JP2015125845A - Transparent electrode and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent electrode or the like having both sufficient conductivity and optical transparency and longer service life.SOLUTION: The transparent electrode includes: a nitrogen-containing layer constituted of a compound which contains a nitrogen atom (N) and has an effective unshared electron pair percentage content [n/M] of 2.0×10or more, where n represents the number of unpaired electron pairs which have no relationship with aromatic property and are not coordinated with metals among unshared electron pairs included in the nitrogen atom (N), and M represents molecular weight; and an electrode layer containing any one kind of metallic element selected from copper, gold and platinum as a main component and at least one kind of element different from the main component element, among silver, aluminum, gold, indium, copper, palladium and platinum as an additional element and arranged adjacently to the nitrogen-containing layer.

Description

  The present invention relates to a transparent electrode and an electronic device. More specifically, the present invention relates to a transparent electrode having both conductivity and light transmittance and having an improved lifetime, and further relates to an electronic device using the transparent electrode.

In an electronic device such as a touch panel, a liquid crystal display device, an organic electroluminescence element, and a solar cell, as an electrode on the light extraction side (transparent electrode), indium tin oxide (SnO ₂ -In ₂ O ₃ : Indium Tin Oxide, hereinafter “ An oxide semiconductor material such as “ITO” is generally used. However, studies on a material aiming at lowering resistance by laminating ITO and silver are disclosed in, for example, JP-A-2002-15623. No. 2006 and Japanese Patent Application Laid-Open No. 2006-164961. However, since ITO uses indium, which is a rare metal, the material cost is high, and in order to lower the resistance, it is necessary to anneal at about 300 ° C. after film formation. We had problems such as limitations.

  In recent years, in consideration of the above problems, studies have been made in which silver (Ag) is applied as a constituent material of the transparent electrode. Silver is superior in conductivity to the ITO, but has a problem of trade-off between resistance characteristics and transmittance.

  Under such circumstances, a technique for forming a thin film using an alloy of silver and magnesium (Mg) having high electrical conductivity, or a technique for forming a thin film using a metal material that is inexpensive and easily available as a raw material instead of indium 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 sheet 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, and in addition to the problem that the drive voltage cannot be lowered. Magnesium is easily oxidized and has a problem that its performance is likely to deteriorate due to long-term storage.

In addition, the invention described in Patent Document 2 discloses a transparent conductive film using a metal material such as zinc (Zn) or tin (Sn) that is inexpensive and easily available as a raw material instead of indium (In). Has been. However, with these alternative metals, the resistance value does not decrease sufficiently, 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 is disclosed in which a thin film having a film thickness of about 15 nm and a highly transmissive silver film is deposited and used as a cathode (see, for example, Patent Document 3). However, in the method proposed in Patent Document 3, since the formed silver film is still thick as an electrode, the light transmittance (transmittance) as a transparent electrode is not sufficient, and migration (movement of atoms) It is easy to cause. Further, if the silver film is made thinner, it becomes difficult to maintain conductivity and the like, and therefore, development of a technique that achieves both light transmittance and conductivity is eagerly desired.

  We have already reported a transparent electrode using a silver thin film and an organic compound having a strong interaction with silver as a nitrogen-containing layer in contact with the silver thin film (see, for example, Patent Document 4). On the other hand, although it is excellent in sheet resistance value, light transmittance, and storage stability, a transparent electrode having further improved conductivity, light transmittance, and life is required for use as an electronic device.

JP 2006-344497 A JP 2007-031786 A US Patent Application Publication No. 2011/0260148 International Publication No. 2013/105569

  The present invention has been made in view of the above-described problems and circumstances, and a solution to the problem is to provide a transparent electrode having sufficient conductivity and light transmittance and having an improved lifetime, and the transparent electrode. It is an object of the present invention to provide an electronic device whose performance is improved by using.

As a result of studying the cause of the above-mentioned problem in order to solve the above-mentioned problems, the present inventor is any one selected from copper (Cu), gold (Au), and platinum (Pt) constituting the electrode layer for the nitrogen-containing layer. The effective unshared electron pair content rate was applied as an index of the bond stability of one kind of metal element, and the nitrogen-containing layer was configured using a compound having this value within a predetermined range. As a result, it is possible to provide a nitrogen-containing layer adjacent to the electrode layer that can reliably obtain the effect of “suppressing the aggregation of any one metal element selected from copper, gold and platinum” as will be described later. I found out. Moreover, this inventor comprises any one chosen from copper, gold | metal | money, and platinum by comprising an electrode layer with the solid solution of any one sort of metal element chosen from copper, gold | metal | money, and platinum and a specific additive element. It has been found that migration of atomic metal elements is suppressed. As a result, the inventor of the present invention has both improved conductivity and improved light transmission in a transparent electrode using any one metal element selected from copper, gold and platinum, as well as reliability and electrode life. It has been found that improvement can be achieved, and the present invention has been achieved.
That is, the said subject which concerns on this invention is solved by the following means.

1. The number of unshared electron pairs that contain a nitrogen atom (N) and that are not involved in aromaticity and that are not coordinated to the metal among the unshared electron pairs that the nitrogen atom (N) has is n, and the molecular weight is M A nitrogen-containing layer formed using a compound having an effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ or more when
One of the metal elements selected from copper, gold and platinum is the main component, and at least one element different from the main component of silver, aluminum, gold, indium, copper, palladium and platinum as the additive element A transparent electrode comprising an element and an electrode layer provided adjacent to the nitrogen-containing layer.

  2. The transparent electrode according to claim 1, wherein the metal element contained in the electrode layer as a main component is copper.

3. The transparent electrode according to the first or second item, wherein the effective unshared electron pair content [n / M] in the compound is 3.9 × 10 ⁻³ or more.

4). The transparent electrode according to Item 1 or 2, wherein the effective unshared electron pair content [n / M] of the compound is 6.5 × 10 ⁻³ or more.

5. The nitrogen-containing layer is any one of the first to fourth items, wherein the effective unshared electron pair content [n / M] at the interface on the electrode layer side is 2.0 × 10 ⁻³ or more. The transparent electrode according to 1.

  6). The transparent electrode according to any one of Items 1 to 5, wherein a concentration of the additive element in the electrode layer is in a range of 0.01 to 10.0 atomic%.

7). The nitrogen-containing layer is composed of another compound together with the compound, and the average value of the effective unshared electron pair content [n / M] in consideration of the mixing ratio of these compounds is 2.0 × 10 The transparent electrode according to any one of Items 1 to 6, which is ⁻³ or more.

  8). The transparent electrode according to any one of Items 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (1).

[However, in the general formula (1),
X11 represents -N (R11)-or -O-,
E101 to E108 each represent -C (R12) = or -N =, and at least one of E101 to E108 is -N =,
R11 and R12 each represent a hydrogen atom (H) or a substituent. ]

  9. The transparent electrode according to item 8, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (1a) in which X11 in the general formula (1) is -N (R11)-.

  10. The transparent electrode according to item 9, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (1a-1) in which E104 in the general formula (1a) is -N =.

  11. The transparent electrode according to item 9, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (1a-2) in which E103 and E106 in the general formula (1a) are -N =.

  12 The nitrogen-containing layer according to item 8, containing a compound having a structure represented by the following general formula (1b) in which X11 in the general formula (1) is -O- and E104 is -N =. Transparent electrode.

  13. The transparent electrode according to any one of Items 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (2).

[However, in general formula (2),
Y21 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof;
E201 to E216 and E221 to E238 each represent -C (R21) = or -N =,
R21 represents a hydrogen atom (H) or a substituent,
At least one of E221 to E229 and at least one of E230 to E238 is -N =;
k21 and k22 represent an integer of 0 to 4, but k21 + k22 is an integer of 2 or more. ]

  14 The transparent electrode according to any one of Items 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (3).

[However, in general formula (3),
E301 to E312 each represent -C (R31) =
R31 represents a hydrogen atom (H) or a substituent,
Y31 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof. ]

  15. The transparent electrode according to any one of items 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (4).

[However, in general formula (4),
E401 to E414 each represent -C (R41) =
R41 represents a hydrogen atom (H) or a substituent,
Ar41 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring;
k41 represents an integer of 3 or more. ]

  16. The transparent electrode according to any one of Items 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (5).

[However, in general formula (5),
R51 represents a substituent,
E501, E502, E511 to E515 and E521 to E525 each represent -C (R52) = or -N =
E503 to E505 each represent -C (R52) =
R52 represents a hydrogen atom (H) or a substituent,
At least one of E501 and E502 is -N =,
At least one of E511 to E515 is -N =,
At least one of E521 to E525 is -N =. ]

  17. The transparent electrode according to any one of items 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (6).

[However, in general formula (6),
E601 to E612 each represent -C (R61) = or -N =
R61 represents a hydrogen atom (H) or a substituent,
Ar61 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring. ]

  18. The transparent electrode according to any one of Items 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (7).

[However, in general formula (7),
R71 to R73 each represents a hydrogen atom (H) or a substituent,
Ar71 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group. ]

  19. The transparent electrode according to any one of items 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (8).

[However, in general formula (8),
R81 to R86 each represent a hydrogen atom (H) or a substituent,
E801 to E803 each represent -C (R87) = or -N =
R87 represents a hydrogen atom (H) or a substituent,
Ar81 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group. ]

  20. 20. The transparent electrode according to item 19, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (8a).

[However, in the general formula (8a),
E804 to E811 each represent -C (R88) = or -N =
Each R88 represents a hydrogen atom (H) or a substituent;
At least one of E808 to E811 is -N =;
E804 to E807 and E808 to E811 may be bonded to each other to form a new ring. ]

  21. An electronic device having the transparent electrode according to any one of items 1 to 20.

By the above means of the present invention, it is possible to provide a transparent electrode having both sufficient conductivity and light transmittance and improved life. In addition, an electronic device with improved performance can be provided by using a transparent electrode.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

The transparent electrode of the present invention has the following configuration. Of the unshared electron pairs that contain a nitrogen atom and that do not participate in aromaticity and are not coordinated to the metal, n is the number of unshared electron pairs and the molecular weight is M. It has a nitrogen-containing layer composed of a compound having a shared electron pair content [n / M] of 2.0 × 10 ⁻³ or more. In addition, any one metal element selected from copper, gold and platinum is used as a main component, and at least one element different from the main component among silver, aluminum, gold, indium, copper, palladium and platinum as an additive element. It has an electrode layer containing an element and provided adjacent to the nitrogen-containing layer.

  The electronic device of the present invention is characterized by having the transparent electrode having the above-described configuration. The electronic device is, for example, a touch panel.

  The transparent electrode configured as described above has, as a main component, any one metal element selected from copper, gold, and platinum with respect to a nitrogen-containing layer configured using a compound containing a nitrogen atom. In this configuration, the electrode layers are provided adjacent to each other. As a result, the electrode layer mainly composed of any one metal element selected from copper, gold and platinum is made from the copper, gold and platinum at the adjacent interface due to the interaction with the nitrogen atoms constituting the nitrogen-containing layer. The diffusion distance of any one selected metal element is reduced and aggregation is suppressed. Therefore, in general, a thin film of any one metal element selected from copper, gold, and platinum, which is easily isolated in an island shape by film growth of a nuclear growth type (Volume-Weber: VW type), is a single layer. The film is formed by growth-type (Frank-van der Merwe: FM type) film growth. Therefore, an electrode layer having a uniform thickness can be obtained even though the layer thickness is thin.

In addition, the effective unshared electron pair content [n / M] is applied as an index of the bond stability of any one metal element selected from copper, gold and platinum constituting the electrode layer with respect to the nitrogen-containing layer. The nitrogen-containing layer was configured using a compound having a value of 2.0 × 10 ⁻³ or more. As a result, it is possible to provide a nitrogen-containing layer adjacent to the electrode layer so that the effect of “suppressing the aggregation of any one metal element selected from copper, gold and platinum” as described above can be reliably obtained. Become. This is because, as will be described in detail in later examples, an electrode layer capable of measuring a sheet resistance value is formed on such a nitrogen-containing layer while being an extremely thin film of 6 nm. confirmed.

  In particular, the electrode layer mainly composed of any one metal element selected from copper, gold and platinum has silver as a solid solution element for any one metal element selected from copper, gold and platinum. Aluminum, gold, indium, copper, palladium and platinum contain at least one element different from the main element. As a result, the electrode layer is composed of a solid solution of any one metal element selected from copper, gold, and platinum and these additive elements, and migration (movement of atoms) of the main metal element is performed. It will be suppressed.

  Therefore, in this transparent electrode, it is possible to reliably obtain an electrode layer in which conductivity is ensured by having a uniform thickness while ensuring light transmittance by being a thin layer thickness, and migration. By suppressing the occurrence of this, it is possible to maintain such light transmittance and conductivity. As a result, it is possible to improve the reliability as well as improve the conductivity and light transmittance of the transparent electrode using any one kind of metal element selected from copper, gold and platinum. .

  In addition, according to the present invention, any one atom selected from copper, gold and platinum interacts more strongly with the nitrogen-containing layer, so that the upper part of the electrode layer (the side not adjacent to the nitrogen-containing layer in the electrode layer) It is presumed that the electron density becomes sparse, and as a result, reactions such as oxidation are suppressed, and as a result, the electrode life is improved.

Cross-sectional schematic diagram showing the configuration of the transparent electrode of the present invention The figure which shows the structural formula of TBAC and Ir (ppy) ₃ for demonstrating the coupling | bonding mode of a nitrogen atom Diagram showing the structural formula and molecular orbitals of the pyridine ring Diagram showing the structural formula and molecular orbitals of the pyrrole ring Diagram showing structural formula and molecular orbital of imidazole ring Diagram showing structural formula and molecular orbital of δ-carboline ring Process flow diagram showing an example of forming an electrode pattern on a transparent electrode by photolithography The perspective view which shows an example of a structure of the touchscreen which is an electronic device provided with the transparent electrode pair which has an electrode pattern The top view which shows an example of the electrode pattern of each transparent electrode which comprises a touch panel Plane schematic diagram showing an example of electrode parts constituting a touch panel Schematic sectional view showing an example of the configuration of the touch panel Schematic sectional view showing an example of the configuration of a touch panel that can be suitably used in the present invention Schematic sectional view showing an example of the configuration of a liquid crystal display device which is an electronic device equipped with the transparent electrode of the present invention The graph which shows the relationship between the effective unshared electron pair content rate [n / M] of a nitrogen containing layer, and the sheet resistance value of the electrode layer laminated | stacked on the nitrogen containing layer

The transparent electrode of the present invention contains a nitrogen atom (N) and is not involved in aromaticity among non-shared electron pairs of the nitrogen atom (N) and is not coordinated to a metal A nitrogen-containing layer composed of a compound having an effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ or more when the number of pairs is n and the molecular weight is M, and copper And at least one element different from the main element among silver, aluminum, gold, indium, copper, palladium and platinum as an additive element. And an electrode layer provided adjacent to the nitrogen-containing layer. This feature is a technical feature common to the inventions according to claims 1 to 21.

  As an embodiment of the present invention, it is preferable that the metal element contained in the electrode layer as a main component is copper from the viewpoint of manifesting the effects of the present invention.

Furthermore, in the present invention, the effective unshared electron pair content [n / M] in the compound is preferably 3.9 × 10 ⁻³ or more, and more preferably 6.5 × 10 ^−3. That's it. Thereby, the effect of further reducing the sheet resistance value is obtained.

In the present invention, the nitrogen-containing layer has an effective unshared electron pair content [n / M] at the interface on the electrode layer side of 2.0 × 10 ⁻³ or more. It is preferable from the viewpoint of effect expression.

  In the present invention, when the concentration of the additive element in the electrode layer is in the range of 0.01 to 10.0 atomic%, the light transmittance, the low sheet resistance value, and the high temperature and high humidity are good. This is preferable because storage stability is obtained.

  Further, in the present invention, the nitrogen-containing layer is composed of another compound together with the compound, and the average value of the effective unshared electron pair content [n / M] in consideration of the mixing ratio of these compounds Is preferably 2.0 × 10 −3 or more from the viewpoint of the effect of the present invention.

  In the present invention, the nitrogen-containing layer may contain a compound having a structure represented by the general formula (1), (1a), (2) to (8) or (8a). It is preferable because a strong interaction can be expressed between the nitrogen in the electrode and the above-described main component metal element constituting the electrode layer.

  The transparent electrode of the present invention can be suitably provided in an electronic device.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention, its components, and modes and modes for carrying out the present invention will be described in detail below in the following order based on the drawings. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.
1. 1. Transparent electrode 2. Use of transparent electrode First example of touch panel (configuration using two transparent substrates)
4). Second example of touch panel (configuration with two layers of transparent electrodes on a transparent substrate)
5. Liquid crystal display

<< 1. Transparent electrode >>
FIG. 1 is a schematic cross-sectional view illustrating a configuration of a transparent electrode according to an embodiment of the present invention. As shown in this figure, the transparent electrode 1 has a two-layer structure in which a nitrogen-containing layer 3 and an electrode layer 5 provided adjacent to the nitrogen-containing layer 3 are laminated. 3 and the electrode layer 5 are provided in this order. Among these, the electrode layer 5 which comprises the electrode part in the transparent electrode 1 is a layer comprised as a main component in any 1 type of metal elements chosen from copper, gold | metal | money, and platinum. The nitrogen-containing layer 3 is composed of a compound containing a nitrogen atom (N), and in particular, any one metal selected from copper, gold, and platinum, which are the main materials constituting the electrode layer 5. An unshared electron pair of a nitrogen atom that is stably bonded to an atom is referred to as an [effective unshared electron pair], and a compound having a content of the [effective unshared electron pair] within a predetermined range is used. . Furthermore, the electrode layer 5 is mainly composed of any one metal element selected from copper, gold, and platinum, and the additive element includes silver, aluminum, gold, indium, copper, palladium, and platinum as the main element. It is characterized by containing at least one element different from the above.
Further, the nitrogen-containing layer 3 may be further laminated on the above-described electrode layer 5. With such a configuration, the electrode layer surface is smoothed, and from the viewpoint of improving the adhesion with the upper layer, etc. preferable.

  Below, a detailed structure is demonstrated in order of the base material 11 with which the transparent electrode 1 of such a laminated structure is provided, the nitrogen-containing layer 3 which comprises the transparent electrode 1, and the electrode layer 5. In FIG. In addition, the transparency of the transparent electrode 1 of the present invention means that the light transmittance at a wavelength of 550 nm is 50% or more.

<Substrate 11>
Examples of the substrate 11 on which the transparent electrode 1 of the present invention is formed include, but are not limited to, glass and plastic. Further, the substrate 11 may be transparent or opaque. When the transparent electrode 1 of the present invention is used in an electronic device that extracts light from the substrate 11 side, the substrate 11 is preferably transparent. Examples of the transparent substrate 11 that is preferably used include glass, quartz, and a transparent resin film. A particularly preferable substrate 11 is a resin film that can give flexibility to the transparent electrode 1 and an electronic device such as a liquid crystal display device constituted by using the transparent electrode 1.

  Examples of the glass include silica glass, soda lime silica glass, lead glass, borosilicate glass, and alkali-free glass. On the surface of these glass materials, from the viewpoint of adhesion with the nitrogen-containing layer 3, durability and smoothness, if necessary, physical treatment such as polishing is performed, a film made of an inorganic material or an organic material, A hybrid film combining these films is formed.

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

On the surface of the resin film, a film made of an inorganic material or an organic material or a hybrid film combining these films may be formed. Such coatings and hybrid coatings have a water vapor transmission rate (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS-K-7129-1992 of 0.01 g / ( m ² · 24 hours) or less of a barrier film (also referred to as a barrier film or the like) 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. It is preferable that it is a high barrier film of g / (m ² · 24 hours) or less.

  The material for forming the barrier film as described above may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like is used. be able to. 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 forming 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 weighting. A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method described in JP-A-2004-68143 is particularly preferable.

  On the other hand, when the base material 11 is opaque, for example, a metal substrate such as aluminum or stainless steel, an opaque resin substrate, a ceramic substrate, or the like can be used. These substrates may be in the form of a film that bends flexibly.

<Nitrogen-containing layer 3>
The nitrogen-containing layer 3 is a layer provided adjacent to the electrode layer 5 and is configured using a compound containing a nitrogen atom (N). In particular, this compound is nitrogen that stably binds to any one metal element selected from copper, gold, and platinum, which are main materials constituting the electrode layer 5 among nitrogen atoms contained in the compound. An atomic unshared electron pair is defined as [effective unshared electron pair], and the content ratio of the [effective unshared electron pair] is within a predetermined range.

  Here, the “effective unshared electron pair” is an unshared electron pair that does not participate in aromaticity and is not coordinated to the metal among the unshared electron pairs of the nitrogen atom contained in the compound. The aromaticity here refers to an unsaturated cyclic structure in which atoms having π electrons are arranged in a ring, and is aromatic according to the so-called “Hückel rule”, and includes the electrons contained in the π electron system on the ring. The condition is that the number is “4n + 2” (n = 0 or a natural number).

  [Effective unshared electron pair] as described above refers to an unshared electron pair possessed by a nitrogen atom regardless of whether or not the nitrogen atom itself provided with the unshared electron pair is a hetero atom constituting an aromatic ring. Is selected depending on whether or not is involved in aromaticity. For example, even if a nitrogen atom is a hetero atom constituting an aromatic ring, the lone pair of the nitrogen atom does not directly participate as an essential element in aromaticity, that is, a conjugated unsaturated ring An unshared electron pair that is not involved in the delocalized π-electron system on the structure (aromatic ring) as an essential element for the expression of aromaticity is [effective unshared electron] It is counted as one of the pair. On the other hand, even if a nitrogen atom is not a heteroatom constituting an aromatic ring, if the lone pair of the nitrogen atom is involved in aromaticity, the lone pair of the nitrogen atom Are not counted as [valid unshared electron pairs]. In each compound, the number n of [effective unshared electron pairs] described above coincides with the number of nitrogen atoms having [effective unshared electron pairs].

  Next, [effective unshared electron pair] will be described in detail with a specific example.

  The nitrogen atom is a Group 15 element and has 5 electrons in the outermost shell. Of these, three unpaired electrons are used for covalent bonds with other atoms, and the remaining two become a pair of unshared electron pairs. For this reason, the number of bonds of nitrogen atoms is usually three.

For example, as a group having a nitrogen atom, an amino group (—NR ¹ R ² ), an amide group (—C (═O) NR ¹ R ² ), a nitro group (—NO ₂ ), a cyano group (—CN), diazo Group (—N ₂ ), azide group (—N ₃ ), urea bond (—NR ¹ C═ONR ² —), isothiocyanate group (—N═C═S) and thioamide group (—C (═S) NR ¹ R ² ) and the like. R ¹ and R ² are each a hydrogen atom (H) or a substituent. The non-shared electron pair of the nitrogen atom constituting these groups does not participate in aromaticity and is not coordinated to the metal, and thus corresponds to [effective unshared electron pair]. Among these, the unshared electron pair possessed by the nitrogen atom of the nitro group (—NO ₂ ) is used for the resonance structure with the oxygen atom, but has a good effect as shown in the following examples. Therefore, it is considered that it exists on nitrogen as an [effective unshared electron pair] that is not involved in aromaticity and coordinated to a metal.

A nitrogen atom can also create a fourth bond by using an unshared electron pair. An example of this case will be described with reference to FIG. FIG. 2 shows the structural formula of tetrabutylammonium chloride (TBAC) and the structural formula of tris (2-phenylpyridine) iridium (III) [Ir (ppy) ₃ ].

  Among these, TBAC is a quaternary ammonium salt in which one of four butyl groups is ionically bonded to a nitrogen atom and has a chloride ion as a counter ion. In this case, one of the electrons constituting the unshared electron pair of the nitrogen atom is donated to the ionic bond with the butyl group. For this reason, the nitrogen atom of TBAC is equivalent to the absence of an unshared electron pair in the first place. Therefore, the unshared electron pair of the nitrogen atom constituting TBAC does not correspond to the [effective unshared electron pair] that is not involved in aromaticity and coordinated to the metal.

Ir (ppy) ₃ is a neutral metal complex in which an iridium atom and a nitrogen atom are coordinated. The unshared electron pair of the nitrogen atom constituting this Ir (ppy) ₃ is coordinated to the iridium atom, and is utilized for coordination bonding. Therefore, the unshared electron pair of the nitrogen atom constituting Ir (ppy) ₃ does not correspond to the [effective unshared electron pair] that is not involved in aromaticity and coordinated to the metal.

  Moreover, a nitrogen atom is general as a hetero atom which can comprise an aromatic ring, and can contribute to the expression of aromaticity. Examples of the “nitrogen-containing aromatic ring” include pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, and tetrazole ring.

  FIG. 3 is a diagram showing a structural formula and molecular orbitals of a pyridine ring which is one of the groups exemplified above. As shown in FIG. 3, in the conjugated (resonant) unsaturated ring structure in which the pyridine ring is arranged in a 6-membered ring, the number of delocalized π electrons is 6, so that 4n + 2 (n = 0 or natural number) Satisfy Hückel's law. Since the nitrogen atom in the 6-membered ring is substituted with —CH═, only one unpaired electron is mobilized to the 6π-electron system, and the unshared electron pair is essential for the expression of aromaticity. Not involved as a thing.

  Therefore, the unshared electron pair of the nitrogen atom constituting the pyridine ring corresponds to an [effective unshared electron pair] that does not participate in aromaticity and is not coordinated to the metal.

  FIG. 4 shows the structural formula and molecular orbitals of the pyrrole ring. As shown in FIG. 4, the pyrrole ring has a structure in which one of the carbon atoms constituting the five-membered ring is substituted with a nitrogen atom, but the number of π electrons is also six and satisfies the Hückel rule. Nitrogen-containing aromatic ring. Since the nitrogen atom of the pyrrole ring is also bonded to a hydrogen atom, an unshared electron pair is mobilized to the 6π electron system.

  Therefore, although the nitrogen atom of the pyrrole ring has an unshared electron pair, since this unshared electron pair is used as an essential element for the expression of aromaticity, it does not participate in aromaticity and is a metal. Does not fall under [Effective unshared electron pair] that is not coordinated to

FIG. 5 is a diagram showing the structural formula and molecular orbitals of the imidazole ring. As shown in FIG. 5, the imidazole ring has a structure in which two nitrogen atoms N ¹ and N ² are substituted at the 1-position and 3-position in a 5-membered ring, and also contains 6 π electrons. Nitrogen aromatic ring. Of these, one nitrogen atom N ¹ is a pyridine ring-type nitrogen atom that mobilizes only one unpaired electron to the 6π-electron system and does not utilize the unshared electron pair for the expression of aromaticity, This unshared electron pair of the nitrogen atom N ¹ corresponds to [effective unshared electron pair]. On the other hand, since the other nitrogen atom N ² is a pyrrole-ring-type nitrogen atom that mobilizes the unshared electron pair to the 6π electron system, the unshared electron pair of the nitrogen atom N ² is [effective Does not fall under [Unshared electron pair].

Therefore, in the imidazole ring, only the unshared electron pair of one nitrogen atom N ¹ out of the two nitrogen atoms N ¹ and N ² constituting the ring corresponds to the “effective unshared electron pair”.

  The selection of the unshared electron pair at the nitrogen atom of the “nitrogen-containing aromatic ring” as described above is similarly applied to a condensed ring compound having a nitrogen-containing aromatic ring skeleton.

FIG. 6 is a diagram showing the structural formula and molecular orbital of the δ-carboline ring. As shown in FIG. 6, the δ-carboline ring is a condensed ring compound having a nitrogen-containing aromatic ring skeleton, and is an azacarbazole compound in which a benzene ring skeleton, a pyrrole ring skeleton, and a pyridine ring skeleton are condensed in this order. Of these, the nitrogen atom N ³ of the pyridine ring mobilizes only one unpaired electron to the π-electron system, and the nitrogen atom N ⁴ of the pyrrole ring mobilizes an unshared electron pair to the π-electron system. Together with the 11 π electrons from the carbon atoms that are formed, the total number of π electrons is an aromatic ring of 14.

Therefore, among the two nitrogen atoms N ³ and N ⁴ of the δ-carboline ring, the unshared electron pair of the nitrogen atom N ³ constituting the pyridine ring corresponds to [effective unshared electron pair], but constitutes the pyrrole ring. The unshared electron pair of the nitrogen atom N ⁴ that does not correspond to [Effective unshared electron pair].

  Thus, the unshared electron pair of the nitrogen atom constituting the condensed ring compound is involved in the bond in the condensed ring compound as well as the bond in the single ring such as the pyridine ring and the pyrrole ring constituting the condensed ring compound.

  The [effective unshared electron pair] described above is important in order to develop a strong interaction with any one metal element selected from copper, gold, and platinum, which are the main components of the electrode layer 5. The nitrogen atom having such [effective unshared electron pair] is preferably a nitrogen atom in the nitrogen-containing aromatic ring from the viewpoint of stability and durability. Therefore, the compound contained in the nitrogen-containing layer 3 preferably has an aromatic heterocycle having a nitrogen atom having [effective unshared electron pair] as a hetero atom.

Particularly in the present embodiment, the number n of [effective unshared electron pairs] with respect to the molecular weight M of such a compound is defined as, for example, the effective unshared electron pair content [n / M]. The nitrogen-containing layer 3 is characterized in that the [n / M] is composed of a compound selected so as to be 2.0 × 10 ⁻³ or more. The nitrogen-containing layer 3 preferably has an effective unshared electron pair content [n / M] defined as described above in the range of 3.9 × 10 ⁻³ or more, and 6.5 × 10 ^−3. If it is the above range, it is still more preferable.

  Further, the nitrogen-containing layer 3 only needs to be configured using a compound having an effective unshared electron pair content [n / M] within the predetermined range described above, or may be configured only with such a compound. Further, such a compound and another compound may be mixed and used. The other compound may or may not contain a nitrogen atom, and the effective unshared electron pair content [n / M] may not be within the predetermined range described above.

  When the nitrogen-containing layer 3 is configured using a plurality of compounds, for example, based on the mixing ratio of the compounds, the molecular weight M of the mixed compound obtained by mixing these compounds is obtained, and [effective non- The total number n of [shared electron pairs] is obtained as an average value of the effective unshared electron pair content [n / M], and this value is preferably within the predetermined range described above. That is, the effective unshared electron pair content [n / M] of the nitrogen-containing layer 3 itself is preferably within a predetermined range.

  In addition, if the nitrogen-containing layer 3 is composed of a plurality of compounds and the composition ratio (content ratio) of the compounds is different in the thickness direction, the nitrogen on the side in contact with the electrode layer 5 The effective unshared electron pair content [n / M] in the surface layer of the containing layer 3 may be in a predetermined range.

Specific examples (No. 1 to No. 48) of compounds satisfying an effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ or more as compounds constituting the nitrogen-containing layer 3 are shown below. Show. Table 1 below shows these compound Nos. 1-No. The molecular weight M of 48, the number n of [effective unshared electron pairs], and the effective unshared electron pair content [n / M] (contents from Table 1 to Table 3) are shown. The following compound No. In 33 copper phthalocyanines, unshared electron pairs that are not coordinated to copper among the unshared electron pairs of the nitrogen atom are counted as [effective unshared electron pairs].

  In Table 1, the corresponding general formulas in the case where these exemplary compounds also belong to the general formulas (1) to (8a) representing other compounds described below are shown.

Moreover, as a compound which comprises the nitrogen containing layer 3, in addition to the compound whose effective unshared electron pair content rate [n / M] is the predetermined range mentioned above, you may use another compound. As the other compound used for the nitrogen-containing layer 3, a compound containing a nitrogen atom is preferably used regardless of whether the effective unshared electron pair content [n / M] is in the predetermined range described above. Among them, a compound containing a nitrogen atom having [effective unshared electron pair] is particularly preferably used. Moreover, the compound which has a property required for every electronic device to which the transparent electrode 1 provided with this nitrogen-containing layer 3 is applied is used for the other compound used for the nitrogen-containing layer 3.
For example, a compound having a structure represented by general formulas (1) to (8a) described below may be used for the transparent electrode 1 as a compound constituting the nitrogen-containing layer 3.

  Among the compounds having the structures represented by the general formulas (1) to (8a), there are also compounds that fall within the range of the effective unshared electron pair content [n / M]. For example, it can be used alone as a compound constituting the nitrogen-containing layer 3 (see Table 1 above). On the other hand, if the compound having the structure represented by the following general formulas (1) to (8a) is a compound that does not fall within the range of the effective unshared electron pair content [n / M], the effective unshared electron pair content [N / M] can be used as a compound constituting the nitrogen-containing layer 3 by mixing with a compound in the range described above.

  X11 in the general formula (1) represents -N (R11)-or -O-. E101 to E108 in the general formula (1) each represent -C (R12) = or -N =. At least one of E101 to E108 is -N =. R11 and R12 each represent a hydrogen atom (H) or a substituent.

  Examples of this substituent include alkyl groups (eg, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl and pentadecyl groups. Etc.), cycloalkyl groups (eg, cyclopentyl and cyclohexyl groups), alkenyl groups (eg, vinyl and allyl groups), alkynyl groups (eg, ethynyl and propargyl groups), aromatic hydrocarbon groups (aromatic 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 and biphenylyl groups), aromatic hetero Groups (e.g. furyl, thienyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, thiazolyl, quinazolinyl, carbazolyl, carbolinyl, diazacarbazolyl ( Any carbon atom constituting the carboline ring of the carbolinyl group is substituted with a nitrogen atom) and phthalazinyl group), a heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.) An alkoxy group (for example, a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group and a dodecyloxy group), a cycloalkoxy group (for example, a cyclopentyloxy group and a cyclohexyloxy group), Aryl Xy group (for example, phenoxy group and naphthyloxy group), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (for example, cyclopentylthio group) Group and cyclohexylthio group), arylthio group (for example, phenylthio group and naphthylthio group), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group and dodecyloxycarbonyl group) Group), aryloxycarbonyl group (for example, phenyloxycarbonyl group and naphthyloxycarbonyl group), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfur group) Phonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group and 2-pyridylaminosulfonyl group) An acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group and pyridylcarbonyl group) Etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group) Dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexyl) Carbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, Pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dode Ruaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group and 2-pyridylaminocarbonyl group), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group) Group, phenylureido group, naphthylureido group and 2-pyridylaminoureido group), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group) Group, naphthylsulfinyl group and 2-pyridylsulfinyl group), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, buty Sulfonylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group ( For example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, piperidyl group (also called piperidinyl group) ), 2,2,6,6-tetramethylpiperidinyl group, etc.], halogen atoms (for example, fluorine atom, chlorine atom and bromine atom), fluorinated hydrocarbon groups (for example, fluoromethyl group, trifluoromethyl) Group, pentaful Roethyl group and pentafluorophenyl group), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group and phenyldiethylsilyl group), phosphate ester Examples thereof include a group (for example, dihexyl phosphoryl group), a phosphite group (for example, diphenylphosphinyl group) and a phosphono group.

  Some of these substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring. As these substituents, those which do not inhibit the interaction between the compound and any one metal element selected from copper, gold and platinum are preferably used, and further, nitrogen having an effective unshared electron pair is used. What has is applied especially preferably. In addition, the description regarding the above substituent applies similarly to the substituent shown in description of general formula (2)-(8a) demonstrated below.

  The compound having the structure represented by the general formula (1) as described above is between nitrogen in the compound and any one metal element selected from copper, gold and platinum constituting the electrode layer 5. Since strong interaction can be expressed, it is preferable.

  The compound having the structure represented by the general formula (1a) is one form of the compound having the structure represented by the general formula (1), and X11 in the general formula (1) is -N (R11)-. A compound. Such a compound is preferable because the above interaction can be expressed more strongly.

  The compound having the structure represented by the general formula (1a-1) is one form of the compound having the structure represented by the general formula (1a), and a compound in which E104 in the general formula (1a) is -N = It is. Such a compound is preferable because the above interaction can be expressed more effectively.

  The compound having the structure represented by the general formula (1a-2) is another embodiment of the compound having the structure represented by the general formula (1a), and E103 and E106 in the general formula (1a) are represented by —N This is a compound marked with =. Such a compound is preferable because the number of nitrogen atoms is large and the above interaction can be expressed more strongly.

  The compound having the structure represented by the general formula (1b) is another embodiment of the compound having the structure represented by the general formula (1), and X11 in the general formula (1) is represented by -O-. -N = is a compound. Such a compound is preferable because the above interaction can be expressed more effectively.

  Furthermore, a compound having a structure represented by the following general formulas (2) to (8a) is preferable because the above interaction can be expressed more effectively.

  The general formula (2) is also an embodiment of the general formula (1). In the general formula (2), Y21 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof. E201 to E216 and E221 to E238 each represent -C (R21) = or -N =. R21 represents a hydrogen atom (H) or a substituent. However, at least one of E221 to E229 and at least one of E230 to E238 represents -N =. k21 and k22 represent an integer of 0 to 4, but k21 + k22 is an integer of 2 or more.

  In the general formula (2), examples of the arylene group represented by Y21 include o-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group, and biphenyldiyl. Groups (for example, [1,1'-biphenyl] -4,4'-diyl group, 3,3'-biphenyldiyl group and 3,6-biphenyldiyl group), terphenyldiyl group, quaterphenyldiyl group And kinkphenyldiyl group, sexiphenyldiyl group, septiphenyldiyl group, octiphenyldiyl group, nobiphenyldiyl group, and deciphenyldiyl group.

  In the general formula (2), examples of the heteroarylene group represented by Y21 include a carbazole ring, a carboline ring, and a diazacarbazole ring (also referred to as a monoazacarboline ring, in which one of carbon atoms constituting the carboline ring is nitrogen. A ring structure with atoms replaced), derived from the group consisting of triazole ring, pyrrole ring, pyridine ring, pyrazine ring, quinoxaline ring, thiophene ring, oxadiazole ring, dibenzofuran ring, dibenzothiophene ring and indole ring And the like.

  As a preferred embodiment of the divalent linking group consisting of an arylene group, heteroarylene group or a combination thereof represented by Y21, among the heteroarylene groups, a condensed aromatic heterocycle formed by condensation of three or more rings. A group derived from a condensed aromatic heterocyclic ring formed by condensing three or more rings is preferably included, and a group derived from a dibenzofuran ring or a dibenzothiophene ring is preferable. Are preferred.

  In the general formula (2), it is preferable that six or more of E201 to E208 and six or more of E209 to E216 are each represented by -C (R21) =.

  In the general formula (2), it is preferable that at least one of E225 to E229 and at least one of E234 to E238 represent -N =.

  Furthermore, in General formula (2), it is preferable that any one of E225-E229 and any one of E234-E238 represent -N =.

  Moreover, in General formula (2), it is mentioned as a preferable aspect that E221-E224 and E230-E233 are each represented by -C (R21) =.

  Further, in the compound represented by the general formula (2), it is preferable that E203 is represented by -C (R21) = and R21 represents a linking site, and E211 is also represented by -C (R21) =. And R21 preferably represents a linking site.

  Further, E225 and E234 are preferably represented by -N =, and E221 to E224 and E230 to E233 are each preferably represented by -C (R21) =.

  The general formula (3) is also an embodiment of the general formula (1a-2). In the general formula (3), E301 to E312 each represent —C (R31) ═, and R31 represents a hydrogen atom (H) or a substituent. Y31 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof.

  Moreover, in General formula (3), as a preferable aspect of the bivalent coupling group which consists of an arylene group represented by Y31, heteroarylene group, or those combinations, the thing similar to Y21 of General formula (2) is mentioned. .

  The general formula (4) is also an embodiment of the general formula (1a-1). In the general formula (4), E401 to E414 each represent —C (R41) ═, and R41 represents a hydrogen atom (H) or a substituent. Ar41 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring. Furthermore, k41 represents an integer of 3 or more.

  In the general formula (4), when Ar41 represents an aromatic hydrocarbon ring, the aromatic hydrocarbon ring includes benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene Ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen And a ring, a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring. These rings may further have the substituents exemplified as R11 and R12 in the general formula (1).

  In the general formula (4), when Ar41 represents an aromatic heterocycle, the aromatic heterocycle includes a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, 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 an azacarbazole ring. The azacarbazole ring refers to one in which at least one carbon atom of the benzene ring constituting the carbazole ring is replaced with a nitrogen atom. These rings may further have the substituents exemplified as R11 and R12 in the general formula (1).

  In the general formula (5), R51 represents a substituent. E501, E502, E511 to E515, and E521 to E525 each represent -C (R52) = or -N =. E503 to E505 each represent -C (R52) =. R52 represents a hydrogen atom (H) or a substituent. At least one of E501 and E502 is -N =, at least one of E511 to E515 is -N =, and at least one of E521 to E525 is -N =.

  In the general formula (6), E601 to E612 each represent —C (R61) ═ or —N═, and R61 represents a hydrogen atom (H) or a substituent. Ar61 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring.

  In the general formula (6), examples of the substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocycle represented by Ar61 include those similar to Ar41 in the general formula (4).

  In the general formula (7), R71 to R73 each represents a hydrogen atom (H) or a substituent, and Ar71 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

  In the general formula (7), the aromatic hydrocarbon ring or aromatic heterocyclic ring represented by Ar71 may be the same as Ar41 in the general formula (4).

  The general formula (8) is also a form of the general formula (7). In the general formula (8), R81 to R86 each represent a hydrogen atom (H) or a substituent. E801 to E803 each represent —C (R87) ═ or —N═, and R87 represents a hydrogen atom (H) or a substituent. Ar81 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

  In the general formula (8), the aromatic hydrocarbon ring or aromatic heterocyclic ring represented by Ar81 may be the same as Ar41 in the general formula (4).

  The compound having the structure represented by the general formula (8a) is one form of the compound having the structure represented by the general formula (8), and Ar81 in the general formula (8) is a carbazole derivative. In the general formula (8a), E804 to E811 each represent —C (R88) ═ or —N═, and R88 represents a hydrogen atom (H) or a substituent. At least one of E808 to E811 is -N =, and E804 to E807 and E808 to E811 may be bonded to each other to form a new ring.

In addition to the compounds represented by the general formulas (1) to (8a) as described above, examples of the other compounds constituting the nitrogen-containing layer 3 include compounds 1 to 166 shown below as specific examples. These compounds are compounds containing nitrogen atoms that interact with atoms of any one metal selected from copper, gold, and platinum constituting the electrode layer 5.
In addition, in these compounds 1-166, the compound applicable to the range of effective unshared electron pair content [n / M] is also contained, and if it is such a compound, the nitrogen-containing layer 3 will be comprised independently. It can be used as a compound. Furthermore, among these compounds 1-166, there are compounds that fall under the general formulas (1)-(8a) described above.

[Examples of compound synthesis]
Specific examples of the synthesis of compound 5 are shown below as typical synthesis examples of the compound, but are not limited thereto.

Step 1: (Synthesis of Intermediate 1)
Under a nitrogen atmosphere, 2,8-dibromodibenzofuran (1.0 mol), carbazole (2.0 mol), copper powder (3.0 mol) and potassium carbonate (1.5 mol) were added to DMAc (dimethylacetamide) 300 ml. Mixed in and stirred at 130 ° C. for 24 hours. The reaction solution thus obtained was cooled to room temperature, 1 L of toluene was added, washed with distilled water three times, the solvent was distilled off from the washed product under a reduced pressure atmosphere, and the residue was subjected to silica gel flash chromatography (n-heptane: Purification was performed using toluene = 4: 1 to 3: 1), and Intermediate 1 was obtained with a yield of 85%.

Step 2: (Synthesis of Intermediate 2)
Intermediate 1 (0.5 mol) was dissolved in 100 ml of DMF (dimethylformamide) at room temperature under air, NBS (N-bromosuccinimide) (2.0 mol) was added, and the mixture was stirred overnight at room temperature. The resulting precipitate was filtered and washed with methanol, yielding intermediate 2 in 92% yield.

Step 3: (Synthesis of Compound 5)
Under a nitrogen atmosphere, intermediate 2 (0.25 mol), 2-phenylpyridine (1.0 mol), ruthenium complex [(η ⁶ -C ₆ H ₆ ) RuCl ₂ ] ₂ (0.05 mol), triphenyl Phosphine (0.2 mol) and potassium carbonate (12 mol) were mixed in 3 L of NMP (N-methyl-2-pyrrolidone) and stirred at 140 ° C. overnight.

After cooling the reaction solution to room temperature, 5 L of dichloromethane was added, and the reaction solution was filtered. Next, the solvent was distilled off from the filtrate under reduced pressure (800 Pa and 80 ° C.), and the residue was purified by silica gel flash chromatography (CH ₂ Cl ₂ : Et ₃ N = 20: 1 to 10: 1).

  After distilling off the solvent from the purified product under reduced pressure, the residue was dissolved again in dichloromethane and washed three times with water. The material obtained by washing was dried over anhydrous magnesium sulfate, and the solvent was distilled off from the dried material in a reduced-pressure atmosphere to obtain Compound 5 in a yield of 68%.

[Method for depositing nitrogen-containing layer 3]
When the nitrogen-containing layer 3 as described above is formed on the substrate 11, the film forming method includes a method using a wet process such as a coating method, an inkjet method, a coating method, and a dip method, Examples include a method using a dry process such as a vapor deposition method (resistance heating and EB method), a sputtering method, and a CVD method. Of these, the vapor deposition method is preferably applied.

  In particular, in the case of forming the nitrogen-containing layer 3 using a plurality of compounds, co-evaporation in which a plurality of compounds are simultaneously supplied from a plurality of evaporation sources is applied. If a polymer material is used as the compound, a coating method is preferably applied. In this case, a coating solution in which the compound is dissolved in a solvent is used. The solvent in which the compound is dissolved is not limited. Furthermore, if the nitrogen-containing layer 3 is formed using a plurality of compounds, a coating solution may be prepared using a solvent capable of dissolving the plurality of compounds.

<Electrode layer 5>
The electrode layer 5 is a layer containing any one metal element selected from copper, gold and platinum as a main component and containing an additive element, and is a layer formed adjacent to the nitrogen-containing layer 3. As the additive element constituting the electrode layer 5, a metal element is particularly used among elements constituting a solid solution by uniformly dissolving with any one metal element selected from copper, gold and platinum. Such an additive element is at least one element different from the main element among silver, aluminum, gold, indium, copper, palladium, and platinum. The electrode layer 5 contains at least one of these elements.

  Further, the concentration of the above-described additive element in the electrode layer 5 is preferably in the range of 0.01 to 10.0 atomic%.

  In the electrode layer 5 as described above, an alloy layer containing any one metal element selected from copper, gold and platinum as a main component and containing an additive element is divided into a plurality of layers as needed. It may be a configuration. In addition, a plurality of types of additive elements may be added to each layer of the single electrode layer 5 or the electrode layer 5 composed of a plurality of layers.

  Furthermore, the electrode layer 5 preferably has a thickness in the range of 4 to 12 nm. A thickness of 12 nm or less is preferable because the absorption component or reflection component of the layer can be kept low and the light transmittance of the electrode layer 5 can be maintained. Further, when the thickness is 4 nm or more, the conductivity of the layer is also ensured.

  As the film formation method of the electrode layer 5 as described above, a method using a wet process such as a coating method, an ink jet method, a coating method and a dip method, a vapor deposition method (resistance heating and EB method, etc.), a sputtering method and a CVD method are used. And a method using a dry process such as

  For example, in the case of forming the electrode layer 5 to which the sputtering method is applied, a sputtering target in which the concentration of the additive element is adjusted in advance with respect to any one metal element selected from copper, gold, and platinum as the main material. Prepare and perform sputter deposition using this sputter gate.

  In particular, when aluminum, gold, or indium is used as the additive element, the electrode layer 5 is formed using an evaporation method. In this case, these additive elements and any one metal element selected from copper, gold and platinum are co-evaporated. At this time, by selecting the deposition rate of the additive element and the deposition rate of any one metal element selected from copper, gold and platinum, respectively, the main material (main component) is selected from copper, gold and platinum. Vapor deposition is performed by adjusting the additive concentration of the additive element with respect to any one of the metal elements.

  The electrode layer 5 is formed on the nitrogen-containing layer 3 so that it has sufficient conductivity even without high-temperature annealing after the film formation. It may be one that has been subjected to high-temperature annealing after film formation.

  Note that the transparent electrode 1 having a laminated structure including the nitrogen-containing layer 3 and the electrode layer 5 provided adjacent thereto as described above is different even if the upper part of the electrode layer 5 is covered with a protective film. The conductive layer may be laminated. In this case, it is preferable that the protective film and the conductive layer have 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 layer as needed also in the lower part of the nitrogen containing layer 3, ie, between the nitrogen containing layer 3 and the base material 11. FIG.

<Effect of transparent electrode 1>
The transparent electrode 1 configured as described above mainly contains any one metal element selected from copper, gold, and platinum adjacent to the nitrogen-containing layer 3 configured using a compound containing nitrogen atoms. The electrode layer 5 as a component is provided. Thereby, when the electrode layer 5 is formed adjacent to the nitrogen-containing layer 3, any one kind of metal atoms selected from copper, gold, and platinum constituting the electrode layer 5 causes the nitrogen-containing layer 3 to be formed. It interacts with the compound containing nitrogen atoms, and the diffusion distance on the surface of the nitrogen-containing layer 3 of any one metal atom selected from copper, gold and platinum is reduced, and selected from copper, gold and platinum. Aggregation of any one of the metal elements is suppressed. Therefore, in general, a thin film of any one metal element selected from copper, gold, and platinum, which is easily isolated in an island shape by film growth of a nuclear growth type (Volume-Weber: VW type), is a single layer. The film is formed by growth-type (Frank-van der Merwe: FM type) film growth. Therefore, the electrode layer 5 having a uniform thickness can be obtained even though the layer thickness is thin.

In particular, the effective unshared electron pair content [n / M] is used as an index of the bond stability of any one metal element selected from copper, gold and platinum constituting the electrode layer 5 with respect to the nitrogen-containing layer 3. The nitrogen-containing layer 3 was configured using a compound having this value of 2.0 × 10 ⁻³ or more. This makes it possible to provide the nitrogen-containing layer 3 that can reliably obtain the effect of “suppressing aggregation of any one metal element selected from copper, gold, and platinum” as described above. This is because, as will be described later in detail, an electrode layer 5 capable of measuring a sheet resistance value is formed on such a nitrogen-containing layer 3 while being an extremely thin film of 6 nm. It was also confirmed from that.

  In particular, the electrode layer 5 containing as a main component any one metal element selected from copper, gold and platinum is a solid solution element for any one metal element selected from copper, gold and platinum. Of silver, aluminum, gold, indium, copper, palladium and platinum, at least one element different from the main component is contained. Thereby, the electrode layer 5 is composed of a solid solution in which any one metal element selected from copper, gold, and platinum and these additive elements are uniformly dissolved. Migration of any one metal element selected from gold and platinum is suppressed. For this reason, deterioration of the film quality due to migration of any one metal element selected from copper, gold and platinum in the electrode layer 5 is prevented. In addition to this, by adding these solid solution elements to any one metal element selected from copper, gold and platinum to form the electrode layer 5, oxidation and sulfurization of the electrode layer 5 can be prevented. .

  Therefore, in this transparent electrode 1, while ensuring light transmittance by being a thin layer thickness, it is possible to reliably obtain the electrode layer 5 having ensured conductivity by being a uniform thickness, In addition, since the occurrence of migration is suppressed, such light transmission and conductivity can be maintained. As a result, it is possible to improve the reliability as well as improve the conductivity and light transmittance in the transparent electrode 1 using any one metal element selected from copper, gold and platinum. Become.

  Further, such a transparent electrode 1 is low in cost because it does not use indium (In), which is a rare metal, and has excellent long-term reliability because it does not use a chemically unstable material such as ZnO. It will be.

≪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 the electronic device include, for example, a touch panel, a liquid crystal display element, an organic electroluminescence element, an LED (light emitting diode), a solar cell, and the like. In these electronic devices, an electrode member that requires light transmission As described above, the transparent electrode 1 of the present invention can be used.

[Touch panel]
Hereinafter, as an example of an electronic device to which the transparent electrode of the present invention is applied, an example in which an electrode pattern by photolithography is formed on the transparent electrode of the present invention and then applied to a touch panel will be described.

(Patterning of transparent electrode)
On the transparent substrate 11 (hereinafter, also referred to as “transparent substrate 11”), the electrode layer 5 containing copper, gold, or platinum as a main component is adjacent to the nitrogen-containing layer 3 and the nitrogen-containing layer 3. The transparent electrode 1 of the present invention having the above can form an electrode pattern as shown in FIGS. 8 to 10, for example, by a photolithography method using, for example, an etching solution containing an organic solvent.

<Etching solution: Organic solvent>
In the present invention, the etching solution preferably contains at least an organic solvent, and the organic solvent is not particularly limited, but is preferably an organic solvent having solubility to the intermediate layer, more preferably. , Ether alcohol, ketone and ester.

  In the present invention, a solvent for each metal element may be used in combination with the above organic solvent for the purpose of more completely dissolving and removing the electrode layer composed of copper, gold, or platinum in the etching solution. it can.

<Manufacturing process>
Hereinafter, a method for forming an electrode pattern by photolithography will be described.

  The photolithographic method applied to the present invention includes resist coating such as curable resin, preheating, exposure, development (removal of uncured resin), rinsing, etching with an etchant containing an organic solvent, and resist stripping. The transparent electrode is processed into a desired pattern as shown in FIGS.

  In the present invention, a conventionally known general photolithography method can be appropriately used. For example, as the resist, either positive or negative resist can be used. In addition, after applying the resist, preheating or prebaking can be performed as necessary. At the time of exposure, a pattern mask having a desired pattern may be disposed, and light having a wavelength suitable for the resist used, generally ultraviolet rays, electron beams, or the like may be irradiated thereon. After the exposure, development is performed with a developer suitable for the resist used. After the development, the resist pattern is formed by stopping the development with a rinse solution such as water and washing. Next, the formed resist pattern is pretreated or post-baked as necessary, and then etched with an etching solution containing an organic solvent to dissolve the intermediate layer in the region not protected by the resist and to form the electrode layer. Perform removal. After etching, the remaining resist is removed to obtain a transparent electrode having an intended pattern. As described above, the photolithography method applied to the present invention is a method generally recognized by those skilled in the art, and the specific application mode is easily selected by those skilled in the art according to the intended purpose. be able to.

  Next, an electrode pattern forming method applicable to the present invention will be described with reference to the drawings.

  FIG. 7 is a process flow diagram showing an example of forming an electrode pattern on a transparent electrode by a photolithography method.

  As a first step, as shown in FIG. 7A, the nitrogen-containing layer 3 and the electrode layer 5 are laminated on the transparent substrate 11 to produce the unprocessed transparent electrode 1.

  Next, in a resist film forming step shown in FIG. 7B, a resist film 6 made of a photosensitive resin composition or the like is uniformly applied on the electrode layer 5. As the photosensitive resin composition, a negative photosensitive resin composition or a positive photosensitive resin composition can be used.

  As a coating method, it is applied on the electrode layer by a known method such as micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating and slit coating, and prebaked with a heating device such as a hot plate or oven. can do. The pre-baking can be performed, for example, using a hot plate or the like within a range of 50 to 150 ° C. for 30 seconds to 30 minutes.

Next, in the exposure step shown in FIG. 7C, using an exposure machine 8 such as a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner, through a mask 7 produced with a predetermined electrode pattern, The resist film 6A to be removed in the next step is irradiated with light of about 10 to 4000 J / m ² (wavelength 365 nm exposure conversion). The exposure light source is not limited, and ultraviolet rays and electron beams, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.

  Next, in the developing step shown in FIG. 7D, the exposed transparent electrode is immersed in a developing solution to dissolve the resist film 6A in the region irradiated with light.

  As a developing method, it is preferable to immerse in a developing solution for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include an aqueous solution containing one or more quaternary ammonium salts such as side and choline. After development, it is preferable to rinse with water, and then dry baking may be performed in the range of 50 ° C. to 150 ° C.

  Next, as shown in FIG. 7E, an etching process using the etching solution 9 described above is performed.

  Specifically, for example, the transparent electrode 1 is immersed in an etching solution containing an organic solvent such as ether alcohol, ketone, or ester, and the nitrogen-containing layer 3 in a region not protected by the resist film 6 is dissolved and intermediate. A predetermined electrode pattern is formed by simultaneously removing the thin film electrode layer held in the layer.

  Finally, as shown in FIG. 7F, the resist film 6 on the electrode layer 5 is removed by immersing in a resist film stripping solution, for example, N-300 manufactured by Nagase ChemteX Corporation.

<Configuration of touch panel>
Next, details of a representative embodiment will be described for the configuration of a touch panel to which the transparent electrode of the present invention can be applied.

[Embodiment 1: Configuration in which two transparent electrodes are provided on two transparent substrates]
FIG. 8 is a perspective view showing a schematic configuration of the touch panel 21 using the above-described transparent electrode of the present invention and having the configuration shown in FIG. 11 described later. FIG. 9 is a plan view of two transparent electrodes 1-1 and 1-2 showing the electrode configuration of the touch panel 21. FIG.

  The touch panel 21 shown in these drawings is a projected capacitive touch panel. The touch panel 21 includes a first transparent electrode 1-1 and a second transparent substrate 11 on one main surface of the two transparent substrates 11 (first transparent substrate 11-1 and second transparent substrate 11-2). Two transparent electrodes 1-2 are arranged in this order, and the upper part is covered with the front plate 13.

  Each of the first transparent electrode 1-1 and the second transparent electrode 1-2 is the transparent electrode 1 on which the electrode pattern for the touch panel described with reference to FIGS. 1 and 7 is formed. Accordingly, the first transparent electrode 1-1 has a configuration in which the first nitrogen-containing layer 3-1 and the first electrode layer 5-1 are laminated in this order. Similarly, the second transparent electrode 1-2 has a configuration in which a second nitrogen-containing layer 3-2 and a second electrode layer 5-2 are laminated in this order.

  Hereinafter, the detail of each main layer which comprises the touchscreen 21 is demonstrated in order from the 1st transparent base material 11-1 and the 2nd transparent base material 11-2 side. Here, description will be made using FIG. 8 and FIG. 9 together with a schematic plan view of the electrode part of FIG. 10 and a schematic cross-sectional view of FIG. Moreover, the same code | symbol is attached | subjected to the component similar to having demonstrated in FIG.1 and FIG.7, and the overlapping description is abbreviate | omitted.

(Transparent substrate 11)
The first transparent base material 11-1 and the second transparent base material 11-2 shown in FIGS. 8 to 10 are the base material 11 described in the previous transparent electrode 1.

(First nitrogen-containing layer 3-1 (first transparent electrode 1-1))
The first nitrogen-containing layer 3-1 is the nitrogen-containing layer 3 described in the previous transparent electrode 1, and is formed on the transparent substrate 11. Here, as an example, the first nitrogen-containing layer 3-1 is patterned in the same shape as the electrode layer 5-1 on the first transparent substrate 11-1.

(First electrode layer 5-1 (first transparent electrode 1-1))
The first electrode layer 5-1 is the electrode layer 5 described in the previous transparent electrode, and a plurality of x electrode patterns 5x1, 5x2, (omitted), etc. patterned on the first nitrogen-containing layer 3-1. It is configured as. Each of the x electrode patterns 5x1, 5x2, (omitted) and the like are arranged in parallel while being spaced apart from each other, with each extending in the x direction. Each of these x electrode patterns 5x1, 5x2, (omitted), etc., for example, has a shape in which rhombus pattern portions arranged in the x direction are linearly connected in the x direction near the apex of the rhombus. .

  Further, x wirings 17x are connected to the respective end portions of the respective x electrode patterns 5x1, 5x2, (omitted) and the like. These x wirings 17x are wired in the peripheral region on the first transparent base material 11-1, and are drawn out to the edge of the first transparent base material 11-1. Each such x wiring 17x is configured as a first electrode layer 5-1 whose main component is copper, gold, or platinum, similarly to the x electrode patterns 5x1, 5x2, (omitted) and the like. .

(Second Nitrogen-Containing Layer 3-2 (Second Transparent Electrode 1-2))
The second nitrogen-containing layer 3-2 is the nitrogen-containing layer 3 described in the previous transparent electrode 1, and is formed on the second transparent substrate 11-2, and the second electrode layer 5- 2 is patterned in the same shape as 2.

(Second electrode layer 5-2 (second transparent electrode 1-2))
The second electrode layer 5-2 is the electrode layer 5 described in the previous transparent electrode 1, and a plurality of y electrode patterns 5y1, 5y2 patterned on the second nitrogen-containing layer 3-2 (omitted). Etc. are configured. The y electrode patterns 5y1, 5y2, (omitted), etc. are arranged in parallel at intervals while being extended in the y direction perpendicular to the x electrode patterns 5x1, 5x2, (omitted), etc. Yes. Each of these y electrode patterns 5y1, 5y2, (omitted), etc., for example, has a shape in which rhombus pattern portions arranged in the y direction are linearly connected in the y direction in the vicinity of the apex of the rhombus.

  Here, as shown in FIG. 10, the rhombus pattern portions constituting the y electrode patterns 5 y 1, 5 y 2, (abbreviated), etc. are the rhombus pattern portions forming the x electrode patterns 5 x 1, 5 x 2, (abbreviated), etc. On the other hand, it is arranged at a position that does not overlap in plan view, and has a shape that occupies as large a range as possible without overlapping. Thereby, in the area | region of the center part of the 2nd transparent base material 11-2, x electrode pattern 5x1, 5x2, (Omitted) etc. comprised by the 1st electrode layer 5-1, and 2nd electrode layer 5 -Y electrode patterns 5y1, 5y2, (omitted), etc. constituted by -2 are difficult to be visually recognized.

The y electrode patterns 5y1, 5y2, (omitted), etc. are stacked with the x electrode patterns 5x1, 5x2, (omitted), etc. only at the connecting portions of the rhombus electrode patterns. In these laminated portions, the second base material 11-2 and the second nitrogen-containing layer 3-2 are sandwiched, whereby the x electrode patterns 5x1, 5x2, (omitted) and the y electrode patterns 5y1, 5y2, (Omitted) etc. are in a state of ensuring insulation.
Further, the laminated first base material 11-1 and second base material 11-2 are bonded together by an adhesive which is not shown here, and even with this adhesive, The first electrode layer 5-1 and the second electrode layer 5-2 are insulated.

  In addition, each of the y electrode patterns 5y1, 5y2, (omitted) and the like is connected to a y wiring 17y at each end. These y wirings 17y are wired in the peripheral region on the second transparent base material 11-2, and are drawn out to the edge of the second transparent base material 11-2 so as to be aligned with the x wiring 17x. Each of the y wirings 17y is configured as a second electrode layer 5-2 mainly composed of copper, gold, or platinum, similarly to the y electrode patterns 5y1, 5y2, (omitted) and the like. .

  Note that a flexible print base material or the like is connected to the x wiring 17x and the y wiring 17y drawn to the edge of the second transparent base material 11-2.

(Front plate 13)
The front plate 13 illustrated in FIGS. 8 and 11 is a plate material on which a portion corresponding to the input position on the touch panel 21 is pressed. Such a front plate 13 is a plate material having optical transparency, and the same material as the transparent substrate 11 is used. Further, the front plate 13 may be used by selecting a material having optical characteristics as required. Such a front plate 13 is attached to the second transparent electrode 1-2 side by, for example, an adhesive 15 (see FIG. 11). The material of the adhesive 15 is not particularly limited as long as it has optical transparency.

  The front plate 13 is provided with a light-shielding film that covers the peripheral edges of the first transparent substrate 11-1 and the second transparent substrate 11-2, and is drawn out from the x electrode patterns 5x1, 5x2, (omitted), and the like. The y wiring 17y drawn out from the x wiring 17x and the y electrode patterns 5y1, 5y2, (omitted) and the like is prevented from being viewed from the front plate 13 side.

(Touch panel operation)
When the touch panel 21 as described above is operated, the x electrode patterns 5x1, 5x2, (omitted), etc. and the y electrode patterns 5y1, 5y2, (omitted) are selected from a flexible printed substrate connected to the x wire 17x and the y wire 17y. ) Or the like. In this state, when a finger or a touch pen touches the surface of the front plate 13, the capacitance of each part existing in the touch panel 21 changes, and the x electrode patterns 5x1, 5x2, (omitted), etc. and the y electrode patterns 5y1, 5y2, ( It appears as a change in voltage. This change differs depending on the distance from the position touched by the finger or touch pen, and is greatest at the position touched by the finger or touch pen. Therefore, the position addressed by the x electrode pattern 5x1, 5x2, (omitted), etc. and the y electrode pattern 5y1, 5y2, (omitted), etc. where the voltage change is maximum is detected as the position touched by the finger or the touch pen. Is done.

(Effect of touch panel 21)
The touch panel 21 as described above uses, as the two-layer transparent electrodes 1-1 and 1-2, a transparent electrode having sufficient conductivity as well as the light transmittance described above. Thereby, the voltage drop at the time of enlarging the transparent electrode for touchscreens can be suppressed, maintaining the visibility of the display image of a foundation | substrate, and the touchscreen 21 can be enlarged.

  In particular, the touch panel 21 is a projection capacitive type having x electrode patterns 5x1, 5x2, (omitted), and the like, and electrode patterns 5y1, 5y2, (omitted), etc. arranged orthogonally thereto. Therefore, high conductivity is required for the x electrode patterns 5x1, 5x2, (omitted), etc., and the y electrode patterns 5y1, 5y2, (omitted), etc. However, since these x electrode patterns 5x1, 5x2, (omitted), etc. and y electrode patterns 5y1, 5y2, (omitted), etc. are the electrode layers 5 of the transparent electrode for touch panel described above, the conductivity is maintained. However, it is possible to reduce the thickness. Therefore, the x electrode patterns 5x1, 5x2, (omitted), etc. and the y electrode patterns 5y1, 5y2, (omitted), etc. are not easily recognized, and the visibility of the underlying display image via the touch panel 21 is degraded. Can also be prevented.

[Embodiment 2: Configuration in which two transparent electrodes are provided on a transparent substrate]
FIG. 12 is a schematic cross-sectional view for explaining another example of the touch panel of the embodiment. The touch panel 21 a illustrated in FIG. 12 includes a first transparent electrode 1-1 and a second transparent electrode on the transparent substrate 11. This is a configuration in which the electrode 1-2 is provided, and other configurations are the same as those in the first embodiment. For this reason, the same code | symbol is attached | subjected to the structure similar to the touch panel 21 of previous embodiment, and the overlapping description is abbreviate | omitted.

[Application to liquid crystal display devices]
Next, an example in which the transparent electrode of the present invention is incorporated in a liquid crystal display device as an electronic device will be described.

  FIG. 13 is a schematic cross-sectional view showing an example of the configuration of a liquid crystal display device provided with the transparent electrode of the present invention. The liquid crystal display device is an example, and the present invention is not limited to this.

  The liquid crystal display device is generally referred to as a liquid crystal display or a liquid crystal panel. Depending on the liquid crystal driving method, liquid crystal display devices of various driving methods such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, and OCB are listed. It is done. Usually, a VA (MVA, PVA) type liquid crystal display device is preferably used as a liquid crystal display such as a TV or a liquid crystal panel.

  A liquid crystal display device 100 shown in FIG. 13 includes a polarizing filter 101A that controls light entering and exiting from the backlight side, a glass substrate 102A that prevents electricity from leaking to other regions from the electrode portion, and a liquid crystal display. The transparent electrode 1A of the present invention, the alignment film 104A for aligning liquid crystal molecules in a certain direction, the liquid crystal 105, the spacer 106, the other alignment film 104B, the other transparent electrode 1B, and RGB are filtered to display the color. Color filter 103, the other glass substrate 102B, and the other polarizing filter 101B. The transparent electrodes 1A and 1B of the present invention have both sufficient conductivity and light transmittance, and have a low sheet resistance value. Excellent durability (heat resistance and oxygen resistance).

≪Preparation of transparent electrode≫
As shown in the following Tables 2 and 3, the transparent electrodes of Samples 101 to 148 were fabricated so that the area of the conductive region was 5 cm × 5 cm.

<Procedure for producing transparent electrodes of samples 101 and 102>
As described below, an electrode layer made of copper was formed as a transparent electrode on a glass substrate with the thicknesses shown in Tables 2 and 3 below.

First, a transparent non-alkali glass base material was fixed to a base material holder of a commercially available vacuum vapor deposition apparatus and attached in a vacuum chamber of the vacuum vapor deposition apparatus. Moreover, copper was put into the resistance heating boat made from tungsten, and it attached in the said 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 the electrode layers made of copper are formed at respective thicknesses at a deposition rate of 0.1 to 0.2 nm / second. Formed. In Sample 101, an electrode layer was formed with a thickness of 6 nm, and in Sample 102, an electrode layer was formed with a thickness of 15 nm.

<Procedure for Producing Transparent Electrode of Sample 103>
An electrode layer in which aluminum was added to copper was formed as a transparent electrode as follows (see Table 2).

First, a transparent alkali-free glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus. Moreover, copper and aluminum were put in each resistance heating boat made of tungsten, and these substrate holders and each resistance heating boat were mounted in a vacuum chamber of a vacuum deposition apparatus. Next, after depressurizing the inside of the vacuum chamber to 4 × 10 ⁻⁴ Pa, aluminum was added to copper at a concentration of 20.0 atomic% by co-evaporation with the deposition rate adjusted by adjusting the current to each resistance heating boat. The alloyed electrode layer was formed with a thickness of 6 nm.

<Procedure for Producing Transparent Electrode of Sample 104>
In the following manner, an electrode layer having a laminated structure of aluminum and copper was formed as a transparent electrode (see Table 2).

First, a transparent alkali-free glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus. Moreover, copper and aluminum were put in each resistance heating boat made of tungsten, and these substrate holders and the heating boat were mounted in a vacuum chamber of a vacuum deposition apparatus. Next, after depressurizing the inside of the vacuum chamber to 4 × 10 ⁻⁴ Pa, first, a resistance heating boat containing aluminum was energized and heated, and the deposition rate was 0.1 to 0.2 nm / sec. It was formed with a thickness of 1 nm. Subsequently, the resistance heating boat containing copper was energized and heated to form a two-layer electrode layer by forming copper with a deposition thickness of 0.1 to 0.2 nm / second and a layer thickness of 6 nm.

<Procedure for producing transparent electrodes of samples 105 to 113>
A transparent electrode having a two-layer structure of a nitrogen-containing layer using each material shown in Table 2 below and an electrode layer made of copper was formed on a glass substrate as follows. In Sample 105, a base layer not containing nitrogen was formed instead of the nitrogen-containing layer.

  First, a transparent alkali-free glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus. Moreover, in preparation of each transparent electrode, each compound shown in following Table 2 was put into the resistance heating boat made from a tantalum. These substrate holders and resistance heating boats were attached to the first vacuum chamber of the vacuum deposition apparatus. Moreover, copper was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.

Of the compounds used here, Compound No. 1x-No. 5x is shown below, and circles are given to nitrogen atoms having [effective unshared electron pairs]. Of these, Compound No. 1x is anthracene which does not contain a nitrogen atom. 2x-No. 5x contains nitrogen but has an effective unshared electron pair content [n / M] of less than 2.0 × 10 ⁻³ .

In addition, Compound No. 1-No. 48 is a compound having an effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ or more appropriately selected from the compounds shown in Table 1 above. Table 2 below also shows the number of effective unshared electron pairs [n], molecular weight [M], and effective unshared electron pair content [n / M] of the compounds used here.

Next, after reducing the pressure in the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing each compound was energized and heated, and the thickness was deposited on the substrate at a deposition rate of 0.1 to 0.2 nm / second. A nitrogen-containing layer (underlayer in the sample 105) composed of each compound having a thickness of 25 nm was provided.

Next, the base material formed up to the nitrogen-containing layer (underlying layer) was transferred to the second vacuum chamber while being vacuumed, and the pressure in the second vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, followed by heating with copper The boat was energized and heated. As a result, an electrode layer made of copper having a thickness of 6 nm was formed at a deposition rate of 0.1 to 0.2 nm / second, and a sample 105 to a laminated structure of a nitrogen-containing layer (underlayer) and the upper electrode layer was formed. 113 transparent electrodes were obtained.

<Procedure for Producing Transparent Electrodes of Samples 114 to 117>
Referring to Table 2 below, compound No. 1 was formed on a glass substrate as follows. A transparent electrode having a two-layer structure including a nitrogen-containing layer using No. 1 and an electrode layer in which aluminum was added as an additive element to copper at each concentration was formed. In addition, Compound No. 1 is an exemplary compound shown in the previous embodiment as having an effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ or more. Table 2 below also shows the number of effective unshared electron pairs [n], molecular weight [M], and effective unshared electron pair content [n / M] of the compounds used here.

  First, a transparent alkali-free glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus. In the production of each transparent electrode, the compound No. 1 was placed in a resistance heating boat made of tantalum. These substrate holders and a heating boat were mounted in the first vacuum chamber of the vacuum deposition apparatus. Further, copper and aluminum were put in each resistance heating boat made of tungsten, and the substrate holder and the heating boat were mounted in the second vacuum chamber of the vacuum evaporation apparatus.

Next, after reducing the pressure in the first vacuum chamber to 4 × 10 ⁻⁴ Pa, Compound No. The heating boat containing 1 was energized and heated, and a compound No. 25 having a thickness of 25 nm was formed on the substrate at a deposition rate of 0.1 to 0.2 nm / second. A nitrogen-containing layer consisting of 1 was formed.

Next, the base material formed up to the nitrogen-containing layer is transferred into the second vacuum chamber while being vacuumed, the pressure inside the second vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, and then the current is adjusted to each resistance heating boat. An electrode layer made of a solid solution in which aluminum was added to copper at each additive element concentration [atomic%] shown in Table 2 was formed to a thickness of 6 nm by co-evaporation with the deposition rate adjusted. Thereby, Compound No. Samples 114 to 117 were obtained in which a nitrogen-containing layer using No. 1 and an electrode layer in which aluminum was added as an additive element to copper at each concentration were laminated in this order.

<Procedure for Producing Transparent Electrodes of Samples 118 to 142>
The transparent electrodes of Samples 118 to 142 were obtained in the same procedure as Samples 114 to 117. However, the compounds constituting the nitrogen-containing layer and the elements that are the main materials of the electrode layer were those listed in Table 2 and Table 3 below. Moreover, aluminum was added to each electrode layer as an additive element at a concentration of 5.0 atomic%.

<Procedure for Producing Transparent Electrodes of Samples 143 and 144>
Each transparent electrode of Samples 143 and 144 was obtained in the same procedure as Samples 114-117. However, the compounds constituting the nitrogen-containing layer are the compounds shown in Table 3 below. In addition, the thickness of the electrode layer containing copper as a main component was 8 nm, and aluminum was added as an additive element at a concentration of 5.0 atomic%.

<Procedure for Producing Transparent Electrodes of Samples 145 and 146>
Each transparent electrode of Samples 145 and 146 was obtained in the same procedure as Samples 114-117. However, the compound which comprises polyethylene terephthalate (PET) as a base material and constitutes the nitrogen-containing layer is a compound shown in Table 3 below. In addition, the thickness of the electrode layer containing copper as a main component was 8 nm, and aluminum was added as an additive element at a concentration of 5.0 atomic%.

<Procedure for Producing Transparent Electrodes of Samples 147 and 148>
Each transparent electrode of Samples 147 and 148 is the same procedure as Samples 114 to 117 except that a nitrogen-containing layer using each material shown in Table 3 below is formed on a substrate made of PET by coating. Got. Compound No. used here 7 and no. 14 is an exemplary compound shown in the previous embodiment. The coating formation of the nitrogen-containing layer was performed as follows.

  Each compound was dissolved in a solvent of toluene: TFP (trifluoroethyl phosphate) = 1: 1 heated to 80 ° C. to prepare a coating solution. This coating solution was spin-coated on a PET substrate. At this time, coating was performed at a rotational speed of 1500 rpm for 30 seconds. Then, the coating liquid was dried by performing a heat treatment at 120 ° C. for 30 minutes to form a nitrogen-containing layer having a thickness of 25 nm.

  After the above, an electrode layer in which aluminum is added as an additive element to copper at a concentration of 5.0 atomic% is formed on the nitrogen-containing layer with a thickness of 8 nm, and the nitrogen-containing layer and the upper electrode layer are stacked. Samples 147 and 148 having transparent structures were obtained.

<Evaluation of each sample of Example 1>
About each transparent electrode of the samples 101-148 produced above, (1) Light transmittance with respect to light with a wavelength of 550 nm, (2) Sheet resistance value, (3) High temperature and high humidity storage property, and (4) Electrode life It was measured.

(1) The light transmittance was measured using a spectrophotometer (U-3300, manufactured by Hitachi High-Technologies Corporation), using the same substrate as the sample as the baseline.
(2) The sheet resistance value was measured using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) by a 4-terminal 4-probe method constant current application method.
(3) In the measurement of high temperature and high humidity storage stability, the sheet resistance value after each transparent electrode of Samples 101 to 148 was stored for 300 hours under a high temperature and high humidity environment (temperature 60 ° C. and humidity 90%) was measured. . And the increase rate (%) of the sheet resistance value after the preservation | save with respect to the sheet resistance value before a preservation | save was computed as high temperature and high humidity preservation property. The smaller the value obtained, the better the result. (4) The electrode life was evaluated by measuring the time required for the sheet resistance value of each sample (transparent electrode) to be double that before immersion under immersion in an acetate buffer solution at a temperature of 25 ° C. and pH 5. The electrode life is shown as a relative value where the electrode life of the sample 118 is 100.
The results of (1) to (4) are shown in Tables 2 and 3 below.

<Evaluation result of Example 1>
As is clear from Tables 2 and 3, each of the transparent electrodes of Samples 114 to 117 and Samples 119 to 148, that is, Compound No. having an effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ or more. . A nitrogen-containing layer composed of 1 and an electrode layer in which any one metal element selected from copper, gold and platinum is used as a main component and aluminum as a solid solution element is added to the adjacent layer. The provided transparent electrode has a sheet resistance value although the electrode layer using any one metal element selected from copper, gold, and platinum, which bears substantial conductivity, is an extremely thin layer of 6 nm or 8 nm. It was confirmed that the film was formed with a substantially uniform thickness by single-layer growth type (Frank-van der Merwe: FM type) film growth. Moreover, it was confirmed that the transparent electrodes of these samples 114 to 117 and samples 119 to 148 have a light transmittance of 50% or more and can be used as transparent electrodes.

  In addition, the transparent electrodes of Samples 114 to 117 and Samples 119 to 148 have a high temperature and high humidity storage stability value of about 100%, and are confirmed to be excellent in high temperature and high humidity resistance.

  The above results were the same whether the substrate was glass or plastic material (PET). Further, the transparent electrodes of these samples 114 to 117 and samples 119 to 148 have a light transmittance of 50% or more regardless of whether the electrode layer is 6 nm or 8 nm, and the electrode layer has a thickness from 6 nm to 8 nm. It was also confirmed that the sheet resistance value was reduced by increasing the film thickness, and it was confirmed that both the improvement of light transmittance and the improvement of conductivity were achieved. Note that the sample 102 having no base layer such as a nitrogen-containing layer has a relatively thin electrode layer thickness of 15 nm, and thus has a low sheet transmittance but a low light transmittance and cannot be used as a transparent electrode. It was.

  Further, each of the transparent electrodes of Samples 114 to 116, that is, each of the Samples 114 to 117 and Samples 119 to 148 in which only the concentration of the additive element in the electrode layer was changed within the range of 0.01 to 10.0 atomic%. The transparent electrode was confirmed to have high light transmittance, low sheet resistance (250Ω / □ or less), and good high-temperature and high-humidity storage stability.

The transparent electrode of the sample 141 is No. A nitrogen-containing layer was formed using a compound having 47 nitro groups, and it was confirmed that good results were obtained in light transmittance, sheet resistance, and high temperature / high humidity storage stability. Therefore, the lone pair of nitro group (—NO ₂ ) is a lone pair that is used for the resonance structure, but does not participate in aromaticity and is not coordinated to the metal. As a shared electron pair], it was confirmed that it was effective in bonding with copper.

In addition, in FIG. 14, the effective unshared electron pair content [n / M] is in the range of 2.0 × 10 ^{−3 to} 1.9 × 10 ⁻² . 1-No. For the transparent electrode in which an electrode layer made of copper having a thickness of 6 nm is provided on the top of the nitrogen-containing layer using No. 20, the effective unshared electron pair content [n / M] of the compound constituting the nitrogen-containing layer, and The graph which plotted the value of the sheet resistance value measured about the transparent electrode is shown.

From the graph of FIG. 14, when the effective unshared electron pair content [n / M] is within the range of 2.0 × 10 ^{−3 to} 1.9 × 10 ⁻² , the effective unshared electron pair content [n / M ] Was large, the tendency for the sheet resistance value of a transparent electrode to become low was seen. If the effective unshared electron pair content [n / M] is in the range of 3.9 × 10 ⁻³ or more with 3.9 × 10 ⁻³ as a boundary, the effect of dramatically reducing the sheet resistance value It was confirmed that In addition, it was confirmed that the effect of reliably reducing the sheet resistance value was obtained when the range was 6.5 × 10 ⁻³ or more.

  The above results were the same for the sample in which the nitrogen-containing layer was formed by coating film formation. Moreover, the same result was obtained also with the sample which mixed the compound containing nitrogen with another compound, and comprised the nitrogen containing layer.

  From the above, a thin film is obtained in order to obtain light transmissivity by selecting and using a compound constituting the nitrogen-containing layer provided adjacent to the electrode layer using the effective unshared electron pair content [n / M] as an index. However, it was confirmed that an electrode film having low resistance (that is, a transparent electrode) was obtained.

DESCRIPTION OF SYMBOLS 1 Transparent electrode 1A Transparent electrode 1B Transparent electrode 3 Nitrogen-containing layer 5 Electrode layer 5x1, 5x2, 5x3 etc. x electrode pattern (1st electroconductive layer)
5y1, 5y2, 5y3, etc. y electrode pattern (second conductive layer)
DESCRIPTION OF SYMBOLS 6 Resist film 6A Resist film 7 Mask 8 Exposure machine 9 Etching liquid 11 (Transparent) base material 13 Front plate 15 Adhesive 17x Wiring 17y Wiring 21 Touch panel 21a Touch panel 100 Liquid crystal display device 101A Polarizing filter 101B Polarizing filter 102A Glass substrate 102B Glass substrate 103 Color Filter 104A Alignment Film 104B Alignment Film 105 Liquid Crystal 106 Spacer

Claims (21)

The number of unshared electron pairs that contain a nitrogen atom (N) and that are not involved in aromaticity and that are not coordinated to the metal among the unshared electron pairs that the nitrogen atom (N) has is n, and the molecular weight is M A nitrogen-containing layer formed using a compound having an effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ or more when
One of the metal elements selected from copper, gold and platinum is the main component, and at least one element different from the main component of silver, aluminum, gold, indium, copper, palladium and platinum as the additive element A transparent electrode comprising an element and an electrode layer provided adjacent to the nitrogen-containing layer.   The transparent electrode according to claim 1, wherein the metal element contained in the electrode layer as a main component is copper. The transparent electrode according to claim 1, wherein the effective unshared electron pair content [n / M] in the compound is 3.9 × 10 ⁻³ or more. The transparent electrode according to claim 1, wherein the effective unshared electron pair content [n / M] in the compound is 6.5 × 10 ⁻³ or more. 5. The nitrogen-containing layer has an effective unshared electron pair content [n / M] at an interface on the electrode layer side of 2.0 × 10 ⁻³ or more. 5. The transparent electrode according to 1.   The transparent electrode according to any one of claims 1 to 5, wherein a concentration of the additive element in the electrode layer is in a range of 0.01 to 10.0 atomic%. The nitrogen-containing layer is composed of another compound together with the compound, and the average value of the effective unshared electron pair content [n / M] in consideration of the mixing ratio of these compounds is 2.0 × 10 It is more than ^-3 , The transparent electrode as described in any one of Claim 1- Claim 6. The transparent electrode according to any one of claims 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (1).

[However, in the general formula (1),
X11 represents -N (R11)-or -O-,
E101 to E108 each represent -C (R12) = or -N =, and at least one of E101 to E108 is -N =,
R11 and R12 each represent a hydrogen atom (H) or a substituent. ] The transparent electrode according to claim 8, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (1a) in which X11 in the general formula (1) is -N (R11)-.

The transparent electrode according to claim 9, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (1a-1) in which E104 in the general formula (1a) is -N =.

The transparent electrode according to claim 9, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (1a-2) in which E103 and E106 in the general formula (1a) are -N =.

The nitrogen-containing layer contains a compound having a structure represented by the following general formula (1b) in which X11 in the general formula (1) is -O- and E104 is -N =. Transparent electrode.

The transparent electrode according to any one of claims 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (2).

[However, in general formula (2),
Y21 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof;
E201 to E216 and E221 to E238 each represent -C (R21) = or -N =,
R21 represents a hydrogen atom (H) or a substituent,
At least one of E221 to E229 and at least one of E230 to E238 is -N =;
k21 and k22 represent an integer of 0 to 4, but k21 + k22 is an integer of 2 or more. ] The transparent electrode according to any one of claims 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (3).

[However, in general formula (3),
E301 to E312 each represent -C (R31) =
R31 represents a hydrogen atom (H) or a substituent,
Y31 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof. ] The transparent electrode according to any one of claims 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (4).

[However, in general formula (4),
E401 to E414 each represent -C (R41) =
R41 represents a hydrogen atom (H) or a substituent,
Ar41 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring;
k41 represents an integer of 3 or more. ] The transparent electrode according to any one of claims 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (5).

[However, in general formula (5),
R51 represents a substituent,
E501, E502, E511 to E515 and E521 to E525 each represent -C (R52) = or -N =
E503 to E505 each represent -C (R52) =
R52 represents a hydrogen atom (H) or a substituent,
At least one of E501 and E502 is -N =,
At least one of E511 to E515 is -N =,
At least one of E521 to E525 is -N =. ] The transparent electrode according to any one of claims 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (6).

[However, in general formula (6),
E601 to E612 each represent -C (R61) = or -N =
R61 represents a hydrogen atom (H) or a substituent,
Ar61 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring. ] The transparent electrode according to any one of claims 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (7).

[However, in general formula (7),
R71 to R73 each represents a hydrogen atom (H) or a substituent,
Ar71 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group. ] The transparent electrode according to any one of claims 1 to 7, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (8).

[However, in general formula (8),
R81 to R86 each represent a hydrogen atom (H) or a substituent,
E801 to E803 each represent -C (R87) = or -N =
R87 represents a hydrogen atom (H) or a substituent,
Ar81 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group. ] The transparent electrode according to claim 19, wherein the nitrogen-containing layer contains a compound having a structure represented by the following general formula (8a).

[However, in the general formula (8a),
E804 to E811 each represent -C (R88) = or -N =
Each R88 represents a hydrogen atom (H) or a substituent;
At least one of E808 to E811 is -N =;
E804 to E807 and E808 to E811 may be bonded to each other to form a new ring. ]   An electronic device having the transparent electrode according to any one of claims 1 to 20.

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