JP6035966B2 - Composite, photoelectrode, dye-sensitized solar cell, and dye-sensitized solar cell module - Google Patents

Description

  The present invention relates to a composite, a photoelectrode, a dye-sensitized solar cell, and a dye-sensitized solar cell module.

Conventionally, as a dye-sensitized solar cell, one that absorbs sunlight and obtains a photocurrent according to the light absorption characteristics of an organic dye adsorbed on TiO ₂ has been proposed. In such a dye-sensitized solar cell, it is necessary to further improve the conversion efficiency, and it is particularly important to improve the photocurrent. Conventionally, organic dyes used in dye-sensitized solar cells have an extended optical absorption characteristic on the long wavelength side because the spectral sensitivity characteristic on the long wavelength side is particularly insufficient with respect to sunlight. It has been studied to improve the photocurrent by using a dye (for example, see Non-Patent Documents 1 and 2).

  In addition, as a dye-sensitized solar cell, a solar cell including a composite containing an organic dye having an electron accepting site and a Cu-based material containing Cu has been proposed (for example, see Patent Document 1). In this solar cell, the light absorption characteristics can be improved by the interaction between the organic dye and Cu ions.

JP 2011-204789 A

Chem. Mater. , 2008, 20, 3993-4003 J. et al. Am. Chem. Soc. , 2004, 26, 12218-12219

  However, in the above-mentioned Non-Patent Documents 1 and 2, a novel organic dye has to be studied. For example, in order to newly synthesize organic dye molecules, advanced techniques are required, and in order to synthesize such organic dyes, it is generally necessary to synthesize in a multi-step reaction, which may take time. . Further, even when an organic dye molecule is designed in advance so as to have a desired light absorption characteristic by molecular simulation or the like, it may not be known whether the synthesized organic dye has a desired light absorption characteristic. Moreover, in patent document 1, although the interaction of an organic pigment | dye and Cu ion is used, the improvement of the further light absorption characteristic was desired. As described above, the structure of organic dye molecules by organic synthesis is optimized, and the light absorption characteristics are improved by the action of ions, but this is not sufficient, and it is required to improve the light absorption characteristics of organic dyes. It was.

  This invention is made | formed in view of such a subject, The composite body which can improve the light absorption characteristic of an organic pigment | dye more, a photoelectrode, a dye-sensitized solar cell, and a dye-sensitized solar cell module The main purpose is to provide.

  As a result of diligent research to achieve the above-mentioned object, the present inventors have found an organic dye molecule, an alkaline material containing one or more of Group 1 elements and Group 2 elements, and one or more transition metals. It has been found that the light absorption characteristics of the organic dye can be further improved by including the transition metal material, and the present invention has been completed.

That is, the complex of the present invention is
An organic dye molecule having an electron accepting site containing at least one of S and N;
An alkaline material containing one or more of Group 1 elements and Group 2 elements;
A transition metal material comprising one or more transition metals;
Is contained.

Alternatively, the complex of the present invention is
An organic dye molecule having an electron accepting site containing at least one of S and N;
A transition metal material containing at least Fe;
Is contained.

Alternatively, the complex of the present invention is
An organic dye molecule having an electron accepting site containing at least one of S and N;
An alkaline material containing one or more of Group 1 elements and Group 2 elements;
Is contained.

Alternatively, the complex of the present invention is
An organic dye molecule having an electron accepting site containing at least one of S and N;
A transition metal material including a Cu-based material including at least one of a semiconductor including Cu and a conductor including Cu and a non-Cu-based material including a transition metal other than Cu;
Is contained.

  The photoelectrode of the present invention is a photoelectrode used for a dye-sensitized solar cell, and is a conductive substrate having a transparent conductive film and a transparent substrate, and an n-type provided adjacent to the conductive substrate. A semiconductor layer and any one of the above-described composites formed in the n-type semiconductor layer are provided.

  The dye-sensitized solar cell of the present invention includes the above-described photoelectrode and a counter electrode provided to face the photoelectrode.

  The dye-sensitized solar cell module of the present invention includes a plurality of the dye-sensitized solar cells described above.

  The present invention can further improve the light absorption characteristics of organic dyes. The reason why such an effect is obtained is not clear, but is presumed as follows. For example, it is presumed that the charge absorption interaction is expanded in the long wavelength side by changing the interaction of charge transfer in the organic dye molecule due to the interaction or bond between the dye and the metal ion. Such interaction or bonding between the organic dye molecule and the metal ion occurs in an overlapping manner between the organic dye molecule and the alkali metal ion and between the organic dye molecule and the transition metal ion. It is presumed that the light absorption characteristics of the dye can be further improved.

FIG. 3 is a cross-sectional view showing an example of a schematic configuration of the dye-sensitized solar cell module 10. Explanatory drawing of the pigment | dyes 1-4 which is an example of the organic pigment | dye molecule | numerator which has a rhodanine structure. Explanatory drawing of the pigment | dyes 5-10 which is an example of the organic pigment | dye molecule | numerator which has CN group. FIG. 3 is a cross-sectional view illustrating an example of a schematic configuration of a dye-sensitized solar cell 40. The measurement result of the absorption spectrum of the composite_body | complex of Experimental example 1,2. The measurement result of the absorption spectrum of the composite of Experimental example 3-6. The measurement result of the absorption spectrum of the composite of Experimental Examples 7-10. The measurement result of the absorption spectrum of the composite_body | complex of Experimental Examples 11-14. The measurement result of the absorption spectrum of the composite body of Experimental example 15 and 16. The measurement result of the absorption spectrum of the composite body of Experimental example 17-20. The measurement result of the absorption spectrum of the composite of Experimental Examples 21-24. Measurement results of light absorption characteristics when a metal-containing material is allowed to act on an organic dye. The measurement result of IPCE with respect to the wavelength of the cell of Experimental Examples 25-27. The measurement result of IPCE with respect to the wavelength of the cell of Experimental Example 28. The measurement result of IPCE with respect to the wavelength of the cell of Experimental Example 29. The measurement result of IPCE with respect to the wavelength of the cell of Experimental Example 30.

  An embodiment of the dye-sensitized solar cell module of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view illustrating an example of a schematic configuration of a dye-sensitized solar cell module 10. As shown in FIG. 1, the dye-sensitized solar cell module 10 according to this embodiment has a configuration in which a plurality of dye-sensitized solar cells 40 (hereinafter also referred to as cells) are sequentially arranged on a transparent conductive substrate 14. It has become. These cells are connected in series. In this dye-sensitized solar cell module 10, a sealing material 32 is formed so as to fill between the cells, and a flat protective member is provided on the surface of the sealing material 32 on the side opposite to the transparent conductive substrate 14. 34 is formed. The dye-sensitized solar cell 40 includes a transparent conductive substrate 14 having a transparent conductive film 12 and a transparent substrate 11 and an n-type semiconductor, and is provided adjacent to the transparent conductive substrate 14 via a base layer 22. A photoelectrode 20 having a porous semiconductor layer 24 and a composite 28 formed on the porous semiconductor layer 24, and a counter electrode 30 provided to face the photoelectrode 20. The dye-sensitized solar cell 40 includes a hole transport layer 26 that includes a p-type semiconductor and is interposed between the photoelectrode 20 and the counter electrode 30. The dye-sensitized solar cell 40 according to this embodiment includes a transparent conductive substrate 12 having a transparent conductive film 12 formed on the surface of a transparent substrate 11 through which light is transmitted, and the transparent conductive film 12 via a base layer 22. And a counter electrode 30 provided to the porous semiconductor layer 24 via a hole transport layer 26 and a separator 29. The photoelectrode 20 is disposed on the transparent conductive substrate 14, the underlying layer 22 disposed on the transparent conductive film 12 formed separately on the surface opposite to the light receiving surface 13 of the transparent substrate 11, and the underlying layer 22. And a porous semiconductor layer 24 that emits electrons upon receiving light. In this porous semiconductor layer 24, a composite 28 containing organic dye molecules and a metal-containing material, which will be described in detail later, is formed. The dye-sensitized solar cell 40 is a so-called all-solid dye-sensitized solar cell in which the photoelectrode 20 and the counter electrode 30 are connected via a hole transport layer 26 that is a solid p-type semiconductor layer. It is configured.

The transparent conductive substrate 14 is composed of the transparent substrate 11 and the transparent conductive film 12, and has light transmittance and conductivity. Specific examples include fluorine-doped SnO ₂ coated glass, ITO coated glass, ZnO: Al coated glass, and antimony-doped tin oxide (SnO ₂ —Sb) coated glass. Also, a transparent electrode obtained by doping tin oxide or indium oxide with cations or anions having different valences, or a metal electrode having a structure capable of transmitting light, such as a mesh shape or a stripe shape, provided on a substrate such as a glass substrate. Can be used. Current collecting electrodes 16 and 17 are provided at both ends of the transparent conductive substrate 14 on the transparent conductive film 12 side. Electric power generated by the dye-sensitized solar cell 40 via the current collecting electrodes 16 and 17 is provided. Can be used.

  Examples of the transparent substrate 11 include transparent glass, a transparent plastic plate, a transparent plastic film, and an inorganic transparent crystal, and among these, transparent glass is preferable. The transparent substrate 11 may be a transparent glass substrate, a glass substrate whose surface is appropriately roughened to prevent reflection of light, or a transparent glass substrate such as a ground glass-like translucent glass substrate. The transparent conductive film 12 can be formed, for example, by depositing tin oxide on the transparent substrate 11. In particular, if a metal oxide such as tin oxide (FTO) doped with fluorine is used, a suitable transparent conductive film 12 can be formed. In the transparent conductive film 12, grooves 18 are formed at predetermined intervals, and a plurality of regions of the transparent conductive film 12 are separately formed at intervals corresponding to the width of the grooves 18.

  The underlayer 22 is a layer that suppresses or prevents leakage current (reverse electron transfer) from the transparent conductive substrate 14 to the hole transport layer 26. For example, a material having translucency and conductivity is preferable. Examples include n-type semiconductors such as titanium oxide, zinc oxide, and tin oxide. Among these, titanium oxide is more preferable. This is because titanium oxide suppresses and prevents leakage current and easily allows electrons to flow from the porous semiconductor layer 24 to the transparent conductive substrate 14. The underlayer 22 is preferably made of a denser material than the porous semiconductor layer 24. Even if the base layer 22 is not formed, the base layer 22 may be omitted because it functions sufficiently as the dye-sensitized solar cell 40.

The porous semiconductor layer 24 includes a composite 28 including an organic dye molecule having an electron accepting site including at least one of S and N, and a metal-containing material that is at least one of a semiconductor and a conductor, and the composite The n-type semiconductor layer to which the organic dye molecules of the body 28 are adsorbed is formed. That is, the porous semiconductor layer 24 is a layer in which the composite 28 and the n-type semiconductor layer are combined. The organic dye molecules are dyes that emit electrons upon receiving light, as will be described in detail later. The metal-containing material includes an alkaline material containing one or more of Group 1 elements and Group 2 elements and a transition metal material containing one or more transition metals. The alkaline material may include, for example, one or more of Li, Na, K, Mg, and Ca. The transition metal material may include one or more transition metals among Cu, Ni, Co, Fe, and Cr. Moreover, it is more preferable that the transition metal material contains at least Cu and further contains one or more transition metals other than Cu. In this way, the light absorption characteristics can be further improved. The transition metal material may include a Cu-based material including at least one of a semiconductor including Cu and a conductor including Cu. The Cu-based material may include one or more of CuI, CuSCN, CuO, Cu ₂ O and Cu, and among these, CuI and CuSCN are preferable. More preferably, the composite 28 includes three types of an alkaline material, a Cu-based material, and a non-Cu-based material containing a transition metal other than Cu. In this way, the interaction between alkali metal ions and organic dyes, the interaction between Cu ions and organic dyes, and the interaction between other transition metal ions and organic dyes occur in a superimposed manner, resulting in more light absorption characteristics. It can be improved greatly. As the combination, for example, a combination of Li, Cu, and Fe, a combination of Li, Cu, and Co, and a combination of Li, Cu, and Ni are preferable. Examples of the anion contained in the complex 28 include bis (trifluoromethanesulfonyl) imide ((CF ₃ SO ₂ ) ₂ N ⁻ , hereinafter also referred to as TFSI), SCN ⁻ , I ^{− and the} like.

  Alternatively, the composite 28 may include at least one of an alkaline material including one or more of Group 1 elements and Group 2 elements and a transition metal material including one or more transition metals. For example, if the composite 28 includes an organic dye molecule having an electron accepting site including at least one of S and N, and an alkaline material, the light absorption characteristics can be improved accordingly. Further, if the composite 28 includes an organic dye molecule having an electron accepting site including at least one of S and N and a transition metal material including at least Fe, the light absorption characteristics are improved accordingly. be able to. The composite 28 is a transition metal material including an organic dye molecule having an electron accepting site including at least one of S and N, a Cu-based material including Cu, and a non-Cu-based material including a transition metal other than Cu. Thus, the light absorption characteristics can be improved accordingly.

As the n-type semiconductor contained in the porous semiconductor layer 24, a metal oxide semiconductor or a metal sulfide semiconductor is suitable. For example, titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), zinc oxide (ZnO) At least one of cadmium sulfide (CdS) and zinc sulfide (ZnS) is preferable, and among these, porous titanium oxide is more preferable. By thinning these semiconductor materials into a microcrystalline or polycrystalline state, a good porous n-type semiconductor layer can be formed. In particular, the porous titanium oxide layer is suitable as an n-type semiconductor layer included in the photoelectrode 20. The organic dye may be adsorbed on the surface of the porous n-type semiconductor. This adsorption can be performed by chemical adsorption or physical adsorption. Specifically, the porous semiconductor layer 24 is a method in which a porous n-type semiconductor layer is formed on the transparent conductive substrate 14, and then a solution containing an organic dye is dropped on the n-type semiconductor layer and then dried. The n-type semiconductor layer can be dipped in a dye solution and dried. Similarly, the composite 28 includes a method in which a solution containing a metal-containing material is dropped on an n-type semiconductor layer in which an organic dye is formed and then drying, or an n-type semiconductor in which an organic dye is formed in a solution containing a metal-containing material. It can be produced by a method of dipping the layer and then drying it. Here, the photoelectrode 20 is a composite 28 in which the organic dye contained in the porous semiconductor layer 24 interacts with the metal contained in the metal-containing material. By this interaction, it is considered that the light absorption characteristic of the organic dye is expanded to the long wavelength side, and as a result, higher photoelectric conversion characteristics can be obtained. Although this complex 28 is considered to be a complex of organic dye molecules and metal ions contained in the metal-containing material, the form may be a complex, for example. The complex 28, particularly the organic dye molecule, will be described in detail below.

The organic dye molecule contained in the porous semiconductor layer 24 has an electron accepting site containing at least one of S and N. For example, the organic dye molecule preferably has a rhodanine structure represented by the formula (1). At this time, the organic dye molecule may have a basic structure represented by Formula (2). Alternatively, the organic dye molecule may have a CN group, and preferably has a thiophene structure to which an ethylene structure having a CN group is bonded as shown in Formula (3). In the formulas (1) to (3), the substituents R ^{1 to} R ⁸ may be the same or different, for example, hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, Alkynyl group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, phosphine oxide group, adjacent It may be selected from a condensed ring formed between the substituent and sulfur. Among these substituents, the alkyl group is, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. This may or may not have a substituent. There are no particular limitations on the additional substituent when it is substituted, and examples include an alkyl group, an aryl group, a heteroaryl group, and the like, and this point is common to the other substituents. In addition, the number of carbon atoms of the substituent such as an alkyl group is not particularly limited, but is preferably in the range of 1 to 20 and more preferably 1 to 12 from the viewpoint of ease of production and cost.

FIG. 2 is an explanatory diagram of dyes 1 to 4 which are examples of organic dye molecules having a rhodanine structure, and FIG. 3 is a dye 5 to 10 which is an example of organic dye molecules having a CN group, an ethylene structure and a thiophene structure. It is explanatory drawing of. First, organic dye molecules having a rhodanine structure will be described (see dyes 1 to 4 in FIG. 2). In the organic dye molecule, the substituent R ¹ bonded to N of the rhodanine structure in formula (1) is a carboxyl group bonded to an alkyl group having 1 to 20 carbon atoms and a carbon chain having 1 to 20 carbon atoms. It is preferable that any one of them. In the case where the substituent R ¹ is an alkyl group, it is preferable that the number of carbon atoms is 1 or more because it is chemically more stable, and the case where the number of carbon atoms is 20 or less is preferable because an organic dye molecule can be easily produced. The number of carbon atoms of the substituent R ¹ is more preferably 2 or more and 12 or less. Further, in the organic dye molecule, it is preferable that at least one of the substituents R ² and R ³ of the rhodanine structure further has a similar rhodanine structure. For example, examples of the substituent R ² having a rhodanine structure include those shown in dyes 1 to 3 in FIG. Further, in the organic dye molecule, in the formula (1), at least one of the substituents R ^{1 to} R ³ of the rhodanine structure includes an aromatic ring containing at least one of N and S, and at least one of N and S is It is preferable that at least one of the bonded aromatic rings is included. Examples of the aromatic ring to which at least one of N and S are bonded include those shown in dyes 1 to 3 in FIG. The organic dye molecules shown in these dyes 1 to 3 have a structure in which the substituent R ³ is S and an acetate group is bonded to N of the rhodanine structure in the substituent R ² . The organic dye molecule preferably has a rhodanine structure and an indoline structure such as those shown in dyes 1 to 3 in FIG. Of these configurations, it is preferable to employ any one of the modes because an interaction between the organic dye molecule and the metal ion of the metal-containing material is induced, and the light absorption property of the organic dye is easily improved.

Next, an organic dye molecule having a CN group will be described (see dyes 5 to 10 in FIG. 3). This organic dye molecule has a structure in which one or more thiophene structures (aromatic rings containing S) are bonded to carbon having a double bond of an ethylene structure (see dyes 5 to 10 in FIG. 3). At this time, the substituent R ⁶ shown in Formula (3) is preferably a carboxyl group. For example, the fixation to a metal oxide such as titanium oxide becomes stronger due to the chemical adsorption of the carboxyl group of the dye and the metal oxide, and the efficiency of electron transfer is also increased. In the thiophene structure, n is preferably 1 or more and 5 or less. The substituent R ^{8 serving as} the terminal of the thiophene structure may be, for example, a substituent represented by the formula (4) or a substituent represented by the formula (5). The substituent R ⁸ may be, for example, any one of hydrogen and an alkyl group having 1 to 20 carbon atoms. Examples of the aromatic ring containing at least one of N and S and the aromatic ring to which at least one of N and S are bonded include substituents represented by formulas (4) to (6) (the dye in FIG. 3). 5-9). The organic dye molecule having a CN group may have a structure in which two or more ethylene structures are linked, or a conjugated structure. That is, it is preferable that at least one of the substituents R ⁵ and R ^{6 in} the formula (3) contains an ethylene structure. At this time, it is preferable that a substituent represented by formula (6) is bonded to at least one terminal of substituents R ⁷ and R ⁸ of formula (3) (see dyes 8 and 9 in FIG. 3). Adopting any one of these configurations is preferable because interaction with metal ions contained in the metal-containing material is induced, and the light absorption characteristics of the organic dye are more easily improved.

The hole transport layer 26 is, for example, a p-type semiconductor material, and may be a layer formed of a semiconductor containing Cu. As the semiconductor containing Cu, for example, one or more of CuI, CuSCN, CuO, and Cu ₂ O are preferably used, and CuI is more preferably used, like the Cu-based material. Alternatively, the hole transport layer 26 may be a conductor layer formed of a conductor containing Cu. In addition, when the composite 28 includes a Cu-based material, the hole transport layer 26 may be made of a material different from the Cu-based material. However, the hole transport layer 26 is easily formed by using the same material. It is more preferable. When the composite 28 includes at least a Cu-based material, the composite 28 may be formed by filling the porous semiconductor layer 24 with the Cu-based material included in the hole transport layer 26.

  The separator 29 is formed in an I-shaped cross section so as to be adjacent to one side surface of the photoelectrode 20 on which the base layer 22, the porous semiconductor layer 24 and the hole transport layer 26 are laminated. One end of the separator 29 is in contact with the groove 18 on the transparent conductive substrate 14. Thereby, the direct contact with the photoelectrode 20 and the counter electrode 30 is avoided. The separator 29 is made of an insulating material, and may be formed of, for example, glass beads, silicon dioxide (silica), rutile titanium oxide, or the like. The separator 29 is preferably an insulator in which silica particles are sintered. Silica particles are preferable for the separator because they have a low refractive index, low light scattering, and good transparency. The separator 29 preferably has an average particle size of 5 to 200 nm from the viewpoint of ensuring good transparency.

  The counter electrode 30 is formed in an L-shaped cross section having a bowl-shaped edge portion 31 so as to contact the outer surface of the separator 29 and the back surface 27 of the hole transport layer 26. One end of the counter electrode 30 is connected to the back surface 27 of the hole transport layer 26, and the other end is connected to the adjacent transparent conductive film 12 via the connection portion 21. The surface of the counter electrode 30 in contact with the back surface 27 is opposed to the photoelectrode 20 with a predetermined interval. The counter electrode 30 is not particularly limited as long as it has conductivity and bondability with the hole transport layer 26, and examples thereof include Pt, Au, and carbon. Among these, carbon is preferable. The counter electrode 30 may be formed of the same material as the hole transport layer 26. That is, a part of the outer surface side of the hole transport layer 26 may be used as the counter electrode 30.

  The sealing material 32 can be used without particular limitation as long as it is an insulating member. As the sealing material 32, for example, a thermoplastic resin film such as polyethylene or an epoxy adhesive can be used.

  The protection member 34 is a member that protects the dye-sensitized solar cell 40, and can be, for example, a moisture-proof film or protective glass.

  When this dye-sensitized solar cell 40 is irradiated with light from the light-receiving surface 13 side of the transparent substrate 11, the light is transmitted through the light-receiving surface 15 of the transparent conductive film 12 and the light-receiving surface 23 of the base layer 22 into the porous semiconductor. It reaches the layer 24 and the organic dye absorbs light to generate electrons. Electrons move from the photoelectrode 20 to the adjacent counter electrode 30 via the transparent conductive film 12 and the connection portion 21. In the dye-sensitized solar cell 40, an electromotive force is generated by the movement of the electrons, and the power generation action of the battery is obtained.

  Next, a method for manufacturing the dye-sensitized solar cell module 10 will be described. The method for producing the dye-sensitized solar cell module 10 includes a substrate manufacturing process, a porous semiconductor layer forming process (composite forming process), a hole transport layer forming process, a separator forming process, a counter electrode forming process, and a protective member forming process. A process may be included. In addition, in the following manufacturing methods, each structure of the dye-sensitized solar cell 40 mentioned above is employable. In the substrate manufacturing process, the transparent conductive film 12 is formed on the transparent substrate 11 while forming the grooves 18 between the plurality of transparent conductive films 12.

In the porous semiconductor layer forming step, an n-type semiconductor layer is formed on the transparent conductive film 12 via the base layer 22. Next, after the organic dye molecules are adsorbed to the n-type semiconductor layer, a metal-containing material is added to form the composite 28, and the porous semiconductor layer 24 is formed. The metal-containing material may be added, for example, by supplying a solution in which the metal-containing material is dissolved to the n-type semiconductor layer, or by immersing the n-type semiconductor layer in a solution in which the metal-containing material is dissolved. The organic dye molecule may have the above-described organic dye molecule having an electron accepting site containing at least one of S and N, for example, a CN group or a rhodanine structure. Further, as the n-type semiconductor layer, those described above can be used, and porous titanium oxide is preferable. In addition, as described above, the metal-containing material may include at least one material among an alkali-based material, a Cu-based material, and a non-Cu-based material including a transition metal other than Cu. More preferably, these three types are included. The transition metal material preferably contains one or more transition metals among Cu, Ni, Co, Fe and Cr. As the Cu-based material, a semiconductor containing Cu (for example, any one or more of CuI, CuSCN, CuO, and Cu ₂ O) is preferably used. When the porous semiconductor layer 24 is formed in this manner, the organic dye molecules contained in the porous semiconductor layer 24 interact with the metal ions contained in the metal-containing material, so that the light absorption characteristics of the organic dye are on the long wavelength side. It is expected to expand. This long wavelength shift is considered to improve the photoelectric conversion characteristics of the dye-sensitized solar cell 40 by expanding the wavelength region that can be used for photoelectric conversion.

  Next, in the hole transport layer forming step, the solid p-type semiconductor may be supplied to the back surface 25 of the porous semiconductor layer 24 and then dried to form the hole transport layer 26. It is preferable to use a semiconductor containing Cu (for example, CuI) as the solid p-type semiconductor. At this time, the hole transport layer 26 may be formed by supplying a solution containing a p-type semiconductor onto the porous semiconductor layer 24. In this way, the composite 28 including the p-type semiconductor material of the hole transport layer 26 can be obtained by filling the porous semiconductor layer 24 with the p-type semiconductor material. Subsequently, in the separator forming step, a separator 29 is formed on the side surface of the photoelectrode 20 in alignment with the groove 18. In the counter electrode forming step, the counter electrode 30 is formed so as to contact the separator 29 and the hole transport layer 26. The counter electrode 30 may be carbon, for example. In the protective member forming step, the sealing material 32 is formed so as to cover each cell, and the protective member 34 is formed on the sealing material 32. In this manner, the dye-sensitized solar cell 40 and the dye-sensitized solar cell module 10 with improved power generation characteristics can be produced.

  In the dye-sensitized solar cell module 10 described in detail above, the interaction between the organic dye and the metal ion contained in the metal-containing material is induced in the composite 28, and the light absorption characteristics of the organic dye are further improved. Higher photoelectric conversion characteristics are shown. For example, in the organic dye molecule, it is considered that the charge transfer interaction changes due to the interaction or bond between the organic dye molecule and the metal ion, thereby expanding the light absorption characteristics to the longer wavelength side. Such an interaction or bond between the organic dye molecule and the metal ion occurs in an overlapping manner between the organic dye molecule and the alkali ion and between the organic dye molecule and the transition metal ion. It is thought that the light absorption characteristics of the can be further improved.

  It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.

  For example, in the above-described embodiment, the dye-sensitized solar cell module 10 is used. However, the present invention is not particularly limited thereto, and the dye-sensitized solar cell 40 may be used. FIG. 4 is a cross-sectional view showing an example of a schematic configuration of the dye-sensitized solar cell 40. In FIG. 4, the same components as those described in FIG. 1 are denoted by the same reference numerals, and the description thereof is omitted. As shown in FIG. 4, in the single body of the dye-sensitized solar cell 40, the counter electrode 30 may be formed in a flat plate shape with the cross-section not being L-shaped and omitting the bowl-shaped edge portion. Further, the separator 29 in FIG. 1 may be omitted. The counter electrode 30 may be, for example, one having the same configuration as that of the transparent conductive substrate 14, or may be one in which platinum is attached to the transparent conductive film 12, or a metal thin film such as platinum.

  In the above-described embodiment, the dye-sensitized solar cell 40 is used. However, the present invention is not particularly limited thereto, and the transparent conductive substrate 14 having the transparent conductive film 12 and the transparent substrate 11 is adjacent to the transparent conductive substrate 14. It is good also as the photoelectrode 20 provided with the porous semiconductor layer 24 containing the n-type semiconductor provided, and the composite 28 mentioned above. Or it is good also as the composite_body | complex 28 containing the organic pigment | dye molecule | numerator which has an electron acceptance part containing at least one among S and N, and a metal containing material.

  The composite includes a transition metal material containing at least one of an alkali-based material containing one or more of Group 1 elements and Group 2 elements as a metal-containing material, a semiconductor containing Cu, and a conductor containing Cu. It is good also as what contains at least 1 or more among Cu-type material as these, and non-Cu-type material as a transition metal material containing transition metals other than Cu. For example, the composite may contain an organic dye molecule having an electron accepting site containing at least one of S and N, and a transition metal material containing at least Fe. Even in this case, the light absorption characteristics of the organic dye can be further improved by the interaction between the organic dye molecules and the Fe ions. In this composite, and a photoelectrode, a dye-sensitized solar cell, and a dye-sensitized solar cell module that employ this composite, any of the configurations of the above-described embodiments can be employed.

  Alternatively, the composite contains an organic dye molecule having an electron accepting site containing at least one of S and N, and an alkaline material containing one or more of Group 1 elements and Group 2 elements. Also good. Even in this case, the light absorption characteristics of the organic dye can be further improved by the interaction between the organic dye molecule and the metal ion contained in the alkaline material. In this composite, and a photoelectrode, a dye-sensitized solar cell, and a dye-sensitized solar cell module that employ this composite, any of the configurations of the above-described embodiments can be employed.

  Alternatively, the composite includes an organic dye molecule having an electron accepting site containing at least one of S and N, a Cu-based material containing at least one of a semiconductor containing Cu and a conductor containing Cu, and a transition metal other than Cu. And a transition metal material containing a non-Cu-based material containing. Even in this case, the light absorption characteristics of the organic dye can be further improved by the interaction between the organic dye molecule, the Cu ion, and the transition metal ion. In this composite, and a photoelectrode, a dye-sensitized solar cell, and a dye-sensitized solar cell module that employ this composite, any of the configurations of the above-described embodiments can be employed.

  In the above-described embodiment, the all-solid-state solar cell including the hole transport layer 26 including the p-type semiconductor has been described. However, the present invention is not particularly limited thereto. For example, the electrolytic solution is provided between the photoelectrode 20 and the counter electrode 30. It is good also as a dye-sensitized solar cell provided with.

  Below, the example which produced the composite_body | complex, photoelectrode, and dye-sensitized solar cell of this invention concretely is demonstrated as an experiment example.

[Evaluation of light absorption characteristics of composite]
Using various metal-containing materials (transition metal materials including alkali-based materials, Cu-based materials, and non-Cu-based materials), as organic dye molecules, dye 1 (also referred to as D149) and dye 5 (also referred to as MK2) shown in FIGS. The composite of the present invention was fabricated on a TiO ₂ substrate which is an n-type semiconductor layer, and the light absorption spectrum was examined. Here, TiO ₂ substrate only, that forms the organic dye TiO ₂ substrate was measured three but to form a complex containing an organic dye and a metal-containing material to a TiO ₂ substrate. In addition, the absorption spectrum of the TiO ₂ substrate formed by subtracting the absorption spectrum of the TiO ₂ substrate from the absorption spectrum of the TiO ₂ substrate on which the organic dye is formed and the absorption spectrum of the composite, and the absorption spectrum obtained with the dye contained in the composite Were compared and their characteristics were evaluated. The absorption spectrum was measured with a spectrophotometer (U-3400 manufactured by Hitachi, Ltd.) in a wavelength region of 290 nm to 900 nm. In this evaluation, the light absorption characteristics of a composite containing only an alkaline material, a composite containing only a transition metal material, and a composite containing both an alkaline material and a transition metal material were examined.

(Production of complex)
A porous TiO ₂ film as an n-type semiconductor layer is applied on a TCO glass substrate by screen printing, dried at 150 ° C., and then heated at 450 ° C. in an electric furnace to produce a porous TiO ₂ film substrate. did. A plurality of porous TiO ₂ film substrates were produced. Next, a dye solution containing each of organic dye 1 (D149) and organic dye 5 (MK2) was prepared. As the dye solution, for example, in D149, a mixed solution of acetonitrile and tert-butyl alcohol was used as a solvent, and in MK2, toluene was used as a solvent. Subsequently, the porous TiO ₂ film substrate was immersed in any of the dye solutions prepared above, and left for 15 hours under a temperature condition of 25 ° C. In this way, porous TiO ₂ film substrates (also referred to as TiO ₂ / dye substrate) on which the organic dye 1 or the organic dye 5 was adsorbed were produced. Thereafter, the TiO ₂ / dye substrate was immersed in an acetonitrile solution in which a metal-containing material (for example, LiTFSI or FeI ₂ ) was dissolved at a predetermined concentration for 30 seconds.

[Experimental Examples 1 to 4 (complex)]
The composite obtained through the above-described step of immersing the TiO ₂ / dye substrate in a solution containing D149 as the organic dye, LiI as the metal-containing material, and a metal-containing material at a concentration of 0.1 M is referred to as Experimental Example 1 did. In addition, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 2 except that the TiO ₂ / dye substrate was immersed in a solution having a LiSCN concentration of 0.1M. Further, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 3, except that the TiO ₂ / dye substrate was immersed in a solution having a LiTFSI concentration of 0.1M. In addition, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 4 except that the TiO ₂ / dye substrate was immersed in a solution having a LiTFSI concentration of 0.01M.

[Experimental Examples 5 and 6 (complex)]
Obtained through the same steps as in Experimental Example 1 except that the TiO ₂ / dye substrate was immersed in a solution having a LiTFSI concentration of 0.01M as the alkaline material and a FeI ₂ concentration of 0.01M as the transfer metal material. The obtained composite was taken as Experimental Example 5. Further, the same steps as in Experimental Example 1 were performed except that the TiO ₂ / dye substrate was immersed in a solution having LiTFSI as a concentration of 0.01M as an alkaline material and CoI ₂ as a transition metal material at a concentration of 0.01M. The composite obtained as a result was designated as Experimental Example 6.

[Experimental Examples 7 and 8 (complex)]
A composite obtained through the same steps as Experimental Example 1 was used as Experimental Example 7, except that the TiO ₂ / dye substrate was immersed in a solution having a KI concentration of 0.01 M as an alkaline material. In addition, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 8, except that the TiO ₂ / dye substrate was immersed in a solution having a NaI concentration of 0.01 M as an alkaline material.

[Experimental Examples 9 and 10 (Composite)]
A composite obtained through the same steps as Experimental Example 1 was used as Experimental Example 9, except that the TiO ₂ / dye substrate was immersed in a solution containing 0.01 M MgI ₂ as an alkaline material. In addition, a composite obtained through the same steps as Experimental Example 1 was used as Experimental Example 10 except that the TiO ₂ / dye substrate was immersed in a solution having CaI ₂ as a concentration of 0.01 M as an alkaline material.

[Experimental Examples 11 to 14 (Composite)]
A composite obtained through the same process as Experimental Example 1 was used as Experimental Example 11 except that the TiO ₂ / dye substrate was immersed in a solution having a FeI ₂ concentration of 0.01 M as a transition metal material. In addition, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 12 except that the TiO ₂ / dye substrate was immersed in a solution having CoI ₂ concentration of 0.01M as a transition metal material. In addition, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 13 except that the TiO ₂ / dye substrate was immersed in a solution having a NiI ₂ concentration of 0.01 M as a transition metal material. In addition, a composite obtained through the same steps as Experimental Example 1 was used as Experimental Example 14, except that the TiO ₂ / dye substrate was immersed in a solution having a CuI concentration of 0.01 M as a transition metal material.

[Experimental Examples 15 and 16 (complex)]
A composite obtained through the above-described step of immersing the TiO ₂ / dye substrate in a solution having MTF2 as the organic dye and a concentration of LiTFSI of 0.1 M was defined as Experimental Example 15. In addition, a composite obtained through the same process as Experimental Example 15 was used as Experimental Example 16, except that the TiO ₂ / dye substrate was immersed in a solution having a LiTFSI concentration of 0.01M.

[Experimental Examples 17 and 18 (complex)]
A composite obtained through the same steps as in Experimental Example 15 was used as Experimental Example 17, except that the TiO ₂ / dye substrate was immersed in a solution having a KI concentration of 0.01 M as an alkaline material. In addition, a composite obtained through the same steps as in Experimental Example 15 was used as Experimental Example 18 except that the TiO ₂ / dye substrate was immersed in a solution having a NaI concentration of 0.01 M as an alkaline material.

[Experimental Examples 19 and 20 (complex)]
A composite obtained through the same process as Experimental Example 15 was used as Experimental Example 19 except that the TiO ₂ / dye substrate was immersed in a solution containing 0.01 M MgI ₂ as an alkaline material. In addition, a composite obtained through the same process as Experimental Example 15 was used as Experimental Example 20 except that the TiO ₂ / dye substrate was immersed in a solution having CaI ₂ as a concentration of 0.01 M as an alkaline material.

[Experimental Examples 21 to 24 (complex)]
A composite obtained through the same process as Experimental Example 15 was used as Experimental Example 21, except that the TiO ₂ / dye substrate was immersed in a solution having a FeI ₂ concentration of 0.01 M as a transition metal material. In addition, a composite obtained through the same process as Experimental Example 15 was used as Experimental Example 22 except that the TiO ₂ / dye substrate was immersed in a solution having CoI ₂ concentration of 0.01M as a transition metal material. In addition, a composite obtained through the same process as Experimental Example 15 was used as Experimental Example 23, except that the TiO ₂ / dye substrate was immersed in a solution having a NiI ₂ concentration of 0.01 M as a transition metal material. In addition, a composite obtained through the same steps as Experimental Example 15 was used as Experimental Example 24 except that the TiO ₂ / dye substrate was immersed in a solution having a CuI concentration of 0.01 M as a transition metal material.

(Experimental result of complex)
The measurement results of the absorption spectra of the composites of Experimental Examples 1 to 14 are shown in Table 1 and FIGS. 5 to 8, and the measurement results of the absorption spectra of the composites of Experimental Examples 15 to 24 are shown in Table 2 and FIGS. Show. In FIG. 5, the absorption of TiO ₂ / dye substrate, and the absorption of TiO ₂ / dye substrate having a metal-containing material, shows the results obtained by subtracting the absorption of TiO _2. Further, in FIG. 6 and subsequent absorption of TiO ₂ / dye substrate, and showing the measurement results of the absorption of TiO ₂ / dye substrate having a metal-containing material. As shown in FIGS. 5 and 6, when the alkaline materials LiTFSI, LiI and LiSCN are allowed to act on the TiO ₂ / dye substrate whose organic dye is D149, it becomes clear that the light absorption spectrum becomes longer. It was. Moreover, as shown in FIG. 6, it turned out that the density | concentration of a metal containing material (LiTFSI) is effective even if it is 0.01M. Further, it was found that Li ⁺ is effective as a metal ion, and TFSI ⁻ , I ⁻ and SCN ⁻ are preferable as anions. Further, it was revealed that when the alkaline material LiTFSI and the transition metal material FeI ₂ are allowed to act on the TiO ₂ / dye substrate, the light absorption spectrum becomes longer. Similarly, when LiTFSI as an alkaline material and CoI _{2 as} a transition metal material are allowed to act on a TiO ₂ / dye substrate, it has been clarified that the light absorption spectrum becomes longer. Therefore, it was suggested that the alkaline material and the transition metal material act on another part of the organic dye (D149). In addition, as shown in FIG. 7, when KI, NaI, MgI ₂ and CaI ₂ as alkaline materials are allowed to act on a TiO ₂ / dye substrate whose organic dye is D149, the light absorption spectrum becomes longer. Became clear. As shown in FIG. 8, when the transition metal materials FeI ₂ , CoI ₂ , NiI ₂ and CuI are allowed to act on a TiO ₂ / dye substrate whose organic dye is D149, the light absorption spectrum becomes longer. It became clear. In particular, it was found that the absorption spectrum of FeI ₂ , CoI ₂ , and NiI ₂ shifts to the longer wavelength side compared to CuI.

As shown in Table 2 and FIG. 9, even when the organic dye is MK2, even if the concentration of the metal-containing material (LiTFSI) is 0.01M or 0.1M, the light absorption spectrum may have an effect of increasing the wavelength. all right. In addition, as shown in FIG. 10, when alkali materials KI, NaI, MgI ₂ and CaI ₂ are allowed to act on a TiO ₂ / dye substrate whose organic dye is MK2, the light absorption spectrum becomes longer. Became clear. As shown in FIG. 11, when the transition metal materials FeI ₂ , CoI ₂ , NiI ₂ and CuI are allowed to act on a TiO ₂ / dye substrate whose organic dye is MK2, the light absorption spectrum becomes longer. It became clear. In particular, it was found that the light absorption spectrum of FeI ₂ , CoI ₂ , and NiI ₂ shifts to the longer wavelength side compared to CuI.

FIG. 12 shows measurement results of light absorption characteristics when a metal-containing material is allowed to act on an organic dye. FIG. 12A shows the shift amount of the peak position with D149 as the organic dye. FIG. 12B is a diagram showing the shift amount of the peak rising position with D149 as the organic dye, and FIG. 12C is a diagram showing the shift amount of the peak position with MK2 as the organic dye. FIG. 4 is a diagram showing the shift amount of the peak rising position when the organic dye is MK2. As shown in FIG. 13, in Experimental Examples 1 to 24, it has been clarified that the light absorption spectrum becomes longer in any organic dye. Further, the metal ions and one, comparing what concentration is 0.01 M, LiTFSI, tend to _{FeI 2, CoI 2, CaI 2} , NiI 2 and MgI ₂ and, to longer wavelength in comparison with CuI I found out.

[Internal quantum efficiency (IPCE) characteristics and evaluation of solar cell characteristics of dye-sensitized solar cell]
A porous TiO ₂ film is applied as a n-type semiconductor layer on a TCO glass substrate by screen printing, dried at 150 ° C., and then heated to 450 ° C. in an electric furnace to produce a porous TiO ₂ film substrate. did. Next, a dye solution containing each of organic dye 1 (D149) and organic dye 5 (MK2) was prepared. As the dye solution, for example, in D149, a mixed solution of acetonitrile and tert-butyl alcohol was used as a solvent, and in MK2, toluene was used as a solvent. Subsequently, the porous TiO ₂ film substrate was immersed in any one of the prepared dye solutions, and left for 15 hours under a temperature condition of 25 ° C. In this way, a TiO ₂ / dye substrate on which the organic dye 1 or the organic dye 5 was adsorbed was produced. Next, CuI was saturated with acetonitrile, and 1-methyl 3-ethylimidazolium thiocyanate (EMISCN) was added to prepare a CuI solution. The obtained TiO ₂ / dye substrate was placed on a hot plate at 40 ° C. to 120 ° C. so that the TiO ₂ film was on top. 500 μL of the prepared CuI solution was dropped on a TiO ₂ / dye substrate to form a complex in which CuI was further adsorbed on the organic dye in the TiO ₂ film. The CuI is filled into the TiO ₂ film by evaporating the solvent contained in the CuI solution, further, to form CuI layer (hole transport layer) on the TiO ₂ film. And the Pt thin film as a counter electrode was arrange | positioned on this CuI layer, and the dye-sensitized solar cell was produced. The produced dye-sensitized solar cell was evaluated by an internal quantum efficiency (IPC) value.

[Experimental Examples 25 to 27 (Dye-sensitized solar cell)]
A dye-sensitized solar cell obtained through the above steps using a solution in which D149 was used as the organic dye, LiTFSI was used as the metal-containing material, and the metal-containing material had a concentration of 1.0 M was defined as Experimental Example 25. Experimental Example 25 includes a composite having an organic dye of D149 and a metal-containing material containing LiTFSI as an alkaline material and CuI as a transition metal material. In addition, Experimental Example 26 was a dye-sensitized solar cell obtained through the same process as Experimental Example 25 except that LiI was used as the metal-containing material. Experimental Example 26 is provided with a composite having an organic dye of D149 and a metal-containing material containing LiI as an alkaline material and CuI as a transition metal material. Further, a dye-sensitized solar cell obtained through the same steps as in Experimental Example 25 was used as Experimental Example 27 except that LiSCN was used as the metal-containing material. Experimental Example 29 is provided with a composite having an organic dye of D149 and a metal-containing material containing LiSCN as an alkaline material and CuI as a transition metal material.

[Experimental Examples 28 to 30 (Dye-sensitized solar cell)]
A dye-sensitized solar cell obtained through the same process as Experimental Example 25 was used as Experimental Example 28 except that D149 was used as the organic dye and CoI ₂ was used as the metal-containing material instead of LiTFSI. Experimental Example 28 is provided with a composite having an organic dye of D149 and a metal-containing material containing CoI ₂ and CuI as transition metal materials. Further, a dye-sensitized solar cell obtained through the same steps as in Experimental Example 25 except that MK2 was used as the organic dye was used as Experimental Example 29. Experimental Example 29 includes a composite having an organic dye of MK2 and a metal-containing material containing LiTFSI as an alkaline material and CuI as a transition metal material. A dye-sensitized solar cell obtained through the same process as Experimental Example 25 was used as Experimental Example 30 except that MK2 was used as the organic dye and CoI ₂ was used as the metal-containing material instead of LiTFSI. Experimental Example 30 is provided with a composite having an organic dye of MK2 and a metal-containing material containing CoI ₂ and CuI as transition metal materials.

[IPCE measurement]
For the IPCE measurement, a monochromator is used to irradiate the photoelectrode of the prepared dye-sensitized solar cell using a spectral sensitivity measuring device CEP-2000 for dye-sensitized / organic thin-film solar cell evaluation manufactured by Spectrometer Co., Ltd. Then, the number of electrons obtained with respect to the number of incident photons was measured.

(Experimental result of dye-sensitized solar cell)
The IPCE measurement result with respect to the wavelength of the cell of Experimental Example 25-27 is shown in FIG. 13, and the IPCE measurement result with respect to the wavelength of the cell of Experimental Example 28-30 is shown in FIGS. 14 to 16 also show the relative IPCE in which the maximum IPCE value is normalized to “1”. As shown in FIGS. 13 and 15, in the cells using the composites of Experimental Examples 25 to 27 and 29, the cells added with the alkali metal compared to the cells not added with the alkali metal (Li) were LiTFSI, LiI. And LiSCN both IPCE shifted to the longer wavelength side. That is, it shifted to an advantageous direction as a dye-sensitized solar cell. These results support the results with the complex. In addition, as shown in FIGS. 14 and 16, IPCE is advantageous as a dye-sensitized solar cell even in a cell using the composites of Experimental Examples 28 and 30 containing CoI ₂ and CuI as transition metal materials. The direction shifted to the long wavelength side.

  From the above measurement results, a composite comprising an organic dye molecule having an electron-accepting site and an alkaline material containing one or more of Group 1 elements and Group 2 elements is preferably improved in light absorption characteristics. I understood. Similarly, it has been found that a complex including an organic dye molecule having an electron accepting site and a transition metal material containing one or more transition metals has improved light absorption characteristics. Moreover, it turned out that the composite provided with the organic pigment | dye molecule | numerator, an alkaline material, and one or more transition metal materials improves a light absorption characteristic further, and is preferable. In particular, it has been found that a composite comprising an organic dye molecule, an alkaline material, a Cu-based material containing Cu, and a transition metal material containing a transition metal other than Cu has the most improved light absorption characteristics. .

  The present invention can be suitably used for a dye-sensitized solar cell and a dye-sensitized solar cell module.

  10 Dye-sensitized solar cell module, 11 Transparent substrate, 12 Transparent conductive film, 13 Light receiving surface, 14 Transparent conductive substrate, 15 Light receiving surface, 16, 17 Current collecting electrode, 18 Groove, 20 Photo electrode, 21 Connection portion, 22 Underlayer, 23 Light-receiving surface, 24 Porous semiconductor layer, 25 Back surface, 26 Hole transport layer, 27 Back surface, 28 Composite, 29 Separator, 30 Counter electrode, 32 Sealing material, 34 Protection member, 40 Dye-sensitized solar battery.

Claims (14)

Possess an electron acceptor site comprising at least one of S and N, and organic dye molecules which have a a rhodanine structure and indoline structure as shown in formula (1),
An alkaline material (excluding hydroxamic acid salt) containing at least one of group 1 elements and group 2 elements and an anion of at least one of (CF ₃ SO ₂ ) ₂ N ⁻ , SCN ⁻ and I ⁻ ;
A transition metal material including one or more transition metals and an anion of one or more of (CF ₃ SO ₂ ) ₂ N ⁻ , SCN ⁻ and I ⁻ ;
A composite containing
The complex according to claim 1 , wherein the organic dye molecule has a basic structure represented by Formula (2).
  An organic dye molecule having an electron accepting site containing at least one of S and N and having a thiophene structure to which an ethylene structure having a CN group is bonded, represented by formula (3);
  An anion containing one or more of group 1 elements and group 2 elements (CF _Three SO ₂ ) ₂ N ^- , SCN ^- And I ^- One or more alkaline materials (excluding hydroxamates),
  An anion containing one or more transition metals (CF _Three SO ₂ ) ₂ N ^- , SCN ^- And I ^- One or more transition metal materials,
  A composite containing
  An organic dye molecule having an electron accepting site containing at least one of S and N and having a carbazole structure represented by formula (4);
  An anion containing one or more of group 1 elements and group 2 elements (CF _Three SO ₂ ) ₂ N ^- , SCN ^- And I ^- One or more alkaline materials (excluding hydroxamates),
  An anion containing one or more transition metals (CF _Three SO ₂ ) ₂ N ^- , SCN ^- And I ^- One or more transition metal materials,
  A composite containing
The transition metal material comprises a Cu-based material comprising at least one of the conductors including a semiconductor and Cu including Cu, complex according to any one of claims 1-4. The transition metal material contains a Cu-based material comprising at least one of the conductors including a semiconductor and Cu containing Cu, and a non-Cu-based material containing a transition metal other than Cu, the claim 1-5 The complex according to any one of the above. The composite according to claim 5 or 6 , wherein the Cu-based material contains one or more of CuI, CuSCN, CuO, Cu ₂ O, and Cu. The composite according to any one of claims 1 to 7 , wherein the transition metal material includes one or more transition metals of Cu, Ni, Co, Fe, and Cr. The composite according to any one of claims 1 to 8 , wherein the alkaline material includes one or more of Li, Na, K, Mg, and Ca. A photoelectrode used in a dye-sensitized solar cell,
A conductive substrate having a transparent conductive film and a transparent substrate;
An n-type semiconductor layer provided adjacent to the conductive substrate;
The composite according to any one of claims 1 to 9 , which is formed in the n-type semiconductor layer,
A photoelectrode. 11. The photoelectrode according to claim 10 , wherein the n-type semiconductor layer includes at least one of titanium oxide, tin oxide, zinc oxide, cadmium sulfide, and zinc sulfide. The photoelectrode according to claim 10 or 11 ,
A counter electrode provided facing the photoelectrode;
A dye-sensitized solar cell comprising: The dye-sensitized solar cell according to claim 12 ,
A dye-sensitized solar cell including a hole transport layer including a Cu-based material including at least one of a semiconductor including Cu and a conductor including Cu interposed between the photoelectrode and the counter electrode. A dye-sensitized solar cell module comprising a plurality of the dye-sensitized solar cells according to claim 12 or 13 .