JP2010192214A - Photoelectric conversion element and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion element of which an absorption wavelength range is wide and conversion efficiency is high, and provide a method of manufacturing the same. <P>SOLUTION: The photoelectric conversion element 1 is formed by laminating a conductive support body, a photoelectric conversion layer 4, an electrolyte layer 5, and a counter electrode 3 sequentially. The photoelectric conversion layer includes semiconductor particles 41, and at least one or more types of sensitizing pixels 43, and silicon-containing fine particles having a light absorption wavelength range different from that of the sensitizing pixel. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photoelectric conversion element and a manufacturing method thereof.

  Current solar cells include silicon solar cells using crystalline silicon and amorphous silicon, compound solar cells using compounds such as GaAs, CuInSe (S) and CdTe, and organic thin film systems using organic thin films. There are solar cells and dye-sensitized solar cells in which a dye is adsorbed as a sensitizer. The dye-sensitized solar cell uses a photoelectric conversion element in which a photoelectric conversion layer is laminated on a glass substrate on which a transparent conductive film is formed and a counter electrode is disposed via an electrolyte layer. The photoelectric conversion layer includes, for example, titanium oxide fine particles and a dye (ruthenium complex) as a photosensitizer attached to the titanium oxide fine particles. Such a dye-sensitized solar cell has lower power generation efficiency than the silicon-based solar cell described above. One of the causes of low power generation efficiency is that the absorption wavelength region of the dye with respect to the wavelength region of sunlight is narrower than that of silicon solar cells, so that the energy of sunlight is not fully absorbed.

For this reason, the dye-sensitized solar cell which expanded the absorption wavelength area | region by having two photoelectric conversion layers which have the pigment | dye from which an absorption wavelength area | region differs is known (for example, refer patent document 1).
JP 2002-222971 A (Claim 1, FIG. 1)

  However, since none of the sensitizing dyes used in the dye-sensitized solar cell has the maximum sensitivity absorption wavelength region (absorption peak) in the long wavelength region (700 nm to), the dye described in Patent Document 1 above. In the sensitized solar cell, the absorption wavelength region cannot be sufficiently expanded to the long wavelength side. For this reason, there exists a problem that the energy of sunlight cannot fully be utilized.

  Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a photoelectric conversion element having a wide absorption wavelength range and high conversion efficiency so as to be able to absorb wavelengths in the long wavelength range, and a method for manufacturing the same. It is what.

  The photoelectric conversion element of the present invention is a photoelectric conversion element in which a conductive support, a photoelectric conversion layer, an electrolyte layer, and a counter electrode are laminated in this order, wherein the photoelectric conversion layer includes at least semiconductor particles, It is characterized by comprising at least one sensitizing dye and silicon-containing fine particles having a light absorption wavelength region different from that of the sensitizing dye.

  Since the silicon-containing fine particles having a light absorption wavelength region different from that of the sensitizing dye are provided, light having a wavelength different from that of the dye can be absorbed. Therefore, the photoelectric conversion element of the present invention has a wide absorption wavelength region. For this reason, the photoelectric conversion element of this invention can improve conversion efficiency more. Here, the term “adhesion” refers to a chemically adsorbed state. The chemically adsorbed state refers to a state in which atoms and molecules are bonded by a covalent bond or an ionic bond. The absorption wavelength region refers to the wavelength region that can be absorbed by the substance in the sunlight spectrum. Different absorption wavelength regions are different not only when the absorption wavelength region is completely different, but also with different maximum sensitivity wavelength regions, and others. This includes the case where the wavelength regions are the same.

  In the photoelectric conversion layer, it is preferable that silicon-containing fine particles are attached to semiconductor particles, and the sensitizing dye is attached around them. Since the photoelectric conversion layer is configured in this way, electrons generated by charge separation in the silicon-containing fine particles and electrons generated by charge separation in the sensitizing dye are injected into the semiconductor particles without interfering with each other. A conductive support can be reached. Further, since the sensitizing dye is attached to the semiconductor particles to which the silicon-containing fine particles are attached, the surface area of the sensitizing dye is increased, and the power generation amount itself by the sensitizing dye is also improved. Therefore, conversion efficiency corresponding to a wide absorption wavelength region can be obtained.

  It is preferable that the silicon-containing fine particles are made of crystalline silicon and the sensitizing dye is made of a ruthenium complex. According to the combination of the silicon-containing fine particles and the sensitizing dye, since the absorption wavelength region extends from about 400 to about 1200 nm, the power generation efficiency is the highest.

  In the method for producing a photoelectric conversion element of the present invention, a photoelectric conversion layer forming step for forming a photoelectric conversion layer on a conductive support, and an electrolytic solution between the photoelectric conversion layer and the counter electrode after the counter electrode is installed In the method of manufacturing a photoelectric conversion element comprising an electrolyte layer forming step of forming an electrolyte layer by injecting a liquid crystal, the photoelectric conversion layer forming step includes providing a semiconductor particle layer made of semiconductor particles on the conductive support, Next, silicon-containing fine particles are attached to the surface of the semiconductor particle layer, and then a sensitizing dye is attached to the entire semiconductor particle layer.

  According to the production method of the present invention, it is possible to produce a photoelectric conversion element having a photoelectric conversion layer provided with silicon-containing fine particles having a light absorption wavelength region different from that of the sensitizing dye. Since this photoelectric conversion element can absorb light having a wavelength different from that of the sensitizing dye, the photoelectric conversion element of the present invention has a wide absorption wavelength region. For this reason, the photoelectric conversion element of this invention can improve conversion efficiency.

  According to the photoelectric conversion element of the present invention and the method for manufacturing the photoelectric conversion element, since the wavelength in the long wavelength region can be absorbed, an excellent effect of improving the conversion efficiency can be obtained.

It is the (a) schematic diagram of the photoelectric conversion element concerning embodiment, (b) It is a partially expanded view. It is a graph which shows the result of an Example and a comparative example.

  The structure of the photoelectric conversion element of the present invention is shown in FIG. 1A and 1B are diagrams for explaining the photoelectric conversion element of the present embodiment, in which FIG. 1A is a schematic cross-sectional view, and FIG. 1B is a partially enlarged view of FIG.

The photoelectric conversion element 1 includes a transparent conductive substrate 2 (conductive support). The transparent conductive substrate 2 functions as a current collecting electrode by forming a transparent conductive film on a light-transmitting substrate such as a glass substrate. A known transparent conductive film can be used as the transparent conductive film. Examples of the known transparent conductive film material include indium oxide, tin oxide, zinc oxide, cadmium oxide, gallium oxide, and In ₂ O ₃ (ZnO). _m , InGaO ₃ (ZnO) _m and the like, and those obtained by adding a dopant to these oxides, for example, tin-added indium oxide (ITO), antimony-added tin oxide (ATO), zinc-added indium oxide (IZO), and aluminum added Examples thereof include zinc oxide (AZO).

  A counter electrode 3 is provided to face the transparent conductive substrate 2. The counter electrode 3 may be configured by forming a transparent conductive film on a transparent substrate, or may be configured by forming an opaque conductive film on the substrate. In the case of forming an opaque conductive film, if the conductive film has reflectivity, light incident from the transparent conductive substrate 2 can be reflected by the counter electrode, and the photoelectric conversion element 1 can be reflected inside. Light that has passed through the photoelectric conversion layer can be reflected and absorbed, improving conversion efficiency. As the conductive film, a known metal film (for example, a metal film made of gold, silver, copper, platinum, or the like, or an alloy film containing at least one of them) or a carbon film can be used.

  Between the transparent conductive substrate 2 and the counter electrode 3, the photoelectric conversion layer 4 and the electrolyte layer 5 are laminated | stacked in this order from the transparent conductive substrate 2 side.

  The photoelectric conversion layer 4 includes a semiconductor particle layer 42 made of semiconductor particles 41. Further, the sensitizing dye 43 and silicon fine particles 44 having an absorption wavelength region different from that of the sensitizing dye 43 are attached to the semiconductor particle 41 as a sensitizer. The silicon fine particles 44 are distributed and attached as a whole near the surface of the semiconductor particle layer 42, and the sensitizing dye 43 is attached almost entirely around the semiconductor particles 41 and the silicon fine particles 44. The surfaces of the partial semiconductor particles 41 and the silicon fine particles 44 are exposed to the electrolyte layer 5.

  The photoelectric conversion element 1 of the present embodiment includes the sensitizing dye 43 and the silicon fine particles 44 having an absorption wavelength region different from that of the sensitizing dye 43, thereby expanding the wavelength region that can be absorbed by the photoelectric conversion element 1. This improves power generation efficiency. That is, the silicon fine particles 44 absorb light in a predetermined wavelength region and charge-separate and supply electrons, and the sensitizing dye 43 also absorbs light in another predetermined wavelength region and charges-separate to emit electrons. Supply. Thus, since the silicon fine particles 44 having an absorption wavelength region different from the absorption wavelength region of the sensitizing dye 43 are used, the absorption wavelength region is widened by the silicon fine particles 44 rather than the photoelectric conversion element using only one dye. be able to. As a result, conversion efficiency can be improved.

  The flow of excited electrons in the sensitizing dye 43 and the silicon fine particles 44 are independent without interfering with each other. That is, in this embodiment, there are two electron generation routes, and the photoelectric conversion by the sensitizing dye 43 and the photoelectric conversion by the silicon fine particles 44 are performed separately. This point will be described with reference to FIG. As shown in FIG. 1B, the electrons e1 generated and excited by charge separation in the sensitizing dye 43 pass through the sensitizing dye 43 and are injected into the semiconductor particles 41 to enter the transparent conductive substrate 2. To reach. On the other hand, the electrons e <b> 2 excited by charge separation in the silicon fine particles 44 flow into the semiconductor particles 41 from the silicon fine particles 44 and reach the transparent conductive substrate 2. As described above, in the present embodiment, each excited electron by charge separation is configured to be collected by independently reaching the transparent conductive substrate 2 that is a current collecting electrode without interfering with each other. Therefore, current collection can be performed corresponding to the wide absorption wavelength region as described above, and the conversion efficiency can be further increased. The holes generated by the charge separation are respectively injected into the electrolyte layer 5 and recombined in the electrolyte layer 5, so that there is no charge-up problem. Incidentally, among the holes generated by the silicon fine particles 44, those remaining in the silicon fine particles 44 without flowing into the electrolyte layer 5 are recombined with the electrons e 1 generated in the sensitizing dye 43. In this case, since the number of electrons e1 to be recombined is small, it is possible to collect current corresponding to a wide absorption wavelength region as compared with a photoelectric conversion element having no silicon fine particles 44 as a whole, and it is possible to further increase the conversion efficiency. It is said.

  In the present embodiment, as will be described later, since the silicon fine particles 44 are attached to the semiconductor particles 41, and then the sensitizing dye 43 is attached to the whole, the area to which the sensitizing dye 43 is attached is larger. Therefore, conversion efficiency increases.

  Therefore, in the present embodiment, since the silicon fine particles 44 hardly interfere with the current collection by the sensitizing dye 43, the current collection by the sensitizing dye 43 and the current collection by the silicon fine particles 44 are performed almost independently. In addition, the adhesion area (specific surface area) of the sensitizing dye 43 is widened. As a result, in the photoelectric conversion element 1 of the present embodiment, more sunlight energy can be absorbed, and the conversion efficiency is further increased.

Examples of the semiconductor particles 41 include known semiconductors, that is, group IV elements such as Si and Ge, group III-V compounds such as GaAsInP, chalcogen compounds, oxides, and organic compounds. In particular, oxides of Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, Si, and Cr are preferable. Of these, TiO ₂ , which is an oxide of Ti, is most preferable in terms of avoiding photodissolution in the electrolyte and high photoelectric conversion characteristics.

  The semiconductor particles 41 have, for example, a particle size of 5 to 300 nm, preferably 20 to 50 nm. By being in this range, the surface area can be made sufficiently large, so the surface area of the sensitizing dye 43 adhering to the semiconductor particles 41 is increased, and the conversion efficiency can be increased. On the other hand, if the particle size is less than 5 nm, it is difficult to produce the dye, and it is difficult to fix the dye to the inside of the semiconductor particle layer because it becomes the same size as the dye molecule. Furthermore, the electrolyte does not enter the inside of the semiconductor particles and power generation performance is reduced. Moreover, it is preferable that the thickness of the semiconductor particle layer 42 is 5-20 micrometers, More preferably, it is 10-14 micrometers. When the film thickness exceeds 20 μm, the path for electrons to reach the transparent conductive substrate becomes long, and the possibility that the electrons are deactivated increases. On the other hand, if it is too thin, the amount of dye adsorption is too small and the conversion efficiency decreases.

Examples of the silicon fine particles 44 include amorphous silicon and crystalline silicon. The silicon fine particles 44 may be non-doped silicon or doped silicon, but are preferably doped with a substance usually used as a dopant such as phosphorus, gallium, or boron. In order to obtain a particularly wide absorption wavelength region, it is preferable to use crystalline silicon fine particles having a long absorption wavelength region (400 to 1200 nm, maximum sensitivity absorption wavelength region of about 900 nm). As such a crystalline silicon fine particle, as a sensitizing dye 43 usually used in a silicon-based solar cell, one having a wavelength absorption region different from that of the crystalline silicon fine particle is selected, and a wide absorption wavelength region in the visible light region. It is preferable to use a ruthenium complex dye having a (400 to 800 nm, maximum sensitivity absorption wavelength region of about 550 nm), particularly a ruthenium-bis (RuL ₂ ) type transition metal complex as a sensitizing dye. In this case, by having both in the photoelectric conversion layer, it is possible to use as a solar cell with high power generation efficiency having the widest absorption wavelength region.

As the sensitizing dye 43, in addition to the ruthenium-bis (RuL ₂ ) type transition metal complex, for example, a RuL ₂ (H ₂ O) ₂ type ruthenium-cis-diaqua-bipyridyl complex or ruthenium-tris ( RuL ₃ ), osnium-tris (OsL ₃ ), osnium-bis (OsL ₂ ) type transition metal complex, or zinc-tetra (4-carboxyphenyl) porphyrin, iron-hexocyanide complex, phthalocyanine, and the like for further absorption The conversion efficiency may be increased by expanding the wavelength region. Moreover, you may contain an organic pigment | dye. As organic dyes, 9-phenylxanthene dyes, coumarin dyes, acridine dyes, triphenylmethane dyes, tetraphenylmethane dyes, quinone dyes, azo dyes, indigo dyes, cyanine dyes, merocyanine dyes Examples thereof include dyes and xanthene dyes. One or more sensitizing dyes 43 may be selected and two or more sensitizing dyes may be contained in the photoelectric conversion layer 4.

  The silicon fine particles 44 preferably have a particle size of 20 nm or less, particularly 1 to 6 nm. By being in this range, adhesion of the sensitizing dye 43 is not hindered, and the silicon fine particles 44 themselves can sufficiently contribute to photoelectric conversion.

  The electrolyte layer 5 is not particularly limited as long as a pair of redox substances consisting of an oxidant and a reductant are contained in the solvent. For example, as a pair of redox substances, chlorine compound-chlorine, iodine compound-iodine, bromine compound-bromine, metal ions (for example, mercury ion (II) -mercury ion (I), copper ion (II) -copper) Ion (I), iron ion (III) -iron ion (II), manganate ion-permanganate ion) and the like. In particular, an iodine compound-iodine is preferable. Examples of the iodine compound include metal iodides such as lithium iodide and potassium iodide, quaternary ammonium iodide compounds such as tetraalkylammonium iodide and pyridinium iodide, and dimethylpropyl iodide. Particularly preferred are diimidazolium iodide compounds such as imidazolium.

  The solvent containing the pair of redox substances is preferably a compound that dissolves the redox constituents and has excellent ion conductivity. As the solvent, any of an aqueous solvent and an organic solvent can be used, but an organic solvent is preferable in order to further stabilize the redox component. For example, examples of the organic solvent include ester compounds, ether compounds, heterocyclic compounds, nitrile compounds, and aprotic polar compounds. These may be used alone or in combination of two or more. In particular, carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazodilinone and 2-methylpyrrolidone, and nitrile compounds such as acetonitrile, methoxyacetonitrile and propionitrile are preferably used.

  A method for forming such a photoelectric conversion element 1 will be described.

  First, the semiconductor particle layer 42 is formed on the transparent conductive substrate 2. Examples of the forming method include known wet coating methods, sputtering methods, and the like, but it is preferable to form the semiconductor particles 41 by, for example, drying at 120 ° C. after coating and forming by a wet coating method, particularly by a squeegee method.

  Next, silicon fine particles 44 are attached on the semiconductor particles 41. In this case, the silicon fine particles 44 are formed so as to be chemically adsorbed to the semiconductor particles 41. This is because if the silicon particles 44 are simply in contact with the semiconductor particles 41, the silicon particles 44 are likely to be removed from the semiconductor particles 41 in the subsequent steps. In order to attach the silicon fine particles 44, there are a method of attaching the silicon fine particles 44 to the semiconductor particles 41 while forming the silicon fine particles 44 and a method of attaching the formed silicon fine particles 44 to the semiconductor particles 41. In order to deposit the silicon fine particles 44 on the semiconductor particles 41 while forming the silicon fine particles 44, for example, a CVD method, a sputtering method, a vacuum vapor deposition method, an arc plasma vapor deposition method or the like can be used. In particular, an arc plasma vapor deposition method that can be easily controlled to have a desired particle size to form particles is preferable. This arc plasma deposition method will be described below.

  In the arc plasma deposition method, silicon fine particles 44 are formed using a coaxial vacuum arc deposition apparatus. In this coaxial vacuum arc deposition apparatus, a cylindrical trigger electrode and a cylindrical cathode electrode whose tip is formed of a material of silicon fine particles 44 (hereinafter referred to as silicon material) sandwich a disc-shaped insulator. And a coaxial vacuum arc deposition source in which a cylindrical anode electrode is coaxially disposed around the cathode electrode and the trigger electrode. As the silicon material, boron-doped silicon, phosphorus-doped silicon, or the like can be used. When the silicon fine particles 44 are produced as crystalline silicon fine particles, it is preferable to use boron-doped silicon.

  Then, a voltage is applied between the trigger electrode and the anode electrode to generate a trigger discharge in a pulse manner, and a voltage is applied from the arc power source between the cathode electrode and the anode electrode to intermittently discharge the arc. By inducing the electrons, electrons generated by melting the surface of the silicon material are emitted as an electron stream. Ions generated from the silicon material are attracted to and emitted from the silicon material by the Coulomb attractive force, and reach and adhere to the semiconductor particles 41. This becomes the silicon fine particles 44. According to this arc plasma deposition method, the number of particles of silicon fine particles 44 can be controlled by the number of occurrences of arc discharge, and the particle size can also be controlled by changing the capacity of the capacitor unit connected to the arc power source. It is.

  In this case, for example, the arc plasma deposition method may be performed by applying a voltage between the trigger electrode and the cathode electrode of 3.4 kV or less, a voltage applied to the arc power source between the cathode electrode and the anode electrode: 60 to 400 V, and an arc power source. The capacity | capacitance of the connected capacitor | condenser unit: 360-8800 micro F is mentioned. Within this range, a desired amount of silicon fine particles 44 can be formed in a desired size.

  Examples of the CVD method include a method in which a silane gas or a borane gas is used as a source gas to form particles while controlling the film formation time. Examples of the sputtering method include a method in which argon gas is introduced as a sputtering gas into a boron-doped silicon target and sputtering is performed to form particles while controlling the film formation time. Examples of the vacuum deposition method include a method of forming particles in a particulate form by controlling the film formation time using boron-doped silicon as a raw material.

  Examples of a method for attaching the formed silicon fine particles 44 onto the semiconductor particles 41 include a fine particle deposition method and a wet coating method. As the fine particle deposition method, for example, silicon fine particles 44 are generated by laser ablation, evaporation condensation method, or the like, and the generated silicon fine particles 44 are charged by, for example, radiation irradiation. Then, charged silicon fine particles 44 are introduced into the deposition chamber by a carrier gas (such as helium) and deposited on the substrate. In this way, the silicon fine particles 44 can be deposited in a scattered state on the substrate.

  As a wet coating method, a coating liquid containing silicon fine particles 44 is applied to the semiconductor particle layer 42 to adhere the silicon fine particles 44 to the semiconductor particles 41. For example, a solution containing the silicon fine particle material 44 is applied onto the substrate by, for example, spin coating to form a film. In this case, in order to prevent aggregation of the silicon fine particles 44 in the solution, a surfactant is added to a solvent (for example, water).

  After the silicon fine particles 44 are attached, the sensitizing dye 43 is attached. As a method for attaching the sensitizing dye 43, a known method can be used. For example, the substrate is immersed in a solution containing the desired sensitizing dye 43 in a state in which the silicon fine particles 44 are attached by an immersion method and washed. It is possible to attach a pigment by drying.

  Conventionally, since it is difficult to quantitatively control the amount of sensitizing dye adsorbed to semiconductor particles, when two or more sensitizing dyes having different absorption wavelength regions are contained, each sensitizing dye is contained. Separate layers were provided. Thus, conventionally, there has been a problem that the number of processes is large and it is not suitable for mass production in order to form two or more photoelectric conversion layers. In this respect, in the present embodiment, the silicon fine particles 44 can be easily formed as described above, and the silicon fine particles 44 and the sensitizing dye 43 can be formed in the same layer. The specific surface area of the dye 43 can be increased. Conventionally, the photoelectric conversion layer has been formed using an electrolytic reaction. However, such a formation method has a problem that it is suitable for forming a small substrate but not for forming a large substrate. . In this respect, in the present embodiment, the silicon fine particles 44 can be formed by a forming method corresponding to a large-sized substrate such as an arc plasma deposition method, which is more suitable for practical use.

  Thereafter, the counter electrode 3 is installed through a waterproof spacer (not shown), and an electrolyte solution is injected between the photoelectric conversion layer 4 and the counter electrode 3 to form the electrolyte layer 5. Thus, the photoelectric conversion element 1 of this embodiment can be obtained.

  The photoelectric conversion element 1 thus obtained can be a dye-sensitized solar cell module by arranging the photoelectric conversion elements 1 in the vertical and horizontal directions as each cell. Since this dye-sensitized solar cell module uses the photoelectric conversion element 1 having higher conversion efficiency than the conventional one, it can be a dye-sensitized solar cell with higher power generation efficiency.

  In this example, the photoelectric conversion element 1 was produced and the current-voltage characteristics were examined.

  First, a titanium oxide paste (trade name: PECC-K01, manufactured by Pexel Technology Co., Ltd.) is applied to a glass substrate on which a fluorine-doped tin oxide film is formed as a transparent conductive film by a squeegee method. And dried at 120 ° C. to form a semiconductor particle layer 42 made of titanium oxide particles (semiconductor particles 41). The film thickness of the formed semiconductor particle layer 42 was 10 μm, and the average particle diameter of the titanium oxide particles was 20 nm.

  Next, crystalline silicon fine particles 44 were deposited on the semiconductor particles 41 by an arc plasma method. The execution conditions of the arc plasma method were as follows: target: boron-doped silicon target, applied voltage between trigger electrode and cathode electrode: 3.4 kV, applied voltage of arc power source between cathode electrode and anode electrode: 80 V, connected to arc power source The capacity of the capacitor unit was 1800 μF.

  After the silicon fine particles 44 were attached, the silicon fine particles 44 were immersed in a solution in which 0.1 wt% of a Ru complex dye was added in a solvent in which acetonitrile and butanol were mixed at a ratio of 1: 1. Thereafter, it was washed with acetonitrile and dried to attach a Ru dye as a sensitizer.

  Next, the obtained substrate was sandwiched between a glass substrate on which a platinum film as a counter electrode was formed via a vinyl sheet as a waterproof spacer. Finally, an electrolytic solution (trade name: PACE-K01, manufactured by Pexel Technology) containing an iodine-based redox pair was injected to obtain a photoelectric conversion element 1 of the present embodiment.

(Comparative Example 1)
A photoelectric conversion element was produced in the same manner as in Example 1 except that the silicon fine particles 44 were not attached. That is, the photoelectric conversion element manufactured in Comparative Example 1 includes titanium oxide particles and a dye in the photoelectric conversion layer, and does not have silicon fine particles 44.

The current-voltage characteristics of the photoelectric conversion elements produced in Example 1 and Comparative Example 1 were measured. For the measurement, solar simulator (trade name: WXS-50S-1, 5, manufactured by Wacom Denso Co., Ltd.) was incident from the transparent conductive substrate 2 side with 100 mW / cm ² simulated sunlight. The results are shown in FIG.

As shown in FIG. 2, the photoelectric conversion element (dye / TiO ₂ ) produced in Comparative Example 1 had a short-circuit current density of 11.1 mA / cm ² and a conversion efficiency of 5.3%. On the other hand, the photoelectric conversion element (dye / Si / TiO ₂ ) produced in Example 1 had a short-circuit current density of 13.0 mA / cm ² and a conversion efficiency of 6.5%. Therefore, the conversion efficiency of the photoelectric conversion element manufactured in Example 1 was improved by about 18%. In Example 1 and Comparative Example 1, the transparent conductive substrate and the counter electrode are not completely sealed, but the conversion efficiency is further improved (for example, 8% or more) by completely sealing. It is expected.

  Thus, according to the photoelectric conversion element 1 in the present embodiment, since the conversion efficiency is higher than that of the conventional one with a simple configuration, it is possible to achieve higher power generation efficiency when a dye-sensitized solar cell is used. is there.

  The photoelectric conversion element of the present invention can be used as a solar cell element. Therefore, it can be used in the solar cell manufacturing field.

DESCRIPTION OF SYMBOLS 1 Photoelectric conversion element 2 Transparent conductive substrate 3 Counter electrode 4 Photoelectric conversion layer 5 Electrolyte layer 41 Semiconductor particle 42 Semiconductor particle layer 43 Sensitizing dye 44 Silicon fine particle

Claims (4)

In a photoelectric conversion element formed by laminating a conductive support, a photoelectric conversion layer, an electrolyte layer, and a counter electrode in this order,
A photoelectric conversion element, wherein the photoelectric conversion layer includes semiconductor particles, at least one sensitizing dye, and silicon-containing fine particles having a light absorption wavelength region different from the sensitizing dye. 3. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion layer has silicon-containing fine particles attached to semiconductor particles, and further the sensitizing dye is attached around these. The photoelectric conversion element according to claim 1, wherein the silicon-containing fine particles are made of crystalline silicon, and the sensitizing dye is made of a ruthenium complex. A photoelectric conversion layer forming step for forming a photoelectric conversion layer on a conductive support, and an electrolyte layer for forming an electrolyte layer by injecting an electrolytic solution between the photoelectric conversion layer and the counter electrode after installing the counter electrode In a method for producing a photoelectric conversion element comprising a forming step,
The photoelectric conversion layer forming step includes
Provide a semiconductor particle layer made of semiconductor particles on the conductive support,
Next, a method for producing a photoelectric conversion element, wherein silicon-containing fine particles are attached to the surface of the semiconductor particle layer, and then a sensitizing dye is attached to the entire semiconductor particle layer.

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