JP2014172961A - Phthalocyanine dye, dye-sensitized solar cell and photo electric conversion element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel dye having a wide range of absorption wavelength in a near-infrared region and good photoelectric conversion efficiency, and a photoelectric conversion element and a dye-sensitized solar cell using the same.SOLUTION: Provided is a phthalocyanine dye represented by the following formula (1) having a phthalocyanine ring structure with a carboxyl group and a trisiloxane structure inside the ring in a form of an axial ligand, and also provided are a photoelectric conversion element and a dye-sensitized solar cell using the same for a dye-absorbed semiconductor layer. In the formula (1), R, R, and Reach independently represent an alkyl group.

Description

  The present invention relates to a phthalocyanine dye suitable for a photoelectric conversion element, a photoelectric conversion element using these alone or in combination with another dye, and a dye-sensitized solar cell.

  Photoelectric conversion elements are used in photovoltaic devices such as optical sensors and solar cells. A photoelectric conversion element using semiconductor fine particles sensitized with a dye is known from Patent Document 1 and the like.

  As a solar cell, a solar cell using a monocrystalline, polycrystalline, or amorphous silicon semiconductor is widely used for electrical products such as a calculator or for a house. However, since high-precision processes such as plasma CVD and high-temperature crystal growth processes are used for manufacturing solar cells using such silicon semiconductors, they require a lot of energy and are expensive, requiring a vacuum. Manufacturing costs are high due to the need for equipment.

  Therefore, as a solar cell that can be manufactured at a low cost, for example, a dye-sensitized solar cell using a material in which a photosensitizing dye such as a ruthenium metal complex is adsorbed on an oxide semiconductor such as titanium oxide has been proposed. Yes. Specifically, the dye-sensitized solar cell is made of, for example, a ruthenium complex on the transparent conductive layer side of a transparent insulating material such as a transparent glass plate or a transparent resin plate provided with a transparent conductive layer such as indium-added tin oxide. An electrolyte between a negative electrode formed with titanium oxide or the like having a dye adsorbed on its surface as a semiconductor layer and a transparent insulating material such as a transparent glass plate or a transparent resin plate provided with a metal layer or conductive layer such as platinum as a positive electrode There is something that encloses the liquid. When the dye-sensitized solar cell is irradiated with light, the electrons of the dye that absorbed the light are excited in the negative electrode, the excited electrons move to the semiconductor layer, and are further guided to the transparent electrode, and from the conductive layer in the positive electrode The electrolyte is reduced by electrons. The reduced electrolyte is oxidized by transferring electrons to the dye, and it is believed that the dye-sensitized solar cell generates electricity during this cycle.

  Currently, dye-sensitized solar cells have lower power generation energy efficiency with respect to irradiation light energy than silicon solar cells, and increasing the efficiency is an important issue in producing effective dye-sensitized solar cells. ing. The efficiency of the dye-sensitized solar cell is considered to be influenced by the characteristics of each element constituting the dye-sensitized solar cell and the combination of these elements, and various attempts have been made. In particular, with regard to dyes having a photosensitizing action, efforts are being made to develop more efficient sensitizing dyes. As a currently known high-efficiency dye, there is a Ru dye exhibiting high performance in the visible light region such as N719. Although these dyes have high photoelectric conversion efficiency in the visible light region, the photoelectric conversion efficiency in the near infrared region is low, and development of a dye having an absorption band near the near infrared region is desired.

  Regarding organic dyes for photoelectric conversion elements having an absorption band in the vicinity of the near infrared region, several compounds are known in Patent Documents 1 to 3, Non-Patent Document 1, and the like. Also, phthalocyanine dyes are known in these documents. However, phthalocyanine dyes do not exhibit sufficient conversion efficiency due to an association phenomenon that occurs strongly between the dyes and a decrease in power generation performance resulting from rapid deactivation from the excited state.

  Non-Patent Documents 2 and 3 disclose a phthalocyanine dye that suppresses an association phenomenon between dyes, but the deactivation rate from an excited state is not improved, so that sufficient conversion efficiency is not expressed, There is a need for further improvements.

  In order to provide a phthalocyanine dye suitable for a photoelectric conversion element and a dye-sensitized solar cell, it is necessary to design a molecule so as to achieve both suppression of an association phenomenon between phthalocyanine dyes and suppression of deactivation from an excited state. However, although many structures of phthalocyanine compounds are disclosed in the prior literature, the fact that none of the structures exhibits sufficient conversion efficiency indicates the difficulty in molecular design.

Japanese Patent Application Laid-Open No. 11-74003 JP 2003-123863 A JP 2011-60669 A

S. Mori et al, J.A. Am. Chem. Soc. 132, 4054-4055 (2010) N. Kobayashi et al. Am. Chem. Soc. 133, 19642-19645 (2011) B. Lim et al, Organic Letters, 15, 4, 784-787 (2013).

  The present invention has been made in view of the above problems, and provides a novel dye having a wide absorption wavelength range in the near infrared region and good photoelectric conversion efficiency, and a photoelectric conversion element and dye sensitization using the same. An object is to provide a solar cell.

式（１）において、Ｒ₁，Ｒ₂,Ｒ₃はアルキル基を表す。 The present invention is a phthalocyanine dye represented by the following formula (1).

In the formula (1), R ₁ , R ₂ and R ₃ represent an alkyl group.

  The present invention is also a photoelectric conversion element using a dye, wherein the dye is the phthalocyanine dye. The present invention also provides a photoelectric conversion element using a dye having an absorption region different from that of the phthalocyanine dye, in addition to the phthalocyanine dye.

  Moreover, this invention is the dye-sensitized solar cell comprised using the said photoelectric conversion element.

  The phthalocyanine dye of the present invention has a structure having a bulky axial ligand containing a silicon atom covalently or coordinately bonded to a phthalocyanine skeleton. Since this bulky axial ligand spreads so as to cover the phthalocyanine skeleton, the association state of the phthalocyanine dye can be prevented. Further, deactivation from the excited state can be suppressed, and the excitation life can be extended. This is presumably because the carboxyl group is directly covalently bonded to the phthalocyanine skeleton. Therefore, the photoelectric conversion element using the phthalocyanine dye of the present invention and the dye-sensitized solar cell configured using the same have high photoelectric conversion efficiency particularly in the near infrared light region.

It is sectional drawing which shows an example of a dye-sensitized solar cell. 3 is an IR spectrum of phthalocyanine dye D-1 of the present invention. 2 is a 1H-NMR spectrum of phthalocyanine dye D-1 of the present invention.

  The photoelectric conversion element or the dye-sensitized solar cell of the present invention contains a phthalocyanine dye represented by the above formula (1) as a sensitizing dye. In addition, since a dye-sensitized solar cell utilizes a photoelectric conversion element, since both description is common, a common description is demonstrated on behalf of a dye-sensitized solar cell.

In formula (1), R ₁ , R ₂ , and R ₃ independently represent an alkyl group, preferably containing 3 or more carbon atoms, more preferably 3 to 30 carbon atoms, and more preferably 4 to 10 carbon atoms. More preferably. Then, the sum of carbon atoms of R ^1, R ^2, R ³ is preferably 10 to 30 range. The alkyl group may be linear or branched, but is preferably linear.

  The phthalocyanine dye represented by the formula (1) can be synthesized according to the following scheme as an example.

  4-tert-butyl-1,2-dicyanobenzene (A-1), ethyl 3,4-dicyanobenzoate (A-2), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) Reflux in pentanol. Add methanol and stir vigorously with a glass rod to obtain intermediate (A-3). The ester group of A-3 is considered to have a structure in which a part of the ethyl ester group derived from the raw material A-2 is converted to a pentyl ester group by transesterification with pentanol used as a solvent. A-3 is a structure in which a tert-butyl group is bonded to the phthalocyanine skeleton at the β1, β3, and β5 positions, a structure that is bonded to the β1, β4, and β5 positions, and the β1, β3, and β6 positions. , Β1, β4, β6, β2, β3, β5, β2, β4, β5, β2, β3, β6 It is considered that this is a mixture of a structure bonded to, a structure bonded to the β2, β4, and β6 positions.

Next, A-3, dichloromethane, and tetrabutylamine (TBA) are put in an argon atmosphere, and then trichlorosilane is added dropwise. Further, triethylamine is added, and the mixture is quenched with water. Then, add hydrochloric acid and stir. After suction filtration, extraction, washing with water and drying. After separation, column purification is performed to obtain an intermediate (A-4) in which the silicon atom is covalently or coordinately bonded to the phthalocyanine skeleton. Chlorotrialkylsilane SiClR ¹ R ² R ³ (R ¹ , R ² and R ³ represent an alkyl group) and pyridine are added and refluxed. After the solvent is distilled off, the column is purified to obtain an intermediate (A-5). Add A-5, tetrahydrofuran and alkaline solution to reflux. Add acidic solution and evaporate. Column purification is performed as it is to obtain phthalocyanine dye D-1. Such a scheme can be applied to the synthesis of the phthalocyanine dyes described above.

  An example of the basic configuration of a photoelectric conversion element or a dye-sensitized solar cell using the dye of the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view illustrating an example of a photoelectric conversion element. An electrode 10 in which a conductive layer 2 and a dye-adsorbing semiconductor layer 3 in which a sensitizing dye is adsorbed on a semiconductor layer are stacked on a substrate 1 and a substrate are illustrated. 4 has a counter electrode 11 provided with a conductive layer 5, and an electrolyte layer 6 is disposed between both electrodes. The dye-adsorbing semiconductor layer 3 is also referred to as a semiconductor electrode because it forms part of the electrode. The dye adsorbing semiconductor layer 3 is a layer coated and sintered as a single layer using titania or metal oxide fine particles, or a layer formed by applying and sintering a plurality of times, and a semiconductor to which a dye is adsorbed This layer is composed of metal oxide particles such as titanium oxide particles and a sensitizing dye present so as to cover the surface of the particles. Light enters from the electrode 10 side. The dye-sensitized solar cell of the present invention has the same basic configuration as described above, but is made to work in an external circuit. And the method of making a dye photoelectric conversion element into a dye-sensitized solar cell is well-known in the said patent documents 1-3 etc., These well-known methods may be sufficient.

  The substrate 1 is not particularly limited as long as it is a transparent insulating material. For example, a normal glass plate or plastic plate may be used, and further, a flexible material may be used. For example, a PET resin may be used. However, it is preferably a heat-resistant material that can withstand the step of baking titanium oxide with an upper limit of about 500 ° C., and a transparent glass plate can be mentioned.

  Next, a conductive layer 2 is provided on the surface of the substrate 1 so as not to impair the transparency of the base material. As the conductive layer, ITO, FTO, ATO known as a so-called transparent electrode, or a combination thereof is used. Moreover, it may be a metal layer having a thickness that does not impair the transparency. The method of providing these conductive layers is not particularly limited, and spin coating, bar coating, screen printing methods using sputtering, vapor deposition (including CVD and PVD), spray, laser ablation, or pasted materials, etc. Known techniques can be used. Among them, a spray method or a sputtering or vapor deposition method performed in a gas phase is suitable.

  On this, the dye adsorption semiconductor layer 3 is provided. Usually, after a metal oxide layer is formed as a semiconductor, a sensitizing dye is adsorbed thereto. As a metal oxide, what is known as a photoelectric conversion material can be used, and titanium oxide, zinc oxide, tungsten oxide, tin oxide, and the like can be used. Of these, titanium oxide and tin oxide are preferable. Titanium oxide may be titanium hydroxide such as anatase type, rutile type, brookite type, titanium hydroxide or hydrous titanium oxide. Further, at least one of Nb, V, or Ta may be doped so as to have a weight concentration (as a metal element) of 30 ppm to 5% with respect to titanium oxide. If it is such a metal oxide, it can be used for this invention, but it is good that it is a fine particle with an average particle diameter of 5-500 nm, Preferably it is the range of 10-200 nm.

  A metal oxide layer is formed on the conductive layer 2, but the method is not particularly limited. For example, each method such as spin coating, printing, spray coating, or the like is used for pasting the metal oxide. May be. It is also possible to sinter for the purpose of sintering a metal oxide such as titanium oxide after film formation. Next, a dye for sensitization is adsorbed on the metal oxide to form a dye adsorbing semiconductor layer 3 as a dye adsorbing metal oxide.

  The present invention is characterized by a sensitizing dye and a layer containing the sensitizing dye, and other layers or materials may have a known structure or material, and are not limited to those having the structure shown in FIG.

  The materials constituting the dye-adsorbing semiconductor layer 3 are a semiconductor and a dye. Usually, since the semiconductor is a metal oxide, preferably titanium oxide or tin oxide, the semiconductor may be represented by a metal oxide or titanium oxide. is there. As the dye for dye sensitization, a phthalocyanine dye represented by the above formula (1) is used. It is also advantageous to use another dye having a maximum absorption wavelength in a different range from this phthalocyanine dye in order to broaden the absorption wavelength region if necessary.

  The dye is dissolved in a solvent that dissolves the dye and adsorbed to the titania semiconductor layer. The adsorption solvent can be used if it is a solvent in which the dye is soluble. Specifically, aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol, nitrile solvents such as acetonitrile and propionitrile, ketones such as acetone and methyl ethyl ketone, dimethyl carbonate, diethyl carbonate and the like Carbonates, lactones and caprolactams can be used. Methanol, ethanol or acetonitrile is preferred.

  The dye solution may be adsorbed using a dye solution in which a coadsorbent such as deoxycholic acid or chenodeoxycholic acid (DCA) is dissolved.

  The dye may be dissolved and adsorbed in a supercritical fluid or a pressurized fluid. Specifically, it is preferably adsorbed by carbon dioxide or a solution obtained by adding an entrainer to carbon dioxide.

The metal oxide adsorbed with the dye may be further adsorbed with carboxylic acid in a CO ₂ supercritical fluid. The effect of adsorbing carboxylic acid is described in Non-Patent Document J. Pat. Photochem. and Photobio. A, Chem. 164 (2004) 117 and the like. However, it is important to effectively adsorb the fine pores of metal oxides such as titanium oxide and tin oxide as in the case of dye adsorption and rinsing. CO formed with a dye-adsorbed metal oxide (which may be a substrate having a dye-adsorbed metal oxide layer) and a carboxylic acid in a pressure range of 5-30 Mpa and a temperature range of 40-60 ° C. ₂ by placing the supercritical fluid or in the pressure CO _2, it can effectively adsorb the carboxylic acid. Preferred examples of the carboxylic acid include benzoic acid, acetic acid, anisic acid, and nicotinic acid. These carboxylic acids are preferably used in a state dissolved in an alcohol containing at least one of methanol, ethanol, propanol, and butanol, and the carboxylic acid concentration is in the range of 0.01 to 10 mol / L. It is preferable. Furthermore, the adsorption of the dye is preferably carried out under subcritical pressure, and the dye is adsorbed in a mixed solution of a solution in which the dye is dissolved in a solvent and carbon dioxide, and the pressure of the carbon dioxide is 1 to 5 MPa and the temperature are preferably in the range of 40 ° C to 60 ° C.

  As described above, the electrode 10 composed of the substrate 1, the conductive layer 2, and the dye-adsorbing semiconductor layer 3 functions as a negative electrode. An electrode (counter electrode) 11 acting as the other positive electrode is disposed to face the electrode 10 as shown in FIG. The electrode serving as the positive electrode may be a conductive metal or the like, or may be a substrate 4 such as a normal glass plate or plastic plate provided with a conductive layer 5 such as a metal film or a carbon film.

  An electrolyte layer 6 is provided between the electrode 10 serving as the negative electrode and the counter electrode 11 serving as the positive electrode. The type of the electrolyte constituting the electrolyte layer 6 is not particularly limited as long as it contains a redox species for reducing the dye after photoexcitation and electron injection into the semiconductor, and even if it is a liquid electrolyte Alternatively, it may be a gelled electrolyte obtained by adding a known gelling agent (polymer or low molecular weight gelling agent) or a quasi-solid obtained by kneading an ionic liquid and a metal oxide.

For example, examples of the electrolyte used in the solution electrolyte, iodine and iodide (LiI, NaI, KI, CsI, metal iodide such as CaI _2, tetraalkylammonium iodide, pyridinium iodide, such as imidazolium iodide 4 Combination of bromine and bromide (metal bromide such as LiBr, NaBr, KBr, CsBr, CaBr ₂ , quaternary ammonium compound bromide such as tetraalkylammonium bromide, pyridinium bromide, etc.), poly Examples thereof include sulfur compounds such as sodium sulfide, alkyl thiol, and alkyl disulfide, viologen dyes, hydroquinone, and quinone. The electrolyte may be used as a mixture.

Further, as the electrolyte, a molten salt electrolyte having a high boiling point is preferable. When the semiconductor electrode is composed of a dye-adsorbed titanium oxide layer, particularly excellent battery characteristics are exhibited by combining with a molten salt electrolyte. The molten salt electrolyte composition includes a molten salt. The molten salt electrolyte composition is preferably liquid at room temperature. The molten salt as the main component is a liquid at room temperature or an electrolyte having a low melting point, and a general example thereof is “Electrochemistry”, 1997, Vol. 65, No. 11, p. 923, etc., pyridinium salts, imidazolium salts, triazolium salts and the like. The molten salt may be used alone or in combination of two or more. In addition, alkali metal salts such as LiI, NaI, KI, LiBF ₄ , CF ₃ COOLi, CF ₃ COONa, LiSCN, NaSCN can be used in combination. Usually, the molten salt electrolyte composition contains iodine. The molten salt electrolyte composition preferably has low volatility and preferably does not contain a solvent. The molten salt electrolyte composition may be used after gelation.

  When a solvent is used in the electrolytic solution, it is desirable that the compound has a low viscosity and high ion mobility and can exhibit excellent ionic conductivity. Examples of such solvents 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 , Chain ethers such as polyethylene 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 and polypropylene glycol monoalkyl ether, ethylene Glycol, propylene glycol, polyethylene glycol, polypropylene glycol Lumpur, polyhydric alcohols such as glycerin, acetonitrile, glutarodinitrile, methoxy acetonitrile, propionitrile, nitrile compounds such as benzonitrile, dimethyl sulfoxide, aprotic polar substances such as sulfolane, water and the like. These solvents can also be used as a mixture.

  The method for providing the electrolyte layer 6 is not particularly limited. For example, a method may be used in which a film-like spacer 7 is disposed between both electrodes to form a gap, and an electrolyte is injected into the gap. Alternatively, a method may be employed in which the positive electrode is loaded at an appropriate interval after the electrolyte is applied to the electrode. It is desirable to seal both electrodes and their surroundings so that the electrolyte does not flow out, but the sealing method and the material of the sealing material are not particularly limited.

  Hereinafter, the present invention will be described in more detail based on synthesis examples and examples.

Example 1 (Synthesis example)

  In a 200 ml eggplant flask, 4-tert-butyl-1,2-dicyanobenzene B-1 (15 mmol), ethyl 3,4-dicyanobenzoate B-2 (5 mmol), 1,8-diazabicyclo [5.4.0] -7 -Undecene (DBU) (0.6 ml) and pentanol (33 ml) were added and refluxed for 14 hours. Thereafter, the solvent was distilled off, and column purification (hexane: toluene = 1: 1) was performed. After adding methanol and stirring vigorously with a glass rod or the like, intermediate (B-3) was obtained in a yield of 20%. The carboxyl group of B-3 is esterified with an alkyl group, and this alkyl group is considered to be a mixture of the ethyl group derived from the raw material B-2 and the pentyl group derived from the solvent pentanol. In B-3, the tert-butyl group is considered to be bonded to the β-position of the phthalocyanine skeleton.

  B-3 (0.94 mmol), dichloromethane (200 ml) and tributylamine (25 ml) were placed in a 500 ml three-necked flask under an argon atmosphere, and then trichlorosilane (2.5 ml) was slowly added dropwise. After stirring at room temperature for 22 hours, triethylamine (80 ml) was added and the mixture was quenched into 40 ml of water in small portions. After stirring at room temperature for 3 hours, 12M hydrochloric acid (60 ml) was added little by little and stirred for 1 hour. After suction filtration, the mixture was extracted with chloroform, washed twice with water, and dried over sodium sulfate. After separation, the solvent was distilled off and short column purification (toluene: ethyl acetate = 9: 1) was performed. After the solvent was concentrated to obtain crude B-4, the following reaction was carried out using crude B-4 as it was. Chlorotrihexylsilane (4.7 mmol) and pyridine (50 ml) were placed in a 200 ml eggplant flask and refluxed for 15 hours. After distilling off the solvent, column purification (toluene: hexane = 1: 2) was performed to obtain B-5 in a yield of 15%.

  B-5 (0.14 mmol), tetrahydrofuran (5 ml) and 40% sodium hydroxide solution (1.2 ml) were placed in a 100 ml eggplant flask and refluxed for 2 days. Then acetic acid (1 ml) was added and the solvent was distilled off. Column purification (toluene: ethyl acetate = 9: 1) was performed as it was to obtain phthalocyanine dye D-2 in a yield of 21%.

Example 2
As a glass substrate with a transparent conductive film of 30 mm × 25 mm × 3 mm, a glass substrate with FTO (fluorine-doped tin oxide) film made by Nippon Sheet Glass (trade name: Low-E glass) was used.
Next, a titanium oxide film was formed on the conductive film of the substrate with the conductive film. As titanium oxide, a commercially available titanium oxide paste (D paste made by Solaronics) was used. A laminated plate in which a titanium oxide layer having a thickness of 15 μm was formed by coating this on a conductive film of a substrate with a conductive film by a squeegee printing method in a range of 5 mm × 5 mm, drying and baking at 450 ° C. Obtained.

The phthalocyanine dye D-1 was used as the dye. This was dissolved in ethanol to 3 × 10 ⁻⁴ mol / L and DCA to 3 × 10 ⁻³ mol / L. For the adsorption of the dye, the above dye solution was placed in a container, and a laminated board on which the above titanium oxide layer was formed was placed.

  A sheet-like thermoplastic adhesive (trade name of Mitsui Dupont Polychemical Co., Ltd .; Himiran sheet) made of ionomer resin with a thickness of 50 μm is injected into the outer peripheral four sides of a 5 mm × 5 mm titanium oxide film of this laminate. In order to make it possible, a gap of about 1 mm was provided at two locations on the outer periphery. This thermoplastic adhesive is not only a sealing material but also serves as a spacer between the two electrodes. Next, a glass substrate on which a platinum film having a thickness of 10 nm serving as a positive electrode was formed by a sputtering method was bonded through the thermoplastic adhesive film so that the platinum side was opposed to the titanium oxide side. From the gap between the thermoplastic adhesive films, an acetonitrile solution containing 1.0M LiI and 0.05M iodine as main components was filled between the base material and the positive electrode by utilizing capillary action. Immediately after filling the electrolyte, the gap was sealed with an epoxy resin adhesive to obtain a photoelectric conversion element F-1.

The produced photoelectric conversion element F-1 was used as a dye-sensitized solar cell, and its characteristics were evaluated by using a solar simulator, AM1.5, 100 mW / cm ² simulated sunlight, and an IV curve tracer. Table 1 shows the results of measuring the characteristics of conversion efficiency (%), short circuit current (Jsc: mA / cm ² ), open circuit voltage (Voc: V), and fill factor (ff: shape factor).

Comparative Example 1

  3- (4-Hydroxyphenyl) propionic acid (25.7 mmol) and 4-nitrophthalonitrile (17.3 mmol) were added to 40 ml of dry dimethyl sulfoxide (DMSO) in a nitrogen atmosphere. After adding 5.26 g of potassium carbonate and stirring for 4 hours, 5.26 g of potassium carbonate was further added. After stirring for 24 hours, 5.26 g of potassium carbonate was further added. The mixture was stirred at room temperature under a nitrogen atmosphere for 4 days. Finally, 500 ml of water and hydrochloric acid were added to adjust to PH2. After obtaining a solid by filtration, it was sufficiently washed with water until it became PH7. This solid was purified by column chromatography (ether: acetone = 8: 2). The product was recrystallized in a tetrahydrofuran solution to obtain a powder of phthalocyanine dye D-3 (2.98 g).

  A photoelectric conversion element F-2 of Comparative Example 1 was produced in the same manner as in Example 1 except that D-3 was used as the dye instead of the phthalocyanine dye D-2.

1: substrate, 2: conductive layer, 3: dye adsorption semiconductor layer, 4: substrate, 5: conductive layer, 6: electrolyte layer, 7: spacer, 10: electrode, 11: counter electrode

Claims (4)

A phthalocyanine dye represented by the following formula (1).

In the formula (1), R ₁ , R ₂ and R ₃ represent an alkyl group.   In the photoelectric conversion element using a pigment | dye, the phthalocyanine pigment | dye of Claim 1 is used as a pigment | dye, The photoelectric conversion device characterized by the above-mentioned.   The photoelectric conversion element according to claim 2, wherein a dye having a different absorption region from the phthalocyanine dye is used in addition to the phthalocyanine dye according to claim 1.   A dye-sensitized solar cell comprising the photoelectric conversion element according to claim 2.

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