JP4500420B2 - Photoelectric conversion element and photovoltaic cell - Google Patents

Photoelectric conversion element and photovoltaic cell Download PDF

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Publication number
JP4500420B2
JP4500420B2 JP2000285461A JP2000285461A JP4500420B2 JP 4500420 B2 JP4500420 B2 JP 4500420B2 JP 2000285461 A JP2000285461 A JP 2000285461A JP 2000285461 A JP2000285461 A JP 2000285461A JP 4500420 B2 JP4500420 B2 JP 4500420B2
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photoelectric conversion
layer
conversion element
semiconductor fine
group
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JP2002100416A (en
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力 宮坂
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富士フイルム株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/54Material technologies
    • Y02E10/542Dye sensitized solar cells

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to the technical fields of photoelectric conversion and optical sensing, and relates to a photoelectric conversion element manufactured by a low-cost manufacturing process that does not include high-temperature baking. Furthermore, the present invention relates to a photovoltaic cell using the same.
[0002]
[Prior art]
Photoelectric conversion elements are widely used in both the energy conversion and optical sensing industrial fields, and so far, solid elements typified by Si pn junctions and compound semiconductor heterojunctions have been used as high-sensitivity elements. I came. Photovoltaic (PV) cells for photovoltaic power generation are important issues for high sensitivity and durability, and are currently compound semiconductors such as single crystal silicon, polycrystalline silicon, amorphous silicon, cadmium telluride and indium copper selenide Photovoltaic cells using these solid junctions are the main technology. However, since these photovoltaic cells all require crystal formation at high temperatures or lamination of high-purity thin films using vacuum technology, there is a problem that the energy consumption of the manufacturing process is large and the cost is high. It is out. Amorphous silicon solar cells, which are considered to be the most powerful in terms of performance and cost ratio, can use visible light up to 800 nm, and provide an open circuit voltage of 0.7 V or more and an energy conversion efficiency close to 10%. However, a vacuum deposition process is required, and there is a limit to significant cost reduction.
[0003]
Under such circumstances, photoelectric conversion elements and solar cells using dye-sensitized semiconductor fine particles disclosed in Nature (Vol. 353, 737-740, 1991) and US Pat. Has been. A typical example is a so-called wet solar cell, an electrochemical photovoltaic cell comprising a titanium dioxide porous thin film spectrally sensitized using a ruthenium complex having excellent light resistance as a dye. The advantage of this wet solar cell is that it can provide a photoelectric conversion element at low cost using an inexpensive oxide semiconductor such as titanium dioxide. The second advantage is that the wavelength of light absorption is selected according to the type of dye used. Or can be extended to longer wavelengths. The porous semiconductor fine particle layer, which is a structural feature of this system, is an essential element for increasing the amount of dye adsorption and realizing high light absorption, and usually disperses a highly viscous dispersion containing semiconductor fine particles. It is obtained by applying the material together with the material on the electrode substrate and firing the material at a relatively high temperature (400 to 500 ° C.) to remove the dispersed material. However, the high-temperature firing step not only hinders cost reduction, but also limits the type of support that supports the semiconductor fine particle layer, so that it is difficult to form an electrode layer on a plastic substrate or the like.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a dye-sensitized semiconductor type photoelectric conversion element and a photovoltaic cell that have high energy conversion efficiency and can be manufactured at low cost.
[0005]
[Means for Solving the Problems]
  The object of the present invention has been achieved by the following matters specifying the present invention and preferred embodiments thereof.
(1) A method for producing a photoelectric conversion element comprising a laminated structure including a conductive support having a conductive layer, a semiconductor fine particle layer, a charge transport layer and a counter electrode, wherein the semiconductor fine particles are electrophoresed on the conductive layer of the conductive support. A step of forming the semiconductor fine particle layer by adhering to the surface, and the formed semiconductor fine particle layerUnder the irradiation of light absorbed by semiconductor fine particlesThe manufacturing method of the photoelectric conversion element characterized by including the process heated at 100 to 250 degreeC.
(2) The method for producing a photoelectric conversion element according to the above (1), wherein the electrophoresis is performed using a semiconductor fine particle dispersion containing no electrolyte.
(3) The photoelectric conversion element according to (1) or (2), wherein the electrophoresis is performed in a direct current electric field, and the strength of the electric field is 50 V / cm or more and 300 V / cm or less. Production method.
(4) The photoelectric conversion element according to (1) or (2), wherein the electrophoresis is performed in a direct current electric field, and the strength of the electric field is 60 V / cm or more and 200 V / cm or less. Production method.
[0006]
(5(1) to (1) above, wherein the conductive layer of the conductive support contains tin oxide.4The manufacturing method of the photoelectric conversion element in any one of.
(6The semiconductor fine particles are semiconductors selected from titanium oxide, zinc oxide, tin oxide, tungsten oxide, niobium oxide, and a composite of two or more thereof. (5The manufacturing method of the photoelectric conversion element in any one of.
[0007]
(7The semiconductor fine particles are semiconductors selected from titanium oxide, zinc oxide, tin oxide, and a composite of two or more thereof.6) The photoelectric conversion element according to any one ofManufacturing method.
(8(1) to (1) above, wherein the semiconductor fine particle layer is sensitized with a dye.7) The photoelectric conversion element according to any one ofManufacturing method.
(9(1) to (1) above, wherein the charge transfer layer contains an electrolyte.8) The photoelectric conversion element according to any one ofManufacturing method.
(10(1) to (1) above, wherein the charge transfer layer contains a molten salt electrolyte.9) The photoelectric conversion element according to any one ofManufacturing method.
(11(1) to (1), wherein the conductive support is a plastic support having a conductive layer.10) The photoelectric conversion element according to any one ofManufacturing method.
(12) A photoelectric conversion element manufactured by the manufacturing method according to any one of (1) to (11).
(13)the above(12)A photovoltaic cell using the photoelectric conversion element described in 1.
(14)the above(12)A solar cell using the photoelectric conversion element described in 1.
(15)the above(12)An optical sensor using the photoelectric conversion element described in 1.
The present invention relates to the above (1) to (3), (5), (6), (8), and (10) to (13), but other matters are also described for reference.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The photoelectric conversion element of the present invention uses a layer of semiconductor fine particles as a photosensitive electrode, and is formed by bonding a charge transport layer such as an electrolyte to the semiconductor fine particle layer. It is characterized by being formed by a kind of electrodeposition using the adhesion of a charged substance (charged semiconductor fine particles) to the substrate by electrophoresis instead of the method according to.
[0009]
[1] Photoelectric conversion element
The main points of the photoelectric conversion element of the present invention will be described with reference to the drawings. FIG. 1 is a partial cross-sectional view showing a typical structure of the photoelectric conversion element of the present invention. In FIG. 1, a conductive layer 10, an undercoat layer 60, a photosensitive layer (semiconductor fine particle layer) 20, a charge transport layer 30, and a counter electrode conductive layer 40 are laminated in this order, and the photosensitive layer 20 is sensitized with a dye 22. And a charge transport material 23 that has permeated into the gaps between the semiconductor fine particles 21. The charge transport material 23 is composed of the same components as the material used for the charge transport layer 30. Further, a substrate 50 may be provided as a base for the conductive layer 10 and / or the counter electrode conductive layer 40 in order to impart strength to the photoelectric conversion element. In the present invention, the layer composed of the conductive layer 10 and the optional substrate 50 is hereinafter referred to as “conductive support”, and the layer composed of the counter electrode conductive layer 40 and the optional substrate 50 is referred to as “counter electrode”. Note that the conductive layer 10, the counter electrode conductive layer 40, and the substrate 50 in FIG. 1 may be the transparent conductive layer 10a, the transparent counter electrode conductive layer 40a, and the transparent substrate 50a, respectively. A photocell is made for the purpose of generating electrical work by connecting this photoelectric conversion element to an external load (power generation), and a photosensor is made for the purpose of sensing optical information. Among the photovoltaic cells, the case where the charge transport material 23 is mainly made of an ion transport material is particularly called a photoelectrochemical cell, and the case where the main purpose is power generation by sunlight is called a solar cell.
[0010]
In the photoelectric conversion element of the present invention shown in FIG. 1, when the semiconductor fine particles are n-type, the light incident on the photosensitive layer 20 containing the semiconductor fine particles 21 sensitized by the dye 22 excites the dye 22 and the like. The high-energy electrons in the dye 22 and the like thus transferred are transferred to the conduction band of the semiconductor fine particles 21, and further reach the conductive layer 10 by diffusion. At this time, the molecule such as the dye 22 is an oxidant. In the photovoltaic cell, electrons in the conductive layer 10 return to an oxidant such as the dye 22 through the counter electrode conductive layer 40 and the charge transport layer 30 while working in an external circuit, and the dye 22 is regenerated. The photosensitive layer 20 functions as a negative electrode (photoanode), and the counter electrode 40 functions as a positive electrode. At each layer boundary (for example, the boundary between the conductive layer 10 and the photosensitive layer 20, the boundary between the photosensitive layer 20 and the charge transport layer 30, the boundary between the charge transport layer 30 and the counter conductive layer 40, etc.) They may be diffusively mixed with each other. Each layer will be described in detail below.
[0011]
(A) Conductive support
The conductive support is composed of (1) a single layer of a conductive layer, or (2) two layers of a conductive layer and a substrate. In the case of (1), a material that can sufficiently maintain strength and hermeticity is used as the conductive layer. For example, a metal material (platinum, gold, silver, copper, zinc, titanium, aluminum, or the like is included) Alloy) can be used. In the case of (2), a substrate having a conductive layer containing a conductive agent on the photosensitive layer side can be used. Preferred conductive agents include metals (eg, platinum, gold, silver, copper, zinc, titanium, aluminum, indium, etc. or alloys containing these), carbon, or conductive metal oxides (indium-tin composite oxide, tin oxide). And those doped with fluorine or antimony). The thickness of the conductive layer is preferably about 0.02 to 10 μm.
[0012]
The lower the surface resistance of the conductive support, the better. The range of the surface resistance is preferably 50Ω / □ or less, more preferably 20Ω / □ or less. In the present invention, the conductive support serves as a substrate electrode for forming a semiconductor fine particle layer. In the formation of the semiconductor fine particle layer of the present invention, since a voltage of several volts is applied to the substrate electrode, the substrate electrode needs to be electrochemically stable. In this respect, a particularly preferable conductive material is , Tin oxide.
[0013]
When irradiating light from the conductive support side, the conductive support is preferably substantially transparent. “Substantially transparent” means that the transmittance is 10% or more in a part or all of the light in the visible to near infrared region (400 to 1200 nm), preferably 50% or more, 80% or more is more preferable. In particular, it is preferable that the transmittance in a wavelength region where the photosensitive layer is sensitive is high.
[0014]
The transparent conductive support is preferably formed by applying or vapor-depositing a transparent conductive layer made of a conductive metal oxide on the surface of a transparent substrate such as glass or plastic. Preferred as the transparent conductive layer is fluorine dioxide or antimony doped tin dioxide or indium-tin oxide (ITO). As the transparent substrate, a glass substrate such as soda glass which is advantageous in terms of low cost and strength, alkali-free glass which is not affected by alkali elution, and a transparent polymer film which is advantageous in cost and flexibility can be preferably used. Transparent polymer film materials include triacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polyester (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr), polysulfone (PSF), polyester sulfone (PES), polyimide (PI), polyetherimide (PEI), cyclic polyolefin, brominated phenoxy resin, and the like. In order to ensure sufficient transparency, the amount of conductive metal oxide applied is 1 m of glass or plastic support.2The amount is preferably 0.01 to 100 g.
[0015]
It is preferable to use a metal lead for the purpose of reducing the resistance of the transparent conductive support. The material of the metal lead is preferably a metal such as platinum, gold, nickel, titanium, aluminum, copper, or silver. The metal lead is preferably provided on a transparent substrate by vapor deposition, sputtering or the like, and a transparent conductive layer made of conductive tin oxide or ITO film is preferably provided thereon. The decrease in the amount of incident light due to the installation of the metal lead is preferably within 10%, more preferably 1 to 5%.
[0016]
(B) Photosensitive layer
In the photosensitive layer, the semiconductor acts as a photoconductor, absorbs light, separates charges, and generates electrons and holes. In a dye-sensitized semiconductor, light absorption and the generation of electrons and holes thereby occur mainly in the dye, and the semiconductor particles play a role of receiving and transmitting these electrons (or holes). The semiconductor used in the present invention is preferably an n-type semiconductor in which conductor electrons become carriers under photoexcitation and give an anode current. A semiconductor preferable as a semiconductor material constituting the photosensitive layer in the present invention has a carrier concentration of 10 for conduction.14-1020Piece / cmThreeIt is a semiconductor of the range.
[0017]
(1) Semiconductor
As the semiconductor, a single semiconductor such as silicon or germanium, a III-V group compound semiconductor, a metal chalcogenide (for example, oxide, sulfide, selenide, or a composite thereof), or a compound having a perovskite structure ( For example, strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate, etc.) can be used.
[0018]
Preferred metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, or tantalum oxide, cadmium, zinc, lead, silver, antimony or Bismuth sulfide, cadmium or lead selenide, cadmium telluride and the like. Examples of other compound semiconductors include phosphides such as zinc, gallium, indium, and cadmium, gallium-arsenic or copper-indium selenides, and copper-indium sulfides. Furthermore, MxOySz or M1xM2yOz (M, M1And M2A composite element such as each of which is a metal element, O is oxygen, and x, y, and z are combinations of which the valence is neutral) can also be preferably used.
[0019]
A preferred specific example of the semiconductor used in the present invention is TiO2, SnO2, Fe2OThree, WOThree, ZnO, Nb2OFive, CdS, ZnS, PbS, Bi2SThree, CdSe, CdTe, SrTiOThree, GaP, InP, GaAs, CuInS2, CuInSe2And more preferably TiO2, ZnO, SnO2, WOThreeOr Nb2OFiveAnd particularly preferably TiO2, SnO2Or ZnO, most preferably TiO2It is. TiO2TiO containing 70% or more of anatase type crystals2And particularly preferably 100% anatase type TiO2It is. It is also effective to dope metals for the purpose of increasing the electronic conductivity in these semiconductors. As the metal to be doped, divalent and trivalent metals are preferable. In order to prevent a reverse current from flowing from the semiconductor to the charge transport layer, it is also effective to dope a monovalent metal into the semiconductor.
[0020]
The particle size of the semiconductor fine particles is generally on the order of nm to μm, but the average particle size of the primary particles obtained from the diameter when the projected area is converted into a circle is preferably 5 to 200 nm, more preferably 8 to 100 nm. preferable. The average particle size of the semiconductor fine particles (secondary particles) in the dispersion is preferably 0.01 to 30 μm. Two or more kinds of fine particles having different particle size distributions may be mixed. In this case, the average size of the small particles is preferably 25 nm or less, more preferably 10 nm or less. For the purpose of improving the light capture rate by scattering incident light, it is also preferable to mix semiconductor particles having a large particle diameter, for example, about 100 nm or more and about 300 nm.
[0021]
Semiconductor fine particles are prepared by Sakuo Sakuo's "Sol-gel Method Science" Agne Jofusha (1998), Technical Information Association "Sol-gel Method Thin Film Coating Technology" (1995), etc. The sol-gel method described, Tadao Sugimoto's "Synthesis of monodisperse particles by the new synthesis gel-sol method and size morphology control", Materia, Vol. 35, No. 9, pp. 1012-1018 (1996) The gel-sol method described in 1 is preferred. Also preferred is a method developed by Degussa to produce an oxide by high-temperature hydrolysis of chloride in an oxyhydrogen salt.
When the semiconductor fine particles are titanium oxide, the sol-gel method, gel-sol method, and high-temperature hydrolysis method in oxyhydrogen salt of chloride are all preferred, but Kiyoshi Manabu's “Titanium oxide properties and applied technology” The sulfuric acid method and the chlorine method described in Gihodo Publishing (1997) can also be used. Further, as a sol-gel method, the method described in Journal of American Ceramic Society, Volume 80, No. 12, pages 3157-3171 (1997) of Barbe et al., Barnside The method described in Chemistry of Materials, Vol. 10, No. 9, pages 2419-2425 is also preferable.
[0022]
(2) Formation of semiconductor fine particle layer
The formation of the semiconductor fine particle layer of the present invention (the electrodeposition method of the present invention) is carried out by causing the semiconductor fine particles to migrate to adhere to the conductive layer side of the conductive support. Usually, it is performed according to the following process and conditions.
First, semiconductor fine particles are added to an appropriate low-conductivity solvent and uniformly dispersed so as not to aggregate. In order to lower the conductivity, it is important that the solvent does not substantially contain a dissociable electrolyte salt and does not contain an electrochemically active redox compound so as not to hinder the formation of a semiconductor fine particle layer. . The solvent is preferably pure water, a polar organic solvent such as alcohol, acetonitrile, or THF, a nonpolar organic solvent such as hexane or chloroform, or a mixed solvent thereof. The particle content of the dispersion is preferably in the range of 0.01 g to 0.1 g / mL.
Secondly, a substrate electrode to be electrodeposited (for example, a support having a conductive tin oxide layer) and a counter electrode for electrodeposition are opposed in parallel at a constant interval, and the dispersion liquid is injected into the gap. The distance between both electrodes is usually 0.1 mm to 2 mm, preferably 0.2 mm to 0.5 mm.
Third, a DC voltage is applied between both electrodes. Specifically, the substrate electrode side is set to be positive or negative depending on the property (surface charge) of the particles, and the applied voltage is 50 V / cm to 300 V / cm, preferably 60 V / cm to 200 V / cm. Set to be strong and apply for 1 to 10 minutes. As a result, the semiconductor fine particles first migrate to the substrate electrode by electrophoresis, and then adhere to the electrode. Since the temperature dependence of electrophoresis is relatively small, it is not necessary to strictly control the temperature, and electrophoresis may be performed at room temperature.
As described above, a uniform semiconductor fine particle layer having an arbitrary thickness can be formed on the substrate electrode by selecting the concentration of the dispersion and the electrode interval. The thickness of the semiconductor layer formed by the electrodeposition method of the present invention is preferably 2 to 20 μm.
[0023]
The layer of semiconductor fine particles is not limited to a single layer, and semiconductor fine particles having different particle sizes and types can be electrodeposited over a plurality of layers, or layers having different thicknesses can be electrodeposited.
Moreover, a semiconductor fine particle layer, for example, a coating film, formed by a method different from electrodeposition can be provided on the electrodeposition layer. Conversely, an electrodeposition layer can be provided on the coating film.
[0024]
A preferable thickness of the entire semiconductor fine particle layer is 0.1 to 100 μm. When used in a solar cell, the thickness of the semiconductor fine particle layer is preferably 1 to 30 μm, and more preferably 2 to 25 μm. Semiconductor fine particle support 1m2The hit load is preferably 0.5 to 400 g, more preferably 5 to 100 g.
[0025]
The semiconductor fine particle layer of the present invention is preferably subjected to a heat treatment in order to enhance the electronic contact between the semiconductor fine particles and improve the adhesion to the support.
Although it is effective to use a temperature of 100 ° C. to 400 ° C. as the heating temperature range, it is preferable for the purpose of reducing adverse effects (deformation, alteration, etc.) due to heating of the conductive support (conductive layer and support). The temperature range is 100 ° C to 250 ° C. When using a support having a low melting point or softening point, such as a polymer film, as the transparent support, the heat treatment temperature is preferably as low as possible (200 ° C. or less). Moreover, the photoelectric conversion element produced by the method of the present invention can obtain sufficient conversion efficiency even at low temperature heating. The heat treatment time varies depending on the heat treatment temperature and the type of semiconductor particles, but is usually a time optimized in the range of 10 minutes to 10 hours.
In the present invention, it is preferable that the semiconductor fine particle layer is irradiated with light absorbed by the fine particles during the heat treatment. Thus, by photoexciting the semiconductor, it is considered that impurities mixed in the fine particle layer can be photodecomposed to clean the fine particle layer and enhance physical bonding between the fine particles. The light to be irradiated is preferably ultraviolet light that is strongly absorbed by the semiconductor.
[0026]
The semiconductor fine particle layer preferably has a large surface area for the purpose of increasing the adsorption amount of the dye, and the ratio of the surface area to the projected area of the layer is preferably 10 times or more, and more preferably 100 times or more. Preferably there is. The upper limit is not particularly limited, but is usually about 1000 times.
[0027]
(3) Dye
As the kind of the dye for sensitizing the semiconductor fine particles, an organometallic complex dye, a porphyrin dye, a phthalocyanine dye or a methine dye is preferable. These dyes can be used in a mixture of two or more in order to widen the wavelength range of photoelectric conversion as much as possible and increase the conversion efficiency. Further, the dye to be mixed and its ratio can be selected so as to match the wavelength range and intensity distribution of the target light source.
[0028]
Such a dye preferably has an appropriate interlocking group capable of adsorbing to the surface of the semiconductor fine particles. Preferred linking groups include COOH groups, OH groups, SO3H group, -P (O) (OH)2Group or -OP (O) (OH)2And chelating groups having π conductivity such as oxime groups, dioxime groups, hydroxyquinoline groups, salicylate groups or α-ketoenolate groups. Among them, COOH group, -P (O) (OH)2Group or -OP (O) (OH)2The group is particularly preferred. These groups may form a salt with an alkali metal or the like, or may form an internal salt. In the case of a polymethine dye, if the methine chain contains an acidic group as in the case where the methine chain forms a squarylium ring or a croconium ring, this part may be used as a linking group.
[0029]
Hereinafter, preferred sensitizing dyes used in the photosensitive layer will be specifically described.
(A) Organometallic complex dye
When the dye is a metal complex dye, a metal phthalocyanine dye, a metal porphyrin dye or a ruthenium complex dye is preferable, and a ruthenium complex dye is particularly preferable. Examples of ruthenium complex dyes include, for example, U.S. Pat. / 50393, JP-A 2000-26487, and the like.
[0030]
Further, the ruthenium complex dye used in the present invention has the following general formula (I):
(A1) pRu (B-a) (B-b) (B-c) (I)
Is preferably represented by: In the general formula (I), A1 represents a monodentate or bidentate ligand, Cl, SCN, H2Preference is given to ligands selected from the group consisting of O, Br, I, CN, NCO and SeCN, and derivatives of β-diketones, oxalic acid and dithiocarbamic acid. p is an integer of 0-3. B-a, B-b and B-c are each independently represented by the following formulas B-1 to B-10:
[0031]
[Chemical 1]
[0032]
(However, RaRepresents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms, and a carbon atom. Examples of the substituted or unsubstituted aryl group of 6 to 12 or the above-mentioned acidic groups (these acidic groups may form a salt) and chelating groups are included. The alkyl part of the alkyl group and the aralkyl group is It may be linear or branched, and the aryl part of the aryl group and aralkyl group represents an organic ligand selected from compounds represented by a single ring or a polycycle (fused ring, ring assembly). B-a, B-b and B-c may be the same or different, and may be any one or two.
[0033]
Although the preferable specific example of an organometallic complex pigment | dye is shown below, this invention is not limited to these.
[0034]
[Chemical 2]
[0035]
[Chemical Formula 3]
[0036]
[Formula 4]
[0037]
(B) Methine dye
Preferred methine dyes for use in the present invention are polymethine dyes such as cyanine dyes, merocyanine dyes, squarylium dyes. Examples of polymethine dyes preferably used in the present invention include JP-A-11-35836, JP-A-11-67285, JP-A-11-86916, JP-A-11-97725, JP-A-11-158395, and JP-A-11. -163378, JP-A-11-214730, JP-A-11-214731, JP-A-11-238905, JP-A2000-26487, European Patents 892411, 911841, and 991092 It is a pigment. Specific examples of preferable methine dyes are shown below.
[0038]
[Chemical formula 5]
[0039]
(4) Adsorption of dye to semiconductor fine particles
In order to adsorb the dye to the semiconductor fine particles, a method of immersing a conductive support having a well-dried semiconductor fine particle layer in a dye solution or coating the dye fine solution on the semiconductor fine particle layer can be used. In the former case, an immersion method, a dip method, a roller method, an air knife method or the like can be used. In the case of the immersion method, the adsorption of the dye may be performed at room temperature or may be performed by heating and refluxing as described in JP-A-7-249790. Examples of the latter application method include a wire bar method, a slide hopper method, an extrusion method, a curtain method, a spin method, and a spray method. Preferred solvents for dissolving the dye include, for example, alcohols (methanol, ethanol, t-butanol, benzyl alcohol, etc.), nitriles (acetonitrile, propionitrile, 3-methoxypropionitrile, etc.), nitromethane, halogenated compounds, etc. Hydrocarbon (dichloromethane, dichloroethane, chloroform, chlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, etc.), dimethyl sulfoxide, amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), N-methyl Pyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, esters (ethyl acetate, butyl acetate, etc.), carbonates (diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), ketones (acetone, 2-butanone) , Cyclohexanone, etc.), Examples include hydrocarbons (hexane, petroleum ether, benzene, toluene, etc.) and mixed solvents thereof.
[0040]
The total amount of dye adsorbed is the unit surface area of porous semiconductor electrode substrate (1m2) Is preferably from 0.01 to 100 mmol. The amount of the dye adsorbed on the semiconductor fine particles is preferably in the range of 0.01 to 1 mmol per 1 g of the semiconductor fine particles. By using such an amount of dye adsorbed, a sensitizing effect in a semiconductor can be sufficiently obtained. On the other hand, if the amount of the dye is too small, the sensitizing effect becomes insufficient, and if the amount of the dye is too large, the dye not attached to the semiconductor floats, which causes a reduction in the sensitizing effect. In order to increase the adsorption amount of the dye, it is preferable to perform a heat treatment before the adsorption. In order to avoid water adsorbing on the surface of the semiconductor fine particles after the heat treatment, it is preferable to quickly perform the dye adsorption operation at a temperature of the semiconductor electrode substrate of 60 to 150 ° C. without returning to normal temperature. Further, for the purpose of reducing the interaction such as aggregation between the dyes, a colorless compound may be added to the dyes and co-adsorbed on the semiconductor fine particles. Compounds effective for this purpose are compounds having surface active properties and structures, and examples thereof include steroid compounds having a carboxyl group (for example, chenodeoxycholic acid) and sulfonates such as the following examples.
[0041]
[Chemical 6]
[0042]
(C) Charge transport layer
The charge transport layer is a layer containing a charge transport material having a function of replenishing electrons to the oxidant of the dye. Examples of typical charge transport materials that can be used in the present invention include: (i) a solution (electrolyte) in which redox pair ions are dissolved as an ion transport material; So-called gel electrolytes impregnated in the above, molten salt electrolytes containing redox counterions, and solid electrolytes. In addition to charge transport materials that involve ions, (ii) electron transport materials and hole transport materials can also be used as charge transport materials that involve carrier movement in solids. These charge transport materials can be used in combination.
[0043]
(1) Molten salt electrolyte
The molten salt electrolyte is particularly preferable from the viewpoint of achieving both photoelectric conversion efficiency and durability. The molten salt electrolyte is an electrolyte that is liquid at room temperature or has a low melting point. For example, WO95 / 18456, JP-A-8-259543, Electrochemistry, Vol. 65, No. 11, p. 923 (1997) And the like, known electrolytes such as pyridinium salts, imidazolium salts, and triazolium salts described in the above. A molten salt that becomes liquid at 100 ° C. or lower, particularly near room temperature, is preferred.
[0044]
Examples of the molten salt that can be preferably used include those represented by any of the following general formulas (Y-a), (Y-b), and (Y-c).
[0045]
[Chemical 7]
[0046]
Q in general formula (Y-a)y1Represents an atomic group capable of forming a 5- or 6-membered aromatic cation with a nitrogen atom. Qy1Is preferably composed of at least one atom selected from the group consisting of carbon atom, hydrogen atom, nitrogen atom, oxygen atom and sulfur atom. Qy1The 5-membered ring formed by is preferably an oxazole ring, thiazole ring, imidazole ring, pyrazole ring, isoxazole ring, thiadiazole ring, oxadiazole ring, triazole ring, indole ring or pyrrole ring, A thiazole ring or an imidazole ring is more preferable, and an oxazole ring or an imidazole ring is particularly preferable. Qy1The 6-membered ring formed by is preferably a pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring or triazine ring, and more preferably a pyridine ring.
[0047]
In general formula (Y-b), Ay1Represents a nitrogen atom or a phosphorus atom.
[0048]
R in general formulas (Y-a), (Y-b) and (Y-c)y1~ Ry6Each independently represents a substituted or unsubstituted alkyl group (preferably having 1 to 24 carbon atoms, which may be linear or branched or cyclic, such as a methyl group or an ethyl group Propyl group, isopropyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, t-octyl group, decyl group, dodecyl group, tetradecyl group, 2-hexyldecyl group, octadecyl group, cyclohexyl group, cyclopentyl group, etc. ), Or a substituted or unsubstituted alkenyl group (preferably having 2 to 24 carbon atoms, which may be linear or branched, such as vinyl group, allyl group, etc.), more preferably carbon An alkyl group having 2 to 18 atoms or an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkyl group having 2 to 6 carbon atoms is particularly preferable.
[0049]
In addition, R in the general formula (Y-b)y1~ Ry4Two or more of them connected to each othery1May form a non-aromatic ring containing R in the general formula (Y-c)y1~ Ry6Two or more of them may be connected to each other to form a ring structure.
Q in general formulas (Y-a), (Y-b) and (Y-c)y1And Ry1~ Ry6May have a substituent, and examples of preferable substituents include halogen atoms (F, Cl, Br, I, etc.), cyano groups, alkoxy groups (methoxy group, ethoxy group, methoxyethoxy group, methoxyethoxy group). Ethoxy groups, etc.), aryloxy groups (phenoxy groups, etc.), alkylthio groups (methylthio groups, ethylthio groups, etc.), alkoxycarbonyl groups (ethoxycarbonyl groups, etc.), carbonate groups (ethoxycarbonyloxy groups, etc.), acyl groups (acetyl groups) , Propionyl group, benzoyl group, etc.), sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), acyloxy group (acetoxy group, benzoyloxy group, etc.), sulfonyloxy group (methanesulfonyloxy group, toluenesulfonyloxy group, etc.), Phosphonyl group (such as diethylphosphonyl group), amide group (a Tilamino group, benzoylamino group, etc.), carbamoyl group (N, N-dimethylcarbamoyl group, etc.), alkyl group (methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, 2-carboxyethyl group, Benzyl group etc.), aryl group (phenyl group, toluyl group etc.), heterocyclic group (pyridyl group, imidazolyl group, furanyl group etc.), alkenyl group (vinyl group, 1-propenyl group etc.), silyl group, silyloxy group etc. Is mentioned.
The compound represented by the general formula (Y-a), (Y-b) or (Y-c) is Qy1Or Ry1~ Ry6A multimer may be formed via
[0050]
These molten salts may be used singly or as a mixture of two or more, and may be used in combination with a molten salt in which the iodine anion is replaced with another anion. Anions that replace iodine anions include halide ions (Cl-, Br-Etc.), SCN-, BFFour -, PF6 -, ClOFour -, (CFThreeSO2)2N-, (CFThreeCF2SO2)2N-, CHThreeSOThree -, CFThreeSOThree -, CFThreeCOO-, PhFourB-, (CFThreeSO2)ThreeC-Etc. are mentioned as preferred examples, such as SCN.-, CFThreeSOThree -, CFThreeCOO-, (CFThreeSO2)2N-Or BFFour -It is more preferable that Also, other iodine salts such as LiI and CFThreeCOOLi, CFThreeAlkali metal salts such as COONa, LiSCN and NaSCN can also be added. The addition amount of the alkali metal salt is preferably about 0.02 to 2% by mass, and more preferably 0.1 to 1% by mass.
[0051]
Specific examples of the molten salt preferably used in the present invention are listed below, but are not limited thereto.
[0052]
[Chemical 8]
[0053]
[Chemical 9]
[0054]
[Chemical Formula 10]
[0055]
Embedded image
[0056]
Embedded image
[0057]
Embedded image
[0058]
The molten salt electrolyte is preferably in a molten state at room temperature, and preferably does not use a solvent. Although the solvent described later may be added, the content of the molten salt is preferably 50% by mass or more, and particularly preferably 90% by mass or more with respect to the entire electrolyte composition. Moreover, it is preferable that 50 mass% or more is an iodine salt among salts.
[0059]
It is preferable to add iodine to the electrolyte composition. In this case, the content of iodine is preferably 0.1 to 20% by mass, and 0.5 to 5% by mass with respect to the entire electrolyte composition. More preferred.
[0060]
(2) Electrolyte
When an electrolytic solution is used for the charge transport layer, the electrolytic solution is preferably composed of an electrolyte, a solvent, and an additive. The electrolyte of the present invention is I2And iodide (as iodide, LiI, NaI, KI, CsI, CaI2 Metal iodides such as tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide and the like quaternary ammonium compounds such as iodine salts), Br2And bromide combinations (LiBr, NaBr, KBr, CsBr, CaBr as bromides)2 Metal bromide such as tetraalkylammonium bromide, pyridinium bromide, bromide salts of quaternary ammonium compounds), metal complexes such as ferrocyanate-ferricyanate and ferrocene-ferricinium ions, sodium polysulfide, Sulfur compounds such as alkylthiol-alkyldisulfides, viologen dyes, hydroquinone-quinones, and the like can be used. I among them2An electrolyte that combines an iodine salt of a quaternary ammonium compound such as LiI, pyridinium iodide, and imidazolium iodide is preferable. The electrolytes described above may be used in combination.
The preferable concentration of the electrolyte is 0.1M to 10M, more preferably 0.2M to 4M. In addition, when iodine is added to the electrolytic solution, a preferable iodine concentration is 0.01M to 0.5M.
[0061]
The solvent used for the electrolyte is desirably a compound having a low viscosity and improving ion mobility, or having a high dielectric constant and an effective carrier concentration, thereby exhibiting excellent ion conductivity. Examples of the solvent include carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, ether compounds such as dioxane and diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, and polyethylene. Chain ethers such as glycol dialkyl ether and polypropylene glycol dialkyl ether, alcohols such as methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, ethylene glycol, Propylene glycol, polyethylene glycol, polyp Examples include polyhydric alcohols such as pyrene glycol and glycerin, nitrile compounds such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, and benzonitrile, aprotic polar substances such as dimethyl sulfoxide and sulfolane, and water. These can also be mixed and used.
[0062]
Further, in the present invention, tert-butylpyridine as described in Journal of American Ceramic Society (J. Am. Ceram. Soc.), Vol. 80 (12) No. 3157-3171 (1997). In addition, it is preferable to add a basic compound such as 2-picoline or 2,6-lutidine to the aforementioned molten salt electrolyte or electrolytic solution. When adding a basic compound, a preferable concentration range is 0.05M to 2M.
[0063]
(3) Gel electrolyte
In the present invention, the electrolyte is used by gelling (solidifying) the above-mentioned molten salt electrolyte or electrolyte by a technique such as addition of a polymer, addition of an oil gelling agent, polymerization including polyfunctional monomers, or a crosslinking reaction of the polymer. You can also In the case of gelation by adding a polymer, the compounds described in “Polymer Electrolyte Revi ews-1 and 2” (JR MacCallum and CA Vincent, edited by ELSEVIER APPLIED SCIENCE) can be used. In particular, polyacrylonitrile and polyvinylidene fluoride can be preferably used. In the case of gelation by adding an oil gelling agent, published by Chemical Society of Japan, Journal of Industrial Chemistry (J. Chem Soc. Japan, Ind. Chem. Sec.), 46, 779 (1943), Journal of American Chemical Society (J. Am. Chem. Soc.), 111, 5542 (1989), J. Chem. Soc., Chem. Commun., (1993), 390, Angew. Chem., 35, 1949 (1996), Chem. Lett., (1996), p. 885, J. Chm. Soc., Chem. Commun., (1997), p. 545 can be used, but preferred compounds Is a compound having an amide structure in the molecular structure. An example of gelling the electrolytic solution is described in JP-A-11-185863, and an example of gelling the molten salt electrolyte is described in JP-A-2000-58140, which can also be applied to the present invention.
[0064]
Further, when the electrolyte is gelled by a polymer crosslinking reaction, it is desirable to use a polymer containing a crosslinkable reactive group and a crosslinking agent in combination. In this case, preferred crosslinkable reactive groups include amino groups and nitrogen-containing heterocyclic groups (for example, pyridine ring, imidazole ring, thiazole ring, oxazole ring, triazole ring, morpholine ring, piperidine ring, piperazine ring and the like as a skeleton). The preferred cross-linking agent is a bifunctional or higher reagent capable of electrophilic reaction with a nitrogen atom (for example, alkyl halides, halogenated aralkyls, sulfonate esters, acid anhydrides, acids Chlorides, isocyanate compounds, α, β-unsaturated sulfonyl group-containing compounds, α, β-unsaturated carbonyl group-containing compounds, α, β-unsaturated nitrile group-containing compounds, and the like. The cross-linking technique described in the publications of 2000-86724 can also be applied.
[0065]
(4) Hole transport material
In the present invention, instead of an ion conductive electrolyte such as a molten salt, a solid hole transport material that is organic or inorganic or a combination of both can be used.
(A) Organic hole transport material
As an organic hole transporting material applicable to the present invention, J. Hagen et al., Synthetic Metal 89 (1997) 215-220, Nature, Vol. 395, 8 Oct., (1998), 583-585 and WO97 / 10617, JP 59-194393, JP 5-234681, U.S. Pat.No. 4,923,774, JP 4-308688, U.S. Pat. 764,625, JP-A-3-269084, JP-A-4-129271, JP-A-4-175395, JP-A-4-264189, JP-A-4-290851, JP-A-4-364153 No. 5, No. 5-25473, No. 5-239455, No. 5-320634, No. 6-1972, No. 7-138562, No. 7-252474, Special Aromatic amines described in each publication of Kaihei 11-144773 and triphenylene derivatives described in each publication of JP-A-11-149821, JP-A-11-148067, JP-A-11-176489, etc. are preferably used. be able to. Adv. Mater. (1997), 9, N0.7, 557, Angew. Chem. (1995), 34, No. 3, 303-307, American Chemical Society (J. Am. Chem) Soc.), 120, N0.4, (1998), pages 664-672, etc., oligothiophene compounds, K. Murakoshi Oka ,; Chem. Lett. (1997), page 471, polypyrrole Polyacetylene and its derivatives described in “Handbook of Organic Conductive Molecules and Polymers, Volumes 1,2,3,4” (by NALWA, published by WILEY), poly (p-phenylene) and its derivatives, poly (p- Conductive polymers such as (phenylene vinylene) and derivatives thereof, polythienylene vinylene and derivatives thereof, polythiophene and derivatives thereof, polyaniline and derivatives thereof, polytoluidine and derivatives thereof can be preferably used.
[0066]
Hole transport materials include Tris (4-bromophenyl) for controlling the dopant concentration level as described in Nature, Vol. 395, (1998, 8 Oct.), pages 583-585. Li [(CF to add compounds containing cation radicals such as aminium hexachloroantimonate or to control the potential of oxide semiconductor surfaces (space charge layer compensation)3SO2)2A salt such as N] may be added.
[0067]
(B) Inorganic hole transport material
A p-type inorganic compound semiconductor can be used as the inorganic hole transport material. The p-type inorganic compound semiconductor for this purpose preferably has a band gap of 2 eV or more, and more preferably 2.5 eV or more. Also, the ionization potential of the p-type inorganic compound semiconductor needs to be smaller than the ionization potential of the dye-adsorbing electrode from the condition that the holes of the dye can be reduced. Although the preferable range of the ionization potential of the p-type inorganic compound semiconductor varies depending on the dye used, it is generally preferably 4.5 eV to 5.5 eV, and more preferably 4.7 eV to 5.3 eV. Preferred p-type inorganic compound semiconductors are compound semiconductors containing monovalent copper. Examples of compound semiconductors containing monovalent copper include CuI, CuSCN, and CuInSe.2, Cu (In, Ga) Se2, CuGaSe2, Cu2O, CuS, CuGaS2, CuInS2, CuAlSe2Etc. Among these, CuI and CuSCN are preferable, and CuI is most preferable. Other p-type inorganic compound semiconductors include GaP, NiO, CoO, FeO, and Bi.2OThree, MoO2, Cr2OThreeEtc. can be used.
[0068]
(D) Counter electrode
Similar to the conductive support described above, the counter electrode may have a single-layer structure of a counter electrode conductive layer made of a conductive material, or may be composed of a counter electrode conductive layer and a support substrate. As a conductive material used for the counter electrode conductive layer, metal (for example, platinum, gold, silver, copper, aluminum, magnesium, indium, etc.), carbon, or conductive metal oxide (indium-tin composite oxide, fluorine-doped tin oxide, Etc.). Among these, platinum, gold, silver, copper, aluminum, and magnesium can be preferably used as the counter electrode layer. An example of a preferable supporting substrate for the counter electrode is glass or plastic, and the above-described conductive agent is applied or vapor-deposited on the glass or plastic. The thickness of the counter electrode conductive layer is not particularly limited, but is preferably 3 nm to 10 μm. The lower the surface resistance of the counter electrode layer, the better. The range of the surface resistance is preferably 50Ω / □ or less, more preferably 20Ω / □ or less.
[0069]
Since light may be irradiated from either or both of the conductive support and the counter electrode, in order for light to reach the photosensitive layer, it is sufficient that at least one of the conductive support and the counter electrode is substantially transparent. . From the viewpoint of improving the power generation efficiency, it is preferable to make the conductive support transparent so that light is incident from the conductive support side. In this case, the counter electrode preferably has a property of reflecting light. As such a counter electrode, glass or plastic on which a metal or a conductive oxide is deposited, or a metal thin film can be used.
[0070]
The counter electrode may be formed by directly applying, plating or vapor-depositing (PVD, CVD) a conductive material on the charge transport layer, or attaching the conductive layer side of the substrate having the conductive layer. Further, as in the case of the conductive support, it is preferable to use a metal lead for the purpose of reducing the resistance of the counter electrode, particularly when the counter electrode is transparent. The preferable metal lead material and installation method, the reduction in the amount of incident light due to the metal lead installation, and the like are the same as those for the conductive support.
[0071]
(E) Other layers
In order to prevent a short circuit between the counter electrode and the conductive support, it is preferable to coat a dense semiconductor thin film layer as an undercoat layer between the conductive support and the photosensitive layer in advance. This is particularly effective when a hole transport material is used. Preferred as an undercoat layer is TiO2, SnO2, Fe2OThree, WOThree, ZnO, Nb2OFiveAnd more preferably TiO2It is. The undercoat layer can be applied by, for example, a sputtering method in addition to the spray pyrolysis method described in Electrochim. Acta 40, 643-652 (1995). The preferred thickness of the undercoat layer is 5 to 1000 nm, and more preferably 10 to 500 nm.
Further, a functional layer such as a protective layer or an antireflection layer may be provided on the outer surface of one or both of the conductive support and the counter electrode acting as an electrode, between the conductive layer and the substrate, or in the middle of the substrate. For forming these functional layers, a coating method, a vapor deposition method, a bonding method, or the like can be used depending on the material.
[0072]
(F) Specific example of internal structure of photoelectric conversion element
As described above, the internal structure of the photoelectric conversion element can take various forms depending on the purpose. If roughly divided into two, a structure that allows light to enter from both sides and a structure that allows only one side are possible. 2 to 9 illustrate some of the internal structures of photoelectric conversion elements that can be preferably applied to the present invention as partial cross-sectional views.
In the embodiment shown in FIG. 2, the photosensitive layer 20 including the electrodeposition layer and the charge transport layer 30 are interposed between the transparent conductive layer 10a and the transparent counter electrode conductive layer 40a. It has an incident structure. In the embodiment shown in FIG. 3, the metal lead 11 is partially provided on the transparent substrate 50a, the transparent conductive layer 10a is further provided, and the undercoat layer 60, the photosensitive layer 20, the charge transport layer 30 and the counter electrode conductive layer 40 are arranged in this order. Further, a support substrate 50 is disposed, and light is incident from the conductive layer side. The embodiment shown in FIG. 4 further includes a conductive layer 10 on a support substrate 50, a photosensitive layer 20 provided via an undercoat layer 60, a charge transport layer 30 and a transparent counter electrode conductive layer 40a, A transparent substrate 50a provided with a metal lead 11 is arranged with the metal lead 11 side inward, and light is incident from the counter electrode side. In the embodiment shown in FIG. 5, an undercoat layer 60, a photosensitive layer 20, and a charge transport layer are provided between a pair of metal leads 11 provided on a transparent substrate 50a and further provided with a transparent conductive layer 10a (or 40a). 30 is interposed, and light is incident from both sides. In the embodiment shown in FIG. 6, a transparent conductive layer 10a, an undercoat layer 60, a photosensitive layer 20, a charge transport layer 30 and a counter electrode conductive layer 40 are provided on a transparent substrate 50a, and a support substrate 50 is disposed thereon. In this structure, light enters from the conductive layer side. In the embodiment shown in FIG. 7, the conductive layer 10 is provided on the support substrate 50, the photosensitive layer 20 is provided through the undercoat layer 60, the charge transport layer 30 and the transparent counter electrode conductive layer 40a are provided, and the transparent layer is provided thereon. The substrate 50a is disposed, and light is incident from the counter electrode side. In the embodiment shown in FIG. 8, the transparent conductive layer 10a is provided on the transparent substrate 50a, the photosensitive layer 20 is provided via the undercoat layer 60, and the charge transport layer 30 and the transparent counter electrode conductive layer 40a are provided thereon. A transparent substrate 50a is disposed, and light is incident from both sides. In the embodiment shown in FIG. 9, the conductive layer 10 is provided on the support substrate 50, the photosensitive layer 20 is provided via the undercoat layer 60, and the solid charge transport layer 30 is further provided. Alternatively, it has a metal lead 11 and has a structure in which light enters from the counter electrode side.
[0073]
[2] Photocell
The photovoltaic cell of the present invention is one in which the photoelectric conversion element is made to work with an external load.
Of the photovoltaic cells, the case where the charge transport material is mainly composed of an ion transport material is particularly called a photoelectrochemical cell, and the case where the main purpose is power generation by sunlight is called a solar cell. In order to prevent deterioration of components and volatilization of the contents of the photovoltaic cell, it is preferable to seal the side surface with a polymer or an adhesive. The external circuit itself connected to the conductive support and the counter electrode via a lead may be a known one. When the photoelectric conversion element of the present invention is applied to a solar cell, the structure inside the cell is basically the same as the structure of the photoelectric conversion element described above. Moreover, the dye-sensitized solar cell of the present invention can basically have the same module structure as a conventional solar cell module. The solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin or protective glass, and light is taken in from the opposite side of the support substrate. It is also possible to use a transparent material such as tempered glass for the support substrate, configure a cell thereon, and take in light from the transparent support substrate side. Specifically, a module structure called a super straight type, a substrate type, a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known, and the dye-sensitized solar cell of the present invention is also used. These module structures can be appropriately selected depending on the place of use and the environment. Specifically, the structure and aspect described in Japanese Patent Application No. 11-8457 are preferable.
[0074]
[Example 1]
Hereinafter, the present invention will be specifically described by way of examples.
In this example, a transparent sheet type photovoltaic cell having the layer structure of FIG. 4 was assembled by the following procedure.
1. Production of transparent conductive support
A 1.9mm-thick alkali-free glass substrate is uniformly coated with fluorine-doped tin dioxide by CVD, with a thickness of 600nm, surface resistance of about 15Ω / □, and light transmittance (500nm) of 85%. A transparent conductive support having a conductive tin dioxide film coated on one side was formed.
[0075]
2. Preparation of semiconductor fine particles
Five types of particle samples of semiconductor fine particles A to E were prepared as follows.
(i) Particle A
C. J. Barbe et al. Am. Ceramic Soc. In accordance with the production method described in the 80th volume, page 3157, titanium tetraisopropoxide was used as the titanium raw material, the temperature of the polymerization reaction in the autoclave was set to 230 ° C., and the anatase type dioxide having a titanium dioxide concentration of 11% by weight. A titanium dispersion was synthesized. The primary particle size of the obtained titanium dioxide particles was 10 to 30 nm. The obtained dispersion was applied to an ultracentrifuge to separate the particles, and the aggregate was pulverized in an agate mortar to obtain a powder.
(ii) Particle B
P-25 manufactured by Nippon Aerosil Co., Ltd. was used. Primary particle size 20nm made by firing method in gas phase, specific surface area 50m determined by BET method2/ g, titanium oxide with anatase content of 77% (TiO2) Particles.
[0076]
(iii) Particle C
Anatase-type titanium oxide (TiO) manufactured by Aldrich2)It was used. High whiteness particles having a particle size distribution of 0.1 to 3 μm and anatase content of 99%.
(iv) Particle D
Average particle size 35 μm (by BET method), specific surface area determined by BET method 30 m2/ g, zinc oxide (ZnO) particles synthesized by a vapor phase method comprising hexagonal polyhedrons.
(V) Particle E
Average particle size 15 μm (by BET method), specific surface area determined by BET method 70 m2  / g., tetragonal tin oxide (SnO) synthesized by the vapor phase method2) Particles.
[0077]
3. Fabrication of semiconductor fine particle layer (electrodeposition)
The five types of fine particles obtained in 2 above were dispersed in a dry mixed solvent of acetonitrile and tert-butanol (1: 1) at an addition amount of 0.035 g / mL to obtain a white dispersion. Originally, the mixture was stirred with ultrasonic waves for 5 minutes. The temperature rise due to ultrasonic stirring was small and thus was not particularly controlled. Two sheets of the above tin oxide transparent conductive support were prepared as an electrodeposition substrate electrode and an electrodeposition counter electrode, and both were made to face the conductive layer side using a 0.3 mm thick Teflon film frame. The semiconductor fine particle dispersion was poured into the gap between the two electrodes and allowed to stand, and the following voltage was applied between the electrodes using a DC power source to perform electrodeposition.
[0078]
[0079]
The obtained electrodeposition layer was dried at room temperature for 30 minutes and then heated in dry air at 120 ° C. The yield by electrodeposition (electrodeposited particles / total particles) was approximately 100% for particles A, B, and C, but particles D and E were unstable in the range of 70 to 90%.
The particle loading of the electrodeposition layer thus obtained was as follows: Substrate A: 9.9 g / m for Substrate A to E carrying Particles A to E, respectively.2Substrate B: 10.0 g / m2Substrate C: 9.8 g / m2Substrate D: 8.0 g / m2Substrate E: 8.2 g / m2It became. The average film thickness of the electrodeposition layer was as follows: substrate A: 7 μm, substrate B: 8 μm, substrate C: 9 μm, substrate D: 6 μm, substrate E: 5.5 μm.
A part of the electrodeposition substrate was further exposed to UV light from a 100 W mercury lamp ultraviolet light source at 150 ° C. for 1 hour for post-treatment.
[0080]
4). Preparation of dye adsorption solution
As a sensitizing dye having absorption up to 750 nm on the long wavelength side and having an absorption peak in the blue to green region, the Ru complex dye (Dye R-1) of the above-mentioned specific example was dried with acetonitrile: t-butanol: ethanol (2 : 3: 1 concentration in mixed solvent of 1: 1)-FourDissolved in mol / liter. As an additive to this dye solution, p-C9H19-C6HFour-O- (CH2CH2-O)Three-(CH2) 4-SOThreeAn organic sulfonic acid derivative having a Na structure was dissolved to a concentration of 0.025 mol / liter to prepare a dye adsorption solution.
[0081]
5. Dye adsorption
The semiconductor fine particle electrodeposition substrates A to E were immersed in the adsorption dye solution and allowed to stand at 40 ° C. for 3 hours with stirring. After the dye was adsorbed on the fine electrodeposition layer in this way, the electrode was washed with acetonitrile to prepare a dye-sensitized electrode used for the photosensitive layer.
[0082]
6). Production of photoelectrochemical cell
The electrodeposition layer of the dye-sensitized semiconductor electrode is scraped off leaving a circular portion having a diameter of about 1.1 cm, and a light receiving area of 1.0 cm2A circular light-receiving layer having a diameter of about 1.1 cm was formed. A counter-plated platinum-deposited glass substrate is superimposed on this electrode by inserting a thermo-compressible polyethylene film frame spacer (thickness 20 μm), and the spacer portion is heated to 120 ° C. to pressure-bond both substrates. . Furthermore, the edge part of the cell was sealed with an epoxy resin adhesive. Room temperature molten salt composed of Y6-2 / Y9-1 / iodine = 15: 35: 1 (weight ratio) as electrolyte through a small hole for electrolyte injection provided in the corner of the counter electrode substrate in advance The space between the electrodes was soaked from the small holes of the substrate using capillary action. The above cell assembling step and electrolyte solution injection step were all performed in the above-described dry air at a dew point of −60 ° C. After injecting the molten salt, the cell was sucked for several hours under vacuum to deaerate the inside of the cell, such as a porous semiconductor electrode and molten salt, and finally the small holes were sealed with low-melting glass.
In the same manner, the transparent photoelectric conversion element of the present invention is produced using a long-wavelength dye R-10 having absorption in the visible region up to 900 nm as the sensitizing dye instead of R-1 used in the above examples. did.
[0083]
7). Measurement of photoelectric conversion efficiency
A 500 W xenon lamp (USHIO) equipped with a correction filter for sunlight simulation (AM1.5 direct manufactured by Oriel) has an incident light intensity of 100 mW / cm with respect to the photoelectric conversion element.2The simulated sunlight was irradiated from the side of the transparent electrode carrying the semiconductor fine particle electrodeposition layer. The element was fixed in close contact on the stage of a thermostat, and the temperature of the element during irradiation was controlled at 50 ° C.
Using a current-voltage measuring device (Keutley source measure unit 238 type), the DC voltage applied to the element is scanned at a constant speed of 10 mV / second, and the photocurrent output from the element is measured, so that photocurrent-voltage Characteristics were measured. Table 1 shows the photocurrent density (Jsc), open circuit electromotive force (Voc), and energy conversion efficiency (η) of the above-described various elements, together with the contents of the cell components (semiconductor fine particles, sensitizing dyes). It was described in.
In the table, as a comparative experiment, the results of devices manufactured by changing the electrodeposition conditions (electrodeposition voltage, heat treatment after electrodeposition) are also shown.
[0084]
[Table 1]
[0085]
[Table 2]
[0086]
From the results in Table 1, the following is clear.
1) Using the electrodeposited layer of semiconductor fine particles according to the production method of the present invention, energy conversion efficiency suitable for practical use as a solar cell can be obtained without firing the electrode at high temperature.
2) As a condition of the electric field used for electrodeposition, electrodeposition using a low electric field having an absolute value of 50 V / cm or less reduces the amount of electrodeposition on the substrate, resulting in a decrease in performance (particularly Jsc). There is a trend. In addition, in electrodeposition using a high electric field having an absolute value of 300 V / cm or more, although the amount of electrodeposition did not decrease, there was a tendency for performance to decrease. The reason for this is unknown, but it is presumed that the substrate resistance increased due to the electrochemical deterioration of the conductive film of the substrate, and the fill factor (FF) was affected.
3) When the electrodeposition film is subjected to heat treatment, performance is improved, and when the heat treatment and UV light irradiation treatment are performed simultaneously, further performance improvement is observed.
[0087]
[Example 2]
A dye is produced by the same steps and operations as in Example 1 except that the transparent conductive glass support and the platinum-deposited glass (counter electrode) used in Example 1 are used instead of the following plastic transparent conductive sheets. A plastic sheet-type photoelectric conversion cell in which both the sensitized semiconductor working electrode and the counter electrode are made of a plastic substrate was produced.
1. Transparent conductive plastic sheet for working electrode
A flexible substrate made by uniformly coating a thin film of conductive indium tin oxide (ITO) with a thickness of 200 nm on one side of a 0.4 mm thick polyester sheet, with a surface resistance of about 20Ω / □, light transmission A transparent conductive plastic sheet having a rate (500 nm) of 88%.
2. Conductive plastic sheet for the counter electrode
A conductive plastic sheet having a surface resistance of about 5 Ω / □, which is obtained by uniformly coating a platinum film with a thickness of 300 nm on one surface of a polyimide Kapton film having a thickness of 0.4 mm by vacuum sputtering.
[0088]
Table 2 shows the configuration and performance of photoelectrochemical cells assembled using these plastic electrode substrates. Compared to the results using the glass substrate shown in Table 1, as a result of the lower FF due to the higher surface resistance of the ITO / polyester substrate (lower conductivity), the cell using the glass substrate However, it is understood that the photoelectric conversion performance at a practical level is obtained. Moreover, especially these cells have the merit as a flexible cell which provided the softness | flexibility by not using glass.
[0089]
[Table 3]
[0090]
As described above, by using the electrodeposited layer of semiconductor fine particles of the present invention as a photosensitive layer, a dye-sensitized photoelectric conversion element can be produced by an inexpensive means not including a baking step, and also as a solar cell. An element having useful performance can be provided using various substrates including a plastic sheet.
[0091]
【The invention's effect】
According to the present invention, a dye-sensitized photoelectric conversion element and a photoelectrochemical cell excellent in energy conversion efficiency and cost performance can be obtained.
[Brief description of the drawings]
FIG. 1 is a partial cross-sectional view showing the structure of a preferred photoelectric conversion element of the present invention.
FIG. 2 is a partial cross-sectional view illustrating a structure of a photoelectric conversion element according to another embodiment of the present invention.
FIG. 3 is a partial cross-sectional view showing the structure of a photoelectric conversion element according to still another embodiment of the present invention.
FIG. 4 is a partial cross-sectional view showing the structure of a photoelectric conversion element according to still another embodiment of the present invention.
FIG. 5 is a partial cross-sectional view showing the structure of a photoelectric conversion element according to still another embodiment of the present invention.
FIG. 6 is a partial cross-sectional view showing a structure of a photoelectric conversion element according to still another embodiment of the present invention.
FIG. 7 is a partial cross-sectional view showing the structure of a photoelectric conversion element according to still another embodiment of the present invention.
FIG. 8 is a partial cross-sectional view showing the structure of a photoelectric conversion element according to still another embodiment of the present invention.
FIG. 9 is a partial cross-sectional view showing the structure of a photoelectric conversion element according to still another embodiment of the present invention.
[Explanation of symbols]
10 ... conductive layer
10a ・ ・ ・ Transparent conductive layer
11 ... Metal lead
20 ... Photosensitive layer
21 ... Semiconductor fine particles
22 ... Dye
23 ... Charge transport material
30 ... Charge transport layer
40 ... Counterelectrode conductive layer
40a ・ ・ ・ Transparent counter conductive layer
50 ... Board
50a ・ ・ ・ Transparent substrate
60 ... Undercoat layer

Claims (10)

  1. A method for producing a photoelectric conversion element having a laminated structure including a conductive support having a conductive layer, a semiconductor fine particle layer, a charge transport layer, and a counter electrode, wherein the semiconductor fine particles are attached to the conductive layer of the conductive support by electrophoresis A step of forming the semiconductor fine particle layer by heating, and a step of heating the formed semiconductor fine particle layer at 100 ° C. to 250 ° C. under irradiation of light absorbed by the semiconductor fine particles. Device manufacturing method.
  2.   The method for producing a photoelectric conversion element according to claim 1, wherein the electrophoresis is performed using a semiconductor fine particle dispersion containing no electrolyte.
  3.   The method for producing a photoelectric conversion element according to claim 1, wherein the electrophoresis is performed in a direct current electric field, and the strength of the electric field is 50 V / cm or more and 300 V / cm or less.
  4. The conductive support of the electrically conductive layer, a method for manufacturing a photoelectric conversion element according to any one of claims 1 to 3, characterized in that it comprises a tin oxide.
  5. The semiconductor fine particles, titanium oxide, zinc oxide, tin oxide, tungsten oxide, according to claim 1-4, wherein the niobium oxide and a semiconductor selected from combinations of two or more of the complex The manufacturing method of the photoelectric conversion element in any one.
  6. The semiconductor fine particle layer, the manufacturing method of the photoelectric conversion device according to any one of claims 1 to 5, characterized in that it is sensitized with dyes.
  7. The method of producing a photoelectric conversion element according to any one of claims 1 to 6 wherein said charge transfer layer is characterized in that it comprises a molten salt electrolyte.
  8. Wherein the conductive support is a method for manufacturing a photoelectric conversion element according to any one of claims 1 to 7, characterized in that a plastic support having a conductive layer.
  9. The photoelectric conversion element manufactured by the manufacturing method in any one of Claims 1-8 .
  10. A photovoltaic cell using the photoelectric conversion element according to claim 9 .
JP2000285461A 2000-09-20 2000-09-20 Photoelectric conversion element and photovoltaic cell Expired - Fee Related JP4500420B2 (en)

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JP4842025B2 (en) 2006-06-19 2011-12-21 日揮触媒化成株式会社 Method for forming metal oxide fine particle layer on conductive substrate
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