JP2015122184A - Transparent electrode and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent electrode that has a sufficient conductivity and a sufficient light-transmitting property, and also has an excellent durability (stability of light transmittance in use for the long term) and an excellent electrode life, and an electronic device having the transparent electrode.SOLUTION: A transparent electrode has an intermediate layer, and a conductive layer provided adjacent to the intermediate layer, having a light transmittance of 50% or more at a wavelength of 550 nm and a sheet resistance value of 20 Ω/sq. or less. The intermediate layer contains an organic compound having a halogen atom. The conductive layer comprises one metal element selected from copper, gold and platinum as the main component.

Description

  The present invention relates to a transparent electrode and an electronic device, and in particular, a transparent electrode having both conductivity and light transmittance and improved durability (light transmittance stability and electrode life), and the transparent electrode. It relates to electronic devices.

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, based on the above problems, studies have been made on the application of silver as a constituent material for transparent electrodes. Silver is superior in conductivity to the ITO, but has a problem of trade-off between resistance characteristics and light transmittance.

  In such a situation, a technique for forming a thin film using an alloy of silver (Ag) and magnesium (Mg) having high electrical conductivity, or using a metal material that is inexpensive and readily available as a raw material instead of indium, is used. The technique to comprise is proposed (for example, refer patent document 1 and 2).

  In the invention described in Patent Document 1, by using an alloy of silver and magnesium as an electrode material, desired conductivity can be obtained under thin film conditions as compared with an electrode formed by silver alone, and light transmittance and conductivity can be obtained. It is said that both can be achieved.

  However, the resistance value of the electrode obtained by the method described in Patent Document 1 is at most about 100Ω / □, which is insufficient as the conductivity of the transparent electrode, and in addition to the problem that the drive voltage cannot be lowered, Since magnesium is easily oxidized, it has a problem that its performance tends 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 device using a thin film having a layer thickness of about 15 nm and a highly light-transmitting silver film as a cathode is disclosed (for example, see 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 (transparency) 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.

  On the other hand, the present inventors, in a transparent electrode having a silver thin film and an intermediate layer below it, form a silver thin film by containing a diazacarbazole derivative having an interaction with silver in the intermediate layer serving as a base. By improving the continuous film-forming property and forming a more uniform silver thin film, low resistance, high permeability and storage stability are achieved (for example, see Patent Document 4).

  However, in recent years, the demand for electronic devices has increased, and in particular, there has been a demand for lower resistance in response to the demand for a larger area. Further, in terms of visibility, higher light transmittance and more than several decades of electronic devices In order to make the life possible, high transmittance stability when used over a long period of time and electrode life are required.

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 problems, and a solution to the problem is a transparent electrode having sufficient conductivity and light transmittance, and excellent durability (light transmittance stability and electrode life). It is to provide an electronic device and an organic electroluminescence element provided with the transparent electrode.

  As a result of intensive studies in view of the above problems, the inventor has a configuration in which an intermediate layer and a conductive layer provided adjacent to the intermediate layer are stacked, and the intermediate layer contains an organic compound having a halogen atom. The transparent layer is composed of a transparent electrode composed mainly of any one metal element selected from copper, gold and platinum, and has a high light transmittance and a low sheet resistance. The electrode can achieve both excellent conductivity and light transmittance, and can realize a transparent electrode excellent in durability (light transmittance stability) and electrode life, and an electronic device using the same. As a result, the inventors have found out that the present invention can be achieved.

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

1. A transparent electrode having an intermediate layer and a conductive layer provided adjacent to the intermediate layer,
The light transmittance at a wavelength of 550 nm is 50% or more and the sheet resistance value is 20 Ω / □ or less, the intermediate layer contains an organic compound having a halogen atom, and the conductive layer is made of copper, gold and platinum. A transparent electrode comprising any one selected metal element as a main component.

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

  3. 3. The transparent electrode according to item 1 or 2, wherein the halogen atom of the organic compound is a bromine atom or an iodine atom.

  4). 4. The transparent electrode according to any one of items 1 to 3, wherein the organic compound having a halogen atom is a compound having a structure represented by the following general formula (1).

General formula (1)
(R) _k -Ar-[(L) _n -X] _m
[Wherein, Ar represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group. X represents a halogen atom, and m is an integer of 1 to 5. L represents a direct bond or a divalent linking group, and n represents 0 or 1. R represents a hydrogen atom or a substituted ring group. k represents an integer of 1 to 5. ]
5. The transparent electrode according to item 4, wherein the compound having the structure represented by the general formula (1) is a compound having a structure represented by the following general formula (2).

〔式中、Ｘはハロゲン原子を表し、ｍ１〜ｍ３は各々０〜５の整数である。ただし、ｍ１＋ｍ２＋ｍ３は少なくとも１以上である。Ｌは直接結合又は２価の連結基を表し、ｎ１〜ｎ３は各々０又は１を表す。〕
６．前記導電性層の上に更に第２の中間層を有し、２層の中間層により前記導電性層を挟持した構成であることを特徴とする第１項から第５項までのいずれか一項に記載の透明電極。

[In formula, X represents a halogen atom and m1-m3 is an integer of 0-5, respectively. However, m1 + m2 + m3 is at least 1 or more. L represents a direct bond or a divalent linking group, and n1 to n3 each represents 0 or 1. ]
6). Any one of Items 1 to 5, wherein a second intermediate layer is further provided on the conductive layer, and the conductive layer is sandwiched between two intermediate layers. The transparent electrode according to item.

  7). An electronic device comprising the transparent electrode according to any one of items 1 to 6.

  ADVANTAGE OF THE INVENTION According to this invention, the transparent electrode which has sufficient electroconductivity and light transmittance, and was excellent in durability (light transmittance stability and electrode lifetime), and an electronic device provided with the same can be provided.

  Although the expression mechanism and the action mechanism of the effect of the present invention that could solve the above problems by the configuration defined by the present invention are not all clarified, it is presumed as follows.

  That is, the transparent electrode of the present invention is provided with a conductive layer containing, as a main component, any one metal element selected from copper, gold and platinum on the intermediate layer, and the intermediate layer. The layer includes a compound having an atom having an affinity for copper, gold, or platinum atoms (hereinafter, also referred to as a compound having an affinity for copper, gold, or platinum).

  With such a configuration, when forming a conductive layer on the intermediate layer, copper, gold, or platinum atoms constituting the conductive layer are contained in the intermediate layer copper, gold, Alternatively, it interacts with a compound having an affinity for platinum, reduces the diffusion distance of copper, gold, or platinum atoms on the surface of the intermediate layer, and suppresses aggregation of copper, gold, or platinum atoms at specific locations. .

  That is, a copper, gold, or platinum atom first forms a two-dimensional nucleus on the surface of the intermediate layer containing a compound having an atom having an affinity for a copper, gold, or platinum atom. The film is formed by layer growth type (Frank-van der Merwe: FM type) film growth in which a one-dimensional single crystal layer is formed.

  In general, islands in which copper, gold, or platinum atoms adhering to the surface of the intermediate layer are bonded while diffusing the surface to form a three-dimensional nucleus and grow into a three-dimensional island. Although it is thought that it is easy to form an island-like film by growth-type film growth (Volume-Weber: VW type), in the present invention, a compound having an affinity for copper, gold, or platinum contained in the intermediate layer Thus, it is assumed that such island growth is prevented and layer growth is promoted.

  That is, a conductive layer having a uniform film thickness even though it is a thin film can be obtained. As a result, it is possible to realize a transparent electrode that has a thin film thickness while maintaining light transmittance, ensuring conductivity, and having excellent durability (stability of light transmittance over a long period of use) and electrode life. I guess it was made.

Schematic sectional view showing an example of the configuration of the transparent electrode of the present invention 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 transparent electrode of the present invention is a transparent electrode having an intermediate layer and a conductive layer provided adjacent to the intermediate layer, having a light transmittance of 50% or more at a wavelength of 550 nm and a sheet resistance of 20Ω / □, and the intermediate layer contains an organic compound having a halogen atom, and the conductive layer is composed mainly of any one metal element selected from copper, gold and platinum. As a feature, it is possible to realize a transparent electrode having sufficient conductivity and light transmittance and excellent durability (light transmittance stability and electrode life). This feature is a technical feature common to the inventions according to claims 1 to 7.

  As an embodiment of the present invention, it is preferable that the metal element contained in the conductive layer as a main component is copper, from the viewpoint that the above-described effect of the present invention can be further expressed.

  Moreover, it is preferable that the halogen atom which the said organic compound has is a bromine atom or an iodine atom.

  Moreover, it is preferable that the organic compound which has the said halogen atom which an intermediate | middle layer contains is a halogenated aryl compound which has a structure represented by the said General formula (1). Furthermore, the compound having a structure represented by the general formula (1) is preferably a halogenated aryl compound having a structure represented by the general formula (2).

  The layer structure of the transparent electrode of the present invention is as follows. It is preferable that after the intermediate layer and the conductive layer are laminated on the substrate, a second intermediate layer is further formed on the conductive layer, and the conductive layer is sandwiched between the two intermediate layers. one of. Thereby, the electroconductivity and durability of the transparent electrode which has a copper, gold | metal | money, or a platinum atom as a main component can be improved.

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

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

  A transparent electrode 1 shown in FIG. 1A has a two-layer structure in which an intermediate layer 3 is provided, and a conductive layer 5 is laminated on the intermediate layer 3. Layer 3 and conductive layer 5 are provided in this order. The intermediate layer 3 according to the present invention is a layer containing an organic compound having a halogen atom, and the conductive layer 5 according to the present invention laminated thereon is selected from copper, gold and platinum. It is a layer constituted by any one kind of metal element as a main component.

  In the present invention, the main component of a metal element means that the content of each metal element of copper, gold or platinum according to the present invention is 90% by mass or more with respect to the total mass of the conductive layer. Preferably, it is 95% by mass or more, more preferably 99% by mass or more, and particularly preferably a configuration of only a metal element of copper, gold or platinum. In the conductive layer 5 according to the present invention, it is the most preferable aspect that each of copper, gold, or platinum does not form an alloy with other metal elements, but is composed of a single metal element. .

  Moreover, as a layer structure of the transparent electrode 1 of this invention, as shown in FIG.1 (b), it has the intermediate | middle layer 3A and the electroconductive layer 5 on the base material 11, and also on the electroconductive layer 5 In addition, it is also a preferable aspect that the second intermediate layer 3B is laminated and the conductive layer 5 is sandwiched between the intermediate layer 3A and the intermediate layer 3B. Thus, by providing the second intermediate layer 3B on the conductive layer 5, the conductive layer 5 made of a metal element is not directly exposed to, for example, an oxygen atmosphere. By protecting the conductive layer 5 with the second intermediate layer 3B, it is possible to prevent the occurrence of scratches and the like.

  In the present invention, in the transparent electrode 1 having a laminated structure including the intermediate layer 3 and the conductive layer 5 formed thereon, the upper portion of the conductive layer 5 is further covered with a protective layer. The structure may be a structure in which the second conductive layer is laminated. In this case, it is preferable that both the protective layer and the second conductive layer have high light transmittance so as not to impair the light transmittance of the transparent electrode 1. Moreover, it is good also as a structure which provided the functional layer as needed also under the intermediate | middle layer 3, ie, between the intermediate | middle layer 3 and the base material 11. FIG.

  Next, further detailed structural requirements will be described in the order of the base material 11 used to hold the transparent electrode 1 having such a laminated structure, the intermediate layer 3 and the conductive layer 5 constituting the transparent electrode 1.

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

  Examples of the glass include silica glass, soda-lime silica glass, lead glass, borosilicate glass, and alkali-free glass. From the viewpoint of adhesion to the intermediate layer 3, durability, and smoothness, the surface of these glass materials may be subjected to physical treatment such as polishing, if necessary, or from an inorganic or organic material. Or a hybrid film in which these films are combined may be formed.

  Examples of the resin film include polyesters such as polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (abbreviation: TAC), cellulose acetate butyrate, Cellulose acetates such as cellulose acetate propionate (abbreviation: CAP), cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, poly Methyl pentene, polyether ketone, polyimide, polyether sulfone (abbreviation: PES), polyphenyle Sulfide, polysulfones, polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name; manufactured by JSR) or Apel (trade name; manufactured by Mitsui Chemicals, Inc.) And a resin film using a cycloolefin-based resin or the like.

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

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

  The method for producing the gas 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. A plasma polymerization method, a plasma CVD method (CVD: Chemical Vapor Deposition), a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but atmospheric pressure plasma described in Japanese Patent Application Laid-Open No. 2004-68143. A polymerization method is particularly preferred.

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

[Middle layer]
The intermediate layer 3 according to the present invention is a layer configured using a halogen compound having a halogen atom. When such an intermediate layer 3 is formed on the substrate 11, the film forming method includes a method using a wet process such as a coating method, an ink jet method, a coating method, a dip method, or a vapor deposition method. Examples thereof include a method using a dry process such as resistance heating, EB method (electron beam method), sputtering method, CVD method, or the like. Of these, the vapor deposition method is preferably applied.

(Organic compounds having halogen atoms)
The transparent electrode 1 of the present invention is characterized in that the intermediate layer 3 contains an organic compound having a halogen atom.

  The organic compound having a halogen atom according to the present invention is a compound containing at least a halogen atom and a carbon atom, and the structure thereof is not particularly limited, but the halogenated aryl compound represented by the following general formula (1) Is preferred.

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

General formula (1)
(R) _k -Ar-[(L) _n -X] _m
In the general formula (1), Ar represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group. X represents a halogen atom, and m is an integer of 1 to 5. L represents a direct bond or a divalent linking group, and n represents 0 or 1. R represents a hydrogen atom or a substituted ring group. k represents an integer of 1 to 5.

  In the general formula (1), examples of the aromatic hydrocarbon ring group represented by Ar (also referred to as an aromatic carbocyclic group or an aryl group) include a phenyl group, a p-chlorophenyl group, a mesityl group, and a tolyl group. And xylyl, naphthyl, anthryl, azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, biphenylyl and the like.

  Examples of the aromatic heterocyclic group represented by Ar include a pyridyl group, a pyrimidinyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a benzimidazolyl group, a pyrazolyl group, a pyrazinyl group, and a triazolyl group (for example, 1,2, 4-triazol-1-yl group, 1,2,3-triazol-1-yl group and the like can be mentioned.

  In the present invention, Ar is preferably an aromatic hydrocarbon ring group, more preferably a phenyl group.

  Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a chlorine atom, a bromine atom or an iodine atom is preferable, and a more preferable example is , Bromine atom or iodine atom.

  m represents an integer of 1 to 5, and is preferably 1 or 2.

L represents a direct bond or a divalent linking group. Examples of the divalent linking group include an alkylene group (eg, methylene group, ethylene group, trimethylene group, propylene group), a cycloalkylene group (eg, 1,2-cyclobutanediyl group, 1,2-cyclopentanediyl group, 1,3-cyclopentanediyl group, 1,2-cyclohexanediyl group, 1,3-cyclohexanediyl group, 1,4-cyclohexanediyl group, 1,2-cycloheptanediyl group, 1,3-cycloheptanediyl group 1,4-cycloheptanediyl group, etc.), arylene group (for example, o-phenylene group, m-phenylene group, p-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 1,3 -Naphthylene group, 1,4-naphthylene group, 2,7-naphthylene group, etc.), heteroarylene group (for example, thiophene-2,5- Yl group, 2,6-pyridinediyl group, 2,3-pyridinediyl group, 2,4-pyridinediyl group, 2,4-dibenzofuranyl group, 2,8-dibenzofuranyl group, 4,6-dibenzofuranyl group 3,7-dibenzofurandiyl group, 2,4-dibenzothiophenediyl group, 2,8-dibenzothiophenediyl group, 4,6-dibenzothiophenediyl group, 3,7-dibenzothiophenediyl group, 1,3-carbazole Diyl group, 1,8-carbazolediyl group, 3,6-carbazolediyl group, 2,7-carbazolediyl group, 1,9-carbazolediyl group, 2,9-carbazolediyl group, 3,9-carbazolediyl group , 4,9-carbazolediyl group, etc.), -O- group, -CO- group, -O-CO- group, -CO-O- group, -O CO-O- group, -S- group, -SO- group, -SO ₂ - and the groups and the like.

  The divalent linking group represented by L is preferably an alkylene group, and more preferably a methylene group.

  n represents 0 or 1, but is preferably 0.

  R represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group). Group), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aromatic hydrocarbon ring group (Also referred to as aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, Indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic complex A group (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2, 3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzo Thienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl group, pyridazinyl group, triazinyl Group, quinazolinyl group, lid Dinyl group etc.), heterocyclic group (eg pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group etc.), alkoxy group (eg methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group) Group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, Propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxy Carbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.) Sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, Naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl groups (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, Tilcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, Butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (eg, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group) Group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenyl Carbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group) Octylureido group, dodecylureido group, phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methyl) Rusulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl Group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group) Etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino) , Dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyl) A diethylsilyl group), a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.). Among these substituents, preferred is an aryl group, and a structure having a plurality of aryl groups and further substituted with a halogen atom is preferred.

  k represents an integer of 1 to 5.

  In the present invention, a compound in which the halogenated aryl compound represented by the general formula (1) further has a structure formed from seven phenyl groups represented by the following general formula (2) as a mother nucleus is preferable.

  In the said General formula (2), X represents a halogen atom and m1-m3 is an integer of 0-5, respectively. However, m1 + m2 + m3 is at least 1 or more. L represents a direct bond or a divalent linking group, and n1 to n3 each represents 0 or 1.

  Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a chlorine atom, a bromine atom or an iodine atom is preferable, and a more preferable one is , Bromine atom or iodine atom.

  L represents a direct bond or a divalent linking group, and has the same meaning as L in formula (1).

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

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

[Conductive layer]
The conductive layer 5 according to the present invention is a layer composed mainly of any one metal element selected from copper, gold and platinum, and is formed on the intermediate layer 3. Examples of the method for forming the conductive layer 5 according to the present invention include a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, and the like. And a method using a dry process such as a CVD method. Among the film forming methods, the vapor deposition method is preferably applied. Further, the conductive layer 5 is formed on the intermediate layer 3 so that the conductive layer 5 is sufficiently conductive even without a high-temperature annealing treatment (for example, a heating process at 150 ° C. or higher) after the formation of the conductive layer. Although it can be expressed, if necessary, high-temperature annealing treatment or the like may be performed after film formation.

  In the present invention, the layer composed mainly of any one metal element selected from copper, gold and platinum is the copper according to the present invention with respect to the total mass of the conductive layer 5 as described above. , Meaning that the content of each metal element of gold or platinum is 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more, particularly preferably copper, gold or It is composed only of platinum metal elements, and an alloy of two or more metal elements is not formed. In the conductive layer 5 according to the present invention, it is the most preferable aspect that each of copper, gold, or platinum does not form an alloy with other metal elements, but is composed of a single metal element. . In the present invention, it is particularly preferable that the metal element contained in the conductive layer as a main component is copper.

  In the conductive layer 5 according to the present invention, a layer composed mainly of any one metal element selected from copper, gold, and platinum is divided into a plurality of layers as needed. It may be a configuration.

  Furthermore, the conductive layer 5 preferably has a layer thickness in the range of 4 to 20 nm. A layer thickness of 20 nm or less is more preferable because the absorption component or reflection component of the layer is reduced and the transmittance of the transparent electrode is improved. A layer thickness of 4 nm or more is preferable because the layer has sufficient conductivity. More preferably, it exists in the range of 5-10 nm.

[Effect of transparent electrode]
As described above, the transparent electrode 1 of the present invention is formed from copper, gold, and platinum on the intermediate layer 3 configured to contain a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity. This is a configuration in which a conductive layer 5 composed mainly of any one selected metal element is provided. Thus, when the conductive layer 5 is formed on the intermediate layer 3, the copper, gold, or platinum atoms constituting the conductive layer 5 are not shared with the aromaticity constituting the intermediate layer 3. By interacting with nitrogen atoms having electron pairs, the diffusion distance of copper, gold, or platinum atoms on the surface of the intermediate layer 3 is reduced, and the formation of copper, gold, or platinum aggregates can be suppressed.

  As described above, in the formation of the conductive layer 5 composed mainly of any one metal element selected from copper, gold and platinum, an island-like growth type (Volume-Weber: VW type) is used. Thus, copper, gold, or platinum particles are easily isolated in an island shape, and when the layer thickness is thin, it is difficult to obtain conductivity and the sheet resistance value is increased. Therefore, in order to ensure conductivity, the layer thickness needs to be increased to some extent. However, if the layer thickness is increased, the light transmittance is lowered, which is not suitable as a transparent electrode.

  However, according to the transparent electrode 1 having a configuration defined in the present invention, on the intermediate layer 3 containing a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity, a nitrogen atom and copper, gold, or Since the agglomeration of copper, gold, or platinum is suppressed by the interaction with platinum, a single layer growth type (Frank) is used in the formation of the conductive layer 5 composed mainly of copper, gold, or platinum. -Van der Merwe (FM type).

  In the present invention, “transparent electrode 1” means that the light transmittance at a wavelength of 550 nm is 50% or more. However, each of the materials used as the intermediate layer 3 includes copper, gold and Compared with the conductive layer 5 containing as a main component any one metal element selected from platinum, it is a good film having sufficient light transmittance. On the other hand, the conductivity of the transparent electrode 1 is ensured mainly by the conductive layer 5. Therefore, as described above, the conductive layer 5 composed mainly of any one metal element selected from copper, gold, and platinum has a thinner layer and the conductivity is ensured. As a result, it is possible to achieve both the improvement of the conductivity of the transparent electrode 1 and the improvement of the light transmittance.

<< 2. Applications of transparent electrodes >>
The transparent electrode 1 of the present invention having the above-described configuration can be used for various electronic devices. Examples of electronic devices include, for example, touch panels, liquid crystal display elements, organic electroluminescence elements, LEDs (light emitting diodes), solar cells, etc. In these electronic devices, electrode members that require 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)
The transparent electrode 1 of the present invention having an intermediate layer 3 and a conductive layer 5 mainly composed of copper, gold, or platinum adjacent to the intermediate layer 3 on the substrate 11 shown in FIG. The electrode pattern as shown in FIGS. 3 to 5 can be formed by, for example, 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.

  Also, in the present invention, the solvent for each metal element is used in combination with the above-mentioned organic solvent in the present invention for the purpose of more completely dissolving and removing the conductive layer composed of copper, gold, or platinum. You can also.

<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 treatment with an organic solvent, and resist peeling. 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 pre-processed or post-baked as necessary, and then etched with an etching solution containing an organic solvent to dissolve the intermediate layer in a region not protected by the resist and to form a conductive layer. Remove. 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. 2 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. 2A, the intermediate layer 3 and the conductive layer 5 are laminated on the transparent substrate 11 to produce the unprocessed transparent electrode 1.

  2B, a resist film 6 made of a photosensitive resin composition or the like is uniformly applied on the conductive layer 5 in the resist film forming step shown in FIG. 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 conductive layer by a known method such as micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, etc., and a heating device such as a hot plate or oven. Can be pre-baked. Pre-baking can be performed, for example, using a hot plate or the like in the range of 50 ° C. or higher and 150 ° C. or lower for 30 seconds to 30 minutes.

Next, in the exposure step shown in FIG. 2C, using an exposure machine 8 such as a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner, etc., 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, 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. 2 (d), 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 developer 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. 2E, 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, ester, etc., and the intermediate layer 3 in a region not protected by the resist film 6 is dissolved and the intermediate layer A predetermined electrode pattern is formed by simultaneously removing the thin conductive layer held on the substrate.

  Finally, as shown in FIG. 2 (f), the resist film 6 on the conductive layer 5 is removed by dipping in a resist film remover, 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 transparent electrodes are provided on two transparent substrates, respectively]
FIG. 3 is a perspective view showing a schematic configuration of the touch panel 21a using the transparent electrode of the present invention described above and having the configuration shown in FIG. 7 described later. 4 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. In the touch panel 21, the first transparent electrode 1-1 and the second transparent electrode 1-2 are arranged in this order on one main surface of the transparent substrates 11-1 and 11-2. Covered with.

  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 2 is formed. Therefore, the first transparent electrode 1-1 has a configuration in which the first intermediate layer 3-1 and the first conductive layer 5-1 are laminated in this order. Similarly, the second transparent electrode 1-2 has a configuration in which a second intermediate layer 3-2 and a second conductive 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 transparent substrates 11-1 and 11-2 side. Here, description will be made with reference to FIG. 3 and FIG. 4 together with a schematic plan view of the electrode portion of FIG. 5 and a schematic sectional view of FIG. 7 corresponding to the AA cross section. Moreover, the same code | symbol is attached | subjected to the component similar to having demonstrated in FIG.1 and FIG.2, and the overlapping description is abbreviate | omitted.

(Transparent substrate 11)
The transparent substrates 11-1 and 11-2 shown in FIGS. 3 and 5 are the substrate 11 (hereinafter also referred to as a transparent substrate) described in the previous transparent electrode 1.

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

(First conductive layer 5-1 (first transparent electrode 1-1))
The first conductive layer 5-1 is the conductive layer 5 described in the previous transparent electrode, and a plurality of x electrode patterns 5x1, 5x2, patterned on the first intermediate layer 3-1, (omitted). Etc. are configured. 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 area on the transparent substrate 11-1, and are drawn out to the edge of the transparent substrate 11-1. Each such x wiring 17x is configured as a first conductive layer 5-1 mainly composed of copper, gold, or platinum, similarly to the x electrode patterns 5x1, 5x2, (omitted) and the like. is there.

(Second intermediate layer 3-2 (second transparent electrode 1-2))
The second intermediate layer 3-2 is the intermediate layer 3 described in the previous transparent electrode 1, is formed on the transparent substrate 11-2, and is patterned in the same shape as the second electrode layer 5-2. Has been.

(Second electrode layer 5-2 (second transparent electrode 1-2))
The second electrode layer 5-2 is the conductive layer 5 described in the previous transparent electrode 1, and a plurality of y electrode patterns 5y1, 5y2 patterned on the second intermediate 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. 5, 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 transparent substrate 11-2, it comprises with x electrode pattern 5x1, 5x2, (omitted) etc. which were comprised by the 1st electrode layer 5-1, and 2nd electrode layer 5-2. The y electrode patterns 5y1, 5y2, (omitted) and the like thus made 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. A second intermediate layer 3-2 is sandwiched between these stacked portions, thereby ensuring insulation between the x electrode patterns 5x1, 5x2, (omitted), etc. and the y electrode patterns 5y1, 5y2, (omitted), etc. It has become a state.

  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 transparent substrate 11-2, and are drawn out to the edge of the transparent substrate 11-2 so as to be aligned with the x wirings 17x. Each of the y wirings 17y is configured as a second conductive layer 5-2 mainly composed of copper, gold, or platinum, similarly to the y electrode patterns 5y1, 5y2, (omitted) and the like. is there.

  A flexible printed circuit board or the like is connected to the x wiring 17x and the y wiring 17y drawn to the edge of the transparent substrate 11-2.

(Front plate 13)
The front plate 13 illustrated in FIG. 3 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. 6). 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 transparent substrates 11-1 and 11-2. The x wiring 17x drawn from the x electrode patterns 5x1, 5x2, (omitted), and the like, and the y electrode pattern The y wiring 17y drawn from 5y1, 5y2, (omitted) or the like is prevented from being visually recognized 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) and the y electrode patterns 5y1, 5y2, (omitted) are connected from the flexible printed circuit board connected to the x wiring 17x and the y wiring 17y. A voltage is applied to the above. 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, these x electrode patterns 5x1, 5x2, (omitted), etc. and y electrode patterns 5y1, 5y2, (omitted), etc. are the conductive layers (electrode layers) 5 of the transparent electrode for touch panel described above. Thin film formation is possible while maintaining conductivity. 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.

  FIG. 7 is a schematic cross-sectional view for explaining a configuration of a touch panel that can be particularly preferably applied to the touch panel of the embodiment, and corresponds to a cross section taken along line AA shown in FIG. 5. The touch panel 21a shown in this figure has a configuration in which a first transparent electrode 1-1 and a second transparent electrode 1-2 are provided on one main surface of two transparent substrates 11-1 and 11-2. Other configurations are the same as those of the first embodiment described above. For this reason, the same code | symbol is attached | subjected to the structure similar to the touch panel of previous Embodiment 1, and the overlapping description is abbreviate | omitted.

  That is, the touch panel 21a shown in FIG. 7 includes a first substrate 11-1 provided with the first transparent electrode 1-1 and a second substrate 11-2 provided with the second transparent electrode 1-2. And have. These substrates 11-1 and 11-2 have the formation surfaces of the transparent electrodes 1-1 and 1-2 in the same direction, and are on the formation surface of the first transparent electrode 1-1 on the first substrate 11-1. In addition, the second substrate 11-2 is placed so as to be positioned.

  The first substrate 11-1 and the second substrate 11-2 are the same substrates 11 as described in the previous transparent electrode. The first transparent electrode 1-1 and the second transparent electrode 1-2 each have the same configuration as that of the first embodiment, and the intermediate layer is formed on the substrates 11-1 and 11-2, respectively. In this configuration, 3-1 and 3-2 and conductive layers 5-1 and 5-2 are stacked in this order.

  Furthermore, the configuration of each of the conductive layers 5-1 and 5-2 is the same as that of the first embodiment, and the x electrode patterns 5x1, 5x2, (omitted), etc. configured by the first conductive layer 5-1. , And the y electrode patterns 5y1, 5y2, (omitted) and the like configured by the second electrode layer 5-2 are difficult to be visually recognized and arranged. However, insulation between the first conductive layer 5-1 and the second conductive layer 5-2 was ensured by the second substrate 11-2 and the second intermediate layer 3-2. It is in a state.

  Further, the laminated first substrate 11-1 and second substrate 11-2 are bonded together by an adhesive not shown here, and the first adhesive also causes the first substrate 11-1 and the second substrate 11-2 to adhere to each other. The electrode layer 5-1 and the second electrode layer 5-2 are insulated.

[Embodiment 2: Configuration in which two transparent electrodes are provided on a transparent substrate]
FIG. 6 is a schematic cross-sectional view for explaining another example of the touch panel of the embodiment. The touch panel 21 shown in FIG. 6 includes a first transparent electrode 1-1 and a second transparent electrode on the transparent substrate 11. 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 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. 8 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, and liquid crystal display devices of various drive methods such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, and OCB are listed depending on the liquid crystal drive method. It is done. In general, 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. 8 has 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 the RGB filters are applied 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).

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

Example 1
<< Preparation of transparent electrode >>
According to the method shown below, the transparent electrodes 1 to 84 were produced so that the area of the conductive region was 5 cm × 5 cm. The transparent electrodes 1 to 4 are prepared as transparent electrodes having a single layer structure, and the transparent electrodes 5 to 73 and the transparent electrodes 82 to 84 are a laminated structure of the intermediate layer 3 and the conductive layer 5 shown in FIG. The transparent electrodes 74 to 81 are transparent electrodes having a three-layer laminated structure of the intermediate layer 3A, the conductive layer 5, and the second intermediate layer 3B shown in FIG.

[Preparation of transparent electrode 1]
A transparent electrode 1 of a comparative example having a single layer structure was produced according to the method shown below.

A transparent non-alkali glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, and this was attached to a vacuum tank of the vacuum deposition apparatus. On the other hand, copper (Cu) was loaded into a resistance heating boat made of tungsten and mounted in the vacuum chamber. Next, after reducing the pressure in the vacuum chamber to 4 × 10 ⁻⁴ Pa, the resistance heating boat was energized and heated, and copper was deposited on the substrate at a deposition rate of 0.1 to 0.2 nm / sec. A transparent electrode 1 was produced by vapor-depositing a single layer of a conductive layer composed of 5% by mass and having a layer thickness of 5 nm.

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

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

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

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

Next, the base material on which the intermediate layer is formed is transferred to the second vacuum tank while being in a vacuum state, and after the pressure of the second vacuum tank is reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing copper is energized and heated, A conductive layer made of copper having a layer thickness of 8 nm is deposited at a deposition rate of 0.1 to 0.2 nm / second to obtain a transparent electrode 6 in which an intermediate layer and a conductive layer made of copper are laminated on top of this. It was.

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

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

Next, after reducing the pressure in the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing the exemplified compound (1) was heated by energization, and the deposition rate was within the range of 0.1 to 0.2 nm / second. It vapor-deposited on the base material and the intermediate | middle layer 3 which consists of exemplary compound (1) whose layer thickness is 25 nm was formed.

Next, the base material on which the intermediate layer 3 is formed is transferred to the second vacuum chamber in a vacuum state, and the second vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing silver is energized and heated. A transparent conductive layer 5 made of silver having a layer thickness of 8 nm was deposited at a deposition rate of 0.1 to 0.2 nm / second, and the intermediate layer 3 and the conductive layer 5 made of silver were laminated thereon. An electrode 9 was obtained.

[Preparation of transparent electrode 10]
A transparent non-alkali glass base material is fixed to a base material holder of a commercially available vacuum deposition apparatus, and the exemplary compound (1) of the present invention is loaded into a resistance heating boat made of tantalum. It attached to the 1st vacuum chamber of a vacuum evaporation system. Moreover, copper (Cu) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.

Next, after reducing the pressure in the first vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing the exemplified compound (1) was heated by energization, and the deposition rate was within the range of 0.1 to 0.2 nm / second. It vapor-deposited on the base material and the intermediate | middle layer 3 which consists of exemplary compound (1) whose layer thickness is 25 nm was formed.

Next, the base material on which the intermediate layer 3 is formed is transferred to the second vacuum chamber while being in a vacuum state, and after the pressure of the second vacuum chamber is reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing copper is energized and heated. The conductive layer 5 made of copper having a layer thickness of 3.5 nm is vapor-deposited at a deposition rate of 0.1 to 0.2 nm / second, and the intermediate layer 3 and the conductive layer 5 made of copper are laminated thereon. A transparent electrode 10 was obtained.

[Production of transparent electrodes 11 to 14]
In the production of the transparent electrode 10, transparent electrodes 11 to 14 were produced in the same manner except that the copper layer thickness of the conductive layer 5 was changed to 5 nm, 8 nm, 10 nm, and 20 nm, respectively.

[Preparation of transparent electrodes 15 to 55]
In preparation of the said transparent electrode 12, it replaced with the exemplary compound (1) used for formation of the intermediate | middle layer 3, and except having used each exemplary compound of Table 1-Table 3, respectively, transparent electrode 15- 55 was produced.

[Production of transparent electrodes 56 and 57]
Transparent electrodes 56 and 57 were produced in the same manner as in the production of the transparent electrode 12 except that the constituent metal elements of the conductive layer 5 were changed to gold (Au) and platinum (Pt), respectively.

[Production of transparent electrodes 58 and 59]
Transparent electrodes 58 and 59 were produced in the same manner as in the production of the transparent electrode 19, except that the constituent metal elements of the conductive layer 5 were changed to gold (Au) and platinum (Pt), respectively.

[Production of transparent electrodes 60 and 61]
In the production of the transparent electrode 20, transparent electrodes 60 and 61 were produced in the same manner except that the constituent metal elements of the conductive layer 5 were changed to gold (Au) and platinum (Pt), respectively.

[Production of transparent electrodes 62 and 63]
Transparent electrodes 62 and 63 were produced in the same manner as in the production of the transparent electrode 21, except that the constituent metal elements of the conductive layer 5 were changed to gold (Au) and platinum (Pt), respectively.

[Production of transparent electrodes 64 and 65]
Transparent electrodes 64 and 65 were produced in the same manner as in the production of the transparent electrode 23 except that the constituent metal elements of the conductive layer 5 were changed to gold (Au) and platinum (Pt), respectively.

[Production of transparent electrodes 66 and 67]
Transparent electrodes 66 and 67 were produced in the same manner as in the production of the transparent electrode 28 except that the constituent metal elements of the conductive layer 5 were changed to gold (Au) and platinum (Pt), respectively.

[Production of transparent electrodes 68 and 69]
Transparent electrodes 68 and 69 were produced in the same manner as in the production of the transparent electrode 32 except that the constituent metal elements of the conductive layer 5 were changed to gold (Au) and platinum (Pt), respectively.

[Production of transparent electrodes 70 and 71]
Transparent electrodes 70 and 71 were produced in the same manner except that the constituent metal elements of the conductive layer 5 were changed to gold (Au) and platinum (Pt), respectively, in the production of the transparent electrode 35.

[Production of transparent electrodes 72 and 73]
In the production of the transparent electrode 40, transparent electrodes 72 and 73 were produced in the same manner except that the constituent metal elements of the conductive layer 5 were changed to gold (Au) and platinum (Pt), respectively.

[Production of transparent electrodes 74 to 81]
In the production of the transparent electrodes 19, 20, 21, 23, 28, 32, 35 and 40, after the intermediate layer 3A and the conductive layer 5 are formed on the base material in the same manner, The second intermediate layer 3B is formed by the same method as the formation of the intermediate layer 3, and the conductive layer 5 shown in FIG. 1B is sandwiched between the two intermediate layers 3A and 3B. Transparent electrodes 74 to 81 were produced.

[Production of transparent electrodes 82 to 84]
In the production of the transparent electrodes 19, 20 and 21, transparent electrodes 82 to 84 were produced in the same manner except that the base material was changed from a non-alkali glass to a PET (polyethylene terephthalate) film.

<< Evaluation of transparent electrode >>
About the produced said transparent electrodes 1-84, according to the following method, the light transmittance, sheet resistance value, and durability (change of the light transmittance under constant current and electrode lifetime) were measured.

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

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

[Evaluation of durability 1: change width of light transmittance under constant current]
About each produced said transparent electrode, the electric current of 125 mA / cm < ² > was flowed at 25 degreeC for 150 hours, and the change ratio of the light transmittance in wavelength 550nm after 150 hours with respect to the light transmittance in initial wavelength 550nm was measured according to the following formula. .

Change ratio of light transmittance = [(initial light transmittance−light transmittance after 150 hours) / initial light transmittance] × 100
The change ratio of the light transmittance of each transparent electrode was displayed as a relative value with the change ratio of the transparent electrode 7 being 100.

[Durability 2 Evaluation: Electrode Life Evaluation (Organic Solvent Resistance)]
For each transparent electrode, after measuring the initial sheet resistance value R1 in the same manner as described in the measurement of the sheet resistance value, each transparent electrode is immersed in a methyl ethyl ketone solution at 25 ° C. and taken out every 30 minutes. After drying, the sheet resistance value is measured, immersion in an ethyl acetate solution and measurement of the sheet resistance value are repeated, and immersion until the sheet resistance value becomes twice the initial sheet resistance value R1. Time T was determined and used as a measure of electrode life. It represents that it is excellent in electrode lifetime (organic solvent tolerance), so that immersion time T is large. In addition, the immersion time T of each transparent electrode was displayed by the relative value which set the immersion time required for the sheet resistance value of the transparent electrode 7 to be double to 100.

  The results obtained as described above are shown in Tables 1 to 4.

  As is clear from the results described in Tables 1 to 4, on the intermediate layer formed using the organic compound having a halogen atom, any one metal element selected from copper, gold and platinum as a main component. Each of the transparent electrodes 10 to 84 of the present invention provided with the conductive layer has a light transmittance of 51% or more and a sheet resistance value of 20Ω / □ or less. This is because the intermediate layer is formed by using an organic compound having a halogen atom, so that aggregation of copper, gold, or platinum film formed thereon and generation of mottle can be suppressed. Even when a copper, gold, or platinum film having a thickness of 5 was formed, aggregation of copper, gold, or platinum was suppressed, and both high light transmittance and low sheet resistance value could be achieved. In addition, it can be seen that the comparative example has an excellent effect on the stability of light transmittance after being used for a long time under a constant current and the life of the electrode after being immersed in an organic solvent.

  Furthermore, it has been confirmed that more preferable results can be obtained in the transparent electrodes 74 to 81 as a configuration in which the conductive layer is sandwiched between two intermediate layers.

On the other hand, in the transparent electrodes 1 to 4 of the comparative example having no intermediate layer, although the sheet resistance value decreases as the film thickness of the conductive layer which is a copper layer is increased, the conductive layer is formed. Decrease in light transmittance due to copper agglomeration (motor) at the time becomes remarkable, and it is impossible to achieve both of light transmittance and sheet resistance value. Further, even in the transparent electrodes 5 to 8 using Alq ₃ or ET-1 to ET- ₃ as the intermediate layer, the light transmittance was low and the sheet resistance value could not be lowered to a desired condition.

  Moreover, the transparent electrode 9 which used silver for the electroconductive layer was a low result in any characteristic with respect to the transparent electrode of this invention.

1, 1-1, 1-2, 1A, 1B Transparent electrode 3, 3A, 3B, 3-1, 3-2 Intermediate layer 5, 5-1, 5-2 Conductive layer 5x1, 5x2, 5x3, etc. x electrode Pattern (first conductive layer)
5y1, 5y2, 5y3, etc. y electrode pattern (second conductive layer)
6 Resist film 7 Mask 8 Exposure machine 9 Etching solution 11, 11-1, 11-2 Transparent substrate 13 Front plate 15 Adhesive 17, 17x, 17y Wiring 21, 21a Touch panel 100 Liquid crystal display device 101A, 101B Polarizing filter 102A, 102B Glass substrate 103 Color filter 104A, 104B Alignment film 105 Liquid crystal 106 Spacer

Claims (7)

A transparent electrode having an intermediate layer and a conductive layer provided adjacent to the intermediate layer,
The light transmittance at a wavelength of 550 nm is 50% or more and the sheet resistance value is 20 Ω / □ or less, the intermediate layer contains an organic compound having a halogen atom, and the conductive layer is made of copper, gold and platinum. A transparent electrode comprising any one selected metal element as a main component.   The transparent electrode according to claim 1, wherein the metal element contained in the conductive layer as a main component is copper.   The transparent electrode according to claim 1, wherein the halogen atom of the organic compound is a bromine atom or an iodine atom. 4. The transparent electrode according to claim 1, wherein the organic compound having a halogen atom is a compound having a structure represented by the following general formula (1).
General formula (1)
(R) _k -Ar-[(L) _n -X] _m
[Wherein, Ar represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group. X represents a halogen atom, and m is an integer of 1 to 5. L represents a direct bond or a divalent linking group, and n represents 0 or 1. R represents a hydrogen atom or a substituted ring group. k represents an integer of 1 to 5. ] The transparent electrode according to claim 4, wherein the compound having the structure represented by the general formula (1) is a compound having a structure represented by the following general formula (2).

[In formula, X represents a halogen atom and m1-m3 is an integer of 0-5, respectively. However, m1 + m2 + m3 is at least 1 or more. L represents a direct bond or a divalent linking group, and n1 to n3 each represents 0 or 1. ]   6. The structure according to claim 1, further comprising a second intermediate layer on the conductive layer, wherein the conductive layer is sandwiched between two intermediate layers. The transparent electrode according to item.   An electronic device comprising the transparent electrode according to any one of claims 1 to 6.

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