JP2014013716A - Dye-sensitized solar cell and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell having excellent generation efficiency and designability.SOLUTION: A dye-sensitized solar cell 1 comprises: a transparent conductive substrate 10; a partition wall part 30 composed of a collection wire 31 arranged on the transparent conductive substrate 10 and a protective layer 32 covering the collection wire 31 and constituting a contour part of a design pattern drawn on the transparent conductive substrate 10; porous semiconductor layers 20 arranged between partition walls of the partition wall part 30; a first sensitizing dye 50 absorbed into at least one porous semiconductor layer 20 formed between the partition walls among the porous semiconductor layers 20 formed between the partition walls; a second sensitizing dye 51 absorbed into a porous semiconductor layer 20 other than the porous semiconductor layer 20 into which the first sensitizing dye 50 was absorbed; and an electrode extraction unit 40 formed on at least one side on the transparent conductive substrate 10 and connected to the collection wire 31.

Description

  The present invention relates to a dye-sensitized solar cell, and more particularly to a dye-sensitized solar cell excellent in design and a manufacturing method thereof.

  Against the backdrop of environmental issues and resource issues, solar cells as clean energy are attracting attention. However, conventional silicon-based solar cells still have problems such as high manufacturing costs and insufficient raw material supply, and have not yet been widely spread. In addition, although compound solar cells such as CIS have excellent characteristics such as extremely high photoelectric conversion efficiency, problems such as cost and environmental load are still an obstacle to widespread use.

  On the other hand, dye-sensitized solar cells are attracting attention as solar cells that are inexpensive and can obtain high photoelectric conversion efficiency. As a general structure of this dye-sensitized solar cell, a porous film using oxide semiconductor nanoparticles such as titanium dioxide is formed on a transparent conductive substrate, and the sensitizing dye is supported thereon. A semiconductor electrode and a counter electrode such as platinum-sputtered conductive glass, and an organic electrolyte containing an oxidizing / reducing species such as iodine / iodide ions between both electrodes as a charge transport layer. it can.

  In addition, about the said dye-sensitized solar cell, what expressed a character, a symbol, a figure, a picture, etc. colorfully using several sensitizing dyes is known (for example, patent document 1, 2). In Patent Document 1, in order to create a dye-sensitized solar cell rich in color, after 1) forming a porous semiconductor layer on a transparent conductive film, 2) forming the porous semiconductor layer into a predetermined pattern 3) A method is disclosed in which partition walls are formed in the removed portion and two or more kinds of sensitizing dyes are adsorbed on the porous semiconductor layer. However, the method of Patent Document 1 has a problem that the manufacturing process is multistage. In addition, when used with a solar cell from the viewpoint of power generation efficiency, a separate current collector must be provided for the solar cell. In such a case, the design formed on the transparent conductive substrate is impaired by the current collector. there were.

  Patent Document 2 discloses a method of forming a bank structure on a transparent conductive substrate in order to produce the dye-sensitized solar cell. However, since the bank structure is created by a photolithographic method, the bank structure is burned during the process of sintering the porous semiconductor layer, as well as the problem that the manufacturing process reaches other stages as in the method of Patent Document 1. There was a problem of flying. Further, since the bank structure does not contribute to power generation, the dye-sensitized solar cell having the bank structure has a problem that the power generation area is reduced. Furthermore, when using with a solar cell, like the case of patent document 1, you had to provide a collector wire in a solar cell separately, and there also existed a problem that the design formed on the transparent conductive substrate was impaired. .

JP 2002-75472 A JP2007-149675

  Accordingly, an object of the present invention is to provide a dye-sensitized solar cell excellent in power generation efficiency and designability, and a production method capable of easily producing a dye-sensitized solar cell.

  In order to achieve the above object, the present invention is configured as follows.

  Below, it demonstrates in detail based on embodiment concerning this invention.

  According to a first aspect of the present invention, there is provided a method for producing a dye-sensitized solar cell in which a plurality of dyes are dyed on a porous semiconductor layer disposed on a transparent conductive substrate, the method comprising: A first step of forming a plurality of the porous semiconductor layers by a printing method at intervals, a second step of forming a current collector at a location spaced from the space, and covering the current collector with a protective layer, Forming a partition wall higher than the height of the porous semiconductor layer, and isolating the plurality of formed porous semiconductor layers, respectively, and adjacent porous semiconductor layers among the isolated porous semiconductor layers; There is provided a method for producing a dye-sensitized solar cell comprising at least a third step of impregnating with a different dye-sensitizer.

  According to the second aspect of the present invention, a dye-sensitized solar cell in which a plurality of dyes are dyed separately on a porous semiconductor layer disposed on a transparent conductive substrate, and a design pattern is drawn on the transparent conductive substrate. An outline portion of a design pattern drawn on the transparent conductive substrate, comprising the transparent conductive substrate, a current collector disposed on the transparent conductive substrate, and a protective layer covering the current collector. Of the partition walls, the porous semiconductor layer disposed between the partition walls, and the porous semiconductor layer formed between the partition walls. A first sensitizing dye adsorbed on the porous semiconductor layer; a second sensitizing dye adsorbed on a porous semiconductor layer other than the porous semiconductor layer on which the first sensitizing dye is adsorbed; and the transparent conductive material. Formed on at least one side of the conductive substrate, An electrode extraction part for connecting the electric wire and extracting the electrons emitted from the first sensitizing dye and the second sensitizing dye to the outside, and the porous semiconductor layer on the porous semiconductor layer so as to face the transparent conductive substrate A counter electrode formed apart from the porous semiconductor layer, a charge transport layer formed between the porous semiconductor layer and the counter electrode, and the transparent conductive material so that the charge transport layer does not come out of the system. Provided is a dye-sensitized solar cell comprising a sealing substrate and a sealing material for sealing the counter electrode.

  According to the third aspect of the present invention, a dye-sensitized solar cell in which a plurality of dyes are dyed separately on a porous semiconductor layer disposed on a transparent conductive substrate, and a design pattern is drawn on the transparent conductive substrate. An outline portion of a design pattern drawn on the transparent conductive substrate, comprising the transparent conductive substrate, a current collector disposed on the transparent conductive substrate, and a protective layer covering the current collector. Of the partition walls, the porous semiconductor layer disposed between the partition walls, and the porous semiconductor layer formed between the partition walls. A first sensitizing dye adsorbed on the porous semiconductor layer; a second sensitizing dye adsorbed on a porous semiconductor layer other than the porous semiconductor layer on which the first sensitizing dye is adsorbed; and the transparent conductive material. Electrode formed on at least one side of the conductive substrate An auxiliary partition part, and the transparent conductive substrate, which are connected to the output part, the partition part, and the electrode extraction part and guide electrons emitted from the first sensitizing dye and the second sensitizing dye to the electrode extraction part A counter electrode formed on the porous semiconductor layer so as to be separated from the porous semiconductor layer, and a charge transport layer formed between the porous semiconductor layer and the counter electrode, Provided is a dye-sensitized solar cell comprising a sealing material that seals the transparent conductive substrate and the counter electrode so that the charge transport layer does not go out of the system.

  According to the 4th aspect of this invention, the dye-sensitized solar cell provided with the partition protective layer which coat | covers the said partition part and connects a partition part and the said counter electrode is provided.

  According to the 5th aspect of this invention, the cross-sectional shape of the said partition part provides a square-shaped dye-sensitized solar cell.

  ADVANTAGE OF THE INVENTION According to this invention, the dye-sensitized solar cell excellent in electric power generation efficiency and the designability, and a dye-sensitized solar cell can be produced simply.

It is a top view of the dye-sensitized solar cell of this invention. It is A-A 'sectional drawing of FIG. It is B-B 'sectional drawing of FIG. It is sectional drawing of the dye-sensitized solar cell of this invention. It is a top view of the dye-sensitized solar cell of this invention. It is sectional drawing which concerns on the manufacturing process of the dye-sensitized solar cell of this invention.

  Hereinafter, embodiments according to the present invention will be described in more detail with reference to the drawings. It should be noted that the dimensions, materials, shapes, relative positions, etc. of the parts and portions described in the embodiments of the present invention are not intended to limit the scope of the present invention only to those unless otherwise specified. This is just an illustrative example.

(Embodiment 1)
FIG. 1 is a plan view of the dye-sensitized solar cell according to Embodiment 1. FIG. FIG. 2 is a diagram of the dye-sensitized solar cell of FIG. 1 cut along the AA ′ cross section. FIG. 3 is a view of the dye-sensitized solar cell of FIG. 1 cut along the BB ′ section.

<Dye-sensitized solar cell>
As shown in FIGS. 1 and 2, the dye-sensitized solar cell 1 includes a partition wall 30 on a transparent conductive substrate 10. The partition wall 30 partitions the porous semiconductor layer 20 in a pattern. In FIG. 1, the porous semiconductor layer 20 is partitioned from a first region 100 to a fifth region 104 by a partition wall 30. As shown in FIG. 2, the first sensitizing dye 50 is adsorbed to the porous semiconductor layer 20 in the first region 100, and the first sensitizing dye 50 and the porous semiconductor layer 20 in other regions are combined. The second sensitizing dye 51 having a different color is adsorbed. As a result, the pattern shape of the first region (“N” shape) appears on the surface, and the dye-sensitized solar cell 1 with high design properties is obtained.

  Moreover, as shown in FIGS. 1 and 3, the partition wall portion 30 includes a current collecting wire 31 and a protective layer 32, and the current collecting wire 31 is an electrode lead-out portion formed at the peripheral edge of the transparent conductive substrate 10. 40. With this configuration, the dye-sensitized solar cell 1 can efficiently extract electrons from the sensitizing dye formed in the first region 100 to the fifth region 104. Therefore, it is not necessary to separately provide the collector line 31 in the dye-sensitized solar cell 1. As a result, the dye-sensitized solar cell 1 of the first embodiment is a dye-sensitized solar cell 1 that has both high designability and high power generation efficiency.

  That is, in Embodiment 1, the partition wall portion has a function of partitioning the porous semiconductor layer into a pattern and a function of taking out electrons from the porous semiconductor layer partitioned as described above. As a result, since the dye-sensitized solar cell of Embodiment 1 does not need to provide a current collector in addition to the partition wall portion, the dye-sensitized solar cell has both high designability and high power generation efficiency. Yes.

<Transparent conductive substrate>
As shown in FIG. 2, the transparent conductive substrate 10 has a configuration in which a transparent conductive film 12 is formed on a substrate 11.

  The substrate is made of a transparent glass plate or plastic plate. The thickness of the substrate is about 0.1 to 5 mm.

  The transparent conductive film is made of an organic material or an inorganic material. As the organic material, a conductive polymer material can be used. Among the conductive polymer materials, it is preferable to use a water-dispersed polythiophene derivative (PEDOT: PSS) prepared using polystyrene sulfonic acid (PSS) and 3,4-ethylenedioxythiophene (EDOT). The water-dispersed polythiophene derivative (PEDOT: PSS) has high transparency and high conductivity. For this reason, by using a water-dispersed polythiophene derivative (PEDOT: PSS) as a transparent conductive film, it is possible to efficiently incorporate light from the outside into the dye-sensitized solar cell and to generate electrons generated from the dye sensitization. It can be efficiently transported to the electrode extraction part. As a result, a dye-sensitized solar cell with high energy efficiency is obtained. In addition to the above, since the water-dispersed polythiophene derivative (PEDOT: PSS) is water-soluble, it has an advantage that a transparent conductive film can be easily formed on the translucent substrate.

  As the inorganic material, an inorganic oxide such as fluorine-doped tin oxide, indium tin oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, or niobium-doped titanium oxide can be used. The thickness of the transparent conductive film is preferably about 0.3 to 2 μm. When the thickness is less than 0.3 μm, the sheet resistance increases, and the series resistance of the dye-sensitized solar cell increases, so that the fill factor characteristic tends to be deteriorated. In this case, the transparent conductive film is formed by a CVD method, a sputtering method, a spray method, or the like.

  Furthermore, the transparent conductive film may be composed of a binder resin such as acrylic, polyester, polyurethane, and polyvinyl chloride, and conductive nanofibers. In this case, the transparent conductive film can be provided by a method such as painting or inkjet, and the thickness of the transparent conductive film can be appropriately set within a range of several tens of nm to several hundreds of nm. When the thickness is less than several tens of nm, the strength as a layer is insufficient, and when the thickness is greater than several hundred nm, the flexibility as the layer is lost and processing becomes difficult. In addition to carbon nanofibers, conductive nanofibers can be made continuously by applying an applied voltage or current from the tip of the probe to the surface of a precursor carrying metal ions such as gold, silver, platinum, copper, and palladium. Gold particles are added to metal nanowires produced by pulling them out, or nanofibers formed by self-organizing graphite nanofibers, peptides or their derivatives produced by introducing a source gas onto a light-transmitting substrate and using the CVD method And peptide nanofibers.

<Porous semiconductor layer>
The porous semiconductor layer 20 adsorbs a sensitizing dye and holds the sensitizing dye on the transparent conductive substrate 10.

  Titanium oxide (TiO2) is optimal as the porous semiconductor layer, and other materials include titanium (Ti), zinc (Zn), tin (Sn), niobium (Nb), indium (In), yttrium ( Y), lanthanum (La), zirconium (Zr), tantalum (Ta), hafnium (Hf), strontium (Sr), barium (Ba), calcium (Ca), vanadium (V), tungsten (W), and other metals A metal oxide semiconductor of at least one kind of element is preferable, and is composed of, for example, at least one of TiO2, WO3, ZnO, Nb2O5, Ta2O5, or SrTiO3. Moreover, you may contain 1 or more types of nonmetallic elements, such as nitrogen (N), carbon (C), fluorine (F), sulfur (S), chlorine (Cl), phosphorus (P). Titanium oxide or the like is preferable because it has an electron energy band gap in the range of 2 to 5 eV, which is larger than the energy of visible light.

  The porous semiconductor layer is preferably a porous n-type oxide semiconductor layer made of the above material and having a large number of fine pores inside. Furthermore, the diameter of the holes is preferably 10 to 40 nm. When the diameter is less than 10 nm, the osmotic adsorption of the alternating copolymer is hindered, it is difficult to obtain a sufficient amount of adsorption for the alternating copolymer, and the diffusion resistance increases because the diffusion of the electrolyte is hindered. Therefore, the photoelectric conversion efficiency tends to decrease. If it exceeds 40 nm, the specific surface area of the porous semiconductor layer is reduced, so that the amount of adsorption of the alternating copolymer is reduced, and light is hardly transmitted, and the alternating copolymer cannot absorb light. In addition, since the transfer distance of the charge injected into the porous semiconductor layer becomes long, loss due to charge recombination increases, and further, the diffusion resistance increases because the diffusion distance of the electrolyte also increases. Efficiency tends to decrease.

  The porous semiconductor layer has a surface area that adsorbs a sensitizing dye by being a granular body, or a linear body such as a needle-shaped body, a tubular body, a columnar body, or a collection of these various linear bodies. And the photoelectric conversion efficiency can be increased. The porous semiconductor layer preferably has a porosity of 20 to 80%, and more preferably 40 to 60%. This is because the surface area as the light-working electrode layer can be increased by 1000 times or more by making the porous body more dense, and light absorption, photoelectric conversion, and electron conduction can be performed efficiently. .

  The porosity of the porous semiconductor layer is determined by obtaining an isothermal adsorption curve of the sample by a nitrogen gas adsorption method using a gas adsorption measuring device, and using a BJH (Barrett-Joyner-Halenda) method, a CI (Chemical Ionizati-on) method , DH (Dollimore-Heal) method or the like can be used to determine the pore volume and obtain it from the particle density of the sample.

  The shape of the porous semiconductor layer is preferably that having a large surface area and low electrical resistance, and is preferably composed of fine particles or fine linear bodies, for example. The average particle diameter or average wire diameter is preferably 5 to 500 nm, and more preferably 10 to 200 nm. If the average particle diameter or the average wire diameter is less than 5 nm, the material cannot be miniaturized, and if it exceeds 500 nm, the junction area is reduced, and the photocurrent is significantly reduced.

  By forming the porous semiconductor layer from a fine porous particle, the alternating copolymer is supported in the fine pores, and the surface becomes uneven, thereby providing a light confinement effect, so that the photoelectric conversion efficiency can be further increased.

  Moreover, it is preferable that the thickness of a porous semiconductor layer is 1-15 micrometers. If the thickness is less than 1 μm, the photoelectric conversion effect is remarkably reduced and is not suitable for practical use. If the thickness exceeds 15 μm, the insulation between the porous semiconductor layer and the counter electrode becomes difficult.

  Further, the porous semiconductor layer is preferably composed of a sintered body of oxide semiconductor fine particles, and the average particle diameter of the oxide semiconductor fine particles is preferably gradually increased in the thickness direction from the translucent substrate side. The semiconductor layer is preferably composed of a two-layer laminate in which the average particle diameter of the oxide semiconductor fine particles is different. Specifically, the oxide semiconductor fine particles having a small average particle diameter are used on the transparent conductive film, and the oxide semiconductor fine particles having a large average particle diameter (scattering particles) are used on the formed semiconductor layer. The porous semiconductor layer having a large diameter produces a light confinement effect due to light scattering and light reflection, and can increase the photoelectric conversion efficiency.

  More specifically, as oxide semiconductor fine particles having a small average particle diameter, 100 wt% (wt%) having an average particle diameter of about 20 nm is used, and as the oxide semiconductor fine particles having a large average particle diameter, the average particle diameter is A mixture having a particle size of about 10 nm and a weight average particle size of about 400 nm is used. By changing the weight ratio, the average particle diameter, and the respective film thicknesses, an optimum light confinement effect can be obtained.

<Partition wall>
As shown in FIGS. 1 and 2, the partition wall portion 30 has a configuration in which a current collecting wire 31 is covered with a protective layer 32.

  In addition, the cross-sectional shape of the partition part 30 has preferable square shape. This is because the covering effect of the current collecting wire is increased. Moreover, since the area of the partition wall can be reduced and the area of the porous semiconductor layer can be increased, the power generation effect can be enhanced.

  The current collector is formed in order to electrically connect the porous semiconductor layer and the electrode extraction part, and is composed of conductive particles and glass fine particles. In this case, it is preferable that about 70 to 95% by weight of conductive particles are contained. When the content of the conductive particles is less than 70% by weight, the conductivity is deteriorated, and when it exceeds 95% by weight, it is difficult to form a printed pattern. The average particle size of the conductive particles is preferably 0.5 to 15 μm. If the thickness is less than 0.5 μm, the contribution to the conductivity is small, and if it exceeds 15 μm, it is difficult to obtain a desired pattern accuracy. In addition, a silver paste can also be used as a current collector.

  Examples of the conductive particles include aluminum, chromium, nickel, cobalt, and titanium. Examples of the glass fine particles include low-melting glass.

  The width of the current collecting wire is preferably 20 to 140 μm. If the thickness is less than 20 μm, the resistance value of the current collecting line becomes high, and if it exceeds 140 μm, the power generation efficiency decreases. The thickness of the current collector is preferably 0.5 μm to 10 μm. If the thickness is less than 0.5 μm, the resistance value is high, and if it exceeds 10 μm, it is difficult to form a current collector. Furthermore, the distance to the counter electrode increases and the efficiency becomes poor, and the scattering intensity in the porous semiconductor layer tends to decrease. When it exceeds 140 μm, current loss tends to increase in the electrolyte.

  The protective layer protects the current collector from the electrolyte of the charge transfer layer. The protective layer is made of glass containing Bi2O3, ZnO, B2O3, SiO2, MgO and the like. The width of the protective layer covering the current collector is preferably 100 to 300 μm. If the thickness is less than 100 μm, the current collector tends to be exposed to the electrolyte solution layer due to a defect in pattern accuracy, and if it exceeds 300 μm, the light receiving area becomes small.

<Electrode extraction part>
The electrode extraction part is a member that receives electrons from the current collector and moves the electrons to the counter electrode (cathode side) via the conducting wire. The material, thickness, and formation method of the electrode extraction part are the same as those of the current collector.

<Outlet protection layer>
The extraction part protective layer protects the electrode extraction part from the charge transport layer. Note that. The material, thickness, and formation method of the extraction part protective layer 41 are the same as those of the protective layer.

<First sensitizing dye and second sensitizing dye>
The first sensitizing dye and the second sensitizing dye emit electrons to the porous semiconductor layer and impart various colors to the surface of the dye-sensitized solar cell. Therefore, the first sensitizing dye and the second sensitizing dye are not particularly limited as long as they have a sensitizing action and have different colors.

  As such a first sensitizing dye and a second sensitizing dye, an organic dye or a metal complex dye can be used. As an organic dye, an acridine type, an azo type, an indigo type, a quinone type, a coumarin type can be used. Merocyanine dyes and phenylxanthene dyes, and ruthenium dyes are preferable as metal complex dyes, and ruthenium bipyridine dyes and ruthenium terpyridine dyes which are ruthenium complexes are particularly preferable. For example, visible light (wavelength of about 400 to 800 nm) can hardly be absorbed with only an oxide semiconductor film, but by supporting a ruthenium complex, visible light can be significantly taken in and photoelectrically converted.

<Charge transport layer>
The charge transport layer is a layer that donates electrons supplied from the counter electrode (cathode side) to the sensitizing dye.

  As a material for the charge transport layer, a liquid electrolyte or a gel electrolyte is preferably used. Photoelectric conversion efficiency is improved by using a liquid electrolyte or a gel electrolyte excellent in charge transport characteristics. The charge transport layer is composed of a solid electrolyte such as a polymer electrolyte, a conductive polymer such as polythiophene / polypyrrole or polyphenylene vinylene, or an organic molecular electron transport agent such as a fullerene derivative, a pentacene derivative, a perylene derivative, or a triphenyldiamine derivative. There may be.

  The charge transport layer contains iodine / iodide salt, bromine / bromide salt, cobalt complex, potassium ferrocyanide and the like.

  The thickness of the charge transport layer is preferably 1 to 500 μm. If it exceeds 500 μm, the resistance increases during charge transport, and the efficiency of the dye-sensitized solar cell cannot be increased.

<Counter electrode>
The counter electrode constitutes a cathode electrode and supplies electrons sent from the transparent conductive substrate to the charge transport layer. The counter electrode has a configuration in which a conductive layer and a catalyst layer are formed in this order on a substrate.

  A board | substrate consists of a glass plate, a plastic plate, etc., and thickness is about 0.1-20 mm.

  Examples of the material for the conductive layer include fluorine-doped tin oxide (FTO), tin-doped indium (ITO), aluminum-doped zinc (AZO), gallium-doped zinc (GZO), and niobium-doped titanium oxide (NTO). Among the above, it is preferable to use fluorine-doped tin oxide (FTO). By using fluorine-doped tin oxide (FTO), the conversion efficiency of the dye-sensitized solar cell is improved.

  The thickness of the conductive layer is preferably 0.1 to 10 μm. If it is less than 0.1 μm, high conductivity cannot be obtained. If it exceeds 10 μm, the dye-sensitized solar cell cannot transmit light. The conductive layer is formed on the substrate by a method such as chemical vapor deposition (CVD), spray pyrolysis (SPD), or sputtering.

  Examples of the material for the catalyst layer include platinum, carbon, and polythiophene derivatives. Among the above, it is preferable to use platinum. By using platinum, conversion efficiency and transparency are improved. The thickness of the catalyst layer is preferably 0.1 to 100 nm. If the thickness is less than 0.1 μm, the material constituting the charge transport layer cannot be reduced. If it exceeds 100 μm, the cost is too high. Furthermore, a dye-sensitized solar cell that transmits light cannot be produced. The catalyst layer is formed on the conductive layer by a method such as doctor blade, screen printing, spray coating, or ink jet.

<Encapsulant>
The encapsulant is a member that encapsulates the charge transport layer in the dye-sensitized solar cell. Since the sealing material seals the charge transport layer, the durability and reliability of the photoelectric conversion element against light irradiation and high-temperature heating can be effectively maintained. That is, leakage of the charge transport layer from the dye-sensitized solar cell due to light irradiation and high-temperature heating can be effectively suppressed.

  Examples of the material of the sealing material include resin adhesives such as acrylate-based UV curable resins, polyethylene, polypropylene, epoxy resins, fluororesins or silicone resins, or inorganic adhesives such as glass frit and ceramics.

  The thickness (height) of the sealing material is preferably 0.5 to 500 μm. If the thickness is less than 0.5 μm, the thickness of the porous semiconductor layer becomes 0.5 μm or less, and the dye cannot sufficiently absorb light. When the thickness exceeds 500 μm, the charge transport layer becomes close to 500 μm and the internal resistance increases. The sealing member is formed by a method such as hot pressing or UV curing.

(Embodiment 2)
FIG. 4 is a cross-sectional view of the dye-sensitized solar cell 1 according to the second embodiment. Since the basic configuration is the same as that of the first embodiment, only the differences will be described here. As shown in FIG. 4, in the second embodiment, a partition protection layer 33 is formed on the partition wall 30, and the partition protection layer 33 reaches the counter electrode 70. The partition protective layer 33 partitions the porous semiconductor layer 20 and the charge transport layer 66 formed between the partition walls 30. By configuring in this manner, the current collecting wire 31 is doubly covered with the protective layer 32 and the partition wall protecting layer 51, so that the corrosion of the current collecting wire 31 by the charge transport layer 60 can be prevented more reliably.

<Partition protective layer>
Examples of the material for the partition protective layer include resin adhesives such as polyethylene, polypropylene, epoxy resin, fluororesin or silicone resin, or inorganic adhesives such as glass frit and ceramics.

  The width of the partition protective layer is preferably 300 to 2000 μm. If it is less than 300 μm, the current collecting protective layer cannot be covered. In addition, if it exceeds 2000 μm, the power generation area will be small, and the power generation efficiency will decrease.

(Embodiment 3)
FIG. 5 is a plan view of the dye-sensitized solar cell 1 according to the third embodiment. Since the basic configuration is the same as that of the first embodiment, only the differences will be described here. As shown in FIG. 5, in Embodiment 3, the partition wall 30 is formed independently on the transparent conductive substrate 10. An auxiliary partition wall 90 is connected to the partition wall 30 and the electrode extraction part 40 in order to connect the partition wall 30 and the electrode extraction part 40. By comprising in this way, since the partition part 30 is formed independently from the electrode extraction part 40, it becomes the dye-sensitized solar cell 1 with higher design property.

  The partition auxiliary portion 90 includes a current collecting auxiliary line 91 and a protective auxiliary layer 92. Further, the current collecting auxiliary line 91 is covered with a protective auxiliary layer 92. The materials and sizes of the auxiliary current collecting wire 91 and the auxiliary protective layer 92 are the same as those constituting the current collecting wire 31 and the protective layer 32, respectively.

Next, a method for manufacturing the dye-sensitized solar cell 1 according to Embodiment 1 will be described.
<Method for producing dye-sensitized solar cell>
The method for obtaining the dye-sensitized solar cell 1 includes the following steps.

  As shown in FIG. 6A, a transparent conductive substrate 10 is obtained by forming a transparent conductive film 12 on one surface of the transparent conductive substrate 11.

  The transparent conductive film is preferably made of indium tin oxide or fluorine-doped tin oxide. This is because it is inexpensive and inactive in the high-temperature sintering process.

  Next, as shown in FIG. 6B, the porous semiconductor layer 20 is patterned on the transparent conductive film 12.

  Note that the porous semiconductor layer is formed by printing and sintering a paste in which an oxide semiconductor is dispersed in a polymer and a solvent. For example, when the porous semiconductor layer is made of titanium oxide, it is formed as follows. First, acetic acid is added to a TiO 2 anatase powder, and then kneaded with deionized water and ethanol to prepare a titanium oxide paste stabilized with a solvent and a polymer. The prepared paste is applied on the transparent conductive film at a constant speed by a screen printing method, a doctor blade method, or a bar coating method, and is heated in the atmosphere at 400 to 600 ° C. for 10 to 60 minutes, preferably 20 to 40 minutes. By doing so, a porous semiconductor layer is obtained.

  Next, as shown in FIG. 6C, a partition wall 30 is formed at a location where the porous semiconductor layer 20 is not formed. The partition wall 30 is formed so that the protective layer 32 covers the current collector 31 after the current collector 31 is formed on the transparent conductive substrate 10. With such a configuration, the porous semiconductor layer 20 is baked twice in the previous step and in this step, so that impurities contained in the porous semiconductor layer 20 can be almost removed. As a result, since the purity of the porous semiconductor layer is increased, the dye-sensitized solar cell 1 with high power generation efficiency is obtained.

  The current collector is formed by blending conductive particles and glass fine particles into a paste form on a transparent conductive substrate using a printing method such as screen printing, and then heating and firing to fuse the conductive particles. Complete by putting on. Although it does not specifically limit as conditions for baking, For example, it carries out at the temperature of 500-550 degreeC over 1 to 4 hours.

  The formation of the protective layer is completed by forming a paste made of low-melting glass or the like on the current collector by a printing method or the like, and then drying and sintering. The partition wall made of the current collector and the protective layer is made thicker than the porous semiconductor layer. If the partition wall is thicker than the porous semiconductor layer, each compartment can be easily impregnated with a different sensitizing dye in the process of impregnating the porous semiconductor layer with the next sensitizing dye.

  The sintering of the protective layer made of low-melting glass or the like is desirably performed at a heat treatment temperature that is 20 ° C. or more lower than the strain point of the substrate. If the difference between the heat treatment temperature of the low-melting glass and the strain point of the substrate is less than 20 ° C., the heat treatment temperature becomes difficult to control, and variations in the heat treatment temperature may adversely affect the substrate such as deformation and cracking. In addition, when the difference between the heat treatment temperature of the low-melting glass and the strain point of the base material is excessively large, the usable low-melting glass is reduced and the choice of the material for the protective layer is narrowed.

  Moreover, the heat processing temperature of the protective layer which consists of low melting glass etc. is adjusted to 400 to 550 degreeC, for example, More preferably, it is 430 to 530 degreeC. If the heat treatment temperature of the protective layer exceeds 550 ° C, the substrate may be adversely affected. Further, when the heat treatment temperature of the protective layer is less than 400 ° C., the choice of the material for the protective layer becomes narrow. The protective layer may be made of various resins in addition to the low melting point glass described above. In this case, a heat treatment temperature of about the melting point of the resin to be used + 50 ° C. is preferable, and for example, it may be in the range of 200 ° C. to 350 ° C. In addition, as a protective layer baking apparatus, a well-known appropriate method can be used, for example, a hot air circulation oven or a belt furnace can be used.

  Next, as shown in FIG. 6D, different kinds of sensitizing dyes (for example, the first sensitizing dye 50 and the second dye sensitizing 51) are placed on the porous semiconductor layer 20 using the dispenser 200. Adsorb to each compartment.

  Different types of sensitizing dyes (for example, the first sensitizing dye 50 and the second dye sensitizing 51) are formed by printing different types of sensitizing dyes on each section using an ink jet method and making the sensitizing dye porous. It is completed by adsorbing on the porous semiconductor layer. After adsorption, in order to remove excess sensitizing dye and remaining liquid agent, the whole is rinsed with ethanol and blown dry with nitrogen. In this production method, different types of sensitizing dyes can be applied to different compartments. Therefore, a high-quality photoelectric conversion element having a resolution of 300 dpi or higher can be manufactured.

  In order to efficiently adsorb the sensitizing dye (for example, the first sensitizing dye 50 and the second dye sensitizing 51) to the porous semiconductor layer, the sensitizing dye has at least one carboxyl group or sulfonyl group. It is effective to have a group, a hydroxamic acid group, an alkoxy group, an aryl group, a phosphoryl group or the like as a substituent. This is because the sensitizing dye itself can be strongly chemically adsorbed to the porous semiconductor layer, and these substituents can easily transfer charges from the excited sensitizing dye to the porous semiconductor layer. Examples of the method for adsorbing the dye include a method in which a porous semiconductor layer formed on a substrate is immersed in a solution in which a sensitizing dye is dissolved.

  Solvents for dissolving the sensitizing dye when adsorbing the sensitizing dye to the porous semiconductor layer include alcohols such as ethanol, ketones such as acetone, ethers such as diethyl ether, nitrogen compounds such as acetonitrile, etc. May be one or a mixture of two or more. The concentration of the sensitizing dye in the solution is preferably about 5 × 10 −5 to 2 × 10 −3 mol / l (l (liter): 1000 cm 3).

  When adsorbing the sensitizing dye to the porous semiconductor layer, the temperature conditions of the solution and the atmosphere are not particularly limited, and examples thereof include conditions under atmospheric pressure or in vacuum, room temperature, or substrate heating. The time required for adsorption of the sensitizing dye can be appropriately adjusted depending on the kind of the sensitizing dye and the solution, the concentration of the solution, the circulation amount of the solution of the sensitizing dye, and the like. Thereby, a sensitizing dye can be made to adsorb | suck to a porous semiconductor layer.

  Next, as shown in FIG. 6E, after forming a sealing material 80 on the peripheral edge of the transparent conductive substrate 10, the transparent conductive substrate 10 and the counter electrode 70 are bonded and sealed. The material and the forming method of the sealing material are as described above.

  Finally, as shown in FIG. 6 (f), an electrolyte solution is injected into a gap formed between the transparent conductive substrate 10 and the counter electrode 70 to form a charge transport layer 60, thereby forming a dye-sensitized solar cell. Get one. The material of the charge transport layer is as described above.

  According to the above method, a step of forming a porous semiconductor layer on a transparent conductive substrate, removing the porous semiconductor layer into a predetermined pattern, and then forming a partition wall in the removed portion, A plurality of sensitizing dyes can be dyed separately in the porous semiconductor layer without going through a process of forming a structure. Therefore, it is a manufacturing method that can easily produce a dye-sensitized solar cell rich in color.

1: Dye-sensitized solar cell 10: Transparent conductive substrate 11: Transparent substrate 12: Transparent conductive film 20: Porous semiconductor layer 30: Partition part 31: Current collector 32: Protection layer 33: Partition protection layer 40: Extraction of electrode Part 41: Extraction part protective layer 50: First dye sensitization 51: Second dye sensitization 60: Charge transport layer 70: Counter electrode 80: Sealing material 90: Auxiliary partition 91: Auxiliary collector 92: Auxiliary protective layer 100: First porous semiconductor region 101: Second porous semiconductor region 102: Third porous semiconductor region 103: Fourth porous semiconductor region 200: Dispenser

Claims (5)

A method for producing a dye-sensitized solar cell in which a plurality of dyes are dyed on a porous semiconductor layer disposed on a transparent conductive substrate,
A first step of forming a plurality of porous semiconductor layers by a printing method at intervals on the transparent conductive substrate;
A second step of forming a current collector at the spaced-apart location;
Covering the current collector with a protective layer, forming a partition wall higher than the height of the porous semiconductor layer, and separating each of the plurality of formed porous semiconductor layers;
A third step of impregnating different porous semiconductor layers among the isolated porous semiconductor layers with different dye sensitizers;
A method for producing a dye-sensitized solar cell comprising at least A dye-sensitized solar cell in which a plurality of dyes are dyed separately on a porous semiconductor layer disposed on a transparent conductive substrate, and a design pattern is drawn on the transparent conductive substrate,
The transparent conductive substrate;
A partition wall portion constituting a contour portion of a design pattern drawn on the transparent conductive substrate, comprising a current collector disposed on the transparent conductive substrate and a protective layer covering the current collector;
A porous semiconductor layer disposed between the partition walls of the partition wall;
A first sensitizing dye adsorbed on the porous semiconductor layer formed between at least one of the porous semiconductor layers formed between the partition walls;
A second sensitizing dye adsorbed on a porous semiconductor layer other than the porous semiconductor layer on which the first sensitizing dye is adsorbed;
An electrode extraction portion formed on at least one side of the transparent conductive substrate, connected to the current collector, and for extracting electrons emitted from the first sensitizing dye and the second sensitizing dye to the outside; and the transparent conductive substrate A counter electrode formed on the porous semiconductor layer so as to be spaced apart from the porous semiconductor layer,
A charge transport layer formed between the porous semiconductor layer and the counter electrode;
A dye-sensitized solar cell comprising: a sealing material that seals the transparent conductive substrate and the counter electrode so that the charge transport layer does not go out of the system. A dye-sensitized solar cell in which a plurality of dyes are dyed separately on a porous semiconductor layer disposed on a transparent conductive substrate, and a design pattern is drawn on the transparent conductive substrate,
The transparent conductive substrate;
A partition wall portion constituting a contour portion of a design pattern drawn on the transparent conductive substrate, comprising a current collector disposed on the transparent conductive substrate and a protective layer covering the current collector;
A porous semiconductor layer disposed between the partition walls of the partition wall;
A first sensitizing dye adsorbed on the porous semiconductor layer formed between at least one of the porous semiconductor layers formed between the partition walls;
A second sensitizing dye adsorbed on a porous semiconductor layer other than the porous semiconductor layer on which the first sensitizing dye is adsorbed;
An electrode extraction portion formed on at least one side of the transparent conductive substrate;
When the partition part and the electrode extraction part are connected and the electrons emitted from the first sensitizing dye and the second sensitizing dye are guided to the electrode extraction part, an auxiliary partition part,
A counter electrode formed on the porous semiconductor layer so as to be opposed to the porous semiconductor layer so as to face the transparent conductive substrate;
A charge transport layer formed between the porous semiconductor layer and the counter electrode;
A dye-sensitized solar cell comprising: a sealing material that seals the transparent conductive substrate and the counter electrode so that the charge transport layer does not go out of the system.   The dye-sensitized solar cell according to claim 2, further comprising a partition wall protective layer that covers the partition wall portion and connects the partition wall portion and the counter electrode.   The dye-sensitized solar cell according to claim 2, wherein the partition wall has a quadrangular cross-sectional shape.

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