JP2012069444A - 光電変換素子及び太陽電池 - Google Patents
光電変換素子及び太陽電池 Download PDFInfo
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- JP2012069444A JP2012069444A JP2010214597A JP2010214597A JP2012069444A JP 2012069444 A JP2012069444 A JP 2012069444A JP 2010214597 A JP2010214597 A JP 2010214597A JP 2010214597 A JP2010214597 A JP 2010214597A JP 2012069444 A JP2012069444 A JP 2012069444A
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- 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
-
- 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
- Y02E10/549—Organic PV cells
Abstract
【解決手段】基板、第1電極、半導体および増感色素を有する光電変換層、電荷輸送層、並びに、第2電極を、順に設置して成る光電変換素子において、前記半導体に下記一般式(1)で表される化合物が吸着されていることを特徴とする光電変換素子。
一般式(1)
R1−X−R2−B
(R1はC(R3)(R4)(R5)を表わし、R3、R4およびR5は水素原子、メチル基またはエチル基を表し、R3、R4およびR5が同時に水素原子であることはなく、Xはシクロヘキサン環、ベンゼン環、またはピリミジン環を表し、R2はメチレン基、エチレン基、または単結合を表わし、Bはカルボキシル基、スルホ基、またはホスホノ基を表わす。)
【選択図】なし
Description
R1−X−R2−B
(R1はC(R3)(R4)(R5)を表わし、R3、R4およびR5は水素原子、メチル基またはエチル基を表し、R3、R4およびR5が同時に水素原子であることはなく、Xは2価のシクロヘキサン環、2価のベンゼン環、または2価のピリミジン環を表し、R2はメチレン基、エチレン基、または単結合を表わし、Bはカルボキシル基、スルホ基、またはホスホノ基を表わす。)
一般式(1)のR1−X−R2−Bの構造は、それぞれ以下の機能により効果を発現していると推定している。
X:比較的剛直な環状構造部分で、分子を密に表面を覆うのを助ける
R2:スペーサー的に働き、吸着基を動かしやすくし、吸着しやすくする部分
B:吸着基
具体的には、本願の一般式(1)の化合物は、色素とともに、半導体に吸着する能力を有する共吸着化合物と推定され、その為には、半導体に吸着する能力有する、カルボキシル基、スルホ基、またはホスホノ基のいずれかの基を有し、電荷輸送剤が半導体に接近することを抑制するとともに広範囲に半導体表面を覆う為に、嵩高い置換基を有する環状構造のシクロヘキサン環、ベンゼン環、またはピリミジン環を有している。さらに、これらの化合物が、うまく、半導体表面に吸着するために、吸着基部分がある程度の可動性を有するスペーサー構造を有していてもよく、該スペーサーとしてはメチレン基、エチレン基が挙げられる。
本発明の光電変換素子は、基板上に第1電極、光電変換層、電荷輸送層、第2電極を順に有し、該光電変換層は前記化合物と増感色素が吸着した半導体を含有する。第1電極と第2電極の一方は透明であり、透明な電極の側に光が照射される。第1電極が透明な場合は基板も透明であり、光は基板側に照射される。第2電極が透明で光が第2電極側に照射される場合、基板は不透明でもよいが、透明な電極の製造の容易性や耐久性の点から第1電極と支持体が透明である形態が好ましい。
(半導体)
光電変換層に用いられる半導体としては、シリコン、ゲルマニウムのような単体、周期表(元素周期表ともいう)の第3族〜第5族、第13族〜第15族系の元素を有する化合物、金属のカルコゲニド(例えば、酸化物、硫化物、セレン化物等)、金属窒化物等を使用することができる。
第1電極を設けた基板上に、前記半導体からなる半導体層を形成する方法について説明する。
まず、半導体の微粉末を含む塗布液を調製する。この半導体微粉末はその1次粒子径が微細な程好ましく、その1次粒子径は1〜5000nmが好ましく、さらに好ましくは2〜50nmである。半導体微粉末を含む塗布液は、半導体微粉末を溶媒中に分散させることによって調製することができる。溶媒中に分散された半導体微粉末は、その1次粒子状で分散する。溶媒としては半導体微粉末を分散し得るものであればよく、特に制約されない。
上記のようにして得られた半導体微粉末含有塗布液を、導電性支持体上に塗布または吹き付け、乾燥等を行った後、空気中または不活性ガス中で焼成して、導電性支持体上に半導体層(半導体膜とも言う)が形成される。
本発明では、半導体に増感色素を担持させている。電荷の半導体への効率的な注入の観点から、上記増感色素はカルボキシル基を有することが好ましい。以下に、増感色素の具体例を示すが、本発明はこれらに限定されるものではない。
本発明では、半導体に増感色素を担持させる前に、前記吸着化合物を該半導体に吸着させることが好ましい。該吸着化合物を適切な溶媒に溶解した溶液に、半導体層を有する積層体(基板上に第1電極と半導体層を順に設けた積層体)を浸漬することによって、該吸着化合物を半導体に吸着させ、積層体1を作製する。
前記化合物は、一般式(1)により表される。
R1−X−R2−B
ただし、R1はC(R3)(R4)(R5)を表わし、R3、R4およびR5は水素原子、メチル基またはエチル基を表し、R3、R4およびR5が同時に水素原子であることはなく、Xはシクロヘキサン環、ベンゼン環、またはピリミジン環を表し、R2はメチレン基、エチレン基、または単結合を表わし、Bはカルボキシル基、スルホ基、またはホスホノ基を表わす。中でも、カルボキシル基は吸着性能と、耐久安定性が高く好ましい。
前記基板としては、ガラス、プラスチックフィルムなどの透明な材料で形成された透明な基板が好ましく用いられる。
第1電極と第2電極の少なくとも一方は透明導電層であるが、第1電極が透明電極であることが好ましい。透明電極と対向する電極は不透明導電層であっても良い。
本発明に用いられる電荷輸送層について説明する。
次のようにして、太陽電池(光電変換素子)を製造した。
シート抵抗20Ω/□のフッ素ドープ酸化スズ(FTO)導電性ガラス基板(15mm×25mm)を第1電極とした。この基板上にテトラキスイソポロポキシチタン1.2mlおよびアセチルアセトン0.8mlをエタノール18mlに希釈した溶液を滴下して、スピンコート法により製膜後、450℃で8分間加熱して、透明導電膜(FTO)上に、厚み30〜50nmの酸化チタン薄膜からなるバリヤ層を形成した。
酸化チタンペースト(アナターゼ型、1次平均粒径(顕微鏡観察平均)18nm、エチルセルロース、を10%アセチルアセトン水に分散)を、上記バリヤ層を形成したFTOガラス基板へスクリーン印刷法(塗布面積25mm2(5mm×5mm))により塗布した。200℃で10分間および500℃で15分間焼成を行い、厚さ2.5μmの酸化チタン薄膜を得た。
前記半導体電極1の光電変換層上に、電荷輸送剤の例示化合物D−15(170mM)、Li[(CF3SO2)2N](15mM)、t−ブチルピリジン(50mM)のクロロベンゼン溶液をスピンコート(塗布法)により塗布し、乾燥膜厚10μmの電荷輸送層を設けた。なお、スピンコートは、回転数を500rpmで行った。
実施例1と同様に光電変換層まで作製した半導体電極2に、チオフェン系モノマーであるEDOT(エチレンジオキシチオフェン)の二量体(K192;KaironKem社製)を1×10−3(モル/l)の濃度で含有し、Li[(CF3SO2)2N]を0.1(モル/l)の濃度で含有するアセトニトリル溶液(電解重合溶液)に浸漬した。作用極を前記半導体電極2、対極を白金線、参照電極をAg/Ag+(AgNO3 0.01M)、保持電圧を−0.16Vとした。半導体層方向から光を照射しながら(キセノンランプ使用、半導体表面での光強度22mW/cm2、430nm以下の波長をカット)積算電荷量4mCになるまで保持してEDOTの二量体を重合し、電荷輸送剤であるPEDOTを有する電荷輸送層を前記半導体電極2の表面に形成した。得られた半導体電極/電荷輸送層の積層体をアセトニトリルで洗浄、乾燥した。
光電変換素子SC−1の作製において、増感色素および化合物を表1,表2の化合物に変更した以外は同様にして光電変換素子 SC−3、5、7、9、11、13、15、17、19、21、23、25、27、29、31、33、35、37、39、41、43、45、47を作製した。
光電変換素子SC−2の作製において、増感色素および化合物を表1,表2の化合物に変更した以外は同様にして光電変換素子 SC−4、6、8、10、12、14、16、18、20、22、24、26、28、30、32、34、36、38、40、42、44、46、48を作製した。
得られた各光電変換素子について下記の評価を行った。
作製した光電変換素子を、ソーラーシミュレータ(英弘精機製)を用い、AMフィルタ(AM−1.5)を通したキセノンランプから100mW/cm2の擬似太陽光を照射することにより行った。半導体層上に5×5mm2のマスクをかけた条件下で光電変換特性の測定を行った。即ち、I−Vテスターを用いて室温にて電流−電圧特性を測定し、短絡電流密度(Jsc)、開放電圧(Voc)、及び形状因子(FF)を求め、これらから光電変換効率(η(%))を求めた。
ここで、Pは入射光強度[mW・cm−2]、Vocは開放電圧[V]、Jscは短絡電流密度[mA・cm−2]、FFは形状因子を示す。
上記により光電変換効率を測定した光電変換素子を短絡させた上で、120mW/cm2の擬似太陽光を720時間照射した後に、上記と同様に電流−電圧特性を測定し、光劣化後の短絡電流密度(JSC1)、開放電圧(VOC1)、光電変換効率(η1(%))を求め、下記式により耐久率を求めた。
前記光電変換素子の評価結果を表1,表2に記す。
Claims (6)
- 基板、第1電極、半導体および増感色素を有する光電変換層、電荷輸送層、並びに、第2電極を有する光電変換素子において、前記光電変換層が下記一般式(1)で表される化合物を含有することを特徴とする光電変換素子。
一般式(1)
R1−X−R2−B
(R1はC(R3)(R4)(R5)を表わし、R3、R4およびR5は水素原子、メチル基またはエチル基を表し、R3、R4およびR5が同時に水素原子であることはなく、Xは2価のシクロヘキサン環、2価のベンゼン環、または2価のピリミジン環を表し、R2はメチレン基、エチレン基、または単結合を表わし、Bはカルボキシル基、スルホ基、またはホスホノ基を表わす。) - 前記一般式(1)のR1がt−ブチル基、i−プロピル基、またはトリエチルメチル基であることを特徴とする請求項1に記載の光電変換素子。
- 前記半導体が酸化チタンであることを特徴とする請求項1または2に記載の光電変換素子。
- 前記光電変換層は、前記半導体に前記化合物が吸着された後に、色素が吸着されて形成されたものであることを特徴とする請求項1〜3のいずれか1項に記載の光電変換素子。
- 前記電荷輸送層がp型化合物半導体を含有することを特徴とする請求項1〜4のいずれか1項に記載の光電変換素子。
- 請求項1〜5のいずれか1項に記載の光電変換素子を有することを特徴とする太陽電池。
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JP2000268891A (ja) * | 1999-03-19 | 2000-09-29 | Toshiba Corp | 多色色素増感透明半導体電極部材とその製造方法、多色色素増感型太陽電池、及び表示素子 |
JP2004006214A (ja) * | 2002-04-12 | 2004-01-08 | Tokuyama Corp | 光電気化学電池用イオン導電性組成物 |
JP2004134200A (ja) * | 2002-10-10 | 2004-04-30 | Hayashibara Biochem Lab Inc | 半導体電極 |
JP2005063833A (ja) * | 2003-08-13 | 2005-03-10 | Mitsubishi Paper Mills Ltd | 光電変換材料、半導体電極並びにそれを用いた光電変換素子 |
JP2007246885A (ja) * | 2006-02-20 | 2007-09-27 | Toyo Ink Mfg Co Ltd | 光機能材料 |
JP2008277206A (ja) * | 2007-05-07 | 2008-11-13 | Konica Minolta Holdings Inc | 光電変換材料用半導体、光電変換素子及び太陽電池 |
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ATE342573T1 (de) * | 2000-08-15 | 2006-11-15 | Fuji Photo Film Co Ltd | Photoelektrische zelle und herstellungsmethode |
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Patent Citations (6)
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JP2000268891A (ja) * | 1999-03-19 | 2000-09-29 | Toshiba Corp | 多色色素増感透明半導体電極部材とその製造方法、多色色素増感型太陽電池、及び表示素子 |
JP2004006214A (ja) * | 2002-04-12 | 2004-01-08 | Tokuyama Corp | 光電気化学電池用イオン導電性組成物 |
JP2004134200A (ja) * | 2002-10-10 | 2004-04-30 | Hayashibara Biochem Lab Inc | 半導体電極 |
JP2005063833A (ja) * | 2003-08-13 | 2005-03-10 | Mitsubishi Paper Mills Ltd | 光電変換材料、半導体電極並びにそれを用いた光電変換素子 |
JP2007246885A (ja) * | 2006-02-20 | 2007-09-27 | Toyo Ink Mfg Co Ltd | 光機能材料 |
JP2008277206A (ja) * | 2007-05-07 | 2008-11-13 | Konica Minolta Holdings Inc | 光電変換材料用半導体、光電変換素子及び太陽電池 |
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