JP2012038436A - Photoelectric conversion element, photoelectrochemical cell using the same, and composition for photoelectric conversion element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectrochemical cell using a photoelectric conversion element with high photoelectric conversion efficiency and high durability, and a composition for the photoelectric conversion element.SOLUTION: The photoelectric conversion element has a photoreceptor layer having composite sensitizing coloring matter and semiconductor fine particles, and is characterized in using, as the composite sensitizing color matter, coloring matter having a structure represented by general formula (1) and coloring matter having a structure represented by general formula (2). In general formula (1), A1 represents a specific nitrogen-containing heterocycle. Lrepresents an electron transferring coupling group including specific heterocycle. Rand Reach represent a specific substituent. Rrepresents a hydrogen atom or a substituent. B1 represents a substituted methylene group having at least one acid group. n11 represents an integer of 1-12. In general formula (2) of M(LL)(LL)(X)CI, M represents a metal atom, and LLand LLeach represent a specific ligand.

Description

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

  Photoelectric conversion elements are used in various optical sensors, copying machines, solar cells, and the like. Various types of photoelectric conversion elements have been put to practical use, such as those using metals, semiconductors, organic pigments and dyes, or combinations thereof. Above all, a solar cell using non-depleting solar energy does not require fuel, and its full-scale practical use is expected greatly as it uses inexhaustible clean energy. Among these, silicon solar cells have been researched and developed for a long time. It is spreading due to the policy considerations of each country. However, silicon is an inorganic material, and its throughput and molecular modification are naturally limited.

  Therefore, research on dye-sensitized solar cells has been vigorously conducted. In particular, Graetzel et al. Of Lausanne University of Technology in Switzerland developed a dye-sensitized solar cell in which a dye composed of a ruthenium complex was fixed on the surface of a porous titanium oxide thin film, and realized conversion efficiency comparable to amorphous silicon. As a result, dye-sensitized solar cells have attracted a great deal of attention from researchers around the world.

  In particular, from the perspective of responding in Japan and other regions where energy resources are scarce, or accelerating the replacement of fossil fuels with green energy that does not emit carbon dioxide, the research and development of solar cells is more proactive in various fields. It has been tackled. The current mainstream is based on silicon (Si), but a great deal of attention is being focused on next-generation technologies that substitute for the above-mentioned viewpoints such as throughput. In particular, organic solar cells are expected to be light and low in cost and excellent in environmental compatibility.

  Patent Documents 1 and 2 disclose dye-sensitized solar cells using metal complex dyes. The dye disclosed therein has light absorption ability in a suitable wavelength region, and realizes good photoelectric conversion efficiency. On the other hand, Patent Documents 3 and 4 disclose organic dye-based sensitizing dyes, which are also supposed to realize high photoelectric conversion efficiency.

JP 2001-291534 A International Publication No. 2007/091525 Pamphlet International Publication No. 2007/119525 Pamphlet International Publication No. 2007/134939 Pamphlet

So far, as described above, in the development of dye-sensitized solar cells, attempts have been made mainly to improve the photoelectric conversion efficiency by modifying the chemical structure of a single dye-sensitized dye. Japanese Patent Application Laid-Open No. 2004-228561 also has a description about partially improving durability, but details regarding the degree of improvement are unclear. Moreover, in each said literature, there is no description regarding the combination of an organic pigment | dye (nonmetallic complex) and a metal complex pigment | dye.
Accordingly, the present invention provides a composite sensitizing dye that combines an organic dye (non-metal complex dye) and a metal complex dye, achieving an equivalent or higher photoelectric conversion efficiency than the single dye, An object of the present invention is to provide a photoelectric conversion element that can further enhance durability, a photoelectrochemical cell using the photoelectric conversion element, and a composition for a photoelectric conversion element.

The object of the present invention has been achieved by the following means.
<1> A photoelectric conversion element comprising a photosensitive layer having a composite sensitizing dye in which two or more kinds of dyes are combined and semiconductor fine particles, wherein the composite sensitizing dye is represented by the following general formula (1). And a dye having a structure represented by the following general formula (2).

［一般式（１）中、Ａ１は、５〜７員環の含窒素複素環を表す。Ｌ^１１はチオフェン環、フラン環、ピロール環、セレノフェン環、及びこれらが縮環した複素環の中から選ばれる少なくとも１種の複素環を含む電子伝達性連結基を表す。Ｒ^１１及びＲ^１３は、それぞれ、水素原子、アルキル基、アルコキシ基、及びアリール基から選ばれる少なくとも１種の置換基を表す。Ｒ^１２は水素原子または置換基を表す。Ｂ１はヘテロ環酸性核または電子求引性基が置換したメチレン基を表す。ただしＢ１は少なくとも一つの酸性基を有する。ｎ１１は１〜１２の整数を示す。］
Ｍ（ＬＬ^１）_ｍ１（ＬＬ^２）_ｍ２（Ｘ）_ｍ３・ＣＩ 一般式（２）
［式中、Ｍは金属原子を表す。ＬＬ^１は下記一般式（３）により表される２座または３座の配位子を表す。

[In General Formula (1), A1 represents a 5- to 7-membered nitrogen-containing heterocyclic ring. L ¹¹ represents an electron-transporting linking group containing at least one heterocyclic ring selected from a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, and a heterocyclic ring condensed with these. R ¹¹ and R ¹³ each represent at least one substituent selected from a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. R ¹² represents a hydrogen atom or a substituent. B1 represents a methylene group substituted by a heterocyclic acidic nucleus or an electron withdrawing group. However, B1 has at least one acidic group. n11 represents an integer of 1 to 12. ]
M (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI General formula (2)
[Wherein M represents a metal atom. LL ¹ represents a bidentate or tridentate ligand represented by the following general formula (3).

（式中、Ｒ^２１およびＲ^２２はそれぞれ独立にカルボキシル基、スルホン酸基、ヒドロキシル基、ヒドロキサム酸基、ホスホリル基、またはホスホニル基を表す。Ｒ^２３およびＲ^２４はそれぞれ独立に置換基を表す。Ｒ^２５およびＲ^２６はそれぞれ独立にアルキル基、アリール基および／またはヘテロ環基を表す。Ｌ^２１およびＬ^２２はそれぞれ独立にエテニレン基および／またはエチニレン基からなる共役鎖を表す。ａ２１およびａ２２はそれぞれ独立に０〜３の整数を表し、ａ２１が２以上のときＲ^２１は同じでも異なっていてもよく、ａ２２が２以上のときＲ^２２は同じでも異なっていてもよい。ｂ２１およびｂ２２はそれぞれ独立に０〜３の整数を表し、ｂ２１が２以上のときＲ^２３は同じでも異なっていてもよく互いに連結して環を形成してもよく、ｂ２２が２以上のときＲ^２４は同じでも異なっていてもよく互いに連結して環を形成してもよい。ｂ２１およびｂ２２が共に１以上のときＲ^２３とＲ^２４が連結して環を形成してもよい。ｎ２１およびｎ２２はそれぞれ独立に０〜５の整数を表す。ｎ２３は０または１を表す。）
ＬＬ^２は下記一般式（４）により表される置換基を有していても良い２座または３座の配位子を表す。

(In the formula, R ²¹ and R ²² each independently represent a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group, or a phosphonyl group. R ²³ and R ²⁴ each independently represent a substituent. R ²⁵ and R ²⁶ each independently represents an alkyl group, an aryl group and / or a heterocyclic group, L ²¹ and L ²² each independently represent a conjugated chain consisting of an ethenylene group and / or an ethynylene group, a ²¹ and a ²² each independently represent an integer of 0 to 3, a21 is often ^{R 21} when two or more be the same or different, a22 is 2 or more when ^{R 22} each may .b21 and b22 to be the same or different independently represent an integer of 0 to 3, with one another may be the R ²³ when b21 is 2 or more the same or different from each other , May form a ring, and b22 is 2 or more when R ²⁴ when b22 .B21 and may be linked to each other to form a ring may be the same or different are both 1 or more R ²³ R ²⁴ may be linked to form a ring. N21 and n22 each independently represents an integer of 0 to 5. n23 represents 0 or 1.)
LL ² represents a bidentate or tridentate ligand which may have a substituent represented by the following general formula (4).

（ただし、Ｚａ、ＺｂおよびＺｃはそれぞれ独立に５または６員環を形成しうる非金属原子群を表し、ｃは０または１を表す。）
Ｘはアシルオキシ基、アシルチオ基、チオアシルオキシ基、チオアシルチオ基、アシルアミノオキシ基、チオカルバメート基、ジチオカルバメート基、チオカルボネート基、ジチオカルボネート基、トリチオカルボネート基、アシル基、チオシアネート基、イソチオシアネート基、シアネート基、イソシアネート基、シアノ基、アルキルチオ基、アリールチオ基、アルコキシ基およびアリールオキシ基からなる群から選ばれた基で配位する１座または２座の配位子、あるいはハロゲン原子、カルボニル、ジアルキルケトン、１，３−ジケトン、カルボンアミド、チオカルボンアミドまたはチオ尿素からなる１座または２座の配位子を表す。Ｘ同士が連結していてもよい。
ｍ１は１〜３の整数を表し、ｍ１が２以上のときＬＬ^１は同じでも異なっていてもよい。
ｍ２は０〜２の整数を表し、ｍ２が２のときＬＬ ２は同じでも異なっていてもよい。
ｍ３は０〜３の整数を表し、ｍ３が２のときＸは同じでも異なっていてもよい。
ＣＩは電荷を中和させるのに対イオンが必要な場合の対イオンを表す。
ただし、一般式（２）で表される色素は、少なくとも１つの酸性吸着基を有する。］
＜２＞前記一般式（２）において、ＭがＲｕであることを特徴とする＜１＞記載の光電変換素子。
＜３＞前記一般式（１）で表される構造を有する色素が、下記一般式（５）または一般式（６）で表されることを特徴とする＜１＞または＜２＞記載の光電変換素子。

(However, Za, Zb, and Zc each independently represent a nonmetallic atom group that can form a 5- or 6-membered ring, and c represents 0 or 1.)
X is an acyloxy group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate group, a dithiocarbonate group, a trithiocarbonate group, an acyl group, a thiocyanate group, A monodentate or bidentate ligand coordinated by a group selected from the group consisting of an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a halogen atom Represents a monodentate or bidentate ligand consisting of carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide or thiourea. Xs may be linked together.
m1 represents an integer of 1 to 3, and when m1 is 2 or more, LL ¹ may be the same or different.
m2 represents an integer of 0 to 2, and when m2 is 2, LL2 may be the same or different.
m3 represents an integer of 0 to 3, and when m3 is 2, X may be the same or different.
CI represents a counter ion when a counter ion is required to neutralize the charge.
However, the dye represented by the general formula (2) has at least one acidic adsorption group. ]
<2> The photoelectric conversion element according to <1>, wherein in the general formula (2), M is Ru.
<3> The photoelectric device according to <1> or <2>, wherein the dye having the structure represented by the general formula (1) is represented by the following general formula (5) or the general formula (6): Conversion element.

［一般式（５）および一般式（６）中、Ｌ^１１、Ｒ^１１、Ｒ^１２、Ｂ１、及びｎ１１は、一般式（１）中のものと同義である。Ｒ^１３〜Ｒ^１７は水素原子、アルキル基、アルコキシ基及びアリール基から選ばれる少なくとも１種の置換基を表す。］
＜４＞前記一般式（１）で表される構造を有する色素が、下記一般式（７）で表されることを特徴とする＜１＞〜＜３＞いずれか記載の光電変換素子。

[In General Formula (5) and General Formula (6), L ¹¹ , R ¹¹ , R ¹² , B 1, and n ^{11 have} the same meaning as in General Formula (1). R ^{13 to} R ¹⁷ represent at least one substituent selected from a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. ]
<4> The photoelectric conversion element according to any one of <1> to <3>, wherein the dye having a structure represented by the general formula (1) is represented by the following general formula (7).

［一般式（７）中、Ｒ^１１〜Ｒ^１３、Ａ１、Ｂ１、及びｎ１１は、一般式（１）中のものと同義である。一般式（７）中のＲ^１１は同じでも異なっていてもよい。ＸはＳ、Ｏ、ＮＨ、Ｓｅから選択される。ｎ１１が２以上の場合Ｘは同じでも異なっていてもよい。］
＜５＞前記Ｂ１が下記一般式（８）または（９）で表されることを特徴とする＜１＞〜＜４＞のいずれか記載の光電変換素子。

[In General Formula (7), R ^{11 to} R ¹³ , A 1, B 1, and n ¹¹ have the same meaning as in General Formula (1). R ¹¹ in the general formula (7) may be the same or different. X is selected from S, O, NH, and Se. When n11 is 2 or more, X may be the same or different. ]
<5> The photoelectric conversion element according to any one of <1> to <4>, wherein B1 is represented by the following general formula (8) or (9).

［一般式（８）においてＲ^１１０、Ｒ^１９は、それぞれ独立に、脂肪族基、芳香族基、または複素環基であり、少なくとも１つの官能基として酸性基を有していてもよい。ｐは０〜３の整数を示す。一般式（８）における炭素−炭素二重結合は、Ｅ型又はＺ型のいずれであってもよい。一般式（８）中のＲ^１８は硫黄原子または一般式（１０）を表し、一般式（１０）における炭素−炭素二重結合は、Ｅ型又はＺ型のいずれであってもよい。
一般式（９）におけるＲ^１１１、Ｒ^１１２は、それぞれ独立に、シアノ基又は酸性基を表し、互いに同一でも異なっていてもよい。一般式（９）における炭素−炭素二重結合は、Ｅ型又はＺ型のいずれであってもよい。
一般式（１０）におけるＲ^１１３、Ｒ^１１４は、それぞれ独立に、シアノ基又は酸性基を表し、互いに同一でも異なっていてもよい。一般式（１０）における炭素−炭素二重結合は、Ｅ型Ｚ型のいずれであってもよい。］
＜６＞前記Ｂ１が下記一般式（１１）で表されることを特徴とする＜１＞〜＜５＞のいずれか記載の光電変換素子。

[In General Formula (8), R ¹¹⁰ and R ¹⁹ are each independently an aliphatic group, an aromatic group, or a heterocyclic group, and may have an acidic group as at least one functional group. p shows the integer of 0-3. The carbon-carbon double bond in the general formula (8) may be either E type or Z type. R ¹⁸ in general formula (8) represents a sulfur atom or general formula (10), and the carbon-carbon double bond in general formula (10) may be either E-type or Z-type.
R ¹¹¹ and R ¹¹² in the general formula (9) each independently represent a cyano group or an acidic group, and may be the same or different from each other. The carbon-carbon double bond in general formula (9) may be either E-type or Z-type.
R ¹¹³ and R ¹¹⁴ in the general formula (10) each independently represent a cyano group or an acidic group, and may be the same as or different from each other. The carbon-carbon double bond in the general formula (10) may be any of E type and Z type. ]
<6> The photoelectric conversion element according to any one of <1> to <5>, wherein B1 is represented by the following general formula (11).

［一般式（１１）においてＲ^１９は、脂肪族基、芳香族基または複素環基である（酸性基を有していてもよい）。］
＜７＞前記Ｂ１が下記一般式（１２）で表されることを特徴とする＜１＞〜＜７＞のいずれか記載の光電変換素子。

[In General Formula (11), R ¹⁹ is an aliphatic group, an aromatic group, or a heterocyclic group (may have an acidic group). ]
<7> The photoelectric conversion element according to any one of <1> to <7>, wherein B1 is represented by the following general formula (12).

［一般式（１２）においてＲ^１１０は、脂肪族基、芳香族基または複素環基であり、酸性基を有していてもよい。］
＜８＞前記Ｂ１が下記一般式（１３）であることを特徴とする＜１＞〜＜７＞のいずれか記載の色素。

[In General Formula (12), R ¹¹⁰ represents an aliphatic group, an aromatic group, or a heterocyclic group, and may have an acidic group. ]
<8> The dye according to any one of <1> to <7>, wherein B1 is the following general formula (13).

＜９＞前記半導体微粒子が酸化チタン微粒子であることを特徴とする＜１＞〜＜８＞のいずれか記載の光電変換素子。
＜１０＞導電性支持体上に、前記感光体層、電荷移動体、および対極をこの順序で積層した構造を有することを特徴とする＜１＞〜＜９＞のいずれかに記載の光電変換素子。
＜１１＞前記複合増感色素が前記半導体微粒子に吸着したことを特徴とする＜１＞〜＜１０＞のいずれかに記載の光電変換素子。
＜１２＞＜１＞〜＜１１＞のいずれかに記載の光電変換素子を備えることを特徴とする光電気化学電池。
＜１３＞有機溶媒中に、下記一般式（１）の構造を有する色素と、下記一般式（２）で表される構造を有する色素の両方の色素を含有し溶解したことを特徴とする光電変換素子用色素組成物。

<9> The photoelectric conversion element according to any one of <1> to <8>, wherein the semiconductor fine particles are fine titanium oxide particles.
<10> The photoelectric conversion according to any one of <1> to <9>, having a structure in which the photosensitive layer, the charge transfer body, and the counter electrode are laminated in this order on a conductive support. element.
<11> The photoelectric conversion element according to any one of <1> to <10>, wherein the composite sensitizing dye is adsorbed to the semiconductor fine particles.
<12> A photoelectrochemical cell comprising the photoelectric conversion element according to any one of <1> to <11>.
<13> Photoelectrics characterized by containing and dissolving both a dye having a structure represented by the following general formula (1) and a dye having a structure represented by the following general formula (2) in an organic solvent. A dye composition for a conversion element.

［一般式（１）中、Ａ１は、５〜７員環の含窒素複素環を表す。Ｌ^１１はチオフェン環、フラン環、ピロール環、セレノフェン環、及びこれらが縮環した複素環の中から選ばれる少なくとも１種の複素環を含む電子伝達性連結基を表す。Ｒ^１１及びＲ^１３は、それぞれ、水素原子、アルキル基、アルコキシ基、及びアリール基から選ばれる少なくとも１種の置換基を表す。Ｒ^１２は水素原子または置換基を表す。Ｂ１はヘテロ環酸性核または電子求引性基が置換したメチレン基を表す。ただしＢ１は少なくとも一つの酸性基を有する。ｎ１１は１〜１２の整数を示す。］
Ｍ（ＬＬ^１）_ｍ１（ＬＬ^２）_ｍ２（Ｘ）_ｍ３・ＣＩ 一般式（２）
［式中、Ｍは金属原子を表す。ＬＬ^１は下記一般式（３）により表される２座または３座の配位子を表す。

[In General Formula (1), A1 represents a 5- to 7-membered nitrogen-containing heterocyclic ring. L ¹¹ represents an electron-transporting linking group containing at least one heterocyclic ring selected from a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, and a heterocyclic ring condensed with these. R ¹¹ and R ¹³ each represent at least one substituent selected from a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. R ¹² represents a hydrogen atom or a substituent. B1 represents a methylene group substituted by a heterocyclic acidic nucleus or an electron withdrawing group. However, B1 has at least one acidic group. n11 represents an integer of 1 to 12. ]
M (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI General formula (2)
[Wherein M represents a metal atom. LL ¹ represents a bidentate or tridentate ligand represented by the following general formula (3).

（式中、Ｒ^２１およびＲ^２２はそれぞれ独立にカルボキシル基、スルホン酸基、ヒドロキシル基、ヒドロキサム酸基、ホスホリル基、またはホスホニル基を表す。Ｒ^２３およびＲ^２４はそれぞれ独立に置換基を表す。Ｒ^２５およびＲ^２６はそれぞれ独立にアルキル基、アリール基および／またはヘテロ環基を表す。Ｌ^２１およびＬ^２２はそれぞれ独立にエテニレン基および／またはエチニレン基からなる共役鎖を表す。ａ２１およびａ２２はそれぞれ独立に０〜３の整数を表し、ａ２１が２以上のときＲ^２１は同じでも異なっていてもよく、ａ２２が２以上のときＲ^２２は同じでも異なっていてもよい。ｂ２１およびｂ２２はそれぞれ独立に０〜３の整数を表し、ｂ２１が２以上のときＲ^２３は同じでも異なっていてもよく互いに連結して環を形成してもよく、ｂ２２が２以上のときＲ^２４は同じでも異なっていてもよく互いに連結して環を形成してもよい。ｂ２１およびｂ２２が共に１以上のときＲ^２３とＲ^２４が連結して環を形成してもよい。ｎ２１およびｎ２２はそれぞれ独立に０〜５の整数を表す。ｎ２３は０または１を表す。）
ＬＬ^２は下記一般式（４）により表される置換基を有していても良い２座または３座の配位子を表す。

(In the formula, R ²¹ and R ²² each independently represent a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group, or a phosphonyl group. R ²³ and R ²⁴ each independently represent a substituent. R ²⁵ and R ²⁶ each independently represents an alkyl group, an aryl group and / or a heterocyclic group, L ²¹ and L ²² each independently represent a conjugated chain consisting of an ethenylene group and / or an ethynylene group, a ²¹ and a ²² each independently represent an integer of 0 to 3, a21 is often ^{R 21} when two or more be the same or different, a22 is 2 or more when ^{R 22} each may .b21 and b22 to be the same or different independently represent an integer of 0 to 3, with one another may be the R ²³ when b21 is 2 or more the same or different from each other , May form a ring, and b22 is 2 or more when R ²⁴ when b22 .B21 and may be linked to each other to form a ring may be the same or different are both 1 or more R ²³ R ²⁴ may be linked to form a ring. N21 and n22 each independently represents an integer of 0 to 5. n23 represents 0 or 1.)
LL ² represents a bidentate or tridentate ligand which may have a substituent represented by the following general formula (4).

（ただし、Ｚａ、ＺｂおよびＺｃはそれぞれ独立に５または６員環を形成しうる非金属原子群を表し、ｃは０または１を表す。）
Ｘはアシルオキシ基、アシルチオ基、チオアシルオキシ基、チオアシルチオ基、アシルアミノオキシ基、チオカルバメート基、ジチオカルバメート基、チオカルボネート基、ジチオカルボネート基、トリチオカルボネート基、アシル基、チオシアネート基、イソチオシアネート基、シアネート基、イソシアネート基、シアノ基、アルキルチオ基、アリールチオ基、アルコキシ基およびアリールオキシ基からなる群から選ばれた基で配位する１座または２座の配位子、あるいはハロゲン原子、カルボニル、ジアルキルケトン、１，３−ジケトン、カルボンアミド、チオカルボンアミドまたはチオ尿素からなる１座または２座の配位子を表す。Ｘ同士が連結していてもよい。
ｍ１は１〜３の整数を表し、ｍ１が２以上のときＬＬ^１は同じでも異なっていてもよい。
ｍ２は０〜２の整数を表し、ｍ２が２のときＬＬ^２は同じでも異なっていてもよい。
ｍ３は０〜３の整数を表し、ｍ３が２のときＸは同じでも異なっていてもよい。
ＣＩは電荷を中和させるのに対イオンが必要な場合の対イオンを表す。
ただし、一般式（２）で表される色素は、少なくとも１つの酸性吸着基を有する。］

(However, Za, Zb, and Zc each independently represent a nonmetallic atom group that can form a 5- or 6-membered ring, and c represents 0 or 1.)
X is an acyloxy group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate group, a dithiocarbonate group, a trithiocarbonate group, an acyl group, a thiocyanate group, A monodentate or bidentate ligand coordinated by a group selected from the group consisting of an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a halogen atom Represents a monodentate or bidentate ligand consisting of carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide or thiourea. Xs may be linked together.
m1 represents an integer of 1 to 3, and when m1 is 2 or more, LL ¹ may be the same or different.
m2 represents an integer of 0 to 2, LL ² when m2 is 2 may be the same or different.
m3 represents an integer of 0 to 3, and when m3 is 2, X may be the same or different.
CI represents a counter ion when a counter ion is required to neutralize the charge.
However, the dye represented by the general formula (2) has at least one acidic adsorption group. ]

  The photoelectric conversion element of the present invention, the photoelectrochemical cell using the same, and the composition for the photoelectric conversion element are a single composite sensitizing dye in which an organic dye (nonmetal complex dye) and a metal complex dye are combined. It achieves the same or higher photoelectric conversion efficiency as compared with that of the dyes of the system, and further has an excellent effect of further improving the durability.

It is sectional drawing shown typically about one embodiment of the photoelectric conversion element manufactured by this invention.

  The photoelectric conversion element of the present invention includes a metal complex dye represented by the general formula (2) functioning as a sensitizing dye used therein and an organic dye represented by the general formula (1) functioning as a coadsorbent thereof. Shows a peculiar interaction and realizes both high photoelectric conversion efficiency and durability. Although the detailed principle includes an unclear point, it is estimated as follows. First, the ligand of the specific metal complex dye has a binuclear structure and a specific acidic adsorption group in the molecule, so that it is closely oriented and adsorbed on the porous semiconductor fine particles formed on the conductive support. Can improve the electron injection efficiency. Furthermore, in order to suppress reverse electron transfer, it is conceivable to obtain a photoelectric conversion element or a photoelectrochemical cell having high conversion efficiency. In addition, there are coexisting and cooperating with specific organic dyes that serve as co-adsorbents, making them less susceptible to attacks such as water and nucleophiles that decompose the dyes that cause them to peel off, increasing durability. It is estimated that it led to. Hereinafter, preferred embodiments of the present invention will be described in detail.

  A preferred embodiment of the photoelectric conversion element of the present invention will be described with reference to the drawings. As shown in FIG. 1, the photoelectric conversion element 10 includes a conductive support 1, a photosensitive layer 2, a charge transfer layer 3, and a counter electrode 4 arranged in that order on the conductive support 1. The conductive support 1 and the photoreceptor 2 constitute a light receiving electrode 5. The photoreceptor 2 has conductive fine particles 22 and a sensitizing dye 21, and the dye 21 is adsorbed on the conductive fine particles 22 at least in part (the dye is in an adsorption equilibrium state, It may be present in the partial charge transfer layer.) The conductive support 1 on which the photoreceptor 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 composed of a conductive support 1 and a photosensitive layer (semiconductor film) 2 including semiconductor fine particles 22 adsorbed with a dye 21 coated on the conductive support. Light incident on the photoreceptor layer (semiconductor film) 2 excites the dye. The excited dye has high energy electrons. Therefore, the electrons are transferred from the dye 21 to the conduction band of the semiconductor fine particles 22 and further reach the conductive support 1 by diffusion. At this time, the molecule of the dye 21 is an oxidant. The electrons on the electrode return to the oxidized dye through the charge transfer layer (3) while working in the external circuit, thereby acting as a photoelectrochemical cell. At this time, the light receiving electrode 5 functions as a negative electrode of the battery.

  The photoelectric conversion element of this embodiment has a photoreceptor having a layer of porous semiconductor fine particles on which a composite sensitizing dye described later is adsorbed on a conductive support. At this time, as described above, a part of the dye may be dissociated in the electrolyte. The photoreceptor is designed according to the purpose, and may have a single layer structure or a multilayer structure. The photoreceptor of the photoelectric conversion element of the present embodiment includes semiconductor fine particles adsorbed with a specific composite sensitizing dye, has high sensitivity, and can be used as a photoelectrochemical cell, and can obtain high conversion efficiency. Furthermore, it has high durability.

[Composite sensitizing dye]
(Organic dye represented by the general formula (1))
In the present invention, a dye represented by the following general formula (1) is used. In this dye, the meaning of each substituent and the preferred range thereof are as follows.

・ A1
In the formula, A1 represents a 5- to 7-membered nitrogen-containing heterocyclic ring. A 5- or 7-membered nitrogen-containing heterocyclic ring or a 6-membered nitrogen-containing sulfur-containing heterocyclic ring is preferable, and a 5- or 7-membered nitrogen-containing heterocyclic ring is more preferable. Specifically, a substituted or unsubstituted phenothiazine, acridan, dihydrodibenzoazepine, carbazole, or indoline is preferable as the skeleton including the benzene ring described in the general formula (1), and a substituted or unsubstituted dihydrodibenzoazepine or indoline. Carbazole is more preferable.

・ L ¹¹
In the formula, L ¹¹ is an electron transporting linking group containing at least one heterocyclic ring selected from a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring and a heterocyclic ring condensed with these. Preferably, it is an electron transfer linking group containing at least one heterocyclic ring selected from a thiophene ring, a pyrrole ring, or a heterocyclic ring condensed with these, more preferably a thiophene ring or a condensed heterocyclic thereof. An electron transporting linking group containing at least one heterocyclic ring selected from the ring. Examples of the condensed ring include a benzene ring, a pyridine ring, a pyrrole ring, a furan ring, and a thiophene ring.

・ R ¹¹ , R ¹³
In the formula, R ¹¹ and R ¹³ each independently represent a hydrogen atom or a substituent. Preferably, R ¹¹ and R ¹³ each independently represents at least one substituent selected from a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. More preferably, it is at least one selected from an alkyl group, an alkoxy group, and an aryl group. Particularly preferred is at least one selected from an alkyl group and an aryl group, and more preferred is an alkyl group. Moreover, when there are two or more R ^{11 s} , they may be the same or different, and may form a ring.
When R ¹¹ _and R ¹³ represent an alkyl group, preferred alkyl groups include linear, branched, and cyclic substituted or unsubstituted alkyl groups. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a carbon number) 5 to 30 substituted or unsubstituted bicycloalkyl groups, that is, monovalent groups in which one hydrogen atom is removed from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptane-2 -Yl, bicyclo [2,2,2] octane-3-yl) and more ring structures Tricyclo structure is intended to encompass such. More preferable alkyl groups include alkyl groups having 1 to 30 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl) or a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), particularly preferably carbon. Examples thereof include an alkyl group of 1 to 20, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl and 2-ethylhexyl.
When R ¹¹ and R ¹³ represent an aryl group, preferred aryl groups include phenyl, naphthyl, thienyl, furyl, pyryl, or a group in which these are condensed, and particularly preferably phenyl, thienyl, or these in a condensed ring. Group. Examples of the condensed ring include a benzene ring, a pyridine ring, a pyrrole ring, a furan ring, and a thiophene ring.
When R ¹¹ and R ¹³ represent an alkoxy group, preferred alkoxy groups include substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-ethylhexyloxy, nonyloxy, 2-methoxyethoxy, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, and more preferably a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. , For example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, particularly preferably carbon Examples thereof include substituted or unsubstituted alkoxy groups of 1 to 10.

· ^{R 12}
In the formula, R ¹² represents a hydrogen atom or a substituent. Preferably, it is a hydrogen atom. When R ¹² represents a substituent, examples of the substituent include a group represented by the substituent W described later. The substituent is preferably a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aromatic group. , Heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, Amino group, acylamino group), aminocarbonylamino group, alkoxycarbonylamino group), aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group), heterocyclic thio Group, sulfamoyl Group sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group (acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyl group) An oxy group, a phosphinylamino group, and a silyl group, more preferably an alkyl group, an alkenyl group, an alkynyl group, an aromatic group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, Aryloxy group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group A silyl group, particularly preferably an alkyl group, alkenyl group, alkynyl group, aromatic group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group , A heterocyclic thio group.

・ B1
In the formula, B1 represents a heterocyclic acidic nucleus or a methylene group substituted with an electron withdrawing group, and B1 has at least one acidic group. As a heterocyclic acid nucleus, T.C. H. “The Theory of the photographic process. Forth edition.” By James, published in 1977, published by McMillan Publishing, 1977. The heterocyclic acid nucleus is preferably rhodanine, hydantoin, thiohydantoin, barbituric acid, thiobarbituric acid, pyrazolidinedione, pyrazolone, indandione, isoxazolone, more preferably rhodanine, hydantoin, thiohydantoin, barbitur Acid, thiobarbituric acid, particularly preferably rhodanine.

When B1 is a methylene group substituted with an electron withdrawing group, examples of the electron withdrawing group include substituents having the following effects.
In general, an electron withdrawing group attenuates the electron density for a particular position in the molecule. The electron withdrawing property or electron donating property cannot be explained only by the difference in electronegativity. In other words, the induction effect and the mesomery effect act in a complex manner, and the appearance changes depending on the presence of aromaticity, conjugated system, and topological positional relationship. Hammett's law is known as an empirical rule for quantitatively evaluating and predicting these effects based on the acid dissociation constants of para- and meta-substituted benzoic acids. In the case of the inductive effect, the electron withdrawing property is represented as the -I effect, and the electron donating property is represented as the + I effect. An atom having a higher electronegativity than carbon exhibits the -I effect. An anion shows a + I effect, and a cation shows a -I effect. In the case of the mesomery effect, the electron withdrawing property is represented as -M effect, and the electron donating property is represented as + M effect. Therefore, the electron-withdrawing substituent is a substituent that exhibits an -I effect and an -M effect.
Examples of electron withdrawing groups include the following.
Induced effect (-I effect)
_{^{· -O + R 2> -N +}} R 3
_{^{· -N + R 3> -P +}} R 3> ...
_{^{· -O + R 2> -S +}} R 2> ...
_{^{· -N + R 3> -NO 2}} > -SO 2 R> -SOR
· _-SO 2 R> _-SO 3 R
· ^-N + _R 3> -NR ₂
· ^-O + _R 2> -OR
· ^-S + _R 2> -SR
-F>-Cl>-Br> -I
・ = O> = NR> = CR ₂
・ = O> -OR
・ ≡N> ≡CR
· ≡N> = NR> -NR _{2
· -C≡CR> -CR = CR 2>} -CR 2 CR 3
Mesomery effect (-M effect)
_{^{· = N + R 3> =}} NR
・ = O> = NR> = CR ₂・ = S> = O> ≡N

  The electron withdrawing group is preferably a cyano group, a nitro group, a sulfonyl group, a sulfoxy group, an acyl group, an alkoxycarbonyl group or a carbamoyl group, more preferably a cyano group, a nitro group or a sulfonyl group, particularly preferably a cyano group. .

  In the present invention, in the general formula (1), the methylene group substituted with a heterocyclic acidic nucleus or electron withdrawing group represented by B1 has at least one acidic group. An acidic group is a group in which the pKa of the most acidic hydrogen atom constituting the group is 13 or less. Examples of acidic groups include carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, phenolic hydroxyl groups, alkylsulfonylcarbamoyl groups, and phosphoric acid groups, preferably carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, and phenols. A hydroxyl group, more preferably a carboxylic acid group or a sulfonic acid group, particularly preferably a carboxylic acid group.

  In formula, n11 shows the integer of 1-12. n11 is preferably an integer of 1 to 10, more preferably an integer of 2 to 8, and particularly preferably an integer of 2 to 6.

  The dye represented by the general formula (1) is preferably represented by the following general formula (5) or the following general formula (6).

The meaning of each substituent etc. of the said General formula (5) and the said General formula (6), and its preferable range are as follows. R ¹¹ , R ¹² , L ¹¹ , n11, and B1 are as defined above.

In the formula, R ^{13 to} R ¹⁷ represent at least one substituent selected from a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. R ^{13 to} R ¹⁷ are preferably a hydrogen atom or an alkyl group.
When R ^{13 to} R ¹⁷ represent an alkyl group, the preferred alkyl group represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a carbon number) 5 to 30 substituted or unsubstituted bicycloalkyl groups, that is, monovalent groups in which one hydrogen atom is removed from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptane-2 -Yl, bicyclo [2,2,2] octane-3-yl) and more ring structures Rishikuro structure is intended to encompass such. More preferable alkyl groups include alkyl groups having 1 to 30 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl) or a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), particularly preferably carbon. Examples thereof include an alkyl group of 1 to 20, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl and 2-ethylhexyl.
When R ^{13 to} R ¹⁷ represent an aryl group, preferred aryl groups include phenyl, naphthyl, thienyl, furyl, pyryl, or a group in which these are condensed, and particularly preferably phenyl, thienyl, or these in a condensed ring. Group. Examples of the condensed ring include a benzene ring, a pyridine ring, a pyrrole ring, a furan ring, and a thiophene ring.
When R ^{13 to} R ¹⁷ represent an alkoxy group, preferred alkoxy groups include substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy is mentioned, More preferably, a C1-C20 substituted or unsubstituted alkoxy group, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy is mentioned. Particularly preferred is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.

  Moreover, what is represented by the following general formula (7) is also used suitably as a pigment | dye represented by the said General formula (1).

  In the formula, X is selected from S, O, NH, and Se. S, NH or Se is preferable. R11 to R13, n11, and B1 have the same meaning as described above.

  B1 is preferably represented by the following general formula (8) or (9).

  The meanings and preferred ranges of the substituents in the general formulas (8) and (9) are as follows.

R ¹¹⁰ and R ¹⁹ are each independently an aliphatic group, an aromatic group or a heterocyclic group (at least one functional group may have the acidic group described above). An aliphatic group and an aromatic group are preferable. More preferred are aliphatic groups and aromatic groups, and particularly preferred are aliphatic groups.
Examples of the aliphatic group include an alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably And a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms (for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl). Preferred aliphatic groups are alkyl groups and alkenyl groups having 1 to 30 carbon atoms, more preferably 1 to 25 carbon atoms, and particularly preferably 1 to 20 carbon atoms, and may have a substituent.
Examples of aromatic groups include benzene, furan, pyrrole, pyridine, thiophene, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole, pyrimidine, pyrazine and condensed. These are cyclic rings, which may be substituted. A benzene ring, a pyrrole ring, a pyridine ring, and a thiophene ring are preferable, and a benzene ring and a thiophene ring are more preferable. Particularly preferred is a benzene ring. These may be substituted.
As the heterocyclic group, a 3- to 6-membered substituted or unsubstituted heterocyclic group, more preferably a 5- or 6-membered unsubstituted heterocyclic group, particularly preferably a 6-membered heterocyclic group (for example, piperidine, Morpholine). These may have a substituent.
p represents 0 or 1; Preferably it is 1.

The carbon-carbon double bond may be either E-type or Z-type. R ¹⁸ represents a sulfur atom or the general formula (10), and the carbon-carbon double bond in the general formula (10) may be either E type or Z type. R ¹¹³ and R ¹¹⁴ in the general formula (10) each independently represent a cyano group or an acidic group, and may be the same as or different from each other.

R ¹¹¹ and R ¹¹² each independently represent a cyano group or an acidic group, and may be the same as or different from each other.

  The general formula (8) is preferably represented by the following general formula (11) or (12).

In the formula, R ¹⁹ and R ¹¹⁰ are an aliphatic group, an aromatic group, or a heterocyclic group (which may have an acidic group). An aliphatic group or an aromatic group is preferable.

  The general formula (9) is preferably represented by the following formula (13).

Examples of the substituent in the present invention (hereinafter referred to as “substituent W”) include those shown below.
・ Halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom),
-Alkyl group [Represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ],
-Alkenyl group [Represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo 2,2,2] oct-2-en-4-yl).
An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group, aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl),
Aromatic groups (for example, benzene ring, furan ring, pyrrole ring, pyridine ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, pyrimidine ring, pyrazine ring or these A ring fused with
A heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably a carbon number of 3 To 30- or 5-membered aromatic heterocyclic group such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl),
・ Cyano group, ・ hydroxyl group, ・ nitro group, ・ carboxyl group,
An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy),
An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylamino Phenoxy),
A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy),
A heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 1 to 30 carbon atoms, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy),
An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy),
A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di -N-octylaminocarbonyloxy, Nn-octylcarbamoyloxy),
An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy),
Aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy ),
Amino groups (preferably amino groups, substituted or unsubstituted alkylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted anilino groups having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino N-methyl-anilino, diphenylamino),
Acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino Pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino),
Aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino) ,
An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),
An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) ,
A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonyl amino),
Alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, Phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino),
・ Mercapto group,
An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio),
An arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio),
A heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio),
A sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N -Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl),
・ Sulfo group,
Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p -Methylphenylsulfinyl),
Alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl),
Acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon group having 4 to 30 carbon atoms A heterocyclic carbonyl group bonded to a carbonyl group at a carbon atom, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl),
Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl) ,
An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl),
A carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- ( Methylsulfonyl) carbamoyl),
Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5 -Ethylthio-1,3,4-thiadiazol-2-ylazo),
An imide group (preferably N-succinimide, N-phthalimide),
A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino),
A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),
A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy),
A phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino),
A silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).
In addition, the substituent may be further substituted. In that case, the above-mentioned substituent W can be mentioned as an example of a substituent.

  In the present invention, the content of the dye represented by the general formula (1) is not particularly limited.

The amount (S) of the dye represented by the general formula (1) is preferably adjusted in relation to the amount (R) of the metal complex dye represented by the following general formula (2). Specifically, in terms of molar ratio, R / S is preferably 0.005 to 0.5, more preferably 0.008 to 0.3, and particularly preferably 0.01 to 0.15. . By using in such a range, the effect of the specific metal complex-based sensitizing dye is sufficiently exhibited, and the function as a co-adhering agent for the specific organic dye is also exhibited without waste, and an extremely high effect is achieved.
In the present invention, two or more dyes represented by the general formula (1) may be used. In the present invention, the term “dye” means not only the dye compound itself but also a salt or ionized salt of an acidic group or basic group.

  The absorption maximum wavelength of the dye represented by the general formula (1) is not particularly limited, but the maximum absorption wavelength in the solution is preferably in the range of 300 to 700 nm, more preferably in the range of 350 to 600 nm, and particularly preferably. Is in the range of 400-500 nm. The difference (Rw−Sw) between the maximum absorption wavelength (Sw) of the dye represented by the general formula (1) and the maximum absorption wavelength (Rw) of the dye represented by the general formula (2) is 0 to 400 nm. Is preferable, and it is more preferable that it is 50-200 nm. By having the maximum absorption wavelength in such a region, in combination with the dye represented by the general formula (2) to be described later, it is possible to perform photoelectric conversion with higher efficiency by light mainly using visible light useful as a solar cell. It becomes.

  For the method for synthesizing the dye represented by the general formula (1), the methods described in Examples below can be referred to, and the synthesis can be performed by appropriately applying the usual method based on it. Moreover, the part represented by B1 of General formula (1) can be synthesize | combined by making the intermediate body of carbonyl group and B1 react.

  Although the preferable specific example of the organic pigment | dye represented by General formula (1) below is shown, this invention is not limited to the following specific examples.

(Metal complex dye represented by general formula (2))
In the photoelectric conversion element of the present invention, a dye having a structure represented by the following general formula (2) is used.
Mz (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI General formula (2)
In the dye having the structure of the general formula (2), the ligand LL ¹ and / or the ligand LL ² and optionally a specific functional group X are coordinated to the metal atom Mz. It is kept electrically neutral by CI.

・ Metal atom Mz
Mz represents a metal atom. Mz is preferably a metal capable of tetracoordinate or hexacoordinate, and more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn Or it is Zn. Particularly preferred is Ru, Os, Zn or Cu, and most preferred is Ru.

・ Ligand LL ¹
The ligand LL ¹ is a bidentate or tridentate ligand represented by the following general formula (3), and is preferably a bidentate ligand. M1 representing the number of the ligand LL ¹ is an integer of 1 to 3, preferably 1 to 2, and more preferably 1. When m1 is 2 or more, LL ¹ may be the same or different. However, the m1, at least one of m2 representing the number of ligands LL ² below is an integer of 1 or more. Thus the metal atom, the ligand LL ¹ and / or ligand LL ² is coordinated.

R ²¹ and R ²² in the general formula (3) each independently represent an acidic group, for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group (preferably a hydroxamic acid group having 1 to 20 carbon atoms, for example, , —CONHOH, —CONCH ₃ OH, etc.), phosphoryl groups (eg —OP (O) (OH) ₂ etc.) and phosphonyl groups (eg —P (O) (OH) ₂ etc.), preferably carboxyl groups A phosphonyl group, more preferably a carboxyl group. R ²¹ and R ²² may be substituted on any carbon atom on the pyridine ring.

In the formula, R ²³ and R ²⁴ each independently represent a substituent, preferably an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1 -Ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms such as vinyl, allyl, oleyl etc.), alkynyl groups (preferably carbon atoms) C2-C20 alkynyl groups such as ethynyl, butadiynyl, phenylethynyl, etc., cycloalkyl groups (preferably C3-C20 cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.) ), An aryl group (preferably an ant having 6 to 26 carbon atoms) Group such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl and the like, a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy, etc.) An aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), an alkoxycarbonyl group (preferably having 2 to 2 carbon atoms) 20 alkoxycarbonyl groups such as ethoxycarbonyl, 2 Ethylhexyloxycarbonyl, etc.), amino group (preferably an amino group having 0-20 carbon atoms, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfonamide group (Preferably a sulfonamide group having 0 to 20 carbon atoms, such as N, N-dimethylsulfonamide, N-phenylsulfonamide, etc.), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, for example, acetyl Oxy, benzoyloxy and the like), 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 having 1 to 20 carbon atoms). An acylamino group such as acetylamino, benzoylamino, etc.), A cyano group or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), 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, an alkenyl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group or a cyano group.

When the ligand LL ¹ contains an alkyl group, an alkenyl group or the like, these may be linear or branched, and may be substituted or unsubstituted. Further, when the ligand LL ¹ contains an aryl group, a heterocyclic group or the like, they may be monocyclic or condensed and may be substituted or unsubstituted.

In general formula (3), R ²⁵ and R ²⁶ are each independently an alkyl group, one or more substituted or unsubstituted aromatic groups (preferably an aromatic group having 6 to 30 carbon atoms, such as phenyl, Substituted phenyl, naphthyl, substituted naphthyl, etc.) and / or one or more substituted or unsubstituted heterocyclic groups (preferably having 1 to 30 carbon atoms, such as 2-thienyl, 2-pyrrolyl, 2- Imidazolyl, 1-imidazolyl, 4-pyridyl, 3-indolyl), preferably a heterocyclic group having 1 to 3 electron-donating groups, more preferably thienyl. 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 hydroxyl group, and is preferably an alkyl group, an alkoxy group, an amino group or a hydroxyl group. Is more preferable, and an alkyl group is particularly preferable. R ²⁵ and R ²⁶ may be the same or different, but are preferably the same.

R ²⁵ and R ²⁶ may be directly bonded to the benzene ring. R ²⁵ and R ²⁶ may be bonded to the benzene ring via L ²¹ and / or L ²² .
Here, L ²¹ and L ²² each independently represent a conjugated chain composed of a substituted or unsubstituted ethenylene group and / or an ethynylene group. When the ethenylene group has a substituent, the substituent is preferably an alkyl group, and more preferably methyl. L ²¹ and L ²² are each independently preferably a conjugated chain having 2 to 6 carbon atoms, more preferably ethenylene, butadienylene, ethynylene, butadienylene, methylethenylene or dimethylethenylene, particularly ethenylene or butadienylene. Preferably, ethenylene is most preferred. L ²¹ and L ²² 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 a trans isomer, a cis isomer, or a mixture thereof. n21 and n22 each independently represents an integer of 0 to 5, preferably an integer of 0 to 2. When n21 is 2 or ^{more, L 21} may be the same or different. When n22 is 2 or ^{more, L 22} may be the same or different.

n23 is 0 or 1, and a21 and a22 each independently represent an integer of 0 to 3. a21 is often R ²¹ when two or more may be the same or different, R ²² when a22 is 2 or more may be the same or different. a21 is preferably 0 or 1, and a22 is preferably an integer of 0 to 2. In particular, when n23 is 0, a22 is preferably 1 or 2, and when n23 is 1, a22 is preferably 0 or 1. The sum of a21 and a22 is preferably an integer of 0-2.

b21 and b22 each independently represent an integer of 0 to 3, preferably an integer of 0 to 2. When b21 is 2 or more, R ²³ may be the same or different and may be connected to each other to form a ring. When b22 is 2 or more, R ²⁴ may be the same or different, and may be connected to each other to form a ring. When both b21 and b22 are 1 or more, R ²³ and R ²⁴ may be linked to form a ring. Preferable examples of the ring to be formed include a benzene ring, a pyridine ring, a thiophene ring, a pyrrole ring, a cyclohexane ring, a cyclopentane ring and the like.

When the sum of a21 and a22 is 1 or more and the ligand LL ¹ has at least one acidic group, m1 in the general formula (2) is preferably 2 or 3, and preferably 2. Is more preferable.

The ligand LL ¹ in the general formula (2) is preferably represented by the following general formula (16-1), (16-2) or (16-3).

In the general formulas (16-1) to (16-3), R ^{101 to} R ¹⁰⁴ , a1, a2, b1 and b2 are R ^{21 to} R ²⁴ , a21, a22 and b21 in the general formula (3), respectively. And b22.

In General Formula (16-2), R ¹⁰⁷ represents an acidic group, preferably a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group, or a phosphonyl group, more preferably a carboxyl group or a phosphoryl group. Yes, particularly preferably a carboxyl group.

In the general formula (16-2), R ¹⁰⁸ represents a substituent, preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an amino group or an acylamino group, more preferably An alkyl group, an alkoxy group, an amino group, or an acylamino group;

In general formulas (16-1) and (16-2), R ^{121 to} R ¹²⁴ each independently represent hydrogen, an alkyl group, an alkenyl group, or an aryl group. Preferred examples of R ^{121 to} R ¹²⁴ are the same as the preferred examples of R ²³ and R ²⁴ in general formula (3). R ^{121 to} R ¹²⁴ are more preferably an alkyl group or an aryl group, and more preferably an alkyl group. When R ^{121 to} R ¹²⁴ are alkyl groups, they may further have a substituent, and the substituent is preferably an alkoxy group, a cyano group, an alkoxycarbonyl group or a carbonamido group, and particularly preferably an alkoxy group. R ¹²¹ and R ^{122 and} R ¹²³ and R ¹²⁴ may be connected to each other to form a ring. As the ring to be formed, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring or the like is preferable.

In formulas (16-1) to (16-3), R ¹²⁵ , R ¹²⁶ , R ¹²⁷ and R ¹²⁸ each independently represent a substituent, 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 hydroxyl group, more preferably an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group or an acylamino group, and particularly preferably an alkyl group or an alkynyl group. is there.

In general formula (16-2), a3 represents the integer of 0-3, Preferably the integer of 0-2 is represented. When n is 0, a3 is preferably 1 or 2, and when n is 1, a3 is preferably 0 or 1. a3 is the ^{R 107} when two or more may be the same or different.

In general formulas (16-1) and (16-2), d1 and d2 each independently represents an integer of 0 to 4. When d1 is 1 or more, R ¹²⁵ may be linked to R ¹²¹ and / or R ¹²² to form a ring. The ring formed is preferably a piperidine ring or a pyrrolidine ring. When d1 is 2 or more, R ¹²⁵ may be the same or different, and may be linked to each other to form a ring. When d2 is 1 or more, R ¹²⁶ may be linked to R ¹²³ and / or R ¹²⁴ to form a ring. The ring formed is preferably a piperidine ring or a pyrrolidine ring. When d2 is 2 or more, R ¹²⁶ may be the same or different, and may be linked to each other to form a ring.

・ Ligand LL ²
In the general formula (2), LL ² represents a bidentate or tridentate ligand. M2 representing the number of ligands LL ² is an integer of 0 to 2, and is preferably 0 or 1. m2 is LL ² when the two may be the same or different. However, the m2, at least one of which is an integer of 1 or more of the m1 representing the number of ligands LL ¹ above.
Ligand LL ² is a bidentate or tridentate ligand represented by the following general formula (4).

一般式（４）中、Ｚａ、Ｚｂ及びＺｃはそれぞれ独立に、５員環又は６員環を形成しうる非金属原子群を表す。形成される５員環又は６員環は置換されていても無置換でもよく、単環でも縮環していてもよい。Ｚａ、Ｚｂ及びＺｃは炭素原子、水素原子、窒素原子、酸素原子、硫黄原子、リン原子及び／又はハロゲン原子で構成されることが好ましく、芳香族環を形成するのが好ましい。５員環の場合はイミダゾール環、オキサゾール環、チアゾール環又はトリアゾール環を形成するのが好ましく、６員環の場合はピリジン環、ピリミジン環、ピリダジン環又はピラジン環を形成するのが好ましい。なかでもイミダゾール環又はピリジン環がより好ましい。
一般式（４）中、ｃは０または１を表す。ｃは０であるのが好ましく、ＬＬ^２は２座配位子であるのが好ましい。

In General Formula (4), Za, Zb, and Zc each independently represent a nonmetallic atom group that can form a 5-membered ring or a 6-membered ring. The formed 5-membered or 6-membered ring may be substituted or unsubstituted, and may be monocyclic or condensed. Za, Zb and Zc are preferably composed of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and / or a halogen atom, and preferably form an aromatic ring. In the case of a 5-membered ring, an imidazole ring, an oxazole ring, a thiazole ring or a triazole ring is preferably formed. In the case of a 6-membered ring, a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferably formed. Of these, an imidazole ring or a pyridine ring is more preferable.
In general formula (4), c represents 0 or 1. c is preferably 0, and LL ² is preferably a bidentate ligand.

Ligand LL ² is preferably represented by any of the following general formula (17-1) - (17-8), the formula (17-1), (17-2), (17-4 ) Or (17-6), more preferably represented by formula (17-1) or (17-2), and represented by formula (17-1). Is most preferred.

In the general formulas (17-1) to (17-8), R ^{151 to} R ¹⁶⁶ are depicted as substituted with one pyridine ring for the convenience of illustration, but even on the ring, Alternatively, it may be bonded on a ring different from that shown.
In general formulas (17-1) to (17-8), R ^{151 to} R ¹⁵⁸ each independently represent an acidic group. R ^{151 to} R ¹⁵⁸ are, for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group (preferably a hydroxamic acid group having 1 to 20 carbon atoms, such as —CONHOH, —CONCH ₃ OH, etc.), a phosphoryl group ( For example, —OP (O) (OH) ₂ etc.) or a phosphonyl group (eg —P (O) (OH) ₂ etc.) is represented. R ^{151 to} R ¹⁵⁸ are preferably a carboxyl group, a phosphoryl group, or a phosphonyl group, more preferably a carboxyl group or a phosphonyl group, and more preferably a carboxyl group.

In general formulas (17-1) to (17-8), R ^{159 to} R ¹⁶⁶ each independently represent a substituent, preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or an alkoxy group. , Aryloxy group, alkoxycarbonyl group, amino group, acyl group, sulfonamido group, acyloxy group, carbamoyl group, acylamino group, cyano group or halogen atom, more preferably alkyl group, alkenyl group, aryl group, heterocyclic ring Group, alkoxy group, alkoxycarbonyl group, amino group, acylamino group or halogen atom, particularly preferably alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, amino group or acylamino group.

In the general formulas (17-1) to (17-8), R ^{167 to} R ¹⁷¹ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom. Of these, an aliphatic group and an aromatic group are preferable. More preferably, it is an aliphatic group having a carboxyl group. When the ligand LL ² contains an alkyl group, an alkenyl group or the like, they may be linear or branched and may be unsubstituted substituted. Further, LL ² is an aryl group, when containing heterocyclic group, they may be a condensed ring may be monocyclic or unsubstituted substituted.

In general formulas (17-1) to (17-8), R ^{151 to} R ¹⁶⁶ may be bonded to any position on the ring to which they are connected. E1 to e6 each independently represents an integer of 0 to 4, preferably an integer of 1 to 2. e7 and e8 each independently represents an integer of 0 to 4, preferably an integer of 1 to 3. e9 to e12 and e15 each independently represents an integer of 0 to 6, and e13, e14 and e16 each independently represents an integer of 0 to 4. e9 to e16 are each independently preferably an integer of 0 to 3.

When e1 to e8 is 2 or more, R ^{151 to} R ¹⁵⁸ may be the same or different. When e9 to e16 is 2 or more, R ^{159 to} R ¹⁶⁶ may be the same or different and are connected to each other. To form a ring.

・ Ligand X
The ligand X represents a monodentate or bidentate ligand. M3 representing the number of ligands X represents an integer of 0 to 2, and m3 is preferably 1 or 2. When X is a monodentate ligand, m3 is preferably 2. When X is a bidentate ligand, m3 is preferably 1. When m3 is 2, Xs may be the same or different, and Xs may be linked together.

The ligand X is an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, benzoyloxy, salicylic acid, glycyloxy, N, N-dimethylglycyloxy, oxalylene (—OC (O) C (O) O-), etc.), an acylthio group (preferably an acylthio group having 1 to 20 carbon atoms, such as acetylthio, benzoylthio, etc.), a thioacyloxy group (preferably a thioacyloxy group having 1 to 20 carbon atoms, For example, a thioacetyloxy group (CH ₃ C (S) O—) and the like)), a thioacylthio group (preferably a thioacylthio group having 1 to 20 carbon atoms, such as thioacetylthio (CH ₃ C (S) S—) , Thiobenzoylthio (PhC (S) S—) and the like)), an acylaminooxy group (preferably an aryl having 1 to 20 carbon atoms) Silaminooxy group, for example, N-methylbenzoylaminooxy (PhC (O) N (CH ₃ ) O—), acetylaminooxy (CH ₃ C (O) NHO—), etc.)), thiocarbamate group (preferably A thiocarbamate group having 1 to 20 carbon atoms, such as N, N-diethylthiocarbamate, etc., a dithiocarbamate group (preferably a dithiocarbamate group having 1 to 20 carbon atoms, such as N-phenyldithiocarbamate, N, N-dimethyldithiocarbamate, N, N-diethyldithiocarbamate, N, N-dibenzyldithiocarbamate, etc.), a thiocarbonate group (preferably a thiocarbonate group having 1 to 20 carbon atoms, such as ethylthiocarbonate) Etc.), dithiocarbonate (preferably dithiocarbonate having 1 to 20 carbon atoms) Such as ethyl dithiocarbonate (C ₂ H ₅ OC (S) S—), etc., trithiocarbonate group (preferably a trithiocarbonate group having 1 to 20 carbon atoms, such as ethyl trithiocarbonate sulphonate _{(C 2 H 5 SC (S} ) S-) and the like), an acyl group (preferably an acyl group having 1 to 20 carbon atoms, e.g., acetyl, benzoyl, etc.), a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate Group, cyano group, alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms such as methanethio, ethylenedithio, etc.), arylthio group (preferably an arylthio group having 6 to 20 carbon atoms such as benzenethio, 1, 2 -Phenylenedithio etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as metho A monodentate or bidentate coordinated with a group selected from the group consisting of an aryloxy group (preferably an aryloxy group having 6 to 20 carbon atoms, such as phenoxy, quinoline-8-hydroxyl, etc.) A ligand, or a halogen atom (preferably a chlorine atom, a bromine atom, an iodine atom, etc.), a carbonyl (... CO), a dialkyl ketone (preferably a dialkyl ketone having 3 to 20 carbon atoms, such as acetone ((CH ₃ ) ₂ ). CO ...), etc.), 1,3-diketone (preferably having 3 to 20 carbon atoms 1,3-diketones, for example, acetylacetone _{(CH 3 C (O ...)} CH = C (O-) CH 3), tri fluoro acetylacetone _{(CF 3 C (O ...)} CH = C (O-) CH 3), dipivaloylmethane _{(tC 4 H 9 C (O} ...) CH = C (O-) tC 4 H ), Dibenzoylmethane (PhC (O ...) CH = C (O-) Ph), 3- chloro-acetylacetone _{(CH 3 C (O ...)} CCl = C (O-) CH 3) , etc.), carbonamido (preferably Is a carbonamide having 1 to 20 carbon atoms, such as CH ₃ N═C (CH ₃ ) O—, —OC (═NH) —C (═NH) O—, etc.), thiocarbonamide (preferably having carbon atoms 1-20 thiocarbonamide, such as CH ₃ N═C (CH ₃ ) S—, or thiourea (preferably a thiourea having 1-20 carbon atoms, such as NH (...) = C (S— ) NH ₂ , CH ₃ N (...) = C (S—) NHCH ₃ , (CH ₃ ) ₂ N—C (S...) N (CH ₃ ) _2, etc.) "..." indicates a coordination bond.

  The ligand X 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 group, a cyanate group, an isocyanate group, a cyano group, A ligand coordinated by a group selected from the group consisting of an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a ligand consisting of a halogen atom, carbonyl, 1,3-diketone or thiourea, More preferably, a ligand coordinated by a group selected from the group consisting of acyloxy group, acylaminooxy group, dithiocarbamate group, thiocyanate group, isothiocyanate group, cyanate group, isocyanate group, cyano group or arylthio group, or Halogen atom 1,3 A ligand comprising a diketone or thiourea, particularly preferably a ligand coordinated by a group selected from the group consisting of a dithiocarbamate group, a thiocyanate group, an isothiocyanate group, a cyanate group and an isocyanate group, or a halogen atom Or a ligand consisting of a 1,3-diketone, most preferably a ligand coordinated with a group selected from the group consisting of a dithiocarbamate group, a thiocyanate group and an isothiocyanate group, or a 1,3-diketone A ligand consisting of In addition, when the ligand X contains an alkyl group, an alkenyl group, an alkynyl group, an alkylene group or the like, these may be linear or branched, and may be substituted or unsubstituted. Moreover, when an aryl group, a heterocyclic group, a cycloalkyl group, etc. are included, they may be substituted or unsubstituted, and may be monocyclic or condensed.

  When X is a bidentate ligand, X is acyloxy group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithio A ligand coordinated by a group selected from the group consisting of a carbonate group, an acyl group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a 1,3-diketone, carbonamide, thiocarbonamide, or thio A ligand composed of urea is preferable. When X is a monodentate ligand, X is a ligand coordinated by 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, or A ligand composed of a halogen atom, carbonyl, dialkyl ketone, or thiourea is preferred.

・ Counterion CI
CI in the general formula (2) represents a counter ion when a counter ion is required to neutralize the charge. In general, whether a dye is a cation or an anion or has a net ionic charge depends on the metal, ligand and substituent in the dye.
The dye of the general formula (2) may be dissociated and have a negative charge because the substituent has a dissociable group. In this case, the entire charge of the dye of the general formula (2) is electrically neutralized by CI.

When the counter ion CI is a positive counter ion, for example, the counter ion CI is an inorganic or organic ammonium ion (for example, tetraalkylammonium ion, 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. For example, halogen anions (eg, fluoride ions, chloride ions, bromide ions, iodide ions, etc.), substituted aryl sulfonate ions (eg, p-toluene sulfonate ions, p-chlorobenzene sulfonate ions, etc.), aryl disulfones Acid ion (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion, etc.), alkyl sulfate ion (for example, methyl sulfate ion, etc.), sulfate ion, thiocyanate ion Perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion and the like. Furthermore, as the charge balance counter ion, an ionic polymer or another dye having a charge opposite to that of the dye may be used, and a metal complex ion (for example, bisbenzene-1,2-dithiolatonickel (III)) can also be used. is there.

Adsorbing group (bonding group)
The dye having the structure represented by the general formula (2) has one or more suitable acidic adsorption groups (bonding groups) to the surface of the semiconductor fine particles. It is more preferable to have 1 to 6 of these groups in the dye, and it is particularly preferable to have 1 to 4 of these groups. Carboxyl group, sulfonic acid group, hydroxyl group, hydroxamic acid group (for example, —CONHOH), phosphoryl group (for example, —OP (O) (OH) _2, etc.), phosphonyl group (for example, —P (O) (OH) _2, etc.) It is preferable that the dye has an acidic group (substituent having a dissociable proton). Among them, a carboxyl group, a phosphoryl group, it preferably has a phosphonyl group on the ligand LL ^2.

  Specific examples of the dye having the structure represented by the general formula (2) used in the present invention are shown below, but the present invention is not limited thereto. In addition, when the pigment | dye in the following specific example contains the ligand which has a proton dissociable group, this ligand may dissociate as needed and may discharge | release a proton.

上記具体例中ｎは直鎖を表す。

In the above specific examples, n represents a straight chain.

  In the present invention, the content of the dye represented by the general formula (2) is not particularly limited.

Although the absorption maximum wavelength of the pigment represented by the general formula (2) is not particularly limited,
It is preferable that it is 700 nm, and it is more preferable that it is 400-600 nm. By having the absorption maximum wavelength in such a region, highly efficient photoelectric change by light centered on visible light useful as a solar cell becomes possible.

  For the method for synthesizing the dye represented by the general formula (1), the methods described in Examples below can be referred to, and the synthesis can be performed by appropriately applying the usual method based on it. In addition, J.H. Am. Chem. Soc. 121, 4047 (1999), Can. J. et al. Chem. , 75, 318 (1997), Inorg. Chem. 27, 4007 (1988), etc. and the methods cited in the literature, and the dyes and methods described herein are cited in this specification. Information described in JP 2001-291534 A and WO 2007/091525 can also be referred to, and the dyes and methods described herein are cited in this specification.

[Charge transfer layer]
A layer made of an electrolyte composition can be applied to the charge transfer layer used in the photoelectric conversion element of this embodiment. As the redox pair, for example, a combination of iodine and iodide (eg, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.), alkyl viologen (eg, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoro) Borate) and its reduced form, a combination of polyhydroxybenzenes (for example, hydroquinone, naphthohydroquinone, etc.) and its oxidized form, a combination of divalent and trivalent iron complexes (for example, red blood salt and yellow blood salt) Etc. Of these, a combination of iodine and iodide is preferred.
The cation of the iodine salt is preferably a 5-membered or 6-membered nitrogen-containing aromatic cation. In particular, when the compound represented by the general formula (2) is not an iodine salt, it is described in WO95 / 18456, JP-A-8-259543, Electrochemistry, Vol. 65, No. 11, page 923 (1997), etc. It is preferable to use iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts.
The electrolyte composition used for the photoelectric conversion element preferably contains iodine together with the heterocyclic quaternary salt compound. The iodine content is preferably 0.1 to 20% by mass, and more preferably 0.5 to 5% by mass with respect to the entire electrolyte composition.

The electrolyte composition may contain a solvent. The content of the solvent in the electrolyte composition is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 10% by mass or less based on the entire composition.
As the solvent, a solvent having a low viscosity and high ion mobility, a high dielectric constant and capable of increasing the effective carrier concentration, or both is preferable because it can exhibit excellent ion conductivity. As such a solvent, carbonate compounds (ethylene carbonate, propylene carbonate, etc.), heterocyclic compounds (3-methyl-2-oxazolidinone, etc.), ether compounds (dioxane, diethyl ether, etc.), chain ethers (ethylene glycol dialkyl ether, Propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.), alcohols (methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, etc.), Polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene glycol , Polypropylene glycol, glycerol, etc.), nitrile compounds (acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, biscyanoethyl ether, etc.), esters (carboxylic esters, phosphate esters, phosphonate esters, etc.) ), Aprotic polar solvent (dimethyl sulfoxide (DMSO), sulfolane, etc.), water, hydrous electrolyte described in JP-A No. 2002-110262, JP-A No. 2000-36332, JP-A No. 2000-243134, and republication Examples include electrolyte solvents described in WO / 00-54361. These solvents may be used as a mixture of two or more.

  Further, as the electrolyte solvent, an electrochemically inert salt that is in a liquid state at room temperature and / or has a melting point lower than room temperature may be used. For example, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, etc., nitrogen-containing heterocyclic quaternary salt compounds such as imidazolium salts and pyridinium salts, or tetraalkylammonium salts Is mentioned.

  A polymer or an oil gelling agent may be added to the electrolyte composition, or it may be gelled (solidified) by a technique such as polymerization of polyfunctional monomers or a crosslinking reaction of the polymer.

  When the electrolyte composition is gelled by adding a polymer, a compound described in Polymer Electrolyte Reviews-1 and 2 (J.R. MacCallum and CA Vincent, co-edited by ELSEVIER APPLIED SCIENCE) is added. be able to. In this case, it is preferable to use polyacrylonitrile or polyvinylidene fluoride.

  When the electrolyte composition is gelled by adding an oil gelling agent, J.I. Chem. Soc. Japan, Ind. Chem. Soc. , 46779 (1943); Am. Chem. Soc. 111, 5542 (1989); Chem. Soc. Chem. Commun. , 390 (1993), Angew. Chem. Int. Ed. Engl. , 35, 1949 (1996), Chem. Lett. , 885 (1996), J. Am. Chem. Soc. Chem. Commun. , 545, (1997) and the like, and a compound having an amide structure is preferably used.

  When gelling the electrolyte composition by polymerization of polyfunctional monomers, prepare a solution from the polyfunctional monomers, polymerization initiator, electrolyte and solvent, and use methods such as casting, coating, dipping, and impregnation. A method in which a sol-like electrolyte layer is formed on an electrode carrying a dye and then gelled by radical polymerization of a polyfunctional monomer is preferred. The polyfunctional monomers are preferably compounds having two or more ethylenically unsaturated groups, such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol Ethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and the like are preferable.

The electrolyte composition, the metal iodide (LiI, NaI, KI, CsI , CaI 2 , etc.), a metal bromide (LiBr, NaBr, KBr, CsBr , CaBr 2 , etc.), quaternary ammonium bromine salt (tetraalkylammonium bromide, Pyridinium bromide, etc.), metal complexes (ferrocyanate-ferricyanate, ferrocene-ferricinium ion, etc.), sulfur compounds (sodium polysulfide, alkylthiol-alkyl disulfides, etc.), viologen dye, hydroquinone-quinone, etc. You can do it. These may be used as a mixture.

Further, in the present invention, J.P. Am. Ceram. Soc. 80, (12), 3157-3171 (1997), and basic compounds such as 2-picoline and 2,6-lutidine may be added. A preferable concentration range in the case of adding a basic compound is 0.05 to 2M.
Further, as the electrolyte, a charge transport layer containing a hole conductor material may be used. As the hole conductor material, 9,9′-spirobifluorene derivative or the like can be used.

  As a structure of the electrochemical element, a conductive support (electrode layer), a photoelectric conversion layer (photosensitive layer and charge transfer layer), a hole transport layer, a conductive layer, and a counter electrode layer can be sequentially laminated. A hole transport material that functions as a p-type semiconductor can be used as a hole transport layer. As a preferred hole transport layer, for example, an inorganic or organic hole transport material can be used. Examples of the inorganic hole transport material include CuI, CuO, and NiO. Examples of the organic hole transport material include high molecular weight materials and low molecular weight materials, and examples of the high molecular weight materials include polyvinyl carbazole, polyamine, and organic polysilane. Moreover, as a low molecular weight thing, a triphenylamine derivative, a stilbene derivative, a hydrazone derivative, a phenamine derivative etc. are mentioned, for example. Among these, organic polysilanes are preferable because, unlike conventional carbon-based polymers, σ electrons delocalized along the main chain Si contribute to photoconductivity and have high hole mobility (Phys. Rev.). B, 35, 2818 (1987)).

The conductive layer is not particularly limited as long as it has good conductivity, and examples thereof include inorganic conductive materials, organic conductive materials, conductive polymers, and intermolecular charge transfer complexes. Among them, an intermolecular charge transfer complex formed from a donor material and an acceptor material is preferable. Among these, what was formed from the organic donor and the organic acceptor can be used preferably. The donor material is preferably a material rich in electrons in the molecular structure. For example, organic donor materials include those having a substituted or unsubstituted amine group, hydroxyl group, ether group, selenium or sulfur atom in the π-electron system of the molecule, specifically, phenylamine-based, triphenylmethane , Carbazole, phenol, and tetrathiafulvalene materials. As the acceptor material, those lacking electrons in the molecular structure are preferable. For example, organic acceptor materials include fullerenes, those having a substituent such as a nitro group, a cyano group, a carboxyl group or a halogen group in the π-electron system of the molecule, specifically, PCBM, benzoquinone, naphthoquinone, etc. Quinone, fluoroenone, chloranil, bromanyl, tetracyanoquinodimethane, tetracyanoethylene and the like.
The thickness of the conductive layer is not particularly limited, but is preferably such that the porous layer can be completely filled.

[Conductive support]
As the conductive support, there can be used a glass or a polymer material having a conductive film layer on the surface, such as a metal that is conductive in the support itself. It is preferable that the conductive support is substantially transparent. Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, particularly preferably 80% or more. As the conductive support, a glass or polymer material coated with a conductive metal oxide can be used. The coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m ² of the support of glass or polymer material. When a transparent conductive support is used, light is preferably incident from the support side. Examples of polymer materials that are preferably used include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), Examples include polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy. On the conductive support, the surface may be provided with a light management function. For example, an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated, The light guide function described in Open 2002-260746 is raised.
In addition to this, a metal support can also 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.

It is preferable that the conductive support has a function of blocking ultraviolet light. For example, a method in which a fluorescent material capable of changing ultraviolet light into visible light is present in the transparent support or on the surface of the transparent support, and a method using an ultraviolet absorber are also included.
A function described in JP-A No. 11-250944 may be further provided on the conductive support.

Preferred conductive films include metals (eg, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, or conductive metal oxides (indium-tin composite oxide, tin oxide doped with fluorine, etc.) ).
The thickness of the conductive film layer is preferably 0.01 to 30 μm, more preferably 0.03 to 25 μm, and particularly preferably 0.05 to 20 μm.
The lower the surface resistance of the conductive support, the better. The range of the surface resistance is preferably 50 Ω / cm ² or less, more preferably 10 Ω / cm ² or less. Although there is no restriction | limiting in particular in this lower limit, Usually, it is about 0.1 ohm / cm < ² >.

Since the resistance value of the conductive film increases as the cell area increases, a collecting electrode may be disposed. A gas barrier film and / or an ion diffusion prevention film may be disposed between the support and the transparent conductive film. As the gas barrier layer, a resin film or an inorganic film can be used.
Moreover, you may provide a transparent electrode and a porous semiconductor electrode photocatalyst content layer. The transparent conductive layer may have a laminated structure, and as a preferable method, for example, FTO can be laminated on ITO.

[Semiconductor fine particles]
As the semiconductor fine particles, metal chalcogenides (for example, oxides, sulfides, selenides, etc.) or perovskite fine particles are preferably used. Preferred examples of the metal chalcogenide include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum oxide, cadmium sulfide, cadmium selenide, and the like. . Preferred perovskites include strontium titanate and calcium titanate. Of these, titanium oxide, zinc oxide, tin oxide, and tungsten oxide are particularly preferable.

There are n-type semiconductors in which the carriers involved in the conduction are electrons and p-types in which the carriers are holes. The use of the n-type is preferable in terms of conversion efficiency. In an n-type semiconductor, in addition to an intrinsic semiconductor (or an intrinsic semiconductor) having no impurity level and having the same carrier concentration due to conduction band electrons and valence band holes, the electron carrier concentration is reduced by structural defects derived from impurities. There are high n-type semiconductors. The n-type inorganic semiconductor preferably used in the present invention is TiO ₂ , TiSrO ₃ , ZnO, Nb ₂ O ₃ , SnO ₂ , WO ₃ , Si, CdS, CdSe, V ₂ O ₅ , ZnS, ZnSe, SnSe, KTaO. ₃ , FeS ₂ , PbS, InP, GaAs, CuInS ₂ , CuInSe ₂ and the like. Of these, the most preferred n-type semiconductors are TiO ₂ , ZnO, SnO ₂ , WO ₃ , and Nb ₂ O ₃ . A semiconductor material in which a plurality of these semiconductors are combined is also preferably used.

  For the purpose of keeping the viscosity of the semiconductor fine particle dispersion high, it is preferable that the average particle size of the primary particles is 2 nm to 50 nm, and the average primary particle size is 2 nm to 30 nm. More preferably, it is a fine particle. Two or more kinds of fine particles having different particle size distributions may be mixed. In this case, the average size of the small particles is preferably 5 nm or less. In addition, for the purpose of scattering incident light and improving the light capture rate, large particles having an average particle size exceeding 50 nm can be added to the ultrafine particles at a low content, or another layer can be applied. In this case, the content of the large particles is preferably 50% or less, more preferably 20% or less of the mass of particles having an average particle size of 50 nm or less. The average particle size of the large particles added and mixed for the above purpose is preferably 100 nm or more, and more preferably 250 nm or more.

By using large particles for light scattering, the haze ratio is preferably 60% or more. The haze ratio is expressed by (diffuse transmittance) / (total light transmittance).
As a method for producing the semiconductor fine particles, the gel-sol method described in Sakuo Sakuo's “Science of Sol-Gel Method”, Agne Jofu Co., Ltd. (1998) and the like is preferable. Also preferred is a method of producing an oxide by hydrolyzing a chloride developed by Degussa in an oxyhydrogen salt. When the semiconductor fine particles are titanium oxide, the above sol-gel method, gel-sol method, and high-temperature hydrolysis method in oxyhydrogen salt of chloride are preferred, but Kiyoshi Manabu's “Titanium oxide properties and applied technology” The sulfuric acid method and the chlorine method described in Gihodo Publishing (1997) can also be used. Further, as the sol-gel method, the method described in Journal of American Ceramic Society, Vol. 80, No. 12, 3157-3171 (1997), or the chemistry of Burnside et al. The method described in Materials, Vol. 10, No. 9, pages 2419-2425 is also preferable.

  In addition to this, as a method for producing semiconductor fine particles, for example, as a method for producing titania nanoparticles, preferably, a method by flame hydrolysis of titanium tetrachloride, a combustion method of titanium tetrachloride, hydrolysis of a stable chalcogenide complex, orthotitanic acid Of semiconductor, forming semiconductor fine particles from soluble and insoluble parts, then dissolving and removing soluble parts, hydrothermal synthesis of peroxide aqueous solution, or production of core / shell structured titanium oxide fine particles by sol-gel method A method is mentioned.

Examples of the crystal structure of titania include anatase type, brookite type, and rutile type, and anatase type and brookite type are preferable.
Titania nanotubes, nanowires, and nanorods may be mixed with titania fine particles.

  Titania may be doped with a nonmetallic element or the like. In addition to the dopant as an additive to titania, an additive may be used on the surface to improve the necking or to prevent reverse electron transfer. Examples of preferred additives include ITO, SnO particles, whiskers, fibrous graphite / carbon nanotubes, zinc oxide necking binders, fibrous materials such as cellulose, metals, organic silicon, dodecylbenzenesulfonic acid, silane compounds, etc. Examples thereof include a mobile binding molecule and a potential gradient dendrimer.

  For the purpose of removing surface defects on titania, titania may be acid-base or redox treated before dye adsorption. Etching, oxidation treatment, hydrogen peroxide treatment, dehydrogenation treatment, UV-ozone, oxygen plasma, or the like may be used.

[Preparation of semiconductor fine particle dispersion and preparation of semiconductor fine particle layer]
In the present invention, the semiconductor fine particle dispersion having a solid content other than the semiconductor fine particles of 10% by mass or less of the entire semiconductor fine particle dispersion is coated on the conductive support and heated to a suitable level. Quality semiconductor fine particle coating layer can be obtained.
In addition to the sol-gel method described above, a method of preparing a semiconductor fine particle dispersion is a method of depositing fine particles in a solvent and using them as they are when synthesizing a semiconductor. Ultrafine particles are irradiated with ultrasonic waves. Or a method of mechanically pulverizing and grinding using a mill or a mortar. As the dispersion solvent, water and / or various organic solvents can 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, acetonitrile and the like.
At the time of dispersion, a small amount of, for example, a polymer such as polyethylene glycol, hydroxyethyl cellulose, carboxymethyl cellulose, a surfactant, an acid, or a chelating agent may be used as a dispersion aid. However, most of these dispersing aids are preferably removed by a filtration method, a method using a separation membrane, a centrifugal method or the like before the step of forming a film on a conductive support. In the semiconductor fine particle dispersion, the solid content other than the semiconductor fine particles can be 10% by mass or less of the total dispersion. This concentration is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. More preferably, it is 0.5% or less, and particularly preferably 0.2%. That is, in the semiconductor fine particle dispersion, the solid content other than the solvent and the semiconductor fine particles can be 10% by mass or less of the entire semiconductor fine dispersion. It is preferable to consist essentially of semiconductor fine particles and a dispersion solvent.
If the viscosity of the semiconductor fine particle dispersion is too high, the dispersion may aggregate and cannot be formed into a film. Conversely, if the viscosity of the semiconductor fine particle dispersion is too low, the liquid may flow and be unable to form a film. is there. 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 method for applying the semiconductor fine particle dispersion, a roller method, a dip method, or the like can be used as an application method. Moreover, an air knife method, a blade method, etc. can be used as a metering method. Further, the application system method and the metering system method can be made the same part. The wire bar method disclosed in Japanese Patent Publication No. 58-4589, the slide hopper method described in US Pat. The method and the curtain method are preferable. It is also preferable to apply by a spin method or a spray method using a general-purpose machine. As the wet printing method, intaglio, rubber plate, screen printing and the like are preferred, including the three major printing methods of letterpress, offset and gravure. From these, a preferred film forming method is selected according to the liquid viscosity and the wet thickness. Further, since the semiconductor fine particle dispersion has a high viscosity and has a viscous property, it may have a strong cohesive force and may not be well adapted to the support during coating. In such a case, by performing cleaning and hydrophilization of the surface by UV ozone treatment, the binding force between the applied semiconductor fine particle dispersion and the surface of the conductive support increases, and the semiconductor fine particle dispersion can be easily applied.
The preferred thickness of the entire semiconductor fine particle layer is 0.1 to 100 μm. The thickness of the semiconductor fine particle layer is further preferably 1 to 30 μm, and more preferably 2 to 25 μm. The amount of the semiconductor fine particles supported per 1 m ² of the support is preferably 0.5 g to 400 g, and more preferably 5 to 100 g.

The applied semiconductor fine particle layer is subjected to heat treatment in order to enhance the electronic contact between the semiconductor fine particles and to improve the adhesion to the support and to dry the applied semiconductor fine particle dispersion. . By this heat treatment, a porous semiconductor fine particle layer can be formed. In addition, the semiconductor fine particle layer may be formed by a known method as appropriate according to the characteristics and application of the member. For example, the materials, preparation methods, and manufacturing methods described in Japanese Patent Application Laid-Open No. 2001-291534 can be referred to, and are cited in this specification.
The coating amount of the semiconductor fine particles per 1 m ² of the support is preferably 0.5 to 500 g, more preferably 5 to 100 g.

In order to adsorb the dye to the semiconductor fine particles, it is preferable to immerse the well-dried semiconductor fine particles in a dye adsorbing dye solution composed of a solution and a dye for a long time. The solution used for the dye solution for dye adsorption can be used without particular limitation as long as the solution can dissolve the dye. For example, ethanol, methanol, isopropanol, toluene, t-butanol, acetonitrile, acetone, n-butanol and the like can be used. Among these, ethanol and toluene can be preferably used.
You may heat the pigment | dye solution for pigment | dye adsorption which consists of a solution and a pigment | dye to 50 to 100 degreeC as needed. The adsorption of the dye may be performed before or after application of the semiconductor fine particles. Further, the semiconductor fine particles and the dye may be applied and adsorbed simultaneously. Unadsorbed dye is removed by washing. When baking a coating film, it is preferable to adsorb | suck a pigment | dye after baking. It is particularly preferable that the dye is quickly adsorbed after the baking and before water adsorbs on the surface of the coating film. The dye to be mixed is selected so as to make the wavelength range of photoelectric conversion as wide as possible. When mixing the dyes, it is preferable to prepare a dye solution for dye adsorption by dissolving all the dyes.

The total amount of the dye used is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, particularly preferably 0.1 to 10 mmol, per 1 m ² of the support. In this case, it is preferable that the usage-amount of a pigment | dye shall be 5 mol% or more.
Further, the adsorption amount of the dye to the semiconductor fine particles is preferably 0.001 to 1 mmol, more preferably 0.1 to 0.5 mmol, with respect to 1 g of the semiconductor fine particles. By using such a dye amount, a sensitizing effect in a semiconductor can be sufficiently obtained.

[Counter electrode]
The counter electrode (counter electrode) serves as the positive electrode of the photoelectrochemical cell. The counter electrode is usually synonymous with the conductive support described above, but the support is not necessarily required in a configuration in which the strength is sufficiently maintained. However, having a support is advantageous in terms of hermeticity. Examples of the material for the counter electrode include platinum, carbon, conductive polymer, and the like. Preferable examples include platinum, carbon, and conductive polymer.

As the structure of the counter electrode, a structure having a high current collecting effect is preferable. Preferable examples include JP-A-10-505192.
As the light receiving electrode, a composite electrode such as titanium oxide and tin oxide (TiO ₂ / SnO ₂ ) may be used. Examples of mixed electrodes other than titania include JP-A Nos. 2001-185243 and 2003-282164.

  The element may have a structure in which a first electrode layer, a first photoelectric conversion layer, a conductive layer, a second photoelectric conversion layer, and a second electrode layer are sequentially stacked. In this case, the dyes used for the first photoelectric conversion layer and the second photoelectric conversion layer may be the same or different, and when they are different, it is preferable that the absorption spectra are different. In addition, structures and members that are applied to this type of electrochemical element can be applied as appropriate.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.

(Preparation of dye)
Hereinafter, the method for synthesizing the dye of the present invention will be described in detail by way of examples. However, the starting material, the dye intermediate, and the synthesis route are not limited thereto.
(Synthesis example)
(I) Preparation of Dye Illustrative Dye A-1 having Structure of General Formula (1) Exemplified dye A-1 was prepared according to the method of the following scheme.

(1) Preparation of Compound A-1a 50.0 g of 10,11-dihydro-5H-dibenz [b, f] azepine was dissolved in 130 ml of DMF with stirring at room temperature and then ice-cooled, and 18.4 g of 50-70% sodium hydride. Was added in four portions and stirred at an internal temperature of 5 ° C. or lower for 0.5 hours. Thereto, 70.3 g of 1-iodoethane was added dropwise over 20 minutes, and the remaining amount was washed with 20 ml of DMF. Thereafter, the temperature was raised to room temperature and the reaction was carried out for 2.5 hours. After completion of the reaction, water was added dropwise to the reaction solution, followed by extraction with ethyl acetate. After liquid separation, the ethyl acetate layer was washed with 1N hydrochloric acid, sodium bicarbonate water and water in this order, and pre-dried with anhydrous sodium sulfate. After removing magnesium sulfate, the mixture was concentrated and the crude product was purified by column chromatography (solvent: hexane) to obtain 41.7 g of Compound A-1a.

(2) Preparation of Compound A-1b 10.0 g of Compound A-1a was stirred and dissolved in 180 ml of DMF at room temperature and then ice-cooled. To this solution, 10.1 g of N-bromosuccinimide was added in four portions and stirred as it was for 1 hour. After completion of the reaction, the reaction solution was extracted with an aqueous sodium thiosulfate solution and ethyl acetate, separated, and then washed with water added to the ethyl acetate layer. After separation, the ethyl acetate layer was pre-dried with anhydrous sodium sulfate, filtered and concentrated. The crude product was roughly purified by column chromatography (solvent: hexane) and further purified by liquid chromatography to obtain 6.5 g of A-1b.

(3) Preparation of Compound A-1c 1.21 g of Compound A-1b, 2.25 g of 4-hexyl-2-boronic acid ester, and 6 ml of a 10 wt% sodium carbonate solution were dissolved in 40 ml of DME, and the system was purged with nitrogen. To this solution, 234 mg of tetrakis (triphenylphosphine) palladium was added and heated under reflux for 3.5 hours. After cooling to room temperature, it was diluted with ethyl acetate, the organic layer was washed twice with water and dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (solvent: ethyl acetate / hexane = 1/15) to obtain 1.54 g of A-1c.

(4) Preparation of Compound A-1d 0.39 g of Compound A-1c was dissolved in 10 ml of DMF and cooled on ice. To this solution, a Vilsmeier reagent prepared in advance from 1.32 ml of DMF and 0.34 ml of phosphorus oxychloride was added dropwise and stirred at room temperature for 1 hour. Thereafter, the temperature was raised to 70 ° C., and the mixture was further stirred for 1 hour and 20 minutes.
After completion of the reaction, the reaction solution was added into a 14 wt% sodium acetate aqueous solution and stirred at room temperature for 30 minutes. This solution was extracted twice with ethyl acetate, and the ethyl acetate extracts were combined and washed with water. After drying with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a compositional organism. This crude product was roughly purified by column chromatography (solvent: ethyl acetate / hexane = 1/10) and further purified by liquid chromatography to obtain 0.28 g of A-1d.

(5) Preparation of Compound A-1 0.20 g of Compound A-1d was dissolved in 3.5 ml of acetonitrile and 3 ml of toluene. To this solution, 81.5 mg of cyanoacetic acid and 2 ml of piperidine were added, and the mixture was heated and stirred at 70 ° C. for 8.5 hours. After cooling, dichloromethane was added to the reaction solution, the organic layer was washed twice with dilute hydrochloric acid and water, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was recrystallized from methanol / dichloromethane and subjected to crude purification, followed by purification by column chromatography (solvent: dichloromethane → dichloromethane / methanol = 10/1) to obtain 0.12 g of A-1.

Preparation of Exemplified Dye A-4 Exemplified Dye A-4 was prepared according to the method of the following scheme.

(1) Preparation of Compound A-4a 5,0.0 g of 10,11-dihydro-5H-dibenz [b, f] azepine was dissolved in 130 ml of DMF with stirring at room temperature and then ice-cooled, and 18.4 g of 50-70% sodium hydride. Was added in four portions and stirred at an internal temperature of 5 ° C. or lower for 0.5 hours. Thereto, 70.3 g of 1-iodoethane was added dropwise over 20 minutes, and the remaining amount was washed with 20 ml of DMF. Thereafter, the temperature was raised to room temperature and the reaction was carried out for 2.5 hours. After completion of the reaction, water was added dropwise to the reaction solution, followed by extraction with ethyl acetate. After liquid separation, the ethyl acetate layer was washed with 1N hydrochloric acid, sodium bicarbonate water and water in this order, and pre-dried with anhydrous sodium sulfate. After removing magnesium sulfate, the mixture was concentrated and the crude product was purified by column chromatography (solvent: hexane) to obtain 41.7 g of Compound A-4a.

  As shown in the above scheme, by repeating the Suzuki coupling reaction and bromination reaction, an azepine derivative in which two hexyl-substituted thiophene rings represented by A-4e are bonded, and a hexyl-substituted thiophene represented by A-4g It was possible to synthesize an azepine derivative in which three rings were bonded and an azepine derivative in which four hexyl-substituted thiophene rings represented by A-4k were bonded.

(7) Preparation of Compound A-4 0.21 g of Compound A-4k was dissolved in 3.5 ml of acetonitrile, 3 ml of benzene and 0.2 ml of DMF. To this solution, 42.1 mg of cyanoacetic acid, 0.6 ml of piperidine and 42.5 mg of ammonium acetate were added, and the mixture was heated to reflux for 33 hours with a Dean-Stark apparatus. After cooling, dichloromethane was added to the reaction solution, the organic layer was washed twice with dilute hydrochloric acid and water, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was roughly purified by column chromatography (solvent: dichloromethane to dichloromethane / methanol = 20/1) and then purified by liquid chromatography to obtain A-40.11 g.
Other compounds were prepared in the same manner.
(II) Dye Having Structure of General Formula (2) Exemplified dye Ru-4 was prepared according to the method of the following scheme.

４，４’−ビス［２−（５−ヘキシル−２−チエニル）ビニル］−２，２’−ビピリジン（０．１５ｇ、０．２４５ｍｍｏｌ）とジクロロ（ｐ−シメン）ルテニウム（ＩＩ）二量体（０．０７４７ｇ、０．１２２ｍｍｏｌ）のＤＭＦ１０ｍｌ溶液をマイクロ波（２００Ｗ）、窒素暗雰囲気下、６０℃で１０分間加熱した。続いて２，２’−ビピリジン−４，４’−ジカルボン酸（０．１２ｇ、０．４９ｍｍｏｌ）を添加し、１５０℃で１０分間加熱した。温度を１００℃に冷却し、チオシアン酸アンモニウム（０．８ｇ、水４ｍｌの溶液）を加え、１２０℃で１０分間反応させた。温度を室温まで下げ、ＤＭＦを真空蒸留した。水８０ｍｌを残留物に添加し、３０分間浸漬した。不溶物を集め、水とジエチルエーテルで洗浄した。粗生成物をＴＢＡＯＨ（水酸化テトラブチルアンモニウム）と共にメタノールに溶解し、メタノールを流出液として、ＳｅｐｈａｄｅｘＬＨ−２０（商品名、Ｐｈａｒｍａｃｉａ Ｆｉｎｅ Ｃｈｅｍｉｃａｌｓ社製）のカラムで精製した。主層の生成物を回収濃縮し、硝酸０．２Ｍを添加して沈殿物を得た。この生成物を集め、室温で真空乾燥後、一般式（２）で表される構造を有する前記例示色素Ｒｕ−４（０．３１ｇ）を得た。
その他の化合物についても同様に調製した。

4,4′-bis [2- (5-hexyl-2-thienyl) vinyl] -2,2′-bipyridine (0.15 g, 0.245 mmol) and dichloro (p-cymene) ruthenium (II) dimer A solution of (0.0747 g, 0.122 mmol) in DMF (10 ml) was heated at 60 ° C. for 10 minutes in a microwave (200 W) under nitrogen dark atmosphere. Subsequently, 2,2′-bipyridine-4,4′-dicarboxylic acid (0.12 g, 0.49 mmol) was added and heated at 150 ° C. for 10 minutes. The temperature was cooled to 100 ° C., ammonium thiocyanate (0.8 g, a solution of 4 ml of water) was added, and the mixture was reacted at 120 ° C. for 10 minutes. The temperature was lowered to room temperature and DMF was distilled in vacuo. 80 ml of water was added to the residue and immersed for 30 minutes. The insoluble material was collected and washed with water and diethyl ether. The crude product was dissolved in methanol together with TBAOH (tetrabutylammonium hydroxide), and purified with a column of Sephadex LH-20 (trade name, manufactured by Pharmacia Fine Chemicals) using methanol as the effluent. The product of the main layer was collected and concentrated, and 0.2M nitric acid was added to obtain a precipitate. This product was collected and vacuum-dried at room temperature to obtain the exemplified dye Ru-4 (0.31 g) having a structure represented by the general formula (2).
Other compounds were prepared in the same manner.

(Measurement of maximum absorption wavelength of dye)
The maximum absorption wavelength of the dye used was measured. The results are shown in Table 1. The measurement was performed with a spectrophotometer (U-4100 (trade name), manufactured by Hitachi High-Tech), and the solution was adjusted to a concentration of 2 μM using THF: ethanol = 1: 1.

Example 1
(Preparation of photoelectric conversion element)
The photoelectric conversion element shown in FIG. 1 was produced as follows.
On the glass substrate, tin oxide doped with fluorine was formed as a transparent conductive film by sputtering, and this was scribed with a laser to divide the transparent conductive film into two parts.
Next, 32 g of anatase-type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) is mixed with 100 ml of a mixed solvent of water and acetonitrile having a volume ratio of 4: 1, and a rotating / revolving mixing conditioner is prepared. The resulting mixture was uniformly dispersed and mixed to obtain a semiconductor fine particle dispersion. This dispersion was applied to a transparent conductive film and heated at 500 ° C. to produce a light receiving electrode.
Thereafter, similarly, a dispersion containing 40:60 (mass ratio) of silica particles and rutile-type titanium oxide is prepared, and this dispersion is applied to the light receiving electrode and heated at 500 ° C. to form an insulating porous material. Formed body. Next, a carbon electrode was formed as a counter electrode.
Next, the glass substrate on which the insulating porous body was formed was immersed in an ethanol solution of a sensitizing dye (mixed or single) described in Table 1 below for 48 hours. The glass dyed with the sensitizing dye was immersed in a 10% ethanol solution of 4-tert-butylpyridine for 30 minutes, then washed with ethanol and naturally dried. The thickness of the photosensitive layer thus obtained was 10 μm, and the coating amount of semiconductor fine particles was 20 g / m ² . As the electrolytic solution, a methoxypropionitrile solution of dimethylpropylimidazolium iodide (0.5 mol / l) and iodine (0.1 mol / l) was used.

(Measurement of photoelectric conversion efficiency)
Simulated sunlight containing no ultraviolet rays was generated by passing the light of a 500 W xenon lamp (manufactured by Ushio) through an AM1.5G filter (manufactured by Oriel) and a sharp cut filter (KenkoL-42, trade name). The intensity of this light was 89 mW / cm ² . The produced photoelectric conversion element was irradiated with this light, and the generated electricity was measured with a current-voltage measuring device (Caseley 238 type, trade name). The results of measuring the conversion efficiency of the photoelectrochemical cell thus obtained are shown in Table 2 below. The results are: conversion efficiency of 3.5% or more ◎, 2.5% or more of less than 3.5% ○, 2.0% or more of less than 2.5% △, 2.0% Those less than were evaluated as x.

  The following sensitizing dyes S-1 and S-2 were used as comparative pigments.

As shown in Table 2, the electrochemical cell produced using the dye of the present invention has A-4 / Ru-4, I-1 / Ru-4, N-1 / in particular as a combination of dyes. Ru-4, α-4 / Ru-4, A-4 / Ru-3, A-4 / Ru-5, α-4 / Ru-5, A-4 / Ru-7, B-3 / Ru- 7. When α-4 / Ru-7 was used, the conversion efficiency was as high as 3.5% or more. Even when other dyes of the present invention were used, the conversion efficiency was at a relatively high level of 2.5% or more and less than 3.5%.
On the other hand, the comparative example of sample number 17 had an insufficient conversion efficiency of less than 2.5%.

(Example 2)
An ITO film was produced on a glass substrate, and an FTO film was laminated thereon to produce a transparent conductive film. Then, a transparent electrode plate was obtained by forming an oxide semiconductor porous film on the transparent conductive film. And the photoelectrochemical cell was produced using the transparent electrode plate, and conversion efficiency was measured. The method is as follows (1)-(5).

(1) Preparation of raw material solution for ITO (indium-tin-oxide) film Indium (III) tetrahydrate 5.58 g and tin (II) chloride dihydrate 0.23 g were dissolved in 100 ml of ethanol. Thus, a raw material compound solution for the ITO film was obtained.

(2) Preparation of FTO (Fluorine Doped Tin Oxide) Film Raw Material Compound Solution 0.701 g of tin (IV) chloride pentahydrate was dissolved in 10 ml of ethanol, and 0.592 g of a saturated aqueous solution of ammonium fluoride was added thereto. This mixture was subjected to an ultrasonic cleaning machine for about 20 minutes and completely dissolved to obtain a raw material compound solution for an FTO film.

(3) Preparation of ITO / FTO transparent conductive film The surface of a heat-resistant glass plate having a thickness of 2 mm was chemically washed and dried, and then this glass plate was placed in a reactor and heated with a heater. When the heating temperature of the heater reached 450 ° C., the raw material compound solution for ITO film obtained in (1) was adjusted from a nozzle having a diameter of 0.3 mm to a pressure of 0.06 MPa and a distance to the glass plate of 400 mm, 25 Sprayed for a minute.
After spraying the raw material compound solution for ITO film, 2 minutes passed (ethanol was sprayed on the glass substrate surface during this period to suppress the rise of the substrate surface temperature), and the heating temperature of the heater became 530 ° C. Occasionally, the FTO membrane raw material compound solution obtained in (2) was sprayed for 2 minutes 30 seconds under the same conditions. As a result, a transparent electrode plate was obtained in which an ITO film having a thickness of 530 nm and an FTO film having a thickness of 170 nm were sequentially formed on the heat-resistant glass plate.
For comparison, similarly, a transparent electrode plate in which only a 530 nm thick ITO film is formed on a heat resistant glass plate having a thickness of 2 mm and a transparent electrode plate in which only a 180 nm thick FTO film is similarly formed are formed. Each was produced.
These three kinds of transparent electrode plates were heated in a heating furnace at 450 ° C. for 2 hours.

(4) Production of photoelectrochemical cell Next, a photoelectrochemical cell having the structure shown in FIG. 2 of Japanese Patent No. 4260494 was produced using the above three types of transparent electrode plates. The oxide semiconductor porous film 15 is formed by dispersing fine particles of titanium oxide having an average particle diameter of about 230 nm in 100 ml of acetonitrile to form a paste, applying this to the transparent electrode 11 to a thickness of 15 μm by a bar coating method, The oxide semiconductor porous film 15 was loaded with the dyes listed in Table 2 by baking at 450 ° C. for 1 hour. The immersion conditions in the dye solution were the same as in Example 1.
Further, a conductive substrate in which an ITO film and an FTO film were laminated on a glass plate was used for the counter electrode 16, and an electrolytic solution made of a non-aqueous solution of iodine / iodide was used for the electrolyte layer 17. The planar dimension of the photoelectrochemical cell was 25 mm × 25 mm.

(5) Evaluation of photoelectrochemical cell About this photoelectrochemical cell, artificial sunlight (AM1.5) was irradiated and the electric power generation efficiency was calculated | required. The results are shown in Table 3. Conversion efficiency is 3.5% or more, ◎, 2.5% or more, less than 3.5%, ○, 2.0% or more, less than 2.5%, △, less than 2.0% Was evaluated as x.

増感色素Ｓ−１、Ｓ−２を用いた試料Ｎｏ．１０〜１２では変換効率が低いのに対し、本発明の例示色素を使用した試料Ｎｏ．１〜９では良好な結果を示すことがわかった。透明電極板として、ＩＴＯ膜とＦＴＯ膜とを積層したものを用いた光電気化学電池では、ＩＴＯ膜のみもしくはＦＴＯ膜のみを成膜したものを用いた場合に比べ特に変換効率が高く、本発明の色素でその効果が高いことがわかった。

Sample No. using sensitizing dyes S-1 and S-2. 10 to 12, the conversion efficiency is low. It turned out that a favorable result is shown in 1-9. In a photoelectrochemical cell using a laminate of an ITO film and an FTO film as a transparent electrode plate, the conversion efficiency is particularly high as compared with the case where only an ITO film or only an FTO film is used. This dye was found to be highly effective.

(Example 3)
A collecting electrode was arranged on the FTO film to produce a photoelectrochemical cell, and the conversion efficiency was evaluated. Evaluation was made into two types, test cell (i) and test cell (iv) as follows.

(Test cell (i))
The surface of a heat-resistant glass plate of 100 mm × 100 mm × 2 mm was chemically washed and dried, and then this glass plate was placed in a reactor and heated with a heater, and then the FTO (fluorine-doped tin oxide) film used in Example 2 The raw material compound solution was sprayed from a nozzle having a diameter of 0.3 mm at a pressure of 0.06 MPa and a distance to the glass plate of 400 mm for 25 minutes to prepare a glass substrate with an FTO film. On the surface, grooves having a depth of 5 μm were formed in a lattice circuit pattern by an etching method. After pattern formation by photolithography, etching was performed using hydrofluoric acid. A metal conductive layer (seed layer) was formed thereon by sputtering in order to enable plating formation, and a metal wiring layer 3 was further formed by additive plating. The metal wiring layer 3 was formed in a convex lens shape from the surface of the transparent substrate 2 to a height of 3 μm. The circuit width was 60 μm. From this, an FTO film having a thickness of 400 nm was formed as the shielding layer 5 by the SPD method to obtain an electrode substrate (i). The cross-sectional shape of the electrode substrate (i) was as shown in FIG. 2 in JP-A No. 2004-146425.
On the electrode substrate (i), a dispersion obtained by dispersing titanium oxide having an average particle diameter of 25 nm in 100 ml of acetonitrile was applied and dried, and heated and sintered at 450 ° C. for 1 hour. This was immersed in an ethanol solution of the dye shown in Table 3 to adsorb the dye. The immersion conditions were the same as in Example 1. It arrange | positioned facing a platinum sputter | spatter FTO board | substrate through a 50-micrometer-thick thermoplastic polyolefin resin sheet, the resin sheet part was heat-melted, and the bipolar plate was fixed.
A methoxyacetonitrile solution containing 0.5M iodide and 0.05M iodine as the main components was injected from the electrolyte solution inlet previously opened on the platinum sputter electrode side, and filled between the electrodes. It was. Further, the peripheral portion and the electrolyte solution injection port were finally sealed using an epoxy-based sealing resin, and a silver paste was applied to the current collecting terminal portion to obtain a test cell (i). The photoelectric conversion characteristics of the test cell (i) were evaluated using pseudo sunlight of AM1.5. The results are shown in Table 4.

(Test cell (iv))
A glass substrate with a 100 × 100 mm FTO film was prepared in the same manner as in the test cell (i). A metal wiring layer 3 (gold circuit) was formed on the FTO glass substrate by additive plating. The metal wiring layer 3 (gold circuit) was formed in a lattice shape on the substrate surface, and had a circuit width of 50 μm and a circuit thickness of 5 μm. On this surface, an FTO film having a thickness of 300 nm was formed as a shielding layer 5 by the SPD method to obtain a test cell (iv). When the cross section of the electrode substrate (iv) was confirmed using SEM-EDX, there was a sneaking in which seems to be caused by the skirting of the plating resist at the bottom of the wiring, and the shadow portion was not covered with FTO.
A test cell (iv) was produced in the same manner as the test cell (i) using the electrode substrate (iv). The photoelectric conversion characteristics of the test cell (iv) were evaluated by AM1.5 artificial sunlight, and the results are shown in Table 4. The results are: conversion efficiency of 3.5% or more ◎, 2.5% or more of less than 3.5% ○, 2.0% or more of less than 2.5% △, 2.0% Those less than were evaluated as x.

  From Table 4, when the pigment | dye of this invention was used, the conversion efficiency in the case of test cell (i) showed a high value with 3.5% or more. On the other hand, when the test cell (iv) was used, the conversion efficiency was higher when the dye of the present invention was used as compared with the case where the dye of the comparative example was used. For this reason, it was found that the degree of freedom in selecting the test cell was increased by using the dye of the present invention (comparison with sample numbers 11 and 12).

Example 4
Tests were conducted on a method for producing peroxotitanic acid and titanium oxide fine particles and a method for producing an oxide semiconductor film using the peroxotitanic acid and titanium oxide fine particles, and a photoelectrochemical cell was produced and evaluated.

(Photovoltaic cell (A))
(1) Preparation of coating liquid (A) for forming an oxide semiconductor film 5 g of titanium hydride is suspended in 1 liter of pure water, 400 g of a 5 mass% hydrogen peroxide solution is added over 30 minutes, and then 80 A solution of peroxotitanic acid was prepared by heating to ° C and dissolution. 90% by volume was taken from the total amount of this solution, adjusted to pH 9 by adding concentrated aqueous ammonia, placed in an autoclave, hydrothermally treated at 250 ° C. for 5 hours under saturated vapor pressure, and titania colloidal particles (A) Was prepared. The obtained titania colloidal particles were anatase type titanium oxide having high crystallinity by X-ray diffraction.
Next, the obtained titania colloidal particles (A) was concentrated to 10 wt%, the peroxotitanic acid solution were mixed, the titanium of the mixed solution TiO ₂ terms, TiO ₂ mass of 30 mass% Then, hydroxypropylcellulose was added as a film formation aid so that a coating solution for forming a semiconductor film was prepared.

(2) Production of oxide semiconductor film (A) Next, the coating solution was applied on a transparent glass substrate on which fluorine-doped tin oxide was formed as an electrode layer, dried naturally, and subsequently 6000 mJ using a low-pressure mercury lamp. The peroxoacid was decomposed by irradiating UV light of / cm ² to cure the coating film. The coating film was heated at 300 ° C. for 30 minutes to decompose and anneal the hydroxypropyl cellulose to form an oxide semiconductor film (A) on the glass substrate.

(3) Adsorption of Dye to Oxide Semiconductor Film (A) Next, an ethanol solution having a concentration shown in the table with the combination dye of the present invention as a spectral sensitizing dye was prepared. This dye solution was applied onto the metal oxide semiconductor film (A) with a 100 rpm spinner and dried. This coating and drying process was performed five times.

(4) Preparation of electrolyte solution In a mixed solvent with a volume ratio of acetonitrile and ethylene carbonate of 1: 5, tetrapropylammonium iodide is 0.46 mol / liter and iodine is 0.07 mol / liter. To prepare an electrolyte solution.

(5) Production of photoelectric cell (A) The glass substrate produced in (2) on which the oxide semiconductor film (A) adsorbing the dye was formed was used as one electrode, and the other electrode was fluorine-doped. A transparent glass substrate formed with tin oxide as an electrode and carrying platinum on it is placed facing it, the sides are sealed with resin, the electrolyte solution (4) is sealed between the electrodes, and the electrodes are lead between Photoelectric cells (A) were prepared by connecting with wires.

(6) Evaluation of Photoelectric Cell (A) Photoelectric cell (A) is irradiated with light of 100 W / m ² with a solar simulator, and η (conversion efficiency) is measured. Indicated.

(Photovoltaic cell (B))
Oxide semiconductor film (A) except that after irradiation with ultraviolet light, peroxo acid was decomposed and the film was cured, Ar gas ion irradiation (Nisshin Electric Co., Ltd .: ion implantation apparatus, irradiation at 200 eV for 10 hours) was performed. ), An oxide semiconductor film (B) was formed.
Similarly to the oxide semiconductor film (A), the dye was adsorbed to the oxide semiconductor film (B).
Thereafter, a photoelectric cell (B) was prepared by the same method as that for the photovoltaic cell A, and η was measured. The results are shown in Table 5.

(Photovoltaic cell (C))
18.3 g of titanium tetrachloride was diluted with pure water to obtain an aqueous solution containing 1.0% by mass in terms of TiO ₂ . While stirring this aqueous solution, 15% by mass of aqueous ammonia was added to obtain a white slurry having a pH of 9.5. This slurry was washed by filtration to obtain a 10.2% by mass hydrated titanium oxide gel cake in terms of TiO ₂ . This cake was mixed with 400 g of a 5 mass% hydrogen peroxide solution, and then heated to 80 ° C. to dissolve to prepare a peroxotitanic acid solution. 90% by volume is taken from the total amount of this solution, and concentrated ammonia water is added to adjust the pH to 9, and the mixture is placed in an autoclave, hydrothermally treated at 250 ° C. for 5 hours under saturated vapor pressure, and titania colloidal particles (C ) Was prepared.
Next, using the peroxotitanic acid solution obtained above and titania colloidal particles (C), an oxide semiconductor film (C) is formed in the same manner as the oxide semiconductor film (A), and the metal oxide semiconductor film In the same manner as (A), the dye of the present invention was adsorbed as a spectral sensitizing dye.
Thereafter, a photoelectric cell (C) was prepared by the same method as that for the photoelectric cell (A), and η was measured. The results are shown in Table 5.

(Photovoltaic cell (D))
18.3 g of titanium tetrachloride was diluted with pure water to obtain an aqueous solution containing 1.0% by mass in terms of TiO ₂ . While stirring this, 15% by mass of ammonia water was added to obtain a white slurry having a pH of 9.5. This slurry was filtered and washed, suspended in pure water to obtain a 0.6 mass% hydrated titanium oxide gel slurry as TiO ₂ , adjusted to pH 2 by adding hydrochloric acid thereto, put in an autoclave, and stirred at 180 ° C. for 5 The titania colloidal particles (D) were prepared by performing hydrothermal treatment for a period of time under saturated vapor pressure.
Next, titania colloidal particles (D) are concentrated to 10% by mass, and hydroxypropyl cellulose is added as a film forming aid so as to be 30% by mass in terms of TiO ₂ to form a semiconductor film. A coating solution was prepared. Next, the coating solution is applied onto a transparent glass substrate on which fluorine-doped tin oxide is formed as an electrode layer, dried naturally, and subsequently irradiated with 6000 mJ / cm ² of ultraviolet rays using a low-pressure mercury lamp to form a film. Cured. Furthermore, it heated at 300 degreeC for 30 minute (s), decomposed | disassembled and annealed hydroxypropyl cellulose, and formed the oxide semiconductor film (D).
Next, the dye of the present invention was adsorbed as a spectral sensitizing dye in the same manner as the oxide semiconductor film (A).
Then, the photoelectric cell (D) was created by the method similar to a photoelectric cell (A), and (eta) was measured. The results are shown in Table 5. The results are: conversion efficiency of 3.5% or more ◎, 2.5% or more of less than 3.5% ○, 2.0% or more of less than 2.5% △, 2.0% Less than were shown as x.

  From Table 5, in the case of the pigment | dye of this invention, when test cell (A)-(C) was used, it turned out that conversion efficiency is especially high.

(Example 5)
Titanium oxide was prepared or synthesized by changing the method, an oxide semiconductor film was prepared from the obtained titanium oxide, and a photoelectrochemical cell was evaluated.

(1) Preparation of titanium oxide by heat treatment Using commercially available anatase-type titanium oxide (trade name ST-01, manufactured by Ishihara Sangyo Co., Ltd.), this is heated to about 900 ° C. and converted to blue kite-type titanium oxide. Further, it was heated to about 1,200 ° C. to obtain a rutile type titanium oxide. Respectively, comparative titanium oxide 1 (anatase type), titanium oxide 1 (blue kite type), and comparative titanium oxide 2 (rutile type) are used.

(2) Synthesis of titanium oxide by wet method (titanium oxide 2 (blue kite type))
954 ml of distilled water is charged into a reaction vessel equipped with a reflux condenser and heated to 95 ° C. While maintaining the stirring speed at about 200 rpm, 46 ml of an aqueous solution of titanium tetrachloride (Ti content: 16.3 mass%, specific gravity 1.59, purity 99.9%) was added to this distilled water at a speed of about 5.0 ml / min. It was dripped at the reaction tank. At this time, care was taken not to lower the temperature of the reaction solution. As a result, the titanium tetrachloride concentration was 0.25 mol / liter (2% by mass in terms of titanium oxide). In the reaction vessel, the reaction solution started to become cloudy immediately after dropping, but kept at the same temperature. After the dropping was completed, the temperature was further raised and heated to the vicinity of the boiling point (104 ° C.). The reaction was terminated.
The sol obtained by the reaction was filtered, and then powdered using a vacuum dryer at 60 ° C. As a result of quantitative analysis of this powder by X-ray diffractometry, the ratio of (peak intensity on the surface of blue kite type 121) / (peak intensity at the position where the three overlap) is 0.38, (rutile main peak intensity) / The ratio (peak intensity at the position where the three lines overlap) was 0.05. From these, the titanium oxide was crystallinity of about 70.0% by mass for the brookite type, about 1.2% by mass for the rutile type, and about 28.8% by mass for the anatase type. Further, when the fine particles were observed with a transmission electron microscope, the average particle diameter of the primary particles was 0.015 μm.

(Titanium oxide 3 (Blue Kite type))
An aqueous solution of titanium trichloride (Ti content: 28% by mass, specific gravity 1.5, purity 99.9%) was diluted with distilled water to obtain a solution having a concentration of 0.25 mol / L in terms of titanium concentration. At this time, it was ice-cooled so as not to increase the liquid temperature and kept at 50 ° C. or lower. Next, 500 ml of this solution was put into a reaction tank equipped with a reflux condenser, and ozone gas with a purity of 80% was bubbled from the ozone gas generator at 1 L / min while heating at 85 ° C. to carry out an oxidation reaction. This state was maintained for 2 hours to complete the reaction. The obtained sol was filtered and vacuum-dried to obtain a powder. As a result of quantitative analysis of this powder by X-ray diffractometry, the ratio of (peak intensity on the surface of blue kite type 121) / (peak intensity at the position where the three overlap) is 0.85, (rutile main peak intensity) / The ratio (peak intensity at the position where the three lines overlap) was 0. From these, the titanium dioxide was about 98% by mass for the blue kite type, 0% by mass for the rutile type, 0% by mass for the anatase type, and about 2% was amorphous. Further, when the fine particles were observed with a transmission electron microscope, the average particle diameter of the primary particles was 0.05 μm.

(Production and evaluation of dye-sensitized photoelectric conversion device)
A photoelectric conversion element having the configuration shown in FIG. 1 of JP-A No. 2000-340269 was produced as follows using titanium oxide prepared by the above titanium oxides 1 to 3 as a semiconductor.
A glass substrate was coated with fluorine-doped tin oxide to form a conductive transparent electrode. A paste using each titanium oxide particle as a raw material was formed on the electrode surface, applied to a thickness of 50 μm by a bar coating method, and then baked at 500 ° C. to form a thin layer having a thickness of about 20 μm. Next, an ethanol solution having the described concentration of the combination of sensitizing dye-1 and sensitizing dye-2 shown in the table is prepared, and the glass substrate on which the above-described titanium oxide thin layer is formed is immersed in this solution for 12 hours at room temperature. Retained.

  A photoelectric conversion element having the configuration shown in FIG. 1 of JP-A No. 2000-340269 was prepared using an iodine salt of tetrapropylammonium as an electrolytic solution and an acetonitrile solution of lithium iodide and using platinum as a counter electrode. For photoelectric conversion, light from a 160-w high-pressure mercury lamp (the infrared part was cut by a filter) was applied to the above-mentioned element, and the conversion efficiency at that time was measured. The results are shown in Table 6. The results are: conversion efficiency of 3.5% or more ◎, 2.5% or more of less than 3.5% ○, 2.0% or more of less than 2.5% △, 2.0% Less than were shown as x.

  From Table 6, it was found that the dye of the present invention has high conversion efficiency.

(Example 6)
Photoelectrochemical cells were fabricated as semiconductor electrodes using titanium oxides having different particle sizes, and the characteristics were evaluated.
[Preparation of paste]
First, a paste for forming a semiconductor layer or a light scattering layer of a semiconductor electrode constituting the photoelectrode was prepared by the following procedure.

(Paste 1)
A titania slurry was prepared by placing spherical TiO ₂ particles (anatase type, average particle size: 25 nm, hereinafter referred to as spherical TiO ₂ particles 1) in a nitric acid solution and stirring. Next, a cellulose binder as a thickener was added to the titania slurry and kneaded to prepare a paste.

(Paste 2)
A titania slurry was prepared by placing spherical TiO ₂ particles 1 and spherical TiO ₂ particles (anatase type, average particle size: 200 nm, hereinafter referred to as spherical TiO ₂ particles 2) in a nitric acid solution and stirring. Next, a cellulose binder as a thickener was added to the titania slurry and kneaded to prepare a paste (mass of TiO ₂ particles 1: mass of TiO ₂ particles 2 = 30:70).

(Paste 3)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase type, diameter: 100 nm, aspect ratio: 5, hereinafter referred to as rod-like TiO ₂ particles 1), the mass of the rod-like TiO ₂ particles 1: the mass of the paste 1 = 10: Ninety pastes were prepared.

(Paste 4)
The paste 1, a rod-shaped TiO ₂ particles 1 were mixed, the mass rod-shaped TiO ₂ particles 1: Paste 1 Mass = 30: 70 paste was prepared.

(Paste 5)
The paste 1, a rod-shaped TiO ₂ particles 1 were mixed, the mass rod-shaped TiO ₂ particles 1: Paste 1 Mass = 50: 50 paste was prepared.

(Paste 6)
The paste 1 is mixed with plate-like mica particles (diameter: 100 nm, aspect ratio: 6, hereinafter referred to as plate-like mica particles 1), and the mass of the plate-like mica particles 1: the mass of the paste 1 = 20: 80 paste. Was prepared.

(Paste 7)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 30 nm, aspect ratio: 6.3, hereinafter referred to as rod-like TiO ₂ particles 2), the mass of the rod-like TiO ₂ particles 2: the mass of the paste 1 = 30: 70 pastes were prepared.

(Paste 8)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 50 nm, aspect ratio: 6.1, hereinafter referred to as rod-like TiO ₂ particles 3), and the mass of the rod-like TiO ₂ particles 3: the mass of the paste 1 = 30. : 70 paste was prepared.

(Paste 9)
The paste 1 is mixed with rod-shaped TiO ₂ particles (anatase, diameter: 75 nm, aspect ratio: 5.8, hereinafter referred to as rod-shaped TiO ₂ particles 4), and the mass of the rod-shaped TiO ₂ particles 4: the mass of the paste 1 = 30. : 70 paste was prepared.

(Paste 10)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 130 nm, aspect ratio: 5.2, hereinafter referred to as rod-like TiO ₂ particles 5), and the mass of the rod-like TiO ₂ particles 5: the mass of the paste 1 = 30. : 70 paste was prepared.

(Paste 11)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 180 nm, aspect ratio: 5, hereinafter referred to as rod-like TiO ₂ particles 6), and the mass of the rod-like TiO ₂ particles 6: the mass of the paste 1 = 30: 70. A paste was prepared.

(Paste 12)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 240 nm, aspect ratio: 5, hereinafter referred to as rod-like TiO ₂ particles 7), the mass of the rod-like TiO ₂ particles 7: the mass of the paste 1 = 30: 70. A paste was prepared.

(Paste 13)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 110 nm, aspect ratio: 4.1, hereinafter referred to as rod-like TiO ₂ particles 8), and the mass of the rod-like TiO ₂ particles 8: the mass of the paste 1 = 30. : 70 paste was prepared.

(Paste 14)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 105 nm, aspect ratio: 3.4, hereinafter referred to as rod-like TiO ₂ particles 9), and the mass of the rod-like TiO ₂ particles 9: the mass of the paste 1 = 30. : 70 paste was prepared.

(Photoelectrochemical cell 1)
A photoelectrode having the same configuration as the photoelectrode 12 shown in FIG. 5 described in JP-A-2002-289274 is prepared by the following procedure, and further, using the photoelectrode, a dye-sensitized type other than the photoelectrode is used. A 10 × 10 mm scale photoelectrochemical cell 1 having the same configuration as that of the solar cell 20 was produced.

A transparent electrode in which a fluorine-doped SnO ₂ conductive film (film thickness: 500 nm) was formed on a glass substrate was prepared. Then, the paste 2 was screen-printed on the SnO ₂ conductive film and then dried. Then, it baked on the conditions of 450 degreeC in the air. Further, by repeating this screen printing and baking using the paste 4, a semiconductor electrode having the same configuration as the semiconductor electrode 2 shown in FIG. 5 on the SnO ₂ conductive film (area of light receiving surface; 10 mm × 10 mm, layer thickness) 10 μm, layer thickness of semiconductor layer; 6 μm, layer thickness of light scattering layer; 4 μm, content of rod-like TiO ₂ particles 1 contained in the light scattering layer; 30% by mass), containing sensitizing dye A photoelectrode was prepared.

Next, the pigment | dye was made to adsorb | suck to a semiconductor electrode as follows. First, an anhydrous ethanol dehydrated with magnesium ethoxide was used as a solvent, and the dyes of the combination of the present invention were dissolved therein so as to have the concentrations shown in the table to prepare a dye solution. Next, the semiconductor electrode was immersed in this solution, thereby adsorbing about 1.5 mmol / m ² of the dye to the semiconductor electrode, and the photoelectrode 10 was completed.

  Next, a platinum electrode (thickness of Pt thin film; 100 nm) having the same shape and size as the above-described photoelectrode as a counter electrode, and an iodine redox solution containing iodine and lithium iodide as an electrolyte E were prepared. Furthermore, a spacer S (trade name: “Surlin”) manufactured by DuPont having a shape corresponding to the size of the semiconductor electrode is prepared. As shown in FIG. 3 of JP-A-2002-289274, the photoelectrode 10 and the counter electrode are prepared. The photoelectrochemical cell 1 was completed by facing the CE through the spacer S and filling the above electrolyte therein.

(Photoelectrochemical cell 2)
The photoelectrode 10 shown in FIG. 1 described in JP-A-2002-289274 and the diagram described in JP-A-2002-289274 are the same as those of the photoelectrochemical cell 1 except that the semiconductor electrode is manufactured as follows. A photoelectrode and a photoelectrochemical cell 2 having the same configuration as the dye-sensitized solar cell 20 shown in FIG.

Paste 2 was used as a semiconductor layer forming paste. Then, paste 2 was screen-printed on the SnO ₂ conductive film and then dried. Then, it baked on the conditions of 450 degreeC in the air, and formed the semiconductor layer.

  Paste 3 was used as the innermost layer forming paste of the light scattering layer. The paste 5 was used as the outermost layer forming paste of the light scattering layer. Then, a light scattering layer was formed on the semiconductor layer in the same manner as in the dye-sensitized solar cell 1.

Then, on the SnO ₂ conductive film, a semiconductor electrode having the same configuration as the semiconductor electrode 2 shown in FIG. 1 described in JP-A-2002-289274 (light receiving surface area: 10 mm × 10 mm, layer thickness: 10 μm, layer thickness of the semiconductor layer) 3 μm, the thickness of the innermost layer; 4 μm, the content of rod-like TiO ₂ particles 1 contained in the innermost layer; 10% by mass, the thickness of the outermost layer; 3 μm, contained in the innermost layer The content ratio of the rod-like TiO ₂ particles 1 to be formed; 50% by mass) was formed, and a photoelectrode containing no sensitizing dye was produced. Similarly to the photoelectrochemical cell 1, the photoelectrochemical cell 2 was completed by making the photoelectrode, the counter electrode CE, and the spacer S face each other and filling the above electrolyte therein.

(Photoelectrochemical cell 3)
The light shown in FIG. 5 was prepared by the same procedure as that of the photoelectrochemical cell 1 except that the paste 1 was used as the semiconductor layer forming paste and the paste 4 was used as the light scattering layer forming paste when the semiconductor electrode was manufactured. A photoelectrode and photoelectrochemical cell 3 having the same configuration as the electrode 10 and the photoelectrochemical cell 20 shown in FIG. 3 described in JP-A-2002-289274 were produced. The semiconductor electrode has a light receiving surface area of 10 mm × 10 mm, a layer thickness of 10 μm, a semiconductor layer thickness of 5 μm, a light scattering layer thickness of 5 μm, and the rod-like TiO ₂ particles 1 contained in the light scattering layer. Content rate: 30% by mass.

(Photoelectrochemical cell 4)
In the production of the semiconductor electrode, the light shown in FIG. 5 was obtained by the same procedure as that of the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 6 was used as the light scattering layer forming paste. A photoelectrode and a photoelectrochemical cell 4 having the same configuration as the electrode 10 and the photoelectrochemical cell 20 shown in FIG. 3 described in JP-A-2002-289274 were produced. The semiconductor electrode has a light receiving surface area: 10 mm × 10 mm, layer thickness: 10 μm, semiconductor layer thickness: 6.5 μm, light scattering layer thickness: 3.5 μm, plate-like contained in the light scattering layer The content of mica particles 1 was 20% by mass.

(Photoelectrochemical cell 5)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 8 was used as the light scattering layer forming paste. Battery 5 was produced. The content ratio of the rod-shaped TiO ₂ particles 3 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

(Photoelectrochemical cell 6)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemical process were performed in the same manner as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 9 was used as the light scattering layer forming paste. A battery 6 was produced. The content ratio of the rod-shaped TiO ₂ particles 4 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

(Photoelectrochemical cell 7)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 10 was used as the light scattering layer forming paste. Battery 7 was produced. The content ratio of the rod-shaped TiO ₂ particles 5 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

(Photoelectrochemical cell 8)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 11 was used as the light scattering layer forming paste. Battery 8 was produced. The content ratio of the rod-shaped TiO ₂ particles 6 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

(Photoelectrochemical cell 9)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 13 was used as the light scattering layer forming paste. A battery 9 was produced. The content ratio of the rod-shaped TiO ₂ particles 8 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

(Photoelectrochemical cell 10)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemical process were performed in the same manner as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 14 was used as the light scattering layer forming paste. Battery 10 was produced. The content of the rod-like TiO ₂ particles 9 contained in the light scattering layer of the semiconductor electrode was 30% by mass.

(Photoelectrochemical cell 11)
Similar to the photoelectrochemical cell 1 except that a semiconductor electrode (light-receiving surface area: 10 mm × 10 mm, layer thickness: 10 μm) made of only the semiconductor layer using only the paste 2 was manufactured in the manufacture of the semiconductor electrode. A photoelectrode and a comparative photoelectrochemical cell 1 were prepared according to the procedure.

(Electrochemical battery 12)
In the production of the semiconductor electrode, the photoelectrode and the comparative photoelectricity were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 7 was used as the light scattering layer forming paste. A chemical battery 2 was produced. The content ratio of the rod-shaped TiO ₂ particles 2 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

[Battery characteristics test]
A battery characteristic test was performed, and conversion efficiency η was measured for photoelectrochemical cells 1 to 10 and comparative photoelectrochemical cells 1 and 2. The battery characteristic test was performed by irradiating 1000 W / m 2 of pseudo sunlight from a xenon lamp that passed through an AM1.5 filter using a solar simulator (manufactured by WACOM, WXS-85H). Current-voltage characteristics were measured using an IV tester, and energy conversion efficiency (η /%) was determined. The results are shown in Table 7. The results are: conversion efficiency of 3.5% or more ◎, 2.5% or more of less than 3.5% ○, 2.0% or more of less than 2.5% △, 2.0% Less than were shown as x.

  As shown in Table 7, it was found that the dye of the present invention has high conversion efficiency.

(Example 7)
A slurry obtained by adding metal alkoxide to metal oxide fine particles was applied to a conductive substrate, and then UV ozone irradiation, UV irradiation or drying was performed to produce an electrode. Then, the photoelectrochemical cell was produced and the conversion efficiency was measured.

(Metal oxide fine particles)
Titanium oxide was used as the metal oxide fine particles. As the titanium oxide, P25 powder (trade name, manufactured by Degussa) having a mass ratio of 30% rutile type and 70% anatase type and an average particle size of 25 nm was used.

(Pretreatment of metal oxide fine particle powder)
The metal oxide fine particles were previously heat-treated to remove surface organic substances and moisture. In the case of titanium oxide fine particles, the fine particles were heated in an oven at 450 ° C. in the atmosphere for 30 minutes.

(Measurement of water content in metal oxide fine particles)
When the moisture content contained in titanium oxide and P25 powder (trade name, manufactured by Degussa) stored in an environment of temperature 26 ° C. and humidity 72% is reduced by thermogravimetry and heated to 300 ° C. The amount of moisture desorbed was determined by Karl Fischer titration.

  When the amount of water desorbed when titanium oxide, P25 powder (trade name, manufactured by Degussa) was heated at 300 ° C. was quantified by Karl Fischer titration, 0.253 mg of water was contained in 0.1033 g of titanium oxide fine powder. It was included. That is, since the titanium oxide fine powder contained about 2.5 wt% of water, the metal oxide fine particle powder was heat-treated in an oven at 450 ° C. for 30 minutes before mixing with the metal alkoxide, and stored in a desiccator after cooling. Used.

(Preparation of metal alkoxide paste)
The metal alkoxide that plays a role in bonding metal oxide fine particles includes titanium (IV) tetraisopropoxide (TTIP) as a titanium raw material, zirconium (IV) tetra n-propoxide as a zirconium raw material, and niobium as a niobium raw material. (V) Pentaethoxide (all manufactured by Aldrich) was used.

The molar concentration ratio between the metal oxide fine particles and the metal alkoxide is appropriately adjusted according to the metal oxide fine particle diameter so that the amorphous layer generated by hydrolysis of the metal alkoxide is not excessively thick and the particles can be sufficiently bonded to each other. did. All metal alkoxides were 0.1M ethanol solutions. When mixing titanium oxide fine particles and titanium (IV) tetraisopropoxide (TTIP), 3.55 g of 0.1M TTIP solution was mixed with 1 g of titanium oxide fine particles. At this time, the titanium oxide concentration in the obtained paste was about 22% by mass, and the viscosity was appropriate for coating. Moreover, the titanium oxide, TTIP, and ethanol at this time were 1: 0.127: 3.42 by mass ratio, and 1: 0.036: 5.92 by molar ratio.
Similarly, a mixed paste of titanium oxide fine particles and an alkoxide other than TTIP was prepared so that the fine particle concentration was 22% by mass. In the paste using zinc oxide and tin oxide fine particles, the content was 16% by mass. In the case of zinc oxide and tin oxide, the metal alkoxide solution was mixed at a ratio of 5.25 g to 1 g of the metal oxide fine particles.

The metal oxide fine particles and the metal alkoxide solution were stirred for 2 hours with a magnetic stirrer in a sealed container to obtain a uniform paste.
As a method for applying the paste to the conductive substrate, a doctor blade method, a screen printing method, a spray coating method, or the like can be used, and an appropriate paste viscosity is appropriately selected depending on the application method. Here, a method of applying simply with a glass rod (similar to the doctor blade method) was used. In this case, the concentration of the metal oxide fine particles giving an appropriate paste viscosity was approximately in the range of 5 to 30% by mass.

  In this embodiment, the layer thickness of the amorphous metal oxide produced by the decomposition of the metal alkoxide is in the range of about 0.1 to 0.6 nm. A range of about 0.05 to 1.3 nm was suitable for room temperature film formation by this method.

(Applying paste on conductive substrate and air-drying treatment)
Two adhesive tapes as spacers on a polyethylene terephthalate (PET) film substrate (20Ω / cm ² ) with tin-doped indium oxide (ITO) conductive film or a glass substrate (10Ω / cm ² ) with fluorine-doped tin oxide (FTO) conductive film The pastes were applied in parallel at regular intervals, and each paste prepared according to the above method was uniformly applied using a glass rod.

After applying the paste and before dye adsorption, a porous film was prepared by changing the conditions for the presence or absence of UV ozone treatment, UV irradiation treatment, or drying treatment.
(Drying process)
The film after application to the conductive substrate was air-dried at room temperature in the atmosphere for about 2 minutes. During this process, the metal alkoxide in the paste was hydrolyzed by moisture in the atmosphere, and amorphous titanium oxide, zirconium oxide, and niobium oxide were formed from Ti alkoxide, Zr alkoxide, and Nb alkoxide, respectively.
Since the produced amorphous metal oxide plays a role of adhering metal oxide fine particles and the film to the conductive substrate, a porous film excellent in mechanical strength and adhesion was obtained only by air drying.

(UV ozone treatment)
NL-UV253 UV ozone cleaner manufactured by Nippon Laser Electronics Co., Ltd. was used for UV ozone treatment. The UV light source was equipped with three 4.5 W mercury lamps having emission lines at 185 nm and 254 nm, and the sample was placed horizontally at a distance of about 6.5 cm from the light source. Ozone is generated by introducing an oxygen stream into the chamber. In this example, this UV ozone treatment was performed for 2 hours. Note that no decrease in the conductivity of the ITO film and the FTO film due to this UV ozone treatment was observed.

(UV treatment)
Similarly to the UV ozone treatment, the treatment was performed for 2 hours, except that the inside of the chamber was replaced with nitrogen. No decrease in the conductivity of the ITO film and FTO film due to the UV treatment was observed.

(Dye adsorption)
The combination dye of the present invention was used as a sensitizing dye, and an ethanol solution having a concentration shown in the table was prepared. In this example, the porous film produced by the above process was dried in an oven at 100 ° C. for 1 hour, then immersed in a sensitizing dye solution, and allowed to stand at room temperature for 50 minutes to adsorb the sensitizing dye on the titanium oxide surface. did. The sample after adsorption of the sensitizing dye was washed with ethanol and air-dried.

(Production of photoelectrochemical cell and evaluation of battery characteristics)
A photoelectrochemical cell was fabricated by using a conductive substrate on which a porous film after dye adsorption was formed as a photoelectrode, and an ITO / PET film or FTO / glass counter electrode in which platinum fine particles were modified by sputtering. The effective area of the photoelectrode was about 0.2 cm ² . As the electrolyte solution, 3-methoxypropionitrile containing 0.5 M LiI, 0.05 M I ₂ and 0.5 M t-butylpyridine was introduced into the gap between the two electrodes by capillary action.

The battery performance was evaluated by photocurrent action spectrum measurement under irradiation with a constant number of photons (1016 cm ⁻² ) and IV measurement under irradiation with AM1.5 simulated sunlight (100 mW / cm ² ). A CEP-2000 type spectral sensitivity measuring device manufactured by Spectrometer Co., Ltd. was used for these measurements.
The obtained output characteristic values are summarized in Table 8. The results are: conversion efficiency of 2.5% or more ◎, 2.0% or more and less than 2.5% ○, 1.5% or more and less than 2.0% △, 1.5% Less than were shown as x.

In Table 8, the columns of “UV ozone”, “UV”, and “dry” indicate the presence or absence of UV ozone treatment, UV irradiation treatment, and drying treatment after formation of the porous film and before sensitizing dye adsorption. The processed one is “◯”, and the unprocessed one is “×”.
The column _“ Pretreatment of TiO ₂ ” in Table 8 indicates the presence or absence of pretreatment of titanium oxide fine particles (heat treatment in an oven at 450 ° C. for 30 minutes). Samples 6, 14, and 22 represent samples using a paste having a high TTIP concentration (titanium oxide: TTIP molar ratio of 1: 0.356). The other samples (samples 1 to 5, 7 to 13, 23, 24) all use a paste of titanium oxide: TTIP = 1: 0.0356.

  From the results shown in Table 8, when the dye of the present invention is used, the photoelectricity is measured regardless of the presence or absence of UV ozone treatment, UV irradiation treatment, and drying treatment after the formation of the porous film and before adsorption of the sensitizing dye. It was found that the conversion efficiency of the chemical battery was high.

(Example 8)
Using acetonitrile as a solvent, an electrolyte solution was prepared in which lithium iodide 0.1 mol / l, iodine 0.05 mol / l, and dimethylpropylimidazolium iodide 0.62 mol / l were dissolved. No. shown below. 1-No. 8 benzimidazole compounds were separately added and dissolved to a concentration of 0.5 mol / l.

A conductive film was formed on a glass substrate by sputtering tin oxide doped with fluorine as a transparent conductive film. Dispersion liquid containing anatase-type titanium oxide particles on this conductive film (
Mixing 32g of anatase-type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) in 100ml of a mixed solvent consisting of water and acetonitrile in a volume ratio of 4: 1, using a mixing conditioner with both rotation and revolution. A semiconductor fine particle dispersion obtained by uniformly dispersing and mixing was applied, and then sintered at 500 ° C. to form a photosensitive layer having a thickness of 15 μm. In this photosensitive layer, no. 1-No. 8 benzimidazole compound electrolyte was added dropwise.
A frame type spacer (thickness: 25 μm) made of a polyethylene film was placed thereon, and this was covered with a platinum counter electrode to produce a photoelectric conversion element.
The obtained photoelectric conversion element was irradiated with light having an intensity of 100 mW / cm ^{2 using} a Xe lamp as a light source. Table 9 shows the obtained open circuit voltage and photoelectric conversion efficiency. The open circuit voltage is 6.3V or more, ◎, 6.0V or more and less than 6.3V is indicated as ◯, 5.7V or more and less than 6.0V is indicated as △, and less than 5.7V is indicated as ×. . The conversion efficiency is ◎ for those with 3.5% or more, ◯ for 2.5% or more and less than 3.5%, △ for 2.0% or more and less than 2.5%, and less than 2.0%. Things were displayed as x.
Table 9 also shows the results of photoelectric conversion elements using an electrolytic solution to which no benzimidazole compound was added.

  From the results in Table 9, it can be seen that the dye of the present invention has high conversion efficiency.

Example 9
(Photoelectrochemical cell 1)
According to the following procedure, a photoelectrode having the same configuration as the photoelectrode 10 shown in FIG. 1 described in JP-A No. 2004-152613 (however, the semiconductor electrode 2 has a two-layer structure) is manufactured. A photoelectrochemical cell having the same configuration as the dye-sensitized solar cell 20 shown in FIG. 1 described in JP-A-2004-152613 except that a photoelectrode is used (the area of the light receiving surface F2 of the semiconductor electrode 2 is 1 cm ² ). Was made. For each layer of the semiconductor electrode 2 having a two-layer structure, the layer disposed on the side close to the transparent electrode 1 is referred to as “first layer”, and the layer disposed on the side close to the porous body layer PS is referred to as “second layer”. It is called “layer”.

  First, P25 powder having an average particle diameter of 25 nm (trade name, manufactured by Degussa), titanium oxide particles having a different particle diameter, and P200 powder (average particle diameter: 200 nm, product name, manufactured by Degussa) were used. And P200 are 15% by mass, and the mass ratio of P25 and P200 is P25: P200 = 30: 70, so that acetylacetone, ion-exchanged water, surfactant (manufactured by Tokyo Chemical Industry Co., Ltd.) , Trade name: “Triton-X”) and kneaded to prepare a slurry for forming a second layer (hereinafter referred to as “slurry 1”).

  Next, a slurry for forming a first layer (P1 content; 15 mass%; hereinafter, “slurry 2” is prepared by the same preparation procedure as that of the slurry 1 except that only P25 is used without using P200. Was prepared).

On the other hand, a transparent electrode (thickness: 1.1 mm) in which a fluorine-doped SnO ₂ conductive film (film thickness: 700 nm) was formed on a glass substrate (transparent conductive glass) was prepared. Then, the SnO ₂ conductive film, the slurry 2 described above was coated with Bakoda, then dried. Then, it baked for 30 minutes at 450 degreeC in air | atmosphere. In this way, the first layer of the semiconductor electrode 2 was formed on the transparent electrode.

Furthermore, the second layer was formed on the first layer by repeating the same application and firing as described above using the slurry 1. In this way, the semiconductor electrode 2 (light-receiving surface area; 1.0 cm ² , the total thickness of the first layer and the second layer: 10 μm (the thickness of the first layer: 3 μm, the first layer) on the SnO ₂ conductive film No. 2 layer thickness: 7 μm)), and a photoelectrode 10 containing no sensitizing dye was prepared.

  Next, as a sensitizing dye, an ethanol solution of the dye of the combination of the present invention (the concentration of the sensitizing dye is described in the table) was prepared. The photoelectrode 10 was immersed in this solution and allowed to stand for 20 hours under a temperature condition of 80 ° C. to adsorb the sensitizing dye. Thereafter, in order to improve the open circuit voltage Voc, the semiconductor electrode after dye adsorption was immersed in an acetonitrile solution of 4-tert-butylpyridine for 15 minutes, and then dried in a nitrogen stream kept at 25 ° C., and the photoelectrode 10 Was completed.

  Next, a counter electrode CE having the same shape and size as the above photoelectrode was produced. First, an isopropanol solution of chloroplatinic acid hexahydrate was dropped on a transparent conductive glass, dried in air, and then baked at 450 ° C. for 30 minutes to obtain a platinum sintered counter electrode CE. The counter electrode CE was previously provided with a hole for injection of the electrolyte E (diameter 1 mm).

  Next, zinc iodide, 1,2-dimethyl-3-propylimidazolium iodide, iodine, and 4-tert-butylpyridine are dissolved in methoxyacetonitrile as a solvent to form a liquid electrolyte (iodide). Zinc concentration: 10 mmol / L, dimethylpropylimidazolium iodide concentration: 0.6 mol / L, iodine concentration: 0.05 mol / L, 4-tert-butylpyridine concentration: 1 mol / L).

  Next, a spacer S (trade name: “HIMILAN”, ethylene / methacrylic acid random copolymer ionomer film) manufactured by Mitsui Dupont Polychemical Co., Ltd. having a shape matched to the size of the semiconductor electrode was prepared. As shown in FIG. 1 described in 15613, the photoelectrode and the counter electrode were opposed to each other through a spacer, and each was bonded by thermal welding to obtain a battery casing (no electrolyte filled).

  Next, after injecting the liquid electrolyte into the housing from the hole of the counter electrode, the hole is closed with a member made of the same material as the spacer, and this member is thermally welded to the hole of the counter electrode to seal the hole. 1 was completed.

(Photoelectrochemical cell 2)
The photoelectrochemical cell 2 was produced in the same procedure and conditions as the photoelectrochemical cell 1 except that the concentration of zinc iodide in the liquid electrolyte was 50 mmol / L.

(Photoelectrochemical cell 3)
The photoelectrochemical cell is the same as the photoelectrochemical cell 1 except that lithium iodide is added instead of zinc iodide in the liquid electrolyte and the concentration of lithium iodide in the liquid electrolyte is 20 mmol / L. 3 was produced.

(Photoelectrochemical cell 4)
Photoelectrochemical cell in the same procedure and conditions as in photoelectrochemical cell 1 except that lithium iodide is added instead of zinc iodide in the liquid electrolyte and the concentration of lithium iodide in the liquid electrolyte is 100 mmol / L. 4 was produced.

(Battery characteristics evaluation test)
The photoelectric conversion efficiency (η (%)) was measured for the photoelectrochemical cells 1 to 4 by the following procedure.

The battery characteristic evaluation test uses a solar simulator (trade name; “WXS-85-H type”, manufactured by Wacom), and the irradiation conditions of pseudo-sunlight from a xenon lamp light source through an AM filter (AM1.5), The measurement was performed under measurement conditions of 100 mW / cm ² (so-called “1Sun” irradiation conditions).

  About each photoelectrochemical cell, the current-voltage characteristic was measured at room temperature using the IV tester, and photoelectric conversion efficiency (eta) [%] was calculated | required from these. The obtained results are shown as “fresh” in Table 10 (1 Sun irradiation conditions). In addition, the photoelectric conversion efficiency η [%] of the dye-sensitized solar cells 1 and 2 and the comparative dye-sensitized solar cells 1 and 2 is 300 hours at 60 ° C. and 1 Sun irradiation under an operating condition of 10Ω load. The results of the durability evaluation test examined after the lapse of time are also shown in Tables 10-1 and 10-2. The conversion efficiency of Fresh is ◎ for those with 3.5% or more, ○ for those with 2.5% to less than 3.5%, △, 2.0% for those with 2.0% or more but less than 2.5% Less than were shown as x.

  As is clear from the results shown in Tables 10-1 and 10-2, it was found that the dye of the present invention was excellent even when zinc iodide was added to the electrolyte.

(Example 10)
1. Preparation of Titanium Dioxide Dispersion 15 g of titanium dioxide fine particles (Nippon Aerosil Co., Ltd., Degussa P-25), water 45 g, dispersant (Aldrich, Triron X −100) 1 g and 30 g of zirconia beads having a diameter of 0.5 mm (manufactured by Nikkato Co., Ltd.) were added, and dispersion treatment was performed at 1500 rpm for 2 hours using a sand grinder mill (manufactured by Imex). Zirconia beads were filtered off from the resulting dispersion. The average particle diameter of the titanium dioxide fine particles in the obtained dispersion was 2.5 μm. The particle size was measured with a master sizer manufactured by MALVERN.

2. Preparation of Titanium Oxide Fine Particle Layer (Electrode A) Adsorbed with Dye 20 mm × 20 mm conductive glass plate coated with fluorine doped tin oxide (Asahi Glass Co., Ltd., TCO glass-U, surface resistance: about 30Ω / m ² ) was prepared, and an adhesive tape for spacers was applied to both ends (a portion having a width of 3 mm from the end) on the conductive layer side, and then the dispersion was applied onto the conductive layer using a glass rod. After application of the dispersion, the adhesive tape was peeled off and air-dried at room temperature for 1 day. Next, this semiconductor-coated glass plate was placed in an electric furnace (muffle furnace FP-32 type manufactured by Yamato Scientific Co., Ltd.) and baked at 450 ° C. for 30 minutes. After the semiconductor-coated glass plate was taken out and cooled, it was immersed in an ethanol solution of dyes having combinations shown in Table 10 for 3 hours. The semiconductor-coated glass plate on which the dye was adsorbed was immersed in 4-tert-butylpyridine for 15 minutes, washed with ethanol, and air dried. The thickness of the dye-sensitized titanium oxide fine particle layer thus obtained was 10 μm, and the coating amount of the titanium oxide fine particles was 20 g / m ² . Moreover, the adsorption amount of the pigment | dye was in the range of 0.1-10 mmol / m < ² > according to the kind.

3. Production of Photoelectrochemical Battery As a solvent, a mixture of acetonitrile and 3-methyl-2-oxazolidinone in a volume ratio of 90/10 was used. To this solvent, iodine and 1-methyl-3-hexylimidazolium iodine salt were added as an electrolyte salt to prepare a solution containing 0.5 mol / L electrolyte salt and 0.05 mol / L iodine. To this solution, 10 parts by mass of nitrogen-containing polymer compound (XA) was added to 100 parts by mass of (solvent + nitrogen-containing polymer compound + salt). Furthermore, 0.1 mol of an electrophile (XB) for reactive nitrogen atoms of the nitrogen-containing polymer compound was mixed to obtain a uniform reaction solution.

On the other hand, on the dye-sensitized titanium oxide fine particle layer formed on the conductive glass plate, the platinum thin film side of the counter electrode made of a glass plate on which platinum is vapor-deposited through a spacer is placed. A glass plate was fixed. The open end of the obtained assembly was immersed in the electrolyte solution, and the reaction solution was infiltrated into the dye-sensitized titanium oxide fine particle layer by capillary action.
Subsequently, it heated at 80 degreeC for 30 minutes, and the crosslinking reaction was performed. In this way, as shown in FIG. 2 of JP 2000-323190 A, the dye-sensitized titanium oxide fine particle layer 20, the electrolyte layer 30, the platinum thin film 42, and the glass are formed on the conductive layer 12 of the conductive glass plate 10. The photoelectrochemical cell 1-1 (sample No. 1) of the present invention in which the counter electrode 40 composed of the plate 41 was sequentially laminated was obtained.
Further, by repeating the above steps except that the combination of the composition of the dye and the electrolyte composition is changed as shown in Table 11, photoelectrochemical cells 1-2, 1- having different photosensitive layers 20 and / or charge transfer layers 30 are obtained. 3 was obtained.

4). Production of photoelectrochemical cells A and B (1) Photoelectrochemical cell A
An electrode A (20 mm × 20 mm) composed of a titanium oxide fine particle layer dye-sensitized with the dye of the present invention as described above was superimposed on a platinum-deposited glass plate of the same size via a spacer. Next, an electrolyte solution (iodine 0.05 mol / L using a mixture of acetonitrile and 3-methyl-2-oxazolidinone in a volume ratio of 90/10 as a solvent using a capillary phenomenon in the gap between both glass plates, lithium iodide 0 .5 mol / L solution) was infiltrated to produce photoelectrochemical cell A-1. Photoelectrochemical cells A-2 and A-3 were obtained by repeating the above steps except that the dye was changed as shown in Table 11.

(2) Photoelectrochemical cell B (electrolyte described in JP-A-9-27352)
The electrolytic solution was applied and impregnated on the electrode A (20 mm × 20 mm) composed of the titanium oxide fine particle layer dye-sensitized with the dye of the present invention as described above. The electrolyte was 1 g of hexaethylene glycol methacrylate (manufactured by Nippon Oil & Fats Chemical Co., Ltd., Bremer PE-350), 1 g of ethylene glycol, and 2-hydroxy-2-methyl-1-phenyl-propane as a polymerization initiator. It was obtained by dissolving 500 mg of lithium iodide in a mixed solution containing 20 mg of -1-one (manufactured by Ciba Geigy Japan, Darocur 1173) and vacuum degassing for 10 minutes. Next, the porous titanium oxide layer impregnated with the mixed solution is placed under a reduced pressure to remove bubbles in the porous titanium oxide layer, promote penetration of the monomer, and then polymerize by irradiation with ultraviolet light. A uniform gel of the compound was filled into the fine pores of the porous titanium oxide layer. The product thus obtained was exposed to an iodine atmosphere for 30 minutes to diffuse iodine in the polymer compound, and then a platinum-deposited glass plate was overlaid to obtain a photoelectrochemical cell B-1. Photoelectrochemical cells B-2 and B-3 were obtained by repeating the above steps except that the dye was changed as shown in Table 11.

5. Measurement of photoelectric conversion efficiency Simulated sun which does not contain ultraviolet rays by passing light of 500W xenon lamp (made by USHIO INC.) Through AM1.5 filter (made by Oriel) and sharp cut filter (Kenko L-42) It was light. The light intensity was 89 mW / cm ² .

  Alligator clips were connected to the conductive glass plate 10 and the platinum-deposited glass plate 40 of the above-described photoelectrochemical cell, and each alligator clip was connected to a current-voltage measuring device (Keutley SMU238 type). This was irradiated with simulated sunlight from the conductive glass plate 10 side, and the generated electricity was measured with a current-voltage measuring device. Table 11 summarizes the initial value (fresh) of the conversion efficiency (η) of the photoelectrochemical cell thus determined and the rate of decrease in conversion efficiency during 300 hours of continuous irradiation. The conversion efficiency of Fresh is ◎ for those with 3.5% or more, ○ for those with 2.5% to less than 3.5%, △, 2.0% for those with 2.0% or more but less than 2.5% Less than were shown as x.

(Remarks)
(1) Symbols of pigments are as described in the text.
(2) Nitrogen-containing polymer 1-1 represents the following compound.

(3) Electrolyte salt MHIm: 1-methyl-3-hexylimidazolium iodine salt MBIm: 1-butyl-3-methylimidazolium iodine salt (4) Solvent AN: acetonitrile.
PC: Propylene carbonate.
NMO: 3-methyl-2-oxazolidinone.
(5) Electrophile

  As is clear from the results shown in Table 11, it was found that the dye of the present invention was excellent in conversion efficiency and durability in this case as well.

(Example 11)
A porous layer of TiO ₂ was applied onto FTO glass by screen printing using a suspension prepared by a sol-gel method, and fired at 450 ° C. To this, combination dyes α-4 (0.15 × 10 ⁻⁴ mol / L) and Ru-6 (2 × 10 ⁻⁴ mol / L) of the present invention, and 10 of sensitizing dyes S-1 and S-2 ^The pigment | dye was made to adsorb | suck by being immersed in ^-4 mol / L ethanol solution.
100 mg of 2,2 ', 7,7'-tetrakis (diphenylamino) -9,9'-spirobifluorene was dissolved in 5 ml of chloroform. The solution was soaked into the pores of the layer by lightly applying the solution to the dye surface. A drop of the solution was then placed directly on the surface and dried at room temperature. The coated support is then attached to a deposition apparatus and further 100 nm thick 2,2 ', 7,7'-tetrakis (diphenylamino) -9,9'-spirobi by thermal deposition under vacuum of about 10-5 mbar. A layer of fluorene was applied. Furthermore, a gold layer having a thickness of 200 nm was coated on the coated support as a counter electrode in a vapor deposition apparatus.
The sample thus prepared was attached to an optical device including a high-pressure lamp, an optical filter, a lens and a mounting. The intensity could be changed by using a filter and moving the lens. The gold layer and the SnO ₂ layer were contacted and attached to the device shown in the current measuring device while the sample was irradiated. For the measurement, light having a wavelength of less than 430 nm was blocked using an appropriate optical filter. Furthermore, the apparatus was adjusted so that the intensity of the radiation substantially coincided with about 1000 W / m2.
Contacts were made on the gold layer and the SnO ₂ layer, and both contacts were connected to a potentiostat while the sample was irradiated. The sample using the sensitizing dyes S-1 and S-2 without applying an external voltage produced a current of about 90 nA, whereas the sample using the combination dyes α-4 and Ru-6 of the present invention had a current of about 190 nA. Produced an electric current. In both samples, the current disappeared if not irradiated.

(Example 12)
Also in the tandem cell prepared in the same manner as in Example 1 of JP-A-2000-90989, the combination dyes A-4 and Ru-6 of the present invention have higher conversion efficiency than the comparison dye combinations S-1 and S-2. Was confirmed.

(Example 14)
Titanium oxide suspension was prepared by dispersing 4.0 g of commercially available titanium oxide particles (manufactured by Teika Co., Ltd., average particle size 20 nm) and 20 ml of diethylene glycol monomethyl ether for 6 hours with a paint shaker using hard glass beads. . Next, this titanium oxide suspension was applied to a glass plate (electrode layer) to which a tin oxide conductive layer had been previously attached using a doctor blade, pre-dried at 100 ° C. for 30 minutes, and then heated to 500 ° C. in an electric furnace. Was baked for 40 minutes to form a titanium oxide film (semiconductor material) on the glass plate. Separately, the sensitizing dye and the comparative dye of the combination of the present invention were dissolved in ethanol to obtain a photosensitizing dye solution.

  The concentration of this photosensitizing dye solution was as described in the table. Next, the glass plate on which the film-like titanium oxide is formed is placed in this solution, dye adsorption is performed at 60 ° C. for 60 minutes, and drying is performed. A photoelectric conversion layer made of a dye-sensitive dye was formed (Sample A). On the photoelectric conversion layer of Sample A, a toluene solution (1%) of polyvinylcarbazole (weight average molecular weight 3,000) as a hole transport material was applied and dried under reduced pressure to form a hole transport layer (Sample B). ). 1.95 g of ethylcarbazole as an intermolecular charge transfer complex and 2.03 g of 5-nitronaphthoquinone were dissolved in 100 ml acetone, and the obtained solution was repeatedly applied on the hole transport layer of Sample B to form a conductive layer. . Next, a gold electrode (counter electrode) was deposited on the conductive layer to obtain a photoelectric conversion element (Sample C). The obtained photoelectric conversion element (sample C) was irradiated with light having an intensity of 100 W / m 2 with a solar simulator. The results are shown in Table 12. Conversion efficiency is 1.5% or more for ◎, 1.0% or more and less than 1.5% for ○, 0.5% or more and less than 1.0% for Δ, and less than 0.5%. Things were displayed as x.

It can be seen that the dye of the present invention is excellent in photoelectric conversion efficiency and is effective even in this system.
(Example 16)
An example of producing a dye-sensitized solar cell using a polymer electrolyte will be described.

  The coating liquid for producing the titanium oxide film was 4.0 g of commercially available titanium oxide particles (trade name AMT-600, anatase type crystal, average particle size 30 nm, specific surface area 50 m 2 / g, manufactured by Teika Co., Ltd.) and diethylene glycol monomethyl ether. 20 ml was dispersed with a glass shaker for 7 hours with a paint shaker to prepare a titanium oxide suspension. Using a doctor blade, this titanium oxide suspension is formed on a glass substrate 1 having a film thickness of about 11 μm and an area of about 10 mm × 10 mm and SnO 2 as a transparent conductive film. And preliminarily dried at 100 ° C. for 30 minutes and then baked under oxygen at 460 ° C. for 40 minutes. As a result, a titanium oxide film A having a thickness of about 8 μm was produced.

Next, the combination dye of the present invention and the comparative dyes S-1 and S-2 were dissolved at the concentrations shown in the table to prepare an adsorption dye solution. The dye solution for adsorption was adsorbed by putting the transparent substrate provided with the titanium oxide film and the transparent conductive film obtained above into a container and allowing it to penetrate for about 4 hours. Thereafter, it was washed several times with absolute ethanol and dried at about 60 ° C. for about 20 minutes.
Next, among the monomer units represented by the general formula (105), a monomer composed of R as a methyl group, A as eight polyethylene oxide groups and two polypropylene oxide groups, and a butanetetrayl group as a central core Units were used.

（式中、Ｒは水素原子またはメチル基であり、Ａはエステル基と炭素原子で結合している残基であり、ｎは２〜４である。）
このモノマー単位をプロピレンカーボネート（以下、ＰＣと記載する）に２０ｗｔ％の濃度で溶解させ、また、熱重合開始剤としてアゾビスイソブチロニトリル（ＡＩＢＮ）をモノマー単位に対して１ｗｔ％の濃度で溶解させモノマー溶液を作製する。このモノマー溶液を上述の酸化チタン膜に含浸させる手順について以下に示す。真空容器内にビーカー等の容器を設置し、その中に透明導電膜を具備した透明基板上の酸化チタン膜Ａを入れ、ロータリーポンプで約１０分間真空引きする。真空容器内を真空状態に保ちながらモノマー溶液をビーカー内に注入し、約１５分間含浸させ酸化チタン中にモノマー溶液を十分に染み込ます。ポリエチレン製セパレーター、ＰＥＴフィルムと押さえ板を設置し冶具にて固定する。その後、約８５℃で３０分間加熱することにより、熱重合させ高分子化合物を作製する。

(In the formula, R is a hydrogen atom or a methyl group, A is a residue bonded to an ester group with a carbon atom, and n is 2 to 4.)
This monomer unit is dissolved in propylene carbonate (hereinafter referred to as PC) at a concentration of 20 wt%, and azobisisobutyronitrile (AIBN) is used as a thermal polymerization initiator at a concentration of 1 wt% with respect to the monomer unit. Dissolve to make a monomer solution. The procedure for impregnating the above-described titanium oxide film with the monomer solution is described below. A container such as a beaker is placed in the vacuum container, and the titanium oxide film A on the transparent substrate provided with the transparent conductive film is placed therein, and is evacuated by a rotary pump for about 10 minutes. Pour the monomer solution into the beaker while keeping the vacuum container in a vacuum state, impregnate it for about 15 minutes, and fully soak the monomer solution in titanium oxide. A polyethylene separator, a PET film and a pressing plate are installed and fixed with a jig. Then, it heat-polymerizes by heating at about 85 degreeC for 30 minutes, and produces a high molecular compound.

Next, a redox electrolyte solution to be impregnated into the polymer compound is prepared. The redox electrolyte was prepared by dissolving 0.5 mol / liter of lithium iodide and 0.05 mol / liter of iodine using PC as a solvent. The polymer compound prepared on the above-described titanium oxide film A was immersed in this solution for about 2 hours, so that the polymer compound was impregnated with the redox electrolyte solution to prepare a polymer electrolyte.

Then, the electroconductive board | substrate which comprised the platinum film | membrane was installed, the periphery was sealed with the epoxy-type sealing agent, and the element A was created.
Further, after the dye adsorption of the titanium oxide film A, the oxidation was performed by dissolving lithium iodide at a concentration of 0.5 mol / liter and iodine at a concentration of 0.05 mol / liter using PC as a solvent without performing monomer treatment. The reduced electrolyte was injected as it was between the counter electrode and sealed to prepare an element B. Using the elements A and B, light having an intensity of 1000 W / m 2 was irradiated with a solar simulator. The results are shown in Table 13. The conversion efficiency is ◎ for those with 3.5% or more, ◯ for 2.5% or more and less than 3.5%, △ for 2.0% or more and less than 2.5%, and less than 2.0%. Things were displayed as x.

  It can be seen that the dye of the present invention is excellent in photoelectric conversion efficiency and is effective even in this system.

(Example 17)
1. Preparation of Titanium Dioxide Dispersion 15 g of titanium dioxide fine particles (Nippon Aerosil Co., Ltd., Degussa P-25), water 45 g, dispersant (Aldrich, Triron X −100) 1 g and 30 g of zirconia beads having a diameter of 0.5 mm (manufactured by Nikkato Co., Ltd.) were added, and dispersion treatment was performed at 1500 rpm for 2 hours using a sand grinder mill (manufactured by Imex). Zirconia beads were filtered off from the resulting dispersion. The average particle diameter of the titanium dioxide fine particles in the obtained dispersion was 2.5 μm. The particle size was measured with a master sizer (trade name) manufactured by MALVERN.

2. Preparation of Titanium Oxide Fine Particle Layer (Electrode A) Adsorbed with Dye 20 mm × 20 mm conductive glass plate coated with fluorine doped tin oxide (Asahi Glass Co., Ltd., TCO glass-U, surface resistance: about 30Ω / m ² ) was prepared, and an adhesive tape for spacers was applied to both ends (a portion having a width of 3 mm from the end) on the conductive layer side, and then the dispersion was applied onto the conductive layer using a glass rod. After application of the dispersion, the adhesive tape was peeled off and air-dried at room temperature for 1 day. Next, this semiconductor-coated glass plate was placed in an electric furnace (muffle furnace FP-32 type manufactured by Yamato Scientific Co., Ltd.) and baked at 450 ° C. for 30 minutes. The semiconductor-coated glass plate was taken out and cooled, and then immersed in an ethanol solution having the dyes and concentrations shown in Table 14 for 3 hours. The semiconductor-coated glass plate on which the dye was adsorbed was immersed in 4-tert-butylpyridine for 15 minutes, then washed with ethanol and naturally dried to obtain a titanium oxide fine particle layer (electrode A) on which the dye was adsorbed. The thickness of the dye-sensitized titanium oxide fine particle layer of the electrode A was 10 μm, and the coating amount of the titanium oxide fine particles was 20 g / m ² . Moreover, the adsorption amount of the pigment | dye was in the range of 0.1-10 mmol / m < ² > according to the kind.

3. Production of Dye-Sensitized Solar Cell Dye-sensitized electrode A (20 mm × 20 mm) produced as described above was superimposed on platinum-deposited glass having the same size. Next, the electrolyte composition was impregnated into the gap between the two glasses using a capillary phenomenon, and the electrolyte was introduced into the titanium oxide electrode. Thus, as shown in FIG. 1, a conductive support 1 made of conductive glass (a conductive layer formed on a glass transparent substrate), a photoreceptor 2, a charge transfer body 3, and a counter electrode made of platinum. 4 and a glass transparent substrate (not shown) are laminated in order, ^{and a glass sphere having a diameter of 25 μm is almost formed in a resin composition comprising Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), a curing agent and a plastic paste.} A dye-sensitized solar cell sealed with ^{a uniformly dispersed sealant} was produced. However, if the electrolyte composition has a high viscosity and it is difficult to impregnate the electrolyte composition using capillary action, the electrolyte composition is heated to 50 ° C. and applied to the titanium oxide electrode. After the electrode was placed under reduced pressure and the electrolyte composition sufficiently penetrated and the air in the electrode escaped, platinum-deposited glass (counter electrode) was overlaid to produce a dye-sensitized solar cell.

  The above steps were performed by changing the dye, and dye-sensitized solar cells of sample numbers 1 to 10 were produced. As the electrolyte composition used for each dye-sensitized solar cell, a composition containing 98% by mass of the following heterocyclic quaternary salt compound and 2% by mass of iodine was used.

4). Measurement of photoelectric conversion efficiency Simulated sunlight that does not contain ultraviolet rays by passing light from a 500 W xenon lamp (manufactured by USHIO ELECTRIC CO., LTD.) Through an AM1.5 filter (manufactured by Oriel) and a sharp cut filter (Kenko L-37) Was generated. The intensity of this light was 70 mW / cm ² . This simulated sunlight was irradiated to a dye-sensitized solar cell at 50 ° C., and the generated electricity was measured with a current-voltage measuring device (Keutley SMU238 type). Moreover, the reduction rate of the conversion efficiency after 1000-hour dark storage at 85 degreeC and the reduction rate of the conversion efficiency after 500-hour continuous light irradiation were also measured. These results are shown in Table 14.

  From the results in Table 14, it can be seen that the dye of the present invention is excellent in photoelectric conversion efficiency and excellent in durability.

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Photoconductor layer 21 Dye 22 Semiconductor fine particle 3 Charge transfer body layer 4 Counter electrode 5 Photosensitive electrode 6 Circuit 10 Photoelectric conversion element 100 Photoelectrochemical cell

Claims (13)

A photoelectric conversion element comprising a photosensitive layer having a composite sensitizing dye combining two or more dyes and semiconductor fine particles, wherein the composite sensitizing dye has a structure represented by the following general formula (1): The photoelectric conversion element characterized by using the pigment | dye which has and the pigment | dye which has a structure represented by following General formula (2).

[In General Formula (1), A1 represents a 5- to 7-membered nitrogen-containing heterocyclic ring. L ¹¹ represents an electron-transporting linking group containing at least one heterocyclic ring selected from a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, and a heterocyclic ring condensed with these. R ¹¹ and R ¹³ each represent at least one substituent selected from a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. R ¹² represents a hydrogen atom or a substituent. B1 represents a methylene group substituted by a heterocyclic acidic nucleus or an electron withdrawing group. However, B1 has at least one acidic group. n11 represents an integer of 1 to 12. ]
M (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI General formula (2)
[Wherein M represents a metal atom. LL ¹ represents a bidentate or tridentate ligand represented by the following general formula (3).

(In the formula, R ²¹ and R ²² each independently represent a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group, or a phosphonyl group. R ²³ and R ²⁴ each independently represent a substituent. R ²⁵ and R ²⁶ each independently represents an alkyl group, an aryl group and / or a heterocyclic group, L ²¹ and L ²² each independently represent a conjugated chain consisting of an ethenylene group and / or an ethynylene group, a ²¹ and a ²² each independently represent an integer of 0 to 3, a21 is often ^{R 21} when two or more be the same or different, a22 is 2 or more when ^{R 22} each may .b21 and b22 to be the same or different independently represent an integer of 0 to 3, with one another may be the R ²³ when b21 is 2 or more the same or different from each other , May form a ring, and b22 is 2 or more when R ²⁴ when b22 .B21 and may be linked to each other to form a ring may be the same or different are both 1 or more R ²³ R ²⁴ may be linked to form a ring. N21 and n22 each independently represents an integer of 0 to 5. n23 represents 0 or 1.)
LL ² represents a bidentate or tridentate ligand which may have a substituent represented by the following general formula (4).

(However, Za, Zb, and Zc each independently represent a nonmetallic atom group that can form a 5- or 6-membered ring, and c represents 0 or 1.)
X is an acyloxy group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate group, a dithiocarbonate group, a trithiocarbonate group, an acyl group, a thiocyanate group, A monodentate or bidentate ligand coordinated by a group selected from the group consisting of an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a halogen atom Represents a monodentate or bidentate ligand consisting of carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide or thiourea. Xs may be linked together.
m1 represents an integer of 1 to 3, and when m1 is 2 or more, LL ¹ may be the same or different.
m2 represents an integer of 0 to 2, and when m2 is 2, LL2 may be the same or different.
m3 represents an integer of 0 to 3, and when m3 is 2, X may be the same or different.
CI represents a counter ion when a counter ion is required to neutralize the charge.
However, the dye represented by the general formula (2) has at least one acidic adsorption group. ]   In the said General formula (2), M is Ru, The photoelectric conversion element of Claim 1 characterized by the above-mentioned. 3. The photoelectric conversion element according to claim 1, wherein the dye having the structure represented by the general formula (1) is represented by the following general formula (5) or the general formula (6).

[In General Formula (5) and General Formula (6), L ¹¹ , R ¹¹ , R ¹² , B 1, and n ^{11 have} the same meaning as in General Formula (1). R ^{13 to} R ¹⁷ represent at least one substituent selected from a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. ] The pigment | dye which has a structure represented by the said General formula (1) is represented by following General formula (7), The photoelectric conversion element of any one of Claims 1-3 characterized by the above-mentioned.

[In General Formula (7), R ^{11 to} R ¹³ , A 1, B 1, and n ¹¹ have the same meaning as in General Formula (1). R ¹¹ in the general formula (7) may be the same or different. X is selected from S, O, NH, and Se. When n11 is 2 or more, X may be the same or different. ] Said B1 is represented by the following general formula (8) or (9), The photoelectric conversion element of any one of Claims 1-4 characterized by the above-mentioned.

[In General Formula (8), R ¹¹⁰ and R ¹⁹ are each independently an aliphatic group, an aromatic group, or a heterocyclic group, and may have an acidic group as at least one functional group. p shows the integer of 0-3. The carbon-carbon double bond in the general formula (8) may be either E type or Z type. R ¹⁸ in general formula (8) represents a sulfur atom or general formula (10), and the carbon-carbon double bond in general formula (10) may be either E-type or Z-type.
R ¹¹¹ and R ¹¹² in the general formula (9) each independently represent a cyano group or an acidic group, and may be the same or different from each other. The carbon-carbon double bond in general formula (9) may be either E-type or Z-type.
R ¹¹³ and R ¹¹⁴ in the general formula (10) each independently represent a cyano group or an acidic group, and may be the same as or different from each other. The carbon-carbon double bond in the general formula (10) may be any of E type and Z type. ] Said B1 is represented by following General formula (11), The photoelectric conversion element of any one of Claims 1-5 characterized by the above-mentioned.

[In General Formula (11), R ¹⁹ is an aliphatic group, an aromatic group, or a heterocyclic group (may have an acidic group). ] Said B1 is represented by following General formula (12), The photoelectric conversion element of any one of Claims 1-7 characterized by the above-mentioned.

[In General Formula (12), R ¹¹⁰ represents an aliphatic group, an aromatic group, or a heterocyclic group, and may have an acidic group. ] Said B1 is following General formula (13), The pigment | dye of any one of Claims 1-7 characterized by the above-mentioned.

  The photoelectric conversion element according to claim 1, wherein the semiconductor fine particles are titanium oxide fine particles.   10. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion element has a structure in which the photosensitive layer, the charge transfer body, and the counter electrode are stacked in this order on a conductive support.   The photoelectric conversion element according to claim 1, wherein the composite sensitizing dye is adsorbed on the semiconductor fine particles.   A photoelectrochemical cell comprising the photoelectric conversion device according to claim 1. For a photoelectric conversion element characterized by containing and dissolving both a dye having a structure represented by the following general formula (1) and a dye having a structure represented by the following general formula (2) in an organic solvent Dye composition.

[In General Formula (1), A1 represents a 5- to 7-membered nitrogen-containing heterocyclic ring. L ¹¹ represents an electron-transporting linking group containing at least one heterocyclic ring selected from a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, and a heterocyclic ring condensed with these. R ¹¹ and R ¹³ each represent at least one substituent selected from a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group. R ¹² represents a hydrogen atom or a substituent. B1 represents a methylene group substituted by a heterocyclic acidic nucleus or an electron withdrawing group. However, B1 has at least one acidic group. n11 represents an integer of 1 to 12. ]
M (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI General formula (2)
[Wherein M represents a metal atom. LL ¹ represents a bidentate or tridentate ligand represented by the following general formula (3).

(In the formula, R ²¹ and R ²² each independently represent a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group, or a phosphonyl group. R ²³ and R ²⁴ each independently represent a substituent. R ²⁵ and R ²⁶ each independently represents an alkyl group, an aryl group and / or a heterocyclic group, L ²¹ and L ²² each independently represent a conjugated chain consisting of an ethenylene group and / or an ethynylene group, a ²¹ and a ²² each independently represent an integer of 0 to 3, a21 is often ^{R 21} when two or more be the same or different, a22 is 2 or more when ^{R 22} each may .b21 and b22 to be the same or different independently represent an integer of 0 to 3, with one another may be the R ²³ when b21 is 2 or more the same or different from each other , May form a ring, and b22 is 2 or more when R ²⁴ when b22 .B21 and may be linked to each other to form a ring may be the same or different are both 1 or more R ²³ R ²⁴ may be linked to form a ring. N21 and n22 each independently represents an integer of 0 to 5. n23 represents 0 or 1.)
LL ² represents a bidentate or tridentate ligand which may have a substituent represented by the following general formula (4).

(However, Za, Zb, and Zc each independently represent a nonmetallic atom group that can form a 5- or 6-membered ring, and c represents 0 or 1.)
X is an acyloxy group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate group, a dithiocarbonate group, a trithiocarbonate group, an acyl group, a thiocyanate group, A monodentate or bidentate ligand coordinated by a group selected from the group consisting of an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a halogen atom Represents a monodentate or bidentate ligand consisting of carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide or thiourea. Xs may be linked together.
m1 represents an integer of 1 to 3, and when m1 is 2 or more, LL ¹ may be the same or different.
m2 represents an integer of 0 to 2, LL ² when m2 is 2 may be the same or different.
m3 represents an integer of 0 to 3, and when m3 is 2, X may be the same or different.
CI represents a counter ion when a counter ion is required to neutralize the charge.
However, the dye represented by the general formula (2) has at least one acidic adsorption group. ]

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