WO2018116923A1 - Électrode transparente et dispositif électronique - Google Patents

Électrode transparente et dispositif électronique Download PDF

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WO2018116923A1
WO2018116923A1 PCT/JP2017/044654 JP2017044654W WO2018116923A1 WO 2018116923 A1 WO2018116923 A1 WO 2018116923A1 JP 2017044654 W JP2017044654 W JP 2017044654W WO 2018116923 A1 WO2018116923 A1 WO 2018116923A1
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layer
ring
transparent electrode
silver
conductive layer
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PCT/JP2017/044654
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English (en)
Japanese (ja)
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邦夫 谷
大津　信也
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コニカミノルタ株式会社
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Priority to JP2018557705A priority Critical patent/JPWO2018116923A1/ja
Priority to CN201780077989.8A priority patent/CN110431919A/zh
Priority to KR1020197014393A priority patent/KR20190070959A/ko
Publication of WO2018116923A1 publication Critical patent/WO2018116923A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/816—Multilayers, e.g. transparent multilayers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

Definitions

  • 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 excellent durability, and an electronic device including the transparent electrode.
  • Organic EL elements using organic electroluminescence are thin, complete solid-state elements that can emit light at a low voltage of several volts to several tens of volts, and have high brightness. It has many excellent features such as high luminous efficiency, thinness and light weight. For this reason, in recent years, it has attracted attention as a backlight for various displays, a display board such as a signboard or emergency light, and a surface light emitter such as an illumination light source.
  • Such an organic EL element has a configuration in which a light emitting layer made of an organic material is interposed between two electrodes arranged opposite to each other. However, since the light generated in the light-emitting layer can be taken out only after passing through the electrode, at least one of the two electrodes needs to be a transparent electrode.
  • the transparent electrode is generally formed of an oxide semiconductor material such as indium tin oxide (SnO 2 —In 2 O 3 : Indium Tin Oxide, hereinafter “ITO”).
  • ITO indium tin oxide
  • studies have been made to reduce resistance by laminating silver on ITO.
  • ITO contains expensive indium (In)
  • a sputtering method has been mainly used for forming a transparent electrode using ITO or the like.
  • a transparent electrode is formed on an organic functional layer mainly made of an organic material. Therefore, when a transparent electrode is formed by a sputtering method, the organic functional layer is generated by vigorously flying atoms. Is damaged, and the original performance of the organic functional layer is impaired.
  • the transparent electrode as described above is used as, for example, a cathode of an organic EL element, high charge injection property to an adjacent layer is required.
  • a method for improving the charge injection property of a transparent electrode a method of incorporating a material having a low work function into the transparent electrode is known.
  • a method using a conductive layer containing a metal element different from silver and silver and a transparent electrode in which silver is laminated see Patent Documents 3 to 7.
  • a conductive layer containing silver and a metal element different from silver is often formed on the surface of lithium fluoride (LiF) that has insufficient affinity with silver.
  • LiF lithium fluoride
  • Japanese Patent No. 5328845 International Publication No. 2013/099867 Japanese Patent No. 4699098 International Publication No. 2011-013393
  • Japanese Patent No. 5603136 Japanese Patent Laying-Open No. 2015-173042 Japanese Patent No. 5901161
  • the present invention has been made in view of the above-described problems and situations, and a solution to the problem is to provide a transparent electrode having sufficient conductivity and light transmittance and excellent in stability over time, and the transparent electrode. Is to provide an electronic device.
  • the present inventor has provided a metal affinity layer containing a compound having a specific structure, and a silver affinity layer provided adjacent to the metal affinity layer. And a first conductive layer containing a metal different from the silver and a second conductive layer mainly composed of silver in this order can prevent silver diffusion, and as a result, excellent It has been found that a transparent electrode having both excellent electrical conductivity and light transmittance and excellent stability over time can be realized. Furthermore, it has been found that device characteristics can be improved by applying the transparent electrode to an electronic device, particularly an organic EL element, and the present invention has been achieved.
  • X 1 and X 2 each independently represent a nitrogen atom or CR 1.
  • R 1 represents a hydrogen atom or a substituent.
  • a 1 in the formula is a 5-membered or 6-membered product. Represents a residue constituting a heteroaryl ring.
  • X 1 , X 2 , X 3 and X 4 each independently represent a nitrogen atom or CR 1.
  • R 1 represents a hydrogen atom or a substituent.
  • a 1 and A in the formula 2 each independently represents a residue constituting a 5- or 6-membered heteroaryl ring
  • L 1 in the formula is a simple bond or a divalent linkage containing an aryl ring or a heteroaryl ring. Represents a group.
  • a 1 and A 2 are each independently a pyridine ring, pyrazine ring, triazine ring, pyridimine ring, azadibenzofuran ring, azadibenzothiophene ring, azacarbazole ring, quinazoline ring, quinoxaline ring, quinoline ring, isoquinoline ring, benzo 4.
  • a 1 and A 2 each independently represent a residue constituting an indole ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, a triazole ring, an oxazole ring or a thiazole ring.
  • the sum of the thickness of the first conductive layer and the thickness of the second conductive layer is in the range of 5 to 25 nm;
  • An electronic device comprising the transparent electrode according to any one of items 1 to 8.
  • Item 10 The electronic device according to Item 9, wherein the electronic device is an organic electroluminescence element.
  • the metal affinity layer and the conductive layer are adjacent to each other, and the first conductive layer and the second conductive layer constituting the conductive layer may be laminated in this order from the metal affinity layer side.
  • the production order of each layer is effective regardless of the order of production, but the mechanism of action and the mechanism of action are not clear at present. However, I guess as follows.
  • the first conductive layer on the surface of the metal affinity layer silver atoms constituting the first conductive layer interact with the silver affinity compound contained in the metal affinity layer, and the metal affinity layer It is considered that the diffusion distance of silver atoms on the surface is reduced, and as a result, migration (migration) and aggregation of silver to a specific location are suppressed. That is, a layer growth type in which silver atoms form a two-dimensional nucleus on the surface of a metal affinity layer having atoms having an affinity for silver atoms, and a two-dimensional single crystal layer is formed around that. It is presumed that it is formed by film growth of (Frank-van der Merwe: FM type).
  • an island-shaped growth type (Volume-) in which silver atoms attached on the surface of the metal affinity layer are bonded while diffusing on the surface to form a three-dimensional nucleus and grow into a three-dimensional island shape. It is considered that it is easy to form in an island shape by the film growth in (Weber: VW type).
  • the first conductive layer containing silver and a metal element different from silver has a silver alloy as a main component by controlling aggregation of silver atoms by the metal affinity layer as described above.
  • the film growth of the first conductive layer is controlled, and as a result, a thin but uniform conductive layer can be obtained. It is considered that this leads to both light transmission and conductivity.
  • the distribution in the thickness direction of the atomic ratio of silver and a metal different from silver is biased, which causes the light transmittance of the conductive layer and the sheet resistance to fluctuate.
  • the distribution of the atomic ratio of metal elements different from silver and silver is controlled by the silver affinity compound contained in the metal affinity layer. As a result, it is considered that a transparent electrode with small performance fluctuation over time can be obtained.
  • the silver atoms constituting the conductive layer are contained in the metal affinity layer. It is speculated that it interacts with atoms that have an affinity for silver atoms, and its mobility is suppressed. Thereby, the surface smoothness of the conductive layer can be improved and irregular reflection can be suppressed, and the light transmittance can be improved. In addition, it is considered that the interaction suppresses changes in the conductive layer in response to physical stimuli such as heat and temperature, and improves aging stability.
  • the electron injection property is improved by using a metal having a low work function as the electrode material and suppressing aggregation of the electrode material. It is important to form the interface with the layer to be uniform without gaps.
  • the transparent electrode configuration of the present invention contains silver and a metal element different from silver by using a metal affinity layer containing a compound having a structure represented by the general formula (1). It is estimated that the electron injecting property is improved because the first conductive layer is formed uniformly.
  • the transparent electrode structure of the present invention can form a thin film uniformly, and the sheet resistance can be lowered by laminating the second conductive layer mainly composed of low-resistance silver, so that in-plane light emission uniformity is improved. I guess that. Furthermore, it is important to improve stability over time that stable charge supply and sheet resistance do not fluctuate.
  • the transparent electrode structure of the present invention has improved stability over time because the distribution of the atomic ratio of the first conductive layer containing silver and a metal element different from silver can be controlled so as to hardly change even when time passes. I guess.
  • the portions other than the above-described electron injecting property are the same, and by adopting the configuration of the present invention, it is possible to provide an anode excellent in in-plane light emission uniformity and temporal stability. It is.
  • Schematic sectional view showing an example of the configuration of the transparent electrode of the present invention Schematic sectional view showing a first example of an organic EL device using the transparent electrode of the present invention
  • the transparent electrode of the present invention is provided with a metal affinity layer containing a compound having a structure represented by the general formula (1), and adjacent to the metal affinity layer, and silver and a metal different from the silver And a second conductive layer containing silver as a main component in that order.
  • This feature is a technical feature common to or corresponding to the claimed invention.
  • the compound having the structure represented by the general formula (1) is preferably an organic compound having a structure represented by the general formula (2).
  • the compound having the structure represented by the general formula (1) is preferably an organic compound having a structure represented by the general formula (2).
  • a 1 and A 2 each independently represent a residue constituting a 6-membered heteroaryl ring. Thereby, the effect of suppressing the diffusion distance of silver atoms and suppressing aggregation is obtained.
  • a 1 and A 2 are each independently a pyridine ring, pyrazine ring, triazine ring, pyridimine ring, azadibenzofuran ring, azadibenzothiophene ring, azacarbazole ring, quinazoline ring, It preferably represents a residue constituting a quinoxaline ring, a quinoline ring, an isoquinoline ring, a benzoquinoline ring, a benzoisoquinoline ring or a phenanthridine ring.
  • a 1 and A 2 each independently represent a residue constituting a 5-membered heteroaryl ring. Thereby, the effect of suppressing the diffusion distance of silver atoms and suppressing aggregation is obtained.
  • a 1 and A 2 each independently represent a residue constituting an indole ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, a triazole ring, an oxazole ring or a thiazole ring.
  • the effect of suppressing the diffusion distance of silver atoms and suppressing aggregation is obtained.
  • the concentration of silver contained in the first conductive layer is in the range of 50 to 99 at% (atomic%, atomic%). Thereby, the effect that the 1st conductive layer can be formed uniformly is acquired.
  • the total thickness of the first conductive layer and the second conductive layer is in the range of 5 to 25 nm, and the thickness of the second conductive layer is Is preferably in the range of 1 to 10 nm.
  • the transparent electrode according to the present invention can be suitably provided in an electronic device, particularly an organic electroluminescence element. Thereby, the effects of low power consumption and long life can be obtained.
  • the transparent electrode of the present invention comprises a metal affinity layer and a conductive layer formed adjacent to the metal affinity layer, wherein the metal affinity layer has the following general formula (1) And a conductive layer containing at least a first conductive layer containing silver and a metal different from the silver, and a second layer containing silver as a main component. A laminated structure including the conductive layers in this order is formed. Thereby, the transparent electrode of this invention can obtain the transparent electrode which has sufficient electroconductivity and light transmittance, and was excellent in temporal stability.
  • FIG. 1 is a schematic cross-sectional view showing an example of the basic configuration of the transparent electrode of the present invention.
  • the transparent electrode (1) has a metal affinity layer (11) and a conductive layer (12) adjacent to the metal affinity layer (11).
  • 12) is a three-layer structure in which a first conductive layer (12a) containing silver and a metal different from the silver and a second conductive layer (12b) containing silver as a main component are laminated in this order. It is.
  • the metal affinity layer (11), the first conductive layer (12a), and the second conductive layer (12b) are preferably provided in this order on the surface of the substrate (2).
  • “containing silver and a metal different from the silver” in the present invention means that silver and a metal different from silver are in a simple mixture state or an alloy.
  • the ratio of silver in the material component constituting the first conductive layer is in the range of 50 to 99 at%, preferably 70 at% or more, more preferably 80 at% or more, and further preferably 90 to 99 at%. Is within the range.
  • a metal different from silver mixed with silver will be described later.
  • “mainly composed of silver” means pure silver, silver in which a very small amount of impurities are naturally mixed, or an element other than a very small amount of silver in order to enhance the effect of the present invention. It is composed of silver contained as an accessory component.
  • the ratio of silver to the material component constituting the second conductive layer is in the range of more than 99 to 100 at%.
  • transparent as used in the transparent electrode (1) of the present invention means that the light transmittance at a wavelength of 500 nm is 50% or more, more preferably 60% or more, More preferably, the transmittance is 65% or more.
  • the material which comprises a base material (2) is not specifically limited, For example, glass, a plastics etc. can be mentioned.
  • the substrate (2) may be transparent or opaque, but when the substrate (2) is made of an opaque material, for example, a metal substrate such as aluminum or stainless steel, a film, An opaque resin substrate, a ceramic substrate, or the like can be used.
  • the transparent electrode (1) of the present invention is used in an electronic device that extracts light from the substrate (2) side, the substrate (2) is preferably transparent.
  • the transparent substrate (2) preferably used include glass, quartz, and a transparent resin film.
  • Examples of usable glass include silica glass, soda lime silica glass, lead glass, borosilicate glass, and alkali-free glass.
  • these glass materials are used as the base material (2), from the viewpoint of adhesion with the metal affinity layer (11), durability, and smoothness, physical surface such as polishing is used on the surface as necessary.
  • the film may be treated, or may be formed with a film made of an inorganic or organic material, or a hybrid film made of a combination thereof.
  • Usable resin films include, for example, polyesters such as polyethylene terephthalate (abbreviation: PET) and polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (abbreviation: TAC), and cellulose acetate.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • TAC cellulose triacetate
  • Cellulose esters such as butyrate, 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, polymethylpentene, polyetherketone, polyimide, polyethersulfone (abbreviation: PES), polyester Phenylene sulfide, polysulfones, polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate (abbreviation: PMMA), acrylic, polyarylates, Arton (trade name, manufactured by JSR) or Appel (trade name) And a film formed of a cycloolefin-based resin such as Mitsui Chemicals. When these resin films are used as the base material (2), a coating film made of an inorganic
  • Such coatings and hybrid coatings have a water vapor transmission rate (25 ⁇ 0.5 ° C., relative humidity 90 ⁇ 2% RH) of 0.01 g / (m 2 ) measured by a method according to JIS K 7129-1992. 24h)
  • the following barrier film also referred to as a barrier film or the like
  • the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 ⁇ 10 ⁇ 3 mL / (m 2 ⁇ 24 h ⁇ atm) or less
  • the water vapor permeability is 1 ⁇ 10 ⁇ 5 g / (m 2 ⁇ 24 h) or less high barrier film is preferable.
  • any material having a function of suppressing intrusion of factors that cause deterioration of electronic devices such as moisture and oxygen and organic EL elements may be used.
  • silicon oxide, silicon dioxide, nitriding Silicon or the like can be used.
  • the method for producing the barrier film is not particularly limited.
  • 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, and the plasma polymerization method are used.
  • An atmospheric pressure plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
  • the metal affinity layer (11) is a layer for preventing aggregation of silver in the conductive layer adjacent to the conductive layer (12), and interacts with silver to cause aggregation of the silver.
  • Examples of the substituent represented by R 1 include pyridine ring, pyrazine ring, triazine ring, pyrimidine ring, azadibenzofuran ring, azadibenzothiophene ring, azacarbazole ring, quinazoline ring, quinoxaline ring, quinoline ring, isoquinoline ring, benzoquinoline ring , Benzoisoquinoline ring, indole ring, imidazole ring, benzimidazole ring, pyrazole ring, triazole ring, oxazole ring, thiazole ring or carbazole ring.
  • a 1 represents a residue constituting a 5-membered or 6-membered heteroaryl ring.
  • the 5-membered one includes an imidazole ring, Examples thereof include a benzimidazole ring, a pyrazole ring, a triazole ring, an oxazole ring and a thiazole ring.
  • heteroaryl ring of the configurable by A as those of 6-membered pyridine ring, a pyrazine ring, a triazine ring, a pyrimidine ring, aza dibenzofuran ring, aza dibenzothiophene ring, a carboline ring, quinazoline ring, quinoxaline Ring, quinoline ring, isoquinoline ring, benzoquinoline ring, benzoisoquinoline ring or phenanthridine ring.
  • a 1 may further have a substituent.
  • a compound in which a lone pair of nitrogen atoms is involved in the formation of an aromatic ring such as an indole ring is also included in the compound having the structure represented by the general formula (1).
  • those constituting a metal complex such as lithium 8-hydroxyquinolate (Liq) and tris (8-quinolinolato) aluminum (Alq 3 ) are excluded from the compounds having the structure represented by the general formula (1). .
  • the compound having the structure represented by the general formula (1) is preferably an organic compound having a structure represented by the following general formula (2).
  • X 1 , X 2 , X 3 and X 4 each independently represent a nitrogen atom or CR 1.
  • R 1 represents a hydrogen atom or a substituent.
  • a 1 and A 2 each independently represent a residue constituting a 5-membered or 6-membered heteroaryl ring.
  • L 1 in the formula represents a simple bond or a divalent linking group containing an aryl ring or a heteroaryl ring.
  • a 1 and R 1 are synonymous with A 1 and R 1 in the general formula (1).
  • the heteroaryl ring that can be configured by including A 2 is preferably selected from the above-described heteroaryl rings that can be configured by including A 1 .
  • a 2 may further have a substituent as in A 1 .
  • a 2 may be the same as or different from A 1 .
  • Examples of the aryl ring that can constitute the divalent linking group represented by L 1 include, for example, a benzene ring, p-chlorophenyl ring, mesitylene ring, toluene ring, xylene ring, naphthalene ring, anthracene ring, azulenyl ring, and acenaphthenyl ring. Fluorenyl ring, phenanthryl ring, indenyl ring, pyrenyl ring, biphenylyl ring and the like.
  • organic compound having the structure represented by the general formula (2) does not include those constituting the metal complex.
  • organic compound having the structure represented by the general formula (1) It is the same.
  • the formation method of the metal affinity layer (11) is not particularly limited.
  • a wet method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, or a vapor deposition method (resistance heating, EB method, etc.).
  • a method using a dry process such as a sputtering method and a CVD method.
  • the vapor deposition method is preferably applied.
  • the thickness of the metal affinity layer (11) is preferably in the range of 1 to 100 nm, more preferably in the range of 3 to 50 nm, and any thickness within this range is acceptable. Even the effect can be obtained.
  • a thickness of 100 nm or less is preferable because the absorption component of the layer is reduced and the light transmittance of the transparent electrode (1) is improved. Moreover, if thickness is 3 nm or more, since a uniform and continuous metal affinity layer (11) is formed, it is preferable.
  • the compound having the structure represented by the general formula (1) or the general formula (2) contained in the metal affinity layer (11) has an energy level of the lowest unoccupied molecular orbital (LUMO) of ⁇ 2.
  • LUMO lowest unoccupied molecular orbital
  • the organic compound is in the range of 2 to ⁇ 1.6 eV, the energy levels of the metal atoms constituting the first conductive layer (12a), particularly the silver atoms, are close, and the electron orbits interact with each other. Is possible.
  • affinity with a 1st electroconductive layer (12) improves and aggregation of silver can be suppressed, it is preferable.
  • it is preferable to use the energy level because carrier injection from the conductive layer (12) and carrier transport to the light emitting layer are preferable.
  • the metal affinity layer (11) contains a material having a structure represented by the general formula (1) or the general formula (2) and a material for lowering the driving voltage or improving the light emission luminance.
  • a material for lowering the driving voltage or improving the light emission luminance There may be.
  • metals such as strontium, aluminum and La metal described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, lithium fluoride, Alkali metal compounds typified by sodium fluoride and potassium fluoride, alkaline earth metal compounds typified by magnesium fluoride and calcium fluoride, metal oxides typified by aluminum oxide, Liq and the like A metal complex etc. are mentioned.
  • the conductive layer (12) constituting the transparent electrode (1) of the present invention is a layer formed adjacent to the metal affinity layer (11).
  • the conductive layer (12) includes, from the metal affinity layer (11) side, a first conductive layer (12a) containing silver and a metal different from the silver, and a second layer mainly composed of silver. And a conductive layer (12b).
  • 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, a CVD method, etc. And a method using a dry process such as a method.
  • the vapor deposition method is preferably applied.
  • the thickness of the conductive layer (12) is preferably in the range of 5 to 25 nm, more preferably 5 to 18 nm, and still more preferably 5 to 12 nm. A thickness of 25 nm or less is more preferable because the absorption component or reflection component of the layer is reduced and the light transmittance of the transparent electrode (1) is improved. A thickness of 5 nm or more is preferable because the layer has sufficient conductivity.
  • the thickness of the first conductive layer (12a) is preferably in the range of 0.5 to 15 nm, and more preferably in the range of 1 to 5 nm. A thickness of 0.5 nm or more is preferable because stability during production can be secured. Further, it is preferable to set the thickness to 15 nm or less because the conductivity can be kept low.
  • the metal different from silver contained in the first conductive layer (12a) examples include magnesium (Mg), copper (Cu), palladium (Pd), indium (In), aluminum (Al), and cesium (Cs). ), Ytterbium (Yb) and the like.
  • the first conductive layer is preferably a silver alloy.
  • magnesium silver (MgAg), copper silver (CuAg), palladium silver (PdAg), indium silver (InAg), aluminum silver (AlAg), cesium silver (CsAg), ytterbium silver (YbAg), palladium copper silver (PdCuAg) and the like can be mentioned, among which magnesium silver (MgAg), aluminum silver (AlAg), and ytterbium silver (YbAg) are preferable.
  • the thickness of the second conductive layer (12b) is preferably 1 to 10 nm, and more preferably 1 to 5 nm. If it is thinner than 10 nm, the absorption component or reflection component of the layer is reduced, and if it is thicker than 1 nm, the entire conductive layer (12) can be formed uniformly, which is preferable from the viewpoint of conductivity.
  • the silver forming the second conductive layer (12b) is preferably as pure as possible.
  • the sheet resistance value of the transparent electrode (1) having a laminated structure including the metal affinity layer (11) and the conductive layer (12) adjacent to the metal affinity layer (11) is several hundred ⁇ / sq. And preferably 100 ⁇ / sq. The following is more preferable. Further, from the viewpoint of increasing the area of the electrode, 50 ⁇ / sq. Or less, preferably 20 ⁇ / sq. It is more preferable that
  • the surface of the electroconductive layer (12) may be covered with the protective film.
  • the protective film has light transmittance so as not to impair the light transmittance of the transparent electrode (1).
  • another conductive layer may be provided adjacent to the opposite side of the second conductive layer (12b) where the first conductive layer (12a) is present. In this case, it is preferable not to impair the light transmittance and conductivity of the transparent electrode (1).
  • a metal affinity layer (11) is further formed on the opposite side of the second conductive layer (12b) to the side where the first conductive layer (12a) is present. The conductive layer (12) may be sandwiched between two metal affinity layers (11).
  • the transparent electrode (1) of the present invention is configured as described above, and thus when the first conductive layer (12a) is formed on the surface of the metal affinity layer (11), the first conductive layer ( The silver atom constituting 12a) interacts with a compound containing in its molecule a heteroatom having an unshared electron pair constituting the metal affinity layer (11). For this reason, it is presumed that the diffusion distance of silver atoms on the surface of the metal affinity layer (11) is reduced and aggregation of silver is suppressed.
  • the thin film growth is generally performed by an island-like growth type (Volume-Weber: VW type). For this reason, silver particles are easily isolated in an island shape, and when the first conductive layer (12a) is thin, it is difficult to obtain conductivity, and there is a problem that the sheet resistance value is increased. In order to ensure conductivity, it is necessary to increase the thickness of the first conductive layer (12a). However, if the thickness is increased, the light transmittance is lowered, so that it is not suitable as a transparent electrode.
  • the transparent electrode (1) of the configuration of the present invention since aggregation of silver is suppressed on the metal affinity layer (11) as described above, formation of the first conductive layer (12a) containing silver is formed. Is estimated to grow a thin film in a layered growth type (Frank-van der Merwe: FM type).
  • the transparent electrode (1) of the present invention is “transparent” when the light transmittance at a wavelength of 500 nm is 50% or more, but it is used as the metal affinity layer (11).
  • Each of these materials forms a sufficiently light-transmitting film as compared with the first conductive layer (12a) containing silver and a metal different from silver.
  • the conductivity of the transparent electrode (1) is ensured by the first conductive layer (12a) and the second conductive layer (12b) mainly composed of silver. That is, although the first conductive layer (12a) and the second conductive layer (12b) are thin, conductivity is ensured. Therefore, it is possible to achieve both the improvement of the conductivity of the transparent electrode (1) and the improvement of the light transmittance.
  • the conductive layer (12) is formed first, and then the metal affinity layer (11) is formed adjacent to the conductive layer (12), the silver atoms constituting the conductive layer
  • the mobility is suppressed by interacting with atoms having an affinity for silver atoms contained in the metal affinity layer.
  • irregular reflection can be suppressed by improving the surface smoothness of the conductive layer (12), and the light transmittance can be improved.
  • the interaction suppresses changes in the conductive layer (12) with respect to physical stimuli such as heat and temperature, and improves the temporal stability.
  • the 1st containing the metal element different from silver and silver is used for the organic compound which the said metal affinity layer (11) contains by using the compound which has a structure represented by the said General formula (1). It is also possible to suppress the element distribution in the thickness direction in the conductive layer (12a). As a result, the electrode characteristics such as light transmittance and sheet resistance of the transparent electrode (1) are improved, and when used as a cathode, the time-dependent fluctuation of the electron injection property to the adjacent metal affinity layer (11) is reduced. Therefore, it is preferable.
  • the transparent electrode (1) of the present invention described above can be used for various electronic devices.
  • Examples of electronic devices include organic EL elements, LEDs (Light Emitting Diodes), liquid crystal elements, solar cells, touch panels, and the like.
  • the transparent electrode (1) described above can be used as an electrode member that requires light transmission in these electronic devices.
  • the transparent electrode (1) of the present invention is preferably applied to an organic EL element.
  • an embodiment of an organic EL element will be described as an example of an electronic device using the transparent electrode (1) of the present invention.
  • FIG. 2 is a schematic cross-sectional view of an organic EL element according to Configuration Example 1.
  • the organic EL element according to this example has a so-called bottom emission type, that is, has a transparent substrate, and takes out light from the transparent substrate side.
  • the transparent electrode (1), the light emitting functional layer (3), and the counter electrode (4) are laminated in this order on the transparent substrate (2). Yes.
  • the transparent electrode (1) of the present invention described above is used as the transparent electrode.
  • the organic EL element (100) is configured to be able to take out the generated light (hereinafter referred to as emitted light (h)) from at least the transparent substrate (2) side.
  • the layer structure of the organic EL element (100) is not limited to the example described below, and may be a general layer structure.
  • the transparent electrode (1) functions as an anode (that is, an anode)
  • the counter electrode (4) functions as a cathode (that is, a cathode).
  • each layer constituting the light emitting functional layer (3) is, for example, from the transparent electrode (1) side which is an anode, for example, a hole injection layer (3a), a hole transport layer (3b), a light emitting layer (3c),
  • the electron transport layer (3d) and the electron injection layer (3e) are stacked in this order, and it is essential to have at least the light emitting layer (3c).
  • the light emitting functional layer (3) may be laminated with a hole blocking layer, an electron blocking layer, or the like as required.
  • the light emitting layer (3c) may have a structure in which each color light emitting layer for generating the emitted light h in each wavelength region is laminated, and each of these color light emitting layers is laminated via a non-light emitting auxiliary layer.
  • the auxiliary layer may function as a hole blocking layer or an electron blocking layer.
  • the counter electrode (4) which is a cathode may also have a laminated structure as required. In such a configuration, only a portion sandwiched between the transparent electrode (1) and the counter electrode (4) in the light emitting functional layer (3) serves as a light emitting region in the organic EL element (100).
  • the hole injection layer (3a) and the hole transport layer (3b) may be a hole transport injection layer having both functions.
  • the electron transport layer (3d) and the electron injection layer (3e) may be electron transport injection layers having both functions.
  • the electron injection layer (3e) may be made of an inorganic material.
  • the organic EL element (100) configured as described above is sealed on the transparent substrate (2) for the purpose of preventing deterioration of the light emitting functional layer (3) configured using an organic material or the like. It is sealed with a material (6).
  • This sealing material (6) is being fixed to the transparent substrate (2) side via the adhesive agent (7).
  • the terminal portions of the transparent electrode (1) and the counter electrode (4) were exposed from the sealing material (6) in a state in which they were insulated from each other by the light emitting functional layer (3) on the transparent substrate (2). It is assumed that it is provided in a state.
  • the details of the main layers for constituting the organic EL element (100) described above are described in the light emitting layer (3c) of the transparent substrate (2), the transparent electrode (1), the counter electrode (4), and the light emitting functional layer (3). ), The other layers (3a, 3b, 3d, 3e) of the light emitting functional layer (3), the auxiliary electrode (5), and the sealing material (6) will be described in this order.
  • the transparent substrate (2) is a base material (2) on which the transparent electrode (1) of the present invention described above is provided, and among the materials of the base material (2) described above, a transparent material having optical transparency. It is formed using things.
  • the transparent electrode (1) is the transparent electrode (1) of the present invention described above, and from the transparent substrate (2) side, the metal affinity layer (11), the first conductive layer (12a), and the second conductive layer. It is the structure which laminated
  • the transparent electrode (1) functions as an anode, and the first conductive layer (12a) and the second conductive layer (12b) are substantial anodes.
  • the transparent electrode (1) may be provided with the auxiliary electrode (5) in contact with each layer (12a, 12b) of the transparent electrode (1). Good.
  • the counter electrode (4) is an electrode film that functions as a cathode for supplying electrons to the light emitting functional layer (3), and is made of a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof. Specifically, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TiO 2 , An oxide semiconductor such as SnO 2 can be given.
  • the counter electrode (4) can be formed by a method such as vapor deposition or sputtering of these conductive materials.
  • the sheet resistance value of the counter electrode (4) is several hundred ⁇ / sq. The following is preferable, and the thickness is usually selected within the range of 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • this organic EL element (100) is what takes out emitted light (h) also from the counter electrode (4) side, it has the favorable light transmittance selected from the electrically conductive material mentioned above.
  • the counter electrode (4) should just be comprised with the electroconductive material.
  • the light emitting layer (3c) used in the present invention contains a light emitting material.
  • a phosphorescent compound phosphorescent material, phosphorescent compound, phosphorescent compound
  • the light emitting layer (3c) is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer (3d) and holes injected from the hole transport layer (3b), and emits light.
  • the portion may be in the layer of the light emitting layer (3c) or the interface between the light emitting layer (3c) and the adjacent layer.
  • a light emitting layer (3c) there is no restriction
  • the total thickness of the light emitting layer (3c) is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained.
  • the sum total of the thickness of a light emitting layer (3c) is a thickness also including the said auxiliary layer, when a nonluminous auxiliary layer exists between light emitting layers (3c).
  • the thickness of each light emitting layer (3c) is preferably adjusted within the range of 1 to 50 nm, and is adjusted within the range of 1 to 20 nm. It is more preferable.
  • the plurality of stacked light emitting layers (3c) correspond to the respective emission colors of blue, green, and red
  • the thickness relationship of each of the blue, green, and red light emitting layers (3c) is not particularly limited. Absent.
  • the light emitting layer (3c) configured as described above is prepared by using a known thin film forming method such as a vacuum evaporation method, a spin coating method, a casting method, an LB method, and an ink jet method, for example, by using a light emitting material and a host compound described later. Can be formed. Further, the light emitting layer (3c) may be configured by mixing a plurality of light emitting materials, and is configured by mixing a phosphorescent compound and a fluorescent compound (fluorescent material, fluorescent dopant). May be. As a structure of the light emitting layer (3c), it is preferable to contain a host compound (light emitting host) and a light emitting material (light emitting dopant) and to emit light from the light emitting material.
  • a host compound light emitting host
  • a light emitting material light emitting dopant
  • the compound whose phosphorescence quantum yield of phosphorescence emission in room temperature (25 degreeC) is less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in a light emitting layer (3c).
  • a well-known host compound may be used independently, or multiple types may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.
  • the host compound used may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .
  • the known host compound a compound having a hole transporting ability and an electron transporting ability while preventing the emission of light from being increased in wavelength and having a high Tg (glass transition temperature) is preferable.
  • the glass transition temperature here is a value determined by a method based on JIS K 7121 using DSC (Differential Scanning Calorimetry).
  • Phosphorescent compound As the luminescent material that can be used in the present invention, a phosphorescent compound is exemplified.
  • a phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C.
  • a preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.
  • the phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, when the phosphorescent compound is used in the present invention, the above phosphorescence quantum yield (0.01 or more) is obtained in any solvent. It only has to be achieved.
  • the phosphorescent compound There are two types of light emission principles of the phosphorescent compound. One is that recombination of carriers occurs on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent compound to emit light from the phosphorescent compound. Energy transfer type. The other is a carrier trap type in which the phosphorescent compound becomes a carrier trap, and recombination of carriers occurs on the phosphorescent compound, and light emission from the phosphorescent compound is obtained. In either case, the condition is that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.
  • the phosphorescent compound can be appropriately selected from known compounds used for a light emitting layer of a general organic EL device, and among them, it contains a metal of group 8 to 10 in the periodic table of elements.
  • the complex compound is preferably an iridium compound, an osmium compound, a platinum compound (platinum complex compound), or a rare earth complex, and more preferably an iridium compound.
  • At least one light emitting layer (3c) may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compounds in the light emitting layer (3c) is the light emitting layer (3c). ) In the thickness direction.
  • the content of the phosphorescent compound is preferably in the range of 0.1 to 30% by volume with respect to the total amount of the light emitting layer (3c).
  • phosphorescent dopants that can be used in the present invention include compounds described in the following documents. Nature 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Application Publication No. 2006/835469, US Patent Application Publication No. 2006 /. No. 0202194, U.S. Patent Application Publication No. 2007/0087321, U.S. Patent Application Publication No. 2005/0244673, Inorg. Chem.
  • a preferable phosphorescent dopant includes an organometallic complex having Ir as a central metal. More preferably, a complex containing at least one coordination mode among a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferable.
  • the above phosphorescent compound (also referred to as a phosphorescent metal complex or the like) is described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, pp. 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, pages 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, pages 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and further synthesized by applying methods such as patent documents described in these documents. can do.
  • the luminescent material that can be used in the present invention includes a fluorescent compound.
  • Fluorescent compounds include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes Examples thereof include dyes, polythiophene dyes, and rare earth complex phosphors.
  • the injection layer is a layer provided between the electrode and the light-emitting layer (3c) for lowering the driving voltage and improving the light emission luminance.
  • the organic EL element and its industrialization front line June 30, 1998, N. 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of “T. S. Co., Ltd.”, which has a hole injection layer (3a) and an electron injection layer (3e).
  • the injection layer can be provided as necessary.
  • hole injection layer (3a) If it is a hole injection layer (3a), it will be between an anode and a light emitting layer (3c) or a hole transport layer (3b), and if it is an electron injection layer (3e), it will be a cathode, a light emitting layer (3c), or an electron transport layer. (3d) may be present.
  • hole injection layer (3a) The details of the hole injection layer (3a) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like, and a specific example is represented by copper phthalocyanine.
  • Phthalocyanine layers oxide layers typified by vanadium oxide, amorphous carbon layers, polymer layers using conductive polymers such as polyaniline (emeraldine) and polythiophene, and the like.
  • the electron injection layer (3e) is desirably a very thin film, and preferably has a thickness in the range of 1 nm to 10 ⁇ m, although it depends on the material.
  • the hole transport layer (3b) is made of a hole transport material having a function of transporting holes.
  • the hole injection layer (3a) and the electron blocking layer are also included in the hole transport layer (3b).
  • the hole transport layer (3b) can be provided as a single layer or a plurality of layers.
  • the hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • triazole derivatives oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives
  • Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • a porphyrin compound an aromatic tertiary amine compound, and a styryl amine compound, especially an aromatic tertiary amine compound.
  • aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminoph
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material. JP-A-11-251067, J. Org. Huang et. al. , Applied Physics Letters, 80 (2002), p.
  • a so-called p-type hole transport material as described in 139 can also be used. In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.
  • the hole transport layer (3b) is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Can be formed.
  • the thickness of the hole transport layer (3b) is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the hole transport layer (3b) may have a single layer structure composed of one or more of the above materials.
  • the material of the hole transport layer (3b) can be doped with impurities to increase the p property.
  • impurities examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
  • the electron transport layer (3d) is made of a material having a function of transporting electrons, and in a broad sense, the electron injection layer (3e) and the hole blocking layer are also included in the electron transport layer (3d).
  • the electron transport layer (3d) can be provided as a single layer structure or a multilayer structure of a plurality of layers.
  • an electron transport material also serving as a hole blocking material constituting a layer portion adjacent to the light emitting layer (3c) in the electron transport layer (3d) having a single layer structure and the electron transport layer (3d) having a multilayer structure
  • a cathode is used as an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer (3c) in the electron transport layer (3d) having a single layer structure and the electron transport layer (3d) having a multilayer structure. It is only necessary to have a function of transmitting more injected electrons to the light emitting layer (3c).
  • any one of conventionally known compounds can be selected and used.
  • Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group are also used as the material for the electron transport layer (3d).
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq 3 ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) Aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc.
  • Mg Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the material for the electron transport layer (3d).
  • metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the material for the electron transport layer (3d).
  • the distyrylpyrazine derivative used also as a material of a light emitting layer (3c) can also be used as a material of an electron carrying layer (3d), and is the same as that of a positive hole injection layer (3a) and a positive hole transport layer (3b).
  • inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the material for the electron transport layer (3d).
  • the electron transport material mentioned here can also be added to the metal affinity layer (11) described above for the purpose of lowering the driving voltage and improving the light emission luminance.
  • the electron transport layer (3d) can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can.
  • the thickness of the electron transport layer (3d) is not particularly limited, but is usually about 5 nm to 5 ⁇ m, preferably 5 to 200 nm.
  • the electron transport layer (3d) may have a single layer structure composed of one or more of the above materials.
  • the electron transport layer (3d) can be doped with impurities to increase the n property.
  • impurities include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
  • the potassium compound for example, potassium fluoride can be used.
  • the material (electron transporting compound) of the electron transport layer (3d) the same material as that constituting the metal affinity layer (11) according to the present invention may be used.
  • the electron injecting and transporting layer also serving as the electron injecting layer (3e)
  • the same material as that constituting the metal affinity layer (11) according to the present invention may be used. It may also serve as an affinity layer.
  • the blocking layer is provided as necessary in addition to the basic constituent layer of the light emitting functional layer (3). For example, it is described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization (published by NTT Corporation on November 30, 1998)” on page 237. There is a hole blocking (hole blocking) layer.
  • the hole blocking layer has a function of an electron transport layer (3d) in a broad sense.
  • the hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved.
  • the structure of said electron carrying layer (3d) can be used as a hole-blocking layer as needed.
  • the hole blocking layer is preferably provided adjacent to the light emitting layer (3c).
  • the electron blocking layer has a function of a hole transport layer (3b) in a broad sense.
  • the electron blocking layer is made of a material that has a function of transporting holes but has a very small ability to transport electrons, and improves the probability of recombination of electrons and holes by blocking electrons while transporting holes. be able to.
  • the structure of said positive hole transport layer (3b) can be used as an electron blocking layer as needed.
  • the thickness of the hole blocking layer is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.
  • the auxiliary electrode (5) is provided for the purpose of reducing the resistance of the transparent electrode (1), and is provided so as to be in contact with the first conductive layer (12a) and the second conductive layer (12b), respectively. Yes.
  • a metal having low resistance such as gold, platinum, silver, copper, and aluminum, is preferable. Since these metals have low light transmittance, a pattern is formed in a range not affected by extraction of the emitted light h from the light extraction surface (2a).
  • Examples of a method for producing such an auxiliary electrode (5) include a vapor deposition method, a sputtering method, a printing method, an ink jet method, and an aerosol jet method.
  • the line width of the auxiliary electrode (5) is preferably 50 ⁇ m or less from the viewpoint of the aperture ratio for extracting light, and the thickness of the auxiliary electrode (5) is preferably 1 ⁇ m or more from the viewpoint of conductivity.
  • the sealing material (6) covers the organic EL element (100), is a plate-shaped (film-shaped) sealing member, and is fixed to the transparent substrate (2) side by an adhesive (7). It may be a thing or a sealing film.
  • a sealing material (6) is provided in a state of covering at least the light emitting functional layer (3) in a state in which the terminal portions of the transparent electrode (1) and the counter electrode (4) in the organic EL element (100) are exposed. It has been.
  • an electrode may be provided in the sealing material (6), and the transparent electrode (1) of the organic EL element (100) and the terminal portion of the counter electrode (4) may be electrically connected to this electrode. .
  • the plate-like (film-like) sealing material (6) include a glass substrate, a polymer substrate, a metal substrate, and the like, and these substrate materials may be used in the form of a thin film.
  • the glass substrate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal substrate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • the polymer substrate in the form of a film has an oxygen permeability of 1 ⁇ 10 ⁇ 3 mL / (m 2 ⁇ 24 h ⁇ atm) or less measured by a method according to JIS K 7126-1987, and JIS K 7129-1992.
  • the water vapor permeability (25 ⁇ 0.5 ° C., relative humidity (90 ⁇ 2)% RH) measured by a method in accordance with the above is 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less. It is preferable.
  • the adhesive (7) for fixing such a plate-shaped sealing material (6) to the transparent substrate (2) side is an organic sandwiched between the sealing material (6) and the transparent substrate (2). Used as a sealant for sealing the EL element (100).
  • the adhesive (7) is a photocuring and thermosetting adhesive having a reactive vinyl group of an acrylic acid-based oligomer or a methacrylic acid-based oligomer, or moisture curing such as 2-cyanoacrylate. Examples thereof include an adhesive such as a mold.
  • the adhesive (7) is preferably one that can be adhesively cured from room temperature to 80 ° C. Further, a desiccant may be dispersed in the adhesive (7).
  • coating of the adhesive agent (7) to the adhesion part of a sealing material (6) and a transparent substrate (2) may use commercially available dispenser, and may print like screen printing.
  • this gap has nitrogen, argon, etc. in the gas phase and liquid phase.
  • an inert liquid such as an inert gas, a fluorinated hydrocarbon, or silicon oil.
  • a vacuum can also be used.
  • a hygroscopic compound can also be enclosed inside.
  • hygroscopic compound examples include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate).
  • metal oxides for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide
  • sulfates for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate.
  • metal halides eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.
  • perchloric acids eg perchloric acid Barium, magnesium perchlorate, and the like
  • anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.
  • a sealing film is used as the sealing material (6), the light emitting functional layer (3) in the organic EL element (100) is completely covered, and the transparent electrode (1) and the counter electrode in the organic EL element (100) are covered.
  • a sealing film is provided on the transparent substrate (2) with the terminal portion (4) exposed.
  • Such a sealing film is configured using an inorganic material or an organic material. In particular, it is made of a material having a function of suppressing entry of a substance that causes deterioration of the light emitting functional layer (3) in the organic EL element (100) such as moisture and oxygen.
  • inorganic materials such as silicon oxide, silicon dioxide, and silicon nitride are used.
  • a laminated structure may be formed by using a film made of an organic material together with a film made of these inorganic materials.
  • the method for producing these films is not particularly limited.
  • a polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.
  • a protective film or a protective plate may be provided so as to sandwich the organic EL element (100) and the sealing material (6) together with the transparent substrate (2).
  • the protective film or the protective plate is for mechanically protecting the organic EL element (100).
  • the sealing material (6) is a sealing film
  • the protective film or the protective plate is used for the organic EL element (100). Since mechanical protection is not sufficient, it is preferable to provide such a protective film or protective plate.
  • a glass plate, a polymer plate, a thinner polymer film, a metal plate, a thinner metal film, a polymer material film or a metal film is applied.
  • a polymer film because it is light and thin.
  • a metal affinity layer (11) containing a compound having a structure represented by the general formula (1) or the general formula (2) according to the present invention is deposited on the transparent substrate (2) by vapor deposition or the like.
  • the film is formed to have a thickness of 1 ⁇ m or less, preferably 10 to 100 nm.
  • a first conductive layer (12a) containing silver and a metal different from silver is formed to have a thickness of 0.5 by an appropriate method such as a vapor deposition method. It is formed to be in the range of ⁇ 15 nm.
  • the second conductive layer (12b) containing silver as a main component on the first conductive layer (12a) has a thickness in the range of 1 to 10 nm by an appropriate method such as vapor deposition. And the thickness combined with the first conductive layer (12a) is in the range of 5 to 25 nm.
  • the transparent electrode (1) serving as the anode is formed on the transparent substrate (2).
  • the conductive layer (12) is formed on the metal affinity layer (11), a high-temperature annealing treatment (for example, a heating process at 150 ° C. or higher) after the formation of the conductive layer (12). ) And the like, the conductive layer 12 is sufficiently conductive. However, if necessary, a high temperature annealing treatment or the like may be performed after the formation.
  • the hole injection layer (3a), the hole transport layer (3b), the light emitting layer (3c), the electron transport layer (3d), and the electron injection are formed on the transparent electrode (1).
  • the light emitting functional layer (3) is formed by laminating the layers (3e) in this order.
  • the electron transporting layer (3d) and the electron injecting layer (3e) may be formed as one layer, for example, an electron injecting and transporting layer. Is possible.
  • each of these layers includes a spin coating method, a cast method, an ink jet method, a vapor deposition method, a printing method, etc., but from the viewpoint that a homogeneous film is easily obtained and pinholes are not easily generated, A spin coating method is particularly preferred. Further, different formation methods may be applied for each layer.
  • the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C. and a degree of vacuum of 1 ⁇ 10 ⁇ 6 to 1 ⁇ 10 ⁇ 2 Pa. It is desirable to appropriately select the respective conditions within the range of the deposition rate of 0.01 to 50 nm / second, the substrate temperature of ⁇ 50 to 300 ° C., and the thickness of 0.1 to 5 ⁇ m.
  • the counter electrode (4) serving as a cathode is formed on the light emitting functional layer (3) by an appropriate method such as vapor deposition or sputtering.
  • the counter electrode (4) has a terminal portion on the periphery of the transparent substrate (2) from above the light emitting functional layer (3) while maintaining an insulating state with respect to the transparent electrode (1) by the light emitting functional layer (3).
  • a pattern is formed in the shape of the extracted layer.
  • an organic EL element (100) is obtained.
  • a sealing material (6) covering at least the light emitting functional layer (3) is provided in a state where the terminal portions of the transparent electrode (1) and the counter electrode (4) in the organic EL element (100) are exposed. .
  • a desired organic EL element (100) is obtained on the transparent substrate (2).
  • the transparent electrode (1) as an anode has a positive polarity and the counter electrode (4) as a cathode has a negative polarity.
  • a voltage of about 2 to 40 V is applied, light emission can be observed.
  • An alternating voltage may be applied.
  • the alternating current waveform to be applied may be arbitrary.
  • the transparent electrode (1) having the conductivity, light transmittance and stability over time of the present invention is used as the anode, and the light emitting functional layer (3) and the cathode are formed thereon.
  • the counter electrode (4) is provided. For this reason, a sufficient voltage is applied between the transparent electrode (1) and the counter electrode (4) to realize high-luminance light emission in the organic EL element (100), and a drive voltage for obtaining a predetermined luminance. Reduction, in-plane uniform light emission, and stability over time can be improved.
  • FIG. 3 is a schematic cross-sectional view of an organic EL element according to Configuration Example 2.
  • the organic EL element (200) according to this example is a bottom emission type as in the configuration example 1, but the transparent electrode (1) is used as a cathode (the counter electrode (4) is an anode). This is different from the configuration example 1 described above.
  • the same components as those of the organic EL element (100) according to the configuration example 1 is omitted, and a characteristic configuration of the organic EL element (200) of the configuration example 2 will be described.
  • the organic EL element (200) is provided on the transparent substrate (2), and the transparent electrode (on the transparent substrate (2) ( The transparent electrode (1) of the present invention described above is used as 1). For this reason, the organic EL element (200) is configured to extract emitted light (h) from at least the transparent substrate (2) side.
  • the layer structure of the organic EL element (200) configured as described above is not limited to the example described below, and may be a general layer structure as in the configuration example 1. .
  • the electron injection layer (3e) / electron transport layer (3d) / light emitting layer (3c) / holes are formed on the transparent electrode (1) functioning as the cathode.
  • stacked the transport layer (3b) / hole injection layer (3a) in this order is illustrated.
  • the light emitting functional layer (3) adopts various configurations as required in the same manner as described in the configuration example 1. In such a configuration, only the portion sandwiched between the transparent electrode (1) and the counter electrode (4) in the light emitting functional layer (3) may be a light emitting region in the organic EL element (200). Similar to Example 1.
  • the auxiliary electrode (5) is provided on each layer (12a, 12b) of the conductive layer (12) for the purpose of reducing the resistance of the transparent electrode (1). This may also be the same as the configuration example 1 shown in FIG.
  • the counter electrode (4) used as the anode is composed of a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof. Specific examples include metals such as gold (Au), oxide semiconductors such as copper iodide (CuI), ITO, ZnO, TiO 2 , and SnO 2 .
  • the counter electrode (4) configured as described above can be produced by forming a thin film of these conductive materials by a method such as vapor deposition or sputtering.
  • the sheet resistance value as the counter electrode (4) is several hundred ⁇ / sq.
  • the thickness is preferably 5 nm to 5 ⁇ m, and preferably 5 to 200 nm.
  • this organic EL element (200) is comprised so that emitted light (h) can be taken out also from a counter electrode (4) side, as a material which comprises a counter electrode (4), it is the electroconductivity mentioned above.
  • a conductive material having good light transmittance is selected and used.
  • the organic EL element (200) having the above configuration may be sealed with a sealing material (6) in the same manner as in the configuration example 1 for the purpose of preventing the deterioration of the light emitting functional layer (3). This is the same as the configuration example 1 shown in FIG.
  • the organic EL element (200) described above uses the transparent electrode (1) having the conductivity, light transmittance and stability over time of the present invention as a cathode, and serves as a light emitting functional layer (3) and an anode thereon.
  • the counter electrode (4) is provided. For this reason, as in the configuration example 1, a sufficient voltage is applied between the transparent electrode (1) and the counter electrode (4) to realize high-luminance emission in the organic EL element (200), while maintaining a predetermined luminance. It is possible to reduce the drive voltage for obtaining the same, improve the in-plane uniform light emission property, and the stability over time.
  • FIG. 4 is a schematic cross-sectional view showing a configuration example 3 of an organic EL element using the transparent electrode (1A) of the present invention as an example of the electronic device of the present invention.
  • the organic EL element (300) of the configuration example 3 shown in FIG. 4 is a so-called top emission type, that is, the counter electrode (4A) is provided on the substrate (2A) side, and the light emitting functional layer (3) is provided on this surface.
  • stacked the transparent electrode (1A) in order is different from the structural example 1.
  • a detailed description of the same constituent elements as those in the configuration example 1 will be omitted, and a characteristic configuration of the organic EL element (300) in the configuration example 3 will be described.
  • the organic EL element (300) shown in FIG. 4 is provided on the substrate (2A). From the substrate (2A) side, the counter electrode (4A) serving as the anode, the light emitting functional layer (3), and the cathode Transparent electrodes (1A) to be formed are laminated in this order. Among these, the transparent electrode (1A) is the same as the transparent electrode (1) of the present invention described above. For this reason, the organic EL element (300) is configured to extract emitted light (h) from at least the transparent electrode (1A) side opposite to the substrate (2A).
  • the layer structure of the organic EL element (300) configured as described above is not limited to the example described below, and may be a general layer structure as in the configuration example 1.
  • the hole injection layer (3a), the hole transport layer (3b), the light emitting layer (3c), the electron transport layer are formed on the surface of the counter electrode (4A) functioning as the anode.
  • stacked (3d) in this order is illustrated.
  • the electron transport layer (3d) and the electron injection layer (3e) are materials having both electron transport properties and electron injection properties, for example, only the electron transport layer (3d) can be used.
  • the characteristic structure of the organic EL element (300) of Structural Example 3 is that the electron injection layer (3e) also functions as the metal affinity layer (11) in the transparent electrode (1A).
  • the transparent electrode (1A) includes an electron injection layer (3e), a first conductive layer (12a) provided adjacent to the surface, a second conductive layer (12b), It consists of This electron injection layer (3e) is comprised using the material which comprises the metal affinity layer (11) of the transparent electrode (1) of this invention mentioned above.
  • the light emitting functional layer (3) may employ various configurations as necessary, similar to those described in the configuration example 1, but the electron injection of the transparent electrode (1A) Between the layer (3e, metal affinity layer) and the first conductive layer (12a) containing a metal element different from silver and silver, and the first conductive containing a metal element different from silver and silver No other layer is provided between the conductive layer (12a) and the second conductive layer (12b) containing silver as a main component.
  • the light emitting functional layer (3) only the portion sandwiched between the transparent electrode (1A) and the counter electrode (4A) becomes a light emitting region in the organic EL element (300). This is the same as the configuration example 1.
  • the second conductive layer (12b) mainly composed of silver of the transparent electrode (1A) is used.
  • the auxiliary electrode (5) may be provided in contact therewith.
  • the counter electrode (4A) used as the anode is composed of a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof.
  • metals such as gold (Au), oxide semiconductors such as copper iodide (CuI), ITO, ZnO, TiO 2 , and SnO 2 .
  • the counter electrode (4A) configured as described above can be produced by forming a thin film from these conductive materials by a method such as vapor deposition or sputtering.
  • the sheet resistance value as the counter electrode (4A) is several hundred ⁇ / sq.
  • the thickness is preferably 5 nm to 5 ⁇ m, and preferably 5 to 200 nm.
  • this organic EL element (300) is comprised so that emitted light (h) can be taken out also from a counter electrode (4A) side
  • a material which comprises a counter electrode (4A) it is the electroconductivity mentioned above.
  • a conductive material having good light transmittance is selected and used.
  • the substrate (2A) the same substrate as the transparent substrate (2) described in the configuration example 1 is used, and the surface facing the outside of the substrate (2A) becomes the light extraction surface (2a).
  • the electron injection layer (3e) constituting the uppermost part of the light emitting functional layer (3) is used as the metal affinity layer (11), and a metal different from silver and silver is formed thereon.
  • a metal affinity layer (11) and a conductive layer (12 on the top) Including a transparent electrode (1A) as a cathode.
  • a sufficient voltage is applied between the transparent electrode (1A) and the counter electrode (4A) to realize high luminance light emission in the organic EL element (300).
  • it is possible to increase the luminance by improving the extraction efficiency of the emitted light (h) from the transparent electrode (1A) side.
  • it becomes possible to reduce the driving voltage for obtaining a predetermined luminance improve the in-plane uniform light emission property, and the stability over time.
  • the counter electrode (4A) is light transmissive, the emitted light (h) can be extracted from the counter electrode (4A).
  • the metal affinity layer (11) of the transparent electrode (1A) has been described as also serving as the electron transport layer (3e) having an electron injection property. Is not limited to this, and the metal affinity layer (11) may also serve as the electron transport layer (3d). Further, the metal affinity layer (11) may be formed as an extremely thin film that does not affect the light emitting function of the organic EL element. In this case, the metal affinity layer (11) is an electron transport layer. And have no electron injection property.
  • the substrate (2A) side The counter electrode (4A) may be a cathode, and the transparent electrode (1A) on the light emitting functional layer (3) may be an anode.
  • the light emitting functional layer (3) is formed, for example, in order from the counter electrode (cathode, 4A) side on the substrate (2A), for example, electron injection layer (3e) / electron transport layer (3d) / light emitting layer (3c) / A hole transport layer (3b) / hole injection layer (3a) is laminated.
  • a transparent electrode (1) having a laminated structure is provided as an anode.
  • FIG. 5 is a schematic sectional drawing which shows the structural example 4 of the organic EL element using the transparent electrode (1, 1A) of this invention as an example of the electronic device of this invention.
  • the organic EL element (400) of the configuration example 4 shown in FIG. 5 uses the transparent electrode (1A) of the configuration example 3 as a counter electrode, that is, the cathode and the anode both have the transparent electrode (1, 1A) of the present invention. ) Is different from the configuration example 1.
  • a detailed description of the same components as those of the configuration examples 1 and 3 will be omitted, and the characteristic configuration of the organic EL element (400) of the configuration example 4 will be described.
  • the organic EL element (400) shown in FIG. 5 is provided on the transparent substrate (2). From the transparent substrate (2) side, the transparent electrode (1) serving as the anode electrode, the light emitting functional layer (3), and A transparent electrode (1A) serving as a cathode is laminated in this order. For this reason, the organic EL element (400) is configured to extract emitted light (h) from both the transparent substrate (2) side and the transparent electrode (1A) side serving as a cathode.
  • the layer structure of the organic EL element (400) configured as described above is not limited to the example described below, and may be a general layer structure as in the configuration example 1.
  • the organic EL element (400) described above is configured to apply a sufficient voltage between the electrodes and realize high-luminance light emission in the organic EL element (400), as in the configuration examples 1, 2, and configuration example 3, It is possible to increase the luminance by improving the extraction efficiency of the emitted light (h) from the transparent electrode (1) side.
  • organic EL elements having the above-described configurations are surface light emitters as described above, they can be used as various light emission sources.
  • lighting devices such as home lighting and interior lighting, backlights for watches and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, Examples include a light source of an optical sensor.
  • it can be effectively used for a backlight of a liquid crystal display device combined with a color filter and a light source for illumination.
  • the organic EL element of the present invention may be used as a kind of lamp for illumination or exposure light source, a projection device for projecting an image, or a type for directly viewing a still image or a moving image. It may be used as a display device (display).
  • the light emitting surface may be enlarged by so-called tiling, in which light emitting panels provided with organic EL elements are joined together in a plane.
  • the drive method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method.
  • a color or full-color display device can be manufactured by using two or more organic EL elements of the present invention having different emission colors.
  • a lighting device will be described as an example of the application, and then a lighting device having a light emitting surface enlarged by tiling will be described.
  • the lighting device according to the present invention can include the organic EL element of the present invention.
  • the organic EL element used in the lighting device according to the present invention may be designed such that each organic EL element having the above-described configuration has a resonator structure.
  • the purpose of use of the organic EL element configured to have a resonator structure includes a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processor, a light source of an optical sensor, etc. It is not limited to. Moreover, you may use for the said use by making a laser oscillation.
  • the material used for the organic EL element of this invention is applicable to the organic EL element (white organic EL element) which produces substantially white light emission.
  • a plurality of luminescent colors can be simultaneously emitted by a plurality of luminescent materials, and white light emission can be obtained by mixing colors.
  • the combination of a plurality of emission colors may include three emission maximum wavelengths of the three primary colors of red, green, and blue, or two of the complementary colors such as blue and yellow, blue green and orange, etc. The thing containing the light emission maximum wavelength may be used.
  • a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and excitation of light from the light emitting materials. Any combination with a pigment material that emits light as light may be used, but in a white organic EL element, a combination of a plurality of light-emitting dopants may be used.
  • Such a white organic EL element is different from a configuration in which organic EL elements emitting each color are individually arranged in parallel to obtain white light emission, and the organic EL element itself emits white light. For this reason, a mask is not required for the formation of most layers constituting the element, and it can be formed on the entire surface by a vapor deposition method, a cast method, a spin coating method, an ink jet method, a printing method, etc., and productivity is improved.
  • a luminescent material used for the light emitting layer (3c) of such a white organic EL element For example, if it is a backlight in a liquid crystal display element, it will be in the wavelength range corresponding to CF (color filter) characteristic. What is necessary is just to select and combine arbitrary things from the above-mentioned metal complex and well-known luminescent material so that it may match, and it may whiten.
  • the white organic EL element described above it is possible to produce a lighting device that emits substantially white light.
  • a layer adjacent to the side on which the second conductive layer (12b) is present of the first conductive layer (12a) may be referred to as “underlayer”.
  • the underlayer may be present not only on the lower side of the conductive layer (12) but also on the upper side.
  • the transparent electrodes 1, 2 and 4 to 10 are prepared as transparent electrodes having a structure composed of the first conductive layer (12 a) and the second conductive layer (12 b) (without the base layer).
  • the transparent electrodes 11 to 25 are
  • the transparent electrodes 3 and 26 to 69 are made of the metal affinity layer (11) and the first conductive layer (12a) and the second conductive layer (12b).
  • a transparent alkali-free glass substrate (2) was fixed to a substrate holder of a commercially available vacuum deposition apparatus, and this substrate holder was attached to a vacuum chamber of the vacuum deposition apparatus. Meanwhile, a tantalum resistance heating boat was filled with silver, and another tantalum resistance heating boat was filled with magnesium (Mg) 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 the deposition rate was 0.01 to 10 so that the ratio (at%) shown in Table I below was obtained.
  • the first conductive layer (12a) made of magnesium-silver (1: 9) having a thickness of 8 nm was formed on the base material (2) at 0.2 nm / second, whereby the transparent electrode 1 was produced. Also,
  • the resistance heating boat made of tantalum is filled with materials (aluminum (Al), magnesium (Mg), ytterbium (Yb), cesium (Cs)) and silver for forming an alloy with silver as shown in Table I below. And mounted in the vacuum chamber. And the 1st electroconductive layer (12a) was formed by the method similar to the transparent electrode 1 except having set it as the ratio (at%) shown in the following Table I, and thickness. Subsequently, the second conductive layer (12b) was formed, and the transparent electrodes 2 and 4 to 10 were produced.
  • materials aluminum (Al), magnesium (Mg), ytterbium (Yb), cesium (Cs)
  • a transparent alkali-free glass base material (2) is fixed to a base material holder of a commercially available vacuum deposition apparatus, and the exemplary compound 65 is filled in a resistance heating boat made of tungsten, and the base material holder and the heating boat are vacuumed. It attached to the 1st vacuum chamber of the vapor deposition apparatus. Moreover, the resistance heating boat made from tantalum was filled with silver and aluminum (Al), and was attached in the 2nd vacuum chamber.
  • the heating boat containing the exemplified compound 65 is energized and heated, and the deposition rate is within the range of 0.1 to 0.2 nm / second.
  • a metal affinity layer (11) made of the exemplified compound 65 having a thickness of 30 nm was provided on the material (2).
  • the base material (2) formed up to the metal affinity layer (11) is transferred to the second vacuum chamber while maintaining a vacuum, and after the second vacuum chamber is depressurized to 4 ⁇ 10 ⁇ 4 Pa, silver and Al are contained.
  • the heated boat was energized and heated, and an aluminum film having a thickness of 8 nm was formed on the substrate (2) at a deposition rate of 0.01 to 0.2 nm / second so that the ratio (at%) shown in the table was obtained.
  • a first conductive layer (12a) made of silver (1: 9) was formed to produce a transparent electrode 3.
  • a resistance heating boat was filled with a material (LiF, Alq 3 , Liq, or ET-1) for forming an underlayer as shown in Table I below, and mounted in the first vacuum chamber. Furthermore, a material for forming a conductive layer (12) as shown in Table I below was filled in a resistance heating boat and mounted in the second vacuum chamber. A base layer (2) having a thickness of 30 nm is formed on a transparent non-alkali glass base (2) in the same manner as the transparent electrode 3, and then the base (2) formed up to the base layer is vacuumed. The first conductive layer (12a) and the second conductive layer (12b) are formed so as to have the ratio (at%) and thickness shown in Table I below, and the transparent electrode 11 To 25 were produced.
  • a metal affinity layer (11) having a thickness of 30 nm is formed on a transparent non-alkali glass substrate (2) in the same manner as the transparent electrode 3, and then the metal affinity layer (11)
  • the base material (2) formed up to is transferred to the second vacuum chamber in a vacuum, and the first conductive layer (12a) so as to have the ratio (at%) and thickness shown in Table I, Table II and Table III below, Then, the second conductive layer (12b) was formed, and transparent electrodes 26 to 69 were produced.
  • the transparent electrodes 1 to 69 produced above were measured for light transmittance, sheet resistance value, and stability over time (amount of change in sheet resistance value) according to the following method.
  • the sheet resistance value ( ⁇ / sq.) was measured using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation) by a four-terminal four-probe method constant current application method.
  • the second electrode is further formed on the first conductive layer (12a) with respect to the transparent electrode 1 provided with only the first conductive layer (12a).
  • the transparent electrode 5 provided with the conductive layer (12b) although the sheet resistance value is improved, the change amount of the sheet resistance value cannot be improved.
  • the transparent electrode 29 provided with the metal affinity layer (11) containing the exemplary compound 10 in addition to the conductive layer (12) is excellent in light transmittance, sheet resistance value, and sheet resistance value variation. I can see it.
  • the transparent electrodes 11 to 17 provided with the base layer containing LiF (transparent electrode 12) and Liq (transparent electrode 16) cannot solve these problems, but the exemplary compound 10 of the present invention is used in combination. It can also be seen that the problem can be solved by using the transparent electrode 59 or 60 provided with the metal affinity layer (11).
  • the transparent electrodes 3 and 58 have the same configuration except for the presence or absence of the second conductive layer, but the transparent electrode 58 having the second conductive layer (12b) mainly composed of silver is light transmissive. It can be seen that the ratio, the sheet resistance value, and the sheet resistance value change amount are excellent.
  • the transparent electrodes 28 and 30, or the transparent electrodes 66 to 69 have the same configuration except for the Ag ratio of the first conductive layer (12a). However, the higher the Ag ratio, the better the light transmittance. It can be seen that the sheet resistance value and the amount of change in the sheet resistance value are reduced.
  • the transparent electrodes 30 and 63 to 65 have the same configuration except for the thickness of the second conductive layer (12b) and the conductive layer (12), but the thickness of the second conductive layer (12b).
  • the transparent electrodes 64 and 65 whose length greatly exceeds 10 nm improve the sheet resistance value and the amount of change in the sheet resistance value, but reduce the light transmittance, compared with the transparent electrodes 30 and 63 which do not exceed 10 nm. Can be seen.
  • the transparent electrodes 28 and 68 have the same configuration except for the thickness ratio of the first conductive layer (12a) and the second conductive layer (12b), but the second conductive layer (12b). It can be seen that the transparent electrode 68 having a high ratio is superior in light transmittance, sheet resistance value, and sheet resistance value change amount compared to the transparent electrode 28 having a low ratio.
  • the transparent electrode 62 has a conductive layer (12) thickness of 5 nm, while the transparent electrode 61 has the same configuration except for only 4 nm. It can be seen that the light transmittance, the sheet resistance value, and the sheet resistance value change amount are superior to the transparent electrode 61.
  • the transparent electrode 64 has a thickness of the second conductive layer (12b) of 22 nm and the thickness of the conductive layer (12) of 25 nm, whereas the transparent electrode 65 has a thickness of the second conductive layer (12b).
  • the transparent electrode 67 has a common Ag ratio of the first conductive layer (12a) exceeding 50 at%, whereas the transparent electrode 66 has the same configuration except for only 40 at%. However, it can be seen that the transparent electrode 67 is superior to the transparent electrode 66 in terms of light transmittance, sheet resistance value, and sheet resistance value variation.
  • Example 2 ⁇ Production of light emitting panel> Light-emitting panels (top emission type organic EL panel, structural example 3) 1-1 to 1-58 using the transparent electrode (1) as a cathode were produced.
  • each layer was formed as follows by sequentially energizing and heating a heating boat containing each material.
  • a counter electrode (4A) made of aluminum (Al) was formed as an anode with a thickness of 100 nm on a glass substrate (2A).
  • a hole injecting layer (3a) made of HAT-CN is formed on the ITO counter electrode (4A) by heating by heating a heating boat containing HAT-CN represented by the following structural formula as a hole injecting material. did. At this time, the thickness was set to 10 nm within the range of the deposition rate of 0.1 to 0.2 nm / second.
  • a heating boat containing exemplary compound H1 (described later) as a host material and a heating boat containing exemplary compound DP1 (described later), which is a fluorescent light emitting compound, are energized independently, and the host material H1 and fluorescent light are emitted.
  • a light-emitting layer (3c) composed of the conductive compound DP1 was formed on the hole transport layer (3b) 1.
  • the thickness was 30 nm.
  • an electric injection boat (3e) made of LiF was formed on the electron transport layer (3d) by energizing and heating a heating boat containing LiF (supra) as an electron injection material.
  • the deposition rate was in the range of 0.01 to 0.02 nm / second, and the thickness was 2 nm.
  • the transparent substrate (2A) formed up to the electron injection layer (3e) is vacuum-filled with silver and magnesium (Mg) from a vapor deposition chamber of a vacuum vapor deposition apparatus into a resistance heating boat made of tungsten as a conductive layer material. It was transferred into the tank while maintaining the vacuum state. Next, after depressurizing the vacuum chamber to 4 ⁇ 10 ⁇ 4 Pa, the resistance heating boat was energized and heated, and the electron injection layer (Ag: 90%) and the thickness shown in Table IV below were obtained. A first conductive layer (12a) and a second conductive layer (12b) were sequentially formed on 3e) as a cathode.
  • Mg silver and magnesium
  • Capping layer formation Thereafter, it was transferred into the original vacuum layer, and although not shown in FIG. 4, ⁇ -NPD (described above) was deposited on the conductive layer (12) at a deposition rate of 0.1 to 0.2 nm / second. Vapor deposition was performed until the thickness became 40 nm within the range to obtain a capping layer.
  • the organic EL element (300) was formed on the transparent substrate (2) by the above procedure.
  • the organic EL element (300) is covered with a sealing material (6) made of a glass substrate having a thickness of 300 ⁇ m, and the organic EL element (300) is surrounded so as to surround the glass substrate (2A) and the sealing material (6).
  • the adhesive (7, sealing material) was sealed between.
  • an epoxy photocurable adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) was used.
  • the adhesive (7) filled between the sealing material (6) and the glass substrate (2A) is irradiated with UV light from the sealing material (6) side to cure the adhesive (7).
  • the organic EL element (300) was sealed.
  • the organic EL element (300) In the formation of the organic EL element (300), an evaporation mask is used for forming each layer, and the central 4.5 cm ⁇ 4.5 cm of the 100 mm ⁇ 100 mm transparent substrate (2A) is used as the light emitting region. A non-light emitting region having a width of 0.25 cm was provided on the entire circumference. Further, the counter electrode (4A) as the anode and the transparent electrode (1) as the cathode are insulated by the light emitting functional layer (3) and have a shape in which the terminal portion is drawn out to the periphery of the glass substrate (2A). Formed.
  • a light-emitting panel 1-1 in which the organic EL element (300) was provided on the glass substrate (2A) and sealed with the sealing material (6) and the adhesive (7) was produced.
  • the emitted light (h) of each color generated in the light emitting layer (3c) is extracted from the transparent electrode (1) side, that is, the sealing material (6) side.
  • Brightness variation (%) ((highest brightness-lowest brightness) / average brightness) x 100 Evaluation rank of luminance variation ⁇ : Less than 5% ⁇ : 5% or more, less than 10% ⁇ : 10% or more, less than 20% ⁇ : 20% or more
  • an electron injection layer (3e) containing a compound having a structure represented by the general formula (1) or the general formula (2) of the present invention is provided. It can be seen that the provision improves the in-plane light emission uniformity and reduces the amount of change in drive voltage, compared to the case where the electron injection layer (3e) not containing the compound is provided.
  • the electron injecting layer (3e) which also serves as the metal affinity layer (11) of the present invention, uniformly forms the first conductive layer (12a) containing a metal element different from silver and silver. It is presumed that the atomic distribution variation in the thickness direction over time can be suppressed.
  • the driving voltage is reduced, the in-plane light emission uniformity is improved, and the driving voltage changes. It can be seen that the amount is reduced.
  • the panels 1-10 and 1-11 or 1-46 and 1-47 all have the same configuration except for the presence or absence of the second conductive layer, but the second conductive layer mainly composed of silver is used. It can be seen that the panels 1-10 and 1-46 having the above have improved in-plane light emission uniformity and reduced drive voltage variation.
  • the panels 1-10 and 1-56 to 1-58 have the same configuration except for the Ag ratio of the first conductive layer 12a. However, the higher the Ag ratio, the lower the drive voltage change amount. You can see that. It can also be seen that the in-plane light emission uniformity is improved in the other three compared to the 1-56 panel with the lowest Ag ratio among the four.
  • the panels 1-53 and 1-54 have the same configuration except for the thickness of the second conductive layer 12b and the conductive layer 12, but the second conductive layer 12b is thicker. It can be seen that this panel has improved in-plane light emission uniformity and reduced drive voltage variation compared to the thin 1-53 panel.
  • the panels 1-10 and 1-53 all have the same configuration except for the thickness ratio of the first conductive layer 12a and the second conductive layer 12b, but the ratio of the second conductive layer 12b. It can be seen that the panel with 1-10 having a higher ratio has improved in-plane light emission uniformity and the amount of change in drive voltage compared to the panel with 1-53 having a lower ratio.
  • a glass substrate (2) of 100 mm ⁇ 100 mm ⁇ 1.1 mm was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • the cleaned glass substrate (2) is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, and each material constituting the light emitting functional layer (3) is filled in an optimum amount with a resistance heating boat made of tungsten.
  • a heating boat were attached to the first vacuum chamber of the vacuum deposition apparatus.
  • a resistance heating boat made of tantalum was filled with an electrode material and attached to the second vacuum chamber.
  • the glass substrate was heated within the range of the deposition rate of 0.1 to 0.2 nm / second by energizing and heating the heating boat containing Alq 3.
  • An underlayer made of Alq 3 having a thickness of 30 nm was provided on the top.
  • the glass substrate (2) formed up to the foundation layer is transferred to the second vacuum chamber while maintaining a vacuum, and after the pressure of the second vacuum chamber is reduced to 4 ⁇ 10 ⁇ 4 Pa, a heating boat containing silver and magnesium is energized. 1 mg of magnesium on the glass substrate (2) at a deposition rate of 0.01 to 0.2 nm / second so that the ratio (at%) shown in Table VI below is obtained.
  • a first conductive layer (12a) made of silver (1: 9) was formed, and then a second conductive layer (12b) made of silver having a thickness of 7 nm was formed to produce a transparent electrode 1.
  • the hole-injecting layer (3a) made of HAT-CN was formed on the ITO counter electrode (4) by energizing and heating the heating boat containing the above-described HAT-CN as the hole-injecting material. At this time, the thickness was set to 10 nm within the range of the deposition rate of 0.1 to 0.2 nm / second.
  • the organic EL element (100) is covered with a sealing material (6) made of a glass substrate having a thickness of 300 ⁇ m, and the sealing material (6) and the transparent substrate (2) are surrounded by the organic EL element (300).
  • the adhesive (7, sealing material) was sealed between.
  • an epoxy photocurable adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) was used.
  • the adhesive (7) filled between the sealing material (6) and the transparent substrate (2) is irradiated with UV light from the sealing material (6) side to cure the adhesive (7).
  • the organic EL element (100) was sealed.
  • the organic EL element (100) In the formation of the organic EL element (100), an evaporation mask is used for forming each layer, and the central 4.5 cm ⁇ 4.5 cm of the 100 mm ⁇ 100 mm transparent substrate (2) is used as the light emitting region. A non-light emitting region having a width of 0.25 cm was provided on the entire circumference. Further, the transparent electrode (1) as the anode and the counter electrode (4) as the cathode are insulated by the light emitting functional layer (3) and have a shape in which a terminal portion is drawn to the periphery of the transparent substrate (2). Formed.
  • a light-emitting panel 2-1 in which the organic EL element (100) was provided on the transparent substrate (2) and sealed with the sealing material (6) and the adhesive (7) was produced.
  • emitted light (h) of each color generated in the light emitting layer (3c) is extracted from the transparent electrode (1) side, that is, the transparent substrate (2) side.
  • a metal affinity layer (11) containing a compound having a structure represented by the general formula (1) or the general formula (2) of the present invention was provided.
  • the driving voltage is reduced and the in-plane is reduced as compared with the case where an underlayer not containing the compound (including Alq 3 (light emitting panel 2-1) and ET-1 (light emitting panel 2-2)) is provided. It can be seen that the light emission uniformity is improved and the drive voltage variation is reduced.
  • Example 4 Provide of light emitting panel> Light-emitting panels (transparent organic EL panel, configuration example 4) 3-1 to 3-6 using the transparent electrode (1) as a cathode and an anode were produced.
  • a glass substrate (2) of 100 mm ⁇ 100 mm ⁇ 1.1 mm was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes.
  • the cleaned glass substrate (2) is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, and each material constituting the light emitting functional layer (3) is filled in an optimum amount with a resistance heating boat made of tungsten.
  • a heating boat were attached to the first vacuum chamber of the vacuum deposition apparatus.
  • a resistance heating boat made of tantalum was filled with an electrode material and attached to the second vacuum chamber.
  • the glass substrate (2) was heated at a deposition rate of 0.1 to 0.2 nm / second by energizing and heating a heating boat containing Alq 3.
  • An underlayer made of Alq 3 having a thickness of 30 nm was provided thereon.
  • the glass substrate (2) formed up to the foundation layer is transferred to the second vacuum chamber while maintaining a vacuum, and after the pressure of the second vacuum chamber is reduced to 4 ⁇ 10 ⁇ 4 Pa, a heating boat containing silver and magnesium is energized. Then, magnesium-silver (1 nm thick) is formed on the underlayer at a deposition rate of 0.01 to 0.2 nm / second so that the ratio (at%) shown in Table VII below is obtained. : 9) was formed, and then a second conductive layer (12b) made of silver having a thickness of 7 nm was formed, whereby the transparent electrode 1 was produced.
  • the hole-injecting layer (3a) made of HAT-CN was formed on the transparent electrode (1) by energizing and heating the heating boat containing the above-described HAT-CN as the hole-injecting material. At this time, the deposition rate was 0.1 to 0.2 nm / second, and the thickness was 10 nm.
  • a heating boat containing exemplary compound H3 (described later) as a host material and a heating boat containing exemplary compound DP2, which is a phosphorescent compound, are energized independently, and the host material H3 and the phosphorescent material are emitted.
  • the glass substrate (2) formed up to the electron injection layer (3e) is vacuum-filled with silver and magnesium (Mg) from a vapor deposition chamber of a vacuum vapor deposition apparatus into a resistance heating boat made of tungsten as a conductive layer material. It was transferred into the tank while maintaining the vacuum state.
  • the resistance heating boat was energized and heated, and the electron injection layer (Ag: 90%) and the thickness shown in Table VII below were obtained.
  • a first conductive layer (12a) and a second conductive layer (12b) were sequentially formed as a cathode on 3e).
  • ⁇ -NPD (described above) is deposited on the conductive layer (12) at a deposition rate of 0.1 to 0.2 nm / second. Vapor deposition was performed until the thickness reached 40 nm to form a capping layer.
  • the organic EL element (400) was formed on the transparent substrate 2 by the above procedure.
  • the organic EL element (400) is covered with a sealing material (6) made of a glass substrate having a thickness of 300 ⁇ m, and the sealing material (6) and the transparent substrate (2) are surrounded by the organic EL element (400).
  • the adhesive (7, sealing material) was sealed between.
  • an epoxy photocurable adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) was used.
  • the adhesive (7) filled between the sealing material (6) and the transparent substrate (2A) is irradiated with UV light from the sealing material (6) side to cure the adhesive (7).
  • the organic EL element (400) was sealed.
  • the organic EL element (400) In the formation of the organic EL element (400), a vapor deposition mask is used for forming each layer, and the central 4.5 cm ⁇ 4.5 cm of the 100 mm ⁇ 100 mm glass substrate (2) is used as the light emitting region. A non-light emitting region having a width of 0.25 cm was provided on the entire circumference.
  • the transparent electrode (1) as the anode and the transparent electrode (1A) as the cathode are insulated by the light emitting functional layer (3) and have a shape in which a terminal portion is drawn out to the periphery of the glass substrate (2). Formed.
  • a light-emitting panel 3-1 in which an organic EL element (400) was provided on a transparent substrate (2) and sealed with a sealing material (6) and an adhesive (7) was produced.
  • emitted light (h) of each color generated in the light emitting layer (3c) is extracted from both the transparent substrate (2) and the sealing material (6) side.
  • a metal affinity layer (11) containing a compound having a structure represented by the general formula (1) or the general formula (2) of the present invention was provided.
  • the driving voltage is reduced and the in-plane light emission uniformity is improved as compared with the case where an underlayer containing no such compound (containing Alq 3 (containing the light emitting panels 3-1 and 3-3)) is provided. It can be seen that the amount of change in drive voltage is reduced.
  • the present invention includes, for example, lighting devices for home lighting and interior lighting, backlights for clocks and liquid crystal display devices, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, optical communication It can be used as various light sources such as a light source for a processing machine and a light source for an optical sensor.
  • the present invention can also be used as a projection device that projects an image or a display device that directly recognizes a still image or a moving image.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne le problème lié à la fourniture : d'une électrode transparente qui possède à la fois une conductivité électrique et une transmissivité de lumière suffisantes en même temps, tout en présentant une excellente stabilité à long terme ; et d'un dispositif électronique qui est pourvu de cette électrode transparente. Une électrode transparente 1 selon la présente invention comprend, dans l'ordre suivant, une couche d'affinité métallique 11 qui contient un composé ayant une structure représentée par la formule générale (1), une première couche conductrice 12a qui est disposée adjacente à la couche d'affinité métallique 11 et contient de l'argent et un métal qui est différent de l'argent, et une seconde couche conductrice 12b qui est principalement composée d'argent. (Dans la formule, chacun de X1 et X2 représente indépendamment un atome d'azote ou CR1; R1 représente un atome d'hydrogène ou un substituant ; et A1 représente un résidu qui constitue un cycle hétéroaryle à cinq ou six chaînons.)
PCT/JP2017/044654 2016-12-19 2017-12-13 Électrode transparente et dispositif électronique WO2018116923A1 (fr)

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