JP5917011B2 - Method for producing photoelectric conversion element and method for producing photoelectrochemical cell - Google Patents

Description

The present invention relates to a process for producing a preparation and photo-electrochemical cell of the photoelectric conversion element.

  As shown in FIG. 2, the photoelectric conversion element 10 includes a conductive support 1, a photosensitive layer 2 arranged in that order on the conductive support 1, It consists of a charge transfer layer 3 and a counter electrode 4. The conductive support 1 and the photoreceptor layer 2 constitute a light receiving electrode 5. The photoreceptor layer 2 has semiconductor fine particles 22 and a sensitizing dye (hereinafter also simply referred to as a dye) 21. At least a part of the sensitizing dye 21 is adsorbed on the semiconductor fine particles 22. At this time, the sensitizing dye 21 is in an adsorption equilibrium state and may partially exist in the charge transfer layer 3. The charge transfer body layer 3 functions as, for example, a hole transport layer that transports holes. The conductive support 1 on which the photoreceptor layer 2 is formed functions as a working electrode in the photoelectric conversion element 10. The photoelectric conversion element 10 can be operated as the photoelectrochemical cell 100 by causing the external circuit 6 to work.

  The light receiving electrode 5 is an electrode composed of a conductive support 1 and a photosensitive layer 2 (semiconductor film) of semiconductor fine particles 22 adsorbed by a sensitizing dye 21 coated on the conductive support 1. Light incident on the photoreceptor layer 2 (semiconductor film) excites the dye. The excited dye has high energy electrons. Therefore, the electrons are transferred from the sensitizing dye 21 to the conduction band of the semiconductor fine particles 22 and reach the conductive support 1 by diffusion. At this time, the molecule of the sensitizing dye 21 is an oxidant. The electrons on the electrode return to the oxidant while working in the external circuit 6, thereby acting as the photoelectrochemical cell 100. At this time, the light receiving electrode 5 functions as a negative electrode of the battery.

  As described above, since the photosensitive layer 2 includes the semiconductor fine particles 22 on which a specific dye is adsorbed, the light receiving sensitivity is increased by the action of the sensitizing dye, and the photoelectric conversion is high when used as the photoelectrochemical cell 100. Efficiency can be obtained. That is, in addition to the development of dyes, it is important in material design to bring about a high electrochemical effect in combination with semiconductor fine particles (for dyes applied to photoelectric conversion elements, see, for example, Patent Documents 1 and 2 below) The following patent document 3 can be referred to for an example of semiconductor fine particles.

Non-Patent Document 1 discloses that TiO ₂ fine particles are prepared by dissolving cetyltrimethylammonium bromide (CTAB) in a H ₂ O / EtOH mixed solvent and dropping Ti (iPr) ₄ . By creating a cell using this semiconductor fine particle and ruthenium metal complex dye N3 dye, a conversion efficiency of 7.5% is achieved compared to the conversion efficiency (5%) when using conventional TiO _2. It is supposed to be possible. However, further performance improvement is indispensable for full-scale practical use in photoelectric conversion elements such as solar cells.

US Pat. No. 5,463,057 JP 2007-73289 A JP 2006-302530 A

Satyanarayana Reddy Gajjela et al., Energy Environ. Sci., 2010, 3, 838-845

As for the interaction (compatibility) between the semiconductor fine particles and the sensitizing dye used in the above-described photoelectric conversion element or the like, research and development has not progressed sufficiently, and there are still many physicochemical aspects that need to be clarified. According to the above non-patent literature, the improvement in the battery performance is that the dye adsorption amount and the necking between the fine particles are improved by the refinement of the TiO ₂ fine particles and the increase in the surface area. In contrast, the present inventors have not only the effect of increasing the surface area by refining fine particles, but also the sensitizing dye has a relationship with the shape and size of pores (micropores) formed on the surface. The inventors searched for a combination of a dye and a semiconductor fine particle that can exhibit a specific effect, further increase the photoelectric conversion efficiency, and improve other performance items.

Thus, the present invention provides a combination of a specific metal complex dye and a specific semiconductor fine particle, which has high photoelectric conversion efficiency, optimizes an absorption wavelength, enhances performance suitability for visible light, and further contributes to improvement of device durability. It aims at providing the manufacturing method of the photoelectric conversion element which has a body layer, and the manufacturing method of a photoelectrochemical cell .

  The present inventors paid attention to the shape and size of pores of semiconductor fine particles such as titania prepared using a specific cationic surfactant and the interaction between dyes adsorbed thereon. Specifically, although some estimation is included, the metal complex dye having a specific hydrophobic group is adsorbed to the vacancies formed on the surface of the fine particles, and the dye is caused by the interaction via the hydrophobic group. We found that it was easy for them to form a superior meeting. The present invention has been completed based on such findings.

That is, the above problem has been solved by the following means .
<1> A semiconductor microparticles prepared using a cationic surfactant represented by the following formula (I), with an average particle size of the fine semiconductor particles is 1 to 20 nm, the roughness factor of 1000 to 1500 And a titanium oxide particle having a specific surface area of 50 to 400 m ² / g, a metal complex dye represented by the following general formula (1) is adsorbed to the semiconductor fine particles to form a photoreceptor layer. A method for manufacturing a conversion element.

ML ¹ L ² (A ⁰¹ ) _n0 (CI1) _n1 ... General formula (1)

(In general formula (1),
M represents a metal element,
AA ⁰¹ represents a ligand,
CI1 represents a counter anion,
-N0 represents the integer of 0-2, n1 represents the integer of 0-4.
· ^{L 1} represents a ligand is Ru represented by the following general formula (2), ^{L 2} represents a ligand represented by the following general formula (17). L ¹ and L ² may be linked to each other at the ortho position of the pyridine ring (position adjacent to the N atom) to form a quarterpyridine ligand. )

［一般式（２）中、
・Ｒ^１、Ｒ^２およびＲ^５は各々独立に、下記一般式（３）〜（１１）、（１３−２）または（１４）〜（１６）のいずれかを表す。
・Ｓ^１、Ｓ^２およびＳ^３は各々独立に、エテニレン基、エチニレン基およびアリーレン基から選ばれた少なくとも１種であって、Ｒ^１、Ｒ^２、Ｒ^５およびピリジン環と共役している。ｌ１、ｌ２およびｌ３は０〜５の整数を表す。
・Ｒ^３、Ｒ^４およびＲ^６は独立に、アルキル基、アルケニル基、アリール基、ヘテロ環基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アミノ基、アシルアミノ基、シアノ基またはハロゲン原子を表し、ｎ２およびｎ７は各々０〜３の整数を表し、ｎ３は０〜２の整数を表し、ｎ２が１以上のときＲ^３はＳ^１と連結して環を形成していてもよく、ｎ３が１以上のときＲ^４はＳ^２と連結して環を形成していてもよく、ｎ７が１以上のときＲ^６はＳ^３と連結して環を形成していてもよい。ｎ２が２以上のとき、Ｒ^３同士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いてもよい。ｎ３が２のとき、Ｒ^４同士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いてもよい。ｎ７が２以上のとき、Ｒ^６同士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いてもよい。ｎ２、ｎ３およびｎ７がともに１以上のときＲ^３、Ｒ^４およびＲ^６は連結して環を形成していてもよい。
・Ａ^１、Ａ^２およびＡ^３は独立に酸性基またはその塩を表す。ｎ４、ｎ５およびｎ６は各々０〜３の整数を表す。ｎ８は０または１を表す。］

［一般式（３）〜（１１）および（１６）中、Ｒ^７〜Ｒ^３５、Ｒ^５２〜Ｒ^５５、Ｒ^６１、Ｒ^６２およびＲ^６９は各々独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アミノ基、ヘテロ環基またはハロゲン原子を表す。Ｒ^５１は、水素原子、アルキル基、アルケニル基、アルキニル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、ヘテロ環基またはハロゲン原子を表す。Ｒ^６８は、アルキル基、アルケニル基、アルキニル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、ヘテロ環基またはハロゲン原子を表す。Ｒ^６９とＲ^７、Ｒ^９〜Ｒ^１２、Ｒ^１４とＲ^１５、Ｒ^１７とＲ^１８、Ｒ^２０〜Ｒ^２３、Ｒ^２５とＲ^２６、Ｒ^２８〜Ｒ^３１、Ｒ^３２とＲ^３３、Ｒ^３４とＲ^３５、Ｒ^５２〜Ｒ^５５は互いに環を形成していてもよい。同一窒素原子上に２つ存在するＲ^２４およびＲ^２７は、２つのＲ ^２４ 同士または２つのＲ ^２７ 同士が、互いに同一でも異なっていてもよく、また、２つのＲ ^２４ 同士または２つのＲ ^２７ 同士が、互いに結合して環を形成していてもよい。ｍ１〜ｍ９およびｍ１１は１〜５の整数を表す。
一般式（１３−２）、（１４）および（１５）中、Ｒ^４０およびＲ^４１は各々独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アミノ基、ヘテロ環基またはハロゲン原子を表す。Ｒ^６５〜Ｒ^６７は各々独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基またはハロゲン原子を表す。
Ｙ^１〜Ｙ^３およびＸは各々独立にＳ、Ｏ、Ｓｅ、ＴｅまたはＮＲ^４２を表し、Ｒ^４２は水素原子、アルキル基、アルケニル基、アルキニル基、アリール基またはヘテロ環基を表す。］

［一般式（１７）中、同一ピリジン環中に４つ存在するＲ^４７はそれぞれ独立に、その少なくとも１つは酸性基またはその塩であり、残りのＲ^４７は水素原子またはアルキル基を表す。同一ピリジン環中に４つ存在するＲ^４８はそれぞれ独立に、その少なくとも１つは酸性基またはその塩であり、残りのＲ^４８は水素原子またはアルキル基を表す。］

［一般式（Ｉ）中、Ｒ ^４３ 〜Ｒ ^４６ は水素原子、アルキル基、アルケニル基、アルキニル基またはアルコキシ基を表す。ＣＩ２はカウンターアニオンを表す。］
＜２＞前記一般式（Ｉ）中、Ｒ ^４３ 〜Ｒ ^４６ が、炭素数１〜３０のアルキル基である＜１＞に記載の光電変換素子の製造方法。
＜３＞前記一般式（Ｉ）中、Ｒ ^４３ 〜Ｒ ^４６ が、炭素数３〜２７のアルキル基である＜２＞に記載の光電変換素子の製造方法。
＜４＞前記金属錯体色素が以下のものである＜１＞〜＜３＞のいずれか１項に記載の光電変換素子の製造方法。
前記一般式（２）中、Ｒ^１およびＲ^２ が各々独立に、一般式（３）、（５）、（６）、（７）、（１０）および（１６）のいずれかである。Ｓ^１およびＳ^２ が各々独立に、エテニレン基およびエチニレン基から選ばれた少なくとも１種であって、Ｒ^１、Ｒ^２およびビピリジンと共役している。ｌ１およびｌ２は０〜３の整数である。Ｒ^３およびＲ^４ が独立に置換基であり、ｎ２が１以上のときＲ^３はＳ１と連結して環を形成していてもよく、ｎ３が１以上のときＲ^４はＳ^２と連結して環を形成していてもよい。ｎ２が２のとき、Ｒ^３同士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いてもよい。ｎ３が２のとき、Ｒ^４同士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いてもよい。ｎ２およびｎ３がともに１以上のときＲ^３とＲ^４は連結して環を形成していてもよい。ただし、ｎ２およびｎ３が各々０〜２の整数であり、Ａ^１およびＡ^２ が酸性基またはその塩である。ｎ４およびｎ５が各々０〜２の整数である。ｎ８が０である。
前記一般式（３）、（５）、（６）、（７）、（１０）および（１６）中、Ｒ^７、Ｒ^１３〜Ｒ^２３、Ｒ^３２、Ｒ^３３、Ｒ^５１、Ｒ^６１およびＲ^６９ が各々独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基またはハロゲン原子である。Ｒ^６８ が、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基またはハロゲン原子である。Ｒ^６９とＲ^７、Ｒ^１４とＲ^１５、Ｒ^１７とＲ^１８、Ｒ^２０〜Ｒ^２３、Ｒ^３２とＲ^３３、Ｒ^５２〜Ｒ^５５は互いに環を形成していてもよい。ｍ１、ｍ３〜ｍ５、ｍ８およびｍ１１が１〜３の整数である。Ｙ^１〜Ｙ^３ が各々独立に、Ｓ、Ｏ、Ｓｅ、ＴｅまたはＮＲ^４２を表し、Ｒ^４２ が水素原子またはアルキル基である。
前記一般式（１７）で表される配位子が下記一般式（１８）で表される配位子である。

［一般式（１８）中、Ｒ^４７およびＲ^４８はそれぞれ独立に、水素原子、アルキル基または酸性基もしくはその塩を表し、Ｒ ^４７ およびＲ ^４８ の少なくとも１つは酸性基またはその塩である。Ｒ^４９およびＲ^５０はそれぞれ独立に水素原子またはアルキル基を表す。］
＜５＞前記金属錯体色素が以下のものである＜４＞に記載の光電変換素子の製造方法。
前記一般式（２）中、Ｒ^１およびＲ^２ が各々独立に、一般式（３）、（７）および（１６）のいずれかである。Ｓ^１およびＳ^２ が各々独立に、エテニレン基であって、Ｒ^１、Ｒ^２およびビピリジンと共役している。ｌ１およびｌ２が０〜２の整数である。ｎ２およびｎ３は各々０または１である。Ｒ^３およびＲ^４ が独立に、アルキル基、アルケニル基、アリール基、ヘテロ環基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アミノ基、アシルアミノ基、シアノ基またはハロゲン原子であり、ｎ２が１のときＲ^３はＳ^１と連結して環を形成していてもよく、ｎ３が１のときＲ^４はＳ^２と連結して環を形成していてもよい。ｎ２およびｎ３がともに１のときＲ^３とＲ^４は連結して環を形成していてもよい。Ａ^１およびＡ^２ が酸性基またはその塩である。ｎ４およびｎ５が各々０または１である。ｎ８が０である。
前記一般式（３）、（７）および（１６）中、Ｒ^７、Ｒ^１９〜Ｒ^２３、Ｒ^５１〜Ｒ^５５およびＲ^６９ が、水素原子、アルキル基、アルケニル基またはアルキニル基である。Ｒ^６８ がアルキル基、アルケニル基またはアルキニル基である。Ｒ^６９とＲ^７、Ｒ^２０〜Ｒ^２３、Ｒ^５２〜Ｒ^５５は互いに環を形成していてもよい。ｍ１、ｍ５およびｍ１１が１または２である。Ｙ^１〜Ｙ^３ が各々独立に、Ｓ、ＯまたはＮＲ^４２ であり、Ｒ^４２ が水素原子またはアルキル基である。
前記一般式（１８）中、Ｒ^４７およびＲ^４８ がそれぞれ独立に、酸性基またはその塩であり、Ｒ^４９およびＲ^５０ が水素原子である。
＜６＞前記金属錯体色素の前記金属元素Ｍが、Ｒｕ、Ｒｅ、Ｒｈ、Ｐｔ、Ｆｅ、Ｏｓ、Ｃｕ、Ｉｒ、Ｐｄ、ＷまたはＣｏである＜１＞〜＜５＞のいずれか１項に記載の光電変換素子の製造方法。
＜７＞前記金属元素Ｍが、Ｒｕ、Ｆｅ、ＯｓまたはＣｏである＜６＞に記載の光電変換素子の製造方法。
＜８＞前記Ｙ ^１がＳ原子である＜１＞〜＜７＞のいずれか１項に記載の光電変換素子の製造方法。
＜９＞前記一般式（２）の酸性基Ａ^１１、Ａ^１２およびＡ^１３、並びに一般式（１７）及び（１８）の酸性基がそれぞれ独立に、カルボキシル基、リン酸基、スルホン酸基またはそれらの塩である＜１＞〜＜８＞のいずれか１項に記載の光電変換素子の製造方法。
＜１０＞前記一般式（１）のＣＩ１がテトラブチルアンモニウムである＜１＞〜＜９＞のいずれか１項に記載の光電変換素子。
＜１１＞前記一般式（１）の配位子のＡ ^０１ がイソチオシアネート、イソシアネート、イソセレノシアネートまたはハロゲン原子である＜１＞〜＜１０＞のいずれか１項に記載の光電変換素子の製造方法。
＜１２＞前記酸化チタン粒子が、粒子の平均粒径が１〜１０ｎｍで、粗さ係数が１０００〜１５００で、比表面積が２００〜２５０ｍ^２／ｇである＜１＞〜＜１１＞のいずれか１項に記載の光電変換素子の製造方法。
＜１３＞ ＜１＞〜＜１２＞のいずれか１項に記載の製造方法で光電変換素子を製造し、得られた光電変換素子を具備させる光電気化学電池の製造方法。

[In general formula (2),
R ¹ , R ² and R ⁵ each independently represent any of the following general formulas (3) to (11), (13-2) or (14) to (16).
S ¹ , S ² and S ³ are each independently at least one selected from an ethenylene group, an ethynylene group and an arylene group, and are conjugated to R ¹ , R ² , R ⁵ and a pyridine ring. l1, l2 and l3 each represents an integer of 0 to 5;
R ³ , R ⁴ and R ⁶ independently represent an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, cyano group or halogen atom. , N2 and n7 each represents an integer of 0 to 3, n3 represents an integer of 0 to 2, and when n2 is 1 or more, R ³ may be linked to S ¹ to form a ring, When it is 1 or more, R ⁴ may be linked to S ² to form a ring, and when n7 is 1 or more, R ⁶ may be linked to S ³ to form a ring. When n2 is 2 or more, R ³ together may be the same or different, may form a ring. When n3 is 2 , R ⁴ may be the same or different, and may be connected to each other to form a ring. When n7 is 2 or more, R ⁶ may be the same or different, and may be connected to each other to form a ring. When n2, n3 and n7 are all 1 or more, R ³ , R ⁴ and R ⁶ may be linked to form a ring.
· ^A 1, ^{A 2} and ^{A 3} represents an acidic group or a salt thereof independently. n4, n5 and n6 each represents an integer of 0 to 3. n8 represents 0 or 1. ]

[In General Formulas (3) to (11) and (16), R ^{7 to} R ³⁵ , R ^{52 to} R ⁵⁵ , R ⁶¹ , R ⁶² and R ⁶⁹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, An alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an amino group, a heterocyclic group, or a halogen atom is represented. R ⁵¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group or a halogen atom. R ⁶⁸ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group or a halogen atom. R ⁶⁹ and ^{R 7, R 9 ~R 12,} R 14 and ^{R 15, R 17} and ^{R 18, R 20 ~R 23,} R 25 and ^{R 26, R 28 ~R 31,} R 32 and ^{R 33, R 34} And R ³⁵ and R ^{52 to} R ⁵⁵ may form a ring with each other. ^{R 24} and ^{R 27} there are two to the same nitrogen atom, two ^{R 24} s or two ^{R 27} each other may be the same as or different from each other and two ^{R 24} s or two ^{R 27} each other may be bonded to each other to form a ring. m1-m9 and m11 represent the integer of 1-5.
In the general formulas (13-2), (14) and (15), R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy Represents a group, an arylthio group, an amino group, a heterocyclic group or a halogen atom. R ^{65 to} R ⁶⁷ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a halogen atom.
Y ^{1 to} Y ³ and X each independently represent S, O, Se, Te or NR ⁴² , and R ⁴² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. ]

[In the general formula (17), four R ⁴⁷ present in the same pyridine ring are each independently at least one of which is an acidic group or a salt thereof, and the remaining R ⁴⁷ represents a hydrogen atom or an alkyl group. Four R ^48s present in the same pyridine ring are each independently at least one of which is an acidic group or a salt thereof, and the remaining R ⁴⁸ represents a hydrogen atom or an alkyl group. ]

[In the general formula (I), R ^{43 to} R ⁴⁶ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. CI2 represents a counter anion. ]
<2> The method for producing a photoelectric conversion element according to <1>, wherein R ^{43 to} R ⁴⁶ in the general formula (I) are alkyl groups having 1 to 30 carbon atoms.
<3> The method for producing a photoelectric conversion element according to <2>, wherein R ^{43 to} R ⁴⁶ are an alkyl group having 3 to 27 carbon atoms in the general formula (I) .
< 4 > The method for producing a photoelectric conversion element according to any one of <1> to <3>, wherein the metal complex dye is as follows.
In formula (2), the ^{R 1} and ^{R 2} are each independently the general formula (3), (5), (6), (7), is either (10) and (16). S ¹ and S ² are each independently at least one selected from an ethenylene group and an ethynylene group, and are conjugated with R ¹ , R ² and bipyridine. l1 and l2 are integers of 0-3. R ³ and ^{R 4} are substituents on independently, ^{R 3} when n2 is 1 or more may form a ring with S1, ^{R 4} when n3 is 1 or more is connected with ^{S 2} May form a ring. When n2 is 2, R ³ together may be the same or different, may form a ring. When n3 is 2 , R ⁴ may be the same or different, and may be connected to each other to form a ring. When both n2 and n3 are 1 or more, R ³ and R ⁴ may be linked to form a ring. However, n2 and n3 are each 0 to 2 integer, ^{A 1} and ^{A 2} is an acidic group or a salt thereof. n4 and n5 are each an integer of 0-2. n8 is 0.
In the general formulas (3), (5), (6), (7), (10) and (16), R ⁷ , R ^{13 to} R ²³ , R ³² , R ³³ , R ⁵¹ , R ⁶¹ and R ⁶⁹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a halogen atom. R ⁶⁸ is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a halogen atom. R ⁶⁹ and ^{R 7, R 14} and ^{R 15, R 17} and ^{R 18, R 20 ~R 23,} R 32 and ^{R 33, R} 52 ^{~R 55} may have each other to form a ring. m1, m3-m5, m8 and m11 are integers of 1-3. The Y ¹ to Y ³ are each independently, represent S, O, Se, and Te, or ^{NR 42, R 42} is a hydrogen atom or an alkyl group.
Ligand represented by the general formula (17) is a ligand represented by the following general formula (18).

[In General Formula (18), R ⁴⁷ and R ⁴⁸ each independently represent a hydrogen atom, an alkyl group, an acidic group or a salt thereof, and at least one of R ⁴⁷ and R ⁴⁸ is an acidic group or a salt thereof. R ⁴⁹ and R ⁵⁰ each independently represent a hydrogen atom or an alkyl group. ]
< 5 > The method for producing a photoelectric conversion element according to < 4 >, wherein the metal complex dye is as follows.
In the general formula (2), R ¹ and R ² are each independently any one of the general formulas (3), (7), and (16). S ¹ and S ² are each independently an ethenylene group, which is conjugated with R ¹ , R ² and bipyridine. l1 and l2 are integers of 0-2. n2 and n3 are each 0 or 1. R ³ and R ⁴ are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, cyano group or halogen atom , and n2 is 1 In this case, R ³ may be linked to S ¹ to form a ring, and when n 3 is 1, R ⁴ may be linked to S ² to form a ring. When n2 and n3 are both 1, R ³ and R ⁴ may be linked to form a ring. A ¹ and ^{A 2} is an acidic group or a salt thereof. n4 and n5 are each 0 or 1. n8 is 0.
Formula (3), in (7) and ^{(16), R 7, R} 19 ~R 23, R 51 ~R 55 and ^{R 69} is a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. R ⁶⁸ is an alkyl group, alkenyl group or alkynyl group. R ⁶⁹ and R ⁷ , R ^{20 to} R ²³ , and R ^{52 to} R ⁵⁵ may form a ring with each other. m1, m5 and m11 is 1 or 2. The Y ¹ to Y ³ are each independently, S, O or ^{NR 42, R 42} is a hydrogen atom or an alkyl group.
In the general formula ^(18), the ^{R 47} and ^{R 48} are each independently an acid group or a salt ^{thereof, R 49} and ^{R 50} are hydrogen atoms.
< 6 > In any one of <1> to < 5 >, the metal element M of the metal complex dye is Ru , Re , Rh , Pt , Fe , Os , Cu , Ir , Pd , W, or Co. The manufacturing method of the photoelectric conversion element of description.
< 7 > The method for producing a photoelectric conversion element according to < 6 >, wherein the metal element M is Ru , Fe , Os, or Co.
<8> method for producing a pre-Symbol ^{Y 1} is S atom <1> to photoelectric conversion element according to any one of <7>.
< 9 > The acidic groups A ¹¹ , A ¹² and A ^{13 in} the general formula (2) and the acidic groups in the general formulas (17) and (18) are each independently a carboxyl group, a phosphoric acid group, a sulfonic acid group or The manufacturing method of the photoelectric conversion element of any one of <1>-< 8 > which is those salts.
<10> The photoelectric conversion device according to item 1 or a <1> ~ <9> CI1 is tetrabutylammonium the general formula (1).
<11> manufacture of the photoelectric conversion device according to any one of ^{A 01} isothiocyanate ligands, isocyanates, and isoselenocyanates or halogen atom <1> to <10> in the general formula (1) Way .
< 12 > Any one of <1> to < 11 >, wherein the titanium oxide particles have an average particle diameter of 1 to 10 nm, a roughness coefficient of 1000 to 1500, and a specific surface area of 200 to 250 m ² / g. The manufacturing method of the photoelectric conversion element of 1 item | term.
< 13 > <1> to produce a photoelectric conversion element manufacturing method according to any one of <12>, the resulting production method of photoelectrochemical cells causes including a photoelectric conversion element.

The photoelectric conversion element manufactured by the manufacturing method of the present invention has a high photoelectric conversion efficiency and an absorption wavelength optimized by a photosensitive layer containing a specific metal complex dye and a specific semiconductor fine particle, and has a performance suitability for visible light. High and further excellent in durability of the element.

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

The photoelectric conversion element manufactured by the manufacturing method of the present invention has, in its photoreceptor layer, specific semiconductor fine particles prepared using a cationic surfactant and a metal complex having a specific ligand. The size and shape of the pores of the semiconductor fine particles are particularly compatible with the specific metal complex dye and can bring out desired performance. Specifically, as described above, including estimation, the size and shape of the pores promote the intermolecular association of Ru dyes (particularly, the association by hydrophobic interaction via the hydrophobic group in the dye side chain). As a result, a dominant J-association in which the light absorption region of the dye becomes a long wave and an increase in the amount of dye adsorbed may occur. Thereby, it is considered that the performance of the photoelectric conversion element is improved.
Hereinafter, the photoelectric conversion element manufactured by the manufacturing method of the present invention is simply referred to as the photoelectric conversion element of the present invention.
Hereinafter , preferred embodiments of the present invention will be described in detail.

[Semiconductor fine particles]
Semiconductor fine particles prepared using a cationic surfactant represented by the following general formula (I) are applied to the photoreceptor layer 5 (see FIG. 1) in the photoelectric conversion element of the present embodiment. First, the cationic surfactant will be described.

一般式(Ｉ)中、Ｒ^４３〜Ｒ^４６は水素原子または置換していてもよいアルキル基、アルケニル基、アルキニル基、又はアルコキシ基を表す。Ｒ^４３〜Ｒ^４６はアルキル基又はアルコキシ基であることが好ましく、アルキル基であることがより好ましい。これらの基の好ましいものは、後述する置換基Ｔで挙げられているものを挙げることができる。なかでも、置換基Ｔは炭素数６〜２０の直鎖アルキル基を持つトリメチルアンモニウムカチオンであり、カウンターアニオンはブロミド、クロロ、フルオロ、ヨードアニオンがよい。さらに好ましくは、炭素数１０〜１９の直鎖アルキル基を持つトリメチルアンモニウムカチオンであり、カウンターアニオンはブロミド、クロロ、ヨードアニオンがよい。特に好ましくは、炭素数１４-１８の直鎖アルキル基を持つトリメチルアンモニウムカチオンであり、カウンターアニオンはブロミド、ヨードアニオンがよい。たとえば、セチルトリメチルアンモニウムブロミド（ＣＴＡＢ、Ｃ１６）、ドデシルトリメチルアンモニウムブロミド（ＤＯＴＡＢ、Ｃ１２）、オクタデシルトリメチルアンモニウムブロミド（ＯＴＡＢ、Ｃ１８）であることが好ましく、セチルトリメチルアンモニウムブロミド（ＣＴＡＢ、Ｃ１６）であることがより好ましい。なお、本明細書において置換基に関してｘｘｘ基というときには、そのｘｘｘ基に任意の置換基を有していてもよい。この任意の置換基としては、後述する置換基Ｔが挙げられる。また、同一の符合で示された基が複数ある場合は、互いに異なっていても同じであってもよい。複数の基が連結して環を形成するときには、その複数の基のすべてが連結していても、その一部が連結していてもよい。 (Surfactant)
General formula (1) is as follows.

In the general formula (I), R ^{43 to} R ⁴⁶ represent a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group, or alkoxy group. R ^{43 to} R ⁴⁶ are preferably an alkyl group or an alkoxy group, and more preferably an alkyl group. The preferable thing of these groups can mention what is mentioned by the substituent T mentioned later. Among them, the substituent T is a trimethylammonium cation having a linear alkyl group having 6 to 20 carbon atoms, and the counter anion is preferably a bromide, chloro, fluoro, or iodo anion. More preferably, it is a trimethylammonium cation having a linear alkyl group having 10 to 19 carbon atoms, and the counter anion is preferably a bromide, chloro or iodo anion. Particularly preferred is a trimethylammonium cation having a linear alkyl group having 14 to 18 carbon atoms, and the counter anion is preferably a bromide or an iodo anion. For example, cetyltrimethylammonium bromide (CTAB, C16), dodecyl trimethyl ammonium bromide (DOTAB, C12), preferably a Okuda decyl trimethyl ammonium bromide (OTAB, C 1 8), cetyltrimethylammonium bromide (CTAB, C16) It is more preferable that In the present specification, when an xxx group is referred to with respect to a substituent, the xxx group may have an arbitrary substituent. As this arbitrary substituent, the substituent T mentioned later is mentioned. In addition, when there are a plurality of groups indicated by the same symbol, they may be different or the same. When a plurality of groups are connected to form a ring, all of the plurality of groups may be connected or a part thereof may be connected.

  Although the above-mentioned cationic surfactant is involved, the mechanism of the formation of vacancies (micropores) that exert a good effect particularly in relation to the sensitizing dye employed in the present invention includes unclear points. It is considered as follows. That is, the alkyl chain introduced into the surfactant (ammonium cation) is aggregated by a hydrophobic interaction in a polar solvent (water, alcohol solvent, etc.) to form an alkyl chain aggregate of 1 nm or less. When oxide semiconductors (such as titanium oxide) are formed in the vicinity of this alkyl chain aggregate, it is considered that micropores having the same size as the aggregated alkyl chain are formed in these oxide semiconductors.

(Metal compound)
For the formation of the semiconductor fine particles, a metal compound serving as the metal source is used. As such a metal compound, a metal complex having a specific ligand can be used. In this embodiment, an example using a titanium compound will be described.
Examples of titanium compounds include titanium complexes, such as titanium isopropoxide [Ti (OiPr) ₄ ], Ti (OEt) ₄ , Ti (OMe) ₄ , Ti (OBu) ₄ , and Ti (OtBu) _4. It is done. Of these, titanium isopropoxide, Ti (OEt) ₄ , and Ti (OtBu) ₄ are preferably used. The input amount of the metal compound and the surfactant is not particularly limited, but it is preferable to add 0.1 to 10.0 mol of the surfactant and more preferably 0.5 to 5.0 mol with respect to 1 mol of the metal complex. It is preferable that the amount added is equal to or more than the above lower limit value because fine micropores are formed by the hydrophobic group in the surfactant. It is preferable for it to be equal to or less than the above upper limit value because the fine pores formed on the surface of the fine particles are bonded to each other and can be prevented from becoming larger pores.

(Preparation conditions)
In this embodiment, the semiconductor fine particles are prepared by adding the metal compound to the cationic surfactant. For example, since titanium isopropoxide (TIPR) is a liquid at room temperature and CTAB is also a liquid, the CTAB is vigorously stirred, and TIPR is added dropwise thereto, thereby depositing desired semiconductor fine particles. Can be obtained. The stirring speed at this time is preferably 200 to 1000 rpm. Although reaction temperature is not limited, For example, it can carry out at 30-60 degreeC. The precipitate is preferably fired after washing with ethanol or the like. Although a calcination temperature is not specifically limited, It is preferable to carry out at 400-500 degreeC for 3 to 9 hours. By pulverizing what is obtained in this way, titania fine particles can be obtained in the case of the CTAB / TIPR described above.

(Characteristics of fine particles)
The shape and size of the fine particles of the present embodiment are not particularly limited, but are preferably nanometer-sized ultrafine particles. The volume average diameter (Mv) is used as the average particle diameter unless otherwise specified. In the present embodiment, the volume average diameter of the semiconductor fine particles is preferably 1 to 20 nm, and more preferably 3 to 10 nm. It is preferable for this value to be equal to or greater than the above lower limit value because the electrolytic solution can easily enter through the gaps between the fine titanium oxide particles and a sufficient oxidation / reduction cycle as a battery can be performed. When the amount is not more than the above upper limit, the surface area of titanium oxide (TiO2) is increased, and as a result, the amount of dye adsorbed on the titanium oxide surface is also increased. As a measuring method of the particle size of the fine particles, those measured by the dynamic light scattering method were evaluated unless otherwise specified, and as a measuring device, a dynamic light scattering photometer DLS-7000 series (both trade names) manufactured by Otsuka Electronics Co., Ltd. ) Is used.
Moreover, it is preferable that the surface roughness coefficient of particle | grains is 1000-1500, and it is more preferable that it is 1100-1400. It is preferable that this value is not less than the above lower limit value because fine pores necessary for association of the dye are formed on the surface of the titanium oxide fine particles. It is preferable for it to be not more than the above upper limit value because the formation of excessive fine pores can be suppressed.

It is preferable that the surface of the semiconductor fine particle has a large number of pores (micropores). As a result, the surface area is increased, and the above-described specific action due to the association of the dyes is suitably expressed. From the viewpoint of this effect, the pores (micropores) are preferably in a specific pore distribution range. The median value of the pore diameter is preferably 0.1 to 0.8 nm, and more preferably 0.3 to 0.6 nm. It is preferable that this value is not less than the above lower limit value because a plurality of dye molecules can enter the micropores and an advantageous association can be formed in the micropores. It is preferable for it to be less than or equal to the above upper limit value because it is possible to suppress excessive dye from entering the micropores and forming inefficient association there. On the other hand, it is preferable that the surface area is large, is preferably 50 to 400 m ² / g for the specific surface area, and more preferably 100 to 350 m ² / g. Most preferably, it is 180-250 m < ² > / g. It is preferable for this value to be equal to or greater than the above lower limit value because the surface area of the titanium oxide fine particles is increased, resulting in an increase in the amount of dye adsorbed. It is preferable that the pore size is not more than the above upper limit value because micropores are sufficiently formed on the surface of the fine particles (the larger the surface area, the smaller the particle size of the fine particles. If the fine particles are too small, the fine particles formed on the fine particle surface are preferred. The pores combine to form large pores, which is inefficient.) The surface area of the fine particles may be measured by an ordinary method, for example, by the BET method using nitrogen gas.
However, in the present invention, the semiconductor fine particles are titanium oxide particles having an average particle diameter of 1 to 20 nm, a roughness coefficient of 1000 to 1500, and a specific surface area of 50 to 400 m ² / g.

［一般式（２）中、
・Ｒ^１、Ｒ^２およびＲ^５は各々独立に、アルキル基、アルコキシ基または下記一般式（３）〜（１６）を表す。なかでも、アルキル基、アルコキシ基、又はチオフェン基（チオフェンは１価の末端基であっても２価の連結基であってもよい）を有する基であることが好ましい。アルキル基、アルコキシ基としては、置換基Ｔで挙げたものが挙げられる。
・Ｓ^１、Ｓ^２およびＳ^３は各々独立に、エテニレン基、エチニレン基およびアリーレン基から選ばれた少なくとも１種であって、Ｒ^１、Ｒ^２、Ｒ^５およびピリジンと共役している。ｌ１、ｌ２およびｌ３は０〜５の整数を表す。
・Ｒ^３、Ｒ^４およびＲ^６は独立に置換基（好ましいものとして置換基Ｔで挙げたものが挙げられる。）を表し、ｎ２およびｎ７は各々０〜３の整数を表し、ｎ３は０〜２の整数を表す。ｎ２が１以上のときＲ^３はＳ^１と連結して環を形成していてもよく、ｎ３が１以上のときＲ^４はＳ^２と連結して環を形成していてもよく、ｎ７が１以上のときＲ^６はＳ^３と連結して環を形成していてもよい。ｎ２が２以上のとき、Ｒ^３同士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いてもよい。ｎ３が２のとき、Ｒ^４同士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いてもよい。ｎ７が２以上のとき、Ｒ^６同士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いてもよい。ｎ２、ｎ３およびｎ７がともに１以上のときＲ^３、Ｒ^４およびＲ^６は連結して環を形成していてもよい。
・Ａ^１、Ａ^２およびＡ^３は独立に酸性基またはその塩を表す。ｎ４、ｎ５およびｎ６は各々０〜３の整数を表す。ｎ８は０又は１を表す。好ましい酸性基としては、後記、結合基に記載のものが挙げられる。］

［一般式（３）〜（１２）、（１６）中、Ｒ^７〜Ｒ^４１、Ｒ^５１〜Ｒ^５５、Ｒ^６１〜Ｒ^６３、Ｒ^６８、Ｒ^６９は各々独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アミノ基、ヘテロ環基、またはハロゲン原子を表し、より好ましくは、水素原子、アルキル基、アルケニル基、アルキニル基、アルコキシ基、アリールオキシ基、アミノ基、ヘテロ環基であり、さらに好ましくは水素原子、アルキル基、アルケニル基、アルキニル基、ヘテロ環基である。なお、Ｒ^４０、Ｒ^４１は一般式（１４）、（１５）の置換基である。
一般式（１３−１）〜（１５）中、Ｒ^６４〜Ｒ^６７は各々独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基、またはハロゲン原子を表し、より好ましくはアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基であり、さらに好ましくはアルキル基、アルケニル基、アルキニル基、ヘテロ環基である。
Ｒ^６９とＲ^７、Ｒ^９〜Ｒ^１２、Ｒ^１４とＲ^１５、Ｒ^１７とＲ^１８、Ｒ^２０〜Ｒ^２３、Ｒ^２５とＲ^２６、Ｒ^２８〜Ｒ^３１、Ｒ^３２とＲ^３３、Ｒ^３４とＲ^３５、Ｒ^３６〜Ｒ^３９、Ｒ^５２〜Ｒ^５５は互いに環を形成していてもよい。同一特性基中に２つ存在するＲ^２４およびＲ^２７は、２つのＲ ^２４ 同士または２つのＲ ^２７ 同士が、互いに同一でも異なっていてもよく、また、２つのＲ ^２４ 同士または２つのＲ ^２７ 同士が、互いに結合して環を形成していてもよい。ｍ１〜ｍ１１は１〜５の整数を表す。Ｙ^１〜Ｙ^３およびＸは各々独立にＳ、Ｏ、Ｓｅ、Ｔｅ、ＮＲ^４２を表し、Ｒ^４２は水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基を表す。］

［同一特性基中に４つ存在するＲ^４７はそれぞれ独立に、その少なくとも１つは酸性基またはその塩であり、残りのＲ^４７は水素原子又はアルキル基（置換基Ｔで挙げたものが挙げられる。）を表す。同一特性基中に４つ存在するＲ^４８はそれぞれ独立に、その少なくとも１つは酸性基またはその塩であり、残りのＲ^４８は水素原子又はアルキル基（置換基Ｔで挙げたものが挙げられる。）を表す。］ [Metal complex dye]
Next, the metal complex dye will be described. In the present embodiment, a metal complex dye represented by the following general formula (1) is used.

ML ¹ L ² (A ⁰¹ ) _n0 (CI1) _n1 ... General formula (1)

(In general formula (1),
M represents a metal element,
A ⁰¹ represents a ligand,
CI1 represents a counter anion,
-N0 represents the integer of 0-2, n1 represents the integer of 0-4.
· ^{L 1} represents a ligand is Ru represented by the following general formula (2), ^{L 2} represents a ligand represented by the following general formula (17). L ¹ and L ² may be linked to each other at the ortho position of the pyridine ring (position adjacent to the N atom) to form a quarterpyridine ligand. )

[In general formula (2),
* R < ¹ >, R < ² > and R < ⁵ > represent an alkyl group, an alkoxy group, or the following general formula (3)-(16) each independently. Among them, a group having an alkyl group, an alkoxy group, or a thiophene group (thiophene may be a monovalent terminal group or a divalent linking group) is preferable. Examples of the alkyl group and alkoxy group include those exemplified for the substituent T.
S ¹ , S ² and S ³ are each independently at least one selected from an ethenylene group, an ethynylene group and an arylene group, and are conjugated with R ¹ , R ² , R ⁵ and pyridine. l1, l2 and l3 each represents an integer of 0 to 5;
· ^R 3, ^{R 4} and ^{R 6} are (include those mentioned substituent T as being preferred.) Independently substituent represents, n 2 Contact and n7 each represent an integer of 0 to 3, n3 is Represents an integer of 0 to 2; When n2 is 1 or more, R ³ may be linked to S ¹ to form a ring, and when n3 is 1 or more, R ⁴ may be linked to S ² to form a ring, and n7 is When it is 1 or more, R ⁶ may be linked to S ³ to form a ring. When n2 is 2 or more, R ³ together may be the same or different, may form a ring. When n3 is 2 , R ⁴ may be the same or different, and may be connected to each other to form a ring. When n7 is 2 or more, R ⁶ may be the same or different, and may be connected to each other to form a ring. When n2, n3 and n7 are all 1 or more, R ³ , R ⁴ and R ⁶ may be linked to form a ring.
· ^A 1, ^{A 2} and ^{A 3} represents an acidic group or a salt thereof independently. n4, n5 and n6 each represents an integer of 0 to 3. n8 represents 0 or 1. Preferable acidic groups include those described later and in the linking group. ]

[In the general formulas (3) to (12) and (16), R ^{7 to} R ⁴¹ , R ^{51 to} R ⁵⁵ , R ^{61 to} R ⁶³ , R ⁶⁸ and R ⁶⁹ are each independently a hydrogen atom, an alkyl group, An alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an amino group, a heterocyclic group, or a halogen atom, and more preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group , An alkoxy group, an aryloxy group, an amino group, and a heterocyclic group, and more preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group. R ⁴⁰ and R ⁴¹ are substituents of the general formulas (14) and (15).
In general formulas (13-1) to (15), R ^{64 to} R ⁶⁷ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or a halogen atom, and more preferably. Is an alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, more preferably an alkyl group, alkenyl group, alkynyl group or heterocyclic group.
R ⁶⁹ and ^{R 7, R 9 ~R 12,} R 14 and ^{R 15, R 17} and ^{R 18, R 20 ~R 23,} R 25 and ^{R 26, R 28 ~R 31,} R 32 and ^{R 33, R 34} And R ³⁵ , R ^{36 to} R ³⁹ , and R ^{52 to} R ⁵⁵ may form a ring with each other. ^{R 24} and ^{R 27} present two to during the same characteristic group, the two ^{R 24} s or two ^{R 27} each other may be the same as or different from each other and two ^{R 24} s or two ^{R 27} each other may be bonded to each other to form a ring. m1-m11 represents the integer of 1-5. Y ^{1 to} Y ³ and X each independently represent S, O, Se, Te, NR ⁴² , and R ⁴² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. ]

[Each of R ^{47 in the} same characteristic group is independently at least one of which is an acidic group or a salt thereof, and the remaining R ⁴⁷ is a hydrogen atom or an alkyl group (the same as those mentioned for the substituent T). Represents.). Four R ^48s present in the same characteristic group are each independently at least one of which is an acidic group or a salt thereof, and the remaining R ⁴⁸ is a hydrogen atom or an alkyl group (those exemplified for the substituent T). .) ]

Here, the hydrophobic group particularly in the side chain of the dye is specifically represented by the structural formula of the general formula (2): R ¹ -S ^1- , R ² -S ^2- , R ⁵ -S It corresponds to the ^3- site. Although the present invention is not construed as being limited thereby, it is typically understood that this site interacts between molecules to exhibit the interaction due to the above-described association unique to the present invention. From this viewpoint, in the present invention, it is important to design the hydrophobic group and a side chain having the hydrophobic group.
In addition, the metal complex pigment | dye used by this invention is as follows among the above.
In the general formula (2), R ¹ , R ² and R ⁵ are each independently any one of the general formulas (3) to (11), (13-2) or (14) to (16), R ³ , R ⁴ and R ⁶ are independently an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, cyano group or halogen atom, n8 is 0 or 1.
In the general formulas (3) to (11) and (16), R ^{7 to} R ³⁵ , R ^{52 to} R ⁵⁵ , R ⁶¹ , R ⁶² and R ⁶⁹ are each independently a hydrogen atom, an alkyl group or an alkenyl group. , An alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an amino group, a heterocyclic group or a halogen atom, and R ⁵¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group , An alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group or a halogen atom, and ^R68 is an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group A group, a heterocyclic group or a halogen atom. m1-m9 and m11 are integers of 1-5.
In the general formulas (13-2), (14) and (15), R ⁴⁰ and R ⁴¹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl group, An aryloxy group, an arylthio group, an amino group, a heterocyclic group or a halogen atom, and R ^{65 to} R ⁶⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a halogen atom. It is. Y ^{1 to} Y ³ and X are each independently S, O, Se, Te or NR ⁴² , and R ⁴² is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

○ Metal element M
The metal element M is not particularly limited as long as it can take the structure of the above general formula. Among them, Ru, Re, Rh, Pt, Fe, Os, Cu, Ir, Pd, W, or Co is preferable. Ru, Fe, Os or Co is more preferable.

○ Ligand A ⁰¹
The ligand A ⁰¹ is not particularly limited as long as it can be a ligand of the above general formula, but is preferably isothiocyanate, isocyanate, isoselenocyanate or a halogen atom.

○ Counter anion CI1
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 the counter ion 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. Of these, tetrabutylammonium is preferable.

  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. Further, 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.

* N0 represents the integer of 0-2, it is preferable that it is 1-2, and it is more preferable that it is 2. When there are a plurality of groups (ligands) whose number is defined by n, they may be different or the same. n1 represents an integer of 0 to 4, preferably 0 to 2, and more preferably 0 to 1. When there are a plurality of anions whose number is defined by n1, they may be different from each other or the same.

○ Ligand L ¹
In the general formula (2), S ¹ and S ² are at least one selected from an ethenylene group, an ethynylene group and an arylene group. Also good. S ¹ and S ² are preferably an ethenylene group or an ethynylene group.
Ligand L ¹ are those represented by the following general formula (2), preferred are those defined below.
[In General Formula (2), R ¹ and R ² are each independently an alkyl group, an alkoxy group, or General Formulas (3), (5), (6), (7), (10), (12) , And (19). S ¹ and S ² are each independently at least one selected from an ethenylene group and an ethynylene group, and are conjugated to R ¹ , R ² and bipyridine. l1 and l2 represent the integer of 0-3. R ³ and R ⁴ represent independently a substituent, n2 is may form one or more when R3 are linked to S1 ring, R ⁴ when n3 is 1 or more are linked with S ² A ring may be formed. When n2 is 2 or more, R ³ together may be the same or different, may form a ring. When n3 is 2 or more, R ⁴ may be the same or different, and may be connected to each other to form a ring. When both n2 and n3 are 1 or more, R ³ and R ⁴ may be linked to form a ring. However, n2 and n3 each represent a integer of 0 to 2, ^{A 1} and ^{A 2} represents an acidic group or a salt thereof. n4 and n5 each represent an integer of 0-2. n8 represents 0. ]
Further preferred are those defined below.
[In General Formula (2), R ¹ and R ² each independently represents an alkyl group, an alkoxy group, or any one of General Formulas (3), (7), (12), and (19). S ¹ and S ² are each independently an ethenylene group, which is conjugated with R ¹ , R ² and bipyridine. l1 and l2 represent an integer of 0-2. n2 and n3 each represents an integer of 0 to 1. R ³ and R ⁴ independently represent a substituent. When n2 is 1, R ³ may be linked to S ¹ to form a ring, and when n3 is 1, R ⁴ is linked to S ² A ring may be formed. When n2 and n3 are both 1, R ³ and R ⁴ may be linked to form a ring. A ¹ and A ² represent an acidic group or a salt thereof. n4 and n5 each represents an integer of 0 to 1. n8 represents 0. ]

［Ｒ^４７、Ｒ^４８はそれぞれ独立に、その少なくとも１つは酸性基またはその塩である。Ｒ^４９及びＲ^５０はそれぞれ独立に水素原子またはアルキル基を表す。］ ○ Ligand L ²
Ligands L ² are those represented by the general formula (17), it is preferably represented by the following general formula (18).

[R ⁴⁷ and R ⁴⁸ are each independently at least one of an acidic group or a salt thereof. R ⁴⁹ and R ⁵⁰ each independently represent a hydrogen atom or an alkyl group. ]

(Acidic group)
The dye having the structure represented by the general formula (1) preferably has at least one suitable acidic group for bonding to the surface of the semiconductor fine particles. It is more preferable to have 1 to 6 bonding groups in the dye, and it is particularly preferable to have 1 to 4 bonding groups. Carboxyl group, sulfonic acid group, hydroxyl group, hydroxamic acid group (for example, —CONHOH, etc.), 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). The acidic groups of the described, each independently, a carboxyl group, a phosphoric acid group, a sulfonic acid Motoma other salts thereof.

Specific examples of the metal complex dye represented by the general formula (1) are shown below, but the present invention is not construed as being 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.
The metal complex dyes A-13 to A-15, A-26 to A-28, T-13 to T-15, and Q-13 to Q-15 are reference examples.

For the method for synthesizing the metal complex dye, known production methods can be referred to, for example, Journal of Photochemistry and Photobiology A: Chemistry, 145 (2001) 117, Inorganic Chemistry, 35 (1996) 4779, WO2004 / 099128A1, JPA2001-139587, JPA2001-302558, JPA2007-302642, JPA2007-332098, JPB4377148, etc. can be referred to. In addition, the dye represented by the general formula (1) can be prepared by a conventional method with reference to JP-A-2001-291534. The amounts of semiconductor fine particles and metal complexes applied in the photoreceptor layer of the photoelectric conversion element of the present invention will be described later in the description of the element.
The values of the maximum absorption wavelength (solution absorption) are shown below for some of the exemplified compounds.
Dye number Maximum absorption wavelength (nm)
A-1 560
A-2 550
A-3 543
A-4 538
A-5 540
A-6 546
A-7 527
A-8 534
B-1 520 (Refer to the description of Examples below)
B-2 533 (Refer to the description of Examples below)

<Substituent T>
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 A group (preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (preferably heterocyclic groups 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) , For example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl groups (preferably C2-C20 alkoxycarbonyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.) ), Amino group (preferably carbon Amino group having 0 to 20 children, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfonamide group (preferably sulfonamide having 0 to 20 carbon atoms) A group such as N, N-dimethylsulfonamide, N-phenylsulfonamide, etc., an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms such as acetyloxy, benzoyloxy, etc.), a carbamoyl group (preferably A carbamoyl group having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.) , A cyano group, or a halogen atom (eg, fluorine atom, chlorine atom, bromine atom) More preferably an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, cyano group or halogen atom, Particularly preferred are 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.

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

[Photoelectric conversion element]
(Photoreceptor layer)
The embodiment of the photoelectric conversion element has already been described with reference to FIG. In the present embodiment, the photoreceptor layer 2 is composed of a porous semiconductor layer composed of a layer of semiconductor fine particles 22 on which a dye described later is adsorbed. This dye may be partially dissociated in the electrolyte. The photoreceptor layer 2 may be designed according to the purpose and may have a multilayer structure.
As described above, since the photosensitive layer 2 includes the semiconductor fine particles 22 on which a specific dye is adsorbed, the light receiving sensitivity is high, and when used as the photoelectrochemical cell 100, high photoelectric conversion efficiency can be obtained. Furthermore, it has high durability.

(Charge transfer body)
The electrolyte composition used for the photoelectric conversion element 10 of the present invention includes, for example, a combination of iodine and iodide (for example, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.) as an oxidation-reduction pair, alkyl Combinations of viologens (for example, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate) and reduced forms thereof, combinations of polyhydroxybenzenes (for example, hydroquinone, naphthohydroquinone, etc.) and oxidized forms thereof, bivalent and trivalent And a combination of iron complexes (for example, red blood salt and yellow blood salt). 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 (1) is not an iodine salt, republished WO95 / 18456, JP-A-8-259543, Electrochemistry, Vol.65, No.11, p.923 (1997) It is preferable to use iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts described in the above.

  The electrolyte composition used for the photoelectric conversion element 10 of the present invention 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 used for the photoelectric conversion element 10 of the present invention 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, those having a low viscosity and high ion mobility, a high dielectric constant and capable of increasing the effective carrier concentration, or both are preferable because they 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 Nitrile compounds (acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, biscyanoethyl ether, etc.), esters (carboxylic esters, phosphate esters, phosphonates, 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 of the present invention, a charge transport layer containing a hole conductor material may be used. As the hole conductor material, a 9,9'-spirobifluorene derivative or the like can be used.

  In addition, an electrode layer, a photoreceptor layer (photoelectric conversion layer), a charge transfer layer (hole transport layer), a conductive layer, and a counter electrode layer can be sequentially stacked. A hole transport material that functions as a p-type semiconductor can be used as the 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)).

(Conductive support)
As shown in FIG. 2, in the photoelectric conversion element of the present invention, a photosensitive layer 2 in which a sensitizing dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1. As will be described later, for example, the photoreceptor layer 2 can be produced by immersing the dispersion of semiconductor fine particles in the dye solution of the present invention after coating and drying on a conductive support.

As the conductive support 1, glass or a polymer material having a conductive film on the surface can be used as the support itself, such as metal. The conductive support 1 is preferably 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 1, 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 1, 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 JP-A-2002-260746 is improved.

  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.

(Semiconductor fine particles)
As shown in FIG. 2, in the photoelectric conversion element 10 of the present invention, a photosensitive layer 2 in which a sensitizing dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1. As will be described later, for example, the photoreceptor layer 2 can be produced by immersing the dispersion of the semiconductor fine particles 22 on the conductive support 1 and then immersing it in the above dye solution. In the present invention, the semiconductor fine particles prepared using the specific surfactant are applied.

(Semiconductor fine particle dispersion)
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 whole of the semiconductor fine particle dispersion is applied to the conductive support 1 and heated appropriately. Quality semiconductor fine particle coating layer can be obtained.

  In addition to the sol-gel method, semiconductor fine particle dispersions can be prepared by depositing fine particles in a solvent and using them as they are when synthesizing semiconductors. Or a method of pulverizing and grinding mechanically using a mill or a mortar. As the dispersion solvent, one or more of water and 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 will aggregate and cannot be formed into a film. Conversely, if the viscosity of the semiconductor fine particle dispersion is too low, the liquid will flow and cannot be formed into 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. No. 2,681,294, etc., the extrusion 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 of the present invention 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 1 is increased, and it becomes easy to apply the semiconductor fine particle dispersion. .

The preferred thickness of the entire semiconductor fine particle layer is 0.1 μm to 100 μm. The thickness of the semiconductor fine particle layer is further preferably 1 μm to 30 μm, and more preferably 2 μm 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 g to 100 g. The method for forming the film by applying the fine particle dispersion is not particularly limited, and a known method may be applied as appropriate.

The coating amount of the semiconductor fine particles 22 per 1 m ² of the support is preferably 0.5 g to 500 g, more preferably 5 g to 100 g.

  In order to adsorb the sensitizing dye 21 to the semiconductor fine particles 22, it is preferable to immerse the well-dried semiconductor fine particles 22 in a dye adsorbing dye solution comprising the solution and the dye according to the present invention for a long time. The solution used for the dye solution for dye adsorption can be used without particular limitation as long as it can dissolve the sensitizing dye 21 according to the present invention. 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.

The total amount of the sensitizing dye 21 used is preferably from 0.01 mmol to 100 mmol, more preferably from 0.1 mmol to 50 mmol, and particularly preferably from 0.1 mmol to 10 mmol, per 1 m ² of the support. . In this case, the amount of the sensitizing dye 21 according to the present invention is preferably 5 mol% or more.

  Further, the adsorption amount of the sensitizing dye 21 to the semiconductor fine particles 22 is preferably 0.001 mmol 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. On the other hand, when the amount of the dye is small, the sensitizing effect is insufficient, and when the amount of the dye is too large, the dye not attached to the semiconductor floats and causes the sensitizing effect to be reduced.

  The counter electrode 4 functions as a positive electrode of the photoelectrochemical cell. The counter electrode 4 is usually synonymous with the conductive support 1 described above, but a support for the counter electrode 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 4 include platinum, carbon, and conductive polymer. Preferable examples include platinum, carbon, and conductive polymer.

  The structure of the counter electrode 4 is preferably a structure having a high current collecting effect. Preferable examples include JP-A-10-505192.

  The light receiving electrode 5 may be a tandem type in order to increase the utilization rate of incident light. Preferred examples of the tandem type configuration include those described in JP-A Nos. 2000-90989 and 2002-90989.

  A light management function for efficiently performing light scattering and reflection inside the layer of the light receiving electrode 5 may be provided. Preferably, the thing of Unexamined-Japanese-Patent No. 2002-93476 is mentioned.

  It is preferable to form a short-circuit prevention layer between the conductive support 1 and the porous semiconductor fine particle layer in order to prevent a reverse current due to direct contact between the electrolyte and the electrode. Preferable examples include Japanese Patent Application Laid-Open No. 06-507999.

  In order to prevent contact between the light receiving electrode 5 and the counter electrode 4, it is preferable to use a spacer or a separator. A preferable example is JP-A No. 2001-283941.

  Cell and module sealing methods include polyisobutylene thermosetting resin, novolak resin, photo-curing (meth) acrylate resin, epoxy resin, ionomer resin, glass frit, method using aluminum alkoxide for alumina, low melting point glass paste It is preferable to use a laser melting method. When glass frit is used, powder glass mixed with acrylic resin as a binder may be used.

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

(Preparation example) Preparation of semiconductor fine particles
According to the method described in Palani Balaya et al., Energy & Environmental Science, 2010, 3, 838-845, 16.4 g of cetyltrimethylammonium bromide (CTAB) is mixed with water: absolute ethanol (volume ratio 4: 1). Dissolve in 25 L to completely dissolve CTAB. The completely dissolved CTAB solution was stirred, and 28.7 mL of Ti (OiPr) ₄ (CTAB: Ti (OiPr) ₄ = 1: 1 molar ratio) was added dropwise to the CTAB solution. After the completion of the dropwise addition, the resulting precipitate was collected by filtration after stirring for 24 hours. After being washed several times with ethanol, it was heated at 450 ° C. for 6 hours to burn off organic components, and 7.34 g (yield 71.7%) of titanium oxide fine particles having fine pores on the surface were obtained. This sample was referred to as Ti-1, and those prepared by appropriately changing the organic amine compound were described as Ti-2 to Ti-5 in the following table.
[Specific surface area measurement]
The BET method using nitrogen gas was used.
[Roughness coefficient]
Sol.Eng.Mater.Sol.Cells, 83, 2004, 1.
[Pore size of TiO ₂ fine particles and compatibility of dyes]
Judgment is made by calculating the correlation between the TiO ₂ surface and the dye and the correlation between the dyes by HPC Technology (Gaussian09 molecular orbit calculation software [trade name]). The better the color, the more regularly the dye is arranged, and the worse, the dye arrangement is disturbed.
A: Recognized as a very regular arrangement B: Recognized as an almost regular arrangement C: Recognized as a slightly irregular arrangement D: Recognized as a very irregular arrangement [Average particle size]
The dynamic light scattering photometer DLS-7000 series (all trade names) manufactured by Otsuka Electronics Co., Ltd. was used. As a sample, a 0.1% by mass dispersion liquid in which the titania fine particle powder was dispersed in methanol (MeOH) or water was used.

(Synthesis Example) Synthesis of Metal Complex Dye <Preparation of Illustrative Dye>
(Preparation of Exemplified Compound A-5)
Exemplified dye A-5 was prepared according to the method of the following scheme.

(I) Preparation of Compound d-1-2 d-1-1 25 g, Pd (dba) 33.8 g, triphenylphosphine 8.6 g, copper iodide 2.5 g, 1-heptin 25.2 g were triethylamine 70 ml. The mixture was stirred in 50 ml of tetrahydrofuran at room temperature and stirred at 80 ° C. for 4.5 hours. After concentration, 26.4 g of compound d-1-2 was obtained by purification by column chromatography.
(Ii) Preparation of d-1-4 6.7 g of d-1-3 was dissolved in 200 ml of THF (terahydrofuran) at −15 ° C. in a nitrogen atmosphere, and separately prepared LDA (lithium diisopropylamide) was d- 2.5 equivalents of 1-3 were added dropwise and stirred for 75 minutes. Thereafter, a solution obtained by dissolving 15 g of d-1-2 in 30 ml of THF was dropped, and the mixture was stirred at 0 ° C. for 1 hour, and stirred at room temperature overnight. After concentration, 150 ml of water was added, liquid separation and extraction were performed with 150 ml of methylene chloride, the organic layer was washed with brine, and the organic layer was concentrated. The obtained crystal was recrystallized from methanol to obtain 18.9 g of d-1-4.

(Iii) Preparation of Compound d-1-5 13.2 g of d-1-4 and 1.7 g of PPTS (pyridinium paratoluenesulfonic acid) were added to 1000 ml of toluene, and the mixture was heated to reflux for 5 hours in a nitrogen atmosphere. After concentration, liquid separation was performed with saturated aqueous sodium hydrogen carbonate and methylene chloride, and the organic layer was concentrated. The obtained crystal was recrystallized from methanol and methylene chloride to obtain 11.7 g of d-1-5.
(Iv) Preparation of Illustrative Dye A-5 Compound d-1-5 (4.0 g) and d-1-6 (2.2 g) were added to DMF (60 ml) and stirred at 70 ° C. for 4 hours. Thereafter, 2.1 g of d-1-7 was added and the mixture was heated and stirred at 160 ° C. for 3.5 hours. Thereafter, 19.0 g of ammonium thiocyanate was added and stirred at 130 ° C. for 5 hours. After concentration, 1.3 ml of water was added and filtered, and washed with diethyl ether. The crude product was dissolved in a methanol solution together with TBAOH (tetrabutylammonium hydroxide) and purified with a Sephadex LH-20 column. The main layer fraction was collected and concentrated, and then 0.2 M nitric acid was added. The precipitate was filtered and washed with water and diethyl ether to obtain 600 mg of crude crystals. The purified product was dissolved in a methanol solution, 1M nitric acid was added, the precipitate was filtered, and washed with water and diethyl ether to obtain 570 mg of A-5.
The structure of the obtained compound A-5 was confirmed by NMR measurement.
1H-NMR (DMSO-d6, 400 MHz): δ (ppm) in aromatic regions: 9.37 (1H, d), 9.11 (1H, d), 9.04 (1H, s), 8.89 ( 2H), 8.74 (1H, s), 8.26 (1H, d), 8.10-7.98 (2H), 7.85-7.73 (2H), 7.60 (1H, d) ), 7.45-7.33 (2H), 7.33-7.12 (5H, m), 6.92 (1H, d)
The obtained Exemplified Dye A-5 (D-1-1a) was prepared with an ethanol solvent such that the dye concentration was 8.5 μmol / l and subjected to spectral absorption measurement. The absorption maximum wavelength was 568 nm. there were.

<Preparation of exemplary dye>
Exemplified dye A-1 was prepared by the following method.

  4,4′-bis [2- (5-hexyl-2-thienyl) vinyl] -2,2′-bipyridine (0.30 g, 0.49 mmol) and dichloro (p-cymene) ruthenium (II) dimer A solution (0.15 g, 0.24 mmol) of DMF in 25 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 (0.24 g, 0.98 mmol) was added and heated at 150 ° C. for 10 minutes. The temperature was cooled to 100 ° C., ammonium thiocyanate (1.6 g, a solution of 10 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. 150 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 Sephadex LH-20 column 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 0.63 g of ruthenium complex A-1.

(Example / Comparative Example) Production of photoelectric conversion element [Experiment 1]
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 titanium oxide described in Table 1 is blended in 100 ml of a mixed solvent having a volume ratio of 4: 1 of water and acetonitrile, and dispersed and mixed uniformly using a mixing conditioner of both rotation and revolution. A fine particle dispersion was obtained. 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 a porous body. Formed. Next, a carbon electrode was formed as a counter electrode.

Next, the glass substrate on which the porous body was formed was immersed in an ethanol solution (3 × 10 ⁻⁴ mol / L) of the metal complex dye described in Table 1 below for 48 hours. The glass stained with the dye was immersed in a 10% ethanol solution of 4-tert-butylpyridine for 30 minutes, and then washed with ethanol and dried naturally. 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 photoelectric conversion characteristics were measured with a current-voltage measuring device (Keithley 238 type, trade name).

The results of measuring the conversion efficiency of the photoelectrochemical cell are shown in Table 1 below. A photoelectrochemical cell having a conversion efficiency of 8.0% or more is ◎, a cell having a conversion efficiency of 5.0% or more and less than 8.0% is ○, a cell having a conversion efficiency of 2.0% or more and less than 5.0% is Δ, or 2. Less than 0% was indicated as x. A conversion efficiency of 5.0% or more was regarded as acceptable.
As comparative dyes, the following B-1 and B-2 were used.

  As shown in Table 1, the photoelectrochemical cell produced using the dye of the present invention has a conversion efficiency of 8.0% or more, particularly when the dye shown in Table 1 below is used. High value was shown. Even when other dyes of the present invention were used, the conversion efficiency was as high as 5.0% or more. In contrast, in the photoelectrochemical cell using the comparative dye, the conversion efficiency could not reach the acceptable level.

[Experiment 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 compound 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 is formed by dispersing titanium oxide fine particles listed in Table A in acetonitrile to form a paste, which is applied to the transparent electrode 11 to a thickness of 15 μm by the bar coating method, and dried at 450 ° C. The baking was carried out for 1 hour. Thereafter, the dyes listed in Table 2 were supported on the oxide semiconductor porous membrane.

  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, and an electrolyte solution made of a non-aqueous solution of iodine / iodide was used for the electrolyte layer. The planar dimension of the photoelectrochemical cell was 25 mm × 25 mm.

(5) Evaluation of photoelectrochemical cell The photoelectrochemical cell obtained in (4) was irradiated with simulated sunlight (AM1.5), the photoelectric conversion characteristics were measured in the same manner as in Experiment 1, and the conversion efficiency Asked. The results are shown in Table 2. Conversion efficiency of 8.0% or more is ◎, 5.0% or more and less than 8.0% ○, 2.0% or more and less than 5.0% △, less than 2.0% Was displayed as x. A conversion efficiency of 5% or more was accepted.

  The photoelectrochemical cell using the comparative dye failed in conversion efficiency, whereas the photoelectrochemical cell using the dye of the present invention had high conversion efficiency and was at an acceptable level. In particular, in the photoelectrochemical cell of the present invention using a laminate of an ITO film and an FTO film as a transparent electrode plate, the conversion efficiency is particularly higher than when using only an ITO film or an FTO film. Was found to be expensive.

[Experiment 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 is chemically cleaned and dried, then this glass plate is placed in a reactor, heated with a heater, and then FTO (fluorine-doped tin oxide) used in Experiment 2 above The membrane raw material compound solution was sprayed for 25 minutes from a nozzle with a diameter of 0.3 mm at a pressure of 0.06 MPa and a distance to the glass plate of 400 mm 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 by sputtering to enable plating formation, and a metal wiring layer was further formed by additive plating. The metal wiring layer was formed in a convex lens shape from the transparent substrate surface 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.

  The titanium oxide dispersion described in Table A was applied and dried on the electrode substrate (i), and heated and sintered at 450 ° C. for 1 hour. This was immersed in an ethanol solution of the dye shown in Table 3 for 40 minutes to carry the dye. In addition, preliminary studies were conducted on the solubility of the dye used in the present invention in various organic solvents. As a result, it was found that it could be dissolved in toluene. Therefore, as shown in Table 3, a solution infiltrated and supported in a toluene solution for 40 minutes was also prepared.

  The platinum sputtered FTO substrate and the substrate were placed facing each other through a 50 μm-thick thermoplastic polyolefin resin sheet, and the resin sheet portion was heat-melted to fix the bipolar plates.

  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. Furthermore, the peripheral part and the electrolyte solution injection port were sealed with an epoxy-based sealing resin, and a silver paste was applied to the current collecting terminal part to obtain a test cell (i). The test cell (i) was irradiated with AM1.5 artificial sunlight in the same manner as in Experiment 1, and the conversion efficiency was measured. The results are shown in Table 3.

(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). On the FTO glass substrate, a metal wiring layer (gold circuit) was formed by additive plating. The metal wiring layer (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 by the SPD method to obtain an electrode substrate (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 bottom 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). AM1.5 simulated sunlight was irradiated in the same manner as in Experiment 1, and the conversion efficiency was measured. The results are shown in Table 3.

  The results of measuring the conversion efficiency of the photoelectrochemical cell are shown in Table 3. Conversion efficiency of 8.0% or more is ◎, 5.0% or more and less than 8.0% ○, 2.0% or more and less than 5.0% △, less than 2.0% Was displayed as x.

  From Table 3, the conversion efficiency of the test cell (i) using the dye of the present invention was a pass level of 5.0% or more. On the other hand, for the test cell (iv), the conversion efficiency was higher when the dye of the present invention was used, compared to the case where the dye of the comparative example was used. For this reason, it was found that the degree of freedom of test cell selection is increased by using the dye of the present invention.

[Experiment 4]
Peroxotitanic acid and titanium oxide fine particles were prepared, and an oxide semiconductor film was prepared using them. Using this, a photoelectrochemical cell was prepared and evaluated.
(Production of photoelectrochemical cell (a))
(1) Preparation of coating liquid for forming oxide semiconductor film (a1) 90% by volume is fractioned from the total amount of the following solution, adjusted to pH 9 by adding concentrated aqueous ammonia, placed in an autoclave, and 5% at 250 ° C. The titania colloidal particles (a2) were prepared by performing hydrothermal treatment for a period of time under saturated vapor pressure. The obtained titania colloidal particles were anatase type titanium oxide having high crystallinity by X-ray diffraction.

Next, titania fine particles (Ti-1) shown in Table A were suspended in 5 liters of titanium hydride in 1 liter of pure water, and 400 g of a 5% by mass hydrogen peroxide solution was added over 30 minutes. was dissolved by heating to 80 ° C. a solution of peroxotitanate mixed with peroxotitanate solution was prepared by the titanium of the mixed solution TiO ₂ terms, film formed to be 30 mass% of TiO ₂ by weight Hydroxypropylcellulose was added as an auxiliary agent to prepare a coating solution (a1) for forming a semiconductor film.

(2) Production of Oxide Semiconductor Film (a3) Next, the coating liquid (a1) is applied on a transparent glass substrate on which fluorine-doped tin oxide is formed as an electrode layer, air-dried, and then a low-pressure mercury lamp is used. It was used to irradiate ultraviolet rays of 6000 mJ / cm ² to decompose the peroxo acid and harden 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 (a3) on the glass substrate.
(3) Adsorption of dye to oxide semiconductor film (a3) Next, an ethanol solution having a concentration of 3 × 10 ⁻⁴ mol / liter of the dye of the present invention was prepared as a spectral sensitizing dye. This dye solution was applied onto the metal oxide semiconductor film (a3) 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 photoelectrochemical cell (a) The glass substrate on which the oxide semiconductor film (a3) adsorbed with the dye produced in (2) is formed is used as one electrode, and fluorine doped as the other electrode. A transparent glass substrate on which platinum oxide is formed as an electrode and platinum supported thereon is placed oppositely, the side surfaces are sealed with resin, the electrolyte solution (4) is sealed between the electrodes, A photoelectrochemical cell (a) was prepared by connecting with lead wires.
(6) Evaluation of Photoelectrochemical Cell (a) The photoelectrochemical cell (a) was irradiated with light having an intensity of 100 W / m ^{2 by} a solar simulator, and η (conversion efficiency) was measured.

(Photoelectrochemical cell (b))
The oxide semiconductor film (a3) except that after irradiation with ultraviolet rays decomposes the peroxo acid and cures the film, Ar gas ion irradiation (Nisshin Electric: ion implantation apparatus, irradiation at 200 eV for 10 hours) is performed. ), An oxide semiconductor film (b3) was formed.

  Similar to the oxide semiconductor film (a), the dye was adsorbed on the oxide semiconductor film (b3).

  Thereafter, a photoelectrochemical cell (b) was prepared in the same manner as in Example 1, and η was measured.

(Photoelectrochemical 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 and 400 g of a 5% by mass hydrogen peroxide solution were mixed and then heated to 80 ° C. to dissolve to prepare a peroxotitanic acid solution.

  Next, an oxide semiconductor film (c3) is formed in the same manner as the oxide semiconductor film (a3) using the peroxotitanic acid solution obtained above and the titania fine particles (Ti-1) shown in Table 1. In the same manner as in the metal oxide semiconductor film (a3), the dye of the present invention was adsorbed as a spectral sensitizing dye.

  Thereafter, a photoelectrochemical cell (c) was produced in the same manner as the photoelectrochemical cell (a), and η was measured.

  With respect to the photoelectrochemical cells (a) to (c), simulated sunlight (AM1.5) was irradiated, the photoelectric conversion characteristics were measured in the same manner as in Experiment 1, and the conversion efficiency was obtained. The results are shown in Table 4. Conversion efficiency of 8.0% or more is ◎, 5.0% or more and less than 8.0% ○, 2.0% or more and less than 5.0% △, less than 2.0% Was displayed as x.

  From Table 4, it was found that the conversion efficiency was particularly high in the case of the photoelectrochemical cells (a) to (c) prepared using the dye of the present invention.

<Experiment 5>
A dye-sensitized solar cell was produced according to the following method.
(1) Production of transparent conductive support As a support for a photosensitive electrode, a conductive tin oxide thin film is uniformly coated at a thickness of 200 nm on one side of a 0.4 mm-thick sheet whose surface is fluorine-coated. Thus, a flexible transparent conductive support was used.

(2) Production of conductive sheet for counter electrode A polyimide Kapton (registered trademark) film having a thickness of 0.4 mm was uniformly coated with a platinum film having a thickness of 300 nm on one side by a vacuum sputtering method. The sheet resistance was 5 Ω / cm ² .

(3) Preparation of semiconductor fine particle dispersion The titanium oxide fine particles listed in Table A were added at a concentration of 32 g per 100 cc of solvent to 100 cc of a mixed solvent having a volume ratio of 4: 1 of water and acetonitrile. The mixture was uniformly dispersed and mixed using a mixing conditioner. As a result, the obtained white semiconductor fine particle dispersion became a paste with a high viscosity of 50 to 150 N · s / m ² , and was found to have liquid properties suitable for use as it is. In Sample No. 12-6, 7.7 g of polyethylene glycol (PEG) powder having an average molecular weight of 500,000 was blended per 100 cc of solvent. Solids other than the semiconductor fine particles were not added to the other semiconductor fine particle dispersions.

(4) Measurement of solid content in semiconductor fine particle dispersion liquid The dispersion liquid was applied to a non-alkali glass substrate having a thickness of 1.9 mm with an applicator, applied to a thickness of 40 to 70 μm, and dried at room temperature for 1 hour. . Thereafter, the sample was heated in air at 350 ° C. for 0.5 hour, and the change in weight before and after heating was measured. As a result, the solid content other than the semiconductor fine particles of Sample No. 12-6 was 1%. The solid content of the sample other than the semiconductor fine particles was 0.3%.

(5) Production of semiconductor fine particle layer On the transparent conductive support prepared in (1), the dispersion prepared in (3) is applied with an applicator, and dried at room temperature for 1 hour. A coating layer having a uniform thickness was formed. Furthermore, this coating layer was processed under the conditions described in Table 12 to prepare a porous semiconductor fine particle layer for dye sensitization. The final average film thickness of the porous semiconductor fine particle layer was 6 to 7 μm.

(6) Preparation of Dye Adsorption Solution Dye concentration is 1 × 10 −4 mol / liter in a 2: 1: 1 mixed solvent of acetonitrile: t-butanol: ethanol by drying the dyes shown in Table 17. It dissolved so that it might become. As an additive to the dye _{solution, p-C 9 H 19 -C} 6 H 4 -O- (CH 2 CH 2 -O) 3 - (CH 2) 0 to 4 _-SO 3 Na organic sulfonic acid derivative of structure A solution for dye adsorption was prepared by dissolving at a concentration of 0.025 mol / liter.

(7) Adsorption of dye The substrate on which the porous semiconductor fine particle layer was coated was immersed in the dye solution for adsorption described above and allowed to stand at 40 ° C for 3 hours with stirring.
In this manner, a dye was adsorbed on the semiconductor fine particle layer to prepare a dye-sensitized electrode (photosensitive electrode) used for the photosensitive layer.

(8) Production of dye-sensitized solar cell The porous semiconductor fine particle layer adsorbed with the dye was scraped off to form a circular photosensitive electrode having a light receiving area of 1.0 cm ² (diameter: about 1.1 cm). A counter-plated platinum-deposited glass substrate is superimposed on this electrode by inserting a thermo-compressible polyethylene film frame spacer (thickness 20 μm), and the spacer portion is heated to 120 ° C. to pressure-bond both substrates. . Furthermore, the edge part of the cell was sealed with an epoxy resin adhesive. Through a small hole for electrolyte solution injection provided in advance in the corner of the counter electrode substrate, the room temperature is composed of any imidazolium ions E1 to E4 / iodine = 50: 1 (mass ratio) described later as the electrolyte. Molten salt was impregnated into the space between the electrodes from the small holes of the substrate using capillary action.
E1: 1,2-dimethyl-3-propylimidazolium iodide E2: 1-butyl-3-methylimidazolium iodide E3: 1-methyl-3-propylimidazolium iodide E4: 1,3-di (2- ( 2- (2-Methoxyethoxy) ethoxy) ethyl) imidazolium iodide The above cell assembly process and electrolyte injection process were all performed in dry air having the above dew point of −60 ° C. After injecting the molten salt, the cell was sucked for several hours under vacuum to deaerate the inside of the cell including the photosensitive electrode and the molten salt, and finally the small holes were sealed with low-melting glass. Thus, a dye-sensitized solar cell in which a conductive support, a porous semiconductor fine particle electrode (photosensitive electrode) on which a dye was adsorbed, an electrolytic solution, a counter electrode, and a support were sequentially laminated was produced.

About the dye-sensitized solar cell produced above, it evaluated as follows. The results are shown in Table B below. In addition, all titania fine particles used Ti-1.
<Conversion efficiency>
Measurement was performed in the same manner as in Experiment 1 above. However, the result is shown as a value of conversion efficiency.

<Dye adsorption amount>
The dye once adsorbed on titanium oxide as a battery (cell) is immersed in a methanol solution of tetrabutylammonium hydroxide (TBAOH) together with the substrate on which titanium oxide is placed, so that the dye is desorbed. The amount of the dye adsorbed on the titanium oxide is calculated by measuring this solution with a UV-Vis spectrum absorption spectrum and calculating the concentration of the dye dissolved in the solution.

<Compatibility of pores and pigments of titania fine particles>
Measurement and evaluation were performed in the same manner as described above.

<Maximum absorption wavelength>
This measurement was performed with a spectrophotometer (U-4100 (trade name), manufactured by Hitachi High-Tech), and the solution was prepared using THF: ethanol = 1: 1 so that the concentration was 2 μM.

  As described above, the photoelectric conversion element using the dye and conductive fine particles of the present invention exhibits a high adsorption amount and good compatibility of the dye to the fine particles, exhibits high conversion efficiency (see Table A and the like), High durability performance was demonstrated (see Experiment 1 etc.). On the other hand, although the compound of the comparative example used a ruthenium complex and titania fine particles as in the present invention, it resulted in inferior photoelectric conversion efficiency and device durability. This difference is considered to be mainly due to the interaction between the hydrophobic group introduced into the side chain of the ruthenium complex and the pores on the titania surface.

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

Claims (13)

A semiconductor microparticles prepared using a cationic surfactant represented by the following formula (I), an average particle diameter of the semiconductor fine particles is 1 to 20 nm, the roughness factor is at 1000-1500, and A photoelectric conversion element comprising titanium oxide particles having a specific surface area of 50 to 400 m ² / g , wherein a metal complex dye represented by the following general formula (1) is adsorbed on the semiconductor fine particles to form a photoreceptor layer. Production method.

ML ¹ L ² (A ⁰¹ ) _n0 (CI1) _n1 ... General formula (1)

(In general formula (1),
M represents a metal element,
A ⁰¹ represents a ligand,
CI1 represents a counter anion,
-N0 represents the integer of 0-2, n1 represents the integer of 0-4.
L ¹ represents a ligand represented by the following general formula (2), and L ² represents a ligand represented by the following general formula (17). L ¹ and L ² may be linked to each other at the ortho position of the pyridine ring (position adjacent to the N atom) to form a quarterpyridine ligand. )

[In general formula (2),
R ¹ , R ² and R ⁵ each independently represent any of the following general formulas (3) to (11), (13-2) or (14) to (16).
S ¹ , S ² and S ³ are each independently at least one selected from an ethenylene group, an ethynylene group and an arylene group, and are conjugated to R ¹ , R ² , R ⁵ and a pyridine ring. l1, l2 and l3 each represents an integer of 0 to 5;
R ³ , R ⁴ and R ⁶ independently represent an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, cyano group or halogen atom. , N2 and n7 each represents an integer of 0 to 3, n3 represents an integer of 0 to 2, and when n2 is 1 or more, R ³ may be linked to S ¹ to form a ring, When it is 1 or more, R ⁴ may be linked to S ² to form a ring, and when n7 is 1 or more, R ⁶ may be linked to S ³ to form a ring. When n2 is 2 or more, R ³ together may be the same or different, may form a ring. When n3 is 2 , R ⁴ may be the same or different, and may be connected to each other to form a ring. When n7 is 2 or more, R ⁶ may be the same or different, and may be connected to each other to form a ring. When n2, n3 and n7 are all 1 or more, R ³ , R ⁴ and R ⁶ may be linked to form a ring.
· ^A 1, ^{A 2} and ^{A 3} represents an acidic group or a salt thereof independently. n4, n5 and n6 each represents an integer of 0 to 3. n8 represents 0 or 1. ]

[In General Formulas (3) to (11) and (16), R ^{7 to} R ³⁵ , R ^{52 to} R ⁵⁵ , R ⁶¹ , R ⁶² and R ⁶⁹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, An alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an amino group, a heterocyclic group, or a halogen atom is represented. R ⁵¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group or a halogen atom. R ⁶⁸ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group or a halogen atom. R ⁶⁹ and ^{R 7, R 9 ~R 12,} R 14 and ^{R 15, R 17} and ^{R 18, R 20 ~R 23,} R 25 and ^{R 26, R 28 ~R 31,} R 32 and ^{R 33, R 34} And R ³⁵ and R ^{52 to} R ⁵⁵ may form a ring with each other. ^{R 24} and ^{R 27} there are two to the same nitrogen atom, two ^{R 24} s or two ^{R 27} each other may be the same as or different from each other and two ^{R 24} s or two ^{R 27} each other may be bonded to each other to form a ring. m1-m9 and m11 represent the integer of 1-5.
In the general formulas (13-2), (14) and (15), R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy Represents a group, an arylthio group, an amino group, a heterocyclic group or a halogen atom. R ^{65 to} R ⁶⁷ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a halogen atom.
Y ^{1 to} Y ³ and X each independently represent S, O, Se, Te or NR ⁴² , and R ⁴² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. ]

[In the general formula (17), four R ⁴⁷ present in the same pyridine ring are each independently at least one of which is an acidic group or a salt thereof, and the remaining R ⁴⁷ represents a hydrogen atom or an alkyl group. Four R ^48s present in the same pyridine ring are each independently at least one of which is an acidic group or a salt thereof, and the remaining R ⁴⁸ represents a hydrogen atom or an alkyl group. ]

[In the general formula (I), R ^{43 to} R ⁴⁶ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group. CI2 represents a counter anion. ] In the general formula ^{(I), R} 43 ~R ⁴⁶ is a method for manufacturing a photoelectric conversion element according to claim 1 is an alkyl group having 1 to 30 carbon atoms. In the general formula ^{(I), R} 43 ~R ⁴⁶ is a method for manufacturing a photoelectric conversion element according to claim 2 is an alkyl group of 3-27 carbon atoms. The said metal complex pigment | dye is the following, The manufacturing method of the photoelectric conversion element of any one of Claims 1-3 .
In formula (2), the ^{R 1} and ^{R 2} are each independently the general formula (3), (5), (6), (7), is either (10) and (16). S ¹ and S ² are each independently at least one selected from an ethenylene group and an ethynylene group, and are conjugated with R ¹ , R ² and bipyridine. l1 and l2 are integers of 0-3. R ³ and ^{R 4} are substituents on independently, ^{R 3} when n2 is 1 or more may form a ring with S1, ^{R 4} when n3 is 1 or more is connected with ^{S 2} May form a ring. When n2 is 2, R ³ together may be the same or different, may form a ring. When n3 is 2 , R ⁴ may be the same or different, and may be connected to each other to form a ring. When both n2 and n3 are 1 or more, R ³ and R ⁴ may be linked to form a ring. However, n2 and n3 are each 0 to 2 integer, ^{A 1} and ^{A 2} is an acidic group or a salt thereof. n4 and n5 are each an integer of 0-2. n8 is 0.
In the general formulas (3), (5), (6), (7), (10) and (16), R ⁷ , R ^{13 to} R ²³ , R ³² , R ³³ , R ⁵¹ , R ⁶¹ and R ⁶⁹ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a halogen atom. R ⁶⁸ is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or a halogen atom. R ⁶⁹ and ^{R 7, R 14} and ^{R 15, R 17} and ^{R 18, R 20 ~R 23,} R 32 and ^{R 33, R} 52 ^{~R 55} may have each other to form a ring. m1, m3-m5, m8 and m11 are integers of 1-3. The Y ¹ to Y ³ are each independently, S, O, Se, a Te or ^{NR 42, R 42} is a hydrogen atom or an alkyl group.
Ligand represented by the general formula (17) is a ligand represented by the following general formula (18).

[In General Formula (18), R ⁴⁷ and R ⁴⁸ each independently represent a hydrogen atom, an alkyl group, an acidic group or a salt thereof, and at least one of R ⁴⁷ and R ⁴⁸ is an acidic group or a salt thereof. R ⁴⁹ and R ⁵⁰ each independently represent a hydrogen atom or an alkyl group. ] The method for producing a photoelectric conversion element according to claim 4 , wherein the metal complex dye is as follows.
In the general formula (2), R ¹ and R ² are each independently any one of the general formulas (3), (7), and (16). S ¹ and S ² are each independently an ethenylene group, which is conjugated with R ¹ , R ² and bipyridine. l1 and l2 are integers of 0-2. n2 and n3 are each 0 or 1. R ³ and R ⁴ are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, cyano group or halogen atom , and n2 is 1 In this case, R ³ may be linked to S ¹ to form a ring, and when n 3 is 1, R ⁴ may be linked to S ² to form a ring. When n2 and n3 are both 1, R ³ and R ⁴ may be linked to form a ring. A ¹ and ^{A 2} is an acidic group or a salt thereof. n4 and n5 are each 0 or 1. n8 is 0.
Formula (3), in (7) and ^{(16), R 7, R} 19 ~R 23, R 51 ~R 55 and ^{R 69} is a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. R ⁶⁸ is an alkyl group, alkenyl group or alkynyl group. R ⁶⁹ and R ⁷ , R ^{20 to} R ²³ , and R ^{52 to} R ⁵⁵ may form a ring with each other. m1, m5 and m11 is 1 or 2. The Y ¹ to Y ³ are each independently, S, O or ^{NR 42, R 42} is a hydrogen atom or an alkyl group.
In the general formula ^(18), the ^{R 47} and ^{R 48} are each independently an acid group or a salt ^{thereof, R 49} and ^{R 50} are hydrogen atoms. The metal element M of the metal complex dye, Ru, Re, Rh, Pt , Fe, Os, Cu, Ir, Pd, photoelectric conversion element according to any one of claims 1 to 5, which is a W or Co Manufacturing method . The method for producing a photoelectric conversion element according to claim 6 , wherein the metal element M is Ru, Fe, Os, or Co. Method of manufacturing a photoelectric conversion device according to any one of claims 1 to 7, wherein Y ¹ is S atom. The acidic groups A ¹ , A ² and A ^{3 of} the general formula (2) and the acidic groups of the general formulas (17) and (18) are each independently a carboxyl group, a phosphoric acid group, a sulfonic acid group or a salt thereof. The method for producing a photoelectric conversion element according to any one of claims 1 to 8 . Process for producing a photovoltaic device according to any one of claims. 1 to 9 CI1 is tetrabutylammonium the general formula (1). A ⁰¹ isothiocyanate ligands of the general formula (1), an isocyanate, a method for manufacturing a photoelectric conversion device according to any one of claims 1 to 10 which is isoselenocyanate or halogen atom. The titanium oxide particles with an average particle diameter of the particles is 1 to 10 nm, with the roughness factor of 1000-1500, a specific surface area according to any one of claims 1 to 11 which is 200~250m ² / g A method for producing a photoelectric conversion element. Any manufacturing the photoelectric conversion device manufacturing method according to item 1, the resulting production method of photoelectrochemical cells causes including a photoelectric conversion element according to claim 1 to 12.

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