200807734 ⑴ 九、發明說明 【發明所屬之技術領域】 本發明係關於色素增感太陽電池及所使 合薄膜。更詳而言之，係關於使用塑膠基材 電性能高之高色素增感太陽電池之色素增感 _ 極、所使用之層合薄膜及該色素增感太陽電 【先前技術】 色素增感太陽電池，自使用色素增感半 光電變換元件被提出以來（「Nature」舞 73 7〜740頁（1991年）），則作爲取代矽系太 太陽電池而受到注目。 ^ 使用塑膠基材之色素增感太陽電池，由 輕量化而受到注目。一般所進行之使用塑膠 感太陽電池時，爲了提高氧化物半導體粒子 或爲了形成用以提昇光電變換效率之多孔質 高溫熱處理。然而，其溫度一般爲400°C以 # 塑膠基板上直接進行高溫熱處理。因此， 1 1 -2 8 8 745號公報，藉由氧化金屬箔、並於 ，製作成使用塑膠基材之色素增感太陽電池 表面積不足夠，而有無法充分提昇光電變換 又，於日本特開2001 - 1 60426號公報記載： 實施一次金屬氧化物之高溫熱處理後，將該 剝離，而以夾子固定於塑膠基材上之方法。 [用之電極及層 ‘而可製造光發 ;太陽電池用電 池。 導體微粒子之 S 3 5 3卷，第. :陽電池之新穎 於可柔軟化及 基材之色素增 間之黏著性、 構造，係實施 上，而難以於 於日本特開平 表面設置凹凸 。然而，其比 效率的問題。 於金屬箔上先 金屬氧化物層 然而，由於製 -5- 200807734 (2) 程複雜而不適於大量生產。又，於日本特開 2002-5 04 1 3 號公報，則記載：藉由將金屬氧化物粒子塗佈於塑膠基材 上，而形成半導體金屬氧化物層之方法。然而，固著於透 明導電層上之金屬氧化物粒子，於操作時會有以粉末裝脫 離、或於電解液中剝離之問題。 . 另外，於日本特開200 1 -93 590號公報及特開200 1 - 3 5 8 3 4 8號公報，則記載者藉由將金屬氧化物之針狀結晶使 用於太陽電池用電極，而提昇電荷輸送效率。然而，爲了 得到良好之多孔質構造以達成高電荷輸送效率，必須適當 地控制金屬氧化物之結晶狀態。例如，當金屬氧化物爲氧 化鈦時，以銳鈦礦相爲佳。然而，製作具有針狀之銳鈦礦 相之氧化鈦係困難，固通常係優先形成較安定之金紅石相 ^ 。結果其光電變換效率並不足夠。 另一方面，製造金屬氧化物之方法，有電氣紡絲 (Electrospinning)法。該方法，係將含聚合物等燒失成分 之氧化物前驅物，以高縱橫比噴出至基材上後，以高溫進 行熱處理而製得金屬氧化物。利用該電氣紡絲法，於玻璃 * 基材上設置金屬氧化物層之色素增感太陽電池用電極係爲 已知。如上述，色素增感太陽電池，係記載於 US2005/0 1 093 8 5 及 Mi Yeon Song 等著，奈米技術，2004 年，p i 861〜1 865 〇 上述之色素增感太陽電池用電極，係將金屬氧化物前 驅物以高縱橫比之狀態噴出至玻璃基板上之透明導電層上 而堆積後，以高溫燒成以製得金屬氧化物層。於該燒成之 -6 - 200807734 (3) 際，由於金屬氧化物自我收縮而使金屬氧化物有由透明導 電層剝離的傾向，故僅以電氣紡絲法設置金屬氧化物層， 亦無法達成充分之高比表面積與高電荷輸送效率。再者， 由於玻璃基材上之金屬氧化物之燒成製程本身係以400 °C 以上進行，故難以將該技術使用於用玻璃基材之色素增感 太陽電池用電極。 【發明內容】 本發明之目的在於提供一種色素增感太陽電池用電極 ，其可使用塑膠基材、吸附足夠量之色素而可得高電荷輸 送效率，且多孔質氧化物膜不會剝離而以良好密合性積層 於基材上，而能製造光發電性能高之色素增感太陽電池。 本發明之另一目的，係提供上述電極所使用之使用塑 膠基材之層合薄膜。 本發明之又一目的，係提供使用上述電極之色素增感 太陽電池。 本發明之其他目的及優點，有由以下之說明明白。 藉由本發明，本發明之上述目的及優點，第1， 可由一種層合薄膜達成， 該層合薄膜之特徵係，由多孔質半導體層、透明導電 層及透明塑膠薄膜所構成， 該多孔質半導體層’係由結晶性氧化鈦纖維與結晶性 氧化鈦微粒子所構成’該結晶性氧化鈦纖維與該結晶性氧 化鈦微粒子，係由銳鈦礦相與金紅石相實質地形成，而由 200807734 (4) χ射線繞射之積分強度比所計算之銳鈦礦相含有比爲 1·〇〇〜〇·32之間，且其係使用於色素增感太陽電池之電極 〇 藉由本發明，本發明之上述目的及優點，第2， 可由一種色素增感太陽電池用電極達成， 其係由本發明之上述層合薄膜、及吸附於該層合薄膜 之多孔質半導體層的色素所構成。 藉由本發明，本發明之上述目的及優點，第3， 可由一種具備本發明之上述電極之色素增感太陽電池 達成。 【實施方式】 於本發明之層合薄膜，多孔質半導體層，係由結晶性 氧化鈦纖維與結晶性氧化鈦微粒子所構成。由於多孔質半 導體層’係由結晶性氧化鈦纖維與結晶性氧化鈦微粒子所 構成’故可得優異之多孔質構造與高比表面積。而該結晶 性氧化鈦纖維與結晶性氧化鈦微粒子，係由銳鈦礦相與金 紅石相實質地形成，且該等結晶性氧化鈦纖維與結晶性氧 化鈦微粒子所構成之多孔質半導體層，其對於銳欽礦相與 金紅石相之金紅石相的X射線繞射之面積比爲1.00〜0.32 之間。面積比若超過1 · 0爲不實際，而若未滿0.3 2則難以 達成高電荷輸送效率，故不佳。 由X射線繞射之積分強度比所計算之銳鈦礦相含有比 ，於進行強度校正之X射線圖中，對於2Θ= 25.3° 、 -8 - 200807734 (5) 2 7.4°附近出現之來自銳鈦礦相與金紅石相氧化鈦之各繞 射峰’估計積分強度IA (銳鈦礦相）、IR (金紅石相） ，並以下式求出含有比。 銳鈦礦相含有比=IA/(IA + IR) 又’由銳鈦礦相與金紅石相實質地形成，係指於X射 線繞射中所有積分強度所占之鈦礦相與金紅石相之比例， 較佳爲80%以上、更佳爲83 %以上、特佳爲88%以上之意 ’該結晶性氧化鈦纖維與結晶性氧化鈦微粒子，若非爲銳 鈦礦相與金紅石相實質地形成，則電荷輸送效率不足夠， 故不佳。 本發明中’於多孔質半導體層之銳鈦礦相之以X射線 繞射所得的平均結晶尺寸，較佳爲10〜l〇〇nm、更佳爲 2 0〜1 0 0 n m之範圍。若未游1 0 n m，則由於結晶間之界面的 增加而使電荷輸送效率降低，故不佳，而若超過1 0 Onm則 多孔性半導體層之比表面積降低，而無法得到足夠之發電 量，故不佳。 平均微晶尺寸之測定，係以X射線繞射來進行。X射 線繞射測定，係使用理學電氣（股）製 ROTA FLEX RU200B採用以半徑185nm之測角計之反射法，X射線係 以單色器單色化之Cu Κα射線。測定樣品，係使用於所得 多孔質半導體添加作爲內部標準之X射線繞射標準用之高 純度砍粉末者。 將上述所得之X射線繞射圖進行強度校正，對繞射角 2Θ以內部標準之矽之1 1 1繞射峰進行校正。此處，矽之 200807734 (6) 111繞射峰之半價寬爲0.15°以下。對校正之x射線繞射 圖，使用25.3°附近出現之繞射峰，以以下之Scherrer式 計算出微晶尺寸。2Θ = 24〜30°範圍之氧化鈦、及矽之繞 射峰，來自Cu Καί、Κα2者並未分離，而全部當作 Cu Κα 〇 . D = Κχλ/βο〇8θ 此處， D :結晶尺寸（nm)、 λ :測定X射線波長（nm)、 β :因微晶尺寸之繞射射線之擴展、 Θ :繞射峰之布勒格角、 Κ :形狀因子（Scherrer常數） 此處，β爲了校正光學系之擴展，係採用將25.3°附 ^ 近出現之氧化鈦之繞射峰的半價寬Β減去內部標準之矽 111繞射峰之半價寬b者（β=Β - b)，而 Κ=1、λ = 0.15418nm 〇 本發明中，該多孔質半導體，較佳爲，於具有透明導 電層之透明塑膠薄膜之該透明導電層上，塗佈將結晶性氧 ' 化鈦纖維與結晶性氧化鈦粒子分散於分散介質之分散液（ 塗佈液）來設置，亦可將結晶性氧化鈦微粒子添加至不織 布狀態之結晶性氧化鈦纖維，藉由層合來設置。 分散液（塗佈液）之分散介質，可使用例如水或有機 溶劑，有機溶劑較佳可使用醇。分散於分散介質之際，亦 可視需要添加少量分散助劑。分散助劑，可使用例如界面 活性劑、酸、螯合劑等。 -10- 200807734 (7) 又’爲了提高結晶性氧化鈦纖維與結晶性氧化鈦微粒 子之黏著性，亦可使用黏結劑。 <結晶性氧化鈦纖維> 結晶性氧化鈦纖維，較佳爲以電氣紡絲製造。 • 電氣紡絲法，係將氧化鈦前驅物及可與其形成錯合物 • 之化合物的混合物、溶劑、與高縱橫比形成性之溶質所構 成之溶液，噴出至集合基板，藉由堆積及燒成而製得結晶 性氧化鈦纖維。 氧化鈦前驅物，可使用例如四甲氧化鈦、四乙氧化鈦 • 、四正丙氧化鈦、四異丙氧化鈦、四正丁氧化鈦、四三級 丁氧化鈦，而由取得容易度考量，以四異丙氧化鈦、四正 丁氧化鈦爲佳。 可與氧化鈦前驅物形成錯合物之化合物，可使用例如 羧酸、醯胺、酯、酮、膦、醚、醇、硫醇等配位性化合物 。較佳爲使用乙醯丙酮、乙酸、四氫呋喃。可與氧化鈦前 驅物形成錯合物之化合物的添加量，對於氧化鈦前驅物， 例如可爲〇·5等量以上、較佳爲1〜1〇等量。 溶劑’可使用例如己烷等脂肪族烴；甲苯、四氫萘等 芳香族烴；正丁醇、乙二醇等醇；四氫呋喃、二噁烷等醚 :二甲亞颯、Ν，Ν-二甲基甲醯胺、正甲基胺基吡啶、水。 該等之中，由對各溶質之親和性的觀點考量，以Ν，Ν-二甲 基甲醯胺、水爲佳。溶劑可單獨使用、亦可組合複數使用 。溶劑之量，對於氧化鈦之前驅物之重量，較佳爲〇 . 5〜3 0 -11 - 200807734 (8) 倍量、更佳爲〇·5〜20倍量。 高縱橫比形成性之溶質，由操作性之觀點或因燒成而 需要除去，以使用有機高分子爲佳。可例示如聚環氧乙垸 、聚乙烯醇、聚乙烯酯、聚乙烯醚、聚乙烯吡啶、聚丙燃 醯胺、醚纖維素、果膠、澱粉、聚氯化乙烯、聚丙燦腈、 _ 聚乳酸、聚乙醇酸、聚乳酸-聚乙醇酸共聚物、聚己內酯 、聚丁二酸丁二醇酯、聚丁二酸乙二醇酯、聚苯乙烯、聚 碳酸酯、聚碳酸六伸甲酯、聚丙烯酸酯、聚異氰酸乙嫌酯 、聚異氰酸丁酯、聚甲基丙烯酸甲酯、聚甲基丙烯酸乙醋 、聚甲基丙烯酸正丙酯、聚甲基丙烯酸正丁酯、聚丙烯酸 甲酯、聚丙烯酸乙酯、聚丙烯酸丁酯、聚對苯二甲酸乙二 醇酯、聚對苯二甲酸三甲二酯、聚萘二甲酸乙二醇酯、聚 ' 對苯二甲醯對苯二胺、聚對苯二甲醯對苯二胺-3,4’-氧二 苯二甲醯對苯二胺共聚物、聚間苯二甲醯間苯二胺、二乙 酸纖維素、三乙酸纖維素、甲基纖維素、丙基纖維素、苄 基纖維素、絲蛋白、天然橡膠、聚乙酸乙烯酯、聚乙烯甲 ' 醚、聚乙烯乙醚、聚乙烯正丙醚、聚乙烯異丙醚、聚乙烯 - 正丁醚、聚乙烯異丁醚、聚乙烯三級丁醚、聚偏二氯乙烯 、聚（Ν-乙烯吡咯烷酮）、聚（Ν-乙烯咔唑）、聚（4-乙烯吡啶） 、聚乙烯甲酮、聚甲基異丙烯酮、聚環氧丙烷、聚環氧環 戊烷、聚苯乙烯颯、尼龍6、尼龍66、尼龍1 1、尼龍12 、尼龍6 1 0、尼龍6 1 2、及該等之共聚物。其中，由對溶 劑之溶解性的觀點考量，以聚丙烯腈、聚環氧乙烷、聚乙 烯醇、聚乙酸乙烯酯、聚（Ν·乙烯吡咯烷酮）、聚乳酸、聚 -12- 200807734 (9) 氯化乙烯、三乙酸纖維素爲佳。 有機高分子之分子量，當分子量過低時，有機高分子 之添加量變大、因燒成所產生之氣體變多，而金屬氧化物 之構造產生缺陷的可能性增高而不佳，故須適當設定。較 佳之分子量，例如當爲聚環氧乙烷中之聚乙二醇時，爲 . 1 00000〜8000000、更佳爲 1 00000〜600000。 高縱橫比形成性之溶質的添加量，由氧化鈦之緻密性 提昇之觀點考量，高縱橫比之所形成之濃度範圍內儘可能 少爲佳，對氧化鈦前驅物之重量，較佳爲0.1〜200重量％ 、更佳爲1〜1 5 0重量％。 電氣紡絲法本身係周知之方法，係將溶解有高縱橫比 形成性之基質之溶液，噴出至電極間所形成之電場，將溶 ' 液朝電極拉絲，而將所形成之高縱橫比形成性物累積於集 合基板上，藉此製得氧化鈦噴出物之方法。氧化鈦噴出物 ，不僅可爲將溶解有高縱橫比形成性之基質之溶劑蒸餾除 去成爲層合體之狀態，即使爲噴出物含有該溶劑之狀態亦 可維持高縱橫比。 ' 通常，電氣紡絲係以室溫進行，但當溶劑之揮發不充 分時等，可視需要控制紡絲環境氣氛之溫度、或控制集合 基板之溫度。 電氣紡絲法之電極，可使用金屬、無機物、或有機物 等之可顯示導電性者，又，亦可爲絕緣物上具有顯示導電 性之金屬、無機物、或有機物之薄膜者。 又，電場可形成於一對或複數之電極間，而於任一之 -13- 200807734 (10) 電極施加高電壓。其亦包含使用2個電壓値相異之高電壓 電極（例如15kV與10kV)、與接地電極之合計3個電極 的情形，且亦包含使用電極數超過3個之情形。 以電氣紡絲法進行噴出之高縱橫比之氧化鈦噴出物， 係噴出、堆積至集合基板之電極。接著，將該氧化鈦噴出 物進行燒成。燒成，可使用一般之電爐，視需要亦可使用 可置換爐內氣體電爐。又，燒成溫度，以可結晶成長充分 及可控制之條件爲佳。爲了控制銳鈦礦相之結晶成長與金 紅石相之晶體斷層，較佳爲以3 00〜900 t ( 5 00〜8 00 °C ) 進行燒成。如此所製得之結晶性氧化鈦纖維，較佳爲具有 下述之性能。 纖維徑爲50〜lOOOnm、纖維長/纖維徑爲5以上（較 佳爲5〜3 00 )。若纖維徑較50nm小，則由於實際上難以 操作故不佳，而若較lOOOnm大，則其表面無法充分吸附 色素而無法充分地發電，故不佳。 由X射線繞射之結晶相的面積比所求得之銳鈦礦相/( 銳鈦礦相+金紅石相）爲1.00〜0.50。未滿0.50時，由於電 何輸送效率降低故不佳。 X射線繞射之銳鈦礦相之微晶尺寸爲10〜20 Onm。當 未滿 1 Onm時，電荷輸送效率會降低故不佳。而超過 2 OOnm時，多孔性半導體層之比表面積降低，而無法得到 充分之發電量，故不佳。 BET比表面積爲0.1〜l〇〇〇m2/g。若較0.1m2/g小則無 法充分吸附色素而無法充分地發電，故不佳，而若超過 _ 14- 200807734 (11) 1 0 00m2/g，則由於實際上難以操作故不佳。 〈結晶性氧化鈦微粒子> 另一方面’結晶性氧化鈦微粒子，以具有2〜5 0 0 n m ( 更佳爲5〜20Onm )之粒徑爲佳。若粒徑小於2nm，則粒子 • 界面增加、而電荷輸送效率降低故不佳。若大於5 00nm， . 則所吸附之色素量降低，而無法得到充分之發電量，故不 佳。 又，氧化鈦微粒子之結晶型可爲銳鈦礦或金紅石，而 氧化鈦微粒子可使用該等結晶型之混合物。 <多孔質半導體層之形成> " 多孔質半導體層，較佳爲，含有結晶性氧化鈦纖維1 0 重量％以上與結晶性氧化鈦微粒子1 5重量％以上。若結晶 性氧化鈦纖維少於1 0重量％，則無法得到充分之多孔性故 不佳，而若結晶性氧化鈦微粒子少於1 5重量％，則無法得 到充分之發電量故不佳。結晶性氧化鈦纖維及結晶性氧化 * 鈦微粒子之更佳含有率，分別爲15〜80重量％及20〜85重 量％。 多孔質半導體層之形成方法，可舉例如：塗佈分散有 結晶性氧化鈦纖維及結晶性氧化鈦微粒子之塗佈液之方法 、將結晶性氧化鈦微粒子添加至不織布狀態之結晶性氧化 鈦纖維使其層合之方法。 當多孔質半導體層係以塗佈分散有結晶性氧化鈦纖維 -15- 200807734 (12) 及結晶性氧化鈦微粒子之塗佈液之方法所形成時，分散液 之固形物濃度，以1〜80重量％爲佳。若未滿1重量％則最 後之多孔質半導體層的厚度會變薄，故不佳。而若超過80 重量％，則黏度過高難以塗佈，故不佳。更佳爲4〜60重量 % 〇 - 分散液之塗佈液，可將結晶性氧化鈦纖維與結晶性氧 . 化鈦微粒子分散於分散介質中來調製。於分散介質中，可 利用球磨機、介質攪拌型磨機、均質機等進行物理性分散 、亦可以超音波處理來分散。該分散液之分散介質，可使 用例如水或有機溶劑，有機溶劑以醇爲佳。 該分散液，亦可再添加氧化鈦微粒子之黏結劑。該黏 結劑，較佳可使用例如氧化鈦前驅物。例如，可使用四甲 * 氧化鈦、四乙氧化鈦、四正丙氧化鈦、四異丙氧化鈦、四 正丁氧化鈦、四三級丁氧化鈦及該等氧化鈦前驅物之水解 物。該等可以單體使用、亦可組合複數使用。 塗佈於透明塑膠薄膜上之透明導電層上之塗佈，可使 用以往塗佈加工時所慣用之任意方法來進行。可使用例如 * 輥法、浸漬法、氣刀法、板塗法、纏線棒塗法、滑槽 (Slide hopper)法、擠壓法、簾幕法。亦可使用以泛用機之 旋塗法或噴塗法，或使用凸版、平版及凹版之3大印刷法 等之凹版、橡膠版、網版印刷等濕式印刷來塗佈。該等之 中，可因應溶液黏度或濕厚度，使用較佳之製膜方法。塗 佈液之塗佈量，乾燥時之支持體之每lm2，較佳爲 0·5〜20g/m2、更佳爲 5〜10 g/m2。 •16- 200807734 (13) 將塗佈液塗佈設置於透明導電層上後，進 以形成多孔質半導體層。該熱處理，亦可不於 進行，可於乾燥後之其他製程進行。熱處理 100〜250°c、1〜120分鐘（更佳爲 150〜23 0 °c 、特佳爲180〜2 2 0°C、1〜60分鐘）之條件進行 該熱處理，可防止支撐透明導電層之薄膜因加 並可縮小多孔質半導體層之電阻上昇。多孔質 最終厚度，較佳爲1〜30μπι、更佳爲2〜ΙΟμηι， 透明度時以2〜6μπι爲最佳。 又，亦可對構成多孔質半導體層之氧化鈦 粒子吸收力強之紫外線等、或照射微波以加熱 來進行增強粒子間之物理性接合之處理。 於透明塑膠薄膜上之透明導電層上之不織 晶性氧化鈦纖維，添加結晶性氧化鈦微粒子使 法’例如，可使用以加壓或輥之壓接或熱壓接 之黏者、或使用組合該等之方法等來進行。 熱壓接時’較佳爲，將不織布狀態的結晶 維或透明導電層之表面活化以改善黏著性。活 可使用：以酸性或鹼性溶液將不織布狀態的結 纖維表面活化之方法、將紫外線或電子射線照 以活化之方法、實施電暈處理或電漿處理以將 方法。較佳爲，使用以酸性或鹼性溶液將表面 、或實施電漿處理以將表面活化之方法。 使用黏結劑時，所使用之黏結劑只要不妨, 行熱處理， 乾燥製程中 ，較佳爲以 、1〜90分鐘 。藉由進行 熱而變形、 半導體層之 特別是提局 粒子，照射 微粒子層， 布狀態的結 其層合之方 、以黏結劑 性氧化鈦纖 化之方法， 晶性氧化鈦 射薄膜表面 表面活化之 活化之方法 礙電荷移動 -17- 200807734 (14) 者即可，可使用例如金屬氧化物或其前驅物、導電性聚合 物或導電性無機物、有機黏著劑，較佳可使用金屬氧化物 或其前驅物。以黏結劑黏著之方法，可使用：於透明導電 層或不織布狀態的結晶性氧化鈦纖維上，塗佈黏結劑或黏 結劑之分散液之後黏著之方法；將不織布狀態的結晶性氧 • 化鈦纖維設置於透明導電層上後，添加黏結劑或含有黏結 劑之分散液之方法。 於多孔質半導體層，係於不織布狀態的結晶性氧化鈦 纖維添加結晶性氧化鈦微粒子。結晶性氧化鈦微粒子之添 加’可使用：將不織布狀態的結晶性氧化鈦纖維含浸於含 結晶性氧化鈦微粒子之分散液後進行熱處理之方法；將含 結晶性氧化鈦微粒子之分散液使用例如噴塗法或棒塗法， ' 塗佈於透明導電層或不織布狀態的結晶性氧化鈦纖維、或 塗佈於不織布狀態的結晶性氧化鈦纖維與透明導電層上雙 方之方法；將不織布狀態的結晶性氧化鈦纖維與結晶性氧 化鈦微粒子熱壓接之方法；將不織布狀態的結晶性氧化鈦 纖維與結晶性氧化鈦微粒子以例如高壓釜處理使其黏結之 ^ 方法；於不織布狀態的結晶性氧化鈦纖維與金屬氧化物前 驅物之存在下藉熱液合成以形成微粒子之方法；於結晶性 氧化鈦纖維之不織布與金屬氧化物前驅物之存在下藉電子 束或UV處理以形成微粒子之方法；於不織布狀態的結晶 性氧化鈦纖維以濺鍍等使結晶性氧化鈦微粒子黏結之方法 。亦可組合該等方法使用。 該等之中，較佳爲使用：將不織布狀態的結晶性氧化 -18- 200807734 (15) 鈦纖維含浸於含結晶性氧化鈦微粒子之分散液後進行 理之方法；將含結晶性氧化鈦微粒子之分散液使用例 塗法或棒塗法，塗佈於透明導電層或不織布狀態的結 氧化鈦纖維、或塗佈於不織布狀態的結晶性氧化鈦纖 透明導電層上雙方之方法。若使用該等方法，可將結 氧化鈦微粒子投入至內部且可簡便地進行，故較佳。 爲了提昇結晶性氧化鈦微粒子與不織布狀態的結晶性 鈦纖維之黏著性，亦可使用上述之表面活性處理、或 黏著劑。 對不織布狀態的結晶性氧化鈦纖維之結晶性氧化 粒子之含浸或塗佈，可於將不織布狀態的結晶性氧化 維層合於透明導電層之前進行、可於之後進行、亦可 進行。使用分散液時，可藉由於分散液添加黏結劑， 進行透明導電層之黏著與微粒子之添加，故較佳。 上述黏結劑，較佳可使用例如氧化鈦前驅物。可 如四甲氧化鈦、四乙氧化鈦、四正丙氧化鈦、四三級 化鈦及該等氧化鈦前驅物之水解物。該等可以單體使 亦可組合複數使用。 使用分散液添加結晶性氧化鈦微粒子時，於分散 使用之結晶性氧化鈦微粒子之量，較佳爲0.05〜90 I 、更佳爲1〜70重量％、特佳爲1〜50重量％。若未滿 重量％，最後之多孔質半導體層的厚度會變薄，故不 而若超過90重量％，則黏度過高難以塗佈，故不佳。 分散液之分散介質，可使用例如水或有機溶劑， 熱處 如噴 晶性 維與 晶性 又， 氧化 使用 鈦微 鈦纖 同時 同時 舉例 丁氧 用、 液所 .量％ 0.05 佳。 有機 -19- 200807734 (16) 溶劑較佳可使用醇。分散於分散介質之際，亦可視需要添 加少量分散助劑。分散助劑，可使用例如界面活性劑、酸 、螯合劑等。 爲了提昇多孔質半導體層之電荷輸送效率，較佳爲， 於透明塑膠薄膜上之透明導電層上之不織布狀的結晶性氧 化鈦纖維添加結晶性氧化鈦微粒子使其層合後進行熱處理 。該加熱處理，亦可不於乾燥製程中進行，可於乾燥後之 其他製程進行。加熱處理，較佳爲以100〜25〇t：、1〜120 分鐘（更佳爲150〜23 0 °C、1〜90分鐘、特佳爲180〜220°C 、：I〜6 0分鐘）之條件進行。藉由進行該加熱處理，可防止 塑膠支持体因加熱而變形，並可縮小多孔質半導體層之電 阻上昇。 亦可對添加有金屬氧化物微粒子之多孔質半導體層， 照射金屬氧化物吸收力強之紫外線等，或照射微波以加熱 金屬氧化物，來進行增強金屬氧化物間之物理性接合之處 理。 又，爲了防止載持多孔質半導體之透明導電層與對極 之電氣短路之目的等，任何之多孔質半導體曾設置之方法 ，亦可事先於透明導電層上設置下塗層。該下塗層，以 Ti〇2、Sn02、ZnO、Nb205爲佳、Ti02爲特佳。該下塗層 ，可藉例如 Electrochim、Acta40、643 〜652(1995)所記載 之噴霧熱裂解法、或濺鍍等來設置。該下塗層之膜厚，較 佳爲5〜lOOOnm、更佳爲10〜500nm。 -20- 200807734 (17) <透明塑膠薄膜> 本發明中，支撐透明導電層之支持體，係使用塑膠薄 膜。塑膠薄膜，以聚酯薄膜較佳，構成該聚酯薄膜之聚酯 ，係由芳香族二價酸或其之酯形成性衍生物、與二醇或其 之酯形成性衍生物所合成之線狀飽和聚酯。 ^ 該聚酯之具體例，可舉例如聚對苯二甲酸乙二醇酯、 聚間苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚（對 苯二甲酸1，4-環己烷二甲酯）、聚2,6-苯二甲酸甲酯、聚 2,6-萘二甲酸乙二醇酯等。可爲該等之共聚物或其與小比 例之其他樹脂之摻合物。該等聚酯之中，由於聚對苯二甲 酸乙二醇酯、聚2,6-萘二甲酸乙二醇酯之力學特性及光學 物性等之平衡性良好，故較佳。 ' 特別是聚2,6-萘二甲酸乙二醇酯，其機械強度大、熱 收縮率小、加熱時之寡聚物產生量小等方面上較聚對苯二 甲酸乙二醇酯爲佳，故爲最佳。 聚對苯二甲酸乙二醇酯，可使用具有對苯二甲酸乙二 * 醇酯單位較佳爲90莫耳％以上、更佳爲95莫耳％以上、 • 特佳爲97莫耳％以上者。聚2,6-萘二甲酸乙二醇酯，可使 用具有2,6-萘二甲酸乙二醇酯單位較佳爲90莫耳％以上、 更佳爲95莫耳％以上、特佳爲97莫耳％以上者。聚酯， 可爲均聚物、亦可爲共聚合有第三成分之共聚物，但以均 聚物爲佳。 聚酯之固有黏度，較佳爲0.40dl/g以上、更佳爲 0.40〜0.90dl/g。當固有黏度未滿〇.4〇dl/g時，常發生製程 -21 - 200807734 (18) 中斷，故不佳，而若超過0.90dl/g，則由於熔化黏度高而 難以熔融擠製，始聚合時間變長而不經濟，故不佳。 聚酯可藉習知之方法製得。例如，可由藉二羧酸與二 醇之反應直接製得低聚合度聚酯之方法來製得。又，亦可 藉將二羧酸之低級烷基酯與二醇使用酯交換反應觸媒反應 . 後，於聚合反應觸媒之存在下進行聚合反應之方法來製得 ^ 。酯交換反應觸媒，可使用習知者，例如含鈉、鉀、鎂、 鈣、鋅、緦、鈦、鉻、錳、鈷之化合物。聚合反應觸媒， 可使用習知者，例如，三氧化銻、五氧化銻等之銻化合物 、以二氧化鍺爲代表之鍺化合物、鈦酸四乙酯、鈦酸四丙 酯、鈦酸四苯酯或該等之部分水解物、草酸鈦銨、草酸鈦 鉀、三乙醯丙酮鈦等鈦化合物。當經酯交換反應來進行聚 ' 合反應時，於聚合反應前，爲了使酯交換觸媒失活，通常 添加磷酸三甲酯、磷酸三乙酯、磷酸三正丁酯、正磷酸等 磷化合物，但磷元素於聚酯中之含量，由熱安定性之觀點 考量，以20〜10Oppm爲佳。又，聚酯，亦可於熔融聚合後 將其碎片化，再於加熱減壓下或氮等惰性氣流中施以固相 - 聚合。 聚酯薄膜，以實質上不含粒子爲佳。若含有粒子，則 會損及高透明性，且表面粗化而使透明導電層之加工變得 困難。薄膜之霾値，較佳爲1.5%以下、更佳爲1.0%以下 、特佳爲0.5 %以下。 聚酯薄膜，較佳爲，於波長3 70nm之光線透過率爲 3%以下、於波長400nm之光線透過率爲70%以上。又， -22- 200807734 (19) 光線透過率係使用（股）島津製作所製分光光度計MPC3 100 所測定之數値。該光線透過率，可藉使用以2，6 -萘二羧酸 等吸收紫外線單體作爲構成成分之聚酯、或使聚酯含有紫 外線吸收劑來獲得。 紫外線吸收劑，可使用例如2.2’-對苯雙（3,1-苯并噁 . 嗪-4-酮）、2.2、對苯雙（6-甲基-3，1-苯并噁嗪·4-酮）、2.2，- 對苯雙（6 -氯- 3，1-苯并噁嗪-4·酮）、2·2’-(4,4’-二苯）雙（3，1-苯并噁嗪-4-酮）及2.2’-(2,6-萘）雙（3,1-苯并噁嗪-4-酮）等環 狀亞胺酯化合物。 聚酯薄膜，3維中心線平均粗度，以兩面皆爲〇.〇〇〇】 〜0·02μιη爲佳、更佳爲0 · 0 0 0 1〜0.0 1 5 μιη、特佳爲〇 · 〇 〇 〇 1〜 0 · 0 1 0 μ m。特別是，若至少一面之3維中心線平均粗度爲 • 0.0001〜〇·〇〇5μιη ，貝IJ由於透明導電層之力口 π：變得容易故較 佳。只少一面之最佳表面粗度，爲0.0005〜0.004μιη。 聚酯薄膜之厚度，較佳爲10〜500μπι、更佳爲20〜400 μιη、特佳爲 50〜300μπι。 ' 接著’說明聚酯薄膜之較佳製造方法。又，玻璃轉移 ' 溫度簡稱爲Tg。聚酯薄膜，可將聚酯熔融擠製成薄膜狀 ，於成型桶冷卻固化作成未拉伸薄膜，將該未拉伸薄膜以 Tg〜（Tg+60)°C朝長邊方向以合計倍率爲3倍〜6倍之方式 拉伸1次或2次以上，之後以Tg〜（Tg+ 60)°C朝寬度方向 以倍率爲3〜5倍之方式拉伸，視需要再以Tm 18 0°C〜25 5 °C 進行熱處理1〜60秒鐘，藉此來製得。爲了縮小聚酯薄膜 之長邊方向與寬度方向之熱收縮率差、及長邊方向之熱收 -23- 200807734 (20) 縮’可使用曰本特開昭5 7-5 762 8號公報所示之於熱處理 製程使其朝縱向收縮之方法、或日本特開平2 7 5 〇 3〗號 公報所不之將薄膜以懸垂狀態進行鬆驰熱處理之方法等。 〈透明導電層> • 透明導電層’可使用例如導電性之金屬氧化物（氟摻 雜氧化錫、銦-錫複合氧化物（ITO)、銦一鋅複合氧化物 (IZ 0))、金屬之薄膜（例如鉑、金、銀、銅、鋁等薄膜）、 碳材料。該透明導電層，可層合2種以上、使其複合化者 。該等之中，由於ITO、IZO光線透過率高、低電阻，故 特佳。 透明導電層之表面電阻，較佳爲100Ω/□以下、更佳 ' 爲40Ω/□以下。若超過1 00Ω/□，則電池內電阻變得過大 而使光發電效率降低，故不佳。 透明導電層之厚度，較佳爲 100〜500nm。若未滿 100nm，則無法充份地降低表面電阻値，若超過5 00nm， * 則光線透過率降低、且透明導電層容易破裂，故不佳。 ’ 透明導電層之表面張力’較佳爲40mN/m以上、更佳 爲65mN/m以上。若表面張力未滿40mN/m’則透明導電 層與多孔質半導體之密合性變差，而若爲65mN/m以上， 則藉由溶劑之主成分爲水之水性塗液的塗佈容易形成多孔 質半導體層，故更佳。 具備上述性質之透明導電層’可使用例如ITO或1Z0 形成透明導電層，以下述之任一方法實施加工來製得。 • 24 - 200807734 (21) (1) 以酸性或鹼性溶液將透明導電層表面活化之方法 〇 (2) 照射紫外線或電子射線於透明導電層表面使其活 化之方法。 (3) 實施電暈處理或電漿處理將透明導電層表面活化 . 之方法。 其中，以電漿處理將表面活化之方法，由於可得高表 面張力故特佳。 <易黏著層> 爲了提昇聚酯薄膜與透明導電層之密合性之方法，可 於聚酯薄膜與透明導電層之間設置易黏著層。易黏著層之 厚度，較佳爲10〜200nm、更佳爲20〜150nm。易黏著層之 厚度若未滿1 〇nm，則提昇密合性之效果差，而若超過 2 OOnm，則容易產生易黏著層之凝集破壞使密合性降低， 故不佳。 設置易黏著層時，較佳爲於聚酯薄膜之製造過程中以 塗佈來設置，並且以塗佈於配向結晶化結束前之聚酯薄膜 爲佳。此處，所謂結晶配向結束前之聚酯薄膜，係包含未 拉伸薄膜、將未拉伸薄膜朝縱向或橫向之任一向配向之單 軸配向薄膜、及朝縱向及橫向之兩方向低倍率拉伸配向者 (最終之朝縱向或橫向再拉伸使配向結晶化完成前之雙軸 拉伸薄膜）。其中，較佳爲，於未拉伸薄膜或朝一方向配 向之單軸拉伸薄膜，塗佈上述組成物之水性塗佈液，直接 -25- 200807734 (22) 實施縱向拉伸及/或橫向拉伸與熱固定。 易黏著層，較佳爲，以對聚酯薄膜與透明_ 具有優異黏著性之材料構成，可使用例如聚酯植 酸樹脂、氨基甲酸酯丙烯酸樹脂、矽丙烯酸樹游 胺樹脂、聚矽氧烷樹脂。該等樹脂可單獨使用、 2種以上之混合物。 <硬塗層> 爲了提昇聚醋薄膜與透明導電層之密合性、 合耐久性，亦可於易黏著層與透明導電層之間藍 。硬塗層之厚度，較佳爲0.01〜20μπι、更佳爲1-設置硬塗層時，較佳爲，於設置有易黏著層 膜上以塗佈來設置。硬塗層，較佳爲，以對易貌 明導電層雙方具有優異黏著性之材料構成，可偯 烯酸係樹脂、氨基甲酸酯樹脂、矽系樹脂、UV 脂、環氧系樹脂等樹脂成分、或該等與無機粒子 。無機粒子，可使用例如氧化鋁、氧化矽、雲母 <抗反射層> 本發明中，爲了提昇光線透過率以提高光發 亦可於透明導電層之相反面設置抗反射層。 設置抗反射層之方法，較佳爲，將與聚醋薄 率具不同折射率之材料單層、或2層以上層合形 。當爲單層構造時，以使用折射率較基材薄膜小 電層雙方 脂、丙烯 、三聚氰 亦可使用 特別是密 :置硬塗層 1 0 μπι 〇 Ρ之聚酯薄 i著層與透 :用例如丙 硬化系樹 ‘之混合物 之粒子。 電效率， 膜之折射 成之方法 之材料爲 -26- 200807734 (23) 佳，而爲2層以上之多層構造時，較佳爲’與層合薄膜鄰 接之層，選擇具有較聚酯薄膜之折射率大之材料，而層合 於其上之層，選擇具有折射率較其小之材料。 構成該抗反射層之材料，無拘於有機材料、無機材料 ，只要可滿足上述折射率之關係者即可’較佳爲使用選自 CaF2、MgF2、NaAlF4、Si02、ThF4、Zr02、Nd203、Sn02 、Ti02、Ce02、ZnS、ln203所構成群中之介電體。 層合抗反射層之方法，可使用例如真空蒸鍍法、濺鍍 法、離子鍍法等乾式被覆法，又，亦可使用例如凹版方式 、逆輥方式、模口方式等濕式被覆法。 於抗反射層之層合之前，亦可先施以電暈處理、電漿 ^ 處理、濺蝕處理、電子射線照射處理、紫外線照射處理、 ' 底漆處理、易黏著處理等前處理。 <色素增感太陽電池及所使用之電極之製作> 使用本發明之電極製作色素增感太陽電池時，可使用 ‘ 周知之方法。具體而言，可以例如下述之方法製作。 • (1)使色素吸附於本發明之層合薄膜之多孔質半導體 層。將以釕聯吡啶系錯合物（釕錯合物）爲代表之有機金 屬錯合物色素、花青系色素、香豆素系色素、咕噸系色素 、卟啉系色素等之具有可吸收可見光及紅外線區域之光之 特性的色素，溶解於乙醇或甲苯等溶劑作成色素溶液，浸 漬多孔質半導體層、或噴霧或塗佈於多孔質半導體層而製 作成一電極A。 -27- 200807734 (24) (2) 相對之電極，係使用於本發明之層合薄膜的透明 導電側’以濺鍍法形成薄鉑層所製作之電極B。 (3) 將上述電極A與電極B，插入熱壓接性之聚乙烯 薄膜製之框型間隔物（厚度20μπι )使其疊合，將間隔物 部加熱至12(TC，將兩電極壓接。並且，將其邊緣部以環 . 氧樹脂黏著劑密封。 (4) 透過事先設置於片之角部之電解液注入用小洞， 注入含有碘化鋰與碘（莫耳比3 : 2 )及3重量％之作爲間 隔物之平均粒徑20 μπι之奈米珠的電解質水溶液。充分進 行內部脫氣，最後以環氧樹脂黏著劑密封小洞。 實施例 接著，以實施例更詳細說明本發明。且以下之各實施 例、比較例之評價項目係以如下之方法實施。 (1 )結晶性氧化鈦微粒子之粒徑及結晶性氧化鈦纖維 之纖維徑 由以掃描型電子顯微鏡（（股）日立製作所製S-2400 ) 攝影（倍率200倍）所得金屬氧化物表面之照片圖，隨機 選取2 0部位，測定結晶性氧化鈦微粒子之徑及結晶性氧 化鈦纖維之纖維徑，求出平均値，作爲平均徑及平均長度 (2)結晶性氧化鈦纖維之纖維徑/纖維長 -28- 200807734 (25) (1)與結晶性氧化鈦微粒子之粒徑及結晶性氧化鈦纖維 之纖維徑以同樣方法計算出平均纖維長與平均纖維徑，求 得其比。 (3) BET比表面積之測定方法： - 所得金屬氧化物之比表面積測定，係以使用氮氣之 BET法來測定。 (4) X射線繞射之測定 X射線繞射測定，係使用理學電氣（股）製 R0TA FLEX RU200B採用以半徑I85nm之測角計之反射法，X 射線係以單色器單色化之Cu Κα射線。測定樣品，係使用 * 於所得陶瓷纖維添加作爲內部標準之X射線繞射標準用之 高純度矽粉末者。 (5) 微晶尺寸之測定 將上述所得之X射線繞射圖進行強度校正，對繞射角 ' 2 Θ以內部標準之矽之1 1 1繞射峰進行校正。此處，矽之 1 1 1繞射峰之半價寬爲0.15°以下。對校正之X射線繞射 圖，使用25.3°附近出現之繞射峰，以以下之Scherrer式 計算出微晶尺寸。2Θ= 24〜30°範圍之氧化鈦、及矽之繞 射峰，來自 Cu Καί、Κα2者並未分離，而全部當作Cu Κα。200807734 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a dye-sensitized solar cell and a resultant film. More specifically, it relates to the dye sensitization of a highly pigment-sensitized solar cell using a plastic substrate with high electrical properties. The laminated film used and the dye-sensitized solar power [Prior Art] Pigment-sensitized sun Since the use of the dye-sensitized semi-optical conversion element has been proposed ("Nature" Dance 73 7 to 740 (1991)), it has attracted attention as a replacement for the solar cell. ^ A pigment-sensitized solar cell using a plastic substrate is attracting attention due to its weight reduction. In general, when a plastic solar cell is used, in order to increase the oxide semiconductor particles or to form a porous high-temperature heat treatment for improving the photoelectric conversion efficiency. However, the temperature is generally 400 ° C to directly perform high temperature heat treatment on the plastic substrate. Therefore, in the case of the oxidized metal foil and the dye-sensitized solar cell using a plastic substrate, the surface area of the solar cell is not sufficient, and the photoelectric conversion cannot be sufficiently improved, and is disclosed in Japanese Patent Publication No. 1 1 - 2 8 8 745. JP-A No. 2001-60426 discloses a method in which a high-temperature heat treatment of a metal oxide is carried out, and then peeled off and fixed to a plastic substrate by a clip. [Use electrodes and layers ‘can make light hair; solar battery. The S 3 5 3 coil of the conductor microparticles, the novelty of the cation battery, the adhesion and the structure of the softening of the pigment and the addition of the pigment of the substrate, and it is difficult to provide irregularities on the surface of the Japanese special opening. However, its specific efficiency problem. On the metal foil, the metal oxide layer is however unsuitable for mass production due to the complexity of the process -5-200807734 (2). Further, Japanese Laid-Open Patent Publication No. 2002-5 041-3 discloses a method of forming a semiconductor metal oxide layer by applying metal oxide particles on a plastic substrate. However, the metal oxide particles fixed on the transparent conductive layer may be detached from the powder or peeled off in the electrolyte during operation. In addition, Japanese Patent Publication No. 2001-93590 and JP-A No. 200 1 - 3 5 8 3 4 8 disclose that needle crystals of metal oxide are used for electrodes for solar cells. Improve charge transport efficiency. However, in order to obtain a good porous structure to achieve high charge transport efficiency, it is necessary to appropriately control the crystal state of the metal oxide. For example, when the metal oxide is titanium oxide, an anatase phase is preferred. However, it is difficult to produce a titania having a needle-like anatase phase, and the solid is usually preferred to form a relatively stable rutile phase. As a result, the photoelectric conversion efficiency is not sufficient. On the other hand, a method of producing a metal oxide is an electrospinning method. In this method, an oxide precursor containing a burn-in component such as a polymer is sprayed onto a substrate at a high aspect ratio, and then heat-treated at a high temperature to obtain a metal oxide. An electrode system for a dye-sensitized solar cell in which a metal oxide layer is provided on a glass* substrate by the electric spinning method is known. As described above, the dye-sensitized solar cell is described in US2005/0 1 093 8 5 and Mi Yeon Song et al., Nanotechnology, 2004, pi 861~1 865 〇, the above-mentioned electrode for dye-sensitized solar cells, The metal oxide precursor is ejected onto the transparent conductive layer on the glass substrate in a high aspect ratio and deposited, and then fired at a high temperature to obtain a metal oxide layer. In the case of the firing of -6 - 200807734 (3), since the metal oxide tends to peel off due to the self-shrinkage of the metal oxide, the metal oxide layer is not provided by the electrospinning method. Fully high specific surface area and high charge transport efficiency. Further, since the firing process of the metal oxide on the glass substrate itself is carried out at 400 ° C or higher, it is difficult to apply this technique to the electrode for sensitizing solar cells using a glass substrate. SUMMARY OF THE INVENTION An object of the present invention is to provide an electrode for a dye-sensitized solar cell which can use a plastic substrate and adsorb a sufficient amount of a pigment to obtain a high charge transport efficiency, and the porous oxide film is not peeled off. The good adhesion is laminated on the substrate, and a dye-sensitized solar cell having high photovoltaic power generation performance can be produced. Another object of the present invention is to provide a laminated film using a plastic substrate for use in the above electrodes. Another object of the present invention is to provide a dye-sensitized solar cell using the above electrode. Other objects and advantages of the present invention will be apparent from the following description. According to the present invention, the above objects and advantages of the present invention can be attained by a laminated film characterized by a porous semiconductor layer, a transparent conductive layer and a transparent plastic film, the porous semiconductor The layer ' is composed of crystalline titanium oxide fibers and crystalline titanium oxide fine particles'. The crystalline titanium oxide fibers and the crystalline titanium oxide fine particles are substantially formed of an anatase phase and a rutile phase, and 200807734 ( 4) The integrated intensity ratio of the x-ray diffraction is calculated to be between 1·〇〇~〇·32, and is used for the electrode of the dye-sensitized solar cell. By the present invention, the present invention The above objects and advantages are achieved by an electrode for a dye-sensitized solar cell, which is composed of the above-described laminated film of the present invention and a dye adsorbed on the porous semiconductor layer of the laminated film. According to the present invention, the above objects and advantages of the present invention can be attained by a dye-sensitized solar cell comprising the above electrode of the present invention. [Embodiment] In the laminated film of the present invention, the porous semiconductor layer is composed of crystalline titanium oxide fibers and crystalline titanium oxide fine particles. Since the porous semiconductor layer ' is composed of crystalline titanium oxide fibers and crystalline titanium oxide fine particles', an excellent porous structure and a high specific surface area can be obtained. The crystalline titanium oxide fiber and the crystalline titanium oxide fine particles are substantially formed of an anatase phase and a rutile phase, and the porous semiconductor layer composed of the crystalline titanium oxide fiber and the crystalline titanium oxide fine particle. The ratio of the area of the X-ray diffraction of the rutile phase of the Ruiqin ore phase to the rutile phase is between 1.00 and 0.32. If the area ratio exceeds 1.0, it is not practical, and if it is less than 0.32, it is difficult to achieve high charge transport efficiency, which is not preferable. The ratio of the integrated intensity of the X-ray diffraction to the calculated anatase phase is in the X-ray diagram for intensity correction, and is from the vicinity of 2Θ= 25.3°, -8 - 200807734 (5) 2 7.4° The diffraction peaks of the titanium ore phase and the rutile phase titanium oxide 'estimate the integrated intensity IA (anatase phase) and IR (rutile phase), and the content ratio is obtained by the following formula. Anatase phase content ratio = IA / (IA + IR) and 'substantially formed by anatase phase and rutile phase, refers to the titanium ore phase and rutile phase occupied by all integral intensities in X-ray diffraction. The ratio is preferably 80% or more, more preferably 83% or more, and particularly preferably 88% or more. The crystalline titanium oxide fiber and the crystalline titanium oxide fine particle are substantially an anatase phase and a rutile phase. When the ground is formed, the charge transport efficiency is insufficient, which is not preferable. In the present invention, the average crystal size obtained by X-ray diffraction of the anatase phase of the porous semiconductor layer is preferably in the range of 10 to 10 nm, more preferably 20 to 1 0 0 m. If it is not 10 nm, the charge transport efficiency is lowered due to an increase in the interface between crystals, which is not preferable, and if it exceeds 10 nm, the specific surface area of the porous semiconductor layer is lowered, and sufficient power generation cannot be obtained. It is not good. The measurement of the average crystallite size is carried out by X-ray diffraction. The X-ray diffraction measurement was carried out using a Neo-Electrical Electric Co., Ltd. ROTA FLEX RU200B using a reflection method with a radius of 185 nm, and the X-ray system was a monochromator Cu Κα ray. The measurement sample was used for adding a high-purity chopped powder for use as an internal standard X-ray diffraction standard to the obtained porous semiconductor. The X-ray diffraction pattern obtained above was subjected to intensity correction, and the diffraction angle 2 校正 was corrected by the 1 1 1 diffraction peak of the internal standard. Here, 矽之 200807734 (6) 111 half-width of the diffraction peak is 0.15 ° or less. For the corrected x-ray diffraction pattern, the diffraction peaks appearing around 25.3° were used, and the crystallite size was calculated by the following Scherrer equation. 2Θ = 24~30° range of titanium oxide and 绕 绕 diffraction peaks, from Cu Καί, Κα2 are not separated, but all are treated as Cu Κα 〇. D = Κχλ/βο〇8θ where D: crystal size (nm), λ: X-ray wavelength (nm), β: diffraction of diffraction ray due to crystallite size, Θ: Bragg angle of diffraction peak, Κ: shape factor (Scherrer constant) Here, β is The extension of the calibrated optical system is obtained by subtracting the half-price width 绕 of the diffraction standard of the titanium oxide appearing at 25.3° from the half-price width b of the internal standard 矽111 diffraction peak (β=Β - b), and Κ =1, λ = 0.15418 nm In the present invention, the porous semiconductor is preferably coated with crystalline oxygenated titanium fiber and crystalline on the transparent conductive layer of a transparent plastic film having a transparent conductive layer. The titanium oxide particles are dispersed in a dispersion liquid (coating liquid) of the dispersion medium, and the crystalline titanium oxide fine particles may be added to the non-woven crystalline titanium oxide fiber and laminated. As the dispersion medium of the dispersion (coating liquid), for example, water or an organic solvent can be used, and an organic solvent is preferably an alcohol. When dispersed in a dispersion medium, a small amount of dispersing aid may be added as needed. As the dispersing aid, for example, an surfactant, an acid, a chelating agent or the like can be used. -10- 200807734 (7) Further, in order to improve the adhesion between the crystalline titanium oxide fiber and the crystalline titanium oxide fine particles, a binder may be used. <Crystalline titanium oxide fiber> The crystalline titanium oxide fiber is preferably produced by electrical spinning. • The electrospinning method is a solution of a mixture of a titanium oxide precursor and a compound capable of forming a complex compound, a solvent, and a high aspect ratio forming solute, which are discharged onto a collecting substrate by stacking and burning. A crystalline titanium oxide fiber is obtained. As the titanium oxide precursor, for example, titanium tetraoxide, tetraethylene titanium oxide, tetra-n-propoxide titanium oxide, titanium tetra-titanium oxide, tetra-n-butyl titanium oxide, tetra- or tertiary-grade titanium oxide can be used, and it is easy to obtain Preferably, titanium tetraisopropoxide and tetra-n-butyl titanium oxide are preferred. A compound which can form a complex with a titanium oxide precursor can be used, for example, a complex compound such as a carboxylic acid, a guanamine, an ester, a ketone, a phosphine, an ether, an alcohol or a thiol. Preferably, acetamidine, acetic acid or tetrahydrofuran is used. The amount of the compound which can form a complex with the titanium oxide precursor can be, for example, an amount of 〇·5 or more, preferably 1 to 1 Å, for the titanium oxide precursor. As the solvent, for example, an aliphatic hydrocarbon such as hexane; an aromatic hydrocarbon such as toluene or tetrahydronaphthalene; an alcohol such as n-butanol or ethylene glycol; or an ether such as tetrahydrofuran or dioxane: dimethyl hydrazine, hydrazine, hydrazine-di Methylformamide, n-methylaminopyridine, water. Among these, it is preferable to use hydrazine, hydrazine-dimethylformamide or water from the viewpoint of affinity for each solute. The solvent may be used singly or in combination. The amount of the solvent is preferably 〇 for the weight of the titanium oxide precursor. 5~3 0 -11 - 200807734 (8) The amount is more preferably 5 to 20 times. The high aspect ratio forming solute is preferably removed from the viewpoint of workability or by firing, and it is preferred to use an organic polymer. For example, polyethylene oxide, polyvinyl alcohol, polyvinyl ester, polyvinyl ether, polyvinyl pyridine, polyacrylamide, ether cellulose, pectin, starch, polyvinyl chloride, polyacrylonitrile, _ poly Lactic acid, polyglycolic acid, polylactic acid-polyglycolic acid copolymer, polycaprolactone, polybutylene succinate, polyethylene succinate, polystyrene, polycarbonate, polycarbonate Methyl ester, polyacrylate, polyethyl isocyanate, polybutyl isocyanate, polymethyl methacrylate, polyethyl methacrylate, poly-n-propyl methacrylate, poly-methyl methacrylate Ester, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, poly 'p-phenylene Indole p-phenylenediamine, polyparaphenylene terephthalamide, p-phenylenediamine-3,4'-oxydiphenyldimethylstilbene p-phenylenediamine copolymer, poly(m-xylylenediphenyl) m-phenylenediamine, diacetate fiber , cellulose triacetate, methyl cellulose, propyl cellulose, benzyl cellulose, silk protein, natural rubber, polyvinyl acetate , polyethylene methyl ether, polyethylene ether, polyethylene n-propyl ether, polyethylene isopropyl ether, polyethylene-n-butyl ether, polyethylene isobutyl ether, polyethylene tert-butyl ether, polyvinylidene chloride, poly (Ν-vinylpyrrolidone), poly(fluorene-vinylcarbazole), poly(4-vinylpyridine), polyvinyl ketone, polymethylisopropenone, polypropylene oxide, polyepoxycyclopentane, polyphenylene Vinyl ruthenium, nylon 6, nylon 66, nylon 1 1, nylon 12, nylon 610, nylon 6-1, and copolymers thereof. Among them, from the viewpoint of solubility in a solvent, polyacrylonitrile, polyethylene oxide, polyvinyl alcohol, polyvinyl acetate, poly(fluorene vinylpyrrolidone), polylactic acid, poly-12-200807734 (9) ) Vinyl chloride or cellulose triacetate is preferred. When the molecular weight of the organic polymer is too low, the amount of the organic polymer added is increased, and the gas generated by the firing is increased, and the possibility of defects in the structure of the metal oxide is increased, so it is necessary to appropriately set . The preferred molecular weight, for example, when it is polyethylene glycol in polyethylene oxide, is from 1,000,000 to 8,000,000, more preferably from 1,000 to 600,000. The addition amount of the high aspect ratio forming solute is considered to be as small as possible from the viewpoint of improving the compactness of titanium oxide, and the concentration range of the high aspect ratio is preferably as small as possible, and the weight of the titanium oxide precursor is preferably 0.1. 〜200% by weight, more preferably 1 to 150% by weight. The electrospinning method itself is a well-known method in which a solution in which a matrix having a high aspect ratio formability is dissolved is ejected to an electric field formed between electrodes, and a solution is drawn toward the electrode to form a high aspect ratio. A method in which a substance is accumulated on a collecting substrate, thereby producing a titanium oxide ejecting material. The titanium oxide ejected material is not only a state in which a solvent in which a matrix having a high aspect ratio-forming property is dissolved is distilled off to form a laminate, and a high aspect ratio can be maintained even in a state in which the ejected material contains the solvent. 'In general, the electrospinning is carried out at room temperature, but when the volatilization of the solvent is insufficient, the temperature of the spinning environment atmosphere or the temperature of the collecting substrate can be controlled as needed. The electrode of the electrospinning method may be one which exhibits conductivity by using a metal, an inorganic substance or an organic substance, or a film of a metal, an inorganic substance or an organic substance which exhibits conductivity on the insulating material. Further, an electric field can be formed between a pair of electrodes or a plurality of electrodes, and a high voltage is applied to any of the electrodes of -13-200807734 (10). It also includes the case where two electrodes of two high voltage electrodes (for example, 15 kV and 10 kV) and a total of three electrodes are used, and the number of electrodes used is more than three. The high aspect ratio titanium oxide ejected by the electrospinning method is ejected and deposited on the electrodes of the collecting substrate. Next, the titanium oxide ejected material was fired. For firing, a general electric furnace can be used, and a gas electric furnace in the furnace can be replaced as needed. Further, the firing temperature is preferably a condition in which crystal growth is sufficient and controllable. In order to control the crystal growth of the anatase phase and the crystal fracture of the rutile phase, it is preferably calcined at 300 to 900 t (500 to 800 ° C). The crystalline titanium oxide fiber thus obtained preferably has the following properties. The fiber diameter is 50 to 100 nm, and the fiber length/fiber diameter is 5 or more (preferably 5 to 300). When the fiber diameter is smaller than 50 nm, it is practically difficult to handle, and if it is larger than 100 nm, the surface is not sufficiently adsorbed and the power cannot be sufficiently generated, which is not preferable. The area ratio of the crystal phase diffracted by X-rays is 1.00 to 0.50 in terms of the anatase phase/(anatase phase + rutile phase) obtained. When it is less than 0.50, it is not good because of the reduced efficiency of electricity transmission. The crystallite size of the anatase phase of the X-ray diffraction is 10 to 20 Onm. When less than 1 Onm, the charge transport efficiency is lowered and it is not good. On the other hand, when the thickness exceeds 200 nm, the specific surface area of the porous semiconductor layer is lowered, and sufficient power generation cannot be obtained, which is not preferable. The BET specific surface area is 0.1 to 1 〇〇〇 m 2 /g. If it is smaller than 0.1 m2/g, the dye cannot be sufficiently adsorbed and the power cannot be sufficiently generated, which is not preferable. If it exceeds _ 14-200807734 (11) 10 00 m 2 /g, it is actually difficult to handle, which is not preferable. <Crystalline titanium oxide fine particles> On the other hand, the crystalline titanium oxide fine particles preferably have a particle diameter of 2 to 500 nm (more preferably 5 to 20 nm). When the particle diameter is less than 2 nm, the particle interface increases and the charge transport efficiency decreases, which is not preferable. If it is more than 500 nm, the amount of the adsorbed pigment is lowered, and sufficient power generation cannot be obtained, which is not preferable. Further, the crystal form of the titanium oxide fine particles may be anatase or rutile, and the titanium oxide fine particles may be a mixture of the crystal forms. <Formation of Porous Semiconductor Layer> The porous semiconductor layer preferably contains 10% by weight or more of the crystalline titanium oxide fiber and 15% by weight or more of the crystalline titanium oxide fine particles. When the crystalline titanium oxide fiber is less than 10% by weight, sufficient porosity cannot be obtained, which is not preferable. When the crystalline titanium oxide fine particles are less than 15% by weight, sufficient power generation cannot be obtained, which is not preferable. The crystalline titanium oxide fiber and the crystalline oxide * the preferable content of the titanium fine particles are 15 to 80% by weight and 20 to 85% by weight, respectively. The method of forming the porous semiconductor layer is, for example, a method of applying a coating liquid in which crystalline titanium oxide fibers and crystalline titanium oxide fine particles are dispersed, and a crystalline titanium oxide fiber in which crystalline titanium oxide fine particles are added to a non-woven state. The method of laminating it. When the porous semiconductor layer is formed by coating a coating liquid in which crystalline titanium oxide fibers -15-200807734 (12) and crystalline titanium oxide fine particles are dispersed, the solid concentration of the dispersion is 1 to 80. The weight % is preferred. If it is less than 1% by weight, the thickness of the last porous semiconductor layer becomes thin, which is not preferable. On the other hand, if it exceeds 80% by weight, the viscosity is too high to be coated, which is not preferable. More preferably, the coating liquid of 4 to 60% by weight of 〇 - dispersion can be prepared by dispersing crystalline titanium oxide fibers and crystalline oxygen-containing titanium fine particles in a dispersion medium. In the dispersion medium, it may be physically dispersed by a ball mill, a medium agitating mill, a homogenizer, or the like, or may be dispersed by ultrasonic treatment. As the dispersion medium of the dispersion, for example, water or an organic solvent can be used, and an organic solvent is preferably an alcohol. The dispersion may further contain a binder of titanium oxide fine particles. As the binder, for example, a titanium oxide precursor can be preferably used. For example, tetramethyl* titanium oxide, tetraethylene titanium oxide, tetra-n-propoxide titanium oxide, titanium tetraisopropoxide, tetra-n-butyl titanium oxide, tetra- or tertiary-sized titanium oxide, and hydrolyzate of the titanium oxide precursor can be used. These may be used singly or in combination. The coating on the transparent conductive layer coated on the transparent plastic film can be carried out by any method conventionally used in the conventional coating process. For example, a roll method, a dipping method, an air knife method, a plate coating method, a wire bar coating method, a slide hopper method, an extrusion method, and a curtain method can be used. It can also be applied by a spin coating method or a spray coating method using a general-purpose machine, or a wet printing such as a gravure, a rubber plate, or a screen printing using a three-color printing method such as a relief plate, a lithographic plate, and a gravure plate. Among these, a preferred film forming method can be used depending on the viscosity or wet thickness of the solution. The coating amount of the coating liquid is preferably from 0.5 to 20 g/m2, more preferably from 5 to 10 g/m2 per lm2 of the support when dried. • 16-200807734 (13) After the coating liquid is applied onto the transparent conductive layer, a porous semiconductor layer is formed. This heat treatment may not be carried out, and may be carried out in other processes after drying. The heat treatment is carried out under the conditions of heat treatment at 100 to 250 ° C for 1 to 120 minutes (more preferably 150 to 23 0 ° C, particularly preferably 180 to 2 2 ° C, 1 to 60 minutes) to prevent support of the transparent conductive layer. The film is added and the resistance of the porous semiconductor layer is increased. The final thickness of the porous layer is preferably from 1 to 30 μm, more preferably from 2 to ΙΟμηι, and the transparency is preferably from 2 to 6 μm. Further, the titanium oxide particles constituting the porous semiconductor layer may be treated with ultraviolet rays or the like having a strong absorption force or by irradiation with microwaves to enhance the physical bonding between the particles. For the non-crystalline titanium oxide fiber on the transparent conductive layer on the transparent plastic film, the crystalline titanium oxide fine particles are added, for example, the adhesive or the pressure-bonding or thermocompression bonding or the use can be used. These methods and the like are combined. In the case of thermocompression bonding, it is preferred to activate the crystal lattice in the non-woven state or the surface of the transparent conductive layer to improve the adhesion. The living method can be used: a method of activating a surface of a non-woven state fiber in an acidic or alkaline solution, a method of activating ultraviolet rays or electron rays, a corona treatment or a plasma treatment to carry out the method. Preferably, a method of treating the surface with an acidic or alkaline solution or performing a plasma treatment to activate the surface is used. When the binder is used, the binder to be used may be heat-treated or dried, preferably in the range of 1 to 90 minutes. The surface of the crystalline titanium oxide film is activated by deformation by heat, a semiconductor layer, in particular, a particle, a fine particle layer, a laminated state of the cloth, and a method of fibrillating titanium oxide. The method of activation may be such that a metal oxide or a precursor thereof, a conductive polymer or a conductive inorganic substance, an organic binder, preferably a metal oxide or Its precursors. In the method of adhering the adhesive, a method of applying a dispersion of a binder or a binder on a transparent conductive layer or a crystalline titanium oxide fiber in a non-woven state; and a crystalline oxygen/titanium in a non-woven state may be used. After the fiber is disposed on the transparent conductive layer, a method of adding a binder or a dispersion containing a binder is added. In the porous semiconductor layer, crystalline titanium oxide fine particles are added to the crystalline titanium oxide fibers in a non-woven state. For the addition of the crystalline titanium oxide fine particles in a non-woven state, a method of performing heat treatment by impregnating a dispersion containing crystalline titanium oxide fine particles, and using a dispersion containing crystalline titanium oxide fine particles, for example, spraying Method or bar coating method, 'Method of coating both crystalline titanium oxide fiber in a transparent conductive layer or non-woven state, or crystalline titanium oxide fiber coated on a non-woven state and a transparent conductive layer; crystallinity in a non-woven state A method of thermocompression bonding of a titanium oxide fiber and a crystalline titanium oxide fine particle; a method of bonding a crystalline titanium oxide fiber in a non-woven state and a crystalline titanium oxide fine particle to, for example, an autoclave; and a crystalline titanium oxide in a non-woven state a method of synthesizing a hot liquid to form fine particles in the presence of a fiber and a metal oxide precursor; a method of forming a fine particle by electron beam or UV treatment in the presence of a non-woven fabric of a crystalline titanium oxide fiber and a metal oxide precursor; The crystalline titanium oxide fiber in a non-woven state is made to have a crystalline titanium oxide by sputtering or the like. The method of particle bonding. These methods can also be used in combination. Among these, it is preferred to use a method in which a crystalline oxidized -18-200807734 (15) titanium fiber in a non-woven state is impregnated into a dispersion containing crystalline titanium oxide fine particles; and crystallized titanium oxide fine particles are used. The dispersion liquid is applied to both the transparent conductive layer or the non-woven state of the titanium oxide fiber or the crystalline titanium oxide fine conductive layer in a non-woven state by a coating method or a bar coating method. According to these methods, the titanium oxide fine particles can be introduced into the interior and can be easily carried out, which is preferable. In order to improve the adhesion of the crystalline titanium oxide fine particles to the crystalline titanium fibers in a non-woven state, the above-mentioned surface active treatment or an adhesive may be used. The impregnation or coating of the crystalline oxidized particles of the crystalline titanium oxide fibers in the non-woven state may be carried out before the crystallization of the non-woven state crystalline oxidized layer is carried out, and may be carried out later or may be carried out. When a dispersion liquid is used, it is preferable to add a binder to the dispersion to carry out adhesion of the transparent conductive layer and addition of fine particles. As the above binder, for example, a titanium oxide precursor can be preferably used. For example, tetrahydrate, tetraethylene titanate, tetra-n-propoxide-titanium oxide, tetra-tri-titanium, and hydrolyzate of the titanium oxide precursors may be used. These may be used in combination with a plurality of monomers. When the crystalline titanium oxide fine particles are added by using the dispersion, the amount of the crystalline titanium oxide fine particles to be dispersed is preferably 0.05 to 90 I, more preferably 1 to 70% by weight, particularly preferably 1 to 50% by weight. If the weight is less than % by weight, the thickness of the last porous semiconductor layer is reduced. Therefore, if it exceeds 90% by weight, the viscosity is too high to be applied, which is not preferable. For the dispersion medium of the dispersion, for example, water or an organic solvent can be used, and the heat is sprayed with crystals and crystals, and the titanium micro-titanium fiber is used for oxidation at the same time, and the amount of the oxygen is preferably used. Organic -19- 200807734 (16) The solvent is preferably an alcohol. When dispersed in a dispersion medium, a small amount of dispersing aid may be added as needed. As the dispersing aid, for example, a surfactant, an acid, a chelating agent or the like can be used. In order to improve the charge transport efficiency of the porous semiconductor layer, it is preferred to add the crystalline titanium oxide fine particles to the non-woven crystalline titanium oxide fibers on the transparent conductive layer on the transparent plastic film to laminate them, followed by heat treatment. This heat treatment may not be carried out in a drying process, and may be carried out in other processes after drying. Heat treatment, preferably 100~25〇t:, 1~120 minutes (more preferably 150~23 0 °C, 1~90 minutes, especially preferably 180~220 °C, 1:I~60 0 minutes) The conditions are carried out. By performing this heat treatment, the plastic support can be prevented from being deformed by heating, and the increase in the resistance of the porous semiconductor layer can be reduced. The porous semiconductor layer to which the metal oxide fine particles are added may be irradiated with ultraviolet rays having a strong metal oxide absorption force or irradiated with microwaves to heat the metal oxide to enhance the physical bonding between the metal oxides. Further, in order to prevent the purpose of electrically shorting the transparent conductive layer of the porous semiconductor and the opposite electrode, any porous semiconductor may be provided in advance, and the undercoat layer may be provided on the transparent conductive layer in advance. The undercoat layer is preferably Ti 2 , SnO 2 , ZnO or Nb 205, and TiO 2 is particularly preferred. The undercoat layer can be provided, for example, by a spray pyrolysis method as described in Electrochim, Acta 40, 643 to 652 (1995), or sputtering. The film thickness of the undercoat layer is preferably from 5 to 100 nm, more preferably from 10 to 500 nm. -20- 200807734 (17) <Transparent Plastic Film> In the present invention, a support for supporting the transparent conductive layer is a plastic film. The plastic film is preferably a polyester film, and the polyester constituting the polyester film is a line synthesized from an aromatic dibasic acid or an ester-forming derivative thereof, and an ester-forming derivative of a diol or an ester thereof. Saturated polyester. ^ Specific examples of the polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, and poly(terephthalic acid 1,4) - cyclohexane dimethyl ester), poly 2,6-methyl phthalate, polyethylene 2,6-naphthalene dicarboxylate, and the like. It may be a blend of such copolymers or other resins with minor ratios. Among these polyesters, polyethylene terephthalate and polyethylene-2,6-naphthalate are preferred because of their good balance between mechanical properties and optical properties. 'In particular, polyethylene-2,6-naphthalene dicarboxylate is better than polyethylene terephthalate in terms of high mechanical strength, low heat shrinkage, and small amount of oligomers generated during heating. Therefore, it is the best. The polyethylene terephthalate can be preferably used in an amount of 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 97 mol% or more. By. The polyethylene-2,6-naphthalenedicarboxylate may be used in an amount of preferably 90 mol% or more, more preferably 95 mol% or more, particularly preferably 97, of ethylene glycol 2,6-naphthalene dicarboxylate. More than Moer. The polyester may be a homopolymer or a copolymer having a third component copolymerized, but a homopolymer is preferred. The inherent viscosity of the polyester is preferably 0.40 dl/g or more, more preferably 0.40 to 0.90 dl/g. When the intrinsic viscosity is less than 〇4〇dl/g, the process often occurs -21,07707734 (18), which is not good, and if it exceeds 0.90 dl/g, it is difficult to melt and melt due to high melt viscosity. The polymerization time is long and uneconomical, so it is not good. Polyester can be obtained by a conventional method. For example, it can be obtained by a method of directly producing a polyester having a low degree of polymerization by reacting a dicarboxylic acid with a diol. Further, a lower alkyl ester of a dicarboxylic acid may be reacted with a diol by a transesterification reaction catalyst, and then a polymerization reaction may be carried out in the presence of a polymerization catalyst to obtain ^. As the transesterification catalyst, a conventional one may be used, for example, a compound containing sodium, potassium, magnesium, calcium, zinc, barium, titanium, chromium, manganese or cobalt. As the polymerization catalyst, a conventional compound such as antimony compound such as antimony trioxide or antimony pentoxide, antimony compound represented by ceria, tetraethyl titanate, tetrapropyl titanate or titanate can be used. a phenyl ester or a partially hydrolyzed product thereof, a titanium compound such as titanium ammonium oxalate, potassium titanium oxalate or titanium triacetylacetonate. When the poly's reaction is carried out by a transesterification reaction, in order to inactivate the transesterification catalyst, a phosphorus compound such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate or orthophosphoric acid is usually added before the polymerization reaction. However, the content of phosphorus in the polyester is preferably from 20 to 10 ppm by the viewpoint of thermal stability. Further, the polyester may be fragmented after melt polymerization, and then subjected to solid phase polymerization by heating under reduced pressure or an inert gas stream such as nitrogen. The polyester film is preferably substantially free of particles. When particles are contained, high transparency is impaired, and the surface is roughened to make processing of the transparent conductive layer difficult. The enthalpy of the film is preferably 1.5% or less, more preferably 1.0% or less, and particularly preferably 0.5% or less. The polyester film preferably has a light transmittance of 3% or less at a wavelength of 3 to 70 nm and a light transmittance of 70% or more at a wavelength of 400 nm. -22-200807734 (19) The light transmittance is measured by the number of spectrophotometers MPC3 100 manufactured by Shimadzu Corporation. The light transmittance can be obtained by using a polyester which absorbs an ultraviolet monomer such as 2,6-naphthalenedicarboxylic acid as a constituent component or a polyester containing an ultraviolet absorber. As the ultraviolet absorber, for example, 2.2'-p-benzoic acid (3,1-benzoxanoxazin-4-one), 2.2, p-benzoic acid (6-methyl-3,1-benzoxazine·4) can be used. -ketone), 2.2,-p-phenylbis(6-chloro-3,1-benzoxazin-4-one), 2·2'-(4,4'-diphenyl)bis(3,1-benzene And a cyclic imine ester compound such as oxazin-4-one) and 2.2'-(2,6-naphthalene)bis(3,1-benzoxazin-4-one). Polyester film, the average thickness of the 3-dimensional centerline is 两.〇〇〇] ~0·02μιη is better, more preferably 0 · 0 0 0 1~0.0 1 5 μιη, especially good for 〇· 〇 〇〇1~ 0 · 0 1 0 μ m. In particular, if the average thickness of the three-dimensional center line of at least one side is • 0.0001 〇 〇〇 μ 5 μιη, it is preferable that the IB of the transparent conductive layer becomes easy. The optimum surface roughness of only one side is 0.0005~0.004μιη. The thickness of the polyester film is preferably from 10 to 500 μm, more preferably from 20 to 400 μm, particularly preferably from 50 to 300 μm. 'Next' illustrates a preferred method of making a polyester film. Also, the glass transfer 'temperature is simply referred to as Tg. The polyester film can be melt-extruded into a film shape, and cooled and solidified in a molding barrel to form an unstretched film. The unstretched film is in a total ratio of Tg~(Tg+60) °C toward the long side. Stretching 1 time or more times 3 times to 6 times, and then stretching at a magnification of 3 to 5 times in the width direction at Tg~(Tg+ 60) °C, and further Tm 18 0 °C as needed ~25 5 °C Heat treatment for 1 to 60 seconds, thereby making it. In order to reduce the difference in thermal shrinkage between the long-side direction and the width direction of the polyester film, and the heat in the long-side direction, -23-200807734 (20) can be used in the Japanese Patent Publication No. 5 7-5 762 8 A method of shrinking the film in the longitudinal direction by a heat treatment process, or a method of performing a relaxation heat treatment in a suspended state by a method disclosed in Japanese Laid-Open Patent Publication No. Hei. <Transparent Conductive Layer> • The transparent conductive layer can use, for example, a conductive metal oxide (fluorine-doped tin oxide, indium-tin composite oxide (ITO), indium-zinc composite oxide (IZ 0)), and metal. Films (such as films of platinum, gold, silver, copper, aluminum, etc.), carbon materials. The transparent conductive layer may be laminated in two or more types to be composited. Among these, ITO and IZO are particularly excellent in light transmittance and low resistance. The surface resistance of the transparent conductive layer is preferably 100 Ω/□ or less, and more preferably 40 Ω/□ or less. If it exceeds 100 Ω/□, the internal resistance of the battery becomes too large, and the photovoltaic power generation efficiency is lowered, which is not preferable. The thickness of the transparent conductive layer is preferably from 100 to 500 nm. If it is less than 100 nm, the surface resistance 値 cannot be sufficiently lowered. If it exceeds 500 nm, * the light transmittance is lowered and the transparent conductive layer is easily broken, which is not preferable. The surface tension of the transparent conductive layer is preferably 40 mN/m or more, more preferably 65 mN/m or more. When the surface tension is less than 40 mN/m', the adhesion between the transparent conductive layer and the porous semiconductor is deteriorated, and if it is 65 mN/m or more, the coating of the aqueous coating liquid in which the main component of the solvent is water is easily formed. The porous semiconductor layer is more preferable. The transparent conductive layer 'having the above properties can be obtained by forming a transparent conductive layer using, for example, ITO or 1Z0, and performing the processing in any of the following methods. • 24 - 200807734 (21) (1) Method of activating the surface of a transparent conductive layer with an acidic or alkaline solution 〇 (2) A method of irradiating ultraviolet rays or electron rays on the surface of a transparent conductive layer to activate it. (3) A method of applying a corona treatment or a plasma treatment to activate the surface of a transparent conductive layer. Among them, the method of activating the surface by plasma treatment is particularly preferable because of the high surface tension. <Easy-adhesive layer> In order to improve the adhesion between the polyester film and the transparent conductive layer, an easy-adhesion layer may be provided between the polyester film and the transparent conductive layer. The thickness of the easy-adhesion layer is preferably from 10 to 200 nm, more preferably from 20 to 150 nm. If the thickness of the easily-adhesive layer is less than 1 〇 nm, the effect of improving the adhesion is poor, and if it exceeds 200 nm, the aggregation failure of the easily-adhesive layer is liable to cause the adhesion to be lowered, which is not preferable. When the easy-adhesion layer is provided, it is preferably provided by coating in the production process of the polyester film, and it is preferably applied to the polyester film before the end of the alignment crystallization. Here, the polyester film before the end of the crystal alignment includes an unstretched film, a uniaxially oriented film in which the unstretched film is oriented in either the longitudinal direction or the transverse direction, and a low-magnification ratio in both the longitudinal direction and the transverse direction. Stretcher (finally stretched in the machine direction or in the transverse direction to make the biaxially stretched film before the completion of the crystallization). Preferably, the uncoated film or the uniaxially stretched film oriented in one direction is coated with the aqueous coating liquid of the above composition, and the longitudinal stretching and/or the transverse stretching are carried out directly from -25 to 200807734 (22). Stretch and heat fixed. The easy-adhesive layer is preferably made of a material having excellent adhesion to the polyester film and the transparent film, and for example, a polyester phytic acid resin, a urethane acrylic resin, an anthraquinone acrylic acid resin, or a polyoxyl oxide can be used. Alkane resin. These resins may be used singly or in combination of two or more. <Hard coat layer> In order to improve the adhesion and durability of the polyester film and the transparent conductive layer, blue may be formed between the easy-adhesion layer and the transparent conductive layer. The thickness of the hard coat layer is preferably 0.01 to 20 μm, more preferably 1 to the case where the hard coat layer is provided, and it is preferably provided by coating on the film which is provided with an easy-adhesion layer. The hard coat layer is preferably made of a material having excellent adhesion to both of the conductive layers, and may be a resin such as a decene-based resin, a urethane resin, a fluorene-based resin, a UV-curable resin or an epoxy resin. Ingredients, or such inorganic particles. For inorganic particles, for example, alumina, cerium oxide, mica can be used. <Anti-reflection layer> In the present invention, an anti-reflection layer may be provided on the opposite side of the transparent conductive layer in order to increase the light transmittance to increase the light emission. In the method of providing the antireflection layer, it is preferable to form a single layer or a laminate of two or more layers having a refractive index different from that of the vinegar. In the case of a single-layer structure, the use of a refractive index lower than that of the base film, the two layers of the epoxy, propylene, and melamine may also be used in a particularly dense manner: a hard coat of 10 μπι 〇Ρ of the polyester thin layer Permeability: Particles of a mixture such as a C-based tree. The electrical efficiency, the method of refraction of the film is -26-200807734 (23), and when it is a multilayer structure of 2 or more layers, it is preferably a layer adjacent to the laminated film, which is selected to have a polyester film. A material having a large refractive index and a layer laminated thereon is selected to have a material having a smaller refractive index. The material constituting the antireflection layer is not limited to an organic material or an inorganic material, and as long as the relationship of the above refractive index can be satisfied, it is preferable to use a selected one selected from the group consisting of CaF2, MgF2, NaAlF4, SiO2, ThF4, Zr02, Nd203, and Sn02. a dielectric body in the group of Ti02, Ce02, ZnS, and ln203. For the method of laminating the antireflection layer, for example, a dry coating method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a wet coating method such as a gravure method, a reverse roll method, or a die method can be used. Before the anti-reflection layer is laminated, corona treatment, plasma treatment, sputtering treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, 'primer treatment, easy adhesion treatment and the like may be applied first. <Production of dye-sensitized solar cell and electrode used> When a dye-sensitized solar cell is produced using the electrode of the present invention, a known method can be used. Specifically, it can be produced, for example, by the following method. (1) A pigment is adsorbed to the porous semiconductor layer of the laminated film of the present invention. An organic metal complex dye, a cyanine dye, a coumarin dye, a xanthene dye, or a porphyrin dye represented by a ruthenium pyridine complex (anthracene complex) is absorbable. The dye having the characteristics of light in the visible light and the infrared region is dissolved in a solvent such as ethanol or toluene to form a dye solution, and the porous semiconductor layer is immersed or sprayed or applied to the porous semiconductor layer to form an electrode A. -27- 200807734 (24) (2) The opposite electrode is an electrode B which is formed by forming a thin platinum layer by sputtering on the transparent conductive side of the laminated film of the present invention. (3) Insert the electrode A and the electrode B into a frame spacer (thickness 20 μm) made of a thermocompression-bonded polyethylene film to laminate the spacer, and heat the spacer to 12 (TC, crimp the two electrodes). And, the edge portion is sealed with a ring. Oxygen resin adhesive. (4) Injecting lithium iodide and iodine (mole ratio 3: 2) through a small hole for electrolyte injection previously placed at the corner of the sheet. And 3 wt% of an aqueous electrolyte solution of nanospheres having an average particle diameter of 20 μm as a spacer. The internal degassing is sufficiently performed, and finally the pores are sealed with an epoxy resin adhesive. EXAMPLES Next, the examples will be described in more detail by way of examples. The evaluation items of the following examples and comparative examples were carried out in the following manner: (1) The particle diameter of the crystalline titanium oxide fine particles and the fiber diameter of the crystalline titanium oxide fibers were obtained by scanning electron microscopy ( ) S-2400 manufactured by Hitachi, Ltd.) Photograph of the surface of the metal oxide obtained by photographing (magnification: 200 times), randomly select 20 parts, measure the diameter of the crystalline titanium oxide fine particles and the fiber diameter of the crystalline titanium oxide fiber, and obtain the average value The average diameter and the average length (2) The fiber diameter of the crystalline titanium oxide fiber/fiber length -28-200807734 (25) (1) The same as the particle diameter of the crystalline titanium oxide fine particles and the fiber diameter of the crystalline titanium oxide fiber The average fiber length and the average fiber diameter were calculated and the ratio was calculated. (3) Method for measuring BET specific surface area: - The specific surface area of the obtained metal oxide was measured by the BET method using nitrogen gas. (4) X X-ray diffraction measurement of ray diffraction is performed by RTOTA FLEX RU200B manufactured by Rigaku Electric Co., Ltd., using a reflection method with a radius of I85 nm, and X-ray system is monochromated with Cu Κα ray. For the sample, the high-purity yttrium powder used as the internal standard X-ray diffraction standard is added to the obtained ceramic fiber. (5) Measurement of crystallite size The X-ray diffraction pattern obtained above is intensity-corrected and wound. The angle of incidence ' 2 Θ is corrected by the 1 1 1 diffraction peak of the internal standard. Here, the half-price width of the 1 1 1 diffraction peak is 0.15° or less. For the corrected X-ray diffraction pattern, 25.3° is used. a diffraction peak appearing nearby Scherrer's equation under the crystallite size was calculated .2Θ = 24~30 ° range of titanium, silicon, and the emission peak around from Cu Καί, Κα2 were not separated, and all as Cu Κα.
D = Κχλ/β cosG -29- 200807734 (26) 此處， D :結晶尺寸（n m)、 λ :測定X射線波長（n m)、 β :因微晶尺寸之繞射射線之擴展、 Θ :繞射峰之布勒格角、 Κ :形狀因子（Scherrer常數） 此處，β爲了校正光學系之擴展，係採用將25.3°附 近出現之氧化鈦之繞射峰的半價寬Β減去內部標準之矽 111繞射峰之半價寬b者（β=Β - b)，而 Κ=1、λ = 0·15418ηιη 〇 (6)由X射線繞射之積分強度所計算出之銳鈦礦相含 有比，係於進行強度校正之X射線圖中，對於2Θ= 25.3° 、27.4°附近出現之來自銳鈦礦相及金紅石相氧化鈦之各 繞射峰，估計積分強度ΙΑ (銳鈦礦相）、IR (金紅石相 )，並以下式求出含有比。 銳鈦礦相含有比=IA/(IA + IR) (7)固有黏度 固有黏度（[Mdl/g)，係以35°C之鄰氯苯酚溶液測定。 (8)薄膜厚度 使用測微計（Anritsu(股）製之K-402B型），於薄膜 之連續製膜方向及寬度方向各以1 0cm之間隔進行測定， 全部測定3 00個部位之厚度。計算所得之3 00個部位厚度 -30- 200807734 (27) 之平均値，視爲薄膜厚度。 (8) 光線透過率 使用（股）島津製作所製分光光度計MPC3 00，測定波 長370nm及400nm之光線透過率。 (9) 塗佈層之厚度 將小片薄膜包埋至環氧樹脂（Refinetec(股）製愛普茂 度）中，使用 Reichert-Jung 公司製 Microtome2050，將每 包埋樹脂切片成 50nm之厚度，以透過型電子顯微鏡 (TopconLEM-2000)以加速電壓100KV、倍率10萬倍觀查 ，測定塗膜層之厚度。 (1 0)表面電阻値 使用4探針式表面電阻測定裝置（三菱化學（股）製， LorestaGP)測定任意5點，將其平均値作爲代表値使用 (1 1) Ι-V特性（光電流一電壓特性） 形成lOOnm2大之色素增感太陽電池，以下述方法計 算光發電效率。使用Peccell technologies公司製太陽光模 擬器（PEC-L10)，將入射光強度爲lOOmW/cm2之模擬太陽 光，以氣溫2 5 °C、濕度5 0 %之環境氣氛測定。使用電流電 壓測定裝置（PECK 2400 )，將施加於系統內之DC電壓 -31 - 200807734 (28) 以lOmV/sec之定速監看，藉由計測元件輸出之光電流 測定光電流-電壓特性，計算出光發電效率。 實施例1 <聚酯薄膜之製作> 將固有黏度爲0.63之實質上不含粒子之聚2,6_萘二 羧酸乙二醇酯之顆粒，以1 7 0 °C乾燥6小時後，供給至擠 製機進料斗，以熔化溫度3 05 °C使其熔融，以平均網目大 小爲1 7 μ m之不鏽鋼細線過濾器過濾、，透過3 m m之狹縫狀 模口擠製至表面溫度爲6CTC之旋轉冷卻桶上，急速冷卻製 得未拉伸薄膜。將如此製得之未拉伸薄膜以1 2 0 °C預熱， 並於低速、高速之輥間，由1 5 mm之上方以8 5 0 °C之IR加 熱器加熱，而朝縱向拉伸3 · 1倍。於該縱向拉伸後之薄膜 的單面，將下述之塗佈劑 A以乾燥後之塗膜厚度爲 0·25μπι之方式，以輥塗佈器塗佈來形成易黏著層。 接著供給至拉幅器，以140°C朝橫向拉伸3.3倍。將 所得之雙軸配向薄膜以245 °C之溫度熱固定5秒鐘，製得 固有黏度爲〇.58dl/g、厚度125μπι之聚酯薄膜。之後，將 該薄膜以懸垂狀態，以鬆弛率〇 · 7 %、溫度2 0 5 °C使其熱鬆 驰。 <塗佈劑A之調製> 將2,6-萘二羧酸二甲酯66份、間苯二甲酸二甲酯47 份、5 -鈉硫代間苯二甲酸二甲酯8份、乙二醇5 4份、二 -32- 200807734 (29) 乙二醇62份裝塡至反應器內，並對其添加四甲氧鈦0.05 份，於氮環境氣氛下將溫度控制於23 0 °C進行加熱，將所 生成之甲醇蒸餾除去以進行酯交換反應。接著，將反應系 之溫度緩緩上升至2 5 5 °C，並使系內減壓至lmmHg以進行 縮聚合反應，製得聚酯。將該聚酯2 5份，溶解於四氫呋 喃75部，對所得之溶液，於1 0000旋轉/分鐘之高速攪拌 下滴入水75份，製得乳白色之分散體，接著，將該分散 體於20mmHg之減壓下蒸餾，將四氫呋喃蒸餾除去，製得 固形分爲25重量％之聚酯之水分散體。 接著，於四口燒瓶中，裝塡界面活性劑之月桂基磺酸 鈉3份、及離子交換水1 8 1份，於氮氣氣流中昇溫至60 °C ，接著添加聚合起始劑之過硫酸銨〇.5份、亞硝酸氫鈉 0.2份，再於邊將液溫調整爲60〜7(TC之下，以3小時滴 入單體類之甲基丙烯酸甲酯30.1份、2-異丙醯-2-噁唑啉 21.9份、甲基丙烯酸聚環氧乙烷（n= 10)酯39.4份、丙烯醯 胺8.6份之混合物。滴入結束後，亦持續保持於同溫度範 圍2小時，於攪拌下使反應繼續，接著冷卻而製得固形分 爲3 5%重量之丙烯酸酯之水分散體。 另一方面，製做添加有0.2重量％之氧化矽（平均粒 徑：100nm)(日產化學（股）製商品名 SnowtexZL)、 0.3重量％之濕潤劑之聚氧乙烯（n = 7)月桂醚（三洋化成（股 )製商品名那羅亞庫鐵N-70 )之水溶液。D = Κχλ/β cosG -29- 200807734 (26) Here, D: crystal size (nm), λ: X-ray wavelength (nm), β: diffraction of diffracted ray due to crystallite size, Θ: winding Bragg angle of the peak, Κ: shape factor (Scherrer constant) Here, in order to correct the expansion of the optical system, β is subtracted from the internal standard by the half-price width of the diffraction peak of titanium oxide appearing near 25.3°. The half-price width b of the diffraction peak of 111 (β = Β - b), and Κ = 1, λ = 0 · 15418 ηιη 〇 (6) The anatase phase ratio calculated from the integrated intensity of the X-ray diffraction In the X-ray diagram for intensity correction, the integrated intensity ΙΑ (anatase phase), IR is estimated for each diffraction peak from the anatase phase and the rutile phase titanium oxide appearing near 2Θ= 25.3° and 27.4°. (rutile phase), and the content ratio is obtained by the following formula. The anatase phase contains a ratio of IA/(IA + IR) (7) intrinsic viscosity intrinsic viscosity ([Mdl/g), determined by an o-chlorophenol solution at 35 °C. (8) Film thickness A micrometer (K-402B type manufactured by Anritsu Co., Ltd.) was used, and the film was measured at intervals of 10 cm in the continuous film forming direction and the width direction of the film, and the thickness of each of the 300 portions was measured. The calculated average thickness of 300 parts of the thickness of -30-200807734 (27) is regarded as the film thickness. (8) Light transmittance The light transmittance of the wavelengths of 370 nm and 400 nm was measured using a spectrophotometer MPC3 00 manufactured by Shimadzu Corporation. (9) Thickness of coating layer A small piece of film was embedded in an epoxy resin (Refinetec), and each of the embedded resin was sliced to a thickness of 50 nm using a Microtome 2050 manufactured by Reichert-Jung Co., Ltd. The thickness of the coating layer was measured by a transmission electron microscope (TopconLEM-2000) at an acceleration voltage of 100 KV and a magnification of 100,000 times. (1 0) Surface resistance 测定 Measure any 5 points using a 4-probe surface resistance measuring device (Mitsubishi Chemical Co., Ltd., Loresta GP), and use the average 値 as a representative ( (1 1) Ι-V characteristics (photocurrent) A voltage characteristic) A pigment-sensitized solar cell having a size of 100 nm was formed, and the photovoltaic power generation efficiency was calculated by the following method. A sunlight simulator (PEC-L10) manufactured by Peccell Technologies Inc. was used to measure the simulated sunlight having an incident light intensity of 100 mW/cm2 at an ambient temperature of 25 ° C and a humidity of 50%. Using a current-voltage measuring device (PECK 2400), the DC voltage -31 - 200807734 (28) applied to the system is monitored at a constant speed of 10 mV/sec, and the photocurrent-voltage characteristics are measured by the photocurrent output from the measuring element. Calculate the efficiency of photovoltaic power generation. Example 1 <Production of Polyester Film> A pellet of polyethylene-2,6-naphthalenedicarboxylate having an intrinsic viscosity of 0.63 and substantially free of particles was dried at 170 ° C for 6 hours. , supplied to the extruder feed hopper, melted at a melting temperature of 3 05 ° C, filtered through a stainless steel fine line filter having an average mesh size of 17 μm, and extruded through a 3 mm slit die to the surface On a rotating cooling drum having a temperature of 6 CTC, rapid cooling was performed to obtain an unstretched film. The unstretched film thus obtained is preheated at 120 ° C, and heated between the low speed and high speed rolls, above the 1 5 mm with an IR heater at 850 ° C, and stretched longitudinally. 3 · 1 time. On one side of the film after the longitudinal stretching, the coating agent A described below was applied by a roll coater so as to form an easy-adhesion layer so that the thickness of the coating film after drying was 0·25 μm. It was then supplied to a tenter and stretched 3.3 times in the transverse direction at 140 °C. The obtained biaxial alignment film was heat-set at 245 ° C for 5 seconds to obtain a polyester film having an intrinsic viscosity of 58.58 dl/g and a thickness of 125 μm. Thereafter, the film was suspended in a suspended state at a relaxation rate of 7 · 7 % and a temperature of 2 0 5 °C. <Preparation of Coating Agent A> 66 parts of dimethyl 2,6-naphthalenedicarboxylate, 47 parts of dimethyl isophthalate, and 8 parts of dimethyl 5-thiothioisophthalate, Ethylene glycol 5 4 parts, bis-32-200807734 (29) Ethylene glycol 62 parts were charged into the reactor, and 0.05 parts of tetramethoxy titanate was added thereto, and the temperature was controlled at 23 0 ° under a nitrogen atmosphere. C is heated, and the produced methanol is distilled off to carry out a transesterification reaction. Next, the temperature of the reaction system was gradually raised to 2 5 5 ° C, and the pressure was reduced to 1 mmHg in the system to carry out a polycondensation reaction to obtain a polyester. 25 parts of the polyester was dissolved in 75 parts of tetrahydrofuran, and 75 parts of water was added dropwise to the obtained solution under high-speed stirring at 100,000 rotations/min to obtain a milky white dispersion, and then the dispersion was at 20 mmHg. The mixture was distilled under reduced pressure, and tetrahydrofuran was distilled off to obtain an aqueous dispersion of a polyester having a solid content of 25% by weight. Next, in a four-necked flask, 3 parts of sodium lauryl sulfonate of a surfactant and 18 parts of ion-exchanged water were placed, and the temperature was raised to 60 ° C in a nitrogen gas stream, followed by addition of a persulfate of a polymerization initiator. 5 parts of ammonium ruthenium, 0.2 parts of sodium hydrogen nitrite, and then adjust the liquid temperature to 60~7 (under TC, 30.1 parts of methyl methacrylate, 2-isopropyl isopropyl monomer was added dropwise for 3 hours 21.9 parts of oxa-2-oxazoline, 39.4 parts of methacrylic acid polyethylene oxide (n=10) ester, and 8.6 parts of acrylamide. After the end of the dropwise addition, it was kept at the same temperature range for 2 hours. The reaction was continued with stirring, followed by cooling to obtain an aqueous dispersion of acrylate having a solid content of 35% by weight. On the other hand, 0.2% by weight of cerium oxide (average particle diameter: 100 nm) was added (Nissan) An aqueous solution of a polyoxyethylene (n = 7) lauryl ether (trade name: Naroya Co., Ltd. N-70, manufactured by Sanyo Chemicals Co., Ltd.) of a oxidizing agent of 0.3% by weight.
將上述聚酯之水分散體8重量份、丙烯酸酯之水分散 體7重量份、與水溶液8 5重量份混合，製作成塗佈劑A -33- 200807734 (30) <硬塗層> 使用所製得之聚酯薄膜，於其易黏著層側，將UV硬 化性硬塗劑（JSR(股）製DeSoliteR750 1 )以後度約爲5μπι 之方式塗佈，並使其UV硬化形成硬塗層。 <透明導電層之形成> 於形成硬塗層之單面，使用主要由氧化銦所構成之添 加有10重量％之氧化鋅之ΙΖΟ靶，以直流磁控濺鍍法， 形成膜厚260nm之ΙΖΟ所構成之透明導電層。藉濺鍍法 之透明導電層之形成，係於電漿之放電前使管內排氣至5x l〇-4Pa後，將氬與氧導入管內並使壓力爲 0.3Pa，以 2W/cm2之電力密度施加電力於IZO靶來進行。氧分壓爲 3.7mPa。透明導電層之表面電阻値爲15Ω/Ε]。 接著，使用常壓電漿表面處理裝置（積水化學工業（ 股）製 AP-T03-L)，於氮氣氣流（60L/分鐘）下，以lm/ 分鐘對透明導電層表面施以電漿處理。此時，表面電阻値 爲16Ω/□、表面張力爲71.5mN/m。 <抗反射層> 分別以高頻濺鍍法，於層合薄膜之形成透明導電層之 面的相反面，製膜厚度75 nm之折射率1.89之Y2〇3層、 於其上製膜厚度120nm之折射率2.3之Ti02層、再於其 -34- 200807734 (31) 上製膜厚度90nm之折射率1.46之Si02層，製作成抗反 射處理層。於製膜各靜電體薄膜之際，皆使真空度爲1 χ 10_3Torr’ 並流通 Ar: 55sccm、〇2: 5sccm 之氣體。又， 基板，於製膜製程中’不加熱亦不冷卻而維持於室溫。 . <以電氣紡絲法之結晶性氧化鈦纖維之製作> 對聚丙烯腈（和光純藥工業（股）製）1重量份、N，N_ 二甲基甲醯胺（和光純藥工業（股）製，特級）9重量份所 構成之溶液，混合四正丁氧化鈦（和光純藥工業（股）製， 一級）1重量份與乙醯丙酮（和光純藥工業（股）製，特級 )1重量份所構成之溶液，調製成紡絲溶液。由該紡絲溶 液使用圖1所示之裝置，製作纖維構造體。噴出噴嘴1之 ' 內徑爲〇.8mm，電壓爲15kV，噴出噴嘴1距電極4之距 離爲1 5 cm。亦即，將保持於溶液保持槽3之溶液2由噴 出噴嘴1朝電極4噴出。其間，電極4與噴出噴嘴1之間 係負載由高電壓產生裝置之15kV之電壓。將所得之纖維 構造體，於空氣環境氣氛下使用電爐以1〇小時昇溫至600 ’ °C，之後，保持於600°C 2小時，藉此製得氧化鈦纖維。 以電子顯微鏡觀察所製得之高縱橫比氧化鈦之結果，纖維 徑爲2 80nm、纖維長/纖維徑爲50以上，於掃描型電子顯 微鏡之視野內未觀察到纖維之兩端。又’對銳鈦礦相與金 紅石相之銳鈦礦相之X設線繞射之面積比爲0 ·94。又’銳 鈦礦微晶尺寸爲22nm。所得之氧化鈦纖維之X射線繞射 結果，於2 Θ = 2 5 . 3 °確認到尖銳之波峰，故確認已形成銳 -35- 200807734 (32) 鈦礦相。BET比表面積爲〇.4m2/g。 <黏結劑> 將四異丁氧化鈦60重量份滴入0.1M硝酸120重量份 後，加熱迴流1 2小時以進行濃縮，製得黏結劑。乾燥後 . 之固形物重量爲1 7重量％。 <多孔質半導體層形成> 將上述之結晶性氧化鈦纖維以於全氧化鈦重量中爲44 重量％、結晶性氧化鈦微粒子之昭和鈦製氧化鈦分散液 SP-200 (氧化鈦含量：25重量％銳鈦礦相及些許金紅石相 )以於全氧化鈦重量中爲44重量％、及上述之黏結劑以於 ， 全氧化鈦重量中爲1 2重量％份之方式，分散於乙醇（和光 純藥（股）製）中，製作成固形物濃度爲12重量％之分散液 ，於40.0Hz之超音波照射下處理30分鐘。結果製得多孔 質半導體層用塗佈液。將該塗佈液立即以棒塗機塗佈於透 ' 明導電層上，於大氣中以180°C進行熱處理5分鐘，以厚 * 度爲5 μπι之方式形成多孔質半導體層。熱處理後之多孔質 半導體層，未觀察到剝離或脆化，而製作成與基材之密合 性良好之色素增感太陽電池之電極。 對如此製得之多孔質半導體層進行X射線繞射的結果 ，觀察到銳鈦礦相與微弱之金紅石相之波峰，由X射線繞 射之積分強度比所計算之銳鈦礦相含有比爲0.92，銳鈦礦 相之微晶尺寸爲24nm。 -36- 200807734 (33) <色素增感太陽電池之製作> 將該電極貝於釘錯合物（Ru535bisTBA、Solaronix 公司製）之3 00 μΜ乙醇溶液中24小時，於光作用電極表 面吸附釕錯合物。又，於上述之層合薄膜之透明導電層上 ，以濺鍍法堆積Pt膜製作成對向電極。將電極與對向電 極，透過熱壓接性之聚乙嫌薄膜製框型間隔物（厚度 2 0μπι )疊合，將間隔物部加熱至1 20°C，以將兩電極熱壓 接。並且，將其邊緣部以環氧樹脂黏著劑密封。注入電解 質溶液（含0.5M之碘化鋰、0.05M之碘與〇.51^之三級丁 基吡啶之3 -甲氧基丙腈溶液）後，以環氧系黏著劑密封。 對所完成之色素增感太陽電池進行I- V特性之測定結 果’斷路電壓、短路電流密度、塡充因子，分別爲0.70V 、8.25mA/cm2、0.47，其結果，光發電效率爲2 71%。 實施例2 除多孔質半導體形成時所使用之結晶性氧化鈦微粒子 爲雲母（股）製光觸媒用氧化鈦AMT-100 (平均粒徑：6nm 銳鈦礦相）以外，係使用同樣的方法。各氧化鈦之特性示 於表1。如此所製得之多孔質半導體層之特性及電池評價 結果係如表2所示。 實施例3 除於製作結晶性氧化欽纖維時之四正丁氧化鈦（和光 -37- 200807734 (34) 純藥工業（股）製，一級）爲0.5重量份以外，與實施例1 使用相同方法。各氧化鈦之特性係示於表1。如此所製得 之多孔質半導體層之特性及電池評價結果係如表2所示。 實施例4 除結晶性氧化鈦纖維之製作及多孔性半導體層形成以 外，與實施例1使用相同方法。 <以電氣紡絲法之結晶性氧化鈦纖維之製作> 於四正丁氧化鈦（和光純藥工業（股）製，一級）1重 量份，添加乙酸（和光純藥工業（股）製，特級）1 · 3重量 份，製得均勻溶液。於該溶液邊攪拌邊添加離子交換水1 重量份，於溶液中生成凝膠。所生成之凝膠，藉由持續攪 拌可解離，而調製成透明之溶液。 對所調製之溶液，混合聚乙二醇（和光純藥工業（股） 製，一級，平均分子量 3 00000〜500000 ) 0.0 1 6重量份， 調製成紡絲溶液。由該紡絲溶液使用圖1所示之裝置進行 紡絲之結果，於電極4上得到平面狀之纖維構造體。噴出 噴嘴1之內徑爲0.4mm，電壓爲15kV，噴出噴嘴1距電 極4之距離爲1 0cm。將所得之纖維構造體，於空氣環境 氣氛下使用電爐以10小時昇溫至60(TC，之後，保持於 6 00 °C 2小時，藉此製作不織布狀態之結晶性氧化鈦纖維之 堆積物。如此製得之結晶性氧化鈦纖維之特性係如表1所 示0 -38- 200807734 (35) <多孔質半導體層形成> 將上述不織布狀態之結晶性氧化鈦纖維（8 . 1 g/m2 )、 結晶性氧化鈦微粒子之昭和鈦製氧化鈦分散液SP-2 00 (氧 化鈦含量：2 5 · 1重量％銳鈦礦相及些許金紅石相）以於全 氧化鈦重量中爲4 3 · 5重量％，及上述之黏結劑以於全氧化 鈦重量中爲1 3重量％份之方式，塗佈於透明電極層上，於 大氣中180 °C進行5分鐘之熱處理以厚度成爲5 μΐΏ之方式 形成多孔質半導體層。熱處理後之多孔質半導體層，未觀 察到剝離或脆化，而製作成與基材之密合性良好之色素增 感太陽電池之電極。如此製得之多孔質半導體層之特性係 如表2所示。 使用如此之製得之多孔質半導體與實施例1以相同方 法製作成色素增感太陽電池。電池性能評價結果係如表2 所示。 實施例5 除結晶性氧化鈦纖維之製作與實施例4相同以外，與 實施例1使用相同方法製作多孔質半導體層。各結晶性氧 化鈦之特性係如表1所示，多孔質半導體層之特性係如表 2所示。使用如此之製得之多孔質半導體與實施例1以相 同方法製作成色素增感太陽電池。電池性能評價結果係如 表2所示。 -39- 200807734 (36) 比較例1 除於多孔質半導體層形成時未添加結晶性氧化鈦微粒 子以外，與實施例1使用相同方法製得多孔質半導體層， 並評價使用其之色素增感太陽電池。由於未添加微粒子， 故短路電流降低、光電變換效率降低。 比較例2 除於多孔質半導體層形成時未添加結晶性氧化鈦微粒 子以外，與實施例5使用相同方法製得多孔質半導體層， 並評價使用其之色素增感太陽電池。結果示於表2。 比較例3 除於多孔質半導體層形成時未添加結晶性氧化鈦纖維 以外，與實施例1使用相同方法製得多孔質半導體層，但 卻確認到一部分已剝離。評價使用其之色素增感太陽電池 。結果示於表2。 -40- 200807734 (37) 屮 Μ m Μ \1 添加率 (wt°/〇) 1 1 m κ m 粒徑 (nm) 〇 5 1 結晶性氧化鈦纖維 添加率 ! (%) 5 1 BET比表面積 (m2/g) 49.0 49.0 65.2 m Ο 〇 49.0 1 銳欽礦結晶尺寸 (nm) 3 S τ—^ 160 8 r—Η 1 結晶相面積比 0.94 0.94 0.98 1.00 1.00 0.94 I ! 1.00 1 纖維長/纖維徑 50< 50< 50< 50< 50< 50< 50< 1 纖維徑 (nm) | 280 280 Τ-Ή 284 284 280 284 1 實施例1 實施例2 實施例3 實施例4 實施例5 比較例1 比較例2 比較例3 -41 - 200807734 (38) <N揪 電池評價 2.71 2.09 2.77 C\ 2.54 0.78 0.10 1.59 & 0.47 0.44 0.45 0.46 0.49 1 0.40 0.60 0.46 〇 i -^ 旦 8.25 7.00 8.80 6.18 7.29 2.95 0.21 3.41 Voc (V) 0.70 0.68 0.70 0.71 0.71 0.69 -1 0.66 1 0.71 多孔質半導體 銳鈦礦結晶尺寸 (nm) ON ON m Os 150 銳欽礦相含有比 0.92 0.95 0.96 0.94 \ 0.95 丨 1 0.93 1.00 0.92 結晶波峰 i銳鈦礦•金紅石 銳鈦礦•金紅石 銳鈦礦•金紅石 銳鈦礦•金紅石 _1 1 銳鈦礦•金紅石 銳鈦礦•金紅石 銳鈦礦 銳鈦礦•金紅石 實施例1 實施例2 實施例3 1 實施例4 ! 實施例5 比較例1 比較例2 比較例38 parts by weight of the above aqueous polyester dispersion, 7 parts by weight of an aqueous acrylate dispersion, and 85 parts by weight of an aqueous solution were mixed to prepare a coating agent A-33-200807734 (30) <hard coat layer> Using the obtained polyester film, a UV curable hard coating agent (Desolite R750 1 manufactured by JSR Co., Ltd.) was applied on the side of the easy-adhesion layer, and the film was applied in a manner of about 5 μm later, and UV-hardened to form a hard coat. Floor. <Formation of Transparent Conductive Layer> On the single side of the hard coat layer, a ruthenium target mainly composed of indium oxide and added with 10% by weight of zinc oxide was used, and a DC magnetron sputtering method was used to form a film thickness of 260 nm. The transparent conductive layer formed by the crucible. The formation of the transparent conductive layer by the sputtering method is performed after the discharge of the plasma to 5×1〇-4Pa before the discharge of the plasma, and the argon and oxygen are introduced into the tube and the pressure is 0.3 Pa, which is 2 W/cm 2 . Power density is applied to the IZO target. The partial pressure of oxygen was 3.7 mPa. The surface resistance 値 of the transparent conductive layer is 15 Ω/Ε]. Next, using a normal piezoelectric slurry surface treatment apparatus (AP-T03-L manufactured by Sekisui Chemical Co., Ltd.), the surface of the transparent conductive layer was subjected to plasma treatment at lm/min under a nitrogen gas flow (60 L/min). At this time, the surface resistance 値 was 16 Ω/□, and the surface tension was 71.5 mN/m. <Anti-reflection layer> The Y2〇3 layer having a refractive index of 1.89 at a thickness of 75 nm was formed by a high-frequency sputtering method on the opposite side of the surface of the laminated film on which the transparent conductive layer was formed, and the film thickness was formed thereon. A TiO2 layer having a refractive index of 2.3 at 120 nm and a SiO 2 layer having a refractive index of 1.46 at a thickness of 90 nm on -34-200807734 (31) were formed into an antireflection treatment layer. At the time of film formation of each of the electrostatic thin films, a vacuum of 1 χ 10_3 Torr' was passed, and a gas of Ar: 55 sccm and 〇 2: 5 sccm was passed. Further, the substrate was maintained at room temperature without heating or cooling during the film forming process. <Production of crystalline titanium oxide fiber by electrospinning method> 1 part by weight of polyacrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), N,N-dimethylformamide (Wako Pure Chemical Industries, Ltd.) (prepared), a special solution of 9 parts by weight of a solution, mixed with tetra-n-butyl titanium oxide (manufactured by Wako Pure Chemical Industries, Ltd., first grade), 1 part by weight, and acetamidine (manufactured by Wako Pure Chemical Industries, Ltd.) A special solution of 1 part by weight of the solution was prepared into a spinning solution. A fiber structure was produced from the spinning solution using the apparatus shown in Fig. 1. The ejection nozzle 1 has an inner diameter of 〇.8 mm, a voltage of 15 kV, and a distance of the ejection nozzle 1 from the electrode 4 of 15 cm. That is, the solution 2 held in the solution holding tank 3 is ejected from the ejection nozzle 1 toward the electrode 4. In the meantime, a voltage of 15 kV from the high voltage generating means was applied between the electrode 4 and the discharge nozzle 1. The obtained fibrous structure was heated to 600 ° C in an air atmosphere using an electric furnace for 1 hour, and then held at 600 ° C for 2 hours to thereby obtain a titanium oxide fiber. As a result of observing the high aspect ratio titanium oxide obtained by an electron microscope, the fiber diameter was 280 nm, and the fiber length/fiber diameter was 50 or more. No fiber ends were observed in the field of view of the scanning electron microscope. Further, the area ratio of the X-ray diffraction of the anatase phase of the anatase phase to the rutile phase is 0·94. Further, the anatase crystallite size is 22 nm. As a result of the X-ray diffraction of the obtained titanium oxide fiber, a sharp peak was confirmed at 2 Θ = 2 5 . 3 °, and it was confirmed that a sharp -35-200807734 (32) titanium ore phase was formed. The BET specific surface area was 〇.4 m 2 /g. <Binder> 60 parts by weight of tetraisobutyltitanate was dropped into 120 parts by weight of 0.1 M nitric acid, and then heated under reflux for 12 hours to carry out concentration to obtain a binder. After drying, the solids weight was 17% by weight. <Formation of Porous Semiconductor Layer> The above-mentioned crystalline titanium oxide fiber is 44% by weight based on the weight of the total titanium oxide, and the titanium oxide dispersion liquid of the crystal titanium oxide fine particles is SP-200 (titanium oxide content: 25 wt% anatase phase and a little rutile phase) dispersed in ethanol in an amount of 44% by weight based on the weight of the total titanium oxide, and the above-mentioned binder is 12% by weight based on the weight of the total titanium oxide (Wako Pure Chemicals Co., Ltd.) A dispersion having a solid concentration of 12% by weight was prepared and treated under ultrasonic irradiation at 40.0 Hz for 30 minutes. As a result, a coating liquid for a porous semiconductor layer was obtained. This coating liquid was immediately applied onto a transparent conductive layer by a bar coater, heat-treated at 180 ° C for 5 minutes in the air, and a porous semiconductor layer was formed to have a thickness of 5 μm. The porous semiconductor layer after the heat treatment was not subjected to peeling or embrittlement, and was prepared as an electrode of a dye-sensitized solar cell having good adhesion to the substrate. As a result of X-ray diffraction of the thus obtained porous semiconductor layer, the peak of the anatase phase and the weak rutile phase was observed, and the integrated intensity ratio of the X-ray diffraction was compared with the calculated anatase phase ratio. It is 0.92 and the anatase phase has a crystallite size of 24 nm. -36- 200807734 (33) <Production of dye-sensitized solar cell> The electrode was adsorbed on a surface of a photoelectrode electrode in a 300 Μ ethanol solution of a nail-filled compound (Ru535bisTBA, manufactured by Solaronix Co., Ltd.) for 24 hours.钌 合物 complex. Further, on the transparent conductive layer of the above laminated film, a Pt film was deposited by sputtering to form a counter electrode. The electrode and the counter electrode were laminated by a thermocompression-bonded frame-type spacer (thickness 20 μm), and the spacer was heated to 1200 ° C to thermally press the electrodes. Further, the edge portion thereof is sealed with an epoxy resin adhesive. An electrolyte solution (containing 0.5 M lithium iodide, 0.05 M iodine and 51.51^ of a tertiary pyridine pyridyl 3-methoxypropionitrile solution) was injected, and then sealed with an epoxy adhesive. The measurement results of the I-V characteristics of the completed dye-sensitized solar cell were as follows: the open circuit voltage, the short-circuit current density, and the charge factor were 0.70 V, 8.25 mA/cm 2 , and 0.47, respectively, and as a result, the photovoltaic power generation efficiency was 2 71. %. Example 2 The same method was used except that the crystalline titanium oxide fine particles used in the formation of the porous semiconductor were titanium oxide AMT-100 (average particle diameter: 6 nm anatase phase) for photocatalyst made of mica (strand). The characteristics of each titanium oxide are shown in Table 1. The characteristics of the porous semiconductor layer thus obtained and the battery evaluation results are shown in Table 2. Example 3 The same method as in Example 1 except that the tetra-n-butyl titanium oxide (Wako-37-200807734 (34) manufactured by Kosei Kogyo Co., Ltd., first grade) was 0.5 parts by weight in the production of crystalline oxidized chin fibers. . The characteristics of each titanium oxide are shown in Table 1. The characteristics of the porous semiconductor layer thus obtained and the battery evaluation results are shown in Table 2. Example 4 The same procedure as in Example 1 was carried out except that the production of the crystalline titanium oxide fibers and the formation of the porous semiconductor layer were carried out. <Production of crystalline titanium oxide fiber by electrospinning method> Acetic acid (Wako Pure Chemical Industries, Ltd.) was added to 1 part by weight of tetra-n-butyl titanium oxide (manufactured by Wako Pure Chemical Industries, Ltd.) , special grade) 1 · 3 parts by weight, to obtain a uniform solution. To the solution, 1 part by weight of ion-exchanged water was added while stirring, and a gel was formed in the solution. The resulting gel was dissociated by continuous stirring to prepare a clear solution. To the prepared solution, polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., first grade, average molecular weight: 300,000 to 500,000) of 0.016 parts by weight was prepared and prepared into a spinning solution. As a result of the spinning of the spinning solution using the apparatus shown in Fig. 1, a planar fiber structure was obtained on the electrode 4. The discharge nozzle 1 has an inner diameter of 0.4 mm, a voltage of 15 kV, and a distance of the discharge nozzle 1 from the electrode 4 of 10 cm. The obtained fiber structure was heated to 60 (TC after 10 hours in an air atmosphere using an electric furnace, and then held at 600 ° C for 2 hours to prepare a deposit of crystalline titanium oxide fibers in a non-woven state. The characteristics of the obtained crystalline titanium oxide fiber are as shown in Table 1 0 - 38 - 200807734 (35) <Porous semiconductor layer formation > The above-mentioned non-woven state crystalline titanium oxide fiber (8.1 g/m2) ), crystalline titanium oxide fine particles of Showa titanium titanium oxide dispersion SP-2 00 (titanium oxide content: 2 5 · 1% by weight anatase phase and a little rutile phase) is 4 3 in total titanium oxide weight 5% by weight, and the above-mentioned binder is applied to the transparent electrode layer in a weight of 13% by weight of the total titanium oxide, and heat-treated at 180 ° C for 5 minutes in the atmosphere to have a thickness of 5 μΐΏ. In the porous semiconductor layer after heat treatment, no peeling or embrittlement was observed, and an electrode of a dye-sensitized solar cell having good adhesion to a substrate was prepared. The porous material thus obtained was obtained. Characteristics of the semiconductor layer As shown in Table 2, a dye-sensitized solar cell was produced in the same manner as in Example 1 using the thus obtained porous semiconductor. The battery performance evaluation results are shown in Table 2. Example 5 In addition to crystalline titanium oxide fiber The production was carried out in the same manner as in Example 1 except that the porous semiconductor layer was produced in the same manner as in Example 1. The characteristics of each of the crystalline titanium oxides are shown in Table 1, and the characteristics of the porous semiconductor layer are shown in Table 2. The porous semiconductor thus obtained was produced into a dye-sensitized solar cell in the same manner as in Example 1. The battery performance evaluation results are shown in Table 2. -39- 200807734 (36) Comparative Example 1 Except for the porous semiconductor layer A porous semiconductor layer was produced in the same manner as in Example 1 except that the crystalline titanium oxide fine particles were not added, and the dye-sensitized solar cell using the same was evaluated. Since no fine particles were added, the short-circuit current was lowered and the photoelectric conversion efficiency was lowered. Comparative Example 2 A porous method was used in the same manner as in Example 5 except that the crystalline titanium oxide fine particles were not added at the time of formation of the porous semiconductor layer. The semiconductor layer was evaluated for the dye-sensitized solar cell, and the results are shown in Table 2. Comparative Example 3 The same procedure as in Example 1 was carried out except that the crystalline titanium oxide fiber was not added at the time of formation of the porous semiconductor layer. The porous semiconductor layer was confirmed to have been partially peeled off. The dye-sensitized solar cell using the same was evaluated. The results are shown in Table 2. -40- 200807734 (37) 屮Μ m Μ \1 Addition rate (wt°/〇) 1 1 m κ m Particle size (nm) 〇5 1 Crystalline titanium oxide fiber addition rate! (%) 5 1 BET specific surface area (m2/g) 49.0 49.0 65.2 m Ο 〇49.0 1 Crystalline size (nm) 3 S τ—^ 160 8 r—Η 1 Crystal phase area ratio 0.94 0.94 0.98 1.00 1.00 0.94 I ! 1.00 1 Fiber length / fiber diameter 50 < 50 < 50 < 50 < 50 < 50 < 50 < 1 Fiber diameter (nm) 280 280 Τ-Ή 284 284 280 284 1 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 -41 - 200807734 (38) <N揪 Battery Evaluation 2.71 2.09 2.77 C\ 2.54 0.78 0.10 1.59 & 0.47 0.44 0.45 0.46 0.49 1 0.40 0 .60 0.46 〇i -^ den 8.25 7.00 8.80 6.18 7.29 2.95 0.21 3.41 Voc (V) 0.70 0.68 0.70 0.71 0.71 0.69 -1 0.66 1 0.71 Porous semiconductor anatase crystal size (nm) ON ON m Os 150 Ruiqin Phase content ratio 0.92 0.95 0.96 0.94 \ 0.95 丨1 0.93 1.00 0.92 Crystalline wave i anatase • rutile anatase • rutile anatase • rutile anatase • rutile _1 1 anatase • rutile Anatase • Rutile anatase anatase • Rutile Example 1 Example 2 Example 3 1 Example 4 ! Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3
榭锬：JJH -42- 200807734 (39) 【圖式簡單說明】 圖1係實施例所使用之使用電氣紡絲法之噴出裝置之 槪略說明圖。 【主要元件之符號說明】 1 z溶液噴出噴嘴 2 :溶液 3 :溶液保持槽 4 :電極 5 :高電壓產生器 -43-榭锬: JJH - 42 - 200807734 (39) [Simple description of the drawings] Fig. 1 is a schematic explanatory view of an ejection device using an electric spinning method used in the embodiment. [Symbol description of main components] 1 z solution ejection nozzle 2 : solution 3 : solution holding tank 4 : electrode 5 : high voltage generator -43-