WO2010150759A1 - 有機電子デバイス及びその製造方法 - Google Patents
有機電子デバイス及びその製造方法 Download PDFInfo
- Publication number
- WO2010150759A1 WO2010150759A1 PCT/JP2010/060499 JP2010060499W WO2010150759A1 WO 2010150759 A1 WO2010150759 A1 WO 2010150759A1 JP 2010060499 W JP2010060499 W JP 2010060499W WO 2010150759 A1 WO2010150759 A1 WO 2010150759A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- gas barrier
- organic
- electronic device
- barrier film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Images
Classifications
-
- 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
- H10K30/88—Passivation; Containers; Encapsulations
-
- 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
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
-
- 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
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/846—Passivation; Containers; Encapsulations comprising getter material or desiccants
-
- 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
-
- 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
- H10K30/50—Photovoltaic [PV] devices
-
- 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
Definitions
- the present invention relates to an organic electronic device and a method for manufacturing the organic electronic device.
- a technique for protecting a solar cell a technique for covering the solar cell with a film has been proposed in order to reduce weight and thickness.
- a solar cell module is formed using, for example, a crystalline silicon solar cell element or an amorphous silicon solar cell element.
- a surface protective sheet layer, a filler layer, a solar cell element as a photovoltaic element, a filler layer, and a back surface protective sheet layer are laminated in this order.
- a solar cell module is manufactured by using a lamination method in which vacuum suction is performed and thermocompression bonding is performed.
- organic thin film solar cell elements that have been developed in recent years are known to be particularly vulnerable to moisture, oxygen, heat, and organic substances generated from components, and organic thin film solar cells In order to extend the life of the device, it was necessary to eliminate them as much as possible.
- Patent Document 2 discloses an organic thin-film solar cell element casing sealing panel in which a hot-melt type member containing a moisture scavenger and wax is disposed between an organic thin-film solar cell element and a sealing casing. Yes.
- the scavenger contacts the element electrode, it causes deterioration of the element.
- an alkali metal oxide or an organometallic complex used as a moisture scavenger reacts with trapped moisture to generate an alkali (hydroxide).
- alkali hydrokali
- these alkalis come into contact with electrodes of organic semiconductor elements including organic thin-film solar battery elements, they corrode the electrodes and degrade the elements. Therefore, according to the study by the present inventors, it has been found that avoiding contact between the moisture scavenger and the electrode of the organic semiconductor element is very important for extending the life.
- Patent Document 1 since a space is provided to avoid contact between the trapping agent and the element electrode, it is considered that contact between the moisture trapping agent and the electrode of the organic semiconductor element is avoided.
- a space is provided to avoid contact between the trapping agent and the element electrode, it is considered that contact between the moisture trapping agent and the electrode of the organic semiconductor element is avoided.
- Covering with a film instead of glass is effective for reducing the weight of the device.
- a film it is pressed from above during use, so that the trapping agent and the device electrode are in contact with each other only when there is a space. End up.
- a flexible organic electronic device using a flexible substrate comes into contact when bent. As described above, the object of the present invention cannot be achieved simply by providing a space.
- Patent Document 2 a method of stacking a hot-melt type member layer containing a moisture scavenger so as to be in close contact with an organic thin film solar cell element to enable device thinning and the like is also achieved. I thought it was one of the means. However, it has been found that there is a possibility that the moisture scavenger may directly touch the electrode in this laminated structure. In such a case, the reaction product with water generated in the contacted part causes the electrode to deteriorate, and the power generation efficiency is likely to decrease with time.
- the moisture scavenger when the moisture scavenger is not directly exposed or covered with a highly gas permeable film, the water scavenger or hot melt type member is water or alkali, solvent used in the process, solvent such as adhesive, etc. Therefore, it is easy to change the quality when it is incorporated into the manufacturing process of an organic solar cell element module (OPV module), and it is necessary to be very careful in handling and process design.
- OSV module organic solar cell element module
- the present invention has been made in view of the above-described conventional situation, and does not degrade the device function in the long term.
- an organic electronic device in which a decrease in power generation efficiency is suppressed and It is an object to provide a manufacturing method thereof.
- An organic electron comprising an organic semiconductor element (B) having at least a pair of electrodes, a layer (C) containing a scavenger that absorbs at least one of moisture and oxygen, and a gas barrier film (D) in this order.
- the film thickness of the anticorrosion layer (E) is 20 ⁇ m or more.
- Pe represents the water vapor transmission rate of the anticorrosion layer (E) in a 40 ° C. and 90% RH environment
- Pd represents the gas barrier film (D) in a 40 ° C. and 90% RH environment.
- the water vapor permeability is shown, and the unit is g / m 2 / day for all.
- the anticorrosion layer (E) and the gas barrier film (D) satisfy the conditions of the following formulas (1) and (2): 15 ⁇ Pe> Pd Formula (1) 10 ⁇ 4 ⁇ Pd ⁇ 10 ⁇ 1 Formula (2)
- Pe represents the water vapor transmission rate of the anticorrosion layer (E) in a 40 ° C. and 90% RH environment
- Pd represents the gas barrier film (D) in a 40 ° C.
- a laminated body layer in which a gas barrier film (D), a layer (C) containing a scavenger that absorbs at least one of moisture and oxygen, and at least one anticorrosion layer (E) are sequentially laminated is manufactured, and an organic semiconductor element ( After manufacturing B) on a board
- An organic electronic device provided in this order, Resin so that the organic semiconductor element (B) and the layer (C) are not in direct contact between the organic semiconductor element (B) and the layer (C) containing a scavenger that absorbs at least one of water and oxygen.
- a layer (F), and the thickness of the resin layer (F) is 20 ⁇ m or more;
- the resin layer (F) and the gas barrier film (D) satisfy the conditions of the following formulas (1) and (2): 15 ⁇ Pe> Pd Formula (1) 10 ⁇ 4 ⁇ Pd ⁇ 10 ⁇ 1 Formula (2)
- Pe represents the water vapor permeability of the resin layer (F) in a 40 ° C.
- Pd represents the gas barrier film (D) in a 40 ° C. and 90% RH environment.
- the water vapor permeability is shown, and the unit is g / m 2 / day for all.
- the substrate (A) and the gas barrier film (D) are bonded directly or through an intermediate layer so that the element (B) and the layer (C) are not in contact with outside air.
- Organic electronic devices [11] Further, the gas barrier film (D) and the resin layer (F) are bonded directly or through an intermediate layer so that the resin layer (F) is not in contact with outside air. 10].
- a plurality of organic semiconductor elements (B) are arranged at intervals from each other, A resin layer (F) is laminated on the plurality of organic semiconductor elements (B), A layer (C) containing a scavenger that absorbs at least one of two or more moisture and oxygen is disposed on the resin layer (F) at an interval from each other, A gas barrier film (D) is laminated on the layer (C), A method for producing an organic electronic device, comprising cutting the substrate (A) so as to include the organic semiconductor element (B) and a layer (C) containing a trapping agent that absorbs at least one of moisture and oxygen.
- the part to be cut is a part where at least the substrate (A) and the gas barrier film (D) are bonded directly or via an intermediate layer Manufacturing method.
- the part to be cut is a part where at least the substrate (A), the gas barrier film (D), and the resin layer (F) are laminated.
- the manufacturing method of the organic electronic device of description [18] The method for producing an organic electronic device according to any one of [15] to [17], wherein the intermediate layer is a layer containing a sealing material.
- the resin layer (F) includes at least one anticorrosion layer (E).
- the resin layer (F) or the anticorrosion layer (E) is an organic semiconductor element (B), more specifically, an electrode and a layer (C) containing a scavenger that absorbs at least one of moisture and oxygen.
- the layer (C) containing the scavenger that absorbs at least one of moisture and oxygen does not directly contact the electrode.
- the layer (C) containing the scavenger that absorbs at least one of moisture and oxygen is disposed in the organic electronic device so as not to come into contact with the outside air, so that the lifetime of the organic electronic device can be increased. became.
- the organic thin film solar cell it is not necessary to provide a space in order to avoid contact between the trapping agent and the electrode, and the device can be thinned.
- the capture agent and the electrode do not come into contact with each other even when pressed from above the film, the organic semiconductor can be covered with a film instead of glass, and the device can be reduced in weight.
- the resin layer (F) is an organic semiconductor element (B) on the side opposite to the substrate (A), more specifically, an electrode and a layer containing a trapping agent that absorbs at least one of moisture and oxygen ( C) is applicable to a bottom light receiving type organic solar cell having a light receiving surface on the substrate (A) side.
- the organic electronic device of the present invention is an organic electronic module that is resistant to pressure in a direction perpendicular to the light receiving surface. Specifically, to make the organic thin-film solar cell device modular and install the module, in order to be practical, so that it can withstand even if it is stepped on or a leopard falls, It is necessary to withstand pressure perpendicular to the light receiving surface. However, when there is only a space between the organic semiconductor element and the scavenger, or when there is only a film with high gas permeability, there is a high risk of direct contact and damage. By providing the layer (F), preferably the anticorrosion layer (E) having specific characteristics, this damage can be prevented.
- the moisture scavenger and the hot melt type member are water and alkali, the adhesive used in the process, the solvent such as an adhesive, the moisture such as the outside air, It can be expected that there will be no deterioration in the process of absorbing the oxygen and the like in the manufacturing process of the OPV module, and the handling work and process design can be simplified and made robust.
- the substrate (A) and the gas barrier film (D) are directly connected so that the organic semiconductor element (B) and the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen do not come into contact with the outside air. Or the said effect can be exhibited more by adhere
- the organic electronic device of the present invention has an organic semiconductor element (B) 20 including at least a pair of electrodes 3 and 4 and an organic semiconductor layer 2, and at least one of moisture and oxygen.
- An organic electronic device in which a layer (C) 6 containing a trapping agent to be absorbed and a gas barrier film (D) 7 covering the organic semiconductor element 20 are sequentially laminated, wherein at least one of the electrodes, the moisture and oxygen At least one anticorrosion layer (E) 5 is provided between the layer (C) 6 containing a scavenger that absorbs at least one of them.
- the organic semiconductor element (B) 20 may be formed on the substrate (A) 1 or a gas barrier film (D) may be used as the substrate.
- the organic semiconductor element (B) is configured by arranging the organic semiconductor layer 2 between the transparent electrode 3 and the metal electrode 4.
- the organic semiconductor element (B) is formed in the organic semiconductor layer 2 by photoelectric conversion.
- the generated electrons are extracted from the transparent electrode 3 and the metal electrode 4 as electric power.
- the film thickness of this anticorrosion layer (E) is 20 micrometers or more.
- the anticorrosion layer (E) and the gas barrier film (D) satisfy the conditions of the following formulas (1) and (2). 15 ⁇ Pe> Pd Formula (1) 10 ⁇ 4 ⁇ Pd ⁇ 10 ⁇ 1 Formula (2)
- Pe represents the water vapor transmission rate of the anticorrosion layer (E) in a 40 ° C. and 90% RH environment
- Pd represents the gas barrier film (D) in a 40 ° C. and 90% RH environment.
- the water vapor permeability is shown, and the unit is g / m 2 / day for all.
- the organic electronic device of the present invention includes at least a substrate (A) 1, an organic semiconductor element (B) 20, a scavenger that absorbs moisture and / or oxygen, as shown in FIGS. 3 and 4.
- the organic semiconductor element (B) and the layer (C) 6 have a resin layer (F) so that the organic semiconductor element (B) and the layer (C) 6 are not in direct contact with each other.
- the substrate (A) 1 and the gas barrier film (D) 7 are bonded directly or through an intermediate layer such as the anticorrosion layer (E) 5 so as not to come into contact with the outside air.
- the film thickness of this resin layer (F) is 20 micrometers or more.
- the resin layer (F) and the gas barrier film (D) satisfy the conditions of the following formulas (1) and (2): 15 ⁇ Pe> Pd Formula (1) 10 ⁇ 4 ⁇ Pd ⁇ 10 ⁇ 1 Formula (2)
- Pe represents the water vapor permeability of the resin layer (F) in a 40 ° C. and 90% RH environment
- Pd represents the gas barrier film (D) in a 40 ° C. and 90% RH environment.
- the water vapor permeability is shown, and the unit is g / m 2 / day for all. And the board
- the organic electronic device of the present invention has a layer (C) containing a scavenger on a gas barrier film (D) 7 on which a gas barrier layer such as a back surface protection sheet (not shown) is formed.
- the resin layer (F) composed of the anticorrosion layer (E) 5 is disposed so as to cover the layer (C) 6 containing the scavenger, and the resin layer (F) is an end face of the organic electronic device. It is bonded to the gas barrier film (D) 7 through the sealing material 8 so as not to be exposed to the outside without reaching.
- the other members are the same as those in the second embodiment.
- the fourth embodiment is a method for manufacturing an organic electronic device.
- a method for manufacturing the organic electronic device shown in FIGS. 3 and 4. that is, in this method, as shown in FIGS. 3 and 4, at least a substrate (A) 1, an organic semiconductor element (B) 20, a layer (C) 6 containing a trapping agent that absorbs at least one of moisture and oxygen,
- the substrate (A) 1 and the gas barrier film (D) 7 are bonded to each other directly or through an intermediate layer.
- at least two or more organic semiconductor elements (B) 20 are arranged on the substrate (A) 1 at intervals.
- the resin layer (F) is laminated on the at least two or more organic semiconductor elements (B) 20, and the scavenger that absorbs at least one of two or more moisture and oxygen is included on the resin layer (F).
- the layers (C) 6 are arranged with a space therebetween, and the gas barrier film (D) 7 is laminated on the layers (C) 6 to absorb the organic semiconductor element (B) 20 and at least one of moisture and oxygen.
- the layer (C) 6 containing a capturing agent may be included. Even in this configuration, it is desirable that the resin layer (F) is the same as in the second embodiment, but the film thickness and moisture absorption rate are easy to manufacture even for those that do not satisfy the above requirements. It is possible to simplify the manufacturing process.
- the organic electronic device according to the present invention is not particularly limited as long as it has at least the (B) to (E) layers or (A) to (F) layers described above. It refers to an EL device or an organic thin film solar cell device. Among these, an organic thin film solar cell device is particularly preferable.
- seat, a film, and a layer all mean a sheet form and a film form, and do not distinguish unless the function of this invention is impaired.
- symbol was attached
- the substrate (A) is a support member that supports the organic semiconductor element (B).
- the material for forming the substrate (A) include inorganic materials such as glass, sapphire, and titania; polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, Fluorine resin film, vinyl chloride, polyethylene, polypropylene, cyclic polyolefin, cellulose, acetyl cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, poly (meth) acrylic resin, phenol resin, epoxy resin, polyarylate, polynorbornene Organic materials such as stainless steel, titanium, nickel, silver, gold, copper, aluminum, and the like.
- organic semiconductor element (B) glass, polyethylene terephthalate, polyethylene naphthalate, polyimide, poly (meth) acrylic resin film, stainless steel, and aluminum are preferable from the viewpoint of easy formation of the organic semiconductor element (B).
- 1 type may be used for the material of a base material, and 2 or more types may be used together by arbitrary combinations and a ratio.
- these organic materials may contain reinforcing fibers such as carbon fibers and glass fibers to reinforce the mechanical strength.
- the substrate (A) is composed of a metal substrate
- an organic semiconductor element is laminated on the upper layer so that a part of the substrate (A) is provided with an insulating property, and a part of the substrate (A) functions as a metal electrode.
- a configuration in which a transparent electrode is laminated on the upper layer is also applicable.
- a gas barrier film may be used as the substrate.
- Organic semiconductor element (B) As the organic semiconductor element (B), an organic thin film solar cell element (hereinafter, also simply referred to as a solar cell element) is described below, but other organic electronic devices are not excluded unless the present invention is significantly impaired. Absent. Furthermore, the organic thin film solar cell element is not limited to the examples described below.
- the organic thin film solar cell element is provided with at least a pair of electrodes and an organic semiconductor layer containing an organic semiconductor provided therebetween.
- the organic semiconductor layer absorbs light to generate electric power, and the generated electric power is extracted from the electrode, and may include other layers such as a buffer layer as described later.
- Organic semiconductor layer It can form with arbitrary organic semiconductors.
- Organic semiconductors are classified into p-type and n-type depending on semiconductor characteristics.
- the p-type and n-type indicate whether it is a hole or an electron that contributes to electrical conduction, and depends on the electronic state, doping state, and trap state of the material. Accordingly, examples of organic semiconductors will be given below.
- p-type and n-type may not always be clearly classified, and some of the same substances exhibit both p-type and n-type characteristics.
- Examples of p-type semiconductors include porphyrin compounds such as tetrabenzoporphyrin, tetrabenzocopper porphyrin, tetrabenzozinc porphyrin; phthalocyanine compounds such as phthalocyanine, copper phthalocyanine, zinc phthalocyanine; naphthalocyanine compounds; polyacenes of tetracene and pentacene; Examples include oligothiophene and derivatives containing these compounds as a skeleton.
- polymers such as polythiophene, polyfluorene, polyphenylene vinylene, polytriallylamine, polyacetylene, polyaniline, polypyrrole and the like including poly (3-alkylthiophene) and the like are exemplified.
- n-type semiconductors include fullerene (C60, C70, C76); octaazaporphyrin; perfluoro compound of the above p-type semiconductor; naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylene.
- aromatic carboxylic acid anhydrides such as tetracarboxylic acid diimide and imidized products thereof; and derivatives containing these compounds as a skeleton.
- the specific configuration of the organic semiconductor layer is arbitrary as long as at least a p-type semiconductor and an n-type semiconductor are contained. It may be constituted only by a single layer film or may be constituted by two or more laminated films. For example, an n-type semiconductor and a p-type semiconductor may be contained in separate films, or an n-type semiconductor and a p-type semiconductor may be contained in the same film. In addition, each of the n-type semiconductor and the p-type semiconductor may be used alone or in combination of two or more in any combination and ratio.
- a bulk heterojunction type having a layer (i layer) in which a p-type semiconductor and an n-type semiconductor are phase-separated in the layer, a layer containing a p-type semiconductor (p layer), and n, respectively.
- Examples include a stacked type (hetero pn junction type) in which a layer containing a p-type semiconductor (p layer) has an interface, a Schottky type, and a combination thereof.
- a bulk heterojunction type and a combination of a bulk heterojunction type and a stacked type are preferable because they exhibit high performance.
- each of the p-layer, i-layer, and n-layer of the organic semiconductor layer is not limited, but is usually 3 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less. Increasing the layer thickness tends to increase the uniformity of the film, and decreasing the thickness tends to improve the transmittance and decrease the series resistance.
- the electrode can be formed of any material having conductivity.
- electrode materials include metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, barium, sodium, and alloys thereof; metal oxides such as indium oxide and tin oxide.
- ITO Indium Tin Oxide
- conductive polymers such as polyaniline, polypyrrole, polythiophene and polyacetylene
- acids such as hydrochloric acid, sulfuric acid and sulfonic acid, Lewis acids such as FeCl 3 and halogens such as iodine Materials containing a dopant such as metal atoms such as atoms, sodium and potassium
- conductive composite materials in which conductive particles such as metal particles, carbon black, fullerene and carbon nanotubes are dispersed in a matrix such as a polymer binder It is done.
- the material which has a deep work function such as Au and ITO, is preferable for the electrode which collects holes.
- a material having a shallow work function such as Al is preferable.
- the electrode on the light receiving surface side is light transmissive for power generation.
- the electrode is not transparent, such as the area of the electrode is smaller than the area of the power generation layer, it does not necessarily need to be transparent if the power generation performance is not adversely affected.
- transparent electrode materials include oxides such as ITO and indium zinc oxide (IZO); and metal thin films.
- the specific range of the light transmittance is not limited, but considering the power generation efficiency of the solar cell element, 80% or more is preferable except for the loss due to partial reflection at the optical interface.
- an electrode may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
- limiting in the formation method of an electrode For example, it can be formed by a dry process such as vacuum deposition or sputtering. Further, for example, it can be formed by a wet process using a conductive ink or the like. At this time, any conductive ink can be used. For example, a conductive polymer, a metal particle dispersion, or the like can be used.
- two or more electrodes may be laminated, and characteristics such as electric characteristics and wetting characteristics may be improved by surface treatment.
- the organic solar cell element shown in the above example may include other layers in addition to the organic semiconductor layer and the electrode described above.
- the position which forms other layers is arbitrary unless the electric power generation of a solar cell element is inhibited.
- buffer layers are exemplified.
- the buffer layer is a layer provided, for example, at the electrode interface facing the organic semiconductor layer for improving electrical characteristics.
- poly (ethylenedioxythiophene): poly (styrenesulfonic acid) (PEDOT: PSS), molybdenum oxide, lithium fluoride, 2,9dimethyl-4,7-diphenyl-1,10-phenanthroline, and the like can be given.
- the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen is a film that absorbs at least one of moisture and oxygen.
- the solar cell element and the like are protected from at least one of moisture and oxygen, and the power generation capacity is kept high.
- the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen does not impede permeation of at least one of moisture and oxygen. It absorbs at least one of oxygen.
- at least one of oxygen and oxygen can be captured by the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen, and the influence of moisture on the solar cell element can be eliminated.
- the moisture absorption capacity (also referred to as moisture absorption amount in the present invention) of the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen is usually 0.1 mg / unit per unit area with respect to the laminated surface. cm 2 or more, preferably 0.5 mg / cm 2 or more, more preferably 1 mg / cm 2 or more.
- it is 15 mg / cm ⁇ 2 > or less.
- the water absorption amount per unit volume of the layer (C) containing the scavenger is usually 1 mg / cm 3 or more, preferably 5 mg / cm 3 or more, more preferably 10 mg / cm 3 or more.
- the method for measuring the amount of water absorption is a method of calculating from the weight change before and after moisture absorption of the test specimen, a method of measuring the water content in the test specimen with a moisture measuring device, and storing the specimen in a sealed container containing moisture.
- the water loss can be measured by a method of detecting with a moisture concentration meter. Since it can implement simply, the method of calculating from a weight change is preferable.
- the storage environment in which moisture exists may be set as appropriate in terms of moisture absorption capacity as long as the conditions for the presence of moisture in excess of the moisture absorption amount of the specimen are satisfied.
- the water concentration is appropriately controlled. In a suitable environment, for example, in the range of 1 ppm to 1%.
- a test body that irreversibly absorbs water may be weighed in a humidity environment of 50% RH or more, but a test body that reversibly absorbs water has a humidity of 85% RH or more. It is necessary to measure the weight in a high humidity environment.
- the gas barrier film (D) when the solar cell element is covered with the gas barrier film (D) or the like when the layer (C) containing the scavenger that absorbs at least one of moisture and oxygen absorbs oxygen, the gas barrier film (D) and the seal
- the layer (C) containing the trapping agent that absorbs at least one of moisture and oxygen is trapped by oxygen that slightly enters the space formed by the material, and the influence of oxygen on the solar cell element can be eliminated.
- the oxygen absorption capacity of the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen is usually 0.01 ml / cm 2 or more, preferably 0.05 ml / cm 2 or more per unit area with respect to the laminated surface.
- limiting in an upper limit Usually, it is 20 ml / cm ⁇ 2 > or less.
- oxygen absorption capacity and oxygen absorption are synonymous.
- the oxygen absorption amount per unit volume of the layer (C) containing the scavenger is usually 0.1 ml / cm 3 or more, preferably 0.5 mg / cm 3 or more, more preferably 1 mg / cm 3 or more.
- the measuring method of oxygen absorption ability is calculated by the method of storing a test body in the airtight container containing oxygen, and detecting the oxygen reduction
- the initial oxygen concentration in the sealed container may be set as appropriate so that oxygen exceeding the oxygen absorption amount of the test specimen exists and becomes a concentration suitable for the sensitivity of the oximeter. Further, the amount of the test body in the sealed container may be appropriately charged so that the oxygen decrease due to absorption is equal to or higher than the detection sensitivity of the oximeter.
- the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen is used on the light-receiving side surface of the solar cell, it is preferable to transmit visible light from the viewpoint of not preventing light absorption of the solar cell element.
- the transmittance of visible light (wavelength 360 to 830 nm) is usually 75% or more, preferably 80% or more, more preferably 85% or more, and still more preferably 90%, excluding loss due to partial reflection at the film interface.
- particularly preferably 95% or more, and particularly preferably 97% or more This is to convert more sunlight into electrical energy.
- the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen also has heat resistance.
- the melting point of the constituent material of the layer (C) containing the scavenger that absorbs at least one of moisture and oxygen is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, It is usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably 300 ° C. or lower.
- the material constituting the layer (C) containing the scavenger that absorbs at least one of moisture and oxygen is arbitrary as long as it can absorb at least one of moisture and oxygen.
- the material include alkali metal, alkaline earth metal, alkaline earth metal oxide, alkali metal or alkaline earth metal hydroxide, silica gel as a substance that absorbs moisture (water absorbing agent, desiccant). , Zeolite compounds, sulfates such as magnesium sulfate, sodium sulfate and nickel sulfate, and organometallic compounds such as aluminum metal complexes and aluminum oxide octylates.
- examples of the alkaline earth metal include Ca, Sr, and Ba.
- alkaline earth metal oxide examples include CaO, SrO, and BaO.
- Other examples include Zr—Al—BaO and aluminum metal complexes.
- alkaline earth metals Ca and Sr and their oxides CaO, SrO, and aluminum metal complexes are preferable, and CaO, SrO, and BaO are more preferable in terms of high moisture scavenging properties, and aluminum metal complexes are scavengers. Is more preferable in that it can be made transparent.
- OleDry manufactured by Futaba Electronics Co., Ltd.
- Inorganic materials such as Fe, Mn, Zn, and inorganic salts such as sulfates, chlorides, and nitrates of these metals as substances that absorb oxygen (deoxygenating agents); ascorbic acid, hydrazine compounds, MXD6 nylon, ethylene Organic unsaturated hydrocarbons, polymers having a cyclohexene group, and the like.
- the layer (C) containing the scavenger that absorbs at least one of moisture and oxygen may be formed of one material or two or more materials.
- the scavengers constituting the layer (C) containing the scavenger that absorbs at least one of water and oxygen in the case of the scavengers that absorb water, alkaline earth metal Ca or Sr and alkaline earth Metal oxide CaO or SrO; alkaline earth metal oxide CaO or SrO and an aluminum metal complex are preferable from the viewpoint of moisture scavenging performance, and in the case of a combination of a moisture absorbing scavenger and an oxygen absorbing scavenger, alkaline earth Alkali metal oxide CaO or SrO and Fe; Alkaline earth metal oxide CaO or SrO and ascorbic acid; Alkaline earth metal oxide CaO or SrO and hydrazine compound; Aluminum metal complex and ascorbic acid; Aluminum metal complex A hydrazine compound is preferable
- the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen may be formed of a single layer film, but may be a laminated film including two or more layers.
- the thickness of the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen is not particularly defined, but is usually 5 ⁇ m or more, preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, and usually 500 ⁇ m or less, preferably It is 400 ⁇ m or less, more preferably 300 ⁇ m or less. Increasing the thickness tends to increase the mechanical strength, while decreasing the thickness tends to increase flexibility, and further has the advantage that the device can be made thinner. For this reason, it is desirable to set it as the said range as a range which has both advantages.
- the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen is provided between the gas barrier film (D) and the organic semiconductor element (B).
- a layer (C) containing a scavenger that absorbs at least one of moisture and oxygen is installed on the light receiving surface side of the organic semiconductor element (B).
- a layer (C) containing a trapping agent that absorbs at least one of moisture and oxygen is installed on the back side of the organic semiconductor element (B) as necessary.
- a layer (C) containing a scavenger that absorbs at least one of moisture and oxygen is provided on both the light receiving surface and the back surface.
- the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen is positioned between the organic semiconductor element (B) and the gas barrier film (D) on both the light receiving surface and the back surface. Is preferred.
- the installation position is further limited. No.
- the seal You may install in the position along the material inner side.
- the layer (C) containing a capturing agent that absorbs at least one of moisture and oxygen can be formed by any method depending on the type of the capturing agent.
- a film in which the capturing agent is dispersed is attached with an adhesive.
- acquisition agent by roll coating, gravure coating, knife coating, dip coating, curtain flow coating, spray coating, bar coating, die coating, spin coating, ink jet, dispenser, etc. can be used.
- a film forming method such as plasma CVD, vacuum deposition, ion plating, or sputtering may be used.
- the film for the scavenger examples include polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin). ), Polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, and the like. Among these, films of polyethylene resin, fluorine resin, cyclic polyolefin resin, and polycarbonate resin are preferable. In addition, the said resin may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
- the layer (C) containing the trapping agent that absorbs at least one of moisture and oxygen arranged on the back surface of the solar cell element opposite to the light receiving surface is not necessarily visible in the constituent members on the back side of the solar cell element. Since it is not necessary to transmit, what does not permeate
- the gas barrier film (D) is a film that prevents permeation of water and oxygen.
- Organic semiconductor elements (B) including organic thin-film solar cells tend to be vulnerable to moisture and oxygen, and the transparent electrode, metal electrode, and organic semiconductor layer may be deteriorated by moisture and oxygen. Therefore, by covering the solar cell element with the gas barrier film (D), the solar cell element can be protected from water and oxygen, and the power generation capacity can be kept high.
- the gas barrier film (D) in this invention satisfy
- the water vapor permeability Pd of the gas barrier film (D) needs to be 10 ⁇ 1 g / m 2 / day or less at a thickness of 100 ⁇ m in a 40 ° C. and 90% RH environment in order to block the entry of moisture from the outside. However, it is more preferably 10 ⁇ 2 g / m 2 / day or less, more preferably 10 ⁇ 3 g / m 2 / day or less, more preferably 10 ⁇ 4 g / m 2 / day, and the higher the barrier performance. However, as the current technology is transparent and flexible and the barrier performance increases, the manufacturing cost will increase accordingly.
- the water vapor transmission rate is measured in an environment of 40 ° C. and 90% by a measurement using an apparatus equipped with a humidity sensor, an infrared sensor, and a gas chromatograph according to JIS K7129, and by the cup method (JIS Z0208).
- a filler in order to fill a vacant space and to improve an optical characteristic and a mechanical characteristic, it may be necessary to enclose a filler.
- the filler layer is a substance containing a free acid, an organic solvent, water vapor, oxygen, or the like, the organic semiconductor element may be deteriorated. Even in such a case, deterioration of the organic semiconductor element can be prevented by disposing the anticorrosion layer between the organic semiconductor element.
- the degree of oxygen permeability required for the gas barrier film (D) varies depending on the type of the organic semiconductor element (B).
- the oxygen permeability per unit area (1 m 2 ) at a thickness of 100 ⁇ m in a 25 ° C. environment is preferably 1 cc / m 2 / day / atm or less, preferably 1 ⁇ 10 It is more preferably ⁇ 1 cc / m 2 / day / atm or less, further preferably 1 ⁇ 10 ⁇ 2 cc / m 2 / day / atm or less, and further preferably 1 ⁇ 10 ⁇ 3 cc / m 2 / day.
- the oxygen permeability can be measured with an apparatus based on a differential pressure method according to JIS K7126A, or an apparatus equipped with an infrared sensor and a gas chromatograph based on an isobaric method according to JIS K7126B.
- the gas barrier film (D) is preferably one that transmits visible light when used on the light incident / exit surface of the organic electronic device.
- the transmittance of visible light (wavelength 360 to 830 nm) is usually 75% or more, preferably 80% or more, more preferably 85% or more, further preferably 90% or more, particularly preferably 95% or more. Among these, 97% or more is particularly preferable.
- an organic thin film solar cell has an advantage of converting more sunlight into electric energy. Further, when it is used on a surface opposite to the light incident / exit surface of the organic electronic device, it is not always necessary to transmit visible light, and it may be opaque.
- the thickness of the gas barrier film is not particularly defined, but is usually 10 ⁇ m or more, preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more, and usually 500 ⁇ m or less, preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less. Increasing the thickness tends to increase mechanical strength, and decreasing the thickness tends to increase flexibility. Furthermore, since organic semiconductor devices are often heated by receiving light, it is preferable that the gas barrier film (D) also has heat resistance. From this viewpoint, the melting point of the constituent material of the gas barrier film (D) is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower. Preferably it is 300 degrees C or less. By increasing the melting point, it is possible to prevent the gas barrier film (D) from melting and deteriorating when the organic semiconductor device is used.
- the specific configuration of the gas barrier film (D) is arbitrary as long as the organic semiconductor element can be protected from at least one of water and oxygen. However, since the production cost increases as the amount of water vapor or oxygen that can permeate the gas barrier film (D) increases, it is preferable to use an appropriate film considering these points comprehensively.
- the configuration of the gas barrier film (D) will be described with examples.
- the first example is a film in which an inorganic barrier layer is disposed on a plastic film substrate.
- the inorganic barrier layer may be formed only on one side of the plastic film substrate, or may be formed on both sides of the plastic film substrate.
- the number of inorganic barrier layers formed on both surfaces may be the same or different.
- the second example is a film in which a unit layer composed of two layers in which an inorganic barrier layer and a polymer layer are laminated adjacent to each other is formed on a plastic film substrate.
- a unit layer composed of two layers in which an inorganic barrier layer and a polymer layer are laminated adjacent to each other is regarded as one unit, and this unit layer is composed of one unit (one inorganic barrier layer and one polymer layer are combined). Only one unit) may be formed, but two or more units may be formed. For example, 2 to 5 units may be laminated.
- the unit layer may be formed only on one side of the plastic film substrate, or may be formed on both sides of the plastic film substrate. When forming on both surfaces, the numbers of inorganic barrier layers and polymer layers formed on both surfaces may be the same or different. Moreover, when forming a unit layer on a plastic film base material, an inorganic barrier layer may be formed on the plastic film base material side, and a polymer layer may be formed on this inorganic barrier layer, or on the plastic film base material side. A polymer layer may be formed, and an inorganic barrier layer may be formed on the polymer layer.
- a protective film may be provided on the surface on which the barrier layer is disposed.
- a protective film may be the same material as the gas barrier film substrate, or a different material.
- it is good also as a laminated body which bonded the surfaces in which the barrier layer was arrange
- the plastic film base material used for the gas barrier film (D) is not particularly limited as long as it is a film capable of holding the above-described inorganic barrier layer and polymer layer, and the purpose of use of the gas barrier film (D), etc. Can be appropriately selected.
- plastic film base materials include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyvinyl alcohol resin, polyamideimide resin. , Polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin And thermoplastic resins such as alicyclic modified polycarbonate resins and acryloyl compounds.
- polyester resins preferred examples include polyester resins, polyarylate resins, polyethersulfone resins, fluorene ring-modified polycarbonate resins, alicyclic modified polycarbonate resins, and acryloyl compounds. It is also preferable to use a condensation polymer containing spirobiindane or spirobichroman.
- polyester resins biaxially stretched polyethylene terephthalate (PET) and biaxially stretched polyethylene naphthalate (PEN) are preferably used as the plastic film substrate in the present invention because of excellent thermal dimensional stability. It is done.
- 1 type may be used for the material of a plastic film base material, and 2 or more types may be used together by arbitrary combinations and a ratio.
- An anchor coat agent layer (anchor coat layer) may be formed on the plastic film substrate in order to improve adhesion to the inorganic barrier layer.
- the anchor coat layer is formed by applying an anchor coat agent.
- the anchor coating agent include polyester resins, urethane resins, acrylic resins, oxazoline group-containing resins, carbodiimide group-containing resins, epoxy group-containing resins, isocyanate-containing resins, and copolymers thereof.
- an anchor coat agent may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
- the thickness of the anchor coat layer is usually 0.005 ⁇ m or more, preferably 0.01 ⁇ m or more, and usually 5 ⁇ m or less, preferably 1 ⁇ m or less. If the thickness is less than or equal to the upper limit of this range, the slipperiness is good, and there is almost no peeling from the plastic film substrate due to the internal stress of the anchor coat layer itself. Moreover, if it is the thickness more than the lower limit of this range, a uniform thickness can be maintained and it is preferable.
- the inorganic barrier layer is usually a layer formed of a metal oxide, nitride or oxynitride.
- the metal oxide, nitride, and oxynitride which form an inorganic barrier layer may be 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
- the metal oxide include oxides such as Si, Al, Mg, In, Ni, Sn, Zn, Ti, Cu, Ce, and Ta, nitrides, and oxynitrides.
- the inorganic barrier layer is composed of two or more kinds of metal oxides, it is desirable that the metal oxides include aluminum oxide and silicon oxide.
- the ratio of each metal atom to oxygen atom is also arbitrary, but in order to improve the transparency of the inorganic barrier layer and prevent coloring, the oxygen atom ratio should be extremely small from the stoichiometric ratio of the oxide. Is desirable. On the other hand, in order to improve the denseness of the inorganic barrier layer and increase the barrier property, it is desirable to reduce oxygen atoms. From this viewpoint, for example, when SiO x is used as the metal oxide, the value of x is particularly preferably 1.5 to 1.8. For example, when AlO x is used as the metal oxide, the value of x is particularly preferably 1.0 to 1.4.
- the appropriate thickness of the inorganic barrier layer is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 200 nm or less.
- the sputtering method can be formed by reactive sputtering using plasma using one or more metal targets and oxygen gas as raw materials.
- any polymer can be used for a polymer layer, for example, what can be formed into a film in a vacuum chamber can be used.
- the polymer which comprises a polymer layer may use 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Examples of the compound that gives the polymer include the following.
- 1 type may be used for a monomer and it may use 2 or more types together by arbitrary combinations and a ratio.
- Examples thereof include siloxanes such as hexamethyldisiloxane, and polysiloxane is obtained as a polymer.
- Examples include paraxylylene such as diparaxylylene, and polyparaxylylene is obtained as a polymer.
- Examples include monomers that can be repeatedly subjected to addition polymerization of two kinds of monomers alternately.
- polyurethane diisocyanate / glycol
- polyurea diisocyanate / diamine
- polythiourea dithioisocyanate / diamine
- polythioether urethane bisethyleneurethane / dithiol
- examples include polyimine (bisepoxy / primary amine), polypeptide amide (bisazolactone / diamine), and polyamide (diolefin / diamide).
- Examples include acrylate monomers. Either monofunctional, bifunctional, or polyfunctional acrylate monomers may be used, but in order to obtain an appropriate evaporation rate, curing degree, curing rate, etc., it is preferable to use a combination of two or more of the above acrylate monomers.
- Examples of monofunctional acrylate monomers include aliphatic acrylate monomers, alicyclic acrylate monomers, ether acrylate monomers, cyclic ether acrylate monomers, aromatic acrylate monomers, hydroxyl group-containing acrylate monomers, carboxy group-containing acrylate monomers, and the like. .
- Examples thereof include monomers capable of obtaining a photocationically cured polymer such as an epoxy-based or oxetane-based polymer. Vinyl acetate is mentioned. Furthermore, polyvinyl alcohol is obtained by saponifying the polymer. Examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, and itaconic anhydride. Furthermore, a copolymer with ethylene can be constituted. Further, a mixture of these, a mixture of glycidyl ether compounds, and a mixture with an epoxy compound can also be used as the polymer.
- the polymerization is usually carried out after a composition containing a monomer is applied or deposited to form a film.
- a thermal polymerization initiator when used, polymerization is started by contact heating with a heater or the like; radiation heating with infrared rays, microwaves or the like.
- a photoinitiator when used, an active energy ray is irradiated and polymerization is started.
- Various light sources can be used when irradiating active energy rays, such as mercury arc lamps, xenon arc lamps, fluorescent lamps, carbon arc lamps, tungsten-halogen radiation lamps, and irradiation light from sunlight. Can do.
- active energy rays such as mercury arc lamps, xenon arc lamps, fluorescent lamps, carbon arc lamps, tungsten-halogen radiation lamps, and irradiation light from sunlight.
- electron beam irradiation and atmospheric pressure plasma treatment can be performed.
- Examples of the method for forming the polymer layer include a coating method and a vacuum film forming method.
- a coating method for example, methods such as roll coating, gravure coating, knife coating, dip coating, curtain flow coating, spray coating, and bar coating can be used.
- film-forming methods such as vapor deposition and plasma CVD, are mentioned, for example.
- the thickness of the polymer layer is not particularly limited, but is usually 10 nm or more, and is usually 5000 nm or less, preferably 2000 nm or less, more preferably 1000 nm or less.
- the uniformity of the thickness can be easily obtained, and structural defects of the inorganic barrier layer can be efficiently filled with the polymer layer, and the barrier property tends to be improved.
- the barrier property is improved because the polymer layer itself is less likely to crack due to external force such as bending. For this reason, it is desirable to determine from the said range as thickness which has barrier property and bending strength.
- Suitable gas barrier film (D) from among described above, for example, an inorganic material on a substrate film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), preferably a vacuum deposition method SiO x or SiOxNy
- a substrate film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN)
- SiO x or SiOxNy The film etc. which vacuum-deposited by are mentioned. That is, the case where the gas barrier film (D) is a film containing a thermoplastic resin and SiO x vacuum-deposited on the thermoplastic resin is included.
- the value of x is particularly preferably 1.5 to 1.8, and Y is an integer.
- SiO x and SiOxNy do not absorb moisture or react with moisture, and achieve barrier performance by regulating the free volume.
- a dense thin film formed by a vacuum evaporation method or the like, particularly a SiO x thin film is more preferable.
- a film made of a thermoplastic resin provided with a SiO x thin film is desirable because it has a higher barrier property.
- the gas barrier film (D) in the present invention defines the gas barrier performance by the water vapor permeability (that is, the water vapor barrier performance). This is because the water vapor barrier is one of the most important functions, This is because the barrier is one of the most difficult gas barriers, that is, easy to permeate among low molecular weight components such as gases such as oxygen, volatile components, alkalis and acids, which are usually problematic.
- the gas barrier film (D) may be formed of one type of material or may be formed of two or more types of materials.
- the gas barrier film (D) may be formed of a single layer film, but may be a laminated film including two or more layers.
- the formation position is not limited. It is characterized in that it is provided on the surface opposite to the substrate of the element (B).
- the edge of the gas barrier film (D) is sealed with a sealing material, and the solar cell element is placed in a space surrounded by the gas barrier film (D) and the sealing material, so that the organic semiconductor element (B) is moistened with oxygen and oxygen. It can be protected from.
- the back surface protection sheet mentioned later has high gas barrier performance, you may serve as a gas barrier film (D) by the use.
- the anticorrosion layer (E) is an important layer constituting the organic semiconductor device.
- the anticorrosion layer (E) in the present invention is different from the filler. Since the anticorrosion layer (E) has at least a pair of electrodes or a substrate (A) provided with the electrodes in the organic semiconductor element, the electrodes and the organic semiconductor element (B) of the electrodes are opposite to each other. And a layer (C) containing a scavenger that absorbs at least one of moisture and oxygen. That is, there is no particular limitation as long as the layer (C) containing the scavenger that absorbs at least one of moisture and oxygen is arranged so as not to directly contact the electrode.
- the scavenger that absorbs at least one of moisture and oxygen diffuses into the electrode and causes electrode corrosion.
- the anticorrosion layer (E) may be a single layer or a plurality of layers, but the characteristics of the anticorrosion layer (E) shown below indicate the characteristics of the entire plurality of layers in the case of a plurality of layers.
- the anticorrosion layer (E) in the present invention exhibits the following water vapor permeability characteristics (that is, excellent gas barrier properties).
- the water vapor permeability Pe in the anticorrosion layer (E) at 40 ° C. and 90% RH has a relationship of 15 g / m 2 / day ⁇ Pe> Pd, preferably 5 g / m 2 / day ⁇ Pe> Pd, and more preferably Is 1 g / m 2 d ⁇ Pe ⁇ Pd ⁇ 5, more preferably 1 g / m 2 / day ⁇ Pe ⁇ Pd ⁇ 10, and most preferably 0.1 g / m 2 / day ⁇ Pe ⁇ Pd ⁇ 10. It is preferable.
- the measurement method uses the method described above.
- organic solvents and low molecular weight components volatilized from adhesives and pressure-sensitive adhesives used in the process cannot be sufficiently blocked, and trapping that absorbs at least one of moisture and oxygen
- the layer (C) containing the agent may be altered and after it is assembled into an organic electronic device, at least one of moisture and oxygen cannot be sufficiently absorbed, and deterioration of the organic semiconductor element (B) may not be prevented. is there.
- the anticorrosion layer (E) when the water vapor transmission rate Pe of the anticorrosion layer (E) is smaller than the lower limit defined from the relationship with the water vapor transmission rate Pd of the gas barrier film (D), the anticorrosion is performed after assembling into the organic electronic device. There is a possibility that the layer cannot penetrate into the organic semiconductor element or the moisture and oxygen remaining during the assembly process cannot be sufficiently absorbed, and the deterioration of the organic semiconductor element (B) cannot be prevented. This is particularly noticeable when the Pd of the gas barrier film (D) is low, aiming at a long life.
- a film or film having gas barrier properties is used for the anticorrosion layer (E), but the gas barrier film is most preferable in view of the simplicity and cost of the assembly process of the organic electronic device.
- the solvent may permeate into the organic semiconductor layer (B0) from the pinhole of the electrode and cause deterioration.
- the film is formed by dry film formation with a vacuum process, the production efficiency is significantly inferior because it is a batch process, unlike the film process in which a film is attached. Further, the organic semiconductor element (B) may be damaged by the internal stress of the film.
- the anticorrosion layer (E) satisfying the water vapor transmission rate it is preferable to include an inorganic material film formed by a vacuum film formation method as a layer.
- barrier properties are achieved mainly by the thickness of the barrier material while dissolving and diffusing a gas such as water vapor in the barrier material. In this case, the amount of dissolved gas in the barrier material is measured In the case of increasing to near saturation solubility, it is not preferable because the gas cannot be blocked into the organic semiconductor element.
- the gas barrier performance is defined by the water vapor permeability (that is, the water vapor barrier performance). This is because the water vapor barrier is one of the most important functions, and the water vapor barrier is usually used. This is because it is one of the most difficult to block (easily permeate) among low molecular weight components such as gases such as oxygen and volatile components, alkalis, and acids. Moreover, as a more preferable function, it has an adhesive function. By having an adhesive function, the element and the capture agent that absorbs at least one of moisture and oxygen are fixed. When the device is deformed by bending or the like, there is no possibility that the capturing agent is displaced and contacts the element electrode.
- the anticorrosion layer (E), the layer containing the scavenger (C), and the gas barrier film (D) are laminated.
- the layer (C) containing the trapping agent is not shifted and does not come into contact with the device electrode.
- the scavenger component reacts with moisture to generate alkali, but if the anticorrosion layer (E) does not have alkali resistance, the alkali may permeate and cause corrosion and deterioration of the electrode. Further, it is preferable that no acid is generated from the anticorrosion layer (E). When the acid comes into contact with the electrode, the electrode corrodes and deteriorates. The absence of acid gives the advantage of preventing corrosion degradation.
- the material that generates an acid include vinyl acetate resins such as ethylene-vinyl acetate copolymers.
- the oxygen permeation ability required for the anticorrosion layer (E) varies depending on the organic semiconductor element (B).
- the oxygen permeability per day of a unit area (1 m 2 ) at a thickness of 100 ⁇ m under a 25 ° C. environment is preferably 500 cc / m 2 / day / atm or less, preferably 100 cc / m 2 / It is more preferably at most day / atm, further preferably at most 10 cc / m 2 / day / atm, particularly preferably at most 1 cc / m 2 / day / atm.
- the oxygen barrier performance is within such a range, deterioration of the element due to oxygen can be suppressed.
- the scavenger used absorbs oxygen, it is preferable that it is a value more than the oxygen permeability of a gas barrier film (D).
- the oxygen permeability is lower than that of the gas barrier film (D)
- the scavenger captures oxygen outside the element sealing region, that is, outside the gas barrier film (D), and the original purpose of preventing element deterioration is lost. I will be broken.
- the oxygen permeability can be measured by the method described above.
- the adhesive function it is required to have an adhesive ability to the layer (C) containing the device electrode and the trapping agent.
- the adhesive strength is 0.1 N / cm or more, preferably 0.4 N / cm or more, more preferably 1 N / cm or more. If the adhesion function is below the lower limit, the scavenger may easily shift and contact the device electrode, causing electrode deterioration. Moreover, 100 N / cm or less is preferable and 50 N / cm or less is more preferable.
- the measurement of the adhesive force will be described later, it can be obtained by performing a peel adhesion strength test according to JIS K6854. Depending on the shape of the test specimen, 180 degree peeling, 90 degree peeling, and T-type peeling can be selected as appropriate.
- an index of alkali resistance it is preferable to withstand a test based on ASTM D543. Specifically, it is preferable that the appearance is not abnormal after being immersed in a 1% sodium hydroxide solution for 24 hours, and the dimensional change is 5% or less, more preferably 1% or less.
- the water absorption rate of the anticorrosion layer (E) is generally preferably 0.005 to 1%, more preferably 0.01 to 0.5%, and further preferably 0.02 to 0.3%. If this upper limit is exceeded, the diffusion of alkali is promoted by the absorbed moisture, and the electrode corrosion prevention effect may be inferior. On the other hand, below the lower limit, the moisture at the interface between the device electrode and the anticorrosion layer (E) is blocked by the anticorrosion layer (E) and may not be absorbed by the scavenger.
- the anticorrosion layer (E) when used on the light receiving surface side of the organic thin film solar cell element, it is preferable to transmit visible light from the viewpoint of not preventing light absorption.
- the transmittance of visible light (wavelength 360 to 830 nm) is usually 75% or more, preferably 80% or more, more preferably 85% or more, and still more preferably 90%, excluding loss due to partial reflection at the film interface. Above all, preferably 95% or more, particularly preferably 97% or more. This is to convert more sunlight into electrical energy.
- the anticorrosion layer (E) when used on the side opposite to the light receiving surface of the organic thin film solar cell element, it is not always necessary to transmit visible light, and may be opaque. Furthermore, since organic semiconductor devices are often heated by receiving light, it is preferable to have resistance to heat. From this viewpoint, the melting point of the constituent material is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably 300 ° C. or lower. .
- the glass transition temperature is usually 0 ° C. or higher, preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and usually 300 ° C. or lower, preferably 200 ° C. or lower, more preferably 160 ° C. or lower.
- the material constituting the anticorrosion layer (E) in the present invention is arbitrary as long as it has the above characteristics.
- Specific examples of the material include polyethylene resin, polypropylene resin, cyclic polyolefin resin, ⁇ -olefin maleic anhydride copolymer, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), styrene.
- SB resin -Butadiene copolymer
- ABS resin acrylonitrile-butadiene-styrene copolymer
- polyvinyl chloride resin polyvinylidene chloride resin
- polyvinyl acetate resin polyvinyl alcohol resin, ethylene- Vinyl alcohol copolymer, polyvinyl butyral resin, polyvinyl pyrrolidone resin, fluorine resin
- resins such as polyethylene resins, cyclic polyolefin resins, ethylene-vinyl acetate copolymers, fluorine resins, poly (meth) acrylic resins, polycarbonate resins, polyester resins, polyimide resins, epoxy resins, etc. More preferred are polyethylene resins, fluorine resins, poly (meth) acrylic resins, polyester resins, polyimide resins, and epoxy resins. Among these, poly (meth) acrylic resins and epoxy resins are particularly preferable because they can provide an adhesive function.
- the anticorrosion layer (E) may be one or more layers, and may be composed of a plurality of layers. In the case of a plurality of layers, a combination such as a polyester resin and a poly (meth) acrylic resin, a polyester resin and an epoxy resin is preferable in that it has both transparency and heat resistance and can provide an adhesive function.
- the thickness per layer of the anticorrosion layer (E) is usually 20 ⁇ m or more, preferably 30 ⁇ m or more.
- an upper limit is 500 micrometers, More preferably, it is 200 micrometers or less, More preferably, it is 100 micrometers or less. If the upper limit is exceeded, the thickness of the flexible organic electronic device increases, making it difficult to bend.
- the scavenger cannot efficiently absorb moisture, oxygen, etc. that have reached the periphery of the metal electrode.
- the value is below the lower limit, the suppression of alkali diffusion becomes insufficient, and there is a possibility that deterioration of the electrode cannot be prevented.
- this anticorrosion layer (E) may be arrange
- the anticorrosion layer (E) can be formed by an arbitrary method depending on the type of the compound to be used.
- a method for producing a film or sheet such as a melt extrusion molding method, a solution casting method, or a calendar method, an anticorrosion layer (E)
- a wet film forming method in which a coating film is formed by roll coating, gravure coating, knife coating, dip coating, curtain flow coating, spray coating, bar coating, die coating, spin coating, ink jet, dispenser, etc. can be used.
- a dry film forming method such as plasma CVD, vacuum deposition, ion plating, or sputtering may be used.
- polymerization, crosslinking, and curing reaction may be performed by heating with a heater, infrared rays, microwaves, or the like, or irradiation with ultraviolet light and / or visible light.
- the resin layer (F) in the present invention is not particularly limited as long as it is a resin that exhibits the effects of the present invention, but is different from the layer (C) or filler containing a scavenger that absorbs at least one of moisture and oxygen. Resin. However, between the organic semiconductor element (B) and the layer (C) containing a trapping agent that absorbs at least one of moisture and oxygen, the organic semiconductor element (B) includes a trapping agent that absorbs at least one of moisture and oxygen.
- the layers (C) are arranged so that they are not in direct contact.
- the resin layer (F) preferably includes a gas barrier film (D) and one or more anticorrosion layers (E), and more preferably a plurality of anticorrosion layers (E). Specific examples are as described above. In addition, when the resin layer (F) is a gas barrier film (D), they may be the same or different.
- the resin used for the resin layer (F) does not contain a polar functional group or an active functional group, or even if it contains a very small amount, does not decompose with water vapor, oxygen, sunlight, etc. What is difficult to do is preferable.
- Examples of more preferable specific resins include stretched polyesters such as PET and PEN, polyolefins not containing active functional groups such as polypropylene and polyethylene, and fluororesins such as ETFE and PVF. These resins may be used in combination.
- the film thickness of the resin layer (F) is desirably 20 ⁇ m or more. The specific reason will be described in detail in the section of the film thickness of components such as the gas barrier film (D) and the anticorrosion layer (E) which are the constituent layers of the resin layer (F).
- the members described in (A) to (F) are different unless otherwise limited.
- the gas barrier film (D) is used so that the substrate (A) and the gas barrier film (D) are bonded via an intermediate layer (other layers) or the resin layer (F) is not in contact with the outside air. ) And the resin layer (F) are bonded to each other through an intermediate layer.
- the sealing material is a member that seals the edge of the laminate constituted by the present invention so that moisture and oxygen do not enter into the space covered with these films. It is a preferable member when adhering the substrate (A) to the layer (C), the anticorrosion layer (E), the resin layer (F) and the like, and the film such as the gas barrier film (D).
- the degree of water vapor permeability required for the sealing material is such that the water vapor permeability per day of a unit area (1 m 2 ) at a thickness of 100 ⁇ m in an environment of 40 ° C. and 90% RH is 500 g / m 2 / day or less. Is preferably 100 g / m 2 / day or less, more preferably 30 g / m 2 / day or less, particularly preferably 10 g / m 2 / day, and particularly preferably 1 g / m 2 / day.
- the adhesion strength is 2 N / mm or more, preferably 4 N / mm or more, more preferably 10 N / mm or more. If it falls below this lower limit, it may be easily peeled off and moisture and oxygen may enter, causing deterioration of the organic electronic device. Furthermore, since the organic electronic device is often heated by receiving light, the sealing material preferably has heat resistance. From this viewpoint, the melting point of the constituent material of the sealing material is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 300 ° C. or lower, more preferably 280. It is below °C. If the melting point is too low, the sealing material may melt when the organic electronic device is used.
- Examples of the material constituting the sealing material include fluorine resin, silicone resin, acrylic resin, ⁇ -olefin maleic anhydride copolymer, urethane resin, cellulose resin, vinyl acetate resin, and ethylene-vinyl acetate copolymer.
- Examples thereof include polymers such as rubber, nitrile rubber, and styrene butadiene copolymer.
- the sealing material may be formed of one kind of material or two or more kinds of materials.
- the sealing material is provided at a position where at least the edge of the gas barrier film (D) can be sealed. Thereby, the space surrounded by at least the gas barrier film (D) and the sealing material can be sealed, and moisture and oxygen can be prevented from entering the space.
- the sealing material has a width of usually 0.5 to 100 mm, preferably 1 to 80 mm, more preferably 2 to 50 mm, and most preferably 3 to 10 mm at the periphery of the substrate (A). Arrange so that B) is inside the square shape.
- the thickness of the sealing material is usually 5 ⁇ m to 1 mm, preferably 10 ⁇ m to 100 ⁇ m, more preferably 20 to 50 ⁇ m, and the organic semiconductor element (B) is disposed so as to be inside the square shape.
- Thickness and width are necessary to fill the unevenness of the substrate and the film and sheet, and to sufficiently protect the interior from water vapor and oxygen, but if the width is too wide, the effective area decreases, and if the thickness is too thick. The above range is appropriate because the permeation amount of water vapor and oxygen increases.
- the sealing form is not particularly limited as long as the substrate (A) and the gas barrier film (D) can be bonded without a gap.
- Examples of the form of adhesion include adhesion by sealing agent curing, fixation by volatilization of a solvent / dispersion medium, hot melt, adhesion (adhesion) by simply bonding together, and the like. From the viewpoint of facilitating production, an adhesive that is simply bonded is preferred.
- the network by hardening makes gas barrier property favorable, when seeking barrier property for a sealing material, adhesion
- Examples of the curing method include curing by a chemical reaction at normal temperature, heat curing, photocuring with visible light or ultraviolet light, electron beam curing, anaerobic curing, and the like. Of these, it is preferable to perform heat curing and ultraviolet curing from the viewpoint that the curing control can be precisely performed.
- the properties of the sealing material liquid, gel, sheet or the like is appropriately selected depending on the bonding method. From the viewpoint of preventing the problem of dripping in the sealing step, a sheet shape is preferable.
- a sealing material may be used for reinforcement of the organic electronic device.
- the sealing material preferably has a high strength from the viewpoint of maintaining the strength of the organic electronic device.
- the specific strength is related to the strength of the weatherproof protective sheet and the back surface protective sheet other than the sealing material, and it is difficult to specify in general. It is desirable to have a strength that does not cause partial peeling.
- the sealing material when used on the light receiving surface side of the organic thin film solar cell element, it is preferable to transmit visible light from the viewpoint of preventing light absorption.
- the transmittance of visible light (wavelength 360 to 830 nm) is usually 75% or more, preferably 80% or more, more preferably 85% or more, further preferably 90% or more, and particularly preferably 95% or more. Particularly preferably, it is 97% or more. This is to convert more sunlight into electrical energy.
- the sealing material when a sealing material is used on the side opposite to the light receiving surface of the organic thin film solar cell element, it is not always necessary to transmit visible light, and may be opaque. Furthermore, since the organic semiconductor device is often heated by receiving light, the sealing material preferably has heat resistance. From this viewpoint, the melting point of the constituent material of the sealing material is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably It is 300 degrees C or less. By increasing the melting point, it is possible to prevent the sealing material from melting and deteriorating when the organic semiconductor device is used.
- the thickness of the sealing material is not particularly defined, but is usually 100 ⁇ m or more, preferably 150 ⁇ m or more, more preferably 200 ⁇ m or more, and usually 1000 ⁇ m or less, preferably 800 ⁇ m or less, more preferably 600 ⁇ m or less. Increasing the thickness tends to increase the overall strength of the organic semiconductor device, and decreasing the thickness tends to increase flexibility and improve the transmittance of visible light. For this reason, it is desirable to set it as the said range as a range which has both advantages.
- a film made of an ethylene-vinyl acetate copolymer (EVA) resin composition (EVA film) can be used.
- EVA resin cross-linking process requires a relatively long time, it may cause a reduction in production speed and production efficiency of the organic semiconductor device.
- the decomposition gas (acetic acid gas) of the EVA resin composition or the vinyl acetate group of the EVA resin itself may adversely affect the organic semiconductor element and reduce the power generation efficiency. Therefore, as the sealing material, a copolymer film made of a propylene / ethylene / ⁇ -olefin copolymer can be used in addition to the EVA film.
- the sealing material may be formed of one kind of material or two or more kinds of materials.
- the sealing material may be formed with the single layer film, the laminated
- limiting in the position which provides a sealing material Usually, in order to protect reliably, it provides so that a solar cell element may be inserted
- the sealing material may be provided with functions such as ultraviolet blocking, heat blocking, conductivity, antireflection, antiglare, light diffusion, light scattering, wavelength conversion, and gas barrier properties.
- functions such as ultraviolet blocking, heat blocking, conductivity, antireflection, antiglare, light diffusion, light scattering, wavelength conversion, and gas barrier properties.
- a layer having a function may be laminated on a sealing material by coating film formation or the like, or a material that exhibits a function is dissolved and dispersed in the sealing material. You may let them.
- the weather-resistant protective sheet is a sheet and film that protects an organic electronic device from a device installation environment such as temperature change, humidity change, light, and wind and rain.
- a weather-resistant protective sheet By covering the device surface with a weather-resistant protective sheet, there is an advantage that the organic electronic device constituent material, particularly the organic semiconductor element (B) is protected and high power generation capability can be obtained without deterioration.
- the weatherproof protective sheet is located on the outermost layer of the organic semiconductor element (B), the surface coating of the organic semiconductor element (B) such as weather resistance, heat resistance, transparency, water repellency, stain resistance, mechanical strength, etc. It is preferable to have properties suitable for a material and to maintain it for a long period of time in outdoor exposure. Moreover, when a weatherproof protective sheet is used for the light-receiving surface side of an organic thin-film solar cell element, it is preferable to transmit visible light from the viewpoint of not preventing light absorption.
- the transmittance of visible light (wavelength 360 to 830 nm) is usually 75% or more, preferably 80% or more, more preferably 85% or more, further preferably 90% or more, and particularly preferably 95% or more. Particularly preferably, it is 97% or more. This is to convert more sunlight into electrical energy.
- the weatherproof protective sheet when a weatherproof protective sheet is used on the side opposite to the light receiving surface of the organic thin film solar cell element, it is not always necessary to transmit visible light, and may be opaque. Furthermore, since the organic semiconductor element (B) is often heated by receiving light, it is preferable that the weatherproof protective sheet also has heat resistance. From this viewpoint, the melting point of the constituent material of the weatherproof protective sheet is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably. Is 300 ° C. or lower. By increasing the melting point, it is possible to reduce the possibility that the weatherproof protective sheet is melted and deteriorated when the organic semiconductor element (B) is used.
- the material constituting the weatherproof protective sheet is arbitrary as long as it can protect the organic electronic device.
- the material include polyethylene resin, polypropylene resin, cyclic polyolefin resin, AS (acrylonitrile-styrene) resin, ABS (acrylonitrile-butadiene-styrene) resin, polyvinyl chloride resin, fluorine resin, polyethylene terephthalate, polyethylene
- polyester resins such as naphthalate, phenol resins, polyacrylic resins, polyamide resins such as various nylons, polyimide resins, polyamide-imide resins, polyurethane resins, cellulose resins, silicone resins, and polycarbonate resins.
- fluorine resin is preferable, and specific examples thereof include polytetrafluoroethylene (PTFE), 4-fluoroethylene-perchloroalkoxy copolymer (PFA), 4-fluoroethylene-6-fluoride.
- PTFE polytetrafluoroethylene
- PFA 4-fluoroethylene-perchloroalkoxy copolymer
- FEP Propylene copolymer
- ETFE 2-ethylene-4-fluoroethylene copolymer
- PCTFE poly-3-fluoroethylene chloride
- PVDF polyvinylidene fluoride
- PVF polyvinyl fluoride
- the weather-resistant protective sheet may be formed of one type of material, or may be formed of two or more types of materials.
- the weather-resistant protective sheet may be formed of a single layer film, but may be a laminated film including two or more layers.
- the thickness of the weatherproof protective sheet is not particularly defined, but is usually 10 ⁇ m or more, preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more, and usually 200 ⁇ m or less, preferably 180 ⁇ m or less, more preferably 150 ⁇ m or less. Increasing the thickness tends to increase mechanical strength, and decreasing the thickness tends to increase flexibility. For this reason, it is desirable to set it as the said range as a range which has both advantages.
- a solar cell since it is exposed to strong ultraviolet rays from sunlight, it preferably has an ultraviolet blocking function.
- a layer having a function may be laminated on a weather-resistant protective sheet by coating film formation or the like, or a material that exhibits a function is dissolved and dispersed in the weather-resistant protective sheet. You may make it contain.
- the back surface protective sheet is the same sheet and film as the above-described weather resistant protective sheet, and the same material as the weather resistant protective sheet can be used in the same manner except that the arrangement position is different. Moreover, if this back surface protection sheet cannot permeate
- the constituent member on the back side of the solar cell element does not necessarily need to transmit visible light
- a member that does not transmit visible light can be used.
- the following examples are mentioned as a back surface protection sheet.
- the back surface protective sheet various resin films and sheets having excellent strength, weather resistance, heat resistance, water resistance, and light resistance can be used.
- polyethylene resin polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine Resins, poly (meth) acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate or polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, polyamideimide resins, polyaryl phthalate resins Sheet of various resins such as silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin, etc.
- AS resin acrylonitrile-styrene copolymer
- ABS resin acrylonitrile-butadiene-styrene copolymer
- polytetrafluoroethylene PTFE
- PVDF polyvinylidene fluoride
- PVF polyvinyl fluoride
- ETFE propylene copolymer
- a sheet of polyolefin resin polycarbonate resin, poly (meth) acrylic resin, polyamide resin, or polyester resin.
- these may use 1 type and may use 2 or more types together by arbitrary combinations and ratios.
- a metal material can also be used as the back surface protection sheet.
- aluminum foil and a board, a stainless steel thin film, a steel plate, etc. are mentioned.
- Such a metal material is preferably subjected to corrosion prevention.
- 1 type may be used and 2 or more types may be used together by arbitrary combinations and ratios.
- a composite material of resin and metal can be used.
- a highly waterproof sheet in which a fluorine resin film is bonded to both surfaces of an aluminum foil may be used.
- fluorine resin examples include ethylene monofluoride (trade name: Tedlar, manufactured by DuPont), polytetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene and ethylene or propylene (ETFE), and a vinylidene fluoride resin. (PVDF), vinyl fluoride resin (PVF) and the like.
- PTFE polytetrafluoroethylene
- ETFE ethylene or propylene
- VDF vinylidene fluoride resin
- PVDF vinyl fluoride resin
- 1 type may be used for fluororesin and it may use 2 or more types together by arbitrary combinations and a ratio.
- a gas barrier layer by an inorganic oxide vapor deposition layer.
- a film thickness of a back surface protection sheet it is 20 micrometers or more normally, Preferably it is 50 micrometers or more, More preferably, it is 100 micrometers or more. Moreover, it is 1000 micrometers or less normally, Preferably it is 500 micrometers or less, More preferably, it is 300 micrometers or less.
- Organic electronic device manufacturing method (device forming step)>
- a substrate (A), an organic semiconductor element (B), a layer (C) containing a scavenger that absorbs at least one of moisture and oxygen, and a gas barrier film (D) covering the organic semiconductor element were sequentially laminated.
- the organic semiconductor element (B) is manufactured to include at least a pair of electrodes, and includes an electrode on the side opposite to the substrate and a layer (C) that absorbs at least one of moisture and oxygen. 1) or a plurality of anticorrosion layers (E).
- Step 1 An organic semiconductor element (B) in which one or two or more organic semiconductor elements (B) are connected in series or in parallel to the substrate (A) is provided.
- Step 2 A scavenger that absorbs at least one of moisture and oxygen.
- Step 3 Producing a laminate in which one or more anticorrosion layers (E) are laminated on the layer (C) containing Into the organic semiconductor element (B) on the substrate (A) produced in Step 1, The layered product of the produced scavenger (C) and the anticorrosion layer (E), and the gas barrier film (D) are at least the substrate (A), the organic semiconductor element (B), the anticorrosion layer (E), and the scavenger. Laminate so as to be in the order of the layer (C) containing gas and the gas barrier film (D).
- Step 1 An organic semiconductor element (B) in which one or two or more organic semiconductor elements (B) are connected in series or in parallel is provided on a substrate (A).
- Step 2 ′ A laminate in which a gas barrier film (D), a layer (C) containing a scavenger that absorbs at least one of moisture and oxygen, and one or more anticorrosive layers (E) are laminated is produced.
- Step 3 ′ Lamination of the gas barrier film (D) manufactured in Step 2 ′, the layer (C) containing the scavenger and the anticorrosion layer (E) on the organic semiconductor element (B) on the substrate (A) manufactured in Step 1
- the body is laminated so that at least the substrate (A), the organic semiconductor element (B), the anticorrosion layer (E), the layer containing the scavenger (C), and the gas barrier film (D) are in this order.
- the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen has a function of protecting the organic semiconductor element by absorbing the water vapor and the like faster than the organic semiconductor element absorbs the water vapor and the like. However, if it touches the outside air, it absorbs the water vapor and the like, so that the absorption ability is lowered and the above function may not be performed.
- FIGS. 3 is a cross-sectional view
- FIG. 4 is a top view.
- the gas barrier film (D) and the resin layer (F) are arranged directly or via an intermediate layer so that the resin layer (F) does not come into contact with the outside air. That is, in order to prevent the resin layer (F) from coming into contact with the outside air, the resin layer (F) is not exposed to the end face of the organic electronic device.
- the resin layer (F) is composed of the anticorrosion layer (E) 5.
- the organic electronic device according to the present invention has a gas barrier film (outside of the resin layer (F) composed of the anticorrosive layer (E) 5 on the end surface of the organic electronic device due to its structure.
- D) 7 is arranged.
- the substrate (A) 1 and the gas barrier film (D) 7 are bonded directly or via an intermediate layer.
- the resin layer (F) reaches the bonding surface (that is, the end of the organic electronic device) where the substrate (A) 1 and the gas barrier film (D) 7 are bonded directly or via an intermediate layer, the resin The layer (F) will be exposed to the outside.
- the substrate (A) 1 and the gas barrier film (D) 7 are interposed through the resin layer (F) composed of the anticorrosion layer (E) 5 and the layer (C) 6 containing the scavenger.
- the resin layer (F) composed of the anticorrosion layer (E) 5 and the layer (C) 6 containing the scavenger.
- a gas barrier layer such as a back protective sheet (not shown) on the organic semiconductor element side of the gas barrier film (D) 7 and prevent the resin layer (F) from being exposed to the outside without reaching the end face of the organic electronic device.
- a layer (C) 6 containing a scavenger is formed on a gas barrier film (D) 7 on which a gas barrier layer such as a back protective sheet (not shown) is formed, and this scavenger.
- the resin layer (F) composed of the anticorrosion layer (E) 5 is disposed so as to cover the layer (C) 6 containing the resin, but the resin layer (F) is exposed to the outside without reaching the end face of the organic electronic device. It is bonded to the gas barrier film (D) 7 through the sealing material 8 so as not to be exposed.
- the above layers may be bonded directly or through an intermediate layer.
- direct bonding for example, after applying a photocurable resin, the layers are bonded, cured by applying UV light, and then cured by heating, for example, at about 80 ° C. for about 20 minutes, or a thermosetting resin is used. After coating, the respective layers are adhered, and for example, a method of curing by heating at around 120 ° C. for about 1 hour can be mentioned.
- Step I An organic semiconductor element (B) in which one or two or more organic semiconductor elements (B) are connected in series or in parallel is provided on a substrate (A).
- Step II A laminate (hereinafter referred to as resin) in which a resin layer (F), more preferably a single layer or a plurality of anticorrosive layers (E) is laminated on a layer (C) containing a scavenger that absorbs at least one of moisture and oxygen. Layer (F)).
- Step III A layered body of the layer (C) and the resin layer (F) containing the scavenger produced in Step II and the gas barrier film (D) on the organic semiconductor element (B) on the substrate (A) produced in Step I
- the layers are laminated in the order of at least the substrate (A), the organic semiconductor element (B), the resin layer (F), the layer (C) containing the scavenger, and the gas barrier film (D).
- Step I An organic semiconductor element (B) in which one or two or more organic semiconductor elements (B) are connected in series or in parallel is provided on a substrate (A).
- Step II ′ Gas barrier film (D), layer (C) containing a trapping agent that absorbs at least one of moisture and oxygen, and a laminate obtained by laminating a resin layer (F) are manufactured
- Step III ′ a substrate manufactured in Step I (A) A laminate of the gas barrier film (D) produced in Step II ′, the layer (C) containing the scavenger and the resin layer (F) is formed on at least the substrate (A) and the organic semiconductor element (B). It laminates
- the above-described sealing material, weather-resistant protective sheet, and back surface protective sheet are manufactured in the above-described step 1 after manufacturing a laminated body that is previously laminated on the substrate (A) and / or the gas barrier film (D).
- the order of the other layers is not particularly limited, but as a preferred order, when the substrate (A) side is a light-receiving surface, a weatherproof protective sheet, a gas barrier film, a sealing material, a substrate (A), an organic semiconductor Device (B), layer (C) containing a scavenger that absorbs at least one of moisture and oxygen, gas barrier film (D), sealing material, back surface protective sheet in this order; weatherproof protective sheet, sealing material, gas barrier film , Substrate (A), organic semiconductor element (B), layer (C) containing a scavenger that absorbs at least one of moisture and oxygen, gas barrier film (D), sealing material, and back surface protective sheet.
- the gas barrier film (D) is a light-receiving surface, a back protective sheet, a sealing material, a substrate (A), an organic semiconductor element (B), a layer (C) containing a trapping agent that absorbs at least one of moisture and oxygen, It becomes order of a gas barrier film (D), a sealing material, and a weather-resistant protective sheet.
- a plurality of the above layers may be appropriately stacked as necessary, or may be omitted, and other functional layers may be inserted.
- the laminating method is not particularly limited as long as the effects of the present invention are not impaired.
- a vacuum laminator by laminating with an adhesive heat sealing by melt bonding, extrusion laminating, coextrusion molding, wet film forming method for coating film formation, etc.
- Laminating by an adhesive, laminating by an adhesive, a heat sealing method by heating or a heating press, and a wet film forming method by coating by a coater Among these, a laminate using a photo-curing adhesive having a proven record in organic EL device sealing and a laminating method using a vacuum laminator having a proven record in a solar cell are preferable in that general-purpose equipment can be used.
- the gas barrier film (D) and the substrate (A) are combined with the sealant, and when there are a plurality of gas barrier films, the gas barrier film and the gas barrier film, the gas barrier film (D) and the back surface protective sheet, and the substrate (A) and the weather resistance.
- the edge part of any 1 type, multiple sets, or all layers of a protective sheet, a weatherproof protective sheet, and a back surface protective sheet is illustrated. From the viewpoint of emphasizing the maintenance of gas barrier properties, gas barrier films and substrates, and edge seals between gas barrier films and gas barrier films are preferable. From the viewpoint of increasing the strength of the entire device, a weatherproof protective sheet, a back surface protective sheet, and all layers are preferable.
- the step of sealing the edge with a sealing agent can be appropriately selected depending on the layer to be bonded, the type of the sealing agent, and the like.
- the organic electronic device constituent layer may be sealed after lamination, or may be sealed simultaneously when the constituent layers are laminated. In order to simplify the manufacturing process, it is preferable to seal simultaneously at the time of lamination.
- ⁇ Method for manufacturing organic electronic devices in mass production> In order to efficiently manufacture an organic electronic device, as shown in a sectional view in FIG. 6 and a plan view in FIG. 7, a large number of organic semiconductor elements (B) 20 are formed on a substrate (A) 1 having a large area.
- the method of laminating and cutting the organic electronic devices laminated in the layer structure of the present invention one by one is very effective in terms of time, work and cost. Since each member is the same as the organic electronic device shown in FIGS. 3 and 4, the description is omitted here, but the same members are denoted by the same reference numerals.
- an organic device having a large area is manufactured at one time and then divided into necessary sizes according to the application.
- a voltage necessary for the purpose is obtained as an electronic device in which cells of an appropriate size are connected in series.
- Productivity improves more by dividing
- the layer (C) 6 containing a scavenger that absorbs at least one of moisture and oxygen is divided into appropriate sizes in advance.
- the boundary and edges are directly bonded with the gas barrier film (D) 7 and the anticorrosion layer (E) 5, thereby simplifying the assembly process and making the work more robust. Therefore, the organic device sheet produced in a large area can be cut and divided into individual cells in a normal atmosphere in which oxygen and water vapor are present.
- the cutting process tends to increase the size of the device, the generation of chips, and workability, it is costly and disadvantageous to build a manufacturing process in an environment where oxygen and water vapor are blocked.
- the fact that the cutting process can be performed in a normal atmosphere is very advantageous as an industrial process. Furthermore, since it can be stored and transported in the normal atmosphere at the stage of the large sheet before cutting, it can be stored in large quantities in the state of the large sheet device, or cut at once in a convenient place after transportation. The merit that can be done is also great.
- the organic electronic device of this invention can be mass-produced more efficiently by further adding the following conditions to the said manufacturing method (described in the manufacturing method of an organic electronic device).
- at least two or more organic semiconductor elements (B) are arranged on the substrate (A) at intervals, and the resin layer (F) is disposed on at least two or more organic semiconductor elements (B).
- a layer (C) containing a scavenger that absorbs at least one of two or more moisture and oxygen is arranged on the resin layer (F) with a space therebetween, and a gas barrier film ( D) is laminated, and cut so as to include the organic semiconductor element (B) and a layer (C) containing a scavenger that absorbs at least one of moisture and oxygen.
- the part to be cut is a part where at least the substrate (A) and the gas barrier film (D) are bonded directly or via an intermediate layer. More preferably, it is a portion where at least the substrate (A), the gas barrier film (D), and the resin layer (F) are laminated. More preferably, the intermediate layer is a layer containing a sealing material. Among them, as shown in FIGS. 4 and 5, a sealing material 8 is formed in advance at a cutting portion, and cutting is performed between the sealing materials 8. To do.
- the manufacturing method of the present invention cuts the organic semiconductor element (B) and the layer (C) containing the trapping agent that absorbs at least one of moisture and oxygen so as not to be in direct contact with each other without being exposed to the outside air.
- This is a preferable means of the production method in the present invention.
- a plurality of organic semiconductor elements arranged on a substrate are cut into individual elements, not in a dry nitrogen atmosphere, but in a normal atmosphere, there is a problem in efficiency and life of the element It is suitable for manufacturing. Inserting a cutting device in a dry nitrogen atmosphere or performing internal cutting treatment tends to increase the cost of holding the dry nitrogen atmosphere or generate dust and oil droplets, leading to an increase in cost and undesirable. .
- the peripheral edge sealing material of the organic semiconductor element after being cut into individual elements is usually 0.5 to 100 mm, preferably 1 to 80 mm, more preferably 2 to 50 mm in width at the peripheral edge of the substrate after cutting. Most preferably, the width is 3 to 10 mm, and the organic semiconductor element after cutting is arranged so as to be inside the square-shaped peripheral edge sealing material.
- the thickness of the sealing material is usually 5 ⁇ m to 1 mm, preferably 10 ⁇ m to 100 ⁇ m, more preferably 20 to 50 ⁇ m, and the organic semiconductor element (B) is disposed so as to be inside the square shape.
- Thickness and width are necessary to fill the unevenness of the substrate and the film and sheet, and to sufficiently protect the interior from water vapor and oxygen, but if the width is too wide, the effective area will decrease, The above range is appropriate because the permeation amount of water vapor and oxygen increases.
- FIGS. 1-10 One specific embodiment is shown in FIGS.
- the organic electronic device according to the present invention is characterized by the following performance.
- performance can be evaluated by performing the following acceleration test and comparing changes in photoelectric conversion characteristics before and after the test.
- Evaluation method The acceleration test is installed in a high-temperature and high-humidity environment in an environmental tester (for example, SH-241 manufactured by Espec Corp.).
- the high temperature and high humidity environment is preferably 40 ° C. 90% RH or 85 ° C. 85% RH.
- the test period can be appropriately selected depending on the device constituent material, but it is preferable to carry out the test for 24 hours or more.
- the current / voltage characteristics are measured by irradiating the organic thin-film solar cell with AM1.5G light with an irradiation intensity of 100 mW / cm 2 using a solar simulator. From the current / voltage curve obtained from such measurement, energy conversion efficiency (PCE), short-circuit current, open-circuit voltage, FF (fill factor), series resistance, and shunt resistance can be obtained.
- PCE energy conversion efficiency
- FF fill factor
- series resistance series resistance
- shunt resistance series resistance
- PCE change rate (PCE after the acceleration test) / (PCE before the acceleration test)
- PCE change rate (PCE after the acceleration test) / (PCE before the acceleration test)
- PCE change rate of the organic electronic device according to the present invention is usually 0.86 or more after the acceleration test with respect to the initial performance, as defined by the above formula, 0.88 or more, more preferably 0.90 or more.
- the organic electronic device according to the present invention does not contact the element electrode with the layer (C) containing the trapping agent even when a load is applied, and has a high performance of preventing deterioration.
- As evaluation what is necessary is just to confirm the presence or absence of a contact, when pressing the layer (C) containing a capture agent from the gas barrier film side to an organic-semiconductor element (B) direction.
- the organic electronic device according to the present invention has good weather resistance. Even if a weather resistance test is performed using an outdoor exposure test or a weather resistance tester, the performance is maintained and high durability performance is exhibited. It is thought that electrode deterioration is suppressed by the presence of the anticorrosion layer. Moreover, when a weather-resistant protective sheet is laminated
- the water vapor transmission rate in a 40 degreeC 90% environment is obtained by the measurement by the apparatus provided with the moisture sensitive sensor according to JISK7129, an infrared sensor, and a gas chromatograph, and a cup method (JIS Z0208).
- the measurement is preferably performed by the MOCON method according to JIS K7129B with higher accuracy, and the measurement is performed using a water vapor transmission rate measuring device PERMATRAN-W manufactured by MOCON.
- As a specific apparatus there is a tensile tester manufactured by Orientec. -Moisture-absorbing ability of scavenger The scavenger was left in an environment of 20 ° C and 65% RH for 15 minutes, and calculated from the weight change before and after the test.
- Example 1 ⁇ Process for producing organic thin film solar cell element> An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate (sheet resistance of 15 ⁇ / ⁇ or less) is patterned into a 2 mm wide stripe using normal photolithography and hydrochloric acid etching. A transparent electrode was formed. The patterned transparent electrode was cleaned in the order of ultrasonic cleaning with a surfactant, water with ultrapure water, and ultrasonic cleaning with ultrapure water, then blown with nitrogen, and dried by heating at 120 ° C. for 10 minutes.
- ITO indium tin oxide
- PEDOT poly (styrenesulfonic acid)
- the substrate was heat-treated at 180 ° C. for 3 minutes in a nitrogen atmosphere.
- a solution prepared by dissolving 0.5% by weight of the following compound (A) in a 1: 2 mixed solvent (weight) of chloroform / chlorobenzene was filtered, spin-coated on the PEDOT: PSS film at 1500 rpm, and then at 180 ° C. for 20 minutes.
- the film of the following compound (B) was obtained by heating.
- a solution obtained by dissolving 0.6% by weight of a compound (A), which is a porphyrin compound, in a 1: 1 mixed solvent (weight) of chloroform / chlorobenzene, and PCBNB (the following compound (C)) manufactured by Frontier Carbon Co., which is a fullerene derivative, are 1 Prepare a 4% by weight solution, mix it at a weight ratio of 1: 1, filter, spin-coat onto the above-mentioned porphyrin compound (B) film at 1500 rpm, and heat at 180 ° C. for 20 minutes A mixed film of (B) and (C) was obtained.
- a solution obtained by dissolving 1.2% by weight of compound (C) in toluene is filtered, spin-coated on the compound (B) and (C) mixed film at 3000 rpm, heated at 65 ° C. for 10 minutes, and compound (C) Film was obtained.
- the substrate on which the series of organic layers was formed was placed in a vacuum deposition apparatus in close contact with a shadow mask having a width of 2 mm so as to be orthogonal to the transparent electrode stripe.
- lithium fluoride (LiF) was vapor-deposited on the organic layer at a vapor deposition rate of about 0.01 nm / second to a film thickness of 0.5 nm.
- the adhesive sheet and the film function as the anticorrosion layer (E) by being present between the metal electrode 4 of the organic semiconductor element and the layer (C) containing the scavenger.
- a double-sided tape (J-7702, manufactured by Soken Chemical Co., Ltd., 200 ⁇ m thick) cut out in a square shape as a sealing material was attached to the periphery of the glass substrate so that the element was inside the square shape.
- a water vapor permeability of 10 ⁇ 2 g / m 2 / day gas barrier film (Tech Barrier manufactured by Mitsubishi Plastics Co., Ltd.) is applied so as to cover the entire surface of the element obtained by laminating the getter sheet and the film and the double-sided tape. The element was sealed.
- the organic thin-film solar cell element provided on the substrate is sealed with the barrier film (D) 7 on the top surface and the sealing material of the double-sided tape on the periphery, and the organic semiconductor element (B) 20,
- An organic thin film solar cell device having a structure in which an anticorrosion layer (E) 5 made of an adhesive sheet and a layer (C) 6 containing a scavenger were sequentially laminated was obtained. This organic thin film solar cell device is shown in FIG.
- ⁇ Device formation process> For sealing, the same getter sheet, gas barrier film 7 and double-sided tape as in Example 1 are used. The getter sheet was adhered to the gas barrier film on the adhesive sheet surface. In the same manner as in Example 1, a double-sided tape cut out in a square shape was applied to the peripheral edge of the substrate, and a gas barrier film to which a getter sheet was adhered was attached so as to cover the entire surface of the device and the double-sided tape, thereby sealing the device. It was.
- the layer (C) 6 containing the scavenger is pressed by the gas barrier film (D) 7, and the metal of the organic semiconductor element (B) 20 constituting the organic thin film solar cell element Direct contact was made with the electrode 4. That is, the organic thin film solar cell element provided on the substrate (A) 1 is sealed with the gas barrier film (D) 7 and the sealing material 8 of the double-sided tape on the periphery, but the organic semiconductor element (B) 20 is captured.
- An organic thin-film solar cell having a structure in which the anticorrosion layer (E) 5 laminated in the order of the layer (C) 6 containing the agent and the adhesive sheet 9 does not exist was obtained. This organic thin film solar cell device is shown in FIG.
- the organic thin film solar cells produced in Examples and Comparative Examples were evaluated as follows. Each of the produced organic thin-film solar cells was subjected to an acceleration test, and the change in photoelectric conversion characteristics before and after the test was compared. The acceleration test was carried out for 24 hours in a 40 ° C. 90% RH environment using a small environmental tester (Espec SH-241).
- Espec SH-241 a small environmental tester
- an organic thin-film solar cell is irradiated with light of an AM1.5G condition with a solar simulator (manufactured by Spectrometer Co., Ltd.) with an irradiation intensity of 100 mW / cm 2 , and energy conversion is performed from the obtained current / voltage curve. Efficiency (PCE) was determined.
- PCE change rate (PCE after acceleration test) / (PCE before acceleration test)
- Example 1 As shown in Table 1, the PCE change rate of Example 1 was small compared to Comparative Example 1, and it was revealed that the organic thin-film solar cell was an excellent organic thin film with little deterioration by the acceleration test. The presence of the anticorrosion layer between the metal electrode and the getter layer is considered to exhibit the effect of suppressing the deterioration of the metal electrode. Moreover, when the organic thin film solar cell which progressed deterioration was observed visually, the location which contacted the getter layer of the metal electrode of the comparative example 1 deteriorated with the alkali, and became transparent.
- Comparative Example 3 In Comparative Example 1, an EVA film (water vapor permeability is 30%) having a VA content of 30 ⁇ m between the layer (C) containing a scavenger that absorbs at least one of moisture and oxygen and the organic thin film solar cell element. 20 g / m 2 / day) was inserted as a filler, assembled into an organic thin film solar cell device, heated at 120 ° C. for about 10 minutes, and adhered to the electrode of the organic thin film solar cell element. The gas and low molecular weight components volatilized from the EVA film permeated through the pinholes of the electrode and damaged the interface with the organic thin film solar cell and the electrode, and the PCE change rate was 0.30. The results are shown in Table 1.
- Example 2 ⁇ Process for producing organic thin film solar cell element> An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate (sheet resistance of 15 ⁇ / ⁇ or less) is patterned into a 2 mm wide stripe using normal photolithography and hydrochloric acid etching. A transparent electrode was formed. The patterned transparent electrode was cleaned in the order of ultrasonic cleaning with a surfactant, water with ultrapure water, and ultrasonic cleaning with ultrapure water, then blown with nitrogen, and dried by heating at 120 ° C. for 10 minutes.
- ITO indium tin oxide
- PEDOT-PSS poly (ethylenedioxythiophene) -poly (styrene sulfonic acid)
- an organic semiconductor layer having a thickness of about 100 nm (the remaining portion of the photoelectric conversion portion) is formed into holes. Formed on the transport layer.
- the organic semiconductor coating solution actually used is a toluene solution of polythiophene (P3HT; poly-3-hexylthiophene) and an indene-added fullerene derivative.
- an aluminum film having a thickness of 80 nm as an upper electrode layer was formed on the organic semiconductor layer by a vapor deposition method.
- the device formation step was performed in the same manner as in Example 1 except that a polypropylene film (Pyrene P2002, 50 ⁇ m thickness, manufactured by Toyobo Co., Ltd.) was used as the anticorrosion layer (E).
- a polypropylene film Polypropylene film (Pyrene P2002, 50 ⁇ m thickness, manufactured by Toyobo Co., Ltd.) was used as the anticorrosion layer (E).
- the organic thin-film solar cell element provided on the substrate is sealed with the sealing material of the barrier film (D) on the upper surface and the double-sided tape on the periphery, and the organic semiconductor element (B), polypropylene film
- An organic thin film solar cell device having a structure in which an anticorrosion layer (E) composed of the above and a layer (C) containing a scavenger were laminated in this order was obtained.
- the layer (C) containing the scavenger was pressed by the gas barrier film (D) and was in direct contact with the metal electrode of the organic thin film solar cell element.
- the organic thin-film solar cell element provided on the substrate is sealed with the gas barrier film (D) and the sealing material of the double-sided tape on the periphery, but the organic semiconductor element (B) and the layer containing the scavenger (C)
- an organic thin film solar cell having a structure in which the anticorrosion layer (E) laminated in the order of the adhesive sheets does not exist was obtained.
- Example 3 ⁇ Process for producing organic thin film solar cell element> An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate (sheet resistance of 15 ⁇ / ⁇ or less) is patterned into a 2 mm wide stripe using normal photolithography and hydrochloric acid etching. A transparent electrode was formed. The patterned transparent electrode was cleaned in the order of ultrasonic cleaning with a surfactant, water with ultrapure water, and ultrasonic cleaning with ultrapure water, then blown with nitrogen, and dried by heating at 120 ° C. for 10 minutes.
- ITO indium tin oxide
- PEDOT poly (styrenesulfonic acid)
- the substrate was heat-treated at 180 ° C. for 3 minutes in a nitrogen atmosphere.
- a solution of 0.5% by weight of the compound (A) dissolved in a 1: 2 mixed solvent (weight) of chloroform / chlorobenzene was filtered, spin-coated on the PEDOT: PSS film at 1500 rpm, and then at 180 ° C. for 20 minutes.
- the film of the compound (B) was obtained by heating.
- a solution obtained by dissolving 0.6% by weight of a compound (A), which is a porphyrin compound, in a 1: 1 mixed solvent (weight) of chloroform / chlorobenzene, and PCBNB (the above compound (C)) manufactured by Frontier Carbon Co., which is a fullerene derivative, are 1 Prepare a 4% by weight solution, mix it at a weight ratio of 1: 1, filter, spin-coat onto the above-mentioned porphyrin compound (B) film at 1500 rpm, and heat at 180 ° C. for 20 minutes A mixed film of (B) and (C) was obtained.
- a solution obtained by dissolving 1.2% by weight of compound (C) in toluene is filtered, spin-coated on the compound (B) and (C) mixed film at 3000 rpm, heated at 65 ° C. for 10 minutes, and compound (C) Film was obtained.
- the substrate on which the series of organic layers was formed was placed in a vacuum deposition apparatus in close contact with a shadow mask having a width of 2 mm so as to be orthogonal to the transparent electrode stripe.
- lithium fluoride (LiF) was vapor-deposited on the organic layer at a vapor deposition rate of about 0.01 nm / second to a film thickness of 0.5 nm.
- the former film functions as a gas barrier film (D)
- the latter film functions as an anticorrosion layer (E).
- the edges of the gas barrier film (D) and the anticorrosion layer (E) film were bonded with a sealing material.
- the adhesive line width of the sealing material was 3 mm, and the adhesive thickness was 20 ⁇ m.
- laminate (I) The laminate produced so far is also referred to as laminate (I) below
- a double-sided tape J-7702, manufactured by Soken Chemical Co., Ltd., 200 ⁇ m thickness
- FIGS. The structure of this organic thin film solar cell device is shown in FIGS.
- the organic semiconductor element (B) 20 that is an organic thin-film solar cell element provided on the substrate (A) 1 is formed by the barrier film (D) 7 on the upper surface and the sealing material 8 of the double-sided tape on the periphery.
- FIG. 4 is a top view of the device of FIG.
- Example 4 In Example 1, the laminate (I) was taken out of the glove box and left in the atmosphere at 25 ° C. and 60% for about 30 minutes. Then, it returned to the glove box again, and produced an organic thin film solar cell device in the same manner as in Example 1 except that. That is, after the laminated film having the structure of the laminated body (I) is manufactured, it can be stored in the air for a short time, and is moved from the storage place in the nitrogen atmosphere to the glove box through the air. It is possible. This can be considered to have a great merit when considering the ease of handling of the laminated film and the robustness of the manufacturing process in the manufacturing process of the organic semiconductor device.
- Example 5 Device formation was performed in the same manner as in Example 4 except for the following description in the device formation step. Thereafter, the work was performed in a glove box purged with dry nitrogen.
- a getter sheet (HD-S07 manufactured by Dynic Co., Ltd.) having a structure in which a layer (C) containing a scavenger and an adhesive sheet are laminated is sandwiched between different grades of Tech Barrier manufactured by KK.
- the former film functions as a gas barrier film (D)
- the latter film functions as an anticorrosion layer (E).
- the sealing material adhered by the sealing material so that the edge part of an anticorrosion layer (E) film might be arrange
- the adhesive line width of the sealing material was 3 mm, and the adhesive thickness was 20 ⁇ m.
- Example 6 Four thin-film solar cell elements as an organic semiconductor element (B) 20 of 2 mm ⁇ 2 mm manufactured in the same manner as described in Example 3 were arranged as shown in FIGS. 6 and 7 with an interval of 8 mm. . Each organic thin film solar cell element was sealed in the same manner as the edge of Example 3. At that time, the sealing material was applied and arranged so that the sealing material 8 and the organic thin film solar cell element were not in contact with each other.
- the structure of this organic solar cell device is shown in FIG.
- FIG. 7 is a view of the device of FIG. 6 as viewed from above. About each member, the same member as the member demonstrated in FIG. 1 thru
- the organic solar cell device of Example 5 was taken out of the glove box and cut into four pieces in the atmosphere of 25 ° C. and 60%. Cutting was performed by cutting the film portion with a cutter and then breaking the glass with a scratch. The cut surface 10 is indicated by a dotted line in FIGS.
- the organic thin film solar cells produced in the examples were evaluated for performance as follows. Each of the produced organic thin-film solar cells was subjected to an acceleration test, and the change in photoelectric conversion characteristics before and after the test was compared. The acceleration test was carried out for 24 hours in a 40 ° C. 90% RH environment using a small environmental tester (Espec SH-241).
- an organic thin-film solar cell is irradiated with light of an AM1.5G condition with a solar simulator (manufactured by Spectrometer Co., Ltd.) with an irradiation intensity of 100 mW / cm 2 , and energy conversion is performed from the obtained current / voltage curve.
- Efficiency (PCE) was determined.
- Table 2 shows the performance evaluation results of the examples.
- Example 3-6 As shown in Table 2, the PCE change rate of Example 3-6 was almost the same, and it was clarified that the organic thin-film solar cell was excellent with little deterioration by the acceleration test.
- the layered sheet (C) containing the scavenger is sandwiched between the gas barrier film (D) and the anticorrosive layer (E), and sealed and shielded from the outside air, so that the laminated sheet in this state is exposed to the atmosphere for a short time in the manufacturing process.
- Examples 5 and 6 considered that the deterioration of the scavenger was suppressed, one by one in the atmosphere No performance degradation was observed even when the solar cell was separated.
- the use of the organic electronic device according to the present invention is not limited and is arbitrary.
- the present invention can be used for building materials.
- it is suitable, for example, for exterior materials and interior materials of buildings such as houses, shops, buildings; interior materials such as tunnels and bridges; signboards, signs and the like.
- it can be used suitably also for an image display apparatus, a planar light source, a display board, etc. regardless of indoor or outdoor.
- Substrate (A) 2. 2. Organic semiconductor layer Transparent electrode4. 4. Metal electrode Anticorrosion layer (E) 6). Layer containing scavenger (C) 7). Gas barrier film (D) 8). Sealing material9. Adhesive sheet 10. Cut surface 20.
- Organic semiconductor element (B)
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
[1] 少なくとも一対の電極を備えた有機半導体素子(B)と、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)と、ガスバリアフィルム(D)とをこの順に備えた有機電子デバイスであって、
該有機半導体素子(B)の、該一対の電極のうち少なくとも一方の電極と該水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)との間に、少なくとも一層の防食層(E)を備えており、
該防食層(E)の膜厚が20μm以上であり、
該防食層(E)およびガスバリアフィルム(D)が、次式(1)および(2)の条件を満たすことを特徴とする有機電子デバイス。
15≧Pe>Pd 式(1)
10-4≦Pd≦10-1 式(2)
上記式(1)及び式(2)中、Peは防食層(E)の40℃90%RH環境での水蒸気透過率を示し、Pdはガスバリアフィルム(D)の40℃90%RH環境での水蒸気透過率を示し、いずれも単位はg/m2/dayとする。
[2] 前記防食層(E)が0.1N/cm以上の接着機能を有する層を含むことを特徴とする上記[1]に記載の有機電子デバイス。
[3] 前記有機半導体素子(B)が、有機太陽電池素子であることを特徴とする上記[1]又は[2]に記載の有機電子デバイス。
[4] 水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)の水分吸収能力が0.1mg/cm2以上15mg/cm2以下であることを特徴とする上記[1]~[3]のいずれか1つに記載の有機電子デバイス。
[5] 前記ガスバリアフィルム(D)が、熱可塑性樹脂と、該熱可塑性樹脂上に真空蒸着されたSiOxとを含むフィルムであることを特徴とする上記[1]~[4]のいずれか1つに記載の有機電子デバイス。
[6] 基板(A)を含むことを特徴とする上記[1]~[5]のいずれか1つに記載の有機電子デバイス。
[7] 封止材及び耐候性保護シートを含むことを特徴とする上記[1]~[6]のいずれか1つに記載の有機電子デバイス。
[8] 基板(A)と、少なくとも一対の電極を備えた有機半導体素子(B)と、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)と、少なくとも一層の防食層(E)と、該有機半導体素子を被覆するガスバリアフィルム(D)とを順に積層した有機電子デバイスの製造方法であって、
該防食層(E)およびガスバリアフィルム(D)が、次式(1)および(2)の条件を満たし、
15≧Pe>Pd 式(1)
10-4≦Pd≦10-1 式(2)
上記式(1)及び式(2)中、Peは防食層(E)の40℃90%RH環境での水蒸気透過率を示し、Pdはガスバリアフィルム(D)の40℃90%RH環境での水蒸気透過率を示し、いずれも単位はg/m2/dayとする。
水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)に少なくとも一層の防食層(E)を積層した積層体層を製造するとともに、基板(A)上に有機半導体素子(B)を製造した後に、上記順に従い、積層することを特徴とする有機電子デバイスの製造方法。
[9] ガスバリアフィルム(D)、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)、少なくとも一層の防食層(E)を順に積層した積層体層を製造し、有機半導体素子(B)を基板(A)上に製造した後に、上記順に従い積層することを特徴とする上記[8]に記載の有機電子デバイスの製造方法。
[10] 基板(A)と、少なくとも一対の電極を備えた有機半導体素子(B)と、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)と、ガスバリアフィルム(D)とを、この順に備えた有機電子デバイスであって、
該有機半導体素子(B)と該水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)の間に、該有機半導体素子(B)と該層(C)が直接接触しないように樹脂層(F)を有し、該樹脂層(F)の膜厚が20μm以上であり、
該樹脂層(F)およびガスバリアフィルム(D)が、次式(1)および(2)の条件を満たし、
15≧Pe>Pd 式(1)
10-4≦Pd≦10-1 式(2)
上記式(1)及び式(2)中、Peは樹脂層(F)の40℃90%RH環境での水蒸気透過率を示し、Pdはガスバリアフィルム(D)の40℃90%RH環境での水蒸気透過率を示し、いずれも単位はg/m2/dayとする。
かつ、該素子(B)と該層(C)が外気に接しないように、該基板(A)と該ガスバリアフィルム(D)とが直接又は中間層を介して接着されていることを特徴とする有機電子デバイス。
[11] 更に該樹脂層(F)が外気に接しないように、該ガスバリアフィルム(D)と該樹脂層(F)が直接又は中間層を介して接着されていることを特徴とする上記[10]に記載の有機電子デバイス。
[12] 該中間層がシール材を含有する層であることを特徴とする上記[10]または[11]に記載の有機電子デバイス。
[13] 該樹脂層(F)が、少なくとも一層の防食層(E)を含むことを特徴とする[10]~[12]のいずれか1つに記載の有機電子デバイス。
[14] 有機半導体素子(B)が、有機太陽電池素子であることを特徴とする上記[10]~[13]のいずれか1つに記載の有機電子デバイス。
[15] 基板(A)上に、複数の有機半導体素子(B)を互いに間隔をあけて配置し、
該複数の有機半導体素子(B)上に樹脂層(F)を積層し、
該樹脂層(F)上に2つ以上の水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)を互いに間隔をあけて配置し、
該層(C)上にガスバリアフィルム(D)を積層し、
該有機半導体素子(B)と水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)を含むように前記基板(A)を切断することを特徴とする有機電子デバイスの製造方法。
[16] 切断する部分が、少なくとも基板(A)と該ガスバリアフィルム(D)が直接又は中間層を介して接着されている部分であることを特徴とする上記[15]に記載の有機電子デバイスの製造方法。
[17] 切断する部分が、少なくとも該基板(A)と該ガスバリアフィルム(D)、該樹脂層(F)が積層されている部分であることを特徴とする上記[15]または[16]に記載の有機電子デバイスの製造方法。
[18] 該中間層がシール材を含有する層であることを特徴とする上記[15]~[17]のいずれか1つに記載の有機電子デバイスの製造方法。
[19] 該樹脂層(F)が、少なくとも一層の防食層(E)を含むことを特徴とする上記[15]~[18]のいずれか1つに記載の有機電子デバイスの製造方法。
[20] 該防食層(E)およびガスバリアフィルム(D)が、次式(3)および(4)の条件を満たすことを特徴とする[19]に記載の有機電子デバイスの製造方法。
5≧Pe>Pd 式(3)
Pd≦10-1 式(4)
上記式(3)及び式(4)中、Peは防食層(E)の40℃90%RH環境での水蒸気透過率を示し、Pdはガスバリアフィルム(D)の40℃90%RH環境での水蒸気透過率を示し、いずれも単位はg/m2/dayとする。
[21] 有機半導体素子(B)が、有機太陽電池素子であることを特徴とする上記[15]~[19]のいずれか1つに記載の有機電子デバイスの製造方法。
なおここで、該樹脂層(F)を基板(A)とは逆側の有機半導体素子(B)、より具体的には電極と、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)との間に備えることで、基板(A)側を受光面とするボトム受光型の有機太陽電池などにも適用可能である。
(実施の形態1)
本発明の有機電子デバイスは、1例を図1に示すように、少なくとも一対の電極3,4と有機半導体層2とを備えた有機半導体素子(B)20と、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)6と、該有機半導体素子20を被覆するガスバリアフィルム(D)7とを順に積層した有機電子デバイスであって、該電極の少なくとも一方と該水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)6との間に、少なくとも一層の防食層(E)5を備えることを特徴とする。なおここで、有機半導体素子(B)20は基板(A)1上に形成されていてもよく、また、ガスバリアフィルム(D)を基板として用いてもよい。ここで有機半導体素子(B)は、有機半導体層2を透明電極3と金属電極4との間に配して構成されており、太陽電池素子の場合は、光電変換により有機半導体層2内で生成された電子を、透明電極3と金属電極4から、電力として取り出すように構成されている。
そして、該防食層(E)の膜厚が20μm以上であり、
該防食層(E)およびガスバリアフィルム(D)が、次式(1)および(2)の条件を満たす。
15≧Pe>Pd 式(1)
10-4≦Pd≦10-1 式(2)
上記式(1)及び式(2)中、Peは防食層(E)の40℃90%RH環境での水蒸気透過率を示し、Pdはガスバリアフィルム(D)の40℃90%RH環境での水蒸気透過率を示し、いずれも単位はg/m2/dayとする。
また、本発明の有機電子デバイスは、1例を図3及び図4に示すように、少なくとも基板(A)1、有機半導体素子(B)20、水分及び/又は酸素を吸収する捕捉剤を含む層(C)6、ガスバリアフィルム(D)7を順に積層した有機電子デバイスであって、該有機半導体素子(B)と該水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)6の間に、該有機半導体素子(B)と該層(C)6が直接接触しないように樹脂層(F)を有し、かつ、該有機半導体素子(B)と該層(C)6が外気に接しないように、該基板(A)1と該ガスバリアフィルム(D)7とが直接又は防食層(E)5などの中間層を介して接着されている。
そして、該樹脂層(F)の膜厚が20μm以上であり、
該樹脂層(F)およびガスバリアフィルム(D)が、次式(1)および(2)の条件を満たし、
15≧Pe>Pd 式(1)
10-4≦Pd≦10-1 式(2)
上記式(1)及び式(2)中、Peは樹脂層(F)の40℃90%RH環境での水蒸気透過率を示し、Pdはガスバリアフィルム(D)の40℃90%RH環境での水蒸気透過率を示し、いずれも単位はg/m2/dayとする。
かつ、該素子(B)と該層(C)が外気に接しないように、該基板(A)と該ガスバリアフィルム(D)とが直接又は中間層を介して接着されている。
また、本発明の有機電子デバイスは、1例を図5に示すように、図示しない裏面保護シートなどのガスバリア層の形成されたガスバリアフィルム(D)7上に、捕捉剤を含む層(C)6を形成し、この捕捉剤を含む層(C)6を覆うように防食層(E)5で構成される樹脂層(F)が配置され、樹脂層(F)はこの有機電子デバイスの端面まで達することなく外部に露出しないように、シール材8を介してガスバリアフィルム(D)7に接着されている。他の部材については前記実施の形態2と同様であるものとする。
実施の形態4は、有機電子デバイスを製造する方法であり、例えば1例を、図3及び図4に示した有機電子デバイスを製造する方法を示すものである。
すなわちこの方法は、図3及び図4に示したように、少なくとも基板(A)1、有機半導体素子(B)20、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)6、ガスバリアフィルム(D)7を順に積層した有機電子デバイスであって、該有機半導体素子(B)20と該水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)6の間に、該有機半導体素子(B)20と該層(C)6が直接接触しないように樹脂層(F)を有し、かつ、該素子(B)と該層(C)6が外気に接しないように、該基板(A)1と該ガスバリアフィルム(D)7とが直接又は中間層を介して接着されていることを特徴とする有機電子デバイスを製造する方法である。
そして、この有機電子デバイスの製造方法においては、図6及び図7に示すように、基板(A)1上に、少なくとも2つ以上の有機半導体素子(B)20を互いに間隔をあけて配置し、該少なくとも2つ以上の有機半導体素子(B)20上に樹脂層(F)を積層し、該樹脂層(F)上に2つ以上の水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)6を互いに間隔をあけて配置し、該層(C)6上にガスバリアフィルム(D)7を積層し、該有機半導体素子(B)20と水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)6を含むように切断することを特徴とする。この構成においても、樹脂層(F)は、実施の形態2と同様とするのが望ましいが、膜厚および水分吸収率については、上記の要件を満たさないものについても、製造が容易であり、製造工程の簡略化をはかることは可能である。
また、本発明において、シート、フィルム及び層は、いずれもシート状及びフィルム状を意味し、本発明の機能を損なわない限り区別するものではない。
上記実施の形態1乃至4において、同一部材には同一符号を付し、説明は省略した。
<基板(A)>
基板(A)は有機半導体素子(B)を支持する支持部材である。基板(A)を形成する材料としては、例えば、ガラス、サファイア、チタニア等の無機材料;ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリエーテルスルホン、ポリイミド、ナイロン、ポリスチレン、ポリビニルアルコール、エチレンビニルアルコール共重合体、フッ素樹脂フィルム、塩化ビニル、ポリエチレン、ポリプロピレン、環状ポリオレフィン、セルロース、アセチルセルロース、ポリ塩化ビニリデン、アラミド、ポリフェニレンスルフィド、ポリウレタン、ポリカーボネート、ポリ(メタ)アクリル樹脂、フェノール樹脂、エポキシ樹脂、ポリアリレート、ポリノルボルネン等の有機材料;ステンレス、チタン、ニッケル、銀、金、銅、アルミニウム等の金属材料;などが挙げられる。
なお、基材の材料は、1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用しても良い。また、これら有機材料に炭素繊維、ガラス繊維などの強化繊維を含ませ、機械的強度を補強させても良い。また、これら金属材料に絶縁性を付与するために表面をコートあるいはラミネートしたものなどの複合材料としてもよい。例えば、基板(A)を金属基板で構成した場合には、一部に絶縁性を付与し、一部が露呈し、金属電極として作用するように、この上層に有機半導体素子を積層し、さらにこの上層に透明電極を積層する構成も適用可能である。また、ガスバリアフィルムを基板として用いるようにしてもよい。
有機半導体素子(B)として、下記に有機薄膜太陽電池素子(本明細書では、単に太陽電池素子ともいう)について記載するが、本発明を著しく損なわない限り他の有機電子デバイスを排除するものではない。さらに、有機薄膜太陽電池素子も、以下に説明される例に限定されるものではない。
任意の有機半導体により形成できる。有機半導体は半導体特性により、p型、n型に分けられる。p型、n型は、電気伝導に寄与するのが、正孔、電子いずれであるかを示しており、材料の電子状態、ドーピング状態、トラップ状態に依存する。したがって、以下に有機半導体の例を挙げるが、p型、n型は必ずしも明確に分類できない場合があり、同一物質でp型、n型両方の特性を示すものもある。
また、n型の半導体及びp型の半導体は、それぞれ、1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用しても良い。
電極としては導電性を有する任意の材料により形成することが可能である。電極の材料の例を挙げると、白金、金、銀、アルミニウム、クロム、ニッケル、銅、チタン、マグネシウム、カルシウム、バリウム、ナトリウム等の金属あるいはそれらの合金;酸化インジウムや酸化錫等の金属酸化物、あるいはその合金(ITO);ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン等の導電性高分子;前記導電性高分子に、塩酸、硫酸、スルホン酸等の酸、FeCl3等のルイス酸、ヨウ素等のハロゲン原子、ナトリウム、カリウム等の金属原子などのドーパントを含有させたもの;金属粒子、カーボンブラック、フラーレン、カーボンナノチューブ等の導電性粒子をポリマーバインダー等のマトリクスに分散した導電性の複合材料などが挙げられる。なかでも、正孔の捕集する電極には、Au、ITO等の深い仕事関数を有する材料が好ましい。一方、電子の捕集する電極には、Alのような浅い仕事関数を有する材料が好ましい。仕事関数を最適化することにより、光吸収により生じた正孔及び電子を良好に捕集する利点がある。
なお、電極の形成方法に制限はない。例えば、真空蒸着、スパッタ等のドライプロセスにより形成することができる。また、例えば、導電性インク等を用いたウェットプロセスにより形成することもできる。この際、導電性インクとしては任意のものを使用することができ、例えば、導電性高分子、金属粒子分散液等を用いることができる。
さらに、電極は2層以上積層してもよく、表面処理により、電気特性やぬれ特性等の特性を改良してもよい。
上記の例に示した有機太陽電池素子 は、上述した有機半導体層、電極以外に、その他の層を備えてもよい。なお、その他の層を形成する位置は太陽電池素子の発電を阻害しない限り任意である。その他の層としては、バッファ層が例示される。
水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)は水分及び酸素の少なくとも一方を吸収するフィルムである。有機薄膜太陽電池素子の構成部品は前述したように水分で劣化するものがあり、また、酸素によって劣化するものもあり、これらを極力排除しなければ発電効率を維持しながら長寿命化をはかることは難しい。
ここで、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)は前記のようなガスバリアフィルム(D)とは異なり、水分及び酸素の少なくとも一方の透過を妨げるものではなく、水分及び酸素の少なくとも一方を吸収するものである。水分及び酸素の少なくとも一方を吸収するフィルムを用いることにより、ガスバリアフィルム(D)等で太陽電池素子を被覆した場合に、ガスバリアフィルム(D)及びシール材で形成される空間に僅かに浸入する水分及び酸素の少なくとも一方を、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)が捕捉して水分による太陽電池素子への影響を排除できる。
なお、水分吸収量の測定方法は、試験体の水分吸収前後での重量変化から算出する方法、試験体中の水分量を水分測定装置で測定する方法、水分を含む密閉容器に試験体を保管し、その水分減少を水分濃度計で検出する方法にて測定することができる。簡便に実施できることから、重量変化から算出する方法が好ましい。
水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)の酸素吸収能力は、積層面に対する単位面積当たり、通常0.01ml/cm2以上、好ましくは0.05ml/cm2以上、より好ましくは0.1ml/cm2以上である。この数値が高いほど酸素吸収能力が高く太陽電池素子の劣化を抑制しうる。また、上限に制限は無いが、通常20ml/cm2以下である。本発明では酸素吸収能力と酸素吸収量は同義とする。
なお、酸素吸収能力の測定方法は、酸素を含む密閉容器内に試験体を保管し、その酸素減少を酸素濃度計で検出する方法により算出される。酸素濃度減少がなくなったときの酸素濃度を記録して、試験前の密閉容器内の酸素濃度との差分を酸素吸収量とする。密閉容器内の初期酸素濃度は、試験体の酸素吸収量以上の酸素が存在し、酸素濃度計の感度に適合した濃度になるように、適宜設定すればよい。また、密閉容器内の試験体量は、吸収による酸素減少分が酸素濃度計の検出感度以上となるように、適宜仕込んでよい。
酸素を吸収する物質(脱酸素剤)として、Fe、Mn、Zn、及びこれら金属の硫酸塩・塩化物塩・硝酸塩等の無機塩等の無機系;アスコルビン酸、ヒドラジン系化合物、MXD6ナイロン、エチレン性不飽和炭化水素、シクロヘキセン基をもつポリマー等の有機系などが挙げられる。
上記水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)を構成する捕捉剤の好ましい組み合わせとしては、水分吸収する捕捉剤どうしの場合では、アルカリ土類金属CaまたはSrとアルカリ土類金属の酸化物CaOまたはSrO;アルカリ土類金属の酸化物CaOまたはSrOとアルミニウム金属錯体が水分捕捉性能の点から好ましく、水分吸収する捕捉剤と酸素吸収する捕捉剤の組合せの場合は、アルカリ土類金属の酸化物CaOまたはSrOとFe;アルカリ土類金属の酸化物CaOまたはSrOとアスコルビン酸;アルカリ土類金属の酸化物CaOまたはSrOとヒドラジン化合物;アルミニウム金属錯体とアスコルビン酸;アルミニウム金属錯体とヒドラジン化合物が水分と酸素の吸収を両立させる点から好ましい。更に、アルカリ土類金属の酸化物CaOまたはSrOとアスコルビン酸;アルカリ土類金属の酸化物CaOまたはSrOとヒドラジン化合物がより高い吸収性能を示す点から好ましい。
水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)の厚みは特に規定されないが、通常5μm以上、好ましくは10μm以上、より好ましくは15μm以上であり、また、通常500μm以下、好ましくは400μm以下、より好ましくは300μm以下である。厚みを厚くすることで機械的強度は高まる傾向にある一方、薄くすることで柔軟性が高まる傾向があり、さらにはデバイスが薄型化できるという利点がある。このため、両方の利点を兼ね備える範囲として、上記範囲とするのが望ましい。
本実施形態の一つでは、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)が有機半導体素子(B)の受光面側に設置される。また、本実施形態の他としては、必要に応じて水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)が有機半導体素子(B)の裏面側に設置される。さらに、別の本実施形態として、受光面、裏面側共に水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)が設置されている。その場合、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)が受光面、裏面ともにそれぞれ有機半導体素子(B)とガスバリアフィルム(D)との間に位置するようになっているのが好ましい。
ガスバリアフィルム(D)は水及び酸素の透過を防止するフィルムである。
有機薄膜太陽電池を含む有機半導体素子(B)は湿気及び酸素に弱い傾向があり、透明電極、金属電極、有機半導体層が水分及び酸素により劣化することがある。そこで、ガスバリアフィルム(D)で太陽電池素子を被覆することにより、太陽電池素子を水及び酸素から保護し、発電能力を高く維持することができる。
なお、本発明におけるガスバリアフィルム(D)は、以下に記載の水蒸気透過率を満たすものである。
ただし、現状の技術では透明かつフレキシブルでバリア性能が上げていくと、製造コストもそれに連動して上がることになるので、太陽電池用途に使用する場合は、製造コストの制約も大きいことから、通常は10-3g/m2/day~10-4g/m2/dayの範囲にあることが現実的に最も好ましいバリア性能となる。なお技術的に可能であれば、10-4g/m2/day以下とするのがさらに望ましいことはいうまでもない。
なお、有機電子デバイス内において、空いた空間を埋めて光学特性や機械特性を改善するため、充填材を封入する必要のある場合がある。その際、充填材層が、遊離酸、有機溶媒、水蒸気、酸素等を含む物質である場合、有機半導体素子を劣化させる恐れがある。そのような場合でも、防食層を有機半導体素子との間に配することで、有機半導体素子の劣化を防ぐことができる。
また、ガスバリアフィルム(D)は、有機電子デバイスの光入射・出射面に用いられる場合には、可視光を透過させるものが好ましい。例えば、可視光(波長360~830nm)の光の透過率は、通常75%以上、好ましくは80%以上、より好ましくは85%以上、さらに好ましくは90%以上、特に好ましくは95%以上、その中でも特に好ましくは97%以上である。例えば、有機薄膜太陽電池においては、太陽光をより多く電気エネルギーに変換する利点がある。また、有機電子デバイスの光入射・出射面とは反対の面に用いられる場合には、必ずしも可視光を透過させる必要がないため、不透明でもよい。
さらに、有機半導体デバイスは光を受けて熱せられることが多いため、ガスバリアフィルム(D)も熱に対する耐性を有することが好ましい。この観点から、ガスバリアフィルム(D)の構成材料の融点は、通常100℃以上、好ましくは120℃以上、より好ましくは130℃以上であり、また、通常350℃以下、好ましくは320℃以下、より好ましくは300℃以下である。融点を高くすることで有機半導体デバイスの使用時にガスバリアフィルム(D)が融解・劣化するのを防止することができる。
以下、ガスバリアフィルム(D)の構成について、例を挙げて説明する。
一つ目の例は、プラスチックフィルム基材に無機バリア層を配置したフィルムである。
この際、無機バリア層は、プラスチックフィルム基材の片面のみに形成してもよいし、プラスチックフィルム基材の両面に形成してもよい。両面に形成するときは、両面に形成する無機バリア層の数が、それぞれ一致していていもよく、異なっていてもよい。
ガスバリアフィルム(D)に使用されるプラスチックフィルム基材は、上記の無機バリア層及びポリマー層を保持しうるフィルムであれば特に制限はなく、ガスバリアフィルム(D)の使用目的等から適宜選択することができる。
プラスチックフィルム基材には、無機バリア層との密着性向上のため、アンカーコート剤の層(アンカーコート層)を形成してもよい。通常、アンカーコート層はアンカーコート剤を塗布して形成される。アンカーコート剤としては、例えば、ポリエステル樹脂、ウレタン樹脂、アクリル樹脂、オキサゾリン基含有樹脂、カルボジイミド基含有樹脂、エポキシ基含有樹脂、イソシアネート含有樹脂及びこれらの共重合体などが挙げられる。なお、アンカーコート剤は、1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用しても良い。
無機バリア層は通常は金属酸化物、窒化物もしくは酸化窒化物により形成される層である。なお、無機バリア層を形成する金属酸化物、窒化物及び酸化窒化物は、1種でもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
金属酸化物としては、例えば、Si、Al、Mg、In、Ni、Sn、Zn、Ti、Cu、Ce、Ta等の酸化物、窒化物もしくは酸化窒化物などが挙げられる。中でも、高いバリア性と高透明性とを両立させるために、酸化アルミニウムまたは酸化珪素を含むことが好ましく、特に水分の透過性、光線透過性の観点から、酸化珪素を含むことが好ましい。2種以上の金属酸化物より無機バリア層を構成する場合、金属酸化物としては酸化アルミニウム及び酸化珪素を含むことが望ましい。
無機バリア層の成膜方法に制限は無いが、一般的にスパッタリング法、真空蒸着法、イオンプレーティング法、プラズマCVD法などで行うことができる。例えばスパッタリング法では1種類のあるいは複数の金属ターゲットと酸素ガスを原料とし、プラズマを用いた反応性スパッタ方式で形成することができる。
ポリマー層にはいずれのポリマーでも使用することができ、例えば真空チャンバー内で成膜できるものも用いることができる。なお、ポリマー層を構成するポリマーは、1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
前記ポリマーを与える化合物としては、例えば以下のものが挙げられる。なお、モノマーは1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
ジパラキシリレン等のパラキシリレンが挙げられ、ポリパラキシリレンがポリマーとして得られる。
二種のモノマーを交互に繰り返し付加重合させることができるモノマーが挙げられる。これにより、重付加ポリマーが得られ、ポリウレタン(ジイソシアナート/グリコール)、ポリ尿素(ジイソシアナート/ジアミン)、ポリチオ尿素(ジチオイソシアナート/ジアミン)、ポリチオエーテルウレタン(ビスエチレンウレタン/ジチオール)、ポリイミン(ビスエポキシ/第一アミン)、ポリペプチドアミド(ビスアゾラクトン/ジアミン)、ポリアミド(ジオレフィン/ジアミド)などが例示される。
酢酸ビニルが挙げられる。さらに、その重合体をケン化することでポリビニルアルコールが得られる。
アクリル酸、メタクリル酸、エタクリル酸、フマル酸、マレイン酸、イタコン酸、マレイン酸モノメチル、マレイン酸モノエチル、無水マレイン酸、無水イタコン酸などの不飽和カルボン酸などが挙げられる。さらに、エチレンとの共重合体を構成させることができる。また、これらの混合物、あるいはグリシジルエーテル化合物を混合した混合物、さらにはエポキシ化合物との混合物もポリマーとして用いることができる。
塗布法でポリマー層を形成する場合、例えば、ロールコート、グラビアコート、ナイフコート、ディップコート、カーテンフローコート、スプレーコート、バーコート等の方法を用いることができる。
他方、真空成膜法でポリマー層を形成する場合、例えば、蒸着、プラズマCVD等の成膜方法が挙げられる。
なお本発明におけるガスバリアフィルム(D)は水蒸気透過率(つまり水蒸気のバリア性能)でガスバリア性能を規定しているが、これは水蒸気のバリアが最も重要な機能の一つであることと共に、水蒸気のバリアが通常問題となる酸素などの気体、揮発成分やアルカリ、酸など低分子量成分の中で最も遮断が難しいすなわち透過し易いものの一つであるためである。
ガスバリアフィルム(D)は、有機半導体素子(B)を被覆して水分及び酸素から保護できるように、本発明に記載の順で積層されていれば、その形成位置に制限は無いが、有機半導体素子(B)の基板と反対面に備えていることが特徴である。また、有機半導体素子(B)の基板設置面背面(受光面とは反対側の面)を同様のガスバリアフィルム(D)で覆っていてもよい。有機半導体デバイスにおいてはその正面及び背面が他の面よりも大面積に形成されることが多いためである。
なお、後述する裏面保護シートが高いガスバリア性能を有する場合には、用途によりガスバリアフィルム(D)を兼ねてもよい。
本発明においては、防食層(E)は有機半導体デバイスを構成する重要な層である。本発明でいう防食層(E)は充填材とは異なるものである。
防食層(E)は、有機半導体素子には少なくとも一対の電極あるいは電極を備えた基板(A)が存在しているので、電極と、該電極の有機半導体素子(B)とは逆側である、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)との間に配置されるものである。つまり、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)が直接電極に接することがないように配置されていれば特に制限はない。
また、防食層(E)は、一層もしくは複数層でもよいが、下記に示す防食層(E)の特性は、複数層の場合、複数層の層全体としての特性を示すものとする。
なお、本発明における防食層(E)は、以下の水蒸気透過率の特性(つまりガスバリア性が優れている)を示すものである。
有機バリア材料の場合、バリア材料中に水蒸気などのガスを溶解、拡散させながら主としてバリア材料の厚さでバリア性を達成するケースが大半であり、この場合、バリア材料中のガス溶解量が計時で飽和溶解度付近まで上がってきた場合には有機半導体素子中へのガス遮断ができなくなるので、好ましくない。
また、より好ましい機能としては接着機能を有するものである。接着機能を有することにより、素子と水分及び酸素の少なくとも一方を吸収する捕捉剤が固定される。曲げなどによるデバイス変形時に、捕捉剤がずれて素子電極に接触するような恐れがなくなる。また、デバイス製造時に、基板(A)と有機半導体素子(B)上に、防食層(E)、捕捉剤を含む層(C)、ガスバリアフィルム(D)が積層されていくが、その際にも、捕捉剤を含む層(C)がずれて素子電極に接触する恐れもなくなる利点が生じる。
捕捉剤成分が水分と反応してアルカリが生じえるが、防食層(E)にアルカリ耐性がないと、アルカリが浸透して電極を腐食劣化させてしまう恐れがある。
また、防食層(E)から酸が発生しないことが好ましい。酸は電極と接触すると、電極を腐食劣化させてしまう。酸が発生しないことにより、腐食劣化を防止する利点が生じる。酸を発生する材料としては、例えば、エチレン-酢酸ビニル共重合体などの酢酸ビニル系樹脂が挙げられる。
防食層(E)に要求される酸素透過能力は、有機半導体素子(B)に応じて様々である。例えば、一般には、25℃環境下で100μm厚での単位面積(1m2)の1日あたりの酸素透過率が、500cc/m2/day/atm以下であることが好ましく、100cc/m2/day/atm以下であることがより好ましく、10cc/m2/day/atm以下であることが更に好ましく、1cc/m2/day/atm以下であることが中でも好ましい。酸素バリア性能がかかる範囲にあることで、素子の酸素による劣化を抑制できる。また、用いられる捕捉剤が酸素を吸収する場合は、ガスバリアフィルム(D)の酸素透過率以上の値であることが好ましい。ガスバリアフィルム(D)よりも酸素透過率が低い場合は、捕捉剤は素子封止領域外、つまりガスバリアフィルム(D)の外部領域の酸素を捕捉することとなり、本来の素子劣化防止の目的が失われてしまう。なお、酸素透過率は上述した方法で測定できる。
接着力の測定については後述するが、JIS K6854に準じたはく離接着強さ試験を実施することによって得ることができる。試験体の形状により、180度はく離、90度はく離、T型はく離を適宜選択可能である。
防食層(E)の吸水率は、一般に0.005~1%が好ましく、0.01~0.5%がより好ましく、0.02~0.3%がさらに好ましい。かかる上限を超えると、吸収した水分によりアルカリ拡散が促進され、電極腐食防止効果が劣ってしまう恐れがある。一方、かかる下限より下回ると、素子電極と防食層(E)界面の水分が防食層(E)により遮られて、捕捉剤で吸収することができなくなる恐れがある。
さらに、有機半導体デバイスは光を受けて熱せられることが多いため、熱に対する耐性を有することが好ましい。この観点から、構成材料の融点は、通常100℃以上、好ましくは120℃以上、より好ましくは130℃以上であり、また通常350℃以下、好ましくは320℃以下、より好ましくは300℃以下である。また、ガラス転移温度は、通常0℃以上、好ましくは30℃以上、より好ましくは60℃以上であり、通常300℃以下、好ましくは200℃以下、より好ましくは160℃以下である。高融点・高ガラス転移温度材料を用いることで耐熱性を良好にすることができ、デバイス使用時に融解、劣化するのを防ぐことができる。
防食層(E)の一層当たりの厚さは、通常20μm以上、好ましくは、30μm以上である。また、上限は500μmであり、より好ましくは、200μm以下、さらに好ましくは、100μm以下である。上限を超えると、可撓性有機電子デバイスでは厚みが増して、曲げることが困難となる。また、素子の金属電極と距離があるために、捕捉剤が金属電極周囲に達した水分、酸素などを効率的に吸収できなくなる恐れがある。一方、下限を下回ると、アルカリ拡散の抑制が不十分になり、電極の劣化防止ができなくなる恐れがある。
防食層(E)は使用する化合物の種類に応じて任意の方法で形成することができるが、例えば、溶融押出し成型法、溶液流延法、カレンダー法などフィルムまたはシートを作製する方法、防食層(E)を構成する溶液をロールコート、グラビアコート、ナイフコート、ディップコート、カーテンフローコート、スプレーコート、バーコート、ダイコート、スピンコート、インクジェット、ディスペンサー等で塗布膜を形成するウェット成膜方法を用いることができる。
さらに、フィルムまたはシート作製後、及び成膜後に、ヒーター、赤外線、マイクロ波などによる加熱、紫外光及び/または可視光照射により、重合、架橋、硬化反応をおこなってもよい。
本発明における樹脂層(F)は、本発明の効果を発揮する樹脂であれば特に制限はされないが、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)や充填材とは異なる樹脂である。ただし、有機半導体素子(B)と水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)の間に、有機半導体素子(B)と水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)が直接接触しないように配置される。
なお、樹脂層(F)がガスバリアフィルム(D)の場合、同一であっても異なっていてもよい。
なお、この樹脂層(F)の膜厚は、20μm以上であるのが望ましい。具体的理由は、この樹脂層(F)の構成層である、ガスバリアフィルム(D)、防食層(E)などの構成要素の膜厚の項で詳述する。
本発明では(A)~(F)に記載の部材とは特に制限がない限り異なるものである。
[シール材]
本発明においては、基板(A)とガスバリアフィルム(D)とが中間層(他の層)を介して接着されている場合や樹脂層(F)が外気に接しないように、ガスバリアフィルム(D)と樹脂層(F)が中間層を介して接着されている場合等に用いられる層である。
シール材は、本発明で構成される積層体の縁部をシールして、これらのフィルムで被覆された空間内に水分及び酸素が浸入しないようにシールする部材であり、本発明においては捕捉剤を含む層(C)、防食層(E)、樹脂層(F)などの層と、ガスバリアフィルム(D)などのフィルムと、基板(A)を接着する際に好ましい部材である。
さらに、有機電子デバイスは光を受けて熱されることが多いため、シール材も熱に対する耐性を有することが好ましい。この観点から、シール材の構成材料の融点は、通常100℃以上、好ましくは120℃以上、より好ましくは130℃以上であり、また、通常350℃以下、好ましくは300℃以下、より好ましくは280℃以下である。融点が低すぎると有機電子デバイスの使用時にシール材が融解する可能性がある。
シール材は、少なくともガスバリアフィルム(D)の縁部をシールできる位置に設ける。これにより、少なくともガスバリアフィルム(D)及びシール材で囲まれた空間を密閉し、この空間内に水分及び酸素が侵入しないようにすることができる。
また、シール材の性状は、接着方法により液状、ゲル状、シート状などが適宜選択される。シール工程において液だれの問題を生じないようにするという観点からは、シート状が好ましい。
本発明においては、有機電子デバイスの補強等のために、封止材を用いてもよい。
封止材は、有機電子デバイスの強度保持の観点から強度が高いことが好ましい。具体的強度については、封止材以外の耐候性保護シートや裏面保護シートの強度とも関係することになり一概には規定しにくいが、有機電子デバイス全体が良好な曲げ加工性を有し、折り曲げ部分の剥離を生じないような強度を有するのが望ましい。
さらに、有機半導体デバイスは光を受けて熱せられることが多いため、封止材も熱に対する耐性を有することが好ましい。この観点から、封止材の構成材料の融点は、通常100℃以上、好ましくは120℃以上、より好ましくは130℃以上であり、また、通常350℃以下、好ましくは320℃以下、より好ましくは300℃以下である。融点を高くすることで有機半導体デバイスの使用時に封止材が融解・劣化するのを防ぐことができる。
しかし、EVA樹脂の架橋処理には比較的時間を要するため、有機半導体デバイスの生産速度及び生産効率を低下させる原因となる場合がある。また、長期間使用の際には、EVA樹脂組成物の分解ガス(酢酸ガス)またはEVA樹脂自体が有する酢酸ビニル基が、有機半導体素子に悪影響を与えて発電効率が低下させる場合がある。そこで、封止材としては、EVAフィルムの他に、プロピレン・エチレン・α-オレフィン共重合体からなる共重合体のフィルムを用いることもできる。
封止材を設ける位置に制限はないが、確実に保護するため、通常は太陽電池素子を挟み込むように設ける。
かかる機能を付与する方法としては、機能を有する層を塗布成膜等により耐封止材上に積層してもよいし、機能を発現する材料を溶解・分散させるなどして封止材に含有させてもよい。
耐候性保護シートは温度変化、湿度変化、光、風雨などデバイス設置環境から有機電子デバイスを保護するシート及びフィルムである。耐候性保護シートでデバイス表面を覆うことにより、有機電子デバイス構成材料、特に有機半導体素子(B)が保護され、劣化することなく、高い発電能力を得ることができるという利点がある。
また、耐候性保護シートは、有機薄膜太陽電池素子の受光面側に用いられる場合、光吸収を妨げない観点から可視光を透過させるものが好ましい。例えば、可視光(波長360~830nm)の光の透過率は、通常75%以上、好ましくは80%以上、より好ましくは85%以上、さらに好ましくは90%以上、なかでも好ましくは95%以上、特に好ましくは97%以上である。太陽光をより多く電気エネルギーに変換するためである。
さらに、有機半導体素子(B)は光を受けて熱せられることが多いため、耐候性保護シートも熱に対する耐性を有することが好ましい。この観点から、耐候性保護シートの構成材料の融点は、通常100℃以上、好ましくは120℃以上、より好ましくは130℃以上であり、また、通常350℃以下、好ましくは320℃以下、より好ましくは300℃以下である。融点を高くすることで有機半導体素子(B)の使用時に耐候性保護シートが融解・劣化する可能性を低減できる。
耐候性保護シートの厚みは特に規定されないが、通常10μm以上、好ましくは15μm以上、より好ましくは20μm以上であり、また、通常200μm以下、好ましくは180μm以下、より好ましくは150μm以下である。厚みを厚くすることで機械的強度が高まる傾向にあり、薄くすることで柔軟性が高まる傾向にある。このため、両方の利点を兼ね備える範囲として、上記範囲とするのが望ましい。
耐候性保護シートは、有機電子デバイスにおいてできるだけ外側に設けることが好ましい。デバイス構成部材のうちより多くのものを保護できるようにするためである。
また、耐候性保護シートに紫外線遮断、熱線遮断、防汚性、親水性、疎水性、防曇性、耐擦性、導電性、反射防止、防眩性、光拡散、光散乱、波長変換、ガスバリア性等の機能を付与してもよい。特に、太陽電池の場合は、太陽光からの強い紫外線にさらされることから、紫外線遮断機能を持つことが好ましい。
[裏面保護シート]
裏面保護シートは、上述した耐候性保護シートと同様のシート及びフィルムであり、配設位置が異なる他は耐候性保護シートと同様のものを同様に用いることができる。また、この裏面保護シートが水及び酸素を透過させ難いものであれば、裏面保護シートをガスバリア層として機能させることも可能である。
裏面保護シートとしては、強度に優れ、耐候性、耐熱性、耐水性、耐光性に優れた各種の樹脂のフィルム及びシートを使用することができる。例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂、環状ポリオレフィン系樹脂、ポリスチレン系樹脂、アクリロニトリルースチレン共重合体(AS樹脂)、アクリロニトリルーブタジエンースチレン共重合体(ABS樹脂)、ポリ塩化ビニル系樹脂、フッ素系樹脂、ポリ(メタ)アクリル系樹脂、ポリカーボネート系樹脂、ポリエチレンテレフタレートまたはポリエチレンナフタレート等のポリエステル系樹脂、各種のナイロン等のポリアミド系樹脂、ポリイミド系樹脂、ポリアミドイミド系樹脂、ポリアリールフタレート系樹脂、シリコーン系樹脂、ポリスルホン系樹脂、ポリフェニレンスルフィド系樹脂、ポリエーテルスルホン系樹脂、ポリウレタン系樹脂、アセタール系樹脂、セルロース系樹脂、その他等の各種の樹脂のシートを使用することができる。これらの樹脂のシートの中でも、ポリテトラフルオロエチレン(PTFE)、ポリフッ化ビニリデン(PVDF)、ポリフッ化ビニル(PVF)、テトラフルオロエチレンとエチレン又はプロピレン共重合体(ETFE)等のフッ素系樹脂、環状ポリオレフィン系樹脂、ポリカーボネート系樹脂、ポリ(メタ)アクリル系樹脂、ポリアミド系樹脂、ポリエステル系樹脂のシートを使用することが好ましい。なお、これらは1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
さらに樹脂と金属の複合材料を用いることができる。例えばアルミニウム箔の両面にフッ素系樹脂フィルムを接着した防水性の高いシートを用いても良い。フッ素系樹脂としては、例えば、一弗化エチレン(商品名:テドラー,デュポン社製)、ポリテトラフルオロエチレン(PTFE)、テトラフルオロエチレンとエチレン又はプロピレンとのコポリマー(ETFE)、フッ化ビニリデン系樹脂(PVDF)、フッ化ビニル系樹脂(PVF)等が挙げられる。なお、フッ素系樹脂は1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用しても良い。
裏面保護シートの膜厚としては、通常20μm以上、好ましくは50μm以上であり、より好ましくは100μm以上である。また、通常1000μm以下、好ましくは500μm以下、より好ましくは300μm以下である。
本実施形態の有機電子デバイスの製造方法に制限は無いが、本発明においては積層する順序が重要である。具体的には、基板(A)、有機半導体素子(B)、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)、有機半導体素子を被覆するガスバリアフィルム(D)を順に積層した有機電子デバイスであって、有機半導体素子(B)は、少なくとも一対の電極を備えるように製造し、基板とは逆側の電極と水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)との間に一層もしくは複数層の防食層(E)を積層するように製造する。
工程1:基板(A)に1個又は2個以上が有機半導体素子(B)を直列又は並列接続された有機半導体素子(B)を設ける
工程2:水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)に一層もしくは複数層の防食層(E)を積層した積層体を製造する
工程3:工程1で製造した基板(A)上の有機半導体素子(B)に、工程2で製造した捕捉剤を含む層(C)と防食層(E)の積層体と、ガスバリアフィルム(D)とを、少なくとも基板(A)、有機半導体素子(B)、防食層(E)、捕捉剤を含む層(C)、ガスバリアフィルム(D)の順になるように積層する。
工程1:基板(A)に1個又は2個以上が有機半導体素子(B)を直列又は並列接続された有機半導体素子(B)を設ける。
工程2':ガスバリアフィルム(D)、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)、一層もしくは複数層の防食層(E)を積層した積層体を製造する。
工程3':工程1で製造した基板(A)上の有機半導体素子(B)に工程2'で製造したガスバリアフィルム(D)と捕捉剤を含む層(C)と防食層(E)の積層体を、少なくとも基板(A)、有機半導体素子(B)、防食層(E)、捕捉剤を含む層(C)、ガスバリアフィルム(D)の順になるように積層する。
(i)有機半導体素子(B)と水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)の間に、有機半導体素子(B)と水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)が直接接触しないように配置する。
(ii)有機半導体素子(B)と水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)が外気に接しないように、該基板(A)と該ガスバリアフィルム(D)とが直接又は中間層を介して接着する。
(i)について、有機半導体素子(B)と層(C)が直接接しないようにする理由は、上述した通りである。
(ii)について、有機半導体素子(B)と水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)が外気に接しないように理由は、有機半導体素子(B)が、外気の水蒸気や酸素や有機溶媒や揮発成分、特に水蒸気に触れると効率が低下する、あるいは寿命が短くなるなどの不都合があるためである。水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)は有機半導体素子に上記の水蒸気などが吸収されるよりも速く上記の水蒸気などを吸収し、有機半導体素子を保護する機能を持つが、もし外気に触れると上記の水蒸気などを吸収して、吸収能力が低下し上記機能を果たせなくなる恐れがある。
つまり樹脂層(F)が外気に接しないようにするには、有機電子デバイスの端面に露出しないようにする。この例では、樹脂層(F)を防食層(E)5で構成している。例えば、図3、図4のように本発明における有機電子デバイスは、構造上、有機電子デバイスの端面において、防食層(E)5で構成される樹脂層(F)よりも外側にガスバリアフィルム(D)7が配置される。そして、基板(A)1とガスバリアフィルム(D)7とが直接又は中間層を介して接着されていることになる。基板(A)1とガスバリアフィルム(D)7とが直接又は中間層を介して接着されている接着面(つまり、有機電子デバイスの端部)まで樹脂層(F)が達してしまうと、樹脂層(F)は外部に露出することになる。図3及び図4に示す例では、基板(A)1とガスバリアフィルム(D)7とが防食層(E)5からなる樹脂層(F)と捕捉剤を含む層(C)6とを介して接着されている。そのため、樹脂層(F)の面方向から水蒸気や酸素や有機溶媒や揮発成分などが浸透し、有機半導体素子(B)、あるいは水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)6に接触あるいは吸収されてこれらにダメージを与えて効率あるいは寿命を低下させるといった状況になり好ましくない場合がある。
直接接着するには、例えば光硬化性の樹脂を塗布後、各層を接着し、UV光を当てて硬化後、例えば80℃前後で20分程度加熱してキュアさせる、あるいは熱硬化性の樹脂を塗布後、各層を接着し、例えば120℃前後で1時間程度加熱してキュアさせる等の方法が挙げられる。
以下により具体的な有機電子デバイスの製造方法を挙げる。
例えば、製造手順が挙げられる。
工程I:基板(A)に1個又は2個以上が有機半導体素子(B)を直列又は並列接続された有機半導体素子(B)を設ける。
工程II:水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)に樹脂層(F)、より好ましくは、一層もしくは複数層の防食層(E)を積層した積層体(以下、樹脂層(F)とする)を製造する。この場合、層(C)は層(F)よりも面積を小さくしなければならない。
工程III:工程Iで製造した基板(A)上の有機半導体素子(B)に工程IIで製造した捕捉剤を含む層(C)と樹脂層(F)の積層体とガスバリアフィルム(D)を、少なくとも基板(A)、有機半導体素子(B)、樹脂層(F)、捕捉剤を含む層(C)、ガスバリアフィルム(D)の順になるように積層する。
工程I:基板(A)に1個又は2個以上が有機半導体素子(B)を直列又は並列接続された有機半導体素子(B)を設ける。
工程II’:ガスバリアフィルム(D)、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)、樹脂層(F)を積層した積層体を製造工程
III’:工程Iで製造した基板(A)上の有機半導体素子(B)に工程II’で製造したガスバリアフィルム(D)と捕捉剤を含む層(C)と樹脂層(F)の積層体を、少なくとも基板(A)、有機半導体素子(B)、樹脂層(F)、捕捉剤を含む層(C)、ガスバリアフィルム(D)の順になるように積層する。
その他の上記層に関しては、順序は特に制限はないが、好ましい順序としては、基板(A)側が受光面の場合は、耐候性保護シート、ガスバリアフィルム、封止材、基板(A)、有機半導体素子(B)、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)、ガスバリアフィルム(D)、封止材、裏面保護シートの順;耐候性保護シート、封止材、ガスバリアフィルム、基板(A)、有機半導体素子(B)、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)、ガスバリアフィルム(D)、封止材、裏面保護シートの順である。ガスバリアフィルム(D)が受光面の場合は、裏面保護シート、封止材、基板(A)、有機半導体素子(B)、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)、ガスバリアフィルム(D)、封止材、耐候性保護シートの順となる。上記層は、適宜必要に応じて、複数積層してもよいし、省略してもよく、他の機能層を挿入してもよい。
有機電子デバイスを効率的に製造するためには、図6に断面図、図7に平面図を示すように、大面積の基板(A)1上に、多数の有機半導体素子(B)20を積層し、本発明における層構成で積層させた有機電子デバイスを一つずつに切断する方法が時間的、作業的、コスト的にも非常に有効である。各部材は図3及び4に示した有機電子デバイスと同様であるためここでは説明を省略するが同一部材には同一符号を付した。
つまり、大面積で一度に有機デバイスを製作後、用途に合わせて必要なサイズに分割して使用することが、製造効率、コストダウンの観点からも好ましい。特に太陽電池用途においては適当なサイズのセルを直列接続した電子デバイスとして目的に必要な電圧を得る場合があり、この場合も上記の通り大面積で一度に有機デバイスを製作後、適当なサイズのセルに分割して有機太陽電池を製造することで、より生産性が向上する。
さらに切断前の大型シートの段階で通常の大気下で保管、輸送が可能となるので、大型シートのデバイスの状態で大量に保管後、あるいは輸送後、切断処理を都合の良い場所で一度に実施できるメリットも大きい。
具体的には、基板(A)上に、少なくとも2つ以上の有機半導体素子(B)を互いに間隔をあけて配置し、少なくとも2つ以上の有機半導体素子(B)上に樹脂層(F)を積層し、樹脂層(F)上に2つ以上の水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)を互いに間隔をあけて配置し、層(C)上にガスバリアフィルム(D)を積層し、有機半導体素子(B)と水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)を含むように切断する。
より好ましくは、少なくとも該基板(A)と該ガスバリアフィルム(D)、該樹脂層(F)が積層されている部分である。
そして、更に好ましくは、中間層がシール材を含有する層であり、その中でも、図4及び5に示すように、あらかじめ切断箇所にシール材8を形成しておき、シール材8の間で切断する。
このような製造方法によれば、基板上に複数配置した有機半導体素子を個別の素子に切断するのは、ドライ窒素雰囲気下では無く、通常の大気中であっても素子の効率や寿命上問題無く、製造上好適である。ドライ窒素雰囲気下に切断装置を入れたり、内部切断処理するのは、ドライ窒素雰囲気を保持する容積が大きくなったり、粉塵や油滴が発生したりするので、コストアップに繋がり好ましくない傾向がある。
具体的な態様の一つを図6及び図7に示す。
本発明に係る有機電子デバイスは、以下のような性能を持つことが特徴である。
評価方法:加速試験は、環境試験機(例えば、エスペック社製SH-241)中にて高温高湿環境に設置することとする。高温高湿環境は、40℃90%RHもしくは85℃85%RHとすることが好ましい。試験期間は、デバイス構成材料により適宜選択できるが、24時間以上はおこなうことが好ましい。また、光電変換特性は、有機薄膜太陽電池にソーラシュミレーターでAM1.5G条件の光を照射強度100mW/cm2照射して、電流・電圧特性の測定をおこなう。かかる測定から得られる電流・電圧曲線から、エネルギー変換効率(PCE)、短絡電流、開放電圧、FF(フィルファクター)、直列抵抗、シャント抵抗を求めることができる。
つまり本発明に係る有機電子デバイスのエネルギー変換効率(PCE)変化率は、上式で定義されるように通常、初期性能に対して加速試験後の値が、0.86以上であり、好ましくは、0.88以上、より好ましくは0.90以上である。
本発明に係わる有機電子デバイスは、耐候性が良好である。屋外暴露試験、耐候性試験機により耐候性試験を実施しても、性能を維持し、高い耐久性能を示す。防食層の存在により電極劣化が抑制されているためと考えられる。また、耐候性保護シートを積層した場合にはより高い耐候性を有する。
以下、本発明を実施例によって、さらに具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例の記載に限定されるものではない。
・水蒸気透過率
JIS K7129に準じた感湿センサ、赤外線センサ、ガスクロマトグラフを備えた装置による測定、カップ法(JIS Z0208)により40℃90%環境での水蒸気透過率が得られる。特に、水蒸気バリア性の高い場合には、より精度の高いJIS K7129Bに準じたMOCON法で測定することが好ましく、MOCON社製水蒸気透過率測定装置PERMATRAN-Wを用いて測定する。
JIS K6854に準じたはく離接着強さ試験を実施することに得られる。試験体形状により、180度はく離、90度はく離、T型はく離を適宜選択してよい。具体的な装置として、オリエンテック社製引張試験機がある。
・捕捉剤の水分吸収能力
捕捉剤を20℃、65%RH環境に15分放置し、試験前後の重量変化から算出した。
<有機薄膜太陽電池素子の作製工程>
ガラス基板上に、インジウム・スズ酸化物(ITO)透明導電膜を堆積したもの(シート抵抗15Ω/□以下)を、通常のフォトリソグラフィ技術と塩酸エッチングとを用いて2mm幅のストライプにパターニングして、透明電極を形成した。パターン形成した透明電極を、界面活性剤による超音波洗浄、超純水による水洗、超純水による超音波洗浄の順で洗浄後、窒素ブローし、120℃で10分間加熱乾燥させた。
これ以降は、基板をグローブボックス中に持ち込み、窒素雰囲気下で作業した。
クロロホルム/クロロベンゼンの1:2混合溶媒(重量)に下記化合物(A)を0.5重量%溶解した液をろ過後、1500rpmで上記PEDOT:PSSの膜上にスピンコートし、180℃で20分加熱し、下記化合物(B)の膜を得た。
次に、上記一連の有機層を成膜した基板を、透明電極ストライプに対して直交するように2mm幅のシャドーマスクと密着させて、真空蒸着装置内に設置した。そして、フッ化リチウム(LiF)を蒸着速度約0.01nm/秒で、膜厚0.5nmになるよう有機層上に蒸着した。引き続き、アルミニウムを蒸着速度0.2nm/秒でLiF層上に膜厚80nmとなるよう蒸着し、金属電極を形成した。
以上のようにして、2mm×2mmのサイズの受光面積部分を有する有機薄膜太陽電池素子が得られた。
作製した上記有機半導体素子の金属電極面に、捕捉剤を含む層(C)と接着シートが積層された構造をもつゲッターシート(ダイニック社製HD-S05)を、水蒸気透過率が1g/m2/dayのフィルム(三菱樹脂(株)社製テックバリア)を介して積層した。ここでは、接着シートと上記フィルムは、有機半導体素子の金属電極4と捕捉剤を含む層(C)の間に存在することで防食層(E)として機能する。次に、ガラス基板の周縁部に、シール材として、ロの字型に切り抜いた両面テープ(綜研化学製J-7702、200μm厚)を上記素子がロの字型内側になるように貼着した。さらに上記ゲッターシートと上記フィルムを積層した素子及び両面テープ全面を覆うように水蒸気透過率が10-2g/m2/dayガスバリアフィルム(三菱樹脂(株)社製テックバリア)を貼りつけて、素子封止をおこなった。
<有機薄膜太陽電池素子の作製>
実施例1と同様にして、有機薄膜太陽電池素子を作製した。
封止には、実施例1と同じゲッターシート、ガスバリアフィルム7、両面テープを用いる。ゲッターシートを接着シート面でガスバリアフィルムに接着させた。実施例1と同様に、基板周縁部に、ロの字型に切り抜いた両面テープを貼り、素子と両面テープ全面を覆うようにゲッターシートが接着したガスバリアフィルムを貼りつけて、素子封止をおこなった。
作製した有機薄膜太陽電池は、それぞれ加速試験をおこない、試験前後での光電変換特性の変化を比較した。加速試験は、小型環境試験機(エスペック社製SH-241)で40℃90%RH環境で24時間実施した。また、光電変換特性値として、有機薄膜太陽電池にソーラシュミレーター(分光計器社製)でAM1.5G条件の光を照射強度100mW/cm2照射して、得られた電流・電圧曲線から、エネルギー変換効率(PCE)を求めた。
PCE変化率=(加速試験後のPCE)/(加速試験前のPCE)
また、劣化が進行した有機薄膜太陽電池を目視で観察すると、比較例1の金属電極はゲッター層と接触した箇所がアルカリにより劣化し、透明化していた。
比較例1と以下の点を除き同様にして有機薄膜太陽電池素子を作製し、性能評価実験を行った。
ガスバリアフィルム(D)及び防食層(E)として水蒸気透過率が10-2g/m2/dayのガスバリアフィルム(三菱樹脂製テックバリア)を使用した。防食層(E)のバリア性能が高いため、組上げ工程中に有機半導体素子に付着あるいは侵入した水蒸気などを、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)で十分に捕捉することができず、PCE変化率は0.70であった。結果を表1に示す。
比較例1において、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)と有機薄膜太陽電池素子との間に厚さが30μのVAコンテント30%となるEVAフィルム(水蒸気透過率が20g/m2/day)を充填材として挿入し、有機薄膜太陽電池デバイスに組上げ後120℃で10分程加熱し、有機薄膜太陽電池素子の電極に密着させた。EVAフィルムから揮発したガスや低分子量成分が電極のピンホールを透過して有機薄膜太陽電池や電極との界面にダメージを与え、PCE変化率は0.30であった。
結果を表1に示す。
<有機薄膜太陽電池素子の作製工程>
ガラス基板上に、インジウム・スズ酸化物(ITO)透明導電膜を堆積したもの(シート抵抗15Ω/□以下)を、通常のフォトリソグラフィ技術と塩酸エッチングとを用いて2mm幅のストライプにパターニングして、透明電極を形成した。パターン形成した透明電極を、界面活性剤による超音波洗浄、超純水による水洗、超純水による超音波洗浄の順で洗浄後、窒素ブローし、120℃で10分間加熱乾燥させた。その後、形成した透明電極3上にPEDOT-PSS(ポリ(エチレンジオキシチオフェン)―ポリ(スチレンスルホン酸))溶液を塗布し、120℃で10分間乾燥させることにより、膜厚がおよそ30nmの正孔輸送層を形成した。
デバイス形成工程は、防食層(E)としてポリプロピレンフイルム(東洋紡社製 パイレン P2002、50μm厚)を使用した以外は実施例1と同様にして行った。
[比較例4]
実施例2と同様にして、有機薄膜太陽電池素子を作製した。
デバイス形成工程は比較例1と同様に行った。
<有機薄膜太陽電池素子の作製工程>
ガラス基板上に、インジウム・スズ酸化物(ITO)透明導電膜を堆積したもの(シート抵抗15Ω/□以下)を、通常のフォトリソグラフィ技術と塩酸エッチングとを用いて2mm幅のストライプにパターニングして、透明電極を形成した。パターン形成した透明電極を、界面活性剤による超音波洗浄、超純水による水洗、超純水による超音波洗浄の順で洗浄後、窒素ブローし、120℃で10分間加熱乾燥させた。
これ以降は、基板をグローブボックス中に持ち込み、窒素雰囲気下で作業した。
クロロホルム/クロロベンゼンの1:2混合溶媒(重量)に上記化合物(A)を0.5重量%溶解した液をろ過後、1500rpmで上記PEDOT:PSSの膜上にスピンコートし、180℃で20分加熱し、上記化合物(B)の膜を得た。
次に、上記一連の有機層を成膜した基板を、透明電極ストライプに対して直交するように2mm幅のシャドーマスクと密着させて、真空蒸着装置内に設置した。そして、フッ化リチウム(LiF)を蒸着速度約0.01nm/秒で、膜厚0.5nmになるよう有機層上に蒸着した。引き続き、アルミニウムを蒸着速度0.2nm/秒でLiF層上に膜厚80nmとなるよう蒸着し、金属電極を形成した。
以上のようにして、2mm×2mmのサイズの受光面積部分を有する有機薄膜太陽電池素子が得られた。
以下、乾燥窒素でパージされたグローブボックス内で作業を行った。水蒸気透過率(水蒸気バリア性能)が10-2g/m2/dayのフィルム(三菱樹脂(株)社製テックバリア)と水蒸気透過率が1g/m2/dayのフィルム(三菱樹脂(株)社製テックバリアの別グレード)により、捕捉剤を含む層(C)と接着シートが積層した構造をもつゲッターシート(ダイニック社製HD-S07)を挟みこんだ。ここで前者のフィルムはガスバリアフィルム(D)として機能し、後者のフィルムは防食層(E)として機能する。ガスバリアフィルム(D)と防食層(E)フィルムの縁部をシール材により接着した。シール材の接着線幅は3mm、接着厚は20μmであった。(*ここまでで製造された積層体を以下、積層体(I)ともいう)
次に、ガラス基板の周縁部に、接着材として、ロの字型に切り抜いた両面テープ(綜研化学製J-7702、200μm厚)を上記素子がロの字型内側になるように貼着した。
以上のようにして、基板(A)1上に設けられた有機薄膜太陽電池素子である有機半導体素子(B)20は、上面のバリアフィルム(D)7と周縁の両面テープのシール材8により封止されており、有機半導体素子(B)20、接着シートからなる防食層(E)5、捕捉剤を含む層(C)6の順に積層した構造となる有機薄膜太陽電池デバイスが得られた。なおバリアフィルム(D)7と防食層(E)5の接着は、図3のように接着してもあるいは下記実施例4で製造された図5のように接着しても、必要な要件を満たす限り問題は無い。なお、図4は図3のデバイスを上から見た図である。
実施例1において、積層体(I)の状態でグローブボックスから外へ出して25℃60%の大気中に30分程放置した。その後、再びグローブボックス内へ戻し、それ以外は実施例1と全く同様にして有機薄膜太陽電池デバイスを試作した。
すなわち、積層体(I)の構造の積層フィルムを製作した後、短時間であれば大気中に保管することが可能であるし、窒素雰囲気中の保管場所から大気中を通してグローブボックス内へ移動させることが可能である。これは、有機半導体デバイスの製造プロセスにおいて上記積層フィルムのハンドリングのし易さや製造プロセスのロバスト性を考えた場合、大きなメリットがあると考えることができる。
デバイス形成工程における下記記載以外は実施例4と同様にしてデバイス形成を実施した。
以下、乾燥窒素でパージされたグローブボックス内で作業を行った。水蒸気透過率(水蒸気バリア性能)が10-2g/m2/dayのフィルム(三菱樹脂(株)社製テックバリア)と水蒸気透過率が1g/m2/dayのフィルム(三菱樹脂(株)社製テックバリアの別グレード)により、捕捉剤を含む層(C)と接着シートが積層した構造をもつゲッターシート(ダイニック社製HD-S07)を挟みこんだ。ここで前者のフィルムはガスバリアフィルム(D)として機能し、後者のフィルムは防食層(E)として機能する。この際、図5に示すようにガスバリアフィルム(D)の内側に防食層(E)フィルムの縁部が配置されるようにシール材により接着した。シール材の接着線幅は3mm、接着厚は20μmであった。ガスバリアフィルム(D)をガラス基板にシール材により接着する際、このシール部分には防食層(E)フィルムの縁部が重ならないことになる。この結果、デバイス形成後、防食層(E)フィルム内部をフィルム面方向に水蒸気や酸素がデバイス内部へ透過して有機半導体層にダメージを与える心配が無くなる。
実施例3に記載の方法で同様に製造された2mm×2mmの有機半導体素子(B)20としての薄膜太陽電池素子を8mmの間隔を置いて図6及び図7に示すように4個並べた。各有機薄膜太陽電池素子の間は実施例3の縁部と同様にシールした。その際、シール材8と有機薄膜太陽電池素子とが接触しないようにシール材は塗布、配置した。この有機太陽電池デバイスの構造を図6に示す。なお、図7は図6のデバイスを上から見た図である。各部材については、図1乃至図5で説明した部材と同一部材は同一符号を付し、説明は省略する。
実施例で作製した有機薄膜太陽電池は以下の通り、性能評価をおこなった。
作製した有機薄膜太陽電池は、それぞれ加速試験をおこない、試験前後での光電変換特性の変化を比較した。加速試験は、小型環境試験機(エスペック社製SH-241)で40℃90%RH環境で24時間実施した。また、光電変換特性値として、有機薄膜太陽電池にソーラシュミレーター(分光計器社製)でAM1.5G条件の光を照射強度100mW/cm2照射して、得られた電流・電圧曲線から、エネルギー変換効率(PCE)を求めた。
ガスバリアフィルム(D)と防食層(E)とで捕捉剤を含む層(C)を挟み込み、しかもシールして外気から遮断することで、この状態の積層シートが製造プロセスにおいて短時間大気中に暴露されても、捕捉剤の劣化が抑制されたと考えられる実施例5,6のような工夫をすることで、一度に複数個の有機薄膜太陽電池を作製した後、大気中で1個1個の太陽電池に切り離す処理を実施しても性能の劣化は認められなかった。
2.有機半導体層
3.透明電極
4.金属電極
5.防食層(E)
6.捕捉剤を含む層(C)
7.ガスバリアフィルム(D)
8.シール材
9.接着シート
10.切断面
20.有機半導体素子(B)
Claims (21)
- 少なくとも一対の電極を備えた有機半導体素子(B)と、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)と、ガスバリアフィルム(D)とをこの順に備えた有機電子デバイスであって、
該有機半導体素子(B)の、該一対の電極のうち少なくとも一方の電極と該水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)との間に、少なくとも一層の防食層(E)を備えており、
該防食層(E)の膜厚が20μm以上であり、
該防食層(E)およびガスバリアフィルム(D)が、次式(1)および(2)の条件を満たすことを特徴とする有機電子デバイス。
15≧Pe>Pd 式(1)
10-4≦Pd≦10-1 式(2)
上記式(1)及び式(2)中、Peは防食層(E)の40℃90%RH環境での水蒸気透過率を示し、Pdはガスバリアフィルム(D)の40℃90%RH環境での水蒸気透過率を示し、いずれも単位はg/m2/dayとする。 - 前記防食層(E)が0.1N/cm以上の接着機能を有する層を含むことを特徴とする請求項1に記載の有機電子デバイス。
- 前記有機半導体素子(B)が、有機太陽電池素子であることを特徴とする請求項1又は2に記載の有機電子デバイス。
- 水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)の水分吸収能力が0.1mg/cm2以上15mg/cm2以下であることを特徴とする請求項1~3のいずれか1項に記載の有機電子デバイス。
- 前記ガスバリアフィルム(D)が、熱可塑性樹脂と、該熱可塑性樹脂上に真空蒸着されたSiOxとを含むフィルムであることを特徴とする請求項1~4のいずれか1項に記載の有機電子デバイス。
- 基板(A)を含むことを特徴とする請求項1~5のいずれか1項に記載の有機電子デバイス。
- 封止材及び耐候性保護シートを含むことを特徴とする請求項1~6のいずれか1項に記載の有機電子デバイス。
- 基板(A)と、少なくとも一対の電極を備えた有機半導体素子(B)と、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)と、少なくとも一層の防食層(E)と、該有機半導体素子を被覆するガスバリアフィルム(D)とを順に積層した有機電子デバイスの製造方法であって、
該防食層(E)およびガスバリアフィルム(D)が、次式(1)および(2)の条件を満たし、
15≧Pe>Pd 式(1)
10-4≦Pd≦10-1 式(2)
上記式(1)及び式(2)中、Peは防食層(E)の40℃90%RH環境での水蒸気透過率を示し、Pdはガスバリアフィルム(D)の40℃90%RH環境での水蒸気透過率を示し、いずれも単位はg/m2/dayとする。
水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)に少なくとも一層の防食層(E)を積層した積層体層を製造するとともに、基板(A)上に有機半導体素子(B)を製造した後に、上記順に従い、積層することを特徴とする有機電子デバイスの製造方法。 - ガスバリアフィルム(D)、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)、少なくとも一層の防食層(E)を順に積層した積層体層を製造し、有機半導体素子(B)を基板(A)上に製造した後に、上記順に従い積層することを特徴とする請求項8に記載の有機電子デバイスの製造方法。
- 基板(A)と、少なくとも一対の電極を備えた有機半導体素子(B)と、水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)と、ガスバリアフィルム(D)とを、この順に備えた有機電子デバイスであって、
該有機半導体素子(B)と該水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)の間に、該有機半導体素子(B)と該層(C)が直接接触しないように樹脂層(F)を有し、該樹脂層(F)の膜厚が20μm以上であり、
該樹脂層(F)およびガスバリアフィルム(D)が、次式(1)および(2)の条件を満たし、
15≧Pe>Pd 式(1)
10-4≦Pd≦10-1 式(2)
上記式(1)及び式(2)中、Peは樹脂層(F)の40℃90%RH環境での水蒸気透過率を示し、Pdはガスバリアフィルム(D)の40℃90%RH環境での水蒸気透過率を示し、いずれも単位はg/m2/dayとする。
かつ、該有機半導体素子(B)と該層(C)が外気に接しないように、該基板(A)と該ガスバリアフィルム(D)とが直接又は中間層を介して接着されていることを特徴とする有機電子デバイス。 - 更に該樹脂層(F)が外気に接しないように、該ガスバリアフィルム(D)と該樹脂層(F)が直接又は中間層を介して接着されていることを特徴とする請求項10に記載の有機電子デバイス。
- 該中間層がシール材を含有する層であることを特徴とする請求項10又は11に記載の有機電子デバイス。
- 該樹脂層(F)が、少なくとも一層の防食層(E)を含むことを特徴とする請求項10~12のいずれか1項に記載の有機電子デバイス。
- 有機半導体素子(B)が、有機太陽電池素子であることを特徴とする請求項10~13のいずれか1項に記載の有機電子デバイス。
- 基板(A)上に、複数の有機半導体素子(B)を互いに間隔をあけて配置し、
該複数の有機半導体素子(B)上に樹脂層(F)を積層し、
該樹脂層(F)上に2つ以上の水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)を互いに間隔をあけて配置し、
該層(C)上にガスバリアフィルム(D)を積層し、
該有機半導体素子(B)と水分及び酸素の少なくとも一方を吸収する捕捉剤を含む層(C)を含むように前記基板(A)を切断することを特徴とする有機電子デバイスの製造方法。 - 切断する部分が、少なくとも基板(A)と該ガスバリアフィルム(D)が直接又は中間層を介して接着されている部分であることを特徴とする請求項15に記載の有機電子デバイスの製造方法。
- 切断する部分が、少なくとも該基板(A)と該ガスバリアフィルム(D)、該樹脂層(F)が積層されている部分であることを特徴とする請求項15又は16に記載の有機電子デバイスの製造方法。
- 該中間層がシール材を含有する層であることを特徴とする請求項15~17のいずれか1項に記載の有機電子デバイスの製造方法。
- 該樹脂層(F)が、少なくとも一層の防食層(E)を含むことを特徴とする請求項15~18のいずれか1項に記載の有機電子デバイスの製造方法。
- 該防食層(E)およびガスバリアフィルム(D)が、次式(3)および(4)の条件を満たすことを特徴とする請求項19に記載の有機電子デバイスの製造方法。
5≧Pe>Pd 式(3)
Pd≦10-1 式(4)
上記式(3)及び式(4)中、Peは防食層(E)の40℃90%RH環境での水蒸気透過率を示し、Pdはガスバリアフィルム(D)の40℃90%RH環境での水蒸気透過率を示し、いずれも単位はg/m2/dayとする。 - 有機半導体素子(B)が、有機太陽電池素子であることを特徴とする請求項15~19のいずれか1項に記載の有機電子デバイスの製造方法。
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020117030884A KR101700989B1 (ko) | 2009-06-24 | 2010-06-21 | 유기 전자 디바이스 및 그 제조 방법 |
| EP10792077.9A EP2448032B1 (en) | 2009-06-24 | 2010-06-21 | Organic electronic device and method for producing the same |
| CN201080028354.7A CN102804440B (zh) | 2009-06-24 | 2010-06-21 | 有机电子器件及其制造方法 |
| JP2011519895A JP5382119B2 (ja) | 2009-06-24 | 2010-06-21 | 有機電子デバイス及びその製造方法 |
| US13/336,420 US20120125431A1 (en) | 2009-06-24 | 2011-12-23 | Organic electronic device and method for manufacturing the same |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009150143 | 2009-06-24 | ||
| JP2009-150143 | 2009-06-24 | ||
| JP2009160791 | 2009-07-07 | ||
| JP2009-160791 | 2009-07-07 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13/336,420 Continuation US20120125431A1 (en) | 2009-06-24 | 2011-12-23 | Organic electronic device and method for manufacturing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2010150759A1 true WO2010150759A1 (ja) | 2010-12-29 |
Family
ID=43386529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2010/060499 Ceased WO2010150759A1 (ja) | 2009-06-24 | 2010-06-21 | 有機電子デバイス及びその製造方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20120125431A1 (ja) |
| EP (1) | EP2448032B1 (ja) |
| JP (1) | JP5382119B2 (ja) |
| KR (1) | KR101700989B1 (ja) |
| CN (1) | CN102804440B (ja) |
| TW (1) | TW201115804A (ja) |
| WO (1) | WO2010150759A1 (ja) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013011741A1 (ja) * | 2011-07-15 | 2013-01-24 | コニカミノルタホールディングス株式会社 | 有機エレクトロルミネッセンスパネル及びその製造方法 |
| JP2013211501A (ja) * | 2012-03-30 | 2013-10-10 | Sumitomo Chemical Co Ltd | 光電変換装置 |
| JP2013214477A (ja) * | 2012-04-04 | 2013-10-17 | Yazaki Corp | 端子付き電線 |
| JP2014049507A (ja) * | 2012-08-29 | 2014-03-17 | Mitsubishi Chemicals Corp | 有機薄膜太陽電池モジュール |
| CN103988578A (zh) * | 2011-08-04 | 2014-08-13 | 3M创新有限公司 | 边缘受保护的阻隔组件 |
| JP2014526150A (ja) * | 2011-08-04 | 2014-10-02 | スリーエム イノベイティブ プロパティズ カンパニー | エッジの保護されたバリアー性組立品 |
| JP2014526985A (ja) * | 2011-08-04 | 2014-10-09 | スリーエム イノベイティブ プロパティズ カンパニー | エッジの保護されたバリアー性組立品 |
| JP2014529882A (ja) * | 2011-08-04 | 2014-11-13 | スリーエム イノベイティブプロパティズカンパニー | バリアアセンブリ |
| US20150295111A1 (en) * | 2012-11-12 | 2015-10-15 | Dow Corning Corporation | Photovoltaic Cell Module |
| WO2016047127A1 (ja) * | 2014-09-22 | 2016-03-31 | 株式会社 東芝 | 光電変換装置 |
| JP2016122768A (ja) * | 2014-12-25 | 2016-07-07 | 国立研究開発法人産業技術総合研究所 | 有機薄膜太陽電池及び有機薄膜太陽電池内の酸素濃度検出装置 |
| JPWO2014156494A1 (ja) * | 2013-03-29 | 2017-02-16 | 共同印刷株式会社 | 吸湿層を有する太陽電池用バックシート及びそれを用いた太陽電池 |
| JP2018037534A (ja) * | 2016-08-31 | 2018-03-08 | 日本放送協会 | 自己組織化単分子膜材料、有機エレクトロルミネッセンス素子、表示装置、照明装置、有機薄膜太陽電池、有機薄膜トランジスタ |
| KR101911582B1 (ko) * | 2011-08-04 | 2018-10-24 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 에지 보호된 배리어 조립체 |
| US10453790B2 (en) | 2017-10-19 | 2019-10-22 | Samsung Electronics Co., Ltd. | Semiconductor package |
| JP7597430B1 (ja) | 2024-04-11 | 2024-12-10 | 今泉工業株式会社 | 光発電装置及びその製造方法 |
| WO2025154757A1 (ja) * | 2024-01-18 | 2025-07-24 | Tdk株式会社 | 太陽電池及びその製造方法 |
Families Citing this family (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9177828B2 (en) * | 2011-02-10 | 2015-11-03 | Micron Technology, Inc. | External gettering method and device |
| US8732940B2 (en) * | 2009-03-12 | 2014-05-27 | Clean Energy Solutions, Inc. | System and method for mounting photovoltaic panels |
| WO2011108020A1 (ja) * | 2010-03-01 | 2011-09-09 | パナソニック株式会社 | 有機el装置およびその製造方法 |
| JP4991901B2 (ja) * | 2010-04-21 | 2012-08-08 | 株式会社東芝 | 磁気抵抗効果素子及び磁気記録再生装置 |
| JP5352703B2 (ja) * | 2011-08-03 | 2013-11-27 | 東洋インキScホールディングス株式会社 | 太陽電池裏面保護シートならびに太陽電池モジュール |
| JP5693515B2 (ja) | 2012-01-10 | 2015-04-01 | エイチズィーオー・インコーポレーテッド | 内部耐水性被覆を備える電子デバイス |
| CN103022382A (zh) * | 2012-12-03 | 2013-04-03 | 彩虹(佛山)平板显示有限公司 | 一种有机电致发光二极管显示器件的封装方法 |
| KR20150097359A (ko) * | 2014-02-18 | 2015-08-26 | 주식회사 엘지화학 | 봉지 필름 및 이를 포함하는 유기전자장치 |
| CN106134288B (zh) * | 2014-03-19 | 2018-01-02 | 琳得科株式会社 | 电子元件封装用层叠片以及电子器件的制造方法 |
| US20180170022A1 (en) * | 2014-03-27 | 2018-06-21 | Lintec Corporation | Sealing sheet, and sealing structure and device |
| JP6002264B1 (ja) * | 2015-03-19 | 2016-10-05 | 株式会社東芝 | 太陽電池モジュール |
| CN107408630B (zh) * | 2015-03-25 | 2020-03-03 | 积水化学工业株式会社 | 太阳能电池 |
| CN105161623B (zh) * | 2015-08-07 | 2018-06-08 | 常州大学 | 一种钙钛矿太阳能电池及其制备方法 |
| TWI703746B (zh) * | 2015-08-28 | 2020-09-01 | 國立大學法人千葉大學 | 有機半導體裝置的製造方法及粉體 |
| KR101835941B1 (ko) * | 2015-10-19 | 2018-03-08 | 삼성에스디아이 주식회사 | 유기발광소자 봉지용 조성물 및 이로부터 제조된 유기발광소자 표시장치 |
| CN109273613A (zh) * | 2017-07-17 | 2019-01-25 | 昆山国显光电有限公司 | Oled器件及其制备方法、显示装置 |
| US11781040B2 (en) | 2017-08-31 | 2023-10-10 | Samsung Sdi Co., Ltd. | Adhesive film and optical member comprising same |
| WO2020049732A1 (ja) * | 2018-09-07 | 2020-03-12 | 三菱電機株式会社 | 気密パッケージ |
| CN109273603B (zh) * | 2018-09-20 | 2020-06-05 | 中国科学院长春应用化学研究所 | 有机光伏模组的制备方法 |
| CN109346622A (zh) * | 2018-10-19 | 2019-02-15 | 武汉华星光电半导体显示技术有限公司 | Oled阵列基板及其制作方法 |
| US20220013741A1 (en) * | 2018-11-26 | 2022-01-13 | Sumitomo Chemical Company, Limited | Method for producing organic photoelectric conversion element |
| CN109616583B (zh) * | 2018-12-12 | 2021-06-11 | 云谷(固安)科技有限公司 | 显示面板及显示装置 |
| CN111668525B (zh) * | 2019-03-06 | 2021-10-12 | 清华大学 | 自充电储能装置 |
| CN110499118A (zh) * | 2019-07-30 | 2019-11-26 | 云谷(固安)科技有限公司 | 屏幕保护膜及其制造方法、电子设备 |
| US20230006158A1 (en) * | 2019-12-03 | 2023-01-05 | Nanoflex Power Corporation | Protective encapsulation of solar sheets |
| KR102430601B1 (ko) | 2020-03-03 | 2022-08-08 | 삼성에스디아이 주식회사 | 점착 필름, 이를 포함하는 광학 부재 및 이를 포함하는 광학표시장치 |
| JP7414597B2 (ja) * | 2020-03-12 | 2024-01-16 | キオクシア株式会社 | 配線形成方法 |
| KR102527459B1 (ko) | 2020-05-29 | 2023-04-28 | 삼성에스디아이 주식회사 | 점착성 보호 필름, 이를 포함하는 광학 부재 및 이를 포함하는 광학표시장치 |
| TWI718980B (zh) * | 2020-08-07 | 2021-02-11 | 新唐科技股份有限公司 | 整合式感測裝置與其製造方法 |
| JP7736295B2 (ja) * | 2021-09-07 | 2025-09-09 | 株式会社エネコートテクノロジーズ | ペロブスカイト太陽電池 |
| CN115915793A (zh) * | 2021-09-30 | 2023-04-04 | 株式会社理光 | 光电转换元件、光电转换模块及电子设备 |
| JP7472409B2 (ja) * | 2022-01-07 | 2024-04-22 | パナソニックホールディングス株式会社 | 太陽電池 |
| CN114361338A (zh) * | 2022-01-07 | 2022-04-15 | 天津大学 | 一种增强n型半导体稳定性的方法 |
| EP4462976A4 (en) * | 2022-01-07 | 2025-05-07 | Panasonic Holdings Corporation | PHOTOELECTRIC CONVERSION MODULE |
| JP7535200B2 (ja) * | 2022-01-07 | 2024-08-15 | パナソニックホールディングス株式会社 | 太陽電池 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007516611A (ja) * | 2003-11-12 | 2007-06-21 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 電子デバイス用の封入アセンブリ |
| JP2007317565A (ja) * | 2006-05-26 | 2007-12-06 | Stanley Electric Co Ltd | 有機光電変換素子 |
| JP2007324259A (ja) * | 2006-05-31 | 2007-12-13 | Optrex Corp | 有機薄膜太陽電池デバイスの製造方法 |
| JP2009099805A (ja) * | 2007-10-17 | 2009-05-07 | Komatsu Seiren Co Ltd | 有機薄膜太陽電池用ホットメルト型部材及び有機薄膜太陽電池素子筐体封止パネル |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09148066A (ja) * | 1995-11-24 | 1997-06-06 | Pioneer Electron Corp | 有機el素子 |
| US6335479B1 (en) * | 1998-10-13 | 2002-01-01 | Dai Nippon Printing Co., Ltd. | Protective sheet for solar battery module, method of fabricating the same and solar battery module |
| CN1222195C (zh) * | 2000-07-24 | 2005-10-05 | Tdk株式会社 | 发光元件 |
| US7378124B2 (en) * | 2002-03-01 | 2008-05-27 | John James Daniels | Organic and inorganic light active devices and methods for making the same |
| JP4165227B2 (ja) * | 2003-01-07 | 2008-10-15 | 株式会社デンソー | 有機el表示装置 |
| KR100556274B1 (ko) * | 2004-04-01 | 2006-03-03 | 엘지전자 주식회사 | 유기 전계 발광 소자의 패시베이션 방법 |
| US7342356B2 (en) * | 2004-09-23 | 2008-03-11 | 3M Innovative Properties Company | Organic electroluminescent device having protective structure with boron oxide layer and inorganic barrier layer |
| TWI253879B (en) * | 2005-02-02 | 2006-04-21 | Au Optronics Corp | Encapsulation structure of organic electroluminescence device |
| US20070295390A1 (en) * | 2006-05-05 | 2007-12-27 | Nanosolar, Inc. | Individually encapsulated solar cells and solar cell strings having a substantially inorganic protective layer |
-
2010
- 2010-06-21 EP EP10792077.9A patent/EP2448032B1/en active Active
- 2010-06-21 JP JP2011519895A patent/JP5382119B2/ja active Active
- 2010-06-21 KR KR1020117030884A patent/KR101700989B1/ko active Active
- 2010-06-21 CN CN201080028354.7A patent/CN102804440B/zh active Active
- 2010-06-21 WO PCT/JP2010/060499 patent/WO2010150759A1/ja not_active Ceased
- 2010-06-24 TW TW099120580A patent/TW201115804A/zh unknown
-
2011
- 2011-12-23 US US13/336,420 patent/US20120125431A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007516611A (ja) * | 2003-11-12 | 2007-06-21 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 電子デバイス用の封入アセンブリ |
| JP2007317565A (ja) * | 2006-05-26 | 2007-12-06 | Stanley Electric Co Ltd | 有機光電変換素子 |
| JP2007324259A (ja) * | 2006-05-31 | 2007-12-13 | Optrex Corp | 有機薄膜太陽電池デバイスの製造方法 |
| JP2009099805A (ja) * | 2007-10-17 | 2009-05-07 | Komatsu Seiren Co Ltd | 有機薄膜太陽電池用ホットメルト型部材及び有機薄膜太陽電池素子筐体封止パネル |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP2448032A4 * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2013011741A1 (ja) * | 2011-07-15 | 2015-02-23 | コニカミノルタ株式会社 | 有機エレクトロルミネッセンスパネル及びその製造方法 |
| WO2013011741A1 (ja) * | 2011-07-15 | 2013-01-24 | コニカミノルタホールディングス株式会社 | 有機エレクトロルミネッセンスパネル及びその製造方法 |
| US10038112B2 (en) | 2011-08-04 | 2018-07-31 | 3M Innovative Properties Company | Edge protected barrier assemblies |
| JP2014529882A (ja) * | 2011-08-04 | 2014-11-13 | スリーエム イノベイティブプロパティズカンパニー | バリアアセンブリ |
| CN103988578A (zh) * | 2011-08-04 | 2014-08-13 | 3M创新有限公司 | 边缘受保护的阻隔组件 |
| JP2014526150A (ja) * | 2011-08-04 | 2014-10-02 | スリーエム イノベイティブ プロパティズ カンパニー | エッジの保護されたバリアー性組立品 |
| JP2014526985A (ja) * | 2011-08-04 | 2014-10-09 | スリーエム イノベイティブ プロパティズ カンパニー | エッジの保護されたバリアー性組立品 |
| JP2014529186A (ja) * | 2011-08-04 | 2014-10-30 | スリーエム イノベイティブ プロパティズ カンパニー | 縁部保護バリアアセンブリ |
| KR101911581B1 (ko) * | 2011-08-04 | 2018-10-24 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 에지 보호된 배리어 조립체 |
| KR101911582B1 (ko) * | 2011-08-04 | 2018-10-24 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 에지 보호된 배리어 조립체 |
| US9614113B2 (en) | 2011-08-04 | 2017-04-04 | 3M Innovative Properties Company | Edge protected barrier assemblies |
| JP2013211501A (ja) * | 2012-03-30 | 2013-10-10 | Sumitomo Chemical Co Ltd | 光電変換装置 |
| JP2013214477A (ja) * | 2012-04-04 | 2013-10-17 | Yazaki Corp | 端子付き電線 |
| JP2014049507A (ja) * | 2012-08-29 | 2014-03-17 | Mitsubishi Chemicals Corp | 有機薄膜太陽電池モジュール |
| JP2016504758A (ja) * | 2012-11-12 | 2016-02-12 | ダウ コーニング コーポレーションDow Corning Corporation | 光電池モジュール |
| US20150295111A1 (en) * | 2012-11-12 | 2015-10-15 | Dow Corning Corporation | Photovoltaic Cell Module |
| JPWO2014156494A1 (ja) * | 2013-03-29 | 2017-02-16 | 共同印刷株式会社 | 吸湿層を有する太陽電池用バックシート及びそれを用いた太陽電池 |
| JP2016063189A (ja) * | 2014-09-22 | 2016-04-25 | 株式会社東芝 | 光電変換装置 |
| WO2016047127A1 (ja) * | 2014-09-22 | 2016-03-31 | 株式会社 東芝 | 光電変換装置 |
| US10403838B2 (en) | 2014-09-22 | 2019-09-03 | Kabushiki Kaisha Toshiba | Photoelectric conversion device |
| JP2016122768A (ja) * | 2014-12-25 | 2016-07-07 | 国立研究開発法人産業技術総合研究所 | 有機薄膜太陽電池及び有機薄膜太陽電池内の酸素濃度検出装置 |
| JP2018037534A (ja) * | 2016-08-31 | 2018-03-08 | 日本放送協会 | 自己組織化単分子膜材料、有機エレクトロルミネッセンス素子、表示装置、照明装置、有機薄膜太陽電池、有機薄膜トランジスタ |
| US10453790B2 (en) | 2017-10-19 | 2019-10-22 | Samsung Electronics Co., Ltd. | Semiconductor package |
| WO2025154757A1 (ja) * | 2024-01-18 | 2025-07-24 | Tdk株式会社 | 太陽電池及びその製造方法 |
| JP7597430B1 (ja) | 2024-04-11 | 2024-12-10 | 今泉工業株式会社 | 光発電装置及びその製造方法 |
| JP2025161017A (ja) * | 2024-04-11 | 2025-10-24 | 今泉工業株式会社 | 光発電装置及びその製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201115804A (en) | 2011-05-01 |
| EP2448032A1 (en) | 2012-05-02 |
| CN102804440A (zh) | 2012-11-28 |
| CN102804440B (zh) | 2016-01-20 |
| KR101700989B1 (ko) | 2017-01-31 |
| KR20120111944A (ko) | 2012-10-11 |
| EP2448032B1 (en) | 2014-09-17 |
| JP5382119B2 (ja) | 2014-01-08 |
| JPWO2010150759A1 (ja) | 2012-12-10 |
| US20120125431A1 (en) | 2012-05-24 |
| EP2448032A4 (en) | 2013-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5382119B2 (ja) | 有機電子デバイス及びその製造方法 | |
| JP2012080060A (ja) | 有機太陽電池モジュール | |
| JP5612658B2 (ja) | 光電子デバイス | |
| JP2012064645A (ja) | 有機光電変換素子及びその製造方法 | |
| US20120125437A1 (en) | Solar cell module | |
| CN102341918A (zh) | 太阳能电池组件用保护片以及使用该保护片的太阳能电池组件 | |
| US20110073169A1 (en) | Gas barrier composite, back sheet for solar cell module and solar cell module | |
| JP5814843B2 (ja) | フレキシブル有機電子デバイス | |
| CN107431132A (zh) | 有机薄膜太阳能电池模块 | |
| JP5621657B2 (ja) | 太陽電池モジュール | |
| WO2014003187A1 (ja) | 有機薄膜太陽電池モジュール | |
| JP6558022B2 (ja) | 薄膜太陽電池モジュール | |
| JP2011254073A (ja) | ロールスクリーンシステム | |
| JP2016225628A (ja) | 有機薄膜太陽電池モジュール | |
| JP2016189466A (ja) | 有機薄膜太陽電池モジュール | |
| JP5515648B2 (ja) | 光電変換素子およびその素子を用いた太陽電池 | |
| JP2012009518A (ja) | 有機太陽電池モジュール | |
| Madogni et al. | Effects of residual oxygen in the degradation of the performance of organic bulk heterojunction solar cells: stability, role of the encapsulation | |
| JP2015090935A (ja) | 薄膜太陽電池モジュール及び薄膜太陽電池アレイ | |
| JP5303828B2 (ja) | 有機薄膜太陽電池 | |
| JP2018134844A (ja) | バリアフィルム及びバリアフィルムを備えた半導体デバイス | |
| JP2011054947A (ja) | 光電変換素子用電極バッファー材料ならびにこれを用いた光電変換素子 | |
| JP2011054948A (ja) | 光電変換素子材料、光電変換素子用電極バッファー材料ならびにこれを用いた光電変換素子 | |
| JP2014239087A (ja) | 有機薄膜太陽電池の設置方法 | |
| JP2014011320A (ja) | 太陽電池モジュール |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WWE | Wipo information: entry into national phase |
Ref document number: 201080028354.7 Country of ref document: CN |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10792077 Country of ref document: EP Kind code of ref document: A1 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2011519895 Country of ref document: JP |
|
| ENP | Entry into the national phase |
Ref document number: 20117030884 Country of ref document: KR Kind code of ref document: A |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 9746/CHENP/2011 Country of ref document: IN Ref document number: 2010792077 Country of ref document: EP |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |