to a conventionally known synthesis method.

  Moreover, as a method of forming the intermediate layer containing the silver compound represented by the general formula (1) according to the present invention, the conductive layer is formed on the base layer containing the compound represented by the following general formula (2). The intermediate layer is preferably formed in the process of forming the conductive layer from the viewpoint of forming the intermediate layer uniformly and efficiently.

Formula (2) R ₁ —Y (—R) _n
(In the formula, Y represents a chlorine atom, a bromine atom, an iodine atom, a sulfur atom, SS or OC (═O). When Y is a chlorine atom, a bromine atom or an iodine atom, n represents 0, and R _1. Represents a substituent, and when Y represents a sulfur atom, SS or OC (═O), n represents 1, R represents a substituent, and R ₁ represents a hydrogen atom or a substituent.
In the general formula (2), when Y represents a sulfur atom or OC (═O), R ₁ is preferably a hydrogen atom.

  In addition, the compound represented by the general formula (2) is a compound represented by the following general formula (3), and in the process of forming the conductive layer, the silver compound is more easily generated and uniform. From the viewpoint of obtaining a conductive layer having a sufficient thickness, it is more preferable.

General formula (3) Ar-X
(In the formula, Ar represents an aromatic group, and X represents a bromine atom or an iodine atom.)
The aromatic group represented by Ar has the same meaning as the aromatic hydrocarbon group and aromatic heterocyclic group represented by R in the general formula (1).

  Specific examples of the compounds represented by the general formula (2) and the general formula (3) according to the present invention are shown below, but the present invention is not limited to these exemplified compounds.

<Synthesis example>
As a synthesis example, a synthesis method of the compound P-20 is described below.

＜中間体３の合成＞
１００ｍｌナスフラスコに１，３−ジヨードベンゼン（原料化合物２）（５．０ｇ ０．０１５ｍｏｌ）、δ−カルボリン（原料化合物１）（２．２ｅｑ．）、Ｋ_３ＰＯ_４（５ｅｑ．）、Ｃｕ_２Ｏ（０．４ｅｑ．）、ｄｉｐｉｖａｌｏｙｌ ｍｅｔｈａｎｅ（１．０ｅｑ．）、及びＤＭＳＯ（５０ｍｌ）を加えて溶解し、窒素雰囲気下、１５０℃で１４時間還流した。

<Synthesis of Intermediate 3>
In a 100 ml eggplant flask, 1,3-diiodobenzene (raw compound 2) (5.0 g 0.015 mol), δ-carboline (raw compound 1) (2.2 eq.), K ₃ PO ₄ (5 eq.), Cu ₂ O (0.4 eq.), Divalent molecule (1.0 eq.), And DMSO (50 ml) were added and dissolved, and the mixture was refluxed at 150 ° C. for 14 hours under a nitrogen atmosphere.

  After returning to room temperature, the solution was transferred to a separatory funnel and extracted. Ethyl acetate and saturated brine were added to separate the organic phase and the aqueous phase, and then the organic phase was taken out and evaporated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain a white solid of Intermediate 3 (4.4 g, yield 71%).

<Synthesis of Compound (6)>
Intermediate 3 (4.0 g 0.0098 mol), NBS (N-bromosuccinimide) (2.2 eq.), And DMF (20 ml) were added to and dissolved in a 100 ml eggplant flask, and at 80 ° C. under a nitrogen atmosphere. The mixture was stirred for 8 hours.

  After returning to room temperature, the solution was transferred to a separatory funnel and extracted. Ethyl acetate and saturated brine were added to separate the organic phase and the aqueous phase, and then the organic phase was taken out and evaporated under reduced pressure. The obtained solid was purified by silica gel column chromatography to obtain a white solid (4.6 g, yield 82%) of compound P-20.

  Other compounds described in the specific examples of the above compounds can be synthesized by applying the above synthesis method or according to a conventionally known synthesis method.

[Conductive layer]
The conductive layer 1b according to the present invention is a layer composed mainly of silver and is formed on the intermediate layer 1a. As a method for forming the conductive layer 1b according to the present invention, for example, a method using a wet process (coating method) such as an inkjet method, a coating method, or a dip method, or a dry process (evaporation method) such as a sputtering method or a CVD method is used. And the like. Among the film forming methods, the vapor deposition method is preferably applied. In addition, the conductive layer 1b is formed on the intermediate layer 1a, so that the conductive layer 1b has sufficient conductivity even without a high-temperature annealing treatment (for example, a heating process at 150 ° C. or higher) after the formation of the conductive layer. However, if necessary, high-temperature annealing treatment may be performed after film formation.

  In addition, in this application, as above-mentioned, "the main component of an electroconductive layer" means the component with the highest composition ratio among the components which comprise an electroconductive layer. The conductive layer according to the present invention is mainly composed of silver, and the composition ratio is preferably 60% by mass or more. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, Most preferably, it is 98 mass% or more.

  The conductive layer 1b may be made of silver alone or may be made of an alloy containing silver (Ag). Examples of such alloys include silver / magnesium (Ag / Mg), silver / copper (Ag / Cu), silver / palladium (Ag / Pd), silver / palladium / copper (Ag / Pd / Cu), silver -Indium (Ag.In) etc. are mentioned.

  The conductive layer 1b according to the present invention may have a configuration in which a layer composed mainly of silver is divided into a plurality of layers as necessary.

  Further, the conductive layer 1b has a layer thickness of preferably 5 to 20 nm, more preferably 5 to 12 nm, and most preferably in the range of 5 to 8 nm. When the layer thickness is thinner than 8 nm, the absorption component or reflection component of the layer is reduced, and the transmittance of the transparent electrode is improved, which is more preferable. Moreover, it is preferable that the layer thickness is thicker than 5 nm because the conductivity of the layer becomes sufficient.

[Underlayer]
Moreover, it is preferable that the conductive layer, the intermediate layer provided adjacent to the conductive layer, and the base layer provided adjacent to the intermediate layer are sequentially stacked. In this case, the underlayer preferably contains a compound represented by the following general formula (2).
Formula (2) R ₁ —Y (—R) _n
In the formula, Y represents a chlorine atom, a bromine atom, an iodine atom, a sulfur atom, SS or OC (═O). When Y is a chlorine atom, a bromine atom or an iodine atom, n represents 0 and R ₁ represents a substituent. When Y represents a sulfur atom, SS or OC (═O), n represents 1, R represents a substituent, and R ₁ represents a hydrogen atom or a substituent.
Specifically, by forming the base layer 1d containing the compound represented by the general formula (2), it reacts with silver atoms contained in the conductive layer 1b at the interface with the conductive layer 1b. It is preferable that the intermediate layer 1a containing the silver compound represented by the formula (1) is formed.

The intermediate layer and the underlayer form one intermediate underlayer, and the intermediate underlayer contains both the compound represented by the general formula (1) and the compound represented by the general formula (2). It is also preferable from the viewpoint of interaction with silver.
Here, the intermediate base layer 1e is formed by forming the base layer 1d and then forming the conductive layer 1b by vapor deposition, and forming the compound represented by the general formula (2) contained in the base layer 1d and the conductive layer 1b. The case where the intermediate layer containing the silver compound produced | generated by the reaction with the silver atom contained becomes one layer without forming a clear interface with the underlayer 1d.

[Effect of transparent electrode]
As described above, the transparent electrode 1 of the present invention has a configuration in which the conductive layer 1b composed mainly of silver is provided on the intermediate layer 1a configured to contain a silver compound. Thus, when the conductive layer 1b is formed on the intermediate layer 1a, the silver atoms constituting the conductive layer 1b interact with the silver compound constituting the intermediate layer 1a, and the intermediate layer 1a of the silver atoms is formed. The diffusion distance on the surface is reduced, and the formation of silver aggregation can be suppressed.

  In the formation of a conductive layer composed mainly of silver as in the prior art, since a thin film is grown by a nuclear growth type (Volume-Weber: VW type), silver particles are easily isolated in an island shape. When the thickness is small, it is difficult to obtain conductivity, and the sheet resistance value becomes high. Therefore, in order to ensure conductivity, the layer thickness needs to be increased to some extent. However, if the layer thickness is increased, the light transmittance is lowered, which is not suitable as a transparent electrode.

  However, according to the transparent electrode 1 having the configuration defined in the present invention, the aggregation of silver is suppressed by the interaction between the silver compound and silver on the intermediate layer 1a containing the silver compound. In the formation of the conductive layer 1b, a thin film is grown by a single-layer growth type (Frank-van der Merwe: FM type).

  In the present invention, “transparent electrode 1” means that the light transmittance at a wavelength of 550 nm is 50% or more. However, each of the materials used as the intermediate layer 1a is mainly composed of silver. Compared to the conductive layer 1b described above, the film is a good film having sufficient light transmittance. On the other hand, the conductivity of the transparent electrode 1 is ensured mainly by the conductive layer 1b. Therefore, as described above, the conductive layer 1b composed of silver as a main component is formed with a uniform layer thickness, so that the conductivity is ensured and the light transmittance is remarkably improved. Thereby, the improvement of the electroconductivity of the transparent electrode 1 and the improvement of light transmittance were able to be aimed at.

<< 2. Applications of transparent electrodes >>
The transparent electrode 1 of the present invention having the above-described configuration can be used for various electronic devices. Examples of electronic devices include organic EL elements, LEDs (Light Emitting Diodes), liquid crystal elements, solar cells, touch panels, etc. In these electronic devices, the present invention is used as an electrode member that requires light transmission. The transparent electrode 1 can be used.

  Hereinafter, as an example of the application, an embodiment of an organic EL element using a transparent electrode will be described.

<< 3. First Example of Organic EL Device >>
[Configuration of organic EL element]
FIG. 2 is a cross-sectional configuration diagram showing a first example of an organic EL element including the transparent electrode 1 of the present invention as an example of the electronic device of the present invention. Hereinafter, the configuration of the organic EL element will be described with reference to FIG.

  An organic EL element 100 shown in FIG. 2A is formed by sequentially laminating a transparent electrode 1, a light emitting functional layer 3 composed of an organic material, and the like, and a counter electrode 5a in this order on a transparent substrate 13. It is configured by sealing with a stopper 17 and an adhesive 19. In the organic EL element 100, the transparent electrode 1 of the present invention described above is used as the transparent electrode 1. For this reason, the organic EL element 100 is configured to extract the generated light (hereinafter referred to as emission light h) from at least the transparent substrate 13 side.

  Next, the layer structure of the organic EL element 100 will be described. However, the present invention is not limited to these exemplified configuration examples, and a general layer structure may be used.

  FIG. 2A shows a configuration in which the transparent electrode 1 functions as an anode (that is, an anode) and the counter electrode 5a functions as a cathode (that is, a cathode). In this case, as the light emitting functional layer 3, as shown in FIG. 2A, the hole injection layer 3a / hole transport layer 3b / light emitting layer 3c / electron transport layer 3d / The electron injection layer 3e is laminated. Among these, it is an indispensable condition for the organic EL element to provide at least the light emitting layer 3c composed of an organic material. The hole injection layer 3a and the hole transport layer 3b may be provided as a hole transport / injection layer. The electron transport layer 3d and the electron injection layer 3e may be provided as an electron transport / injection layer. Of these light emitting functional layers 3, for example, the electron injection layer 3e may be made of an inorganic material.

  Further, the light emitting functional layer 3 may be laminated at a necessary place as required, such as a hole blocking layer or an electron blocking layer, in addition to the constituent layers exemplified above. Furthermore, the light emitting layer 3c may have a structure in which each color light emitting layer that generates emitted light in each wavelength region is laminated, and each of these color light emitting layers is laminated via a non-light emitting auxiliary layer. The auxiliary layer may function as a hole blocking layer or an electron blocking layer. Furthermore, the counter electrode 5a, which is a cathode, may have a laminated structure as necessary. In such a configuration, only a portion where the light emitting functional layer 3 is sandwiched between the transparent electrode 1 and the counter electrode 5 a becomes a light emitting region in the organic EL element 100.

  Further, in the layer configuration as described above, for the purpose of reducing the resistance of the transparent electrode 1, the auxiliary electrode 15 as shown in FIG. 2A is in contact with the conductive layer 1 b of the transparent electrode 1. It may be provided.

  The organic EL element 100 having the above-described configuration is provided with a sealing material 17 to be described later on the transparent substrate 13 for the purpose of preventing deterioration of the light emitting functional layer 3 mainly composed of an organic material or the like. And a sealing structure is formed. The sealing material 17 is fixed to the transparent substrate 13 side with an adhesive 19. However, the terminal portions of the transparent electrode 1 and the counter electrode 5a are provided on the transparent substrate 13 so as to be exposed from the encapsulant 17 while being insulated from each other by the light emitting functional layer 3.

  Hereinafter, the details of the main layers for constituting the organic EL device 100 shown in FIG. 2A are described in detail with respect to the transparent substrate 13, the transparent electrode 1, the counter electrode 5a, the light emitting layer 3c of the light emitting functional layer 3, and the light emitting functional layer 3. The other functional layers, the auxiliary electrode 15, and the sealing material 17 will be described in this order.

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

[Transparent electrode]
The transparent electrode 1 (anode: anode) is the transparent electrode 1 of the present invention that has already been described in detail, and includes an intermediate layer 1a containing a silver compound and a conductive layer 1b containing silver as a main component in order from the transparent substrate 13 side. It is the structure which formed into a film in order. Here, in particular, the transparent electrode 1 functions as an anode (anode), and the conductive layer 1b is a substantial anode. In FIG. 2A, the base layer 1d is omitted.
Further, as shown in FIG. 2B, the conductive layer 1b may be formed adjacent to the intermediate base layer 1e in which the intermediate layer 1a and the base layer 1d are formed as one layer.

[Counter electrode]
The counter electrode 5a (cathode: cathode) is an electrode film that functions as a cathode (cathode) for supplying electrons to the light emitting functional layer 3, and includes, for example, a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof. It is composed of Specifically, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TiO ₂ , An oxide semiconductor such as SnO ₂ can be given.

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

  In the case where the organic EL element 100 sometimes takes out the emitted light h from the counter electrode 5a side, it can be countered by selecting a conductive material having good light transmittance from the above-described conductive materials. What is necessary is just to comprise the electrode 5a.

(Light emitting functional layer)
(Light emitting layer)
The light emitting layer 3c constituting the organic EL element of the present invention contains a light emitting material. Among them, it is preferable that a phosphorescent light emitting compound is contained as the light emitting material.

  The light emitting layer 3c is a layer that emits light by recombination of electrons injected from the counter electrode 5a or the electron transport layer 3d and holes injected from the transparent electrode 1 or the hole transport layer 3b. The portion that emits light may be in the layer of the light emitting layer 3c or may be the interface between the light emitting layer 3c and the adjacent layer.

  There is no restriction | limiting in particular in the structure as such a light emitting layer 3c, if the light emitting material contained satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting auxiliary layer between the light emitting layers 3c.

  The total layer thickness of the light emitting layer 3c is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm from the viewpoint of obtaining a lower driving voltage. In addition, the sum total of the layer thickness of the light emitting layer 3c is a layer thickness also including the said auxiliary layer, when the nonluminous auxiliary layer exists in the light emitting layer 3c.

  In the case of the light emitting layer 3c having a configuration in which a plurality of layers are laminated, the thickness of each light emitting layer is preferably adjusted to a range of 1 to 50 nm, and more preferably adjusted to a range of 1 to 20 nm. When the plurality of stacked light emitting layers correspond to the respective emission colors of blue, green, and red, there is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.

  The light emitting layer 3c configured as described above is formed by forming a light emitting material or a host compound, which will be described later, according to a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, and an ink jet method. Can be formed.

  In addition, the light emitting layer 3c may be configured by mixing a plurality of light emitting materials, and is configured by mixing a phosphorescent light emitting material and a fluorescent light emitting material (hereinafter also referred to as a fluorescent dopant or a fluorescent compound). May be.

  As a structure of the light emitting layer 3c, it is preferable to contain a host compound (hereinafter also referred to as a light emitting host or the like) and a light emitting material (hereinafter also referred to as a light emitting dopant compound or a dopant compound) to emit light.

<Host compound>
As the host compound contained in the light emitting layer 3c, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in the light emitting layer 3c.

  As a host compound, a well-known host compound may be used independently, or multiple types may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

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

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

  Although the specific example (H1-H79) of a host compound is shown below, the host compound which can be used by this invention is not limited to these. In the host compounds H68 to H79, x and y represent the ratio of the random copolymer. The ratio can be, for example, x: y = 1: 10.

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

<Light emitting material>
As a light-emitting material that can be used in the present invention, a phosphorescent compound (also referred to as a phosphorescent compound or a phosphorescent material) can be given.

  A phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. A preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.

  The 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 the solution can be measured using various solvents, but when using a phosphorescent compound in the present invention, the phosphorescence quantum yield is 0.01 or more in any solvent. Should be achieved.

  There are two methods for the light emission of the phosphorescent compound. One method is that recombination of carriers occurs on a host compound to which carriers are transported, and an excited state of the host compound is generated, and this energy is transferred to the phosphorescent compound, thereby transferring the energy from the phosphorescent compound. It is an energy transfer type that obtains luminescence. Another method is a carrier trap type in which a phosphorescent compound becomes a carrier trap, carrier recombination occurs on the phosphorescent compound, and light emission from the phosphorescent compound is obtained. In either case, the condition is that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

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

  In the present invention, at least one light emitting layer 3c may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light emitting layer 3c is the thickness direction of the light emitting layer 3c. It may be an aspect that changes.

  As content of a phosphorescence-emitting compound, Preferably it is the range of 0.1-30 volume% with respect to the total amount of the light emitting layer 3c.

<1> Compound Represented by General Formula (A) The light emitting layer 3c according to the present invention preferably contains a compound represented by the following general formula (A) as the phosphorescent compound.

  The phosphorescent compound represented by the following general formula (A) (also referred to as a phosphorescent metal complex) is preferably contained in the light emitting layer 3c of the organic EL element 100 as a light emitting dopant. However, it may be contained in the light emitting functional layer 3 other than the light emitting layer 3c.

In the general formula (A), P and Q each represent a carbon atom or a nitrogen atom. A ₁ represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with P—C. A ₂ represents an atomic group that forms an aromatic heterocycle with QN. P ₁ -L ₁ -P ₂ represents a bidentate ligand, and P ₁ and P ₂ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L ₁ represents an atomic group that forms a bidentate ligand together with P ₁ and P ₂ . j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. M ₁ represents a group 8-10 transition metal element in the periodic table.

  In general formula (A), P and Q each represent a carbon atom or a nitrogen atom.

In the general formula (A), examples of the aromatic hydrocarbon ring that A ₁ forms with P—C include, for example, a benzene ring, a biphenyl ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, Naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, Examples include a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring.

  These rings may further have a substituent. Examples of such a substituent include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group). Hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, vinyl group, allyl group, etc.), alkynyl group (For example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group , Anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group Pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group) Group, carbolinyl group, diazacarbazolyl group (in which one of carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), phthalazinyl group, etc.), heterocyclic group (for example, pyrrolidyl) Group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group ( For example, a cyclopentyloxy group, Chlorooxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), A cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), an arylthio group (eg, phenylthio group, naphthylthio group, etc.), an alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, Octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfo group) Nyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2- Pyridylaminosulfonyl group, etc.), acyl groups (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl) Group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octyl) Carbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group) 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propyl) Aminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl Bonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group) , Dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group) , Phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group) Group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), Amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, piperidinyl group (piperidinyl group) Group), 2,2,6,6-tetramethylpiperidinyl group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, Trifluoromethyl group, pentaf Oroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphate ester A group (for example, a dihexyl phosphoryl group), a phosphite group (for example, a diphenylphosphinyl group), a phosphono group, and the like.

The general formula (A), the aromatic heterocyclic ring A ₁ is formed together with P-C, for example, furan ring, thiophene ring, oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, Triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring And azacarbazole ring.

  Here, the azacarbazole ring refers to one in which one or more carbon atoms of the benzene ring constituting the carbazole ring are replaced with a nitrogen atom.

  These rings may further have the above-described substituent.

In the general formula (A), examples of the aromatic heterocycle formed by A ₂ together with QN include an oxazole ring, an oxadiazole ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, a thiadiazole ring, and a thiatriazole ring. , Isothiazole ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, triazole ring and the like.

  These rings may further have the above-described substituent.

In the general formula (A), P ₁ -L ₁ -P ₂ represents a bidentate ligand, and P ₁ and P ₂ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L ₁ represents an atomic group forming a bidentate ligand together with P ₁ and P ₂ .

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

  In the general formula (A), j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, j1 + j2 represents 2 or 3, and j2 is preferably 0.

In General Formula (A), as M ₁ , a transition metal element of Group 8 to Group 10 (also simply referred to as a transition metal) in the periodic table is used, and among these, iridium is preferable.

<2> Compound Represented by General Formula (B) The compound represented by General Formula (A) described above is more preferably a compound represented by General Formula (B) below.

In the general formula (B), Z represents a hydrocarbon ring group or a heterocyclic group. P and Q each represent a carbon atom or a nitrogen atom. A ₁ represents an atomic group that forms an aromatic hydrocarbon ring or an aromatic heterocyclic ring together with P—C. A ₃ represents -C (R ₀₁ ) = C (R ₀₂ )-, -N = C (R ₀₂ )-, -C (R ₀₁ ) = N- or -N = N-, and R ₀₁ and R ₀₂ Each represents a hydrogen atom or a substituent. P ₁ -L ₁ -P ₂ represents a bidentate ligand. P ₁ and P ₂ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L ₁ represents an atomic group that forms a bidentate ligand together with P ₁ and P ₂ . j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. M ₁ represents a group 8-10 transition metal element in the periodic table.

In the general formula (B), examples of the hydrocarbon ring group represented by Z include a non-aromatic hydrocarbon ring group and an aromatic hydrocarbon ring group, and examples of the non-aromatic hydrocarbon ring group include a cyclopropyl group. , Cyclopentyl group, cyclohexyl group and the like. These groups may be unsubstituted or may have the same substituents that the ring represented by A ₁ in the general formula (A) may have.

  Examples of the aromatic hydrocarbon ring group (also referred to as aromatic hydrocarbon group, aryl group, etc.) include, for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl. Group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like.

These groups may be unsubstituted or may have a substituent, and as such a substituent, the ring represented by A ₁ in the general formula (A) may have. The same thing as a substituent is mentioned.

  In the general formula (B), examples of the heterocyclic group represented by Z include a non-aromatic heterocyclic group and an aromatic heterocyclic group. Examples of the non-aromatic heterocyclic group include an epoxy ring and an aziridine group. Ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ε-caprolactone ring, ε- Caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thiomorpholine Ring, thiomorpholine-1,1-dioxide And groups derived from a ring, a pyranose ring, a diazabicyclo [2,2,2] -octane ring, and the like.

These groups may be unsubstituted or may have a substituent, and as such a substituent, the ring represented by A ₁ in the general formula (A) may have. The same thing as a substituent is mentioned.

  Examples of the aromatic heterocyclic group include pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl). Group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group , Benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl Group, pyridazinyl group, triazinyl group, key Zoriniru group, phthalazinyl group, and the like.

These groups may be unsubstituted or may have a substituent, and as such a substituent, the ring represented by A ₁ in the general formula (A) may have. The same thing as a substituent is mentioned.

  Preferably, the group represented by Z is an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

In the general formula (B), examples of the aromatic hydrocarbon ring that A ₁ forms with P—C include, for example, a benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, Naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, Examples include a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring.

These rings may further have a substituent, and examples of such a substituent are the same as the substituent that the ring represented by A ₁ in the general formula (A) may have. Things.

In the general formula (B), examples of the aromatic heterocycle formed by A ₁ together with P—C include a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a triazine. Ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring, Examples thereof include a carboline ring and an azacarbazole ring.

  Here, the azacarbazole ring refers to one in which one or more carbon atoms of the benzene ring constituting the carbazole ring are replaced with a nitrogen atom.

These rings may further have a substituent, and examples of such a substituent are the same as the substituent that the ring represented by A ₁ in the general formula (A) may have. Things.

In -C (R ₀₁ ) = C (R ₀₂ )-, -N = C (R ₀₂ )-, or -C (R ₀₁ ) = N- represented by A ₃ in the general formula (B), R ₀₁ And the substituent represented by R ₀₂ has the same meaning as the substituent which the ring represented by A ₁ in the general formula (A) may have.

In the general formula (B), examples of the bidentate ligand represented by P ₁ -L ₁ -P ₂ include phenylpyridine, phenylpyrazole, phenylimidazole, phenyltriazole, phenyltetrazole, pyrazabol, acetylacetone, and picoline. An acid etc. are mentioned.

  J1 represents an integer of 1 to 3, and j2 represents an integer of 0 to 2, j1 + j2 represents 2 or 3, and j2 is preferably 0.

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

<3> Compound Represented by General Formula (C) In the present invention, one preferred embodiment of the compound represented by the general formula (B) is a compound represented by the following general formula (C). It is done.

In the above general formula (C), R ₀₃ represents a substituent. R ₀₄ represents a hydrogen atom or a substituent, and a plurality of R ₀₄ may be bonded to each other to form a ring. n01 represents an integer of 1 to 4. R ₀₅ represents a hydrogen atom or a substituent, and a plurality of R ₀₅ may be bonded to each other to form a ring. n02 represents an integer of 1 to 2. R ₀₆ represents a hydrogen atom or a substituent, and may combine with each other to form a ring. n03 represents an integer of 1 to 4. Z ₁ represents an atomic group necessary for forming a 6-membered aromatic hydrocarbon ring or a 5-membered or 6-membered aromatic heterocycle together with C—C. Z ₂ represents an atomic group necessary for forming a hydrocarbon ring group or a heterocyclic group. P ₁ -L ₁ -P ₂ represents a bidentate ligand, and P ₁ and P ₂ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. L ₁ represents an atomic group forming a bidentate ligand together with P ₁ and P ₂ . j1 represents an integer of 1 to 3, j2 represents an integer of 0 to 2, and j1 + j2 is 2 or 3. M ₁ represents a group 8-10 transition metal element in the periodic table. R ₀₃ and R ₀₆ , R ₀₄ and R _06, and R ₀₅ and R ₀₆ may be bonded to each other to form a ring.

In the general formula (C), each of the substituents represented by R ₀₃ , R ₀₄ , R ₀₅ and R ₀₆ may be substituted by the ring represented by A ₁ in the general formula (A). Synonymous with group.

In the general formula (C), examples of the 6-membered aromatic hydrocarbon ring formed by Z ₁ together with C—C include a benzene ring.

These rings may further have a substituent, and such a substituent is the same as the substituent which the ring represented by A ₁ in the general formula (A) may have. Things.

In the general formula (C), examples of the 5-membered or 6-membered aromatic heterocycle formed by Z ₁ together with C—C include an oxazole ring, an oxadiazole ring, an oxatriazole ring, an isoxazole ring, a tetrazole ring, Examples include thiadiazole ring, thiatriazole ring, isothiazole ring, thiophene ring, furan ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, triazole ring and the like.

These rings may further have a substituent, and such a substituent is the same as the substituent which the ring represented by A ₁ in the general formula (A) may have. Things.

In the general formula (C), examples of the hydrocarbon ring group represented by Z ₂ include a non-aromatic hydrocarbon ring group and an aromatic hydrocarbon ring group, and examples of the non-aromatic hydrocarbon ring group include cyclopropyl. Group, cyclopentyl group, cyclohexyl group and the like. These groups may be unsubstituted or may have a substituent. Examples of such a substituent include a substituent that the ring represented by A ₁ in General Formula (A) may have. The same thing as a group is mentioned.

Examples of the aromatic hydrocarbon ring group (also referred to as aromatic hydrocarbon group, aryl group, etc.) include, for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl. Group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like. These groups may be unsubstituted or may have a substituent. Examples of such a substituent include a substituent that the ring represented by A ₁ in General Formula (A) may have. The same thing as a group is mentioned.

In the general formula (C), examples of the heterocyclic group represented by Z ₂ include a non-aromatic heterocyclic group and an aromatic heterocyclic group. Examples of the non-aromatic heterocyclic group include an epoxy ring, Aziridine ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ε-caprolactone ring, ε -Caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thio Morpholine ring, thiomorpholine-1,1-dioxy De ring, pyranose ring, a diazabicyclo [2,2,2] - and the groups derived from the octane ring. These groups may be unsubstituted or may have a substituent. Examples of such a substituent include a substituent that the ring represented by A ₁ in the general formula (A) may have. The same thing is mentioned.

  Examples of the aromatic heterocyclic group include pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl). Group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group , Benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (indicating that one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl Group, pyridazinyl group, triazinyl group, key Zoriniru group, phthalazinyl group, and the like.

It These rings may be unsubstituted, may have a substituent, and examples of the substituent which may have the rings represented by A ₁ in the general formula (A) substitution The same thing as a group is mentioned.

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

In formula _(C), bidentate ligand represented by P 1 _-L 1 -P _2, the In formula _(A), the bidentate represented by P 1 _-L 1 -P ₂ Synonymous with ligand.

In the formula (C), expressed group 8-10 transition metal elements in the periodic table is at _{M 1,} wherein in the general formula (A), group 8 in the periodic table represented by _{M 1} to 10 It is synonymous with the group transition metal element.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer 3 c of the organic EL element 100.

  The phosphorescent compound according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound). ), Rare earth complexes, and most preferred are iridium compounds.

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

  The phosphorescent compound (also referred to as a phosphorescent metal complex) is described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and the methods described in the references in these documents should be applied. Can be synthesized.

<Fluorescent material>
Fluorescent materials include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes Examples thereof include dyes, polythiophene dyes, and rare earth complex phosphors.

(Injection layer)
The injection layer (the hole injection layer 3a and the electron injection layer 3e) is a layer provided between the electrode and the light emitting layer 3c in order to lower the driving voltage and improve the light emission luminance. The details are described in Chapter 2 “Electrode Materials” (pages 123 to 166) of the second volume of “Forefront (November 30, 1998, issued by NTS Corporation)”. There is an electron injection layer 3e.

  The injection layer can be provided as necessary. The hole injection layer 3a may be present between the anode and the light emitting layer 3c or the hole transport layer 3b, and the electron injection layer 3e may be present between the cathode and the light emitting layer 3c or the electron transport layer 3d. .

  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. As a specific example, a phthalocyanine layer represented by copper phthalocyanine And 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, specifically, metals represented by strontium, aluminum, and the like. Examples thereof include 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. In the present invention, the electron injection layer 3e is preferably a very thin film, and although depending on the material, the layer thickness is preferably in the range of 1 nm to 10 μm.

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

  The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

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

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (abbreviation: TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1 -Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-di-p -Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, '-Di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) c Audriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N- Examples include diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4′-N, N-diphenylaminostilbenzene, N-phenylcarbazole, and the like, and further, in US Pat. No. 5,061,569. Those having two condensed aromatic rings described in the molecule, for example, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviation: NP) ), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenyl] in which three triphenylamine units described in JP-A-4-308688 are linked in a starburst type. Amino] triphenylamine (abbreviation: 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, these materials are preferably used from the viewpoint of obtaining a light-emitting element with higher efficiency.

  For the hole transport layer 3b, the hole transport material may be a known material such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, an LB method (Langmuir Brodget, Langmuir Brodgett method), or the like. The thin film can be formed by the method. Although there is no restriction | limiting in particular about the layer thickness of the positive hole transport layer 3b, Usually, 5 nm-about 5 micrometers, Preferably it is 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.

  Moreover, p property can also be made high by doping the material of the positive hole transport layer 3b with an impurity. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

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

(Electron transport layer)
The electron transport layer 3d is made of a material having a function of transporting electrons. In a broad sense, the electron transport layer 3e and a hole blocking layer (not shown) are also included in the electron transport layer 3d. The electron transport layer 3d can be provided as a single layer structure or a multilayer structure of a plurality of layers.

  In the electron transport layer 3d having a single layer structure and the electron transport layer 3d having a multilayer structure, an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer 3c is an electron injected from the cathode. As long as it has a function of transmitting the light 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 (abbreviation: Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8- Quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (abbreviation: Znq), etc., and the central metal of these metal complexes A metal complex in which In, Mg, Cu, Ca, Sn, Ga, or Pb is replaced can also be used as the material of the electron transport layer 3d.

  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 exemplified also as a material of the light emitting layer 3c can be used as a material of the electron transport layer 3d, and similarly to the hole injection layer 3a and the hole transport layer 3b, n-type -Si, n An inorganic semiconductor such as type-SiC can also be used as the material of the electron transport layer 3d.

  The electron transport layer 3d can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the layer thickness of 3 d of electron carrying layers, Usually, 5 nm-about 5 micrometers, Preferably it exists in the range of 5-200 nm. The electron transport layer 3d may have a single layer structure composed 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, by increasing the n property of the electron transport layer 3d, an organic EL element with lower power consumption can be obtained.

  Further, as the material (electron transporting compound) of the electron transport layer 3d, the same material as that of the intermediate layer 1a described above may be used. The same applies to the electron transport layer 3d that also serves as the electron injection layer 3e, and the same material as that of the intermediate layer 1a described above may be used.

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

  The hole blocking layer has the function of the electron transport layer 3d in a broad sense. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of the electron carrying layer 3d mentioned later can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer 3c.

  On the other hand, the electron blocking layer has the function of the hole transport layer 3b in a broad sense. The electron blocking layer is made of a material that has the ability to transport holes and has a very small ability to transport electrons. By blocking holes while transporting holes, the probability of recombination of electrons and holes is improved. Can be made. Moreover, the structure of the positive hole transport layer 3b mentioned later can be used as an electron blocking layer as needed. The layer thickness of the hole blocking layer applied to the present invention is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.

[Auxiliary electrode]
The auxiliary electrode 15 is an electrode provided for the purpose of reducing the resistance of the transparent electrode 1, and is provided in contact with the conductive layer 1 b of the transparent electrode 1. The material forming the auxiliary electrode 15 is preferably a metal having low resistance such as gold, platinum, silver, copper, or aluminum. Since many of these metals have low light transmissivity, they are formed at positions as shown in FIG. 2A within a range not affected by extraction of the emitted light h from the light extraction surface 13a. Examples of the method for forming the auxiliary electrode 15 include a vapor deposition method, a sputtering method, a printing method, an ink jet method, and an aerosol jet method. The line width of the auxiliary electrode 15 is preferably 50 μm or less from the viewpoint of the aperture ratio of the light extraction region, and the thickness of the auxiliary electrode 15 is preferably 1 μm or more from the viewpoint of conductivity.

(Encapsulant)
The sealing material 17 covers the organic EL element 100 and may be a plate-shaped (film-shaped) sealing member that is fixed to the transparent substrate 13 by the adhesive 19. It may be a sealing film. Such a sealing material 17 is provided so as to cover at least the light emitting functional layer 3 in a state where the terminal portions of the transparent electrode 1 and the counter electrode 5a in the organic EL element 100 are exposed. Moreover, an electrode may be provided on the sealing material 17 so that the transparent electrode 1 of the organic EL element 100 and the terminal portions of the counter electrode 5a are electrically connected to this electrode.

  Specific examples of the plate-like (film-like) sealing material 17 include a glass substrate, a polymer substrate, a metal substrate, and the like. These substrate materials may be used in the form of a thin film. Examples of the glass substrate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal substrate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

  Among these, from the viewpoint that the organic EL element can be thinned, a thin film-like polymer substrate or metal substrate can be preferably used as the sealing material.

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

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

  An adhesive 19 for fixing the plate-shaped sealing material 17 to the transparent substrate 13 side seals the organic EL element 100 sandwiched between the sealing material 17 and the transparent substrate 13. It is used as a sealing agent. 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.

  Moreover, as such an adhesive agent 19, the heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

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

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

  In addition, when a gap is formed between the plate-shaped sealing material 17, the transparent substrate 13, and the adhesive 19, in this gap, in the gas phase and the liquid phase, an inert gas such as nitrogen or argon or a fluorine is used. It is preferable to inject an inert liquid such as activated hydrocarbon or silicon oil. A vacuum can also be used. Moreover, a hygroscopic compound can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate, and the like), and anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.

  On the other hand, when a sealing film is used as the sealing material 17, the light emitting functional layer 3 in the organic EL element 100 is completely covered and the terminal portions of the transparent electrode 1 and the counter electrode 5a in the organic EL element 100 are exposed. A sealing film is provided on the transparent substrate 13.

  Such a sealing film is configured using an inorganic material or an organic material. In particular, it is made of a material having a function of suppressing intrusion of a substance that causes deterioration of the light emitting functional layer 3 in the organic EL element 100 such as moisture and oxygen. 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 forming these films is not particularly limited. For example, vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

[Protective film, protective plate]
Although not shown in the drawings illustrated above, a protective film or a protective plate may be provided between the transparent substrate 13 and the organic EL element 100 and the sealing material 17. This protective film or protective plate is for mechanically protecting the organic EL element 100, and in particular when the sealing material 17 is a sealing film, sufficient mechanical protection is provided for the organic EL element 100. Therefore, it is preferable to provide such a protective film or protective plate.

  As the above 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. Among these, it is particularly preferable to use a polymer film because it is light and thin.

[Method for producing organic EL element]
The method for producing a transparent electrode of the present invention is a method for producing a transparent electrode having a conductive layer containing silver as a main component, and reacts with a silver compound and silver derived from the conductive layer to form the silver compound. It has the process of forming the layer containing at least any one among the compounds to perform, and the process of forming the said electroconductive layer, It is characterized by the above-mentioned.
Here, as an example, a method of manufacturing the organic EL element 100 shown in FIG.

  First, the intermediate layer 1a containing a silver compound is formed on the transparent substrate 13 by appropriately selecting a method such as a vapor deposition method so as to have a layer thickness of 1 μm or less, preferably 10 to 100 nm. Next, a method such as a vapor deposition method is appropriately selected so that the conductive layer 1b composed of silver or an alloy containing silver as a main component has a layer thickness of 12 nm or less, preferably 5 to 8 nm. A transparent electrode 1 formed on the intermediate layer 1a and serving as an anode is produced.

Next, the hole injection layer 3a, the hole transport layer 3b, the light emitting layer 3c, the electron transport layer 3d, and the electron injection layer 3e are formed in this order on the transparent electrode 1 to form the light emitting function layer 3. 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 can be easily obtained and pinholes are difficult to generate. The method or spin coating method is particularly preferred. Further, a different film forming method 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 the boat heating temperature is in the range of 50 to 450 ° C., and the degree of vacuum is 1 × 10 ⁻⁶ to 1 Each condition is appropriately selected within a range of × 10 ⁻² Pa, a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −50 to 300 ° C., and a layer thickness of 0.1 to 5 μm. It is desirable.

  After the light emitting functional layer 3 is formed as described above, the counter electrode 5a serving as a cathode is formed thereon by appropriately selecting a film forming method such as a vapor deposition method or a sputtering method. 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 light emitting functional layer 3 to the periphery of the transparent substrate 13 while maintaining the insulating state with respect to the transparent electrode 1 by the light emitting functional layer 3. Thereby, the organic EL element 100 is obtained. Thereafter, a sealing material 17 that covers at least the light emitting functional layer 3 is provided in a state in which the terminal portions of the transparent electrode 1 and the counter electrode 5a in the organic EL element 100 are exposed.

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

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

(Method of forming the intermediate layer in the process of forming the conductive layer)
Moreover, as a manufacturing method of the organic EL element 100 shown to Fig.2 (a), the intermediate layer containing the compound represented by the said General formula (1) contains the compound represented by the said General formula (2). A method of forming the conductive layer in the process of forming the conductive layer on the base layer can be employed.

  First, an underlayer containing the compound represented by the general formula (2) is formed on the transparent substrate 13. Next, a conductive layer 1b composed of silver or an alloy containing silver as a main component is formed on the underlayer by a method such as vapor deposition.

  In the process of forming the conductive layer, silver deposited in the conductive layer reacts with the compound represented by the general formula (2) of the base layer and diffuses at the interface or from the interface to react inside the base layer. Thus, the silver compound represented by the general formula (1) is produced, and the intermediate layer 1a containing the silver compound is formed. At this time, a portion where the silver compound is not generated may remain in a portion far from the interface with the conductive layer of the base layer, and the portion not including the silver compound serves as the base layer as the transparent electrode 1 and the transparent substrate 13. Exists between. In FIG. 2A, the base layer is omitted.

  The formation of the intermediate layer in the process of forming the conductive layer can be confirmed by analyzing using XPS (X-ray electron spectroscopy) (ESCALab 200R manufactured by Vacuum Generators) and detecting the shifted Ag peak.

A transparent substrate provided with an underlayer containing a compound represented by the general formula (2) is fixed to a sample stage and brought into a high vacuum state, and then irradiated with X-rays to give a peak of R ₁ -Y binding energy. Observe. Next, after the transparent electrode having the conductive layer 1b formed on the underlayer is similarly fixed to the sample stage and brought into a high vacuum state, the X-ray is irradiated to bond the energy of R ₁ -Y and Ag—Y. Observe the peak. In the transparent electrode, a new peak is observed at a position 1 to several eV lower than the binding energy peak of the underlayer.

  If a binding energy peak lower than the binding energy peak of the underlayer is observed in XPS of the transparent electrode, the conductive layer is formed on the underlayer containing the compound represented by the following general formula (2). In the process of forming, it can be confirmed that the intermediate layer containing the compound represented by the general formula (1) is formed.

  In addition, since the measurement by XPS analyzes the intermediate layer from the interface with the conductive layer to a depth of several nm, the general formula (1) is limited to the interface where the conductive layer and the intermediate layer are bonded. It is estimated that the abundance ratio of the compound represented by) is higher than the ratio determined from the peak intensity.

[Effect of the organic EL element shown in the first example (FIG. 2A)]
The organic EL element 100 having the configuration shown in FIG. 2A described above uses the transparent electrode 1 of the present invention having both conductivity and light transmission as an anode, and a light emitting functional layer 3 and a cathode are formed on the upper part. The counter electrode 5a is provided. For this reason, the extraction efficiency of the emitted light h from the transparent electrode 1 side is improved while applying a sufficient voltage between the transparent electrode 1 and the counter electrode 5a to realize high luminance light emission in the organic EL element 100. Thus, it is possible to increase the luminance. Further, in order to obtain a desired luminance, it is possible to improve the light emission lifetime by reducing the drive voltage.

<< 4. Second Example of Organic EL Device >>
[Configuration of organic EL element]
FIG. 3 is a cross-sectional configuration diagram illustrating a second example of the organic EL element using the transparent electrode described above as an example of the electronic device of the present invention. The difference between the organic EL element 200 of the second example shown in FIG. 3 and the organic EL element 100 of the first example shown in FIG. 2A is that the transparent electrode 1 is used as a cathode. Hereinafter, a detailed description of the same components as in the first example will be omitted, and a characteristic configuration of the organic EL element 200 in the second example will be described below.

  The organic EL element 200 shown in FIG. 3 is provided on the transparent substrate 13, and the transparent electrode 1 of the present invention described above is used as the transparent electrode 1 on the transparent substrate 13 as in the first example. Yes. For this reason, the organic EL element 200 is configured to extract the emitted light h from at least the transparent substrate 13 side. However, the transparent electrode 1 is used as a cathode (cathode), and the counter electrode 5b is used as an anode (anode).

  The layer structure of the organic EL element 200 configured as described above is not limited to the example described below, and may be a general layer structure as in the first example.

  As an example of the layer structure shown in the second example, an electron injection layer 3e / electron transport layer 3d / light emitting layer 3c / hole transport layer 3b / hole injection layer 3a are formed on the transparent electrode 1 functioning as a cathode. The light emitting functional layer 3 laminated in order is illustrated. However, among these, it is an essential condition to have at least the light emitting layer 3c made of an organic material.

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

  In the layer configuration as described above, the auxiliary electrode 15 may be provided in contact with the conductive layer 1b of the transparent electrode 1 for the purpose of reducing the resistance of the transparent electrode 1. Similar to the example.

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

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

  In addition, when this organic EL element 200 is comprised so that emitted light h can be taken out also from the counter electrode 5b side, as a material which comprises the counter electrode 5b, favorable light transmittance is mentioned among the electrically conductive materials mentioned above. A suitable conductive material is selected and used.

  The organic EL element 200 having the above configuration is sealed with the sealing material 17 in the same manner as in the first example for the purpose of preventing deterioration of the light emitting functional layer 3.

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

[Method for producing organic EL element]
In the manufacture of the organic EL element 200 shown in FIG. 3, the transparent electrode 1 has << 3. It can be formed by the same method as in the first example of the organic EL element.

  The intermediate layer containing the compound represented by the general formula (1) is formed in the process of forming the conductive layer on the base layer containing the compound represented by the general formula (2). be able to. In the organic EL device manufactured by this manufacturing method, the base layer remaining without being converted into the intermediate layer is omitted in FIG.

[Effect of organic EL element shown in second example]
The organic EL element 200 shown in FIG. 3 described above uses the transparent electrode 1 of the present invention having both conductivity and light transmission as a cathode, and a light emitting functional layer 3 and a counter electrode 5b serving as an anode are formed thereon. This is a configuration provided. For this reason, as in the first example, a sufficient voltage is applied between the transparent electrode 1 and the counter electrode 5b to realize high-luminance light emission in the organic EL element 200, and light emitted from the transparent electrode 1 side. It is possible to increase the luminance by improving the extraction efficiency of h. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance.

<< 5. Third Example of Organic EL Device >>
[Configuration of organic EL element]
FIG. 4 is a cross-sectional configuration diagram showing a third example of the organic EL element using the transparent electrode described above as an example of the electronic device of the present invention. The organic EL element 300 of the third example shown in FIG. 4 is different from the organic EL element 100 of the first example described with reference to FIG. 2A in that a counter electrode 5c is provided on the substrate 131 side, and an upper portion thereof is provided. The light emitting functional layer 3 and the transparent electrode 1 are laminated in this order. Hereinafter, the detailed description of the same components as those in the first example will be omitted, and the characteristic configuration of the organic EL element 300 in the third example will be described.

  The organic EL element 300 shown in FIG. 4 is provided on a substrate 131, and the counter electrode 5c serving as an anode, the light emitting functional layer 3, and the transparent electrode 1 serving as a cathode are laminated in this order from the substrate 131 side. . Among these, as the transparent electrode 1, the transparent electrode 1 of the present invention described above is used. For this reason, the organic EL element 300 is configured to extract the emitted light h from at least the transparent electrode 1 side opposite to the substrate 131.

  The layer structure of the organic EL element 300 configured as described above is not limited to the example described below, and may be a general layer structure as in the first example. As an example in the case of the third example, as shown in FIG. 4, a hole injection layer 3a / hole transport layer 3b / light emitting layer 3c / electron transport layer 3d are formed on the counter electrode 5c functioning as an anode. The structure laminated | stacked in order is illustrated. However, it is essential to have at least the light emitting layer 3c configured using an organic material. The electron transport layer 3d also serves as the electron injection layer 3e, and is provided as an electron transport layer 3d having electron injection properties.

  In particular, a characteristic configuration of the organic EL element 300 shown as the third example is that an electron transporting layer 3d having an electron injecting property is provided as the intermediate layer 1a in the transparent electrode 1. That is, in the third example, the transparent electrode 1 used as a cathode is composed of an intermediate layer 1a also serving as an electron transport layer 3d having electron injection properties, and a conductive layer 1b provided on the intermediate layer 1a. It is.

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

  In addition to these layers, the light emitting functional layer 3 can employ various functional layers as necessary, as described in the first example, but the intermediate layer 1a of the transparent electrode 1 can be used. The electron injection layer and the hole blocking layer are not provided between the electron transport layer 3d serving also as the conductive layer 1b and the conductive layer 1b of the transparent electrode 1. In the configuration as described above, only the portion where the light emitting functional layer 3 is sandwiched between the transparent electrode 1 and the counter electrode 5c becomes the light emitting region in the organic EL element 300, as in the first example.

  In the layer structure as described above, the auxiliary electrode 15 may be provided in contact with the conductive layer 1b of the transparent electrode 1 for the purpose of reducing the resistance of the transparent electrode 1. The same as in the example.

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

  In addition, when the organic EL element 300 shown in FIG. 4 is configured so that the emitted light h can be extracted also from the counter electrode 5c side, the material constituting the counter electrode 5c may be light among the conductive materials described above. A conductive material having good permeability is selected and used. In this case, the substrate 131 is the same as the transparent substrate 13 described in the first example. In such a configuration, the surface facing the outside of the substrate 131 is the light extraction surface 131a.

[Method for producing organic EL element]
In the manufacture of the organic EL element 300 shown in FIG. 4, the conductive layer 1b of the transparent electrode 1 is formed by << 3. It can be formed by the same method as in the first example of the organic EL element.

  In the third example of the organic EL element, the electron transport layer 3d contains a silver compound and functions also as the intermediate layer 1a in the transparent electrode 1.

  The intermediate layer containing the compound represented by the general formula (1) is formed in the process of forming the conductive layer on the base layer containing the compound represented by the general formula (2). In this case, the electron transport layer 3d becomes a base layer containing the compound of the general formula (2).

  The intermediate layer formed as described above contains the compound represented by the general formula (1), and may or may not serve as the electron transport layer 3d. The intermediate layer in the case where the intermediate layer does not serve as the electron transport layer 3d is omitted in FIG.

[Effect of organic EL element shown in third example]
In the organic EL element 300 shown in the third example described above, the electron transporting layer 3d having the electron injecting property constituting the uppermost part of the light emitting functional layer 3 is used as the intermediate layer 1a, and the conductive layer 1b is provided thereon. The transparent electrode 1 comprising the intermediate layer 1a and the upper conductive layer 1b is provided as a cathode. Therefore, similarly to the first example and the second example, a sufficient voltage is applied between the transparent electrode 1 and the counter electrode 5c to realize high-luminance light emission in the organic EL element 300, while the transparent electrode 1 side. It is possible to increase the luminance by improving the extraction efficiency of the emitted light h from the light source. Further, it is possible to improve the light emission life by reducing the drive voltage for obtaining a predetermined luminance. Further, when the counter electrode 5c is made of a light-transmissive electrode material, the emitted light h can be extracted from the counter electrode 5c.

  In the third example described above, the intermediate layer 1a of the transparent electrode 1 has been described as also serving as the electron transport layer 3d having electron injection properties. However, in the present invention, the configuration is limited to these examples. Instead, the intermediate layer 1a may also serve as the electron transport layer 3d that does not have electron injection properties, or the intermediate layer 1a may serve as the electron injection layer instead of the electron transport layer. May be. In addition, the intermediate layer 1a may be formed as an extremely thin film that does not affect the light emitting function of the organic EL element. In this case, the intermediate layer 1a has electron transport properties and electron injection properties. Not.

  Further, when the intermediate layer 1a of the transparent electrode 1 is formed as an extremely thin film that does not affect the light emitting function of the organic EL element, the counter electrode on the substrate 131 side is used as a cathode, and the light emitting functional layer 3 The transparent electrode 1 may be an anode. In this case, the light emitting functional layer 3 is formed in order from the counter electrode 5c (cathode) side on the substrate 131, for example, electron injection layer 3e / electron transport layer 3d / light emitting layer 3c / hole transport layer 3b / hole injection layer 3a. Are stacked. A transparent electrode 1 having a laminated structure of an extremely thin intermediate layer 1a and a conductive layer 1b is provided as an anode on the top.

<< 6. Applications of organic EL devices >>
Since the organic EL element which consists of each structure demonstrated with the said each figure is a surface light-emitting body as mentioned above, it can be applied as various light emission light sources. For example, lighting devices such as home lighting and interior lighting, backlights for watches and liquid crystal display devices, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, optical communication processors Examples include, but are not limited to, a light source and a light source of an optical sensor. In particular, the light source can be effectively used as a backlight of a liquid crystal display device combined with a color filter and an illumination light source.

  Further, the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a type for directly viewing a still image or a moving image. It may be used as a display device (display). In this case, with the recent increase in the size of lighting devices and displays, the light emitting surface may be enlarged by so-called tiling, in which light emitting panels provided with organic EL elements are joined together in a plane.

  The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. A color or full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.

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

<< 7. Illumination device-1 >>
The lighting device according to the present invention can include the organic EL element of the present invention.

  The organic EL element used in the lighting device according to the present invention may be designed such that each organic EL element having the above-described configuration has a resonator structure. The purpose of use of the organic EL element configured to have a resonator structure includes a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processor, a light source of an optical sensor, etc. It is not limited to. Moreover, you may use for the said use by making a laser oscillation.

  In addition, the material used for the organic EL element of this invention is applicable to the organic EL element (it is also called white organic EL element) which produces substantially white light emission. For example, a plurality of light emitting materials can simultaneously emit a plurality of light emission colors to obtain white light emission by color mixing. The combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of red, green and blue, or two using the complementary colors such as blue and yellow, blue green and orange. The thing containing the light emission maximum wavelength may be used.

  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 for example, an electrode film can be formed on one side by vapor deposition, casting, spin coating, ink jet, printing, etc., and productivity is improved. To do.

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

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

<< 8. Illumination device-2 >>
FIG. 5 shows a cross-sectional configuration diagram of a lighting device in which a plurality of organic EL elements having the above-described configurations are used to increase the light emitting surface area. The illuminating device 21 shown in FIG. 5 has a large light emitting surface by, for example, arranging a plurality of light emitting panels 22 provided with the organic EL elements 100 on the transparent substrate 13 on the support substrate 23 (that is, tiling). It is the structure which made the area. The support substrate 23 may also serve as a sealing material, and each light-emitting panel 22 is tied with the organic EL element 100 sandwiched between the support substrate 23 and the transparent substrate 13 of the light-emitting panel 22. Ring. An adhesive 19 may be filled between the support substrate 23 and the transparent substrate 13, thereby sealing the organic EL element 100. In addition, the edge part of the transparent electrode 1 which is an anode, and the counter electrode 5a which is a cathode are exposed around the light emission panel 21. FIG. However, only the exposed portion of the counter electrode 5a is shown in the drawing. Moreover, in FIG. 5, as the light emission functional layer 3 which comprises the organic EL element 100, on the transparent electrode 1, hole injection layer 3a / hole transport layer 3b / light emission layer 3c / electron transport layer 3d / electron injection layer A configuration in which 3e is sequentially laminated is shown as an example.

In the illuminating device 21 having the configuration shown in FIG. 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.
The organic EL element shown in FIGS. 3 and 4, the illumination device shown in FIG. 5, and the light-emitting panel shown in FIG. 6 are the same even if the intermediate base layer 1e used in FIG. Can be produced.

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

Example 1
<< Preparation of transparent electrode substrate >>
According to the method shown below, the transparent electrode substrates 1 to 73 were prepared so that the area of the conductive region was 5 cm × 5 cm. The transparent electrode substrates 1 to 4 are produced by laminating a transparent electrode having a single layer structure on a base material, and the transparent electrode substrates 5 to 73 are transparent electrodes having a laminated structure of an intermediate layer and a conductive layer on the base material. Was prepared.

[Preparation of transparent electrode substrate 1]
In accordance with the method shown below, a transparent electrode substrate 1 of a comparative example having a single layer structure was produced.

A transparent non-alkali glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, and this was attached to a vacuum tank of the vacuum deposition apparatus. On the other hand, a resistance heating boat made of tungsten was filled with silver (Ag) and mounted in the vacuum chamber. Next, after depressurizing the inside of the vacuum chamber to 4 × 10 ⁻⁴ Pa, the resistance heating boat is energized and heated, and is made of silver on the base material within a deposition rate range of 0.1 to 0.2 nm / second. A single layer of a conductive layer having an average layer thickness of 5 nm was deposited to produce a transparent electrode substrate 1.

[Production of transparent electrode substrates 2 to 4]
In the production of the transparent electrode substrate 1, transparent electrode substrates 2 to 4 were produced in the same manner except that the average layer thickness of the conductive layer was changed to 8 nm, 10 nm, and 15 nm, respectively.

[Preparation of transparent electrode substrate 5]
On the transparent base material made of alkali-free glass, Alq ₃ having the following structure is formed as an intermediate layer having a layer thickness of 25 nm by sputtering, and on top of this, in the production of the transparent electrode substrate 1, the conductive layer A transparent electrode substrate 5 was produced by vapor deposition of a conductive layer made of silver (Ag) having an average layer thickness of 8 nm by the same method (vacuum vapor deposition method) used for the formation.

[Preparation of transparent electrode substrate 6]
A transparent non-alkali glass base material is fixed to a base material holder of a commercially available vacuum deposition apparatus, and ET-1 having a structure shown below is filled in a resistance heating boat made of tantalum. It attached to the 1st vacuum chamber of a vacuum evaporation system. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.

Next, after reducing the pressure in the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing ET-1 was energized and heated, and the substrate was within a deposition rate range of 0.1 to 0.2 nm / second. It vapor-deposited on top and the intermediate | middle layer which consists of ET-1 whose layer thickness is 25 nm was formed.

Next, the base material on which the intermediate layer is formed is transferred to the second vacuum tank while being in a vacuum state, and after the second vacuum tank is depressurized to 4 × 10 ⁻⁴ Pa, the heating boat containing silver is energized and heated, A transparent electrode substrate 6 in which a conductive layer made of silver having an average layer thickness of 8 nm is vapor-deposited at a deposition rate of 0.1 to 0.2 nm / second, and an intermediate layer and a conductive layer made of silver are laminated on the intermediate layer is formed. Obtained.

[Production of transparent electrode substrates 7 and 8]
In the production of the transparent electrode substrate 6, transparent electrode substrates 7 and 8 were produced in the same manner except that ET-1 used for forming the intermediate layer was changed to ET-2 and ET-3, respectively.

[Preparation of transparent electrode substrate 9]
A transparent non-alkali glass base material is fixed to a base material holder of a commercially available vacuum deposition apparatus, the exemplary compound S-1 of the present invention is filled in a resistance heating boat made of tantalum, and these substrate holder and heating boat are combined. It attached to the 1st vacuum chamber of a vacuum evaporation system. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.

Next, after reducing the pressure in the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing the exemplary compound S-1 was heated by energization, and the deposition rate was within the range of 0.1 to 0.2 nm / second. It vapor-deposited on the base material and the intermediate | middle layer 1a which consists of exemplary compound S-1 whose layer thickness is 25 nm was formed.

Next, the base material on which the intermediate layer 1a is formed is transferred to the second vacuum chamber while being in a vacuum state, and after the pressure of the second vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing silver is energized and heated. A transparent conductive layer 1b made of silver having an average layer thickness of 5 nm is deposited at a deposition rate of 0.1 to 0.2 nm / second, and a conductive layer 1b made of silver is laminated on the intermediate layer 1a. An electrode substrate 9 was obtained.

[Production of transparent electrode substrates 10 to 12]
In the production of the transparent electrode substrate 9, transparent electrode substrates 10 to 12 were produced in the same manner except that the average layer thickness of the conductive layer 1b was changed to 8 nm, 10 nm, and 20 nm, respectively.

[Production of transparent electrode substrates 13 and 14]
In the production of the transparent electrode substrate 10, the transparent electrode substrates 13 and 14 were similarly prepared except that each of the exemplary compounds shown in Table 1 was used instead of the exemplary compound S-1 used for forming the intermediate layer 1a. Was made.

[Preparation of transparent electrode substrate 15]
A transparent non-alkali glass base material is fixed to a base material holder of a commercially available vacuum deposition apparatus, and the exemplary compound P-1 of the present invention is filled in a resistance heating boat made of tantalum. It attached to the 1st vacuum chamber of a vacuum evaporation system. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.

Next, after reducing the pressure of the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing the exemplary compound P-1 was heated by energization, and the deposition rate was within the range of 0.1 to 0.2 nm / second. It vapor-deposited on the base material and formed the base layer which consists of exemplary compound P-1 whose layer thickness is 25 nm.

Next, the base material on which the base layer is formed is transferred to the second vacuum chamber while being in a vacuum state, and after the second vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, the heating boat containing silver is energized and heated, The conductive layer 1b made of silver having an average layer thickness of 8 nm was deposited at a deposition rate of 0.1 to 0.2 nm / second.

  By the above operation, the intermediate layer 1a made of the compound S-27 which is a silver compound is formed on the surface layer portion of the base layer made of the compound P-1, and the conductive layer 1b made of silver is laminated on the transparent layer 1a. A substrate 15 was obtained. In addition, it was confirmed by the XPS peak shift that the intermediate layer 1a made of the compound S-27 was formed in the process of forming the conductive layer.

  That is, the C-Br binding energy in Compound P-1 was observed at 70 to 72 eV, while a new peak was observed at 67 to 69 eV. Since this new peak coincides with the binding energy of AgBr, it was confirmed that the transparent electrode substrate 15 contained AgBr and that AgBr was generated during the formation process. In addition, the intensity | strength of the new peak was about 1/6 times the peak of C-Br in the compound P-1.

[Preparation of transparent electrode substrates 16 to 64]
In the production of the transparent electrode substrate 15, the transparent electrode substrates 16 to 64 were produced in the same manner except that the underlayer was formed using the material of the underlayer described in Tables 1 and 2 instead of the compound P-1. did. It was confirmed by XPS peak shift that the intermediate layer 1a made of the intermediate layer material (silver compound) shown in Tables 1 and 2 was formed in the process of forming the conductive layer.

[Production of transparent electrode substrates 65 and 66]
In the production of the transparent electrode substrates 42 and 43, transparent electrode substrates 65 and 66 were produced in the same manner except that the base material was changed from a non-alkali glass to a PET (polyethylene terephthalate) film. It was confirmed by XPS peak shift that the intermediate layer 1a made of the intermediate layer material (silver compound) shown in Table 2 was formed in the process of forming the conductive layer.

[Production of transparent electrode substrates 67 to 71]
In the production of the transparent electrode substrate 15, the base layer was transparent in the same manner except that the base layer was formed using the base layer material and the intermediate layer material shown in Table 2 instead of the compound P-1. Electrode substrates 67 to 71 were produced. It was confirmed by the XPS peak shift that the intermediate base layer 1e containing the base layer material and the intermediate layer material (silver compound) shown in Table 2 was formed in the process of forming the conductive layer. It was.

[Production of transparent electrode substrates 72 and 73]
In the production of the transparent electrode substrates 70 and 71, transparent electrode substrates 72 and 73 were produced in the same manner except that the base material was changed from non-alkali glass to a PET (polyethylene terephthalate) film. It was confirmed by the XPS peak shift that the intermediate base layer 1e containing the base layer material and the intermediate layer material (silver compound) shown in Table 2 was formed in the process of forming the conductive layer. It was.

<< Evaluation of transparent electrode >>
About the produced said transparent electrodes 1-73, according to the following method, the light transmittance, the sheet resistance value, and durability were measured.

[Measurement of average thickness of conductive layer]
The mass per unit area of the transparent base material of about 100 cm ² and the prepared transparent electrode substrate was measured. The difference between the mass per unit area (g / cm ² ) was divided by the silver density of 10.5 to obtain the average layer thickness (unit: cm), and the unit was converted to nm.

(Measurement of light transmittance)
About each produced said transparent electrode substrate, the light transmittance (%) in wavelength 550nm was measured using the base material used for preparation of each transparent electrode substrate using the spectrophotometer (Hitachi Ltd. U-3300). .

[Measurement of sheet resistance]
About each produced said transparent electrode board | substrate, the sheet resistance value (ohm / square) was measured by the 4 terminal 4 probe method constant current application system using the resistivity meter (MCP-T610 by Mitsubishi Chemical Analytech Co., Ltd.).

[Measurement of the area ratio of defects under high temperature and high humidity storage]
The prepared transparent electrode substrate was stored for 100 hours in an environment of 60 ° C. and 90% RH to prepare a sample for observation. Using a microscope, defects generated by peeling of the conductive layer were observed, and the ratio of the defect area to the total area of the conductive layer of the transparent electrode was calculated. Tables 1 and 2 show relative values when the ratio of the defect area of the transparent electrode substrate 8 is 100.

  Note that the size of the defect is approximately 0.2 mm or more in diameter.

  As is clear from the results shown in Tables 1 and 2, the transparent electrode substrates 9 to 73 of the present invention in which a conductive layer mainly composed of silver (Ag) is provided on an intermediate layer formed using a silver compound. Each has a light transmittance of 51% or more and a sheet resistance value of 20Ω / □ or less. Moreover, the ratio (relative value) of the defect area under storage at high temperature and high humidity is as low as 52 or less. This is because by forming the intermediate layer using a silver compound, it is possible to suppress the aggregation of the silver layer formed thereon and the generation of mottle. It is thought that both high light transmittance and low sheet resistance value could be achieved.

On the other hand, in the transparent electrode substrates 1 to 4 of the comparative example having no intermediate layer, although the sheet resistance value decreases as the layer thickness of the conductive layer that is a silver layer is increased, the conductive layer The light transmittance due to silver aggregation (motor) at the time of formation becomes remarkably low, and a sufficiently low resistance value cannot be obtained, so that both the light transmittance and the sheet resistance value cannot be achieved. Further, even in the transparent electrode substrates 5 to 8 using Alq ₃ or ET-1 to ET- ₃ as the intermediate layer, the light transmittance was low and the sheet resistance value could not be reduced to a desired condition.

Example 2
<Production of light emitting panel>
[Preparation of light-emitting panel 1]
Using the transparent electrode of the transparent electrode substrate 1 produced in Example 1 as an anode, the double-sided light-emitting panel 1 having the configuration shown in FIG. 6 (however, the intermediate layer 1a is not provided) is prepared according to the following procedure. Produced.

  First, the transparent electrode 1 having only the conductive layer 1b formed in Example 1 and the transparent electrode substrate 1 having the transparent substrate 13 are fixed to a substrate holder of a commercially available vacuum deposition apparatus, and the transparent electrode 1 (conductive layer 1) A vapor deposition mask was arranged opposite to the formation surface side of 1b only). Moreover, each material which comprises the light emission functional layer 3 was filled in each heating boat in a vacuum evaporation system in the optimal quantity for film forming of each layer. In addition, as a heating boat, what was produced with the resistance heating material made from tungsten was used.

Next, the vapor deposition chamber of the vacuum vapor deposition apparatus is depressurized to a vacuum degree of 4 × 10 ⁻⁴ Pa, and each layer constituting the light emitting functional layer 3 shown below is heated by sequentially energizing and heating a heating boat containing each material. A film was formed.

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

  Next, a heating boat containing Exemplified Compound H4 as a host compound and a heating boat containing Exemplified Compound Ir-4 as a phosphorescent compound were energized independently, and Exemplified Compound H4 as a host compound and Phosphorus A light-emitting layer 3 c composed of Illustrative Compound Ir-4, which is a light-emitting compound, was formed on the hole transport / injection layer 31. At this time, the deposition rate (nm / second) is adjusted to the exemplary compound H4: exemplary compound Ir-4 = 100: 6, and the current-carrying conditions of the heating boat are appropriately adjusted so that the thickness of the light emitting layer is 30 nm. I made it.

  Next, a heating boat containing BAlq shown below as a hole blocking material was energized and heated to form a hole blocking layer 33 made of BAlq on the light emitting layer 3c. At this time, vapor deposition was performed under the condition that the vapor deposition rate was in the range of 0.1 to 0.2 nm / second and the layer thickness was 10 nm.

  Thereafter, a heating boat containing ET-4 shown below as an electron transporting material and a heating boat containing potassium fluoride are energized independently, and an electron transport layer composed of ET-4 and potassium fluoride. 3d was formed on the hole blocking layer 33. At this time, under the condition that the deposition rate (nm / second) is ET-4: potassium fluoride = 75: 25, the energization conditions of the heating boat are adjusted as appropriate so that the layer thickness of the electron transport layer 3d is 30 nm. And deposited.

  Next, a heating boat containing potassium fluoride as an electron injection material was energized and heated to form an electron injection layer 3e made of potassium fluoride on the electron transport layer 3d. At this time, vapor deposition was performed at a vapor deposition rate of 0.01 to 0.02 nm / second so as to have a layer thickness of 1 nm.

  Thereafter, the transparent substrate 13 formed up to the electron injection layer 3e was transferred from the vapor deposition chamber of the vacuum vapor deposition apparatus to the processing chamber of the sputtering apparatus to which an ITO target as a counter electrode material was attached while maintaining the vacuum state. Next, in the processing chamber, a film was formed at a film forming speed of 0.3 to 0.5 nm / second using a light-transmitting counter electrode 5a made of ITO having a layer thickness of 150 nm as a cathode.

  As described above, the organic EL element 400 was formed on the transparent substrate 13.

  Next, the organic EL element 400 is covered with a sealing material 17 made of a glass substrate having a thickness of 300 μm, and the adhesive 19 (sealing material) is interposed between the sealing material 17 and the transparent substrate 13 so as to surround the organic EL element 400. ). As the adhesive 19, an epoxy photocurable adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) was used. The adhesive 19 filled between the sealing material 17 and the transparent substrate 13 is irradiated with UV light from the glass substrate (sealing material 17) side to cure the adhesive 19 and seal the organic EL element 400. Stopped.

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

  As described above, the light-emitting panel 1 in which the organic EL element 400 was provided on the transparent substrate 13 and sealed with the sealing material 17 and the adhesive 19 was manufactured. In this light emitting panel 1, the light emission h of each color generated in the light emitting layer 3c is extracted from both the transparent electrode 1 side, that is, the transparent substrate 13 side, and the counter electrode 5a side, that is, the sealing material 17 side. It has become.

[Production of light emitting panels 2 to 73]
In the production of the light-emitting panel 1, light-emitting panels 2 to 73 were produced in the same manner except that the transparent electrode substrates 2 to 73 produced in Example 1 were used in place of the transparent electrode substrate 1, respectively.

<Evaluation of luminous panel>
About the produced said light emission panels 1-73, the light transmittance, the drive voltage, and durability were evaluated in accordance with the following method.

(Measurement of light transmittance)
About each produced said light emission panel, the light transmittance (%) in wavelength 550nm was measured using the base material used for preparation of each transparent electrode substrate using the spectrophotometer (Hitachi Ltd. U-3300).

[Measurement of drive voltage]
The front luminance is measured on both sides of the transparent electrode 1 side (that is, the transparent substrate 13 side) and the counter electrode 5a side (that is, the sealing material 17 side) of each of the produced light emitting panels, and the sum is 1000 cd / m ^2. Was measured as a drive voltage (V). For the measurement of luminance, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Optics) was used. It represents that it is so preferable that the numerical value of the obtained drive voltage is small.

[Percentage of DS (dark spot) area under high temperature and high humidity storage]
The prepared transparent electrode substrate was stored for 100 hours in an environment of 60 ° C. and 90% RH to prepare a sample for observation. The change with time of the dark spot area was observed using a microscope, and the ratio to the total light emitting area of the light emitting panel was calculated. Tables 3 and 4 show relative values when the ratio of the dark spot area of the light-emitting panel 8 is 100.

  The results obtained as described above are shown in Tables 3 and 4.

  As is clear from the results shown in Tables 3 and 4, the light-emitting panels 9 to 73 of the present invention using the transparent electrode of the present invention for the anode of the organic EL element all have a light transmittance of 50% or more. In addition, the drive voltage is suppressed to 4.1 V or less. On the other hand, the light-emitting panels 1 to 8 using the transparent electrode of the comparative example as the anode of the organic EL element have a light transmittance of less than 50%, and do not emit light even when a voltage is applied. Or even if it emitted light, the drive voltage exceeded 4.1V.

  In addition, the light emitting panels 9 to 73 of the present invention using the transparent electrode of the present invention as the anode of the organic EL element have a significantly lower defect area ratio under high temperature and high humidity storage than the light emitting panels 1 to 8 of the comparative example. It has become.

  Thereby, it was confirmed that the light emitting panel provided with the transparent electrode of the present invention can emit light with high luminance at a low driving voltage and is excellent in durability. In addition, it has been confirmed that this is expected to reduce the driving voltage for obtaining a predetermined luminance and improve the light emission lifetime.

DESCRIPTION OF SYMBOLS 1 Transparent electrode 1a Intermediate layer 1b Conductive layer 1d Underlayer 1e Intermediate underlayer 3 Light emitting functional layer 3a Hole injection layer 3b Hole transport layer 3c Light emission layer 3d Electron transport layer 3e Electron injection layer 5a, 5b, 5c Counter electrode 11 Base material 13, 131 Transparent substrate 13a, 131a Light extraction surface 15 Auxiliary electrode 17 Sealing material 19 Adhesive 21 Illumination device 22 Light emitting panel 23 Support substrate 31 Hole transport / injection layer 33 Hole blocking layer 100, 200, 300, 400 Organic electroluminescent element A Light emitting area B Non-light emitting area h Light emission

Claims (9)

A transparent electrode having an intermediate layer and a conductive layer provided adjacent to the intermediate layer, having a light transmittance of 50% or more at a wavelength of 550 nm and a sheet resistance value of 20Ω / □ or less. The intermediate layer contains a silver compound, the conductive layer contains silver as a main component ,
The said silver compound is a compound represented by following General formula (1), The transparent electrode characterized by the above-mentioned.
General formula (1) Ag-Y (-R) _n
(In the formula, Y represents a chlorine atom, a bromine atom, an iodine atom, a sulfur atom or OC (═O). R represents an organic substituent. N represents 0 or 1.) In the above general formula (1), Y is bromine atom or iodine atom, a transparent electrode according to claim 1 which n is equal to or represents 0. The conductive layer, an intermediate layer provided adjacent to the conductive layer, and a base layer provided adjacent to the intermediate layer are sequentially stacked,
The underlying layer, a transparent electrode according to claim 1 or claim 2, characterized in that it contains a compound represented by the following general formula (2).
Formula (2) R ₁ —Y (—R) _n
(In the formula, Y represents a chlorine atom, a bromine atom, an iodine atom, a sulfur atom, SS or OC (═O). When Y is a chlorine atom, a bromine atom or an iodine atom, n represents 0, and R _1. Represents a substituent, and when Y represents a sulfur atom, SS or OC (═O), n represents 1, R represents a substituent, and R ₁ represents a hydrogen atom or a substituent. The intermediate layer and the base layer form one intermediate base layer,
The transparent electrode according to claim 3 , wherein the intermediate underlayer contains both the compound represented by the general formula (1) and the compound represented by the general formula (2). A method for producing a transparent electrode having a conductive layer containing silver as a main component,
A step of forming a layer containing at least one of a silver compound and a compound that reacts with silver derived from the conductive layer to form the silver compound;
Have a, and forming the conductive layer,
An intermediate layer containing the silver compound represented by the following general formula (1) is formed in the process of forming the conductive layer on an underlayer containing the compound represented by the following general formula (2) A method for producing a transparent electrode, comprising:
General formula (1) Ag-Y (-R) _n
(In the formula, Y represents an atom or group that forms a bond with one silver atom. R represents an organic substituent. N represents 0 or 1.)
Formula (2) R ₁ —Y (—R) _n
(In the formula, Y represents a chlorine atom, a bromine atom, an iodine atom, a sulfur atom, SS or OC (═O). When Y is a chlorine atom, a bromine atom or an iodine atom, n represents 0, and R _1. Represents a substituent, and when Y represents a sulfur atom, SS or OC (═O), n represents 1, R represents a substituent, and R ₁ represents a hydrogen atom or a substituent. In the said General formula (2), Y represents a bromine atom or an iodine atom, The manufacturing method of the transparent electrode of Claim 5 characterized by the above-mentioned. The method for producing a transparent electrode according to claim 6 , wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).
General formula (3) Ar-X
(In the formula, Ar represents an aromatic group, and X represents a bromine atom or an iodine atom.) An electronic device comprising the transparent electrode according to any one of claims 1 to 4 . An organic electroluminescence device comprising the transparent electrode according to any one of claims 1 to 4 .

Images