JP4289823B2 - Method for producing dye-sensitized solar cell - Google Patents
Method for producing dye-sensitized solar cell Download PDFInfo
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- JP4289823B2 JP4289823B2 JP2002095763A JP2002095763A JP4289823B2 JP 4289823 B2 JP4289823 B2 JP 4289823B2 JP 2002095763 A JP2002095763 A JP 2002095763A JP 2002095763 A JP2002095763 A JP 2002095763A JP 4289823 B2 JP4289823 B2 JP 4289823B2
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、色素増感太陽電池の製造方法、特に、電子受容型の電荷輸送層、電子供給型の電荷輸送層、これら電荷輸送層間に存在する光吸収層を少なくとも有する色素増感太陽電池の製造方法に関するものである。
【０００２】
【従来の技術】
従来、光エネルギーを電気エネルギーに変換する方法としては、シリコンやガリウム−砒素等の半導体接合を用いた太陽電池が一般的である。中でも半導体のｐｎ接合を用いた単結晶シリコン太陽電池や多結晶シリコン太陽電池、ｐｉｎ接合を用いたアモルファスシリコン太陽電池がよく知られており、実用化が進みつつある。しかしながら、シリコン太陽電池は製造コストが高く、また製造自体でエネルギーを多く消費するので、導入コストや消費エネルギ−を回収するには、長期間の使用が必要がある。現在の普及のネックになっているのは主にこのコストにある。
【０００３】
一方、近年、第２世代薄膜太陽電池として、CdTeやCuIn(Ga)Se等の実用化研究も進展しているが、これらの材料系では環境問題や資源的な問題が提起されている。
【０００４】
上記半導体接合以外の方法として、半導体と電解質溶液との界面で起きる光電気化学反応を利用した湿式太陽電池が報告されている。この湿式太陽電池において用いられる酸化チタン、酸化錫等の金属酸化物半導体は、乾式太陽電池において用いられるシリコン、ガリウム−砒素等と比較して、低コストで製造が可能であり、特に酸化チタンは光電変換特性と安定性との両面において優れていることから、将来のエネルギー変換材料として期待されている。
【０００５】
しかし、酸化チタン等の安定な光半導体は、バンドギャップが３ｅＶ以上と広いため、太陽光の約４％である紫外光しか利用できず、変換効率が十分に高いとは言えなかった。
【０００６】
そこで、光半導体の表面に、色素を吸着した光化学電池（色素増感太陽電池）が研究されている。初期の頃は半導体の単結晶電極が用いられてきた。この電極としては、酸化チタン、酸化亜鉛、硫化カドミウム、酸化錫等がある。しかし、単結晶電極は色素の吸着量が少ないため、効率が低く、コストが高くなっており、半導体電極を多孔質にする試みがなされている。
【０００７】
例えば、坪村氏らは微粒子を焼結した多孔質酸化亜鉛からなる半導体電極に色素を吸着させて効率を改善した報告をしている（NATURE,261（1976）p402）。また、Graetzel氏らは色素と半導体電極を更に改善してシリコン太陽電池並みの性能が得られたことを報告している（J. Am. Chem. Soc. 115(1993)6382、米国特許第５３５０６４４号）。ここでは色素にルテニウム系色素を用い、半導体電極としてはアナターゼ型の多孔質酸化チタン（ＴｉＯ2）を用いている。
【０００８】
また、近年このGraetzel型セルを種々の形で改良した多孔質半導体電極も報告されている。例えば、酸化ニオブ微粒子を用いてGraetzel型セルを作製した特開平９−２３７６４１号公報である。更に、酸化亜鉛微粒子と酸化錫微粒子の混合により高効率のセルを作製したこともTennakone等によって報告されている（J.Chem.Soc.,Chem.Commun.,15(1999)）。
【０００９】
図８はGraetzel型の色素増感半導体電極を用いた光化学電池（以下、本願明細書中では、Graetzel型セルという）の概略構成を示す模式的な断面図である。図中６４はガラス基板、６５はその表面に形成した透明電極である。また、６１はアナターゼ型多孔質酸化チタン層であり、酸化チタン微粒子同士が接合したポーラス状の接合体から形成されている。また、６２はその酸化チタン微粒子表面に接合させた色素であり光吸収層として作用する。
【００１０】
このGraetzel型セルの動作原理について説明する。図８の左側から光が入射すると、入射光により光吸収層６２を構成する色素中の電子が励起され、酸化チタンの伝導帯に移動する。電子を失って酸化状態にある色素は迅速に電解液６３のヨウ素イオンから電子を受け取って還元され元の状態に戻る。酸化チタン層６１に注入された電子は、酸化チタン微粒子の間をホッピング伝導等の機構により移動しアノード６５に到達する。また、色素に電子を供給して酸化状態（Ｉ3 -）になったヨウ素イオンはカソード６６から電子を受け取って還元され、元の状態（Ｉ-）に戻る。
【００１１】
上記動作原理から推測できるように、色素で生成した電子とホールが効率良く分離、移動するためには、色素の励起状態の電子のエネルギー準位はTiO2の伝導帯より高い必要があり、色素のホールのエネルギー準位はレドックス準位より低い必要性がある。
【００１２】
この様なGraetzel型セルがシリコン太陽電池にとって代わるためには今まで以上に高いエネルギー変換効率や、更に高い短絡電流、開放電圧、形状因子、耐久性が必要になってくる。
【００１３】
また、一般的に半導体結晶を製造する手段としては、スパッタリング法、蒸着法、CVD法、電着法等様々な方法で現在作製可能である。例えば、大面積の導電性基板上に膜状の酸化亜鉛を均一に製造できる方法が、特開平８−２１７４４３号公報や特開平８−２６０１７５号公報に記載されている。
【００１４】
更に、酸化亜鉛の針状結晶を作製する手段として、"J. Crystal Growth, 102, 965, (1990)"に、金属Znの気相酸化を用いてテトラポッド状の針状酸化亜鉛結晶を920度で製造したことが報告されている。
【００１５】
また、"Jpn.J.Appl.Phys.,Vol.38(1999)pp.L586"に、大気開放型のCVD法を用いて直径1．5μmで、長さが100μmに達する酸化亜鉛の針状結晶を製造できることが報告されている。
【００１６】
更に、基体をエッチングする手段としては、一般的に気相若しくは液相で行われる。気相でのエッチングとは、主に減圧下でのプラズマエッチングが挙げられ、液相でのエッチングとは、酸やアルカリ溶液が金属や半導体、絶縁物を除去する為に使用される手段である。また、液相でのエッチングは化学エッチングと電解エッチングに分けられ、これらは一般的な手法として広く用いられている。
【００１７】
【発明が解決しようとする課題】
しかしながら、上記従来技術の色素増感半導体電極は、チタニア微粒子を分散させた溶液を透明導電膜付きの基板上に塗布し、乾燥後に高温焼結して得られた酸化チタン膜を用いていたために、透明電極とチタニア微粒子の界面や、酸化チタン微粒子間の界面において電子伝導が散乱される傾向があった。このため、透明導電膜と酸化チタン膜との界面、及び酸化チタン微粒子同士の界面に生じる内部抵抗が大きくなり、その結果、光電変換効率が低下する原因となっていた。これは、チタニア以外の微粒子を用いた場合も同様であった。
【００１８】
また、色素増感半導体電極が微粒子の焼結体で構成されていたため、透明電極近傍の微粒子には色素を吸着させるのに時間がかかり、また電解液中のイオンの拡散も遅い等の問題点があった。
【００１９】
本発明は、上記従来の問題点に鑑みなされたもので、その目的は、電子の授受をスムーズに行うことができ、変換効率が高い色素増感太陽電池の製造方法を提供することにある。
【００２０】
また、本発明の別の目的は、色素等の光吸収層や電解液等の電荷輸送層のしみ込みや移動が速い半導体電極を有する色素増感太陽電池の製造方法を提供することにある。
【００２１】
更に、本発明の別の目的は、短絡電流値が大きい色素増感太陽電池の製造方法を提供することにある。
【００２４】
【課題を解決するための手段】
本発明は、２つの基板の間に、ｎ型の電荷輸送層、光吸収層、ｐ型の電荷輸送層を有する色素増感太陽電池の製造方法において、針状結晶をエッチングすることにより少なくとも側面に凹凸を有する針状結晶を形成する工程を含み、前記側面に凹凸を有する針状結晶を前記ｎ型の電荷輸送層とすることを特徴とする。
【００２５】
また、本発明は、２つの基板の間に、ｎ型の電荷輸送層、光吸収層、ｐ型の電荷輸送層を有する色素増感太陽電池の製造方法において、針状結晶をエッチングすることにより少なくとも側面に凹凸を有する針状結晶を形成する工程、前記凹凸を有する針状結晶の表面に半導体結晶を吸着させて半導体混合結晶を形成する工程を含み、前記半導体混合結晶を前記ｎ型の電荷輸送層とすることを特徴とする。
【００２６】
また、本発明は、基板上に針状結晶を形成する工程、前記針状結晶をエッチングすることにより少なくとも側面に凹凸を有する針状結晶を形成する工程、前記側面に凹凸を有する針状結晶上に光吸収層を形成する工程、前記光吸収層が形成された針状結晶にｐ型の電荷輸送層を形成する工程、前記電荷輸送層が形成された針状結晶を他方側の基板で挟んで光電変換セルを作製する工程を含むことを特徴とする。
【００２７】
また、本発明は、針状結晶をエッチングすることにより少なくとも側面に凹凸を有する針状結晶を作製する工程、前記側面に凹凸を有する針状結晶を含む混合物を基板上に塗布して焼成する工程、前記基板上に形成された針状結晶上に光吸収層を形成する工程、前記光吸収層が形成された針状結晶にｐ型の電荷輸送層を形成する工程、前記電荷輸送層が形成された針状結晶を他方側の基板で挟んで光電変換セルを作製する工程を含むことを特徴とする。
【００２８】
また、本発明は、基板上に針状結晶を形成する工程、前記針状結晶をエッチングすることにより少なくとも側面に凹凸を有する針状結晶を形成する工程、前記側面に凹凸を有する針状結晶の表面に半導体結晶を吸着させて半導体混合結晶を形成する工程、前記半導体混合結晶上に光吸収層を形成する工程、前記光吸収層が形成された前記半導体混合結晶にｐ型の電荷輸送層を形成する工程、前記電荷輸送層が形成された前記半導体混合結晶を他方側の基板で挟んで光電変換セルを作製する工程を含むことを特徴とする。
【００２９】
また、本発明は、基板上に針状結晶を形成する工程、前記針状結晶の表面に半導体結晶を吸着させて半導体混合結晶を形成する工程、前記半導体混合結晶をエッチングすることにより少なくとも側面に凹凸を形成する工程、前記側面に凹凸を有する前記半導体混合結晶上に光吸収層を形成する工程、前記光吸収層が形成された前記半導体混合結晶にｐ型の電荷輸送層を形成する工程、前記電荷輸送層が形成された前記半導体混合結晶を他方側の基板で挟んで光電変換セルを作製する工程を含むことを特徴とする。
【００３０】
また、本発明は、針状結晶を含む混合物を基板上に塗布して焼成する工程、前記焼成後の針状結晶をエッチングすることにより少なくとも側面に凹凸を有する針状結晶を作製する工程、前記基板上に形成された針状結晶上に光吸収層を形成する工程、前記光吸収層が形成された針状結晶にｐ型の電荷輸送層を形成する工程、前記電荷輸送層が形成された針状結晶を他方側の基板で挟んで光電変換セルを作製する工程を含むことを特徴とする。
【００３１】
【発明の実施の形態】
以下、本発明の実施形態について図面を参照して詳細に説明する。本発明にかかる光電変換装置の主たる特徴は、電子やホールの授受及び移動がスムーズに行われ、内部抵抗や再結合確率が低く変換効率が高い電子移動型の電荷輸送層とすることである。この光電変換装置及びその製造方法に関して、以下に詳細に説明する。
【００３２】
まず、本発明による光電変換装置の一実施形態の構成について説明する。前述したGraetzel型セルを始めとする色素増感型セルでは、色素１層の光吸収率が十分ではないために、表面積を大きくして実質的な光吸収量を大きくしている。この表面を大きくする方法には上記Graetzel型セルの様に微粒子を分散、接合する方法が簡単ではあるが、電子の移動が十分効率的ではない問題がある。
【００３３】
例えば、上記Graetzel型セルにおいて酸化チタン半導体層６１を有するアノード透明電極６５側から光入射を行った場合と、カソード透明電極６６側から光入射を行った場合を比較すると、前者の方が光電変換効率が良い場合が多い。これは、単なる色素による光吸収量の差だけではなく、光吸収により励起された電子が酸化チタン半導体層６１を移動してアノード透明電極６５に到達する確率が、透明電極から光励起位置が離れるに従って低下していくことを示唆している。即ち、結晶粒界が多いGraetzel型セルでは十分効率的な電子移動が達成されていないことを示唆している。
【００３４】
図１（ａ）は本実施形態による光電変換装置の一実施形態の構成を示す断面図である。また、図１（ｂ）は図１（ａ）の電極付き基板１３を除く部分を詳細に示す断面図である。図１において、１０は電極付き基板、１１は吸収層修飾半導体結晶層、１２は電荷輸送層、１３は電極付き基板である。電極付き基板１０は、図１（ｂ）に示すように、例えば、透明電極層１５が設けられたガラス基板１４からなっている。
【００３５】
また、電極付き基板１３は同様に電極と基板を含んでいるが、図面の右側から光を入射する場合は、電極層１５と基板１４は透光性とする必要がある。光を入射しない場合には、その限りではない。また、吸収層修飾半導体結晶層１１は、図１（ｂ）に示すように少なくとも側面に凹凸を有する針状結晶１７とその表面上に形成された光吸収層１６から構成されている。
【００３６】
図１（ｃ）は同様に図１（ａ）の電極付き基板１３を除く部分を詳細に示す断面図であり、本発明の他の実施形態を示すものである。この実施形態では、吸収層修飾半導体結晶層１１は図１（ｃ）に示すように少なくとも側面に凹凸を有する針状結晶１７とその表面上に形成された半導体結晶１８と更にその表面上に形成された光吸収層１６からなっている。
【００３７】
図１（ｂ）、（ｃ）のいずれにおいても側面に凹凸を有する針状結晶層１７は一方の電荷輸送層（ｎ型）となり、この電荷輸送層と電荷輸送層（ｐ型）１２との間に光吸収層１６が設けられている。
【００３８】
本実施形態による側面に凹凸を有する針状結晶層１７と微粒子結晶層を比較すると、側面に凹凸を有する針状結晶層１７の方が光励起により生成した電子もしくはホールが集電極へ移動するまでに粒界により散乱される確率が少なくなる。特に、図１（ｂ）に示すように全ての側面に凹凸を有する針状結晶の一端が電極に接合された状態で構成されている場合には、電子もしくはホールの移動において、Graetzel型セルと比較すると、粒界の影響はほどんど解消することが可能である。
【００３９】
また、図1（ｃ）に示す構成とGraetzel型セルとを比較すると、粒界の影響がほとんど解消されることにより電子及びホールの移動が容易にでき、且つ、半導体微粒子１８が吸着しているため、粒界の影響が小さいままラフネスファクター（実際の表面積／見かけの表面積）を向上することができる。
【００４０】
本実施形態にかかる光電変換装置では、凹凸を有する針状結晶はｎ型ワイドギャップ半導体であるため、色素の様な光吸収層１６を挟んでｐ型のワイドギャップ半導体やレドックス対を含んだ電解液、高分子導電体等の電子供与型の電荷輸送層１２が必要である。
【００４１】
ここで、光の照射面はどの面に透明電極（ガラス基板１４と透明電極層１５）を用いるかによって決まる。図２（ａ）に示す構成はGraetzel型セルと同様に半導体結晶層側に透明電極を用い、図面の左側から光を入射する場合の例である。図２（ｂ）に示す構成はそれとは逆の構成であり、電荷輸送層側に透明電極を設けて図面の右側から光を入射する場合の例である。光吸収層までの照射光の吸収や反射が少なければ、図２（ａ）、（ｂ）のどちらの構成でも良い。
【００４２】
また、図２（ｃ）に示す様にどちらの面からの光照射でも利用可能に出来る構成でも良い。即ち、半導体結晶層側、電荷輸送層側の両方に透明電極を設け、図面の左側と右側から光を入射する構成としても良い。これらの構成は凹凸を有する針状結晶の作製方法、及び組み合わせる電荷輸送層の製法や組成に依存する。例えば、Pt膜上への電着による凹凸を有する針状結晶の作製の場合には、凹凸を有する針状結晶面からは光照射は出来なくなる。凹凸を有する針状結晶粉の焼成の様な低温プロセスで凹凸を有する針状結晶面を作製する場合には透明電極層を劣化させずに作製できるので、どちらの面でも光照射面にできる。
【００４３】
次に、ｎ層である側面に凹凸を有する針状結晶１７及び半導体混合結晶について説明する。側面に凹凸を有する針状結晶とは針状結晶の外周面に凹凸部を有する半導体結晶のことを指し、その凹凸部の表面荒さの大きさによって表面積が増大した結晶構造をいう。
【００４４】
図３（ａ）はこの側面に凹凸を有する針状結晶１７を拡大して示す図である。図３（ａ）に示すように凹部位４１が針状結晶を抉るように存在している。ラフネスファクターを増大させる為に、図３（ｂ）に示すように大きい凹部４１が少数存在するよりも、図３（ａ）に示すように小さく表面が荒れるような構造を持つことが望ましい。
【００４５】
凹凸の凹部深さは、針状結晶１７の最外周の最短距離（針状結晶の断面における最外周間の厚みの最小値をいうが、この定義は後述する）の２％以上が好ましく、更には１０％以上の時は針状結晶の効果を保ちつつ、表面積を拡大できる為好ましい。また、凹凸部の高低差は、針状結晶１７の横切断面の断面中心から表面までの最長距離の２％以上が好ましく、更には１０％以上の時は針状結晶の効果を保ちつつ、表面積を拡大できる為好ましい。
【００４６】
図４（ａ）、（ｂ）は針状結晶１７の横断面図の一例を示す。ここで、凹凸部の凹部深さとは、図４（ａ）に５４として示すように針状結晶１７における凹部５２の最外周５１からの窪み深さのことである（即ち、凹部５２における最外周の直線上から外周までの垂直距離の最長距離）。最外周５１とは、図４（ａ）に示すように針状結晶１７の横切断面における外周５３の凹部５２を線で結んだ外形を指す。また、凹部５２とは、針状結晶１７の外周上の1点より凹凸を有する針状結晶の内部を通ること無く、異なる外周上の1点以上を通る直線で囲まれた内部を指す。
【００４７】
更に、前述の針状結晶の最外周の最短距離とは、図４（ｂ）に示すように針状結晶の外周に接する２本の平行線５５の距離ｄが最も短くなる長さのことを指す。凹凸部の高低差とは、図５（ａ）に示すように凹凸を有する針状結晶の横切断面の断面中心７１から表面７４までの最短距離７２と最長距離７３の差である。この針状結晶１７の断面中心７１とは、横切断面の重心を指す。
【００４８】
また、図５（ｂ）に示すように針状結晶７８よりエッチングした時に針状結晶７８の横切断面の断面中心７５から針状結晶１７の表面７４までの最小値７６と、その延長上に存在する針状結晶７８の表面７９までの距離７７との比は１／５０以上が好ましく、更には１／１０以上であることが、針状結晶の効果を保ちつつ、表面積を拡大できる為好ましい。この針状結晶の断面中心７４とは、横切断面の重心を指す。
【００４９】
ここで、針状結晶とは円柱及び円錐、円錐で先端が平坦なもの、円柱で先端が尖っているものや先端が平坦なもの等すべてを含む。更に、三角錐、四角錐、六角錐、それ以外の多角錐状やその多角錐の先端が平坦なもの、或いは三角柱、四角柱、六角柱、それ以外の多角柱状、或いは先端が尖った三角柱、四角柱、六角柱、それ以外の多角柱状やその先端が平坦なもの等も含まれ、更に、これらの折れ線状構造も含まれる。
【００５０】
また、針状結晶の側面とは、先端が尖っているものならその先端以外で、平坦なものならその平坦な部分以外を指す。更に、側面に凹凸を有する針状結晶に不純物となるSn、Sb、Al、Ga等の金属若しくは金属の化合物若しくはＳ、Ｃｌ、Ｎ等が混入している場合も含まれる。更に、基板上成長を伴う方が電子移動効率が向上するため、図６（ａ）に示すように側面に凹凸を有する針状結晶を作製後、塗布して焼成する方法よりも、図６（ｂ）に示すように基板上から形成することが好ましい。
【００５１】
また、半導体混合結晶とはｎ型の電荷輸送層が少なくとも2種類以上の異なった様態若しくは組成の単体若しくは混合物から成る半導体層であり、且つ、半導体層の１種類以上が針状結晶を含む混合結晶を意味するものとする。図１（ｃ）は半導体混合結晶の具体的な構成例を示す。半導体結晶１８が吸着することにより、粒界の影響が小さくラフネスファクターを向上することができる。
【００５２】
半導体結晶１８の直径は１００ｎｍ以下、できれば２０ｎｍ以下の微粒子が好ましい。また、半導体結晶１８は凹凸を側面に有する針状結晶１７の表面に存在することが好ましい。ここで、半導体微粒子とは、エネルギーギャップが大きなものが好ましく、具体的にはエネルギーギャップが3eV以上のものが好ましく、例えば、TiO2、ZnO 、SnO2等が挙げられ、それらがエッチングされたものも微粒子に含まれる。
【００５３】
次に、ｎ層に当たる凹凸を有する針状結晶及び半導体混合結晶の製造方法について説明する。本実施形態による凹凸を有する針状結晶の製造方法は、針状結晶をエッチングする工程を含むことを特徴とし、針状結晶をエッチングするための手法として、一般的に気相若しくは液相で行う。気相でのエッチングとは、主に減圧下でのプラズマエッチングが挙げられ、その他の方法としてはガスエッチング、イオンエッチング等が挙げられる。
【００５４】
一方、液相でのエッチングとは、酸やアルカリ溶液が金属や半導体、絶縁物を除去する為に使用される手段である化学エッチングと、電位を印加することにより基体が溶液中に溶解する電解エッチングに分けられる。エッチング方法はこれらに限るものではない。
【００５５】
また、表面を容易に不均等に荒らすことによりラスネスファクターが増大する液相でのエッチングが好まれ、特に、酸及びアリカリ溶液を使用することが好ましい。この時、使用する酸としては、硫酸、酢酸、蟻酸、塩酸、硝酸、フッ酸、りん酸、クロム酸、乳酸等が挙げられ、アルカリとしては、水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム、りん酸ナトリウム、炭酸ナトリウム、炭酸ソーダ等が挙げられ、その水溶液や混合液も含まれるが、これらに限定されるものではない。
【００５６】
更に、針状結晶の組成により適宜酸及びアルカリの種類を決める必要がある。例えば、ＴｉＯ２針状結晶を酸を用いてエッチングする場合は硫酸が好ましく、酸化亜鉛針状結晶をアルカリを用いてエッチングする場合は、ほとんどのアルカリで溶解可能な為、ＮａＯＨ等扱いの容易な試薬が好まれる。この時の凹凸部の高低差は、酸及びアルカリの種類は当然のことながら、濃度、溶液温度、溶解時間等により適宜選択することが好ましい。
【００５７】
また、側面に凹凸を有する針状結晶の製法としては、針状結晶の径や長さや成長方向を制御した後に、エッチングを行うことが好ましい。このことにより、針状結晶の表面積が不十分な場合でもラフネスファクターが大きい半導体結晶を作製する事ができ、且つ、電子もしくはホールの移動において粒界の影響が少ない凹凸を有する針状結晶を作製する事ができる。
【００５８】
また、半導体混合結晶の製造方法としては、半導体結晶１８を吸着してから針状結晶をエッチングしても、針状結晶をエッチングしてから半導体結晶１８を吸着しても、少なくとも針状結晶をエッチングする限り規制されるものではない。つまり、半導体結晶１８は前者なら凹凸を有する針状結晶上に、後者なら針状結晶上に、側面に凹凸を有する針状結晶若しくは針状結晶と異なる様態若しくは組成の単体若しくは混合物を用いたゲル溶液等を塗布する事により、前者なら図１（ｃ）に示す様に凹凸を有する針状結晶１７の表面に半導体結晶１８が存在する構造をとる事ができる。後者の場合、半導体結晶１８を吸着した後に上記エッチング法を用いて凹凸を有する針状結晶を形成する。
【００５９】
次に、光吸収層１６について説明する。本実施形態による光電変換装置の光吸収層１６としては、各種の半導体や色素が利用可能である。半導体としてはｉ型の光吸収係数が大きなアモルファス半導体や直接遷移型半導体が好ましい。色素としては金属錯体色素及び／もしくはポリメチン色素、ペリレン色素、ローズベンガル、エオシンＹ、マーキュロクロム、サンタリン（Santalin）色素、シアニン（Cyanin）色素などの有機色素や天然色素が好ましい。
【００６０】
色素としては半導体微粒子の表面に対する適当な結合基を有していることが好ましい。好ましい結合基としては、COOH基、シアノ基、PO3H2 基、または、オキシム、ジオキシム、ヒドロキシキノリン、サリチレート及びαケトエノレートのようなπ伝導性を有するキレート化基が挙げられる。この中でもCOOH基、PO3H2 基が特に好ましい。
【００６１】
本実施形態に使用する色素が金属錯体色素の場合、ルテニウム錯体色素｛Ru(dcbpy)2(SCN)2、（dcbpy=2,2-bipyridine-4,4'-dicarboxylic acid）等]が利用できるが、酸化・還元体が安定であることが重要である。また、光吸収層の励起された電子の電位、即ち、光励起した色素の電位（色素のLUMO電位）や半導体中の伝導帯電位が、電子受容型電荷輸送層の電子受容電位（ｎ型半導体の伝導帯電位等）より高く、且つ、光吸収層で光励起により生成したホール電位が、電子供与型電荷移動層の電子供与電位（ｐ型半導体の価電子帯電位、レドックス対のポテンシャル電位等）より低いことが必要である。光吸収層近傍における励起された電子−ホールの再結合確率を低くすることも、光電変換効率を増大させる上で重要となる。
【００６２】
次に、電荷輸送層１２について説明する。ｎ型の半導体結晶を用いた場合、光吸収層を挟んでホール輸送層を作製する必要がある。このホール輸送層には湿式太陽電池同様レドックス系が利用可能である。レドックスを用いる場合でも単純な溶液系のみでなく、カーボンパウダーを保持材にしたり、電解質をゲル化する方法がある。また、溶融塩やイオン伝導性ポリマーを用いる方法もある。更に、電子（ホール）を輸送する方法として電界重合有機ポリマーやCuI、CuSCN、NiO等のｐ型半導体を用いることも出来る。
【００６３】
上記輸送層は側面に凹凸を有する針状結晶間に入り込む必要があるため、作製には液体や高分子等に利用できる浸透法や、固体の輸送層に利用できる電着、CVD法等が適している。
【００６４】
次に、電極層について説明する。電荷輸送層、凹凸を有する針状結晶に隣接するように電極層が設けられている。電極層はこれらの層の外側の全面に設けてもよいし一部に設けてもよい。電荷輸送層が固体でない場合、電荷輸送層を保持するという観点から全面に電極層を設けた方がよい。電荷輸送層に隣接する電極の表面には、例えば、レドックス対の還元を効率よく行わせる為にPt、Ｃ等の触媒を設けておくことが好ましい。
【００６５】
光入射側の電極層としては、インジウム−スズ複合酸化物、酸化スズにフッ素をドープしたもの等からなる透明電極を好適に用いることができる。光入射側の電極に接する層（電荷輸送層或いは凹凸を有する針状結晶層）の抵抗が十分低い場合には、光入射側の電極として部分的な電極、例えば、フィンガー電極等を設けることも可能である。光入射側とはならない電極としては、Ｃｕ，Ａｇ，Ａｌ等からなる金属電極を好適に用いることができる。
【００６６】
次に、基板１４について説明する。基板の材質、厚さは、光起電力装置に要求される耐久性に応じて適宜設計することができる。光入射側の基板は透光性である限り、ガラス基板、プラスチック基板等を好適に用いることができる。光入射側とはならない基板としては、金属基板、セラミック基板等を適宜用いることができる。光入射側の基板の表面には、ＳｉＯ２等からなる反射防止膜を設けることが好ましい。
【００６７】
なお、前述した電極に基板としての機能を兼ねさせることにより、電極とは別部材の基板を設けない様にしても良い。
【００６８】
次に、封止について説明する。図示してはないが、光電変換装置の湿式のものは、少なくとも基板以外の部分を封止することが、耐候性を高める観点から好ましい。封止材としては接着剤や樹脂を用いることができる。なお、光入射側を封止する場合、封止材は透光性であることが好ましい。
【００６９】
【実施例】
次に、本発明の実施例について説明する。本願発明者は、以上の実施形態で説明した光電変換装置を作製し、評価実験を試みた。以下、これを実施例１〜６として説明する。
【００７０】
（実施例１）
実施例１では、図７の電着装置を用いて酸化亜鉛針状結晶を製造し、酸化亜鉛針状結晶をアルカリ溶液に浸すことにより凹凸を有する針状結晶を作製し、これを用いて光電変換装置を作製した。なお、実施例１の光電変換装置は図６（ｂ）に対応する。
【００７１】
まず、導電性ガラス基板（FドープSnO2、10Ω／□）を用意し、この基板を作用極８３として2mmol/L硝酸亜鉛水溶液８５に浸し、−１．２Ｖ(vs. Ag/AgCl：参照極８１)の電位を５０００秒間印加を行った。導電性ガラス基板は、光電変換セルの一方の基板に相当し、例えば、図１の電極付き基板１０に相当する。また、対極８２は亜鉛板であり、マントルヒーター８６でビーカー８４内の電解液８５を８５度に加熱して行った。電解後、基板表面には酸化亜鉛針状結晶が電極から成長していた。この酸化亜鉛針状結晶の径は４０〜５０ｎｍであり、長さはその２０〜３０倍であった。この基板を、１．０mol/L ＮａＯＨ水溶液中に１分間浸すことにより、凹凸を有する針状結晶を得ることが出来た。
【００７２】
また、色素としてRu錯体であるRu((dcbpy)(COOH)2)2(SCN)2を用いた。この色素を蒸留エタノールに溶解し、この中に前述のように凹凸を有する針状結晶が形成された針状結晶電極を２４ｈ浸して色素を電極に吸着させた後取りだし、８０℃で乾燥させた。次に、導電性ガラス（FドープSnO2、10Ω／□）上に白金を１０ｎｍ厚にスパッタ成膜した対極（光電変換セルの他方側の基板に相当し、例えば、図１の電極付き基板１３に相当する）を用い、レドックス対はＩ-／Ｉ3 -を用いた。
【００７３】
溶質はテトラプロピルアンモニウムヨウ化物（tetrapropylammonium iodide ） （0.46mol/L）とヨウ素（0.06mol/L）、溶媒はエチレンカルボナート（ethylene carbonate）（80vol%）とacetonitrile（20vol%）の混合液を用いた。この混合液（電荷輸送層１２に対応）を凹凸を有する針状結晶上に滴下し、対極の基板で挟んで光電変換セルを作製した。
【００７４】
また、比較例として粒径約１００ｎｍを主成分とした酸化亜鉛微粒子を熱処理したものを用いて同様にセルを組み立てた。そして、紫外線カットフィルターを取り付けた５００Ｗのキセノンランプ光を対極側から照射した。この時生じた光電変換反応による光電流の値を測定した。測定結果は、実施例１の方が比較例に比べて短絡電流、光電変換効率ともに１２％程度大きかった。これは凹凸を有する針状結晶電極を用いたことによって電子受容型電荷輸送層の内部抵抗が減少したことに起因すると考えられる。
【００７５】
（実施例２）
実施例２では、酸化チタン針状結晶を酸溶液に浸すことにより凹凸を有する酸化チタン針状結晶を作製し、これを用いて光電変換装置を作製した。実施例２は図６（ａ）に対応する。
【００７６】
まず、市販の酸化チタン針状結晶（長さ1.68μｍ、径0.13μｍ、FTL-100：石原産業製）を、1.0mol/L H2SO4水溶液中に1分間浸すことにより凹凸を有する針状結晶を得た。その3ｇを水5ｍＬ、アセチルアセトン0.2ｍＬ、トリトン-X（登録商標：ユニオン・カーバイト社）0.2mLと混合しスラリー状にした。このスラリーを導電性ガラス（FドープSnO2、10Ω／□）上に、スペーサーを用いて厚み約５０μｍ、１ｃｍ角に塗布した。導電性ガラスは光電変換セルの一方の基板に相当し、例えば、図１の電極付きガラス基板１０に相当する。次に、これを酸素ガスを100sccm流しながら５５０℃、１時間焼成を行った。焼成後の凹凸を有する針状結晶層１７の膜厚は約１０μｍであった。
【００７７】
また、色素として市販のマーキュロクロムを用いた。この色素を蒸留エタノールに溶解し、この中に前述のように凹凸を有する針状結晶が形成された針状結晶電極を２４時間浸して色素を電極に吸着させた後取りだし、８０℃で乾燥させた。また、導電性ガラス（FドープSnO2、10Ω／□）上に白金を１０ｎｍ厚にスパッタ成膜した対極（光電変換セルの他方側基板に相当し、例えば、図１の電極付き基板１３に相当する）を用い、レドックス対はＩ-／Ｉ3 -を用いた。
【００７８】
溶質は0.05mol/L I2（ヨウ素）と0.1mol/L LiI（よう化リチウム）と0.6mol/L DMPI（Im）（1,2-ジメチル-3-プロピルイミダゾリウム アイオダイド）と0.5mol/L TBP（4-tert-ブチルピリジン）、溶媒はMAN（MeOAN）（メトキシアセトニトリル）を用いた。この混合液（電荷輸送層１２に対応）を凹凸を有する針状結晶上に滴下し、対極の基板で挟んで光電変換セルを作製した。
【００７９】
また、比較例として酸化チタン針状結晶（長さ1.68μｍ、径0.13μｍ、FTL-100：石原産業製）を熱処理したものを用いて同様にセルを組み立てた。そして紫外線カットフィルターを取り付けた５００Ｗのキセノンランプ光を対極側から照射した。この時生じた光電変換反応による光電流の値を測定した。測定結果は実施例２の方が比較例に比べて短絡電流、光電変換効率ともに８％程度大きかった。これは凹凸を有する針状結晶電極を用いたことによって表面積が増大したことに起因すると考えられる。
【００８０】
（実施例３）
実施例３では、図７の電着装置を用いて酸化亜鉛針状結晶を製造し、この酸化亜鉛針状結晶に酸化電位を印加することにより凹凸を有する針状結晶を作製し、これを用いて光電変換装置を作製した。実施例３は図６（ｂ）の光電変換装置に対応する。
【００８１】
まず、実施例1と同様に導電性ガラス基板（FドープSnO2、10Ω／□）を用意し、この基板を作用極８３として2mmol/L硝酸亜鉛水溶液８５に浸し、−１．２Ｖ(vs. Ag/AgCl：参照極８１)の電位を５０００秒間印加を行った。導電性ガラス基板は光電変換セルの一方の基板に相当、例えば、図１の電極付き基板１０に相当する。また、対極８２は亜鉛板であり、マントルヒーター８６でビーカー８４内の電解液８５を８５度に加熱して行った。電解後、基板表面には酸化亜鉛針状結晶が電極から成長していた。この酸化亜鉛針状結晶の径は４０〜５０ｎｍであり、長さはその２０〜３０倍であった。更に、この酸化亜鉛針状結晶電極に＋１．０Ｖ(vs. Ag/AgCl：参照極８１)の電位を１０秒間印加することにより凹凸を有する針状結晶を得た。
【００８２】
色素はGraetzelらが報告しているRu錯体であるRu((dcbpy)(COOH)2)2(SCN)2を用いた。この色素を蒸留エタノールに溶解し、この中に前述のように酸化亜鉛針状結晶が形成された酸化亜鉛電極を２４ｈ浸して色素を電極に吸着させた後取りだし、80℃で乾燥させた。また、導電性ガラス（FドープSnO2、10Ω／□）上に白金を10nm厚にスパッタ成膜した対極（光電変換セルの他方側基板に相当し、例えば、図１の電極付き基板１３に相当する）を用い、レドックス対はＩ-／Ｉ3 -を用いた。
【００８３】
溶質はテトラプロピルアンモニウムヨウ化物（tetrapropylammonium iodide ） （0.46mol/L）とヨウ素（0.06mol/L）、溶媒はエチレンカルボナート（ethylene carbonate）（80vol%）とacetonitrile（20vol%）の混合液を用いた。この混合液（電荷輸送層１２に対応）を凹凸を有する針状結晶上に滴下し、対極の基板で挟んで光電変換セルを作製した。
【００８４】
また、比較例として粒径１００ｎｍを主成分とした酸化亜鉛粉末を熱処理したものを用いて同様にセルを組み立てた。そして紫外線カットフィルターを取り付けた５００Ｗのキセノンランプ光を対極側から照射した。この時生じた光電変換反応による光電流の値を測定した。測定結果は、実施例３のセルの方が比較例に比べて短絡電流、光電変換効率ともに３％程度大きかった。これは凹凸を有する針状結晶電極を用いたことによって電子受容型電荷輸送層の内部抵抗が減少したことに起因すると考えられる。
【００８５】
（実施例４）
実施例４では、図７の電着装置を用いて酸化亜鉛針状結晶を作製し、この酸化亜鉛針状結晶を実施例１と同様にエッチングした後、微粒子結晶を塗布することにより半導体混合結晶を作製し、これを用いて光電変換装置を作製した。実施例４は図１（ｃ）に対応する。
【００８６】
まず、実施例1と同様に導電性ガラス基板（FドープSnO2、10Ω／□）を用意し、この基板を作用極８３として2mmol/L硝酸亜鉛水溶液８５に浸し、−１．２Ｖ(vs. Ag/AgCl：参照極８１)の電位を5000秒間印加を行った。導電性ガラス基板は光電変換セルの一方の基板に相当し、例えば、図１の電極付き基板１０に相当する。また、対極８２は亜鉛板であり、マントルヒーター８６でビーカー８４内の電解液８５を８５度に加熱して行った。電解後、基板表面には酸化亜鉛針状結晶が電極から成長していた。この酸化亜鉛針状結晶の径は４０〜５０ｎｍであり、長さはその２０〜３０倍であった。
【００８７】
この基板を実施例１と同様に１．０ｍｏｌ／Ｌ ＮａＯＨ水溶液中に１分間浸すことにより凹凸を有する針状結晶を得た。このように凹凸を有する針状結晶が形成された電極を粒径２０ｎｍを主成分とした酸化錫コロイド溶液に浸漬し、更に、酸素を１．６７×１０−３Ｌ／ｓ流しながら５５０℃で１時間焼成を行い、図１（ｃ）に示すような半導体混合結晶を作製した。
【００８８】
色素は市販のマーキュロクロムを用いた。この色素を蒸留エタノールに溶解し、この中に前述のように半導体混合結晶が形成された半導体混合結晶電極を２４時間浸して色素を電極に吸着させた後取りだし、80℃で乾燥させた。また、導電性ガラス（FドープSnO2、10Ω／□）上に白金を10nm厚にスパッタ成膜した対極（光電変換セルの他方側基板に相当し、例えば、図１の電極付き基板１３に相当）を用い、レドックス対はＩ-／Ｉ3 -を用いた。溶質は0.05mol/L I2（ヨウ素）と0.1mol/L LiI（よう化リチウム）と0.6mol/L DMPI（Im）（1,2-ジメチル-3-プロピルイミダゾリウム アイオダイド）と0.5mol/L TBP（4-tert-ブチルピリジン）、溶媒はMAN（MeOAN）（メトキシアセトニトリル）を用いた。この混合液（図１の電荷輸送層１２に対応）を半導体混合結晶上に滴下し、対極の基板で挟んで光電変換セルを作製した。
【００８９】
また、比較例として粒径約１００ｎｍを主成分とした酸化亜鉛微粒子に粒径約２０ｎｍを主成分とした酸化錫微粒子を塗布し、熱処理したものを用いて同様にセルを組み立てた。そして紫外線カットフィルターを取り付けた５００Ｗのキセノンランプ光を対極側から照射した。この時生じた光電変換反応による光電流の値を測定した。測定結果は、実施例４のセルの方が比較例に比べて短絡電流、光電変換効率ともに１２％程度大きかった。これは、半導体混合結晶電極を用いたことによって電子受容型電荷輸送層の内部抵抗が減少したことに起因すると考えられる。
【００９０】
（実施例５）
実施例５では、図７の電着装置を用いて電解電着により基板電極から酸化亜鉛針状結晶を作製し、酸化チタン微粒子結晶を塗布し焼成した後に、アルカリ溶液に浸すことにより半導体混合結晶を作製し、これを用いて光電変換装置を作製した。実施例５は図１（ｃ）に対応する。
【００９１】
まず、導電性ガラス基板（FドープSnO2、10Ω／□）を用意し、この基板を作用極８３として2mmol/L硝酸亜鉛水溶液８５に浸し、−１．２Ｖ(vs. Ag/AgCl：参照極８１)の電位を５０００秒間印加を行った。導電性ガラス基板は光電変換セルの一方の基板に相当し、例えば、図１の電極付き基板１０に相当する。また、対極８２は亜鉛板であり、マントルヒーター８６でビーカー８４内の電解液８５を８５度に加熱して行った。電解後、基板表面には酸化亜鉛針状結晶が電極から成長していた。この酸化亜鉛針状結晶の径は４０〜５０ｎｍであり、長さはその２０〜３０倍であった。
【００９２】
この電極を粒径約２０ｎｍを主成分とした酸化チタン微粒子溶液に浸漬し、更に酸素を1.67×10-3L/s流しながら５５０℃で１時間焼成を行い、半導体混合結晶を作製した。この基板を、１０mol/L ＮａＯＨ水溶液中に１０分間浸すことにより図１（ｃ）に示すような凹凸を有する針状結晶を得た。
【００９３】
色素は市販のエオシンＹを用いた。この色素を蒸留エタノールに溶解し、この中に前述のように半導体混合結晶が形成された半導体混合結晶電極を２４時間浸して色素を電極に吸着させた後取りだし、８０℃で乾燥させた。また、導電性ガラス（FドープSnO2、10Ω／□）上に白金を１０ｎｍ厚にスパッタ成膜した対極（光電変換セルの他方側基板に相当し、例えば、図１の電極付き基板１３に相当）を用い、レドックス対はＩ-／Ｉ3 -を用いた。
【００９４】
溶質は0.05mol/L I2（ヨウ素）と0.1mol/L LiI（よう化リチウム）と0.6mol/L DMPI（Im）（1,2-ジメチル-3-プロピルイミダゾリウム アイオダイド）と0.5mol/L TBP（4-tert-ブチルピリジン）、溶媒はMAN（MeOAN）（メトキシアセトニトリル）を用いた。この混合液（図１の電荷輸送層１２に対応）を半導体混合結晶上に滴下し、対極の基板で挟んで光電変換セルを作製した。
【００９５】
また、比較例として粒径約１００ｎｍを主成分とした酸化チタン微粒子に粒径約２０ｎｍを主成分とした酸化亜鉛微粒子を塗布し熱処理したものを用いて同様にセルを組み立てた。そして紫外線カットフィルターを取り付けた５００Ｗのキセノンランプ光を対極側から照射した。この時生じた光電変換反応による光電流の値を測定した。測定結果は、実施例５のセルの方が比較例に比べて短絡電流、光電変換効率ともに１２％程度大きかった。これは、導体混合結晶電極を用いたことによって電子受容型電荷輸送層の内部抵抗が減少したことに起因すると考えられる。
【００９６】
（実施例６）
実施例６では、気相でのエッチング装置を用いて凹凸を有する針状結晶を製造し、これを用いて光電変換装置を作製した。実施例６は図６（ａ）の光電変換装置に対応する。
【００９７】
まず、市販の酸化チタン針状結晶（長さ5.15μｍ、径0.27μｍ、FTL-300：石原産業製）の3ｇを水5ｍＬ、アセチルアセトン0.2ｍＬ、トリトン-X（登録商標：ユニオン・カーバイト社）0.2mLと混合しスラリー状にした。このスラリーを導電性ガラス（FドープSnO2、10Ω／□）上に、スペーサーを用いて厚み約５０μｍ、１ｃｍ角に塗布した。導電性ガラス基板は光電変換セルの一方の基板に相当し、例えば、図１の電極付き基板１０に相当する。次に、この基板を酸素ガスを100sccm流しながら５５０℃、１時間焼成を行った。焼成後の針状結晶層の膜厚は約１０μｍであった。この電極を気相でエッチングした。エッチング条件として、ＢＣｌ３を５〜１０Ｐａ下で２００Ｗ、３０〜１２０秒間行った。
【００９８】
色素はRu錯体であるRu((dcbpy)(COOH)2)2(SCN)2を用いた。この色素を蒸留エタノールに溶解し、この中に凹凸を有する針状結晶電極を２４ｈ浸して色素を電極に吸着させた後取りだし、80℃で乾燥させた。また、導電性ガラス（FドープSnO2、10Ω／□）上に白金を10nm厚にスパッタ成膜した対極（光電変換セルの他方側基板に相当し、例えば、図１の電極付き基板１３に相当）を用い、レドックス対はＩ-／Ｉ3 -を用いた。
【００９９】
溶質はテトラプロピルアンモニウムヨウ化物（tetrapropylammonium iodide ） （0.46mol/L）とヨウ素（0.06mol/L）、溶媒はエチレンカルボナート（ethylene carbonate）（80vol%）とacetonitrile（20vol%）の混合液を用いた。この混合液（電荷輸送層１２に対応）を凹凸を有する針状結晶上に滴下し、対極の基板で挟んで光電変換セルを作製した。
【０１００】
また、比較例として市販の酸化チタン針状結晶（長さ5.15μｍ、径0.27μｍ、FTL-300：石原産業製）を熱処理したものを用いて同様にセルを組み立てた。そして紫外線カットフィルターを取り付けた５００Ｗのキセノンランプ光を対極側から照射した。この時生じた光電変換反応による光電流の値を測定した。測定結果は、実施例５のセルの方が比較例に比べて短絡電流、光電変換効率ともに１％程度大きかった。これは凹凸を有する針状結晶電極を用いたことによって表面積が増大したことに起因すると考えられる。
【０１０１】
【発明の効果】
以上説明したように本発明によれば、ｎ型の電荷輸送層として側面に凹凸を有する針状結晶を用いているため、電子の授受をスムーズに行うことができ、変換効率の高い光電変換装置を実現することができる。また、色素等の光吸収層や電解液などの電荷輸送層のしみ込みや移動が速い半導体電極を有する光電変換装置を実現できると共に、短絡電流値が大きい光電変換装置を実現できる。
【図面の簡単な説明】
【図１】本発明の光電変換装置の一実施形態を示す断面図である。
【図２】本発明による光電変換装置の光照射方向と透明電極との関係を説明するための図である。
【図３】側面に凹凸を有する針状結晶を示す図である。
【図４】側面に凹凸を有する針状結晶の断面図である。
【図５】側面に凹凸を有する針状結晶の断面図である。
【図６】本発明の光電変換装置の製法の違いによる針状結晶を示す断面図である。
【図７】電着を用いた針状結晶膜の製造装置を示す図である。
【図８】従来例のGraetzelセルを示す断面図である。
【符号の説明】
１０ 電極付き基板
１１ 吸収層修飾半導体結晶層
１２ 電荷輸送層
１３ 電極付き基板
１４ ガラス基板
１５ 透明電極層
１６ 光吸収層
１７ 凹凸を有する針状結晶（凹凸を有する針状結晶層）
１８ 半導体結晶
４１ 凹部位
５１ 最外周
５２ 凹部
５３ 外周
５４ 凹部深さ
５５ 平行線
５６ 平行線の距離（ｄ）
６１ アナターゼ型TiO2微粒子
６２ 光吸収層
６３ 電解液
６４ ガラス
６５ 透明電極層（アノード）
６６ 透明電極層（カソード）
７１ 凹凸を有する針状結晶層の横切断面中心
７２ 凹凸を有する針状結晶層の最短距離
７３ 凹凸を有する針状結晶層の最長距離
７４ 凹凸を有する針状結晶層の表面
７５ 針状結晶の横切断面中心
７６ 針状結晶の最短距離
７７ 針状結晶の横切断面の表面までの距離
７８ 針状結晶
７９ 針状結晶層の表面
８１ 参照極
８２ 対極
８３ サンプル（作用極）
８４ ビーカー
８５ 電解液
８６ マントルヒーター[0001]
BACKGROUND OF THE INVENTION
The present inventionMethod for producing dye-sensitized solar cellIn particular, it has at least an electron-accepting charge transport layer, an electron supply charge transport layer, and a light absorption layer present between these charge transport layers.Method for producing dye-sensitized solar cellIt is about.
[0002]
[Prior art]
Conventionally, as a method for converting light energy into electric energy, a solar cell using a semiconductor junction such as silicon or gallium-arsenic is generally used. Among them, single crystal silicon solar cells using polycrystalline semiconductor pn junctions, polycrystalline silicon solar cells, and amorphous silicon solar cells using pin junctions are well known and are being put into practical use. However, since silicon solar cells are expensive to manufacture and consume a lot of energy in the manufacturing itself, it is necessary to use them for a long time to recover the introduction cost and energy consumption. This cost is mainly the bottleneck of the current spread.
[0003]
On the other hand, research on practical application of CdTe, CuIn (Ga) Se, etc. has been progressing as a second generation thin film solar cell in recent years, but environmental problems and resource problems have been raised in these material systems.
[0004]
As a method other than the above semiconductor bonding, a wet solar cell using a photoelectrochemical reaction that occurs at the interface between a semiconductor and an electrolyte solution has been reported. Metal oxide semiconductors such as titanium oxide and tin oxide used in this wet solar cell can be manufactured at a lower cost than silicon, gallium-arsenide, etc. used in dry solar cells. It is expected as a future energy conversion material because it is excellent in both photoelectric conversion characteristics and stability.
[0005]
However, since stable optical semiconductors such as titanium oxide have a wide band gap of 3 eV or more, only ultraviolet light that is about 4% of sunlight can be used, and it cannot be said that the conversion efficiency is sufficiently high.
[0006]
Therefore, photochemical cells (dye-sensitized solar cells) in which a dye is adsorbed on the surface of an optical semiconductor have been studied. In the early days, semiconductor single crystal electrodes have been used. Examples of the electrode include titanium oxide, zinc oxide, cadmium sulfide, and tin oxide. However, since the single crystal electrode has a small amount of dye adsorption, the efficiency is low and the cost is high, and attempts have been made to make the semiconductor electrode porous.
[0007]
For example, Tsubomura et al. Reported that the efficiency was improved by adsorbing a dye to a semiconductor electrode made of porous zinc oxide obtained by sintering fine particles (NATURE, 261 (1976) p402). Furthermore, Graetzel et al. Reported that the dye and the semiconductor electrode were further improved to obtain the performance equivalent to that of a silicon solar cell (J. Am. Chem. Soc. 115 (1993) 6382, US Pat. No. 5,350,644). issue). Here, a ruthenium dye is used as the dye, and the anatase type porous titanium oxide (TiO 2) is used as the semiconductor electrode.2) Is used.
[0008]
In recent years, porous semiconductor electrodes obtained by improving the Graetzel type cell in various forms have also been reported. For example, Japanese Patent Laid-Open No. 9-237641 in which a Graetzel type cell is manufactured using niobium oxide fine particles. Furthermore, it has also been reported by Tennakone et al. (J. Chem. Soc., Chem. Commun., 15 (1999)) that high-efficiency cells were produced by mixing zinc oxide fine particles and tin oxide fine particles.
[0009]
FIG. 8 is a schematic cross-sectional view showing a schematic configuration of a photochemical battery (hereinafter referred to as a Graetzel type cell) using a Graetzel type dye-sensitized semiconductor electrode. In the figure, 64 is a glass substrate, and 65 is a transparent electrode formed on the surface thereof. Reference numeral 61 denotes an anatase-type porous titanium oxide layer, which is formed from a porous joined body in which titanium oxide fine particles are joined together. Reference numeral 62 denotes a dye bonded to the surface of the titanium oxide fine particles and functions as a light absorption layer.
[0010]
The principle of operation of this Graetzel cell will be described. When light enters from the left side of FIG. 8, the electrons in the dye constituting the light absorption layer 62 are excited by the incident light and move to the conduction band of titanium oxide. The dye that has lost electrons and is in an oxidized state quickly receives electrons from iodine ions in the electrolytic solution 63 and is reduced to return to the original state. The electrons injected into the titanium oxide layer 61 move between the titanium oxide fine particles by a mechanism such as hopping conduction and reach the anode 65. In addition, an electron is supplied to the dye to produce an oxidation state (IThree -The iodine ions that have become) are reduced by receiving electrons from the cathode 66, and the original state (I-Return to).
[0011]
As can be inferred from the above operating principle, in order to efficiently separate and move the electrons and holes generated in the dye, the energy level of the excited electron of the dye is TiO.2The energy level of the dye hole needs to be lower than the redox level.
[0012]
In order for such a Graetzel cell to replace a silicon solar cell, higher energy conversion efficiency, higher short-circuit current, open-circuit voltage, form factor, and durability are required.
[0013]
In general, as means for producing a semiconductor crystal, it can be currently produced by various methods such as sputtering, vapor deposition, CVD, and electrodeposition. For example, JP-A-8-217443 and JP-A-8-260175 describe a method for uniformly producing film-like zinc oxide on a large-area conductive substrate.
[0014]
Furthermore, as means for producing zinc oxide needle-like crystals, "J. Crystal Growth, 102, 965, (1990)" was reported in 920 by using tetrapod-like needle-like zinc oxide crystals by vapor phase oxidation of metal Zn. It is reported that it was manufactured at the same time.
[0015]
In addition, "Jpn.J.Appl.Phys., Vol.38 (1999) pp.L586" has a zinc oxide needle shape with a diameter of 1.5μm and a length of 100μm using the open-air CVD method. It has been reported that crystals can be produced.
[0016]
Further, the means for etching the substrate is generally performed in a gas phase or a liquid phase. Etching in the gas phase mainly includes plasma etching under reduced pressure, and etching in the liquid phase is a means in which an acid or alkali solution is used to remove metals, semiconductors, and insulators. . Liquid phase etching is divided into chemical etching and electrolytic etching, and these are widely used as general techniques.
[0017]
[Problems to be solved by the invention]
However, the dye-sensitized semiconductor electrode of the above prior art uses a titanium oxide film obtained by applying a solution in which titania fine particles are dispersed on a substrate with a transparent conductive film and drying at a high temperature after drying. Electron conduction tended to be scattered at the interface between the transparent electrode and the titania fine particles or at the interface between the titanium oxide fine particles. For this reason, the internal resistance which arises in the interface of a transparent conductive film and a titanium oxide film, and the interface of titanium oxide microparticles | fine-particles becomes large, and as a result, it became the cause of photoelectric conversion efficiency falling. The same was true when fine particles other than titania were used.
[0018]
In addition, since the dye-sensitized semiconductor electrode is composed of a sintered body of fine particles, it takes time to adsorb the dye to the fine particles in the vicinity of the transparent electrode, and the diffusion of ions in the electrolyte is slow. was there.
[0019]
The present invention has been made in view of the above-described conventional problems, and its purpose is to enable smooth transfer of electrons and high conversion efficiency.Method for producing dye-sensitized solar cellIs to provide.
[0020]
Another object of the present invention is to have a semiconductor electrode in which a light absorption layer such as a dye or a charge transport layer such as an electrolyte solution penetrates or moves quickly.Method for producing dye-sensitized solar cellIs to provide.
[0021]
Furthermore, another object of the present invention is to provide a large short circuit current value.Method for producing dye-sensitized solar cellIs to provide.
[0024]
[Means for Solving the Problems]
BookThe invention has an n-type charge transport layer, a light absorption layer, and a p-type charge transport layer between two substrates.Dye-sensitized solar cellIn the manufacturing method of the above, the needle-like crystal having irregularities on at least the side surface by etching the needle-like crystalTheFormationIncluding the process ofThe needle-like crystal having irregularities on the side surfaceTheThe n-type charge transport layer;DoIt is characterized by that.
[0025]
Further, the present invention has an n-type charge transport layer, a light absorption layer, and a p-type charge transport layer between two substrates.Dye-sensitized solar cellA method of forming a needle-like crystal having irregularities on at least a side surface by etching the needle-shaped crystal, and the needle-like crystals having the irregularitiesSemiconductor mixed crystal by adsorbing semiconductor crystal on the surface ofForming the semiconductor mixed crystalTheThe n-type charge transport layer;DoIt is characterized by that.
[0026]
The present invention also includes a step of forming a needle crystal on a substrate, a step of forming a needle crystal having irregularities on at least a side surface by etching the needle crystal, A step of forming a light absorption layer, a step of forming a p-type charge transport layer on the acicular crystal formed with the light absorption layer, and sandwiching the acicular crystal formed with the charge transport layer between the other substrate And a step of producing a photoelectric conversion cell.
[0027]
Further, the present invention provides a process for producing a needle-like crystal having irregularities on at least side surfaces by etching the needle-shaped crystals, and a needle-shaped crystal having irregularities on the side surfaces.Apply the mixture to the substrate and bakeA step of forming a light absorption layer on the needle-like crystal formed on the substrate, a step of forming a p-type charge transport layer on the needle-like crystal on which the light absorption layer is formed, and the charge transport layer comprising: It includes a step of manufacturing a photoelectric conversion cell by sandwiching the formed acicular crystal with the substrate on the other side.
[0028]
The present invention also includes a step of forming a needle crystal on a substrate, a step of forming a needle crystal having irregularities on at least a side surface by etching the needle crystal, and a needle crystal having irregularities on the side surface. On the surfaceAdsorb semiconductor crystalsForming a semiconductor mixed crystal,Semiconductor mixed crystalA step of forming a light absorption layer thereon, the light absorption layer formedThe semiconductor mixed crystalForming a p-type charge transport layer on the substrate, the charge transport layer formedThe semiconductor mixed crystalIncluding a step of manufacturing a photoelectric conversion cell with the substrate sandwiched between the substrates on the other side.
[0029]
Further, the present invention provides a process for forming a needle crystal on a substrate, the surface of the needle crystalAdsorb semiconductor crystalsForming a semiconductor mixed crystal,Semiconductor mixed crystalUnevenness on at least the side surface by etchingTheStep of forming, having irregularities on the side surfaceThe semiconductor mixed crystalA step of forming a light absorption layer thereon, the light absorption layer formedThe semiconductor mixed crystalForming a p-type charge transport layer on the substrate, the charge transport layer formedThe semiconductor mixed crystalIncluding a step of manufacturing a photoelectric conversion cell with the substrate sandwiched between the substrates on the other side.
[0030]
The present invention also provides needle crystals.A mixture containingA step of firing, a step of producing needle-like crystals having at least side surfaces by etching the needle-like crystals after firing, a step of forming a light absorption layer on the needle-like crystals formed on the substrate, A step of forming a p-type charge transport layer on the needle-like crystal on which the light absorption layer is formed, and a step of manufacturing a photoelectric conversion cell by sandwiching the needle-like crystal on which the charge transport layer is formed between the substrates on the other side. It is characterized by including.
[0031]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The main feature of the photoelectric conversion device according to the present invention is that it is an electron transport type charge transport layer in which transfer and transfer of electrons and holes are smoothly performed, internal resistance and recombination probability are low, and conversion efficiency is high. The photoelectric conversion device and the manufacturing method thereof will be described in detail below.
[0032]
First, the configuration of an embodiment of a photoelectric conversion device according to the present invention will be described. In the dye-sensitized cells such as the above-described Graetzel type cell, the light absorption rate of one layer of the dye is not sufficient. Therefore, the surface area is increased to increase the substantial light absorption amount.ThisAs for the method of enlarging the surface, although a method of dispersing and bonding fine particles as in the Graetzel type cell is simple, there is a problem that the movement of electrons is not sufficiently efficient.
[0033]
For example, comparing the case where light is incident from the anode transparent electrode 65 side having the titanium oxide semiconductor layer 61 and the case where light is incident from the cathode transparent electrode 66 side in the Graetzel type cell, the former is photoelectric conversion. It is often efficient. This is not only a difference in the amount of light absorption by the dye, but also the probability that electrons excited by light absorption move through the titanium oxide semiconductor layer 61 and reach the anode transparent electrode 65 as the photoexcitation position moves away from the transparent electrode. This suggests a decline. That is, it is suggested that a sufficiently efficient electron transfer is not achieved in a Graetzel type cell with many crystal grain boundaries.
[0034]
FIG. 1A is a cross-sectional view showing a configuration of one embodiment of the photoelectric conversion device according to the present embodiment. FIG. 1B is a cross-sectional view showing in detail a portion excluding the electrode-attached substrate 13 of FIG. In FIG. 1, 10 is a substrate with an electrode, 11 is an absorption layer modified semiconductor crystal layer, 12 is a charge transport layer, and 13 is a substrate with an electrode. As shown in FIG. 1B, the electrode-attached substrate 10 is composed of, for example, a glass substrate 14 provided with a transparent electrode layer 15.
[0035]
Similarly, the substrate with electrode 13 includes an electrode and a substrate. However, when light is incident from the right side of the drawing, the electrode layer 15 and the substrate 14 must be translucent. This is not the case when light is not incident. Further, the absorbing layer-modified semiconductor crystal layer 11 is composed of a needle-like crystal 17 having at least side surface irregularities and a light absorbing layer 16 formed on the surface thereof, as shown in FIG.
[0036]
Similarly, FIG. 1C is a cross-sectional view showing in detail a portion excluding the substrate with electrode 13 of FIG. In this embodiment, the absorption layer-modified semiconductor crystal layer 11 is formed on the surface of the needle crystal 17 having irregularities on at least the side surface, the semiconductor crystal 18 formed on the surface thereof, and further on the surface thereof, as shown in FIG. The light absorption layer 16 is formed.
[0037]
In both FIG. 1B and FIG. 1C, the acicular crystal layer 17 having unevenness on the side surface becomes one charge transport layer (n-type), and the charge transport layer and the charge transport layer (p-type) 12 A light absorption layer 16 is provided therebetween.
[0038]
When the acicular crystal layer 17 having irregularities on the side surface and the fine particle crystal layer according to the present embodiment are compared, the needle-like crystal layer 17 having irregularities on the side surface moves until electrons or holes generated by photoexcitation move to the collector electrode. The probability of being scattered by the grain boundary is reduced. In particular, as shown in FIG. 1 (b), when one end of an acicular crystal having irregularities on all side surfaces is joined to an electrode, in the movement of electrons or holes, In comparison, the effects of grain boundaries can be almost eliminated.
[0039]
In addition, when the configuration shown in FIG. 1C is compared with the Graetzel type cell, the influence of the grain boundary is almost eliminated, so that the movement of electrons and holes can be facilitated, and the semiconductor fine particles 18 are adsorbed. Therefore, the roughness factor (actual surface area / apparent surface area) can be improved while the influence of the grain boundary is small.
[0040]
In the photoelectric conversion device according to the present embodiment, the acicular crystal having irregularities is an n-type wide gap semiconductor, and therefore, an electrolysis including a p-type wide gap semiconductor and a redox pair with a light absorption layer 16 such as a dye interposed therebetween. An electron donating type charge transport layer 12 such as a liquid or a polymer conductor is required.
[0041]
Here, the light irradiation surface is determined by which surface the transparent electrode (glass substrate 14 and transparent electrode layer 15) is used. The configuration shown in FIG. 2A is an example in the case where a transparent electrode is used on the semiconductor crystal layer side and light is incident from the left side of the drawing as in the Graetzel type cell. The configuration shown in FIG. 2B is the opposite configuration, and is an example in which a transparent electrode is provided on the charge transport layer side and light is incident from the right side of the drawing. If there is little absorption and reflection of the irradiation light to a light absorption layer, either structure of Fig.2 (a) and (b) may be sufficient.
[0042]
Moreover, as shown in FIG.2 (c), the structure which can be utilized by the light irradiation from which surface may be sufficient. In other words, a transparent electrode may be provided on both the semiconductor crystal layer side and the charge transport layer side, and light may be incident from the left and right sides of the drawing. These structures depend on a method for producing acicular crystals having irregularities, and a method and composition of the charge transport layer to be combined. For example, in the case of producing acicular crystals having irregularities by electrodeposition on a Pt film, light irradiation cannot be performed from the acicular crystal surfaces having irregularities. When the acicular crystal surface having irregularities is produced by a low-temperature process such as firing of acicular crystal powder having irregularities, the transparent electrode layer can be produced without deteriorating, and either surface can be a light irradiation surface.
[0043]
Next, the acicular crystal 17 and the semiconductor mixed crystal having irregularities on the side surface which is the n layer will be described. The acicular crystal having irregularities on the side surface refers to a semiconductor crystal having irregularities on the outer peripheral surface of the acicular crystal, and refers to a crystal structure in which the surface area is increased by the size of the surface roughness of the irregularities.
[0044]
FIG. 3A is an enlarged view showing the needle-like crystal 17 having irregularities on the side surface. As shown in FIG. 3A, the concave portion 41 exists so as to crawl the needle-like crystal. In order to increase the roughness factor, it is desirable to have a structure with a small and rough surface as shown in FIG. 3A, rather than a small number of large recesses 41 as shown in FIG. 3B.
[0045]
The concave / convex recess depth is preferably 2% or more of the shortest distance of the outermost periphery of the needle crystal 17 (which is the minimum value of the thickness between the outermost periphery in the cross section of the needle crystal, this definition will be described later). Is preferably 10% or more because the surface area can be increased while maintaining the effect of needle-like crystals. Further, the height difference of the concavo-convex portion is preferably 2% or more of the longest distance from the center of the cross section of the transverse cut surface of the acicular crystal 17 to the surface, and more preferably 10% or more while maintaining the effect of the acicular crystal, This is preferable because the surface area can be enlarged.
[0046]
4A and 4B show an example of a cross-sectional view of the acicular crystal 17. Here, the recess depth of the concavo-convex portion is the depth of the depression from the outermost periphery 51 of the
[0047]
Further, the shortest distance of the outermost periphery of the needle-shaped crystal described above is a length in which the distance d between the two parallel lines 55 in contact with the outer periphery of the needle-shaped crystal is the shortest as shown in FIG. Point to. The height difference of the concavo-convex portion is a difference between the shortest distance 72 and the longest distance 73 from the cross-sectional center 71 to the surface 74 of the transverse cut surface of the acicular crystal having the concavo-convex as shown in FIG. The cross-sectional center 71 of the needle crystal 17 indicates the center of gravity of the transverse cut surface.
[0048]
Further, as shown in FIG. 5B, when etching is performed from the acicular crystal 78, the minimum value 76 from the cross-sectional center 75 of the transverse cut surface of the acicular crystal 78 to the surface 74 of the acicular crystal 17, and the extension thereof The ratio of the distance 77 to the surface 79 of the existing acicular crystal 78 is preferably 1/50 or more, and more preferably 1/10 or more, since the surface area can be increased while maintaining the effect of the acicular crystal. . The cross-sectional center 74 of the acicular crystal refers to the center of gravity of the transverse cut surface.
[0049]
Here, the acicular crystal includes all of a cylinder and a cone, a cone and a tip having a flat tip, a cylinder and a tip having a sharp tip, a tip having a flat tip, and the like. Furthermore, a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, a polygonal pyramid other than that, or a polygonal pyramid with a flat tip, or a triangular prism, a quadrangular prism, a hexagonal column, another polygonal pyramid, or a triangular prism with a sharp tip A quadrangular column, a hexagonal column, other polygonal column shapes, those having a flat tip, and the like are also included, and these broken line structures are also included.
[0050]
Further, the side surface of the needle-like crystal means a portion other than the tip if the tip is sharp, and a portion other than the flat portion if the tip is flat. Furthermore, the case where a metal such as Sn, Sb, Al, Ga or a compound of metal or S, Cl, N, or the like, which is an impurity, is mixed in a needle-like crystal having irregularities on the side surface is included. Furthermore, since the electron transfer efficiency is improved with growth on the substrate, as shown in FIG. 6 (a), a needle-like crystal having irregularities on the side surface is prepared, and then applied and baked as compared with the method of applying and baking. It is preferable to form it from the substrate as shown in b).
[0051]
Further, a semiconductor mixed crystal is a semiconductor layer in which an n-type charge transport layer is composed of a single substance or a mixture of at least two or more different modes or compositions, and one or more of the semiconductor layers include a needle-like crystal. It shall mean a crystal. FIG. 1C shows a specific configuration example of a semiconductor mixed crystal. By adsorbing the semiconductor crystal 18, the influence of the grain boundary is small and the roughness factor can be improved.
[0052]
The diameter of the semiconductor crystal 18 is preferably 100 nm or less, preferably 20 nm or less. Moreover, it is preferable that the semiconductor crystal 18 exists on the surface of the acicular crystal 17 having irregularities on the side surfaces. Here, the semiconductor fine particles preferably have a large energy gap, specifically, those having an energy gap of 3 eV or more are preferable.2, ZnO, SnO2The fine particles also include those obtained by etching.
[0053]
Next, the manufacturing method of the acicular crystal | crystallization which has the unevenness | corrugation which hits n layer, and a semiconductor mixed crystal is demonstrated. The method for producing acicular crystals having irregularities according to the present embodiment includes a step of etching the acicular crystals, and is generally performed in a gas phase or a liquid phase as a technique for etching the acicular crystals. . Etching in the gas phase mainly includes plasma etching under reduced pressure, and other methods include gas etching and ion etching.
[0054]
On the other hand, etching in the liquid phase is chemical etching, which is a means used for removing metals, semiconductors, and insulators by acid and alkali solutions, and electrolysis in which the substrate is dissolved in the solution by applying a potential. Divided into etching. The etching method is not limited to these.
[0055]
In addition, etching in a liquid phase in which the roughness factor increases by roughening the surface easily and unevenly is preferred, and it is particularly preferable to use an acid and ant potassium solution. At this time, examples of the acid used include sulfuric acid, acetic acid, formic acid, hydrochloric acid, nitric acid, hydrofluoric acid, phosphoric acid, chromic acid, and lactic acid. Examples of the alkali include sodium hydroxide, potassium hydroxide, ammonium hydroxide, Examples thereof include sodium phosphate, sodium carbonate, sodium carbonate, and the like, including but not limited to aqueous solutions and mixed solutions thereof.
[0056]
Furthermore, it is necessary to appropriately determine the type of acid and alkali depending on the composition of the needle crystal. For example, when etching TiO2 needle crystals using acid, sulfuric acid is preferred. When etching zinc oxide needle crystals using alkali, it can be dissolved in almost any alkali, so it can be easily treated with NaOH or the like. Is preferred. The height difference of the concavo-convex portion at this time is preferably selected as appropriate depending on the concentration, solution temperature, dissolution time, etc., as a matter of course, the type of acid and alkali.
[0057]
Moreover, as a manufacturing method of the acicular crystal which has an unevenness | corrugation on a side surface, it is preferable to perform etching, after controlling the diameter, length, and growth direction of an acicular crystal. This makes it possible to produce a semiconductor crystal having a large roughness factor even when the surface area of the needle-like crystal is insufficient, and to produce a needle-like crystal having irregularities with less influence of grain boundaries in the movement of electrons or holes. I can do it.
[0058]
In addition, as a method for manufacturing a semiconductor mixed crystal, at least acicular crystals can be obtained by adsorbing the semiconductor crystals 18 and then etching the acicular crystals, or by etching the acicular crystals and adsorbing the semiconductor crystals 18. As long as etching is performed, it is not restricted. That is, the semiconductor crystal 18 is a gel using a single crystal or a mixture of needles or crystals different in shape or composition from the needle-like crystals having irregularities on the side surfaces, on the needle-like crystals having irregularities in the former case, or on the needle-like crystals in the latter case. By applying a solution or the like, in the former case, as shown in FIG. 1C, a structure in which the semiconductor crystal 18 exists on the surface of the acicular crystal 17 having irregularities can be taken. In the latter case, after the semiconductor crystal 18 is adsorbed, needle-like crystals having irregularities are formed using the etching method.
[0059]
Next, the light absorption layer 16 will be described. As the light absorption layer 16 of the photoelectric conversion device according to the present embodiment, various semiconductors and pigments can be used. As the semiconductor, an amorphous semiconductor having a large i-type light absorption coefficient or a direct transition type semiconductor is preferable. As the dye, organic dyes such as metal complex dyes and / or polymethine dyes, perylene dyes, rose bengal, eosin Y, mercurochrome, Santalin dyes, cyanine dyes, and natural dyes are preferable.
[0060]
The dye preferably has an appropriate bonding group to the surface of the semiconductor fine particles. Preferred linking groups include COOH groups, cyano groups, PO3H2 groups, or chelating groups having π conductivity such as oximes, dioximes, hydroxyquinolines, salicylates and α-ketoenolates. Among these, a COOH group and a PO3H2 group are particularly preferable.
[0061]
When the dye used in this embodiment is a metal complex dye, a ruthenium complex dye {Ru (dcbpy) 2 (SCN) 2, (dcbpy = 2,2-bipyridine-4,4'-dicarboxylic acid), etc.] can be used. However, it is important that the oxidized / reduced substance is stable. In addition, the potential of the excited electron in the light absorption layer, that is, the potential of the photoexcited dye (LUMO potential of the dye) and the conduction charged position in the semiconductor are determined by the electron accepting potential (of the n-type semiconductor) of the electron accepting charge transporting layer. The hole potential generated by photoexcitation in the light absorption layer is higher than the electron donation potential of the electron donating charge transfer layer (valence charge potential of the p-type semiconductor, potential potential of the redox pair, etc.). It needs to be low. Reducing the probability of excited electron-hole recombination in the vicinity of the light absorption layer is also important in increasing the photoelectric conversion efficiency.
[0062]
Next, the charge transport layer 12 will be described. When an n-type semiconductor crystal is used, it is necessary to produce a hole transport layer with a light absorption layer interposed therebetween. A redox system can be used for this hole transport layer as well as a wet solar cell. Even when redox is used, not only a simple solution system but also a method of using carbon powder as a holding material or gelling an electrolyte. There is also a method using a molten salt or an ion conductive polymer. Furthermore, as a method for transporting electrons (holes), an electropolymerized organic polymer or a p-type semiconductor such as CuI, CuSCN, or NiO can be used.
[0063]
Since the above transport layer needs to penetrate between the needle-shaped crystals with irregularities on the side, the infiltration method that can be used for liquids and polymers, electrodeposition that can be used for the solid transport layer, CVD method, etc. are suitable ing.
[0064]
Next, the electrode layer will be described. An electrode layer is provided so as to be adjacent to the charge transport layer and the acicular crystal having irregularities. The electrode layer may be provided on the entire outer surface of these layers or a part thereof. When the charge transport layer is not solid, it is better to provide an electrode layer on the entire surface from the viewpoint of holding the charge transport layer. For example, a catalyst such as Pt or C is preferably provided on the surface of the electrode adjacent to the charge transport layer in order to efficiently reduce the redox couple.
[0065]
As the electrode layer on the light incident side, a transparent electrode made of indium-tin composite oxide, tin oxide doped with fluorine, or the like can be suitably used. If the resistance of the layer in contact with the light incident side electrode (charge transport layer or uneven needle-like crystal layer) is sufficiently low, a partial electrode such as a finger electrode may be provided as the light incident side electrode. Is possible. As the electrode that does not become the light incident side, a metal electrode made of Cu, Ag, Al or the like can be suitably used.
[0066]
Next, the substrate 14 will be described..The material and thickness of the substrate can be appropriately designed according to the durability required for the photovoltaic device. As long as the substrate on the light incident side is translucent, a glass substrate, a plastic substrate, or the like can be preferably used. As the substrate that does not become the light incident side, a metal substrate, a ceramic substrate, or the like can be used as appropriate. On the surface of the substrate on the light incident side, SiO2It is preferable to provide an antireflection film made of, for example.
[0067]
Note that a substrate separate from the electrode may not be provided by having the above-described electrode function as a substrate.
[0068]
Next, sealing will be described. Although not shown, it is preferable from the viewpoint of enhancing the weather resistance that the wet type photoelectric conversion device is sealed at least a portion other than the substrate. An adhesive or a resin can be used as the sealing material. Note that when the light incident side is sealed, the sealing material is preferably translucent.
[0069]
【Example】
Next, examples of the present invention will be described. This inventor produced the photoelectric conversion apparatus demonstrated by the above embodiment, and tried evaluation experiment. Hereinafter, this will be described as Examples 1 to 6.
[0070]
Example 1
In the first embodiment, FIG.7A zinc oxide needle-like crystal was produced using the electrodeposition apparatus of No. 1 and a needle-like crystal having irregularities was produced by immersing the zinc oxide needle-like crystal in an alkaline solution, and a photoelectric conversion device was produced using this. Note that the photoelectric conversion device of Example 1 corresponds to FIG.
[0071]
First, conductive glass substrate (F-doped SnO210 Ω / □), this substrate was immersed in a 2 mmol / L zinc nitrate aqueous solution 85 as a working electrode 83, and a potential of -1.2 V (vs. Ag / AgCl: reference electrode 81) was applied for 5000 seconds. . The conductive glass substrate corresponds to one substrate of the photoelectric conversion cell, and corresponds to, for example, the electrode-attached substrate 10 in FIG. Further, the counter electrode 82 was a zinc plate, and the electrolyte solution 85 in the beaker 84 was heated to 85 degrees with a mantle heater 86. After the electrolysis, zinc oxide needle crystals grew from the electrodes on the substrate surface. The zinc oxide needle crystal had a diameter of 40 to 50 nm and a length of 20 to 30 times the length. By immersing this substrate in a 1.0 mol / L NaOH aqueous solution for 1 minute, acicular crystals having irregularities could be obtained.
[0072]
In addition, Ru ((dcbpy) (COOH) which is a Ru complex as a dye2)2(SCN)2Was used. This dye was dissolved in distilled ethanol, and the needle-like crystal electrode on which the needle-like crystals having irregularities were formed as described above was immersed for 24 hours so that the dye was adsorbed to the electrode, and then taken out and dried at 80 ° C. . Next, conductive glass (F-doped SnO2, 10Ω / □) using a counter electrode (corresponding to the substrate on the other side of the photoelectric conversion cell, for example, corresponding to the substrate with electrode 13 in FIG. 1) in which platinum is sputtered to a thickness of 10 nm.-/ IThree -Was used.
[0073]
Solute is tetrapropylammonium iodide (0.46mol / L) and iodine (0.06mol / L), and solvent is ethylene carbonate (80vol%) and acetonitrile (20vol%). It was. This mixed liquid (corresponding to the charge transport layer 12) was dropped on a needle-like crystal having projections and depressions, and sandwiched between counter electrodes to produce a photoelectric conversion cell.
[0074]
As a comparative example, a cell was similarly assembled using a heat-treated zinc oxide fine particle having a particle size of about 100 nm as a main component. And the 500W xenon lamp light which attached the ultraviolet-ray cut filter was irradiated from the counter electrode side. The value of the photocurrent due to the photoelectric conversion reaction generated at this time was measured. As for the measurement results, both the short-circuit current and the photoelectric conversion efficiency of Example 1 were about 12% greater than those of the comparative example. This is considered to be due to the decrease in the internal resistance of the electron-accepting charge transport layer due to the use of the needle-like crystal electrode having irregularities.
[0075]
(Example 2)
In Example 2, titanium oxide needle crystals having irregularities were produced by immersing the titanium oxide needle crystals in an acid solution, and a photoelectric conversion device was produced using the titanium oxide needle crystals. Example 2 corresponds to FIG.
[0076]
First, a commercially available titanium oxide needle crystal (length 1.68 μm, diameter 0.13 μm, FTL-100: manufactured by Ishihara Sangyo) is immersed in a 1.0 mol / L H2SO4 aqueous solution for 1 minute to obtain a needle crystal having irregularities. It was. 3 g of the mixture was mixed with 5 mL of water, 0.2 mL of acetylacetone, and 0.2 mL of Triton-X (registered trademark: Union Carbide) to form a slurry. This slurry is made of conductive glass (F-doped SnO2, 10Ω / □) with a spacer of about 50 μm and a 1 cm square. The conductive glass corresponds to one substrate of the photoelectric conversion cell, and corresponds to, for example, the glass substrate with electrode 10 in FIG. Next, this was baked at 550 ° C. for 1 hour while flowing oxygen gas at 100 sccm. The film thickness of the acicular crystal layer 17 having unevenness after firing was about 10 μm.
[0077]
Commercially available mercurochrome was used as the pigment. This dye is dissolved in distilled ethanol, and the needle-like crystal electrode on which the needle-like crystals having irregularities as described above are soaked for 24 hours so that the dye is adsorbed to the electrode and then taken out and dried at 80 ° C. It was. Conductive glass (F-doped SnO2, 10Ω / □) using a counter electrode (corresponding to the other substrate of the photoelectric conversion cell, for example, corresponding to the electrode-attached substrate 13 in FIG. 1) in which platinum is sputtered to a thickness of 10 nm.-/ IThree -Was used.
[0078]
Solutes are 0.05 mol / L I2 (iodine), 0.1 mol / L LiI (lithium iodide), 0.6 mol / L DMPI (Im) (1,2-dimethyl-3-propylimidazolium iodide) and 0.5 mol / L TBP. (4-tert-butylpyridine), MAN (MeOAN) (methoxyacetonitrile) was used as the solvent. This mixed liquid (corresponding to the charge transport layer 12) was dropped on a needle-like crystal having projections and depressions, and sandwiched between counter electrodes to produce a photoelectric conversion cell.
[0079]
As a comparative example, a cell was similarly assembled using a heat-treated titanium oxide needle crystal (length: 1.68 μm, diameter: 0.13 μm, FTL-100: manufactured by Ishihara Sangyo). Then, a 500 W xenon lamp light equipped with an ultraviolet cut filter was irradiated from the counter electrode side. The value of the photocurrent due to the photoelectric conversion reaction generated at this time was measured. As for the measurement results, both the short-circuit current and the photoelectric conversion efficiency of Example 2 were about 8% greater than those of the comparative example. This is considered to be due to the increase in the surface area due to the use of acicular crystal electrodes having irregularities.
[0080]
(Example 3)
In Example 3, the figure7A zinc oxide needle crystal was manufactured using the electrodeposition apparatus of No. 1, and an acicular crystal having irregularities was produced by applying an oxidation potential to the zinc oxide needle crystal, and a photoelectric conversion device was produced using this. . Example 3 corresponds to the photoelectric conversion device of FIG.
[0081]
First, as in Example 1, a conductive glass substrate (F-doped SnO210 Ω / □), this substrate was immersed in a 2 mmol / L zinc nitrate aqueous solution 85 as a working electrode 83, and a potential of -1.2 V (vs. Ag / AgCl: reference electrode 81) was applied for 5000 seconds. . The conductive glass substrate corresponds to one substrate of the photoelectric conversion cell, for example, the electrode-attached substrate 10 in FIG. Further, the counter electrode 82 was a zinc plate, and the electrolyte solution 85 in the beaker 84 was heated to 85 degrees with a mantle heater 86. After the electrolysis, zinc oxide needle crystals grew from the electrodes on the substrate surface. The zinc oxide needle crystal had a diameter of 40 to 50 nm and a length of 20 to 30 times the length. Furthermore, by applying a potential of +1.0 V (vs. Ag / AgCl: reference electrode 81) to the zinc oxide needle crystal electrode for 10 seconds, a needle crystal having irregularities was obtained.
[0082]
The dye is Ru ((dcbpy) (COOH), a Ru complex reported by Graetzel et al.2)2(SCN)2Was used. This dye was dissolved in distilled ethanol, and the zinc oxide electrode on which the zinc oxide needle-like crystals were formed as described above was immersed in this for 24 hours so that the dye was adsorbed to the electrode, and then taken out and dried at 80 ° C. Conductive glass (F-doped SnO2, 10Ω / □) using a counter electrode (corresponding to the other substrate of the photoelectric conversion cell, for example, the substrate with electrode 13 in FIG. 1) in which platinum is sputtered to a thickness of 10 nm.-/ IThree -Was used.
[0083]
Solute is tetrapropylammonium iodide (0.46mol / L) and iodine (0.06mol / L), and solvent is ethylene carbonate (80vol%) and acetonitrile (20vol%). It was. This mixed liquid (corresponding to the charge transport layer 12) was dropped on a needle-like crystal having projections and depressions, and sandwiched between counter electrodes to produce a photoelectric conversion cell.
[0084]
Moreover, the cell was similarly assembled using what heat-processed the zinc oxide powder which has a particle size of 100 nm as a main component as a comparative example. Then, a 500 W xenon lamp light equipped with an ultraviolet cut filter was irradiated from the counter electrode side. The value of the photocurrent due to the photoelectric conversion reaction generated at this time was measured. As a result of the measurement, the cell of Example 3 was larger by about 3% in both the short-circuit current and the photoelectric conversion efficiency than the comparative example. This is considered to be due to the decrease in the internal resistance of the electron-accepting charge transport layer due to the use of the needle-like crystal electrode having irregularities.
[0085]
(Example 4)
In Example 4, the figure7A zinc oxide needle-like crystal was prepared using the electrodeposition apparatus of No. 1, and after the zinc oxide needle-like crystal was etched in the same manner as in Example 1, a semiconductor mixed crystal was prepared by applying a fine particle crystal, and this was used. Thus, a photoelectric conversion device was manufactured. Example 4 is a diagram.1Corresponds to (c).
[0086]
First, as in Example 1, a conductive glass substrate (F-doped SnO210 Ω / □), this substrate was immersed in a 2 mmol / L zinc nitrate aqueous solution 85 as a working electrode 83, and a potential of -1.2 V (vs. Ag / AgCl: reference electrode 81) was applied for 5000 seconds. . The conductive glass substrate corresponds to one substrate of the photoelectric conversion cell, and corresponds to, for example, the electrode-attached substrate 10 in FIG. Further, the counter electrode 82 was a zinc plate, and the electrolyte solution 85 in the beaker 84 was heated to 85 degrees with a mantle heater 86. After the electrolysis, zinc oxide needle crystals grew from the electrodes on the substrate surface. The zinc oxide needle crystal had a diameter of 40 to 50 nm and a length of 20 to 30 times the length.
[0087]
The substrate was immersed in a 1.0 mol / L NaOH aqueous solution for 1 minute in the same manner as in Example 1 to obtain needle crystals having irregularities. Thus, the electrode in which the acicular crystal | crystallization which has an unevenness | corrugation was formed was immersed in the tin-oxide colloid solution which has a particle size of 20 nm as a main component, and also oxygen flowed 1.67 * 10 <-3> L / s, and it is 1 at 550 degreeC. Perform time firing, figure1A semiconductor mixed crystal as shown in (c) was produced.
[0088]
Commercially available mercurochrome was used as the dye. This dye was dissolved in distilled ethanol, and the semiconductor mixed crystal electrode on which the semiconductor mixed crystal was formed as described above was immersed for 24 hours to adsorb the dye on the electrode, and then taken out and dried at 80 ° C. Conductive glass (F-doped SnO2, 10Ω / □) using a counter electrode (corresponding to the other substrate of the photoelectric conversion cell, for example, the substrate with electrode 13 in FIG. 1) in which platinum is sputtered to a thickness of 10 nm.-/ IThree -Was used. Solutes are 0.05 mol / L I2 (iodine), 0.1 mol / L LiI (lithium iodide), 0.6 mol / L DMPI (Im) (1,2-dimethyl-3-propylimidazolium iodide) and 0.5 mol / L TBP. (4-tert-butylpyridine), MAN (MeOAN) (methoxyacetonitrile) was used as the solvent. This mixed liquid (corresponding to the charge transport layer 12 in FIG. 1) was dropped onto the semiconductor mixed crystal and sandwiched between the counter electrode substrates to produce a photoelectric conversion cell.
[0089]
As a comparative example, a cell was assembled in the same manner using a zinc oxide fine particle having a particle size of about 100 nm as a main component and a tin oxide fine particle having a particle size of about 20 nm as a main component and heat-treated. Then, a 500 W xenon lamp light equipped with an ultraviolet cut filter was irradiated from the counter electrode side. The value of the photocurrent due to the photoelectric conversion reaction generated at this time was measured. As a result of the measurement, the cell of Example 4 was larger by about 12% in both the short-circuit current and the photoelectric conversion efficiency than the comparative example. This is considered due to the decrease in internal resistance of the electron-accepting charge transport layer due to the use of the semiconductor mixed crystal electrode.
[0090]
(Example 5)
In Example 5, the figure7Using this electrodeposition apparatus, a zinc oxide needle-like crystal is produced from a substrate electrode by electrolytic electrodeposition, a titanium oxide fine particle crystal is applied and baked, and then a semiconductor mixed crystal is produced by dipping in an alkaline solution. Thus, a photoelectric conversion device was manufactured. Example 5 is a diagram.1Corresponds to (c).
[0091]
First, conductive glass substrate (F-doped SnO210 Ω / □), this substrate was immersed in a 2 mmol / L zinc nitrate aqueous solution 85 as a working electrode 83, and a potential of -1.2 V (vs. Ag / AgCl: reference electrode 81) was applied for 5000 seconds. . The conductive glass substrate corresponds to one substrate of the photoelectric conversion cell, and corresponds to, for example, the electrode-attached substrate 10 in FIG. Further, the counter electrode 82 was a zinc plate, and the electrolyte solution 85 in the beaker 84 was heated to 85 degrees with a mantle heater 86. After the electrolysis, zinc oxide needle crystals grew from the electrodes on the substrate surface. The zinc oxide needle crystal had a diameter of 40 to 50 nm and a length of 20 to 30 times the length.
[0092]
This electrode was immersed in a titanium oxide fine particle solution having a particle size of about 20 nm as a main component, and further fired at 550 ° C. for 1 hour while flowing oxygen at 1.67 × 10 −3 L / s to produce a semiconductor mixed crystal. The substrate is immersed in a 10 mol / L NaOH aqueous solution for 10 minutes.1Acicular crystals having irregularities as shown in (c) were obtained.
[0093]
A commercially available eosin Y was used as the dye. This dye was dissolved in distilled ethanol, and the semiconductor mixed crystal electrode on which the semiconductor mixed crystal was formed as described above was immersed for 24 hours to adsorb the dye on the electrode, and then taken out and dried at 80 ° C. Conductive glass (F-doped SnO2, 10Ω / □) using a counter electrode (corresponding to the other substrate of the photoelectric conversion cell, for example, the substrate with electrode 13 in FIG. 1) in which platinum is sputtered to a thickness of 10 nm.-/ IThree -Was used.
[0094]
Solutes are 0.05 mol / L I2 (iodine), 0.1 mol / L LiI (lithium iodide), 0.6 mol / L DMPI (Im) (1,2-dimethyl-3-propylimidazolium iodide) and 0.5 mol / L TBP. (4-tert-butylpyridine), MAN (MeOAN) (methoxyacetonitrile) was used as the solvent. This mixed liquid (corresponding to the charge transport layer 12 in FIG. 1) was dropped onto the semiconductor mixed crystal and sandwiched between the counter electrode substrates to produce a photoelectric conversion cell.
[0095]
As a comparative example, a cell was similarly assembled using a titanium oxide fine particle mainly having a particle size of about 100 nm and a heat-treated zinc oxide fine particle mainly having a particle size of about 20 nm. Then, a 500 W xenon lamp light equipped with an ultraviolet cut filter was irradiated from the counter electrode side. The value of the photocurrent due to the photoelectric conversion reaction generated at this time was measured. As a result of the measurement, both the short-circuit current and the photoelectric conversion efficiency of the cell of Example 5 were about 12% larger than those of the comparative example. This is considered to be due to the decrease in internal resistance of the electron-accepting charge transport layer by using the conductor mixed crystal electrode.
[0096]
(Example 6)
In Example 6, acicular crystals having irregularities were manufactured using an etching apparatus in a gas phase, and a photoelectric conversion apparatus was manufactured using this. Example 6 corresponds to the photoelectric conversion device of FIG.
[0097]
First, 3 g of commercially available titanium oxide needle crystals (length: 5.15 μm, diameter: 0.27 μm, FTL-300: made by Ishihara Sangyo) 5 ml of water, 0.2 mL of acetylacetone, Triton-X (registered trademark: Union Carbide) Mix with 0.2 mL to make a slurry. This slurry is made of conductive glass (F-doped SnO2, 10Ω / □) with a spacer of about 50 μm and a 1 cm square. The conductive glass substrate corresponds to one substrate of the photoelectric conversion cell, and corresponds to, for example, the electrode-attached substrate 10 in FIG. Next, this substrate was baked at 550 ° C. for 1 hour while flowing oxygen gas at 100 sccm. The film thickness of the acicular crystal layer after firing was about 10 μm. This electrode was etched in the gas phase. As etching conditions, BCl3 was performed at 5 to 10 Pa under 200 W for 30 to 120 seconds.
[0098]
The dye is Ru complex Ru ((dcbpy) (COOH)2)2(SCN)2Was used. This dye was dissolved in distilled ethanol, and an acicular crystal electrode having projections and depressions was immersed in it for 24 hours to adsorb the dye to the electrode, and then taken out and dried at 80 ° C. Conductive glass (F-doped SnO2, 10Ω / □) using a counter electrode (corresponding to the other substrate of the photoelectric conversion cell, for example, the substrate with electrode 13 in FIG. 1) in which platinum is sputtered to a thickness of 10 nm.-/ IThree -Was used.
[0099]
Solute is tetrapropylammonium iodide (0.46mol / L) and iodine (0.06mol / L), and solvent is ethylene carbonate (80vol%) and acetonitrile (20vol%). It was. This mixed liquid (corresponding to the charge transport layer 12) was dropped on a needle-like crystal having projections and depressions, and sandwiched between counter electrodes to produce a photoelectric conversion cell.
[0100]
As a comparative example, a cell was assembled in the same manner using a commercially available titanium oxide needle crystal (length: 5.15 μm, diameter: 0.27 μm, FTL-300: manufactured by Ishihara Sangyo). Then, a 500 W xenon lamp light equipped with an ultraviolet cut filter was irradiated from the counter electrode side. The value of the photocurrent due to the photoelectric conversion reaction generated at this time was measured. As a result of the measurement, both the short-circuit current and the photoelectric conversion efficiency of the cell of Example 5 were about 1% larger than those of the comparative example. This is considered to be due to the increase in the surface area due to the use of acicular crystal electrodes having irregularities.
[0101]
【The invention's effect】
As described above, according to the present invention, since an acicular crystal having irregularities on the side surface is used as the n-type charge transport layer, electrons can be transferred smoothly and a photoelectric conversion device with high conversion efficiency. Can be realized. Further, it is possible to realize a photoelectric conversion device having a semiconductor electrode in which a light absorption layer such as a dye or a charge transport layer such as an electrolytic solution penetrates and moves quickly, and a photoelectric conversion device having a large short-circuit current value.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an embodiment of a photoelectric conversion device of the present invention.
FIG. 2 is a diagram for explaining a relationship between a light irradiation direction of a photoelectric conversion device according to the present invention and a transparent electrode.
FIG. 3 is a diagram showing a needle-like crystal having irregularities on its side surface.
FIG. 4 is a cross-sectional view of a needle-like crystal having irregularities on its side surface.
FIG. 5 is a cross-sectional view of a needle-like crystal having irregularities on its side surface.
FIG. 6 is a cross-sectional view showing acicular crystals due to a difference in the manufacturing method of the photoelectric conversion device of the present invention.
FIG. 7 is a view showing an acicular crystal film manufacturing apparatus using electrodeposition.
FIG. 8 is a cross-sectional view showing a conventional Graetzel cell.
[Explanation of symbols]
10 Substrate with electrodes
11 Absorbing layer modified semiconductor crystal layer
12 Charge transport layer
13 Substrate with electrodes
14 Glass substrate
15 Transparent electrode layer
16 Light absorption layer
17 Acicular crystals with irregularities (acicular crystal layers with irregularities)
18 Semiconductor crystal
41 Recessed position
51 outermost circumference
52 recess
53 outer circumference
54 Depth of recess
55 parallel lines
56 Parallel line distance (d)
61 Anatase TiO2Fine particles
62 Light absorption layer
63 Electrolyte
64 glass
65 Transparent electrode layer (anode)
66 Transparent electrode layer (cathode)
71 Center of transverse cut surface of acicular crystal layer having irregularities
72 Shortest distance of acicular crystal layer with irregularities
73 Longest distance of acicular crystal layer with irregularities
74 Surface of acicular crystal layer with irregularities
75 Center of transverse cross section of acicular crystal
76 Minimum distance of acicular crystals
77 Distance to the surface of the transverse cut surface of the needle-like crystal
78 acicular crystals
79 Surface of acicular crystal layer
81 Reference electrode
82 Counter electrode
83 samples (working electrode)
84 Beaker
85 electrolyte
86 Mantle heater
Claims (8)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2002095763A JP4289823B2 (en) | 2002-03-29 | 2002-03-29 | Method for producing dye-sensitized solar cell |
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| JP4807020B2 (en) * | 2005-09-21 | 2011-11-02 | 東洋製罐株式会社 | Method for producing binder composition for dispersing semiconductor fine particles |
| JP4942349B2 (en) * | 2006-01-25 | 2012-05-30 | シャープ株式会社 | Dye-sensitized solar cell, manufacturing method thereof, and manufacturing apparatus |
| CN114715971A (en) * | 2022-04-19 | 2022-07-08 | 浙江大学 | Preparation method and application of solar-driven interface sewage treatment device |
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