WO2018116923A1 - 透明電極及び電子デバイス - Google Patents
透明電極及び電子デバイス Download PDFInfo
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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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- Prior art keywords
- layer
- ring
- transparent electrode
- silver
- conductive layer
- Prior art date
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- 229920000570 polyether Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical class C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- DLJHXMRDIWMMGO-UHFFFAOYSA-N quinolin-8-ol;zinc Chemical compound [Zn].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 DLJHXMRDIWMMGO-UHFFFAOYSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 150000003378 silver Chemical group 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000008096 xylene Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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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Abstract
Description
このような有機EL素子は、対向配置された2枚の電極間に有機材料からなる発光層を介在させた構成となっている。しかし、発光層で生じた光は電極を透過してはじめて外部に取り出し可能となるため、2枚の電極のうちの少なくとも一方は透明電極とする必要がある。
しかしながら、ITOは高価なインジウム(In)を含有するため、透明電極や電子デバイスの製造コストを上昇させてしまうという問題がある。
また、ITO等を用いた透明電極の形成には主としてスパッタ法が用いられてきた。しかしながら、有機EL素子の場合、主に有機材料からなる有機機能層上に透明電極を形成することになるので、スパッタ法で透明電極の形成を行うと、勢いよく飛んでくる原子によって有機機能層がダメージを受け、有機機能層本来の性能が損なわれてしまうという問題もある。
しかし、銀又は銀とマグネシウムからなる薄膜層を透明電極の導電性層として用いると、銀がマイグレーションを起こし、導電性を低下させてしまう可能性がある。導電性の低下は、例えば、有機EL素子を照明として用いた場合に、発光域の面内均一性の低下につながるため、非常に大きな問題となる。一方、マイグレーションを抑制するために導電性層を厚くすると、光透過性が低下してしまう。つまり、銀又は銀とマグネシウムからなる透明電極においては、導電性と光透過性とを両立させることが困難であった。
しかし、それらの方法は、導電性、光透過性及び電子注入性をともに満たすという点においていまだ不十分であった。また、従来は、銀と銀とは異なる金属元素を含む導電性層が形成されるのは、多くの場合、銀との親和性が十分でないフッ化リチウム(LiF)の表面であったため、時間経過とともに厚さ方向の原子比率の分布に偏りが生じてしまい、経時安定性に課題を残していた。
さらに、この透明電極を、電子デバイス、特に有機EL素子に適用することで、デバイス特性を向上させることができることを見いだし、本発明に至った。
1.下記一般式(1)で表される構造を有する化合物を含有する金属親和性層と、
当該金属親和性層に隣接して設けられ、銀と当該銀とは異なる金属とを含有する第1導電性層と、
銀を主成分とする第2導電性層と、をこの順で有する透明電極。
かつ、前記第2導電性層の厚さが1~10nmの範囲内である第1項から第7項までのいずれか一項に記載の透明電極。
本発明においては、金属親和性層と導電性層が隣接し、当該導電性層を構成する第1導電性層及び第2導電性層が金属親和性層側からこの順に積層されていればよく、各層の製造の順は問わず効果を有するが、効果の発現機構・作用機構については、現時点では明確になっていない。しかし、以下のように推察している。
金属親和性層の表面に第1導電性層を形成する際、第1導電性層を構成する銀原子が金属親和性層に含有されている銀親和性化合物と相互作用し、金属親和性層表面上での銀原子の拡散距離が減少し、その結果、特異箇所への銀の移動(マイグレーション)及び凝集が抑制されるものと考えられる。すなわち、銀原子が、銀原子と親和性のある原子を有する金属親和性層表面上で2次元的な核を形成し、それを中心に2次元の単結晶層を形成するという層状成長型(Frank-van der Merwe:FM型)の膜成長によって形成されているものと推察される。
一般的には、金属親和性層表面において付着した銀原子が表面を拡散しながら結合して3次元的な核を形成し、3次元的な島状に成長するという島状成長型(Volumer-Weber:VW型)での膜成長により、島状に形成しやすいと考えられている。しかし、本発明においては、金属親和性層に含有されている銀親和性化合物により、島状成長が抑制され、層状成長が促進されているものと推察される。本発明における、銀と銀とは異なる金属元素とを含有する第1導電性層は、上述した様に、銀原子の凝集が金属親和性層により制御されることで、銀の合金を主成分とする第1導電性層の膜成長が制御され、その結果、薄いながらも均一な厚さの導電性層が得られるようになる。それが、光透過性と導電性の両立につながっているものと考えられる。
また、従来の透明電極においては、銀と銀とは異なる金属との原子比率の厚さ方向の分布に偏りが生じ、導電性層の光透過率、シート抵抗を変動させる原因となっていたが、本発明においては、金属親和性層に含有されている銀親和性化合物によって、銀と銀とは異なる金属元素の原子比率の分布が制御されていると推測している。その結果、経時での性能変動が小さい透明電極とすることができているものと考えられる。
なお、導電性層を先に形成し、その後、導電性層の表面に金属親和性層を形成した場合であっても、導電性層を構成する銀原子が金属親和性層に含有されている、銀原子と親和性のある原子と相互作用し、運動性が抑制されると推測している。これによって、導電性層の表面平滑性が良化して乱反射を抑制することができ、光透過率を向上することが可能である。また該相互作用によって、熱や温度といった物理刺激に対する導電性層の変化が抑制され、経時安定性を向上させることができているものと考えられる。
また、本発明の透明電極を、有機EL素子のカソードとして用いた場合について、電子注入性の向上は、電極材料に仕事関数の低い金属を用いて、かつ、電極材料の凝集を抑制し、下地となる層との界面を空隙なく均一に形成することが重要である。前述した様に、本発明の透明電極構成は、一般式(1)で表される構造を有する化合物を含有する金属親和性層を用いたことで、銀と銀とは異なる金属元素とを含有する第1導電性層が均一に形成できているため電子注入性が向上したものと推測している。
次に、面内発光均一性の向上には、低抵抗の金属を用いてシート抵抗を下げることと、上述した様に金属薄膜を均一形成することが非常に重要である。本発明の透明電極構成は、薄膜の均一形成ができ、かつ低抵抗の銀を主成分とする第2導電性層を積層することによってシート抵抗を下げることができたため面内発光均一性が向上したものと推測している。
更に、経時安定性の向上は、安定した電荷供給とシート抵抗が変動しないことが重要である。本発明の透明電極構成は、経時した場合でも銀と銀とは異なる金属元素とを含有する第1導電性層の原子比率の分布がほとんど変わらないように制御できたため経時安定性が向上したものと推測している。
また、アノードとして用いた場合は、上述の電子注入性以外の部分は同様であり、本発明の構成とすることで、面内発光均一性と経時安定性に優れたアノードを提供することが可能である。
なお、本願において、数値範囲を表す「~」は、その前後に記載される数値を下限値及び上限値として含む意味で使用している。
また、各図の説明において、構成要素の末尾に括弧書きした数字は、各図における符号を表す。
本発明の透明電極は、金属親和性層と、当該金属親和性層に隣接して形成された導電性層と、を備えたものであって、前記金属親和性層が、下記一般式(1)で表される構造を有する化合物を含有し、かつ、前記導電性層が、少なくとも、銀と当該銀とは異なる金属とを含有する第1導電性層と、銀を主成分とする第2導電性層と、をこの順で含む積層構造をなしている。これにより、本発明の透明電極は、十分な導電性と光透過性とを兼ね備え、かつ経時安定性に優れた透明電極を得ることができるものとなっている。
図1は、本発明の透明電極の基本的な構成の一例を示した概略断面図である。
図1に示したように、透明電極(1)は、金属親和性層(11)と、この金属親和性層(11)に隣接する導電性層(12)を有し、該導電性層(12)が、銀と当該銀とは異なる金属とを含有する第1導電性層(12a)、銀を主成分とする第2導電性層(12b)とがこの順で積層された3層構造である。特に、基材(2)の表面に、金属親和性層(11)、第1導電性層(12a)及び第2導電性層(12b)がこの順に設けられていることが好ましい形態である。
第1導電性層を構成する材料成分に占める銀の比率は、50~99at%の範囲内であり、好ましくは、70at%以上、より好ましくは80at%以上であり、さらに好ましくは90~99at%の範囲内である。なお、銀と混合する銀とは異なる金属については後述する。
また、本発明でいう「銀を主成分とする」とは、純粋な銀、ごく微量の不純物が自然に混入された銀、又は本発明の効果を高めるためにごく微量の銀以外の元素を副成分として含有させた銀で構成されることをいう。この場合の第2導電性層を構成する材料成分に占める銀の比率は、99超~100at%の範囲内である。
また、本発明の透明電極(1)でいう「透明」とは、波長500nmでの光透過率が50%以上であることをいい、光透過率が60%以上であることがより好ましく、光透過率が65%以上であることが更に好ましい。
基材(2)を構成する材料は、特に限定されるものではないが、例えば、ガラス、プラスチック等を挙げることができる。なお、基材(2)は、透明であっても不透明であってもよいが、基材(2)を不透明な材料で構成する場合には、例えば、アルミニウム、ステンレス等の金属基板、フィルムや不透明樹脂基板、セラミック製の基板等を用いることができる。
一方、本発明の透明電極(1)が、基材(2)側から光を取り出す電子デバイスに用いられる場合には、基材(2)は透明であることが好ましい。好ましく用いられる透明な基材(2)としては、ガラス、石英、透明樹脂フィルムを挙げることができる。
これらのガラス材料を基材(2)として使用する場合には、金属親和性層(11)との密着性、耐久性、平滑性の観点から、必要に応じて、表面に研磨等の物理的処理が施されたものとしてもよいし、無機物又は有機物からなる被膜、若しくはこれらの組み合わせからなるハイブリッド被膜が形成されたものとしてもよい。
これらの樹脂フィルムを基材(2)として使用する場合には、基材(2)をガラスで形成する場合と同様、表面に無機物又は有機物からなる被膜、若しくはこれらを組み合わせたハイブリッド被膜が形成されたものとしてもよい。
こうしたバリア性フィルムを形成する材料としては、水分や酸素等の電子デバイスや有機EL素子の劣化をもたらす要因の浸入を抑制する機能を有する材料であればよく、例えば、酸化ケイ素、二酸化ケイ素、窒化ケイ素等を用いることができる。さらに、当該バリア性フィルムの脆弱性を改良するために、これら無機層と有機材料からなる層(有機機能層)の積層構造を持たせることがより好ましい。無機層と有機機能層との積層順については特に制限はないが、両者を交互に複数回積層させることが好ましい。
本発明に係る金属親和性層(11)とは、導電性層(12)に隣接して当該導電性層の銀の凝集を防ぐための層であり、銀と相互作用し当該銀の凝集を防ぐ下記一般式(1)で表される構造を有する化合物を少なくとも1種類含有する層をいう。
また、式中のA1は、5員又は6員のヘテロアリール環を構成する残基を表す。)
また、A1によって構成可能となるヘテロアリール環のうち、6員のものとしては、ピリジン環、ピラジン環、トリアジン環、ピリミジン環、アザジベンゾフラン環、アザジベンゾチオフェン環、カルボリン環、キナゾリン環、キノキサリン環、キノリン環、イソキノリン環、ベンゾキノリン環、ベンゾイソキノリン環又はフェナンスリジン環等が挙げられる。
また、A1はさらに置換基を有していても良い。
なお、本発明においては、インドール環のように窒素原子の孤立電子対が芳香環の形成に関与している化合物も、上記一般式(1)で表される構造を有する化合物に含む。
一方、リチウム8-ヒドロキシキノレート(Liq)やトリス(8-キノリノラト)アルミニウム(Alq3)のように金属錯体を構成するものは上記一般式(1)で表される構造を有する化合物から除かれる。
式中のA1及びA2は、それぞれ独立に、5員又は6員のヘテロアリール環を構成する残基を表す。
式中のL1は、単なる結合手、又はアリール環若しくはヘテロアリール環を含む2価の連結基を表す。
また、A2を含むことによって構成可能となるヘテロアリール環は、前述したA1を含むことによって構成可能となるヘテロアリール環として挙げたものの中から選択するのが好ましい。
また、A2もA1と同様にさらに置換基を有していてもよい。
なお、A2はA1と同一のものとしてもよいし、異なるものとしてもよい。
また、L1が表す2価の連結基を構成可能なヘテロアリール環としては、例えば、ピリジン環、ピリミジニル環、フリル環、ピロリル環、イミダゾリル環、ベンゾイミダゾリル環、ピラゾリル環、ピラジニル環、トリアゾリル環(例えば、1,2,4-トリアゾール-1-イル環、1,2,3-トリアゾール-1-イル環等)、オキサゾリル環、ベンゾオキサゾリル環、チアゾリル環、イソオキサゾリル環、イソチアゾリル環、フラザニル環、チエニル環、キノリル環、ベンゾフリル環、ジベンゾフリル環、ベンゾチエニル環、ジベンゾチエニル環、インドリル環、カルバゾリル環、カルボリニル環、ジアザカルバゾリル環(前記カルボリン環を構成する炭素原子の一つが窒素原子で置き換わったものを示す。)、キノキサリニル環、ピリダジニル環、トリアジニル環、キナゾリニル環又はフタラジニル環等が挙げられる。
この金属親和性層(11)の厚さは、1~100nmの範囲内にあることが好ましく、3~50nmの範囲内にあることがより好ましく、この範囲内であればいずれの厚さであっても効果を得ることができる。具体的には、厚さが100nm以下であれば、層の吸収成分が少なくなり、透明電極(1)の光透過率が向上するため好ましい。また、厚さが3nm以上であれば、均一で連続的な金属親和性層(11)が形成されるため好ましい。
本発明の透明電極(1)を構成する導電性層(12)は、金属親和性層(11)に隣接して形成された層である。また、導電性層(12)は、金属親和性層(11)側から、銀と当該銀とは異なる金属とを含有する第1導電性層(12a)と、銀を主成分とする第2導電性層(12b)と、を含む積層構造をなしている。
第1導電性層(12a)の厚さは、0.5~15nmの範囲内であることが好ましく、更に好ましくは1~5nmの範囲内である。厚さを0.5nm以上にすると生産時の安定性が確保できるため好ましい。また、厚さを15nm以下にすると導電性を低く保つことができるので好ましい。
本発明においては、第1導電性層を銀の合金とするのが好ましい。具体的には、マグネシウム銀(MgAg)、銅銀(CuAg)、パラジウム銀(PdAg)、インジウム銀(InAg)、アルミニウム銀(AlAg)、セシウム銀(CsAg)、イッテルビウム銀(YbAg)、パラジウム銅銀(PdCuAg)等が挙げられるが、中でも、マグネシウム銀(MgAg)、アルミニウム銀(AlAg)、イッテルビウム銀(YbAg)が好ましい。
第2導電性層(12b)を形成する銀は、できるだけ純粋なものとするのが好ましい。
また、第2導電性層(12b)の第1導電性層(12a)が存在する側と反対側に隣接して、さらに別の導電性層が設けられていても良い。この場合、透明電極(1)の光透過性や導電性を損なうことのないようにすることが好ましい。
また、透明電極(1)においては、第2導電性層(12b)の第1導電性層(12a)が存在する側と反対側に更に金属親和性層(11)を形成することにより、導電性層(12)を、2層の金属親和性層(11)で挟んだ構成としてもよい。
本発明の透明電極(1)は、前述したように構成されることで、金属親和性層(11)の表面に第1導電性層(12a)を形成する際に、第1導電性層(12a)を構成する銀原子が、金属親和性層(11)を構成する非共有電子対を有するヘテロ原子を分子内に含む化合物と相互作用する。このため、金属親和性層(11)表面における銀原子の拡散距離が減少し、銀の凝集が抑えられると推定している。
しかしながら、本発明構成の透明電極(1)によれば、上述したように金属親和性層(11)上において銀の凝集が抑えられるため、銀を含有する第1導電性層(12a)の形成においては、層状成長型(Frank-van der Merwe:FM型)で薄膜成長するようになると推定している。
上述した本発明の透明電極(1)は、各種電子デバイスに用いることが可能である。
電子デバイスの例としては、有機EL素子、LED(Light Emitting Diode)、液晶素子、太陽電池、タッチパネル等が挙げられる。これらの電子デバイスにおいて光透過性を必要とされる電極部材として、上述の透明電極(1)を用いることができる。特に、本発明の透明電極(1)では、有機EL素子に適用することが好ましい。
以下、本発明の透明電極(1)を用いた電子デバイスの一例として、有機EL素子の実施の形態について説明する。
〔構成例1に係る有機EL素子の構成〕
図2は、構成例1に係る有機EL素子の概略断面図である。
本例に係る有機EL素子は、いわゆるボトムエミッション型、すなわち、透明基板を有し、透明基板側から光を取り出すようにしたものである。具体的には、図2に示したように、透明基板(2)上に、透明電極(1)、発光機能層(3)、対向電極(4)をこの順で積層することにより構成されている。
この有機EL素子(100)においては、透明電極として、先に説明した本発明の透明電極(1)を用いている。このため有機EL素子(100)は、発生させた光(以下、発光光(h)と記す)を、少なくとも透明基板(2)側から取り出すことが可能に構成されている。
この場合、発光機能層(3)を構成する各層は、アノードである透明電極(1)側から、例えば、正孔注入層(3a)、正孔輸送層(3b)、発光層(3c)、電子輸送層(3d)、電子注入層(3e)の順で積層されることになるが、このうち少なくとも発光層(3c)を有することが必須である。
透明基板(2)は、先に説明した本発明の透明電極(1)が設けられる基材(2)であり、先に説明した基材(2)の材料うち、光透過性を有する透明なものを用いて形成されている。
透明電極(1)は、先に説明した本発明の透明電極(1)であり、透明基板(2)側から、金属親和性層(11)、第1導電性層(12a)、第2導電性層(12b)を順に積層した構成である。ここでは特に、透明電極(1)はアノードとして機能するものであり、第1導電性層(12a)及び第2導電性層(12b)が実質的なアノードとなっている。
なお、透明電極(1)には、低抵抗化を図ることを目的とし、透明電極(1)の各層(12a,12b)に、補助電極(5)を、各層にそれぞれ接するように設けてもよい。
対向電極(4)は、発光機能層(3)に電子を供給するカソードとして機能する電極膜であり、金属、合金、有機若しくは無機の導電性化合物、又はこれらの混合物等から構成されている。具体的には、アルミニウム、銀、マグネシウム、リチウム、マグネシウム/銅混合物、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、インジウム、リチウム/アルミニウム混合物、希土類金属、ITO、ZnO、TiO2、SnO2等の酸化物半導体等が挙げられる。
なお、この有機EL素子(100)が、対向電極(4)側からも発光光(h)を取り出すものである場合には、上述した導電性材料のうちから選択される光透過性の良好な導電性材料により対向電極(4)が構成されていればよい。
本発明に用いられる発光層(3c)は、発光材料が含有されているが、中でも発光材料としてリン光発光性化合物(リン光発光材料、リン光発光化合物、リン光性化合物)が含有されていることが好ましい。
この発光層(3c)は、電極又は電子輸送層(3d)から注入された電子と、正孔輸送層(3b)から注入された正孔とが再結合して発光する層であり、発光する部分は発光層(3c)の層内であっても発光層(3c)と隣接する層との界面であってもよい。
このような発光層(3c)としては、含まれる発光材料が発光要件を満たしていれば、その構成には特に制限はない。また、同一の発光スペクトルや発光極大波長を有する層が複数層あってもよい。この場合、各発光層(3c)間には非発光性の補助層(図示せず)を有していることが好ましい。
複数層を積層した構成の発光層(3c)の場合、個々の発光層(3c)の厚さとしては、1~50nmの範囲内に調整することが好ましく、1~20nmの範囲内に調整することがより好ましい。積層された複数の発光層(3c)が、青、緑、赤のそれぞれの発光色に対応する場合、青、緑、赤の各発光層(3c)の厚さの関係については、特に制限はない。
また、発光層(3c)は、複数の発光材料が混合されて構成されていてもよく、またリン光発光性化合物と蛍光性化合物(蛍光発光材料、蛍光ドーパント)とが混合されて構成されていてもよい。
発光層(3c)の構成として、ホスト化合物(発光ホスト)、発光材料(発光ドーパント)を含有し、発光材料より発光させることが好ましい。
発光層(3c)に含有されるホスト化合物としては、室温(25℃)におけるリン光発光のリン光量子収率が0.1未満の化合物が好ましい。さらに好ましくはリン光量子収率が0.01未満である。また、発光層(3c)に含有される化合物の中で、その層中での体積比が50%以上であることが好ましい。
用いられるホスト化合物としては、従来公知の低分子化合物でも、繰り返し単位をもつ高分子化合物でもよく、ビニル基やエポキシ基のような重合性基を有する低分子化合物(蒸着重合性発光ホスト)でもよい。
ここでいうガラス転移温度とは、DSC(Differential Scanning Calorimetry:示差走査熱量法)を用いて、JIS K 7121に準拠した方法により求められる値である。
(1)リン光発光性化合物
本発明で用いることのできる発光材料としては、リン光発光性化合物が挙げられる。
リン光発光性化合物とは、励起三重項からの発光が観測される化合物であり、具体的には室温(25℃)にてリン光発光する化合物であり、リン光量子収率が25℃において0.01以上の化合物であると定義されるが、好ましいリン光量子収率は0.1以上である。
上記リン光量子収率は、第4版実験化学講座7の分光IIの398頁(1992年版、丸善)に記載の方法により測定できる。溶液中でのリン光量子収率は種々の溶媒を用いて測定できるが、本発明においてリン光発光性化合物を用いる場合、任意の溶媒のいずれかにおいて上記リン光量子収率(0.01以上)が達成されればよい。
一つは、キャリアが輸送されるホスト化合物上でキャリアの再結合が起こってホスト化合物の励起状態が生成し、このエネルギーをリン光発光性化合物に移動させることでリン光発光性化合物からの発光を得るというエネルギー移動型である。
もう一つは、リン光発光性化合物がキャリアトラップとなり、リン光発光性化合物上でキャリアの再結合が起こりリン光発光性化合物からの発光が得られるというキャリアトラップ型である。
いずれの場合においても、リン光発光性化合物の励起状態のエネルギーはホスト化合物の励起状態のエネルギーよりも低いことが条件となる。
また、リン光発光性化合物の含有量は、発光層(3c)の総量に対し0.1~30体積%の範囲内とするのが好ましい。
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本発明で用いることのできる発光材料には、蛍光発光性化合物も含まれる。
蛍光性化合物としては、クマリン系色素、ピラン系色素、シアニン系色素、クロコニウム系色素、スクアリウム系色素、オキソベンツアントラセン系色素、フルオレセイン系色素、ローダミン系色素、ピリリウム系色素、ペリレン系色素、スチルベン系色素、ポリチオフェン系色素、又は希土類錯体系蛍光体等が挙げられる。
注入層とは、駆動電圧低下や発光輝度向上のために電極と発光層(3c)の間に設けられる層のことで、「有機EL素子とその工業化最前線(1998年11月30日エヌ・ティー・エス社発行)」の第2編第2章「電極材料」(123~166頁)に詳細に記載されており、正孔注入層(3a)と電子注入層(3e)とがある。
注入層は、必要に応じて設けることができる。正孔注入層(3a)であれば、アノードと発光層(3c)又は正孔輸送層(3b)との間、電子注入層(3e)であればカソードと発光層(3c)又は電子輸送層(3d)との間に存在させてもよい。
正孔輸送層(3b)は、正孔を輸送する機能を有する正孔輸送材料からなり、広い意味で正孔注入層(3a)、電子阻止層も正孔輸送層(3b)に含まれる。正孔輸送層(3b)は単層又は複数層設けることができる。
正孔輸送材料としては、上記のものを使用することができるが、ポルフィリン化合物、芳香族第3級アミン化合物及びスチリルアミン化合物、特に芳香族第3級アミン化合物を用いることが好ましい。
また、特開平11-251067号公報、J.Huang et.al.,Applied Physics Letters,80(2002),p.139に記載されているような、いわゆるp型正孔輸送材料を用いることもできる。本発明においては、より高効率の発光素子が得られることから、これらの材料を用いることが好ましい。
これらの文献に記載されているように、正孔輸送層(3b)のp性を高くすると、より低消費電力の素子を作製することができるため好ましい。
電子輸送層(3d)は、電子を輸送する機能を有する材料からなり、広い意味で電子注入層(3e)、正孔阻止層も電子輸送層(3d)に含まれる。電子輸送層(3d)は単層構造又は複数層の積層構造として設けることができる。
なお、ここで挙げた電子輸送材料は、前述した金属親和性層(11)に、駆動電圧低下や発光輝度向上を目的として添加することも可能である。
電子輸送層(3d)の厚さは、特に制限されるものではないが、通常は5nm~5μm程度、好ましくは5~200nmの範囲内である。電子輸送層(3d)は上記材料の1種又は2種以上からなる1層構造であってもよい。
阻止層は、上記した発光機能層(3)の基本構成層の他に、必要に応じて設けられるものである。例えば、特開平11-204258号公報、同11-204359号公報、及び「有機EL素子とその工業化最前線(1998年11月30日エヌ・ティー・エス社発行)」の237頁等に記載されている正孔阻止(ホールブロック)層がある。
補助電極(5)は、透明電極(1)の抵抗を下げる目的で設けられるものであって、第1導電性層(12a)及び第2導電性層(12b)にそれぞれ接するように設けられている。補助電極(5)を形成する材料としては、金、白金、銀、銅、アルミニウム等の抵抗が低い金属が好ましい。これらの金属は光透過性が低いため、光取り出し面(2a)からの発光光hの取り出しの影響のない範囲でパターン形成される。このような補助電極(5)の作製方法としては、蒸着法、スパッタリング法、印刷法、インクジェット法、エアロゾルジェット法等が挙げられる。補助電極(5)の線幅は、光を取り出す開口率の観点から50μm以下であることが好ましく、補助電極(5)の厚さは、導電性の観点から1μm以上であることが好ましい。
封止材(6)は、有機EL素子(100)を覆うものであって、板状(フィルム状)の封止部材であって接着剤(7)によって透明基板(2)側に固定されるものであってもよく、封止膜であってもよい。このような封止材(6)は、有機EL素子(100)における透明電極(1)及び対向電極(4)の端子部分を露出させる状態で、少なくとも発光機能層(3)を覆う状態で設けられている。また、封止材(6)に電極を設け、有機EL素子(100)の透明電極(1)及び対向電極(4)の端子部分と、この電極とを導通させるように構成されていてもよい。
さらには、フィルム状としたポリマー基板は、JIS K 7126-1987に準拠した方法で測定された酸素透過度が1×10-3mL/(m2・24h・atm)以下、JIS K 7129-1992に準拠した方法で測定された、水蒸気透過度(25±0.5℃、相対湿度(90±2)%RH)が、1×10-3g/(m2・24h)以下のものであることが好ましい。
また、このような板状の封止材(6)を透明基板(2)側に固定するための接着剤(7)は、封止材(6)と透明基板(2)とに挟まれる有機EL素子(100)を封止するためのシール剤として用いられる。このような接着剤(7)は、具体的には、アクリル酸系オリゴマー、メタクリル酸系オリゴマーの反応性ビニル基を有する光硬化及び熱硬化型接着剤、2-シアノアクリル酸エステル等の湿気硬化型等の接着剤を挙げることができる。
なお、有機EL素子(100)を構成する有機材料は、熱処理により劣化する場合がある。このため、接着剤(7)は、室温から80℃までに接着硬化できるものが好ましい。また、接着剤(7)中に乾燥剤を分散させておいてもよい。
また、板状の封止材(6)と透明基板(2)と接着剤(7)との間に隙間が形成される場合、この間隙には、気相及び液相では、窒素、アルゴン等の不活性気体やフッ化炭化水素、シリコンオイルのような不活性液体を注入することが好ましい。また、真空とすることも可能である。また、内部に吸湿性化合物を封入することもできる。
このような封止膜は、無機材料や有機材料を用いて構成される。特に、水分や酸素等、有機EL素子(100)における発光機能層(3)の劣化をもたらす物質の浸入を抑制する機能を有する材料で構成されることとする。このような材料として、例えば、酸化ケイ素、二酸化ケイ素、窒化ケイ素等の無機材料が用いられる。さらに封止膜の脆弱性を改良するために、これら無機材料からなる膜とともに、有機材料からなる膜を用いて積層構造としてもよい。
透明基板(2)とともに、有機EL素子(100)及び封止材(6)を挟むようにして保護膜又は保護板を設けてもよい。この保護膜又は保護板は、有機EL素子(100)を機械的に保護するためのものであり、特に封止材(6)が封止膜である場合には、有機EL素子(100)に対する機械的な保護が十分ではないため、このような保護膜又は保護板を設けることが好ましい。
有機EL素子の製造方法の一例として、図2に示した有機EL素子(100)の製造方法について説明する。
次に、金属親和性層(11)の上に、銀と銀とは異なる金属とを含有する第1導電性層(12a)を、蒸着法等の適宜の方法により、厚さが0.5~15nmの範囲内となるように形成する。そして、第1導電性層(12a)の上に、銀を主成分とする第2導電性層(12b)を、蒸着法等の適宜の方法により、厚さが1~10nmの範囲内となるように、かつ第1導電性層(12a)と併せた厚さが5~25nmの範囲内となるように形成する。こうして透明基板(2)の上に、アノードとなる透明電極(1)が形成される。
以上説明した有機EL素子(100)は、本発明の導電性、光透過性及び経時安定性を兼ね備えた透明電極(1)をアノードとして用い、この上に発光機能層(3)とカソードとなる対向電極(4)とを設けた構成となっている。このため、透明電極(1)と対向電極(4)との間に十分な電圧を印加して有機EL素子(100)での高輝度発光を実現しつつ、所定輝度を得るための駆動電圧の低減、面内均一発光性、及び経時安定性の向上を図ることが可能になる。
〔構成例2に係る有機EL素子の構成〕
図3は、構成例2に係る有機EL素子の概略断面図である。
本例に係る有機EL素子(200)は、構成例1と同様、ボトムエミッション型のものであるが、透明電極(1)をカソード(対向電極(4)をアノード)として用いているが点が上述した構成例1と相違している。以下、構成例1に係る有機EL素子(100)と同様の構成要素についての重複する詳細な説明は省略し、構成例2の有機EL素子(200)の特徴的な構成について説明する。
図3に示した構成例2の場合の一例としては、カソードとして機能する透明電極(1)の上に、電子注入層(3e)/電子輸送層(3d)/発光層(3c)/正孔輸送層(3b)/正孔注入層(3a)をこの順に積層した構成が例示される。ただし、このうち少なくとも有機材料で構成された発光層(3c)を有することが必須である。
以上のように構成されている対向電極(4)は、これらの導電性材料を蒸着やスパッタリング等の方法により薄膜を形成させることにより作製することができる。また、対向電極(4)としてのシート抵抗値は、数百Ω/sq.以下が好ましく、厚さは通常5nm~5μm、好ましくは5~200nmの範囲内とされる。
以上説明した有機EL素子(200)は、本発明の導電性、光透過性及び経時安定性を兼ね備えた透明電極(1)をカソードとして用い、この上に発光機能層(3)とアノードとなる対向電極(4)とを設けた構成となっている。このため、構成例1と同様に、透明電極(1)と対向電極(4)との間に十分な電圧を印加して有機EL素子(200)での高輝度発光を実現しつつ、所定輝度を得るための駆動電圧の低減、面内均一発光性、及び経時安定性の向上を図ることが可能になる。
〔構成例3に係る有機EL素子の構成〕
図4は、本発明の電子デバイスの一例として、本発明の透明電極(1A)を用いた有機EL素子の構成例3を示す概略断面図である。
図4に示した構成例3の有機EL素子(300)は、いわゆるトップエミッション型である点、すなわち、基板(2A)側に対向電極(4A)を設け、この表面に発光機能層(3)、透明電極(1A)を順に積層した点が、構成例1と相違している。以下、構成例1と同様の構成要素についての重複する詳細な説明は省略し、構成例3の有機EL素子(300)の特徴的な構成を説明する。
図4に示した構成例3の場合は、アノードとして機能する対向電極(4A)の表面に、正孔注入層(3a)、正孔輸送層(3b)、発光層(3c)、電子輸送層(3d)をこの順に積層した構成が例示される。ただし、このうち少なくとも有機材料を用いて構成された発光層(3c)を有することが必須である。また、電子輸送層(3d)と電子注入層(3e)は電子輸送性と電子注入性を併せ持つ材料である場合は、例えば電子輸送層(3d)のみとすることも可能である。
この電子注入層(3e)は、上述した本発明の透明電極(1)の金属親和性層(11)を構成する材料を用いて構成されている。
以上説明した有機EL素子(300)は、発光機能層(3)の最上部を構成する電子注入層(3e)を金属親和性層(11)とし、この上に、銀と銀とは異なる金属元素とを含有する第1導電性層(12a)と、銀を主成分とする第2導電性層(12b)を設けることにより、金属親和性層(11)とこの上の導電性層(12)とを含む透明電極(1A)をカソードとして設けた構成となっている。このため、構成例1及び構成例2と同様に、透明電極(1A)と対向電極(4A)との間に十分な電圧を印加して有機EL素子(300)での高輝度発光を実現しつつ、透明電極(1A)側からの発光光(h)の取り出し効率が向上することによる高輝度化を図ることが可能である。さらに、所定輝度を得るための駆動電圧の低減、面内均一発光性、及び経時安定性の向上を図ることが可能になる。また、対向電極(4A)が光透過性を有する場合には、対向電極(4A)からも発光光(h)を取り出すことができる。
図5は、本発明の電子デバイスの一例として、本発明の透明電極(1,1A)を用いた有機EL素子の構成例4を示す概略断面図である。
〔有機EL素子の効果〕
以上説明した有機EL素子(400)は、構成例1、2及び構成例3と同様に、電極間に十分な電圧を印加して有機EL素子(400)での高輝度発光を実現しつつ、透明電極(1)側からの発光光(h)の取り出し効率が向上することによる高輝度化を図ることが可能である。
上述した各構成の有機EL素子は、上述したように面発光体であるため各種の発光光源として用いることができる。例えば、家庭用照明や車内照明等の照明装置、時計や液晶用のバックライト、看板広告用照明、信号機の光源、光記憶媒体の光源、電子写真複写機の光源、光通信処理機の光源、光センサーの光源等が挙げられる。特に、カラーフィルターと組み合わせた液晶表示装置のバックライト、照明用光源としての用途に有効に用いることができる。
本発明に係る照明装置は、本発明の有機EL素子を具備することができる。
なお、本実施例では、第1導電性層(12a)の第2導電性層(12b)が存在する側と反対側に隣接する層(本発明では金属親和性層(11)又は電子注入層(3e))を「下地層」と称することがある。下地層は、導電性層(12)の下側だけでなく、上側に存在していてもよい。
(実施例1)
《透明電極の作製》
下記の方法に従って、透明電極1~69を、導電性領域の面積が5cm×5cmとなるように作製した。透明電極1、2及び4~10は、第1導電性層(12a)と第2導電性層(12b)からなる(下地層のない)構造の透明電極として作製し、透明電極11~25は、下地層と第1導電性層(12a)と第2導電性層(12b)との積層構造の透明電極として作製し、透明電極3及び26~69は、金属親和性層(11)と第1導電性層(12a)と第2導電性層(12b)との積層構造の透明電極として作製した。
透明な無アルカリガラス製の基材(2)を、市販の真空蒸着装置の基材ホルダーに固定し、この基材ホルダーを真空蒸着装置の真空槽に取り付けた。一方、タンタル製の抵抗加熱ボートに銀、別のタンタル製の抵抗加熱ボートにマグネシウム(Mg)を充填し、当該真空槽内に取り付けた。次に、真空槽内を4×10-4Paまで減圧した後、抵抗加熱ボートを通電して加熱し、下記表Iに示した比率(at%)となるように、蒸着速度0.01~0.2nm/秒で、基材(2)上に厚さ8nmのマグネシウム-銀(1:9)からなる第1導電性層(12a)を形成し、透明電極1を作製した。
また、
下記表Iに示すような銀と合金を形成するための材料(アルミニウム(Al)、マグネ
シウム(Mg)、イッテルビウム(Yb)、セシウム(Cs))及び銀をそれぞれタンタル製の抵抗加熱ボートに充填し、当該真空槽内に取り付けた。そして、下記表Iに示した
比率(at%)、及び厚さとする以外は透明電極1と同様の方法にて第1導電性層(12a)を形成した。続いて、第2導電性層(12b)を形成して、透明電極2及び4~10を作製した。
透明な無アルカリガラス製の基材(2)を市販の真空蒸着装置の基材ホルダーに固定し、例示化合物65をタングステン製抵抗加熱ボートに充填し、これらの基材ホルダーと加熱ボートとを真空蒸着装置の第1真空槽に取り付けた。また、タンタル製の抵抗加熱ボートに銀、及びアルミニウム(Al)を充填し、第2真空槽内に取り付けた。
下記表Iに示すような下地層を形成するための材料(LiF、Alq3、Liq又はET-1)を抵抗加熱ボートに充填し、当該第1真空槽内に取り付けた。更に、下記表Iに示す様な導電性層(12)を形成するための材料を抵抗加熱ボートに充填し、当該第2真空槽内に取り付けた。透明電極3と同様の方法にて、透明な無アルカリガラス製の基材(2)上に、厚さが30nmの下地層を形成し、次いで、下地層まで形成した基材(2)を真空のまま第2真空槽に移し、下記表Iに示す比率(at%)及び厚さとなる様に第1導電性層(12a)、及び第2導電性層(12b)を形成し、透明電極11~25を作製した。
下記表I、表II及び表IIIに示すような金属親和性層(11)を形成するための材料(各種例示化合物等)を抵抗加熱ボートに充填し、当該第1真空槽内に取り付けた。更に、下記表I、表II及び表IIIに示す様な導電性層(12)を形成するための材料を抵抗加熱ボートに充填し、当該第2真空槽内に取り付けた。透明電極3と同様の方法にて、透明な無アルカリガラス製の基材(2)上に、厚さが30nmの金属親和性層(11)を形成し、次いで、金属親和性層(11)まで形成した基材(2)を真空のまま第2真空槽に移し、下記表I、表II及び表IIIに示す比率(at%)及び厚さとなる様に第1導電性層(12a)、及び第2導電性層(12b)を形成し、透明電極26~69を作製した。
上記作製した透明電極1~69について、下記の方法に従い、光透過率、シート抵抗値及び経時安定性(シート抵抗値の変化量)の測定を行った。
作製した各透明電極1~69について、分光光度計(日立製作所製U-3300)を用い、各透明電極1~69の基材(2)をリファレンスとして、波長500nmにおける光透過率(%)を測定した。
上記作製した各透明電極1~69について、抵抗率計(三菱化学社製MCP-T610)を用い、4端子4探針法定電流印加方式でシート抵抗値(Ω/sq.)を測定した。
上記作製した各透明電極1~69について、温度80℃、湿度50%の環境下で、100時間保存した後のシート抵抗値(Ω/sq.)を測定し、その変化量(Ω/sq.)を算出した。
また、透明電極3と58は、第2導電性層の有無以外の構成が全て共通しているが、銀を主成分とする第2導電性層(12b)を有する透明電極58は、光透過率、シート抵抗値、シート抵抗値変化量ともに優れていることが見て取れる。
また、透明電極30及び63~65は、第2導電性層(12b)及び導電性層(12)の厚さ以外の構成が全て共通しているが、第2導電性層(12b)の厚さが10nmを大きく超える透明電極64,65は、10nmを超えない透明電極30,63に比べ、シート抵抗値やシート抵抗値の変化量は良化するものの、光透過率が低下してしまうことが見て取れる。
また、透明電極28と68は、第1導電性層(12a)と第2導電性層(12b)の厚さの比率以外の構成が全て共通しているが、第2導電性層(12b)の比率が高い透明電極68は、比率が低い透明電極28に比べ、光透過率、シート抵抗値、シート抵抗値変化量ともに優れていることが見て取れる。
また、透明電極64は、第2導電性層(12b)の厚さが22nmで導電性層(12)の厚さが25nmであるのに対し、透明電極65は、第2導電性層(12b)の厚さが25nmで導電性層(12)の厚さが28nmもある点を除いて他の構成が全て共通しているが、透明電極64は、光透過率が透明電極65よりも優れていることが見て取れる。
また、透明電極67は、第1導電性層(12a)のAg比率が50at%を超えているのに対し、透明電極66は、40at%しかない点を除いて他の構成は全て共通しているが、透明電極67は、光透過率、シート抵抗値、シート抵抗値変化量ともに透明電極66よりも優れていることが見て取れる。
《発光パネルの作製》
透明電極(1)をカソードとして用いた発光パネル(トップエミッション型有機ELパネル、構成例3)1-1~1-58を作製した。
以下、図4を参照して発光パネルの作製手順を説明する。
100mm×100mm×1.1mmのガラス基板(2A)をイソプロピルアルコールで超音波洗浄し、乾燥窒素ガスで乾燥して、UVオゾン洗浄を5分間行った。
洗浄済みのガラス基板(2A)を市販の真空蒸着装置の基板ホルダーに固定し、発光機能層(3)を構成する各材料を最適な量でタングステン製抵抗加熱ボートに充填し、加熱ボートを真空蒸着装置の第1真空槽に取り付けた。また、電極材料を構成する各材料を最適な量でタンタル製の抵抗加熱ボートに銀、及びマグネシウム(Mg)を充填し、基板ホルダーと加熱ボートとを第2真空槽内に取り付けた。
まず、ガラス基板(2A)上にアノードとしてアルミニウム(Al)からなる対向電極(4A)を厚さ100nmで形成した。
次いで、正孔注入材料として下記構造式に示すHAT-CNが入った加熱ボートに通電して加熱し、HAT-CNよりなる正孔注入層(3a)を、ITO対向電極(4A)上に形成した。この際、蒸着速度0.1~0.2nm/秒の範囲内で、厚さ10nmとした。
次いで、正孔輸送注入材料としてα-NPD(後述)が入った加熱ボートに通電して加熱し、α-NPDよりなる正孔輸送層(3b)を、正孔注入層(3a)上に形成した。この際、蒸着速度0.1~0.2nm/秒の範囲内、厚さ120nmとした。
次いで、ホスト材料として例示化合物H1(後述)の入った加熱ボートと、蛍光発光性化合物である例示化合物DP1(後述)の入った加熱ボートとを、それぞれ独立に通電し、ホスト材料H1と蛍光発光性化合物DP1とよりなる発光層(3c)を、正孔輸送層(3b)1上に形成した。この際、蒸着速度がホスト材料H1:蛍光発光性化合物DP1=95:5(質量比)となるように、加熱ボートの通電を調節した。また、厚さを30nmとした。
その後、電子輸送材料としてAlq3(前出)の入った加熱ボートを通電し、Alq3よりなる電子輸送層(3d)を、発光層(3c)上に形成した。この際、蒸着速度を0.1~0.2nm/秒の範囲内とし、厚さを30nmとした。
次に、電子注入材料としてLiF(前出)の入った加熱ボートに通電して加熱し、LiFよりなる電子注入層(3e)を、電子輸送層(3d)上に形成した。この際、蒸着速度を0.01~0.02nm/秒の範囲内とし、厚さを2nmとした。
その後、電子注入層(3e)まで形成した透明基板(2A)を、真空蒸着装置の蒸着室から、導電性層材料としてタングステン製の抵抗加熱ボートに銀、及びマグネシウム(Mg)が充填された真空槽内に、真空状態を保持したまま移送した。次に、真空槽を4×10-4Paまで減圧した後、抵抗加熱ボートを通電して加熱し、下記表IVに示す比率(Ag:90%)及び厚さとなる様に、電子注入層(3e)上に、第1導電性層(12a)及び第2導電性層(12b)をカソードとして順に形成した。
その後、元の真空層内に移送し、図4には図示しなかったが、導電性層(12)上に、α-NPD(前出)を蒸着速度0.1~0.2nm/秒の範囲内で厚さが40nmとなるまで蒸着し、キャッピング層とした。
以上の手順により、透明基板(2)上に有機EL素子(300)を形成した。
その後、有機EL素子(300)を、厚さ300μmのガラス基板からなる封止材(6)で覆い、有機EL素子(300)を囲む状態で、ガラス基板(2A)と封止材(6)との間に接着剤(7、シール材)をシールした。接着剤(7)としては、エポキシ系光硬化型接着剤(東亞合成社製ラックストラックLC0629B)を用いた。封止材(6)とガラス基板(2A)との間に充填した接着剤(7)に対して、封止材(6)側からUV光を照射し、接着剤(7)を硬化させて有機EL素子(300)を封止した。
発光パネル1-1においては、発光層(3c)で発生した各色の発光光(h)が、透明電極(1)側、すなわち封止材(6)側から取り出される。
電子輸送層(3d)、電子注入層(3e)及び導電性層(12)の構成材料及び厚さを、下記表IV及び表Vに記載の条件に変更した以外は上記発光パネル1-1と同様の方法にて発光パネル1-2~1-58を作製した。
上記作製した発光パネル1-1~1-58について、下記の方法に従い、初期駆動電圧、面内発光均一性、駆動電圧の変化量について測定を行った。
上記作製した各発光パネルについて、各発光パネルの透明電極(1)側(すなわち、封止剤17側)での正面輝度を測定し、1000cd/m2となるときの電圧を初期駆動電圧(V)として測定した。なお、輝度の測定には、分光放射輝度計CS-1000(コニカミノルタ株式会社製)を用いた。評価は、同様の製造方法により別バッチで作製した5パネルについて測定し、その平均値を表す。得られた初期駆動電圧(V)の数値が小さいほど、好ましい結果であることを表す。
定電圧電源を用いて、有機EL素子に2.5mA/cm2の直流定電流を流し、サンプルの発光部から無作為に選んだ10か所の輝度を、分光放射輝度計CS-1000(コニカミノルタ株式会社製)を用いて測定し、下記計算式を用いて輝度のバラツキを求めた。なお、式中の平均輝度は、選んだ10か所からそれぞれ得た測定値の平均である。
輝度バラツキ(%)=((最高輝度-最低輝度)/平均輝度)×100
輝度バラツキの評価ランク
◎:5%未満
○:5%以上、10%未満
△:10%以上、20%未満
×:20%以上
上記作製した各発光パネルについて、温度80℃、湿度50%の環境下で、100時間保存した後に、上述した初期駆動電圧の測定方法と同じ手法(1000cd/m2)で、発光パネルの透明電極(1)側での正面輝度が1000cd/m2となるときの電圧を保存後駆動電圧(V′)として測定し、下記式を用いて駆動電圧の変化量(ΔV/%)を算出した。その値が小さい程、良好であることを示している。
ΔV(駆動電圧変化量%)=保存後駆動電圧(V′)/初期駆動電圧(V)
また、本発明以外の材料との組合せを用いた場合(発光パネル1-4、1-5、1-6)についても、駆動電圧が低減し、面内発光均一性が向上し、駆動電圧変化量が低減していることが見て取れる。
また、1-10と1-11又は1-46と1-47のパネルは、第2導電性層の有無以外の構成が全て共通しているが、銀を主成分とする第2導電性層を有する1-10や1-46のパネルは、面内発光均一性が向上し、駆動電圧変化量が低減していることが見て取れる。
また、1-53と1-54のパネルは、第2導電性層12b及び導電性層12の厚さ以外の構成が全て共通しているが、第2導電性層12bがより厚い1-54のパネルは、薄い1-53のパネルに比べ、面内発光均一性が向上し、駆動電圧変化量が低減していることが見て取れる。
また、1-10と1-53のパネルは、第1導電性層12aと第2導電性層12bの厚さの比率以外の構成が全て共通しているが、第2導電性層12bの比率が高い1-10のパネルは、比率が低い1-53のパネルに比べ、面内発光均一性が向上し、駆動電圧変化量が低減していることが見て取れる。
《発光パネルの作製》
また、透明電極(1)をアノードとして用いた発光パネル(ボトムエミッション型有機ELパネル、構成例1)2-1~2-9を作製した。
以下、図2を参照して発光パネルの作製手順を説明する。
(ガラス基板及び透明電極(1)の形成)
100mm×100mm×1.1mmのガラス基板(2)をイソプロピルアルコールで超音波洗浄し、乾燥窒素ガスで乾燥して、UVオゾン洗浄を5分間行った。
洗浄済みのガラス基板(2)を市販の真空蒸着装置の基板ホルダーに固定し、発光機能層(3)を構成する各材料を最適な量でタングステン製抵抗加熱ボートに充填し、これらの基板ホルダーと加熱ボートとを真空蒸着装置の第1真空槽に取り付けた。また、タンタル製の抵抗加熱ボートに電極材料を充填し、第2真空槽内に取り付けた。
次いで、正孔注入材料として上述したHAT-CNが入った加熱ボートに通電して加熱し、HAT-CNよりなる正孔注入層(3a)を、ITO対向電極(4)上に形成した。この際、蒸着速度0.1~0.2nm/秒の範囲内にて、厚さが10nmとなるようにした。
次いで、正孔輸送注入材料としてα-NPD(前出)が入った加熱ボートに通電して加熱し、α-NPDよりなる正孔輸送層(3b)を、正孔注入層(3a)上に形成した。この際、蒸着速度0.1~0.2nm/秒の範囲内にて、厚さが120nmとなるようにした。
次いで、ホスト材料として例示化合物H2の入った加熱ボートと、リン光発光性化合物である例示化合物DP2の入った加熱ボートとを、それぞれ独立に通電し、ホスト材料H2とリン光発光性化合物DP2とよりなる発光層(3c)を、正孔輸送層(3b)1上に形成した。この際、蒸着速度がホスト材料H2:リン光発光性化合物DP2=85:15(質量比)となるように、加熱ボートの通電を調節した。また、厚さを30nmとした。
その後、電子輸送材料としてAlq3(前出)の入った加熱ボートを通電し、Alq3よりなる電子輸送層(3d)を、発光層(3c)上に形成した。この際、蒸着速度を0.1~0.2nm/秒の範囲内とし、厚さを30nmとした。
次に、電子注入材料としてLiq(前出)の入った加熱ボートに通電して加熱し、LiFよりなる電子注入層(3e)を、電子輸送層(3d)上に形成した。この際、蒸着速度0.01~0.02nm/秒の範囲内とし、厚さを2nmとした。
(対向電極の形成)
その後、電子注入層(3e)まで形成したガラス基板(2)を、真空蒸着装置の蒸着室から、導電性層材料としてタングステン製の抵抗加熱ボートにアルミニウム(Al)が充填された真空槽内に、真空状態を保持したまま移送した。次に、真空槽を4×10-4Paまで減圧した後、抵抗加熱ボートに通電して加熱し、厚さ100nmのカソードとして形成した。
その後、元の真空層内に移送し、図2には図示していないが、対向電極(4)上に、α-NPD(前出)を蒸着速度0.1~0.2nm/秒で厚さが40nmとなるように蒸着し、キャッピング層とした。
以上の手順により、透明基板2上に有機EL素子(100)を形成した。
その後、有機EL素子(100)を、厚さ300μmのガラス基板からなる封止材(6)で覆い、有機EL素子(300)を囲む状態で、封止材(6)と透明基板(2)との間に接着剤(7、シール材)をシールした。接着剤(7)としては、エポキシ系光硬化型接着剤(東亞合成社製ラックストラックLC0629B)を用いた。封止材(6)と透明基板(2)との間に充填した接着剤(7)に対して、封止材(6)側からUV光を照射し、接着剤(7)を硬化させて有機EL素子(100)を封止した。
発光パネル2-1においては、発光層(3c)で発生した各色の発光光(h)が、透明電極(1)側、すなわち透明基板(2)側から取り出される。
上記発光パネル2-1の作製において、下地層(金属親和性層(11))、及び導電性層(12a,12b)の構成材料及び厚さを、下記表VIに記載の条件に変更した以外は同様にして、発光パネル2-2~2-9を作製した。
《発光パネルの評価》
上記作製した発光パネル2-1~2-9について、各発光パネルの透明アノード(1)側(すなわち、基板(2)側)での正面輝度を測定した以外は、実施例2で説明した方法と同様に測定を行った。
《発光パネルの作製》
透明電極(1)をカソード及びアノードとして用いた発光パネル(透明型有機ELパネル、構成例4)3-1~3-6を作製した。
以下、図5を参照して発光パネルの作製手順を説明する。
(ガラス基板及び透明電極(1)の形成)
100mm×100mm×1.1mmのガラス基板(2)をイソプロピルアルコールで超音波洗浄し、乾燥窒素ガスで乾燥して、UVオゾン洗浄を5分間行った。
洗浄済みのガラス基板(2)を市販の真空蒸着装置の基板ホルダーに固定し、発光機能層(3)を構成する各材料を最適な量でタングステン製抵抗加熱ボートに充填し、これらの基板ホルダーと加熱ボートとを真空蒸着装置の第1真空槽に取り付けた。また、タンタル製の抵抗加熱ボートに電極材料を充填し、第2真空槽内に取り付けた。
次いで、正孔注入材料として上述したHAT-CNが入った加熱ボートに通電して加熱し、HAT-CNよりなる正孔注入層(3a)を、透明電極(1)上に形成した。この際、蒸着速度0.1~0.2nm/秒、厚さ10nmとした。
次いで、正孔輸送注入材料としてα-NPD(前出)が入った加熱ボートに通電して加熱し、α-NPDよりなる正孔輸送層(3b)を、正孔注入層(3a)上に形成した。この際、蒸着速度0.1~0.2nm/秒、厚さ120nmとした。
次いで、ホスト材料として例示化合物H3(後述)の入った加熱ボートと、リン光発光性化合物である例示化合物DP2の入った加熱ボートとを、それぞれ独立に通電し、ホスト材料H3とリン光発光性化合物DP2とよりなる発光層(3c)を、正孔輸送層(3b)1上に形成した。この際、蒸着速度がホスト材料H3:リン光発光性化合物DP2=85:15(質量比)となるように、加熱ボートの通電を調節した。また、厚さは30nmとした。
その後、電子輸送材料としてAlq3(前出)の入った加熱ボートを通電し、Alq3よりなる電子輸送層(3d)を、発光層(3c)上に形成した。この際、蒸着速度0.1~0.2nm/秒、厚さ30nmとした。
次に、電子注入材料としてAlq3の入った加熱ボートとLiq(前出)の入った加熱ボートに通電して加熱し、下記表VIIに示す比率にて、電子注入層(3e)を、発光層(3c)上
に形成した。この際、蒸着速度0.01~0.02nm/秒、厚さ30nmとした。
その後、電子注入層(3e)まで形成したガラス基板(2)を、真空蒸着装置の蒸着室から、導電性層材料としてタングステン製の抵抗加熱ボートに銀、及びマグネシウム(Mg)が充填された真空槽内に、真空状態を保持したまま移送した。次に、真空槽を4×10-4Paまで減圧した後、抵抗加熱ボートを通電して加熱し、下記表VIIに示す比率(Ag:90%)及び厚さとなる様に、電子注入層(3e)上に第1導電性層(12a)及び第2導電性層(12b)をカソードとして順に形成した。
その後、元の真空層内に移送し、図5には図示していないが、導電性層(12)上に、α-NPD(前出)を蒸着速度0.1~0.2nm/秒で厚さが40nmとなるまで蒸着し、キャッピング層とした。
以上の手順により、透明基板2上に有機EL素子(400)を形成した。
その後、有機EL素子(400)を、厚さ300μmのガラス基板からなる封止材(6)で覆い、有機EL素子(400)を囲む状態で、封止材(6)と透明基板(2)との間に接着剤(7、シール材)をシールした。接着剤(7)としては、エポキシ系光硬化型接着剤(東亞合成社製ラックストラックLC0629B)を用いた。封止材(6)と透明基板(2A)との間に充填した接着剤(7)に対して、封止材(6)側からUV光を照射し、接着剤(7)を硬化させて有機EL素子(400)を封止した。
上記発光パネル3-1の作製において、下地層(金属親和性層(11))及び導電性層(12)の構成材料及び厚さを、下記表VIIに記載の条件に変更した以外は同様にして、発光パネル3-2~3-6を作製した。
上記作製した発光パネル3-1~3-6について、各発光パネルの透明カソード側(すなわち、封止剤6側)と、透明アノード側(1)側(すなわち、透明基板(2)側)との両側での正面輝度を測定し、その和が1000cd/m2となるときの電圧を駆動電圧(V)として測定した以外は、実施例2と同様の方法で評価を行った。
また、本発明は、画像を投影するタイプのプロジェクション装置や、静止画像や動画像を直接視認するタイプの表示装置として用いることもできる。
11 金属親和性層
12 導電性層
12a 第1導電性層
12b 第2導電性層
2,2A 基板(基材)
2a 光取り出し面
100,200,300,400 有機EL素子
3 発光機能層
3a 正孔注入層
3b 正孔輸送層
3c 発光層
3d 電子輸送層
3e 電子注入層
4,4A 対向電極
5 補助電極
6 封止材
7 接着剤
h 発光光
Claims (10)
- 前記A1及びA2が、それぞれ独立に、6員のヘテロアリール環を構成する残基を表す請求項1又は2に記載の透明電極。
- 前記A1及びA2が、それぞれ独立に、ピリジン環、ピラジン環、トリアジン環、ピリジミン環、アザジベンゾフラン環、アザジベンゾチオフェン環、アザカルバゾール環、キナゾリン環、キノキサリン環、キノリン環、イソキノリン環、ベンゾキノリン環、ベンゾイソキノリン環又はフェナンスリジン環を構成する残基を表す請求項3に記載の透明電極。
- 前記A1及びA2が、それぞれ独立に、5員のヘテロアリール環を構成する残基を表す請求項1又は請求項2に記載の透明電極。
- 前記A1及びA2が、それぞれ独立に、インドール環、イミダゾール環、ベンズイミダゾール環、ピラゾール環、トリアゾール環、オキサゾール環又はチアゾール環を構成する残基を表す請求項5に記載の透明電極。
- 前記第1導電性層に含まれる銀の濃度が、50~99at%の範囲内である請求項1から請求項6までのいずれか一項に記載の透明電極。
- 前記第1導電性層の厚さと前記第2導電性層の厚さの合計が5~25nmの範囲内であり、
かつ、前記第2導電性層の厚さが1~10nmの範囲内である請求項1から請求項7までのいずれか一項に記載の透明電極。 - 請求項1から請求項8までのいずれか一項に記載の透明電極が具備されている電子デバイス。
- 前記電子デバイスが、有機エレクトロルミネッセンス素子である請求項9に記載の電子デバイス。
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