KR20140072860A - Photoelectric conversion element, photoelectrochemical cell, and dye used in photoelectric conversion element and photoelectrochemical cell - Google Patents

Abstract

1. A photoelectric conversion element having a laminate structure in which a counter electrode is disposed on a photosensitive support having a layer of semiconductor fine particles adsorbed thereon, a charge carrier, and a counter electrode arranged on a conductive support, wherein a metal complex dye represented by the following formula (1) A photoelectric conversion element used.
ML ¹ L ² X (1)
Wherein M represents a transition metal selected from ruthenium, osmium, iron, rhenium, and technetium. X ^{is, NCS -, Cl -, Br} -, I -, CN -, NCO - represents a ^-, H ₂ O, NCN or _2. L ¹ Represents a specific three-digit ligand, and L < ² > Represents a specific two-digit ligand.]

Description

PHOTOELECTRIC CONVERSION ELEMENT, PHOTOELECTROCHEMICAL CELL, AND DYE USED IN PHOTOELECTRIC CONVERSION ELEMENT AND PHOTOELECTROCHEMICAL CELL BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoelectric conversion element,

The present invention relates to a photoelectric conversion element and a photoelectrochemical cell, and a dye used for the same.

Photoelectric conversion elements are used in various optical sensors, copying machines, solar cells, and the like. In this photoelectric conversion element, various methods such as a method using a metal, a method using a semiconductor, an method using an organic pigment or a dye, or a combination thereof have been put to practical use. Among them, solar cells using solar energy of non-refractory nature require no fuel and utilize clean energy of no-excitation, and full-scale practical use of solar cells is expected. Among these, silicon-based solar cells have been undergoing research and development for a long time. There is policy consideration of each country and diffusion is proceeding. However, silicon is an inorganic material, and throughput and molecular modification are naturally limited.

Therefore, the research of the dye-sensitized solar cell is energetically performed. Particularly, it was the research result of Graetzel et al. They adopted a structure in which a dye made of a ruthenium complex is fixed on the surface of a porous titanium oxide thin film to realize a conversion efficiency similar to that of amorphous silicon. As a result, dye-sensitized solar cells have attracted attention from researchers in the world of hematology.

Patent Document 1 describes a dye-sensitized photoelectric conversion element using semiconductor fine particles increased or decreased by a ruthenium complex dye by applying this technique. Further, thereafter, development of a ruthenium complex type sensitizing dye has continued to improve photoelectric conversion efficiency (see Patent Documents 2 and 3).

U.S. Patent No. 5463057 U.S. Patent Application Publication No. 2010/0258175 International Patent Publication No. 98/50393 pamphlet

According to the techniques described in Patent Documents 2 and 3, devices with high photoelectric conversion efficiency have been provided. However, the inventor of the present invention has confirmed that it plays an important role as a full-scale supply source of green energy, and can not be said to be sufficient in its performance, so that development of a photoelectric conversion element exhibiting even higher characteristics including improvement in durability Oriented.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a photovoltaic device which achieves high performance such as high photoelectric conversion efficiency and has a photovoltaic device with excellent IPCE (Incident Photon to Current Conversion Efficiency) Batteries, and pigments used in them.

The above problem has been solved by the following means.

[1] A photoelectric conversion element having a laminate structure in which a counter electrode is disposed on a conductive support, a photosensitive member layer having a layer of semiconductor fine particles adsorbed thereon, a charge carrier layer, and a counter electrode, 1). ≪ / RTI >

ML ¹ L ² X (1)

Wherein M represents a transition metal selected from ruthenium, osmium, iron, rhenium, and technetium. X ^{is, NCS -, Cl -, Br} -, I -, CN -, NCO - represents the, or H ₂ O. L ¹ Represents a three-digit ligand represented by the following formula (L1), and L < ² > Represents a two-digit ligand represented by any of the following formulas (L2-1) to (L2-5).]

[Chemical Formula 1]

[In the formula (L1), Za, Zb and Zc each independently represent a group of a nonmetal atom capable of forming a 5 or 6-membered ring. Provided that at least one of the rings formed by Za, Zb and Zc has an acidic group.

(2)

Wherein G < ^{1 >} Represents a structure shown by any one of formula (G1-1) ~ (G1-6), G 2 Represents a structure represented by any one of the following formulas (G2-1) to (G2-3). R represents a substituent. n1 represents an integer of 0 to 3; and n2 represents an integer of 0 to 5.]

(3)

Wherein R ¹ to R ³ (OH) ² , PO (OR) (OH), or CO (NHOH), each independently represents a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group, COOH, PO R ⁴ Represents a hydrogen atom, an alkyl group, or an aryl group. Wherein R represents an alkyl group, a heteroaryl group, or an aryl group. * Indicates a combined hand.]

[2] L ² The photoelectric conversion element according to [1], wherein the formula (L2-1) or (L2-2) is satisfied.

[3] G ¹ The photoelectric conversion element according to (1) or (2), which is represented by (G1-1), (G1-2) or (G1-5).

[4] G ² Is a photoelectric conversion element according to any one of [1] to [3], which is represented by (G2-1) or (G2-2).

[5] R ¹ Is an alkyl group substituted with an electron-withdrawing group, and the photoacid generator is an alkyl group substituted with an electron-withdrawing group.

[6] The compound according to [1], wherein Za, Zb and Zc are each independently selected from an imidazole ring, an oxazole ring, a thiazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, To [5].

[7] The photoelectric conversion element according to any one of [1] to [6], wherein the photoconductor layer further contains a dye represented by the following formula (2).

MzL ³ _m3 L ⁴ _m4 Y _mY · CI (2)

[In the formula (2), Mz represents a metal atom. L ³ Represents a ligand represented by the following formula (L3). L ⁴ Represents a ligand represented by the following formula (L4). Y represents a 1-position or 2-position ligand. m3 represents an integer of 0 to 3; and m4 represents an integer of 1 to 3. and mY represents an integer of 0 to 2. CI indicates the counter ion when counter ion is required to neutralize charge.]

[Chemical Formula 4]

(In the formula (L3), Ac represents an acidic group, R ^a Represents a substituent. R ^b represents an alkyl group or an aromatic ring group. e1 and e2 each independently represent an integer of 0 to 5; L ^c and L ^d Represents a conjugated chain. e3 represents 0 or 1; f represents an integer of 0 to 3; and g represents an integer of 0 to 3.)

[Chemical Formula 5]

Z represents a group of atoms capable of forming a 5 or 6-membered ring, and Z represents 0 or 1. Zd, Ze and Zf each independently represents a group of atoms capable of forming a 5- or 6-membered ring, And at least one of the forming rings has an acidic group.

[8] A photoelectrochemical cell using the photoelectric conversion element according to any one of [1] to [7].

[9] A coloring matter represented by the following general formula (1).

ML ¹ L ² X (1)

Wherein M represents a transition metal selected from ruthenium, osmium, iron, rhenium, and technetium. X ^{is, NCS -, Cl -, Br} -, I -, CN -, NCO - represents the, or H ₂ O. L ¹ Represents a three-digit ligand represented by the following formula (L1), and L < ² > Represents a two-digit ligand represented by any of the following formulas (L2-1) to (L2-5).

[Chemical Formula 6]

In the formula (L1), Za, Zb and Zc each independently represent a group of a nonmetal atom capable of forming a 5 or 6-membered ring. Provided that at least one of the rings formed by Za, Zb and Zc has an acidic group.

(7)

In the formula, G ¹ Represents a structure shown by any one of formula (G1-1) ~ (G1-6), G 2 Represents a structure represented by any one of the following formulas (G2-1) to (G2-3).

[Chemical Formula 8]

In the formulas, R ¹ to R ³ Represents a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group, COOH, PO (OH) ₂ , PO (OR) (OH), or CO (NHOH). R ⁴ Represents a hydrogen atom, an alkyl group, or an aryl group. Wherein R represents an alkyl group, a heteroaryl group, or an aryl group. * Indicates a combined hand.]

The photoelectric conversion element and the photoelectrochemical cell using the dye of the present invention exhibit high performance such as high photoelectric conversion efficiency and have high IPCE in the long wavelength region and excellent durability.

These and other features and advantages of the present invention will become more apparent from the following description.

1 is a cross-sectional view schematically showing an embodiment of a photoelectric conversion element according to the present invention.
Fig. 2 is a cross-sectional view schematically showing the dye-sensitized solar cell produced in Example 1. Fig.
3 is a cross-sectional view schematically showing a dye-sensitized solar cell produced in Example 2. Fig.
Fig. 4 is a cross-sectional view schematically showing a modified example of the photoelectric conversion element shown in Fig. 1 in an enlarged portion (circle) of the dye sensitized solar cell manufactured in Example 3. Fig.

The metal complex coloring matter of the present invention has a structure in which a three-dimensional ligand containing nitrogen is coordinated to the center metal. Thus, in the photoelectric conversion element, a high IPCE is exhibited even in a long wavelength region exceeding 800 nm, Conversion efficiency is realized, and high durability is achieved.

This reason includes the unresolved points, but it can be explained as follows including the estimation. The types and substitution positions of the substituents on the two-digit ligands including nitrogen are different from each other in the electronic effect and the stereoscopic effect on the dye adsorbed to the semiconductor fine particles via the three-position ligand including nitrogen, The position has a desirable effect in terms of (1) the viewpoint of electron injection, (2) the recombination of electrons injected into the semiconductor fine particles, and (3) the dissociation inhibition . As a result, it is considered that both the high photoelectric conversion efficiency and the improvement in durability are realized. Hereinafter, the present invention will be described in detail on the basis of preferred embodiments thereof.

[Device Structure]

Preferred embodiments of the photoelectric conversion element using the dye of the present invention will be described with reference to the drawings. 1, the photoelectric conversion element 10 includes an electrically conductive substrate 1, a photoconductor layer 2, a charge carrier layer 3, and a counter electrode (not shown) arranged in this order on the electrically conductive substrate 1 4). The light receiving electrode 5 is constituted by the conductive support 1 and the photosensitive layer 2. The photoconductor layer 2 includes semiconductor fine particles 22 and a dye 21 and the dye 21 is adsorbed to the semiconductor fine particles 22 at least in part thereof (the dye is in an adsorption equilibrium state, It may be present in some charge transport layer). The electroconductive support 1 on which the photoconductor layer 2 is formed functions as a working electrode in the photoelectric conversion element 10. [ The photoelectric conversion element 10 can be operated as the photoelectrochemical cell 100 by causing the external circuit 6 to work.

The light receiving electrode 5 is an electrode consisting of a conductive support 1 and a photoconductor layer (semiconductor film) 2 containing semiconductor fine particles 22 on which a dye 21 to be coated and formed on the conductive support is adsorbed. Light incident on the photoconductor layer (semiconductor film) 2 excites the dye. Here, the dye has high energy electrons. Thus, the electrons are transferred from the dye 21 to the conduction band of the semiconductor fine particles 22 and reach the conductive support 1 by diffusion. At this time, the molecules of the dye 21 are oxidized. The oxidized dye absorbs electrons from a reducing agent (for example, I < ^- >) in the electrolyte and returns to the base dye, thereby acting as a photoelectrochemical cell. At this time, the light-receiving electrode 5 acts as a negative electrode of the battery.

The photoelectric conversion element of this embodiment has a photoconductor layer having a layer of semiconductor fine particles on which a dye described below is adsorbed on a conductive support. In this case, the dye may be dissociated in some electrolytes. The photoconductor layer is designed according to purposes, and may be a single layer structure or a multilayer structure. The photoconductor layer of the photoelectric conversion element of the present embodiment contains high-sensitivity semiconductors in which specific dye is adsorbed, and thus high photoelectric conversion efficiency can be obtained when the photoconductor layer is used as a photoelectrochemical cell.

In this specification, based on what is shown in the specification, the side of the counter electrode 4 is referred to as the top (top) direction, and the side of the counter electrode 4, which is the light receiving side, (1) is set to the lower (bottom) direction.

[Coloring matter represented by formula (1)] [

The dye of the present invention is represented by the following formula (1).

ML ¹ L ² X (1)

* M

Wherein M represents a transition metal selected from ruthenium, osmium, iron, rhenium, and technetium. Among them, ruthenium is preferable.

* X

X ^{is, NCS -, Cl -, Br} -, I -, CN -, NCO - represents the, or H ₂ O.

* L ¹

L ¹ Is expressed by the following formula (L1).

[Chemical Formula 9]

In the formula (L1), Za, Zb and Zc each independently represent a group of a nonmetal atom capable of forming a 5 or 6-membered ring. Provided that at least one of the rings formed by Za, Zb and Zc has an acidic group.

Za, Zb, Zc

Za, Zb and Zc each independently represent a group of a nonmetal atom capable of forming a five-membered ring or a six-membered ring. The formed 5-membered ring or 6-membered ring may be substituted or unsubstituted, or may be monocyclic or pendant. Za, Zb and Zc are preferably composed of at least one of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and a halogen atom, and more preferably form an aromatic ring. In the case of a 5-membered ring, it is preferable to form an imidazole ring, an oxazole ring, a thiazole ring or a triazole ring, and in the case of a 6-membered ring, a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring . Among them, an imidazole ring or a pyridine ring is more preferable.

· Acidic group

In the present invention, the acidic group is a substituent group having a dissociative proton, and examples thereof include a carboxyl group, a phosphonyl group, a phosphoryl group, a sulfo group, a boric acid group, and the like, Carboxy group or a group having the same. The acidic group may be in a form dissociated by releasing a proton, or may be a salt. The counter ion is not particularly limited when it becomes a salt, and examples thereof include a positive ion in the counter ion CI of the following formula (2). The acidic groups may be bonded to each other via a linking group. For example, a carboxyvinylene group, a dicarboxyvinylene group, a cyanocarboxyvinylene group, or a carboxyphenyl group may be preferably used. In addition, the examples of the acid group and the preferred range thereof are sometimes referred to as acid group Ac. Further, as described above, the acid group Ac may be a group having a group showing acidity, in other words, a group showing acidity may be introduced via a predetermined linking group.

The acid group of at least one of the rings formed by Za, Zb and Zc is preferably COOH, PO (OH) ₂ , PO (OR) (OH), or CO (NHOH) PO (OH) ₂ , or PO (OR) (OH), particularly preferably COOH. Wherein R represents an alkyl group, a heteroaryl group, or an aryl group.

* L ²

L ² (L2-1), (L2-2), (L2-3), (L2-4), or (L2-5). Among the formulas (L2-1) to (L2-5), preferably, the formula (L2-1), (L2-2), (L2-4), or (L2-5) Is the formula (L2-1) or (L2-2), and particularly preferably the formula (L2-1).

[Chemical formula 10]

· G1

G1 represents a structure represented by the following formulas (G1-1) to (G1-6). (G1-1), (G1-2), (G1-3), (G1-5) or (G1-6) out of the groups (G1-1) to (G1-6) (G1-1), (G1-2), (G1-5) or (G1-6), and particularly preferably, (G1-1) 5).

· G2

G2 represents a structure represented by the following formulas (G2-1) to (G2-3). Among (G2-1) to (G2-3), preferably (G2-1) or (G2-2), and more preferably (G2-2).

R, n1, n2

In the formulas (L2-1) to (L2-5), R represents a substituent, and preferred examples thereof include an example of a late substituent T. n1 is an integer of 0 to 3, and n2 is an integer of 0 to 5.

(11)

R ¹ to R ³

R ¹ , R ² , R ³ (Preferably having 1 to 6 carbon atoms), an aryl group (preferably having 6 to 12 carbon atoms), COOH, PO (OH) ₂ , PO (OR) (OH), or CO (NHOH). R represents an alkyl group (preferably having 1 to 6 carbon atoms), a heteroaryl group (preferably having 2 to 6 carbon atoms), or an aryl group (preferably having 6 to 12 carbon atoms).

R ¹ to R ³ are preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group substituted with an electron-withdrawing group (for example, a halogen atom, particularly preferably a fluorine atom).

R ⁴ Is preferably a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms), or an aryl group (preferably having 6 to 12 carbon atoms). Preferably an alkyl group or an aryl group, and particularly preferably an alkyl group.

The dye represented by the formula (1) has a maximum absorption wavelength in the ethanol solution, preferably in the range of 500 to 700 nm, more preferably in the range of 550 to 650 nm.

Specific preferred examples of the dye represented by formula (1) of the present invention are shown below, but the present invention is not limited thereto.

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

(A coloring matter comprising the compound of formula (2)

In the photoelectric conversion element and photoelectrochemical cell of the present invention, it is preferable to use it in combination with another metal complex coloring matter. By using the dyes in combination with other metal complex dyes, the adsorption states of the dyes can be controlled to achieve higher conversion efficiency and durability. In this case, the photoconductor layer containing semiconductor fine particles sensitized by the two types of sensitizing dyes may be different layers.

The other metal complex coloring matter is preferably a coloring matter represented by the following formula (2).

MzL ³ _m3 L ⁴ _m4 Y _mY · CI (2)

Metal atom Mz

Mz agrees with M in equation (1).

* L ³ (Formula (L3))

L ³ Represents a two-digit ligand represented by the following formula (L3).

[Chemical Formula 15]

· M3

m3 is an integer of 0 to 3, preferably 1 to 3, more preferably 1. When m3 is 2 or more, L < ³ > May be the same or different.

Ac

Ac each independently represents an acidic group. Preferred of Ac is the same as defined in formula (1). Ac may be substituted on the pyridine ring or any substituent thereof.

R ^a

R ^a Each independently represents a substituent, and examples of the substituent T are preferably exemplified. An alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an amino group, an acyl group, a sulfonamide group, An alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group or a halogen atom, and particularly preferably an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group , An amino group or an acylamino group.

R ^b

R ^b Represents an alkyl group or aromatic ring group. The aromatic ring group is preferably an aromatic ring group having 6 to 30 carbon atoms, such as phenyl, substituted phenyl, naphthyl, substituted naphthyl, and the like. The heterocyclic group is preferably a heterocyclic group having 1 to 30 carbon atoms, such as 2-thienyl, 2-pyrrolyl, 2-imidazolyl, 1-imidazolyl, 4 - pyridyl, 3-indolyl, and combinations of two or more thereof. Preferably a heterocyclic group having 1 to 3 electron hole groups, and more preferably two or more thienyl and thienyl groups. The electron donating group is preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group or a hydroxy group, more preferably an alkyl group, an alkoxy group, an amino group or a hydroxy group, Is particularly preferable.

· E1, e2

e1 and e2 each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

· L ^c and L ^d

L ^c and L ^d Each independently represents a conjugated chain, and includes, for example, a conjugated chain composed of at least one of an arylene group, a heteroarylene group, an ethenylene group and an ethynylene group. The ethenylene group, ethynylene group and the like may be unsubstituted or substituted. When the ethenylene group has a substituent, the substituent is preferably an alkyl group, more preferably methyl. L ^c and L ^d Are preferably each independently a conjugated chain having 2 to 6 carbon atoms and more preferably thiophenediyl, ethenylene, butadienylene, ethynylene, butadienylene, methylethenylene or dimethylethenylene, , Ethenylene or butadienylene is particularly preferable, and ethenylene is most preferable. L ^c And L ^d May be the same or different, but are preferably the same. When the conjugated chain contains a carbon-carbon double bond, each double bond may be E-type, Z-type, or a mixture thereof.

· E3

e3 is 0 or 1; In particular, when e3 is 0, f on the right side of the formula is preferably 1 or 2, and when e3 is 1, f on the right side is preferably 0 or 1. The sum of f is preferably an integer of 0 to 2.

· G

g each independently represent an integer of 0 to 3, preferably an integer of 0 to 2.

· F

f each independently represent an integer of 0 to 3; f is at least 1, and the ligand L ³ When at least one of the acid groups is present, m3 in the formula (2) is preferably 2 or 3, more preferably 2. When f is 2 or more, Ac may be the same or different. It is preferable that f on the left side of the equation is 0 or 1, and f on the right side is preferably an integer of 0 to 2.

The ligand L ³ in the formula (2) Is preferably represented by the following general formula (L3-1), (L3-2) or (L3-3).

[Chemical Formula 16]

Ac, Ra, f, g and e3 are as defined in formula (L3). However, Ra substituted by the N position may be a hydrogen atom. e4 is an integer of 0 to 4;

* L ⁴ (Formula (L4))

L ⁴ Represents a two-digit or three-digit ligand represented by the following formula (L4).

[Chemical Formula 17]

In the formula (L4), Zd, Ze and Zf represent a group of atoms capable of forming a 5 or 6-membered ring. h represents 0 or 1. Provided that at least one of the rings formed by Zd, Ze and Zf has an acidic group.

· M4

m4 is an integer of 1 to 3, preferably 1 to 2. When m4 is 2 or more, L < ⁴ > may be the same or different.

· Zd, Ze, Zf

Zd, Ze and Zf are synonymous with Za, Zb and Zc in the formula (1).

· H

h represents 0 or 1. h is preferably 0, and L < ⁴ > Is preferably a two-digit ligand.

Ligand L ⁴ Is preferably represented by any one of the following formulas (L4-1) to (L4-8), and is preferably represented by any one of the formulas (L4-1), (L4-2), (L4-4) , More preferably represented by the formula (L4-1) or (L4-2), and particularly preferably represented by the formula (L4-1).

[Chemical Formula 18]

In the formulas, each Ac independently represents an acidic group or a salt thereof. Ac is preferably exemplified as the above-mentioned acid group Ac.

Wherein R < ^a > is the same as that in the formula (1). However, R < ^a > substituted at the N position may be ^a hydrogen atom.

i independently represents the number (integer) of positions of carbon atoms which can be substituted with 0 or more. The number of replaceable units is indicated by () next to the number of the formula. R ^a May be connected to each other, or they may be axially connected to form a loop.

In the above formulas L4-1 to L4-8, the substituent R &^lt; a > is shown extending to the ring in ^a predetermined direction. However, the ring is not limited to those substituted in the ring. In short, for example, in the formula L4-1, Ac, R ^a May be replaced with a pyridine ring on the right side.

* Ligand Y

In the formula (2), Y represents a 1-digit or 2-digit ligand. and m Y represents the number of ligands Y. mY represents an integer of 0 to 2, and mY is preferably 1 or 2. When Y is a 1-position ligand, mY is preferably 2, and when Y is a 2-position ligand, mY is preferably 1. When mY is 2 or more, Ys may be the same or different, and Ys may be connected to each other.

The ligand Y is preferably an acyloxy group, a thioacylthio group, an acylaminooxy group, a dithiocarbamate group, a dithiocarbonate group, a trithiocarbonate group, a thiocyanate group, an isothiocyanate A ligand coordinated with a group selected from the group consisting of a halogen atom, a cyano group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, Is a ligand composed of urea. More preferably a group selected from the group consisting of an acyloxy group, an acylaminooxy group, a dithiocarbamate group, a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group or an arylthio group Or a ligand composed of a halogen atom, 1,3-diketone or thiourea, and particularly preferably a ligand composed of a dithiocarbamate group, a thiocyanate group, an isothiocyanate group, a cyanate group and an isocyanate group And a ligand composed of a halogen atom or a 1,3-diketone, and most preferably a group selected from the group consisting of a dithiocarbamate group, a thiocyanate group and an isothiocyanate group A coordinating ligand, or a ligand composed of 1,3-diketones. When the ligand Y includes an alkyl group, an alkenyl group, an alkynyl group, an alkylene group and the like, they may be linear or branched, substituted or unsubstituted. When they include an aryl group, a heterocyclic group, a cycloalkyl group and the like, they may be substituted or unsubstituted, or may be monocyclic or cyclic.

Y is a bidentate ligand, Y is an acyloxy group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate A ligand which is coordinated with a group selected from the group consisting of a dithiocarbonate group, a trithiocarbonate group, an acyl group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, It is preferably a ligand composed of a main amide, thiocarbamido, or thiourea. When Y is a 1-position ligand, Y is a ligand coordinated with a group selected from the group consisting of a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group and an arylthio group, , A carbonyl, a dialkyl ketone, and a thiourea.

* Counter ion CI

CI in the formula (2) represents a counter ion when a counter ion is required to neutralize the charge. In general, whether or not the dye has a positive or negative ion or a net ionic charge depends on the metal, the ligand and the substituent in the dye.

The dye of formula (2) may dissociate and have a negative charge due to the fact that the substituent has a dissociable group. In this case, the electric charge of the whole dye of the formula (2) becomes electrically neutral by the CI.

When the counter ion CI is a positive counter ion, for example, the counter ion CI is an inorganic or organic ammonium ion (e.g., a tetraalkylammonium ion, a pyridinium ion, etc.), an alkali metal ion or a proton.

When the counter ion CI is a negative counter ion, for example, the counter ion CI may be an inorganic anion or an organic anion. (E.g., a fluoride ion, a chloride ion, a bromide ion, an iodide ion, etc.), a substituted arylsulfonate ion (such as a p-toluenesulfonic acid ion or a p-chlorobenzenesulfonic acid ion) (E.g., 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion and the like), alkylsulfuric acid ion (e.g. methylsulfate ion) Sulfuric acid ion, thiocyanic acid ion, perchloric acid ion, tetrafluoroboric acid ion, hexafluorophosphate ion, picric acid ion, acetic acid ion, trifluoromethanesulfonic acid ion and the like. As the charge balance counter ion, an ionic polymer or another dye having a reversed charge to the dye may be used, or a metal complex ion (for example, bisbenzene-1,2-dithiolato nickel (III)) may be used Do.

* Coupler

The dye having the structure represented by the formula (2) preferably has at least one suitable interlocking group for the surface of the semiconductor fine particles. More preferably 1 to 6 of these couplers in the dye, and particularly preferably 1 to 4 thereof. As the coupler, the former Ac may be mentioned.

Specific examples of the dye having the structure represented by the formula (2) are shown below, but the present invention is not limited thereto. When the dye in the following specific example contains a ligand having a proton-dissociable group, the ligand may dissociate as needed to release the proton.

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

The dye represented by formula (2) can be synthesized with reference to Japanese Laid-Open Patent Publication No. 2001-291534 or the method cited in the publication.

The coloring matter represented by the formula (2) has a maximum absorption wavelength in the solution, preferably in the range of 300 to 1000 nm, more preferably in the range of 350 to 950 nm, and particularly preferably in the range of 370 to 900 nm Range.

In the photoelectric conversion element and the photoelectrochemical cell of the present invention, by using at least the dye represented by the formula (1) and the dye represented by the formula (2), a high conversion efficiency can be secured have.

The preferable mixing ratio of the metal complex dye having the structure represented by the formula (2) and the dye having the structure represented by the formula (1) is R / S = 90 / 10 to 10/90, preferably R / S = 80/20 to 20/80, more preferably R / S = 70/30 to 30/70, still more preferably R / S = To 40/60, and most preferably R / S = 55/45 to 45/55, and usually both are equally used.

In the present specification, the expression of a compound (including a complex and a coloring matter) is used in the meaning including not only the compound itself but also salts, complexes and ions thereof. It is meant to include a derivative modified in a predetermined form within a range that exhibits a desired effect. In the present specification, a substituent (including a connecting group and a ligand) which does not specify substitution or non-substitution may have an arbitrary substituent at that position. This is also true for compounds that do not specify substitution or non-substitution. As the preferable substituent, the following substituent T can be mentioned.

As the substituent T, the following may be mentioned.

(Preferably an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, (Preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, for example, (Preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.) (Preferably an aryl group having 6 to 26 carbon atoms such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl and 3-methylphenyl), a heterocyclic group Is a heterocyclic group having 2 to 20 carbon atoms, for example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2- An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryl (Preferably an aryloxy group having 6 to 26 carbon atoms such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy and the like), an alkoxycarbonyl group Is an alkoxycarbonyl group having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), an amino group (preferably an amino group having 0 to 20 carbon atoms, such as amino N, N-diethylamino, N-ethylamino, anilino), a sulfonamide group (preferably a sulfonamide group having 0 to 20 carbon atoms such as N, N-dimethylamino, N-dimethylsulfonamide, N-phenylsulfonamide and the like), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, A carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.) An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms such as acetylamino or benzoylamino), a cyano group or a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, More preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an amino group, an acylamino group, a cyano group or a halogen atom, particularly preferably an alkyl group, A heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group or a cyano group.

When the compounds or substituents include an alkyl group, an alkenyl group and the like, they may be linear or branched, substituted or unsubstituted. When they include an aryl group, a heterocyclic group and the like, they may be monocyclic or cyclic, substituted or unsubstituted.

[Photoelectric conversion element]

(Photoreceptor layer)

A preferred embodiment of the photoelectric conversion element of the present invention has already been described with reference to Fig. In the present embodiment, the photoconductor layer 2 is composed of a porous semiconductor layer comprising a layer of the semiconductor fine particles 22 on which the dye of the present invention is adsorbed. This dye may be dissociated in some electrolytes. The photoconductor layer 2 may be designed to have a multi-layer structure according to the purpose.

As described above, the photoreceptor layer 2 has high light-receiving sensitivity in that it contains the semiconductor fine particles 22 on which specific coloring matters are adsorbed. Therefore, when the photoreceptor layer 2 is used as a photo-electrochemical cell 100, And has higher durability.

(Charge transport layer)

The electrolyte used in the photoelectric conversion element 10 of the present invention includes, for example, a combination of iodine and iodide (for example, lithium iodide, tetrabutylammonium iodide, tetramethylammonium iodide, etc.) (For example, methylviologen chloride, hexylbiologen bromide, benzyl birogen tetrafluoroborate) and a reducing agent thereof, a combination of polyhydroxybenzenes (for example, hydroquinone, naphthohydro Quinone, etc.) and an oxidized form thereof, a combination of a divalent and trivalent iron complex (for example, a red blood salt and a sulfur white salt), a combination of a divalent and trivalent cobalt complex, and the like. The combination of iodine and iodide in these is preferred.

When a combination of iodine and iodide is used as the electrolyte, it is preferable to additionally use an iodide salt of a nitrogen-containing aromatic cations of a five-membered ring or a six-membered ring. Particularly, when the compound represented by the general formula (1) is not an iodide salt, the compound represented by the general formula (1) 1997), and the like are preferably used in combination with iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts.

The content of iodine in the electrolyte used in the photoelectric conversion element 10 of the present invention is preferably 0.1 to 20 mass%, more preferably 0.5 to 5 mass%, with respect to the whole electrolyte.

The electrolyte used in the photoelectric conversion element 10 of the present invention may contain a solvent. The content of the solvent in the electrolyte is preferably 50 mass% or less, more preferably 30 mass% or less, and particularly preferably 10 mass% or less.

As the electrolyte of the present invention, a charge transport layer containing a hole conductor material may be used. As the hole conductor material, 9,9'-spirobifluorene derivatives and the like can be used.

In addition, an electrode layer, a photoconductor layer (photoelectric conversion layer), a charge carrier layer (hole transport layer), a conductive layer, and a counter electrode layer can be sequentially laminated. a hole transporting material functioning as a p-type semiconductor can be used as the hole transporting layer. As the preferable hole transporting layer, for example, an inorganic or organic hole transporting material can be used. Examples of the inorganic hole transporting material include CuI, CuO, NiO and the like. Examples of the organic-based hole transporting material include high-molecular-weight and low-molecular-weight materials. Examples of the high molecular weight material include polyvinylcarbazole, polyamine and organic polysilane. Examples of low-molecular-weight compounds include triphenylamine derivatives, stilbene derivatives, hydrazone derivatives, and phenamine derivatives. Of these, organic polysilanes are preferred because σ electrons that are not localized along the Si of the main chain contribute to light conduction, unlike conventional carbon-based polymers (Phys. Rev. B, 35 , 2818 (1987)).

(Conductive support)

1, in the photoelectric conversion element of the present invention, a photoconductor layer 2 on which a dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1. As described later, the photoconductor layer 2 can be produced, for example, by applying a dispersion of semiconductor fine particles to an electrically conductive substrate and drying the same, followed by immersion in the dye solution of the present invention.

As the conductive support 1, a conductive material such as a metal may be used as the support itself, or a glass or a polymeric material having a conductive film layer on the surface thereof may be used. The conductive support 1 is preferably substantially transparent. Means that the transmittance of light is 10% or more, preferably 50% or more, and particularly preferably 80% or more. As the conductive support 1, glass or a polymer material coated with a conductive metal oxide can be used. The amount of the conductive metal oxide to be applied at this time is preferably 0.1 to 100 g per 1 m 2 of the glass or the support of the polymeric material. When a transparent conductive support is used, it is preferable that light is incident from the support side. Examples of the polymer material that is preferably used include triacetylcellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin and phenoxy bromide. For example, an antireflection film obtained by alternately laminating a high-refraction film and a low-refraction ratio oxide film described in Japanese Patent Application Laid-Open No. 2003-123859, A light guide function described in JP-A-2002-260746.

In addition, a metal support may be preferably used. Examples thereof include titanium, aluminum, copper, nickel, iron, stainless steel, and copper. These metals may be alloys. More preferably, titanium, aluminum and copper are preferable, and titanium and aluminum are particularly preferable.

(Semiconductor fine particles)

1, the photoelectric conversion element 10 of the present invention is provided with a photoconductor layer 2 on which a dye 21 is adsorbed on a porous semiconductor fine particle 22 on a conductive support 1. As described later, the photoconductor layer 2 can be produced, for example, by applying a dispersion liquid of the semiconductor fine particles 22 to the electroconductive substrate 1, drying it, and then immersing the solution in the above-described dye solution. In the present invention, as the semiconductor fine particles, those prepared using the above specific surfactant are applied.

(Semiconductor fine particle dispersion)

In the present invention, a semiconductor fine particle dispersion in which the content of solids other than the semiconductor fine particles is 10% by mass or less based on the total amount of the semiconductor fine particle dispersion is applied to the conductive support 1 and heated appropriately to obtain the porous semiconductor fine particle coating layer .

Examples of the method for producing the semiconductor fine particle dispersion include a method in which a semiconductor is precipitated as fine particles in a solvent for synthesis of semiconductors as they are, a method in which fine particles are irradiated with ultrasonic waves to be pulverized with ultrafine particles, And mechanically grinding and grinding. As the dispersion solvent, one or more of water and various organic solvents may be used. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol, ketones such as acetone, esters such as ethyl acetate, dichloromethane and acetonitrile.

When dispersed, a small amount of a polymer such as polyethylene glycol, hydroxyethylcellulose, carboxymethylcellulose, a surfactant, an acid, or a chelating agent may be used as a dispersion aid, if necessary. However, it is preferable that most of these dispersion auxiliary agents are removed by a filtration method, a separation membrane method, or a centrifugal separation method before the step of forming a film on the conductive support. In the semiconductor fine particle dispersion, the content of solid matter other than the semiconductor fine particles may be 10 mass% or less of the total dispersion. This concentration is preferably 5 mass% or less, more preferably 3 mass% or less, and particularly preferably 1 mass% or less. More preferably 0.5% by mass or less, and particularly preferably 0.2% by mass or less. That is, the solids other than the solvent and the semiconductor fine particles in the semiconductor fine particle dispersion can be made up to 10 mass% or less of the whole semiconductor micro dispersion. It is preferable that it is composed substantially only of the semiconductor fine particles and the dispersion solvent.

If the viscosity of the semiconductor microparticle dispersion is too high, the dispersion may aggregate and the film can not be formed. Conversely, if the viscosity of the semiconductor microparticle dispersion is too low, the solution may flow and the film can not be formed. Therefore, the viscosity of the dispersion is preferably 10 to 300 N · s / m 2 at 25 ° C. More preferably, it is 50 to 200 N · s / m 2 at 25 ° C.

As a coating method of the semiconductor fine particle dispersion, a usual application such as a roller method and a dipping method can be used as an application system method. As a metering method, an air knife method, a blade method, or the like can be used.

A preferable thickness of the entire semiconductor fine particle layer is 0.1 mu m to 100 mu m. The thickness of the semiconductor fine particle layer is also preferably 1 mu m to 30 mu m, more preferably 2 mu m to 25 mu m. The supported amount of the semiconductor fine particles per 1 m 2 of the support is preferably 0.5 g to 400 g, more preferably 5 g to 100 g. The method of applying the fine particle dispersion to form a film is not particularly limited, and a known method may be appropriately applied.

The amount of the dye 21 to be used is preferably 0.01 mmol to 100 mmol, more preferably 0.1 mmol to 50 mmol, particularly preferably 0.1 mmol to 10 mmol, per 1 m 2 of the support. In this case, the amount of the dye 21 to be used in the present invention is preferably 5 mol% or more. The adsorption amount of the dye 21 to the semiconductor fine particles 22 is preferably 0.001 mmol to 1 mmol, more preferably 0.1 to 0.5 mmol, per 1 g of the semiconductor fine particles. By using such a small amount of color, the effect of increasing or decreasing in the semiconductor can be sufficiently obtained. On the other hand, if the amount of dye is small, the effect of increasing and decreasing becomes insufficient, and if the amount of dye is too large, a dye not attached to the semiconductor floats to cause a decrease / decrease effect.

(The main pole)

The counter electrode (4) acts as a positive electrode of a photoelectrochemical cell. The counter electrode 4 is usually in agreement with the above-described conductive support 1, but in the configuration in which the strength is sufficiently maintained, the counter electrode support is not necessarily required. However, the side having the support is advantageous in terms of hermeticity. Examples of the material of the counter electrode 4 include platinum, carbon, and a conductive polymer. Preferable examples thereof include platinum, carbon, and conductive polymers. As the structure of the counter electrode 4, a structure having a high current collecting effect is preferable. As a preferable example, JP-A-10-505192 and the like can be mentioned.

(Light receiving electrode)

The light receiving electrode 5 may be of a tandem type in order to increase the utilization ratio of the incident light. Examples of preferable configurations of the tandem type include those described in JP-A-2000-90989 and JP-A-2002-90989. An optical management function for efficiently performing light scattering and reflection within the layer of the light receiving electrode 5 may be set. Preferably, those described in JP-A-2002-93476 can be mentioned.

It is preferable to form a short-circuit prevention layer between the conductive support 1 and the porous semiconductor fine particle layer in order to prevent a reverse current due to the direct contact between the electrolyte and the electrode. A preferable example is JP-A-06-507999. In order to prevent contact between the light-receiving electrode 5 and the counter electrode 4, it is preferable to use a spacer or a separator. A preferable example is Japanese Laid-Open Patent Publication No. 2001-283941.

As the sealing method of cells and modules, there are a method of using a polyisobutylene thermosetting resin, a novolac resin, a photocurable (meth) acrylate resin, an epoxy resin, an ionomer resin, a glass frit, an aluminum alkoxide in alumina, And a method of laser melting the melting point glass paste. In the case of using glass frit, powder glass may be mixed with an acrylic resin to be a binder.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not construed as being limited thereto.

≪ Synthesis Example of Pigments >

Intermediate D4-5 was synthesized from the route shown in Scheme 1.

[Chemical Formula 22]

Using Intermediate D4-5, the literature Chem. Commun., 2009, 5844. Dye 4 was synthesized.

Similarly, Dye 1 to Dye 3 and Dye 5 to Dye 11 were synthesized.

(Example 1)

A semiconductor layer of a semiconductor electrode constituting a photoelectrode or various pastes for forming a light scattering layer were prepared, and a dye-sensitized solar cell was produced using this paste.

[Preparation of paste]

First, a semiconductor layer or a paste for forming a light scattering layer of a semiconductor electrode constituting a photoelectrode was prepared in the composition shown in Table A below. Further, in the following formulation, TiO ₂ was added to a medium and stirred to prepare a slurry, and a thickener was added thereto, followed by kneading to obtain a paste.

[Table A]

TiO ₂ Particle 1: Anatase, average particle diameter: 25 nm

TiO ₂ Particle 2: Anatase, average particle diameter: 200 nm

Rod-shaped TiO ₂ particle S1: anatase, diameter: 100 nm, aspect ratio: 5

Rod-shaped TiO ₂ particle S2: anatase, diameter: 30 nm, aspect ratio: 6.3

Rod-shaped TiO ₂ particle S3: anatase, diameter: 50 nm, aspect ratio: 6.1

Rod-shaped TiO ₂ particles S4: anatase, diameter: 75 nm, aspect ratio: 5.8

Rod-shaped TiO ₂ particles S5: anatase, diameter: 130 nm, aspect ratio: 5.2

Rod-shaped TiO ₂ particle S6: anatase, diameter: 180 nm, aspect ratio: 5

Rod-shaped TiO ₂ particles S7: anatase, diameter: 240 nm, aspect ratio: 5

Rod-shaped TiO ₂ particle S8: anatase, diameter: 110 nm, aspect ratio: 4.1

Rod-shaped TiO ₂ particle S9: anatase, diameter: 105 nm, aspect ratio: 3.4

Plate-like mica particles P1: Diameter: 100 nm, aspect ratio: 6

CB: Cellulosic binder

A photoelectrode having the same structure as that of the photoelectrode 12 shown in Fig. 5 described in JP-A-2002-289274 was fabricated by the following procedure, and using photoelectrodes, Sensitized solar cell 1 having a scale of 10 mm x 10 mm having the same structure as that of the dye-sensitized solar cell 20 except for the photo-electrode was prepared. The specific structure is shown in Fig. 2 attached hereto. 41 is a transparent electrode, 42 is a semiconductor electrode, 43 is a transparent conductive film, 44 is a substrate, 45 is a semiconductor layer, 46 is a light scattering layer, 40 is a photoelectrode, 20 is a dye sensitized solar cell, The electrolyte, S, is a spacer.

A transparent electrode having a fluorine-doped SnO ₂ conductive film (film thickness: 500 nm) formed on a glass substrate was prepared. Then, the above-mentioned paste 2 was screen-printed on the SnO ₂ conductive film, and then dried. Thereafter, it was fired in air at 450 캜. Further, by using a silver paste (4) repeating the screen printing and firing, SnO ₂ conductive film image on the semiconductor electrode of the same construction as the semiconductor electrode 42 shown in Fig. 2 (the area of the light-receiving surface; 10 mm × 10 mm , The thickness of the semiconductor layer, the thickness of the light scattering layer, the thickness of the light scattering layer, and the content of the rod-shaped TiO ₂ particles 1 contained in the light scattering layer: 30% by mass) Was prepared.

Next, the dye was adsorbed onto the semiconductor electrode as follows. First, a dye solution described below in Table 1 was dissolved in anhydrous ethanol dehydrated with magnesium ethoxide to have a concentration of 3 × 10 ^-4 mol / l. Next, the semiconductor electrode was immersed in this solution, whereby the dye was adsorbed to the semiconductor electrode at about 1.5 × 10 ^-7 mol / cm 2 to complete the photo-electrode 40.

Next, an iodide redox solution containing iodine and lithium iodide as the electrolyte E was prepared as a platinum electrode (Pt thin film thickness: 100 nm) having the same shape and size as the above-mentioned counter electrode as the counter electrode. In addition, a spacer S (trade name: "Surlyn") manufactured by Du Pont Co., Ltd., having a shape corresponding to the size of the semiconductor electrode, was prepared and as shown in FIG. 3 described in Japanese Patent Application Laid-Open No. 2002-289274, And the counter electrode CE and the spacer S were disposed to face each other, and the above electrolyte was filled in the inside, thereby completing a dye-sensitized solar cell.

(Test Methods)

The cell characteristics test was conducted, and the conversion efficiency? Was measured for the dye-sensitized solar cell. The battery characteristics test was carried out by irradiating with a solar light of 1000 W / m 2 from a xenon lamp passed through an AM 1.5 filter using a solar simulator (WACS-85H manufactured by WACOM). The current-voltage characteristic was measured using an I-V tester, and conversion efficiency (? /%) And the like were obtained.

Further, the IPCE (quantum yield) at 400 to 900 nm was measured by an IPCE measuring apparatus manufactured by PECEL. (IPCE at 850 nm is shown in Table 1 below).

Evaluation and judgment were carried out for each of the following items. A rating of A or higher for all can give a high evaluation in the market.

(Initial conversion efficiency)

AA: More than 7.5%

A: 7.0% or more and less than 7.5%

B: More than 5.0% and less than 7.0%

C: Less than 5.0%

(850 nm IPCE)

AA: More than 10%

A: 8% to less than 10%

B: More than 6% and less than 8%

C: Less than 6%

(Reduction rate [γd] of conversion efficiency after storage in a dark place)

And the photoelectric conversion efficiency (eta _f ) after 80 hours of curing for 300 hours was measured. The durability factor (? D: the following formula) with respect to the initial conversion efficiency (? _I ) of this? _F was determined and evaluated.

Expression: Dropout rate (? D) = (? _I -? _F ) / (? _I )

AA: γd is less than 5%

A: The value of? D is 5% or more and less than 10%

B:? D is 10% or more but less than 20%

C: γd is 20% or more

(The reduction rate [γL] of conversion efficiency after irradiation)

The photoelectric conversion efficiency (? _G ) after 500 hours of continuous light irradiation was measured. The reduction rate (? L: the following formula) with respect to the initial conversion efficiency (? _I ) of this? _G was determined and evaluated.

Formula: rate of descent _{(γL) = (η i -η} g) / (η i)

AA: γL less than 5%

A: γL of 5% or more and less than 10%

B:? L of 10% or more and less than 15%

C: γL of 15% or more

The results are shown in Table 1 below.

Comparison dye

(23)

The comparative pigment A is a ruthenium complex pigment described in International Patent Publication No. 98/50393 pamphlet.

As can be seen from the above results, the coloring matter of the present invention exhibits excellent results over IPCE and conversion efficiency in the long wavelength region, other current / voltage characteristics, and durability over conventional pigments Able to know. Among them, those having a specific substituent at the 4-position (Tests Dye 1 and 4) in the pyridine ring of the bicyclic ligand (Formula L2) exhibited remarkable effects.

The combination effect with the combined dye (2) was also deteriorated in the conventional pigments A and B (initial conversion efficiency and durability tended to be the same but deteriorated in the determination sequence) A good combination effect was confirmed for the dyes of the invention (see tests 201-203).

Tests were similarly conducted on Paste 1 to Paste 14 other than Paste 2, and it was confirmed that good performance was obtained by the coloring matter of the present invention. In particular, Paste 10 and Paste 13 exhibited high performance in photoelectric conversion efficiency and durability.

(Example 2)

A dye-sensitized solar cell having the same structure as that shown in Fig. 1 described in JP-A-2010-218770 was produced by the following procedure. The specific structure is shown in FIG. 3 attached hereto. 51 is a transparent substrate, 52 is a transparent conductive film, 53 is a barrier layer, 54 is an n-type semiconductor electrode, 55 is a p-type semiconductor layer, 56 is a p-type semiconductor film, 57 is a counter electrode (57a is a projection of a counter electrode).

(Transparent Conductive Oxide: TCO) formed by CVD of SnO ₂ : F (fluorine-doped tin oxide) as the transparent conductive film 52 on a transparent glass plate as a transparent substrate 51 of 20 mm x 20 mm x 1 mm ) Glass substrate was prepared.

Next, 5 ml of a solution prepared by mixing Ti (OCH (CH ₃ ) ₂ ) ₄ and water in a volume ratio of 4: 1 was mixed with 40 ml of an ethyl alcohol solution adjusted to pH 1 with hydrochloric acid salt to prepare a solution of TiO ₂ precursor It was prepared. This solution was spin-coated on a TCO glass substrate at 1000 rpm and subjected to sol-gel synthesis, then heated at 78 캜 for 45 minutes under vacuum, and annealed at 450 캜 for 30 minutes to obtain a titanium oxide thin film The barrier layer 53 was formed.

On the other hand, anatase type titanium oxide particles having an average particle diameter of 18 nm (particle diameter: 10 nm to 30 nm) were uniformly dispersed in a mixed solvent of ethanol and methanol (ethanol: methanol = 10: 1 (volume ratio) To prepare a slurry. At this time, the titanium oxide particles were homogeneously dispersed at a ratio of 10 mass% with respect to 100 mass% of the mixed solvent using a homogenizer.

Next, a solution obtained by dissolving ethyl cellulose as a viscosity adjusting agent in ethanol at a concentration of 10% by mass and an alcohol-based organic solvent (terpineol) were added to the slurry of the titanium oxide prepared above, and the mixture was again homogenized And homogeneously dispersed. Thereafter, alcohols other than terpineol were removed by a twin-blender and mixed with a mixer to prepare a paste-containing titanium oxide particle-containing composition. The composition of the titanium oxide particle-containing composition thus prepared was 100% by mass of the titanium oxide particle-containing composition, 20% by mass of the titanium oxide particles, and 5% by mass of the viscosity adjusting agent.

The titanium oxide particle-containing composition thus prepared was applied on the barrier layer 53 formed as described above so as to form a predetermined pattern by screen printing, dried at 150 占 폚 and then heated to 450 占 폚 in an electric furnace Thus, a laminate in which the n-type semiconductor electrode 54 was laminated on the TCO glass substrate was obtained. Subsequently, this laminate was immersed in a solution of zinc nitrate (ZnNO ₃ ) overnight, and then subjected to surface treatment by heating at 450 ° C for 45 minutes. Thereafter, the surface-treated laminate was immersed in the ethanol solution (concentration of the sensitizing dye: 3 x 10 ^-4 mol / l) using the various dyes shown in Table 1, left at 25 ° C for 40 hours, the dye was adsorbed to the interior of the n-type semiconductor electrode 54.

Subsequently, CuI was added to acetonitrile to prepare a saturated solution. 6 ml of the supernatant was taken out, and 15 mg of 1-methyl-3-ethylimidazolium thiocyanate was added to adjust the solution of the p-type semiconductor did. Then, a laminate after containing the dye in the above-mentioned n-type semiconductor electrode 54 is placed on a hot plate heated to 80 DEG C and the solution of the p-type semiconductor is dripped into the n-type semiconductor electrode 54 with a pipette The resultant was allowed to stand for one minute and dried to produce a p-type semiconductor layer 55.

Next, a copper plate having a thickness of 1 mm was washed with hydrochloric acid having a concentration of 1 M, washed with anhydrous ethanol, and then heated at 500 캜 for 4 hours in the air to obtain a CuO nanowire having a maximum diameter of 100 nm and a height of 10 탆 (57a)) was grown. This copper plate was sealed in a sealed container with iodine crystals and heated in a thermostatic chamber at 60 DEG C for 1 hour to prepare a counter electrode 57 having a thin CuI layer (p-type semiconductor film 56) coated on its surface. Then, the counter electrode 57 was laminated on the laminate manufactured as described above by pressing it on the p-type semiconductor layer 55 side.

The conversion efficiency of the dye-sensitized solar cell fabricated as described above was tested in the same manner as in Example 1. As a result, it was confirmed that all of the dyes of the present invention had good performance and improvement effects.

(Example 3)

The dye-sensitized photovoltaic cell shown in Fig. 4 was produced by using CdSe quantum dot processing on the photoelectrode and an electrolyte using a cobalt complex in the following manner.

An ethanol solution of titanium (IV) bis (acetylacetonate) diisopropoxide was sprayed 16 times onto the surface of an FTO glass (1), a surface resistance of 8 Ωsq ^-1 manufactured by Nippon Pan Glass Co., For 30 minutes or more. On this substrate, a transparent layer of about 2.1 탆 with 20 nm - TiO ₂ and a transparent layer of 60 nm - TiO ₂ (Manufactured by SHOWA TITANIUM CO., LTD.) Was layered by screen printing and post-treated with an aqueous TiCl ₄ solution to prepare an FTO / TiO ₂ film.

The FTO / TiO ₂ film was immersed in a 0.03 M Cd (NO ₃ ) ₂ ethanol solution in a glove bag under an inert gas atmosphere for 30 seconds and then immersed in a 0.03 M selenide ethanol solution for 30 seconds successively. Thereafter, it was rinsed in ethanol for one minute or more, and excess precursor was removed and dried. This immersion → cleaning → drying process was repeated five times to grow CdSe quantum dots 23 in the titanium oxide layer 22 and surface stabilization treatment with CdTe to produce a CdSe-treated optical electrode.

Selenide (Se ^{2 -} ) can be either Ar or N ₂ Atmosphere, of 0.068 g NaBH ₄ (So as to have a concentration of 0.060 M) was added to a 0.030 M solution of SeO _{2 in} ethanol.

After the CdSe-treated photo-electrode was immersed in the dye solution for 4 hours to adsorb the dye 21 to the photoelectrode, the photoelectrode and the counter electrode (4, a solution of hexachloroplatinic acid 2-propanol (0.05 M) (Manufactured by DuPont Co., Ltd.) having a thickness of 25 탆 was sandwiched therebetween and sealed by thermal dissolution. (0.75 M Co (o-phen) ₃ ²⁺ , 0.075 M Co (o-phen) ₃ ³⁺ and 0.20 M LiClO ₄ in acetonitrile / ethylene carbonate (4: 6 / v: v) solution) The pores of the dye-sensitized solar cell 10 (10) are injected into the gap 3 between the electrodes from holes previously formed in the side surfaces of the counter electrode, and then the holes are closed by heat with a sheet of Binnell ).

The cobalt complex added to the electrolyte was adjusted by the method described in Chemical Communications, Vol. 46, pp. 8788-8790 (2010).

The conversion efficiency of the dye-sensitized solar cell fabricated as described above was tested in the same manner as in Example 1. As a result, it was confirmed that all of the dyes of the present invention had good performance and improvement effects.

While the present invention has been described in conjunction with the embodiments thereof, it is to be understood that the invention is not to be limited to any details of the description thereof except as otherwise specified, and that the invention is not limited to the details and spirit of the invention as set forth in the appended claims. I think it should be interpreted.

The present application claims priority based on Japanese Patent Application No. 2011-214663, filed on September 29, 2011, which is incorporated herein by reference and its contents as part of the description of this specification.

1: conductive support
2: Photoconductor layer
21: Pigment
22: Semiconductor fine particles
23: CdSe quantum dot
3: charge carrier layer
4: antipode
5: Light receiving electrode
6: Circuit
10: Photoelectric conversion element
100: Photoelectrochemical cell
M: Electric motor (electric fan)
41: transparent electrode
42: Semiconductor electrode
43: transparent conductive film
44: substrate
45: Semiconductor layer
46: light scattering layer
40: photoelectrode
20: dye-sensitized solar cell
CE: The great pole
E: electrolyte
S: Spacer
51: transparent substrate
52: transparent conductive film
53: barrier layer
54: n-type semiconductor electrode
55: p-type semiconductor layer
56: p-type semiconductor film
57: The great pole
57a: protrusion

Claims (9)

1. A photoelectric conversion element having a laminate structure in which a counter electrode is disposed by arranging a photoconductor layer having a layer of semiconductor fine particles on which a dye is adsorbed, a charge carrier layer and a counter electrode on a conductive support, wherein the metal complex represented by the following formula (1) A photoelectric conversion element using a dye.
ML ¹ L ² X (1)
Wherein M represents a transition metal selected from ruthenium, osmium, iron, rhenium, and technetium. X ^{is, NCS -, Cl -, Br} -, I -, CN -, NCO - represents the, or H ₂ O. L ¹ Represents a three-digit ligand represented by the following formula (L1), and L < ² > Represents a two-digit ligand represented by any of the following formulas (L2-1) to (L2-5).]
[Chemical Formula 1]

[In the formula (L1), Za, Zb and Zc each independently represent a group of a nonmetal atom capable of forming a 5 or 6-membered ring. Provided that at least one of the rings formed by Za, Zb and Zc has an acidic group.
(2)

Wherein G < ^{1 >} Represents a structure shown by any one of formula (G1-1) ~ (G1-6), G 2 Represents a structure represented by any one of the following formulas (G2-1) to (G2-3). R represents a substituent. n1 represents an integer of 0 to 3; and n2 represents an integer of 0 to 5.]
(3)

Wherein R ¹ to R ³ (OH) ² , PO (OR) (OH), or CO (NHOH), each independently represents a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group, COOH, PO R ⁴ Represents a hydrogen atom, an alkyl group, or an aryl group. Wherein R represents an alkyl group, a heteroaryl group, or an aryl group. * Indicates a combined hand.] The method according to claim 1,
The L ² Is expressed by the formula (L2-1) or (L2-2). 3. The method according to claim 1 or 2,
The G ¹ The photoelectric conversion element represented by (G1-1), (G1-2), or (G1-5). 4. The method according to any one of claims 1 to 3,
The G ² Is represented by (G2-1) or (G2-2). 5. The method according to any one of claims 1 to 4,
The R ¹ Is an alkyl group substituted with an electron-withdrawing group. 6. The method according to any one of claims 1 to 5,
Wherein Za, Zb and Zc are each independently selected from an imidazole ring, an oxazole ring, a thiazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring. 7. The method according to any one of claims 1 to 6,
Wherein the photoconductor layer further contains a dye represented by the following formula (2).
MzL ³ _m3 L ⁴ _m4 Y _mY · CI (2)
[In the formula (2), Mz represents a metal atom. L ³ Represents a ligand represented by the following formula (L3). L ⁴ Represents a ligand represented by the following formula (L4). Y represents a 1-position or 2-position ligand. m3 represents an integer of 0 to 3; and m4 represents an integer of 1 to 3. and mY represents an integer of 0 to 2. CI indicates the counter ion when counter ion is required to neutralize charge.]
[Chemical Formula 4]

(In the formula (L3), Ac represents an acidic group, R ^a Represents a substituent. R ^b represents an alkyl group or an aromatic ring group. e1 and e2 each independently represent an integer of 0 to 5; L ^c and L ^d Represents a conjugated chain. e3 represents 0 or 1; f represents an integer of 0 to 3; and g represents an integer of 0 to 3.)
[Chemical Formula 5]

Z represents a group of atoms capable of forming a 5 or 6-membered ring, and Z represents 0 or 1. Zd, Ze and Zf each independently represents a group of atoms capable of forming a 5- or 6-membered ring, And at least one of the forming rings has an acidic group. A photoelectrochemical cell using the photoelectric conversion element according to any one of claims 1 to 7. A coloring matter represented by the following general formula (1).
ML ¹ L ² X (1)
Wherein M represents a transition metal selected from ruthenium, osmium, iron, rhenium, and technetium. X ^{is, NCS -, Cl -, Br} -, I -, CN -, NCO - represents the, or H ₂ O. L ¹ Represents a three-digit ligand represented by the following formula (L1), and L < ² > Represents a two-digit ligand represented by any of the following formulas (L2-1) to (L2-5).
[Chemical Formula 6]

In the formula (L1), Za, Zb and Zc each independently represent a group of a nonmetal atom capable of forming a 5 or 6-membered ring. Provided that at least one of the rings formed by Za, Zb and Zc has an acidic group.
(7)

In the formula, G ¹ Represents a structure shown by any one of formula (G1-1) ~ (G1-6), G 2 Represents a structure represented by any one of the following formulas (G2-1) to (G2-3).
[Chemical Formula 8]

In the formulas, R ¹ to R ³ Represents a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group, COOH, PO (OH) ₂ , PO (OR) (OH), or CO (NHOH). R ⁴ Represents a hydrogen atom, an alkyl group, or an aryl group. Wherein R represents an alkyl group, a heteroaryl group, or an aryl group. * Indicates a combined hand.]

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