JP5135774B2 - 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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- JP5135774B2 JP5135774B2 JP2006312615A JP2006312615A JP5135774B2 JP 5135774 B2 JP5135774 B2 JP 5135774B2 JP 2006312615 A JP2006312615 A JP 2006312615A JP 2006312615 A JP2006312615 A JP 2006312615A JP 5135774 B2 JP5135774 B2 JP 5135774B2
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- photoelectric conversion
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- oxide semiconductor
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- 239000007924 injection Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- GGYFMLJDMAMTAB-UHFFFAOYSA-N selanylidenelead Chemical compound [Pb]=[Se] GGYFMLJDMAMTAB-UHFFFAOYSA-N 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 239000001040 synthetic pigment Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- 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
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- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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- 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
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- 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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- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
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- 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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
2.前記酸化物半導体が酸化チタンであることを特徴とする前記1に記載の光電変換素子。
本発明に係る酸化物半導体電極に用いられる酸化物半導体としては、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。
上記の酸化物半導体を前記一般式(1)で表される色素により増感処理することにより、本発明に記載の目的である、光電変換効率と耐久性に優れた本発明の光電変換素子を得ることができる。
4−(2,2−ジフェニルビニル)−トリフェニルアミンに6当量のオキシ塩化リン並びに8当量のN,N′−ジメチルホルムアミドを加え、窒素雰囲気下にて16時間、90℃で加熱することによりジホルミル化を行った。ジホルミル体、2当量のシアノ酢酸並びに2.2当量の酢酸アンモニウムからなる酢酸溶液を1時間加熱還流することによって、色素(1)をを得ることができた。
色素(1)の合成において、シアノ酢酸に代えてローダニン−N−酢酸を用いた他は同様にして、色素(2)を合成した。
本発明の光電変換素子は、導電性支持体上の酸化物半導体に色素を吸着させてなる酸化物半導体電極と対向電極とを電荷移動層を介して対向配置してなる。以下、酸化物半導体電極、電荷移動層、対向電極について説明する。
本発明に係る酸化物半導体電極の作製方法について説明する。
本発明の光電変換素子や本発明の太陽電池に用いられる導電性支持体には、金属板のような導電性材料や、ガラス板やプラスチックフイルムのような非導電性材料に導電性物質を設けた構造のものを用いることができる。導電性支持体に用いられる材料の例としては金属(例えば、白金、金、銀、銅、アルミニウム、ロジウム、インジウム)あるいは導電性金属酸化物(例えば、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)や炭素を挙げることができる。導電性支持体の厚さは特に制約されないが、0.3〜5mmが好ましい。
まず、酸化物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、更に好ましくは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つけ、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)が形成される。
酸化物半導体の増感処理は上記のように色素を適切な溶媒に溶解し、その溶液に前記半導体を焼成した基板を浸漬することによって行われる。その際には、半導体層(半導体膜ともいう)を焼成により形成させた基板を、予め減圧処理したり加熱処理したりして膜中の気泡を除去し、前記一般式(1)で表される色素が半導体層(半導体膜)内部深くに進入できるようにしておくことが好ましく、半導体層(半導体膜)が多孔質構造膜である場合には特に好ましい。
酸化物半導体を焼成した基板を前記一般式(1)で表される色素を含む溶液に浸漬する時間は、半導体層(半導体膜)に前記色素が深く進入して吸着等を十分に進行させ、半導体を十分に増感させ、且つ溶液中のでの前記色素の分解等により生成して分解物が色素の吸着を妨害することを抑制する観点から、25℃条件下では3〜48時間が好ましく、更に好ましくは4〜24時間である。この効果は、特に半導体膜が多孔質構造膜である場合において顕著である。但し、浸漬時間については25℃条件での値であり、温度条件を変化させて場合には上記の限りではない。
本発明に用いられる電荷移動層について説明する。
本発明に用いられる対向電極について説明する。
本発明の太陽電池について説明する。
〔光電変換素子1の作製〕
市販の酸化チタンペースト(粒径18nm)を、フッ素ドープ酸化スズ(FTO)導電性ガラス基板へドクターブレード法により塗布した。60℃で10分間加熱してペーストを乾燥させた後、500℃で30分間焼成を行い、厚さ5μmの酸化チタン薄膜を得た。
光電変換素子1の作製において、色素(1)に代えて色素(2)〜色素(8)、比較色素、Ru錯体(ジチオシアナト−ビス(2,2′−ビピリジル−4,4′−ジカルボキシラート)ルテニウム)をそれぞれ用いた他は同様にして、光電変換素子2〜10を作製した。
強度100mW/cm2のキセノンランプ照射下、酸化物半導体電極に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。
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]、F.F.は形状因子を示す。
Claims (3)
- 導電性支持体上の酸化物半導体に色素を吸着させてなる酸化物半導体電極と対向電極とを電荷移動層を介して対向配置してなる光電変換素子において、該色素が下記一般式(1)で表されることを特徴とする光電変換素子。
- 前記酸化物半導体が酸化チタン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。
- 請求項1または2に記載の光電変換素子を備えたことを特徴とする太陽電池。
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US8247687B2 (en) * | 2008-04-07 | 2012-08-21 | Konica Minolta Business Technologies, Inc. | Photoelectric conversion element and solar cell |
JP2010267611A (ja) * | 2009-04-15 | 2010-11-25 | Konica Minolta Business Technologies Inc | 光電変換素子および太陽電池 |
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