JP2007018909A - Manufacturing method for photoelectric conversion device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of the photoelectric conversion device, wherein the range of selection of material for a translucent substrate or a collector electrode can be expanded, and which has high conversion efficiency and high reliability and can be easily manufactured. <P>SOLUTION: In this manufacturing method for a photoelectric conversion device 1, a laminate is formed by laminating a sintered porous oxide-semiconductor layer 7 and a transparent conductive layer 5 by turns, on the upper surface of a flexible supporting body 13 with prescribed thickness, then, the transparent conductive layer 5 of the laminate is bonded to a translucent substrate 2 through the transparent resin layer 4, then the support body is removed from the laminate, then, the porous oxide-semiconductor layer 7 is made to support dye 6 to make the laminate and the translucent substrate 2 a optical working electrode side board; then the optical working electrode side group plate and a counter electrode side board 11, having a counter electrode layer (catalyst conductive layer 12) in one main surface are arranged so that the porous oxide-semiconductor layer 7 and the counter electrode layer face each other; then outer peripheral parts of the optical working electrode side board and the counter electrode side board 11 are sealed via a sealing member 10; and an electrolyte is injected into a gap between the porous oxide-semiconductor layer 7 and the counter electrode layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a dye-sensitized photoelectric conversion device for a solar cell, a light receiving element or the like having excellent photoelectric conversion efficiency and reliability.

  Conventionally, a dye-sensitized solar cell, which is a type of photoelectric conversion device, does not require a vacuum device for its production, and thus has been recognized as a low-cost and low environmental load solar cell. Research and development is underway.

  This dye-sensitized solar cell usually forms a porous titanium oxide layer having a thickness of about 10 μm obtained by sintering titanium oxide fine particles having a particle size of about 20 nm on a conductive glass substrate at about 450 ° C. The porous electrode is composed of a photoactive electrode side substrate in which a dye is adsorbed on the surface of titanium oxide particles of the porous titanium oxide layer, and a counter electrode side substrate in which a platinum or carbon counter electrode layer is formed on a conductive glass substrate. The titanium oxide layer and the counter electrode layer are opposed to each other, and both substrates are bonded by hot pressing through a frame-shaped thermoplastic resin sheet as a spacer and sealing material, and an iodine / iodide redox pair is interposed between these substrates. The electrolyte solution containing is injected through a through hole formed in the counter electrode side substrate, and the through hole is closed (see, for example, Non-Patent Document 1).

  Conventionally, it has been studied to use a resin substrate such as polyethylene terephthalate (PET) as a material for both the substrates. If a resin substrate can be used, the dye-sensitized solar cell can be reduced in weight and bent during use, and a dye-sensitized solar cell excellent in operability and versatility can be provided.

  However, the resin substrate cannot form a porous titanium oxide layer made of titanium oxide particles, which is a sintered body having a high sintering temperature as described above. Therefore, electrodeposition, electrophoretic deposition, hydrothermal synthesis, etc. are performed as low-temperature processes for forming the porous titanium oxide layer, and post-treatment to improve the electron transport properties of the porous titanium oxide layer. Microwave treatment, plasma treatment by CVD method, thermal catalyst treatment, UV irradiation treatment, etc. have been used, but high conversion efficiency obtained by porous titanium oxide layer formed by high temperature process is formed by low temperature process It is difficult to obtain a porous titanium oxide layer.

Therefore, Non-Patent Document 2 is a conventional example that solves such problems. According to this, a TiO ₂ paste is applied onto a glass substrate, sintered in a furnace at a temperature of 550 ° C., and a transparent conductive film (ITO film) serving as an electrode is formed on the sintered TiO ₂ layer to a thickness of 500 nm. For flexible dye sensitization by using a PET film as a resin film substrate, pasting the PET film on the ITO film through a transparent resin layer, and then removing the glass substrate The light working electrode side substrate is obtained. Then, a photoelectrode side substrate in which a Ru sensitizing dye is supported on a TiO ₂ layer and a counter electrode side substrate in which a Pt layer is formed on a conductive glass substrate by a sputtering method are bonded together, and electrolysis is performed between both substrates. The liquid is injected to obtain a solar cell.
Published by Information Technology Co., Ltd., “Frontiers and Future Prospects of Dye-Sensitized Solar Cells and Solar Cells”, P26-P27 The Electrochemical Society, 72nd Annual Meeting, 2005, P466

According to the conventional non-patent document 1 and the like, a glass substrate (hereinafter referred to as an FTO glass substrate) coated with a conductive film usually made of SnO ₂ : F (fluorine-doped tin oxide; FTO) or the like is used as the photoactive electrode side substrate. However, when a porous titanium oxide layer having a thickness of 10 μm or more is formed on the FTO glass substrate by baking at a high temperature after applying the titanium oxide paste, internal stress is generated in the formed porous titanium oxide layer. Therefore, if the thickness of the glass substrate is 1 mm or less, the FTO glass may break, or conversely if the thickness of the glass substrate exceeds 1 mm, the porous titanium oxide layer is cracked or porous from the FTO glass substrate. There was a problem that the titanium oxide layer peeled off.
Further, the FTO film of the FTO glass substrate has heat resistance, and the sheet resistance does not change even at the firing temperature of titanium oxide, and the translucency does not change. However, the FTO film is made of indium oxide (ITO, In ₂ O ₃ etc.) There was a problem that sheet resistance was higher than the transparent conductive film. Therefore, a glass substrate provided with an ITO film having a low sheet resistance is preferable. However, there is a problem that the sheet resistance and translucency deteriorate at the firing temperature of titanium oxide, and a transparent conductive film made of an indium oxide is used. I couldn't.

  Further, since the sheet resistance of the FTO glass substrate is about 10Ω / □, when the length of the photoelectric conversion element becomes 1 cm or more, the resistance loss is large and the FF value (curve fill factor: curve fill factor) ) Becomes small and high photoelectric conversion efficiency (hereinafter also referred to as conversion efficiency) cannot be obtained.

  Therefore, it has been studied to provide a comb-shaped collector electrode on the FTO glass substrate. However, a collector electrode having a low resistance is required to have a thickness of several μm to several tens of μm. In this case, a comb-shaped collector electrode is required. It was difficult to form a thin porous titanium oxide layer having a thickness of about 10 μm on the electrode due to a limitation in the coating formation method and the like. Further, the arrangement of the thin electric wires can reduce the electric resistance, but the wire diameter is several tens to several hundreds of μm, and the formation of the porous titanium oxide layer is more difficult. Even if a titanium oxide paste can be applied, the formed porous titanium oxide layer has irregularities on the surface, so that the layer has low reliability. As a result, the thickness of the electrolyte formed by bonding the photoelectrode side substrate and the counter electrode side substrate and injecting them between them varies, resulting in unstable conversion efficiency and low reliability of the dye-sensitized solar It was a battery.

  In addition, the sintering temperature of the porous titanium oxide layer formed by sintering is as high as about 450 ° C. When a conductive paste for low temperature formation is used for the collector electrode, metal diffusion from the collector electrode, resin contained in the conductive paste There is a problem that the porous titanium oxide layer is adversely affected due to contamination by the above.

  In addition, when a plurality of photoelectric conversion elements are arranged to be connected in series or in parallel, a larger protective glass substrate for integration is required for arranging the plurality of photoelectric conversion elements on the light incident side. There are problems that the substrate on the light incident side is doubled, the conversion efficiency is lowered, and the cost is increased.

  Moreover, since the collector electrode is not provided in the configuration described in Non-Patent Document 2, there is a problem that high conversion efficiency cannot be obtained due to a large resistance loss. Although the glass substrate used in the manufacturing process is removed, the glass substrate is usually thick, and even a cover glass thinned by machining or polishing has a thickness of 0.12 mm or more, and even this thickness is toxic. It is difficult to etch away with hydrofluoric acid. In the first place, it is technically difficult to make a thin glass substrate with a large size, and it is difficult to manufacture a large photoelectric conversion device by the method described in Non-Patent Document 2. Furthermore, since glass is rigid and inflexible, the glass substrate could not be removed by peeling.

  Accordingly, the present invention has been completed in view of the above-described problems in the prior art, and an object thereof is to provide a method for manufacturing a photoelectric conversion device that can obtain the following various functions and effects. That is, 1) the porous titanium oxide layer can be formed by a high temperature firing method, 2) the adverse effect of the internal stress of the porous titanium oxide layer can be eliminated, and the reliability can be improved. 4) The degree of freedom in selecting the material of the transparent conductive layer can be increased. 5) A paste capable of forming the collector electrode at a low temperature can be used. This makes it possible to increase the degree of freedom in selecting the material for the collector electrode and reduce the manufacturing cost by forming at a low temperature. 6) It is possible to use an electric wire with lower electrical resistance as the collector electrode. 7) Flatten the porous titanium oxide layer. In addition, it can be uniformly formed in a large area and can improve reliability. 8) It is easy to form a plurality of photoelectric conversion elements, so it is excellent in integration. 9) It is porous even if the substrate on the side of the working electrode becomes large. Since the stack of oxide semiconductor layers can be made small, the internal stress is small and excellent in reliability. 10) A plurality of photoelectric conversion elements can be formed by stacking, so that the stacking is excellent. 11) Dye-sensitized solar with high conversion efficiency. An object of the present invention is to provide a method for manufacturing a photoelectric conversion device capable of obtaining an effect of being able to obtain a battery.

  In the method for producing a photoelectric conversion device of the present invention, a sintered porous oxide semiconductor layer and a transparent conductive layer are sequentially laminated on the upper surface of a flexible support, and then a laminate is formed. Adhering the transparent conductive layer of the laminate to a translucent substrate through a transparent resin layer, then removing the support from the laminate, and then supporting the dye on the porous oxide semiconductor layer The laminate and the translucent substrate are formed as a light working electrode side substrate, and then the light working electrode side substrate and a counter electrode side substrate having a counter electrode layer on one main surface are formed as the porous oxide semiconductor layer and the It arrange | positions so that a counter electrode layer may oppose, and the outer peripheral part of the said optical working electrode side board | substrate and the said counter electrode side board | substrate is sealed through a sealing member, Between the said porous oxide semiconductor layer and the said counter electrode layer Formed in any one of the light working electrode side substrate, the counter electrode side substrate and the sealing member Characterized by injecting an electrolyte through the through holes.

  Preferably, in the method for producing a photoelectric conversion device of the present invention, the support is peeled off from the laminate when the support is removed from the laminate.

  Preferably, in the method for manufacturing a photoelectric conversion device of the present invention, when the support is removed from the laminate, the support is dissolved and removed by etching.

  In the method for producing a photoelectric conversion device of the present invention, preferably, a collector electrode is formed on the transparent conductive layer when the transparent conductive layer of the laminate is bonded to a translucent substrate through a transparent resin layer. In addition, the transparent resin layer is formed on a portion of the transparent conductive layer without the collector electrode.

  Preferably, in the method for producing a photoelectric conversion device of the present invention, a number of irregularities are formed in advance on the upper surface of the support, and the irregularities are removed from the porous oxidation when the support is removed from the laminate. It transfers to the surface of a physical semiconductor layer, It is characterized by the above-mentioned.

  In the method for producing a photoelectric conversion device of the present invention, preferably, the porous oxide semiconductor layer is made of a sintered body of oxide semiconductor fine particles, and the particle diameter of the oxide semiconductor fine particles is from the support side to the porous The oxide semiconductor layer is formed so as to gradually become smaller in the thickness direction.

  In the method for producing a photoelectric conversion device of the present invention, a sintered porous oxide semiconductor layer and a transparent conductive layer are sequentially laminated on the upper surface of a flexible support to form a laminate, and then the laminate is laminated. The transparent conductive layer of the body is bonded to the translucent substrate through the transparent resin layer, and then the support is removed from the laminate, and then the dye is supported on the porous oxide semiconductor layer and the laminate and the translucent The conductive substrate is formed with the light working electrode side substrate, and then the light working electrode side substrate and the counter electrode side substrate having a counter electrode layer on one main surface are arranged so that the porous oxide semiconductor layer and the counter electrode layer face each other. In addition, the outer peripheral portions of the light working electrode side substrate and the counter electrode side substrate are sealed with a sealing member, and the light working electrode side substrate, the counter electrode side substrate, and the sealing are placed in a gap between the porous oxide semiconductor layer and the counter electrode layer. Since the electrolyte is injected through a through-hole formed in one of the stop members, A porous oxide semiconductor layer can be formed by applying a paste composed of oxide semiconductor fine particles such as titanium oxide, water and a surfactant, and then sintering at a high temperature (about 450 ° C. for about 30 minutes). Therefore, as a result of the porous oxide semiconductor layer having excellent surface flatness and high reliability, a photoelectric conversion device with high conversion efficiency can be manufactured.

  In addition, since the internal stress of the porous oxide semiconductor layer formed by sintering is released by deformation or removal of the flexible support, the porous oxide semiconductor layer is transferred to the substrate on the light working electrode side. However, a porous oxide semiconductor layer having no internal stress can be formed on the photoactive electrode side substrate.

  Furthermore, since the transparent conductive layer can be formed after the porous oxide semiconductor layer is fired, the adhesion between the transparent conductive layer and the porous oxide semiconductor layer can be improved, and as a result, a photoelectric conversion device with high conversion efficiency is manufactured. be able to.

  Further, by inserting an extremely thin dense oxide semiconductor layer between the porous oxide semiconductor layer and the transparent conductive layer, the reverse current can be suppressed and the photoelectric conversion efficiency is increased.

  In addition, since the porous oxide semiconductor layer has no internal stress, there is no possibility of breaking the photoactive electrode side substrate, and a highly reliable photoelectric conversion device can be manufactured.

  In the method for producing a photoelectric conversion device of the present invention, a laminated body is formed by sequentially laminating a sintered porous oxide semiconductor layer and a transparent conductive layer on an upper surface of a support. Since the transparent conductive layer is bonded to the translucent substrate through the transparent resin layer, and then the support is removed from the laminate, the material and thickness of the translucent substrate (light working electrode side substrate) can be freely selected. be able to. That is, it is a flexible material having a low melting point and made of a resin that cannot withstand the sintering temperature of the porous oxide semiconductor layer, and a low-cost translucent substrate can be used. Therefore, it is possible to realize a light and low-cost photoelectric conversion device that can be bent, and there is an effect that the application is expanded.

  Moreover, since the transparent conductive layer is formed after the porous oxide semiconductor layer is sintered, the material of the transparent conductive layer can be freely selected. For example, an indium-based material having a low sheet resistance can be used as the transparent conductive layer, and the conversion efficiency of the photoelectric conversion device can be increased.

  In addition, the method for producing a photoelectric conversion device of the present invention preferably uses a flexible support because the support is peeled off from the laminate when the support is removed from the laminate. Can be peeled off, and thus the support can be easily removed.

  In the method for producing a photoelectric conversion device of the present invention, since the support is preferably dissolved and removed by etching when the support is removed from the laminate, the support is flexible. The support can be made thin enough to be etched away, and therefore the support can be easily removed.

  In the method for producing a photoelectric conversion device of the present invention, preferably, when the transparent conductive layer of the laminate is bonded to the translucent substrate through the transparent resin layer, a collector electrode is formed on the transparent conductive layer and is transparent. Since the transparent resin layer is formed on the conductive layer without the collector electrode, the collector electrode is provided in addition to the transparent conductive layer, so the resistance on the current output side (collector electrode) obtained by photoelectric conversion Is extremely low, and a photoelectric conversion device capable of obtaining high conversion efficiency can be manufactured. As a result, there is an effect that the size of the photoelectric conversion device can be increased.

  Further, in this case, a portion (concave portion) having no collecting electrode made of a comb-shaped electrode or the like on the transparent conductive layer is filled with the transparent resin layer. As a result, the porous oxide semiconductor layer or the electrolyte layer is a flat layer. Becomes uneven. Therefore, the thickness and shape of the porous oxide semiconductor layer and the electrolyte layer are uniform for each product, and the reliability of these layers is increased. Therefore, the conversion efficiency of the photoelectric conversion device is stabilized and the reliability is high. It becomes.

  In the method for producing a photoelectric conversion device of the present invention, it is preferable that a large number of irregularities are formed in advance on the upper surface of the support, and the irregularities are formed on the surface of the porous oxide semiconductor layer when the support is removed from the laminate. Therefore, the light that has passed through the porous oxide semiconductor layer is scattered in the unevenness, thereby producing a light confinement effect, and the conversion efficiency is increased.

  In the method for producing a photoelectric conversion device of the present invention, preferably, the porous oxide semiconductor layer is composed of a sintered body of oxide semiconductor fine particles, and the particle diameter of the oxide semiconductor fine particles is from the support side to the porous oxide semiconductor layer. Therefore, light passing through the porous oxide semiconductor layer is favorably scattered. In particular, long-wavelength light that is easily transmitted can be well reflected by the oxide semiconductor fine particles having a larger particle diameter, and the light confinement effect can be enhanced and the conversion efficiency can be improved.

  Embodiments of a method for manufacturing a photoelectric conversion device according to the present invention will be described below in detail with reference to the drawings. In addition, the same code | symbol is attached | subjected to the same member in drawing.

  1 is a cross-sectional view showing a photoelectric conversion device obtained by the manufacturing method of the present invention, and FIG. 2 is a cross-sectional view of the photoelectric conversion device for explaining the manufacturing method of the present invention.

  In the production method of the present invention, the porous oxide semiconductor layer 7 and the transparent conductive layer 5 are sequentially laminated on the upper surface of the flexible support to form a laminate, and then the laminate is formed. The transparent conductive layer 5 is bonded to the translucent substrate 2 through the transparent resin layer 4, then the support is removed from the laminate, and then the dye 6 is supported on the porous oxide semiconductor layer 7. And the translucent substrate 2 as the light working electrode side substrate, and then the light working electrode side substrate and the counter electrode side substrate 11 having the counter electrode layer (catalytic conductive layer 12) on one main surface, the porous oxide semiconductor layer 7 and the counter electrode layer are arranged so as to face each other, and the outer peripheral portion of the light working electrode side substrate and the counter electrode side substrate 11 is sealed through the sealing member 10, so that the porous oxide semiconductor layer 7 and the counter electrode layer Electricity is passed through a through-hole formed in one of the light working electrode side substrate, the counter electrode side substrate 11 and the sealing member 10 in the gap between them. It is intended to inject quality.

  The photoelectric conversion device 1 shown in FIG. 1 obtained by the manufacturing method of the present invention is formed so as to fill a space between the collector electrode 3 and the collector electrode 3 on one main surface of the translucent substrate 2 constituting the light working electrode side substrate. The porous oxide semiconductor layer 7, the electrolyte layer 9, and the counter electrode made of sintered fine particles carrying the transparent conductive layer 5 and the dye 6 on the collector electrode 3 and the transparent resin layer 4. The catalyst conductive layer 12 and the counter electrode side substrate 11 as layers are sequentially laminated. The sealing surrounds the side surface of the laminated structure including the transparent resin layer 4, the transparent conductive layer 5, the porous oxide semiconductor layer 7, the electrolyte layer 9, and the catalyst conductive layer 12 (consisting of the conductive layer 12x and the catalyst layer 12y). A member 10 is formed.

  The photoelectric conversion device 1 illustrated in FIG. 1 can be manufactured through one step illustrated in a cross-sectional view including a part of the photoelectric conversion device 1 illustrated in FIG. That is, when removing the support 13 from the laminate composed of the porous oxide semiconductor layer 7 and the transparent conductive layer 5, the support 13 is peeled off from the laminate. In FIG. 2, a porous oxide semiconductor layer 7, a transparent conductive layer 5, and a collector electrode 3 are sequentially stacked on a sheet-like flexible support 13, and then the gap between the collector electrodes 3 is filled. A transparent resin layer 4 is provided and adhered to the translucent substrate 2. Here, the support 13 is preferably a foil or a sheet whose main component is aluminum.

  Next, the support 13 is removed from the laminate of the porous oxide semiconductor layer 7, the transparent conductive layer 5, the collector electrode 3, and the transparent resin layer 4, and then the oxide semiconductor fine particles forming the porous oxide semiconductor layer 7. The dye 6 is supported on the surface of the substrate. As the support 13, a sheet or foil that can withstand a temperature of about 500 ° C. is preferable, and an aluminum foil is particularly preferable. The flexible support 13 is preferably removed by mechanical peeling with an adhesive tape. Alternatively, the support 13 may be etched and dissolved with acids or alkalis diluted with pure water. In the case of the support 13 made of aluminum, it may be etched with hydrochloric acid diluted with pure water, and can be easily removed by etching. When removing by etching, as the transparent conductive layer 5, an FTO film or the like excellent in chemical resistance can be used alone, or an ITO film or the like can be laminated on the FTO film.

  Here, a large number of irregularities may be formed on the surface of the support 13 in advance, and the irregularities are transferred to the surface of the porous oxide semiconductor layer 7 formed on the surface of the support 13. In order to give a large number of irregularities to the surface of the support 13, it can be easily formed by a press molding method using a mold, a sand blast method, a wet etching method using an acid or alkali, an ultrasonic method, or the like.

  Further, in the present invention, the oxide semiconductor fine particles of the porous oxide semiconductor layer 7 have a variation in particle diameter, or the particle diameter of the oxide semiconductor fine particles gradually decreases in the thickness direction from the support 13 side. A light confinement effect can be imparted to the porous oxide semiconductor layer 7 by, for example, applying a paste that becomes the porous oxide semiconductor layer 7 a plurality of times.

  Next, as shown in FIG. 1, the porous oxide semiconductor layer 7 integrated with the translucent substrate 2 and the surface of the catalyst conductive layer 12 formed on the counter electrode side substrate 11 have a gap 9. Then, the sealing member 10 is provided on the outer peripheral portions of the translucent substrate 2 and the counter electrode side substrate 11 and sealed. Here, it is possible to employ a configuration in which various spacers are installed in the gap so that the gap is uniformly formed without causing an electrical short circuit between the porous oxide semiconductor layer 7 and the catalyst conductive layer 12.

  Next, the electrolyte 9 fills the gap and the pores inside the porous oxide semiconductor layer 7 from the through hole (injection hole) formed in any of the translucent substrate 2, the counter electrode side substrate 11, and the sealing member 10. An electrolyte is injected so as to seal the injection hole.

  A photoelectric conversion device 1a shown in FIG. 3 has a translucent structure including a collector electrode 3, a transparent resin layer 4, a transparent conductive layer 5, a porous oxide semiconductor layer 7, an electrolyte layer 9, and a catalyst conductive layer 12. A plurality of substrates are formed side by side between the substrate 2 and the counter electrode side substrate 11, and a sealing member 10 is formed between the laminated structures. In other words, a plurality of collector electrodes 3a, 3b, 3c and transparent resin layers 4a, 4b, 4c are embedded on one main surface of the translucent substrate 2 so as to fill the space between the collector electrodes 3a, 3b, 3c. Is formed. Furthermore, the porous electrode comprises sintered fine particles of an oxide semiconductor carrying transparent conductive layers 5a, 5b, 5c and dyes 6a, 6b, 6c on the collecting electrodes 3a, 3b, 3c and the transparent resin layers 4a, 4b, 4c. The oxide semiconductor layers 7a, 7b, and 7c, the electrolyte layers 9a, 9b, and 9c, the catalyst conductive layers 12a, 12b, and 12c, and the counter electrode side substrate 11 are sequentially stacked.

  The photoelectric conversion device 1a of FIG. 3 can be easily manufactured through one step shown in a cross-sectional view including a part of the photoelectric conversion device shown in FIG. In FIG. 4, porous oxide semiconductor layers 7a, 7b, and 7c, transparent conductive layers 5a, 5b, and 5c, collector electrodes 3a, and the like are respectively formed on a plurality of sheet-like flexible supports 13a, 13b, and 13c. 3b and 3c are sequentially laminated, and then transparent resin layers 4a, 4b and 4c are provided so as to fill the space between collector electrodes 3a, 3b and 3c, and support 13a, porous oxide semiconductor layer 7a and transparent conductive layer are provided. Layer 5a, collector electrode 3a, laminate a of transparent resin layer 4a, support 13b, porous oxide semiconductor layer 7b, transparent conductive layer 5b, collector electrode 3b, laminate b of transparent resin layer 4b, support 13c, The laminated body c of the porous oxide semiconductor layer 7c, the transparent conductive layer 5c, the collector electrode 3c, and the transparent resin layer 4c is bonded onto the translucent substrate 2 with a space therebetween. Here, the sheet-like flexible supports 13a, 13b, and 13c are preferably foils or sheets whose main component is aluminum.

  Next, the supports 13a, 13b, and 13c are removed, and then the dyes 6a, 6b, and 6c are supported on the surface of the oxide semiconductor fine particles of the porous oxide semiconductor layers 7a, 7b, and 7c. In order to carry the dyes 6a, 6b, and 6c, it is only necessary to immerse the light-transmitting substrate 2 together with the dye solution in a state where the supports 13a, 13b, and 13c are removed in FIG. The porous oxide semiconductor layers 7a, 7b, and 7c of c can support the dyes 6a, 6b, and 6c.

  Removal of the supports 13a, 13b, and 13c is performed in the same manner as described above.

  Next, the electrolyte 9 is injected and filled into the gap and the hole inside the porous oxide semiconductor layer 7 through the through hole (injection hole) formed in the counter electrode side substrate 11 or the sealing member 10, and the injection hole is sealed. Stop.

  In the photoelectric conversion device 1a in which a plurality of stacked bodies a to c shown in FIG. 3 are arranged, a plurality of photoelectric conversion element portions are independently formed on a pair of translucent substrate and counter electrode side substrate. Applications can be expanded because it is possible to freely select whether to connect in series or in parallel. Moreover, since the connection lead which connects a photoelectric conversion element part can be covered with a sealing member, it can prevent that a connection lead is corroded by electrolyte, and there exists an effect that it is excellent in reliability.

  FIG. 6 shows a stacked photoelectric conversion device 1b. The manufacturing method of this stacked photoelectric conversion device 1b can be manufactured using the same procedure as the manufacturing method of one photoelectric conversion device 1 shown in FIG. That is, after manufacturing the photoelectric conversion device 1 of FIG. 1, the process of FIG. 2 is performed on the second photoelectric conversion device 1. At this time, the transparent resin layer 4 of the second photoelectric conversion device 1 is changed to the first one. It adheres to the counter electrode side substrate 11 of the photoelectric conversion device 1. In this case, the counter electrode side substrate 11 needs to be translucent. In this way, a stacked photoelectric conversion device 1b in which two photoelectric conversion devices 1 are stacked can be manufactured. By repeating this manufacturing method, a plurality of photoelectric conversion devices 1 can be stacked, and a stacked photoelectric conversion device 1b having the same effect as the photoelectric conversion device 1a of FIG. 3 can be manufactured.

  In addition, according to the manufacturing method of the stacked photoelectric conversion device 1b formed by stacking a plurality of photoelectric conversion devices 1, the material and thickness of the photoactive electrode side substrate 11 can be freely selected by repeating the above manufacturing method. can do. That is, it is possible to use the flexible working electrode side substrate 11 made of a resin that cannot withstand the sintering temperature of the porous oxide semiconductor layer 7 and having a low melting point and a low cost, resulting in high conversion efficiency and light weight. A low-cost stacked photoelectric conversion device 1b that can be bent can be realized, and the application can be expanded.

  Here, an electrical connection structure of the photoelectric conversion device 1 will be described. The cross-sectional view shown in FIG. 5 is a view in which the cross-sections taken along the lines AA ′ and BB ′ shown in FIGS. From FIG. 5, it can be seen that a part of the ends of the collector electrode 3 and the catalyst conductive layer 12 are drawn out from the sealing member 10 in the cross section along the line AA ′. Electrical connection can be made at the part drawn out to the outside. Connection with the adjacent photoelectric conversion device 1 and the laminated body can also be performed at this part. Moreover, it is good to seal this connection site | part with the sealing member 10 after connecting.

  Next, each element which comprises the photoelectric conversion apparatus 1 mentioned above is demonstrated in detail.

<Support>
As the flexible support 13, a foil or sheet whose main component is aluminum as described above is generally available. In addition, zinc, titanium, iron, stainless steel, silver, copper, nickel, etc., or alloys thereof formed in foil or sheet form can be used.

  The thickness of the support 13 is preferably 10 μm to 0.3 mm (300 μm), more preferably 10 μm to 100 μm. If the thickness of the support 13 exceeds 0.3 mm, it will be difficult to chemically remove it, the flexibility will be lost, and removal by peeling will not be possible. If the thickness of the support 13 is less than 10 μm, it becomes difficult in terms of strength to form a foil having a required area, and therefore the support 13 cannot be removed by a peeling method. Commercially available aluminum foil has a thickness of 15 μm to 20 μm, and can be removed by chemical etching or peeling.

  Another material of the support 13 may be a heat resistant resin film. For example, the polyimide film has heat resistance and can have a thickness of 10 μm to 0.3 mm, and the support 13 that is thin and excellent in flexibility can be obtained. The support 13 made of polyimide film can be removed by chemical etching, but since it has strength, it is better to remove it by the peeling method.

<Porous oxide semiconductor layer>
The porous oxide semiconductor layer 7 is preferably a porous n-type metal oxide composed of fine particles such as titanium dioxide.

The material and composition of the n-type porous oxide semiconductor layer 7 is optimally titanium oxide (TiO ₂ ), and other materials include titanium (Ti), zinc (Zn), tin (Sn), and niobium. (Nb), indium (In), yttrium (Y), lanthanum (La), zirconium (Zr), tantalum (Ta), hafnium (Hf), strontium (Sr), barium (Ba), calcium (Ca), vanadium (V), a metal oxide semiconductor composed of at least one oxide of a metal element such as tungsten (W) is preferable, and nitrogen (N), carbon (C), fluorine (F), sulfur (S), You may contain 1 or more types of nonmetallic elements, such as chlorine (Cl), phosphorus (P), and aluminum (Al). Metal oxide semiconductors such as titanium oxide are all preferable because their electronic energy band gap is in the range of 2 to 5 eV, which is larger than the energy of visible light. The porous oxide semiconductor layer 7 is preferably an n-type semiconductor whose conduction band is lower than the conduction band of the dye at the electron energy level.

  The porous oxide semiconductor layer 7 is a porous body that is a granular body, or a linear body such as a needle-shaped body, a tubular body, or a columnar body, or a collection of these various linear bodies. As a result, the surface area for supporting the dye increases and the conversion efficiency can be increased. The porous oxide semiconductor layer 7 has a shape that increases its surface area and decreases electrical resistance, and is preferably composed of fine particles or fine linear bodies as described above. The average particle diameter or average wire diameter is preferably 5 to 500 nm, and more preferably 10 to 200 nm. If the lower limit of the average particle diameter or the average wire diameter in the range of 5 to 500 nm is less than this, the material cannot be miniaturized, and if the upper limit exceeds this, the junction area is reduced and the photocurrent is significantly reduced.

  The porous oxide semiconductor layer 7 may be a porous body having a porosity of 20 to 80%, more preferably 40 to 60%. The surface area of the porous oxide semiconductor layer 7 that is a light working electrode can be increased by 1000 times or more as compared with the case of being dense, and the light absorption, photoelectric conversion (power generation), and electron conduction can be performed efficiently. be able to. In addition, by forming the porous oxide semiconductor layer 7 as a porous body, the surface of the dye-sensitized photoelectric conversion body in which the dye is supported becomes uneven, thereby providing a light confinement effect and improving the conversion efficiency. Can be increased.

  The thickness of the porous oxide semiconductor layer 7 is preferably 0.1 to 50 μm, more preferably 1 to 20 μm. Here, the lower limit value at 0.1 to 50 μm is not suitable for practical use because the photoelectric conversion action is remarkably reduced when the film thickness is smaller than this, and the upper limit value is not suitable for practical use. This is because no light enters.

The porous oxide semiconductor layer 7 made of titanium oxide is manufactured as follows. First, acetylacetone is added to TiO ₂ anatase powder, and then kneaded with deionized water to prepare a titanium oxide paste stabilized with a surfactant. The prepared paste is applied onto a support at a constant speed by a doctor blade method, a bar coating method, or the like, and is 300 to 600 ° C., preferably 400 to 500 ° C., preferably 10 to 60 minutes, preferably 20 in the atmosphere. The porous oxide semiconductor layer 7 is formed by heat treatment for ˜40 minutes. This method is simple and can be formed on the support 13 that can withstand these temperatures, and a material having good characteristics such as conversion efficiency can be obtained.

Further, the surface of the porous oxide semiconductor layer 7 may be treated with TiCl ₄ treatment, that is, immersed in a TiCl ₄ solution for 10 hours, washed with water, and baked at 450 ° C. for 30 minutes, resulting in improved electronic conductivity and conversion. Increases efficiency.

  In addition, an ultrathin n-type oxide semiconductor dense layer may be inserted between the porous oxide semiconductor layer 7 and the transparent conductive layer 5, and the reverse current can be suppressed, so that the conversion efficiency is increased.

Further, instead of the n-type porous oxide semiconductor layer 7, an inorganic p-type porous oxide semiconductor layer 7 may be used. In that case, CoO, NiO, FeO, Bi ₂ O ₃ , MoO ₂ , MoS ₂ , Cr ₂ O ₃ , SrCu ₂ O ₂ , CaO—Al ₂ O _{3 and the} like are preferable. As the p-type porous compound semiconductor of inorganic, _CuI containing monovalent _{copper, CuInSe 2, Cu 2 O,} CuSCN, CuS, CuInS 2, CuAlO, CuAlO 2, CuAlSe 2, CuGaO 2, CuGaS 2, CuGaSe ₂ or the like, or GaP, GaAs, Si, Ge, SiC, or the like is preferable.

  In addition, when an extremely thin dense oxide semiconductor layer is provided between the porous oxide semiconductor layer 7 and the transparent conductive layer 5, a reverse current can be suppressed and conversion efficiency is increased. An extremely thin dense oxide semiconductor film can be formed by a sputtering method, a vacuum evaporation method, a sol-gel method, a spray pyrolysis method, or the like.

<Transparent conductive layer>
As the transparent conductive layer 5, a tin-doped indium oxide film (ITO film), an impurity-doped indium oxide film (In ₂ O ₃ film), an impurity-doped oxidation film formed by sputtering or spray pyrolysis, which are low-temperature growth methods. A tin film (SnO ₂ ) or the like is good, and these may be laminated and used. In addition, an impurity-doped (Ga, Al, etc.) zinc oxide film (ZnO film) formed by a solution growth method is preferable. Alternatively, a fluorine-doped tin dioxide film (SnO ₂ : F film) formed by a thermal CVD method may be used. Other film forming methods of these films include a vacuum deposition method, an ion plating method, a dip coating method, and a sol-gel method. If surface irregularities in the order of the wavelength of incident light are formed by crystallization of these growth films, etc., there is still a light confinement effect. Further, as the transparent conductive layer 5 made of another material, a thin metal film such as Au, Pd, or Al formed by a vacuum deposition method or a sputtering method may be used.

<Collecting electrode>
As the collector electrode 3, a conductive paste made of conductive particles such as silver, aluminum, nickel, copper, tin, and carbon, an epoxy resin that is an organic matrix, and a curing agent can be used. Among these, Ag paste and Al paste are particularly good and can be used for both low temperature baking paste and high temperature baking paste.

  Moreover, an electric wire may be used for the collector electrode, an electric wire may be provided in the collector electrode, and the collector electrode may be formed of an aggregate of electric wires. It is preferable to use Ag paste or solder for bonding the electric wires.

<Transparent resin layer>
The transparent resin layer 4 preferably has a moisture absorption preventing function and sufficient adhesive strength, such as ethylene vinyl acetate copolymer resin (EVA), polyvinyl butyral (PVB), ethylene-ethyl acrylate copolymer (EEA). , Fluorine resin, epoxy resin, acrylic resin, saturated polyester resin, amino resin, phenol resin, polyamideimide resin, UV curable resin, silicone resin, urethane resin, silicone polyester resin, high weather resistance polyester resin, polyvinyl chloride resin, etc. Good.

  This transparent resin layer 4 is responsible for adhesion between the translucent substrate 2 and the laminate (the porous oxide semiconductor layer 7 and the transparent conductive layer 5), so that the electrolyte 9 together with the transparent conductive layer 5 does not leak outside. Or provided to protect the photoelectric conversion function from the external environment.

  The thickness of the transparent resin layer 4 is 0.1 μm to 6 mm, preferably 1 μm to 2 mm. In addition, anti-glare, heat-shielding, heat resistance, low contamination, antibacterial, anti-fungal, design, high workability, wear resistance, snow-sliding properties due to the treatment of various additives mixed into the resin. By imparting anti-static properties, far-infrared radiation properties, acid resistance, corrosion resistance, environmental compatibility, and the like to the transparent resin layer, reliability and merchantability can be further improved.

  In addition, by applying the transparent resin layer 4 so as to have a thickness having sufficient mechanical strength, it can serve as the translucent substrate 2 having a supporting function. At this time, the transparent resin layer 4 is also supported by the counter electrode side substrate 11. Since the function exists, the individual translucent substrate 2 is unnecessary, and only one substrate is required. Further, in order to integrate a plurality of stacked bodies, the electrical connection is covered and sealed with the transparent resin layer 4 and the sealing member 10 to obtain the highly reliable photoelectric conversion device 1.

<Translucent substrate>
As a material for the translucent substrate 2, a resin sheet made of PET (polyethylene terephthalate), PEN (polyethylene naphthalate), adhesive fluororesin, polycarbonate, polyester, polyethylene, polypropylene, silicon, polyimide, etc. is lightweight and can be bent. Yes, depending on the application, the product value is high.

  Further, as a material having excellent weather resistance and high reliability, various kinds of glass such as white plate glass, soda glass, borosilicate glass, inorganic substrates such as ceramics, and organic-inorganic hybrid substrates are preferable.

  Further, when an antireflection film is formed on the light incident side surface of the translucent substrate 2, the amount of incident light may be increased. Further, the surface of the translucent substrate 2 may be flat, but the surface having irregularities in the order of the wavelength of incident light may have an antiglare property and a light confinement effect.

<Dye>
Examples of the sensitizing dye 6 include, for example, ruthenium-tris, ruthenium-bis, osmium-tris, osmium-bis type transition metal complexes, polynuclear complexes, ruthenium-cis-diaqua-bipyridyl complexes, phthalocyanines, porphyrins, many Xanthene dyes such as ring aromatic compounds and rhodamine B are preferred.

  In order to adsorb the dye 6 to the porous oxide semiconductor layer 7, the dye 6 has at least one carboxyl group, sulfonyl group, hydroxamic acid group, alkoxy group, aryl group, phosphoryl group as a substituent. It is valid. Here, the substituent is not particularly limited as long as it can strongly chemisorb the dye 6 itself to the porous oxide semiconductor layer 7 and can easily transfer charges from the excited dye 6 to the porous oxide semiconductor layer 7. Good.

As a method for adsorbing the dye 6 to the porous oxide semiconductor layer 7, the above method can be adopted. Specifically, as shown in FIGS. 2 and 4, after removing the support, only the porous oxide semiconductor layer 7 exposed on the translucent substrate 2 and the transparent resin layer 4 is coated with the dye 6. The method of immersing in the melt | dissolved solution is mentioned. Examples of the solvent used for dissolving the dye 6 include a mixture of one or more alcohols such as ethanol, ketones such as acetone, ethers such as diethyl ether, nitrogen compounds such as acetonitrile, and the like. The concentration of the dye 6 in the solution is preferably about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol / l (liter: 1000 cm ³ ).

  When immersing the porous oxide semiconductor layer 7 exposed on the translucent substrate 2 or the thick transparent resin layer 4 in a solution in which the pigment 6 is dissolved, the temperature conditions of the solution and the atmosphere are not particularly limited. For example, the conditions of atmospheric pressure and room temperature can be mentioned, and the immersion time can be appropriately adjusted depending on the type of the dye 6, the solution, the concentration of the solution, and the like. Thereby, the dye 6 can be adsorbed to the porous oxide semiconductor layer 7.

<Counter electrode side substrate and catalyst conductive layer>
As the counter electrode side substrate 11, a substrate in which a catalyst conductive layer 12 is formed on an insulating substrate is preferable, and the catalyst conductive layer 12 is preferably a laminate of a conductive layer 12 x and a catalyst layer 12 y. Further, the counter electrode side substrate 11 may be a conductive substrate. In this case, the conductive layer 12a is unnecessary, and only the catalyst layer 12y is required.

  When a plurality of laminated structures are integrated on one counter electrode side substrate 11, it is preferable that the catalyst conductive layer 12 be formed on the insulating substrate. That is, it is convenient because each laminated structure can be electrically insulated and freely integrated.

  Further, the counter electrode side substrate 11 may be either a translucent substrate or a non-translucent substrate. When the counter electrode side substrate 11 is a translucent substrate, it is possible to increase the conversion efficiency by making light incident from both sides. Further, a see-through solar cell or the like can be obtained.

  Further, the surface of the counter electrode side substrate 11 and the surface of the conductive layer 12x may be flat. However, by using a surface having irregularities in the order of the wavelength of incident light, it has a light confinement effect, and conversion efficiency is increased.

  When the counter electrode side substrate 11 is made of a translucent insulating substrate, the material of the translucent insulating substrate is a resin material such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide, polycarbonate, white plate glass, etc. Various kinds of glass such as soda glass and borosilicate glass, inorganic materials such as ceramics, and organic-inorganic hybrid materials are preferable. In the present invention, an insulating substrate such as translucent PET, which is inferior in heat resistance but can be reduced in weight and bent, and can obtain high conversion efficiency, is most preferable.

  When the counter electrode side substrate 11 is made of a non-translucent insulating substrate, the non-translucent insulating substrate includes an inorganic substrate such as colored resin, colored glass, and ceramics, and an organic-inorganic hybrid substrate. Forming irregularities in the order of the wavelength of incident light on the surface of these substrates may further provide a light confinement effect. The thickness of these substrates is 0.005 mm to 5 mm, preferably 0.01 mm to 2 mm in terms of mechanical strength.

As the conductive layer 12x, any of a light-transmitting layer and a non-light-transmitting layer can be used depending on the application. As the translucent conductive layer 12x, a tin-doped indium oxide film (ITO film), an impurity-doped indium oxide film (In ₂ O ₃ film), formed by a sputtering method of a low-temperature film growth method or a low-temperature spray pyrolysis method, An impurity-doped tin oxide film (SnO ₂ film), an impurity-doped zinc oxide film (ZnO film), or the like is preferable. Further, a fluorine-doped tin dioxide film (SnO ₂ : F film) or the like formed by a thermal CVD method may be inexpensive. Moreover, the laminated body which improved the adhesiveness which laminated | stacked Ti layer, ITO layer, and Ti layer one by one may be sufficient. In addition, an impurity-doped zinc oxide film (ZnO film) formed by a simple solution growth method may be used.

  As other film forming methods of these films, there are a vacuum deposition method, an ion plating method, a dip coating method, a sol-gel method, and the like. If the surface irregularities of the wavelength order of incident light are formed on the conductive layer 12x by these film forming methods, there is still a light confinement effect. Further, a thin metal film such as light-transmitting Au, Pd, or Al formed by vacuum vapor deposition or sputtering may be used. The thickness of the translucent conductive layer is 0.001 to 10 μm, preferably 0.05 to 2.0 μm from the viewpoint of high conductivity and high light transmittance.

  The non-translucent conductive layer 12x is preferably made of titanium, stainless steel, aluminum, silver, copper, gold, nickel, or the like. Further, a resin or conductive resin impregnated with fine particles or fine wires of carbon or metal may be used. For the light-reflective non-transparent conductive layer 12x, a thin metallic thin film such as aluminum, silver, copper, nickel, titanium, stainless steel or the like, or for preventing corrosion by the electrolyte 9 What coated the translucent conductive layer 12x on the glossy metal thin film is good.

  The counter electrode substrate 11 and the conductive layer 12x may be composed of only a conductive substrate. As the conductive substrate, a metal sheet may be used alone, such as titanium, stainless steel, aluminum, silver, copper, nickel, etc. The thing which consists of is good. Further, it may be made of a resin or conductive resin impregnated with fine particles or fine wires of carbon or metal. The thickness of this conductive substrate is 0.01 mm to 5 mm, preferably 0.5 mm to 3 mm.

As the counter electrode side substrate 11 which is a light-reflecting support, a glossy metal thin plate such as aluminum, silver, copper, nickel, titanium, stainless steel or the like is used alone, or transparent to prevent corrosion by the electrolyte 9. A photoconductive film (ITO film, SnO ₂ : F film, ZnO: Al film, etc.) coated on a glossy metal plate is preferable. The thickness of the translucent conductive film is 0.001 μm to 10 μm, preferably 0.05 μm to 2 μm.

  Further, on these supports, a Ti layer, an Al layer, a Ti layer are sequentially laminated, a laminated body with improved adhesion, a Ti layer, an Ag layer, a Ti layer are laminated in order, and a laminated body with enhanced adhesion, etc. It is preferable to form a light reflecting layer, and to cover these laminates with a light-transmitting conductive film in order to prevent corrosion by the electrolyte 9.

  These light-transmitting conductive layers 12a and light reflecting layers can be formed by vacuum deposition, ion plating, sputtering, electrolytic deposition, or the like.

<Catalyst layer>
As the catalyst layer 12y, an ultrathin film of platinum, carbon or the like is preferable. In addition, an electrodeposited ultrathin film such as gold (Au), palladium (Pd), and aluminum (Al) can be used. Further, by making the surface of the catalyst layer 12y uneven or making the catalyst layer 12y porous, the surface area increases and the conversion efficiency increases.

<Electrolyte>
Examples of the electrolyte 9 include an ion conductive electrolyte such as an electrolyte solution, a gel electrolyte, and a solid electrolyte, and an organic hole transport agent.

  As the electrolyte solution, a quaternary ammonium salt, a Li salt, or the like is used. As the composition of the electrolyte solution, for example, a solution prepared by mixing tetrapropylammonium iodide, lithium iodide, iodine or the like with ethylene carbonate, acetonitrile, methoxypropionitrile, or the like can be used.

  Gel electrolytes are roughly classified into chemical gels and physical gels. A chemical gel is a gel formed by a chemical bond by a cross-linking reaction or the like, and a physical gel is gelled near room temperature by a physical interaction. The gel electrolyte is a gel obtained by mixing a host polymer such as polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polyvinyl alcohol, polyacrylic acid, or polyacrylamide into acetonitrile, ethylene carbonate, propylene carbonate, or a mixture thereof. An electrolyte is preferred. When a gel electrolyte or solid electrolyte is used, a low-viscosity precursor is contained in the porous oxide semiconductor layer, and a two-dimensional or three-dimensional crosslinking reaction is caused by means such as heating, ultraviolet irradiation, or electron beam irradiation. Can be gelled or solidified.

  As the ion conductive solid electrolyte, a solid electrolyte having a polymer chain such as polyethylene oxide, polyethylene oxide or polyethylene having a salt such as sulfonimidazolium salt, tetracyanoquinodimethane salt or dicyanoquinodiimine salt is preferable. As the molten salt of iodide, an iodide such as an imidazolium salt, a quaternary ammonium salt, an isoxazolidinium salt, an isothiazolidinium salt, a pyrazolidium salt, a pyrrolidinium salt, or a pyridinium salt can be used.

  Examples of the molten salt of iodide include 1,1-dimethylimidazolium iodide, 1, methyl-3-ethylimidazolium iodide, 1-methyl-3-pentylimidazolium iodide, 1-methyl- 3-isopentylimidazolium iodide, 1-methyl-3-hexylimidazolium iodide, 1-methyl-3-ethylimidazolium iodide, 1,2-dimethyl-3-propylimidazole iodide, 1-ethyl- Examples thereof include 3-isopropylimidazolium iodide and pyrrolidinium iodide.

  A spacer may be provided in the electrolyte 9. As the spacer, an organic substance such as various polymers that are inert to the electrolyte, an inorganic substance such as glass or ceramic, etc., is made into particles and dispersed and mixed in the electrolyte 9, or particles or fibers. Is preferably used as a porous body, and the gap can be controlled over a wide area, and the condition is good.

<Sealing member>
The sealing member 10 is provided to prevent the electrolyte 9 from leaking to the outside, to reinforce the mechanical strength for maintaining the thickness of the electrolyte 9, and to protect the photoelectric conversion function from the external environment.

  The material of the sealing member 10 is preferably a material having a moisture absorption preventing function and sufficient adhesive strength, such as ethylene vinyl acetate copolymer resin (EVA), polyvinyl butyral (PVB), ethylene-ethyl acrylate copolymer ( EEA), fluorine resin, epoxy resin, acrylic resin, saturated polyester resin, amino resin, phenol resin, polyamideimide resin, UV curable resin, silicone resin, fluorine resin, urethane resin and the like are preferable.

  Moreover, the photoelectric conversion apparatus 1 of this invention is not limited to a solar cell as the use, It can apply if it has a photoelectric conversion function, and can also apply it to various light receiving elements, an optical sensor, etc.

  Moreover, it can be set as the photovoltaic power generation apparatus which used the said photoelectric conversion apparatus 1 as an electric power generation means, and supplied the electric power generated from this electric power generation means to load. In other words, when one or a plurality of the photoelectric conversion devices 1 are used, a series, parallel or series-parallel connection is used as a power generation means, and the generated power is directly supplied from this power generation means to the DC load. May be. In addition, after the photovoltaic power generation means converts the generated power into appropriate AC power via power conversion means such as an inverter, the generated power can be supplied to an AC load such as a commercial power system or various electric devices. It is good also as a possible electric power generating apparatus. Furthermore, it is also possible to use such a power generation device as a photovoltaic power generation device such as a solar power generation system of various aspects by installing it in a building with good sunlight, and thereby high conversion efficiency and durability. A photovoltaic device can be provided.

  Further, the photovoltaic power generation apparatus of the present invention uses the photoelectric conversion apparatus 1 of the present invention as a power generation means and supplies the generated power of the power generation means to a load. It has the effects of increasing the reliability, increasing the application, expanding the use, and facilitating the manufacturing and reducing the cost.

  A first embodiment embodying the present invention will be described below.

First, an aluminum foil having a thickness of 20 μm and a 5 cm square was used as a flexible support. This aluminum foil was subjected to a heat treatment to make the surface hydrophilic. Next, a porous oxide semiconductor layer made of titanium dioxide was formed on the support. The porous oxide semiconductor layer made of titanium dioxide was formed as follows. First, acetylacetone was added to TiO ₂ anatase powder, and then kneaded with deionized water to prepare a titanium oxide paste stabilized with a surfactant. The prepared paste was applied onto the support at a constant speed by a doctor blade method, and baked at 450 ° C. for 30 minutes in the air.

An ITO film as a transparent conductive layer is formed on the porous oxide semiconductor layer by using a sputtering apparatus and an atmosphere gas composed of a mixed gas of an ITO target, Ar gas, and O ₂ gas (10 vol%). It was formed with a thickness of 3 μm. Further, an Ag paste was applied on the ITO film and heated to form a linear pattern serving as a collector electrode.

  Next, a PET film was used as a translucent substrate, and a transparent resin layer made of EVA (ethylene vinyl acetate copolymer resin) was formed on one main surface of the PET film. This transparent resin layer is a process comprising sandwiching an EVA sheet between an ITO film and a translucent substrate, melting the EVA sheet by heating, pressure bonding, thermosetting, primary cooling, opening to atmospheric pressure, and secondary cooling. It was produced by.

  Next, the aluminum foil as a flexible support was slowly removed by a peeling method. Next, the resulting porous oxide semiconductor layer was prepared by dissolving a dye (Solaronics SA “N719”) in a solvent acetonitrile and t-butanol (1: 1 by volume) (1: 1 by volume). The dye was supported on the porous oxide semiconductor layer by immersing in 0.3 mmol / l) for 12 hours. Thereafter, the porous oxide semiconductor layer was washed with ethanol and dried to produce a light working electrode side substrate comprising a translucent substrate, a transparent resin layer, a collector electrode, a transparent conductive layer, and a porous oxide semiconductor layer.

  Next, a glass substrate with a transparent conductive layer made of fluorine-doped tin oxide was used for the counter electrode side substrate. On this transparent conductive layer, a Pt layer as a catalyst layer was formed to a thickness of 50 nm by sputtering, and this was used as a counter electrode side substrate.

These optical working electrode side substrate and counter electrode side substrate are arranged so that the porous oxide semiconductor layer and the catalyst layer face each other, and are formed into a frame shape olefin resin (Mitsui / DuPont Polychemical Co., Ltd.) Both substrates were pressed and heated to be sealed with a sealing member composed of a trade name “HIMILAN” between them. And electrolyte was inject | poured through the through-hole of the counter electrode side board | substrate opened beforehand. In this example, the electrolyte was prepared using iodine (I ₂ ), lithium iodide (LiI), and acetonitrile solution, which are liquid electrolytes.

When the photoelectric conversion characteristics of the photoelectric conversion device thus obtained were evaluated, the conversion efficiency was 4.1% at AM 1.5 and 100 mW / cm ² .

  As described above, in this example, the photoelectric conversion device 1 of the present invention could be easily produced and high conversion efficiency could be realized.

  A second embodiment of the present invention will be described below.

As shown in Table 1, a photoelectric conversion device was manufactured by the same manufacturing method as in Example 1 using 10 types of aluminum foil in the range of 6 μm to 400 μm (0.4 mm) as shown in Table 1. In addition, five photoelectric conversion apparatuses were produced and evaluated for one type of aluminum foil. And the result shown in Table 1 was obtained with respect to 4 evaluation items.

  In Table 1, the tensile strength indicates the peeling strength of the support when the support made of aluminum foil is peeled off from the laminate made of the porous oxide semiconductor layer and the transparent conductive layer, and x is the laminate of the support. When the support is broken in the middle of two or more photoelectric conversion devices when peeled from the body, Δ is the support broken in the middle of one of the photoelectric conversion devices, ○ is the support for all of the photoelectric conversion devices Shows the cases where no breaks.

  Flexibility refers to moderate flexibility (flexibility) of a support made of an aluminum foil that can prevent cracks and the like from being generated in the laminate, and x indicates that the photoelectric conversion device is being manufactured. When a crack occurs in the laminate for two or more, Δ indicates that a crack occurs for one during the manufacture of the photoelectric conversion device, ○ indicates that there is no crack in the laminate during the manufacture of the photoelectric conversion device. The case where it did not occur is shown respectively.

  Sand blasting refers to the formation of irregularities on the surface of a support made of aluminum foil by sandblasting, and when removing the support from the laminate, the support is transferred to the surface of the porous oxide semiconductor layer. Indicates whether or not it can withstand the pressure of sandblasting, x indicates that damage has occurred on two or more of the supports during the formation of irregularities, and Δ indicates that damage has occurred on one of the supports during the formation of irregularities. In this case, ◯ indicates the case where no damage occurred during the formation of the unevenness.

The warpage after firing of the porous oxide semiconductor layer (TiO ₂ layer) indicates whether or not warpage (warpage of about 5 mm at 1 cm square) occurred after firing of the porous oxide semiconductor layer, and × indicates support When warping occurs in the porous oxide semiconductor layer for two or more photoelectric conversion devices when the porous oxide semiconductor layer is baked and formed on the body, Δ indicates the porous oxide for one photoelectric conversion device. In the case where warpage occurs in the semiconductor layer, ◯ indicates the case where warpage does not occur in the porous oxide semiconductor layer for all of the photoelectric conversion devices.

From the results of Table 1, when the thickness of the support made of aluminum foil is less than 10 μm, the tensile strength and the warp after firing of the TiO ₂ layer are very bad. Conversely, when the thickness of the support exceeds 300 μm, It has been found that the flexibility of the support is very poor, and therefore the thickness of the support is preferably 10 μm to 300 μm (0.3 mm).

It is sectional drawing which shows an example of embodiment about the photoelectric conversion apparatus obtained by the manufacturing method of this invention. It is sectional drawing of the photoelectric conversion apparatus which shows an example of embodiment about 1 process of the manufacturing method of this invention. It is sectional drawing which shows the other example of embodiment about the photoelectric conversion apparatus obtained by the manufacturing method of this invention. It is sectional drawing of the photoelectric conversion apparatus which shows the other example of embodiment about 1 process of the manufacturing method of this invention. It is sectional drawing which shows an example of embodiment about the photoelectric conversion apparatus obtained by the manufacturing method of this invention. It is sectional drawing which shows the other example of embodiment about the photoelectric conversion apparatus obtained by the manufacturing method of this invention.

Explanation of symbols

1: Photoelectric conversion device 2: Translucent substrate 3: Collector electrode 4: Transparent resin layer 5: Transparent conductive layer 6: Dye 7: Porous oxide semiconductor layer 9: Electrolyte 10: Sealing member 11: Counter electrode side substrate 12 : Catalyst conductive layer (counter electrode layer)
13: Support

Claims (6)

A porous oxide semiconductor layer and a transparent conductive layer are sequentially laminated on the upper surface of the flexible support to form a laminate, and then the transparent conductive layer of the laminate is formed as a transparent resin layer. The substrate is then bonded to the light-transmitting substrate, and then the support is removed from the stacked body. Next, the porous oxide semiconductor layer is loaded with a dye to light the stacked body and the light-transmitting substrate. The working electrode side substrate is formed, and then the light working electrode side substrate and the counter electrode side substrate having a counter electrode layer on one main surface are arranged so that the porous oxide semiconductor layer and the counter electrode layer face each other. The outer periphery of the light working electrode side substrate and the counter electrode side substrate is sealed with a sealing member, and the light working electrode side substrate, the gap between the porous oxide semiconductor layer and the counter electrode layer, An electrolyte is injected through a through-hole formed in either the counter electrode side substrate or the sealing member. Process for producing a photovoltaic device comprising and. The method for producing a photoelectric conversion device according to claim 1, wherein the support is peeled off from the laminate when the support is removed from the laminate. The method for manufacturing a photoelectric conversion device according to claim 1, wherein when removing the support from the laminate, the support is dissolved and removed by etching. When adhering the transparent conductive layer of the laminate to a translucent substrate through a transparent resin layer, a collector electrode is formed on the transparent conductive layer and at a portion without the collector electrode on the transparent conductive layer. The method for manufacturing a photoelectric conversion device according to claim 1, wherein the transparent resin layer is formed. A number of irregularities are formed in advance on the upper surface of the support, and the irregularities are transferred to the surface of the porous oxide semiconductor layer when the support is removed from the stacked body. The manufacturing method of the photoelectric conversion apparatus in any one of 1-4. The porous oxide semiconductor layer is made of a sintered body of oxide semiconductor fine particles, and the particle diameter of the oxide semiconductor fine particles gradually decreases from the support side toward the thickness direction of the porous oxide semiconductor layer. The method of manufacturing a photoelectric conversion device according to claim 1, wherein the photoelectric conversion device is formed.

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