JP2009252726A - 色素増感型太陽電池 - Google Patents
色素増感型太陽電池 Download PDFInfo
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- JP2009252726A JP2009252726A JP2008103440A JP2008103440A JP2009252726A JP 2009252726 A JP2009252726 A JP 2009252726A JP 2008103440 A JP2008103440 A JP 2008103440A JP 2008103440 A JP2008103440 A JP 2008103440A JP 2009252726 A JP2009252726 A JP 2009252726A
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- dye
- solar cell
- sensitized solar
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- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- UTXIVEZZTQLQDT-UHFFFAOYSA-N silver nitric acid nitrate Chemical compound [N+](=O)(O)[O-].[N+](=O)([O-])[O-].[Ag+] UTXIVEZZTQLQDT-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
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- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- KICVIQZBYBXLQD-UHFFFAOYSA-M sodium;2,5-dihydroxybenzenesulfonate Chemical compound [Na+].OC1=CC=C(O)C(S([O-])(=O)=O)=C1 KICVIQZBYBXLQD-UHFFFAOYSA-M 0.000 description 1
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- 239000007962 solid dispersion Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 230000003637 steroidlike Effects 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
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- 125000004962 sulfoxyl group Chemical group 0.000 description 1
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- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 239000013077 target material Substances 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- KEBMUYGRNKVZOX-UHFFFAOYSA-N tetra(propan-2-yl)silane Chemical compound CC(C)[Si](C(C)C)(C(C)C)C(C)C KEBMUYGRNKVZOX-UHFFFAOYSA-N 0.000 description 1
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- 239000002562 thickening agent Substances 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
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- 125000005580 triphenylene group Chemical group 0.000 description 1
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- ZRXVCYGHAUGABY-UHFFFAOYSA-O tris(4-bromophenyl)azanium Chemical compound C1=CC(Br)=CC=C1[NH+](C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 ZRXVCYGHAUGABY-UHFFFAOYSA-O 0.000 description 1
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
【解決手段】少なくとも導電体を含む基材1上に、少なくとも増感色素2を吸着させた半導体多孔質層3を有するアノード電極と、該アノード電極の半導体多孔質層側に対向する透光性導電性基板4からなるカソード電極、及び前記アノード電極と該カソード電極の2枚の電極間に電解質層を封止した構成を有する色素増感型太陽電池において、該透光性導電性基板4が、少なくとも透明基材上に、線幅が5μm〜20μm、且つ、開口率が84%〜98%である集電線42を有し、該集電線の表面が第1の導電性被覆層43によって被覆されていることを特徴とする色素増感型太陽電池。
【選択図】図1
Description
該透光性導電性基板が、少なくとも透明基材上に、線幅が5μm〜20μm、且つ、開口率が84%〜98%である集電線を有し、該集電線の表面が第1の導電性被覆層によって被覆されていることを特徴とする色素増感型太陽電池。
本発明に係る透光性導電性基板(カソード電極ともいう)について説明する。
本発明に係る透光性導電性基板は、透明基材上に、線幅が5μm〜20μmであり、且つ、開口率が84%〜98%の範囲である集電線(以下、「集電グリッド」と呼ぶこともある)を有し、少なくとも前記集電線の表面が第1の導電性被覆層によって被覆されていることが特徴である。
〔(開口率)={(全体の面積)−(集電線が締める面積)}/(全体の面積)×100〕(%)で表される。
〔(線幅比)=(集電線の線幅)/(銀細線の線幅)〕の関係である。
本発明に係る集電線(以下、「集電グリッド」ともいう)の銀塩法による形成方法について詳細に説明する。
本発明で用いられるハロゲン化銀粒子の組成は、塩化銀、臭化銀、塩臭化銀、沃臭化銀、塩沃臭化銀、塩沃化銀など任意のハロゲン組成を有するものであってもよいが、階調を硬くし、露光安定性を向上させるためには塩臭化銀粒子が好ましく用いられる。臭素を含有させることによりハロゲン化銀粒子の保存安定性が向上するが、臭素含有率が高くなりすぎると現像性が低下しやすく、またハロゲン化銀塗布量が1.5g/m2未満と少ない場合は特に軟調化しやすいことから、臭素含有率は2から30モル%、更に好ましくは5から20モル%である。
本発明に係るハロゲン化銀乳剤含有層において、ハロゲン化銀粒子を均一に分散させ、且つハロゲン化銀粒子を支持体上に担持し、ハロゲン化銀乳剤含有層と支持体の接着性を確保する目的でバインダを用いる。本発明に用いることができるバインダには特に制限がなく、非水溶性ポリマ及び水溶性ポリマのいずれも用いることができるが、現像性向上の観点からは水溶性ポリマを用いることが好ましい。
本発明においては、エッジが明瞭な銀細線パターンを描くために感光材料は硬調である態様が好ましく、その方法として、塩化銀含有量を高くして粒径の分布を狭くする方法、あるいはヒドラジン化合物やテトラゾリウム化合物を硬調化剤として使用することが好ましい。ヒドラジン化合物は−NHNH−基を有する化合物であり、代表的なものを下記一般式(1)で示す。
式中、Tは各々置換されてもよいアリール基、ヘテロ環基を表す。Tで表されるアリール基はベンゼン環やナフタレン環を含むもので、この環は置換基を有してもよく、好ましい置換基として、直鎖、分岐のアルキル基(好ましくは炭素数1〜20のメチル基、エチル基、イソプロピル基、n−ドデシル基など)、アルコキシ基(好ましくは炭素数2〜21のメトキシ基、エトキシ基など)、脂肪族アシルアミノ基(好ましくは炭素数2〜21のアルキル基を持つ、アセチルアミノ基、ヘプチルアミノ基など)、芳香族アシルアミノ基などが挙げられ、これらの他に、例えば、上記のような置換または未置換の芳香族環が−CONH−、−O−、−SO2NH−、−NHCONH−、−CH2CH=N−などの連結基で結合しているものも含む。
(H−2):1−トリフロロメチルカルボニル−2−{4−〔2−(2,4−ジ−t−ペンチルフェノキシ)ブチルアミド〕フェニル}ヒドラジン
(H−3):1−(2,2,6,6−テトラメチルピペリジル−4−アミノ−オキザリル)−2−{4−〔2−(2,4−ジ−t−ペンチルフェノキシ)ブチルアミド〕フェニル}ヒドラジン
(H−4):1−(2,2,6,6−テトラメチルピペリジル−4−アミノ−オキザリル)−2−{4−〔2−(2,4−ジ−t−ペンチルフェノキシ)ブチルアミド〕フェニルスルホンアミド}ヒドラジン
(H−5):1−(2,2,6,6−テトラメチルピペリジル−4−アミノ−オキザリル)−2−{4−〔3−(4−クロロフェニル−4−フェニル−3−チア)ブタンアミド〕ベンゼンスルホンアミド}ヒドラジン
(H−6):1−(2,2,6,6−テトラメチルピペリジル−4−アミノ−オキザリル)−2−(4−(3−チア−6,9,12,15−テトラオキサトリコサンアミド)ベンゼンスルホンアミド)フェニルヒドラジン
(H−7):1−(1−メチレンカルボニルピリジニウム)−2−(4−(3−チア−6,9,12,15−テトラオキサトリコサンアミド)ベンゼンスルホンアミド)フェニルヒドラジンクロライド。
本発明に係る透明基材は、光の透過率が50%以上であることを意味し、80%以上であることが好ましく、95%以上であることが特に好ましい。材質としてはガラス板や、酸化チタンやアルミナなどのセラミックの研磨板、更に公知の種々のプラスチックシートを使用することが可能である。
本発明に係る感光材料においては、後述する現像、物理現像、メッキ処理により、導電性金属パターンを形成するために感光材料の露光を行う。露光に用いられる光源としては、例えば、可視光線、紫外線などの光、電子線、X線などの放射線などが挙げられるが、紫外線または近赤外線を用いることが好ましい。更に露光には波長分布を有する光源を利用してもよく、波長分布の狭い光源を用いてもよい。
本発明では、感光材料を露光した後、現像処理が行われる。現像処理は発色現像主薬を含有しない、いわゆる黒白現像処理であることが好ましい。
本発明では、後に説明する電解メッキ処理を効率よく行うため、物理現像処理によって現像銀同士の接触を促し、導電性を高めることが好ましい。物理現像処理とは現像処理中、あるいは処理後に予め感光材料中に含有されていない銀源を外部から供給し、導電性を高める処理のことを指す。物理現像は、潜像を有するハロゲン化銀乳剤を含有する感光材料を銀イオンあるいは銀錯イオンと還元剤を含有する処理液に浸漬することで、これを施すことができる。
本発明に係る集電線においては、メッキ処理により導電性金属パターンを形成してなることが好ましいが、このメッキ処理には従来公知の種々のメッキ方法を用いることができ、例えば、電解メッキ及び無電解メッキを単独、あるいは組み合わせて実施することができる。
本発明においては、現像処理あるいは物理現像またはメッキ処理後に酸化処理を行うことが好ましい。酸化処理により、不要な金属成分をイオン化して溶解除去することが可能となり、透過率をより高めることが可能となる。
本発明に係る導電性被覆層(第1の導電性被覆層、第2の導電性被覆層)について説明する。
本発明に係る導電体を含む基材としては、公知種々の金属や金属酸化物等からなる無機系導電性材料、無機有機複合型の導電性材料、カーボン系材料、またはこれらを任意に混合した導電性材料など、あらゆるものを使用することができる。
本発明に係る半導体多孔質膜層を形成する多孔質体は、金属酸化物に代表されるセラミック半導体微粒子から成ることが好ましい。半導体微粒子の組成は価電子帯(VB)と伝導帯(CB)のバンドギャップが3eV程度あれば特に限定しないが、ナノポーラス膜の形成し易さから金属酸化物であることが好ましい。
M(R1)x(R2)y(R3)z
上記一般式において、Mは金属(例えば、Li、Be、B、Na、Mg、Al、Si、K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、Rb、Sr、Y、Zr、Nb、Mo、Cd、In、Ir、Sn、Sb、Cs、Ba、La、Hf、Ta、W、Tl、Pb、Bi、Ce、Pr、Nd、Pm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等)を表し、R1はアルキル基、R2はアルコキシ基、R3はβ−ジケトン配位基、β−ケトカルボン酸エステル配位基、β−ケトカルボン酸配位基及びケトオキシ基(ケトオキシ配位基)から選ばれる基であり、金属Mの価数をmとした場合、x+y+z=mであり、x=0〜m、またはx=0〜m−1であり、y=0〜m、z=0〜mで、何れも0または正の整数である。
(1)半導体微粒子を含有する懸濁液を導電性基材上に塗布し、乾燥及び焼成を行って半導体層を形成する方法、
(2)コロイド溶液中に導電性基材を浸漬して電気泳動により半導体微粒子を導電性基材上に付着させる泳動電着法、
(3)コロイド溶液や分散液に発泡剤を混合して塗布した後、焼結して多孔質化する方法、
(4)ポリママイクロビーズを混合して塗布した後、このポリママイクロビーズを加熱処理や化学処理により除去して空隙を形成させ多孔質化する方法などを適用することができる。
本発明において、前述した半導体多孔質膜層2の表面に吸着させる色素3としては、種々の可視光領域及び/または赤外光領域に吸収を有し、金属酸化物半導体の伝導帯より高い最低空準位を有する色素が好ましく、公知の様々な色素を使用することができる。例えば、アゾ系色素、キノン系色素、キノンイミン系色素、キナクリドン系色素、スクアリリウム系色素、シアニン系色素、シアニジン系色素、メロシアニン系色素、トリフェニルメタン系色素、キサンテン系色素、ポルフィリン系色素、ペリレン系色素、インジゴ系色素、フタロシアニン系色素、ナフタロシアニン系色素、ローダミン系色素、ローダニン系色素などが挙げられる。なお、金属錯体色素も好ましく使用され、その場合においては、Cu、Ni、Fe、Co、V、Sn、Si、Ti、Ge、Cr、Zn、Ru、Mg、Al、Pb、Mn、In、Mo、Y、Zr、Nb、Sb、La、W、Pt、Ta、Ir、Pd、Os、Ga、Tb、Eu、Rb、Bi、Se、As、Sc、Ag、Cd、Hf、Re、Au、Ac、Tc、Te、Rhなどの種々の金属を用いることができる。
電荷移動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層である。本発明で用いることのできる代表的な電荷輸送材料の例としては、酸化還元対イオンが溶解した溶剤や酸化還元対イオンを含有する常温溶融塩などの電解液、酸化還元対イオンの溶液をポリママトリクスや低分子ゲル化剤等に含浸したゲル状の擬固体化電解質、更には高分子固体電解質等が挙げられる。また、イオンが関わる電荷輸送材料の他に、固体中のキャリア移動が電気伝導に関わる材料として、電子輸送材料や正孔(ホール)輸送材料を挙げることもでき、これらは併用してすることも可能である。
《透光性導電性基材の作製》
〔下引層形成〕
2mm厚のガラス基板片面に12W・min/m2のコロナ放電処理を施し、下引塗布液B−1を乾燥膜厚0.1μmになるように塗布し、その上に12W・分/m2のコロナ放電処理を施し、下引塗布液B−2を乾燥膜厚0.06μmになるように塗布した。
スチレン20質量部、グリシジルメタクリレート40質量部、ブチルアクリレート40質量部の共重合体ラテックス液(固形分質量30%) 50g
SnO2ゾル(A) 440g
化合物(UL−1) 0.2g
水で仕上げる 1000ml
〈下引塗布液B−2〉
ゼラチン 10g
化合物(UL−1) 0.2g
化合物(UL−2) 0.2g
シリカ粒子(平均粒径3μm) 0.1g
硬膜剤(UL−3) 1g
水で仕上げる 1000ml
(SnO2ゾル(A)の調製)
65gのSnCl4・5H2Oを蒸留水2000mlに溶解して均一溶液とし、次いでこれを煮沸し、沈澱物を得た。生成した沈澱物をデカンテーションにより取り出し、蒸留水にて何度も水洗する。
反応容器内で、下記の溶液−Aを34℃に保ち、特開昭62−160128号公報記載の混合撹拌装置を用いて高速に撹拌しながら、硝酸(濃度6%)を用いてpHを2.95に調整した。
アルカリ処理不活性ゼラチン(平均分子量10万) 18.7g
塩化ナトリウム 0.31g
下記(溶液−I) 1.59ml
純水 1246ml。
硝酸銀 169.9g
硝酸(濃度6%) 5.89ml
純水にて317.1mlに仕上げる。
アルカリ処理不活性ゼラチン(平均分子量10万) 5.66g
塩化ナトリウム 58.8g
臭化カリウム 13.3g
(溶液−I) 0.85ml
(溶液−II) 2.72ml
純水にて317.1mlに仕上げる。
2−メチル−4ヒドロキシ−1,3,3a,7−テトラアザインデン 0.56g
純水 112.1ml。
アルカリ処理不活性ゼラチン(平均分子量10万) 3.96g
下記(溶液−I) 0.40ml
純水 128.5ml。
界面活性剤:ポリイソプロピレンポリエチレンオキシジコハク酸エステルナトリウム塩の10質量%メタノール溶液
(溶液−II)
6塩化ロジウム錯体の10質量%水溶液。
アルカリ処理不活性ゼラチン(平均分子量10万) 16.5g
純水 139.8ml。
上記で作製した、下引き済みガラス基板(Base1)上に、前述のハロゲン化銀微粒子乳剤EMP−1を、塗布銀量が銀換算で0.8g/m2となるように塗布を行った後、乾燥して、感光材料101を作製した。
上記で作製した感光材料101に対して、ライン幅(銀細線の線幅ともいう)が8μm、ライン同士の間隔が250μmの格子状のフォトマスクを介して、紫外線ランプを用いて露光を行った。
純水 500ml
メトール 2g
無水亜硫酸ナトリウム 80g
ハイドロキノン 4g
ホウ砂 4g
チオ硫酸ナトリウム 10g
臭化カリウム 0.5g
水を加えて全量を1Lとする。
純水 750ml
チオ硫酸ナトリウム 250g
無水亜硫酸ナトリウム 15g
氷酢酸 15ml
カリミョウバン 15g
水を加えて全量を1Lとする。
純水 800ml
クエン酸 31g
ハイドロキノン 7.8g
リン酸水素二ナトリウム 1.1g
アンモニア水(28%) 2.2ml
硝酸銀 1.5g
水を加えて全量を1Lとする。
硫酸銅(五水和物) 200g
硫酸 50g
塩化ナトリウム 0.1g
水を加えて全量を1Lとする。
透光性導電性基板S101の作製において、感光材料101に対して、ライン幅が8μm、ライン同士の間隔が500μmの格子状のフォトマスクを用いて露光を行った以外は同様にして透光性導電性基板S102を作製した。
透光性導電性基板S101の作製において、感光材料101に対して、ライン幅が8μm、ライン同士の間隔が150μmの格子状のフォトマスクを用いて露光を行った以外は同様にして透光性導電性基板S103を作製した。
透光性導電性基板S101の作製において、感光材料101に対して、ライン幅が8μm、ライン同士の間隔が100μmの格子状のフォトマスクを用いて露光を行った以外は同様にして透光性導電性基板S104を作製した。
透光性導電性基板S101の作製において、感光材料101に対して、ライン幅が5μm、ライン同士の間隔が150μmの格子状のフォトマスクを介して露光を行い、更に、電界銅メッキは印加電流及び処理時間を調整し、集電線の線幅が8.5μmになるまで処理した以外は同様にして透光性導電性基板S105を作製した。
透光性導電性基板S101の作製において、感光材料101に対して、ライン幅が12μm、ライン同士の間隔が400μmの格子状のフォトマスクを介して露光を行い、更に、電界銅メッキは印加電流及び処理時間を調整し、集電線の線幅が20μmになるまで処理した以外は同様にして透光性導電性基板S106を作製した。
透光性導電性基板S101の作製において、感光材料101に対して、ライン幅が8μm、ライン同士の間隔が300μmの格子状のフォトマスクを介して露光を行い、更に、電界銅メッキは印加電流及び処理時間を調整し、集電線の線幅が20μmになるまで処理した以外は同様にして透光性導電性基板S107を作製した。
透光性導電性基板S101の作製において、感光材料101に対して、ライン幅が12μm、ライン同士の間隔が500μmの格子状のフォトマスクを介して露光を行い、更に、電界銅メッキは印加電流及び処理時間を調整し、集電線の線幅が25μmになるまで処理した以外は同様にして透光性導電性基板S108を作製した。
透光性導電性基板S101の作製において、感光材料101に対して、ライン幅が12μm、ライン同士の間隔が1000μmの格子状のフォトマスクを介して露光を行い、更に、電界銅メッキは印加電流及び処理時間を調整し、集電線の線幅が30μmになるまで処理した以外は同様にして透光性導電性基板S109を作製した。
透光性導電性基板S101の作製において、集電グリッド上及び開口部にスズドープ酸化インジウム(ITO)の層及び白金層を形成しない以外は前記S101と同様にして透光性導電性基板S110を作製した。
前記2mm厚のガラス基板に、スズドープ酸化インジウム(ITO)材をターゲットに、高周波マグネトロンスパッタリング装置を用い、膜厚が150nmになるように導電性被覆層を形成させ、更に同様にして、白金板をターゲットに膜厚が2nmになるようにPtを形成させ、透光性導電性基板S111を作製した。
透光性導電性基板S101の作製において、スズドープ酸化インジウム(ITO)材に換えて、フッ素ドープ酸化スズ(FTO)材をターゲットに、高周波マグネトロンスパッタリング装置を用い、膜厚が150nmになるように導電性被覆層を形成させた以外は同様にして透光性導電性基板S112を作製した。
透光性導電性基板S101の作製において、高周波マグネトロンスパッタリング装置を用いて形成させた導電性被覆層に換えて、H.C.スタルク社製バイトロンPH510(BAYTRON−PH510にDMSOを5%添加した水溶液を使用)を乾燥膜厚が100nmになるように形成させた以外は同様にして透光性導電性基板S113を作製した。
透光性導電性基板S101〜S113において、電解銅メッキ処理前、及び処理後において、格子パターンを形成しているラインの線幅をマイクロスコープMS−804(モリテックス製)を用いて測定した。
透光性導電性基板S101〜S113において、電解銅メッキ処理後、表面を導電性被覆層で被覆した透光性導電性基板における表面抵抗値を、抵抗率計(ロレスタGP(MCP−T610型):(株)ダイヤインスツルメンツ製)を用いて測定した。測定は基板の中心部で行った。
チタン板上に、高周波マグネトロンスパッタリング装置を用い、短絡防止層として酸化チタン板をターゲット材に10nm厚の半導体膜を形成させた。その上に、光吸収層用の酸化チタンペースト(SOLARONIX社製Ti−Nanoxide−D/SP)をスクリーン印刷機により印刷した。
色素増感型太陽電池SC−101の作製において、透光性導電性基板S101に代えて、透光性導電性基板S102〜S113を用いた以外は同様にして、色素増感型太陽電池SC−102〜SC−113を各々作製した。
上記で作製した色素増感型太陽電池(太陽電池セルともいう)について、ソーラーシミュレーター(英弘精機社製SS−100XIL)により、AM1.5フィルタ、100mW/m2の強度の光を照射した時の特性として、短絡電流Jsc(mA/cm2)及び開放電圧値Voc(V)を、同じ構成及び作製方法で各々3つ評価し平均値で表した。
《透光性導電性基材の作製》
実施例1と同様に、下引層を施したBase1上に、前述のように調製したハロゲン化銀微粒子乳剤EMP−1を、塗布銀量が銀換算で0.4g/m2となるように塗布を行った以外は実施例1と同様にして感光材料201を作製した。
上述のようにして作製した感光材料201に対して、ライン幅(銀細線の線幅ともいう)が12μm、ライン同士の間隔が250μmの格子状のフォトマスクを介して、紫外線ランプを用いて露光を行った。
透光性導電性基板S201の作製において、感光材料201に対して、ライン幅が8μm、ライン同士の間隔が250μmの格子状のフォトマスクを介して露光を行い、更に、電界銅メッキは印加電流及び処理時間を調整し、線幅が12.5μmになるまで処理した以外は同様にして、透光性導電性基板S202を作製した。
《メッキ前後の線幅比、集電線の断面積測定》
実施例1の透光性導電性基板S101及び、上記で得られた透光性導電性基板S201〜S202において、電解銅メッキ処理前、及び処理後において、格子パターンを形成しているラインの線幅をマイクロスコープMS−804(モリテックス製)を用いて測定し、その比率を求め表2に示した。
透光性導電性基板S101及びS201〜S202において、電解銅メッキ処理後、表面を導電性被覆層で被覆した透光性導電性基板における表面抵抗値を、抵抗率計(ロレスタGP(MCP−T610型):(株)ダイヤインスツルメンツ製)を用いて測定した。測定は基板の中心部で行い、その結果を表3に示した。
色素増感型太陽電池SC−101の作製において、透光性導電性基板S101に換えて、S201、S202を各々用いた以外は同様にして色素増感型太陽電池SC−201、SC−202を各々作製した。
上記で作製した色素増感型太陽電池(太陽電池セルともいう)SC−201、202について、ソーラーシミュレーター(英弘精機社製SS−100XIL)により、AM1.5フィルタ、100mW/m2の強度の光を照射した時の特性を測定し、短絡電流Jsc(mA/cm2)及び開放電圧値Voc(V)を、同じ構成及び作製方法で3つ評価し平均値を求めた。また、Jsc、VocとFF(フィルファクター)から光電変換効率η(%)を求めた。
《フレキシブル色素増感型太陽電池の作製》
実施例1において、透光性導電性基板SC−101の作製に用いた2mm厚のガラス基板に替えてポリエチレンテレフタレート(PEN)基板を用い、アノード極に用いたチタン板に替えてチタン箔膜フィルムを用い、更に、光吸収層用の酸化チタンペーストをSOLARONIX社製Ti−Nanoxide−D/SPに替えて同社製Ti−Nanoxide−DLをスクリーン印刷機により印刷し120℃で焼結させた以外は同様にして、フレキシブルな色素増感型太陽電池を作製した。
2 増感色素分子
3 半導体多孔質層
4 透光性導電性基板(カソード電極)
5 電荷移動層
6 封止材
41 透明基材
42 集電線
42a 導電性メッキ層
42b 金属細線
43 導電性被覆層
Claims (10)
- 少なくとも導電体を含む基材上に、少なくとも増感色素を吸着させた半導体多孔質層を有するアノード電極と、該アノード電極の半導体多孔質層側に対向する透光性導電性基板からなるカソード電極、及び前記アノード電極と該カソード電極の2枚の電極間に電解質層を封止した構成を有する色素増感型太陽電池において、
該透光性導電性基板が、少なくとも透明基材上に、線幅が5μm〜20μm、且つ、開口率が84%〜98%である集電線を有し、該集電線の表面が第1の導電性被覆層によって被覆されていることを特徴とする色素増感型太陽電池。 - 前記集電線が、銀細線に導電性金属が電解メッキされた2層構成を有し、前記集電線と該銀細線との線幅比が1.2〜2.0(線幅比=集電線の線幅/銀細線の線幅)であることを特徴とする請求項1に記載の色素増感型太陽電池。
- 前記集電線の断面積が30μm2〜200μm2であることを特徴とする請求項1または2に記載の色素増感型太陽電池。
- 前記導電性被覆層が、金属酸化物からなることを特徴とする請求項1〜3のいずれか1項に記載の色素増感型太陽電池。
- 前記導電性被覆層が、導電性高分子からなることを特徴とする請求項1〜3のいずれか1項に記載の色素増感型太陽電池。
- 前記集電線の表面が第1の導電性被覆層により被覆されており、且つ、透光性導電性基板の開口部が第2の導電性被覆層によって被覆されていることを特徴とする請求項1〜5のいずれか1項に記載の色素増感型太陽電池。
- 前記第1の導電性被覆層が、レドックス触媒能を有する材料からなることを特徴とする請求項6に記載の色素増感型太陽電池。
- 前記第2の導電性被覆層が、金属酸化物からなることを特徴とする請求項6または7に記載の色素増感型太陽電池。
- 前記第2の導電性被覆層が、導電性高分子からなることを特徴とする請求項1〜7のいずれか1項に記載の色素増感型太陽電池。
- 前記透明基材が、各々可撓性基材からなることを特徴とする請求項1〜9のいずれか1項に記載の色素増感型太陽電池。
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