JP4776871B2 - Semiconductor fine particle film, photoelectric conversion element and photovoltaic cell - Google Patents

Description

【００５３】
(b)メチン色素
好ましいメチン色素は、シアニン色素、メロシアニン色素、スクワリリウム色素等のポリメチン色素である。好ましいポリメチン色素の例としては、特開平11-35836号、同11-158395号、同11-163378号、同11-214730号、同11-214731号、欧州特許892411号及び同911841号に記載の色素が挙げられる。これらのポリメチン色素の合成法については、エフ・エム・ハーマー（F. M. Hamer）著「ヘテロサイクリック・コンパウンズ−シアニンダイズ・アンド・リレィティド・コンパウンズ（Heterocyclic Compounds - Cyanine Dyes and Related Compounds）」、ジョン・ウィリー・アンド・サンズ（John Wiley & Sons）社、ニューヨーク、ロンドン（1964年刊）、デー・エム・スターマー（D. M. Sturmer）著「ヘテロサイクリック・コンパウンズ−スペシャル・トピックス・イン・ヘテロサイクリック・ケミストリー（Heterocyclic Compounds - Specialtopics in Heterocyclic Chemistry）」、第18章、第14節、第482から515頁、ジョン・ウィリー・アンド・サンズ（John Wiley & Sons）社、ニューヨーク、ロンドン（1977年刊）、「ロッズ・ケミストリー・オブ・カーボン・コンパウンズ（Rodd's Chemistry of Carbon Compounds）」、2nd. Ed.、vol. IV、part B、第15章、第369から422頁、エルセビア・サイエンス・パブリック・カンパニー・インク（Elsevier Science Publishing Company Inc.）社、ニューヨーク（1977年刊）、英国特許第1,077,611号、Ukrainskii Khimicheskii Zhurnal, 第40巻, 第３号, 253〜258頁、Dyes and Pigments, 第21巻, 227〜234頁、これらの引用文献等に記載されている。
【００５４】
(3)半導体微粒子膜への色素の吸着
半導体微粒子膜に色素を吸着させる際には、色素の溶液中によく乾燥した半導体微粒子膜を有する導電性支持体を浸漬する方法、又は色素の溶液を半導体微粒子膜に塗布する方法を用いることができる。前者の方法の場合、浸漬法、ディップ法、ローラ法、エアーナイフ法等が利用可能である。浸漬法を用いる場合、色素の吸着は室温で行ってもよいし、特開平7-249790号に記載されているように加熱還流して行ってもよい。後者の方法の場合、ワイヤーバー法、スライドホッパー法、エクストルージョン法、カーテン法、スピン法、スプレー法等が利用できる。また、インクジェット法等によって色素を画像状に塗布し、この画像そのものを光電変換素子とすることもできる。
【００５５】
色素の溶液（吸着液）に用いる溶媒は、好ましくはアルコール類（メタノール、エタノール、t-ブタノール、ベンジルアルコール等）、ニトリル類（アセトニトリル、プロピオニトリル、3-メトキシプロピオニトリル等）、ニトロメタン、ハロゲン化炭化水素（ジクロロメタン、ジクロロエタン、クロロホルム、クロロベンゼン等）、エーテル類（ジエチルエーテル、テトラヒドロフラン等）、ジメチルスルホキシド、アミド類（N,N-ジメチルホルムアミド、N,N-ジメチルアセタミド等）、N-メチルピロリドン、1,3-ジメチルイミダゾリジノン、3-メチルオキサゾリジノン、エステル類（酢酸エチル、酢酸ブチル等）、炭酸エステル類（炭酸ジエチル、炭酸エチレン、炭酸プロピレン等）、ケトン類（アセトン、2-ブタノン、シクロヘキサノン等）、炭化水素（へキサン、石油エーテル、ベンゼン、トルエン等）又はこれらの混合溶媒である。
【００５６】
色素の吸着量は、半導体微粒子膜の単位面積（１m²）当たり0.01〜100 mmolとするのが好ましい。また色素の半導体微粒子に対する吸着量は、半導体微粒子１g当たり0.01〜１mmolであるのが好ましい。このような色素の吸着量とすることにより半導体微粒子の増感効果が十分に得られる。色素の吸着量が少なすぎると増感効果が不十分となり、色素の吸着量が多すぎると半導体に付着していない色素が浮遊し、増感効果が低減する。色素の吸着量を増やすためには、吸着前に半導体微粒子を加熱処理するのが好ましい。半導体微粒子表面に水が吸着するのを避けるために、加熱処理後には常温に戻さずに半導体微粒子膜の温度が60〜150℃の間で素早く色素の吸着を行うのが好ましい。
【００５７】
色素間の凝集等の相互作用を低減するために、界面活性剤としての性質を持つ無色の化合物を色素吸着液に添加し、半導体微粒子に共吸着させてよい。このような無色の化合物の例としては、カルボキシル基やスルホ基を有するステロイド化合物（コール酸、デオキシコール酸、ケノデオキシコール酸、タウロデオキシコール酸等）や、下記のようなスルホン酸塩類等が挙げられる。
【００５８】
【化２】

【００５９】
未吸着の色素は、吸着工程後、速やかに洗浄により除去するのが好ましい。洗浄は湿式洗浄槽中でアセトニトリル、アルコール系溶剤のような有機溶媒等を用いて行うのが好ましい。
【００６０】
色素を吸着した後、アミン類、４級アンモニウム塩、少なくとも１つのウレイド基を有するウレイド化合物、少なくとも１つのシリル基を有するシリル化合物、アルカリ金属塩、アルカリ土類金属塩等を用いて半導体微粒子の表面を処理してもよい。好ましいアミン類の例としてはピリジン、4-t-ブチルピリジン、ポリビニルピリジン等が挙げられる。好ましい４級アンモニウム塩の例としてはテトラブチルアンモニウムヨージド、テトラヘキシルアンモニウムヨージド等が挙げられる。これらは有機溶媒に溶解して用いてもよく、液体の場合はそのまま用いてもよい。
【００６１】
(C)電荷輸送層
電荷輸送層は、色素の酸化体に電子を補充する機能を有する電荷輸送材料を含有する。本発明で用いる電荷輸送材料は、(i)イオンが関わる電荷輸送材料であっても、(ii)固体中のキャリアー移動が関わる電荷輸送材料であってもよい。(i)イオンが関わる電荷輸送材料としては、酸化還元対イオンを含有する溶融塩電解質組成物、酸化還元対のイオンが溶解した溶液（電解液、電解質溶液）、酸化還元対の溶液をポリマーマトリクスのゲルに含浸したいわゆるゲル電解質組成物、固体電解質組成物等が挙げられ、(ii)固体中のキャリアー移動が関わる電荷輸送材料としては、電子輸送材料や正孔（ホール）輸送材料等が挙げられる。これらの電荷輸送材料は複数併用してもよい。本発明では、電荷輸送層に溶融塩電解質組成物又はゲル電解質組成物を用いるのが好ましい。
【００６２】
(1)溶融塩電解質組成物
溶融塩電解質組成物は溶融塩を含む。溶融塩電解質組成物は常温で液体であるのが好ましい。主成分である溶融塩は室温において液状であるか、又は低融点の電解質であり、その一般的な例としてはWO95/18456号、特開平8-259543号、電気化学, 第65巻, 11号, 923頁 (1997年)等に記載のピリジニウム塩、イミダゾリウム塩、トリアゾリウム塩等が挙げられる。溶融塩の融点は50℃以下であるのが好ましく、25℃以下であるのが特に好ましい。溶融塩の具体例は特開2001-320068号の段落番号0066〜0082に詳しく記載されている。
【００６３】
溶融塩は単独で使用しても２種以上混合して使用してもよい。また、LiI、NaI、KI、LiBF₄、CF₃COOLi、CF₃COONa、LiSCN、NaSCN等のアルカリ金属塩を併用することもできる。アルカリ金属塩の添加量は、組成物全体に対して２質量％以下であるのが好ましく、１質量％以下がさらに好ましい。また、溶融塩電解質組成物に含まれるアニオンの50モル％以上がヨウ化物イオンであることが好ましい。
【００６４】
通常、溶融塩電解質組成物はヨウ素を含有する。ヨウ素の含有量は、溶融塩電解質組成物全体に対して0.1〜20質量％であるのが好ましく、0.5〜５質量％であるのがより好ましい。
【００６５】
溶融塩電解質組成物の揮発性は低いことが好ましく、溶媒を含まないことが好ましい。溶媒を添加する場合でも、溶媒の添加量は溶融塩電解質組成物全体に対して30質量％以下に留めることが好ましい。溶融塩電解質組成物は後述のようにゲル化して使用してもよい。
【００６６】
(2)電解液
電解液は電解質、溶媒及び添加物から構成されることが好ましい。電解液に用いる電解質の例としては、I₂とヨウ化物（LiI、NaI、KI、CsI、CaI₂等の金属ヨウ化物、テトラアルキルアンモニウムヨーダイド、ピリジニウムヨーダイド、イミダゾリウムヨーダイド等の４級アンモニウム化合物ヨウ素塩等）の組み合わせ、Br₂と臭化物（LiBr、NaBr、KBr、CsBr、CaBr₂等の金属臭化物、テトラアルキルアンモニウムブロマイド、ピリジニウムブロマイド等の４級アンモニウム化合物臭素塩等）の組み合わせ、フェロシアン酸塩−フェリシアン酸塩やフェロセン−フェリシニウムイオン等の金属錯体、ポリ硫化ナトリウム、アルキルチオール−アルキルジスルフィド等のイオウ化合物、ビオロゲン色素、ヒドロキノン−キノン等が挙げられる。中でも、I₂とLiI又はピリジニウムヨーダイド、イミダゾリウムヨーダイド等の４級アンモニウム化合物ヨウ素塩を組み合わせた電解質が好ましい。電解質は混合して用いてもよい。
【００６７】
電解液中の電解質濃度は好ましくは0.1〜10 Mであり、より好ましくは0.2〜４ Mである。また、電解液にヨウ素を添加する場合の好ましいヨウ素の添加濃度は0.01〜0.5 Mである。
【００６８】
電解液に使用する溶媒は、粘度が低くイオン移動度を向上したり、若しくは誘電率が高く有効キャリアー濃度を向上したりして、優れたイオン伝導性を発現できる化合物であることが望ましい。このような溶媒の例としては、エチレンカーボネート、プロピレンカーボネート等のカーボネート化合物、3-メチル-2-オキサゾリジノン等の複素環化合物、ジオキサン、ジエチルエーテル等のエーテル化合物、エチレングリコールジアルキルエーテル、プロピレングリコールジアルキルエーテル、ポリエチレングリコールジアルキルエーテル、ポリプロピレングリコールジアルキルエーテル等の鎖状エーテル類、メタノール、エタノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、ポリエチレングリコールモノアルキルエーテル、ポリプロピレングリコールモノアルキルエーテル等のアルコール類、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン等の多価アルコール類、アセトニトリル、グルタロジニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル化合物、ジメチルスルホキシド、スルフォラン等の非プロトン極性物質、水等が挙げられる。これらの溶媒は混合して用いることもできる。
【００６９】
また、J. Am. Ceram. Soc., 80 (12) 3157-3171 (1997)に記載されているようなtert-ブチルピリジンや、2-ピコリン、2,6-ルチジン等の塩基性化合物を前述の溶融塩電解質組成物や電解液に添加することが好ましい。塩基性化合物を電解液に添加する場合の好ましい濃度範囲は0.05〜２Mである。溶融塩電解質組成物に添加する場合、塩基性化合物はイオン性基を有することが好ましい。溶融塩電解質組成物全体に対する塩基性化合物の質量比は好ましくは1〜40質量％であり、より好ましくは５〜30質量％である。
【００７０】
(3)ゲル電解質組成物
本発明では、ポリマー添加、オイルゲル化剤添加、多官能モノマー類を含む重合、ポリマーの架橋反応等の手法により、前述の溶融塩電解質組成物や電解液をゲル化（固体化）させて使用することもできる。ポリマー添加によりゲル化する場合は、“Polymer Electrolyte Reviews-１及び２”（J. R. MacCallumとC. A. Vincentの共編、ELSEVIER APPLIED SCIENCE）に記載された化合物を使用することができるが、特にポリアクリロニトリル及びポリフッ化ビニリデンが好ましく使用できる。オイルゲル化剤添加によりゲル化する場合は工業科学雑誌（J. Chem. Soc. Japan, Ind. Chem. Sec.）, 46, 779 (1943)、J. Am. Chem. Soc., 111, 5542 (1989)、J. Chem. Soc., Chem. Commun., 1993, 390、Angew. Chem. Int. Ed. Engl., 35, 1949 (1996)、Chem. Lett., 1996, 885、及びJ. Chem. Soc., Chem. Commun., 1997, 545に記載されている化合物を使用することができるが、アミド構造を有する化合物を使用するのが好ましい。電解液をゲル化した例は特開平11-185863号に、溶融塩電解質をゲル化した例は特開2000-58140号にも記載されており、これらも本発明に適用できる。
【００７１】
また、ポリマーの架橋反応によりゲル化させる場合、架橋可能な反応性基を含有するポリマー及び架橋剤を併用することが望ましい。この場合、好ましい架橋可能な反応性基は、アミノ基、含窒素複素環（ピリジン環、イミダゾール環、チアゾール環、オキサゾール環、トリアゾール環、モルホリン環、ピペリジン環、ピペラジン環等）であり、好ましい架橋剤は、窒素原子に対して求電子反応可能な２官能以上の試薬（ハロゲン化アルキル類、ハロゲン化アラルキル類、スルホン酸エステル類、酸無水物、酸クロライド類、イソシアネート化合物、α,β-不飽和スルホニル化合物、α,β-不飽和カルボニル化合物、α,β-不飽和ニトリル化合物等）である。特開2000-17076号及び同2000-86724号に記載されている架橋技術も適用できる。
【００７２】
(4)正孔輸送材料
本発明では、溶融塩等のイオン伝導性電解質のかわりに、有機固体正孔輸送材料、無機固体正孔輸送材料、或いはこの両者を組み合わせた材料を使用することができる。
【００７３】
(a)有機正孔輸送材料
本発明において好ましく使用できる有機正孔輸送材料の例としては、J. Hagen, et al., Synthetic Metal, 89, 215-220 (1997)、Nature, Vol.395, 8 Oct., p583-585 (1998)、WO97/10617、特開昭59-194393号、特開平5-234681号、米国特許第4,923,774号、特開平4-308688号、米国特許第4,764,625号、特開平3-269084号、同4-129271号、同4-175395号、同4-264189号、同4-290851号、同4-364153号、同5-25473号、同5-239455号、同5-320634号、同6-1972号、同7-138562号、同7-252474号、同11-144773号等に記載の芳香族アミン類、特開平11-149821号、同11-148067号、同11-176489号等に記載のトリフェニレン誘導体類等が挙げられる。また、Adv. Mater., 9, No.7, p557 (1997)、Angew. Chem. Int. Ed. Engl., 34, No.3, p303-307 (1995)、JACS, Vol.120, No.4, p664-672 (1998)等に記載のオリゴチオフェン化合物、K. Murakoshi, et al., Chem. Lett. p471 (1997)に記載のポリピロール、“Handbook of Organic Conductive Molecules and Polymers, Vol. 1,2,3,4”（NALWA著、WILEY出版）に記載のポリアセチレン及びその誘導体、ポリ(p-フェニレン)及びその誘導体、ポリ(p-フェニレンビニレン)及びその誘導体、ポリチエニレンビニレン及びその誘導体、ポリチオフェン及びその誘導体、ポリアニリン及びその誘導体、ポリトルイジン及びその誘導体等の導電性高分子も好ましく使用することができる。
【００７４】
Nature, Vol.395, 8 Oct., p583-585 (1998)に記載されているように、ドーパントレベルをコントロールするためにトリス(4-ブロモフェニル)アミニウムヘキサクロロアンチモネートのようなカチオンラジカルを含有する化合物を正孔輸送材料に添加してもよい。また、酸化物半導体表面のポテンシャル制御（空間電荷層の補償）を行うためにLi[(CF₃SO₂)₂N]のような塩を添加してもよい。
【００７５】
(b)無機正孔輸送材料
無機正孔輸送材料としてはp型無機化合物半導体を用いることができ、そのバンドギャップは好ましくは２eV以上、より好ましくは2.5 eV以上である。また、p型無機化合物半導体のイオン化ポテンシャルは、色素の正孔を還元するためには色素吸着電極のイオン化ポテンシャルより小さいことが必要である。使用する色素によってp型無機化合物半導体のイオン化ポテンシャルの好ましい範囲は異なるが、一般に好ましくは4.5〜5.5 eV、より好ましくは4.7〜5.3 eVである。好ましいp型無機化合物半導体は１価の銅を含む化合物半導体であり、その例としてはCuI、CuSCN、CuInSe₂、Cu(In,Ga)Se₂、CuGaSe₂、Cu₂O、CuS、CuGaS₂、CuInS₂、CuAlSe₂等が挙げられる。中でも、CuI及びCuSCNが好ましく、CuIが最も好ましい。他のp型無機化合物半導体の例としては、GaP、NiO、CoO、FeO、Bi₂O₃、MoO₂、Cr₂O₃等が挙げられる。
【００７６】
(5)電荷輸送層の形成
電荷輸送層は２通りの方法のいずれかにより形成できる。１つは感光層の上に先に対極を貼り合わせておき、その間隙に液状の電荷輸送層を挟み込む方法である。もう１つは感光層上に直接電荷輸送層を付与する方法で、対極はその後付与することになる。
【００７７】
前者の方法の場合、電荷輸送層を挟み込む際には、浸漬等による毛管現象を利用する常圧プロセス又は常圧より低い圧力にして間隙の気相を液相に置換する真空プロセスを利用できる。
【００７８】
後者の方法において、湿式の電荷輸送層を用いる場合は、通常未乾燥のまま対極を付与しエッジ部の液漏洩防止措置を施す。またゲル電解質組成物を用いる場合には、これを湿式で塗布した後で重合等の方法により固体化してよい。固体化は対極を付与する前に行っても後に行ってもよい。電解液、湿式有機正孔輸送材料、ゲル電解質組成物等からなる電荷輸送層を形成する場合は、前述の半導体微粒子層の形成方法と同様の方法を利用できる。
【００７９】
固体電解質組成物や固体正孔輸送材料を用いる場合には、真空蒸着法やCVD法等のドライ成膜処理で電荷輸送層を形成し、その後対極を付与することもできる。有機正孔輸送材料は真空蒸着法、キャスト法、塗布法、スピンコート法、浸漬法、電解重合法、光電解重合法等により電極内部に導入することができる。無機固体化合物はキャスト法、塗布法、スピンコート法、浸漬法、電解析出法、無電解メッキ法等により電極内部に導入することができる。
【００８０】
(D)対極
対極は前述の導電性支持体と同様に、導電性材料からなる対極導電層の単層構造でもよいし、対極導電層と支持基板から構成されていてもよい。対極導電層に用いる導電剤の例としては、金属（白金、金、銀、銅、アルミニウム、マグネシウム、インジウム等）、炭素、導電性金属酸化物（インジウム−スズ複合酸化物、フッ素ドープ酸化スズ等）等が挙げられる。この中でも白金、金、銀、銅、アルミニウム及びマグネシウムが好ましい。対極に用いる基板は、好ましくはガラス基板又はプラスチック基板であり、これに上記の導電剤を塗布又は蒸着して用いることができる。対極導電層の厚さは特に制限されないが、好ましくは３nm〜10μmである。対極導電層の表面抵抗は低い程よく、好ましくは50Ω／□以下、より好ましくは20Ω／□以下である。
【００８１】
導電性支持体と対極のいずれか一方又は両方から光を照射してよいので、感光層に光が到達するためには、導電性支持体と対極の少なくとも一方が実質的に透明であればよい。発電効率の向上の観点からは導電性支持体を透明にして光を導電性支持体側から入射させるのが好ましい。この場合、対極は光を反射する性質を有するのが好ましい。このような性質を得るためには、対極として金属又は導電性酸化物を蒸着したガラス又はプラスチック、或いは金属薄膜を使用してよい。
【００８２】
対極は電荷輸送層上に直接導電剤を塗布、メッキ又は蒸着（PVD、CVD）するか、導電層を有する基板の導電層側を貼り付けて設置すればよい。導電性支持体の場合と同様に、特に対極が透明の場合には、対極の抵抗を下げる目的で金属リードを用いるのが好ましい。金属リードの好ましい態様は導電性支持体の場合と同じである。
【００８３】
(E)その他の層
対極と導電性支持体の短絡を防止するため、導電性支持体と感光層の間には緻密な半導体の薄膜層を下塗り層として予め塗設しておくことが好ましい。この下塗り層により短絡を防止する方法は、電荷輸送層に電子輸送材料や正孔輸送材料を用いる場合は特に有効である。下塗り層は好ましくはTiO₂、SnO₂、Fe₂O₃、WO₃、ZnO又はNb₂O₅からなり、さらに好ましくはTiO₂からなる。下塗り層は、例えばElectrochim. Acta, 40, 643-652 (1995)に記載のスプレーパイロリシス法や、スパッタ法等により塗設することができる。下塗り層の膜厚は好ましくは５〜1000 nmであり、より好ましくは10〜500 nmである。
【００８４】
また、導電性支持体と対極の一方又は両方の外側表面、導電層と基板の間又は基板の中間に、保護層、反射防止層等の機能性層を設けてもよい。これらの機能性層の形成方法は、その材質に応じて塗布法、蒸着法、貼り付け法等から適宜選択できる。
【００８５】
(F)光電変換素子の内部構造の具体例
上述のように、光電変換素子の内部構造は目的に合わせ様々な形態が可能である。大きく２つに分ければ、両面から光の入射が可能な構造と、片面からのみ可能な構造が可能である。本発明の光電変換素子の好ましい内部構造の例を、前述の図１及び図２〜図９に示す。
【００８６】
図２に示す構造は、透明導電層10aと透明対極導電層40aとの間に、感光層20と電荷輸送層30とを介在させたものであり、両面から光が入射する構造となっている。図３に示す構造は、透明基板50a上に一部金属リード11を設け、その上に透明導電層10aを設け、下塗り層60、感光層20、電荷輸送層30及び対極導電層40をこの順で設け、更に支持基板50を配置したものであり、導電層側から光が入射する構造となっている。図４に示す構造は、支持基板50上に導電層10を有し、下塗り層60を介して感光層20を設け、更に電荷輸送層30と透明対極導電層40aとを設け、一部に金属リード11を設けた透明基板50aを金属リード11側を内側にして配置したものであり、対極側から光が入射する構造である。図５に示す構造は、透明基板50a上に一部金属リード11を設け、更に透明導電層10a（又は40a）を設けたもの１組の間に下塗り層60、感光層20及び電荷輸送層30を介在させたものであり、両面から光が入射する構造である。図６に示す構造は、透明基板50a上に透明導電層10a、下塗り層60、感光層20、電荷輸送層30及び対極導電層40を設け、この上に支持基板50を配置したものであり、導電層側から光が入射する構造である。図７に示す構造は、支持基板50上に導電層10を有し、下塗り層60を介して感光層20を設け、更に電荷輸送層30及び透明対極導電層40aを設け、この上に透明基板50aを配置したものであり、対極側から光が入射する構造である。図８に示す構造は、透明基板50a上に透明導電層10aを有し、下塗り層60を介して感光層20を設け、更に電荷輸送層30及び透明対極導電層40aを設け、この上に透明基板50aを配置したものであり、両面から光が入射する構造となっている。図９に示す構造は、支持基板50上に導電層10を設け、下塗り層60を介して感光層20を設け、更に固体の電荷輸送層30を設け、この上に一部対極導電層40又は金属リード11を有するものであり、対極側から光が入射する構造となっている。
【００８７】
[3]光電池
本発明の光電池は、本発明の光電変換素子に外部負荷で仕事をさせるようにしたものである。光電池のうち、電荷輸送材料が主としてイオン輸送材料からなる場合を特に光電気化学電池と呼び、また、太陽光による発電を主目的とする場合を太陽電池と呼ぶ。
【００８８】
光電池の側面は、構成物の劣化や内容物の揮散を防止するためにポリマーや接着剤等で密封するのが好ましい。導電性支持体及び対極にリードを介して接続する外部回路自体は公知のものでよい。
【００８９】
本発明の光電変換素子を太陽電池に適用する場合も、そのセル内部の構造は基本的に上述した光電変換素子の構造と同じである。また、本発明の光電変換素子を用いた色素増感型太陽電池は、従来の太陽電池モジュールと基本的には同様のモジュール構造をとりうる。太陽電池モジュールは、一般的には金属、セラミック等の支持基板の上にセルが構成され、その上を充填樹脂や保護ガラス等で覆い、支持基板の反対側から光を取り込む構造をとるが、支持基板に強化ガラス等の透明材料を用い、その上にセルを構成してその透明の支持基板側から光を取り込む構造とすることも可能である。具体的には、スーパーストレートタイプ、サブストレートタイプ、ポッティングタイプと呼ばれるモジュール構造、アモルファスシリコン太陽電池等で用いられる基板一体型モジュール構造等が知られており、本発明の光電変換素子を用いた色素増感型太陽電池も使用目的や使用場所及び環境により、適宜モジュール構造を選択できる。具体的には、特願平11-8457号、特開2000-268892号等に記載の構造や態様とすることが好ましい。
【００９０】
【実施例】
以下、本発明を実施例によって具体的に説明するが、本発明はそれらに限定されるものではない。
【００９１】
１．二酸化チタン粒子塗布液の作製
オートクレーブ温度を230℃にしたこと以外はバルベらのジャーナル・オブ・アメリカン・セラミック・ソサエティ, 第80巻, 3157頁に記載の方法と同様の方法で、二酸化チタン濃度が11質量％の二酸化チタン粒子分散物を得た。この分散物中の二酸化チタン粒子の平均粒径は約10 nmであった。この分散物に二酸化チタンに対して20質量％のポリエチレングリコール（分子量20000、和光純薬工業（株）製）を添加し、混合して二酸化チタン粒子塗布液を得た。
【００９２】
２．二酸化チタン電極の作製
フッ素をドープした酸化スズをコーティングした透明導電性ガラス（日本板硝子（株）製、表面抵抗：約10Ω／cm²）の導電面側に上記二酸化チタン粒子塗布液をドクターブレードで120μmのウェット厚みで塗布し、25℃で30分間乾燥した後、電気炉（ヤマト科学（株）製「マッフル炉FP-32型」）を用いて450℃で30分間加熱処理して二酸化チタン層を形成し、二酸化チタン電極を得た。透明導電性ガラスの単位面積あたりの二酸化チタン塗布量は16.0 g/m²であり、二酸化チタン層の膜厚は約11μmであった。また、得られた二酸化チタン層のラフネスファクターをBET法で測定したところ、約1000であった。
【００９３】
３．カソード電析及び色素の吸着
上記二酸化チタン電極を10 mm×12 mmの大きさに切断した。ただし、二酸化チタン層の面積は10 mm×10 mmとした。続いて、対極に白金を用い参照電極として銀・塩化銀電極を用いて、ポテンシオスタットを使用した３極式の方法により、上記二酸化チタン電極にカソード電析処理を施した。0.02 Mの金属硝酸塩Zn(NO₃)₂、0.02 Mの硝酸リチウム及び0.01 Mの硝酸を含む水溶液からなる電解質を使用し、この電解質中で二酸化チタン電極をカソード側に分極した後、水及びアセトニトリルで順次洗浄し、450℃で30分間焼成した。なお、カソード電析は分極電圧−1.1 V、電析時間30分の条件下で行った。カソード電析処理によって単位面積あたりの半導体微粒子層の重量は17.5 g/m²に増加したが、ラフネスファクターは殆ど変化しなかった。
焼成終了後、カソード電析処理を施した二酸化チタン電極を冷却し、下記色素１を含有する色素吸着液に３時間浸漬した。浸漬は振とう機で振とうしながら行った。色素吸着液の温度は45℃、色素吸着液中の色素１の濃度は0.3 mmol/lとし、溶媒としてはエタノール、2-メチル-2-プロパノール及びアセトニトリルの混合溶媒（エタノール：2-メチル-2-プロパノール：アセトニトリル＝１：１：２（体積比））を用いた。浸漬後、エタノール及びアセトニトリルで順次洗浄し、暗所・窒素気流下で乾燥して色素吸着二酸化チタン電極E-4を得た。
【００９４】
【化３】

【００９５】
また、電解質溶液に用いた金属硝酸塩及び溶媒、並びに電析条件を下記表１に示すように変えたこと以外は電極E-4の作製と同様にして、電極E-1〜E-3及びE-5〜E-20をそれぞれ作製した。これら電極の単位面積あたりの半導体微粒子層の重量を表１に示す。ラフネスファクターはE-4と同様に殆ど変化が認められなかった。なお、分極後の洗浄は、電解質溶液に用いた溶媒及びアセトニトリルで順次行った。また、電極E-3、E-5及びE-8を作製する際には、カソード電析に用いる電解質溶液に表１に示す濃度で色素１を添加した。
【００９６】
【表１】

【００９７】
４．光電変換素子の作製
上記電極E-1を15 mm×20 mmの白金蒸着ガラスと重ね合わせた。次に、両ガラスの隙間に毛細管現象を利用して電解液（ヨウ化1,3-ジメチルイミダゾリウム（0.6 mol/l）、ヨウ化リチウム（0.1 mol/l）及びヨウ素（0.05 mol/l）のアセトニトリル溶液）をしみこませて電極中に導入し、比較用の光電変換素子C-1を作製した。この光電変換素子は、図10に示すような、導電性ガラス１（ガラス２上に導電層３を設けたもの）、色素吸着二酸化チタン層４、電荷輸送層５、白金層６及びガラス７が順に積層された構造を有する。
電極E-1に換えて下記表２に示す電極を用いたこと以外は光電変換素子C-1の作製と同様にして、比較用の光電変換素子C-2、C-3及びC-16、並びに本発明の光電変換素子C-4〜C-15及びC-17〜C-20をそれぞれ作製した。
【００９８】
５.光電変換効率の評価
500 Wのキセノンランプ（ウシオ電機（株）製）の光を分光フィルター（Oriel社製「AM1.5」）を通すことにより模擬太陽光を発生させた。この模擬太陽光の強度は垂直面において100 mW/cm²であった。各光電変換素子C-1〜C-20の導電性ガラスの端部に銀ペーストを塗布して負極とし、この負極と白金蒸着ガラス（正極）を電流電圧測定装置（ケースレーSMU238型）に接続した。各光電変換素子に模擬太陽光を垂直に照射しながら電流電圧特性を測定し、光電変換効率を求めた。表２に各光電変換素子の変換効率を示す。
【００９９】
【表２】

【０１００】
表２に示した通り、比較例の光電変換素子C-1〜C-3及びC-16と比較して、本発明の光電変換素子C-4〜C-15及びC-17〜C-20は優れた変換効率を示した。
【０１０１】
【発明の効果】
以上詳述したように、本発明では、カソード電析処理を施すことで良質の半導体微粒子膜が得られ、この半導体微粒子膜に色素を吸着させて感光層を形成することによって変換効率に優れた色素増感光電変換素子が得られる。
【図面の簡単な説明】
【図１】 本発明の好ましい光電変換素子の構造を示す部分断面図である。
【図２】 本発明の好ましい光電変換素子の構造を示す部分断面図である。
【図３】 本発明の好ましい光電変換素子の構造を示す部分断面図である。
【図４】 本発明の好ましい光電変換素子の構造を示す部分断面図である。
【図５】 本発明の好ましい光電変換素子の構造を示す部分断面図である。
【図６】 本発明の好ましい光電変換素子の構造を示す部分断面図である。
【図７】 本発明の好ましい光電変換素子の構造を示す部分断面図である。
【図８】 本発明の好ましい光電変換素子の構造を示す部分断面図である。
【図９】 本発明の好ましい光電変換素子の構造を示す部分断面図である。
【図１０】 実施例で作製した光電変換素子の構造を示す部分断面図である。
【符号の説明】
10・・・導電層
10a・・・透明導電層
11・・・金属リード
20・・・感光層
21・・・半導体微粒子
22・・・色素
23・・・電荷輸送材料
30・・・電荷輸送層
40・・・対極導電層
40a・・・透明対極導電層
50・・・基板
50a・・・透明基板
60・・・下塗り層
１・・・導電性ガラス
２・・・ガラス
３・・・導電層
４・・・色素吸着二酸化チタン層
５・・・電荷輸送層
６・・・白金層
７・・・ガラス[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a semiconductor fine particle film, a method for producing a photoelectric conversion element using the semiconductor fine particle film, a photoelectric conversion element produced by the method, and a photovoltaic cell using the photoelectric conversion element.
[0002]
[Prior art]
Some semiconductors including titanium oxide are known as n-type semiconductors and have the property of emitting electrons when receiving light or the like. Utilizing such characteristics, n-type semiconductors are widely used for photocatalysts and the like, and are also studied as materials for photoelectric conversion elements. Photoelectric conversion elements are used in various photosensors, copiers, photovoltaic devices, and the like. Photoelectric conversion elements include those using metals, those using semiconductors, those using organic pigments and dyes, and those using combinations of these, and various systems have been put into practical use.
[0003]
U.S. Pat. Nos. 4,927,721, 4,684,537, 5,844,365, 5,350,644, 5,630,57, 5,525,440, WO98 / 50393, JP-A-7-249790, and JP-T-10-504521 (Patent Documents 1 to 9) ) Discloses a photoelectric conversion element using semiconductor fine particles sensitized with a dye (hereinafter also referred to as “dye-sensitized photoelectric conversion element”), a material for producing the photoelectric conversion element, and a manufacturing technique. The advantage of the dye-sensitized photoelectric conversion element is that an inexpensive oxide semiconductor such as titanium dioxide can be used without being purified to a high purity, so that it can be manufactured at a relatively low cost. However, such a photoelectric conversion element does not necessarily have a sufficiently high conversion efficiency, and further improvement in conversion efficiency is desired.
[0004]
[Patent Document 1]
U.S. Pat.No. 4,927,721
[Patent Document 2]
US Pat. No. 4,684,537
[Patent Document 3]
US Patent No. 5084365
[Patent Document 4]
U.S. Pat.No. 5,350,644
[Patent Document 5]
US Pat. No. 5463057
[Patent Document 6]
U.S. Pat.No. 5,525,440
[Patent Document 7]
WO 98/50393 pamphlet
[Patent Document 8]
Japanese Patent Laid-Open No. 7-249790
[Patent Document 9]
Japanese National Patent Publication No. 10-504521
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a semiconductor fine particle film useful for a photoelectric conversion device, a method for producing a dye-sensitized photoelectric conversion device exhibiting excellent conversion efficiency by using this semiconductor fine particle film, and a photoelectric device produced by the method. It is providing the conversion element and the photovoltaic cell using this photoelectric conversion element.
[0006]
[Means for Solving the Problems]
As a result of diligent research in view of the above object, the present inventor used a semiconductor fine particle film in which a metal oxide layer is formed by cathode electrodeposition on a porous semiconductor fine particle layer as a photosensitive layer, thereby converting a photoelectric conversion element. It was discovered that efficiency can be improved and the present invention has been conceived.
[0007]
That is, in the method for producing a semiconductor fine particle film of the present invention, on a porous semiconductor fine particle layer having a roughness factor of 10 or more,In electrolyte solutions containing metal nitratesIt includes a step of forming a metal oxide layer by cathodic electrodeposition.
[0008]
Further, the method for producing a photoelectric conversion element of the present invention is a method for producing a photoelectric conversion element having a photosensitive layer containing a semiconductor fine particle adsorbed with a dye and a conductive support, and the method for producing the semiconductor fine particle film of the present invention. A photosensitive layer is formed by adsorbing a dye to a semiconductor fine particle film manufactured by a manufacturing method.
[0009]
The photoelectric conversion element of the present invention is produced by the method for producing a photoelectric conversion element of the present invention, and usually has a conductive support, a photosensitive layer, a charge transport layer, and a counter electrode. The photovoltaic cell of the present invention uses the photoelectric conversion element.
[0010]
In the present invention, the porous semiconductor fine particle layer is preferably made of an oxide semiconductor, particularly preferably made of titanium oxide, zinc oxide, niobium oxide, tin oxide, tungsten oxide, indium oxide, zirconium oxide or strontium titanate. . The metal oxide layer formed by cathodic electrodeposition is preferably a layer made of zinc oxide or titanium oxide. A working electrode in which a semiconductor fine particle layer is formed on a conductive support is immersed in a titanium tetranitrate solution. A layer made of titanium oxide formed by performing cathodic electrodeposition is particularly preferable. Moreover, it is preferable that the solvent of the electrolyte used for cathode electrodeposition is water. In the method for producing a photoelectric conversion element, it is preferable to dissolve the dye in advance in the electrolyte, and it is more preferable when the zinc oxide layer is formed. The dye is particularly preferably a ruthenium complex dye.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
[1] Method for producing semiconductor fine particle film
The method for producing a semiconductor fine particle film of the present invention includes a step of forming a metal oxide layer on the porous semiconductor fine particle layer by cathode electrodeposition (cathode electrodeposition step). The semiconductor fine particle film obtained by the method of the present invention is useful for an antifouling film, a photocatalyst film represented by a superhydrophilic film, a photoelectric conversion element, and the like. Hereinafter, an embodiment in which the semiconductor fine particle film is used for the photosensitive layer of the photoelectric conversion element will be described in detail.
[0012]
(A) Porous semiconductor fine particle layer
The semiconductors forming the porous semiconductor fine particle layer are single semiconductors (silicon, germanium, etc.), III-V group compound semiconductors, metal chalcogenides (oxides, sulfides, selenides, etc.), compounds having a perovskite structure (strontium titanate) , Calcium titanate, sodium titanate, barium titanate, potassium niobate, etc.). Among these, an oxide semiconductor can be preferably used.
[0013]
Examples of metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum oxide, cadmium, zinc, lead, silver, antimony or Examples thereof include bismuth sulfide, cadmium or lead selenide, and cadmium telluride. Examples of other compound semiconductors include phosphides such as zinc, gallium, indium, and cadmium, gallium-arsenic or copper-indium selenides, and copper-indium sulfides.
[0014]
The semiconductor used in the present invention is preferably titanium oxide, zinc oxide, niobium oxide, tin oxide, tungsten oxide, indium oxide, zirconium oxide or strontium titanate, more preferably titanium oxide or niobium oxide, particularly preferably. Titanium oxide. Known crystal forms of titanium oxide include anatase type, rutile type, brookite type, and the like. The titanium oxide used in the present invention may have any of these crystal forms.
[0015]
The semiconductor used in the present invention may be single crystal or polycrystal, but single crystal is preferable from the viewpoint of conversion efficiency, and polycrystal is advantageous from the viewpoint of manufacturing cost, securing raw materials, energy payback time, and the like. In addition, the semiconductor used in the present invention may include an amorphous part.
[0016]
The particle size of the semiconductor fine particles is generally on the order of nm to μm, but the average particle size of the primary particles obtained from the diameter when the projected area is converted into a circle is preferably 5 to 200 nm, more preferably 8 to 100 nm. It is. Moreover, the average particle diameter of the semiconductor fine particles (secondary particles) in the dispersion is preferably 0.01 to 100 μm.
[0017]
Two or more kinds of semiconductor fine particles having different particle size distributions may be mixed and used. In this case, the average particle size of small particles is preferably 5 to 50 nm, and the average size of large particles is preferably 100 to 600. nm. Small particles have the effect of increasing the surface area on which the dye is adsorbed, and large particles have the effect of improving the light capture rate by scattering incident light. The mixing ratio (mass ratio) is preferably 50 to 99% for small particles and 1 to 50% for large particles, more preferably 70 to 95% for small particles and 5 to 30% for large particles.
[0018]
Semiconductor fine particles are prepared by Sakuo Sakuo's "Sol-gel Method Science" Agne Jofusha (1998), Technical Information Association "Sol-gel Method Thin Film Coating Technology" (1995), etc. The sol-gel method described, Tadao Sugimoto's "Synthesis and size control of monodisperse particles by the new synthetic gel-sol method", Materia, Vol. 35, No. 9, pp. 1012-1018 (1996) The gel-sol method described in the above, the sulfuric acid method and the chlorine method described in Kiyoshi Manabu's “Titanium oxide properties and applied technology”, Gihodo Shuppan (1997), and chlorides developed by Degussa were hydrolyzed in an oxyhydrogen salt at high temperature. A method of producing an oxide by decomposition can be preferably used.
[0019]
When titanium oxide fine particles are used as semiconductor fine particles, Barbe et al. Journal of American Ceramic Society, Vol. 80, No. 12, pp. 3157-3171 (1997), Burnside et al., Chemistry of Materials, Volume 10, Issue 9,
The sol-gel method described on pages 2419 to 2425 and the like can be particularly preferably used.
[0020]
When forming the porous semiconductor fine particle layer made of the semiconductor on the conductive support, it is common to use a method of applying a dispersion or colloidal solution containing the semiconductor fine particles on the conductive support. . Considering mass production of photoelectric conversion elements, physical properties of a dispersion or colloidal solution containing semiconductor fine particles, flexibility of a conductive support, etc., it is relatively desirable to use a wet film forming method. As a wet film forming method, a coating method and a printing method are typical.
[0021]
Examples of methods for preparing a dispersion of semiconductor fine particles include a method of using the dispersion or colloidal solution prepared by the sol-gel method as described above, a method of grinding with a mortar, and a method of dispersing while grinding using a mill. Etc.
[0022]
The dispersion medium used for the dispersion of semiconductor fine particles may be water or various organic solvents (methanol, ethanol, isopropyl alcohol, dichloromethane, acetone, acetonitrile, ethyl acetate, etc.). When dispersing, if necessary, a polymer such as polyethylene glycol, a surfactant, an acid, a chelating agent, or the like may be used as a dispersion aid. By changing the molecular weight of polyethylene glycol, the viscosity of the dispersion can be adjusted and a semiconductor fine particle layer that is difficult to peel off can be formed. Therefore, it is preferable to add polyethylene glycol.
[0023]
Examples of preferred coating methods include the roller method and dip method as application systems, the air knife method and blade method as metering systems, and the application and metering disclosed in Japanese Examined Patent Publication No. 58-4589. And the wire hopper method, the slide hopper method, the extrusion method, the curtain method and the like described in US Pat. Nos. 2681294, 2761419, 2761791 and the like. Moreover, a spin method and a spray method are also preferable as a general purpose machine. As the wet printing method, intaglio, rubber plate, screen printing and the like are preferred, including the three major printing methods of letterpress, offset and gravure. A film forming method may be selected from these according to the liquid viscosity and the wet thickness.
[0024]
The viscosity of the dispersion of semiconductor fine particles greatly depends on the type and dispersibility of the semiconductor fine particles, the type of solvent used, and additives such as surfactants and binders. When the dispersion has a high viscosity (for example, 0.01 to 500 Poise), it is preferable to use an extrusion method, a casting method, or a screen printing method. When the viscosity is low (for example, 0.1 Poise or less), it is preferable to use a slide hopper method, a wire bar method, or a spin method in order to form a uniform film. When the coating amount is large to some extent, it is possible to apply the extrusion method even if the viscosity is low. Thus, a film forming method may be appropriately selected according to the viscosity of the dispersion, the coating amount, the support, the coating speed, and the like.
[0025]
The porous semiconductor fine particle layer is not limited to a single layer, and a multilayer coating of a dispersion of semiconductor fine particles having different particle diameters or a layer containing different types of semiconductor fine particles (or different binders, additives, etc.) is applied. You can also do it. Multi-layer coating is also effective when the film thickness is insufficient with a single coating. The extrusion method and slide hopper method are suitable for multilayer coating. In the case of applying multiple layers, the multiple layers may be applied at the same time, or may be applied one after the other several times. A screen printing method can also be preferably used for successive overcoating.
[0026]
In general, as the thickness of the porous semiconductor fine particle layer increases, the amount of the supported dye increases per unit projected area and thus the light capture rate increases. However, the diffusion distance of the generated electrons increases and the loss due to charge recombination also increases. . Therefore, the preferred thickness of the porous semiconductor fine particle layer is 0.1 to 100 μm. When using the photoelectric conversion element of this invention for a solar cell, the thickness of a porous semiconductor fine particle layer becomes like this. Preferably it is 1-30 micrometers, More preferably, it is 2-25 micrometers. Conductive support 1m²The coating amount of the semiconductor fine particles is preferably 0.5 to 400 g, more preferably 5 to 100 g.
[0027]
After coating the semiconductor fine particles on the conductive support, it is preferable to heat-treat the semiconductor fine particles to bring them into electronic contact and improve the coating strength and the adhesion to the conductive support. The heating temperature in the heat treatment is preferably 40 to 700 ° C, more preferably 100 to 600 ° C. The heating time is about 10 minutes to 10 hours. When using a substrate having a low melting point or softening point such as a polymer film, high temperature treatment is not preferable because it causes deterioration of the substrate. Also from the viewpoint of cost, it is preferable to perform the heat treatment at the lowest possible temperature. When the heat treatment is performed in the presence of small semiconductor fine particles of 5 nm or less, mineral acid, or the like, the heating temperature can be lowered.
[0028]
After heat treatment, an aqueous solution of titanium tetrachloride as described in US Pat. No. 5084365, etc., for the purpose of increasing the surface area of the semiconductor fine particles or increasing the electron injection efficiency from the dye to the semiconductor fine particles by increasing the purity in the vicinity of the semiconductor fine particles You may perform the chemical plating process which used, and the electrochemical plating process using the titanium trichloride aqueous solution.
[0029]
The porous semiconductor fine particle layer preferably has a large surface area so that a large amount of dye can be adsorbed. The roughness factor of the porous semiconductor fine particle layer is 10 or more, preferably 100 or more. The upper limit of the roughness factor is not particularly limited, but is usually about 1000. In the present invention, the roughness factor means the value of the surface area / projected area of the porous semiconductor fine particle layer formed on the conductive support or the like.
[0030]
(B) Cathode electrodeposition
Cathodic electrodeposition can be performed with reference to, for example, the method described in Applied Physics Letter, 1996, Vol. 68, (17), pages 2439 to 2440. Typically, a semiconductor electrode (working electrode) is obtained by applying semiconductor fine particles to a conductive support and the like, and it works in an electrolyte solution containing a metal nitrate using a tripolar method using a potentiostat. What is necessary is just to polarize a pole to the cathode side. The set potential of the working electrode may be appropriately selected according to the metal to be used. However, when the reference electrode is a silver / silver chloride electrode, it is preferably about −2 to −0.5 V, more preferably −1.5 to −0.7. V, particularly preferably −1.1 to −0.9 V. The voltage application time is usually 1 minute to 24 hours, preferably 1 minute to 1 hour. By this step, the metal oxide or metal hydroxide adheres to the working electrode, and further, the metal oxide layer is formed by drying or heating. Usually, drying or heating may be performed at 50 to 450 ° C. for about 30 minutes to 24 hours. The mass ratio of the metal oxide layer to the porous semiconductor fine particle layer is preferably 0.01 to 10%, more preferably 0.05 to 1%.
[0031]
The metal nitrate may be used as it is dissolved in the electrolyte solution. Alternatively, a metal halide or a metal alkoxide compound may be added to a nitric acid acidic (usually 0.001 to 10 N, preferably 0.01 to 1 N) aqueous solution to generate a metal nitrate by hydrolysis, and this solution may be used as an electrolyte solution. The concentration of the metal nitrate in the electrolyte solution is preferably 0.001 to 5 mol / l, more preferably 0.01 to 1 mol / l.
[0032]
Metals contained in the metal nitrate are, for example, titanium, tin, zinc, iron, tungsten,germanium,It may be zirconium, hafnium, strontium, indium, cerium, scandium, yttrium, lanthanum, vanadium, niobium, tantalum, cadmium, lead, antimony, gallium, etc., preferably titanium, tin, zinc, tungsten, zirconium, indium, scandium Yttrium, niobium or gallium, more preferably zinc or titanium, and still more preferably titanium.
[0033]
The electrolyte solution used for cathode electrodeposition usually contains an electrolyte salt and a solvent. The metal nitrate is preferably used as an electrolyte salt, but other electrolyte salts may be used. The cation of the electrolyte salt is preferably an alkali metal ion (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺Etc.), more preferably K⁺It is. The anion of the electrolyte salt is preferably a conjugated anion of a strong acid. Specific examples include halide ions (F^-, Cl^-, Br^-, I^-Etc.), sulfate ion, nitrate ion, phosphate ion, ClO_Four ^-, BF_Four ^-, PF₆ ^-, SbF₆ ^-, AsF₆ ^-Trifluoroacetate ion, methanesulfonate ion, p-toluenesulfonate ion, trifluoromethanesulfonate ion, bis (trifluoroethanesulfonyl) imide ion, tris (trifluoromethanesulfonyl) methide ion, and the like. Of these, nitrate ions are particularly preferred.
[0034]
The electrolyte salt may be used alone or as a mixture of two or more. The concentration of the electrolyte salt in the electrolyte solution used for the cathode electrodeposition is preferably 0.001 to 5 mol / l, more preferably 0.01 to 1 mol / l.
[0035]
The solvent of the electrolyte solution used for cathode electrodeposition is not particularly limited as long as it can dissolve a salt, but is usually water or an organic solvent, preferably water. Examples of organic solvents include alcohols (methanol, ethanol, t-butyl alcohol, benzyl alcohol, etc.), nitriles (acetonitrile, propionitrile, 3-methoxypropionitrile, etc.), nitromethane, halogenated hydrocarbons (dichloromethane) , Dichloroethane, chloroform, chlorobenzene, etc.), ethers (dimethoxyethane, tetrahydrofuran, etc.), dimethyl sulfoxide, amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), N-methylpyrrolidone, 1,3 -Dimethylimidazolidinone, 3-methyloxazolidinone, esters (ethyl acetate, butyl acetate, etc.), carbonates (diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), ketones (acetone, 2-butanone, cyclohexanone, etc.), These mixtures etc. Can be mentioned.
[0036]
After the cathodic electrodeposition, the working electrode is preferably washed. Usually, washing is performed using the same solvent as that used for the electrolyte solution.
[0037]
A dye can be dissolved in advance in an electrolyte solution used for cathode electrodeposition. This is particularly preferable when a zinc oxide layer is formed on the semiconductor fine particle layer. The density | concentration of the pigment | dye in electrolyte solution becomes like this. Preferably it is 0.0001-5 mol / l, More preferably, it is 0.001-0.1 mol / l. The dye is not particularly limited as long as it dissolves in the electrolyte solution, but is preferably a ruthenium complex dye.
[0038]
[2] photoelectric conversion element
The method for producing a photoelectric conversion element of the present invention includes a step of adsorbing a dye to the semiconductor fine particle film produced by the method for producing a semiconductor fine particle film of the present invention. In the present invention, the conversion efficiency of the photoelectric conversion element is improved by forming the metal oxide layer by cathode electrodeposition. The photoelectric conversion element of the present invention has a photosensitive layer containing a semiconductor fine particle adsorbed with a dye and a conductive support, and the photosensitive layer is obtained by adsorbing the dye on the semiconductor fine particle film.
[0039]
The photoelectric conversion element of the present invention is preferably formed by laminating a conductive layer 10, a photosensitive layer 20, a charge transport layer 30 and a counter electrode conductive layer 40 in this order as shown in FIG. The semiconductor fine particles 21 and the charge transport material 23 that has penetrated into the gaps between the semiconductor fine particles 21 are formed. The charge transport material 23 in the photosensitive layer 20 is usually the same material used for the charge transport layer 30. An undercoat layer 60 may be provided between the conductive layer 10 and the photosensitive layer 20. Further, a substrate 50 may be provided as a base for the conductive layer 10 and / or the counter electrode conductive layer 40 in order to impart strength to the photoelectric conversion element. In the present invention, the layer composed of the conductive layer 10 and the optionally provided substrate 50 is referred to as “conductive support”, and the layer composed of the counter electrode conductive layer 40 and the optionally provided substrate 50 is referred to as “counter electrode”. Note that the conductive layer 10, the counter electrode conductive layer 40, and the substrate 50 in FIG. 1 may be the transparent conductive layer 10a, the transparent counter electrode conductive layer 40a, and the transparent substrate 50a, respectively. Among such photoelectric conversion elements, a photoelectric cell is connected to an external load in order to perform electrical work (power generation), and a photoelectric sensor is a sensor made for the purpose of sensing optical information. Among photovoltaic cells, those in which the charge transport material is mainly made of an ion transport material are called photoelectrochemical cells, and those whose main purpose is power generation by sunlight are called solar cells.
[0040]
In the photoelectric conversion element shown in FIG. 1, the light incident on the photosensitive layer 20 containing the semiconductor fine particles 21 sensitized by the dye 22 excites the dye 22 and the like, and the high energy electrons in the excited dye 22 and the like are the semiconductor fine particles. It is passed to the conduction band 21 and further diffuses to reach the conductive layer 10. At this time, the dye 22 is an oxidant. In the photovoltaic cell, the electrons in the conductive layer 10 return to the oxidized form of the dye 22 through the counter electrode conductive layer 40 and the charge transport layer 30 while working in the external circuit, and the dye 22 is regenerated. The photosensitive layer 20 functions as a negative electrode, and the counter electrode conductive layer 40 functions as a positive electrode. At each layer boundary (for example, the boundary between the conductive layer 10 and the photosensitive layer 20, the boundary between the photosensitive layer 20 and the charge transport layer 30, the boundary between the charge transport layer 30 and the counter conductive layer 40, etc.) They may be diffusively mixed with each other. Each layer will be described in detail below.
[0041]
(A) Conductive support
The conductive support is composed of (1) a single layer of a conductive layer or (2) two layers of a conductive layer and a substrate. In the case of (1), as the material of the conductive layer, the conductive layer can have sufficient strength and hermeticity and has conductivity (for example, platinum, gold, silver, copper, zinc, titanium, aluminum, A metal material such as an alloy containing these can be used. In the case of (2), a substrate having a conductive layer made of a conductive agent on the photosensitive layer side can be used as the conductive support. Examples of preferable conductive agents include metals (platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon and conductive metal oxides (indium-tin composite oxide, tin oxide doped with fluorine, etc.) Is mentioned. The thickness of the conductive layer is preferably about 0.02 to 10 μm.
[0042]
The lower the surface resistance of the conductive support, the better. This surface resistance is preferably 100Ω / □ or less, more preferably 40Ω / □ or less. The lower limit of the surface resistance is not particularly limited, but is usually about 0.1Ω / □.
[0043]
When irradiating light from the conductive support side, the conductive support is preferably substantially transparent. Substantially transparent means that the light transmittance is 10% or more. The light transmittance of the conductive support is preferably 50% or more, particularly preferably 70% or more.
[0044]
As the transparent conductive support, one formed by applying a transparent conductive layer made of a conductive metal oxide on the surface of a transparent substrate made of glass, plastic, or the like by vapor deposition or the like can be preferably used. Examples of a preferable material for forming the transparent conductive layer include fluorine-doped tin dioxide. As the transparent substrate, a glass substrate made of soda lime float glass advantageous in terms of cost and strength, a transparent polymer film useful for obtaining a flexible photoelectric conversion element at low cost, and the like can be used. Examples of materials forming the transparent polymer film include tetraacetylcellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), Examples include polyarylate (PAr), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy resin. In order to ensure sufficient transparency, the amount of the conductive metal oxide applied is 1 m of glass or plastic substrate.²It is preferably 0.01 to 100 g per unit.
[0045]
For the purpose of reducing the resistance of the transparent conductive support, a metal lead can be used as a current collector. The metal lead is preferably made of a metal such as platinum, gold, nickel, titanium, aluminum, copper, or silver, and particularly preferably made of aluminum or silver. It is preferable that a metal lead is disposed on the transparent substrate by vapor deposition, sputtering, or the like, and a transparent conductive layer made of tin oxide doped with fluorine, ITO film, or the like is disposed thereon. It is also preferable that a metal lead is provided on the transparent conductive layer after the transparent conductive layer is provided on the transparent substrate. The decrease in the amount of incident light due to the installation of the metal lead is preferably within 10%, more preferably 1 to 5%.
[0046]
(B) Photosensitive layer
In the photosensitive layer, the semiconductor fine particles act as a photoconductor, absorb light and separate charges to generate electrons and holes. In the dye-sensitized semiconductor fine particles, light absorption and generation of electrons and holes thereby occur mainly in the dye, and the semiconductor fine particles play a role of receiving and transmitting these electrons or holes. The semiconductor used in the present invention is preferably an n-type semiconductor which gives an anode current by conducting electrons as carriers under photoexcitation. Preferred embodiments and formation methods of the semiconductor and porous semiconductor fine particle layer used in the photosensitive layer are as described in the column “[1] Method for producing semiconductor fine particle film”.
[0047]
(1) Processing
In the present invention, the semiconductor fine particles used for the photosensitive layer may be treated with a solution of a metal compound. As the metal compound, for example, a metal alkoxide or halide selected from the group consisting of scandium, yttrium, lanthanoid, zirconium, hafnium, niobium, tantalum, gallium, indium, germanium, and tin can be used. The metal compound solution (treatment liquid) is usually an aqueous solution or an alcohol solution. Note that “treatment” means an operation of bringing the semiconductor fine particles into contact with the treatment liquid for a certain period of time before adsorbing the pigment to the semiconductor fine particles. The metal compound may or may not be adsorbed on the semiconductor fine particles after contact. The treatment is preferably performed after the semiconductor fine particle layer is formed.
[0048]
As a specific method for the treatment, a method (immersion method) in which the semiconductor fine particles are immersed in the treatment liquid is given as a preferred example. Moreover, the method (spray method) which sprays a process liquid in a spray form for a fixed time is also applicable. The temperature (immersion temperature) of the treatment liquid when performing the immersion method is not particularly limited, but is typically −10 to 70 ° C., and preferably 0 to 40 ° C. The treatment time is also not particularly limited, and is typically 1 minute to 24 hours, preferably 30 minutes to 15 hours. After the immersion, the semiconductor fine particles may be washed with a solvent such as distilled water. Moreover, you may bake in order to strengthen the coupling | bonding of the substance adhering to semiconductor fine particle by the immersion process. The firing conditions may be set similarly to the above-described heat treatment conditions.
[0049]
(2) Dye
The sensitizing dye used in the photosensitive layer is not particularly limited as long as it has absorption characteristics in the visible range and near-infrared range and can sensitize a semiconductor. However, a metal complex dye, a methine dye, a porphyrin dye, and a phthalocyanine dye Can be preferably used, among which metal complex dyes are more preferable, and ruthenium complex dyes are particularly preferable. Phthalocyanines, naphthalocyanines, metal phthalocyanines, metal naphthalocyanines, porphyrins such as tetraphenylporphyrin and tetraazaporphyrin, metal porphyrins, derivatives thereof, and the like can also be used. Dyes used for dye lasers can also be used in the present invention. Moreover, in order to make the wavelength range of photoelectric conversion as wide as possible and increase the conversion efficiency, two or more kinds of dyes can be used in combination. In this case, it is possible to select the dye to be used in combination and its ratio so as to match the wavelength range and intensity distribution of the target light source.
[0050]
The dye preferably has a suitable interlocking group having an adsorption ability to the surface of the semiconductor fine particles. Examples of preferred linking groups include -COOH group, -OH group, -SO₂H group, -P (O) (OH)₂Group and -OP (O) (OH)₂And chelating groups having π conductivity such as oximes, dioximes, hydroxyquinolines, salicylates and α-ketoenolates. -COOH group, -P (O) (OH)₂Group and -OP (O) (OH)₂The group is particularly preferred. These bonding groups may form a salt with an alkali metal or the like, or may form an internal salt. In the case of a polymethine dye, if the methine chain contains an acidic group as in the case where the methine chain forms a squarylium ring or a croconium ring, this part may be used as a linking group. Hereinafter, preferred sensitizing dyes used in the photosensitive layer will be specifically described.
[0051]
(a) Metal complex dye
The metal atom of the metal complex dye used in the present invention is preferably ruthenium Ru. Examples of ruthenium complex dyes include U.S. Pat.Nos. 4927721, 4684537, 5084365, 5350644, 5463057, 5525440, JP 7-249790, JP 10-504512, WO 98 / No. 50393, JP-A No. 2000-26487 and the like. Specific examples of preferable metal complex dyes include those described in paragraph numbers 0051 to 0057 of JP-A No. 2001-320068. The most typical metal complex dyes include D-1 and D-2 below.
[0052]
[Chemical 1]

[0053]
(b) Methine dye
Preferred methine dyes are polymethine dyes such as cyanine dyes, merocyanine dyes and squarylium dyes. Examples of preferable polymethine dyes are described in JP-A Nos. 11-35836, 11-158395, 11-163378, 11-214730, 11-214731, European Patents 892411 and 918441. Pigments. For the synthesis of these polymethine dyes, see FM Hamer, “Heterocyclic Compounds-Cyanine Dyes and Related Compounds”, John Willie. "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry" by John Wiley & Sons, New York, London (1964), DM Sturmer Compounds-Special topics in Heterocyclic Chemistry ”, Chapter 18, Section 14, pp. 482-515, John Wiley & Sons, New York, London (1977),“ Rods Chemistry ”・ Rodd's Chemistry of Carbon Compounds ", 2nd. Ed., Vol. IV, part B, Chapter 15, pages 369-422, Elsevier Science Publishing Company Inc., New York (1977) , British Patent No. 1,077,611, Ukrainskii Khimicheskii Zhurnal, Vol. 40, No. 3, pp. 253-258, Dyes and Pigments, Vol. 21, pp. 227-234, and references cited therein.
[0054]
(3) Adsorption of dye on semiconductor fine particle film
When adsorbing the dye to the semiconductor fine particle film, a method of immersing a conductive support having a well-dried semiconductor fine particle film in a dye solution or a method of applying a dye solution to the semiconductor fine particle film is used. it can. In the case of the former method, a dipping method, a dip method, a roller method, an air knife method, etc. can be used. When the immersion method is used, the adsorption of the dye may be performed at room temperature or may be performed by heating and refluxing as described in JP-A-7-249790. In the case of the latter method, a wire bar method, a slide hopper method, an extrusion method, a curtain method, a spin method, a spray method, or the like can be used. In addition, a dye can be applied in an image form by an inkjet method or the like, and the image itself can be used as a photoelectric conversion element.
[0055]
Solvents used for the dye solution (adsorption solution) are preferably alcohols (methanol, ethanol, t-butanol, benzyl alcohol, etc.), nitriles (acetonitrile, propionitrile, 3-methoxypropionitrile, etc.), nitromethane, Halogenated hydrocarbons (dichloromethane, dichloroethane, chloroform, chlorobenzene, etc.), ethers (diethyl ether, tetrahydrofuran, etc.), dimethyl sulfoxide, amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), N -Methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, esters (ethyl acetate, butyl acetate, etc.), carbonates (diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), ketones (acetone, 2 -Butanone, cyclohexanone, etc.), It is a hydrocarbon (hexane, petroleum ether, benzene, toluene, etc.) or a mixed solvent thereof.
[0056]
The amount of dye adsorbed is the unit area of the semiconductor fine particle film (1 m²) Is preferably 0.01 to 100 mmol. The amount of the dye adsorbed on the semiconductor fine particles is preferably 0.01 to 1 mmol per 1 g of the semiconductor fine particles. By using such an amount of adsorbed dye, the effect of sensitizing the semiconductor fine particles can be sufficiently obtained. If the amount of dye adsorbed is too small, the sensitizing effect will be insufficient, and if the amount of dye adsorbed is too large, the dye not attached to the semiconductor will float and the sensitizing effect will be reduced. In order to increase the adsorption amount of the dye, it is preferable to heat-treat the semiconductor fine particles before the adsorption. In order to prevent water from adsorbing on the surface of the semiconductor fine particles, it is preferable to quickly adsorb the dye when the temperature of the semiconductor fine particle film is between 60 to 150 ° C. without returning to room temperature after the heat treatment.
[0057]
In order to reduce the interaction such as aggregation between the dyes, a colorless compound having properties as a surfactant may be added to the dye adsorbing liquid and co-adsorbed on the semiconductor fine particles. Examples of such colorless compounds include steroid compounds having a carboxyl group or a sulfo group (cholic acid, deoxycholic acid, chenodeoxycholic acid, taurodeoxycholic acid, etc.), sulfonates as described below, and the like. .
[0058]
[Chemical 2]

[0059]
It is preferable to remove the unadsorbed dye by washing immediately after the adsorption step. Cleaning is preferably performed in a wet cleaning tank using an organic solvent such as acetonitrile or an alcohol solvent.
[0060]
After adsorbing the dye, the fine particles of the semiconductor particles are formed using amines, quaternary ammonium salts, ureido compounds having at least one ureido group, silyl compounds having at least one silyl group, alkali metal salts, alkaline earth metal salts, etc. The surface may be treated. Examples of preferred amines include pyridine, 4-t-butylpyridine, polyvinylpyridine and the like. Examples of preferable quaternary ammonium salts include tetrabutylammonium iodide and tetrahexylammonium iodide. These may be used by dissolving in an organic solvent, or may be used as they are in the case of a liquid.
[0061]
(C) Charge transport layer
The charge transport layer contains a charge transport material having a function of replenishing electrons to the oxidant of the dye. The charge transport material used in the present invention may be (i) a charge transport material related to ions, or (ii) a charge transport material related to carrier movement in a solid. (i) Charge transport materials involving ions include molten salt electrolyte compositions containing redox counter ions, solutions in which redox pair ions are dissolved (electrolytic solutions, electrolyte solutions), and redox couple solutions in polymer matrix. (Ii) charge transport materials that involve carrier movement in solids include electron transport materials and hole transport materials, and the like. It is done. A plurality of these charge transport materials may be used in combination. In the present invention, it is preferable to use a molten salt electrolyte composition or a gel electrolyte composition for the charge transport layer.
[0062]
(1) Molten salt electrolyte composition
The molten salt electrolyte composition includes a molten salt. The molten salt electrolyte composition is preferably liquid at room temperature. The molten salt as the main component is a liquid at room temperature or is an electrolyte having a low melting point, and typical examples thereof include WO95 / 18456, JP-A-8-259543, Electrochemistry, Vol. 65, No. 11. , P. 923 (1997), and the like, and pyrazonium salts, imidazolium salts, and triazolium salts. The melting point of the molten salt is preferably 50 ° C. or less, and particularly preferably 25 ° C. or less. Specific examples of the molten salt are described in detail in JP-A-2001-320068, paragraph numbers 0066 to 0082.
[0063]
The molten salt may be used alone or in combination of two or more. Also, LiI, NaI, KI, LiBF_Four, CF_ThreeCOOLi, CF_ThreeAlkali metal salts such as COONa, LiSCN and NaSCN can also be used in combination. The addition amount of the alkali metal salt is preferably 2% by mass or less, more preferably 1% by mass or less, based on the entire composition. Moreover, it is preferable that 50 mol% or more of the anions contained in the molten salt electrolyte composition are iodide ions.
[0064]
Usually, the molten salt electrolyte composition contains iodine. The iodine content is preferably 0.1 to 20% by mass and more preferably 0.5 to 5% by mass with respect to the entire molten salt electrolyte composition.
[0065]
The molten salt electrolyte composition preferably has low volatility and preferably does not contain a solvent. Even when a solvent is added, the amount of the solvent added is preferably 30% by mass or less based on the entire molten salt electrolyte composition. The molten salt electrolyte composition may be used after gelation as described below.
[0066]
(2) Electrolyte
The electrolytic solution is preferably composed of an electrolyte, a solvent, and an additive. Examples of electrolytes used in the electrolyte include I₂And iodide (LiI, NaI, KI, CsI, CaI₂A combination of metal iodides such as tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide and other quaternary ammonium compound iodine salts), Br₂And bromide (LiBr, NaBr, KBr, CsBr, CaBr₂A combination of metal bromides such as tetraalkylammonium bromide, pyridinium bromide, etc., metal complexes such as ferrocyanate-ferricyanate and ferrocene-ferricinium ion, sodium polysulfide, alkyl Examples thereof include sulfur compounds such as thiol-alkyl disulfides, viologen dyes, hydroquinone-quinones, and the like. Above all, I₂An electrolyte in which LiI or a quaternary ammonium compound iodine salt such as pyridinium iodide or imidazolium iodide is combined is preferable. The electrolyte may be used as a mixture.
[0067]
The electrolyte concentration in the electrolytic solution is preferably 0.1 to 10 M, more preferably 0.2 to 4 M. Moreover, the preferable addition density | concentration of iodine when adding iodine to electrolyte solution is 0.01-0.5M.
[0068]
The solvent used in the electrolytic solution is preferably a compound that has low viscosity and improved ion mobility, or has a high dielectric constant and improved effective carrier concentration, and can exhibit excellent ion conductivity. Examples of such solvents include carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, ether compounds such as dioxane and diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether , Chain ethers such as polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether, alcohols such as methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether and polypropylene glycol monoalkyl ether, ethylene Glycol, propylene glycol, polyethylene glycol, polypropylene glycol Lumpur, polyhydric alcohols such as glycerin, acetonitrile, glutarodinitrile, methoxy acetonitrile, propionitrile, nitrile compounds such as benzonitrile, dimethyl sulfoxide, aprotic polar substances such as sulfolane, water and the like. These solvents can also be used as a mixture.
[0069]
Further, basic compounds such as tert-butylpyridine, 2-picoline and 2,6-lutidine as described in J. Am. Ceram. Soc., 80 (12) 3157-3171 (1997) are mentioned above. It is preferable to add to the molten salt electrolyte composition or electrolyte solution. A preferable concentration range when adding the basic compound to the electrolytic solution is 0.05 to 2M. When added to the molten salt electrolyte composition, the basic compound preferably has an ionic group. The mass ratio of the basic compound to the entire molten salt electrolyte composition is preferably 1 to 40% by mass, more preferably 5 to 30% by mass.
[0070]
(3) Gel electrolyte composition
In the present invention, the molten salt electrolyte composition or the electrolytic solution is gelated (solidified) by a method such as addition of a polymer, addition of an oil gelling agent, polymerization including polyfunctional monomers, or a crosslinking reaction of the polymer. You can also. In the case of gelation by adding a polymer, the compounds described in “Polymer Electrolyte Reviews-1 and 2” (JR MacCallum and CA Vincent, edited by ELSEVIER APPLIED SCIENCE) can be used. Particularly, polyacrylonitrile and polyfluoride can be used. Vinylidene can be preferably used. In the case of gelation by adding an oil gelling agent, Journal of Industrial Science (J. Chem. Soc. Japan, Ind. Chem. Sec.), 46, 779 (1943), J. Am. Chem. Soc., 111, 5542 ( 1989), J. Chem. Soc., Chem. Commun., 1993, 390, Angew. Chem. Int. Ed. Engl., 35, 1949 (1996), Chem. Lett., 1996, 885, and J. Chem Although compounds described in Soc., Chem. Commun., 1997, 545 can be used, it is preferable to use compounds having an amide structure. An example of gelling the electrolytic solution is described in JP-A No. 11-185863, and an example of gelling the molten salt electrolyte is also described in JP-A No. 2000-58140, which can also be applied to the present invention.
[0071]
Moreover, when making it gelatinize by the crosslinking reaction of a polymer, it is desirable to use together the polymer and crosslinking agent containing the reactive group which can be bridge | crosslinked. In this case, preferred crosslinkable reactive groups are amino groups and nitrogen-containing heterocycles (pyridine ring, imidazole ring, thiazole ring, oxazole ring, triazole ring, morpholine ring, piperidine ring, piperazine ring, etc.), and preferred bridges. The agent is a bifunctional or higher functional reagent capable of electrophilic reaction with nitrogen atom (halogenated alkyls, halogenated aralkyls, sulfonic acid esters, acid anhydrides, acid chlorides, isocyanate compounds, α, β Saturated sulfonyl compounds, α, β-unsaturated carbonyl compounds, α, β-unsaturated nitrile compounds, etc.). The crosslinking techniques described in JP-A Nos. 2000-17076 and 2000-86724 can also be applied.
[0072]
(4) Hole transport material
In the present invention, instead of an ion conductive electrolyte such as a molten salt, an organic solid hole transport material, an inorganic solid hole transport material, or a material in which both are combined can be used.
[0073]
(a) Organic hole transport material
Examples of organic hole transport materials that can be preferably used in the present invention include J. Hagen, et al., Synthetic Metal, 89, 215-220 (1997), Nature, Vol. 395, 8 Oct., p583-585 ( 1998), WO 97/10617, JP-A-59-194393, JP-A-5-34681, U.S. Pat.No. 4,923,774, JP-A-4-308688, U.S. Pat.No. 4,764,625, JP-A-3-269084, 4 -129271, 4-175395, 4-264189, 4-90851, 4-364153, 4-364153, 5-54773, 5-239455, 5-320634, 6-1972 Aromatic amines described in JP-A-11-149821, JP-A-11-148067, JP-A-11-176489, etc. And triphenylene derivatives. Also, Adv. Mater., 9, No. 7, p557 (1997), Angew. Chem. Int. Ed. Engl., 34, No. 3, p303-307 (1995), JACS, Vol. 120, No. 4, p664-672 (1998) etc., oligothiophene compounds described in K. Murakoshi, et al., Chem. Lett. P471 (1997), “Handbook of Organic Conductive Molecules and Polymers, Vol. 1, 2,3,4 "(by NALWA, published by WILEY), polyacetylene and derivatives thereof, poly (p-phenylene) and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, polythienylene vinylene and derivatives thereof, Conductive polymers such as polythiophene and derivatives thereof, polyaniline and derivatives thereof, polytoluidine and derivatives thereof can also be preferably used.
[0074]
Contains cation radicals such as tris (4-bromophenyl) aminium hexachloroantimonate to control the dopant level as described in Nature, Vol. 395, 8 Oct., p583-585 (1998) The compound to be added may be added to the hole transport material. Li [(CF is also used to control the potential of the oxide semiconductor surface (space charge layer compensation)._ThreeSO₂)₂A salt such as N] may be added.
[0075]
(b) Inorganic hole transport material
A p-type inorganic compound semiconductor can be used as the inorganic hole transport material, and the band gap is preferably 2 eV or more, more preferably 2.5 eV or more. In addition, the ionization potential of the p-type inorganic compound semiconductor needs to be smaller than the ionization potential of the dye adsorption electrode in order to reduce the holes of the dye. Although the preferred range of the ionization potential of the p-type inorganic compound semiconductor varies depending on the dye used, it is generally preferably 4.5 to 5.5 eV, more preferably 4.7 to 5.3 eV. A preferred p-type inorganic compound semiconductor is a compound semiconductor containing monovalent copper, and examples thereof include CuI, CuSCN, and CuInSe.₂, Cu (In, Ga) Se₂, CuGaSe₂, Cu₂O, CuS, CuGaS₂, CuInS₂, CuAlSe₂Etc. Among these, CuI and CuSCN are preferable, and CuI is most preferable. Examples of other p-type inorganic compound semiconductors include GaP, NiO, CoO, FeO, Bi₂O_Three, MoO₂, Cr₂O_ThreeEtc.
[0076]
(5) Formation of charge transport layer
The charge transport layer can be formed by one of two methods. One is a method in which a counter electrode is first bonded onto the photosensitive layer, and a liquid charge transport layer is sandwiched between the gaps. The other is a method in which a charge transport layer is directly provided on the photosensitive layer, and the counter electrode is subsequently provided.
[0077]
In the case of the former method, when the charge transport layer is sandwiched, a normal pressure process using capillary action due to immersion or the like, or a vacuum process in which the gas phase in the gap is replaced with a liquid phase at a pressure lower than normal pressure can be used.
[0078]
In the latter method, when a wet charge transport layer is used, a counter electrode is usually applied in an undried state to prevent liquid leakage at the edge. Moreover, when using a gel electrolyte composition, you may solidify by methods, such as superposition | polymerization, after apply | coating this with a wet process. Solidification may be performed before or after applying the counter electrode. In the case of forming a charge transport layer made of an electrolytic solution, a wet organic hole transport material, a gel electrolyte composition, or the like, the same method as the method for forming a semiconductor fine particle layer described above can be used.
[0079]
When a solid electrolyte composition or a solid hole transport material is used, a charge transport layer can be formed by a dry film forming process such as a vacuum deposition method or a CVD method, and then a counter electrode can be provided. The organic hole transport material can be introduced into the electrode by a vacuum deposition method, a casting method, a coating method, a spin coating method, a dipping method, an electrolytic polymerization method, a photoelectrolytic polymerization method, or the like. The inorganic solid compound can be introduced into the electrode by a casting method, a coating method, a spin coating method, a dipping method, an electrolytic deposition method, an electroless plating method, or the like.
[0080]
(D) Counter electrode
Similar to the conductive support described above, the counter electrode may have a single-layer structure of a counter electrode conductive layer made of a conductive material, or may be composed of a counter electrode conductive layer and a support substrate. Examples of the conductive agent used for the counter electrode conductive layer include metal (platinum, gold, silver, copper, aluminum, magnesium, indium, etc.), carbon, conductive metal oxide (indium-tin composite oxide, fluorine-doped tin oxide, etc.) ) And the like. Among these, platinum, gold, silver, copper, aluminum and magnesium are preferable. The substrate used for the counter electrode is preferably a glass substrate or a plastic substrate, and can be used by applying or vapor-depositing the above-mentioned conductive agent. The thickness of the counter electrode conductive layer is not particularly limited, but is preferably 3 nm to 10 μm. The surface resistance of the counter electrode conductive layer is preferably as low as possible, preferably 50Ω / □ or less, more preferably 20Ω / □ or less.
[0081]
Since light may be irradiated from either or both of the conductive support and the counter electrode, in order for light to reach the photosensitive layer, at least one of the conductive support and the counter electrode may be substantially transparent. . From the viewpoint of improving power generation efficiency, it is preferable to make the conductive support transparent so that light is incident from the conductive support side. In this case, the counter electrode preferably has a property of reflecting light. In order to obtain such properties, glass or plastic on which a metal or a conductive oxide is deposited or a metal thin film may be used as a counter electrode.
[0082]
The counter electrode may be installed by directly applying, plating or vapor-depositing (PVD, CVD) a conductive agent on the charge transport layer, or attaching the conductive layer side of the substrate having the conductive layer. As in the case of the conductive support, it is preferable to use a metal lead for the purpose of reducing the resistance of the counter electrode, particularly when the counter electrode is transparent. The preferred embodiment of the metal lead is the same as that of the conductive support.
[0083]
(E) Other layers
In order to prevent a short circuit between the counter electrode and the conductive support, it is preferable that a dense semiconductor thin film layer is preliminarily applied as an undercoat layer between the conductive support and the photosensitive layer. This method of preventing a short circuit by the undercoat layer is particularly effective when an electron transport material or a hole transport material is used for the charge transport layer. The undercoat layer is preferably TiO₂, SnO₂, Fe₂O_Three, WO_Three, ZnO or Nb₂O_FiveMore preferably TiO₂Consists of. The undercoat layer can be applied by, for example, a spray pyrolysis method described in Electrochim. Acta, 40, 643-652 (1995), a sputtering method, or the like. The thickness of the undercoat layer is preferably 5 to 1000 nm, more preferably 10 to 500 nm.
[0084]
In addition, a functional layer such as a protective layer or an antireflection layer may be provided on the outer surface of one or both of the conductive support and the counter electrode, between the conductive layer and the substrate, or in the middle of the substrate. The method for forming these functional layers can be appropriately selected from a coating method, a vapor deposition method, a pasting method, and the like according to the material.
[0085]
(F) Specific example of internal structure of photoelectric conversion element
As described above, the internal structure of the photoelectric conversion element can take various forms depending on the purpose. If roughly divided into two, a structure that allows light to enter from both sides and a structure that allows only one side are possible. Examples of a preferable internal structure of the photoelectric conversion element of the present invention are shown in FIG. 1 and FIGS.
[0086]
In the structure shown in FIG. 2, the photosensitive layer 20 and the charge transport layer 30 are interposed between the transparent conductive layer 10a and the transparent counter electrode conductive layer 40a, and light is incident from both sides. . In the structure shown in FIG. 3, a metal lead 11 is partially provided on a transparent substrate 50a, a transparent conductive layer 10a is provided thereon, and an undercoat layer 60, a photosensitive layer 20, a charge transport layer 30, and a counter electrode conductive layer 40 are arranged in this order. In addition, a support substrate 50 is arranged, and light is incident from the conductive layer side. The structure shown in FIG. 4 has a conductive layer 10 on a support substrate 50, a photosensitive layer 20 provided through an undercoat layer 60, a charge transport layer 30 and a transparent counter electrode conductive layer 40a, and a metal in part. The transparent substrate 50a provided with the leads 11 is disposed with the metal lead 11 side inward, and has a structure in which light enters from the counter electrode side. In the structure shown in FIG. 5, the subbing layer 60, the photosensitive layer 20 and the charge transport layer 30 are provided between a pair of metal leads 11 provided on a transparent substrate 50a and further provided with a transparent conductive layer 10a (or 40a). In this structure, light enters from both sides. In the structure shown in FIG. 6, a transparent conductive layer 10a, an undercoat layer 60, a photosensitive layer 20, a charge transport layer 30 and a counter electrode conductive layer 40 are provided on a transparent substrate 50a, and a support substrate 50 is disposed thereon. In this structure, light enters from the conductive layer side. The structure shown in FIG. 7 has a conductive layer 10 on a support substrate 50, a photosensitive layer 20 provided through an undercoat layer 60, a charge transport layer 30 and a transparent counter electrode conductive layer 40a, and a transparent substrate thereon. 50a is arranged, and light is incident from the counter electrode side. In the structure shown in FIG. 8, a transparent conductive layer 10a is provided on a transparent substrate 50a, a photosensitive layer 20 is provided via an undercoat layer 60, a charge transport layer 30 and a transparent counter electrode conductive layer 40a are provided, and a transparent layer is provided thereon. The substrate 50a is disposed, and light is incident from both sides. In the structure shown in FIG. 9, the conductive layer 10 is provided on the support substrate 50, the photosensitive layer 20 is provided via the undercoat layer 60, and the solid charge transport layer 30 is further provided. It has a metal lead 11 and has a structure in which light is incident from the counter electrode side.
[0087]
[3] Photocell
The photovoltaic cell of the present invention is one in which the photoelectric conversion element of the present invention is caused to work with an external load. Among photocells, the case where the charge transport material is mainly composed of an ion transport material is particularly called a photoelectrochemical cell, and the case where the main purpose is power generation by sunlight is called a solar cell.
[0088]
The side surface of the photovoltaic cell is preferably sealed with a polymer, an adhesive or the like in order to prevent deterioration of the constituents and volatilization of the contents. The external circuit itself connected to the conductive support and the counter electrode via a lead may be a known one.
[0089]
Even when the photoelectric conversion element of the present invention is applied to a solar cell, the structure inside the cell is basically the same as the structure of the photoelectric conversion element described above. Moreover, the dye-sensitized solar cell using the photoelectric conversion element of the present invention can basically have the same module structure as a conventional solar cell module. The solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin or protective glass, and light is taken in from the opposite side of the support substrate. It is also possible to use a transparent material such as tempered glass for the support substrate, configure a cell thereon, and take in light from the transparent support substrate side. Specifically, a module structure called a super straight type, a substrate type, a potting type, a substrate integrated module structure used in amorphous silicon solar cells, and the like are known, and dye sensitization using the photoelectric conversion element of the present invention is known. As for the type solar cell, the module structure can be appropriately selected according to the purpose of use, the place of use and the environment. Specifically, the structures and embodiments described in Japanese Patent Application Nos. 11-8457 and 2000-268892 are preferable.
[0090]
【Example】
Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
[0091]
1. Preparation of titanium dioxide particle coating solution
Titanium dioxide particles with a titanium dioxide concentration of 11% by mass in the same manner as described in Barbe et al., Journal of American Ceramic Society, Volume 80, page 3157, except that the autoclave temperature was 230 ° C. A dispersion was obtained. The average particle size of the titanium dioxide particles in this dispersion was about 10 nm. To this dispersion, 20% by mass of polyethylene glycol (molecular weight 20000, manufactured by Wako Pure Chemical Industries, Ltd.) with respect to titanium dioxide was added and mixed to obtain a titanium dioxide particle coating solution.
[0092]
2. Production of titanium dioxide electrode
Transparent conductive glass coated with tin oxide doped with fluorine (Nippon Sheet Glass Co., Ltd., surface resistance: approx. 10Ω / cm²) Apply the above titanium dioxide particle coating solution to the conductive surface side with a doctor blade with a wet thickness of 120μm, and dry at 25 ° C for 30 minutes. ) To form a titanium dioxide layer by heating at 450 ° C. for 30 minutes to obtain a titanium dioxide electrode. The coating amount of titanium dioxide per unit area of transparent conductive glass is 16.0 g / m²The thickness of the titanium dioxide layer was about 11 μm. Further, when the roughness factor of the obtained titanium dioxide layer was measured by the BET method, it was about 1000.
[0093]
3. Cathodic electrodeposition and dye adsorption
The titanium dioxide electrode was cut to a size of 10 mm × 12 mm. However, the area of the titanium dioxide layer was 10 mm × 10 mm. Subsequently, the titanium dioxide electrode was subjected to cathode electrodeposition treatment by a three-pole method using a potentiostat using platinum as a counter electrode and a silver / silver chloride electrode as a reference electrode. 0.02 M metal nitrate Zn (NO_Three)₂Using an electrolyte consisting of an aqueous solution containing 0.02 M lithium nitrate and 0.01 M nitric acid, the titanium dioxide electrode was polarized on the cathode side in this electrolyte, washed sequentially with water and acetonitrile, and baked at 450 ° C. for 30 minutes did. The cathode electrodeposition was performed under the conditions of a polarization voltage of −1.1 V and an electrodeposition time of 30 minutes. The weight of the semiconductor fine particle layer per unit area is 17.5 g / m by cathodic electrodeposition treatment.²However, the roughness factor hardly changed.
After completion of the firing, the titanium dioxide electrode subjected to the cathode electrodeposition treatment was cooled and immersed in a dye adsorbing solution containing the following dye 1 for 3 hours. Immersion was performed while shaking with a shaker. The temperature of the dye adsorbing solution is 45 ° C., the concentration of the dye 1 in the dye adsorbing solution is 0.3 mmol / l, and the solvent is a mixed solvent of ethanol, 2-methyl-2-propanol and acetonitrile (ethanol: 2-methyl-2 -Propanol: acetonitrile = 1: 1: 2 (volume ratio)). After soaking, it was washed successively with ethanol and acetonitrile and dried in a dark place under a nitrogen stream to obtain a dye-adsorbed titanium dioxide electrode E-4.
[0094]
[Chemical Formula 3]

[0095]
Further, except that the metal nitrate and solvent used in the electrolyte solution and the electrodeposition conditions were changed as shown in Table 1 below, electrodes E-1 to E-3 and E -5 to E-20 were produced. Table 1 shows the weight of the semiconductor fine particle layer per unit area of these electrodes. As with E-4, the roughness factor hardly changed. In addition, the washing | cleaning after polarization was sequentially performed with the solvent and acetonitrile which were used for the electrolyte solution. In preparing the electrodes E-3, E-5, and E-8, the dye 1 was added to the electrolyte solution used for cathode electrodeposition at the concentrations shown in Table 1.
[0096]
[Table 1]

[0097]
4). Production of photoelectric conversion element
The electrode E-1 was superposed on a 15 mm × 20 mm platinum-deposited glass. Next, an electrolyte solution (1,3-dimethylimidazolium iodide (0.6 mol / l), lithium iodide (0.1 mol / l) and iodine (0.05 mol / l) using a capillary phenomenon in the gap between the two glasses) (Sodium chloride solution) was soaked and introduced into the electrode to produce a comparative photoelectric conversion element C-1. As shown in FIG. 10, this photoelectric conversion element comprises conductive glass 1 (with conductive layer 3 provided on glass 2), dye-adsorbed titanium dioxide layer 4, charge transport layer 5, platinum layer 6 and glass 7. It has a stacked structure.
Photoelectric conversion elements C-2, C-3 and C-16 for comparison were produced in the same manner as the production of the photoelectric conversion element C-1, except that the electrodes shown in Table 2 below were used instead of the electrode E-1. In addition, photoelectric conversion elements C-4 to C-15 and C-17 to C-20 of the present invention were prepared, respectively.
[0098]
5. Evaluation of photoelectric conversion efficiency
Simulated sunlight was generated by passing light from a 500 W xenon lamp (USHIO INC.) Through a spectral filter ("AM1.5" manufactured by Oriel). The intensity of this simulated sunlight is 100 mW / cm in the vertical plane.²Met. A silver paste was applied to the edge of the conductive glass of each photoelectric conversion element C-1 to C-20 to form a negative electrode, and this negative electrode and platinum-deposited glass (positive electrode) were connected to a current-voltage measuring device (Keutley SMU238 type). . The current-voltage characteristics were measured while irradiating each photoelectric conversion element with simulated sunlight vertically, and the photoelectric conversion efficiency was obtained. Table 2 shows the conversion efficiency of each photoelectric conversion element.
[0099]
[Table 2]

[0100]
As shown in Table 2, the photoelectric conversion element of the comparative exampleC-1 to C-3And compared with C-16, the photoelectric conversion elements C-4 to C-15 and C-17 to C-20 of the present invention showed excellent conversion efficiency.
[0101]
【The invention's effect】
As described above in detail, in the present invention, a high-quality semiconductor fine particle film can be obtained by performing a cathodic electrodeposition treatment, and a dye is adsorbed to the semiconductor fine particle film to form a photosensitive layer, which is excellent in conversion efficiency. A dye-sensitized photoelectric conversion element is obtained.
[Brief description of the drawings]
FIG. 1 is a partial cross-sectional view showing the structure of a preferred photoelectric conversion element of the present invention.
FIG. 2 is a partial cross-sectional view showing the structure of a preferred photoelectric conversion element of the present invention.
FIG. 3 is a partial cross-sectional view showing the structure of a preferred photoelectric conversion element of the present invention.
FIG. 4 is a partial cross-sectional view showing the structure of a preferred photoelectric conversion element of the present invention.
FIG. 5 is a partial cross-sectional view showing the structure of a preferred photoelectric conversion element of the present invention.
FIG. 6 is a partial cross-sectional view showing the structure of a preferred photoelectric conversion element of the present invention.
FIG. 7 is a partial cross-sectional view showing the structure of a preferred photoelectric conversion element of the present invention.
FIG. 8 is a partial cross-sectional view showing the structure of a preferred photoelectric conversion element of the present invention.
FIG. 9 is a partial cross-sectional view showing a structure of a preferable photoelectric conversion element of the present invention.
FIG. 10 is a partial cross-sectional view illustrating a structure of a photoelectric conversion element manufactured in an example.
[Explanation of symbols]
10 ... conductive layer
10a ・ ・ ・ Transparent conductive layer
11 ... Metal lead
20 ... Photosensitive layer
21 ... Semiconductor fine particles
22 ... Dye
23 ... Charge transport material
30 ... Charge transport layer
40 ... Counterelectrode conductive layer
40a ・ ・ ・ Transparent counter electrode conductive layer
50 ... Board
50a ・ ・ ・ Transparent substrate
60 ... Undercoat layer
1 ... conductive glass
2 ... Glass
3. Conductive layer
4 ... Dye adsorption titanium dioxide layer
5 ... Charge transport layer
6 ... Platinum layer
7 ... Glass

Claims (4)

A method for producing a semiconductor fine particle film in which a metal oxide layer is formed on a porous semiconductor fine particle layer having a roughness factor of 10 or more, the step of cathodic electrodeposition in an electrolyte solution containing a metal nitrate , and A method for producing a semiconductor fine particle film, comprising a step of firing after cathode electrodeposition .  2. The method for producing a semiconductor fine particle film according to claim 1, wherein the metal oxide layer is made of zinc oxide or titanium dioxide.  3. The method for producing a semiconductor fine particle film according to claim 1, wherein the metal oxide layer is formed by cathode electrodeposition in a titanium tetranitrate solution.  A method for producing a photoelectric conversion element comprising a photosensitive layer containing semiconductor fine particles adsorbed with a dye and a conductive support, wherein the dye is applied to the semiconductor fine particle film produced by the method according to claim 1. A method for producing a photoelectric conversion element, wherein the photosensitive layer is formed by adsorbing an organic compound.

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