WO2013038535A1 - Photoelectric conversion device - Google Patents

Photoelectric conversion device Download PDF

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Publication number
WO2013038535A1
WO2013038535A1 PCT/JP2011/071049 JP2011071049W WO2013038535A1 WO 2013038535 A1 WO2013038535 A1 WO 2013038535A1 JP 2011071049 W JP2011071049 W JP 2011071049W WO 2013038535 A1 WO2013038535 A1 WO 2013038535A1
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WO
WIPO (PCT)
Prior art keywords
electrode
layer
organic semiconductor
photoelectric conversion
conversion device
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PCT/JP2011/071049
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French (fr)
Japanese (ja)
Inventor
善孝 長草
裕之 潮田
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トヨタ自動車東日本株式会社
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Application filed by トヨタ自動車東日本株式会社 filed Critical トヨタ自動車東日本株式会社
Priority to PCT/JP2011/071049 priority Critical patent/WO2013038535A1/en
Priority to PCT/JP2012/072998 priority patent/WO2013039019A1/en
Priority to JP2013533648A priority patent/JP5881050B2/en
Priority to PCT/JP2012/072999 priority patent/WO2013039020A1/en
Priority to JP2013533649A priority patent/JP5957787B2/en
Publication of WO2013038535A1 publication Critical patent/WO2013038535A1/en

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    • 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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • 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

Definitions

  • the present invention relates to a photoelectric conversion device.
  • a photoelectric conversion device is a device that converts light into electrical energy and a device that converts electrical energy into light.
  • Examples of the former include solar cells, and examples of the latter include light emitting diodes.
  • the Si solar cell will be described by taking a single crystal Si solar cell as an example.
  • a p-type single crystal wafer is converted into a pn junction by changing the surface layer of the wafer to an n-type semiconductor by vapor phase diffusion or implantation of n-type impurity ions.
  • a pin junction is created.
  • a solar cell having a sandwich structure is manufactured by forming the front electrode and the back electrode.
  • a chalcopyrite solar cell will be described as an example. This is a solar cell provided with a CIGS layer made of a chalcopyrite compound (Cu (In + Ga) Se 2 ) containing elements of Group I, Group III and Group VI as constituent components as a p-type light absorption layer (for example, Patent Documents). 1).
  • a CIGS layer made of a chalcopyrite compound (Cu (In + Ga) Se 2 ) containing elements of Group I, Group III and Group VI as constituent components as a p-type light absorption layer (for example, Patent Documents). 1).
  • This solar cell with a CIGS layer generally prevents a back electrode layer, which is a positive electrode made of a Mo metal layer, on a glass substrate such as a soda lime glass (SLG) substrate, and Na unevenness caused by the SLG substrate.
  • a back electrode layer which is a positive electrode made of a Mo metal layer
  • SLG soda lime glass
  • a back electrode layer which is a positive electrode made of a Mo metal layer
  • a glass substrate such as a soda lime glass (SLG) substrate
  • SLG soda lime glass
  • the CIGS light absorbing layer is obtained by the following process. That is, the substrate itself provided with the In layer and the Cu—Ga layer as a precursor is accommodated in the annealing chamber and preheated. Thereafter, the precursor is converted into a CIGS layer by raising the temperature of the chamber to a temperature range of 500 to 520 ° C. while introducing H 2 Se gas through a gas introducing tube inserted into the annealing chamber.
  • organic semiconductor thin film solar cells are attracting attention as solar cells suitable for mass production because they can be formed by a coating method.
  • the organic solar cell has a so-called bulk heterojunction structure in which an organic donor material and an organic acceptor material are mixed.
  • an organic thin-film solar cell capable of forming a cathode on a flexible substrate by coating and a low-temperature process has been developed (for example, Patent Document 2).
  • an organic semiconductor thin film solar cell has a structure in which an anode, a photoelectric conversion layer having a bulk heterojunction structure, and a cathode are sequentially laminated on one surface of a substrate, and a silver oxide and a reducing agent
  • a laminated structure in which an electron transport layer doped with an organic metal is applied in the vicinity of the cathode not only the cathode is formed at a low temperature, but also the bonding between the organic metal doped layer and the cathode is improved. It is said.
  • the light irradiation side electrode is required to have good light transmittance and low electrical resistance.
  • the light irradiation side electrode needs to be formed by vapor deposition or plating of an expensive rare metal.
  • the process steps are complicated accordingly.
  • an object of the present invention is to provide a photoelectric conversion device that does not require optical transparency as an electrode material.
  • a photoelectric conversion device of the present invention is a photoelectric conversion device comprising a photoelectric conversion layer that converts light and electric energy, and a pair of electrodes provided on one side of the photoelectric conversion layer.
  • One electrode and the other electrode are provided side by side, a p-layer organic semiconductor made of a hole transport material is provided on the one electrode, and an electron transport is provided on the other electrode.
  • An n-layer organic semiconductor made of a material is provided, the one electrode functions as a p-type electrode, and the other electrode functions as an n-type electrode.
  • the p-layer organic semiconductor and the n-layer organic semiconductor are preferably covered with a transparent protective layer.
  • a p-layer organic semiconductor is laminated on one electrode and an n-layer organic semiconductor is laminated thereon to form a pn junction, and a transparent electrode is formed on the n-layer organic semiconductor as the other electrode.
  • the photoelectric conversion device is configured by sequentially stacking, according to the present invention, one electrode functioning as a p-type electrode and the other electrode functioning as an n-type electrode are formed on the same surface. Therefore, the transparent electrode material conventionally required as the electrode material becomes unnecessary.
  • the present invention can be manufactured on a flexible substrate such as a glass substrate.
  • an organic semiconductor can be provided over the electrode by coating, the manufacturing process is not complicated, and the organic semiconductor can be manufactured at low cost.
  • the photoelectric conversion device will be described assuming that a solar cell converts light into electric energy.
  • the present invention can also be applied to a device that converts electric energy into light energy.
  • FIG. 1 is a cross-sectional view of a photoelectric conversion device 1 according to a first embodiment of the present invention.
  • the photoelectric conversion device 1 according to the embodiment of the present invention includes a pair of electrodes 110 and 120 arranged side by side, and a photoelectric conversion layer 130 that covers the electrodes 110 and 120. I have.
  • the photoelectric conversion layer 130 is provided on one electrode 110, the other electrode 120 disposed side by side on the same plane with a predetermined distance from the one electrode 110, and the positive electrode provided on the one electrode 110. It is composed of a p-layer organic semiconductor 15 made of a hole transport material and an n-layer organic semiconductor 16 made of an electron transport material provided on the other electrode 120. The p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 are arranged adjacent to each other in the lateral direction to form a pn junction. The p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 including the pn junction are formed. A protective layer 17 is provided so as to cover the entire surface.
  • the p-layer organic semiconductor 15 is formed of a hole transport material.
  • a hole transport material in addition to triphenylamine (TAPC) represented by the chemical formula (1), TPD and other aromatic amines which are dimers of triphenylamine represented by the chemical formula (2), the chemical formula (3) ⁇ -NPD represented by formula (4), (DTP) DPPD represented by formula (4), m-MTDATA represented by formula (5), HTM1 represented by formula (6), 2-TNATA represented by formula (7), TPTE1 represented by the chemical formula (8), TCTA represented by the chemical formula (9), NTPA represented by the chemical formula (10), spiro TAD represented by the chemical formula (11), TFREL represented by the chemical formula (12), and the like are used.
  • TAPC triphenylamine
  • the n-layer organic semiconductor 16 is formed of an electron transport material.
  • the electron transport material include Alq 3 represented by the chemical formula (13), BCP represented by the chemical formula (14), an oxadiazole derivative represented by the chemical formula (15), and an oxadiazole dimer represented by the chemical formula (16).
  • the protective layer 17 is formed of, for example, resin or the like as long as it is a material that transmits irradiation light such as sunlight.
  • a pair of electrodes 110 and 120 are formed on the same surface.
  • the same surface may be either a virtual surface or a substrate surface, but when formed on the substrate surface, it may be a flat substrate or a flexible substrate that can be bent.
  • An appropriate method such as vapor deposition, sputtering, or plating is used to form the electrode. Photolithographic techniques may be used as necessary.
  • One electrode 1110 and the other electrode 120 are formed by the same process.
  • a hole transport material to be the p-layer organic semiconductor 15 is applied to a predetermined portion, for example, one electrode 110.
  • a printing method using an inkjet printer can be applied.
  • an electron transport material to be the n-layer organic semiconductor 16 is applied between the p layer and the p layer, for example, the other electrode 120.
  • a printing technique using an inkjet printer can be used for coating.
  • a pn junction is formed by the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16.
  • the n-layer organic semiconductor 16 may be applied, and then the p-layer organic semiconductor 15 may be applied.
  • the photoelectric conversion device 1 is manufactured by forming the protective layer 17 by painting or the like. Note that the method is not limited to the above-described method as long as the photoelectric conversion device 1 illustrated in FIG. 1 is manufactured.
  • the electrodes for the photoelectric conversion device are alternately arranged planes in which one electrode functioning as a p-type electrode and the other electrode functioning as an n-type electrode are formed side by side. It has an electrode structure. Therefore, it is not necessary to provide a p-layer organic semiconductor on one electrode and an n-layer organic semiconductor on the other electrode to form a pn junction in layers and to provide a transparent electrode on the organic semiconductor. . Therefore, in the present invention, it is not necessary to use a transparent electrode material as the electrode material.
  • the photoelectric conversion device 1 can be manufactured on a flexible substrate such as a glass substrate or the like. Since an organic semiconductor can be provided on the electrode by coating, the manufacturing process is not complicated, and the organic semiconductor can be manufactured at low cost.
  • FIG. 2 is a cross-sectional view of a photoelectric conversion device 1A according to a first modification of the embodiment of the present invention.
  • the photoelectric conversion device 1 ⁇ / b> A includes an insulating base material 11, one electrode 13 and the other electrode 14 as photoelectric conversion device electrodes 12 formed side by side on the base material 11, A p-layer organic semiconductor 15 made of a hole transport material provided on one electrode 13, an n-layer organic semiconductor 16 made of an electron transport material provided on the other electrode 14, and a p-layer organic semiconductor 15 And a protective layer 17 provided so as to cover the n-layer organic semiconductor 16.
  • the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 form a pn junction.
  • the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 are formed side by side on the photoelectric conversion device electrode 12.
  • one electrode 13 and the other electrode 14 constituting the photoelectric conversion device electrode 12 are formed side by side on the surface of the base material 11, similarly to the organic semiconductor 15 and the organic semiconductor 16. Therefore, it is not necessary to provide an electrode on the light incident surface as in Patent Document 2, and it is not necessary to use a rare metal for the transparent electrode provided on the light irradiation side of Patent Document 2 as a material. Therefore, as will be described later, the photoelectric conversion device electrode 12 may use Cu, Al, or the like.
  • the base material 11 may be various types such as a glass substrate, a resin substrate, and a printed circuit board.
  • the mounting surface of the photoelectric conversion device may not be a flat surface but may be a curved surface.
  • FIG. 3 is a plan view of the electrode for the photoelectric conversion device 1A shown in FIG. 2, and FIG. 4 is an enlarged view of a portion A in FIG.
  • one electrode 13 and the other electrode 14 are configured as comb electrodes.
  • the comb-tooth electrode has a structure in which a plurality of electrode fingers 13a and 14a arranged in a comb-like shape in parallel at an appropriate interval are electrically connected at one end by connection electrodes 13b and 14b.
  • connection electrode 13b and the other connection electrode 14b are arranged opposite to each other, and the electrode fingers 13a and 14a are arranged within the space between each other, whereby the electrode finger 13a of one electrode and the other electrode The electrode fingers 14a are alternately arranged.
  • an interdigital electrode is formed by one electrode 13 and the other electrode 14.
  • the interdigital electrode is composed of comb electrodes interleaved with each other, and the electrode fingers 13a and electrode fingers 14a of the comb electrodes are alternately arranged.
  • One electrode 13 and the other electrode 14 are respectively connected to electrode electrodes 13a, 14a and one end of the connection electrodes 13b, 14b, and one end of the connection electrodes 13b, 14b, and a connection terminal for external wiring And lead-out electrodes 13c and 14c extending to 13d and 14d.
  • the electrode fingers 13 a and 14 a are formed to extend left and right, and the electrode fingers 13 a and the electrode fingers 14 a are alternately spaced at predetermined intervals in a direction substantially perpendicular to the extending direction. The same number is lined up.
  • the left end of each electrode finger 13a is connected to the connection electrode 14b, and the lead-out electrode 13c extends from the lower end of the connection electrode 14b to the connection terminal 13d with the external wiring along the aforementioned extending direction.
  • the right end of each electrode finger 14a is connected to the connection electrode 14b, and a connection terminal 14d for external wiring is formed at the lower end of the connection electrode 14b. In other words, depending on the position of the connection terminal with the external wiring, the lead electrode may not be necessary.
  • Organic semiconductors 15 and 16 are provided on such an electrode structure.
  • a p-layer organic semiconductor 15 is formed on at least the electrode finger 13 a of one electrode 13, and an n-layer organic semiconductor 16 is formed on at least the electrode finger 14 a of the other electrode 14. Therefore, the electrode finger 13a of one electrode 13 functions as a p-type electrode, and the electrode finger 14a of the other electrode 14 functions as an n-type electrode.
  • a hole transport material to be the p-layer organic semiconductor 15 is applied to a predetermined portion, for example, one electrode 13.
  • a printing method using an inkjet printer can be applied.
  • an electron transport material to be the n-layer organic semiconductor 16 is applied between the p layer and the p layer, for example, the other electrode 14.
  • a printing technique using an inkjet printer can be used for the application.
  • a pn junction is formed by the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16.
  • the n-layer organic semiconductor 16 may be applied, and then the p-layer organic semiconductor 15 may be applied.
  • the protective layer 17 is formed by painting or the like to produce the photoelectric conversion device 1A. Note that the method is not limited to the above-described method as long as the photoelectric conversion device 1A illustrated in FIG. 2 is manufactured.
  • this photoelectric conversion device 1A like the above-described photoelectric conversion device 1, an alternating array in which one electrode functioning as a p-type electrode and the other electrode functioning as an n-type electrode are formed side by side on a substrate. It has a planar electrode structure. Therefore, it is not necessary to provide a p-layer organic semiconductor on one electrode and an n-layer organic semiconductor on the other electrode to form a pn junction and provide an electrode on the organic semiconductor. Therefore, it is not necessary to use a transparent electrode material as the electrode material.
  • FIG. 5 is a cross-sectional view of a photoelectric conversion device 1B according to a second modification of the embodiment of the present invention
  • FIG. 6 is a perspective view of the photoelectric conversion device 1B.
  • the photoelectric conversion device 1B includes an insulating base material 11 ′, an electrode 12 ′ provided on the upper surface of the base material 11 ′, a photoelectric conversion layer 130 that covers the electrode 12 ′, and a protective layer that covers the upper surface of the photoelectric conversion layer 130. 17. In FIG. 6, the display of the photoelectric conversion layer 130 and the protective layer 17 is omitted.
  • the base material 11 ′ is formed in a sheet shape and has flexibility. For example, what was formed as a flexible substrate by PET etc. is used. In this embodiment, as shown in FIG. 6, the base material 11 ′ has a rectangular outline.
  • the short side is referred to as the first side 11A ′
  • the long side is referred to as the second side 11B ′.
  • the electrode 12 ′ will be described with reference to FIG.
  • a plurality of weft yarns 12B ′ disposed at a predetermined pitch in the extending direction of the first side 11A ′.
  • the warp yarns 12A 'and the weft yarns 12B' are woven so as to intersect each other. That is, the electrode 12 'is formed in a plain weave net shape.
  • the warp yarn 12A ′ As the warp yarn 12A ′ extending along the first side 11A ′, three kinds of wires are used. Specifically, the first metal wire 121 ′, the second metal wire 122 ′, and the first insulating wire 123 ′ are used. As shown in FIG. 6, the first metal wire 121 ′ and the second metal wire 122 ′ are alternately arranged, and the first metal wire 121 ′ and the second metal wire 122 ′ are arranged between the first metal wire 121 ′ and the second metal wire 122 ′. An insulating wire 123 'is provided.
  • first metal wire 121 ′ and the second metal wire 122 ′ for example, a copper wire, a stainless wire, a wire obtained by performing metal plating on the surface of a chemical fiber, or the like can be used.
  • One end 121E ′ of each first metal wire 121 ′ is connected to the first bus bar 121A ′ as shown in FIG.
  • Each second metal wire 122 ' has an end 122E' located on the other end 121F 'side of the first metal wire 121' connected to the second bus bar 122A '.
  • the first insulating wire 123 ′ is made of a flexible insulating resin such as nylon resin, silicone resin, urethane resin, epoxy resin, polycarbonate resin, vinyl resin, or the like.
  • the second insulating wire is used as the weft 12B 'extending along the second side 11B'. Similar to the first insulating wire 123 ', the second insulating wire is made of a flexible insulating resin such as nylon resin, silicone resin, urethane resin, epoxy resin, polycarbonate resin, or vinyl resin.
  • a flexible insulating resin such as nylon resin, silicone resin, urethane resin, epoxy resin, polycarbonate resin, or vinyl resin.
  • the first metal wire 121 ′, the second metal wire 122 ′, the first insulating wire 123 ′, and the second insulating wire are set to a thickness of about 20 ⁇ m to 30 ⁇ m.
  • FIG. 7 is a schematic enlarged view of a circle B region in FIG.
  • the photoelectric conversion layer 130 is provided on one electrode, that is, the p-layer organic semiconductor 15 made of a hole transport material provided on the first metal wire 121 ′ and the second metal wire 122 ′ as the other electrode.
  • an n-layer organic semiconductor 16 made of an electron transport material. Therefore, one first metal wire 121 ′ functions as a p-type electrode, and the other second metal wire 122 ′ functions as an n-type electrode.
  • the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 form a pn junction.
  • the first metal wire 121 ′ and the second metal wire 122 ′ constituting the photoelectric conversion device electrode 12 ′ are formed on the base material 11 ′, and the first metal wire 121 ′ and the second metal wire 121 ′ are further formed.
  • a p-layer organic semiconductor 13A ′ and an n-layer organic semiconductor 13B ′ are formed on the same surface so as to cover the metal wire 122 ′. Therefore, the surface on which light is incident can be the protective layer 17 instead of the photoelectric conversion device electrode 12 side.
  • the protective layer 17 is provided so as to cover the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16.
  • the protective layer 17 is formed of, for example, a resin or the like as long as it is a material that transmits irradiation light such as sunlight.
  • a method for manufacturing the photoelectric conversion device 1B shown in FIG. First, the base material 11 ′ is prepared. Next, the first metal wire 121 ′, the second metal wire 122 ′, the first insulating wire 123 ′, and the second insulating wire are prepared and plain woven. An electrode 12 ′ formed by plain weaving is fixed on the substrate 11 with, for example, an adhesive. Thereafter, a hole transport material to be the p-layer organic semiconductor 15 is applied on a predetermined portion, for example, on the first metal wire 121 ′ as one electrode. For the application, for example, a printing method using an inkjet printer can be applied.
  • an electron transport material to be the n-layer organic semiconductor 16 is applied between the p layer and the p layer, for example, on the second metal wire 122 ′ as the other electrode.
  • a printing technique using an inkjet printer can be used for coating.
  • a pn junction is formed by the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16.
  • the n-layer organic semiconductor 16 may be applied, and then the p-layer organic semiconductor 15 may be applied.
  • the protective layer 17 is formed by painting or the like to produce the photoelectric conversion device 1B. Note that the method is not limited to the above method as long as the photoelectric conversion device 1B illustrated in FIG. 5 is manufactured.
  • the first metal wire 121 ′ and the second metal wire 122 ′ constituting the photoelectric conversion device electrode 12 ′ are formed on the base material 11 ′, and the first metal wire 121 is further formed.
  • a p-layer organic semiconductor 15 and an n-layer organic semiconductor 16 are formed on the base material 11 'so as to cover' and the second metal wire 122 '. Therefore, the surface on which light is incident can be the protective layer 17 instead of the photoelectric conversion device electrode 12 ′ side. Therefore, it is not necessary to configure the electrode with a transparent electrode, and it is not necessary to use a rare metal for the transparent electrode as a material. Therefore, Cu, Al, etc. can be used for electrode 12 'for photoelectric conversion devices. Further, in the photoelectric conversion device 1B, since the electrode 12 'is formed of a flexible net, it can be attached to a curved surface after being formed in a flat shape.
  • the present invention can be implemented with appropriate modifications within the scope of the present invention.
  • the configuration in which one first insulating wire 123 ′ is provided between the first metal wire 121 ′ and the second metal wire 122 ′ is described, but a plurality of the first insulating wire 123 ′ may be provided.
  • the photoelectric conversion device 1B may be configured by omitting the base material 11 '.

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  • Photovoltaic Devices (AREA)

Abstract

A photoelectric conversion device (1) which is provided with: a photoelectric conversion layer (130) that performs conversion between light and electrical energy; and a pair of electrodes (110, 120) that are provided on one surface of the photoelectric conversion layer. One electrode (110) and the other electrode (120) are arranged abreast of each other. An organic semiconductor (15) of a p-layer, which is composed of a hole transport material, is provided on the electrode (110), and an organic semiconductor (16) of an n-layer, which is composed of an electron transport material, is provided on the electrode (120). The electrode (110) functions as a p-type electrode, and the electrode (120) functions as an n-type electrode.

Description

光電変換デバイスPhotoelectric conversion device
　本発明は、光電変換デバイスに関する。 The present invention relates to a photoelectric conversion device.
　光電変換デバイスは、光を電気エネルギーに変換するデバイス及び電気エネルギーを光に変換するデバイスである。前者の例としては太陽電池などがあり、後者の例としては発光ダイオードなどがある。 A photoelectric conversion device is a device that converts light into electrical energy and a device that converts electrical energy into light. Examples of the former include solar cells, and examples of the latter include light emitting diodes.
　今日、クリーンエネルギーの一つとして太陽電池による電力供給の必要性が再認識されている。太陽電池にはＳｉ太陽電池、化合物太陽電池のほか有機半導体薄膜太陽電池など各種のものがある。 Today, the need for solar power supply as a clean energy is recognized again. There are various types of solar cells such as Si solar cells, compound solar cells, and organic semiconductor thin film solar cells.
　Ｓｉ太陽電池について単結晶Ｓｉ太陽電池を例にとって説明すると、ｐ型の単結晶ウエハに気相拡散やｎ型不純物イオンの打ち込み等によってウエハの表面層をｎ型半導体にするなどしてｐｎ接合やｐｉｎ接合が作られる。そして表面電極と裏面電極とを形成してサンドイッチ構造の太陽電池が作製される。 The Si solar cell will be described by taking a single crystal Si solar cell as an example. A p-type single crystal wafer is converted into a pn junction by changing the surface layer of the wafer to an n-type semiconductor by vapor phase diffusion or implantation of n-type impurity ions. A pin junction is created. Then, a solar cell having a sandwich structure is manufactured by forming the front electrode and the back electrode.
　化合物太陽電池の中には各種のものがあるが、エネルギー変換効率が高く、経年変化による光劣化が起こりにくく、耐放射性特性に優れ、光吸収波長領域が広く、光吸収係数が大きいといった利点を有するカルコパイライト型太陽電池を例にとって説明する。これはＩ族、ＩＩＩ族及びＶＩ族の元素を構成成分とするカルコパイライト化合物（Ｃｕ（Ｉｎ＋Ｇａ）Ｓｅ2）から成るＣＩＧＳ層をｐ型の光吸収層として備えた太陽電池である（例えば特許文献１）。 There are various types of compound solar cells, but they have the advantages of high energy conversion efficiency, low light degradation due to secular change, excellent radiation resistance, wide light absorption wavelength range, and large light absorption coefficient. A chalcopyrite solar cell will be described as an example. This is a solar cell provided with a CIGS layer made of a chalcopyrite compound (Cu (In + Ga) Se 2 ) containing elements of Group I, Group III and Group VI as constituent components as a p-type light absorption layer (for example, Patent Documents). 1).
　このＣＩＧＳ層を備えた太陽電池は、一般的に、ソーダライムガラス（ＳＬＧ）基板といったガラス基板上に、Ｍｏ金属層からなる正極たる裏面電極層と、ＳＬＧ基板に由来して生じるＮａムラを防止するためのＮａディップ層と、ＣＩＧＳ光吸収層と、ｎ型のバッファ層と、負極たる透明電極層による最外表面層と、を備えた多層積層構造で構成される。
　ここで、ｎ型のバッファ層はＣｄＳ、ＺｎＯ、ＩｎＳなどで形成され、透明電極層はＺｎＯＡｌなどが用いられる。 This solar cell with a CIGS layer generally prevents a back electrode layer, which is a positive electrode made of a Mo metal layer, on a glass substrate such as a soda lime glass (SLG) substrate, and Na unevenness caused by the SLG substrate. For forming a multilayer structure including a Na dip layer, a CIGS light absorption layer, an n-type buffer layer, and an outermost surface layer formed of a transparent electrode layer as a negative electrode.
Here, the n-type buffer layer is made of CdS, ZnO, InS or the like, and the transparent electrode layer is made of ZnOAl or the like.
　この多層積層構造にあっては、表面の受光部から照射光が入射すると、多層積層構造のｐ－ｎ接合付近では、バンドギャップ以上のエネルギーを有する照射光によって励起されて一対の電子及び正孔が生じる。励起された電子と正孔とは拡散によりｐ－ｎ接合部に達し、接合の内部電界により、電子がｎ領域に、正孔がｐ領域に集合して分離される。この結果、ｎ領域が負に帯電し、ｐ領域が正に帯電し、各領域に設けた電極間で電位差が生じる。この電位差を起電力として、各電極間を導線で結線したときに光電流が得られる。 In this multilayer laminated structure, when irradiation light enters from the light receiving portion on the surface, a pair of electrons and holes are excited in the vicinity of the pn junction of the multilayer laminated structure by the irradiation light having energy greater than the band gap. Occurs. The excited electrons and holes reach the pn junction by diffusion, and the electrons are collected in the n region and the holes are separated in the p region due to the internal electric field of the junction. As a result, the n region is negatively charged, the p region is positively charged, and a potential difference is generated between the electrodes provided in each region. Using this potential difference as an electromotive force, a photocurrent is obtained when the electrodes are connected by a conductive wire.
　ＣＩＧＳ光吸収層は次のような工程によって得られる。即ち、Ｉｎ層とＣｕ－Ｇａ層とを積層状態にして前駆体として備える基板自体をアニール処理室内に収容してプレヒートを行う。その後、アニール処理室内に挿入したガス導入管によってＨ2Ｓｅガスを導入しつつ室内を５００乃至５２０℃の温度範囲に昇温することによって、前駆体をＣＩＧＳ層に変換する。 The CIGS light absorbing layer is obtained by the following process. That is, the substrate itself provided with the In layer and the Cu—Ga layer as a precursor is accommodated in the annealing chamber and preheated. Thereafter, the precursor is converted into a CIGS layer by raising the temperature of the chamber to a temperature range of 500 to 520 ° C. while introducing H 2 Se gas through a gas introducing tube inserted into the annealing chamber.
　これに対し、有機半導体薄膜太陽電池は塗布法によって形成することができるため、大量生産に適した太陽電池として注目されている。有機太陽電池は、有機ドナー材料と有機アクセプター材料を混合した、所謂バルクヘテロジャンクション構造を有している。その中でも、塗布及び低温プロセスでフレキシブル基板への陰極形成を可能とした有機薄膜太陽電池が開発されている（例えば、特許文献２）。 On the other hand, organic semiconductor thin film solar cells are attracting attention as solar cells suitable for mass production because they can be formed by a coating method. The organic solar cell has a so-called bulk heterojunction structure in which an organic donor material and an organic acceptor material are mixed. Among them, an organic thin-film solar cell capable of forming a cathode on a flexible substrate by coating and a low-temperature process has been developed (for example, Patent Document 2).
　特許文献２によれば、有機半導体薄膜太陽電池が、基板の一方面上に、陽極、バルクヘテロジャンクション構造を有する光電変換層及び陰極が順に積層された構造を有していて、酸化銀と還元剤からなる陰極と、陰極近傍に有機金属をドープした電子輸送層を塗布した積層構造とすることにより、低温で陰極が形成されるだけでなく、有機金属ドープ層と陰極との接合が改良されるとしている。 According to Patent Document 2, an organic semiconductor thin film solar cell has a structure in which an anode, a photoelectric conversion layer having a bulk heterojunction structure, and a cathode are sequentially laminated on one surface of a substrate, and a silver oxide and a reducing agent By forming a laminated structure in which an electron transport layer doped with an organic metal is applied in the vicinity of the cathode, not only the cathode is formed at a low temperature, but also the bonding between the organic metal doped layer and the cathode is improved. It is said.
特開２００６－１９６７７１号公報Japanese Patent Laid-Open No. 2006-196771 特開２０１１－１２４４６８号公報JP 2011-124468 A
　しかしながら、従来の構造においては、ｐｎ接合となる領域を挟んで一対の電極を設ける必要があった。そのため、光照射側の電極は、光透過性がよく、かつ電気抵抗が小さいものが要求されており、そのために、光照射側の電極は高価なレアメタルを蒸着やメッキにより形成する必要がある。またそれに伴いプロセス工程が複雑であった。 However, in the conventional structure, it is necessary to provide a pair of electrodes across a region that becomes a pn junction. For this reason, the light irradiation side electrode is required to have good light transmittance and low electrical resistance. For this reason, the light irradiation side electrode needs to be formed by vapor deposition or plating of an expensive rare metal. In addition, the process steps are complicated accordingly.
　そこで、本発明は、電極材料として光透過性を要求しない、光電変換デバイスを提供することを目的とする。 Therefore, an object of the present invention is to provide a photoelectric conversion device that does not require optical transparency as an electrode material.
　上記目的を達成するために、本発明の光電変換デバイスは、光と電気エネルギーとを変換する光電変換層と、上記光電変換層の片面に設けられる一対の電極と、を備えた光電変換デバイスであって、一方の電極と他方の電極とが横並びに設けられており、上記一方の電極上には正孔輸送材料でなるｐ層の有機半導体が設けられ、上記他方の電極上には電子輸送材料でなるｎ層の有機半導体が設けられ、上記一方の電極がｐ型電極として機能し、上記他方の電極がｎ型電極として機能することを特徴としている。
　本発明において、好ましくは前記ｐ層の有機半導体及び前記ｎ層の有機半導体は透明の保護層で覆われている。 In order to achieve the above object, a photoelectric conversion device of the present invention is a photoelectric conversion device comprising a photoelectric conversion layer that converts light and electric energy, and a pair of electrodes provided on one side of the photoelectric conversion layer. One electrode and the other electrode are provided side by side, a p-layer organic semiconductor made of a hole transport material is provided on the one electrode, and an electron transport is provided on the other electrode. An n-layer organic semiconductor made of a material is provided, the one electrode functions as a p-type electrode, and the other electrode functions as an n-type electrode.
In the present invention, the p-layer organic semiconductor and the n-layer organic semiconductor are preferably covered with a transparent protective layer.
　従来では、一方の電極上にｐ層の有機半導体を積層しその上にｎ層の有機半導体を積層してｐｎ接合を形成すると共に、このｎ層の有機半導体上に他方の電極として透明電極を順次積層して光電変換デバイスを構成していたが、本発明によれば、電極が、ｐ型電極として機能する一方の電極とｎ型電極として機能する他方の電極とが同一面上に形成されていることから、電極材料として従来必要としていた透明電極材料が不要となる。本発明は、ガラス基板などのフレキシブル性のない基板上でもフレキシブル性のある基板上にも作製することができる。また、電極上に塗布によって有機半導体を設けることができるため、作製工程が複雑とならず、また、安価に作製することができる。 Conventionally, a p-layer organic semiconductor is laminated on one electrode and an n-layer organic semiconductor is laminated thereon to form a pn junction, and a transparent electrode is formed on the n-layer organic semiconductor as the other electrode. Although the photoelectric conversion device is configured by sequentially stacking, according to the present invention, one electrode functioning as a p-type electrode and the other electrode functioning as an n-type electrode are formed on the same surface. Therefore, the transparent electrode material conventionally required as the electrode material becomes unnecessary. The present invention can be manufactured on a flexible substrate such as a glass substrate. In addition, since an organic semiconductor can be provided over the electrode by coating, the manufacturing process is not complicated, and the organic semiconductor can be manufactured at low cost.
本発明の実施形態に係る光電変換デバイスの断面図である。It is sectional drawing of the photoelectric conversion device which concerns on embodiment of this invention. 本発明の実施形態の第１変形例に係る光電変換デバイスの断面図である。It is sectional drawing of the photoelectric conversion device which concerns on the 1st modification of embodiment of this invention. 図２に示す光電変換デバイスにおける電極構造を示す平面図である。It is a top view which shows the electrode structure in the photoelectric conversion device shown in FIG. 図３において符号Ａの領域の拡大図である。FIG. 4 is an enlarged view of a region A in FIG. 3. 本発明の実施形態の第２変形例に係る光電変換デバイスの断面図である。It is sectional drawing of the photoelectric conversion device which concerns on the 2nd modification of embodiment of this invention. 図５に示す光電変換デバイスにおける電極構造を示す斜視図である。It is a perspective view which shows the electrode structure in the photoelectric conversion device shown in FIG. 図５に示す符号Ａの領域の拡大図である。It is an enlarged view of the area | region of the code | symbol A shown in FIG.
　以下図面を参照しながら、本発明の実施形態を詳細に説明する。特に光電変換デバイスが、光を電気エネルギーに変換するものとして太陽電池を想定して説明するが、電気エネルギーを光エネルギーに変換するものであっても同様に適用することができる。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In particular, the photoelectric conversion device will be described assuming that a solar cell converts light into electric energy. However, the present invention can also be applied to a device that converts electric energy into light energy.
　図１は、本発明の第１実施形態に係る光電変換デバイス１の断面図である。図１に示すように、本発明の実施形態に係る光電変換デバイス１は、横並びに配置された一対の電極１１０，１２０と、これらの電極１１０，１２０の上を覆う光電変換層１３０と、を備えている。 FIG. 1 is a cross-sectional view of a photoelectric conversion device 1 according to a first embodiment of the present invention. As shown in FIG. 1, the photoelectric conversion device 1 according to the embodiment of the present invention includes a pair of electrodes 110 and 120 arranged side by side, and a photoelectric conversion layer 130 that covers the electrodes 110 and 120. I have.
　光電変換層１３０は、一方の電極１１０と、この一方の電極１１０と所定の距離をあけて同一面上に横並びに配置された他方の電極１２０と、上記一方の電極１１０上に設けられて正孔輸送材料でなるｐ層の有機半導体１５と、上記他方の電極１２０上に設けられ電子輸送材料でなるｎ層の有機半導体１６とから構成されている。ｐ層の有機半導体１５及びｎ層の有機半導体１６は互いに横方向に隣接して配置されてｐｎ接合を形成しており、このｐｎ接合を含むｐ層の有機半導体１５及びｎ層の有機半導体１６の表面全体を被覆するように保護層１７が設けられる。 The photoelectric conversion layer 130 is provided on one electrode 110, the other electrode 120 disposed side by side on the same plane with a predetermined distance from the one electrode 110, and the positive electrode provided on the one electrode 110. It is composed of a p-layer organic semiconductor 15 made of a hole transport material and an n-layer organic semiconductor 16 made of an electron transport material provided on the other electrode 120. The p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 are arranged adjacent to each other in the lateral direction to form a pn junction. The p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 including the pn junction are formed. A protective layer 17 is provided so as to cover the entire surface.
　ｐ層の有機半導体１５は、正孔輸送材料によって形成される。正孔輸送材料としては、化学式（１）で示されるトリフェニルアミン（ＴＡＰＣ）、化学式（２）で示されるトリフェニルアミンの二量体であるＴＰＤその他の芳香族アミンのほか、化学式（３）で示されるα－ＮＰＤ、化学式（４）で示される（ＤＴＰ）ＤＰＰＤ、化学式（５）で示されるｍ－ＭＴＤＡＴＡ、化学式（６）で示されるＨＴＭ１、化学式（７）で示される２－ＴＮＡＴＡ、化学式（８）で示されるＴＰＴＥ１、化学式（９）で示されるＴＣＴＡ、化学式（１０）で示されるＮＴＰＡ、化学式（１１）で示されるスピローＴＡＤ、化学式（１２）で示されるＴＦＬＥＬなどが用いられる。 The p-layer organic semiconductor 15 is formed of a hole transport material. As a hole transport material, in addition to triphenylamine (TAPC) represented by the chemical formula (1), TPD and other aromatic amines which are dimers of triphenylamine represented by the chemical formula (2), the chemical formula (3) Α-NPD represented by formula (4), (DTP) DPPD represented by formula (4), m-MTDATA represented by formula (5), HTM1 represented by formula (6), 2-TNATA represented by formula (7), TPTE1 represented by the chemical formula (8), TCTA represented by the chemical formula (9), NTPA represented by the chemical formula (10), spiro TAD represented by the chemical formula (11), TFREL represented by the chemical formula (12), and the like are used.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　ｎ層の有機半導体１６は電子輸送材料によって形成される。電子輸送材料には、化学式（１３）で示されるＡｌｑ3、化学式（１４）で示されるＢＣＰ、化学式（１５）で示されるオキサジアゾール誘導体、化学式（１６）で示されるオキサジアゾール二量体、化学式（１７）で示されるスターバストオキサジアゾール、化学式（１８）で示されるトリアゾール誘導体、化学式（１９）で示されるフェニルキシキサリン誘導体、化学式（２０）で示されるシロール誘導体などが挙げられる。 The n-layer organic semiconductor 16 is formed of an electron transport material. Examples of the electron transport material include Alq 3 represented by the chemical formula (13), BCP represented by the chemical formula (14), an oxadiazole derivative represented by the chemical formula (15), and an oxadiazole dimer represented by the chemical formula (16). And Starbust Oxadiazole represented by Chemical Formula (17), Triazole Derivative represented by Chemical Formula (18), Phenylxoxaline Derivative represented by Chemical Formula (19), Silole Derivative represented by Chemical Formula (20), and the like.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　保護層１７については、太陽光などの照射光を透過する材料であればその種類は問わず、例えば樹脂等によって形成される。 The protective layer 17 is formed of, for example, resin or the like as long as it is a material that transmits irradiation light such as sunlight.
　　図１に示す光電変換デバイス１の製造方法について概略説明する。まず、一対の電極１１０，１２０を同一面上に形成する。ここで同一面とは、仮想面又は基板面の何れであってもよいが、基板面に形成する場合は、それが平面基板であっても湾曲可能なフレキシブル基板であってもよい。電極の形成には蒸着、スパッタリング又はメッキなどの適宜の方法が用いられる。必要に応じてフォトリソグラフィー技術を用いてもよい。一方の電極１１１０、他方の電極１２０は同一の工程により形成される。 A method for manufacturing the photoelectric conversion device 1 shown in FIG. First, a pair of electrodes 110 and 120 are formed on the same surface. Here, the same surface may be either a virtual surface or a substrate surface, but when formed on the substrate surface, it may be a flat substrate or a flexible substrate that can be bent. An appropriate method such as vapor deposition, sputtering, or plating is used to form the electrode. Photolithographic techniques may be used as necessary. One electrode 1110 and the other electrode 120 are formed by the same process.
　その後、ｐ層の有機半導体１５となる正孔輸送材料を所定の箇所、例えば一方の電極１１０に塗布する。塗布には、例えばインクジェットプリンタによる印刷方法を適用可能である。 Thereafter, a hole transport material to be the p-layer organic semiconductor 15 is applied to a predetermined portion, for example, one electrode 110. For the application, for example, a printing method using an inkjet printer can be applied.
　次に、ｎ層の有機半導体１６となる電子輸送材料をｐ層とｐ層との間、例えば他方の電極１２０に塗布する。塗布にはｐ層の有機半導体１５の場合と同様、インクジェットプリンタによる印刷技術を用いることができる。 Next, an electron transport material to be the n-layer organic semiconductor 16 is applied between the p layer and the p layer, for example, the other electrode 120. As in the case of the p-layer organic semiconductor 15, a printing technique using an inkjet printer can be used for coating.
　これにより、ｐ層の有機半導体１５とｎ層の有機半導体１６とによってｐｎ接合が形成される。なお、ｎ層の有機半導体１６から塗布しその後ｐ層の有機半導体１５を塗布してもよい。 Thereby, a pn junction is formed by the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16. The n-layer organic semiconductor 16 may be applied, and then the p-layer organic semiconductor 15 may be applied.
　その後、保護層１７を塗装などによって形成して光電変換デバイス１が作製される。なお、図１に示す光電変換デバイス１が作製される手法であれば上述の方法に限定されない。 Thereafter, the photoelectric conversion device 1 is manufactured by forming the protective layer 17 by painting or the like. Note that the method is not limited to the above-described method as long as the photoelectric conversion device 1 illustrated in FIG. 1 is manufactured.
　本実施形態に係る光電変換デバイス１によれば、光電変換デバイス用電極が、ｐ型電極として機能する一方の電極とｎ型電極として機能する他方の電極とが横並びに形成されている交互配列平面電極構造となっている。そのため、一方の電極上にｐ層の有機半導体を設けかつ他方の電極上にｎ層の有機半導体を設けてｐｎ接合を層状に形成して、その有機半導体の上に透明電極を設ける必要がない。そのため、本発明では電極材料として透明電極材料を用いる必要がない。光電変換デバイス１は、ガラス基板などのフレキシブル性のない基板でもフレキシブル性のある基板上にも作製することができる。電極上に塗布によって有機半導体を設けることができるため、作製工程が複雑とならず、また、安価に作製することができる。 According to the photoelectric conversion device 1 according to the present embodiment, the electrodes for the photoelectric conversion device are alternately arranged planes in which one electrode functioning as a p-type electrode and the other electrode functioning as an n-type electrode are formed side by side. It has an electrode structure. Therefore, it is not necessary to provide a p-layer organic semiconductor on one electrode and an n-layer organic semiconductor on the other electrode to form a pn junction in layers and to provide a transparent electrode on the organic semiconductor. . Therefore, in the present invention, it is not necessary to use a transparent electrode material as the electrode material. The photoelectric conversion device 1 can be manufactured on a flexible substrate such as a glass substrate or the like. Since an organic semiconductor can be provided on the electrode by coating, the manufacturing process is not complicated, and the organic semiconductor can be manufactured at low cost.
［実施形態の第１変形例］
　図２は、本発明の実施形態の第１変形例に係る光電変換デバイス１Ａの断面図である。図２に示すように、光電変換デバイス１Ａは、絶縁性の基材１１と、この基材１１の上に並べて形成された光電変換デバイス用電極１２として一方の電極１３及び他方の電極１４と、一方の電極１３上に設けられて正孔輸送材料でなるｐ層の有機半導体１５と、他方の電極１４上に設けられ電子輸送材料でなるｎ層の有機半導体１６と、ｐ層の有機半導体１５及びｎ層の有機半導体１６を被覆するように設けられる保護層１７とで構成される。ｐ層の有機半導体１５とｎ層の有機半導体１６とはｐｎ接合を形成している。 [First Modification of Embodiment]
FIG. 2 is a cross-sectional view of a photoelectric conversion device 1A according to a first modification of the embodiment of the present invention. As shown in FIG. 2, the photoelectric conversion device 1 </ b> A includes an insulating base material 11, one electrode 13 and the other electrode 14 as photoelectric conversion device electrodes 12 formed side by side on the base material 11, A p-layer organic semiconductor 15 made of a hole transport material provided on one electrode 13, an n-layer organic semiconductor 16 made of an electron transport material provided on the other electrode 14, and a p-layer organic semiconductor 15 And a protective layer 17 provided so as to cover the n-layer organic semiconductor 16. The p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 form a pn junction.
　このように、ｐ層の有機半導体１５とｎ層の有機半導体１６とが光電変換デバイス用電極１２の上に並べて形成されている。また、光電変換デバイス用電極１２を構成する一方の電極１３と他方の電極１４とが、有機半導体１５及び有機半導体１６と同様に、基材１１の面上に並んで形成されている。よって、光が入射する面に、特許文献２のように電極を設ける必要がなく、ひいては特許文献２の光照射側に設ける透明電極のためのレアメタルを材料として使用しなくて済む。そのため、後述するように、光電変換デバイス用電極１２はＣｕやＡｌなどを使用することができる。 Thus, the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 are formed side by side on the photoelectric conversion device electrode 12. Also, one electrode 13 and the other electrode 14 constituting the photoelectric conversion device electrode 12 are formed side by side on the surface of the base material 11, similarly to the organic semiconductor 15 and the organic semiconductor 16. Therefore, it is not necessary to provide an electrode on the light incident surface as in Patent Document 2, and it is not necessary to use a rare metal for the transparent electrode provided on the light irradiation side of Patent Document 2 as a material. Therefore, as will be described later, the photoelectric conversion device electrode 12 may use Cu, Al, or the like.
　基材１１は、ガラス基板、樹脂基板、プリント基板等各種のものが用いられ得る。基材１１として樹脂基板等を用いた場合には、光電変換デバイスの取付面が平面でなくても湾曲した曲面であっても構わない。 The base material 11 may be various types such as a glass substrate, a resin substrate, and a printed circuit board. When a resin substrate or the like is used as the base material 11, the mounting surface of the photoelectric conversion device may not be a flat surface but may be a curved surface.
　一方の電極１３及び他方の電極１４について説明する。図３は図２に示す光電変換デバイス１Ａ用電極の平面図であり、図４は図３においてＡの部分の拡大図である。図３に示すように、一方の電極１３及び他方の電極１４は櫛歯電極として構成されている。櫛歯電極は、適宜の間隔で並行して櫛歯状に配置された複数本の電極指１３ａ，１４ａが、一端で接続用電極１３ｂ，１４ｂによって電気的に接続された構造を有する。一方の接続用電極１３ｂと他方の接続用電極１４ｂとは互いに対向配置され、それらの電極指１３ａ，１４ａが互いの間隔内に配置されることで、一方の電極の電極指１３ａと他方の電極の電極指１４ａとが交互に並んでいる。 One electrode 13 and the other electrode 14 will be described. 3 is a plan view of the electrode for the photoelectric conversion device 1A shown in FIG. 2, and FIG. 4 is an enlarged view of a portion A in FIG. As shown in FIG. 3, one electrode 13 and the other electrode 14 are configured as comb electrodes. The comb-tooth electrode has a structure in which a plurality of electrode fingers 13a and 14a arranged in a comb-like shape in parallel at an appropriate interval are electrically connected at one end by connection electrodes 13b and 14b. One connection electrode 13b and the other connection electrode 14b are arranged opposite to each other, and the electrode fingers 13a and 14a are arranged within the space between each other, whereby the electrode finger 13a of one electrode and the other electrode The electrode fingers 14a are alternately arranged.
　つまり、一方の電極１３及び他方の電極１４によりインターデジタル電極が形成されている。インターデジタル電極は互いに間挿し合う櫛歯電極で構成されており、各櫛歯電極の電極指１３ａと電極指１４ａとが交互に並んでいる。 That is, an interdigital electrode is formed by one electrode 13 and the other electrode 14. The interdigital electrode is composed of comb electrodes interleaved with each other, and the electrode fingers 13a and electrode fingers 14a of the comb electrodes are alternately arranged.
　一方の電極１３及び他方の電極１４は、それぞれ、電極指１３ａ，１４ａとその一端を接続する接続用電極１３ｂ，１４ｂと、その接続用電極１３ｂ，１４ｂの一端に接続され外部配線との接続端子１３ｄ，１４ｄまで延びる引き回し電極１３ｃ，１４ｃとを有する。 One electrode 13 and the other electrode 14 are respectively connected to electrode electrodes 13a, 14a and one end of the connection electrodes 13b, 14b, and one end of the connection electrodes 13b, 14b, and a connection terminal for external wiring And lead-out electrodes 13c and 14c extending to 13d and 14d.
　図３に示す場合にあっては、各電極指１３ａ，１４ａが左右に延びて形成されており、その延設方向にほぼ直交する方向に電極指１３ａと電極指１４ａとが交互に所定の間隔をあけて同数本並んでいる。各電極指１３ａの左一端が接続用電極１４ｂに接続され、引き回し電極１３ｃがその接続用電極１４ｂの下端から前述の延設方向に沿って外部配線との接続端子１３ｄまで延びている。一方、各電極指１４ａの右一端が接続用電極１４ｂに接続され、接続用電極１４ｂの下端に外部配線との接続端子１４ｄが形成されている。つまり、外部配線との接続端子の位置によっては引き回し電極が不要となる場合もある。 In the case shown in FIG. 3, the electrode fingers 13 a and 14 a are formed to extend left and right, and the electrode fingers 13 a and the electrode fingers 14 a are alternately spaced at predetermined intervals in a direction substantially perpendicular to the extending direction. The same number is lined up. The left end of each electrode finger 13a is connected to the connection electrode 14b, and the lead-out electrode 13c extends from the lower end of the connection electrode 14b to the connection terminal 13d with the external wiring along the aforementioned extending direction. On the other hand, the right end of each electrode finger 14a is connected to the connection electrode 14b, and a connection terminal 14d for external wiring is formed at the lower end of the connection electrode 14b. In other words, depending on the position of the connection terminal with the external wiring, the lead electrode may not be necessary.
　このような電極構造の上に、有機半導体１５，１６が設けられている。一方の電極１３のうち少なくとも電極指１３ａ上にはｐ層の有機半導体１５が形成され、他方の電極１４のうち少なくとも電極指１４ａ上にはｎ層の有機半導体１６が形成される。よって、一方の電極１３のうち電極指１３ａはｐ型電極として機能し、他方の電極１４のうち電極指１４ａはｎ型電極として機能する。 Organic semiconductors 15 and 16 are provided on such an electrode structure. A p-layer organic semiconductor 15 is formed on at least the electrode finger 13 a of one electrode 13, and an n-layer organic semiconductor 16 is formed on at least the electrode finger 14 a of the other electrode 14. Therefore, the electrode finger 13a of one electrode 13 functions as a p-type electrode, and the electrode finger 14a of the other electrode 14 functions as an n-type electrode.
　　図２に示す光電変換デバイス１Ａの製造方法について概略説明する。まず、基材１１を用意し、この基材１１上に所定間隔を置いて一方の電極１３及び他方の電極１４を形成する。電極形成には蒸着、スパッタリング又はメッキなどの適宜の方法が用いられる。必要に応じてフォトリソグラフィー技術を用いてもよい。一方の電極１３、他方の電極１４は同一の工程により形成される。 A method for manufacturing the photoelectric conversion device 1A shown in FIG. First, a base material 11 is prepared, and one electrode 13 and the other electrode 14 are formed on the base material 11 at a predetermined interval. An appropriate method such as vapor deposition, sputtering, or plating is used for electrode formation. Photolithographic techniques may be used as necessary. One electrode 13 and the other electrode 14 are formed by the same process.
　その後、ｐ層の有機半導体１５となる正孔輸送材料を所定の箇所、例えば一方の電極１３に塗布する。塗布には、例えばインクジェットプリンタによる印刷方法を適用可能である。 Thereafter, a hole transport material to be the p-layer organic semiconductor 15 is applied to a predetermined portion, for example, one electrode 13. For the application, for example, a printing method using an inkjet printer can be applied.
　次に、ｎ層の有機半導体１６となる電子輸送材料をｐ層とｐ層との間、例えば他方の電極１４に塗布する。塗布には、ｐ層の有機半導体１５の場合と同様、インクジェットプリンタによる印刷技術を用いることができる。 Next, an electron transport material to be the n-layer organic semiconductor 16 is applied between the p layer and the p layer, for example, the other electrode 14. As in the case of the p-layer organic semiconductor 15, a printing technique using an inkjet printer can be used for the application.
　これにより、ｐ層の有機半導体１５とｎ層の有機半導体１６とによってｐｎ接合が形成される。なお、ｎ層の有機半導体１６から塗布しその後ｐ層の有機半導体１５を塗布してもよい。 Thereby, a pn junction is formed by the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16. The n-layer organic semiconductor 16 may be applied, and then the p-layer organic semiconductor 15 may be applied.
　その後、保護層１７を塗装などによって形成して光電変換デバイス１Ａが作製される。なお、図２に示す光電変換デバイス１Ａが作製される手法であれば上述の方法に限定されない。 Thereafter, the protective layer 17 is formed by painting or the like to produce the photoelectric conversion device 1A. Note that the method is not limited to the above-described method as long as the photoelectric conversion device 1A illustrated in FIG. 2 is manufactured.
　この光電変換デバイス１Ａにおいても、前述の光電変換デバイス１と同様に、ｐ型電極として機能する一方の電極とｎ型電極として機能する他方の電極とが基材上に並べて形成されている交互配列平面電極構造となっている。そのため、一方の電極上にｐ層の有機半導体を設けかつ他方の電極上にｎ層の有機半導体を設けてｐｎ接合を形成して、その有機半導体の上に電極を設ける必要がない。そのため、電極材料として透明電極材料を用いる必要がない。 Also in this photoelectric conversion device 1A, like the above-described photoelectric conversion device 1, an alternating array in which one electrode functioning as a p-type electrode and the other electrode functioning as an n-type electrode are formed side by side on a substrate. It has a planar electrode structure. Therefore, it is not necessary to provide a p-layer organic semiconductor on one electrode and an n-layer organic semiconductor on the other electrode to form a pn junction and provide an electrode on the organic semiconductor. Therefore, it is not necessary to use a transparent electrode material as the electrode material.
［実施形態の第２変形例］
　図５は本発明の実施形態の第２変形例に係る光電変換デバイス１Ｂの断面図であり、図６は光電変換デバイス１Ｂの斜視図である。 [Second Modification of Embodiment]
FIG. 5 is a cross-sectional view of a photoelectric conversion device 1B according to a second modification of the embodiment of the present invention, and FIG. 6 is a perspective view of the photoelectric conversion device 1B.
　光電変換デバイス１Ｂは、絶縁性の基材１１′と、基材１１′の上面に設けた電極１２′と、電極１２′を覆う光電変換層１３０と、光電変換層１３０の上面を覆う保護層１７と、から構成されている。なお、図６では、光電変換層１３０と、保護層１７との表示を省略している。 The photoelectric conversion device 1B includes an insulating base material 11 ′, an electrode 12 ′ provided on the upper surface of the base material 11 ′, a photoelectric conversion layer 130 that covers the electrode 12 ′, and a protective layer that covers the upper surface of the photoelectric conversion layer 130. 17. In FIG. 6, the display of the photoelectric conversion layer 130 and the protective layer 17 is omitted.
　基材１１′はシート状に形成され、可撓性を有する。例えば、ＰＥＴなどによってフレキシブル基板として形成されたものを用いる。本実施形態では、図６に示すように基材１１′は輪郭が長方形に形成されている。以下、説明の便宜上、短い辺を第１辺１１Ａ′と呼び、長い辺を第２辺１１Ｂ′とする。 The base material 11 ′ is formed in a sheet shape and has flexibility. For example, what was formed as a flexible substrate by PET etc. is used. In this embodiment, as shown in FIG. 6, the base material 11 ′ has a rectangular outline. Hereinafter, for convenience of explanation, the short side is referred to as the first side 11A ′, and the long side is referred to as the second side 11B ′.
　図６を用いて電極１２′について説明する。電極１２′は、基材１１′の第１辺１１Ａ′に沿って延びていてさらに第２辺１１Ｂ′の延出方向に所定のピッチで配置された複数の縦糸１２Ａ′と、基材１１′の第２辺１１Ｂ′に沿って延びていてさらに第１辺１１Ａ′の延出方向に所定のピッチで配置された複数の横糸１２Ｂ′と、を備えている。縦糸１２Ａ′と横糸１２Ｂ′とは１本ごとに交差するように織られている。つまり電極１２′は平織りのネット状に形成されている。 The electrode 12 ′ will be described with reference to FIG. The electrode 12 'extends along the first side 11A' of the base material 11 'and further has a plurality of warps 12A' arranged at a predetermined pitch in the extending direction of the second side 11B ', and the base material 11'. And a plurality of weft yarns 12B ′ disposed at a predetermined pitch in the extending direction of the first side 11A ′. The warp yarns 12A 'and the weft yarns 12B' are woven so as to intersect each other. That is, the electrode 12 'is formed in a plain weave net shape.
　第１辺１１Ａ′に沿って延びる縦糸１２Ａ′として、３種の線材を利用する。具体的には、第１金属線材１２１′と第２金属線材１２２′と第１絶縁線材１２３′とを利用する。
　図６に示すように、第１金属線材１２１′と第２金属線材１２２′とは交互に並べられており、これらの第１金属線材１２１′と第２金属線材１２２′との間に第１絶縁線材１２３′が設けられている。なお、第１金属線材１２１′と第２金属線材１２２′との間隔は、それらの間に挟まれる第１絶縁線材１２３′の断面の直径と同等であるが、図面では、構成の理解を容易にするために各部材同士の間に空隙を設けて表している。 As the warp yarn 12A ′ extending along the first side 11A ′, three kinds of wires are used. Specifically, the first metal wire 121 ′, the second metal wire 122 ′, and the first insulating wire 123 ′ are used.
As shown in FIG. 6, the first metal wire 121 ′ and the second metal wire 122 ′ are alternately arranged, and the first metal wire 121 ′ and the second metal wire 122 ′ are arranged between the first metal wire 121 ′ and the second metal wire 122 ′. An insulating wire 123 'is provided. In addition, although the space | interval of 1st metal wire 121 'and 2nd metal wire 122' is equivalent to the diameter of the cross section of 1st insulated wire 123 'pinched | interposed between them, it is easy to understand a structure in drawing. Therefore, a gap is provided between the members.
　これらの第１金属線材１２１′と第２金属線材１２２′として、例えば銅線、ステンレス線、化学繊維の表面に金属めっき処理を施した線などを利用することができる。各第１金属線材１２１′の一端部１２１Ｅ′は図６に示すように第１のバスバー１２１Ａ′に接続されている。各第２金属線材１２２′は第１金属線材１２１′の他端部１２１Ｆ′側に位置する端部１２２Ｅ′を第２のバスバー１２２Ａ′に接続されている。 As the first metal wire 121 ′ and the second metal wire 122 ′, for example, a copper wire, a stainless wire, a wire obtained by performing metal plating on the surface of a chemical fiber, or the like can be used. One end 121E ′ of each first metal wire 121 ′ is connected to the first bus bar 121A ′ as shown in FIG. Each second metal wire 122 'has an end 122E' located on the other end 121F 'side of the first metal wire 121' connected to the second bus bar 122A '.
　第１絶縁線材１２３′は、例えばナイロン樹脂、シリコーン樹脂、ウレタン樹脂、エポキシ樹脂、ポリカーボネート樹脂、ビニル樹脂などの柔軟性に富む絶縁樹脂によって構成されている。 The first insulating wire 123 ′ is made of a flexible insulating resin such as nylon resin, silicone resin, urethane resin, epoxy resin, polycarbonate resin, vinyl resin, or the like.
　第２辺１１Ｂ′に沿って延びる横糸１２Ｂ′として第２絶縁線材を用いる。第２絶縁線材は、第１絶縁線材１２３′と同様に、例えばナイロン樹脂、シリコーン樹脂、ウレタン樹脂、エポキシ樹脂、ポリカーボネート樹脂、ビニル樹脂などの柔軟性に富む絶縁樹脂によって構成されている。 The second insulating wire is used as the weft 12B 'extending along the second side 11B'. Similar to the first insulating wire 123 ', the second insulating wire is made of a flexible insulating resin such as nylon resin, silicone resin, urethane resin, epoxy resin, polycarbonate resin, or vinyl resin.
　第１金属線材１２１′、第２金属線材１２２′、第１絶縁線材１２３′及び第２絶縁線材は、２０μｍ～３０μｍ程度の太さに設定されている。 The first metal wire 121 ′, the second metal wire 122 ′, the first insulating wire 123 ′, and the second insulating wire are set to a thickness of about 20 μm to 30 μm.
　次に、光電変換層１３０について説明する。
　図７は図５の円Ｂ領域の模式的拡大図である。光電変換層１３０は、一方の電極、つまり第１金属線材１２１′上に設けられて正孔輸送材料でなるｐ層の有機半導体１５と、他方の電極としての第２金属線材１２２′上に設けられ電子輸送材料でなるｎ層の有機半導体１６と、から構成されている。よって、一方の第１金属線材１２１′はｐ型電極として機能し、他方の第２金属線材１２２′はｎ型電極として機能する。ｐ層の有機半導体１５とｎ層の有機半導体１６とはｐｎ接合を形成している。 Next, the photoelectric conversion layer 130 will be described.
FIG. 7 is a schematic enlarged view of a circle B region in FIG. The photoelectric conversion layer 130 is provided on one electrode, that is, the p-layer organic semiconductor 15 made of a hole transport material provided on the first metal wire 121 ′ and the second metal wire 122 ′ as the other electrode. And an n-layer organic semiconductor 16 made of an electron transport material. Therefore, one first metal wire 121 ′ functions as a p-type electrode, and the other second metal wire 122 ′ functions as an n-type electrode. The p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 form a pn junction.
　以上のように、基材１１′上に、光電変換デバイス用電極１２′を構成する第１金属線材１２１′と第２金属線材１２２′とが形成され、さらに第１金属線材１２１′と第２金属線材１２２′とを覆うように、ｐ層の有機半導体１３Ａ′とｎ層の有機半導体１３Ｂ′とが同一面上に形成されている。よって、光が入射する面を光電変換デバイス用電極１２側ではなく、保護層１７とすることが可能となる。 As described above, the first metal wire 121 ′ and the second metal wire 122 ′ constituting the photoelectric conversion device electrode 12 ′ are formed on the base material 11 ′, and the first metal wire 121 ′ and the second metal wire 121 ′ are further formed. A p-layer organic semiconductor 13A ′ and an n-layer organic semiconductor 13B ′ are formed on the same surface so as to cover the metal wire 122 ′. Therefore, the surface on which light is incident can be the protective layer 17 instead of the photoelectric conversion device electrode 12 side.
　保護層１７は、ｐ層の有機半導体１５及びｎ層の有機半導体１６を被覆するように設けられている。保護層１７については、太陽光などの照射光を透過する材料であればその種類は問わず、例えば樹脂等によって形成される。 The protective layer 17 is provided so as to cover the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16. The protective layer 17 is formed of, for example, a resin or the like as long as it is a material that transmits irradiation light such as sunlight.
　図５に示す光電変換デバイス１Ｂの製造方法について概略説明する。まず、基材１１′を用意する。次に、第１金属線材１２１′、第２金属線材１２２′、第１絶縁線材１２３′、第２絶縁線材を準備し、平織りする。平織りして形成した電極１２′を基材１１上に例えば接着剤などによって固定する。その後、ｐ層の有機半導体１５となる正孔輸送材料を所定の箇所、例えば一方の電極としての第１金属線材１２１′上に塗布する。塗布には、例えばインクジェットプリンタによる印刷方法を適用可能である。 A method for manufacturing the photoelectric conversion device 1B shown in FIG. First, the base material 11 ′ is prepared. Next, the first metal wire 121 ′, the second metal wire 122 ′, the first insulating wire 123 ′, and the second insulating wire are prepared and plain woven. An electrode 12 ′ formed by plain weaving is fixed on the substrate 11 with, for example, an adhesive. Thereafter, a hole transport material to be the p-layer organic semiconductor 15 is applied on a predetermined portion, for example, on the first metal wire 121 ′ as one electrode. For the application, for example, a printing method using an inkjet printer can be applied.
　次に、ｎ層の有機半導体１６となる電子輸送材料をｐ層とｐ層との間、例えば他方の電極としての第２金属線材１２２′上に塗布する。塗布にはｐ層の有機半導体１５の場合と同様、インクジェットプリンタによる印刷技術を用いることができる。 Next, an electron transport material to be the n-layer organic semiconductor 16 is applied between the p layer and the p layer, for example, on the second metal wire 122 ′ as the other electrode. As in the case of the p-layer organic semiconductor 15, a printing technique using an inkjet printer can be used for coating.
　これにより、ｐ層の有機半導体１５とｎ層の有機半導体１６とによってｐｎ接合が形成される。なお、ｎ層の有機半導体１６から塗布しその後ｐ層の有機半導体１５を塗布してもよい。 Thereby, a pn junction is formed by the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16. The n-layer organic semiconductor 16 may be applied, and then the p-layer organic semiconductor 15 may be applied.
　その後、保護層１７を塗装などによって形成して光電変換デバイス１Ｂが作製される。なお、図５に示す光電変換デバイス１Ｂが作製される手法であれば上述の方法に限定されない。 Thereafter, the protective layer 17 is formed by painting or the like to produce the photoelectric conversion device 1B. Note that the method is not limited to the above method as long as the photoelectric conversion device 1B illustrated in FIG. 5 is manufactured.
　このように本発明によれば、基材１１′上に、光電変換デバイス用電極１２′を構成する第１金属線材１２１′と第２金属線材１２２′とが形成され、さらに第１金属線材１２１′と第２金属線材１２２′とを覆うように、ｐ層の有機半導体１５とｎ層の有機半導体１６とが基材１１′上に形成されている。よって、光が入射する面を光電変換デバイス用電極１２′側ではなく、保護層１７とすることが可能となる。よって、電極を透明電極で構成することが不要であり、透明電極のためのレアメタルを材料として使用しなくて済む。そのため、光電変換デバイス用の電極１２′はＣｕやＡｌなどを使用することができる。
　また、光電変換デバイス１Ｂは、電極１２′が可撓性を有するネットで構成されているため、平面状に形成した後に、曲面状の表面に取り付けることができる。 As described above, according to the present invention, the first metal wire 121 ′ and the second metal wire 122 ′ constituting the photoelectric conversion device electrode 12 ′ are formed on the base material 11 ′, and the first metal wire 121 is further formed. A p-layer organic semiconductor 15 and an n-layer organic semiconductor 16 are formed on the base material 11 'so as to cover' and the second metal wire 122 '. Therefore, the surface on which light is incident can be the protective layer 17 instead of the photoelectric conversion device electrode 12 ′ side. Therefore, it is not necessary to configure the electrode with a transparent electrode, and it is not necessary to use a rare metal for the transparent electrode as a material. Therefore, Cu, Al, etc. can be used for electrode 12 'for photoelectric conversion devices.
Further, in the photoelectric conversion device 1B, since the electrode 12 'is formed of a flexible net, it can be attached to a curved surface after being formed in a flat shape.
　以上本発明の実施形態を説明したが、本発明の範囲において適宜変更して実施することができる。
　上記図５の構成では、第１絶縁線材１２３′が第１金属線材１２１′と第２金属線材１２２′との間に１本設けられる構成を説明したが、複数本設けられてもよい。
　また、光電変換デバイス１Ｂは基材１１′を省略して構成されてもよい。 Although the embodiments of the present invention have been described above, the present invention can be implemented with appropriate modifications within the scope of the present invention.
In the configuration of FIG. 5 described above, the configuration in which one first insulating wire 123 ′ is provided between the first metal wire 121 ′ and the second metal wire 122 ′ is described, but a plurality of the first insulating wire 123 ′ may be provided.
Further, the photoelectric conversion device 1B may be configured by omitting the base material 11 '.
１，１Ａ，１Ｂ　：光電変換デバイス
１１０，１２０　：電極
１１，１１′　　：基材
１２，１２′　　：光電変換デバイス用電極
１２Ａ′　　　　：縦糸
１２Ｂ′　　　　：横糸
１２１′　　　　：第１金属線材
１２２′　　　　：第２金属線材
１２３′　　　　：第１絶縁線材
１３　　　　　　：一方の電極
１４　　　　　　：他方の電極
１３ａ，１４ａ　：電極指
１３ｂ，１４ｂ　：接続用電極
１３ｃ　　　　　：引き回し電極
１３ｄ，１４ｄ　：外部配線との接続端子
１５　　　　　　：ｐ層の有機半導体
１６　　　　　　：ｎ層の有機半導体
１７　　　　　　：保護層 1, 1A, 1B: Photoelectric conversion devices 110, 120: Electrodes 11, 11 ': Base material 12, 12': Electrode conversion device electrodes 12A ': Warp yarn 12B': Weft yarn 121 ': First metal wire 122': First 2 metal wires 123 ′: first insulating wire 13: one electrode 14: other electrodes 13a, 14a: electrode fingers 13b, 14b: connection electrodes 13c: routing electrodes 13d, 14d: connection terminals 15 to the external wiring 15: p Layer organic semiconductor 16: n layer organic semiconductor 17: protective layer

Claims (2)

  1. 　光と電気エネルギーとを変換する光電変換層と、上記光電変換層の片面に設けられる一対の電極と、を備えた光電変換デバイスであって、
    　一方の電極と他方の電極とが横並びに設けられており、
    　上記一方の電極上には正孔輸送材料でなるｐ層の有機半導体が設けられ、
    　上記他方の電極上には電子輸送材料でなるｎ層の有機半導体が設けられ、
    　上記一方の電極がｐ型電極として機能し、上記他方の電極がｎ型電極として機能することを特徴とする、光電変換デバイス。     A photoelectric conversion device comprising a photoelectric conversion layer for converting light and electric energy, and a pair of electrodes provided on one side of the photoelectric conversion layer,
    One electrode and the other electrode are provided side by side,
    A p-layer organic semiconductor made of a hole transport material is provided on the one electrode,
    An n-layer organic semiconductor made of an electron transport material is provided on the other electrode,
    The photoelectric conversion device, wherein the one electrode functions as a p-type electrode and the other electrode functions as an n-type electrode.
  2. 　前記ｐ層の有機半導体及び前記ｎ層の有機半導体は、透明の保護層で覆われている、請求項１に記載の光電変換デバイス。 The photoelectric conversion device according to claim 1, wherein the organic semiconductor of the p layer and the organic semiconductor of the n layer are covered with a transparent protective layer.
PCT/JP2011/071049 2011-09-14 2011-09-14 Photoelectric conversion device WO2013038535A1 (en)

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PCT/JP2011/071049 WO2013038535A1 (en) 2011-09-14 2011-09-14 Photoelectric conversion device
PCT/JP2012/072998 WO2013039019A1 (en) 2011-09-14 2012-09-09 Electrode for photoelectric conversion device, and photoelectric conversion device
JP2013533648A JP5881050B2 (en) 2011-09-14 2012-09-09 Photoelectric conversion device
PCT/JP2012/072999 WO2013039020A1 (en) 2011-09-14 2012-09-09 Method for manufacturing photoelectric conversion device, electrode for photoelectric conversion device, photoelectric conversion device, and light-emitting device
JP2013533649A JP5957787B2 (en) 2011-09-14 2012-09-09 Method for producing photoelectric conversion device and photoelectric conversion device

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57172778A (en) * 1981-09-02 1982-10-23 Sharp Corp Solar battery
JPH04109681A (en) * 1990-08-29 1992-04-10 Oki Electric Ind Co Ltd Vertical pn junction solar battery
JP2004103939A (en) * 2002-09-11 2004-04-02 Japan Science & Technology Corp Upright type superlattice, manufacturing method thereof, and device
JP2005011841A (en) * 2003-06-16 2005-01-13 Japan Science & Technology Agency Vertical junction organic photovoltaic device and its manufacturing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57172778A (en) * 1981-09-02 1982-10-23 Sharp Corp Solar battery
JPH04109681A (en) * 1990-08-29 1992-04-10 Oki Electric Ind Co Ltd Vertical pn junction solar battery
JP2004103939A (en) * 2002-09-11 2004-04-02 Japan Science & Technology Corp Upright type superlattice, manufacturing method thereof, and device
JP2005011841A (en) * 2003-06-16 2005-01-13 Japan Science & Technology Agency Vertical junction organic photovoltaic device and its manufacturing method

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