KR20050024344A - Coloring matter sensitization type photoelectric conversion device - Google Patents

Abstract

The present invention provides a dye-sensitized photoelectric conversion device that generates power using sunlight, comprising a semiconductor layer formed by supporting a sensitizing dye comprising an acid group-containing porphyrin multimer represented by the following general formula (1), and an electrolyte layer: do.

General formula (1):

(However, in the general formula (1), R ¹ to R ¹⁸ are substituents such as a hydrogen atom and a halogen atom and at least one of them is an acidic substituent such as a 4-carboxyphenyl group.)

Description

Dye-sensitized photoelectric conversion device {COLORING MATTER SENSITIZATION TYPE PHOTOELECTRIC CONVERSION DEVICE}

The present invention relates to a dye-sensitized photoelectric conversion device.

This application claims priority based on Japanese Patent Application No. 2002-193154 for which it applied on July 2, 2002 in Japan, This application is integrated in this application by reference.

Conventionally, various solar cells using sunlight have been developed as energy sources instead of fossil fuels. Conventionally, the most widely used and commercially available solar cells include silicon. Examples of solar cells using silicon include crystalline silicon solar cells using monocrystalline silicon or polycrystalline silicon, and amorphous (amorphous) silicon solar cells.

In particular, as the solar cell, a large amount of single crystal or polycrystalline silicon has been used.

These crystalline silicon solar cells have higher conversion efficiency than the amorphous silicon, which shows the performance of converting light (solar) energy into electrical energy, but are low in productivity because they require a lot of energy and time for crystal growth. It was disadvantageous in terms.

In addition, the amorphous silicon solar cell has a lower conversion efficiency than the crystalline silicon solar cell, but has higher light absorbency, a wider selection range of the substrate, and easier large area than the crystalline silicon solar cell. have. However, although the productivity is higher than that of the crystalline silicon solar cell, the energy burden is still large because a vacuum process is required.

Since these solar cells use materials with high toxicity, such as gallium, arsenic, and silane gas, they also have a problem in environmental pollution.

On the other hand, solar cells using organic materials have been studied for a long time as a means of solving the above-mentioned problems, but most of them have low photoelectric conversion efficiency of about 1% and have not been put to practical use.

Among them, the dye-sensitized solar cell disclosed in Nature Vol.353, p737, 1991 has been proposed to realize a high photoelectric conversion efficiency of 10% so far, and is thought to be inexpensive to manufacture. It is attracting attention.

In addition to the ruthenium bipyridine complex, this dye-sensitized solar cell has been proposed as a pigment as a chlorophyll derivative, a zinc complex of porphyrin, and the like (see Japanese Patent Laid-Open No. 2002-63949). Since these pigment | dyes have low photoelectric conversion characteristics, they were not satisfactory for practical use as a solar cell.

The reason why these photoelectric conversion characteristics are low is that the absorption in the visible light region of the dye is low. Existing pigments, such as monomers of zinc porphyrin, chlorophyll derivatives, ruthenium bipyridine complexes, have low absorbance in the visible region. Recently, stable pigments having a large absorption in the visible region have been developed by sewage water or the like (Science). Vol. 293, p79, 2001, Japanese Patent Laid-Open No. 2001-294591, Japanese Patent Laid-Open No. 2002-5357B).

In the conventional dye-sensitized solar cell as described above, the sensitization effect in the visible light region (400 to 800 nm) occupying the placenta of the solar energy is low, and there is a problem in terms of stability, so that practical use is difficult.

(Initiation of invention)

An object of the present invention is to provide a novel dye-sensitized photoelectric conversion apparatus capable of solving the problems of the conventional dye-sensitized solar cell as described above.

Another object of the present invention is to provide a dye-sensitized photoelectric conversion device having high light conversion efficiency, low cost and excellent durability.

The dye-sensitized photoelectric conversion device according to the present invention includes a semiconductor layer and an electrolyte layer formed by supporting a sensitizing dye having an acidic group-containing porphyrin multimer represented by the following general formula (1) as a base skeleton between the counter electrodes. Is installed.

General formula (1):

(However, in the general formula (1), R ¹ to R ¹⁸ may be the same or different, and represent a hydrogen atom or an optional substituent. However, at least one of R ¹ to R ¹⁸ is an acidic substituent.)

Another sensitized photoelectric conversion device according to the present invention is a semiconductor layer formed by supporting a sensitizing dye having an acidic group-containing porphyrin multimer represented by the following general formula (2) as a base skeleton between an opposing electrode, and an electrolyte. The floor is installed.

General formula (2):

(However, in the general formula (2), R ¹ to R ¹⁸ may be the same or different, and represent a hydrogen atom or an optional substituent. However, at least one of R ¹ to R ¹⁸ is an acidic substituent.) The metal group represented by M is any metal species.)

Another dye-sensitized photoelectric conversion device according to the present invention includes a semiconductor layer formed by supporting a sensitizing dye having an acidic group-containing porphyrin multimer represented by the following general formula (3) as a base skeleton between counter electrodes; An electrolyte layer is provided.

General formula (3):

(However, in the general formula (3), R ¹ to R ²⁴ may be the same or different and represent a hydrogen atom or an arbitrary substituent. However, at least one of R ¹ to R ²⁴ is an acidic substituent. n is an integer of 1 or more.)

Furthermore, another dye-sensitized photoelectric conversion device according to the present invention is a semiconductor layer formed by supporting a sensitizing dye having an acidic group-containing porphyrin multimer represented by the following general formula (4) as a base skeleton between opposing electrodes. And an electrolyte layer are provided.

General formula (4):

(However, in the general formula (4), R ¹ to R ²⁴ may be the same or different, and represent a hydrogen atom or an optional substituent. However, at least one of R ¹ to R ²⁴ is an acidic substituent.) The metal group represented by M is any metal species, and n is an integer of 1 or more.)

According to the dye-sensitized photoelectric conversion device according to the present invention, the semiconductor layer has an acidic group-containing porphyrin multimer represented by General Formula (1), (2), (3) or (4) as a basic skeleton (hereinafter as follows). (Consisting of an acidic group-containing porphyrin multimer).) Since it is formed by supporting sensitizing dyes, it can have a very large light absorption band in the visible light region (400 to 800 nm), in particular directly from solar energy to electrical energy. The conversion efficiency at the time of conversion can be improved remarkably.

In addition, since the sensitizing dye which consists of the acidic group containing porphyrin multimer represented by General formula (1), (2), (3) or (4) is easy synthesis | combination, and is a cheap and safe material, it is excellent in productivity. Has the advantage.

Furthermore, since the sensitizing dye consisting of the acid group-containing porphyrin multimer represented by the general formulas (1), (2), (3) or (4) can form a firm bonding state with the semiconductor surface via its acid group, The dye-sensitized photoelectric conversion device becomes excellent in durability.

Further objects of the present invention and specific advantages obtained by the present invention will become more apparent from the description of the embodiments described below with reference to the drawings.

1 is a schematic cross-sectional view showing a dye-sensitized solar cell according to the present invention.

Hereinafter, the dye-sensitized photoelectric conversion device according to the present invention will be described in detail. As an acidic substituent used for the dye-sensitized photoelectric conversion apparatus which concerns on this invention, a carboxyl group, a sulfonic acid group, a hydroxyl group, 4-carboxyphenyl group, etc. are mentioned.

R ¹ to R ¹⁸ of General Formula (1) or (2) above, or R ¹ to R ²⁴ of General Formula (3) or (4) represent a hydrogen atom, a halogen atom, a mercapto group, an amino group, a nitro group, Cyano group, carboxyl group, sulfonic acid group, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group , Substituted or unsubstituted arylthio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted carboxylic acid ester group, substituted or unsubstituted carboxylic acid amide group, substituted or unsubstituted Or a substituent such as a substituted or unsubstituted sulfonic acid amide group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted siloxy group, and at least one of R ¹ to R ¹⁸ , or Red of R ¹ to R ²⁴ It is preferable that at least one is an acidic substituent, such as a carboxyl group, a sulfonic acid group, a hydroxyl group, and 4-carboxyphenyl group.

In the dye-sensitized photoelectric conversion device including the dye-sensitized solar cell according to the present invention, the semiconductor layer is preferably made of an oxide semiconductor.

Here, in the general formula (1), (2), (3) or (4), R ¹ ~R ¹⁸ or at least one of substituents represented by R ¹ ~R ^24, acid substituent, for example, Since it is a carboxyl group, a sulfonic acid group, a hydroxyl group, and 4-carboxyphenyl group, even if a semiconductor layer consists of an oxide semiconductor, it is excellent in adsorption ability and it is advantageous also in forming a complex of an oxide semiconductor and a sensitizing dye. At this time, it is especially preferable to contain a carboxyl group and 4-carboxyphenyl group among the above-mentioned illustrated acidic substituents.

In General Formula (3) or (4), n is an integer of 1 or more, but the upper limit is more preferably 2. In particular, by keeping n within the above range, the absorption wavelength of the visible light portion does not shift to the long wavelength side, and the absorption efficiency of the visible light region can be maintained.

Furthermore, in the general formula (2) or (4), as the metal group (center metal) represented by M, Zn, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Th, U, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi 1 type, or 2 types or 2 or more types of metal species are mentioned. That is, the metal group represented by M may be two or more kinds different from each other in addition to the same species. In particular, in the metal group represented by M, Zn, Ni, Cu, Pd, and Mg are more preferable.

In this case, the sensitizing dye used in the present invention is based on the structure (one-dimensional planar porphyrin multimer) in which porphyrin derivatives are bound in one-dimensional direction, but a form that can be easily thought of in the form of the sensitizing dye, for example For example, it may be a two-dimensional structure in which the same porphyrin derivative as described above in the backbone is bonded in a two-dimensional direction.

The semiconductor layer may be a semiconductor layer formed by supporting a sensitizing dye composed of at least two kinds of acidic group-containing porphyrin multimers represented by the general formulas (1), (2), (3) or (4), or , Sensitizing dyes consisting of at least one of the acidic group-containing porphyrin multimers represented by the general formulas (1), (2), (3) or (4), ruthenium bipyridine complexes, chlorophyll derivatives, zinc complexes of porphyrins, and the like. May be a semiconductor layer formed by supporting other sensitizing dyes.

In the dye-sensitized photoelectric conversion device according to the present invention, a semiconductor layer and the electrolyte layer are provided between a transparent substrate having a transparent conductive film and a conductive substrate forming an opposite pole of the transparent substrate, and are transparently conductive by photoelectric conversion. Electrical energy can be generated between the film and the conductive substrate.

The dye-sensitized photoelectric conversion device according to the present invention is preferably configured as, for example, a dye-sensitized solar cell. An example in which the present invention is applied to a dye-sensitized solar cell will be described with reference to FIG. 1.

The dye-sensitized solar cell 1 according to the present invention shown in FIG. 1 includes a transparent substrate 2 having a transparent conductive film 3 and a conductive film 6 forming opposite poles of the transparent substrate 2. The semiconductor layer 4 and the electrolyte layer 7 are provided between the board | substrates 5 which have. These are protected by the case 8. The semiconductor layer 4 consists of an oxide semiconductor, for example, and is carried with the sensitizing dye which consists of an acidic group containing porphyrin multimer represented by General formula (1), (2), (3) or (4). . The transparent conductive film 3 and the conductive film 6 are connected by conducting wires to form a current circuit 9 with an ammeter 10 attached thereto.

The operation mechanism of this dye-sensitized solar cell 1 will be described below.

When sunlight L is incident on the projection substrate 2 having the transparent conductive film 3, the light energy causes general formulas (1), (2), (3), or (4) inside the semiconductor layer 4. A sensitizing dye consisting of an acid group-containing porphyrin multimer represented by is excited to generate electrons. As described above, since the transparent conductive film 3 and the conductive film 6 are connected by the current circuit 9, electrons flow to the transparent conductive film 3 through the semiconductor inside the semiconductor layer 4, As a result, electrical energy can be extracted between the transparent conductive film 3 and the conductive film 6.

The dye-sensitized solar cell 1 has a sensitizing dye composed of an acid group-containing porphyrin multimer represented by the general formula (1), (2), (3) or (4), It can have a very large light absorption band in the visible light region (400 ~ 800nm), it is possible to dramatically improve the conversion efficiency of directly converting solar energy to electrical energy.

In addition, since the sensitizing dye which consists of the acidic group containing porphyrin multimer represented by General formula (1), (2), (3) or (4) is easy synthesis | combination, and is a cheap and safe material, it is excellent in productivity. Has the advantage.

Further, the sensitizing dye consisting of the acid group-containing porphyrin multimer represented by the general formulas (1), (2), (3) or (4) can form a firm bonding state with the oxide semiconductor surface via its acid group. Excellent durability.

Oxide semiconductor, it is possible to use a publicly known one, optionally, there may be mentioned Ti, Zn, Nb, Zr, Sn, Y, La, or a metal oxide such as Ta, SrTiO _3, etc. perovskite teugye oxide, such as CaTiO ₃ .

The shape of the semiconductor layer (also called a semiconductor electrode) made of an oxide semiconductor or the like is not particularly limited, and may be various shapes such as a film form, a plate form, a pillar form, and a cylindrical form.

As a transparent substrate having a transparent conductive film, a thin film of indium oxide, tin oxide, tin indium oxide, or the like is formed on a heat-resistant substrate such as a plastic substrate such as glass or polyethylene terephthalate (PET), or a fluorine-doped conductive glass substrate. Can be used. Although the thickness of this transparent conductor substrate is not specifically limited, Usually, it is about 0.3-5 mm.

It is necessary to form the semiconductor layer which consists of oxide semiconductors as porous by sintering of semiconductor particle, etc., For example, referring to a well-known method ("the latest technique of a dye-sensitized solar cell" (CMC)), titanium isopro The fox seed is dissolved in a nitric acid solution, hydrothermal reaction is carried out to prepare a stable titanium oxide colloidal solution, the solution is mixed with polyethylene oxide (PEO) as a caking agent and homogenized in a planetary ball mill. It can manufacture by screen-printing on a fluorine dope electroconductive glass substrate (sheet resistance 3 (ohm) / square), and baking at 450 degreeC.

In order to support at least one sensitizing dye in the acidic group-containing porphyrin multimer represented by the general formulas (1), (2), (3) or (4) on the porous semiconductor layer, for example, this dye is dimethyl After dissolving in a suitable solvent such as formamide, the porous semiconductor layer is immersed in this solution, and the dye is sufficiently impregnated in the pores of the porous semiconductor layer until it is sufficiently adsorbed. To be implemented.

As the counter electrode, any one known as a counter electrode in a conventional solar cell such as aluminum, silver, tin, or indium can be used arbitrarily, but the catalytic ability to promote the reduction reaction of oxidized redox ions such as I ₃ ^- ions. More preferred are platinum, rhodium, ruthenium, ruthenium oxide, carbon and the like. These metal films are preferably formed by physical vapor deposition or chemical vapor deposition on the surface of the conductive material.

As an electrolyte inserted between both electrodes, it can use arbitrarily from what has conventionally been used as electrolyte of a solar cell. As such a thing, there exist some which melt | dissolved iodine and potassium iodide in the mixed solvent of 25 weight% of polypropylene carbonate, and 75 weight% of ethylene carbonate, for example.

In a dye-sensitized photoelectric conversion device such as a solar cell having such a structure, both electrodes are connected by conducting wires to form a current circuit, and pseudo solar light (AM (Air Mass) 1.5, 100 mW / cm ^{2 on the} transparent conductive film side). ), It is possible to generate power with high photoelectric conversion efficiency of 13.2% or more. This photoelectric conversion efficiency depends on the film thickness, the state of the semiconductor layer, the state of adsorption of the dye, the type of the electrolyte, and the like, so that the optimum conditions can be further improved.

EMBODIMENT OF THE INVENTION Hereinafter, although the specific Example of this invention is described, this invention is not limited to this Example.

Synthesis Example 1

Using a 50 ml eggplant flask, the meso-meso bound Zn (II) -diporphyrin compound (18 mg, 8 mmol) was dissolved in 30 ml of toluene. 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (hereinafter referred to as DDQ: 9 mg, 40 mmol) as an oxidant and scandium trifluoromethanesulfonate (hereinafter referred to as Sc (OTf) ₃ ) : 20 mg, 40 mmol) was added and the mixed solution was refluxed for 1 hour. This mixture was diluted with methanol and tetrahydrofuran (THF). The solvent was removed in a rotary evaporator and the product dissolved in THF and passed through an alumina column. Then recrystallized with benzene / acetonitrile, the sum of the meso-meso bonds in which the two porphyrin rings are bonded to carbon at the meso position and the two beta -β bonds bonded at the β position carbon adjacent to the meso-meso bonds. Planar porphyrin dimers were obtained (12.9 mg, yield 86%), bound by three bonds.

The 1H-NMR spectrum, the UV-Vis spectrum, and the MALDI-TOF MAS spectrum of the compound were examined. As a result, R ¹ , R ⁴ , R ¹⁰ , and R ^{13 in} General Formula (2) are 4-carboxyphenyl groups and others. It was confirmed that it is a hydrogen atom and M is a planar metal porphyrin dimer which shows Zn. Hereinafter, the planar metal (zinc) porphyrin dimer obtained as mentioned above is called compound (A).

Synthesis Example 2

The planar zinc porphyrin dimer (compound (A)) obtained as described above was subjected to demetallization treatment with concentrated sulfuric acid and trifluoroacetic acid, thereby obtaining a planar porphyrin dimer of metal-free.

The 1H-NMR spectrum, the UV-Vis spectrum, and the MALDI-TOF MAS spectrum of the compound were examined. As a result, R ¹ , R ⁴ , R ¹⁰ , and R ^{13 in} General Formula (1) are 4-carboxyphenyl groups and others. It was confirmed that it is a planar porphyrin dimer which is a hydrogen atom. Hereinafter, the planar porphyrin dimer obtained as described above is called compound (B).

Synthesis Example 3

Using a 50 ml eggplant flask, the meso-meso bound Zn (II) -hexaporphyrin compound (30 mg, 4.7 mmol) was dissolved in 50 ml of toluene. The oxidizing agent DDQ (27 mg, 120 mmol) and Sc (OTf) ₃ (60 mg, 120 mmol) were added and the mixed solution was refluxed for 2 hours. This mixture was diluted with methanol and THF. The solvent was removed with a rotary evaporator and the product dissolved in THF and passed through an alumina column. Then recrystallized with benzene / acetonitrile, the sum of the meso-meso bonds in which the six porphyrin rings are bonded to carbon at the meso position and the two beta -β bonds bonded at the β position carbon adjacent to the meso-meso bonds. Planar porphyrin hexamer was obtained (18.5 mg, yield 62%), bound by three binding.

The 1H-NMR spectrum, the UV-Vis spectrum, and the MALDI-TOF MAS spectrum of the compound were examined. According to the general formula (4), R ¹ , R ⁴ , R ¹⁰ , R ¹³ , R ¹⁶ , R ²² , and R ²⁴ It was confirmed that is a 4-carboxyphenyl group and other than that, a hydrogen atom and M is a planar metal porphyrin hexamer which shows Zn and n = 4. Hereinafter, the planar metal (zinc) porphyrin hexamer obtained as mentioned above is called compound (C).

Synthesis Example 4

The planar zinc porphyrin hexamer (compound (C)) obtained as described above was subjected to demetallization treatment with concentrated sulfuric acid and trifluoroacetic acid to obtain a planar porphyrin hexamer free of metal.

The 1 H-NMR spectrum, the UV-Vis spectrum, and the MALDI-TOF MAS spectrum of the compound were examined, and R ¹ , R ⁴ , R ¹⁰ , R ¹³ , R ¹⁶ , R ²² , and R ²⁴ in General Formula (3) It was confirmed that 4-carboxyphenyl group and others are hydrogen atoms and planar porphyrin hexamer which shows n = 4.

Hereinafter, the planar porphyrin hexamer obtained as described above is called compound (D).

Example 1

The production of TiO ₂ paste was performed with reference to "the latest technology of dye-sensitized solar cell" (CMC). 125 ml of titanium isopropoxide was slowly added dropwise to 750 ml of 0.1 M aqueous nitric acid solution with stirring at room temperature. When dripping was complete, it moved to the 80 degreeC thermostat and stirred for 8 hours, and the cloudy semitransparent sol solution was obtained. The sol solution was allowed to stand at room temperature and cooled, filtered through a glass filter, and the volume thereof was made up to 700 ml. The obtained sol solution was transferred to an autoclave and subjected to hydrothermal treatment at 220 ° C. for 12 hours, followed by dispersion treatment by ultrasonic treatment for 1 hour. Next, by concentration of the solution at 40 ℃ by the evaporator, when the content of TiO ₂ was prepared such that 11% by weight. PEO (polyethylene oxide) having a molecular weight of 500,000 was added to this concentrated sol solution, and the mixture was uniformly mixed with an oily ball mill to obtain a thickened TiO ₂ paste.

The TiO ₂ paste obtained as described above was applied to the fluorine-doped conductive glass substrate (sheet resistance 30Ω / □) by screen printing in a size of 0.2 cm × 0.2 cm, and then held at 450 ° C. for 30 minutes to maintain TiO ₂ paste. ₂ was sintered on the conductive glass substrate to form a porous titanium oxide film.

Planar zinc porphyrin dimer (compound (A)) obtained in Synthesis Example 1, planar porphyrin dimer (compound (B)) obtained in Synthesis Example 2, planar zinc porphyrin hexamer (compound (C)) obtained in Synthesis Example 3, The above-mentioned porous titanium oxide membrane was immersed in a solution prepared by dissolving planar porphyrin hexamer (compound (D)) obtained in Synthesis Example 4 in dimethylformamide at 5 x 10 ^-4 M, respectively, and left at 80 ° C for 12 hours. Then, methanol was washed under argon atmosphere and dried.

As the counter electrode, a platinum film having a thickness of 10 µm was deposited on a substrate with ITO (Indium Tin Oxide: doped with tin indium oxide) by a sputtering method, and 0.38 g of iodine and potassium iodide were used as an electrolyte. The solar cell of the structure as shown in FIG. 1 was produced using what melt | dissolved 2.49 g of mixture in 30 g of mixtures of 25 weight% of propylene carbonate and 75 weight% of ethylene carbonate.

Pseudo sunlight (AM1.5, 100 mW / cm ² ) was used as a light ray for operating the solar cell produced as described above. The performance of each solar cell using the compounds (A) to (D) obtained as described above as a sensitizing dye is measured, and the results are shown together in Table 1 below. At this time, as a comparative example, the compound which does not contain an acidic group (4-carboxyphenyl group) in compound (A)-(D), and the porphyrin compound (5, 10, 15, 20- which is a monomer although it contains an acidic group) Tetrakis- (4-carboxyphenyl) porphyrin) was prepared in the same manner as described above, and solar cells used as sensitizing dyes were produced, respectively, and the performance of each of these solar cells was also shown in Table 1 below.

In this case, in Table 1, the short-circuit current means a current measured by shorting the opposing electrodes, and the open voltage means a voltage generated by opening the opposing electrodes, and the photoelectric conversion efficiency is expressed by the following equation ( Is indicated by 1).

Formula (1)

Conversion efficiency (%) = (output electric energy) / (incident solar energy) * 100

TABLE 1

Type of dye Short circuit current (μA) Open voltage (V) Photoelectric conversion rate (%) (A) of Synthesis Example 1 705 0.79 11.1 (B) of Synthesis Example 2 650 0.70 8.0 (C) of Synthesis Example 3 620 0.65 7.6 (D) of Synthesis Example 4 595 0.63 7.2 Acid free (A) 12 0.50 0.08 Acid free (B) 11 0.45 0.09 Acid free (C) 13 0.56 0.1 Acid free (D) 15 0.48 0.08 5, 10, 15-, 20-tetrakis (4-carboxyphenyl) porphyrin 72 0.35 1.2

As can be seen from the above, in the dye-sensitized solar cell according to the present invention, the semiconductor layer is an acid group-containing planar porphyrin multimer represented by the general formula (1), (2), (3) or (4). Since it is made by supporting the sensitizing dye, it is possible to have a very large light absorption band in the visible region (400-800 nm), compared with the case of using a compound containing no acidic group and the monomer, and from electrical energy to solar energy It is possible to dramatically improve the conversion efficiency of directly converting to.

Further, the sensitizing dyes composed of acid group-containing planar porphyrin multimers represented by the general formulas (1), (2), (3) or (4) are materials that can be synthesized safely and inexpensively and are easily available and have high productivity. In addition to being excellent, a dye-sensitized solar cell is excellent in durability because it can form a firm bonding state with the semiconductor surface.

As mentioned above, although this invention was demonstrated based on embodiment and Example, the above-mentioned example can be variously modified based on the technical idea of this invention.

For example, in the above-mentioned embodiment, although the semiconductor layer showed the example which carried the sensitizing dye which consists of the acidic group containing porphyrin multimer represented by the said General formula (1), (2), (3) or (4), The semiconductor layer may be a semiconductor layer formed by supporting a sensitizing dye composed of at least two kinds of acidic group-containing porphyrin multimers represented by the general formulas (1), (2), (3) or (4), or Sensitizing dyes composed of at least one of the acid group-containing porphyrin multimers represented by the general formulas (1), (2), (3) or (4), ruthenium bipyridine complexes, chlorophyll derivatives, zinc complexes of porphyrins, and the like. It may be a semiconductor layer formed by supporting other sensitizing dyes.

In addition, the acidic group-containing porphyrin multimers represented by the general formulas (1), (2), (3) or (4) can be easily conceived from the form of the sensitizing dye, for example, two-dimensional. It may be a structure or the like.

In addition, the form, structure and material of the dye-sensitized photoelectric conversion device are not limited to the above-described embodiments, and may be appropriately selected without departing from the scope of the appended claims and their known features, and various modifications may be made. It is apparent to those skilled in the art that the substitution, or the equivalent thereof can be performed.

According to the dye-sensitized photoelectric conversion apparatus according to the present invention, the semiconductor layer carries a sensitizing dye consisting of an acid group-containing porphyrin multimer represented by the general formulas (1), (2), (3) or (4) described above. In this case, it is possible to have a very large light absorption band in the visible light region (400 to 800 nm), and in particular, the conversion efficiency when directly converting solar energy into electrical energy can be remarkably improved.

The sensitizing dyes composed of the acid group-containing porphyrin multimers represented by the general formulas (1), (2), (3) or (4) are easy to synthesize, and are an inexpensive and safe material. Have

Furthermore, since the sensitizing dye consisting of the acid group-containing porphyrin multimer represented by the general formulas (1), (2), (3) or (4) can form a firm bonding state with the semiconductor surface via its acid group, The dye-sensitized photoelectric conversion device is excellent in durability.

Claims (12)

Dye-sensitized photoelectricity is provided between the counter electrode provided with the semiconductor layer which carries out the sensitizing dye which uses the acidic group containing porphyrin multimer represented by following General formula (1) as a base frame, and an electrolyte layer. Inverter: General formula (1): (However, in the general formula (1), R ¹ to R ¹⁸ may be the same or different, and represent a hydrogen atom or an optional substituent. However, at least one of R ¹ to R ¹⁸ is an acidic substituent.). Dye-sensitized photoelectricity is provided between the counter electrode provided with the semiconductor layer which carries out the sensitizing dye which uses the acidic group containing porphyrin multimer represented by following General formula (2) as a base frame, and an electrolyte layer. Inverter: General formula (2): (However, in the general formula (2), R ¹ to R ¹⁸ may be the same or different, and represent a hydrogen atom or an optional substituent. However, at least one of R ¹ to R ¹⁸ is an acidic substituent.) The metal group represented by M is any metal species.). Dye-sensitized photoelectricity is provided between the counter electrode provided with the semiconductor layer which carries out the sensitizing dye which uses the acidic group containing porphyrin multimer represented by following General formula (3) as a base frame, and an electrolyte layer. Inverter: General formula (3): (However, in the general formula (3), R ¹ to R ²⁴ may be the same or different and represent a hydrogen atom or an arbitrary substituent. However, at least one of R ¹ to R ²⁴ is an acidic substituent. n is an integer of 1 or more). Dye-sensitized photoelectricity is provided between the counter electrode provided with the semiconductor layer which carries out the sensitizing dye which uses the acidic group containing porphyrin multimer represented by following General formula (4) as a base frame, and an electrolyte layer. Inverter: General formula (4): (However, in the general formula (4), R ¹ to R ²⁴ may be the same or different, and represent a hydrogen atom or an optional substituent. However, at least one of R ¹ to R ²⁴ is an acidic substituent.) The metal group represented by M is any metal species, and n is an integer of 1 or more.). The method according to any one of claims 1, 2, 3 or 4, A dye-sensitized photoelectric conversion device, wherein the acidic substituent is a carboxyl group, a sulfonic acid group, a hydroxyl group, a 4-carboxyphenyl group, or the like. The method according to any one of claims 1, 2, 3 or 4, R ¹ to R ¹⁸ of the general formula (1) or (2), or R ¹ to R ²⁴ of the general formula (3) or (4) represent a hydrogen atom, a halogen atom, a mercapto group, an amino group, a nitro group, and a cyan No group, carboxyl group, sulfonic acid group, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, Substituted or unsubstituted arylthio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted carboxylic acid ester group, substituted or unsubstituted carboxylic acid amide group, substituted or unsubstituted Substituents such as sulfonic acid esters, substituted or unsubstituted sulfonic acid amide groups, substituted or unsubstituted carbonyl groups, substituted or unsubstituted silyl groups, substituted or unsubstituted siloxy groups, and at least one of R ¹ to R ¹⁸ or R Write down ¹ to R ²⁴ 1 is an acidic substituent such as a carboxyl group, a sulfonic acid group, a hydroxyl group, and a 4-carboxyphenyl group. The method according to claim 1 or 4, In the general formula (2) or (4), the metal group represented by M is Zn, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy , Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Th, U, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir At least one metal selected from the group consisting of Ni, Pd, Pt, Cu, Ag, Au, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi A dye-sensitized photoelectric conversion device, characterized in that the species. The method according to any one of claims 1 to 4, The dye-sensitized photoelectric conversion device, characterized in that the semiconductor layer is made of an oxide semiconductor. The method according to any one of claims 1 to 4, The semiconductor layer is made of a semiconductor layer formed by supporting a sensitizing dye composed of at least two kinds of acidic group-containing porphyrin multimers represented by the general formulas (1), (2), (3) or (4). Dye-sensitized photoelectric conversion apparatus. The method according to any one of claims 1 to 4, The semiconductor layer is a sensitizing dye consisting of at least one of an acid group-containing porphyrin multimer represented by the general formulas (1), (2), (3) or (4), a ruthenium bipyridine complex, a chlorophyll derivative, A dye-sensitized photoelectric conversion device, characterized in that the semiconductor layer is formed by supporting another sensitizing dye such as a zinc complex of porphyrin. The method according to any one of claims 1 to 4, The semiconductor layer and the electrolyte layer are provided between the transparent substrate having the transparent conductive film and the conductive substrate forming the opposite pole of the transparent substrate, and the electrical energy is transferred between the transparent conductive film and the conductive substrate by photoelectric conversion. A dye-sensitized photoelectric conversion device, characterized in that generated. The method of claim 11, The device is a dye-sensitized photovoltaic device, characterized in that the dye-sensitized solar cell.