TW200422379A - Photo functional material - Google Patents

Photo functional material Download PDF

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Publication number
TW200422379A
TW200422379A TW093101139A TW93101139A TW200422379A TW 200422379 A TW200422379 A TW 200422379A TW 093101139 A TW093101139 A TW 093101139A TW 93101139 A TW93101139 A TW 93101139A TW 200422379 A TW200422379 A TW 200422379A
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TW
Taiwan
Prior art keywords
photoelectric conversion
group
substituted
patent application
electrode
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TW093101139A
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Chinese (zh)
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TWI318638B (en
Inventor
Tadao Yagi
Motonori Ando
Ryuichiro Kurata
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Toyo Ink Mfg Co
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Publication of TW200422379A publication Critical patent/TW200422379A/en
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Publication of TWI318638B publication Critical patent/TWI318638B/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
    • C07F9/3826—Acyclic unsaturated acids
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
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    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4015—Esters of acyclic unsaturated acids
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    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/409—Compounds containing the structure P(=X)-X-acyl, P(=X) -X-heteroatom, P(=X)-X-CN (X = O, S, Se)
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    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/5537—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom the heteroring containing the structure -C(=O)-N-C(=O)- (both carbon atoms belong to the heteroring)
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    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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    • C07F9/60—Quinoline or hydrogenated quinoline ring systems
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    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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    • C07F9/64—Acridine or hydrogenated acridine ring systems
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    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/65031—Five-membered rings having the nitrogen atoms in the positions 1 and 2
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
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    • C07F9/6509—Six-membered rings
    • C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
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    • C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
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    • C07F9/653—Five-membered rings
    • C07F9/65324—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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    • C07F9/6539—Five-membered rings
    • C07F9/6541—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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    • C07F9/6544—Six-membered rings
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    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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    • C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
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    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

This invention provides a photo functional material having vinylphosphonic acid group, preferably a photo functional material having chemical structure represented by the following formula (1), (in the formula, X represents a 1-valent organic residual group; R1 and R2 respectively represent a hydrogen or a 1-valent organic residual group; M1 and M2 respectively represent a hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted silyl group, or a cation. R1 and R2, R1 and X, or R2 and X may respectively bound to each other to form a ring. Further, X and R2 maybe exchanged to each other.) The photo functional material of the invention may be preferably used as the sensitized dye for photoelectric transforming a dye-sensitized photoconductivity cell, and can be provided as the sensitized dye for photoconductivity having high photoelectric transforming efficiency and strong adhesion with an inorganic semiconductor surface.

Description

200422379 玫、發明說明： 【發明所屬之技術領域】 …本發明係有關光機能材料，該光機能材料係可使用於 光電轉變材料、光發光材料或光吸收材料等。再者，本發 月係有關使用該光機能材料之光電轉換用增感色素、光電 轉換材料、光電轉換電極、以及使用該光機能材料之光電 轉變電池（太陽能電池）。 【先前技術】 、關於太陽光發電，較實用性的為單結晶矽太陽能電 池、多結晶石夕太陽能電池、非晶石夕太陽能電池、蹄化録以 及石西化鋼等化合物之太陽能電池，且雖已成為研究開發對 象，但若加以普及，則須克服：製造成本高、原材料二確 保困難、能源回收期間長等問題…方面，使用以大面積 化、低價格為取向的有機材料之太陽電池至目前為止雖有 很多提案’但有所謂轉換效率低、对久性差等問題。 -,丨ί:種狀況下，便揭示以使用由色素增感之半導體微 ί之二粗之光電轉換電極以及光電轉換電池，以及製成該 以及製造技術（參照自然雜誌，353卷·· Μ?至7仂 :二991年；美國專利彻721號說明書卜此係 =、Γ二氧化：薄膜之表面上，亦即為色素增感型太 化钬,孔所田而^ ’係以由舒錯體色素所分光增感之氧 化鈦夕孔質溥層作為作用 八為主體之電解質層以 eIec—^ 电、〜此方式的第-優點係因使用氧化鈦等廉價氧 315399 5 200422379 化物半導體而可提供廉價之光電轉換單元，第二優點係所 使用之釕錯體色素在可視光區域内有廣泛吸收，因此可得 _ 到比較高的轉換效率。 . 《其，最近’非釕錯體色素在色素增感型太陽能電池 中作為增感色素之研究頗為活躍。該例可 系色素，歌菁系色素，香豆素系色素，深藍系色：： 糸色素，偶氮系色素等。該等之有機色素與舒錯體相比， • S吸光係數大，分子設計之自由度亦大，因此便期待著高 光電轉換效率。儘管如此，因色素之光吸收區域狹窄，且 將電何注入氧化鈦上係無效率，因此並非優良之有機增感 色素。 為解決該等問題，開發出與氧化鈦之吸附末端上置有 特徵之增感色素，該增感色素為具有取代丙烯酸部位之增 感色素’顯不出具有較高之轉換效率（參照特開2〇〇2_ 164089號公報，W〇02/11213號簡介）。此增感色素之優點 % 為將色素骨架與取代丙烯酸部位結合，由增感色素提升對 氧化鈦等之無機半導體上之電荷注入效率。但是使用羧基 以作為對氧化鈦表面之吸附基時，由於羧基之吸附力弱， 因此便有指出如在電解液上混入少量水時，色素因pH而 從氧化欽表面脫離，使電池之壽命減少（無機化學，36卷： 5937至5946頁，1997年；無機化學，39卷：4542至4547 頁，2000 年）。 y 因此’期待所開發之色素增感型太陽能電池之色素， 能具有高光電轉換效率，且為穩定性高之材料。 6 315399 200422379 【發明内容】 本發明係有關具有乙烯膦酸基之光機能材料。例如較 好使用含有通式（1)中表示之化學結構的光機能材料。200422379 Description of the invention: [Technical field to which the invention belongs] ... The present invention relates to optical functional materials, which can be used for photoelectric conversion materials, light emitting materials or light absorbing materials. In addition, this issue is related to photoelectric conversion sensitizing dyes, photoelectric conversion materials, photoelectric conversion electrodes, and photoelectric conversion cells (solar cells) using the optical functional materials. [Previous technology] For solar power generation, the more practical ones are monocrystalline silicon solar cells, polycrystalline stone solar cells, amorphous stone solar cells, hoofing records, and chemical compounds such as Shixi Chemical Steel. It has become a research and development object, but if it is popularized, it must be overcome: problems such as high manufacturing costs, difficulty in securing raw materials, long energy recovery periods, etc. In terms of large-area, low-price organic materials, solar cells are used to Although there are many proposals so far, there are problems such as low conversion efficiency and poor durability. -, 丨 ί: Under these conditions, it will be revealed that the use of dye-sensitized semiconductor micro-solar photoelectric conversion electrodes and photoelectric conversion cells, as well as the production and manufacturing technology (see Nature Magazine, Vol. 353 ·· M ~ 7 仂: 2991; U.S. Patent No. 721 Specification This series =, Γ dioxide: on the surface of the film, that is, pigment-sensitized Taihua 钬, Kong Suotian and ^ 'Yue Youshu The photosensitized titanium oxide porosity layer formed by the distorted pigment serves as the electrolyte layer whose main function is eIec- ^ electricity. The first advantage of this method is due to the use of inexpensive oxygen such as titanium oxide 315399 5 200422379 compound semiconductor. A cheap photoelectric conversion unit can be provided. The second advantage is that the ruthenium complex pigment used has a wide absorption in the visible light region, so a relatively high conversion efficiency can be obtained. "It's the recent 'non-ruthenium complex pigment' Research on dye-sensitized solar cells has been active as a sensitizing dye. This example can be a pigment, a cyanine-based pigment, a coumarin-based pigment, a dark blue-based color: a tincture pigment, an azo-based pigment, etc. Organic pigments Compared with the wrong body, • S has a large light absorption coefficient and a large degree of freedom in molecular design, so high photoelectric conversion efficiency is expected. However, the light absorption region of the pigment is narrow, and the injection of electricity onto the titanium oxide is inefficient. Therefore, it is not an excellent organic sensitizing dye. In order to solve these problems, a sensitizing dye with characteristics on the adsorption end of titanium oxide has been developed. Has a high conversion efficiency (refer to Japanese Patent Application Publication No. 2000_164089, WO02 / 11213). The advantage of this sensitizing dye is to combine the pigment skeleton with the substitution of acrylic parts. The charge injection efficiency on inorganic semiconductors such as titanium oxide. However, when a carboxyl group is used as an adsorption group on the surface of titanium oxide, the adsorption force of the carboxyl group is weak, so it is pointed out that when a small amount of water is mixed in the electrolyte, the pigment is affected by pH. Detachment from the surface of oxidants reduces battery life (Inorganic Chemistry, Vol. 36: 5937-5946, 1997; Inorganic Chemistry, Vol. 39: 4542-4547, 2000 ) Y Therefore, 'the pigments of the dye-sensitized solar cells developed are expected to have high photoelectric conversion efficiency and high stability. 6 315399 200422379 [Summary of the Invention] The present invention relates to a polymer having a vinylphosphonic acid group. Optical functional materials. For example, optical functional materials containing a chemical structure represented by the general formula (1) are preferably used.

(1) (式中’ X表示1價的有機殘基，R1以及R2各自獨立，表 示氮原子或1價的有機殘基，M1以及M2各自獨立，表示 負*原子、取代或非取代之烷基、取代或非取代之芳基、取 代或非取代之甲矽烷基或陽離子。R〗與R2、R1與X以及 R與X ’各自之間可以互相結合形成環。且，X與R2可以 互換。） $夕卜本發明係有關光電轉換用增感色素，該光電轉換 用増感色素含上述本發明之光機能材料。 I ’另外本發明係有關光電轉換材料，該光電轉換材 料包括無機半導體與無機半導體上連接之本發明之光電轉 換用增感色素。 且’另外本發明係有關光電轉換電極，該光電轉換電 極含透明電極盘兮 〃 4透明電極上層疊之本發明之光電轉換材 料。 、且另外本發明係有關光電轉換電池，該光電轉換電 池包括上述本發明 月之先電轉換電極、電解質層與導電性對 7 315399 200422379 應電極。 本务月之光機能材料之特徵係以具有乙稀膦酸基者。 即本發明之光機能材料係只要具有乙烯膦酸基者，則無 ° 制尤其’係以具有下述通式（1)表示之化學結構之 化合物者為佳。(1) (In the formula, 'X represents a monovalent organic residue, R1 and R2 are each independent, representing a nitrogen atom or a monovalent organic residue, and M1 and M2 are each independently representing a negative * atom, a substituted or unsubstituted alkane Group, substituted or unsubstituted aryl group, substituted or unsubstituted silyl group or cation. Each of R and R2, R1 and X, and R and X 'may be combined with each other to form a ring. In addition, X and R2 may be interchanged. .) The present invention relates to a sensitizing dye for photoelectric conversion, and the sensitizing dye for photoelectric conversion contains the above-mentioned light-functional material of the present invention. I 'In addition, the present invention relates to a photoelectric conversion material including the inorganic semiconductor and the sensitizing dye for photoelectric conversion of the present invention connected to the inorganic semiconductor. In addition, the present invention relates to a photoelectric conversion electrode which includes a transparent electrode plate. 4 The photoelectric conversion material of the present invention is laminated on a transparent electrode. In addition, the present invention relates to a photoelectric conversion battery, which includes the above-mentioned first electric conversion electrode, an electrolyte layer, and a conductive counter electrode of the present invention. The characteristics of the light function material of this month are those having an ethyl phosphonic acid group. That is, as long as the optical functional material of the present invention has a vinylphosphonic acid group, it is not particularly preferred if it is a compound having a chemical structure represented by the following general formula (1).

M1 (1) (式X表示1價的有機殘基，R】以及R2各自獨立，表 :氫原子或1價的有機殘基，以及M2各自獨立，表示 气^子取代或非取代之烷基、取代或非取代之芳基、取 \或非取代之甲；5夕燒基或陽離子。R】與r2、r〗與X以及 R X，各自之間可以互相結合形成環。且，X與R2可以 口本I月中，光機能材料係表示，經由光的吸收而重 新=現其具有增感效果、發熱效果、發色效果、褪色效果、 蓄光效果、相變化效果、光電轉換效果、光磁氣效果、光 催：效果、光變調效果、光紀錄效果、自由基產生效果等 此之材料’或相反地接受該等效果以具有發光機能之材 此光機能材料可廣泛地使用例如光電轉換材料、發光 ;斗光、、、己錄材料、影像形成材料、光致變色材料、電致 發光材料、光導電材料、二色性材料、自由基產生材料、 315399 8 200422379 酸產生材料、鹼產生材料、蓄光材料 第二高譜波產生材料、第三高譜波產生材料、2 、 光吸收材料、近紅外光譜吸收材料、光化學燒^ ^ 科T材料、光化學治療用增感材料、光相變化 、、、己錄材枓、光燒結紀錄材料、 十尤磁乳紀錄材料、光線力學 療法用色素以及光電轉換用增感色素等。 以下，係說明有關將含乙烯膦酸基，尤其是主要以具 ::式(1)中化學結構的光機能材料，作為光電轉換用增感 ^時，在本說明書中將此光機能材料作為其代表適用形 悲’雖稱為光電轉換用增感色素或單稱為增感色素，但並 不否定上述的廣泛應用。 光電轉換用增感色素之必要機能，係例如色素廣泛具 2吸收領域以及#效率地將電荷注入氧化鈦#之無機半導 體上。為擴大色素之吸收領域，則以在上述通式（1)之X上 導入能夠擴大吸收領域之有機殘基為佳。為了使該吸收領 域廣化，X係以電子供給性之有機殘基為佳，如胺基等之 有機殘基可發揮高的效果。 為有效率地注入電荷，增感色素上須有固定基，能夠 吸附於無機半導體表面，而本發明之光機能材料因有膦酸 基’作為增感色素使用時，能滿足此條件。膦酸基和羧酸 基相比’對於氧化鈦等無機半導體，具有更強的吸附能， 因此難於引起色素之脫離，因此可期待元件之耐久化。 尤其’一個磷原子有二個酸性基（-ΟΜ1與-ΟΜ2)，由各 自的相加效果與螯合效果，可發揮強烈的吸附效果。且， 9 315399 200422379 更口有更強的吸附能，在元件完成時，可加快無機半導體 電極上吸附色素時的吸附速度，而亦有可縮短製造時間之 優點。 ^ 述口疋基與無機半導體表面之間生成強的化學結 a使彼此的電子雲有效地重疊在一起，可迅速實現從增 感色素到無機半導體表面上的電子移動。加上，因有膦酸 基：對水、醇等之溶解性亦變佳，因此作為吸附用溶劑， 翁該等可成為對環境負荷為小之吸附用溶劑，且作為色素溶 液，不僅可使用時間化“旧幻長，進而可降低製造成本。 在光電轉換用增感色素之發色團部位吸收光而生成之 激發電子，有效地注入到吸附有增感色素之無機半導體之 傳導f上，為传到具有高光電轉換效率之元件，增感色素 之吸附部位（固定基）周邊須有強力之拉電子性。且，發色 團之7Γ電子共軛若連不到固定基，不能夠將增感色素内生 成之激發電子有效地傳達至固定基。 ^ 命J舉如，通式⑴的結構上，該Rl位置上可引入取代 基。R上右引入拉電子取代基，乙烯膦酸基成為更強的電 子接收體，使分子内的電荷移動更為有效。因此由增感色 素向氧化鈦等之無機帛導體上注入電荷能更有j文地進行之 點看來，其效果極佳。 亦即，乙烯膦酸基係將發色團部位之π電子共輛結構 k才目連到膦酸之結合位置，便具有首次可將拉電子基配置在 /脚I附近之化學結構。相對於此，如直接結合在苯膦酸基 之方香％之膦酸結構中’在附近因無法引入拉電子基，與 315399 200422379 乙烯膦酸基相比，其注 如此，由本發明之 表示之化學結構，首次 定基係對使無機半導體 性0 入電荷效率差，光電轉換效率亦低。 乙稀膦酸結構，經由取得如通式（工） 實現了增感色素具有固定基，該固 同時具有強吸附能與強電子接收 /、次，說明通式（1)中的各官能基。 通式⑴中X表示i價之有機殘基。在此所述之有機殘 :並無特別限制’例舉如：亦可具有取代基(即取代或非取 :的)之一價芳香族煙殘基’取代或非取代之-價雜環殘 取代或非取代之一價脂肪族不飽和烴殘基，取代或非 取代之—價胺基，取代或非取代之_價有機金屬錯體殘 基0 芳香族烴殘基之芳香環雖 苯、萘、蒽、萘并萘、芘、菲 聯笨、聯三苯等。 無特別限制，惟可例舉如 、印、奠、二萘嵌苯、芴、 雜環殘基之雜環雖無特 吩、吡咯、噁唑、異噁唑、 咲咱、吡啶、噠嗪、嘧啶、 桊吩、嗤琳、口卡嗤、卩丫 σ定、 咯烷、吡咯啉、咪唑琳、咪 等環、吡喃、四氫吡喃、二 噻吩等。 別限制，惟可例舉如呋喃、嘆 噻唑、異噻唑、咪唑、卩比嗤、 吡嗪、吲哚、苯并呋喃、笨并 氧雜蒽、吩噻嗪、吩σ惡嗪、卩比 唑烷、哌啶、哌嗦、嗎啉、奎 氧雜環己烷、四氫呋喃、四氫 卜泫寺之雜環可為4級化，亦可有抗衡離子。此時的 衡離子並無特別限制，一般的陰離子即可。例舉如，鹵 315399 11 200422379 子、高氯酸離子、四氟化硼離子、六氟鱗酸離子、氯氧化 物離子、甲續酸離子、甲苯石黃酸離子等。無抗衡離 - 亦可以分子内或分子間之羧基等酸性基中和。 > |，雜環係包含用於染料、顏料之色素骨架。所使用 之色素骨架例舉如，偶氮系色素、嗤0丫嗣系色素、二綱吼 嘻并吼"各系色素、史考林⑽色素hualelium)、深藍系色 素、部花青系色素、三苯甲烷系色素、氧雜I系色：:、卩卜 •琳系色素、葉綠素系色素、釕錯體系色素、彀藍系色素、 二奈嵌苯系色素、二噁嗪系色素、蒽醌系色素、酞 素、萘酞菁系色素。 脂肪族不飽和烴殘基，雖無特別限制，惟可例舉如乙 稀基、丁二烯基、H5·己三稀基，其不飽和結合的總 和較好為1至20之範圍。 胺基雖無特別限制，惟可例舉如，胺基、單或二烷胺 基、一或二芳胺基等，具體而言例舉如，N-甲胺基、N_乙 響基N，N 一乙胺基、n，n一二異丙胺基、n，N-二丁胺基、 N_卞月女基、ν，Ν·二苄胺基，义苯胺基、N,N-二苯胺基、 雙（間甲苯基）胺基，N，N-雙（對甲苯基）胺基，队；^_雙（對聯 本基）胺基等。 有機金屬錯體殘基之有機金屬錯體雖無特別限制，惟 可例舉如，二茂鐵、二茂釕、二茂鈦、二茂锆、酞菁、萘 - 駄菁、卩卜啉、聯吡啶釕絡合物。 , 以上所述’在通式U)中，X表示之有機殘基之芳香族 烴殘基、雜環殘基、脂肪族不飽和烴殘基、胺基以及有機 12 315399 200422379 金屬錯體殘基，係如上述 丌T具有1以上之取代基。該取 代基雖供特別限制，惟 # 氓了例舉如，烷基、芳基、雜環基、 夕：2 基方乳基、烷硫基、芳硫基、取代或非取代 女二取代或非取代之酸胺基、絲基统基、烧氧基幾 ::芳氧基幾基、羧基、磺基、膦酸基、氰基、異氰基、 硫氧酸g旨基、里石奋鸯酿 ” "氰i酉曰基、硝基、亞硝基、鹵原子、羥 基0 烧基之例舉如’碳數為1至30的取代或非取代之直鍵 狀、分支狀以及環狀烴。 芳土之例舉如上述芳香族烴殘基之芳香環，該等芳基 更亦可有取代基。 雜環基之例舉如前述具有雜環殘基之雜環。該些雜環 基更亦可有取代基。 外烷氧基之例舉如’甲氧基、乙t基、丙氧基、丁氧基、 第三丁氧基、辛氧基、第三辛氧基等碳數為1至20的烧氧 基。 醯基之例舉如，烷基羰基以及芳基羰基，具體而言可 例舉如，乙醯基，丙醯基，$曱醯基，甲苯醯基等碳數為 1至20的醯基。 芳氧基之例舉如，苯氧基、4_第三丁苯氧基、卜萘氧 基、2-萘氧基、9-蒽氧基等碳數為6至2〇的芳氧基。 烷硫基之例舉如，甲硫基、乙硫基、第三丁硫基、己 硫基、辛硫基等碳數為1至2()的烷硫基。 芳硫基之例舉如，苯硫基、2_甲基苯硫基、4_第三丁 315399 13 200422379 基苯硫基等碳數為6至20的芳硫基。 取代或非取代之胺基之例舉如，可以有取代基之上述 一價胺基。 取代或非取代醯胺基之例舉如，醯胺基、烷醯胺基、 芳香族醯胺基。 烷氧基烷基之例舉如，甲氧基甲基、乙氧基甲基、異 丙氧基甲基等碳數為1至20之烷氧基烷基。 烷氧基羰基之例舉如，甲氧基羰基、乙氧基羰基、第 二丁氧基羰基等碳數為1至2〇之烧氧基幾基。 芳氧基羰基之例舉如，苯氧基羰基、萘氧基羰基等碳 數為5至30之芳氧基羰基。 羧基，膦酸基，磺基等酸性基可形成金屬鹽、銨鹽。 結合於上述X之取代基以複數狀態存在時，該等之間 可相同或不同，又，該取代基之間亦可互相結合形成環。 且，X或結合於X之取代基，亦可與後述之Rl和R2結合 而形成環。 上述X中較佳的為有取代或非取代胺基之一價有機殘 基，例舉如，二芳基胺基苯基、二烷基胺基苯基、二烷基 月女基笨乙稀基。且，為了具有高光電轉換效率，X為具有 取代或非取代胺基之一價有機殘基，並且具有長共軛鏈， 該共軛鏈較好為剛性骨架。若具有長共軛鏈，則色素的光 吸收領域變廣，而且對於無機半導體上電荷注入部位之乙 烯私馱基，具有如胺基的電子供給性的取代基之單元結合 剛性骨架，可使提供體（donor)至接收體（acceptor)有效^ 315399 14 200422379 行分子内的電荷移動。 其次，說明通式⑴中的r1、r2cr1、 表示氫原子或1價之有機殘基。 在此所述之有機焱I、， 戈I亚無特別限制，惟可 述X同樣之有機殘基、取 ^ 或非取代鏈式煙殘基、經基、拉電子基。 取代 取代或非取代之環式煙殘基之環式煙之例可舉如環己 烷、環戊烷等碳數為3至 一 至20的飽和j辰式烴，如環己 戊稀' %己一細、環戊_嫌装#叙& 叹一烯寺奴數為3至30之不飽和環式 烴0 取代或非取代之鏈式烴殘基之鍵式煙基之例舉如，碳 數為1至3G之直鏈狀或分支鏈的烧基，該等鏈狀烴基亦可 含有不飽和結構。 拉電子基表示哈梅特之取代基定數σ大於〇的值。該 等之取代基並無特別限制，料例舉如，氰基、㈣、硝 基、醯基、烧氧基幾基、芳氧基幾基、统基續酿基、芳基 石黃醢基' 取代或非取代酿胺基、全氟縣、全氟燒硫基、 全氟院基m基、取代或非取代續醯胺基、4_氛苯基、齒原 子。又，其他例可舉為，化學，新發現（Rev)，91卷：165 至195頁，1991年（在此引用其揭示内容）記載之口大於〇 的值之拉電子基。 上述拉電子基中，醯基、烷氧基羰基、芳氧基羰基、 取代或非取代醯胺基之例可舉如：在χ表示之有機殘基中 作為取代基與例示之醯基、烷氧基羰基、芳氧基羰基、取 315399 15 200422379 代或非取代醯胺基相同者。 甲石黃酸基、乙基磺醯基、丙 烧基確醯基之例可舉如 基磺醯基等。 芳基石黃醯基之例可舉如，苯石黃酿基、甲苯石黃酿基等。 全氟烧基之例可舉如，三氣甲基、五氣乙基等。 全氣烧硫基之例可舉如，：r翁田六 牛戈一既甲硫基，五氟乙硫基等。 全氟烷基羰基之例可舉如，二麄 牛如一鼠乙醯基、五氟乙基羰 基等。 取代或非取代之石黃胺基之例可舉如n安基、二甲 基磺醯基、二乙胺基磺醯基、二苯胺基磺醯基等。 以上所述之R、R可相互結合形成環，亦可R】、R2 與x結合形成環。在此，R1及/或R2有取代基時，該等 之取代基間亦可彼此結合形成環，該取代基亦可與乂或X 之取代基結合形成環。 R1較佳為吸電子基。該吸電子基在無機半導體吸附部 位’並且’吸電子基結合於電荷注入部位之乙烯膦酸基上， 使乙烯膦酸基成為更強的電子接收基。因&，將可效率地 將電荷注入無機半導體中。 且，R1為拉電子基中以氰基者為佳。因為氰基為強拉 電子基，且穩定性亦高。 接著，說明通式（1)中的Μ1，M2。 以及M2各自獨立’表示氫原子、取代或非取代烧 基、取代或非取代芳基、取代或非取代甲石夕烷基或陽離子。 在此所述之烷基表示碳數為1至2〇之直鏈、分支鏈或 315399 16 200422379 環狀烴基，該等烴基亦可有不飽和結構。該等燒基中較好 的例舉如，甲基、乙基、異丙基、第三丁基、苄基等。 芳基之例可舉如，在上述X表示之有機殘基中芳香族 fe殘基以及卩夫喃、噻吩、卩比哈、噁TT坐、異噁唾、噻嗤、異 噻唑、咪唑、吡唑、呋咱、吡啶、噠嗦、嘧啶、吡嗪、吲 哚、苯并呋喃、苯并噻吩、喹啉、咔唑、吖啶、氧雜萆、 吩噻嗪、吩噁嗪等雜環芳香環基。該等之芳基中較佳之例 可舉如苯基，甲苯基等。 曱矽烷基之例可舉如，烷基曱矽烷基、芳基曱石夕院基 等’具體言之例舉如，三曱矽烷基、三乙矽烷基、三苯甲 矽烷基。 上述烷基、芳基、曱矽烷基，係可以i以上之取代基 任意取代，該等取代基之例可舉如與上述x的取代基相同 之取代基。 陽離子係只要與膦酸形成鹽之陽離子即可並無特別限 制，例舉如：鋰、鈉、鉀、鎂、鈣等金屬離子或四丁銨鹽， 吡啶鹽，咪唑鹽等四級銨離子。 息 將光電轉換用增感色素吸附於無機半導體上使用時， Μ1，M2較好為氫原子或4級銨鹽，但M1，M2除此之外’ 使用其他亦不成問題。例舉如，Μ1，μ2以产美 μ美 矽烷基等之磷酸酯的形態存在亦可，膦 方土曱 恥敲酯吸附於無機半 V體柃，使用適當的催化劑等，在體李中 版乐千可一邊加水分解 一邊吸附。 因此有順式、反式等 通式（1)表示之化合物，有雙鍵 315399 17 15 ’、構體’但纟立體結構並& 電轉換用秘π么主 制都可作為優良的光 得換用增感色素使用，即，式 的先 又從RI盥R2 &關焱+主 X與R可以互換， 任一幾何異構體。 1式遇疋反式，可選擇 式（υ中表示之化合物之例 示之方法合成。 由以下方案⑴所表 方案（1) ,0M1 (1) (Formula X represents a monovalent organic residue, R] and R2 are each independent. Table: a hydrogen atom or a monovalent organic residue, and M2 are each independent, and represent a substituted or unsubstituted alkyl group. , Substituted or non-substituted aryl, taken as \ or non-substituted formazanyl; or alkyl group or cation. R] and r2, r] and X and RX, each may be combined with each other to form a ring. And, X and R2 It can be said that in the middle of this month, the optical functional material indicates that it regains through the absorption of light = now it has a sensitization effect, a heating effect, a color development effect, a fade effect, a light storage effect, a phase change effect, a photoelectric conversion effect, and an optical magnetism Gas effect, photocatalysis: materials such as effects, light modulation effects, light recording effects, free radical generating effects, etc., or materials that accept these effects to have a light-emitting function. This light-functional material can be widely used, for example, photoelectric conversion materials 、 Light; light, material, image forming material, photochromic material, electroluminescent material, photoconductive material, dichroic material, radical generating material, 315399 8 200422379 acid generating material, alkali generating material , Photomaterials Second high-spectrum wave generating material, third high-spectrum wave generating material, 2, light absorbing material, near-infrared spectroscopy absorbing material, photochemical firing ^ T material, photochemical treatment sensitizing material, light phase change ,,, and other recording materials, photo-sintering recording materials, Shiyou magnetic milk recording materials, pigments for photodynamic therapy, and sensitizing pigments for photoelectric conversion, etc. The following is a description of the use of vinylphosphonic acid groups, especially the With: When the optical functional material of the chemical structure in formula (1) is used as a photosensitizer for photoelectric conversion ^, this optical functional material is used as its representative in this specification. It is simply called a sensitizing dye, but it does not deny the above-mentioned widespread application. The necessary functions of the sensitizing dye for photoelectric conversion are, for example, that the pigment has a wide range of absorption fields and #efficiently injects charge into the inorganic semiconductor of titanium oxide. In order to expand the absorption area of a pigment, it is preferable to introduce an organic residue capable of expanding the absorption area into X of the above general formula (1). In order to widen the absorption area, X is based on the electron supply property. Organic residues are preferred, and organic residues such as amine groups can exert a high effect. In order to efficiently inject charge, the sensitizing dye must have a fixed group that can be adsorbed on the surface of the inorganic semiconductor, and the light functional material of the present invention This condition is satisfied when a phosphonic acid group is used as a sensitizing dye. Phosphonic acid groups and carboxylic acid groups have a stronger adsorption capacity for inorganic semiconductors such as titanium oxide than carboxylic acid groups. The durability of the element can be expected. In particular, 'a phosphorus atom has two acidic groups (-OM1 and -OM2), and the strong addition effect can be exerted by the addition effect and the chelation effect. Moreover, 9 315399 200422379 is more attractive It has stronger adsorption energy. When the element is completed, it can accelerate the adsorption speed when the pigment is adsorbed on the inorganic semiconductor electrode, and it also has the advantage of shortening the manufacturing time. ^ The formation of a strong chemical junction between the base and the surface of the inorganic semiconductor a effectively overlaps the electron clouds of each other, and the electron movement from the sensitizing dye to the surface of the inorganic semiconductor can be quickly realized. In addition, due to the presence of phosphonic acid groups: solubility in water, alcohols, etc. is also improved. Therefore, as adsorption solvents, Weng Zhi can be used as an adsorption solvent with a small environmental load, and can be used as a pigment solution. The "aging time" is longer, which can reduce manufacturing costs. Excited electrons generated by absorbing light at the chromophore site of the photoelectric conversion sensitizing dye are effectively injected into the conduction f of the inorganic semiconductor to which the sensitizing dye is adsorbed. In order to reach the element with high photoelectric conversion efficiency, the strong electron-drawing property must be around the adsorption site (fixed base) of the sensitizing dye. In addition, if the 7Γ electron conjugate of the chromophore is not connected to the fixed base, the The excited electrons generated in the sensitizing dye are effectively transmitted to the fixed group. ^ J. For example, on the structure of the general formula ⑴, a substituent can be introduced at the R1 position. An electron-drawing substituent is introduced to the right of R, a vinylphosphonic acid group. Become a stronger electron receiver, and make the charge transfer in the molecule more effective. Therefore, the injection of the charge from the sensitizing dye to the inorganic plutonium conductor, such as titanium oxide, can be performed more easily. That is, the vinylphosphonic acid group has a π-electron common structure k at the chromophore site before it is connected to the binding position of the phosphonic acid, and it has a chemical structure where the electron-drawing group can be arranged near / pin I for the first time. Here, if the phosphonic acid structure directly bound to the fragrant% of the phenylphosphonic acid group is not able to introduce an electron-drawing group in the vicinity, compared with the 315399 200422379 vinylphosphonic acid group, it is noted that the chemistry represented by the present invention The structure, for the first time, bases the system to make the inorganic semiconductors have low charge efficiency and low photoelectric conversion efficiency. Acetylphosphonic acid structure, by obtaining the general formula (work), realizes that the sensitizing dye has a fixed base, and the solid has strong Adsorption energy and strong electron acceptance / order are described for each functional group in the general formula (1). X in the general formula 表示 represents an i-valent organic residue. The organic residues described herein are not particularly limited. For example, a monovalent aromatic tobacco residue which may have a substituent (that is, substituted or unselected) is a substituted or unsubstituted-valent heterocyclic residue substituted or unsubstituted monovalent aliphatic unsaturated hydrocarbon residue, Substituted or unsubstituted—valent amine, substituted or unsubstituted Substituted _valent organometallic complex residues 0 The aromatic rings of the aromatic hydrocarbon residues are benzene, naphthalene, anthracene, naphthacene, fluorene, phenanthrene, biphenyl, etc. There are no particular restrictions, but examples are Although the heterocyclic residues of benzene, imprint, perylene, perylene, fluorene, and heterocyclic residues are free of phenphene, pyrrole, oxazole, isoxazole, hydrazine, pyridine, pyridazine, pyrimidine, phenanthrene, pyrene, and Carbohydrazine, pyrazidine, pyrrolidine, imidazoline, imidazole, pyran, tetrahydropyran, dithiophene, etc. Don't limit, but can be exemplified by furan, thiothiazole, isothiazole, imidazole , Pyridoxine, pyrazine, indole, benzofuran, benzoxanthene, phenothiazine, phenσoxazine, pyridazolidine, piperidine, piperidine, morpholine, quinoxaline The heterocyclic ring of tetrahydrofuran, tetrahydrofuran temple can be quaternary, and there can also be counter ions. The counter ions at this time are not particularly limited, and general anions are sufficient. For example, halogen 315399 11 200422379 ions, perchlorate ion, boron tetrafluoride ion, hexafluoroscale acid ion, chlorine oxide ion, formic acid ion, toluene xanthate ion, and the like. No counter-ion-can also be neutralized with acidic groups such as carboxyl groups within or between molecules. > |, the heterocyclic system includes a pigment skeleton for dyes and pigments. Examples of pigment skeletons used are: azo pigments, 嗤 0 嗣 pigments, two-dimensional pigments " various pigments, scholin pigment (hualelium), dark blue pigments, merocyanine pigments Triphenylmethane-based pigments, oxa-I-based colors ::, 卩 ••••••••••••••••••••••••••••••• ······················································· Quinone-based pigments, phthalates, and naphthalocyanine-based pigments. Although the aliphatic unsaturated hydrocarbon residue is not particularly limited, it may be exemplified by ethylene, butadienyl, and H5. Hexatrisyl. The sum of the unsaturated bonds is preferably in the range of 1 to 20. Although the amine group is not particularly limited, it can be exemplified by, for example, an amine group, a mono- or dialkylamino group, a mono- or diarylamino group, and the like, and specifically, it is exemplified by N-methylamino group and N-ethoxy group N , N-ethylamino, n, n-diisopropylamino, n, N-dibutylamino, N-methylbenzene, ν, N · dibenzylamino, anilide, N, N-di Aniline, bis (m-tolyl) amino, N, N-bis (p-tolyl) amine, ^ _bis (paraben) amino, etc. Although the organometallic complex of the organometallic complex residue is not particularly limited, it can be exemplified by, for example, ferrocene, ruthenium, titanocene, zirconocene, phthalocyanine, naphthalene-fluorene, osmium, Bipyridine ruthenium complex. In the general formula U) above, aromatic hydrocarbon residues, heterocyclic residues, aliphatic unsaturated hydrocarbon residues, amine groups, and organic residues of organic residues represented by X 12 315399 200422379 metal complex residues , As described above, 丌 T has 1 or more substituents. Although this substituent is specifically limited, ### is exemplified by, for example, alkyl, aryl, heterocyclyl, evening: 2-base lactyl, alkylthio, arylthio, substituted or unsubstituted female disubstituted or Unsubstituted acid amine group, silk group group, alkoxy group :: aryloxy group, carboxyl group, sulfo group, phosphonic acid group, cyano group, isocyano group, thiooxy acid group, Li Shifen Examples of the "cyano group", cyano group, nitro group, nitroso group, halogen atom, and hydroxyl group. Examples include substituted or unsubstituted straight-bonded, branched, and cyclic carbons having 1 to 30 carbon atoms. Examples of aromatic earths are the aromatic rings of the above-mentioned aromatic hydrocarbon residues, and these aryl groups may also have substituents. Examples of heterocyclic groups are the aforementioned heterocyclic rings having heterocyclic residues. The cyclic group may also have a substituent. Examples of the outer alkoxy group include a 'methoxy group, an ethyl t group, a propoxy group, a butoxy group, a third butoxy group, an octyloxy group, a third octyloxy group, and the like. Carbonyl group having 1 to 20 carbon atoms. Examples of the fluorenyl group include an alkylcarbonyl group and an arylcarbonyl group, and specific examples thereof include an ethylfluorenyl group, a propylfluorenyl group, a fluorenyl group, and a toluenyl group. Iso carbon number of 1 to 20 Examples of aryloxy groups include aryloxy groups having 6 to 20 carbon atoms, such as phenoxy, 4-tert-butylphenoxy, p-naphthyloxy, 2-naphthyloxy, and 9-anthracenyloxy. Examples of the alkylthio group include, for example, methylthio, ethylthio, tertiary butylthio, hexylthio, octylthio and the like having an alkylthio group having 1 to 2 carbon atoms. Examples of the arylthio group For example, arylthio groups having 6 to 20 carbon atoms, such as phenylthio, 2-methylphenylthio, 4-tert-butyl 315399 13 200422379, and the like, are examples of substituted or non-substituted amine groups. The above monovalent amine group may have a substituent. Examples of substituted or non-substituted fluorenylamino groups include fluorenylamino, alkylamino, and aromatic fluorenylamino. Examples of alkoxyalkyl are, for example, methyl Alkoxyalkyl groups having 1 to 20 carbon atoms, such as oxymethyl, ethoxymethyl, and isopropoxymethyl. Examples of alkoxycarbonyl include methoxycarbonyl, ethoxycarbonyl, The second butoxycarbonyl group has a carbon number of 1 to 20. Examples of the aryloxycarbonyl group include, for example, a phenoxycarbonyl group, a naphthyloxycarbonyl group, and an aryloxy group having 5 to 30 carbon atoms. Carbonyl, acidic groups such as carboxyl, phosphonic acid, and sulfo groups can form metal salts, Salt. When the substituents bound to X exist in a plural state, they may be the same or different, and the substituents may be combined with each other to form a ring. In addition, X or a substituent bonded to X may also It may be combined with R1 and R2 described later to form a ring. Among the above X, a substituted or unsubstituted amine monovalent organic residue is preferable, and examples thereof include a diarylaminophenyl group and a dialkylamino group. Phenyl, dialkyl, triphenylene, and ethylene. In order to have high photoelectric conversion efficiency, X is a monovalent organic residue having a substituted or unsubstituted amine group, and has a long conjugated chain. It is preferably a rigid skeleton. If it has a long conjugated chain, the light absorption range of the pigment will be widened, and the vinyl private group of the charge injection site on the inorganic semiconductor will have a unit combination with an electron-supplying substituent such as an amine group. The rigid skeleton can effectively move the donor to the acceptor ^ 315399 14 200422379 to move the charge in the molecule. Next, r1, r2cr1 in the general formula ⑴ will be described to represent a hydrogen atom or a monovalent organic residue. The organic compounds I, G, and I described herein are not particularly limited, but the same organic residues as X, ^ or unsubstituted chain cigarette residues, meridian groups, and electron-withdrawing groups can be mentioned. Examples of cyclic cigarettes that substitute substituted or non-substituted cyclic tobacco residues include saturated hydrocarbons having 3 to 1 to 20 carbon atoms, such as cyclohexane and cyclopentane, such as cyclohexylpentane. One thin, cyclopentyl_suspicion # Su & seneene number 3 to 30 unsaturated cyclic hydrocarbons 0 substituted or non-substituted chain hydrocarbon residues of bonded nicotyl groups, for example, carbon The linear or branched alkyl group having a number of 1 to 3G, and the chain hydrocarbon group may also contain an unsaturated structure. The electron-pull group represents a value where the substituent number σ of Hammett is greater than 0. These substituents are not particularly limited, and examples thereof include, for example, cyano, fluorene, nitro, fluorenyl, alkoxyl, aryloxyl, sulfonyl, arylsulfinyl ', or Non-substituted amino group, perfluorinated county, perfluorinated sulfur group, perfluorinated m-based group, substituted or unsubstituted fluorenylamino group, 4-aminophenyl group, tooth atom. In another example, chemistry, New Discovery (Rev.), Vol. 91, pp. 165 to 195, and 1991 (the disclosure of which is cited herein) have an electron radical of a value greater than 0. Among the above-mentioned electron-withdrawing groups, examples of fluorenyl, alkoxycarbonyl, aryloxycarbonyl, substituted or unsubstituted fluorenylamino can be exemplified as the substituents in the organic residues represented by χ and the exemplified fluorenyl and alkyl groups. Oxycarbonyl, aryloxycarbonyl, the same as 315399 15 200422379 substituted or unsubstituted fluorenylamino. Examples of methoxanthenyl, ethylsulfonyl, and propylsulfinyl include sulfonyl. Examples of the aryl stilbene group include, for example, benzene stilbene group, toluene stilbene group and the like. Examples of perfluorocarbons include tris-methyl and penta-ethyl. Examples of full-gas burning sulfur groups include: r Weng Tian Liu Niu Ge-both methylthio, pentafluoroethylthio and so on. Examples of the perfluoroalkylcarbonyl group include dioxolium, such as muramidine, pentafluoroethylcarbonyl, and the like. Examples of the substituted or non-substituted lutein amino group include n-anthyl, dimethylsulfofluorenyl, diethylaminosulfofluorenyl, diphenylaminosulfonyl and the like. R and R described above may be combined with each other to form a ring, or R], R2 and x may be combined to form a ring. Here, when R1 and / or R2 has a substituent, these substituents may be combined with each other to form a ring, and the substituent may also be combined with a substituent of 形成 or X to form a ring. R1 is preferably an electron withdrawing group. The electron withdrawing group is at the inorganic semiconductor adsorption site 'and the electron withdrawing group is bonded to the vinylphosphonic acid group at the charge injection site, making the vinylphosphonic acid group a stronger electron accepting group. Because of &, the charge can be efficiently injected into the inorganic semiconductor. Moreover, R1 is preferably a cyano group among the electron-drawing groups. Because the cyano group is a strong pull electron group, and also has high stability. Next, M1 and M2 in the general formula (1) will be described. And M2 each independently 'represents a hydrogen atom, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted methylsilyl group or a cation. The alkyl group described herein means a linear, branched or 315 399 16 200422379 cyclic hydrocarbon group having a carbon number of 1 to 20, and these hydrocarbon groups may have an unsaturated structure. Preferred examples of such alkyl groups include methyl, ethyl, isopropyl, third butyl, and benzyl. Examples of the aryl group include, for example, the aromatic fe residues in the organic residues represented by X and xanthanes, thiophenes, fluorenes, TTs, isoxal, thiazine, isothiazole, imidazole, pyridine Azole, furazine, pyridine, pyridine, pyrimidine, pyrazine, indole, benzofuran, benzothiophene, quinoline, carbazole, acridine, oxafluorene, phenothiazine, phenoxazine Ring base. Preferred examples of these aryl groups include phenyl and tolyl. Examples of the fluorinated silyl group include, for example, an alkyl fluorinated silyl group, an aryl vermiculite group, and the like. Specific examples include a fluorinated silyl group, a triethylsilyl group, and a triphenylsilyl group. The above-mentioned alkyl group, aryl group, and fluorsilyl group may be arbitrarily substituted with a substituent of i or more. Examples of such substituents include the same substituents as the substituents of x. The cation system is not particularly limited as long as it forms a cation with a phosphonic acid, and examples thereof include metal ions such as lithium, sodium, potassium, magnesium, and calcium, or quaternary ammonium ions such as tetrabutylammonium salts, pyridine salts, and imidazole salts. When the sensitizing dye for photoelectric conversion is used by being adsorbed on an inorganic semiconductor, M1 and M2 are preferably hydrogen atoms or a fourth-order ammonium salt. However, it is not a problem to use other than M1 and M2. For example, M1, μ2 may exist in the form of phosphate esters such as US-made mesyl groups. Phosphate earth stilbene ester is adsorbed on inorganic semi-V body 柃, using appropriate catalysts, etc. Leqian can adsorb while decomposing with water. Therefore, there are compounds represented by the general formula (1) such as cis, trans, etc., which have double bonds 315399 17 15 ', conformation', but the three-dimensional structure and & electrical conversion can be used as excellent light. Use a sensitizing pigment instead, that is, the formula can be interchanged from RI R2 & Guan X + main X and R, any geometric isomer. Formula 1 meets the trans form, and can be synthesized by selecting the method exemplified by the compound represented by formula (υ). Scheme (1), 0

•0M1 W 催化劑 —賴—• 0M1 W catalyst —lai—

VL 110^/p-== Μ2。’ 方案⑴中，作為催化劑可使用呢咬 於該等，例舉如可使用有機反應，15卷：；等章但=限 年⑽…版X在此引用其揭示内容)記載之一催化劑；7 :案⑴中，作為溶劑可使用如乙醇、四氫 ΐ非特別限於該等，例舉如可使用有機反應，15卷：第: 二，1967年（1978年再版）(在此引用其揭示 ： 劑。反應難於進行時，不使❹劑之反應有時亦為有效果: 反應溫度通常在室溫下，可根據需要加熱反應。 在δ成Μ與Μ2同時為氫原子的化合物時，因反廡 於進行’此時’引入甲基、乙基等以取代Μ1，Μ2上之氣 原子，進行反應所製得之化合物經加水分解，可得到目 化合物。 、 以下係呈示，可使用作為本發明之光機能材料之化合 物的代表例，但本發明並非限定於該等例示。 口 315399 18 200422379VL 110 ^ / p-== M2. 'In Scheme ，, you can use it as a catalyst. For example, you can use organic reactions, Vol. 15:; etc. chapters but = limited years ⑽ ... Edition X refers to its disclosure content); 7 : In the case, solvents such as ethanol and tetrahydrofluorene can be used. In particular, organic solvents can be used. For example, organic reactions can be used. Vol. 15: No. 2, 1967 (reprinted in 1978) (the disclosure is cited here: When the reaction is difficult to proceed, the reaction without elixir is sometimes effective: the reaction temperature is usually at room temperature, and the reaction can be heated as needed. When the compound δ and M2 are hydrogen atoms at the same time, In the case of introducing a methyl group, an ethyl group, etc. to replace the gas atoms on M1 and M2 at this time, the compound obtained by performing the reaction can be hydrolyzed to obtain the target compound. The following compounds are shown and can be used as the present invention Representative examples of compounds of light-functional materials, but the present invention is not limited to these examples. 315399 18 200422379

(2) 首先，下述通式（2)表示之化合物例示於表1。表1中 Me表示甲基，Et表示乙基，iPr表示異丙基，Ph表示苯基， DMAPh表示4-二曱基胺基苯基。又，作為各化合物之代 表結構式，以下雖然揭示部分因雙鍵結構產生的順-反式異 構體，但包括了可能存在的異構體， 19 315399 200422379 (表1)(2) First, the compound represented by the following general formula (2) is shown in Table 1. In Table 1, Me represents methyl, Et represents ethyl, iPr represents isopropyl, Ph represents phenyl, and DMAPh represents 4-diamidoaminophenyl. In addition, as the representative structural formula of each compound, although the cis-trans isomers partially due to the double bond structure are disclosed below, the possible isomers are included, 19 315399 200422379 (Table 1)

化合物 R1 R2 R3 R4 M1 M2 1 CN H Me Me H H 2 CN H Et Et H H 3 CN H ipr 丨Pr H H 4 CN H Ph Ph H H 5 CN H p-tolyl />tolyl H H 6 CN H Me Me Et H 7 CN H Ph Ph Et H 8 CN H Me Me Et Et 9 CN H Ph Ph Et Et 10 CN H Me Me Si(CH3)3 · Si(CH3)3 11 CN H Ph Ph Si(CH3)3 Si(CH3)3 12 CN H Me Me +n(c4h9)4 +n(c4h9)4 13 CN H Ph Ph +n(c4h9)4 +n(c4h9)4 14 CN H Me Me +n(c4h9)4 H 15 CN H Ph Ph +n(c4h9)4 H 16 CN H DMAPh DMAPh H H 17 CN Me Me Me H H 18 CN CN Me Me H H 19 CN Ph Me Me H H 2 0 c〇ch3 H Me Me H H 2 1 c〇ch3 H Ph Ph H H 2 2 S02Ph H Me Me H H 2 3 S02Ph H Ph Ph H H 20 315399 200422379 2 4 S02Me H Ph Ph H H 2 5 C〇NMe2 H Me Me H H 2 6 C〇NMe2 H Ph Ph H H 2 7 COCF3 H Ph Ph H H 2 8 n〇2 H Ph Ph H H 2 9 Br H Ph Ph H H 接著，下述通式（3):Compound R1 R2 R3 R4 M1 M2 1 CN H Me Me HH 2 CN H Et Et HH 3 CN H ipr 丨 Pr HH 4 CN H Ph Ph HH 5 CN H p-tolyl / > tolyl HH 6 CN H Me Me Et H 7 CN H Ph Ph Et H 8 CN H Me Me Et Et 9 CN H Ph Ph Et Et 10 CN H Me Me Si (CH3) 3Si (CH3) 3 11 CN H Ph Ph Si (CH3) 3 Si (CH3 ) 3 12 CN H Me Me + n (c4h9) 4 + n (c4h9) 4 13 CN H Ph Ph + n (c4h9) 4 + n (c4h9) 4 14 CN H Me Me + n (c4h9) 4 H 15 CN H Ph Ph + n (c4h9) 4 H 16 CN H DMAPh DMAPh HH 17 CN Me Me Me HH 18 CN CN Me Me HH 19 CN Ph Me Me HH 2 0 c〇ch3 H Me Me HH 2 1 c〇ch3 H Ph Ph HH 2 2 S02Ph H Me Me HH 2 3 S02Ph H Ph Ph HH 20 315399 200422379 2 4 S02Me H Ph Ph HH 2 5 C〇NMe2 H Me Me HH 2 6 C〇NMe2 H Ph Ph HH 2 7 COCF3 H Ph Ph HH 2 8 n〇2 H Ph Ph HH 2 9 Br H Ph Ph HH Next, the following general formula (3):

(3) 表示之化合物例示於表2。表2中Me，Et的簡稱係與上述 表1相同。(表2)Examples of the compounds represented by (3) are shown in Table 2. The abbreviations of Me and Et in Table 2 are the same as those in Table 1 above. (Table 2)

化合物 R1 R2 R3 R4 R5 R6 M1 M2 3 0 CN H Me Me H H H H 3 1 CN H Ph Ph H H H H 3 2 CN H p-tolyl p-tolyl H H H H 3 3 CN H Ph Ph H H Et H 3 4 CN H Ph Ph H H Et Et 3 5 CN H Me Me H H Si(CH3)3 Si(CH3)3 3 6 CN H Me Me H H +n(c4h9)4 +n(c4h9)4 3 7 CN H Ph Ph H H +n(c4h9)4 +N(C4H9)4 3 8 CN H Ph Ph H H +n(c4h9)4 H 3 9 CN H DMAPh DMAPh H H H H 21 315399 200422379Compound R1 R2 R3 R4 R5 R6 M1 M2 3 0 CN H Me Me HHHH 3 1 CN H Ph Ph HHHH 3 2 CN H p-tolyl p-tolyl HHHH 3 3 CN H Ph Ph HH Et H 3 4 CN H Ph Ph HH Et Et 3 5 CN H Me Me HH Si (CH3) 3 Si (CH3) 3 3 6 CN H Me Me HH + n (c4h9) 4 + n (c4h9) 4 3 7 CN H Ph Ph HH + n (c4h9) 4 + N (C4H9) 4 3 8 CN H Ph Ph HH + n (c4h9) 4 H 3 9 CN H DMAPh DMAPh HHHH 21 315399 200422379

4 0 CN Me Me Me H H H H 4 1 CN CN Me Me H H H H 4 2 CN Ph Me Me H H H H 4 3 c〇ch3 H Ph Ph H H H H 4 4 S〇2Ph H Ph Ph H H H H 4 5 C〇NMe2 H Me Me H H H H 4 6 S〇2Me H Ph Ph H H H H 4 7 CONMe2 H Ph Ph H H H H 4 8 COCF3 H Ph Ph H H H H 4 9 N〇2 H Ph Ph H H H H 5 0 Br H Ph Ph H H H H 5 1 CN H Me Me CN H H H 5 2 CN H Ph Ph CN H H H 5 3 CN H Me Me H CN H H 5 4 CN H Ph Ph H CN H H 且，在上述通式（l)中表示之光機能材料的其他例，示於表4 0 CN Me Me Me HHHH 4 1 CN CN Me Me HHHH 4 2 CN Ph Me Me HHHH 4 3 c〇ch3 H Ph Ph HHHH 4 4 S〇2Ph H Ph Ph HHHH 4 5 C〇NMe2 H Me Me HHHH 4 6 S〇2Me H Ph Ph HHHH 4 7 CONMe2 H Ph Ph HHHH 4 8 COCF3 H Ph Ph HHHH 4 9 N〇2 H Ph Ph HHHH 5 0 Br H Ph Ph HHHH 5 1 CN H Me Me CN HHH 5 2 CN H Ph Ph CN HHH 5 3 CN H Me Me H CN HH 5 4 CN H Ph Ph H CN HH In addition, other examples of the optical functional materials represented by the general formula (l) are shown in the table.

22 315399 200422379 (表3)22 315399 200422379 (Table 3)

23 315399 20042237923 315399 200422379

24 315399 20042237924 315399 200422379

25 315399 20042237925 315399 200422379

26 315399 200422379 8 7 Q yo (HO)2OP^CN 9 1 〇v"〇h ^CN 〇rNi〇 8 8 〇V°〇hh V°〇hh xxxNj〇yN s 9 2 Y〇°hH r^^cN Me2N 人^八〆^NMe2 8 9 NC 〇 9 3 V〇H r^COOH Φ 9 0 0 NMe2 ho%An 0 NMe2 0 9 4 h〇h9 Ί为H Η〇Γ H〇r 27 315399 20042237926 315399 200422379 8 7 Q yo (HO) 2OP ^ CN 9 1 〇v " 〇h ^ CN 〇rNi〇8 8 〇V ° 〇hh V ° 〇hh xxxNj〇yN s 9 2 Y〇 ° hH r ^^ cN Me2N person ^ 〆〆NMe2 8 9 NC 〇9 3 V〇H r ^ COOH Φ 9 0 0 NMe2 ho% An 0 NMe2 0 9 4 h〇h9 Ί is H Η〇Γ H〇r 27 315399 200422379

9 5 9 9 V〇H f^COOH Φ 9 6 i /OH 二。· L JTCN 、N+、 10 0 °W ^OH NCyP-〇H 9 7 % /OH NC^p\〇H \^^〇ch2 V〇H och3 10 1 °W ^OH NC>|j"P、OH V^〇ch3 V^OH och3 9 8 % /OH Νεγρ-〇Η H3CO 人Α〇Η och3 10 2 % /OH NCNj"P^OH I 28 315399 2004223799 5 9 9 V〇H f ^ COOH Φ 9 6 i / OH two. L JTCN, N +, 10 0 ° W ^ OH NCyP-〇H 97% / OH NC ^ p \ 〇H \ ^^ 〇ch2 V〇H och3 10 1 ° W ^ OH NC > | j " P, OH V ^ 〇ch3 V ^ OH och3 9 8% / OH Νεγρ-〇Η H3CO human Α〇Η och3 10 2% / OH NCNj " P ^ OH I 28 315399 200422379

29 315399 20042237929 315399 200422379

30 315399 200422379 119 ；tW 0 12 3 IkS 12 0 ；W hH〇% 九0 ll 0 12 4 〇 CN 0 12 1 ^rVp N^{ W 12 5 OrN<P ^-Nn n^( W 12 2 12 6 H^ro^) Ή Ή 5199 20042237930 315399 200422379 119; tW 0 12 3 IkS 12 0; W hH〇% 90 0 ll 0 12 4 〇CN 0 12 1 ^ rVp N ^ {W 12 5 OrN < P ^ -Nn n ^ (W 12 2 12 6 H ^ ro ^) Ή Ή 5199 200422379

12 7 13 1 9 Nn-〇 H^pr〇^> 12 8 9 13 2 Ph\ /Ph 1 12 9 H〇、声 H〇X>=\ (A 13 3 NC^^C 0=P、 HO 〇H 13 0 hH〇V 32 315399 200422379 13 4 Me2NcijCUNP〇3H2 13 8 / 〜N %： Ht> V^CN PO3H2 13 5 H2〇3fy/ NC 13 9 / 〜N H H Q \^CN PO3H2 13 6 Ph3SiO N Alv ,N 夕孤H2 14 0 〜/ o^C^o ^C^CN PO3H2 13 7 Me2N HWH 0 6 Ncj P〇3H2 14 1 -v3^^p〇3H2 33 315399 20042237912 7 13 1 9 Nn-〇H ^ pr〇 ^ > 12 8 9 13 2 Ph \ / Ph 1 12 9 H〇, sound H〇X> = \ (A 13 3 NC ^^ C 0 = P, HO 〇H 13 0 hH〇V 32 315399 200422379 13 4 Me2NcijCUNP〇3H2 13 8 / ~ N%: Ht> V ^ CN PO3H2 13 5 H2〇3fy / NC 13 9 / ~ NHHQ \ ^ CN PO3H2 13 6 Ph3SiO N Alv, N 孤 孤 H2 14 0 〜 / o ^ C ^ o ^ C ^ CN PO3H2 13 7 Me2N HWH 0 6 Ncj P〇3H2 14 1 -v3 ^^ p〇3H2 33 315399 200422379

14 2 η Η NC 广 3Η2 14 6 η2〇3Ρ\ Ν^Ρ ΗΝ ,S 14 3 0 Η NC^P03H2 _j〇Xc^ Η 〇 1 4 7 / -Ν Q Q .3¾^ χ ρ〇3η2 14 4 喻人0 ΝΜβ2 14 8 NCV Η2Ο3Ρ /^vj3 _ Et 、0 14 5 η2〇3Αν 0， 14 9 α Ν(γρ〇3Η2 ΜβίΛψ：Χ? Cl14 2 η Η NC Η3Η2 14 6 η2〇3P \ Ν ^ Ρ ΗΝ, S 14 3 0 Η NC ^ P03H2 _j〇Xc ^ Η 〇1 4 7 / -N QQ .3¾ ^ χ ρ〇3η2 14 4 0 ΝΜβ2 14 8 NCV Η2Ο3Ρ / ^ vj3 _ Et, 0 14 5 η2〇3Αν 0, 14 9 α Ν (γρ〇3Η2 ΜβίΛψ: χ? Cl

34 IIMQQ 200422379 15 0 / CN \ COOH 15 4 jD VnQi Me、N^^^〇3H2 m! CN 15 1 / CN )=\ /=(~^P03H2 、 P〇3H2 15 5 Me、N^^^^03H2 Ml ^ CN 15 2 ,CN ^^(=CP〇3H2 -N \=QCN PO3H2 15 6 Me Me-N A O^N^O NC^ PO3H2 15 3 NCvP03H2 rpY0Na H203PyJ CN 15 7 CN h2〇3p"S Ph/N\ Ph 35 315399 20042237934 IIMQQ 200422379 15 0 / CN \ COOH 15 4 jD VnQi Me, N ^^^ 〇3H2 m! CN 15 1 / CN) = \ / = (~ ^ P03H2, P〇3H2 15 5 Me, N ^^^^ 03H2 Ml ^ CN 15 2, CN ^^ (= CP〇3H2 -N \ = QCN PO3H2 15 6 Me Me-N AO ^ N ^ O NC ^ PO3H2 15 3 NCvP03H2 rpY0Na H203PyJ CN 15 7 CN h2〇3p " S Ph / N \ Ph 35 315399 200422379

15 8 CN h2〇3p、 Ph/N\ph Ph 16 2 、N〆 、N〆 NC-f NC<f po3h2 po3h2 15 9 Ph ph，NXX T po3h2 Ph 16 3 、N〆 、N〆 tiC<f NC<f po3h2 po3h2 16 0 yCN p〇3H2 po3h2 16 4 -x . ? j〇arHz 16 1 \s)=<cli 、N、s po3h2 \ 16 5 、#Ί2 36 315399 200422379 16 6 ^τγ^Ρ03Η2 、NiJCs’CU、sX^ ΓΝ 1 ^^P03H2 17 0 0 NV^O^VCN h2o3p 16 7 Η u ^>03H2 17 1 H2〇3Pv^ 〜 16 8 H2〇3Pv NC<Vq V 0 GN^NrNp 0 ^ 〇=< )=N -N、 a==C<cn po3h2 17 2 、N- NC (Λ ^py>yr NC o 16 9 H2〇3^n=n-^ V。 17 3 PhN-Ph h2o3p 37 315399 20042237915 8 CN h2〇3p, Ph / N \ ph Ph 16 2, N〆, N〆NC-f NC &f; po3h2 po3h2 15 9 Ph ph, NXX T po3h2 Ph 16 3, N〆, N〆tiC < f NC < f po3h2 po3h2 16 0 yCN p〇3H2 po3h2 16 4 -x.? j〇arHz 16 1 \ s) = < cli, N, s po3h2 \ 16 5, # Ί2 36 315399 200422379 16 6 ^ τγ ^ P03Η2,, NiJCs'CU, sX ^ ΓΝ 1 1 ^^ P03H2 17 0 0 NV ^ O ^ VCN h2o3p 16 7 Η u ^ > 03H2 17 1 H2〇3Pv ^ ~ 16 8 H2〇3Pv NC < Vq V 0 GN ^ NrNp 0 ^ 〇 = <) = N -N, a == C < cn po3h2 17 2, N- NC (Λ ^ py > yr NC o 16 9 H2〇3 ^ n = n- ^ V. 17 3 PhN-Ph h2o3p 37 315399 200422379

17 4 ^>-po3h2 \ 17 8 HO^CClo 17 5 ucP\ H203p u 17 9 ρο3η2 Ph2N^^N^〇 CN 17 6 NC 丫 P03H2 18 0 h2o3p-^"^^n CN 17 7 -H03P丫 CN 丫、NPh2 NPh2 18 1 Μθ2ΝΤ^νζ=/ΝΥ^ι 9N HO 38 315399 20042237917 4 ^ > -po3h2 \ 17 8 HO ^ CClo 17 5 ucP \ H203p u 17 9 ρο3η2 Ph2N ^^ N ^ 〇CN 17 6 NC Ya P03H2 18 0 h2o3p-^ " ^^ n CN 17 7 -H03P Ya CN Ya, NPh2 NPh2 18 1 Μθ2ΝΤ ^ νζ = / ΝΥ ^ ι 9N HO 38 315399 200422379

石黃酸基之光機能材料所無法吸收領域的太陽光吸收，可合 用1種以上的其他（即，不含乙烯磺酸基）光機能材料。換 言之，通式（1)等表示之增感色素可單獨使用，或複數種組 合使用外，可與1種以上的其他增感色素合用。相關本發 明之光電轉換用增感色素與其他增感色素的調配比例，雖 無特別限^，但以# !摩爾相關本發明之光電轉換用增感 色素，宜含其他增感色素001至100摩爾為佳，以0」 至10摩爾為更佳。 其他增感色素之例可舉如偶氮系色素，_系色 素、二時各并吡洛系色素、史考林鎗系色素 —ium)、深藍系色素、部花青系色素、三笨 色 素、氧雜蒽系色素、㈣系色素、葉綠素系色辛㈣ 系色素、㈣系色素、二萘嵌苯系色素、二物色：、 :::糸色素、欧菁系色素、萘歌菁系色素，以及該等之衍 7 moo 39 200422379 可以連結無機半 光激發之色素的 。在此所述之官 該等之增感色素，其結構中較好含有 導體表面之官能團。其理由之例可舉如， 激發電子迅速傳到無機半導體之傳導帶上 能團之例可舉如’缓基、羥基、烴肟酸基、磺酸基、膦酸 基、以及次膦酸基等’但只要具有無機半導體表面上連結 增感色素，使色素的激發電子迅速轉移到無機半導體之傳 導帶上之功能，之取代基，則並不局限於該等。The absorption of solar light in areas that cannot be absorbed by lutein-based light-functional materials can be combined with one or more other (ie, ethylene sulfonate-free) light-functional materials. In other words, the sensitizing dye represented by the general formula (1) or the like may be used alone or in combination of a plurality of kinds, and may be used in combination with one or more other sensitizing dyes. The mixing ratio of the photoelectric conversion sensitizing dye of the present invention and other sensitizing pigments is not particularly limited ^, but the photoelectric conversion sensitizing dye of the present invention is related to other sensitizing pigments 001 to 100. Molar is more preferred, and 0 "to 10 moles is more preferred. Examples of other sensitizing pigments include azo-based pigments, _-based pigments, dipyridopirol-based pigments, skolin pigments-ium), dark blue-based pigments, merocyanine-based pigments, and tri-benzine pigments. , Xanthane-based pigments, saccharine-based pigments, chlorophyll-based chroma-based pigments, stilbene-based pigments, perylene-based pigments, two substance colors: ::: hydrazone-based pigments, eucyanine-based pigments, naphthalene-based pigment , And the like 7 moo 39 200422379 can be linked to inorganic semi-light-excited pigments. The official sensitizing dyes described herein preferably have functional groups on the surface of the conductor. Examples of the reason include, for example, an example in which an excited electron is rapidly transferred to a conduction band of an inorganic semiconductor, such as a 'branching group, a hydroxyl group, a hydroxamic acid group, a sulfonic acid group, a phosphonic acid group, and a phosphinic acid group. Etc. 'But as long as it has the function of connecting the sensitizing dye on the surface of the inorganic semiconductor to quickly transfer the excited electrons of the dye to the conduction band of the inorganic semiconductor, the substituent is not limited to these.

以下，说明使用上述相關本發明之光電轉換用增感色 素所製得之本發明的光電轉換材料、光電轉換電極以及光 電轉換電池，包括增感色素以外之材料。 1 ·光電轉換材料 上述光電轉換用增感色素，通過連結基連結於無機半 導體表面，便可得到無機半導體增感之光電轉換材料，亦 即，含無機半導體與該無機半導體上連結之增感色素之光 電轉換材料。在此所述之連結意味著無機半導體與增感色 素以化學性或物理性結合在一起，包括兩者由吸附結合在 一起。又，在本說明書中，連結基、固定基、吸附基可作 為同等作用之基團使用。 (無機半導體） 無機半導體通常對於部分領域的光有光電轉換作用， 若此表面上連結增感色素，使光電轉換到可視光及/或近紅 外光領域。無機半導體之材質，雖以無機氧化物為主，但 只要連結增感色素以具有光電轉換作用之無機半導體，則 並無特別限制。 40 315399 200422379 例舉如，不以無機氧化物為材質之無機半導體之例可 舉如，矽、鍺、III族-V族系半導體、金屬硫族等。 無機氧化物半導體之例可舉如氧化鈦、氧化錫、氧化 鎢、氧化辞、氧化銦、氧化鈮、氧化鐵、氧化鎳、氧化鈷、 氧思、氧化鈕、氧化銻、氧化鑭、氧化釔、氧化鈀等， 但右此表面上經連結增感色素，使光電轉換到可視光及/ 或近紅外光領域則並不局限於該等。為了使無機氧化物半 導體之表面由增感色素增感，無機氧化物之傳導帶最好位 灰攸增敏色素之光激發順位起至易吸收電子的位置。因 〔匕’在無機氧化物半導體中，氧化鈦、氧化錫、氧化鋅、 氧化銳等尤其適用。又於押 又攸饧袼、環境衛生等角度來看， 以氧化鈦為最適用。 该專無機半導體，；^ μ、+、士、昨 上述中選擇一種使用，或選擇複 數種搭配使用。 (無機半導體之多孔質化） 將上述半導體多孔質化 貝化取好使用作為無機半導體多 貝體。無機半導體多孔質 Β 甘主 貝肢如將多$增感色素連結於 具表面，使其具有高效率 千（先電轉換能力，且因多孔質化 具有了更廣的表面積。對於多 將粒子徑為數奈米至數十^孔:化的方法，已知方法有 鲰4 十不米之氧化鈦等無機氧化物粒子 忑糊化後而燒結的方法 面積之方法即T L、要疋多孔質化而得到寬廣表 積之方去即可，而並非局限於上述方法。 無機氣化物粒子之也 I /化方法，無機半導體多孔質體之 車乂 "ί土厚度以及盈機丰盡雕 …、 導肢夕孔貝體表面上連結增感色素之 315399 41 200422379 方法，在後面敘述。 2.光電轉換電極 ， 上述光電轉換材料經層疊於透明電極上，形成光電轉 換電極，亦即形成含透明電極與此透明電極上層疊之光電 轉換材料之光電轉換電極。透明電極通常為透明基材表面 上形成之導電層，即，具有導電性表面之透明基材之導電 面。 φ (導電性表面） 所使用之導電性表面（透明電極），對太陽光的可視光 至近紅外光領域的光吸收少之導電材料則無特別限制，但 以ITO(銦-錫氧化物）氧化錫（含摻混氟等物），氧化鋅等導 電ϋ良好之金屬氧化物為佳。基板（有導電性表面之透明基 材）之測片電阻（表面電阻）以盡可能地低為理想，具體而言 較好為20〇/口（〇/叫.）以了者，|電層係以具有對應其電 阻的厚度為佳。 φ (透明基材） 所使用之透明基材只要對太陽光之可視光至近紅外光 領域的光吸收少之導電材料即可並無特別限制，但可使用 石英、普通玻璃、ΒΚ7、錯玻璃等玻璃基材；聚對苯二甲 酸乙二醇酿、聚萘乙烯醋、聚酿亞胺、聚醋、聚乙稀、聚 碳酸酯、聚乙烯丁酸酯、平 ^ 歎丙烯、四乙醯纖維素、間規聚 •苯乙烯，聚苯硫醚、烯芳酯、聚楓、聚酯碉、聚醚醯亞胺、 環狀聚稀烴、溴化苯氧基、氣化乙稀等樹脂基材等。 (層疊方法） 315399 42 200422379 在有導電性表面之透明基材之導電面上層疊光電轉換 材料之方法之例可舉如，導電面上塗布糊化之無機氧化物 粒子後，經乾燥或燒結形成無機氧化物半導體多孔質體， 將此連透明基材浸潰於溶解增感色素之溶液中，利用無機 氧化物半導體的多孔質表面與增感色素的固定基之親和 性，將增感色素與其多孔質表面結合，其係一般所使用之 方法，但並非局限於該方法。 在無機氧化物粒子糊化上，只要能將無機氧化物粒子 分散於水或適當的有機溶劑中即可。以均質作為表面積大 的無機多孔質體層疊，配製分散性良好的糊聚極為重要， 根據需要，最好以硝酸、乙醯基丙_等酸、聚乙二醇，氣 等分散劑混合在糊漿成分，使用塗料分散器等使 在透明基材之導電面的方法有由旋轉塗布器 =的方法和㈣（SKREEN)印職，❹橡㈣刀之 方法、浸潰法、喷塗法、爷锌 传由乾mm \ /衰同法4。塗布之無機氧化物糊 心、由乾^燃燒以去除糊中的揮發成分，在” 電面上形成無機氧化物半 " 件如，通常在彻至500t溫戶下1體早n戈燃燒之條 埶能量之方本 C皿度下，給予3〇分至！小時的 光⑼要透明基枯之導電面具有貼密性，太陽 =:有良好的起電力之乾燥或燃燒方法即可，但並非 等醇I::解二，所使用之溶劑如乙"醇 ^乙腈、丙腈等腈系溶劑；氣仿、二氯甲烧、 315399 43 200422379 氯笨等鹵素系溶劑；二乙醚、四氫卩夫喃等醚系溶劑；醋酸 乙酉曰、醋酸丁酯等酯系溶劑；丙綱、曱基乙酮、環己酮等 嗣系溶劑；碳酸二乙酯、碳酸丙酯等碳酸酯系溶劑；己烷、 辛烧、苯、甲苯等烴系溶劑；二甲基甲醯胺、二曱基乙醯 胺、二曱基亞楓，丨，^二甲基咪唑g同、N甲基吡咯烷酮、 水等，但並不限於該等。溶液的濃度並無特別限制，較好 為 0·01 至 l〇mmol/L 程度。 對浸潰於溶解增感色素之溶液中之無機半導體多孔質 體體之條件並無特別限制，但若想得到理想的光電轉換效 率只要適當地設置即可’通常為…〇小時，室溫約8〇 C者為佳。 厚較佳為〇 · 5至2 0 // m。b替后、去f . 以111膜厚達不到該範圍時，惟恐得不 到有的轉換效率。2 He工 成腺日洋η/ 膜厚若高於該範®，則在 成膜時’因產生破参j名丨贫 於益機丰… 洛寺’而難於形成膜的同時，由 方、”、、械+導體多孔質體表層 蔣所吝4 Μ #从丄 〒电167距離過長，而不能夠 、 生的電何有效地傳到導電面上，而热、 轉換效率。 難以得到良好的 3.光電轉換電池 由以上得到的光電轉換電極 性對應電極形成光電轉電％貝層組合導電 电ff*供电池，亦即， 電極、電解質層、f電性"乂成3光電轉換 (電解質層） 、a -、極之光電轉換電池。 電解質層較好者係由電解 解貝、介質以及添加物所構 315399 44 200422379 在此％解貝可使用與破化物（例舉如，LiI、NaI、 碰1必α'Ά12、㈤2、Μ、蛾化四烧基錢、峨Π比咬鎗、 Ά哇鐵等）之混合物，％與漠化物（例# L此等）之混合 機熔融鹽化合物等，但並非局限於此。在此所述之 機熔融鹽化合物係指由有機陽離子與無機或有機陰離子 所構成之離子對化合物，熔點在室溫以下者。Hereinafter, the photoelectric conversion material, photoelectric conversion electrode, and photoelectric conversion battery of the present invention, which are prepared using the above-mentioned photoelectric conversion sensitizing color of the present invention, include materials other than the sensitizing dye. 1 · Photoelectric conversion material The above-mentioned photoelectric conversion sensitizing dye is connected to the surface of the inorganic semiconductor through a linking group to obtain an inorganic semiconductor sensitized photoelectric conversion material, that is, a sensitizing dye containing an inorganic semiconductor connected to the inorganic semiconductor. Of photoelectric conversion material. The connection described here means that the inorganic semiconductor and the sensitizing pigment are chemically or physically combined, including the two are bonded together by adsorption. In this specification, a linking group, a fixing group, and an adsorbing group can be used as groups having the same function. (Inorganic semiconductor) Inorganic semiconductors usually have photoelectric conversion effect on light in some fields. If a sensitizing dye is connected to this surface, the photoelectric is converted into visible light and / or near-infrared light. The material of the inorganic semiconductor is mainly an inorganic oxide, but it is not particularly limited as long as the inorganic semiconductor having a photoelectric conversion function is connected to the sensitizing dye. 40 315399 200422379 Examples include inorganic semiconductors that do not use inorganic oxides as materials, such as silicon, germanium, III-V semiconductors, and metal chalcogens. Examples of the inorganic oxide semiconductor include titanium oxide, tin oxide, tungsten oxide, oxide, indium oxide, niobium oxide, iron oxide, nickel oxide, cobalt oxide, oxygen oxide, oxide button, antimony oxide, lanthanum oxide, and yttrium oxide. , Palladium oxide, etc., but the right side of this surface is connected to the sensitizing dye to convert photoelectricity to visible light and / or near-infrared light. In order for the surface of the inorganic oxide semiconductor to be sensitized by the sensitizing dye, the conductive band of the inorganic oxide is preferably located in the light-excited order of the gray sensitizing dye to a position where electrons are easily absorbed. [In the inorganic oxide semiconductor, titanium oxide, tin oxide, zinc oxide, sharp oxide, etc. are particularly suitable. From the perspectives of environmental protection and sanitation, titanium oxide is the most suitable. This special inorganic semiconductor, ^ μ, +, taxi, yesterday, choose one of the above, or choose a plurality of combinations. (Porousization of Inorganic Semiconductor) The above-mentioned semiconductor is made porous and used as an inorganic semiconductor multilayer body. Inorganic semiconductor porous β-glycerin limbs, such as multi-sensitized pigments, are attached to the surface, so that it has a high efficiency (first electrical conversion ability, and has a wider surface area due to porosity. For multi-particle diameter The method is from several nanometers to tens of pores. There are known methods such as the method of sintering the inorganic oxide particles, such as titanium oxide, and the sintering method. It is only necessary to obtain a broad surface area, but is not limited to the above method. Inorganic gaseous particles I / I method, inorganic semiconductor porous body's thickness " ί soil thickness and surplus machine engraving ..., guide The method of connecting sensitizing pigments on the surface of limbs and shellfish body 315399 41 200422379 will be described later. 2. Photoelectric conversion electrode, the above photoelectric conversion material is laminated on a transparent electrode to form a photoelectric conversion electrode, that is, a transparent electrode and a transparent electrode are formed. The photoelectric conversion electrode of the photoelectric conversion material laminated on the transparent electrode. The transparent electrode is usually a conductive layer formed on the surface of a transparent substrate, that is, a transparent substrate having a conductive surface. Conductive surface φ (conductive surface) The conductive surface (transparent electrode) used is not limited to conductive materials with low light absorption from visible light to near-infrared light, but ITO (indium-tin oxide) Materials) tin oxide (containing mixed fluorine and other materials), zinc oxide and other conductive metal oxides are preferred. Substrate (transparent substrate with conductive surface) chip resistance (surface resistance) should be as low as possible It is ideal, and specifically, it is preferably 20 / port (〇 / 叫.), And the electric layer preferably has a thickness corresponding to its resistance. Φ (transparent substrate) As long as the transparent substrate is used, There are no particular restrictions on conductive materials with low light absorption in the visible to near-infrared light range of sunlight, but glass substrates such as quartz, ordinary glass, Β7, and plexiglass can be used; polyethylene terephthalate , Polynaphthalene vinegar, polyimide, polyacetate, polyethylene, polycarbonate, polyvinyl butyrate, flat acrylic, tetraethyl cellulose, syndiotactic polystyrene, polyphenylene sulfide , Arylene ester, polymaple, polyester 碉, polyether 醯 imine Resin substrates such as cyclic polyhydrocarbons, brominated phenoxy groups, vaporized ethylene, etc. (Lamination method) 315399 42 200422379 Example of a method for laminating photoelectric conversion materials on the conductive surface of a transparent substrate with a conductive surface For example, after the gelled inorganic oxide particles are coated on the conductive surface, the inorganic oxide semiconductor porous body is formed by drying or sintering. The transparent substrate is immersed in a solution in which the sensitizing dye is dissolved, and the inorganic oxidation is used. The affinity of the porous surface of the bio-semiconductor and the fixed base of the sensitizing dye, which combines the sensitizing dye with its porous surface, is a method generally used, but is not limited to this method. In the pasting of inorganic oxide particles As long as the inorganic oxide particles can be dispersed in water or an appropriate organic solvent, homogeneous inorganic porous bodies with large surface areas are laminated, and it is extremely important to prepare a paste with good dispersibility. If necessary, nitric acid, Dispersants such as acetopropylpropane and other acids, polyethylene glycol, and gas are mixed with the paste ingredients, and the method of using a paint disperser to make the conductive surface of the transparent substrate is reasonable. Transfer coater method and (iv) = (SKREEN) grade printing, (iv) a method ❹ rubber knife, dipping method, spray coating method, a dry mass of zinc Lord mm \ / failure with Method 4. The coated inorganic oxide paste is dried and burned to remove the volatile components in the paste to form an inorganic oxide half on the electrical surface. For example, it is usually burned at a temperature of 500t in 1 h. The energy of the barn is given by 30 minutes to 100 hours. The light is transparent and the conductive surface of the dry base is tight. The sun =: Drying or burning methods with good starting power can be used, but It is not equivalent to alcohol I :: Solution 2. Solvents such as ethyl alcohol and acetonitrile, propionitrile and other nitrile solvents; aerobic, dichloromethane, 315399 43 200422379 chlorobenzene and other halogen solvents; diethyl ether, tetra Ether-based solvents such as hydrofuran; ester-based solvents such as ethyl acetate and butyl acetate; fluorene-based solvents such as propionate, fluorenyl ethyl ketone and cyclohexanone; carbonate-based solvents such as diethyl carbonate and propyl carbonate ; Hexane, octane, benzene, toluene, and other hydrocarbon solvents; dimethylformamide, dimethylacetamide, difluorenylsulfenyl chloride, ^, dimethylimidazole g, N methylpyrrolidone, Water, etc., but not limited to this. The concentration of the solution is not particularly limited, but is preferably from 0.01 to 10 mmol / L. There are no particular restrictions on the conditions for the inorganic semiconductor porous body immersed in the solution in which the sensitizing dye is dissolved, but if the desired photoelectric conversion efficiency is desired, it can be set appropriately. 'Usually ... 0 hours, room temperature is about 80 ° C is preferred. Thickness is preferably from 0.5 to 2 // // m. After b is replaced, go to f. When the film thickness cannot reach this range with 111, the conversion efficiency may not be obtained. 2 He If the film thickness of the processed glands is higher than this range, it will be difficult to form a film at the same time as the film formation due to the occurrence of broken ginseng 丨 poor in Yijifeng ... Luosi, ", The surface of the porous body of the machine + conductor Jiang Suo 吝 4 Μ #The distance from the electric power 167 is too long, and the generated electricity can not be transmitted to the conductive surface effectively, and the heat and conversion efficiency. It is difficult to obtain a good 3. Photoelectric conversion battery The photoelectric conversion electrode obtained from the above-mentioned corresponding photoelectric conversion electrode is formed into a photoelectric conversion% shell layer combined with conductive electricity ff * for the battery, that is, the electrode, the electrolyte layer, and the electrical properties " 乂 成 3 Photoelectric conversion (electrolyte layer), a-, polar photoelectric conversion battery. The better electrolyte layer is composed of electrolytic solution, medium, and additives. 315399 44 200422379 Here,% solution can be used and broken compounds (for example, LiI, NaI, P1α1Ά12, ㈤2, M, Mixtures of moth-based burners, Ebi-biting guns, wow iron, etc.),% and molten salt compounds such as mixers with deserts (eg #L etc.), but not limited to this. The organic molten salt compound described herein refers to an ion-pair compound composed of an organic cation and an inorganic or organic anion, and has a melting point below room temperature.

具體言之，構成有機炫融鹽化合物之有機陽離子之例 2如，芳香族系陽離子類，如N_甲基_N，_乙基_唾鐵陽 搏子、N·甲基_N’_正丙基咪讀陽離子、&甲基抓正己 基咪哇鍚陽離子等N_院基ϋ㈣讀陽離子類；n•己 基吼咬_料、时錢讀陽料等咬鐵陽 離子類等。月旨肪族陽離子類可例舉如，n，n,n_三甲基N 丙基錄陽離子等脂肪族系陽離子類；n，n_甲基卩比咬鐵等環 狀脂肪族陽離子類。 構成有機熔融化合物之無機或有機陰離子如，氣化物 離子H物離子、蛾化物離子等.自化物離子，六敦化碟 離子、四氣化㈣子、2 a化甲續酸鹽、高氣酸離子、次 氯酸離子、氯酸離子、硫酸離子、㈣離子等無機陰離子 類；雙(三氟甲磺醯基)醯亞胺等醯胺、醯亞胺系陰離子類。 有機熔融鹽之其他例，如無機化學，3 5卷：11 Μ至 頁，1996年(在此引用其揭示内容。）記載之有機溶融 鹽。 以上所舉的碘化物、溴化物等可單獨使用，或複數種 組合使用。其中，“與碘化物的組合，例舉如，ΐ2與混合 315399 45 200422379Specifically, Example 2 of the organic cations constituting the organic fused salt compound is, for example, aromatic cations such as N_methyl_N, _ethyl_sialiton, N · methyl_N'_ N-Hexyl cations, such as n-propyl imide cations, & methyl-n-hexyl imidazolium cations, etc .; iron nuclide cations, such as n • hexyl sulfide bites, Shiqian yang materials, etc. Examples of the aliphatic cations include aliphatic cations such as n, n, n-trimethyl N propyl cation; and cyclic aliphatic cations such as n, n-methylpyrene than iron. Inorganic or organic anions constituting the organic molten compound, such as gaseous ion H substance ion, moth ion, etc. Autogenous ion, six-density dish ion, four-gassed gardenia, 2a-formyl formate, and high gas acid ion , Hypochlorous acid ion, chloric acid ion, sulfate ion, sulfonium ion and other inorganic anions; bis (trifluoromethanesulfonyl) sulfonium amine and other sulfonium amines, sulfonium amine-based anions. Other examples of the organic molten salt are organic molten salts described in Inorganic Chemistry, Vol. 35: 11M to page, 1996 (the disclosure of which is incorporated herein). The above-mentioned iodides, bromides, and the like may be used alone or in combination. Among them, "the combination with iodide, for example, ΐ2 and mixed 315399 45 200422379

Lil、碘咄啶鎗、或碘咪唑鎗等 適用，但 並非局限於該等例。 、夕 电解質較為 較佳之電解質濃度係在介質中之^ =物及/或漠化物等(複數種時係該等:混:=·5Μ， 15M以下。 初）為0.1至 使用在電解質層的介質較好為能夠 導性之化合物。液態介質有：二。惡燒、二乙鍵等=離子傳 ?二醇二烧趟、丙二醇…1乙二醇二燒物； 知-烷醚等鏈狀醚；甲醇、乙醇、乙二醇單烷*丙： 單烷醚、$乙二醇單烷醚、聚丙二醇單類丙：酵 醇、丙二醇…二醇、聚丙二醇、 類，乙二 ?腈、戍二腈、甲氧基乙腈、丙腈、”腈等腈化 奴酸乙烯酯、碳酸丙烯酯等碳酸酯化合 T吞2-噪〇圭 院酮等雜環化合物;二甲亞楓、環丁碼等非質子極性物質、 水等。該等可單獨使用或複數種組合使用。 以使用固態（包括凝膠狀）之介質為目的，使液態介質 中可含聚合物。此時，將聚丙烯腈、聚偏二氟乙烯等聚合 物添加到上述液態介質中，或將具有乙烯性不飽和基團之 多官能性單體在上述液態介質中聚合，得到固態介質。 電解質層除這些以外，可使用Cul、CuSCN(這類化合 物為不需液態介質之p型半導體，而可作為電解質作用。） 等，且可使用自然，395卷·· 5 83至585頁（1998年10月8 曰）（在此引用其揭示内容）記載之如2,2’，7,7’-四（N，N-二-對曱氧基苯胺）-9,9’-螺旋二芴的電洞傳輸（holetransport) 46 315399 材料。 =解貝上’係以作為提高光電轉換電池之财久性和電 ㈣，可添加各種添加物。例如，以提高财久性為 的者則則亦可添加蛾化鎮等無機鹽類，若以提高輸出為目 啶等二：添加第三丁基吡啶、2-甲基吡啶、2,6-二曱基吡 =類；脫氧膽酸等類固醇類；葡萄糖、葡糖胺、葡糖 棉:ΐ4單糖類以及此類的糖醇類；麥芽糖等二糖類； μ接1等直鏈狀募聚糖類；環糊精等環狀募聚糖類；乳募 ♦糖等加水分解寡聚糖類。 若這類添加劑與上述增感色素合用，可更有 本發明效果。 所幵/成之包解質層厚度雖無特別限制，但只要導電性 制電極與吸附色素之無機半導體層以不直接接觸之最小 厚度為佳。具體言之’較佳為01至10—範圍。 (導電性對應電極） 導電性對應電極，其作用為光電轉換電池之正極。使 用於對應電極之導電性材料，可例舉如金屬（翻、金、銀、 銅、紹、錢、銦等）、金屬氧化物（ΙΤ0(钢-錫氧化物）、氧化 錫（包括#混有說等化合物）、氧化辞等）' 或碳等。對應電 極之膜厚雖無特別限制’但以5nm以上…⑴以下者為 佳。 (組裝方法） 上述光電轉換電極與導電性對應電極，通過電解質層 組合在-起’形成光電轉換電池。根據需要，為防止電‘ 315399 47 200422379 =之茂漏、揮發’對光電轉換電池之周圍進。② 封mx熱可純材料、光硬化性樹脂、破璃 : =封材料。光電轉換電池也可根據所需將小面：光電轉 =:連結製成。例如’將光電轉換電池串聯，而可提高 【實施方式】Lil, iodopyridine gun, or imidazole gun are applicable, but are not limited to these examples. The better electrolyte concentration of the electrolyte is ^ = substances and / or deserts in the medium (multiple kinds of these: these: mixed: = · 5M, 15M or less. Initial) is 0.1 to the use in the electrolyte layer The medium is preferably a conductive compound. The liquid media are: 2. Smoldering, diethyl bond, etc. = ion-transmitting glycol dioxane, propylene glycol ... 1 ethylene glycol dicarbonate; chiral ethers such as alkyl ether; methanol, ethanol, ethylene glycol monoalkane * propane: monoalkane Ethers, $ ethylene glycol monoalkyl ethers, polypropylene glycol monopropenes: fermented alcohols, propylene glycols ... glycols, polypropylene glycols, phenols, ethylene dinitrile, acrylonitrile, methoxyacetonitrile, propionitrile, and nitriles Hexanoic acid vinyl esters, propylene carbonate and other carbonates are combined with T 2-2-ketones and other heterocyclic compounds; dimethyl acer, cyclobutadiene and other aprotic polar substances, water, etc. These can be used alone or Multiple types are used in combination. In order to use solid (including gel) media, the liquid medium can contain polymers. At this time, polymers such as polyacrylonitrile and polyvinylidene fluoride are added to the liquid medium. Or, a polyfunctional monomer having an ethylenically unsaturated group is polymerized in the above liquid medium to obtain a solid medium. In addition to these electrolyte layers, Cul and CuSCN can be used (such compounds are p-types that do not require a liquid medium) Semiconductor, and can function as an electrolyte.) Etc., and can use natural Volume 395 ·· 5 Pages 83 to 585 (October 8, 1998) (the disclosure is cited here) as described in 2,2 ', 7,7'-tetrakis (N, N-di-p-fluorenyloxy) Aniline) -9,9'-helical difluoride hole transport (holetransport) 46 315399 material. = Jiebei 'is used to improve the longevity and electrical properties of photoelectric conversion batteries, and various additives can be added. For example, If you want to improve the longevity, you can also add inorganic salts such as moth town. If you want to increase the output, you can add the second and third: add third butylpyridine, 2-methylpyridine, 2,6-dipyridine Gyptopyridines; steroids such as deoxycholic acid; glucose, glucosamine, glucosamine: ΐ4 monosaccharides and sugar alcohols of this type; disaccharides such as maltose; μ-linked linear polysaccharides such as 1; ring Cyclonic polysaccharides such as dextrin; hydrolyzed oligosaccharides such as milk and sugar. If such additives are used in combination with the above sensitizing pigments, the effect of the present invention can be more effective. Although the thickness of the encapsulating layer is not It is particularly limited, but as long as the minimum thickness of the conductive electrode and the inorganic semiconductor layer to which the pigment is adsorbed is not in direct contact, specifically, It is preferably in the range of 01 to 10. (Conductive corresponding electrode) The conductive corresponding electrode functions as the positive electrode of a photoelectric conversion battery. The conductive material used for the corresponding electrode can be exemplified by metal (turn, gold, silver, copper). , Shao, Qian, Indium, etc.), metal oxides (ITO 0 (steel-tin oxide), tin oxide (including #mixed with other compounds), oxidation terms, etc.) or carbon, etc. Although the film thickness of the corresponding electrode is not It is particularly restricted, but it is preferably 5nm or more ... or less. (Assembling method) The above-mentioned photoelectric conversion electrode and conductive counterpart electrode are combined with each other through an electrolyte layer to form a photoelectric conversion battery. If necessary, in order to prevent electricity, 315399 47 200422379 = The leakage and volatilization of the photoelectric conversion battery into the surroundings. ② Sealing mx thermally pure material, photocurable resin, broken glass: = sealing material. The photoelectric conversion battery can also be made by connecting the small face: photoelectric conversion =: as required. For example, 'connecting a photoelectric conversion battery in series can improve

以下以具體的實施例詳細說明本發明，但本發明並不 只限定於此。 首先，在實施例之前，敘述光電轉換用增感色素之合 成例。化合物所附括號内之數字對應上述表丨至3的化l 物號碼。 合成例1化合物（1)之合成方法 在200ml乙醇中加入對二曱基胺基苯甲醛1〇〇g (67mm〇l)，氰曱基膦酸二乙酯13.lg(74mm〇1)，哌啶〇 ^， 至溫下授拌5小時後，減壓蒸餘去除溶劑，得到橙色固體。 所付粗製化合物以石夕膠色譜柱精製，得到[1 _氰基_2_(4_二 曱基胺基-苯基）乙烯基]-膦酸二乙酯15.8g(收率76%)。 其次’將所得之[1-氰基-2-(4-二甲基胺基-苯基）乙烯 基]-膦酸二乙酯10.0g置於乙腈中，加水分解，所得固體 用乙醇進行再結晶，得到[1-氰基-2-(4-二曱基胺基-苯基） 乙烯基]-膦酸7.9g(收率91%)。由質譜，核磁共振（NMR) 譜，紅外（IR)光譜，元素分析，確認化合物（1)的結構。 合成例2化合物（4)之合成方法 使用對二苯基胺基苯甲醛以取代合成例（1)中之對二 48 315399 200422379 曱基胺基苯甲m卜，進行與合成例⑴相同操作，得到總 收率為54%之化合物⑷。由光譜，核磁共振（nmr)譜，^ 外（IR)光譜，元素分析，確認化合物（4)的結構。 合成例3化合物（3〇)之合成方法 使用對二甲基胺基肉桂醛以取代合成例（丨）中之對二 甲基胺基苯甲醛以外，進行與合成例（1)之相同操作，得到 總收率為60%之化合物（30)。由光譜，核磁共振（nmr)譜， 紅外（IR)光譜，元素分析，確認化合物（3〇)的結構。 第二圖表示所得化合物（3〇)之核磁共振nmr譜。圖的 上端和下端分別表示化合物（30)之乙酯化物與將其加水分 解之化合物（30)之光譜。 合成例4化合物（73)之合成方法 4-溴节基溴化物25.(^(1〇〇111111〇1)與亞膦酸三乙醋 19.9g(120mmol)在乾燥氮氣、l〇〇°c下加熱攪拌。反應約進 行4小時後，減壓容器，在120°C下攪拌1小時，去除未 反應之亞膦酸三乙酯，得到30.6g(收率1〇〇%)(4_溴节基）一 膦酸二乙酯。 所得之（4_溴苄基）-膦酸二乙酯l2.3g(4〇mm〇l)、與4-二苯基胺基苯甲醛l〇.9g(40mmol)與乾燥二曱基甲醯胺 (dry DMF) 150ml加入300ml燒瓶中，在氮氣流下溶解攪 拌。在此緩緩滴入第三丁氧基鉀9.0g(80mmol)之DMF (1 00ml)懸浮液。將該液通宵攪拌之後，在所得反應液中緩 緩滴入水，析出結晶濾過’乾燥，得到{4-[2-(4-溴苯基）-乙烯基]-苯基}-二苯胺16.〇g(收率94。/〇)。 315399 49 200422379 乾燥四氫呋喃（dry THF)50ml中加入所得之{4·[2_(4_ 漠苯基）-乙烯基]-苯基卜二苯胺9.0g(21 mmol)，在氮氣流 下，以冰鹽（ice-salt)浴（-15°C )冷卻。在此中緩緩滴入正丁 基鋰之戊烷溶液（2.59M)9.4ml，攪拌1小時後，滴入溶解 於THF之N-甲醯基哌啶2.75g(24mm〇1)。反應液逐漸恢復 到室溫，且攪拌2小時後，反應液中加入飽和氯化銨水溶 液攪拌’反應液中的有機層以甲苯5〇ml萃取兩次。 所得之有機層用飽和食鹽水與水洗淨，以Mgs〇4乾燥 後，蒸發溶劑，通過矽膠色譜柱精製（洗提液曱苯），得到 4-[2-(4-二苯基胺基-苯基）_乙烯基μ苯甲醛3 2g(收率 40%) 〇 使用所得之4-[2-(4-二苯基胺基-苯基）_乙烯基]_苯甲 酸’以取代上述合成例之對二曱基胺基苯甲醛外，進行與 上述合成例1相同之其他操作，得到收率為85%之化合物 (73)。由光譜，核磁共振（NMR”#，紅外（IR)光譜，元素分 析，確認化合物（73)的結構。 合成例5化合物（74)之合成方法 將異佛爾酮l〇.〇g(72mmol)，氰甲基膦酸二乙酯12.8 g(72mmol) ’ 醋酸銨 〇·77 g(1〇mmc)1)混合，在氮氣流、1〇〇 C下授拌5小時。反應結束後，在減壓條件下，加熱反應 液’去除未反應的原料，之後將反應液通過矽膠色譜柱， 得到[氰基-(3，5,5-三甲基-環己基-2-烯基）-甲基]-膦酸二乙 酯 13.4 g(收率 70%)。 接著’在DMF 100ml中加入所得之[氰基彳3，5,5-三甲 50 315399 200422379 f -環己-2-稀基）-甲基]-膦酸二乙酿1〇 〇 g(37mm〇i)與心二 苯基胺基苯甲酸10.2(37mm〇l)，卩^定〇 3ml，在氣氣流、 ’C下授拌7小時。反應液中加入m鹽酸i〇〇mi與氯仿 100ml，分離有機層後，在硫酸鎂中乾燥。硫酸鎂濾別後， 從渡液中館去氣仿’將所得之油通過妙膠色譜柱精製，得 到（氰基-{3-[2-(4-二苯基胺基·苯基）_乙烯基]_5,5_二甲基_ 環己_2-烯基卜甲基）_膦酸二乙酯8·3 g(收率4〇0/〇)。 再將所得之（氰基-{3-[2-(4-二笨基胺基-苯基）_乙烯基] _5，5-二甲基-環己-2-烯基卜甲基）_膦酸二乙酯5 〇g (9.0mm〇l)置於乙腈中，加水分解，得到（氰基_{3_[2_(‘二 苯基胺基-苯基）-乙烯基]-5,5-二甲基_環己烯基曱基）_ 膦酸4.0g(收率90%)。以乙醇_水再結晶，得到純化合物 (74)3.5 g。由光譜、核磁共振（nmr)讀、紅外（ir)光譜、元 素分析，確認化合物（74)的結構。 合成例6化合物（82)之合成方法 4 - >臭卞基漠化物25.0g( 1 OOmmol)與亞石粦酸三乙醋 19.9g(120mmol)在乾燥氮氣、10(TC下加熱攪拌。反應約進 行4小時後，減壓容器，且在120°C下攪拌1小時，去除 未反應之亞ί粦酸二乙醋，得到3 0 · 6 g (收率1 〇 〇 %)之（4 -漠节 基）-膦酸二乙酯。 將所得之（4_溴苄基）-膦酸二乙酯12.3g(40mmol)、及 4-{雙-[4-(1，1，2,2-四甲基-丙基）-苯基]_胺基卜苯曱醛18.8§ (40mmol)與乾燥DMF 150ml加入300ml燒瓶中，在氮氣流 下溶解攪拌。在此緩緩滴入第三丁氧基鉀9.0g(80mmol)之 51 315399 200422379 DMF(1 00ml)懸浮液，將此通宵攪拌之後，在所得反應液中 緩緩滴入水。析出結晶過濾、乾燥，得到{4_[2_(‘溴苯基）_ • 乙烯基卜苯基卜雙四甲基-丙基）_苯基]•胺 ; 24.4g(收率 98%)。 ' 所得之{4_[2-(4-溴苯基）·乙烯基]-苯基卜雙-[4-(1，1， 2,2-四曱基·丙基）_苯基]•胺7·8 g(12 5mm〇1)、2_噻吩佛爾 酮酸 2.4g(18.8mmol)、氟化鉀 2.4g(41mmol)、三-二苯亞甲 基丙酮把70nig以及二-第三丁基碗化氫80mg溶解於乾燥 THF 100m卜在氮氣流、室溫下攪拌3小時。反應液中加入 甲笨100 ml ’攪拌後’過濾不溶物，蒸發濾液。所得固體 用乙醇/甲苯再結晶，得到雙，2_四甲基-丙基）_苯 基]-{4-[2-(4-噻吩-2-基-苯基）-乙烯基]_苯基卜胺6 3 g(收 率 80%)。 再將所得之雙-[4-(1，1，2,2-四甲基_丙基）-苯基]-{4-[2· (4-¾¾ -2-基-本基）_乙晞基]_苯基卜胺2·3 g(3.7mmol)溶解 % 於乾燥THF ，在氮氣流、-78°C下冷卻，在此中緩緩 滴入正丁基鋰之戊烷溶液（1·6Μ)2·4 ml。攪拌1小時後， 滴入DMF0.8 g，攪拌1小時。反應液逐漸恢復到室溫、且 授拌2小時後，反應液中加入飽和氣化銨水溶液進行揽 拌’反應液中的有機層以曱苯50ml萃取兩次。 所得有機層用飽和食鹽水與水充分洗淨，以MgS04 、 乾燥後，蒸發溶劑，以矽膠色譜柱精製（洗提液甲苯），得 ，到5-{4-[2-(4-{雙-[4-(l，l，2,2-四曱基-丙基）-苯基]-胺基}-苯基）-乙烯基卜苯基レ噻吩-2-碳醛l·2g(收率50%)。 52 315399 200422379 除了使用所得之5-{4-[2-(4-{雙-[4-(1，1，2,2-四甲基-丙 基）-苯基]胺基卜苯基）_乙烯基]-苯基卜噻吩_2_碳醛，以取 代上述合成例1之對二曱基胺基苯甲醛外，進行與上述合 成例1相同之其他操作，得到收率為65%之化合物（82)。 由光譜、核磁共振（NMR)譜、紅外（IR)光譜、元素分析， 確認化合物（82)的結構。 其次’關於光電轉換用增感色素之評價方法之組合使 用增感色素之光電轉換電池、光電轉換電池之轉換效率測 定法’則依照第1圖所示之光電轉換電池之實驗樣品加以 說明。 透明電極 使用付玻璃基板51(旭玻璃公司製造，U-TCO型）之氟 摻混型氧化錫層（透明電極層）3 1。 導電性對應電極 在付玻璃基板52(旭玻璃公司製造，υ-TCO型）之氟推 混型氧化錫層（透明電極層）32導電層32上，使用由濺射法 層疊白金層（白金電極層）4(厚度丨5〇nm)之導電性對應電 極〇 氧化鈦糊狀物的配製 在下述處方中與氧化鍅玻璃珠混合，用塗料分散器分 散，付到氧化鈦糊狀物（《份》係表示重量份）。 氧化鈦（日本氣相二氧化矽公司製造p25粒徑2lnm) 6份 水（以添加硝酸調整為pH2) 14份 315399 53 200422379 乙醯丙酮 0.6份 界面活性劑（ICN公司製造氚核X-1〇〇) 〇·04份 PEG-#50〇,〇〇〇 〇 3 份 乳化鈦多孔質層的製作 透明電極之導電面（透明電極層31)貼上厚度為6〇#化 之嵌折用膠帶，將絕緣帶去除丨立方公分以製成屏蔽，在Hereinafter, the present invention will be described in detail with specific examples, but the present invention is not limited thereto. First, a synthesis example of a photoelectric conversion sensitizing dye will be described before the examples. The numbers in parentheses attached to the compounds correspond to the compound numbers in Tables 1 to 3 above. Synthesis method of compound (1) in Synthesis Example 1 In 200 ml of ethanol were added 100 g (67 mm) of p-diamidoaminobenzaldehyde, 13.lg (74 mm) of diethyl cyanophosphonophosphonate, Piperidine was stirred at room temperature for 5 hours, and then the solvent was distilled off under reduced pressure to obtain an orange solid. The crude compound thus obtained was purified by a Shixijia chromatography column to obtain 15.8 g of [1_cyano_2_ (4_diamidinoamino-phenyl) vinyl] -phosphonic acid diethyl ester (yield 76%). Next, '10 .0 g of the obtained [1-cyano-2- (4-dimethylamino-phenyl) vinyl] -phosphonic acid diethyl ester was placed in acetonitrile, and the resulting solid was decomposed with ethanol. Crystallization gave 7.9 g of [1-cyano-2- (4-diamidoamino-phenyl) vinyl] -phosphonic acid (91% yield). The structure of the compound (1) was confirmed by mass spectrometry, nuclear magnetic resonance (NMR) spectrum, infrared (IR) spectrum, and elemental analysis. Synthesis method of compound (4) in Synthesis Example 2 p-diphenylaminobenzaldehyde was used instead of p-di 48 48 315399 200422379 fluorenylamino benzaldehyde in Synthesis Example (1), and the same operation as in Synthesis Example ⑴ was performed. Compound VII was obtained in a total yield of 54%. The structure of the compound (4) was confirmed from a spectrum, a nuclear magnetic resonance (nmr) spectrum, an outer (IR) spectrum, and elemental analysis. The synthesis method of the compound (30) in Synthesis Example 3 uses p-dimethylamino cinnamaldehyde in place of the p-dimethylamino benzaldehyde in Synthesis Example (丨), and performs the same operation as in Synthesis Example (1). Compound (30) was obtained in a total yield of 60%. The structure of the compound (30) was confirmed from the spectrum, nuclear magnetic resonance (nmr) spectrum, infrared (IR) spectrum, and elemental analysis. The second figure shows the nuclear magnetic resonance nmr spectrum of the obtained compound (30). The upper and lower ends of the figure show the spectra of the ethylate of compound (30) and the compound (30) which hydrolyzes it, respectively. Synthesis Example 4 Compound (73) Synthesis Method 4-Bromobenzyl bromide 25. (^ (100111111〇1) and 19.9g (120mmol) of triethyl phosphinic acid in dry nitrogen at 100 ° C The mixture was stirred under heating. After the reaction was carried out for about 4 hours, the container was decompressed and stirred at 120 ° C for 1 hour to remove unreacted triethyl phosphinate to obtain 30.6 g (yield 100%) (4-bromo Benzyl) diethyl monophosphonate. The obtained (4-bromobenzyl) -diethyl phosphonic acid was 12.3 g (40 mm) and 10.9 g with 4-diphenylaminobenzaldehyde. (40mmol) and 150ml of dry dimethylformamide (dry DMF) were added to a 300ml flask, and dissolved and stirred under a nitrogen stream. DMF (100ml) of 9.0g (80mmol) of third butoxypotassium was slowly added dropwise thereto. Suspension. After stirring the solution overnight, water was slowly added dropwise to the obtained reaction solution, and the crystals precipitated were filtered and dried to obtain {4- [2- (4-bromophenyl) -vinyl] -phenyl}- 16.0.0 g of diphenylamine (yield: 94%). 315399 49 200422379 50 ml of dry tetrahydrofuran (dry THF) was added to the obtained {4 · [2_ (4_ molylphenyl) -vinyl] -phenylbodiphenylamine. 9.0g (21 mmol), under a stream of nitrogen, in an ice-salt bath (-15 ° C) After cooling, 9.4 ml of a pentane solution (2.59M) of n-butyllithium was slowly added dropwise, and after stirring for 1 hour, 2.75 g (24 mm) of N-formylpiperidine dissolved in THF was added dropwise. The reaction solution was gradually returned to room temperature, and after stirring for 2 hours, a saturated ammonium chloride aqueous solution was added to the reaction solution, and the organic layer in the reaction solution was extracted twice with 50 ml of toluene. The obtained organic layer was saturated brine and water. After washing and drying with Mgs〇4, the solvent was evaporated and purified through a silica gel column (eluent toluene) to obtain 4- [2- (4-diphenylamino-phenyl) _vinyl μbenzaldehyde. 3 2 g (yield 40%) 〇 The obtained 4- [2- (4-diphenylamino-phenyl) _vinyl] _benzoic acid 'was used in place of the p-difluorenylaminobenzene of the above synthesis example. Except for formaldehyde, the same operation as in Synthesis Example 1 was performed to obtain compound (73) in a yield of 85%. Compound (73) was confirmed from the spectrum, nuclear magnetic resonance (NMR) #, infrared (IR) spectrum, and elemental analysis. Structure of Compound (74) in Synthesis Example 5 Isophorone 1.0 g (72 mmol), diethyl cyanomethylphosphonate 12.8 g (72 mmol) 'ammonium acetate 0.7 7 g (10 mmc) 1) were mixed and stirred for 5 hours under a nitrogen flow at 100 C. After the reaction was completed, the reaction solution was heated under reduced pressure to remove unreacted raw materials, and the reaction solution was passed through A silica gel column obtained 13.4 g of [cyano- (3,5,5-trimethyl-cyclohexyl-2-enyl) -methyl] -phosphonic acid diethyl ester (yield 70%). Next, 100 g of the obtained [cyanofluorene 3,5,5-trimethyl 50 315399 200422379 f-cyclohex-2-diyl) -methyl] -phosphonic acid diethyl alcohol was added to 100 ml of DMF (37 mm. i) It is mixed with cardiodiphenylaminobenzoic acid 10.2 (37 mm), and adjusted to 0.3 ml, and the mixture is stirred for 7 hours under a gas flow at 'C. To the reaction solution, 100 ml of m hydrochloric acid and 100 ml of chloroform were added, the organic layer was separated, and then dried over magnesium sulfate. After filtering through magnesium sulfate, degassing from the liquid in the library, the oil obtained was purified through a wonderful gel chromatography column to obtain (cyano- {3- [2- (4-diphenylamino · phenyl) _ Vinyl] _5,5_dimethyl_cyclohex_2-alkenylmethyl) _diethylphosphonic acid 8.3 g (yield 400 / 〇). The obtained (cyano- {3- [2- (4-dibenzylamino-phenyl) _vinyl] _5,5-dimethyl-cyclohex-2-enylbromyl) _phosphonic acid 50 g (9.0 mm) of diethyl ester was placed in acetonitrile and hydrolyzed to obtain (cyano_ {3_ [2 _ ('diphenylamino-phenyl) -vinyl] -5,5-di Methyl_cyclohexenylfluorenyl) _phosphonic acid 4.0 g (yield 90%). Recrystallization from ethanol-water gave 3.5 g of pure compound (74). The structure of the compound (74) was confirmed by spectrum, nuclear magnetic resonance (nmr) reading, infrared (ir) spectrum, and elemental analysis. Synthesis Example 4 of Synthesis Example 6 Compound (82)-> 25.0 g (1000 mmol) of stinky desert and 19.9 g (120 mmol) of triethyl vinegar acid were heated and stirred under dry nitrogen at 10 (TC). The reaction proceeded approximately After 4 hours, the vessel was decompressed and stirred at 120 ° C for 1 hour to remove unreacted diethyl acetite, and obtain 30.6 g (yield of 100%) Group) -diethyl phosphonate. The obtained (4-bromobenzyl) -diethyl phosphonate 12.3 g (40 mmol) and 4- {bis- [4- (1,1,2,2-tetramethyl) Methyl-propyl) -phenyl] -aminophenylbenzaldehyde 18.8§ (40 mmol) and 150 ml of dry DMF were added to a 300 ml flask, and dissolved and stirred under a nitrogen stream. The third butoxypotassium potassium 9.0 was slowly added dropwise thereto. g (80mmol) of 51 315399 200422379 DMF (100ml) suspension. After stirring this overnight, slowly add water to the resulting reaction solution. The precipitated crystals are filtered and dried to obtain {4_ [2 _ ('bromophenyl). _ • vinyl phenyl phenyl bis-tetramethyl-propyl) phenyl] amine; 24.4 g (98% yield). 'The obtained {4_ [2- (4-bromophenyl) · vinyl] -phenylbubis- [4- (1,1,2,2-tetrafluorenyl · propyl) _phenyl] • amine 7.8 g (12 5 mm), 2.4 g (18.8 mmol) of 2-thiophene fulvic acid, 2.4 g (41 mmol) of potassium fluoride, 70-nig of di-diphenylmethylene acetone and di-tert-butyl 80 mg of basic hydrogenated hydrogen was dissolved in 100 m of dry THF and stirred at room temperature for 3 hours under a nitrogen stream. 100 ml of methylbenzyl was added to the reaction solution ‘stirred’ and the insoluble matter was filtered, and the filtrate was evaporated. The obtained solid was recrystallized from ethanol / toluene to obtain bis, 2-tetramethyl-propyl) _phenyl]-{4- [2- (4-thien-2-yl-phenyl) -vinyl] _benzene Gibamine 63 g (yield 80%). The obtained bis- [4- (1,1,2,2-tetramethyl_propyl) -phenyl]-{4- [2 · (4-¾¾-2-yl-benzyl) _ethyl Fluorenyl] -phenylbutiamine 2.3 g (3.7 mmol) dissolved in dry THF, cooled under a nitrogen flow at -78 ° C, and then slowly added n-butyllithium pentane solution (1 6M) 2.4 ml. After stirring for 1 hour, 0.8 g of DMF was added dropwise and the mixture was stirred for 1 hour. The reaction solution was gradually returned to room temperature, and after being stirred for 2 hours, a saturated ammonium hydroxide aqueous solution was added to the reaction solution for stirring. The organic layer in the reaction solution was extracted twice with 50 ml of toluene. The obtained organic layer was sufficiently washed with saturated brine and water, dried with MgS04, and the solvent was evaporated. The residue was purified by a silica gel column (eluent toluene) to obtain 5- {4- [2- (4- {double -[4- (l, 1,2,2-tetrafluorenyl-propyl) -phenyl] -amino} -phenyl) -vinylphenylphenylthiophene-2-carbaldehyde 1.2 g (received Rate 50%). 52 315399 200422379 In addition to using 5- {4- [2- (4- {bis- [4- (1,1,2,2-tetramethyl-propyl) -phenyl] aminophenylphenyl) _Vinyl] -phenylthiophene_2_carbaldehyde, in place of p-diamidoaminobenzaldehyde in Synthesis Example 1, and performing the same operation as in Synthesis Example 1, yielding a yield of 65% Compound (82). The structure of the compound (82) was confirmed from a spectrum, a nuclear magnetic resonance (NMR) spectrum, an infrared (IR) spectrum, and elemental analysis. Next, the "combination of evaluation methods for sensitizing dyes for photoelectric conversion using photoelectric conversion cells using sensitizing dyes and the method for measuring the conversion efficiency of photoelectric conversion batteries" will be described in accordance with the experimental samples of the photoelectric conversion battery shown in Fig. 1. As the transparent electrode, a fluorine-blended tin oxide layer (transparent electrode layer) 31 of a glass substrate 51 (manufactured by Asahi Glass Co., Ltd.) was used. The conductive corresponding electrode is a fluorine push-mixed tin oxide layer (transparent electrode layer) 32 on a glass substrate 52 (manufactured by Asahi Glass Co., Ltd.) (transparent electrode layer) 32, and a platinum layer (platinum electrode) is laminated by a sputtering method. Layer) 4 (thickness: 50nm) conductive counterpart electrode. Preparation of titanium oxide paste. Mix with osmium oxide glass beads in the following recipe, disperse with a paint disperser, and apply to the titanium oxide paste ("parts." 》 Means parts by weight). Titanium oxide (p25 particle size 2lnm manufactured by Japan Gaseous Silica Co., Ltd.) 6 parts of water (adjusted to pH 2 with the addition of nitric acid) 14 parts 315399 53 200422379 Acetylacetone 0.6 parts of surfactant (Thin core X-1 manufactured by ICN Corporation) 〇) 04 parts of PEG- # 50,000,000 parts of emulsified titanium porous layer, the conductive surface of the transparent electrode (transparent electrode layer 31) was affixed with a tape of 60-fold inlay, Remove the insulation tape to make a shield.

空的部分滴入數滴上述氧化鈦糊，之後以刮刀去除剩餘之 糊。風乾後，去除全部屏蔽，在450°C的烘烤箱中烘！小 時，得到具有有效面積為丨cm2之氧化鈦多孔質層的氧化鈦 電極。 增感色素之吸附 光電轉換用增感色素溶解於乙醇或水（濃度Ο ” mmol/L)，根據需要以膜濾器去除不溶性成份，將上述氧 化鈦電極浸於該色素溶液中，在室溫下，或根據需要加熱， 放置數小時或數天。浸潰時間可實際尋求由電池所完成之 轉換效率，設定能夠成為該最大轉換效率。 著色之電極表面，以用於溶解之溶劑以及醇洗淨後， 浸於4-第三丁基卩比咬之2mol%醇溶液3〇分鐘後，經乾燥， 得到具有吸附增感色素之氧化鈦多孔質層i之光電轉 極。 ％ 電解質溶液之配製A few drops of the above-mentioned titanium oxide paste were dropped into the empty portion, and then the remaining paste was removed with a spatula. After air drying, remove all shields and bake in a baking oven at 450 ° C! In one hour, a titanium oxide electrode having a titanium oxide porous layer having an effective area of ?? cm2 was obtained. Adsorption of sensitizing pigments The sensitizing pigments for photoelectric conversion are dissolved in ethanol or water (concentration 0 ”mmol / L), and insoluble components are removed by a membrane filter as required. The titanium oxide electrode is immersed in the pigment solution at room temperature. , Or heating as required, leaving it for several hours or days. The immersion time can actually seek the conversion efficiency completed by the battery, and set it to become the maximum conversion efficiency. The surface of the colored electrode is used for solvent and alcohol washing Then, after immersing in a 4 mol% alcohol solution of 4-tert-butylpyrene for 30 minutes, and then drying, a photoelectrode of a titanium oxide porous layer i having an sensitizing dye was obtained.% Electrolyte solution preparation

溶劑係使用甲氧乙腈。 0.1M 以下述配方配製電解質溶液 LilAs the solvent, methoxyacetonitrile was used. 0.1M Lil

0.05M 315399 54 200422379 心第三丁基吡啶 〇.5Μ 1-丙基_2,3·二甲基咪唑鎗碘化物 〇6Μ 光電轉換電池之組裝 如第1圖所示，組裝光電轉換電池之實驗樣品。亦即， 如上述’由吸附光電轉換用增感色素之氧化鈦多孔質層！ 所形成之上述透明電極（氟摻混型氧化錫層31付玻璃基板 51)與在氟摻混型氧化錫層32付玻璃基板52之導電層上層 豐白金層4之導電性對應電極，夾樹脂薄膜製墊片6丨、62 (一井杜邦聚乙稀化學公司製造<himilan>薄膜（25 // m厚 度））固定，該空隙中注入上述電解質溶液形成電解質溶液 層2。玻璃基板5丨、52上分別固定轉換效率測定用之導線 71 > 72 〇 轉換效率之測定方法 oriel公司製造太陽模擬器（#8116)與空氣聚集過濾 器（airmassfilter)搭配，以光量計調整為100mW/Cm2之光 量，以該光量作為測定用光源，光照射於光電轉換電池之 實驗樣品上，使用英弘精機公司製造Ι-V曲線掃描器 (MP 160)測定曲線特性。轉換效率π係由曲線特性 測定所得到的Voc(開路電壓值），Isc(短路電流值），饵非 爾係數值）根據下式算出。 η = ‘ V 〇 c (V) X I s c (mA) X 1 〇 〇 1 0 0 (mW/cm2) x 1 (cm2) 實施例1至13以及比較例1至12 實施例1至13以及比較例1至12分別使用下表4之 315399 55 200422379 、感色素，配製各增感色素之漢度為Q 6匪。i之乙醇溶液 (EtOH) ’如上述使氧化鈦多孔質層上吸附增感色素，組裝 光電轉換電池。但是’在實施例7、比較例5以及比較例 11中使用水作為色素之吸附用溶劑。且，實施例9中，使 用η、、加2重里％葡萄糖之電解質溶液以取代上述之電解質0.05M 315399 54 200422379 Heart tertiary butylpyridine 0.5M 1-propyl_2,3 · dimethylimidazolium iodide 06M Assembly of photoelectric conversion battery As shown in Figure 1, the experiment of assembling photoelectric conversion battery sample. In other words, as described above, 'the porous layer of titanium oxide from which a sensitizing dye for photoelectric conversion is adsorbed! The above-mentioned transparent electrode (a fluorine-blended tin oxide layer 31 on the glass substrate 51) and a conductive counterpart electrode of the platinum layer 4 on the conductive layer of the fluorine-blended tin oxide layer 32 on the glass substrate 52 are formed of resin. Thin film gaskets 6 and 62 (< himilan > film (25 // m thickness) made by Ichii DuPont Polyethylene Chemical Co., Ltd.) are fixed, and the above-mentioned electrolyte solution is injected into the gap to form an electrolyte solution layer 2. A lead 71 for measuring the conversion efficiency is fixed on the glass substrates 5 and 52, respectively. A method for measuring the conversion efficiency is 71. The solar simulator (# 8116) manufactured by Oriel Co., Ltd. is matched with an air-mass filter. The light quantity of 100mW / Cm2 was used as the light source for the measurement. The light was irradiated on the experimental sample of the photoelectric conversion cell, and the curve characteristics were measured using an I-V curve scanner (MP 160) manufactured by Hidehiro Seiki. The conversion efficiency π is calculated from the Voc (open-circuit voltage value), Isc (short-circuit current value), and baitfield coefficient value obtained from the measurement of the curve characteristics according to the following formula. η = 'V 〇c (V) XI sc (mA) X 1 〇00 0 0 (mW / cm2) x 1 (cm2) Examples 1 to 13 and Comparative Examples 1 to 12 Examples 1 to 13 and Comparative Examples From 1 to 12, the 315399 55 200422379 and sensitizing pigments in Table 4 below were used respectively, and the preparedness of each sensitizing pigment was Q 6 bandit. The ethanol solution (EtOH) of i was used as described above to sensitize the dye to the porous titanium oxide layer to assemble a photoelectric conversion battery. However, in Example 7, Comparative Example 5, and Comparative Example 11, water was used as a solvent for the adsorption of the pigment. Moreover, in Example 9, an electrolyte solution containing η, and 2% by weight glucose was used instead of the above-mentioned electrolyte.

表4之化合物（A)至（D)分別為有下述結構之化合物， (A)為釕錯體色素，化合物（B)與（〇為WO02/ll213號簡介 所記載之化合物（結構式中，以N<記載之N的取代基表示 甲基。（D)為對二甲基胺基苯膦酸。The compounds (A) to (D) in Table 4 are compounds having the following structures, respectively, (A) is a ruthenium complex dye, and compounds (B) and (0 are compounds described in the introduction of WO02 / ll213 (in the structural formula The substituent of N described in N < represents a methyl group. (D) is p-dimethylaminophenylphosphonic acid.

C00HC00H

/N、 56 315399 200422379/ N, 56 315399 200422379

^ OH NP-〇H^ OH NP-〇H

(〇) 實施例1 2以及1 3中，2種增感色素之調配比（摩爾比） 分別為化合物（A):化合物（30)=10 : 1，化合物（A):化合 物（73) = 5 : 1。 實施例4至6，比較例2至4以及8至10中，更將吸 附色素後之基板浸潰於所定pH之水溶液，測定有無色素 脫離以及光電轉換效率。 綜合將所得結果示於表4。(〇) In Examples 12 and 13, the blending ratio (molar ratio) of the two sensitizing pigments is compound (A): compound (30) = 10: 1, compound (A): compound (73) = 5: 1. In Examples 4 to 6, and Comparative Examples 2 to 4, and 8 to 10, the substrate after absorbing the pigment was immersed in an aqueous solution of a predetermined pH, and the presence or absence of pigment release and photoelectric conversion efficiency were measured. The obtained results are shown in Table 4.

57 315399 200422379 (表4)57 315399 200422379 (Table 4)

化合物 轉換效率 V (%) 以所定Ph 水溶液處理 光譜變化 氺 吸附溶劑 實施例1 1 1.7 無 — EtOH 實施例2 4 2.3 無 — EtOH 實施例3 30 3.2 無 — EtOH 實施例4 30 3.2 pH5 A EtOH 實施例5 30 3.1 pH7 A EtOH 實施例6 30 3.0 pH9 A EtOH 實施例7 30 3.2 無 — 水 實施例8 73 3.6 無 _ EtOH 實施例9 73 3.9 無 一 EtOH 實施例10 74 3.4 無 — EtOH 實施例11 82 4.0 無 — EtOH 實施例12 (A)+30 5.5 無 — EtOH 實施例13 (A)+73 6.1 無 — EtOH 比較例1 (A) 5.3 無 — EtOH 比較例2 (A) 3.0 pH5 C EtOH 比較例3 (A) 3.2 pH7 C EtOH 比較例4 (A) 1.5 pH9 c EtOH 比較例5 (A) 2.2 無 — 水 比較例6 (B) 1.9 無 — EtOH 比較例7 (C) 3.2 無 — EtOH 比較例8 (C) 2.3 pH5 B EtOH 比較例9 (C) 2.5 pH7 B EtOH 比較例10 (C) 1.8 pH9 C EtOH 比較例11 (C) 1.9 無 — 水 比較例12 (D) 0.3 無 — EtOH 58 315399 200422379 *組裝電池前，測定基板之擴散反射光譜。由所定水溶液處 理進行評價，無吸光度減少的為A，略減少的為B，減少 的為C。 第3圖中表示使用化合物（7 3)之實施例8之光電轉換 電池的電流-電壓特性，第4圖中表示與實施例8相同光電 轉換電池之IPCE光譜（入射光子轉為電子的比例的波長依 賴性）。 【圖式簡單說明】 第1圖係為光電轉換電池之一例，在實施例中，將實 驗樣品以模式呈示之剖面圖。 第2圖係表示質子核磁共振圖譜。上端表示化合物（3〇) 之乙酯化物，下端表示將其加水分解之化合物（3〇)。 第3圖係表示使用化合物（73)之光電轉換電池的 特性。 第4圖係表示使用化合物（73)之光電轉換電池的入射 光子-電流轉換效率（IPCE : incident monochromatic photon-to-current conversion efficiency)圖譜。 如以上所述，本發明在作為對無機半導體之吸附末端 係使用特定之化學結構，即乙烯膦酸基。由本發明，將具 有乙烯膦酸基之增感色素，連接於層疊於透明導電性基板 上之無機半導體表面，可製成優良光電轉換電池。此增感 色素因具有乙烯膦酸基，以致比具有羧酸末端之色素更能 舍揮強的吸附力，因此具有高光電轉換效率以及無機半導 體界面間之強吸附力，可以作為穩定的光電轉換用增感色 315399 59 200422379 素作用。又，作為吸附溶劑，不管是使用水，還是有機溶 劑都可以發揮相等的性能，因此可為低污染的增感色素。 、 且’此增感色素與其他增感色素搭配使用，比起各種色素 j 單獨使用，對於太陽光，可在更廣泛的波長領域下呈現光Compound conversion efficiency V (%) Spectral change in treatment with a predetermined Ph aqueous solution 氺 Adsorption solvent Example 1 1 1.7 None—EtOH Example 2 4 2.3 None—EtOH Example 3 30 3.2 None—EtOH Example 4 30 3.2 pH5 A EtOH Implementation Example 5 30 3.1 pH7 A EtOH Example 6 30 3.0 pH9 A EtOH Example 7 30 3.2 None-water Example 8 73 3.6 None-EtOH Example 9 73 3.9 None-EtOH Example 10 74 3.4 None-EtOH Example 11 82 4.0 None—EtOH Example 12 (A) +30 5.5 None—EtOH Example 13 (A) +73 6.1 None—EtOH Comparative Example 1 (A) 5.3 None—EtOH Comparative Example 2 (A) 3.0 pH5 C EtOH Comparison Example 3 (A) 3.2 pH7 C EtOH Comparative Example 4 (A) 1.5 pH9 c EtOH Comparative Example 5 (A) 2.2 None-Water Comparative Example 6 (B) 1.9 None-EtOH Comparative Example 7 (C) 3.2 None-EtOH Comparison Example 8 (C) 2.3 pH5 B EtOH Comparative Example 9 (C) 2.5 pH7 B EtOH Comparative Example 10 (C) 1.8 pH9 C EtOH Comparative Example 11 (C) 1.9 None-Water Comparative Example 12 (D) 0.3 None-EtOH 58 315399 200422379 * Measure the diffuse reflectance spectrum of the substrate before assembling the battery. The evaluation was performed by the treatment of the predetermined aqueous solution. The one with no decrease in absorbance is A, the one with slight decrease is B, and the one with decrease is C. Figure 3 shows the current-voltage characteristics of the photoelectric conversion battery of Example 8 using compound (7.3), and Figure 4 shows the IPCE spectrum (the ratio of incident photons to electrons) of the same photoelectric conversion battery as in Example 8. Wavelength dependent). [Brief description of the drawing] Fig. 1 is an example of a photoelectric conversion cell. In the embodiment, a cross-sectional view showing a test sample in a pattern is shown. Figure 2 shows a proton nuclear magnetic resonance spectrum. The upper end represents the ethylate of compound (30), and the lower end represents the compound (30) which is hydrolyzed. Fig. 3 shows the characteristics of a photoelectric conversion cell using the compound (73). Fig. 4 is a graph showing an incident photon-to-current conversion efficiency (IPCE) of a photoelectric conversion cell using the compound (73). As described above, the present invention uses a specific chemical structure, i.e., a vinylphosphonic acid group, as an adsorption terminal for an inorganic semiconductor. According to the present invention, a sensitizing dye having a vinylphosphonic acid group can be connected to the surface of an inorganic semiconductor laminated on a transparent conductive substrate to form an excellent photoelectric conversion battery. This sensitizing dye has a vinyl phosphonic acid group, so it has a stronger adsorption force than a pigment with a carboxylic acid terminal, so it has high photoelectric conversion efficiency and strong adsorption force between inorganic semiconductor interfaces, which can be used as stable photoelectric conversion. With sensitizing color 315399 59 200422379 element effect. In addition, as the adsorption solvent, even if water or an organic solvent is used, the same performance can be exhibited, so that it can be a low-pollution sensitizing dye. ’This sensitizing pigment is used in combination with other sensitizing pigments. Compared to various pigments j alone, it can show light in a wider range of wavelengths for sunlight.

K 電轉換作用，因此可以製作高效率光電轉換材料、光電轉 換電極以及光電轉換電池。 本申請係與2003年1月16曰已申請之專利2003- Φ 0085 19號所揭示之主題相關，該等揭示内容亦可引用於 此。 不脫離本發明之新穎且有利的特徵下，除已敘述的以 外’應留意亦可對於上述實施形態進行各種各樣的修正和 變更。因此如上述之全部修正和變更，亦包括在附加申靖 專利範圍中。 i 315399 60K electric conversion effect, so you can make high-efficiency photoelectric conversion materials, photoelectric conversion electrodes, and photoelectric conversion batteries. This application is related to the subject matter disclosed in Patent Application No. 2003-Φ 0085 19, which was filed on January 16, 2003, and the disclosure content may also be incorporated herein by reference. Without departing from the novel and advantageous features of the present invention, it should be noted that various modifications and changes can be made to the above-mentioned embodiments in addition to those already described. Therefore, all the amendments and changes mentioned above are also included in the scope of the additional patent application. i 315399 60

Claims (1)

200422379 拾、申請專利範圍： l :種光機能材料，係具有下述通式⑴表示之乙稀膦酸 以及R2中至少一方為吸電子基，200422379 Scope of patent application: l: a kind of optical function material, at least one of ethylene phosphonic acid and R2 having the following general formula ⑴ is an electron withdrawing group, R2 (式中，X矣-1 y ^ 、不價的有機殘基，R1以及R2各自獨立， ^ Γ ^原子或1價的有機殘基，以及M2各自獨立， ^、氫原子、取代或非取代之烧基、取代或非取代之芳 ^取代或非取代之甲石夕烷基或陽離子。R1與R2、R1 /、 x及R與x，彼此之間可以互相結合形成環，且， X與R2可以替換）。 2·如申請專利範圍第1項之光機能材料，其中，R1以及 R2中至少一方為氰基。 3·如申請專利範圍帛i項或第2項之光機能材料，其中， X為έ取代或非取代氰基之一價有機殘基。 4· 一種*電轉換用增⑨色素，係包含申請專利範圍第^項 之光機能材料。 、 5 ·如申请專利範圍第4項之光電轉換用增感色素，其中， 該光電轉換用增感色素更含申請專利範圍第1項之光 機能材料以外之其他光機能材料。 6· —種光電轉換材料，係包括無機半導體以及連結於前述 315399 61 200422379 4項或第5項之光電轉換 無機半導體之申請專利範圍第 用增感色素。 7· —種光電轉換電極，係#乜$ 1 屯T你巴祜透明電極以及層疊於前述透 明電極之申請專利範圍第6項之光電轉換材料。 8. —種光電轉換電池，係包括申請專利範圍第7項之光電 轉換電極與電解質層以及導電性對應電極。R2 (In the formula, X 矣 -1 y ^, an unvalent organic residue, R1 and R2 are independent, ^ Γ ^ atom or monovalent organic residue, and M2 are each independent, ^, hydrogen atom, substituted or non- Substituted alkyl, substituted or unsubstituted aryl ^ substituted or unsubstituted methylsilyl or cation. R1 and R2, R1 /, x, and R and x may be combined with each other to form a ring, and X Can be replaced with R2). 2. The optical function material according to item 1 of the patent application scope, wherein at least one of R1 and R2 is a cyano group. 3. If the scope of the patent application is item i or item 2 of the optical function material, wherein X is a monovalent organic residue of a substituted or unsubstituted cyano group. 4. A type of dysprosin pigment for electrical conversion, which is a photofunctional material containing item ^ of the patent application scope. 5. If the sensitizing dye for photoelectric conversion according to item 4 of the patent application scope, wherein the sensitizing dye for photoelectric conversion further contains other optical functional materials than the light functional material in application scope 1 of the patent application. 6. A kind of photoelectric conversion material, which includes inorganic semiconductors and sensitized pigments in the scope of patent application for the photoelectric conversion inorganic semiconductors which are connected to 4 or 5 of 315399 61 200422379 mentioned above. 7 · — A type of photoelectric conversion electrode, which is a transparent electrode and a photoelectric conversion material laminated on the aforementioned transparent electrode in the patent application No.6. 8. A type of photoelectric conversion battery, which includes the photoelectric conversion electrode and electrolyte layer and the corresponding conductive electrode in item 7 of the scope of patent application. 315399 62 200422379315399 62 200422379 射入 第1圖 200422379Injection Picture 1 200422379 鲷2a gj oo - J ] J §1 Xk _ Ca> _ §Ί Γ° il o - -a L ' ^=- E ?==ί— 厂 ? ZS·' r - 囊.：DMSOId 200422379 5.0 230 U Μ 06 〇!δ 電壓(V) 第3圖Bream 2a gj oo-J] J §1 Xk _ Ca > _ Ί Γ ° il o--a L '^ =-E? == ί— factory? ZS ·' r-capsule .: DMSOId 200422379 5.0 230 U Μ 06 〇! Δ Voltage (V) Figure 3 波長(nm) 第4圖 200422379 柒、指定代表圖： (一） 本案指定代表圖為：第（ ）圖。 (二) 本代表圖之元件代表符號簡單說明： 本案無圖式。Wavelength (nm) Figure 4 200422379 柒. Designated Representative Map: (1) The designated representative map in this case is: (). (2) Brief description of the component representative symbols of this representative drawing: There is no drawing in this case. 捌、本案若有化學式時，請揭示最能顯示發明特徵的化學式：捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: 4 3153994 315399
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