WO2011152092A1 - 電極箔および有機デバイス - Google Patents
電極箔および有機デバイス Download PDFInfo
- Publication number
- WO2011152092A1 WO2011152092A1 PCT/JP2011/054628 JP2011054628W WO2011152092A1 WO 2011152092 A1 WO2011152092 A1 WO 2011152092A1 JP 2011054628 W JP2011054628 W JP 2011054628W WO 2011152092 A1 WO2011152092 A1 WO 2011152092A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- organic
- electrode foil
- foil
- layer
- electrode
- Prior art date
Links
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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
-
- 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
- H10K2102/301—Details of OLEDs
- H10K2102/302—Details of OLEDs of OLED structures
- H10K2102/3023—Direction of light emission
- H10K2102/3026—Top emission
-
- 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
- H10K2102/301—Details of OLEDs
- H10K2102/321—Inverted OLED, i.e. having cathode between substrate and anode
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12431—Foil or filament smaller than 6 mils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12431—Foil or filament smaller than 6 mils
- Y10T428/12438—Composite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12993—Surface feature [e.g., rough, mirror]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to an electrode foil using a metal foil, and an organic device such as an organic EL element, an organic EL lighting, and an organic solar battery using the electrode foil.
- organic EL lighting has attracted attention as an environmentally friendly green device.
- Features of organic EL lighting include 1) low power consumption compared to incandescent lamps, 2) thin and lightweight, and 3) flexibility.
- organic EL lighting is being developed to realize the features 2) and 3). In this respect, it is impossible to realize the features 2) and 3) above with a glass substrate that has been conventionally used in a flat panel display (FPD) or the like.
- FPD flat panel display
- Ultra-thin glass is excellent in heat resistance, barrier properties, and light transmission properties, and also has good flexibility, but handling properties are slightly inferior, thermal conductivity is low, and material cost is high.
- the resin film is excellent in handling properties and flexibility, has a low material cost, and has good light transmittance, but has poor heat resistance and barrier properties, and has low thermal conductivity.
- the metal foil has excellent characteristics such as excellent heat resistance, barrier properties, handling properties, thermal conductivity, good flexibility, and low material cost, except that it has no light transmittance.
- the thermal conductivity of a typical flexible glass or film is as low as 1 W / m ° C. or less, whereas in the case of a copper foil, it is as high as about 280 W / m ° C.
- Patent Document 1 discloses an organic light-emitting device including a lower electrode layer, an organic layer, and an upper electrode layer on a flexible substrate.
- a metal foil that may be covered with an insulating layer is disclosed. It is described that it can be used.
- Patent Document 2 discloses a flexible insulating metal foil for an electronic device provided with a stainless steel foil having a surface roughness Ra of 30 nm to 500 nm. This metal foil is used as a support base material for forming an electronic device such as a thin film transistor (TFT) by covering the surface with an insulating film.
- TFT thin film transistor
- Patent Document 3 discloses a flexible metal foil laminate in which a thermocompression bonding polyimide coating is laminated on a metal foil surface having a surface roughness Ra of about 0.2 ⁇ m or less.
- Patent Document 4 discloses an electrolytic copper foil in which the surface roughness (Rzjis) on the deposition surface side is less than 1.0 ⁇ m in order to reduce the profile of the bonding surface with the insulating layer constituent material.
- the surface roughness (Rzjis) disclosed in the literature is at most 0.27 ⁇ m at the most flat.
- the present inventor has recently developed a flexible electronic device having functions as a support base, an electrode, and a reflective layer, and having excellent thermal conductivity by extremely flattening at least one surface of a metal foil. The knowledge that a useful electrode foil was obtained was acquired.
- an object of the present invention is to provide an electrode foil useful for a flexible electronic device having functions as a support base, an electrode, and a reflective layer, and having excellent thermal conductivity.
- an electrode foil comprising a metal foil
- An electrode foil is provided in which at least one outermost surface of the electrode foil is an ultra-flat surface having an arithmetic average roughness Ra of 10.0 nm or less as measured in accordance with JIS B 0601-2001.
- the electrode foil An organic semiconductor layer comprising an organic EL layer and / or an organic solar cell active layer provided directly on the outermost surface of the electrode foil on the ultra-flat surface side; A transparent or translucent counter electrode provided on the organic semiconductor layer; An organic device that is an organic EL element and / or an organic solar cell is provided.
- organic EL illumination comprising the organic device as an organic EL element.
- FIG. 10 is a diagram showing voltage dependency characteristics of luminance measured in Example 6. It is a figure which shows the wavelength dependence characteristic of the absolute reflectance (%) measured about various metal foil in Example 8.
- FIG. 10 is a schematic cross-sectional view showing a layer configuration of an electrode foil produced in Example 9.
- FIG. 12 is a schematic cross-sectional view showing a layer configuration of an organic EL element produced in Example 10.
- FIG. 1 shows a schematic cross-sectional view of an example of an electrode foil according to the present invention.
- An electrode foil 10 shown in FIG. 1 includes a metal foil 12 and, if desired, a buffer layer 14 provided directly on the metal foil. That is, the electrode foil 10 has a two-layer configuration including the metal foil 12 and the buffer layer 14, but the electrode foil of the present invention is not limited thereto, and may have a one-layer configuration including only the metal foil 12. .
- At least one outermost surface of the electrode foil 10 is 10.0 nm or less, preferably 7.0 nm or less, more preferably 5.0 nm, still more preferably 3.0 nm or less, even more preferably 2.5 nm or less, particularly preferably.
- the lower limit of the arithmetic average roughness Ra is not particularly limited and may be zero. However, in consideration of the efficiency of the flattening process, 0.5 nm is cited as a guideline for the lower limit value.
- the arithmetic average roughness Ra can be measured using a commercially available roughness measuring device in accordance with JIS B 0601-2001.
- the outermost surface of at least one of the electrode foils 10 means the surface 12a of the metal foil 12 in the case of a one-layer structure, and the surface 14a of the buffer layer 14 in the case of a two-layer structure.
- the above-described arithmetic average roughness Ra on the surface 14a of the buffer layer 14 is achieved by setting the arithmetic average roughness Ra of the surface 12a of the metal foil 12 on which the buffer layer is formed to the same as above. Range, that is, 10.0 nm or less, preferably 6.0 nm or less, more preferably 3.0 nm or less, still more preferably 2.0 nm or less, and even more preferably 1.5 nm or less.
- the surface 14a of the buffer layer 14 thus formed has a thickness of 10.0 nm or less, preferably 7.0 nm or less, more preferably 5.0 nm, even more preferably 3.0 nm or less, particularly preferably 2.5 nm or less, particularly more preferably
- the arithmetic average roughness Ra is preferably 2.0 nm or less. As described above, it is preferable that an arithmetic average roughness Ra that is equal to or slightly smaller than the arithmetic average roughness Ra to be applied on the outermost surface is provided on the surface of the metal foil below the arithmetic average roughness Ra.
- the arithmetic average roughness Ra of the surface of the metal foil that does not constitute the outermost surface due to the laminated state is evaluated by creating a cross section from the surface of the metal foil by FIB (Focused Ion Beam) processing, and using the transmission electron microscope ( (TEM).
- FIB Flucused Ion Beam
- TEM transmission electron microscope
- metal foils especially copper foils having such an ultra-flat surface have not been industrially produced until now, and even attempts to apply them as electrodes of flexible electronic devices are not possible. It has never been done before.
- copper foil with a flattened surface is commercially available, the level of flattening of such a copper foil is insufficient as an electrode for an organic EL element, and short-circuits due to surface irregularities in the case of an organic EL element. As a result, light emission cannot be obtained.
- the arithmetic average roughness Ra of the ultra-flat surface of the electrode foil or metal foil according to the present invention is extremely small as described above, no short circuit occurs between the counter electrode and the like even when used as an electrode for an organic EL element. .
- the absolute reflectance on the surface of the metal foil is greatly improved in the entire wavelength region due to the super-flattening, the reflection layer that has been essential in the top emission type light emitting device can be eliminated.
- Such an ultra-flat surface can be realized by polishing a metal foil by CMP (Chemical Mechanical Polishing).
- the CMP treatment can be performed according to known conditions using a known polishing liquid and a known polishing pad.
- a preferred polishing liquid contains about 0.5 to 2% by weight of one or more abrasive grains selected from ceria, silica, alumina, zirconia and the like, and an oxidizing agent such as benzotriazole (BTA). And / or further comprising an organic complex-forming agent such as quinarsinic acid, quinolinic acid, nicotinic acid, a surfactant such as a cationic surfactant or an anionic surfactant, and optionally an anticorrosive agent Can be mentioned.
- a preferable polishing pad includes a urethane pad. The polishing conditions are not particularly limited as long as the pad rotation speed, work load, polishing liquid application flow rate, etc.
- the rotation speed is in the range of 20 to 1000 rpm
- the work load is in the range of 100 to 500 gf / cm 2 .
- the ultra-flat surface 12a can also be realized by polishing the metal foil 12 using an electrolytic polishing method, a buff polishing method, a chemical polishing method, or a combination thereof.
- the chemical polishing method is not particularly limited as long as the chemical solution, the chemical solution temperature, the chemical solution immersion time, etc. are appropriately adjusted.
- the chemical polishing of copper foil uses a mixture of 2-aminoethanol and ammonium chloride. Can be performed.
- the temperature of the chemical solution is preferably room temperature, and it is preferable to use an immersion method (Dip method). Further, since the chemical solution immersion time tends to deteriorate the flatness as it becomes longer, it is preferably 10 to 120 seconds, and more preferably 30 to 90 seconds.
- the metal foil after chemical polishing is preferably washed with running water. According to such a planarization process, it is possible to planarize a surface having a Ra arithmetic average roughness Ra of about 12 nm to Ra 10.0 nm or less, for example, about 3.0 nm.
- the ultra-flat surface 12a may be realized by a method of polishing the surface of the metal foil 12 by blasting, a method of rapidly cooling the surface of the metal foil 12 by melting it by a technique such as laser, resistance heating, or lamp heating. it can.
- a metal foil that can be plated such as copper, nickel, or chrome
- an ultra-flat surface can be realized using a transfer method.
- the transfer method may be performed based on a known method and known conditions. For example, the surface of the electrode plate made of SUS, titanium, or the like is planarized using an electrolytic polishing method and a buff polishing method so that the arithmetic average roughness Ra is 10.0 nm or less, for example, 3.0 nm or less.
- the material of the metal foil 12 is plated on the surface of the flattened electrode plate, and when the desired thickness is reached, the material of the metal foil 12 is peeled off from the electrode plate.
- an ultra-flat surface can be realized.
- the metal foil 12 is not particularly limited as long as it is a foil-like metal material having strength as a support substrate, electrical characteristics required as an electrode, and light reflection characteristics acceptable as a reflective layer.
- a preferred metal foil is a nonmagnetic metal foil from the viewpoint of preventing adhesion of particulate matter generated during processing due to magnetism.
- the nonmagnetic metal include copper, aluminum, nonmagnetic stainless steel, titanium, tantalum, molybdenum, and the like, and copper, aluminum, and nonmagnetic stainless steel are more preferable.
- the most preferred metal foil is copper foil. Copper foil is excellent in strength, flexibility, electrical characteristics and the like while being relatively inexpensive. Moreover, when warm white light with a color temperature of about 3000K is required for organic EL illumination, the copper foil can reflect light of an optimum color because there is no reflective layer. This is because the copper foil has a characteristic that the absolute reflectance is relatively low in the blue wavelength region as compared with other wavelength regions.
- the thickness of the metal foil 12 is not particularly limited as long as it is a thickness that can be handled alone as a foil without impairing flexibility, but it is 1 to 250 ⁇ m, preferably 25 to 250 ⁇ m, more preferably 35 to 150 ⁇ m. is there. With such a thickness, it is possible to easily cut using a commercially available cutting machine.
- the metal foil 12 has no problems such as cracking and chipping, and has advantages such as less generation of particles during cutting.
- the metal foil 12 can have various shapes other than a quadrangle, for example, a circle, a triangle, a polygon, and can be cut and welded. It is also possible to produce a light emitter. In this case, it is preferable not to form a light emitting layer at the cut portion or welded portion of the metal foil 12.
- the ultra flat surface 12a is preferably washed with an alkaline solution.
- an alkaline solution a known alkaline solution such as a solution containing ammonia, a sodium hydroxide solution, or a potassium hydroxide solution can be used.
- a preferred alkaline solution is a solution containing ammonia, more preferably an organic alkaline solution containing ammonia, and even more preferably a tetramethylammonium hydroxide (TMAH) solution.
- TMAH tetramethylammonium hydroxide
- a preferable concentration of the TMAH solution is 0.1 to 3.0 wt%.
- cleaning is performed at 23 ° C. for 1 minute using a 0.4% TMAH solution.
- a similar cleaning effect can be obtained by performing UV (Ultra Violet) treatment in combination with the cleaning with the alkaline solution or in place of the cleaning with the alkaline solution.
- UV Ultra Violet
- an acidic cleaning solution such as dilute sulfuric acid.
- the acid cleaning it is possible to perform cleaning for 30 seconds using dilute sulfuric acid.
- the dry ice blasting method is a method of removing particles by spraying carbon dioxide, which has been solidified at a low temperature, onto the ultra-flat surface 12a by spraying carbon dioxide gas compressed to a high pressure from a thin nozzle. Unlike the wet process, this dry ice blasting method has the advantages that the drying process can be omitted and organic substances can be removed.
- the dry ice blasting method can be performed using a commercially available apparatus such as a dry ice snow system (manufactured by Air Water).
- the buffer layer 14 is directly provided on the metal foil 12.
- the buffer layer 14 is not particularly limited as long as it is in contact with the organic EL layer in the organic EL element to improve the hole injection efficiency or the electron injection efficiency and provide a desired work function.
- the buffer layer in the present invention is preferably transparent or translucent from the viewpoint of allowing the metal foil to function as a reflective layer.
- the buffer layer 14 is preferably at least one selected from a conductive amorphous carbon film, a conductive oxide film, a magnesium-based alloy film, and a fluoride film, and is used and required as an anode or a cathode. What is necessary is just to select suitably according to a characteristic.
- the conductive amorphous carbon film various amorphous carbon films imparted with conductivity by controlling the hydrogen concentration or impurity concentration can be used.
- the formation of the conductive amorphous carbon film is preferably performed by a sputtering method.
- a carbon target used for sputtering it is desirable to use a purified product. It is also possible to use porous carbon impregnated with B, Si, Al, Cu.
- a preferable conductive amorphous carbon film is composed of conductive amorphous carbon having a hydrogen concentration of 15 at% or less.
- a more preferable hydrogen concentration is 12 at% or less, and further preferably 5 at% or less.
- the lower limit of the hydrogen concentration is not particularly limited and may be zero. However, considering the inevitable mixing of hydrogen due to the film formation environment during sputtering, 3 at% is an example of the lower limit.
- the hydrogen concentration in the buffer layer can be measured by various known methods, but is preferably performed by HFS (hydrogen forward scattering). In this specification, the hydrogen concentration in the conductive amorphous carbon film is defined as the hydrogen concentration when carbon and hydrogen are quantified with HFS or the like and the total number of these atoms is 100 at%.
- the conductive amorphous carbon is not substantially doped with impurities other than carbon and hydrogen.
- substantially undoped means that impurities are not intentionally doped in order to provide some function, and inevitably mixed due to the film forming environment during sputtering. Impurities are allowed.
- the conductive amorphous carbon in the present invention preferably has an oxygen concentration of 0 to 300 wtppm, a halogen element concentration of 0 to 1000 wtppm, and a nitrogen concentration of 0 to 500 ppm.
- the thickness of the buffer layer 14 is not particularly limited, but is preferably 3 to 30 nm, more preferably 3 to 15 nm, and still more preferably 5 to 10 nm.
- Preferred InO x as the conductive oxide film SnO x, ZnO x, MoO x, GaO x, VO x, WO x, RuO x, AlO x, 1 kind selected from the group consisting of TiO x, and GeO x or
- a film composed of two or more kinds is exemplified, and typical examples include ITO (indium tin oxide) and IZO (indium zinc oxide).
- the conductive oxide film may be formed by a known method such as a sputtering method or a vacuum deposition method, and is preferably performed by a DC magnetron sputtering method. Since the target material used for the sputtering method can be manufactured by a hot press method or a cold press method, desired characteristics can be obtained by appropriately combining the above oxides.
- a preferable magnesium-based alloy film includes a film made of an alloy in which one or more selected from Ag, Al, Zn, Li, Y, and Ca are added to Mg.
- the magnesium-based alloy film may be formed by a known method such as a sputtering method or a vacuum deposition method, and is preferably performed by a vacuum deposition method.
- Preferable fluoride films include films composed of one or more selected from LiF, MgF 2 , CaF 2 , AlF 3 , Na 3 AlF 6 and NaF 6 .
- the fluoride film may be formed by a known method such as a sputtering method or a vacuum deposition method, and is preferably performed by a vacuum deposition method.
- the surface 14a of the buffer layer 14 is 10.0 nm or less, preferably 7.0 nm or less, more preferably 5.0 nm, still more preferably 3.0 nm or less, even more preferably 2.5 nm or less, particularly preferably 2.0 nm or less.
- these layers and the organic EL layer containing them are conventionally provided. It can be made thinner. As a result, the production cost can be reduced by reducing the amount of extremely expensive organic raw materials used, and the light emission efficiency can be improved by reducing the thickness of the organic EL layer.
- the electrode foil according to the present invention preferably has a thickness of 1 to 300 ⁇ m, more preferably 25 to 250 ⁇ m, still more preferably 35 to 150 ⁇ m, and most preferably 40 to 100 ⁇ m.
- the surface 12b opposite to the ultra-flat surface 12a of the metal foil 12 has a 10-point average roughness of 1.0 ⁇ m or more, more preferably 2.0 ⁇ m or more, and even more preferably 5.0 ⁇ m or more. You may process so that it may become the roughening surface which has thickness Rz.
- the ten-point average roughness Rz can be measured using a commercially available roughness measuring device in accordance with JIS B 0601-1994.
- This roughening process can be preferably performed by a known method such as dry ice blasting, sand blasting, wet etching, or dry etching.
- the heat dissipation characteristics can be improved by the unevenness formed on the surface of the roughened surface.
- the electrode foil according to the present invention is based on a metal foil, it can be efficiently produced by, for example, a roll-to-roll process without particularly requiring a supporting substrate.
- the electrode foil according to the present invention can be preferably used as an anode or a cathode (particularly a reflective electrode) of various flexible electronic devices (particularly flexible light emitting or power generating devices).
- flexible electronic devices include organic EL elements, organic EL lighting, organic EL displays, electronic paper, thin film solar cells, liquid crystal displays, inorganic EL elements, inorganic EL displays, LED lighting, and LED displays.
- the organic EL element is preferably an organic EL element, an organic EL illumination, an organic EL display, an organic solar cell, or a dye-sensitized solar cell, and more preferably an organic EL illumination in that ultra-thin and high-luminance emission can be obtained.
- the electrode foil according to the present invention can be preferably used as an anode or a cathode of the organic solar cell.
- the organic device can be configured as either an organic EL element or an organic solar cell by appropriately selecting the type of the organic semiconductor layer to be laminated on the electrode foil according to the present invention in accordance with a known technique.
- a light emitting element and a power generating element can be formed on the same electrode at the same time, whereby a composite device having both the function of an organic EL element and the function of an organic solar cell can be manufactured.
- the electrode foil according to the present invention can be used not only for electrodes of organic EL elements but also for LED mounting substrates.
- the electrode foil according to the present invention can be preferably used as an anode or a cathode for LED illumination in that LED elements can be densely mounted.
- Organic EL Element and Organic EL Lighting Using the electrode foil according to the present invention as a reflective electrode, a top emission type organic EL element and organic EL lighting can be constructed.
- FIG. 2 shows an example of a layer structure of a top emission type organic EL element using the electrode foil of the present invention as an anode.
- the organic EL element shown in FIG. 2 includes an anode electrode foil 20 including a metal foil 22 and a buffer layer 24, an organic EL layer 26 provided directly on the buffer layer 24, and a counter provided directly on the organic EL layer 26. And a cathode 28 as an electrode.
- the buffer layer 24 is preferably composed of a conductive amorphous carbon film or a conductive oxide film so as to be suitable as an anode.
- organic EL layer 26 various known EL layer configurations used for organic EL elements can be used.
- the electron injection layer may be sequentially provided from the anode electrode foil 20 toward the cathode 28.
- layers having various known configurations and compositions can be used as appropriate, and are not particularly limited.
- an organic solar cell can be configured by replacing the organic EL layer 26 with a known organic solar cell active layer.
- a hole transport layer PEDOT: PSS (30 nm)
- a p-type organic semiconductor layer for example, BP (benzoporphyrin) are formed on a buffer layer (for example, a carbon buffer layer).
- An i-type mixing layer of an n-type organic semiconductor and a p-type organic semiconductor for example, BP: PCBNB (fullerene derivative)
- an n-type organic semiconductor layer for example, PCBM (fullerene derivative)
- a buffer layer having a low work function for example, a solar cell can be formed by sequentially laminating Mg—Ag) and a transparent electrode layer (for example, IZO).
- a known material can be appropriately used as a material constituting each of these layers, and is not particularly limited.
- the electrode used for the organic solar cell may have the same material and structure as the electrode used for the organic EL element. Since the electrode foil of the present invention has a function as a reflective layer, an improvement in power generation efficiency due to light confinement due to the cavity effect is expected.
- FIG. 3 shows an example of a layer configuration of a top emission type organic EL lighting in which the organic EL element shown in FIG. 2 is incorporated.
- the organic EL element can be electrically connected to the power source 30 through the metal foil 22 of the anode electrode foil 20.
- a region on the buffer layer 24 that is not in contact with the organic EL layer 26 is covered with an interlayer insulating film 29.
- the interlayer insulating film 29 a Si-based insulating film formed by CVD is preferable because it has a high barrier property against moisture and oxygen that cause deterioration of the organic layer, and more preferably a SiN-based insulating film.
- a more preferred interlayer insulating film is a SiNO insulating film in that the internal stress of the film is small and the flexibility is excellent.
- a sealing material 32 is provided above the cathode 28 so as to face the organic EL element, and a sealing resin 34 is filled between the sealing material 32 and the organic EL element 20 to form a sealing film 34.
- the sealing material 32 glass or a film can be used. In the case of glass, it can be directly bonded onto the sealing film 34 using a hydrophobic adhesive tape. In the case of a film, both surfaces and end surfaces can be covered with a Si-based insulating film. When a film having a high barrier property is developed in the future, it is possible to perform sealing without performing a coating treatment, and it is expected that the film has excellent mass productivity.
- a film is desirable from the viewpoint of imparting flexibility, but a desired performance is obtained by using a sealing material in which a film is bonded to a very thin glass having a thickness of 20 to 100 ⁇ m. It is also possible.
- cathode 28 various known cathodes used for top emission type organic EL elements can be used, and since it is necessary to transmit light, it is not particularly limited as long as it is transparent or translucent. A low one is preferred.
- Preferred cathodes include conductive oxide films, magnesium-based alloy films, and fluoride films, and it is more preferable to combine these in two or more layers. These films can be the same as those described for the buffer layer of the electrode foil.
- a particularly preferable cathode has a two-layer structure in which a transparent oxide layer as a cathode layer made of a conductive oxide film is laminated with a semi-transmissive metal layer as a buffer layer made of a magnesium alloy film and / or a fluoride film.
- a semi-transmissive metal layer as a buffer layer made of a magnesium alloy film and / or a fluoride film.
- the most preferred example is a cathode structure in which a transparent oxide layer (cathode layer) made of IZO (indium zinc oxide) and a semi-transmissive metal layer (buffer layer) made of Mg—Ag are laminated. Further, the cathode structure may include two or more transparent oxide layers and / or two or more semi-transmissive metal layers.
- the light generated in the organic EL layer 26 passes through the cathode 28, the sealing film 34, and the sealing material 32 and is emitted to the outside.
- assistant base material suitably in the back surface of the electrode foil 20 according to a usage form. Since this portion does not affect the light emission characteristics, the degree of freedom in material selection is high. For example, if resin films such as polyethylene terephthalate (PET), polyimide (PI), polycarbonate (PC), polyethersulfone (PES), and polyethernitrile (PEN) are used, the flexibility is not compromised, so it is optimal. I can say that.
- PET polyethylene terephthalate
- PI polyimide
- PC polycarbonate
- PES polyethersulfone
- PEN polyethernitrile
- FIG. 4 shows an example of a layer structure of a top emission type organic EL element using the electrode foil of the present invention as a cathode.
- the organic EL element shown in FIG. 4 includes a cathode electrode foil 40 including a metal foil 42 and a buffer layer 44, an organic EL layer 46 provided directly on the buffer layer 44, and a counter provided directly on the organic EL layer 46. And an anode 48 as an electrode.
- the organic EL layer 46 can be configured in the same manner as the organic EL layer 26 shown in FIG. 2, and the buffer layer 44 can be configured in the same manner as the cathode 28 shown in FIG. It is preferably composed of a system alloy film, a fluoride film, or a combination of two or more layers thereof.
- a more preferable buffer layer 44 is a semi-transmissive metal layer made of a magnesium-based alloy film and / or a fluoride film.
- the organic EL element using the cathode electrode foil 40 shown in FIG. 4 is the same as the organic EL element using the anode electrode foil 20 shown in FIG. 26 corresponds to a configuration in which the stacking order from the anode side to the cathode side in the interior 26 is reversed.
- a magnesium alloy film or a fluoride film is formed as the buffer layer 44 of the cathode electrode foil 40 by sputtering or vapor deposition, while a conductive amorphous carbon, MoO 3 or V 2 O 5 film is vapor deposited as the anode 48. It is preferable to form by.
- a conductive amorphous carbon film is formed on the organic EL layer, it is preferable to use a vacuum deposition method in order to avoid plasma damage during sputtering.
- the present invention will be described more specifically with reference to the following examples.
- the electrode foil of this invention does not require a reflection layer
- the electrode foil with a reflection layer is also disclosed below for reference. This is because the presence or absence of light emission of the organic EL element can be evaluated regardless of the presence or absence of the reflective layer.
- Example 1 Preparation of Cu / Al alloy / ITO electrode foil As a metal foil, a commercially available double-sided flat electrolytic copper foil having a thickness of 64 ⁇ m (DFF (Dual Flat Foil) manufactured by Mitsui Metal Mining Co., Ltd.) was prepared.
- DFF Double Flat Foil
- This copper foil was subjected to a CMP (Chemical Mechanical Polishing) process using a polishing machine manufactured by MTT.
- This CMP treatment was performed using a polishing pad with XY grooves and a colloidal silica-based polishing liquid under the conditions of pad rotation speed: 30 rpm, load: 200 gf / cm 2 , and liquid supply amount: 100 cc / min.
- the roughness of the copper foil surface thus subjected to CMP treatment was measured in accordance with JIS B 0601-2001 using a scanning probe microscope (Veeco, Nano Scope V). The arithmetic average roughness Ra: 0.7 nm Met. This measurement was performed by Tapping Mode AFM for a range of 10 ⁇ m square.
- the thickness of the copper foil after the CMP treatment was 48 ⁇ m.
- a 150 nm-thick Al alloy reflective layer was formed on the surface of the CMP-treated copper foil by sputtering.
- This sputtering is performed using a magnetron sputtering apparatus (MSL-) in which an aluminum alloy target (diameter 203.2 mm ⁇ 8 mm thickness) having a composition of Al-0.2B-3.2Ni (at.%) Is connected to a cryo pump. 464, manufactured by Tokki Co., Ltd.), input power (DC): 1000 W (3.1 W / cm 2 ), ultimate vacuum: ⁇ 5 ⁇ 10 ⁇ 5 Pa, sputtering pressure: 0.5 Pa, Ar flow rate: The measurement was performed under the conditions of 100 sccm and substrate temperature: room temperature.
- MSL- magnetron sputtering apparatus
- An ITO buffer layer having a thickness of 10 nm was formed on the surface of the aluminum alloy reflective layer thus obtained by sputtering.
- an ITO (In 2 O 3 —SnO 2 ) target (diameter: 203.2 mm ⁇ 6 mm thickness) containing 10% by weight of Sn is connected to a magnetron sputtering apparatus (MSL-464, Tokki) connected with a Cryo pump.
- MSL-464, Tokki magnetron sputtering apparatus
- Example 2 Preparation of Cu / Al alloy / C electrode foil An electrode foil was prepared in the same manner as in Example 1 except that a carbon buffer layer having a film thickness of 1.7 nm or 3.5 nm was formed by sputtering instead of the ITO buffer layer. Produced. As a carbon target for this sputtering, an untreated carbon target with a purity of 3N (99.9%) made from a carbon material (IGS743 material, manufactured by Tokai Carbon Co., Ltd.) and a purification treatment with halogen gas on this carbon material. Two types of carbon targets having a purity of 5N (99.999%) were prepared. A carbon buffer layer was formed by sputtering using each of these targets.
- a carbon buffer layer having a film thickness of 1.7 nm or 3.5 nm was formed by sputtering instead of the ITO buffer layer.
- each carbon target (diameter 203.2 mm ⁇ 8 mm thickness) was mounted on a magnetron sputtering apparatus (multi-chamber single-wafer type film forming apparatus MSL-464, manufactured by Tokki Co., Ltd.) connected to a cryo pump.
- ultimate vacuum ⁇ 5 ⁇ 10 ⁇ 5 Pa
- sputtering pressure 0.5 Pa
- Ar flow rate 100 sccm
- substrate temperature room temperature.
- the film thickness was controlled by controlling the discharge time.
- the roughness of the surface of the buffer layer thus obtained was measured in the same manner as in Example 1, the arithmetic average roughness Ra was 2.45 nm.
- the total thickness of the obtained electrode foil was 48 ⁇ m.
- Example 3 Preparation of Cu / C electrode foil An electrode foil with a carbon buffer layer was prepared in the same manner as in Example 2 except that the Al alloy reflective layer was not formed. When the roughness of the buffer layer surface thus obtained was measured in the same manner as in Example 1, the arithmetic average roughness Ra was 1.42 nm. The total thickness of the obtained electrode foil was 48 ⁇ m.
- Example 4 Preparation of Cu / Ag alloy / ITO electrode foil A buffer layer and a reflective layer were provided in the same manner as in Example 1 except that a 150 nm-thick Ag alloy reflective layer was formed by sputtering instead of the Al alloy reflective layer. An electrode foil is prepared.
- a magnetron sputtering apparatus MSL- in which a silver alloy target (diameter 101.6 mm ⁇ 5 mm thickness) having a composition of Ag-1.0Cu-1.0Pd (at.%) Is connected to a Cryo pump.
- Example 5 Production of Organic EL Element An organic EL element having a structure as shown in FIGS. 2 and 3 was produced using the electrode foil (Cu / Al alloy / ITO) produced in Example 1 as an anode. First, a glass substrate (3 cm square ⁇ 0.5 mm thickness) was placed on the electrode foil 20 (5 cm square) for masking, and an interlayer insulating film 29 made of silicon nitride was formed by a plasma CVD (Chemical Vapor Deposition) method. This plasma CVD uses a plasma CVD apparatus (PD2202L, manufactured by Samco) connected with a mechanical booster pump (MBP) and a rotary pump (RP).
- PD2202L plasma CVD apparatus
- MBP mechanical booster pump
- RP rotary pump
- the surface of the electrode foil on which the interlayer insulating film was formed was washed as follows. First, in a tank filled with ultrapure water (> 18.0 M ⁇ ), ultrasonic cleaning for 3 minutes was performed twice by replacing ultrapure water. Subsequently, after moisture was removed using nitrogen gas, after-curing was performed at 100 ° C. for 3 hours. The surface thus treated was cleaned by UV irradiation.
- ultrapure water > 18.0 M ⁇
- the organic EL layer 26, the cathode 28, the sealing layer 34, and the sealing material 32 were laminated. Specifically, a 50-nm-thick hole injection layer made of copper phthalocyanine, 4,4′-bis (N, N ′-(3-tolyl) amino) -3,3 ′ is formed on the buffer layer surface of the electrode foil.
- a 40 nm thick hole transport layer made of dimethylbiphenyl (HMTPD), a 30 nm thick light emitting layer doped with tris (2-phenylpyridine) iridium complex (Ir (ppy) 3 ) in a host material, Alq3 A 30 nm thick electron transport layer, a 10 nm thick Mg—Ag semi-transmissive film layer (Mg: Ag 9: 1), a 100 nm thick IZO (In—Zn—O) transparent oxide layer, a thickness A 300 nm silicon nitride passivation film (sealing layer), a 2000 nm thick adhesive layer, and a 200 ⁇ m thick sealing glass (sealing material) were laminated in this order.
- HMTPD dimethylbiphenyl
- Ir (ppy) 3 tris
- Alq3 A 30 nm thick electron transport layer
- IZO In—
- the sealing glass layer is laminated with a double-sided tape, and this double-sided tape corresponds to the adhesive layer.
- an organic EL element sample having a size of 50 mm square x thickness of 300 ⁇ m and a light emitting area of 30 mm square as shown in FIG. 3 was obtained.
- a voltage of 5.0 V was applied, strong light emission as shown in FIG. 5 could be confirmed.
- the change in luminance (cd / m 2 ) and current density (mA / cm 2 ) was measured by changing the applied voltage, the results shown in FIG. 6 and FIG. 7 were obtained (“ITO” in the figure). ”).
- ITO in the figure.
- Example 6 Preparation of organic EL device 3 In the same manner as in Example 5, except that the electrode foil (Cu / Al alloy / C) having the following three types of carbon buffer layers prepared in Example 2 was used. Various types of organic EL element samples were prepared. Sample “5N-C 35 mm”: an organic EL device using a carbon buffer layer having a thickness of 3.5 nm formed using a carbon target having a purity of 5N, Sample “3N-C 17 ⁇ ”: an organic EL element using a carbon buffer layer having a thickness of 1.7 nm formed using a carbon target having a purity of 3N, and Sample “5N-C 17 ⁇ ”: carbon having a purity of 5N An organic EL device using a carbon buffer layer having a thickness of 1.7 nm formed using a target.
- each of the samples was connected to a power supply 30 as shown in FIG.
- changes in luminance (cd / m 2 ) and / or current density (mA / cm 2 ) were measured by changing the applied voltage, the results shown in FIGS. 6 to 8 were obtained.
- the electrode foil of the present invention it can be seen that light emission with extremely high luminance can be obtained at a low voltage.
- Example 7 Production of Organic EL Element An organic EL element was produced in the same manner as in Example 5 except that the electrode foil without a reflective film (Cu / C) produced in Example 3 was used. When a power source was connected to this sample and a voltage of 5.0 V was applied, strong light emission could be confirmed. This shows that it can be used as organic EL illumination without a reflective film.
- Example 8 Measurement of wavelength dependence characteristic of absolute reflectance The wavelength dependence characteristic of the absolute reflectance was measured for various metal foils shown below using an absolute reflectance measuring apparatus.
- Untreated copper foil Double-sided flat electrolytic copper foil (DFF (Dual Flat Foil) (Ra: 12.20 nm) manufactured by Mitsui Mining & Smelting Co., Ltd.)
- Ultra-flattened copper foil Copper foil (Ra: 0.7 nm) treated in the same manner as in Example 1, and Reflective aluminum alloy: Aluminum alloy with composition Al-0.2B-3.2Ni (at%) (Ra: 1.8 nm).
- the measurement results were as shown in FIG. From this result, it can be seen that the copper foil having a flattened surface exhibits a significantly higher absolute reflectance than an untreated copper foil that has not been subjected to CMP treatment. Also, unlike aluminum alloys that exhibit extremely high absolute reflectivity in all wavelength ranges, ultra-flattened copper foils are organic because the absolute reflectivity is relatively low in the blue wavelength range compared to other wavelength ranges. It can be seen that warm white light having a color temperature of about 3000K, which is highly needed as EL lighting, can be reflected.
- Example 9 Production of Cu / Al Alloy Electrode Foil
- an Al alloy reflective layer 143 having a film thickness of 150 nm was formed by sputtering on a copper foil 142 produced under the same conditions as in Example 1. .
- This sputtering is performed using a magnetron sputtering apparatus (MSL-464, manufactured by Tokki Co., Ltd.) in which an aluminum alloy target (diameter 203.2 nm ⁇ 8 mm thickness) having a composition of Al-4Mg (at.%) Is connected to a Cryo pump.
- MSL-464 magnetron sputtering apparatus
- Example 10 Production of Organic EL Element Using the electrode foil 140 (Cu / Al alloy) produced in Example 9 as a cathode, an organic EL element having a structure as shown in FIGS. 10 and 11 was produced. First, a glass substrate (3 cm square ⁇ 0.5 mm thickness) was placed on the electrode foil 140 (5 cm square) for masking, and an interlayer insulating film 129 made of silicon nitride was formed by a plasma CVD (Chemical Vapor Deposition) method. This plasma CVD uses a plasma CVD apparatus (PD2202L, manufactured by Samco) connected with a mechanical booster pump (MBP) and a rotary pump (RP).
- P2202L plasma CVD apparatus
- MBP mechanical booster pump
- RP rotary pump
- the organic EL layer 146, the anode 148, the sealing layer 134, and the sealing material 132 were laminated.
- an ⁇ -NPD layer 146b with a thickness of 50 nm, an Alq3 layer 146a with a thickness of 50 nm, a MoO 3 layer 148b with a thickness of 20 nm, an IZO (In—Zn) with a thickness of 100 nm are formed on the surface of the reflective layer 144 of the electrode foil.
- a transparent oxide layer 148a, a 300 nm thick silicon nitride passivation film (sealing layer 134), a 2000 nm thick adhesive layer, and a 200 ⁇ m thick sealing glass (sealing material 132) were laminated in this order.
- the sealing glass layer is laminated with a double-sided tape, and this double-sided tape corresponds to the adhesive layer.
- an organic EL element sample of 50 mm square ⁇ thickness 300 ⁇ m and light emitting area 30 mm square was obtained. When this sample was connected to the power supply 130 and a voltage of 10 V was applied, green light emission caused by Alq3 could be confirmed.
Abstract
Description
前記電極箔の少なくとも一方の最表面が、JIS B 0601-2001に準拠して測定される、10.0nm以下の算術平均粗さRaを有する超平坦面である、電極箔が提供される。
前記電極箔の前記超平坦面側の最表面に直接設けられる有機EL層および/または有機太陽電池活性層からなる有機半導体層と、
前記有機半導体層上に設けられる、透明又は半透明の対向電極と、
を備えた、有機EL素子および/または有機太陽電池である、有機デバイスが提供される。
図1に本発明による電極箔の一例の模式断面図を示す。図1に示される電極箔10は、金属箔12、および所望により金属箔上に直接設けられるバッファ層14を備えてなる。
すなわち、電極箔10は金属箔12およびバッファ層14を備えた2層構成であるが、本発明の電極箔はこれに限定されず、金属箔12のみを備えた1層構成であってもよい。電極箔10の少なくとも一方の最表面は、10.0nm以下、好ましくは7.0nm以下、より好ましくは5.0nm、さらに好ましくは3.0nm以下、さらにより好ましくは2.5nm以下、特に好ましくは2.0nm以下、最も好ましくは1.5nm以下の算術平均粗さRaを有する超平坦面である。算術平均粗さRaの下限は特に限定されずゼロであってもよいが、平坦化処理の効率を考慮すると0.5nmが下限値の目安として挙げられる。この算術平均粗さRaは、JIS B 0601-2001に準拠して市販の粗さ測定装置を用いて測定することができる。
このドライアイスブラスト法は、ウェット工程とは異なり、乾燥工程を省くことができ、また有機物の除去ができる等の利点を有する。ドライアイスブラスト法は、例えばドライアイススノーシステム(エアウォーター社製)等の市販の装置を用いて行うことができる。
本発明による電極箔を反射電極として用いて、トップエミッション型有機EL素子および有機EL照明を構築することができる。
この部分は、発光特性に影響を与えない為、材料選択の自由度は高い。例えば、ポリエチレンテレフタレート(PET)、ポリイミド(PI)、ポリカーボネート(PC)、ポリエーテルサルフォン(PES)、ポリエーテルニトリル(PEN)等の樹脂フィルムを使用すればフレキシブル性を損なうことが無いので最適といえる。
金属箔として、厚さ64μmの市販の両面平坦電解銅箔(三井金属鉱業社製DFF(Dual Flat Foil)を用意した。銅箔表面の粗さを走査型プローブ顕微鏡(Veeco社製、Nano Scope V)を用いてJIS B 0601-2001に準拠して測定したところ、算術平均粗さRa:12.20nmであった。この測定は、10μm平方の範囲について、Tapping Mode AFMにて行った。
ITOバッファ層の代わりに膜厚1.7nmまたは3.5nmのカーボンバッファ層をスパッタリング法により形成したこと以外は例1と同様にして電極箔を作製した。このスパッタリングのためのカーボンターゲットとしては、カーボン材料(IGS743材、東海カーボン社製)から作製された未処理の純度3N(99.9%)のカーボンターゲットと、このカーボン材料にハロゲンガスによる純化処理を施して作製された純度5N(99.999%)のカーボンターゲットの2種類を用意した。これらのターゲットの各々を用いてスパッタリング法によりカーボンバッファ層を成膜した。このスパッタリングは、各カーボンターゲット(直径203.2mm×8mm厚)をクライオ(Cryo)ポンプが接続されたマグネトロンスパッタ装置(マルチチャンバー枚葉式成膜装置MSL-464、トッキ株式会社製)に装着した後、投入パワー(DC):250W(0.8W/cm2)、到達真空度:<5×10-5Pa、スパッタ圧力:0.5Pa、Ar流量:100sccm、基板温度:室温の条件で行った。膜厚の制御は、放電時間を制御することにより行った。こうして得られたバッファ層表面の粗さを例1と同様にして測定したところ、算術平均粗さRa:2.45nmであった。得られた電極箔の全体としての厚さは48μmであった。
Al合金反射層を形成しなかったこと以外は例2と同様にして、カーボンバッファ層付き電極箔を作製した。こうして得られたバッファ層表面の粗さを例1と同様に測定したところ、算術平均粗さRa:1.42nmであった。得られた電極箔の全体としての厚さは48μmであった。
Al合金反射層の代わりに膜厚150nmのAg合金反射層をスパッタリング法により形成したこと以外は例1と同様にして、バッファ層および反射層付き電極箔を作製する。
このスパッタリングは、Ag-1.0Cu-1.0Pd(at.%)の組成を有する銀合金ターゲット(直径101.6mm×5mm厚)をクライオ(Cryo)ポンプが接続されたマグネトロンスパッタ装置(MSL-464、トッキ株式会社製)に装着した後、投入パワー(DC):150W(1.9W/cm2)、到達真空度:<5×10-5Pa、スパッタ圧力:0.5Pa、Ar流量:90sccm、基板温度:室温の条件で行う。膜厚の制御は、放電時間を制御することにより行う。
例1で作製された電極箔(Cu/Al合金/ITO)をアノードとして用いて図2および3に示されるような構造の有機EL素子を作製した。まず、電極箔20(5cm平方)の上にガラス基板(3cm平方×0.5mm厚)を載せてマスキングし、窒化ケイ素からなる層間絶縁膜29をプラズマCVD(Chemical Vapor Deposition)法により形成した。このプラズマCVDは、メカニカルブースターポンプ(MBP)およびロータリーポンプ(RP)が接続されたプラズマCVD装置(PD-2202L、サムコ社製)を用い、成膜エリア:有効エリア直径8inch、投入パワー(RF):250W(0.8W/cm2)、 到達真空度:<5×10-3Pa、スパッタ圧力:80Pa、ガス:SiH4(H2希釈10%):NH3:N2=100:10: 200sccm、基板温度:250℃の条件で行った。その後、ガラスを電極箔20から除去して、3cm平方の開口部を有する層間絶縁膜29を電極箔上に得た。
なお、封止ガラス層の積層は両面テープで行い、この両面テープが接着層に相当する。こうして、図3に示されるような、50mm平方×厚さ300μm、発光面積30mm平方の有機EL素子サンプルを得た。このサンプルを電源30に接続して5.0Vの電圧を加えたところ、図5に示されるような強い発光を確認することができた。また、印加電圧を変化させて、輝度(cd/m2)および電流密度(mA/cm2)の変化を測定したところ、図6および図7に示される結果を得た(図中、「ITO」と表記されるプロットを参照)。このように、本発明の電極箔を用いれば、低電圧で極めて高い輝度の発光を得ることができる。
例2で作製された、以下の3種類のカーボンバッファ層を有する電極箔(Cu/Al合金/C)を用いたこと以外は、例5と同様にして、3種類の有機EL素子サンプルを作製した。
・サンプル「5N-C 35Å」:純度5Nのカーボンターゲットを用いて形成された厚さ3.5nmのカーボンバッファ層を用いた有機EL素子、
・サンプル「3N-C 17Å」:純度3Nのカーボンターゲットを用いて形成された厚さ1.7nmのカーボンバッファ層を用いた有機EL素子、および
・サンプル「5N-C 17Å」:純度5Nのカーボンターゲットを用いて形成された厚さ1.7nmのカーボンバッファ層を用いた有機EL素子。
例3で作製された反射膜無しの電極箔(Cu/C)を用いたこと以外は、例5と同様にして、有機EL素子を作製した。このサンプルに電源を接続して5.0Vの電圧を加えたところ、強い発光を確認することができた。このことから、反射膜が無くとも有機EL照明として使用可能であることが分かる。
以下に示される各種の金属箔について、絶対反射率測定装置を用いて絶対反射率の波長依存特性を測定した。
・未処理銅箔:両面平坦電解銅箔(三井金属鉱業社製DFF(Dual Flat Foil)(Ra:12.20nm)、
・超平坦化銅箔:例1と同様にしてCMP処理された銅箔(Ra:0.7nm)、および・反射アルミニウム合金:組成Al-0.2B-3.2Ni(at%)のアルミニウム合金(Ra:1.8nm)。
図10に示されるように、例1と同様の条件で作製した銅箔142上に、膜厚150nmのAl合金反射層143をスパッタリング法により成膜した。このスパッタリングは、Al-4Mg(at.%)の組成を有するアルミニウム合金ターゲット(直径203.2nm×8mm厚)をクライオ(Cryo)ポンプが接続されたマグネトロンスパッタ装置(MSL-464、トッキ株式会社製)に装着した後、投入パワー(DC):1000W(3.1W/cm2)、到達真空度:<5×10-5Pa、スパッタ圧力:0.5Pa、Ar流量:100sccm、基板温度:室温の条件で行った。こうして、有機EL素子においてカソード電極として用いることができる電極箔140を得た。
例9で作製された電極箔140(Cu/Al合金)をカソードとして用いて、図10および図11に示されるような構造の有機EL素子を作製した。まず、電極箔140(5cm平方)の上にガラス基板(3cm平方×0.5mm厚)を載せてマスキングし、窒化ケイ素からなる層間絶縁膜129をプラズマCVD(Chemical Vapor Deposition)法により形成した。このプラズマCVDは、メカニカルブースターポンプ(MBP)およびロータリーポンプ(RP)が接続されたプラズマCVD装置(PD-2202L、サムコ社製)を用い、成膜エリア:有効エリア直径8inch、投入パワー(RF):250W(0.8W/cm2)、 到達真空度:<5×10-3Pa、スパッタ圧力:80Pa、ガス:SiH4(H2希釈10%):NH3:N2=100:10: 200sccm、基板温度:250℃の条件で行った。その後、ガラスを電極箔140から除去して、3cm平方の開口部を有する層間絶縁膜129を電極箔上に得た。
Claims (16)
- 少なくとも金属箔を備えてなる電極箔であって、
前記電極箔の少なくとも一方の最表面が、JIS B 0601-2001に準拠して測定される、10.0nm以下の算術平均粗さRaを有する超平坦面である、電極箔。 - 前記算術平均粗さRaが3.0nm以下である、請求項1に記載の電極箔。
- 有機EL素子または有機太陽電池のアノードまたはカソードとして用いられる、請求項1または2に記載の電極箔。
- 少なくとも前記超平坦面側に絶縁層を有しない、請求項1~3のいずれか一項に記載の電極箔。
- 前記金属箔が、1~250μmの厚さを有する、請求項1~4のいずれか一項に記載の電極箔。
- 前記金属箔が、非磁性金属箔である、請求項1~5のいずれか一項に記載の電極箔。
- 前記金属箔が、銅箔である、請求項1~6のいずれか一項に記載の電極箔。
- 前記金属箔上に直接設けられる透明または半透明のバッファ層をさらに備えてなり、前記バッファ層の表面が前記超平坦面を構成する、請求項1~7のいずれか一項に記載の電極箔。
- 前記バッファ層が、導電性非晶質炭素膜、導電性酸化物膜、マグネシウム系合金膜、およびフッ化物膜からなる群から選択される少なくとも一種である、請求項8に記載の電極箔。
- 前記電極箔が、1~300μmの厚さを有する、請求項1~9のいずれか一項に記載の電極箔。
- 前記金属箔の前記超平坦面と反対側の表面が、JIS B 0601-1994に準拠して測定される、1.0μm以上の十点平均粗さRzを有する粗化面である、請求項1~10のいずれか一項に記載の電極箔。
- 少なくとも一方の表面が、JIS B 0601-2001に準拠して測定される、10.0nm以下の算術平均粗さRaを有する、銅箔。
- 前記算術平均粗さRaが3.0nm以下である、請求項12に記載の銅箔。
- 請求項1~11のいずれか一項に記載の電極箔と、
前記電極箔の前記超平坦面側の最表面に直接設けられる有機EL層および/または有機太陽電池活性層からなる有機半導体層と、
前記有機半導体層上に設けられる、透明又は半透明の対向電極と、
を備えた、有機EL素子および/または有機太陽電池である、有機デバイス。 - 前記対向電極が、導電性非晶質炭素膜、導電性酸化物膜、マグネシウム系合金膜、およびフッ化物膜からなる群から選択される少なくとも一種を備えてなる、請求項14に記載の有機デバイス。
- 請求項14または15に記載の有機デバイスを有機EL素子として備えてなる、有機EL照明。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/696,684 US8816338B2 (en) | 2010-06-04 | 2011-03-01 | Electrode foil and organic device |
EP11789504.5A EP2579687A4 (en) | 2010-06-04 | 2011-03-01 | ELECTRODE FILM AND ORGANIC DEVICE |
JP2012518273A JPWO2011152092A1 (ja) | 2010-06-04 | 2011-03-01 | 電極箔および有機デバイス |
US14/063,485 US8791565B2 (en) | 2010-06-04 | 2013-10-25 | Electrode foil and organic device |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010129083 | 2010-06-04 | ||
JP2010-129083 | 2010-06-04 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/696,684 A-371-Of-International US8816338B2 (en) | 2010-06-04 | 2011-03-01 | Electrode foil and organic device |
US14/063,485 Continuation US8791565B2 (en) | 2010-06-04 | 2013-10-25 | Electrode foil and organic device |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011152092A1 true WO2011152092A1 (ja) | 2011-12-08 |
Family
ID=45066481
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/054628 WO2011152092A1 (ja) | 2010-06-04 | 2011-03-01 | 電極箔および有機デバイス |
Country Status (5)
Country | Link |
---|---|
US (2) | US8816338B2 (ja) |
EP (1) | EP2579687A4 (ja) |
JP (1) | JPWO2011152092A1 (ja) |
TW (1) | TWI531469B (ja) |
WO (1) | WO2011152092A1 (ja) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012527100A (ja) * | 2009-05-12 | 2012-11-01 | ウニヴェルシタ デグリ ステュディ ディ ミラノ‐ビコッカ | 有機半導体に電気接点を形成する方法 |
WO2013118325A1 (ja) | 2012-02-07 | 2013-08-15 | 三井金属鉱業株式会社 | 電極箔および電子デバイス |
JP2013182853A (ja) * | 2012-03-05 | 2013-09-12 | Dainippon Printing Co Ltd | 薄膜素子用基板、薄膜素子、有機エレクトロルミネッセンス表示装置、および電子ペーパー |
WO2013161129A1 (ja) | 2012-04-23 | 2013-10-31 | 三井金属鉱業株式会社 | 電極箔及び電子デバイス |
WO2014017135A1 (ja) | 2012-07-27 | 2014-01-30 | 三井金属鉱業株式会社 | 金属箔及び電子デバイス |
WO2014017183A1 (ja) | 2012-07-24 | 2014-01-30 | 三井金属鉱業株式会社 | 電極箔及び有機発光デバイス |
WO2014109081A1 (ja) | 2013-01-09 | 2014-07-17 | 三井金属鉱業株式会社 | 電解銅箔及び電子デバイス |
WO2015025530A1 (ja) * | 2013-08-23 | 2015-02-26 | 三井金属鉱業株式会社 | 有機半導体デバイス |
WO2015087566A1 (ja) * | 2013-12-13 | 2015-06-18 | 三井金属鉱業株式会社 | 電解銅箔及びその製造方法 |
JP2022172080A (ja) * | 2012-06-25 | 2022-11-15 | ザ リージェンツ オブ ザ ユニヴァシティ オブ ミシガン | 大面積の有機太陽電池 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8816338B2 (en) * | 2010-06-04 | 2014-08-26 | Mitsui Mining & Smelting Co., Ltd. | Electrode foil and organic device |
TWI539033B (zh) | 2013-01-07 | 2016-06-21 | Chang Chun Petrochemical Co | Electrolytic copper foil and its preparation method |
US9202694B2 (en) | 2013-03-04 | 2015-12-01 | Sandisk 3D Llc | Vertical bit line non-volatile memory systems and methods of fabrication |
JP5870148B2 (ja) * | 2013-11-27 | 2016-02-24 | Jx金属株式会社 | キャリア付銅箔、プリント回路板の製造方法、銅張積層板、銅張積層板の製造方法、及び、プリント配線板の製造方法 |
JP6761276B2 (ja) * | 2015-05-28 | 2020-09-23 | 株式会社半導体エネルギー研究所 | 表示装置の作製方法、および電子機器の作製方法 |
JPWO2019111091A1 (ja) | 2017-12-07 | 2020-12-03 | 株式会社半導体エネルギー研究所 | 半導体装置、および半導体装置の作製方法 |
US10697082B1 (en) * | 2019-08-12 | 2020-06-30 | Chang Chun Petrochemical Co., Ltd. | Surface-treated copper foil |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001270036A (ja) | 2000-03-28 | 2001-10-02 | Ube Ind Ltd | フレキシブル金属箔積層体 |
JP2002015859A (ja) * | 2000-06-30 | 2002-01-18 | Sony Corp | 有機エレクトロルミネッセンス素子及び有機エレクトロルミネッセンス表示装置 |
JP2004006221A (ja) * | 2002-03-27 | 2004-01-08 | Sumitomo Metal Mining Co Ltd | 透明導電性薄膜、その製造方法と製造用焼結体ターゲット、及び有機エレクトロルミネッセンス素子とその製造方法 |
JP2004087451A (ja) * | 2002-07-05 | 2004-03-18 | Sumitomo Metal Mining Co Ltd | 透明導電性薄膜、その形成方法、それを用いた表示パネル用透明導電性基材及び有機エレクトロルミネッセンス素子 |
JP2006269224A (ja) * | 2005-03-23 | 2006-10-05 | Fuji Electric Holdings Co Ltd | 有機発光素子及びその製造方法 |
JP2006331694A (ja) * | 2005-05-23 | 2006-12-07 | Matsushita Electric Works Ltd | 有機発光素子及び有機発光素子用基板 |
JP2007217787A (ja) | 2005-03-31 | 2007-08-30 | Mitsui Mining & Smelting Co Ltd | 電解銅箔の製造方法及びその製造方法で得られた電解銅箔、その電解銅箔を用いて得られた表面処理電解銅箔、その表面処理電解銅箔を用いた銅張積層板及びプリント配線板 |
JP2007536697A (ja) | 2003-12-30 | 2007-12-13 | エージェンシー フォー サイエンス,テクノロジー アンド リサーチ | フレキシブルエレクトロルミネッセンスデバイス |
JP2008142970A (ja) | 2006-12-07 | 2008-06-26 | Nippon Steel Materials Co Ltd | 電子デバイス作製用絶縁被覆金属箔 |
WO2009060916A1 (ja) * | 2007-11-09 | 2009-05-14 | Asahi Glass Co., Ltd. | 透光性基板、その製造方法、有機led素子およびその製造方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6887623B2 (en) * | 2001-04-09 | 2005-05-03 | Sanyo Electric Co., Ltd. | Electrode for rechargeable lithium battery and rechargeable lithium battery |
TWI254080B (en) | 2002-03-27 | 2006-05-01 | Sumitomo Metal Mining Co | Transparent conductive thin film, process for producing the same, sintered target for producing the same, and transparent, electroconductive substrate for display panel, and organic electroluminescence device |
JP2005032852A (ja) * | 2003-07-09 | 2005-02-03 | Matsushita Electric Ind Co Ltd | 有機光電変換素子 |
CN101146933B (zh) | 2005-03-31 | 2010-11-24 | 三井金属矿业株式会社 | 电解铜箔及电解铜箔的制造方法、采用该电解铜箔得到的表面处理电解铜箔、采用该表面处理电解铜箔的覆铜层压板及印刷电路板 |
JP4770268B2 (ja) | 2005-05-23 | 2011-09-14 | トヨタ自動車株式会社 | 燃料電池システム |
JP2008243772A (ja) * | 2007-03-29 | 2008-10-09 | Seiko Epson Corp | 発光装置およびその製造方法 |
DE102008031533B4 (de) * | 2008-07-03 | 2021-10-21 | Pictiva Displays International Limited | Organisches elektronisches Bauelement |
IN2012DN03223A (ja) * | 2009-10-15 | 2015-10-23 | Asahi Glass Co Ltd | |
US8816338B2 (en) * | 2010-06-04 | 2014-08-26 | Mitsui Mining & Smelting Co., Ltd. | Electrode foil and organic device |
JP5016712B2 (ja) * | 2010-09-21 | 2012-09-05 | 三井金属鉱業株式会社 | 電極箔および有機デバイス |
-
2011
- 2011-03-01 US US13/696,684 patent/US8816338B2/en not_active Expired - Fee Related
- 2011-03-01 JP JP2012518273A patent/JPWO2011152092A1/ja active Pending
- 2011-03-01 EP EP11789504.5A patent/EP2579687A4/en not_active Withdrawn
- 2011-03-01 WO PCT/JP2011/054628 patent/WO2011152092A1/ja active Application Filing
- 2011-03-04 TW TW100107337A patent/TWI531469B/zh not_active IP Right Cessation
-
2013
- 2013-10-25 US US14/063,485 patent/US8791565B2/en not_active Expired - Fee Related
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001270036A (ja) | 2000-03-28 | 2001-10-02 | Ube Ind Ltd | フレキシブル金属箔積層体 |
JP2002015859A (ja) * | 2000-06-30 | 2002-01-18 | Sony Corp | 有機エレクトロルミネッセンス素子及び有機エレクトロルミネッセンス表示装置 |
JP2004006221A (ja) * | 2002-03-27 | 2004-01-08 | Sumitomo Metal Mining Co Ltd | 透明導電性薄膜、その製造方法と製造用焼結体ターゲット、及び有機エレクトロルミネッセンス素子とその製造方法 |
JP2004087451A (ja) * | 2002-07-05 | 2004-03-18 | Sumitomo Metal Mining Co Ltd | 透明導電性薄膜、その形成方法、それを用いた表示パネル用透明導電性基材及び有機エレクトロルミネッセンス素子 |
JP2007536697A (ja) | 2003-12-30 | 2007-12-13 | エージェンシー フォー サイエンス,テクノロジー アンド リサーチ | フレキシブルエレクトロルミネッセンスデバイス |
JP2006269224A (ja) * | 2005-03-23 | 2006-10-05 | Fuji Electric Holdings Co Ltd | 有機発光素子及びその製造方法 |
JP2007217787A (ja) | 2005-03-31 | 2007-08-30 | Mitsui Mining & Smelting Co Ltd | 電解銅箔の製造方法及びその製造方法で得られた電解銅箔、その電解銅箔を用いて得られた表面処理電解銅箔、その表面処理電解銅箔を用いた銅張積層板及びプリント配線板 |
JP2006331694A (ja) * | 2005-05-23 | 2006-12-07 | Matsushita Electric Works Ltd | 有機発光素子及び有機発光素子用基板 |
JP2008142970A (ja) | 2006-12-07 | 2008-06-26 | Nippon Steel Materials Co Ltd | 電子デバイス作製用絶縁被覆金属箔 |
WO2009060916A1 (ja) * | 2007-11-09 | 2009-05-14 | Asahi Glass Co., Ltd. | 透光性基板、その製造方法、有機led素子およびその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2579687A4 |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012527100A (ja) * | 2009-05-12 | 2012-11-01 | ウニヴェルシタ デグリ ステュディ ディ ミラノ‐ビコッカ | 有機半導体に電気接点を形成する方法 |
WO2013118325A1 (ja) | 2012-02-07 | 2013-08-15 | 三井金属鉱業株式会社 | 電極箔および電子デバイス |
JP2013161698A (ja) * | 2012-02-07 | 2013-08-19 | Mitsui Mining & Smelting Co Ltd | 電極箔および電子デバイス |
JP2013182853A (ja) * | 2012-03-05 | 2013-09-12 | Dainippon Printing Co Ltd | 薄膜素子用基板、薄膜素子、有機エレクトロルミネッセンス表示装置、および電子ペーパー |
US9029885B2 (en) | 2012-04-23 | 2015-05-12 | Mitsui Mining & Smelting Co., Ltd. | Electrode foil and electronic device |
WO2013161129A1 (ja) | 2012-04-23 | 2013-10-31 | 三井金属鉱業株式会社 | 電極箔及び電子デバイス |
JP2013225447A (ja) * | 2012-04-23 | 2013-10-31 | Mitsui Mining & Smelting Co Ltd | 電極箔及び電子デバイス |
EP2844038A4 (en) * | 2012-04-23 | 2016-01-13 | Mitsui Mining & Smelting Co | ELECTRODE SHEET AND ELECTRONIC DEVICE |
JP2022172080A (ja) * | 2012-06-25 | 2022-11-15 | ザ リージェンツ オブ ザ ユニヴァシティ オブ ミシガン | 大面積の有機太陽電池 |
WO2014017183A1 (ja) | 2012-07-24 | 2014-01-30 | 三井金属鉱業株式会社 | 電極箔及び有機発光デバイス |
US9508951B2 (en) | 2012-07-24 | 2016-11-29 | Mitsui Mining & Smelting Co., Ltd. | Electrode foil and organic light-emitting device |
KR20150032291A (ko) | 2012-07-27 | 2015-03-25 | 미쓰이금속광업주식회사 | 금속박 및 전자 디바이스 |
JPWO2014017135A1 (ja) * | 2012-07-27 | 2016-07-07 | 三井金属鉱業株式会社 | 金属箔及び電子デバイス |
US9786404B2 (en) | 2012-07-27 | 2017-10-10 | Mitsui Mining & Smelting Co., Ltd. | Metal foil and electronic device |
WO2014017135A1 (ja) | 2012-07-27 | 2014-01-30 | 三井金属鉱業株式会社 | 金属箔及び電子デバイス |
WO2014109081A1 (ja) | 2013-01-09 | 2014-07-17 | 三井金属鉱業株式会社 | 電解銅箔及び電子デバイス |
US9985238B2 (en) | 2013-01-09 | 2018-05-29 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil and electronic device |
WO2015025530A1 (ja) * | 2013-08-23 | 2015-02-26 | 三井金属鉱業株式会社 | 有機半導体デバイス |
WO2015087566A1 (ja) * | 2013-12-13 | 2015-06-18 | 三井金属鉱業株式会社 | 電解銅箔及びその製造方法 |
JP2015113521A (ja) * | 2013-12-13 | 2015-06-22 | 三井金属鉱業株式会社 | 電解銅箔及びその製造方法 |
CN105814969A (zh) * | 2013-12-13 | 2016-07-27 | 三井金属矿业株式会社 | 电解铜箔及其制造方法 |
KR20160098196A (ko) | 2013-12-13 | 2016-08-18 | 미쓰이금속광업주식회사 | 전해 동박 및 그 제조 방법 |
US10283728B2 (en) | 2013-12-13 | 2019-05-07 | Mitsui Mining & Smelting Co., Ltd. | Electrolytic copper foil and manufacturing method therefor |
Also Published As
Publication number | Publication date |
---|---|
US8816338B2 (en) | 2014-08-26 |
EP2579687A1 (en) | 2013-04-10 |
TWI531469B (zh) | 2016-05-01 |
US20130048976A1 (en) | 2013-02-28 |
TW201204556A (en) | 2012-02-01 |
EP2579687A4 (en) | 2014-06-11 |
US20140048791A1 (en) | 2014-02-20 |
JPWO2011152092A1 (ja) | 2013-07-25 |
US8791565B2 (en) | 2014-07-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2011152092A1 (ja) | 電極箔および有機デバイス | |
JP5832034B2 (ja) | 電極箔および有機デバイス | |
JP5016712B2 (ja) | 電極箔および有機デバイス | |
WO2013118325A1 (ja) | 電極箔および電子デバイス | |
JP5297546B1 (ja) | 電極箔及び電子デバイス | |
WO2012137525A1 (ja) | 有機デバイス用電極シート、有機デバイスモジュールおよびその製造方法 | |
KR101970167B1 (ko) | 전해 동박 및 그 제조 방법 | |
EP2879466B1 (en) | Metal foil and electronic device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11789504 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13696684 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012518273 Country of ref document: JP |
|
REEP | Request for entry into the european phase |
Ref document number: 2011789504 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011789504 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |