TWI750333B - Sensitizing dye, sensitizing dye composition for photoelectric conversion, photoelectric conversion element using the same, and dye-sensitized solar bettery - Google Patents

Abstract

[式中，Ar表示芳基； R¹ ～R⁴ 表示氫原子、鹵素原子、氰基、羥基、硝基、亞硝基、硫醇基、烷基、環烷基、烷氧基、環烷氧基、烯基、芳基、或胺基； X表示硫原子、氧原子或CR⁵ R⁶ ；R⁵ 、R⁶ 表示烷基、或芳基； Z表示1價基] 所表示之增感色素係具有廣泛之感光波長區域之新穎之增感色素，藉由將其用作光電轉換用增感色素組合物，可提供光電轉換效率高之光電轉換元件及色素增感太陽電池。The following general formula (1) of the present invention:

[In the formula, Ar represents an aryl group; R ¹ to R ⁴ represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a nitroso group, a thiol group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkane group Oxy group, alkenyl group, aryl group, or amine group; X represents a sulfur atom, an oxygen atom or CR ⁵ R ⁶ ; R ⁵ and R ⁶ represent an alkyl group or an aryl group; Z represents a monovalent group] The sensitization represented by The dye is a novel sensitizing dye having a wide photosensitive wavelength region, and by using it as a sensitizing dye composition for photoelectric conversion, a photoelectric conversion element and a dye-sensitized solar cell with high photoelectric conversion efficiency can be provided.

Description

Sensitizing dye, sensitizing dye composition for photoelectric conversion, photoelectric conversion element using the same, and dye-sensitized solar cell

The present invention relates to a sensitizing dye, a sensitizing dye composition for photoelectric conversion used in a dye-sensitized photoelectric conversion element, a photoelectric conversion element using the sensitizing dye composition for photoelectric conversion, and a dye-sensitized solar cell .

系色素等(例如，參照專利文獻1～3)。 又，作為吸附於氧化鈦等半導體粒子表面、且用以將由增感色素產生之激發電子高效率地搬運至半導體之電子吸引部，亦提出有具有二氫茚酮結構之化合物(例如，參照專利文獻4～6)。然而，該等有機色素雖然具有廉價且吸光係數較大、且藉由結構之多樣性可控制吸收特性之優點，但就光電轉換效率及經時穩定性方面而言，目前無法獲得充分滿足所要求之特性者。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開平11-214730號公報 [專利文獻2]日本專利特開平11-238905號公報 [專利文獻3]日本專利特開2011-26376號公報 [專利文獻4]日本專利特開2011-207784號公報 [專利文獻5]日本專利特開2012-51854號公報 [專利文獻6]日本專利特開2016-6811號公報 [非專利文獻] [非專利文獻1]「Nature」，(英國)，1991年，第353卷，p.737-740In recent years, carbon dioxide generated from fossil fuels such as coal, oil, and natural gas has been used as a greenhouse gas to cause global warming, or environmental damage caused by global warming, and due to the increase in population, global energy consumption has increased, and Concerns about the ongoing environmental destruction on a planetary scale. Under such circumstances, efforts have been made to study the utilization of renewable energy sources, which are different from fossil fuels and have less concern about depletion. Instead of fossil fuel-consuming thermal power generation or atomic power generation, the use of solar power, centered on solar power generation, has become increasingly important as a power generation method using the next generation of major renewable energy sources that can contribute to preventing global warming. Or portable small-scale electronic equipment for power generation and charging, to small-scale power generation facilities in houses, buildings or fallow land that can save light and heat costs, and for development or application in various fields. As a method of solar power generation, photoelectric conversion elements that convert sunlight energy into electrical energy are used in solar cells. As solar cells, monocrystalline, polycrystalline, amorphous silicon systems, gallium arsenide, and cadmium sulfide are mainly studied. , Inorganic solar cells such as compound semiconductors such as indium copper selenide, etc., are now widely used in residential and small-scale power generation facilities. However, these inorganic solar cells have the following problems: high production cost and difficulty in securing raw materials. On the other hand, although the photoelectric conversion efficiency and durability are still very low compared to inorganic solar cells, organic solar cells such as organic thin-film solar cells and dye-sensitized solar cells using various organic materials have also been developed. Organic solar cells are more advantageous than inorganic solar cells in terms of production cost, large area, light weight, thin film, light transmittance, wide absorption wavelength range, flexibility, and securing of raw materials. . Among them, a dye-sensitized solar cell proposed by Grätzel et al. (refer to Non-Patent Document 1) includes a thin-film electrode comprising a porous titanium oxide as a semiconductor, a ruthenium complex dye adsorbed on the surface of the semiconductor to extend the photosensitive wavelength region, Wet solar cells containing iodine-based electrolytes are expected to have high photoelectric conversion efficiency comparable to amorphous silicon solar cells. The dye-sensitized solar cell has attracted attention as a next-generation solar cell because the element structure is relatively simple compared with other solar cells, and it can be produced even without large-scale production equipment. As a sensitizing dye for dye-sensitized solar cells, ruthenium complexes are considered to be the best in terms of photoelectric conversion efficiency. However, since ruthenium is a noble metal, it is disadvantageous in terms of production cost, and a large amount is required for practical application. In the case of ruthenium complexes, resource constraints also become a problem. Therefore, as a sensitizing dye, research on dye-sensitized solar cells using organic dyes that do not contain precious metals such as ruthenium is prevalent. As organic dyes that do not contain precious metals, coumarin-based dyes, cyanine-based dyes, merocyanine-based dyes, rhodaniline-based dyes, phthalocyanine-based dyes, porphyrin-based dyes, and cyanine-based dyes have been reported.

dyes, etc. (for example, refer to Patent Documents 1 to 3). In addition, compounds having an indanone structure have also been proposed as an electron-attracting portion that is adsorbed on the surface of semiconductor particles such as titanium oxide and used to efficiently transport excited electrons generated by a sensitizing dye to a semiconductor (for example, refer to patent References 4 to 6). However, although these organic pigments have the advantages of being cheap, having a large absorption coefficient, and being able to control the absorption characteristics through the diversity of their structures, they are currently unable to fully satisfy the requirements in terms of photoelectric conversion efficiency and stability over time. characteristic of. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 11-214730 [Patent Document 2] Japanese Patent Laid-Open No. 11-238905 [Patent Document 3] Japanese Patent Laid-Open No. 2011-26376 Publication [Patent Document 4] Japanese Patent Laid-Open No. 2011-207784 [Patent Document 5] Japanese Patent Laid-Open No. 2012-51854 [Patent Document 6] Japanese Patent Laid-Open No. 2016-6811 [Non-Patent Document] [Non-Patent Document 6] Patent Document 1] "Nature", (UK), 1991, Vol. 353, p.737-740

[式中，Ar表示亦可具有取代基之碳原子數6～36之芳基； R¹ ～R⁴ 可相同亦可不同，表示氫原子、鹵素原子、氰基、羥基、硝基、亞硝基、硫醇基、 亦可具有取代基之碳原子數1～36之直鏈狀或支鏈狀之烷基、 亦可具有取代基之碳原子數3～36之環烷基、 亦可具有取代基之碳原子數1～36之直鏈狀或支鏈狀之烷氧基、 亦可具有取代基之碳原子數3～36之環烷氧基、 亦可具有取代基之碳原子數2～36之直鏈狀或支鏈狀之烯基、 亦可具有取代基之碳原子數6～36之芳基、 或亦可具有取代基之碳原子數0～36之胺基； R¹ ～R⁴ 亦可彼此為相鄰基且相互鍵結而形成環； X表示硫原子、氧原子或CR⁵ R⁶ ；R⁵ 、R⁶ 可相同亦可不同，表示亦可具有取代基之碳原子數1～36之直鏈狀或支鏈狀之烷基、或亦可具有取代基之碳原子數6～36之芳基；Z表示1價基。] 2.一種增感色素，其中於上述通式(1)中，Z為下述通式(2)所表示之1價基。 [化2]

[式中，R⁷ ～R¹² 可相同亦可不同，表示氫原子、 亦可具有取代基之碳原子數1～18之直鏈狀或支鏈狀之烷基、 亦可具有取代基之碳原子數1～18之直鏈狀或支鏈狀之烷氧基、 或亦可具有取代基之碳原子數2～18之直鏈狀或支鏈狀之烯基； R⁷ 與R⁸ 、R⁹ 與R¹⁰ 、R¹¹ 與R¹² 亦可分別相互鍵結而形成環；m表示0～2之整數，n表示0～4之整數，於m為2之情形或n為2～4之整數之情形時，複數個存在之R⁷ ～R¹² 係其R⁷ 彼此、R⁸ 彼此、R⁹ 彼此、R¹⁰ 彼此、R¹¹ 彼此、R¹² 彼此可分別相互相同亦可不同； R¹³ 及R¹⁴ 表示氫原子或酸性基，設為至少R¹³ 或R¹⁴ 之任一個為酸性基。] 3.如上述2中記載之增感色素，於上述通式(2)中，R⁷ ～R¹² 為氫原子或未經取代之碳原子數1～6之直鏈狀或支鏈狀之烷基。 4.如上述2或3中記載之增感色素，其中於上述通式(2)中，m為0、且n為0。 5.一種光電轉換用增感色素組合物，其包含上述增感色素。 6.一種光電轉換元件，其使用上述光電轉換用增感色素組合物。 7.一種色素增感太陽電池，其使用上述光電轉換元件。 [發明之效果] 根據本發明之增感色素，可獲得可高效率地取出電流之光電轉換用增感色素組合物。又，藉由使用該光電轉換用增感色素組合物，可獲得高效率且高耐久性之光電轉換元件及色素增感太陽電池。[Problem to be Solved by the Invention] The problem to be solved by the present invention is to provide a sensitizing dye with a novel structure that can expand the photosensitive wavelength region, and further provide a photoelectric conversion sensitizer that enables the sensitizing dye to extract current efficiently. A photoelectric conversion element and a dye-sensitized solar cell with good photoelectric conversion properties used in the form of a dye-sensitive composition. [Means for Solving the Problems] In order to solve the above-mentioned problems, the inventors have made efforts to improve the photoelectric conversion properties of sensitizing dyes. As a result, they have found that by using a sensitizing dye having a specific structure as a sensitizing dye for photoelectric conversion, it is possible to A high-efficiency and high-durability photoelectric conversion element is obtained. That is, the present invention is constituted by the following contents. 1. A sensitizing dye represented by the following general formula (1). [hua 1]

[In the formula, Ar represents an aryl group with 6 to 36 carbon atoms which may have a substituent; R ¹ to R ⁴ may be the same or different, and represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a nitroso group group, a thiol group, a linear or branched alkyl group with 1 to 36 carbon atoms which may have a substituent, a cycloalkyl group with 3 to 36 carbon atoms which may have a substituent, A linear or branched alkoxy group with 1 to 36 carbon atoms as a substituent, a cycloalkoxy group with 3 to 36 carbon atoms as a substituent, or a substituted group with 2 carbon atoms A linear or branched alkenyl group of ~36, an aryl group of 6 to 36 carbon atoms that may also have a substituent, or an amino group of 0 to 36 carbon atoms that may also have a substituent; R ¹ ~ R ⁴ may also be adjacent groups and bond with each other to form a ring; X represents a sulfur atom, an oxygen atom or CR ⁵ R ⁶ ; R ⁵ and R ⁶ may be the same or different, and may also represent a carbon atom with a substituent A linear or branched alkyl group of 1 to 36 or an aryl group of 6 to 36 carbon atoms which may have a substituent; Z represents a monovalent group. ] 2. A sensitizing dye wherein, in the above general formula (1), Z is a monovalent group represented by the following general formula (2). [hua 2]

[In the formula, R ⁷ to R ¹² may be the same or different, and represent a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms that may have a substituent, and a carbon that may have a substituent A linear or branched alkoxy group having 1 to 18 atoms, or a linear or branched alkenyl group having 2 to 18 carbon atoms that may also have a substituent; R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² can also be bonded to each other to form a ring; m represents an integer from 0 to 2, and n represents an integer from 0 to 4, when m is 2 or n is an integer from 2 to 4 In this case, a plurality of R ⁷ to R ¹² exist in which R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be the same or different from each other; R ¹³ and R ¹⁴ represents a hydrogen atom or an acidic group, and at least one of R ¹³ or R ¹⁴ is an acidic group. ] 3. The sensitizing dye described in the above 2, in the above general formula (2), R ⁷ to R ¹² are hydrogen atoms or unsubstituted linear or branched carbon atoms having 1 to 6 carbon atoms. alkyl. 4. The sensitizing dye according to the above 2 or 3, wherein m is 0 and n is 0 in the above general formula (2). 5. A sensitizing dye composition for photoelectric conversion, comprising the above-mentioned sensitizing dye. 6. A photoelectric conversion element using the above-mentioned sensitizing dye composition for photoelectric conversion. 7. A dye-sensitized solar cell using the above-mentioned photoelectric conversion element. ADVANTAGE OF THE INVENTION According to the sensitizing dye of this invention, the sensitizing dye composition for photoelectric conversion which can extract electric current efficiently can be obtained. Moreover, by using the sensitizing dye composition for photoelectric conversion, a photoelectric conversion element and a dye-sensitized solar cell with high efficiency and high durability can be obtained.

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將通式(1)所表示之本發明之增感色素之化合物之具體例示於以下之式，但本發明並不限定於該等。例如，通式(1)所表示之增感色素中X雖然表示硫原子、氧原子或CR⁵ CR⁶ ，但於以下之例示化合物之X之部分中亦可僅例示具有該等中任一者之化合物，作為例示化合物，亦可為具有其他X之化合物。又，以下之例示化合物係表示可存在之立體異構物中之一例，設為包含其他所有之立體異構物。又，亦可為各者兩種以上之立體異構物之混合物。 [化5]

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通式(1)所表示之本發明之增感色素可藉由公知之方法而合成。以下，於通式(1)中，例示Z為通式(2)所表示之1價基之情形之合成例。於通式(2)中，除m為0、且n為0(m＝n＝0)之情形以外，可藉由進行下述通式(5)所表示之具有相應之取代基之溴化體、與下述通式(6)或下述通式(7)所表示之分別具有相應之取代基及甲醯基之硼酸進行Suzuki偶合等交叉偶合反應，而合成下述通式(8)所表示之甲醯體。 [化67]

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於上述通式(8)所表示之甲醯體之合成例中，於m為1或2、且n為0之情形時，作為具有通式(6)所表示之甲醯基之硼酸，可列舉：4-甲醯基苯基硼酸或4-(4-甲醯基苯基)苯基硼酸等。又，於上述合成例中，於m為0、且n為1～4之情形時，作為具有通式(7)所表示之甲醯基之硼酸，可列舉：5-甲醯基-2-噻吩硼酸或5'-甲醯基-2,2'-雙噻吩-5-硼酸等。進而，於m為1或2、且n為1～4之情形時，可藉由使用通式(5)所表示之溴化體與上述同樣之通式(7)所表示之具有甲醯基之硼酸進行與上述合成例同樣之交叉偶合反應，而合成通式(8)所表示之甲醯體。 於上述通式(8)所表示之甲醯體之合成例中，於m為0、且n為0(m＝n＝0)之情形時，可將由通式(5)所表示之溴化體與丁基鋰等之金屬鹵素交換所獲得之芳基鋰利用N,N-二甲基甲醯胺(DMF)進行捕捉，藉此而合成通式(8)所表示之甲醯體(m＝n＝0)。 繼而，可藉由進行如上所述般獲得之通式(8)所表示之甲醯體、與下述通式(9)所表示之茚酮化合物之縮合反應，而合成本發明之增感色素。然而，上述合成例中之通式(5)～(9)中之Ar及R¹ ～R¹⁴ 表示與本發明之通式(1)及通式(2)中之Ar及R¹ ～R¹⁴ 相同之意思。然而，於通式(5)～(9)中，於m或n為複數個之情形時，關於複數個存在之R⁷ ～R¹² ，其R⁷ 彼此、R⁸ 彼此、R⁹ 彼此、R¹⁰ 彼此、R¹¹ 彼此、R¹² 彼此亦可分別相互相同，亦可不同，R¹³ 及R¹⁴ 表示氫原子或酸性基，設為至少R¹³ 或R¹⁴ 之任一個為酸性基。 [化71]

再者，關於成為起始原料之上述式(5)等，可使用市售者，亦可使用藉由公知之方法所合成者。上述通式(9)所表示之茚酮化合物可利用上述專利文獻4～6中記載之方法而容易地合成。 作為通式(1)所表示之本發明之增感色素之化合物之精製方法，可列舉：藉由管柱層析法之精製；藉由矽膠、活性碳、活性白土等之吸附精製；藉由溶劑之再結晶或晶析法等公知之方法。又，該等化合物之鑑定可藉由核磁共振分析(NMR)等而進行。 本發明之增感色素可單獨使用，亦可併用兩種以上。又，本發明之增感色素可與不屬於本發明之其他增感色素併用。作為其他增感色素之具體例，可列舉：釕錯合物、香豆素系色素、花青系色素、部花青系色素、羅達苯胺系色素、酞菁系色素、卟啉系色素、𠮿

系色素等上述通式(1)所表示之增感色素以外之增感色素。於將本發明之增感色素、與該等之外之增感色素組合而用作光電轉換用增感色素組合物之情形時，較佳為將其他增感色素相對於本發明之增感色素之使用量設為10～200重量%，更佳為設為20～100重量%。 本發明之增感色素可用作鹵化銀、氧化鋅、氧化鈦等各種成像材料用之感光體、光觸媒、光功能性材料等分光增感色素，亦可用作色素增感型之光電轉換元件等中所使用之光電轉換用增感色素組合物等。於本發明中，製作色素增感型之光電轉換元件之方法並無特別限定，較佳為於導電性支持體(電極)上形成半導體層，使該半導體層吸附(擔載)本發明之光電轉換用增感色素組合物，而製作光電極(參照圖1。再者，不必說，由於以圖易於理解為優先，故而並非實際之元件之忠實之縮小比例)。作為吸附色素之方法，通常為將半導體層長時間浸漬於使色素溶解於溶劑中所獲得之溶液中之方法。於將本發明之增感色素併用兩種以上之情形時，或於將本發明之增感色素與其他增感色素併用之情形時，可製備使用之所有色素之混合溶液並將半導體層浸漬，又，亦可對各色素分別製備溶液，並將半導體層依次浸漬於各溶液中。 於本發明中，作為導電性支持體，除金屬板以外，可使用設置有表面具有導電性材料之導電層之玻璃基板或塑膠基板。作為導電性材料之具體例，可列舉：金、銀、銅、鋁、鉑等金屬、摻氟之氧化錫、銦-錫複合氧化物等導電性透明氧化物半導體、碳等，較佳為使用塗佈有摻氟之氧化錫薄膜之玻璃基板。 於本發明中，作為形成半導體層之半導體之具體例，可列舉：氧化鈦、氧化鋅、氧化錫、氧化銦、氧化鋯、氧化鎢、氧化鉭、氧化鐵、氧化鎵、氧化鎳、氧化釔等金屬氧化物；硫化鈦、硫化鋅、硫化鋯、硫化銅、硫化錫、硫化銦、硫化鎢、硫化鎘、硫化銀等金屬硫化物；硒化鈦、硒化鋯、硒化銦、硒化鎢等金屬硒化物；矽、鍺等單獨半導體等。該等半導體可單獨使用，亦可將兩種以上混合而使用。於本發明中，作為半導體，較佳為使用選自氧化鈦、氧化鋅、氧化錫中之一種或兩種以上。 本發明之半導體層之態樣並無特別限定，較佳為具有由微粒子構成之多孔質結構之薄膜。藉由多孔質結構等，而半導體層之實質性之表面積增大，若於半導體層之色素吸附量增大，則可獲得高效率之光電轉換元件。半導體粒徑較佳為5～500 nm，更佳為10～100 nm。半導體層之膜厚通常為2～100 μm，更佳為5～20 μm。作為半導體層之製作方法，可列舉：將包含半導體微粒子之焊膏利用旋轉塗佈法、刮刀法、擠壓法、網版印刷法等濕式塗佈法塗佈於導電性基板上後，藉由焙燒而將溶劑或添加物去除而製膜之方法，或藉由濺鍍法、蒸鍍法、電沈積法、電析法、微波照射法等而製膜之方法等，但並不限定於該等。 於本發明中，包含半導體微粒之焊膏可使用市售品，亦可使用藉由將市售之半導體微粉末分散於溶劑中所以製備之焊膏等。作為製備焊膏時使用之溶劑之具體例，可列舉：水；甲醇、乙醇、異丙醇等醇系溶劑；丙酮、甲基乙基酮、甲基異丁基酮等酮系溶劑；正己烷、環己烷、苯、甲苯等烴系溶劑，但並不限定於該等。又，該等溶劑可單獨使用或以兩種以上之混合溶劑之形式使用。 於本發明中，作為使半導體微粉末分散於溶劑中之方法，可將粉末利用乳缽等磨碎後進行，亦可使用球磨機、塗料調節器、垂直型珠磨機、水平型珠磨機、磨碎機等分散機。於製備焊膏時，為了防止半導體微粒子之凝集，較佳為添加界面活性劑等，為了增黏，較佳為添加聚乙二醇等增黏劑。 本發明之光電轉換用增感色素組合物於半導體層表面上之吸附例如可藉由於該色素溶液中浸漬半導體層，於室溫下放置30分鐘～100小時或於加熱條件下放置10分鐘～24小時放置而進行。於該情形時，較佳為於室溫下放置10～20小時，該色素溶液中之色素濃度較佳為10～2000 μm，更佳為50～500 μm。 作為用於使本發明之光電轉換用增感色素組合物吸附於半導體層表面上時之溶劑，具體而言，可列舉：甲醇、乙醇、異丙醇、第三丁醇等醇系溶劑；丙酮、甲基乙基酮、甲基異丁基酮等酮系溶劑；甲酸乙酯、乙酸乙酯、乙酸正丁酯等酯系溶劑；二乙醚、1,2-二甲氧基乙烷、四氫呋喃、1,3-二氧戊環等醚系溶劑；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等醯胺系溶劑；乙腈、甲氧基乙腈、丙腈等腈系溶劑；二氯甲烷、氯仿、三溴甲烷、鄰二氯苯等鹵化烴系溶劑；正己烷、環己烷、苯、甲苯等烴系溶劑等，但並不限定於該等。該等溶劑可單獨使用或以兩種以上之混合溶劑之形式使用。該等溶劑中，較佳為使用選自甲醇、乙醇、第三丁醇、丙酮、甲基乙基酮、四氫呋喃、乙腈中之一種或兩種以上。 於使本發明之光電轉換用增感色素組合物吸附於半導體層表面上時，亦可使膽酸或脫氧膽酸、鵝去氧膽酸、溶膽酸、去氫膽酸等膽酸衍生物溶解於色素溶液中，與色素進行共吸附。藉由使用膽酸或膽酸衍生物，可抑制色素彼此之締合，於光電轉換元件中自色素高效率地電子注入至半導體層。於使用膽酸或膽酸衍生物之情形時，色素溶液中之該等之濃度較佳為0.1～100 mM，更佳為0.5～10 mM。 作為用於本發明之光電轉換元件之相對電極(電極)，只要為具有導電性者，則並無特別限定，為了促進氧化還原離子之氧化還原反應，較佳為使用具有觸媒能力之導電性材料。作為該導電性材料之具體例，可列舉：鉑、銠、釕、碳等，但並不限定於該等。於本發明中，尤佳為將於導電性支持體上形成有鉑之薄膜者用作相對電極。又，作為導電性薄膜之製作方法，可列舉：將包含導電性材料之焊膏藉由旋轉塗佈法、刮刀法、擠壓法、網版印刷法等濕式塗佈法塗佈於導電性基板上後，藉由焙燒而將溶劑或添加物去除而製膜之方法，或藉由濺鍍法、蒸鍍法、電沈積法、電析法、微波照射法等而進行製膜之方法等，但並不限定於該等。 於本發明之光電轉換元件中，於一對之對向之電極間填充電解質而形成電解質層。作為使用之電解質，較佳為氧化還原電解質。作為氧化還原電解質，可列舉碘、溴、錫、鐵、鉻、蒽醌等氧化還原離子對，但並不限定於該等。該等中，較佳為碘系電解質、溴系電解質。於碘系電解質之情形時，例如可使用：碘化鉀、碘化鋰、碘化二甲基丙基咪唑鎓等與碘之混合物。於本發明中，較佳為使用將該等電解質溶解於溶劑中所獲得之電解液。電解液中之電解質之濃度較佳為0.05～5 M，更佳為0.2～1 M。 作為使電解質溶解之溶劑，可列舉：乙腈、甲氧基乙腈、丙腈、3-甲氧基丙腈、苯甲腈等腈系溶劑；二乙醚、1,2-二甲氧基乙烷、四氫呋喃等醚系溶劑；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺系溶劑；碳酸乙二酯、碳酸丙二酯等碳酸酯系溶劑；γ-丁內酯、γ-戊內酯等內酯系溶劑等，但並不限定於該等。該等溶劑可單獨使用或以兩種以上之混合溶劑之形式使用。該等溶劑中，較佳為腈系溶劑。 於本發明中，為了進一步提高色素增感型光電轉換元件之開路電壓及填充因數，亦可使上述電解液中含有胺系化合物。作為胺系化合物，可列舉：4-第三丁基吡啶、4-甲基吡啶、2-乙烯基吡啶、N,N-二甲基-4-胺基吡啶、N,N-二甲基苯胺、N-甲基苯并咪唑等。電解液中之胺系化合物之濃度較佳為0.05～5 M，更佳為0.2～1 M。 作為本發明之光電轉換元件中之電解質，亦可使用添加膠化劑或聚合物等所獲得之凝膠狀電解質或使用聚環氧乙烷衍生物等聚合物之固體電解質。藉由使用凝膠狀電解質、固體電解質，可減少電解液之揮發。 於本發明之光電轉換元件中，亦可於一對之對向之電極間形成固體電荷傳輸層而代替電解質。固體電荷傳輸層中所含之電荷傳輸物質較佳為電洞傳輸物質。作為電荷傳輸物質之具體例，可列舉：碘化銅、溴化銅、硫氰化銅等無機電洞傳輸物質、聚吡咯、聚噻吩、聚對苯乙炔、聚乙烯咔唑、聚苯胺、㗁二唑衍生物、三苯胺衍生物、吡唑啉衍生物、茀酮衍生物、腙化合物、茋化合物等有機電洞傳輸物質，但並不限定於該等。 於本發明中，於使用有機電洞傳輸物質而形成固體電荷傳輸層之情形時，亦可併用膜形成性黏合劑樹脂。作為膜形成性黏合劑樹脂之具體例，可列舉：聚苯乙烯樹脂、聚乙烯醇縮醛樹脂、聚碳酸酯樹脂、聚碸樹脂、聚酯樹脂、聚苯醚樹脂、聚芳酯樹脂、醇酸樹脂、丙烯酸樹脂、苯氧樹脂等，但並不限定於該等。該等樹脂可單獨使用或以共聚物之形式混合一種或兩種以上而使用。該等黏合劑樹脂相對於有機電洞傳輸物質之使用量較佳為20～1000重量%，更佳為50～500重量%。 於本發明之光電轉換元件中，設置有吸附有光電轉換用增感色素組合物之半導體層之電極(光電極)成為陰極，相對電極成為陽極。太陽光等光可自光電極側、相對電極側之任一側進行照射，較佳為自光電極側進行照射。藉由太陽光等之照射，而色素吸收光而成為激發狀態而釋放電子。該等電子經由半導體層而流向外部並移動至相對電極。另一方面，釋放電子而成為氧化狀態之色素係藉由經由電解質中之離子而接收自相對電極供給之電子，而返回至基底狀態。藉由該等循環而電流流動，作為光電轉換元件而發揮功能。 於評價本發明之光電轉換元件之性能(特性)時，進行短路電流、開路電壓、填充因數、光電轉換效率之測定。所謂短路電流，係表示使輸出端子短路時於兩端子間流動之每1 cm² 之電流，所謂開路電壓，係表示使輸出端子開放時之兩端子間之電壓。又，所謂填充因數，係指用最大輸出(電流與電壓之積)除以短路電流與開路電壓之積所得之值，主要取決於內部電阻。光電轉換效率係作為用最大輸出(W)除以每1 cm² 之光強度(W)所得之值乘以100而以百分比表示之值而求出。 本發明之光電轉換元件可用於色素增感太陽電池或各種光感測器等。本發明之色素增感太陽電池係藉由如下方式而獲得：使含有包含上述通式(1)所表示之增感色素之光電轉換用增感色素組合物之光電轉換元件成為單元，使該單元進行必需片數排列而模組化，並設置特定之電氣配線。 [實施例] 以下，藉由實施例而對本發明具體地進行說明，但本發明並不限定於以下之實施例。再者，於合成實施例中，化合物之鑑定係藉由¹ H-NMR分析(日本電子股份有限公司製造之核磁共振裝置，JNM-ECA-600)而進行。 [合成實施例1]增感色素(A-4)之合成 於進行過氮置換之反應容器中，放入下述式(10)所表示之溴化體1.20 g、脫水四氫呋喃16 mL，一面於-72℃下進行攪拌，一面滴加1.6 M之正丁基鋰己烷溶液1.5 mL，進行1小時反應。反應後，於反應液中滴加脫水二甲基甲醛0.3 mL，進行2小時反應。將反應液倒空至冰水50 mL中，利用二氯甲烷提取有機層。將有機層進行水洗後，進行分離，利用硫酸鎂進行乾燥，並進行減壓濃縮而獲得粗產物。將粗產物進行管柱層析法(載體：矽膠、溶離液：己烷/甲苯＝9/1(體積比))進行精製，獲得下述式(11)所表示之甲醯體化合物之黃色固體(0.78 g)。 [化72]

[化73]

於進行過氮置換之反應容器中，放入上述式(11)所表示之甲醯體化合物0.300 g、下述式(12)所表示之茚酮化合物0.179 g、乙酸/甲苯＝5/2(體積比)混合液13.5 mL，於90℃下攪拌3小時。將反應液放冷至25℃後，添加水50 mL進行攪拌，提取有機層。將有機層利用水及飽和食鹽水依次洗淨並乾燥，以濃紫色固體獲得目標之增感色素 (0.294 g，產率75%)。 [化74]

進行所獲得之濃紫色固體之NMR分析，檢測出以下之26個氫之訊號，鑑定為下述式(A-4)所表示之結構(未觀測到羧基之氫)。¹ H-NMR (600 MHz, CDCl₃ ) : δ (ppm)＝6.01-6.05(2H)、6.90-6.95(2H)、7.05-7.08(1H)、7.23-7.27(5H)、7.30-7.40(8H)、7.42-7.50(2H)、7.55-7.65(1H)、7.94-8.01(2H)、8.28-8.32(1H)、8.36-8.40(1H)、8.50-8.55(1H). [化75]

[合成實施例2]增感色素(A-10)之合成 於進行過氮置換之反應容器中，放入上述式(10)所表示之溴化體1.50 g、甲苯30 mL、乙醇8 mL、水8 mL、5'-甲醯基-2,2'-雙噻吩-5-硼酸0.81 g、碳酸鉀0.62 g並攪拌5小時，攪拌後，重複3次反應容器內之減壓、脫氣、氮置換。繼而，添加四(三苯基膦)鈀0.18 g，於80℃下攪拌5小時。將反應液放冷至25℃後，添加乙酸乙酯10 mL、水30 mL並攪拌，提取有機層。將有機層利用硫酸鎂進行乾燥並進行減壓濃縮而獲得粗產物。將粗產物進行管柱層析法(載體：矽膠、溶離液：氯仿/己烷＝3/1(體積比))進行精製，並進行乾燥，獲得下述式(13)所表示之甲醯體化合物之黃褐色固體(1.20 g)。 [化76]

於進行過氮置換之反應容器中，放入上述式(13)所表示之甲醯體化合物0.64 g、乙酸/甲苯＝5/2(體積比)混合液13.5 mL、上述式(12)所表示之茚酮化合物0.29 g，於90℃下攪拌3小時。將反應液放冷至25℃後，添加水80 mL進行攪拌，提取有機層。將有機層利用水及飽和食鹽水依序洗淨並進行乾燥，以黑色固體獲得目標之增感色素(0.53 g，產率65%)。 進行所獲得之黑色固體之NMR分析，檢測出以下之30個氫之訊號，鑑定為下述式(A-10)所表示之結構(未觀測到羧基之氫)。¹ H-NMR (600 MHz, CDCl₃ ) : δ (ppm)＝5.96-6.06(1H)、6.08-6.18(1H)、6.85-6.95(3H)、6.94-7.04(1H)、7.04-7.14(4H)、7.15-7.25(3H)、7.32-7.42(2H)、7.46-7.56(9H)、7.66-7.76(1H)、7.78-7.88(2H)、8.06-8.16(1H)、8.57-8.67(2H). [化77]

[合成實施例3]增感色素(A-51)之合成 於進行過氮置換之反應容器中，放入下述式(14)所表示之溴化體2.0g、脫水四氫呋喃30 mL，一面於-72℃下進行攪拌，一面滴加1.6 M之正丁基鋰己烷溶液3.0 mL，進行1小時反應。反應後，於反應液中滴加脫水二甲基甲醛0.6 mL並進行2小時反應。其後，將反應液倒空至冰水150 mL中，利用二氯甲烷提取有機層。將有機層進行水洗並進行分離，利用硫酸鎂進行乾燥，並進行減壓濃縮。將殘渣進行管柱層析法(載體：矽膠、溶劑：己烷/甲苯＝9/1(體積比))進行精製，獲得下述式(15)所表示之甲醯體化合物之黃白色固體(0.99 g)。 [化78]

[化79]

於進行過氮置換之反應容器中，放入上述式(15)所表示之甲醯體化合物0.300 g、上述式(12)所表示之茚酮化合物0.150 g、乙酸/甲苯＝5/2(體積比)混合液13.5 mL，於90℃下攪拌4小時。將反應液放冷至25℃後，添加甲苯30 mL並進行攪拌，提取有機層。利用水及飽和食鹽水進行依次洗淨，將所獲得之有機層進行乾燥，以黑褐色固體獲得目標之增感色素(0.286 g，產率74%)。 進行所獲得之黑褐色固體之NMR分析，檢測出以下之30個氫之訊號，鑑定為下述式(A-51)所表示之結構(未觀測到羧基之氫)。¹ H-NMR (600 MHz, CDCl₃ ) : δ (ppm)＝1.87-1.90(6H)、6.34-6.39(2H)、7.33-7.36(1H)、7.39-7.42(1H)、7.44-7.48(3H)、7.54-7.60(4H)、7.66-7.69(2H)、7.82-7.86(4H)、7.99-8.02(3H)、8.03-8.08(1H)、8.12-8.20(1H)、8.30-8.40(2H). [化80]

[合成實施例4]增感色素(A-60)之合成 於進行過氮置換之反應容器中，放入上述式(14)所表示之溴化體0.55g、5-甲醯基-2-噻吩硼酸0.197 g、二甲基亞碸20 mL、碳酸鉀0.124 g並攪拌5小時，攪拌後，重複5次反應容器內之減壓、脫氣、氮置換。繼而，添加乙酸鈀0.012 g、丁基雙(1-金剛烷基)膦0.038 g，重複5次反應容器內之減壓、脫氣、氮置換。其後，於75℃下攪拌3小時。將反應液放冷至25℃後，添加氯仿150 mL、水60 mL並進行攪拌，提取有機層。將有機層利用硫酸鎂進行乾燥，並進行減壓濃縮而獲得粗產物。將粗產物進行管柱層析法(載體：矽膠、溶離液：己烷/甲苯＝1/4(體積比))進行精製，並進行乾燥，獲得下述式(16)所表示之甲醯體化合物之黃色固體(0.543 g)。 [化81]

於進行過氮置換之反應容器中，放入上述式(16)所表示之甲醯體化合物0.542 g、式(12)所表示之茚酮化合物0.256 g、乙酸/甲苯＝5/2(體積比)混合液28 mL，於90℃下攪拌10小時。將反應液放冷至25℃後，添加甲苯50 mL並進行攪拌，提取有機層。利用水及飽和食鹽水依序洗淨，將所獲得之有機層進行乾燥，以紅褐色固體獲得目標之增感色素 (0.453 g，產率67%)。 進行所獲得之紅褐色固體之NMR分析，檢測出以下之32個氫之訊號，鑑定為式(A-60)所表示之結構(未觀測到羧基之氫)。¹ H-NMR (600 MHz, CDCl₃ ) : δ (ppm)＝1.82-1.86(6H)、6.32-6.40(2H)、7.30-7.35(1H)、7.35-7.40(1H)、7.41-7.49(3H)、7.53-7.59(5H)、7.64-7.69(2H)、7.80-7.88(4H)、8.00-8.10(5H)、8.27-8.34(2H)、8.36-8.40(1H)。 [化82]

[合成實施例5]增感色素(A-48)之合成 使用4-甲醯基苯基硼酸代替合成實施例4中之原料5-甲醯基-2-噻吩硼酸，除此以外，與合成實施例4同樣地進行合成，以紅褐色固體獲得目標之增感色素(0.486 g，產率75%)。 進行所獲得之紅褐色固體之NMR分析，檢測出以下之34個氫之訊號，鑑定為式(A-48)所表示之結構(未觀測到羧基之氫)。¹ H-NMR (600 MHz, CDCl₃ ) : δ (ppm)＝1.83-1.87(6H)、6.31-6.39(2H)、7.28-7.34(1H)、7.33-7.39(1H)、7.41-7.49(3H)、7.53-7.60(5H)、7.63-7.68(2H)、7.81-7.88(3H)、7.92-7.99(3H)、8.01-8.08(4H)、8.34-8.41(1H)、8.41-8.45(1H)、8.63-8.69(2H)。 [化83]

[合成實施例6]增感色素(A-61)之合成 於進行過氮置換之反應容器中，放入下述式(17)所表示之甲醯體化合物0.251 g、式(12)所表示之茚酮化合物0.124 g、乙酸/甲苯＝5/2(體積比)混合液15 mL，於90℃下攪拌6小時。將反應液放冷至25℃後，添加甲苯30 mL並進行攪拌，提取有機層。利用水及飽和食鹽水依序洗淨，將所獲得之有機層進行乾燥，以紅紫色固體獲得目標之增感色素(0.268 g，產率87%)。 [化84]

進行所獲得之紅紫色固體之NMR分析，檢測出以下之34個氫之訊號，鑑定為式(A-61)所表示之結構(未觀測到羧基之氫)。¹ H-NMR (600 MHz, CDCl₃ ) : δ (ppm)＝1.50-1.54(6H)、1.76-1.80(6H)、6.31-6.40(2H)、7.31-7.36(1H)、7.38-7.48(6H)、7.62-7.67(1H)、7.65-7.70(2H)、7.71-7.76(1H)、7.80-7.84(1H)、7.87-7.92(1H)、7.96-8.08(2H)、8.12-8.23(2H)、8.28-8.37(1H)、8.35-8.41(1H)、9.22-9.28(1H)。 [化85]

[合成實施例7]增感色素(A-62)之合成 使用下述式(18)所表示之溴化體代替合成實施例4中之上述式(14)所表示之溴化體，除此以外，與合成實施例4同樣地進行合成，獲得下述式(19)所表示之甲醯體。 [化86]

[化87]

於進行過氮置換之反應容器中，使上述式(19)所表示之甲醯體化合物與合成實施例4同樣地與上述式(12)所表示之茚酮化合物進行反應，以紫色固體獲得目標之增感色素(0.37 g，產率73%)。 進行所獲得之紫色固體之NMR分析，檢測出以下之36個氫之訊號，鑑定為式(A-62)所表示之結構(未觀測到羧基之氫)。¹ H-NMR (600 MHz, CDCl₃ ) : δ (ppm)＝1.50-1.54(6H)、1.83-1.87(6H)、6.32-6.38(2H)、7.28-7.34(1H)、7.33-7.38(1H)、7.38-7.47(5H)、7.50-7.56(1H)、7.61-7.71(4H)、7.77-7.82(1H)、7.83-7.87(1H)、7.94-8.02(3H)、8.03-8.07(1H)、8.16-8.21(1H)、8.25-8.32(2H)、8.33-8.40(1H)。 [化88]

[實施例1] 於塗佈有摻氟之氧化錫薄膜之玻璃基板上，藉由擠壓法塗佈氧化鈦焊膏(Nikki觸媒化成股份有限公司製造之PST-18NR)。於110℃下乾燥1小時後，於450℃下焙燒30分鐘，獲得膜厚6 μm之氧化鈦薄膜。繼而，將合成實施例1中所獲得之增感色素(A-4)溶解於乙腈/第三丁醇＝1/1(體積比)混合液中而製備濃度100 μm之溶液50 mL，於該溶液中，使將氧化鈦進行過塗佈燒結之玻璃基板於25±2℃下浸漬15小時而吸附色素，作為光電極。 於塗佈有摻氟之氧化錫薄膜之玻璃基板上，使用自動取景器(日本電子股份有限公司製造之JFC-1600)並藉由濺鍍法而形成膜厚15 nm之鉑薄膜，作為相對電極。 繼而，於光電極與相對電極之間夾持厚度60 μm之間隔片(熱熔膜)並藉由熱熔而貼合，自相對電極之孔注入電解液(0.1 M之碘化鋰、0.6 M之碘化二甲基丙基咪唑鎓、0.05 M之碘、0.5 M之4-第三丁基吡啶)/3-甲氧基丙腈溶液)後將孔密封，製作光電轉換元件。 自上述光電轉換元件之光電極側，照射利用模擬太陽光照射裝置(分光計器股份有限公司製造之OTENTO-SUN III型)所產生之光，使用電源電錶(KEITHLEY製造之Model 2400 General-Purpose SourceMeter)測定電流-電壓特性。光之強度係調整為100 mW/cm² 。將所獲得之測定結果與初期光電轉換效率示於表1。又，針對照射光20小時後之特性變化，將同樣地測定之光電轉換效率之結果彙總示於表1。 [實施例2～實施例11] 作為光電轉換用增感色素，分別使用表1所表示之增感色素代替(A-4)，除此以外，與實施例1同樣地製作光電轉換元件，並將所得之光電轉換元件之電流-電壓特性、初期及20小時光照射後之光電轉換效率彙總示於表1。 [比較例1～比較例5] 作為光電轉換用增感色素，使用不屬於本發明之以下之(B-1)～(B-5)所示之增感色素代替(A-4)，除此以外，與實施例1同樣地製作光電轉換元件，並將所得之光電轉換元件之電流-電壓特性、初期及20小時光照射後之光電轉換效率示於表1。 [化89]

[化90]

[化91]

[化92]

[化93]

[表1]

由表1之結果可判斷，藉由使用包含本發明之增感色素之光電轉換用增感色素組合物，可獲得光電轉換效率較高、且即便長時間持續光照射亦可維持較高之光電轉換效率之光電轉換元件。另一方面，使用比較例之光電轉換用增感色素之光電轉換元件之光電轉換效率不充分。 [產業上之可利用性] 由本發明之增感色素構成之光電轉換用增感色素組合物係於高效率且高耐久性之光電轉換元件以及色素增感太陽電池中較為有用，可作為可將太陽光能高效率地轉換為電能之太陽電池，而提供清潔能量。Hereinafter, embodiments of the present invention will be described in detail. The sensitizing dye composition for photoelectric conversion containing the sensitizing dye of the present invention is used as a sensitizer in a dye-sensitized photoelectric conversion element. Furthermore, in the present specification, the term "sensitizing dye" refers to a compound represented by the general formula (1), and the term "sensitizing dye composition for photoelectric conversion" refers to a compound containing the compound represented by the general formula (1). One or two or more, optionally a composition containing other sensitizing dyes that do not belong to the present invention. The photoelectric conversion element of the present invention is typically obtained by arranging a photoelectrode and a counter electrode in which a dye is adsorbed to a semiconductor layer on a conductive support so as to face each other via an electrolyte layer. Hereinafter, although the sensitizing dye represented by the said General formula (1) is demonstrated concretely, this invention is not limited to these. In general formula (1), as Ar or R ¹ ~R ⁶ The "aryl group having 6 to 36 carbon atoms" in the "aryl group having 6 to 36 carbon atoms that may have a substituent" specifically includes phenyl, naphthyl, and biphenyl. , Anthracenyl, phenanthryl, pyrenyl, triphenyl, indenyl, indenyl and other aryl groups. Here, the "aryl group" in the present invention means an aromatic hydrocarbon group and a condensed polycyclic aromatic group, and among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. In general formula (1), as R ¹ ~R ⁴ The "halogen atom" represented specifically includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. In general formula (1), as R ¹ ~R ⁶ "Linear or branched alkyl group with 1 to 36 carbon atoms" in the "linear or branched alkyl group with 1 to 36 carbon atoms that may have a substituent", Specifically, straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; isopropyl, isobutyl , 2-butyl, 3-butyl, isooctyl and other branched alkyl groups. In general formula (1), as R ¹ ~R ⁴ The "cycloalkyl group having 3 to 36 carbon atoms" in the "cycloalkyl group having 3 to 36 carbon atoms that may have a substituent" specifically includes cyclopropyl, cyclobutyl, Cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. In general formula (1), as R ¹ ~R ⁴ "Linear or branched alkoxy group having 1 to 36 carbon atoms" in the "linear or branched alkoxy group having 1 to 36 carbon atoms that may have a substituent"", specifically, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, etc. Chain alkoxy; branched alkoxy such as isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyloxy, etc. In general formula (1), as R ¹ ~R ⁴ The "cycloalkoxy group having 3 to 36 carbon atoms" in the "cycloalkoxy group having 3 to 36 carbon atoms which may have a substituent" specifically includes cyclopropyloxy, Cycloalkoxy groups such as cyclobutoxy, cyclopentyloxy, and cyclohexyloxy. In general formula (1), as R ¹ ~R ⁴ The "linear or branched alkenyl group having 2 to 36 carbon atoms" in the "linear or branched alkenyl group having 2 to 36 carbon atoms which may have a substituent", Specifically, alkenyl groups such as vinyl group, allyl group, isopropenyl group, 2-butenyl group, 1-hexenyl group, or the like, or straight-chain or branched groups in which a plurality of these alkenyl groups are bonded are mentioned. Chain alkenyl. In general formula (1), as R ¹ ~R ⁴ The "amino group having 0 to 36 carbon atoms which may have a substituent" specifically includes: unsubstituted amino group; methylamino group, dimethylamino group, diethylamino group, An amino group having a substituent having a carbon number of 0 to 36, such as an ethylmethylamino group, a methylpropylamino group, a di-tert-butylamino group, and a diphenylamino group. In general formula (1), as Ar or R ¹ ~R ⁶ The "substituent" in the "substituted aryl group having 6 to 36 carbon atoms" represented, or R ¹ ~R ⁴ "Cycloalkyl group having 3 to 36 carbon atoms having a substituent", "a linear or branched alkoxy group having 1 to 36 carbon atoms having a substituent", "a group having a substituent The "substituent group" in the "cycloalkoxy group having 3 to 36 carbon atoms" or "the amine group having 0 to 36 carbon atoms having a substituent", specifically, a fluorine atom, a chlorine atom, and a bromine atom. , halogen atoms such as iodine atom; cyano group; hydroxyl group; nitro group; nitroso group; thiol group; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group Linear alkyl groups with 1 to 30 carbon atoms such as radicals; branched alkanes with 3 to 30 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, and isooctyl cycloalkyl group with 3 to 30 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.; methoxy, ethoxy, propoxy, butoxy, pentyloxy linear alkoxy groups with 1 to 30 carbon atoms such as radicals, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy; isopropoxy, isobutoxy, second butyl Branched alkoxy groups having 3 to 30 carbon atoms such as oxy, tert-butoxy, isooctyloxy; carbons such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy Cycloalkoxy with 3 to 30 atoms; vinyl, allyl, isopropenyl, 2-butenyl, 1-hexenyl, or a plurality of these alkenyl groups bonded to carbon number 2 ～30 linear or branched alkenyl; phenyl, naphthyl, biphenyl, anthracenyl, phenanthryl, pyrenyl, triphenyl, indenyl, indenyl and other carbon atoms 6～30 aryl; unsubstituted amino; methylamino, dimethylamino, diethylamino, ethylmethylamino, methylpropylamino, di-tert-butylamino, di- An amino group having a substituent having a carbon number of 1 to 30 such as a phenylamino group; a carboxyl group; a carboxylate group such as a carboxyl group and an ethyl ester group; and the like. These "substituents" may include one or a plurality of them, and when a plurality of them are included, they may be the same or different from each other. In addition, these "substituents" may further have the above-exemplified substituents. In general formula (1), as R ¹ ~R ⁶ represented by "a linear or branched alkyl group having 1 to 36 carbon atoms having a substituent", or R ¹ ~R ⁴ The "substituent" in the "linear or branched alkenyl group having 2 to 36 carbon atoms having a substituent" specifically includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Halogen atom such as atom; cyano group; hydroxyl group; nitro group; nitroso group; thiol group; ; Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy and other straight chains with 1 to 34 carbon atoms alkoxy in the form of alkoxy; branched alkoxy with 3 to 34 carbon atoms such as isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyloxy, etc.; cyclopropyl Cycloalkoxy with 3 to 34 carbon atoms such as oxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy; phenyl, naphthyl, biphenyl, anthracenyl, phenanthryl, pyrenyl, biphenyl Aryl with 6 to 34 carbon atoms such as triphenyl, indenyl, and indenyl; unsubstituted amino; methylamino, dimethylamino, diethylamino, ethylmethylamino, methyl Amino groups having substituents of 1 to 34 carbon atoms, such as propylpropylamine, di-tert-butylamine, and diphenylamine; Carboxyl; Carboxylate, such as carboxyl and ethyl ester; Wait. These "substituents" may include one or a plurality of them, and when they include a plurality of them, they may be the same or different from each other. In addition, these "substituents" may further have the above-exemplified substituents. In general formula (1), R ¹ ~R ⁴ Preferably, a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms which may have a substituent, an aryl group having 6 to 24 carbon atoms which may have a substituent, or An amino group having 0 to 24 carbon atoms which may have a substituent, more preferably a hydrogen atom or an aryl group having 6 to 24 carbon atoms which may have a substituent. In general formula (1), R ¹ ~R ⁴ Indicates the substituents as described above, but adjacent groups may be bonded to each other to form a ring, and these rings may also be bonded through a single bond, or any atom of nitrogen, oxygen or sulfur. , and bond with each other to form a ring. The rings are preferably benzene rings. In general formula (1), X is CR ⁵ R ⁶ R in case of ⁵ and R ⁶ Preferably it is a linear or branched alkyl group having 1 to 24 carbon atoms which may have a substituent, or an aryl group which may have 6 to 24 carbon atoms which may have a substituent, more preferably A straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms in the substituent. In the general formula (1), Z represents a monovalent group, preferably a monovalent group represented by the general formula (2). In general formula (2), as R ⁷ ~R ¹² "Linear or branched alkyl group with 1 to 18 carbon atoms" in the "linear or branched alkyl group with 1 to 18 carbon atoms that may have a substituent", Specifically, straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; isopropyl, isobutyl , 2-butyl, 3-butyl, isooctyl and other branched alkyl groups. In general formula (2), as R ⁷ ~R ¹² "Linear or branched alkoxy group having 1 to 18 carbon atoms" in the "linear or branched alkoxy group having 1 to 18 carbon atoms which may have a substituent"", specifically, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, etc. Chain alkoxy; branched alkoxy such as isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyloxy, etc. In general formula (2), as R ⁷ ~R ¹² The "linear or branched alkenyl group having 2 to 18 carbon atoms" in the "linear or branched alkenyl group having 2 to 36 carbon atoms which may have a substituent", Specifically, alkenyl groups such as vinyl group, allyl group, isopropenyl group, 2-butenyl group, 1-hexenyl group, or the like, or straight-chain or branched groups in which a plurality of these alkenyl groups are bonded are mentioned. Chain alkenyl. In general formula (2), as R ⁷ ~R ¹² The "linear or branched alkyl group having 1 to 18 carbon atoms having a substituent", "a straight chain or branched alkoxy group having 1 to 18 carbon atoms having a substituent"" or the "substituent" in the "linear or branched alkenyl group having 2 to 18 carbon atoms having a substituent", specifically, fluorine atom, chlorine atom, bromine atom, iodine atom and other halogen atoms; cyano group; hydroxyl group; nitro group; nitroso group; thiol group; Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, etc. straight chain with 1 to 16 carbon atoms alkoxy; branched alkoxy with 3 to 16 carbon atoms such as isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyloxy, etc.; cyclopropoxy cycloalkoxy with 3 to 16 carbon atoms such as cyclobutoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy; phenyl, naphthyl, biphenyl, anthracenyl, phenanthryl, pyrenyl, bitriphenyl Aryl with 6 to 34 carbon atoms such as phenyl, indenyl and indenyl; unsubstituted amino; methylamino, dimethylamino, diethylamino, ethylmethylamino, methyl Amino groups having substituents of 1 to 16 carbon atoms, such as propylamino, di-tert-butylamino, and diphenylamino; carboxyl; carboxylates, such as carboxyl and ethyl ester; . These "substituents" may include one or a plurality of them, and when they include a plurality of them, they may be the same or different from each other. In addition, these "substituents" may further have the above-exemplified substituents. In general formula (2), R ⁷ ~R ¹² A hydrogen atom or a straight-chain or branched alkyl group having 1 to 18 carbon atoms which may have a substituent is preferable, and a hydrogen atom is more preferable. In general formula (2), R ⁷ ~R ¹² Indicates the substituents as described above, but adjacent groups may be bonded to each other to form a ring, and these rings may also be bonded through a single bond, or any atom of nitrogen, oxygen or sulfur. , and bond with each other to form a ring. In the general formula (2), m and n respectively represent the number of aryl groups and thienyl groups having a function of transferring electrons excited by the dye moiety to the linking group of the indanone group serving as the electron attracting part. m represents an integer of 0 to 2, preferably 0 or 1, and n is preferably 0 to 2, more preferably 0 or 1. In general formula (2), R ¹³ and R ¹⁴ Represents a hydrogen atom or an acidic group, at least R ¹³ or R ¹⁴ Either one is set as an acidic group. as R ¹³ and R ¹⁴ Specific examples of the acidic group represented include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a hydroxamic acid group, a phosphonic acid group, a boronic acid group, a phosphinic acid group, and a silanol group. Among these acidic groups, a carboxyl group or a phosphonic acid group is preferable, and a carboxyl group is more preferable in terms of easily adsorbing the sensitizing dye on the surface of the semiconductor layer and improving the photoelectric conversion characteristics. In the present invention, the sensitizing dye represented by the general formula (1) is set to include a stereoisomer that should be present. Any stereoisomer can be preferably used as the sensitizing dye in the present invention. For example, in the general formula (1), Z is a monovalent group represented by the general formula (2), and R ¹³ is a hydrogen atom, R ¹⁴ In the case of a carboxyl group, the sensitizing dye of the present invention includes compounds represented by the following general formulae (3) and (4). Moreover, it may be a mixture of two or more kinds selected from these stereoisomers. [hua 3]

[hua 4]

A specific example of the compound of the sensitizing dye of the present invention represented by the general formula (1) is shown in the following formula, but the present invention is not limited to these. For example, although X in the sensitizing dye represented by the general formula (1) represents a sulfur atom, an oxygen atom or CR ⁵ CR ⁶ However, in the part of X of the following exemplified compounds, only the compound having any of these may be exemplified, and the compound having other X may be used as the exemplified compound. In addition, the following exemplified compounds show one example of possible stereoisomers, and it is assumed that all other stereoisomers are included. Moreover, each may be a mixture of two or more stereoisomers. [hua 5]

[hua 6]

[hua 7]

[hua 8]

[Chemical 9]

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[hua 20]

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[Chemical 65]

[Chemical 66]

The sensitizing dye of the present invention represented by the general formula (1) can be synthesized by a known method. Hereinafter, in the general formula (1), a synthesis example in which Z is a monovalent group represented by the general formula (2) is illustrated. In the general formula (2), except for the case where m is 0 and n is 0 (m=n=0), bromination with the corresponding substituent represented by the following general formula (5) can be carried out. The following general formula (8) is synthesized by carrying out a cross-coupling reaction such as Suzuki coupling with a boronic acid represented by the following general formula (6) or the following general formula (7) having corresponding substituents and formyl groups, respectively. The body represented by the carapace. [Chemical 67]

[Chemical 68]

[Chemical 69]

[Chemical 70]

In the synthesis example of the carboxyl group represented by the general formula (8), when m is 1 or 2 and n is 0, the boronic acid having the carboxyl group represented by the general formula (6) can be Examples include 4-formylphenylboronic acid, 4-(4-formylphenyl)phenylboronic acid, and the like. Furthermore, in the above synthesis example, when m is 0 and n is 1 to 4, examples of the boronic acid having a carboxyl group represented by the general formula (7) include: 5-carboxy-2- Thiophene boronic acid or 5'-carboxy-2,2'-bisthiophene-5-boronic acid, etc. Furthermore, when m is 1 or 2 and n is 1 to 4, the bromide represented by the general formula (5) and the bromide represented by the above-mentioned general formula (7) having a carboxyl group can be used. The boronic acid was subjected to the same cross-coupling reaction as in the above-mentioned synthesis example to synthesize the formamate represented by the general formula (8). In the synthesis example of the formazan represented by the general formula (8), when m is 0 and n is 0 (m=n=0), the brominated compound represented by the general formula (5) can be brominated The aryllithium obtained by exchanging metal halide such as butyllithium with butyllithium is captured by N,N-dimethylformamide (DMF) to synthesize the carboxylide (m) represented by the general formula (8). =n=0). Then, the sensitizing dye of the present invention can be synthesized by carrying out the condensation reaction of the formazan compound represented by the general formula (8) obtained as described above and the indanone compound represented by the following general formula (9). . However, Ar and R in the general formulae (5) to (9) in the above synthesis examples ¹ ~R ¹⁴ represents Ar and R in the general formula (1) and general formula (2) of the present invention ¹ ~R ¹⁴ same meaning. However, in the general formulae (5) to (9), when m or n are plural, about R that exists in plural ⁷ ~R ¹² , whose R ⁷ each other, R ⁸ each other, R ⁹ each other, R ¹⁰ each other, R ¹¹ each other, R ¹² They may be the same or different from each other, R ¹³ and R ¹⁴ represents a hydrogen atom or an acidic group, set at least R ¹³ or R ¹⁴ Either one is an acidic group. [Chemical 71]

In addition, about the said formula (5) etc. which become a starting material, a commercially available thing can be used, and the thing synthesized by a well-known method can also be used. The indanone compound represented by the above-mentioned general formula (9) can be easily synthesized by the methods described in the above-mentioned Patent Documents 4 to 6. Examples of methods for purifying the compound of the sensitizing dye of the present invention represented by the general formula (1) include: purification by column chromatography; purification by adsorption of silica gel, activated carbon, activated clay, etc.; Known methods such as solvent recrystallization and crystallization methods can be used. In addition, identification of these compounds can be performed by nuclear magnetic resonance analysis (NMR) or the like. The sensitizing dyes of the present invention may be used alone or in combination of two or more. In addition, the sensitizing dye of the present invention may be used in combination with other sensitizing dyes that do not belong to the present invention. Specific examples of other sensitizing dyes include ruthenium complexes, coumarin-based dyes, cyanine-based dyes, merocyanine-based dyes, rhodaniline-based dyes, phthalocyanine-based dyes, porphyrin-based dyes, 𠮿

It is a sensitizing dye other than the sensitizing dye represented by the above-mentioned general formula (1), such as a dye. When the sensitizing dye of the present invention and other sensitizing dyes are combined and used as a sensitizing dye composition for photoelectric conversion, it is preferable to compare the other sensitizing dyes with the sensitizing dye of the present invention. The usage-amount is 10-200 weight%, More preferably, it is 20-100 weight%. The sensitizing dyes of the present invention can be used as photoreceptors, photocatalysts, photofunctional materials and other photosensitive dyes for various imaging materials such as silver halide, zinc oxide, titanium oxide, etc., and can also be used as dye-sensitized photoelectric conversion elements. Sensitizing dye composition for photoelectric conversion, etc. used in etc. In the present invention, the method for producing the dye-sensitized photoelectric conversion element is not particularly limited, and it is preferable to form a semiconductor layer on a conductive support (electrode), and to make the semiconductor layer adsorb (support) the photoelectric conversion element of the present invention. The sensitizing dye composition is converted to produce a photoelectrode (refer to FIG. 1. Needless to say, since the drawing is easy to understand, it is not a faithful reduction scale of the actual element). As a method of adsorbing a dye, a method of immersing the semiconductor layer in a solution obtained by dissolving the dye in a solvent for a long time is usually employed. When two or more kinds of the sensitizing dyes of the present invention are used in combination, or when the sensitizing dyes of the present invention are used in combination with other sensitizing dyes, a mixed solution of all the dyes used can be prepared and the semiconductor layer can be dipped, Moreover, a solution may be prepared separately for each dye, and the semiconductor layer may be sequentially immersed in each solution. In the present invention, as the conductive support, in addition to the metal plate, a glass substrate or a plastic substrate provided with a conductive layer having a conductive material on the surface can be used. Specific examples of the conductive material include metals such as gold, silver, copper, aluminum, and platinum, fluorine-doped tin oxide, conductive transparent oxide semiconductors such as indium-tin composite oxide, carbon, and the like, preferably used. A glass substrate coated with a fluorine-doped tin oxide film. In the present invention, specific examples of the semiconductor forming the semiconductor layer include titanium oxide, zinc oxide, tin oxide, indium oxide, zirconium oxide, tungsten oxide, tantalum oxide, iron oxide, gallium oxide, nickel oxide, and yttrium oxide. and other metal oxides; titanium sulfide, zinc sulfide, zirconium sulfide, copper sulfide, tin sulfide, indium sulfide, tungsten sulfide, cadmium sulfide, silver sulfide and other metal sulfides; titanium selenide, zirconium selenide, indium selenide, selenide Metal selenides such as tungsten; separate semiconductors such as silicon and germanium, etc. These semiconductors may be used alone or in combination of two or more. In the present invention, it is preferable to use one or two or more selected from the group consisting of titanium oxide, zinc oxide, and tin oxide as the semiconductor. The aspect of the semiconductor layer of the present invention is not particularly limited, but it is preferably a thin film having a porous structure composed of fine particles. Due to the porous structure or the like, the substantial surface area of the semiconductor layer is increased, and if the amount of dye adsorbed on the semiconductor layer is increased, a high-efficiency photoelectric conversion element can be obtained. The particle size of the semiconductor is preferably 5 to 500 nm, more preferably 10 to 100 nm. The film thickness of the semiconductor layer is usually 2 to 100 μm, more preferably 5 to 20 μm. Examples of a method for producing the semiconductor layer include applying a solder paste containing semiconductor fine particles on a conductive substrate by wet coating methods such as spin coating, doctor blade, extrusion, screen printing, etc. A method of forming a film by removing the solvent or additives by firing, or a method of forming a film by sputtering, vapor deposition, electrodeposition, electrolysis, microwave irradiation, etc., but not limited to such. In the present invention, as the solder paste containing semiconductor fine particles, a commercially available product may be used, or a solder paste prepared by dispersing commercially available semiconductor fine powder in a solvent, or the like may be used. Specific examples of the solvent used in preparing the solder paste include: water; alcohol-based solvents such as methanol, ethanol, and isopropanol; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; n-hexane , cyclohexane, benzene, toluene and other hydrocarbon-based solvents, but are not limited to these. In addition, these solvents may be used alone or as a mixed solvent of two or more. In the present invention, as a method of dispersing the semiconductor fine powder in a solvent, the powder can be ground by a mortar or the like, or a ball mill, a paint conditioner, a vertical type bead mill, a horizontal type bead mill, Grinders and other dispersers. When preparing the solder paste, in order to prevent the aggregation of semiconductor fine particles, it is preferred to add a surfactant or the like, and in order to increase the viscosity, it is preferred to add a tackifier such as polyethylene glycol. The adsorption of the sensitizing dye composition for photoelectric conversion of the present invention on the surface of the semiconductor layer can be achieved by, for example, immersing the semiconductor layer in the dye solution, and leaving it at room temperature for 30 minutes to 100 hours or under heating conditions for 10 minutes to 24 hours. placed for hours. In this case, it is preferable to stand at room temperature for 10-20 hours, and the pigment concentration in the pigment solution is preferably 10-2000 μm, more preferably 50-500 μm. Specific examples of the solvent used when the sensitizing dye composition for photoelectric conversion of the present invention is adsorbed on the surface of the semiconductor layer include alcohol-based solvents such as methanol, ethanol, isopropanol, and tert-butanol; acetone. , methyl ethyl ketone, methyl isobutyl ketone and other ketone solvents; ethyl formate, ethyl acetate, n-butyl acetate and other ester solvents; diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran , 1,3-dioxolane and other ether solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amides Solvents; nitrile-based solvents such as acetonitrile, methoxyacetonitrile, and propionitrile; halogenated hydrocarbon-based solvents such as dichloromethane, chloroform, bromomethane, and o-dichlorobenzene; hydrocarbon-based solvents such as n-hexane, cyclohexane, benzene, and toluene, etc. , but not limited to these. These solvents can be used alone or in the form of two or more mixed solvents. Among these solvents, one or more selected from methanol, ethanol, tert-butanol, acetone, methyl ethyl ketone, tetrahydrofuran, and acetonitrile are preferably used. When the sensitizing dye composition for photoelectric conversion of the present invention is adsorbed on the surface of the semiconductor layer, cholic acid or cholic acid derivatives such as deoxycholic acid, chenodeoxycholic acid, lysocholic acid, and dehydrocholic acid can also be adsorbed. Dissolved in pigment solution and co-adsorbed with pigment. By using cholic acid or a cholic acid derivative, the association of dyes can be suppressed, and electrons can be efficiently injected from the dye into the semiconductor layer in the photoelectric conversion element. In the case of using cholic acid or cholic acid derivatives, the concentration of these in the pigment solution is preferably 0.1-100 mM, more preferably 0.5-10 mM. The counter electrode (electrode) used in the photoelectric conversion element of the present invention is not particularly limited as long as it has conductivity, and in order to promote the redox reaction of redox ions, it is preferable to use conductivity having catalytic ability. Material. Specific examples of the conductive material include platinum, rhodium, ruthenium, carbon, and the like, but are not limited to these. In the present invention, a thin film of platinum formed on a conductive support is preferably used as a counter electrode. In addition, as a method for producing the conductive film, there may be mentioned applying a solder paste containing a conductive material to a conductive material by a wet coating method such as spin coating, doctor blade method, extrusion method, and screen printing method. After being placed on the substrate, a method of forming a film by removing the solvent or additives by firing, or a method of forming a film by sputtering, vapor deposition, electrodeposition, electrolysis, microwave irradiation, etc. , but not limited to these. In the photoelectric conversion element of the present invention, an electrolyte layer is formed by filling an electrolyte between a pair of opposed electrodes. As the electrolyte to be used, a redox electrolyte is preferred. Examples of the redox electrolyte include redox ion pairs such as iodine, bromine, tin, iron, chromium, and anthraquinone, but are not limited to these. Among these, iodine-based electrolytes and bromine-based electrolytes are preferred. In the case of an iodine-based electrolyte, for example, a mixture of potassium iodide, lithium iodide, dimethylpropylimidazolium iodide, etc. and iodine can be used. In the present invention, an electrolyte solution obtained by dissolving these electrolytes in a solvent is preferably used. The concentration of the electrolyte in the electrolyte solution is preferably 0.05-5 M, more preferably 0.2-1 M. Examples of the solvent for dissolving the electrolyte include nitrile-based solvents such as acetonitrile, methoxyacetonitrile, propionitrile, 3-methoxypropionitrile, and benzonitrile; diethyl ether, 1,2-dimethoxyethane, Ether-based solvents such as tetrahydrofuran; amide-based solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; carbonate-based solvents such as ethylene carbonate and propylene carbonate; γ- Lactone-based solvents such as butyrolactone and γ-valerolactone, etc., are not limited to these. These solvents can be used alone or in the form of two or more mixed solvents. Among these solvents, nitrile-based solvents are preferred. In the present invention, in order to further improve the open circuit voltage and fill factor of the dye-sensitized photoelectric conversion element, an amine-based compound may be contained in the electrolyte solution. Examples of the amine compound include 4-tert-butylpyridine, 4-picoline, 2-vinylpyridine, N,N-dimethyl-4-aminopyridine, and N,N-dimethylaniline , N-methylbenzimidazole, etc. The concentration of the amine compound in the electrolyte is preferably 0.05 to 5 M, more preferably 0.2 to 1 M. As the electrolyte in the photoelectric conversion element of the present invention, a gel-like electrolyte obtained by adding a gelling agent, a polymer, or the like, or a solid electrolyte using a polymer such as a polyethylene oxide derivative can also be used. By using gel electrolyte and solid electrolyte, the volatilization of electrolyte can be reduced. In the photoelectric conversion element of the present invention, instead of the electrolyte, a solid charge transport layer may be formed between a pair of opposed electrodes. The charge transport material contained in the solid charge transport layer is preferably a hole transport material. Specific examples of the charge transport material include inorganic hole transport materials such as copper iodide, copper bromide, and copper thiocyanate, polypyrrole, polythiophene, polyparaphenylene vinylene, polyvinylcarbazole, polyaniline, Organic hole-transporting substances such as oxadiazole derivatives, triphenylamine derivatives, pyrazoline derivatives, phenone derivatives, hydrazone compounds, and stilbene compounds, are not limited to these. In the present invention, when a solid charge transport layer is formed using an organic hole transport material, a film-forming binder resin may be used together. Specific examples of the film-forming adhesive resins include polystyrene resins, polyvinyl acetal resins, polycarbonate resins, polysilicon resins, polyester resins, polyphenylene ether resins, polyarylate resins, alcohols Acid resin, acrylic resin, phenoxy resin, etc. are not limited to these. These resins may be used alone or in combination of one or two or more of them in the form of a copolymer. The amount of the binder resin used relative to the organic hole transport material is preferably 20 to 1000% by weight, more preferably 50 to 500% by weight. In the photoelectric conversion element of this invention, the electrode (photoelectrode) provided with the semiconductor layer which adsorb|sucked the sensitizing dye composition for photoelectric conversion becomes a cathode, and the opposing electrode becomes an anode. Light such as sunlight can be irradiated from either the photoelectrode side or the opposite electrode side, preferably from the photoelectrode side. When irradiated with sunlight or the like, the dye absorbs the light, becomes an excited state, and releases electrons. The electrons flow to the outside through the semiconductor layer and move to the opposite electrode. On the other hand, the dye which releases electrons and becomes an oxidized state returns to the base state by receiving electrons supplied from the opposite electrode via ions in the electrolyte. A current flows by these cycles, and functions as a photoelectric conversion element. When evaluating the performance (characteristics) of the photoelectric conversion element of the present invention, measurements of short-circuit current, open-circuit voltage, fill factor, and photoelectric conversion efficiency were performed. The so-called short-circuit current refers to every 1 cm that flows between the two terminals when the output terminal is short-circuited. ² The current, the so-called open-circuit voltage, refers to the voltage between the two terminals when the output terminal is opened. In addition, the so-called fill factor refers to the value obtained by dividing the maximum output (the product of current and voltage) by the product of short-circuit current and open-circuit voltage, and mainly depends on the internal resistance. Photoelectric conversion efficiency is calculated as the maximum output (W) divided by each 1 cm ² The value of the light intensity (W) was multiplied by 100 to obtain the value expressed as a percentage. The photoelectric conversion element of the present invention can be used for dye-sensitized solar cells or various light sensors. The dye-sensitized solar cell of the present invention is obtained by forming a photoelectric conversion element containing a sensitizing dye composition for photoelectric conversion containing the sensitizing dye represented by the above general formula (1) into a unit, and making the unit Arrange the required number of sheets to be modularized, and set up specific electrical wiring. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. Furthermore, in the synthesis examples, the compounds were identified by ¹ The H-NMR analysis was carried out (a nuclear magnetic resonance apparatus manufactured by JEOL Ltd., JNM-ECA-600). [Synthesis Example 1] Synthesis of Sensitizing Pigment (A-4) In a reaction vessel subjected to nitrogen replacement, 1.20 g of a bromide represented by the following formula (10) and 16 mL of dehydrated tetrahydrofuran were placed in While stirring at -72°C, 1.5 mL of a 1.6 M n-butyllithium hexane solution was added dropwise, and the reaction was carried out for 1 hour. After the reaction, 0.3 mL of dehydrated dimethylformaldehyde was added dropwise to the reaction solution, and the reaction was carried out for 2 hours. The reaction solution was emptied into 50 mL of ice water, and the organic layer was extracted with dichloromethane. After the organic layer was washed with water, it was separated, dried over magnesium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: hexane/toluene = 9/1 (volume ratio)) to obtain a yellow solid of the formamate compound represented by the following formula (11). (0.78 g). [Chemical 72]

[Chemical 73]

In the reaction vessel subjected to nitrogen substitution, 0.300 g of the carboxyl compound represented by the above formula (11), 0.179 g of the indanone compound represented by the following formula (12), acetic acid/toluene=5/2 ( 13.5 mL of the mixed solution by volume ratio) was stirred at 90° C. for 3 hours. After the reaction solution was allowed to cool to 25°C, 50 mL of water was added, followed by stirring, and the organic layer was extracted. The organic layer was washed successively with water and saturated brine and dried to obtain the target sensitizing dye (0.294 g, yield 75%) as a dark purple solid. [Chemical 74]

NMR analysis of the obtained dark purple solid was carried out, and the following 26 hydrogen signals were detected, and it was identified as the structure represented by the following formula (A-4) (the hydrogen of the carboxyl group was not observed). ¹ H-NMR (600 MHz, CDCl ₃ ) : δ (ppm)=6.01-6.05(2H), 6.90-6.95(2H), 7.05-7.08(1H), 7.23-7.27(5H), 7.30-7.40(8H), 7.42-7.50(2H), 7.55 -7.65(1H), 7.94-8.01(2H), 8.28-8.32(1H), 8.36-8.40(1H), 8.50-8.55(1H). [Chem. 75]

[Synthesis Example 2] Synthesis of Sensitizing Pigment (A-10) In a reaction vessel subjected to nitrogen replacement, 1.50 g of the bromide represented by the above formula (10), 30 mL of toluene, 8 mL of ethanol, 8 mL of water, 0.81 g of 5'-formyl-2,2'-bisthiophene-5-boronic acid, and 0.62 g of potassium carbonate were stirred for 5 hours. After stirring, the pressure reduction, degassing, and Nitrogen replacement. Next, 0.18 g of tetrakis(triphenylphosphine)palladium was added, and the mixture was stirred at 80°C for 5 hours. After the reaction solution was allowed to cool to 25°C, 10 mL of ethyl acetate and 30 mL of water were added and stirred, and the organic layer was extracted. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: chloroform/hexane = 3/1 (volume ratio)), and dried to obtain a formamide represented by the following formula (13). Compound as a tan solid (1.20 g). [Chemical 76]

In a reaction vessel subjected to nitrogen replacement, put 0.64 g of the carboxylate compound represented by the above formula (13), 13.5 mL of a mixed solution of acetic acid/toluene=5/2 (volume ratio), and 13.5 mL of the mixed solution represented by the above formula (12). 0.29 g of the indanone compound was obtained, and the mixture was stirred at 90° C. for 3 hours. After the reaction solution was allowed to cool to 25°C, 80 mL of water was added, followed by stirring, and the organic layer was extracted. The organic layer was washed with water and saturated brine in this order and dried to obtain the target sensitizing dye (0.53 g, yield 65%) as a black solid. NMR analysis of the obtained black solid was carried out, and the following 30 hydrogen signals were detected, and the structure was identified as the structure represented by the following formula (A-10) (the hydrogen of the carboxyl group was not observed). ¹ H-NMR (600 MHz, CDCl ₃ ) : δ (ppm)=5.96-6.06(1H), 6.08-6.18(1H), 6.85-6.95(3H), 6.94-7.04(1H), 7.04-7.14(4H), 7.15-7.25(3H), 7.32 -7.42(2H), 7.46-7.56(9H), 7.66-7.76(1H), 7.78-7.88(2H), 8.06-8.16(1H), 8.57-8.67(2H). [Chem.77]

[Synthesis Example 3] Synthesis of Sensitizing Pigment (A-51) In a reaction vessel subjected to nitrogen replacement, 2.0 g of a bromide represented by the following formula (14) and 30 mL of dehydrated tetrahydrofuran were placed in While stirring at -72°C, 3.0 mL of a 1.6 M n-butyllithium hexane solution was added dropwise, and the reaction was carried out for 1 hour. After the reaction, 0.6 mL of dehydrated dimethylformaldehyde was added dropwise to the reaction solution, and the reaction was carried out for 2 hours. Then, the reaction liquid was emptied into 150 mL of ice water, and the organic layer was extracted with dichloromethane. The organic layer was washed with water, separated, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: hexane/toluene = 9/1 (volume ratio)) to obtain a yellow-white solid of the formate compound represented by the following formula (15) ( 0.99 g). [Chemical 78]

[Chemical 79]

Into the reaction vessel subjected to nitrogen substitution, put 0.300 g of the carboxyl compound represented by the above formula (15), 0.150 g of the indanone compound represented by the above formula (12), acetic acid/toluene=5/2 (volume) ratio) mixed solution 13.5 mL, and stirred at 90° C. for 4 hours. After the reaction liquid was left to cool to 25°C, 30 mL of toluene was added and stirred, and the organic layer was extracted. The organic layer was washed with water and saturated brine in this order, and the obtained organic layer was dried to obtain the target sensitizing dye (0.286 g, yield 74%) as a dark brown solid. NMR analysis of the obtained black-brown solid was carried out, and the following 30 hydrogen signals were detected, and the structure was identified as the structure represented by the following formula (A-51) (the hydrogen of the carboxyl group was not observed). ¹ H-NMR (600 MHz, CDCl ₃ ) : δ (ppm)=1.87-1.90(6H), 6.34-6.39(2H), 7.33-7.36(1H), 7.39-7.42(1H), 7.44-7.48(3H), 7.54-7.60(4H), 7.66 -7.69(2H), 7.82-7.86(4H), 7.99-8.02(3H), 8.03-8.08(1H), 8.12-8.20(1H), 8.30-8.40(2H). [Chem.80]

[Synthesis Example 4] Synthesis of sensitizing dye (A-60) In a reaction vessel subjected to nitrogen substitution, 0.55 g of the bromide represented by the above formula (14), 5-formyl-2- 0.197 g of thiopheneboronic acid, 20 mL of dimethylsulfoxide, and 0.124 g of potassium carbonate were added and stirred for 5 hours. After stirring, the pressure reduction, degassing, and nitrogen replacement in the reaction vessel were repeated 5 times. Next, 0.012 g of palladium acetate and 0.038 g of butylbis(1-adamantyl)phosphine were added, and the pressure reduction, degassing, and nitrogen replacement in the reaction vessel were repeated five times. Then, it stirred at 75 degreeC for 3 hours. The reaction solution was allowed to cool to 25°C, 150 mL of chloroform and 60 mL of water were added and stirred, and the organic layer was extracted. The organic layer was dried over magnesium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: silica gel, eluent: hexane/toluene = 1/4 (volume ratio)), and dried to obtain a formamide represented by the following formula (16). Compound as a yellow solid (0.543 g). [Chemical 81]

In the reaction vessel subjected to nitrogen replacement, 0.542 g of the carboxyl compound represented by the above formula (16), 0.256 g of the indanone compound represented by the formula (12), acetic acid/toluene=5/2 (volume ratio) were placed. ) mixture was 28 mL, and was stirred at 90° C. for 10 hours. After the reaction liquid was left to cool to 25°C, 50 mL of toluene was added and stirred, and the organic layer was extracted. Washed with water and saturated brine in this order, the obtained organic layer was dried to obtain the target sensitizing dye (0.453 g, yield 67%) as a reddish-brown solid. The obtained reddish-brown solid was subjected to NMR analysis, and the following 32 hydrogen signals were detected, which was identified as the structure represented by the formula (A-60) (the hydrogen of the carboxyl group was not observed). ¹ H-NMR (600 MHz, CDCl ₃ ) : δ (ppm)=1.82-1.86(6H), 6.32-6.40(2H), 7.30-7.35(1H), 7.35-7.40(1H), 7.41-7.49(3H), 7.53-7.59(5H), 7.64 -7.69(2H), 7.80-7.88(4H), 8.00-8.10(5H), 8.27-8.34(2H), 8.36-8.40(1H). [Chemical 82]

[Synthesis Example 5] Synthesis of sensitizing dye (A-48) In addition to using 4-formylphenylboronic acid instead of the raw material 5-formyl-2-thiopheneboronic acid in Synthesis Example 4, the same Example 4 was synthesized in the same manner to obtain the target sensitizing dye (0.486 g, yield 75%) as a reddish-brown solid. The obtained reddish-brown solid was subjected to NMR analysis, and the following 34 hydrogen signals were detected, which were identified as the structure represented by the formula (A-48) (the carboxyl group hydrogen was not observed). ¹ H-NMR (600 MHz, CDCl ₃ ) : δ (ppm)=1.83-1.87(6H), 6.31-6.39(2H), 7.28-7.34(1H), 7.33-7.39(1H), 7.41-7.49(3H), 7.53-7.60(5H), 7.63 -7.68(2H), 7.81-7.88(3H), 7.92-7.99(3H), 8.01-8.08(4H), 8.34-8.41(1H), 8.41-8.45(1H), 8.63-8.69(2H). [Chemical 83]

[Synthesis Example 6] Synthesis of Sensitizing Dye (A-61) In a reaction vessel subjected to nitrogen substitution, 0.251 g of a carboxyl compound represented by the following formula (17), represented by the formula (12) was placed 0.124 g of the indanone compound and 15 mL of a mixed solution of acetic acid/toluene=5/2 (volume ratio) were stirred at 90° C. for 6 hours. After the reaction liquid was left to cool to 25°C, 30 mL of toluene was added and stirred, and the organic layer was extracted. Washed with water and saturated brine in this order, the obtained organic layer was dried to obtain the target sensitizing dye (0.268 g, yield 87%) as a reddish-purple solid. [Chemical 84]

The obtained red-purple solid was subjected to NMR analysis, and the following 34 hydrogen signals were detected, which were identified as the structure represented by the formula (A-61) (the carboxyl group hydrogen was not observed). ¹ H-NMR (600 MHz, CDCl ₃ ) : δ (ppm)=1.50-1.54(6H), 1.76-1.80(6H), 6.31-6.40(2H), 7.31-7.36(1H), 7.38-7.48(6H), 7.62-7.67(1H), 7.65 -7.70(2H), 7.71-7.76(1H), 7.80-7.84(1H), 7.87-7.92(1H), 7.96-8.08(2H), 8.12-8.23(2H), 8.28-8.37(1H), 8.35- 8.41(1H), 9.22-9.28(1H). [Chemical 85]

[Synthesis Example 7] Synthesis of sensitizing dye (A-62) The brominated compound represented by the following formula (18) was used instead of the brominated compound represented by the above formula (14) in Synthesis Example 4, except that Other than that, the synthesis was carried out in the same manner as in Synthesis Example 4, and the formazan body represented by the following formula (19) was obtained. [Chemical 86]

[Chemical 87]

In a reaction vessel subjected to nitrogen substitution, the carboxamide compound represented by the above formula (19) was reacted with the indanone compound represented by the above formula (12) in the same manner as in Synthesis Example 4, and the target was obtained as a purple solid. the sensitizing pigment (0.37 g, 73% yield). The NMR analysis of the obtained purple solid was carried out, and the following 36 hydrogen signals were detected, which were identified as the structure represented by the formula (A-62) (the hydrogen of the carboxyl group was not observed). ¹ H-NMR (600 MHz, CDCl ₃ ) : δ (ppm)=1.50-1.54(6H), 1.83-1.87(6H), 6.32-6.38(2H), 7.28-7.34(1H), 7.33-7.38(1H), 7.38-7.47(5H), 7.50 -7.56(1H), 7.61-7.71(4H), 7.77-7.82(1H), 7.83-7.87(1H), 7.94-8.02(3H), 8.03-8.07(1H), 8.16-8.21(1H), 8.25- 8.32 (2H), 8.33-8.40 (1H). [Chemical 88]

[Example 1] On a glass substrate coated with a fluorine-doped tin oxide film, a titanium oxide solder paste (PST-18NR manufactured by Nikki Catalyst Chemical Co., Ltd.) was applied by extrusion. After drying at 110°C for 1 hour, it was calcined at 450°C for 30 minutes to obtain a titanium oxide thin film with a thickness of 6 μm. Then, the sensitizing dye (A-4) obtained in Synthesis Example 1 was dissolved in a mixed solution of acetonitrile/tertiary butanol = 1/1 (volume ratio) to prepare 50 mL of a solution with a concentration of 100 μm, and in this In the solution, the glass substrate coated and sintered with titanium oxide was immersed at 25±2° C. for 15 hours to adsorb the dye and used as a photoelectrode. On a glass substrate coated with a fluorine-doped tin oxide film, an automatic viewfinder (JFC-1600 manufactured by Nippon Electronics Co., Ltd.) was used to form a platinum film with a thickness of 15 nm by sputtering as a counter electrode . Then, a spacer (hot-melt film) with a thickness of 60 μm was sandwiched between the photoelectrode and the opposite electrode and bonded by hot-melting, and an electrolyte (0.1 M lithium iodide, 0.6 M lithium iodide, 0.6 M dimethylpropylimidazolium iodide, 0.05 M iodine, 0.5 M 4-tert-butylpyridine)/3-methoxypropionitrile solution), and then the hole was sealed to prepare a photoelectric conversion element. From the photoelectrode side of the above-mentioned photoelectric conversion element, light generated by a simulated sunlight irradiation device (OTENTO-SUN III manufactured by Spectrometer Co., Ltd.) was irradiated, and a power meter (Model 2400 General-Purpose SourceMeter manufactured by KEITHLEY) was used. The current-voltage characteristics were measured. The intensity of light is adjusted to 100 mW/cm ² . The obtained measurement results and initial photoelectric conversion efficiencies are shown in Table 1. In addition, the result of the photoelectric conversion efficiency measured similarly about the characteristic change after irradiating light for 20 hours is collectively shown in Table 1. [Example 2 to Example 11] As the sensitizing dye for photoelectric conversion, a photoelectric conversion element was produced in the same manner as in Example 1, except that the sensitizing dye shown in Table 1 was used instead of (A-4). Table 1 summarizes the current-voltage characteristics of the obtained photoelectric conversion element, and the photoelectric conversion efficiency at the initial stage and after 20 hours of light irradiation. [Comparative Examples 1 to 5] As sensitizing dyes for photoelectric conversion, the sensitizing dyes shown in (B-1) to (B-5) below which do not belong to the present invention were used instead of (A-4), except that Otherwise, a photoelectric conversion element was produced in the same manner as in Example 1, and Table 1 shows the current-voltage characteristics of the obtained photoelectric conversion element, and the photoelectric conversion efficiency at the initial stage and after 20 hours of light irradiation. [Chemical 89]

[Chemical 90]

[Chemical 91]

[Chemical 92]

[Chemical 93]

[Table 1]

From the results in Table 1, it can be judged that by using the sensitizing dye composition for photoelectric conversion comprising the sensitizing dye of the present invention, a high photoelectric conversion efficiency can be obtained, and a high photoelectricity can be maintained even if the light irradiation is continued for a long time. Photoelectric conversion element with conversion efficiency. On the other hand, the photoelectric conversion efficiency of the photoelectric conversion element using the sensitizing dye for photoelectric conversion of the comparative example was insufficient. [Industrial Applicability] The sensitizing dye composition for photoelectric conversion composed of the sensitizing dye of the present invention is useful for high-efficiency and high-durability photoelectric conversion elements and dye-sensitized solar cells, and can be used as a Solar cells that efficiently convert solar energy into electrical energy provide clean energy.

1‧‧‧Conductive support 2‧‧‧Dye-supported semiconductor layer 3‧‧‧Electrolyte layer 4‧‧‧Counter electrode 5‧‧‧Conductive support

FIG. 1 is a schematic cross-sectional view showing the structure of a photoelectric conversion element according to an example and a comparative example of the present invention.

1‧‧‧Conductive support

2‧‧‧Dye-supported semiconductor layer

3‧‧‧Electrolyte layer

4‧‧‧Reverse electrode

5‧‧‧Conductive support

Claims (6)

A sensitizing dye, which is represented by the following general formula (1),

In the formula, Ar represents an aryl group with 6 to 36 carbon atoms that may also have a substituent; R ¹ to R ⁴ may be the same or different, and represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, and a nitroso group , thiol group, a straight-chain or branched alkyl group with 1 to 36 carbon atoms that may have a substituent, a cycloalkyl group with 3 to 36 carbon atoms that may have a substituent, or a substituted group A linear or branched alkoxy group with 1 to 36 carbon atoms in the group, a cycloalkoxy group with 3 to 36 carbon atoms that may have a substituent, or a substituted group with 2 to 2 carbon atoms. 36 linear or branched alkenyl groups, aryl groups with 6 to 36 carbon atoms that can also have substituents, or amine groups with 0 to 36 carbon atoms that can also have substituents; R ¹ ~R ⁴ can also be adjacent groups bonded to each other to form a ring; X represents a sulfur atom, an oxygen atom or CR ⁵ R ⁶ ; R ⁵ and R ⁶ can be the same or different, and represent the number of carbon atoms that can also have a substituent 1 A linear or branched alkyl group of ~36, or an aryl group of 6 to 36 carbon atoms that may also have a substituent; Z is a monovalent group represented by the following general formula (2),

In the formula, R ⁷ to R ¹² may be the same or different, and represent a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms as a substituent, or a carbon atom with a substituent. A linear or branched alkoxy group of 1 to 18, or a linear or branched alkenyl of 2 to 18 carbon atoms that may also have substituents; R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² can also be bonded to each other to form a ring; m represents an integer of 0~2, n represents an integer of 0~4, when m is 2 or n is an integer of 2~4 In this case, regarding a plurality of R ⁷ to R ¹² , the R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be the same or different from each other; R ¹³ and R ¹⁴ represents a hydrogen atom or an acidic group, and at least ^{either one of R 13} or R ¹⁴ is an acidic group. The sensitizing dye according to claim 1, wherein in the general formula (2), R ⁷ to R ¹² are hydrogen atoms or unsubstituted linear or branched alkyl groups with 1 to 6 carbon atoms. The sensitizing dye according to claim 1 or 2, wherein m is 0 and n is 0 in the above general formula (2). A sensitizing dye composition for photoelectric conversion, which contains the sensitizing dye according to any one of claims 1 to 3. A photoelectric conversion element using the sensitizing dye composition for photoelectric conversion as claimed in claim 4. A dye-sensitized solar cell using the photoelectric conversion element as claimed in claim 5.

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