WO2013039019A1 - Electrode for photoelectric conversion device, and photoelectric conversion device - Google Patents
Electrode for photoelectric conversion device, and photoelectric conversion device Download PDFInfo
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- WO2013039019A1 WO2013039019A1 PCT/JP2012/072998 JP2012072998W WO2013039019A1 WO 2013039019 A1 WO2013039019 A1 WO 2013039019A1 JP 2012072998 W JP2012072998 W JP 2012072998W WO 2013039019 A1 WO2013039019 A1 WO 2013039019A1
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- electrode
- photoelectric conversion
- organic semiconductor
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
-
- 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
- H10K30/80—Constructional details
- H10K30/81—Electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K30/83—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising arrangements for extracting the current from the cell, e.g. metal finger grid systems to reduce the serial resistance of transparent electrodes
-
- 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 electrode for a photoelectric conversion device used for a photoelectric conversion device and a photoelectric conversion device using the same.
- 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 taking a single crystal Si solar cell as an example.
- a pn junction or a pin junction is formed by making the surface layer of the wafer an n-type semiconductor by vapor phase diffusion or implantation of n-type impurity ions into a p-type single crystal wafer.
- a solar cell having a sandwich structure is manufactured by forming a front electrode and a back electrode.
- This chalcopyrite solar cell includes 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.
- a chalcopyrite compound Cu (In + Ga) Se 2
- Group I, Group III, and Group VI as constituent components as a p-type light absorption layer.
- 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 the gas introduction 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 the cathode is oxidized by coating. It consists of silver and a reducing agent, and the electron transport layer is formed by doping an organic metal in the vicinity of the cathode by coating, so that not only the cathode is formed at a low temperature, but also the bonding between the organic metal doped layer and the cathode is achieved. It is going to be improved.
- 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 an electrode for a photoelectric conversion device that does not require optical transparency as an electrode material and a photoelectric conversion device using the same.
- the electrode for a photoelectric conversion device of the present invention has one electrode and the other electrode formed on the same surface, one electrode functions as a p-type electrode, and the other electrode Functions as an n-type electrode.
- one electrode and the other electrode are provided side by side.
- the one electrode and the other electrode are preferably composed of comb electrodes having a structure in which a plurality of electrode fingers are electrically connected at one end, and the electrode fingers of one electrode and the electrode fingers of the other electrode Are lined up alternately.
- One electrode and the other electrode can be formed of either Cu or Al.
- the photoelectric conversion device of the present invention comprises the electrode for a photoelectric conversion device of the present invention, a p-layer organic semiconductor made of a hole transport material provided on one electrode, and an electron transport material provided on the other electrode.
- an n-layer organic semiconductor, and the p-layer organic semiconductor and the n-layer organic semiconductor are alternately formed on the same surface.
- the photoelectric conversion device of the present invention includes the above-mentioned electrode for a photoelectric conversion device, an n-layer organic semiconductor made of an electron transport material provided on one electrode, and a p made of a hole transport material provided on the other electrode.
- a p-layer organic semiconductor and an n-layer organic semiconductor are alternately formed on the same surface.
- the p-layer organic semiconductor and the n-layer organic semiconductor are covered with a transparent protective layer.
- an electrode for a photoelectric conversion device is formed on an insulating base material having a plurality of through holes according to a pattern, and the base material surface while filling the through holes of the base material with a conductive material
- one electrode is mutually connected by the electroconductive film formed in the back surface of a base material.
- one electrode has the protrusion part protruded from the surface of the base material.
- the external connection part of one electrode is provided on the back surface of the base material, and the external connection part of the other electrode is provided on the surface of the base material.
- One electrode and the other electrode can be formed of either Cu or Al.
- the photoelectric conversion device of the present invention includes the above-described electrode for a photoelectric conversion device, a p-layer organic semiconductor made of a hole transport material provided on one electrode, and an n transport material made of an electron transport material provided on the other electrode.
- a p-layer organic semiconductor and an n-layer organic semiconductor are alternately formed on the same surface.
- the p-layer organic semiconductor and the n-layer organic semiconductor are covered with a transparent protective layer.
- one electrode functioning as a p-type electrode and the other electrode functioning as an n-type electrode can be formed on one surface side of the photoelectric conversion device, There is no need to provide an electrode on the surface to be irradiated.
- This electrode for a photoelectric conversion device can be produced on a substrate having no flexibility or a substrate having flexibility. Since an organic semiconductor can be provided on the electrode by coating, the manufacturing process is not complicated, and the electrode can be manufactured at a low cost.
- Photoelectric conversion device 2 Electrode for photoelectric conversion device 3, 4: Electrode 5: Photoelectric conversion layer 6: p-layer organic semiconductor 7: n-layer organic semiconductor 8: protective layer 9: light 10: photoelectric conversion device 11: Substrate 12: Electrode for photoelectric conversion device 13: One electrode 14: The other electrode 13a, 14a: Electrode finger 13b, 14b: Connection electrode 13c: Lead-out electrode 13d, 14d: Connection terminal with external wiring 15: P layer Organic semiconductor 16: n-layer organic semiconductor 17: protective layer 18: photoelectric conversion layer 19: light 20: photoelectric conversion device 21: base material 21a: through hole 22 of base material: electrode 23 for photoelectric conversion device: one electrode 23a: Electrode body (dot electrode) 23b: Filling part (via conductor part) 23c: Wiring electrode portion 23d: External connection portion 24: Other electrode 24d: Connection portion with external wiring (external connection portion) 25: p-layer organic semiconductor 26: n-layer organic semiconductor 27: protective layer 28: conductive material 29: gap
- the photoelectric conversion device will be described assuming a solar cell as a device that converts light into electric energy, but the present invention can be similarly 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 the first embodiment of the present invention.
- a photoelectric conversion device 1 according to an embodiment of the present invention includes a pair of electrodes 3 and 4 arranged side by side, and a photoelectric conversion layer 5 that covers the pair of electrodes 3 and 4. I have.
- the one electrode 3 and the other electrode 4 are provided side by side on the same surface, for example, on the substrate, with a predetermined distance from each other.
- a p-layer organic semiconductor 6 made of a hole transport material is provided on one electrode 3.
- An n-layer organic semiconductor 7 made of an electron transport material is provided on the other electrode 4.
- the p-layer organic semiconductor 6 and the n-layer organic semiconductor 7 are arranged laterally adjacent to each other to form a pn junction.
- the p-layer organic semiconductor 6 and the n-layer organic semiconductor 7 include the pn junction surface.
- a protective layer 8 is provided so as to cover the entire surface.
- the p-layer organic semiconductor 6 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 chemical formula (8), TCTA represented by chemical formula (9), NTPA represented by chemical formula (10), spiro-TAD represented by chemical formula (11), TFREL represented by chemical formula (12), etc. are used. .
- the n-layer organic semiconductor 7 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).
- Alq 3 represented by the chemical formula (13)
- BCP represented by the chemical formula (14)
- triazole derivative represented by chemical formula (18) phenylquinoxaline derivative represented by chemical formula (19), silole derivative represented by chemical formula (20), and the like.
- the protective layer 8 is formed of a resin or the like, for example, as long as it is a material that transmits light 9 such as sunlight.
- the same surface may be either a virtual surface or a substrate surface, but when a pair of electrodes 3 and 4 is formed on a substrate surface, it is a flexible substrate that can be bent even if it is a flat substrate. There may be.
- 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 3 and the other electrode 4 are formed by the same process.
- a hole transport material to be the p-layer organic semiconductor 6 is applied to a predetermined portion, for example, one electrode 3.
- a printing method using an inkjet printer can be applied.
- an electron transport material to be the n-layer organic semiconductor 7 is applied between the p layer and the p layer, for example, the other electrode 4.
- a printing technique using an inkjet printer can be used for coating.
- a pn junction is formed by the p-layer organic semiconductor 6 and the n-layer organic semiconductor 7.
- the n-layer organic semiconductor 7 may be applied, and then the p-layer organic semiconductor 6 may be applied.
- the photoelectric conversion device 1 is manufactured by forming the protective layer 8 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 photoelectric conversion device electrode 2 is formed such that one electrode 3 functioning as a p-type electrode and the other electrode 4 functioning as an n-type electrode are arranged side by side.
- An alternating array planar electrode structure is formed. Therefore, it is not necessary to provide a transparent electrode on the organic semiconductor.
- the photoelectric conversion device 1 can be manufactured on a non-flexible substrate such as a glass substrate or on a flexible substrate. 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 according to the second embodiment of the present invention.
- the photoelectric conversion device 10 according to the second embodiment of the present invention includes an insulating base material 11 and one electrode as a photoelectric conversion device electrode 12 formed on the surface of the base material 11. 13 and the other electrode 14, a p-layer organic semiconductor 15 made of a hole transport material provided on one electrode 13, and an n-layer organic semiconductor 16 made of an electron transport material provided on the other electrode 14. And a protective layer 17 provided so as to cover the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16.
- the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 form a pn junction.
- a photoelectric conversion layer 18 is formed by the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16.
- one electrode 13 and the other electrode 14 are formed on the surface of the substrate 11 as the photoelectric conversion device electrode 12, and the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 are photoelectrically connected. It is formed side by side on the conversion device electrode 12. Therefore, it is not necessary to provide an electrode on the surface on which the light 19 is incident as in Patent Document 2, and it is not necessary to use a rare metal as a material because a transparent electrode is not provided on the light irradiation side.
- the photoelectric conversion device electrode 12 can be formed of Cu, Al, or the like.
- the base material 11 can be applied to various types such as a glass substrate, a resin substrate, and a printed board.
- 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.
- FIG. 3 is a plan view showing an electrode structure in the photoelectric conversion device shown in FIG. 2, and FIG. 4 is an enlarged view of a region 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 a distance, so that the electrode finger 13a of one electrode and the electrode of the other electrode The 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 fingers 13a and 14a, connection electrodes 13b and 14b for connecting one end thereof, and one end of the connection electrodes 13b and 14b for connection to an external wiring. It has the routing electrodes 13c and 14c extending to the terminals 13d and 14d.
- each electrode finger 13a, 14a is formed extending in the left-right direction, and the electrode finger 13a and the electrode finger 14a are alternately arranged in a predetermined direction in a direction substantially perpendicular to the extending direction. The same number is arranged at intervals.
- 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.
- the p-layer organic semiconductor 15 is formed on at least the electrode finger 13 a of the one electrode 13, and the 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.
- the photoelectric conversion layer 18 is comprised by forming the organic semiconductors 15 and 16.
- the p-layer organic semiconductor 15 is formed of various hole transport materials exemplified in the first embodiment.
- the n-layer organic semiconductor 16 is formed of various electron transport materials exemplified in the first embodiment.
- 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.
- 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.
- a hole transport material to be the p-layer organic semiconductor 15 is applied to a predetermined portion, for example, one electrode 13 by a printing method using, for example, an ink jet printer.
- 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 photoelectric conversion device 10 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 10 illustrated in FIG. 2 is manufactured.
- a p-layer organic semiconductor is stacked on one electrode and an n-layer organic semiconductor is stacked thereon to form a pn junction as in the prior art.
- a transparent electrode is sequentially laminated as the other electrode to form a photoelectric conversion device. That is, one electrode 13 functioning as a p-type electrode and the other electrode 14 functioning as an n-type electrode are alternately arranged on the same plane. Therefore, it is not necessary to provide a transparent electrode on the organic semiconductor.
- the photoelectric conversion device 10 can be manufactured on a non-flexible substrate such as a glass substrate or a flexible substrate. 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. 5 is a cross-sectional view of a photoelectric conversion device according to the third embodiment of the present invention.
- an insulating base material 21 having a plurality of through holes 21 a according to a pattern and the through holes 21 a of the base material 21 are filled with a conductive material 28 and exposed to the surface of the base material 21.
- the other electrode 24 provided with, for example, a gap 29 so as not to contact the one electrode 23 on the surface of the base material 21, and provided on the one electrode 23 a p-layer organic semiconductor 25, an n-layer organic semiconductor 26 provided on the other electrode 24, a protective layer 27 provided to cover the p-layer organic semiconductor 25 and the n-layer organic semiconductor 26, Consists of.
- the one electrode 23 and the other electrode 24 are formed so as to be alternately arranged on the upper surface side of the base material 21 in the direction in which the surface expands, and constitute the photoelectric conversion device electrode 22.
- the p-layer organic semiconductor 25 and the n-layer organic semiconductor 26 are alternately stacked on the electrodes 23 and 24 to form the photoelectric conversion layer 30. Therefore, the protective layer 26 can be disposed on the surface side on which the light 31 is incident without providing an electrode as in Patent Document 2. Thereby, it is not necessary to use a rare metal as a material so that the electrode has optical transparency.
- One electrode 23 and the other electrode 24 can use Cu, Al, or the like.
- the interface between the one electrode 23 and the photoelectric conversion layer 30 and the interface between the other electrode 24 and the photoelectric conversion layer 30 are not only arranged on the same plane, Since it can arrange
- the external connection portion 23d of one electrode 23 is provided on the back surface of the base material 21, the external connection portion 24d of the other electrode 24 is provided on the surface of the base material 21, and the external connection portions 23d and 24d are provided. Provided with the base material 21 in between. Therefore, one external connection terminal can be connected to the external connection portions 23d and 24d. This external connection terminal forms two conductive paths.
- the base material 21 can be various types such as a ceramic substrate such as a glass substrate, a resin substrate, a printed circuit board, and the like.
- a resin substrate or the like is used as the base material 21, the mounting surface of the photoelectric conversion device 20 may not be a flat surface but may be a curved surface.
- One electrode 23 will be described. As shown in FIG. 5, with respect to one electrode 23, the through hole 21 a of the base material 21 is filled with the conductive material 28 and one end thereof is exposed at least on the surface of the base material 21. It becomes the main body 23a.
- the conductive material 28, particularly the filling portion 23b, may be referred to as a via conductor portion.
- FIG. 6 is a plan view showing an electrode structure in the photoelectric conversion device shown in FIG. 5, and FIG. 7 is an enlarged view of a region B in FIG.
- dot-like electrode main body portions 23 a are arranged on the surface of the base material 21 at intervals in the row direction, and they are also arranged at intervals in the column direction.
- the electrode main body portions 23a are formed at intervals in each row, and the odd-numbered electrode main body portions 23a and the even-numbered electrode main body portions 23a are in the row direction. It is staggered and is provided alternately. That is, they are not aligned in the column direction.
- the electrode main body portions 23a may be aligned in the row direction and the column direction, and may be arranged in a matrix at intervals.
- each electrode main body 23 a preferably has its tip projecting from the surface of the substrate 21.
- An organic semiconductor dot is formed on the protruding tip by coating. Since the tip of the electrode main body portion 23a protrudes from the surface of the substrate 21, the connection between the n-layer organic conductor 26 and the electrode main body portion 23a is ensured.
- One electrode 23 extends from the electrode main body portion 23 a protruding from the surface of the base material 21 to the back surface of the base material 21 by a filling portion 28 b in which the through hole 21 a of the base material 21 is filled with the conductive material 28.
- the filling portions 23b are electrically connected to each other by a wiring electrode portion 23c formed on the back surface of the substrate 21.
- An end portion of the wiring electrode portion 23c serves as an external connection portion 23d.
- the filling portions 23b can be electrically connected to each other according to the planar shape.
- the other electrode 24 will be described. Corresponding to each electrode body 23a of one electrode 23 being arranged in a dot shape on the surface of the substrate 21, the other electrode 24 is not in contact with each electrode body 23a. Further, a conductive layer is formed on the surface of the base material 21 so as to surround each electrode main body 23a. That is, the other electrode 24 is formed so as to surround each electrode main body 23 a on the same surface as the surface of the base 21 on which the electrode main body 23 a of one electrode 23 is provided on the surface of the base 21. The parts of the other electrodes 24 arranged with the gaps 29 provided in the electrode bodies 23a are connected to each other. Further, the peripheral edge portion of the other electrode 24 functions as a connection portion 24d with an external wiring.
- the organic semiconductors 25 and 26 are provided on the one electrode 23 and the other electrode 24, respectively.
- a p-layer organic semiconductor 25 is formed on the electrode body 23 a of one electrode 23, and an n-layer organic semiconductor 26 is formed on the other electrode 24. . Therefore, the electrode body 23a of one electrode 23 functions as a p-type electrode, and the portion of the other electrode 24 covered with the n-type organic semiconductor 26 functions as an n-type electrode.
- an n-layer organic semiconductor is formed on the electrode body 23 a of one electrode 23, and a p-layer organic semiconductor is formed on the other electrode 24. It may be formed.
- the electrode body portion 23a of one electrode 23 functions as an n-type electrode, and the portion of the other electrode 24 covered with a p-type organic semiconductor functions as a p-type electrode.
- the p-layer organic semiconductor 25 is formed of various hole transport materials exemplified in the first embodiment.
- the n-layer organic semiconductor 26 is formed of various electron transport materials exemplified in the first embodiment.
- a photoelectric conversion layer 30 is formed by the p-layer organic semiconductor 26 and the n-layer organic semiconductor 25.
- the protective layer 27 may be formed of, for example, a resin or the like as long as it is a material that transmits light 31 such as sunlight.
- the metal in a portion where one electrode and the other electrode are not formed is removed by etching or the like, and the one electrode and the other A seed electrode is formed as a source of the electrode.
- one electrode and the other electrode may be formed by a printing method without using the plating process.
- a hole transport material to be the p-layer organic semiconductor 25 is applied to a predetermined portion, for example, one electrode 23 by, for example, a printing method using an ink jet printer.
- an electron transport material to be the n-layer organic semiconductor 26 is applied between the p layer and the p layer, for example, the other electrode 24.
- a printing technique using an ink jet printer may be used for coating.
- a pn junction is formed by the p-layer organic semiconductor 25 and the n-layer organic semiconductor 26.
- the n-layer organic semiconductor 26 may be applied, and then the p-layer organic semiconductor 25 may be applied.
- the photoelectric conversion device 20 is manufactured by forming the protective layer 27 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. 5 is manufactured.
- the third embodiment of the present invention may be appropriately changed depending on device performance, design, and the like.
- the pattern in plan view of one electrode 23 and the other electrode 24 is not limited to that shown in FIG. 7 and can be changed as appropriate.
- the electrode body 23a of one electrode 23 is rectangular in plan view, but may be a triangle, polygon, circle, ellipse, or other geometric pattern.
- FIG. 8 is a plan view showing a modification of the photoelectric conversion device electrode.
- the through hole 21a is formed as a rhombus in plan view on the base material 21, the electrode body 23a of one electrode 23 is formed in a rhombus, and the other electrode is formed as a pattern in which rhombus similar to the electrode body 23a is arranged in a matrix. May be.
- the one electrode 23 and the other electrode 24 are separated from each other as in the above configuration example.
- the area of each electrode may be a geometric pattern that is uniform between the p-type electrode and the n-type electrode.
Abstract
An electrode (22) for a photoelectric conversion device, the electrode being arranged on one side of a photoelectric conversion layer (30), is configured by arranging one electrode (23) functioning as a p-type electrode and another electrode (24) functioning as an n-type electrode on substantially the same surface. It is thereby possible to provide a variety of types of photoelectric conversion devices (20) without using a transparent electrode material.
Description
本発明は、光電変換デバイスに用いられる光電変換デバイス用電極と、それを用いた光電変換デバイスに関する。
The present invention relates to an electrode for a photoelectric conversion device used for a photoelectric conversion device and a photoelectric conversion device using the same.
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、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。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 taking a single crystal Si solar cell as an example. A pn junction or a pin junction is formed by making the surface layer of the wafer an n-type semiconductor by vapor phase diffusion or implantation of n-type impurity ions into a p-type single crystal wafer. A solar cell having a sandwich structure is manufactured by forming a front electrode and a back electrode.
化合物太陽電池の中には各種のものがある。ここでは、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。このカルコパイライト型太陽電池は、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ものである（例えば特許文献１）。
There are various types of compound solar cells. Here, a chalcopyrite solar cell, which has advantages such as high energy conversion efficiency, low light deterioration due to secular change, excellent radiation resistance, a wide light absorption wavelength region, and a large light absorption coefficient, will be described as an example. . This chalcopyrite solar cell includes 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. There is (for example, Patent Document 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 separated into the n region and the holes are collected in the p region by 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 the gas introduction 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、陰極が塗布により酸化銀と還元剤からなり、電子輸送層が塗布により陰極近傍に有機金属をドープして形成されていることにより、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 the cathode is oxidized by coating. It consists of silver and a reducing agent, and the electron transport layer is formed by doping an organic metal in the vicinity of the cathode by coating, so that not only the cathode is formed at a low temperature, but also the bonding between the organic metal doped layer and the cathode is achieved. It is going to be improved.
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、光電変換デバイス用電極とそれを用いた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 an electrode for a photoelectric conversion device that does not require optical transparency as an electrode material and a photoelectric conversion device using the same.
上記目的を達成するため、本発明の光電変換デバイス用電極は、同一面上に一方の電極と他方の電極とが形成されてなり、一方の電極がｐ型電極として機能し、他方の電極がｎ型電極として機能する。
好ましくは、一方の電極と他方の電極とは横並びに一つずつ設けられる。一方の電極及び他方の電極は、好ましくは、複数本の電極指が一端で電気的に接続された構造を有する櫛歯電極で構成され、一方の電極の電極指と他方の電極の電極指とが交互に並んでいる。一方の電極及び他方の電極はＣｕ、Ａｌの何れかで形成され得る。 In order to achieve the above object, the electrode for a photoelectric conversion device of the present invention has one electrode and the other electrode formed on the same surface, one electrode functions as a p-type electrode, and the other electrode Functions as an n-type electrode.
Preferably, one electrode and the other electrode are provided side by side. The one electrode and the other electrode are preferably composed of comb electrodes having a structure in which a plurality of electrode fingers are electrically connected at one end, and the electrode fingers of one electrode and the electrode fingers of the other electrode Are lined up alternately. One electrode and the other electrode can be formed of either Cu or Al.
好ましくは、一方の電極と他方の電極とは横並びに一つずつ設けられる。一方の電極及び他方の電極は、好ましくは、複数本の電極指が一端で電気的に接続された構造を有する櫛歯電極で構成され、一方の電極の電極指と他方の電極の電極指とが交互に並んでいる。一方の電極及び他方の電極はＣｕ、Ａｌの何れかで形成され得る。 In order to achieve the above object, the electrode for a photoelectric conversion device of the present invention has one electrode and the other electrode formed on the same surface, one electrode functions as a p-type electrode, and the other electrode Functions as an n-type electrode.
Preferably, one electrode and the other electrode are provided side by side. The one electrode and the other electrode are preferably composed of comb electrodes having a structure in which a plurality of electrode fingers are electrically connected at one end, and the electrode fingers of one electrode and the electrode fingers of the other electrode Are lined up alternately. One electrode and the other electrode can be formed of either Cu or Al.
本発明の光電変換デバイスは、本発明の光電変換デバイス用電極と、一方の電極上に設けられ正孔輸送材料でなるｐ層の有機半導体と、他方の電極上に設けられ電子輸送材料でなるｎ層の有機半導体と、を備え、ｐ層の有機半導体及びｎ層の有機半導体が同一面上に互い違いに形成されている。
本発明の光電変換デバイスは、上述の光電変換デバイス用電極と、一方の電極上に設けられ電子輸送材料でなるｎ層の有機半導体と、他方の電極上に設けられ正孔輸送材料でなるｐ層の有機半導体と、を備え、ｐ層の有機半導体及びｎ層の有機半導体が同一面上に互い違いに形成されている。
好ましくは、ｐ層の有機半導体及びｎ層の有機半導体は透明の保護層で覆われている。 The photoelectric conversion device of the present invention comprises the electrode for a photoelectric conversion device of the present invention, a p-layer organic semiconductor made of a hole transport material provided on one electrode, and an electron transport material provided on the other electrode. an n-layer organic semiconductor, and the p-layer organic semiconductor and the n-layer organic semiconductor are alternately formed on the same surface.
The photoelectric conversion device of the present invention includes the above-mentioned electrode for a photoelectric conversion device, an n-layer organic semiconductor made of an electron transport material provided on one electrode, and a p made of a hole transport material provided on the other electrode. A p-layer organic semiconductor and an n-layer organic semiconductor are alternately formed on the same surface.
Preferably, the p-layer organic semiconductor and the n-layer organic semiconductor are covered with a transparent protective layer.
本発明の光電変換デバイスは、上述の光電変換デバイス用電極と、一方の電極上に設けられ電子輸送材料でなるｎ層の有機半導体と、他方の電極上に設けられ正孔輸送材料でなるｐ層の有機半導体と、を備え、ｐ層の有機半導体及びｎ層の有機半導体が同一面上に互い違いに形成されている。
好ましくは、ｐ層の有機半導体及びｎ層の有機半導体は透明の保護層で覆われている。 The photoelectric conversion device of the present invention comprises the electrode for a photoelectric conversion device of the present invention, a p-layer organic semiconductor made of a hole transport material provided on one electrode, and an electron transport material provided on the other electrode. an n-layer organic semiconductor, and the p-layer organic semiconductor and the n-layer organic semiconductor are alternately formed on the same surface.
The photoelectric conversion device of the present invention includes the above-mentioned electrode for a photoelectric conversion device, an n-layer organic semiconductor made of an electron transport material provided on one electrode, and a p made of a hole transport material provided on the other electrode. A p-layer organic semiconductor and an n-layer organic semiconductor are alternately formed on the same surface.
Preferably, the p-layer organic semiconductor and the n-layer organic semiconductor are covered with a transparent protective layer.
上記目的を達成するために、本発明の光電変換デバイス用電極は、パターンに従って複数の貫通穴を有する絶縁性の基材と、基材の貫通穴を導電材で充填しつつ基材の表面に露出するように形成された一方の電極と、基材の表面で一方の電極との間に隙間を有するように設けられた他方の電極と、を有する。
好ましくは、一方の電極は、基材の裏面に形成された導電性の被膜によって相互に接続されている。
好ましくは、一方の電極は、基材の表面から張り出した突出部を有している。
好ましくは、一方の電極の外部接続部が基材の裏面に設けられ、他方の電極の外部接続部が基材の表面に設けられる。一方の電極及び他方の電極は、Ｃｕ、Ａｌの何れかで形成され得る。 In order to achieve the above object, an electrode for a photoelectric conversion device according to the present invention is formed on an insulating base material having a plurality of through holes according to a pattern, and the base material surface while filling the through holes of the base material with a conductive material One electrode formed so as to be exposed, and the other electrode provided so as to have a gap between the one electrode on the surface of the substrate.
Preferably, one electrode is mutually connected by the electroconductive film formed in the back surface of a base material.
Preferably, one electrode has the protrusion part protruded from the surface of the base material.
Preferably, the external connection part of one electrode is provided on the back surface of the base material, and the external connection part of the other electrode is provided on the surface of the base material. One electrode and the other electrode can be formed of either Cu or Al.
好ましくは、一方の電極は、基材の裏面に形成された導電性の被膜によって相互に接続されている。
好ましくは、一方の電極は、基材の表面から張り出した突出部を有している。
好ましくは、一方の電極の外部接続部が基材の裏面に設けられ、他方の電極の外部接続部が基材の表面に設けられる。一方の電極及び他方の電極は、Ｃｕ、Ａｌの何れかで形成され得る。 In order to achieve the above object, an electrode for a photoelectric conversion device according to the present invention is formed on an insulating base material having a plurality of through holes according to a pattern, and the base material surface while filling the through holes of the base material with a conductive material One electrode formed so as to be exposed, and the other electrode provided so as to have a gap between the one electrode on the surface of the substrate.
Preferably, one electrode is mutually connected by the electroconductive film formed in the back surface of a base material.
Preferably, one electrode has the protrusion part protruded from the surface of the base material.
Preferably, the external connection part of one electrode is provided on the back surface of the base material, and the external connection part of the other electrode is provided on the surface of the base material. One electrode and the other electrode can be formed of either Cu or Al.
本発明の光電変換デバイスは、上述の光電変換デバイス用電極と、一方の電極上に設けられ正孔輸送材料でなるｐ層の有機半導体と、他方の電極上に設けられ電子輸送材料でなるｎ層の有機半導体と、を備え、ｐ層の有機半導体及びｎ層の有機半導体が同一面上に交互に形成されている。
好ましくは、ｐ層の有機半導体及びｎ層の有機半導体は透明の保護層で覆われている。 The photoelectric conversion device of the present invention includes the above-described electrode for a photoelectric conversion device, a p-layer organic semiconductor made of a hole transport material provided on one electrode, and an n transport material made of an electron transport material provided on the other electrode. A p-layer organic semiconductor and an n-layer organic semiconductor are alternately formed on the same surface.
Preferably, the p-layer organic semiconductor and the n-layer organic semiconductor are covered with a transparent protective layer.
好ましくは、ｐ層の有機半導体及びｎ層の有機半導体は透明の保護層で覆われている。 The photoelectric conversion device of the present invention includes the above-described electrode for a photoelectric conversion device, a p-layer organic semiconductor made of a hole transport material provided on one electrode, and an n transport material made of an electron transport material provided on the other electrode. A p-layer organic semiconductor and an n-layer organic semiconductor are alternately formed on the same surface.
Preferably, the p-layer organic semiconductor and the n-layer organic semiconductor are covered with a transparent protective layer.
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光電変換デバイスの一方の面側に形成することが可能であるため、光の照射する面側に電極を設ける必要がない。この光電変換デバイス用電極は、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。この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 present invention, since one electrode functioning as a p-type electrode and the other electrode functioning as an n-type electrode can be formed on one surface side of the photoelectric conversion device, There is no need to provide an electrode on the surface to be irradiated. This electrode for a photoelectric conversion device can be produced on a substrate having no flexibility or a substrate having flexibility. Since an organic semiconductor can be provided on the electrode by coating, the manufacturing process is not complicated, and the electrode can be manufactured at a low cost.
１：光電変換デバイス
２：光電変換デバイス用電極
３，４：電極
５：光電変換層
６：ｐ層の有機半導体
７：ｎ層の有機半導体
８：保護層
９：光
１０：光電変換デバイス
１１：基材
１２：光電変換デバイス用電極
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
１８：光電変換層
１９：光
２０：光電変換デバイス
２１：基材
２１ａ：基材の貫通穴
２２：光電変換デバイス用電極
２３：一方の電極
２３ａ：電極本体部（ドット状電極）
２３ｂ：充填部（ビア導体部）
２３ｃ：配線電極部
２３ｄ：外部接続部
２４：他方の電極
２４ｄ：外部配線との接続部（外部接続部）
２５：ｐ層の有機半導体
２６：ｎ層の有機半導体
２７：保護層
２８：導電材
２９：隙間
３０：光電変換層
３１：光 1: Photoelectric conversion device 2: Electrode forphotoelectric conversion device 3, 4: Electrode 5: Photoelectric conversion layer 6: p-layer organic semiconductor 7: n-layer organic semiconductor 8: protective layer 9: light 10: photoelectric conversion device 11: Substrate 12: Electrode for photoelectric conversion device 13: One electrode 14: The other electrode 13a, 14a: Electrode finger 13b, 14b: Connection electrode 13c: Lead- out electrode 13d, 14d: Connection terminal with external wiring 15: P layer Organic semiconductor 16: n-layer organic semiconductor 17: protective layer 18: photoelectric conversion layer 19: light 20: photoelectric conversion device 21: base material 21a: through hole 22 of base material: electrode 23 for photoelectric conversion device: one electrode 23a: Electrode body (dot electrode)
23b: Filling part (via conductor part)
23c:Wiring electrode portion 23d: External connection portion 24: Other electrode 24d: Connection portion with external wiring (external connection portion)
25: p-layer organic semiconductor 26: n-layer organic semiconductor 27: protective layer 28: conductive material 29: gap 30: photoelectric conversion layer 31: light
２：光電変換デバイス用電極
３，４：電極
５：光電変換層
６：ｐ層の有機半導体
７：ｎ層の有機半導体
８：保護層
９：光
１０：光電変換デバイス
１１：基材
１２：光電変換デバイス用電極
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
１８：光電変換層
１９：光
２０：光電変換デバイス
２１：基材
２１ａ：基材の貫通穴
２２：光電変換デバイス用電極
２３：一方の電極
２３ａ：電極本体部（ドット状電極）
２３ｂ：充填部（ビア導体部）
２３ｃ：配線電極部
２３ｄ：外部接続部
２４：他方の電極
２４ｄ：外部配線との接続部（外部接続部）
２５：ｐ層の有機半導体
２６：ｎ層の有機半導体
２７：保護層
２８：導電材
２９：隙間
３０：光電変換層
３１：光 1: Photoelectric conversion device 2: Electrode for
23b: Filling part (via conductor part)
23c:
25: p-layer organic semiconductor 26: n-layer organic semiconductor 27: protective layer 28: conductive material 29: gap 30: photoelectric conversion layer 31: light
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。ここでは、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. Here, the photoelectric conversion device will be described assuming a solar cell as a device that converts light into electric energy, but the present invention can be similarly applied to a device that converts electric energy into light energy.
〔第１実施形態〕
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電極３，４の対と、電極３，４の対の上を覆う光電変換層５と、を備えている。 [First Embodiment]
FIG. 1 is a cross-sectional view of aphotoelectric conversion device 1 according to the first embodiment of the present invention. As shown in FIG. 1, a photoelectric conversion device 1 according to an embodiment of the present invention includes a pair of electrodes 3 and 4 arranged side by side, and a photoelectric conversion layer 5 that covers the pair of electrodes 3 and 4. I have.
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電極３，４の対と、電極３，４の対の上を覆う光電変換層５と、を備えている。 [First Embodiment]
FIG. 1 is a cross-sectional view of a
一方の電極３と他方の電極４とは互いに所定の距離をあけて同一面上、例えば基材上に横並びに設けられる。一方の電極３の上には、正孔輸送材料でなるｐ層の有機半導体６が設けられる。他方の電極４上には、電子輸送材料でなるｎ層の有機半導体７が設けられる。ｐ層の有機半導体６及びｎ層の有機半導体７は互いに横に隣接して配置されてｐｎ接合を形成しており、ｐｎ接合面を含んでｐ層の有機半導体６及びｎ層の有機半導体７の表面全体を被覆するように保護層８が設けられる。
The one electrode 3 and the other electrode 4 are provided side by side on the same surface, for example, on the substrate, with a predetermined distance from each other. On one electrode 3, a p-layer organic semiconductor 6 made of a hole transport material is provided. An n-layer organic semiconductor 7 made of an electron transport material is provided on the other electrode 4. The p-layer organic semiconductor 6 and the n-layer organic semiconductor 7 are arranged laterally adjacent to each other to form a pn junction. The p-layer organic semiconductor 6 and the n-layer organic semiconductor 7 include the pn junction surface. A protective layer 8 is provided so as to cover the entire surface.
ｐ層の有機半導体６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－ＴＡＤ、化学式（１２）で示されるＴＦＬＥＬなどが用いられる。
The p-layer organic semiconductor 6 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 chemical formula (8), TCTA represented by chemical formula (9), NTPA represented by chemical formula (10), spiro-TAD represented by chemical formula (11), TFREL represented by chemical formula (12), etc. are used. .
ｎ層の有機半導体７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ー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ノキサリン誘導体、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 7 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 starburst oxadiazole represented by chemical formula (17), triazole derivative represented by chemical formula (18), phenylquinoxaline derivative represented by chemical formula (19), silole derivative represented by chemical formula (20), and the like.
保護層８については、太陽光などの光９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 8 is formed of a resin or the like, for example, as long as it is a material that transmits light 9 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、電極３，４の対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、電極３，４の対を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３、他方の電極４は同一の工程により形成される。
A method for producing the photoelectric conversion device 1 shown in FIG. First, a pair of electrodes 3 and 4 is formed on the same plane. Here, the same surface may be either a virtual surface or a substrate surface, but when a pair of electrodes 3 and 4 is formed on a substrate surface, it is a flexible substrate that can be bent even if it is a flat substrate. There may be. 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 3 and the other electrode 4 are formed by the same process.
その後、ｐ層の有機半導体６となる正孔輸送材料を所定の箇所、例えば一方の電極３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 6 is applied to a predetermined portion, for example, one electrode 3. 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７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４に塗布する。塗布にはｐ層の有機半導体６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 7 is applied between the p layer and the p layer, for example, the other electrode 4. As in the case of the p-layer organic semiconductor 6, 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６とｎ層の有機半導体７とによってｐｎ接合が形成される。なお、ｎ層の有機半導体７から塗布し、その後ｐ層の有機半導体６を塗布してもよい。
Thereby, a pn junction is formed by the p-layer organic semiconductor 6 and the n-layer organic semiconductor 7. Alternatively, the n-layer organic semiconductor 7 may be applied, and then the p-layer organic semiconductor 6 may be applied.
最後に、保護層８を塗装などによって形成することで、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。
Finally, the photoelectric conversion device 1 is manufactured by forming the protective layer 8 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２が、ｐ型電極として機能する一方の電極３と、ｎ型電極として機能する他方の電極４とが横並びに形成されて交互配列平面電極構造を構成している。そのため、有機半導体の上に透明電極を設ける必要がない。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上にも又は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 photoelectric conversion device electrode 2 is formed such that one electrode 3 functioning as a p-type electrode and the other electrode 4 functioning as an n-type electrode are arranged side by side. An alternating array planar electrode structure is formed. Therefore, it is not necessary to provide a transparent electrode on the organic semiconductor. The photoelectric conversion device 1 can be manufactured on a non-flexible substrate such as a glass substrate or on a flexible substrate. 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.
〔第２実施形態〕
図２は、本発明の第２実施形態に係る光電変換デバイスの断面図である。図２に示すように、本発明の第２実施形態に係る光電変換デバイス１０は、絶縁性の基材１１と、基材１１の面上に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。また、ｐ層の有機半導体１５とｎ層の有機半導体１６により光電変換層１８が形成される。 [Second Embodiment]
FIG. 2 is a cross-sectional view of a photoelectric conversion device according to the second embodiment of the present invention. As shown in FIG. 2, thephotoelectric conversion device 10 according to the second embodiment of the present invention includes an insulating base material 11 and one electrode as a photoelectric conversion device electrode 12 formed on the surface of the base material 11. 13 and the other electrode 14, a p-layer organic semiconductor 15 made of a hole transport material provided on one electrode 13, and an n-layer organic semiconductor 16 made of an electron transport material provided on the other electrode 14. And a protective layer 17 provided so as to cover the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16. The p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 form a pn junction. Further, a photoelectric conversion layer 18 is formed by the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16.
図２は、本発明の第２実施形態に係る光電変換デバイスの断面図である。図２に示すように、本発明の第２実施形態に係る光電変換デバイス１０は、絶縁性の基材１１と、基材１１の面上に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。また、ｐ層の有機半導体１５とｎ層の有機半導体１６により光電変換層１８が形成される。 [Second Embodiment]
FIG. 2 is a cross-sectional view of a photoelectric conversion device according to the second embodiment of the present invention. As shown in FIG. 2, the
このように、一方の電極１３と他方の電極１４とが基材１１の面上に並んで光電変換デバイス用電極１２として形成され、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る。よって、光１９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、光照射側に透明電極を設けないためレアメタルを材料として使用しなくて済む。光電変換デバイス用電極１２はＣｕやＡｌなどにより形成することができる。
In this way, one electrode 13 and the other electrode 14 are formed on the surface of the substrate 11 as the photoelectric conversion device electrode 12, and the p-layer organic semiconductor 15 and the n-layer organic semiconductor 16 are photoelectrically connected. It is formed side by side on the conversion device electrode 12. Therefore, it is not necessary to provide an electrode on the surface on which the light 19 is incident as in Patent Document 2, and it is not necessary to use a rare metal as a material because a transparent electrode is not provided on the light irradiation side. The photoelectric conversion device electrode 12 can be formed of 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、各種のものが適用可能である。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 can be applied to various types such as a glass substrate, a resin substrate, and a printed 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における電極構造を示す平面図であり、図４は図３においてＡの領域の拡大図である。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とが互いに対向配置され、それらの電極指１３ａ，１４ａが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 showing an electrode structure in the photoelectric conversion device shown in FIG. 2, and FIG. 4 is an enlarged view of a region 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 a distance, so that the electrode finger 13a of one electrode and the electrode of the other electrode The 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 fingers 13a and 14a, connection electrodes 13b and 14b for connecting one end thereof, and one end of the connection electrodes 13b and 14b for connection to an external wiring. It has the routing electrodes 13c and 14c extending to the terminals 13d and 14d.
図３に示す場合にあっては、各電極指１３ａ，１４ａが左右方向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, each electrode finger 13a, 14a is formed extending in the left-right direction, and the electrode finger 13a and the electrode finger 14a are alternately arranged in a predetermined direction in a direction substantially perpendicular to the extending direction. The same number is arranged at intervals. 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.
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。このように有機半導体１５，１６が形成されることにより、光電変換層１８が構成される。
The p-layer organic semiconductor 15 is formed on at least the electrode finger 13 a of the one electrode 13, and the 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. Thus, the photoelectric conversion layer 18 is comprised by forming the organic semiconductors 15 and 16.
ｐ層の有機半導体１５は、第１実施形態で例示した各種の正孔輸送材料によって形成される。ｎ層の有機半導体１６は、第１実施形態で例示した各種の電子輸送材料によって形成される。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 p-layer organic semiconductor 15 is formed of various hole transport materials exemplified in the first embodiment. The n-layer organic semiconductor 16 is formed of various electron transport materials exemplified in the first embodiment. 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２に示す光電変換デバイス１０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上に所定間隔をおいて一方の電極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 10 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、例えばインクジェットプリンタによる印刷方法により塗布する。
Thereafter, a hole transport material to be the p-layer organic semiconductor 15 is applied to a predetermined portion, for example, one electrode 13 by a printing method using, for example, an ink jet printer.
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.
こうして、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。
Thus, 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.
最後に、保護層１７を塗装などによって形成することにより、光電変換デバイス１０が作製される。なお、図２に示す光電変換デバイス１０が作製される手法であれば上述の方法に限定されない。
Finally, the photoelectric conversion device 10 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 10 illustrated in FIG. 2 is manufactured.
第２実施形態では、従来のように、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、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ない。つまり、ｐ型電極として機能する一方の電極１３と、ｎ型電極として機能する他方の電極１４とが、同一面上に交互に配列されている。そのため、有機半導体上に透明電極を設ける必要がない。光電変換デバイス１０は、ガラス基板などのフレキシブル性のない基板上にも或いはフレキシブル性のある基板上にも作製できる。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。
In the second embodiment, a p-layer organic semiconductor is stacked on one electrode and an n-layer organic semiconductor is stacked thereon to form a pn junction as in the prior art. A transparent electrode is sequentially laminated as the other electrode to form a photoelectric conversion device. That is, one electrode 13 functioning as a p-type electrode and the other electrode 14 functioning as an n-type electrode are alternately arranged on the same plane. Therefore, it is not necessary to provide a transparent electrode on the organic semiconductor. The photoelectric conversion device 10 can be manufactured on a non-flexible substrate such as a glass substrate or a flexible substrate. 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.
〔第３実施形態〕
図５は、本発明の第３実施形態に係る光電変換デバイスの断面図である。第３実施形態に係る光電変換デバイス２０は、パターンに従って複数の貫通穴２１ａを有する絶縁性の基材２１と、基材２１の貫通穴２１ａを導電材２８で充填し基材２１の表面に露出して形成された一方の電極２３と、基材２１の表面で一方の電極２３と接触しないよう例えば隙間２９を有するように設けられた他方の電極２４と、一方の電極２３上に設けられたｐ層の有機半導体２５と、他方の電極２４上に設けられたｎ層の有機半導体２６と、ｐ層の有機半導体２５及びｎ層の有機半導体２６を被覆するように設けられる保護層２７と、で構成される。 [Third Embodiment]
FIG. 5 is a cross-sectional view of a photoelectric conversion device according to the third embodiment of the present invention. In thephotoelectric conversion device 20 according to the third embodiment, an insulating base material 21 having a plurality of through holes 21 a according to a pattern and the through holes 21 a of the base material 21 are filled with a conductive material 28 and exposed to the surface of the base material 21. One electrode 23 formed in this manner, the other electrode 24 provided with, for example, a gap 29 so as not to contact the one electrode 23 on the surface of the base material 21, and provided on the one electrode 23 a p-layer organic semiconductor 25, an n-layer organic semiconductor 26 provided on the other electrode 24, a protective layer 27 provided to cover the p-layer organic semiconductor 25 and the n-layer organic semiconductor 26, Consists of.
図５は、本発明の第３実施形態に係る光電変換デバイスの断面図である。第３実施形態に係る光電変換デバイス２０は、パターンに従って複数の貫通穴２１ａを有する絶縁性の基材２１と、基材２１の貫通穴２１ａを導電材２８で充填し基材２１の表面に露出して形成された一方の電極２３と、基材２１の表面で一方の電極２３と接触しないよう例えば隙間２９を有するように設けられた他方の電極２４と、一方の電極２３上に設けられたｐ層の有機半導体２５と、他方の電極２４上に設けられたｎ層の有機半導体２６と、ｐ層の有機半導体２５及びｎ層の有機半導体２６を被覆するように設けられる保護層２７と、で構成される。 [Third Embodiment]
FIG. 5 is a cross-sectional view of a photoelectric conversion device according to the third embodiment of the present invention. In the
一方の電極２３及び他方の電極２４は、基材２１の上面側で当該面の広がる方向へ交互に並べられるように形成され、光電変換デバイス用電極２２を構成する。その光電変換デバイス用電極２２上に、ｐ層の有機半導体２５とｎ層の有機半導体２６とが交互に電極２３，２４上に重ねて並べられ、光電変換層３０が形成される。よって、光３１が入射する面側には、特許文献２のように電極を設けずに、保護層２６を配置することが可能となる。これにより、電極が光透過性を有するようにレアメタルを材料として使用しなくて済む。一方の電極２３及び他方の電極２４はＣｕやＡｌなどを使用することができる。
The one electrode 23 and the other electrode 24 are formed so as to be alternately arranged on the upper surface side of the base material 21 in the direction in which the surface expands, and constitute the photoelectric conversion device electrode 22. On the photoelectric conversion device electrode 22, the p-layer organic semiconductor 25 and the n-layer organic semiconductor 26 are alternately stacked on the electrodes 23 and 24 to form the photoelectric conversion layer 30. Therefore, the protective layer 26 can be disposed on the surface side on which the light 31 is incident without providing an electrode as in Patent Document 2. Thereby, it is not necessary to use a rare metal as a material so that the electrode has optical transparency. One electrode 23 and the other electrode 24 can use Cu, Al, or the like.
第３の実施形態では、一方の電極２３の光電変換層３０との界面と他方の電極２４の光電変換層３０との界面とがほぼ同一面に配置されるのみならず、配線の取り出し部位を基材２１の表面と裏面に配置できるため、取り出し配線の構造が複雑化しない。また、一方の電極２３の外部接続部２３ｄが基材２１の裏面に設けられ、他方の電極２４の外部接続部２４ｄが基材２１の表面に設けられ、しかも、各外部接続部２３ｄ，２４ｄが基材２１を挟んで設けられる。よって、外部接続部２３ｄ，２４ｄに一つの外部接続端子を接続することもできる。なお、この外部接続端子は、２つの導電パスを形成している。
In the third embodiment, the interface between the one electrode 23 and the photoelectric conversion layer 30 and the interface between the other electrode 24 and the photoelectric conversion layer 30 are not only arranged on the same plane, Since it can arrange | position on the surface and the back surface of the base material 21, the structure of extraction wiring is not complicated. Further, the external connection portion 23d of one electrode 23 is provided on the back surface of the base material 21, the external connection portion 24d of the other electrode 24 is provided on the surface of the base material 21, and the external connection portions 23d and 24d are provided. Provided with the base material 21 in between. Therefore, one external connection terminal can be connected to the external connection portions 23d and 24d. This external connection terminal forms two conductive paths.
基材２１は、ガラス基板などのセラミック基板、樹脂基板、プリント基板等、各種のものが適用可能である。基材２１として樹脂基板等を用いた場合には、光電変換デバイス２０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 21 can be various types such as a ceramic substrate such as a glass substrate, a resin substrate, a printed circuit board, and the like. When a resin substrate or the like is used as the base material 21, the mounting surface of the photoelectric conversion device 20 may not be a flat surface but may be a curved surface.
一方の電極２３について説明する。図５に示すように、一方の電極２３については、基材２１の貫通穴２１ａに導電材２８が充填されてその一端が少なくとも基材２１の表面に露出することで、その露出した部分が電極本体部２３ａとなる。導電材２８、特に充填部２３ｂは、ビア導体部と呼んでもよい。
One electrode 23 will be described. As shown in FIG. 5, with respect to one electrode 23, the through hole 21 a of the base material 21 is filled with the conductive material 28 and one end thereof is exposed at least on the surface of the base material 21. It becomes the main body 23a. The conductive material 28, particularly the filling portion 23b, may be referred to as a via conductor portion.
図６は、図５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り、図７は図６においてＢの領域の拡大図である。基材２１の表面にドット状の電極本体部２３ａが、図６に示すように、行方向に間隔をおいて並んでおり、かつそれらが列方向にも間隔をおいて並んでいる。図５及び図６に示す形態にあっては、電極本体部２３ａが各行毎に間隔をあけて形成されており、かつ奇数行の電極本体部２３ａと偶数行の電極本体部２３ａとは行方向にずれて互い違いに設けられている。つまり列方向に整列していない。各電極本体部２３ａは行方向と列方向とに沿って整列し、それぞれ間隔をあけてマトリックス状に配置されていてもよい。
6 is a plan view showing an electrode structure in the photoelectric conversion device shown in FIG. 5, and FIG. 7 is an enlarged view of a region B in FIG. As shown in FIG. 6, dot-like electrode main body portions 23 a are arranged on the surface of the base material 21 at intervals in the row direction, and they are also arranged at intervals in the column direction. 5 and 6, the electrode main body portions 23a are formed at intervals in each row, and the odd-numbered electrode main body portions 23a and the even-numbered electrode main body portions 23a are in the row direction. It is staggered and is provided alternately. That is, they are not aligned in the column direction. The electrode main body portions 23a may be aligned in the row direction and the column direction, and may be arranged in a matrix at intervals.
各電極本体部２３ａは図５に示すように、その先端が基材２１の表面から張り出して突出していることが好ましい。この突出した先端には塗布によって有機半導体のドットが形成される。電極本体部２３ａの先端が基材２１の表面から張り出していることで、ｎ層の有機導電体２６と電極本体部２３ａとの接続が確実になる。
As shown in FIG. 5, each electrode main body 23 a preferably has its tip projecting from the surface of the substrate 21. An organic semiconductor dot is formed on the protruding tip by coating. Since the tip of the electrode main body portion 23a protrudes from the surface of the substrate 21, the connection between the n-layer organic conductor 26 and the electrode main body portion 23a is ensured.
一方の電極２３は、基材２１の表面から張り出した電極本体部２３ａから、基材２１の貫通穴２１ａに導電材２８が充填されてなる充填部２８ｂにより基材２１の裏面まで延びている。充填部２３ｂ同士は、基材２１の裏面に形成された配線電極部２３ｃによって電気的につながれている。配線電極部２３ｃの端部が外部接続部２３ｄとなる。ここで、配線電極部２３ｃを所定の平面形状とすることにより、充填部２３ｂ同士をその平面形状に応じて電気的に接続することができる。
One electrode 23 extends from the electrode main body portion 23 a protruding from the surface of the base material 21 to the back surface of the base material 21 by a filling portion 28 b in which the through hole 21 a of the base material 21 is filled with the conductive material 28. The filling portions 23b are electrically connected to each other by a wiring electrode portion 23c formed on the back surface of the substrate 21. An end portion of the wiring electrode portion 23c serves as an external connection portion 23d. Here, by making the wiring electrode portion 23c have a predetermined planar shape, the filling portions 23b can be electrically connected to each other according to the planar shape.
他方の電極２４について説明する。基材２１の表面には、一方の電極２３の各電極本体部２３ａがドット状に並んで設けられているのに対応して、他方の電極２４が、各電極本体部２３ａに接触しないよう、さらに各電極本体部２３ａを囲むように基材２１の表面に導電層として形成されている。つまり、他方の電極２４は、基材２１の表面に一方の電極２３の各電極本体部２３ａが設けられる基材２１の面と同じ面に各電極本体部２３ａを囲むように形成されている。各電極本体２３ａに隙間２９を設けて配置される他の電極２４の部分同士は、互いに接続されている。さらに、他方の電極２４の周縁部は、外部配線との接続部２４ｄとして機能する。
The other electrode 24 will be described. Corresponding to each electrode body 23a of one electrode 23 being arranged in a dot shape on the surface of the substrate 21, the other electrode 24 is not in contact with each electrode body 23a. Further, a conductive layer is formed on the surface of the base material 21 so as to surround each electrode main body 23a. That is, the other electrode 24 is formed so as to surround each electrode main body 23 a on the same surface as the surface of the base 21 on which the electrode main body 23 a of one electrode 23 is provided on the surface of the base 21. The parts of the other electrodes 24 arranged with the gaps 29 provided in the electrode bodies 23a are connected to each other. Further, the peripheral edge portion of the other electrode 24 functions as a connection portion 24d with an external wiring.
本実施形態にあっては、このような一方の電極２３及び他方の電極２４の上に、有機半導体２５，２６がそれぞれ設けられている。図５に示す形態にあっては、一方の電極２３の電極本体部２３ａ上にはｐ層の有機半導体２５が形成され、他方の電極２４の上にはｎ層の有機半導体２６が形成される。よって、一方の電極２３の電極本体部２３ａがｐ型電極として機能し、他方の電極２４のうちｎ型の有機半導体２６で覆われている部分はｎ型電極として機能する。
In the present embodiment, the organic semiconductors 25 and 26 are provided on the one electrode 23 and the other electrode 24, respectively. In the form shown in FIG. 5, a p-layer organic semiconductor 25 is formed on the electrode body 23 a of one electrode 23, and an n-layer organic semiconductor 26 is formed on the other electrode 24. . Therefore, the electrode body 23a of one electrode 23 functions as a p-type electrode, and the portion of the other electrode 24 covered with the n-type organic semiconductor 26 functions as an n-type electrode.
図５に示す形態とは逆に、図示を省略するが、一方の電極２３の電極本体部２３ａ上にはｎ層の有機半導体が形成され、他方の電極２４の上にｐ層の有機半導体が形成されてもよい。この形態では、一方の電極２３の電極本体部２３ａがｎ型電極として機能し、他方の電極２４のうちｐ型の有機半導体で覆われている部分はｐ型電極として機能する。
Contrary to the configuration shown in FIG. 5, although not shown, an n-layer organic semiconductor is formed on the electrode body 23 a of one electrode 23, and a p-layer organic semiconductor is formed on the other electrode 24. It may be formed. In this embodiment, the electrode body portion 23a of one electrode 23 functions as an n-type electrode, and the portion of the other electrode 24 covered with a p-type organic semiconductor functions as a p-type electrode.
ｐ層の有機半導体２５は、第１の実施形態で例示した各種の正孔輸送材料によって形成される。ｎ層の有機半導体２６は、第１実施形態で例示した各種の電子輸送材料によって形成される。ｐ層の有機半導体２６とｎ層の有機半導体２５とで光電変換層３０が形成される。保護層２７については、太陽光などの光３１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し得る。
The p-layer organic semiconductor 25 is formed of various hole transport materials exemplified in the first embodiment. The n-layer organic semiconductor 26 is formed of various electron transport materials exemplified in the first embodiment. A photoelectric conversion layer 30 is formed by the p-layer organic semiconductor 26 and the n-layer organic semiconductor 25. The protective layer 27 may be formed of, for example, a resin or the like as long as it is a material that transmits light 31 such as sunlight.
図５に示す光電変換デバイス２０の製造方法について概略説明する。まず、基材に所定のパターンで複数の貫通穴２１ａを開ける。
A method for manufacturing the photoelectric conversion device 20 shown in FIG. First, a plurality of through holes 21a are formed in a predetermined pattern in the base material.
次に、貫通穴２１ａを開けた基材を無電解メッキで基材の全表面をメッキした後に、一方の電極及び他方の電極を形成しない部分の金属をエッチング等により取り除き、一方の電極及び他方の電極の元となる種電極を形成する。
Next, after plating the whole surface of the base material by electroless plating on the base material with the through holes 21a, the metal in a portion where one electrode and the other electrode are not formed is removed by etching or the like, and the one electrode and the other A seed electrode is formed as a source of the electrode.
そして、必要に応じてマスクをかぶせて電解メッキ処理を行い、貫通穴２１ａに導電材２７を充填して一方の電極２３及び他方の電極２４を形成する。なお、メッキ処理を用いず、印刷法により一方の電極及び他方の電極を形成してもよい。
Then, if necessary, an electroplating process is performed by covering the mask, and the conductive material 27 is filled in the through hole 21a to form one electrode 23 and the other electrode 24. Note that one electrode and the other electrode may be formed by a printing method without using the plating process.
その後、ｐ層の有機半導体２５となる正孔輸送材料を所定の箇所、例えば一方の電極２３に、例えばインクジェットプリンタによる印刷方法により塗布する。
Thereafter, a hole transport material to be the p-layer organic semiconductor 25 is applied to a predetermined portion, for example, one electrode 23 by, for example, a printing method using an ink jet printer.
次に、ｎ層の有機半導体２６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２４に塗布する。塗布にはｐ層の有機半導体２５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てもよい。
Next, an electron transport material to be the n-layer organic semiconductor 26 is applied between the p layer and the p layer, for example, the other electrode 24. As in the case of the p-layer organic semiconductor 25, a printing technique using an ink jet printer may be used for coating.
これにより、ｐ層の有機半導体２５とｎ層の有機半導体２６とによってｐｎ接合が形成される。なお、ｎ層の有機半導体２６から塗布しその後ｐ層の有機半導体２５を塗布してもよい。
Thereby, a pn junction is formed by the p-layer organic semiconductor 25 and the n-layer organic semiconductor 26. The n-layer organic semiconductor 26 may be applied, and then the p-layer organic semiconductor 25 may be applied.
最後に、保護層２７を塗装などによって形成することで、光電変換デバイス２０が作製される。なお、図５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。
Finally, the photoelectric conversion device 20 is manufactured by forming the protective layer 27 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. 5 is manufactured.
本発明の第３実施形態はデバイス性能や設計等により適宜変更しても構わない。例えば、一方の電極２３と他方の電極２４の平面視によるパターンは図７に示すものに限らず、適宜変更することができる。図７では、一方の電極２３の電極本体部２３ａは平面視で矩形であるが、三角形、多角形、円形、楕円、その他の幾何学模様であってもよい。
The third embodiment of the present invention may be appropriately changed depending on device performance, design, and the like. For example, the pattern in plan view of one electrode 23 and the other electrode 24 is not limited to that shown in FIG. 7 and can be changed as appropriate. In FIG. 7, the electrode body 23a of one electrode 23 is rectangular in plan view, but may be a triangle, polygon, circle, ellipse, or other geometric pattern.
図８は、光電変換デバイス用電極の変形例を示す平面図である。基材２１で貫通穴２１ａを平面視で菱形として、一方の電極２３の電極本体部２３ａを菱形に形成し、他方の電極を電極本体部２３ａと相似した菱形をマトリックス状に配置したパターンとして形成してもよい。この場合、上記構成例と同様に、一方の電極２３と他方の電極２４とが離間するように構成することは勿論である。このように、各電極の面積がｐ型電極とｎ型電極とで等しく一様な幾何学パターンとしてもよい。
FIG. 8 is a plan view showing a modification of the photoelectric conversion device electrode. The through hole 21a is formed as a rhombus in plan view on the base material 21, the electrode body 23a of one electrode 23 is formed in a rhombus, and the other electrode is formed as a pattern in which rhombus similar to the electrode body 23a is arranged in a matrix. May be. In this case, it is a matter of course that the one electrode 23 and the other electrode 24 are separated from each other as in the above configuration example. In this way, the area of each electrode may be a geometric pattern that is uniform between the p-type electrode and the n-type electrode.
Claims (13)
- パターンに従って複数の貫通穴を有する絶縁性の基材と、
上記基材の貫通穴を導電材で充填し上記基材の表面に露出させて形成された一方の電極と、
上記基材の表面で上記一方の電極との間に隙間を有するように設けられた他方の電極と、
を有する、光電変換デバイス用電極。 An insulating substrate having a plurality of through holes according to a pattern;
One electrode formed by filling the through hole of the base material with a conductive material and exposing the surface of the base material;
The other electrode provided so as to have a gap between the one electrode and the surface of the substrate;
An electrode for a photoelectric conversion device. - 前記一方の電極は、前記基材の裏面に形成された導電性の被膜によって相互に接続されている、請求項１に記載の光電変換デバイス用電極。 The electrode for a photoelectric conversion device according to claim 1, wherein the one electrode is connected to each other by a conductive film formed on a back surface of the base material.
- 前記一方の電極は、前記基材の表面から張り出した突出部を有している、請求項１に記載の光電変換デバイス用電極。 The electrode for a photoelectric conversion device according to claim 1, wherein the one electrode has a protruding portion protruding from the surface of the base material.
- 前記一方の電極の外部接続部が前記基材の裏面に設けられ、前記他方の電極の外部接続部が前記基材の表面に設けられる、請求項１に記載の光電変換デバイス用電極。 The electrode for a photoelectric conversion device according to claim 1, wherein the external connection portion of the one electrode is provided on the back surface of the base material, and the external connection portion of the other electrode is provided on the surface of the base material.
- 前記一方の電極及び前記他方の電極が、Ｃｕ、Ａｌの何れかで形成されている、請求項１に記載の光電変換デバイス用電極。 The electrode for a photoelectric conversion device according to claim 1, wherein the one electrode and the other electrode are formed of Cu or Al.
- 請求項１乃至５の何れかに記載の光電変換デバイス用電極と、
前記一方の電極上に設けられ正孔輸送材料でなるｐ層の有機半導体と、
前記他方の電極上に設けられ電子輸送材料でなるｎ層の有機半導体と、
を備え、
上記ｐ層の有機半導体及び上記ｎ層の有機半導体が同一面上に互い違いに形成されている、光電変換デバイス。 An electrode for a photoelectric conversion device according to any one of claims 1 to 5,
A p-layer organic semiconductor made of a hole transport material provided on the one electrode;
An n-layer organic semiconductor made of an electron transport material provided on the other electrode;
With
The photoelectric conversion device in which the organic semiconductor of the p layer and the organic semiconductor of the n layer are alternately formed on the same surface. - 請求項１乃至５の何れかに記載の光電変換デバイス用電極と、
前記一方の電極上に設けられ電子輸送材料でなるｎ層の有機半導体と、
前記他方の電極上に設けられ正孔輸送材料でなるｐ層の有機半導体と、
を備え、
上記ｐ層の有機半導体及び上記ｎ層の有機半導体が同一面上に互い違いに形成されている、光電変換デバイス。 An electrode for a photoelectric conversion device according to any one of claims 1 to 5,
An n-layer organic semiconductor made of an electron transport material provided on the one electrode;
A p-layer organic semiconductor made of a hole transport material provided on the other electrode;
With
The photoelectric conversion device in which the organic semiconductor of the p layer and the organic semiconductor of the n layer are alternately formed on the same surface. - 同一面上に一方の電極と他方の電極とが形成されてなり、
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、光電変換デバイス用電極。 One electrode and the other electrode are formed on the same surface,
An electrode for a photoelectric conversion device, wherein the one electrode functions as a p-type electrode and the other electrode functions as an n-type electrode. - 前記一方の電極と前記他方の電極とが横並びに一つずつ設けられている、請求項８に記載の光電変換デバイス用電極。 The electrode for a photoelectric conversion device according to claim 8, wherein the one electrode and the other electrode are provided side by side.
- 前記一方の電極及び前記他方の電極は、複数本の電極指が一端で電気的に接続された構造を有する櫛歯電極で構成され、
前記一方の電極の電極指と前記他方の電極の電極指とが交互に並んでいる、請求項８に記載の光電変換デバイス用電極。 The one electrode and the other electrode are composed of comb electrodes having a structure in which a plurality of electrode fingers are electrically connected at one end,
The electrode for a photoelectric conversion device according to claim 8, wherein the electrode fingers of the one electrode and the electrode fingers of the other electrode are alternately arranged. - 前記一方の電極及び前記他方の電極がＣｕ、Ａｌの何れかで形成されている、請求項８に記載の光電変換デバイス用電極。 The electrode for a photoelectric conversion device according to claim 8, wherein the one electrode and the other electrode are formed of Cu or Al.
- 請求項８乃至１１の何れかに記載の光電変換デバイス用電極と、
前記一方の電極上に設けられ正孔輸送材料でなるｐ層の有機半導体と、
前記他方の電極上に設けられ電子輸送材料でなるｎ層の有機半導体と、を備え、
上記ｐ層の有機半導体及び上記ｎ層の有機半導体が同一面上に交互に形成されている、光電変換デバイス。 An electrode for a photoelectric conversion device according to any one of claims 8 to 11,
A p-layer organic semiconductor made of a hole transport material provided on the one electrode;
An n-layer organic semiconductor made of an electron transport material provided on the other electrode,
A photoelectric conversion device, wherein the p-layer organic semiconductor and the n-layer organic semiconductor are alternately formed on the same surface. - 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６、７又は１２に記載の光電変換デバイス。 The photoelectric conversion device according to claim 6, wherein the p-layer organic semiconductor and the n-layer organic semiconductor are covered with a transparent protective layer.
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