JP6061475B2 - 全固体光増感太陽電池 - Google Patents
全固体光増感太陽電池 Download PDFInfo
- Publication number
- JP6061475B2 JP6061475B2 JP2012034959A JP2012034959A JP6061475B2 JP 6061475 B2 JP6061475 B2 JP 6061475B2 JP 2012034959 A JP2012034959 A JP 2012034959A JP 2012034959 A JP2012034959 A JP 2012034959A JP 6061475 B2 JP6061475 B2 JP 6061475B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- blocking layer
- solar cell
- layer
- porous titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 206010034972 Photosensitivity reaction Diseases 0.000 title claims description 27
- 239000007787 solid Substances 0.000 title description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 84
- 230000000903 blocking effect Effects 0.000 claims description 63
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 60
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 35
- 239000006096 absorbing agent Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 32
- 239000000395 magnesium oxide Substances 0.000 claims description 23
- 239000004065 semiconductor Substances 0.000 claims description 16
- 230000005525 hole transport Effects 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- 229910002113 barium titanate Inorganic materials 0.000 claims description 12
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 11
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical group [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 5
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims description 4
- 229910020159 Pb—Cd Inorganic materials 0.000 claims description 3
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- 239000000203 mixture Substances 0.000 description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
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- 229940056932 lead sulfide Drugs 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
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- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
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- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
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- 229940078552 o-xylene Drugs 0.000 description 1
- QADJHAOXTKCYFT-UHFFFAOYSA-N octyl 3-(3-octoxy-3-oxopropyl)sulfanylpropanoate Chemical compound CCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCC QADJHAOXTKCYFT-UHFFFAOYSA-N 0.000 description 1
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- 229910052762 osmium Inorganic materials 0.000 description 1
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- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
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- 150000004291 polyenes Chemical class 0.000 description 1
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- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
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- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000004963 sulfonylalkyl group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AWDRATDZQPNJFN-VAYUFCLWSA-N taurodeoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCS(O)(=O)=O)C)[C@@]2(C)[C@@H](O)C1 AWDRATDZQPNJFN-VAYUFCLWSA-N 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- VRKHAMWCGMJAMI-UHFFFAOYSA-M tetrahexylazanium;iodide Chemical compound [I-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC VRKHAMWCGMJAMI-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- GSURLQOINUQIIH-UHFFFAOYSA-N triheptyl phosphate Chemical compound CCCCCCCOP(=O)(OCCCCCCC)OCCCCCCC GSURLQOINUQIIH-UHFFFAOYSA-N 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- ZOPCDOGRWDSSDQ-UHFFFAOYSA-N trinonyl phosphate Chemical compound CCCCCCCCCOP(=O)(OCCCCCCCCC)OCCCCCCCCC ZOPCDOGRWDSSDQ-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- IDMWGAKKAOEHPM-UHFFFAOYSA-L zinc propan-2-one dichloride Chemical compound [Cl-].[Cl-].[Zn+2].CC(C)=O IDMWGAKKAOEHPM-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- 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
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- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Description
1.基板上に、光吸収体で修飾した多孔質酸化チタン電極、ホール輸送層及び対極が当該順に積層された構造を有する全固体光増感太陽電池であって、
前記光吸収体で修飾した多孔質酸化チタン電極は、多孔質酸化チタンが誘電体からなるブロッキング層により被覆されており、前記ブロッキング層の表面が光吸収体で修飾されていることを特徴とする全固体光増感太陽電池。
2.前記ブロッキング層は、チタン酸バリウム、酸化マグネシウム及び酸化アルミニウムからなる群から選択される少なくとも1種を含有する、上記項1に記載の全固体光増感太陽電池。
3.前記ブロッキング層は、チタン酸バリウム層及び酸化マグネシウム層の積層体である、上記項1又は2に記載の全固体光増感太陽電池。
4.前記光吸収体は、硫化アンチモン、硫化鉛、Pb-Sn-Se(1-n)、CdS及びPb-Cdn-Se(1-n)からなる群から選択される少なくとも1種の半導体を含有する、上記項1〜3のいずれかに記載の全固体光増感太陽電池。
5.前記半導体は、さらに、ビスマス、亜鉛及びチタンからなる群から選択される少なくとも一種を有する、上記項4に記載の全固体光増感太陽電池。
6.前記ホール輸送層は、CuSCN、CuI、P3HT及びSpiro-OMeTADからなる群から選択される少なくとも1種を含有する、上記項1〜5のいずれかに記載の全固体光増感太陽電池。
前記光吸収体で修飾した多孔質酸化チタン電極は、多孔質酸化チタンが誘電体からなるブロッキング層により被覆されており、前記ブロッキング層の表面が光吸収体で修飾されていることを特徴とする。
基板としては、従来から色素増感太陽電池及び全固体光増感太陽電池の基板として公知の樹脂基板又はガラス基板が挙げられる。
光吸収体で修飾した多孔質酸化チタン電極に用いられる多孔質酸化チタンとしては、例えば、公知又は市販のチタニアナノ粒子;公知又は市販のチタニアナノチューブ;チタニアナノロッド;チタニアナノファイバー;チタニアナノ粒子のチューブ状集合体(特開2010-24132号公報等)等を1種単独で用いてもよいし、2種以上を組合せて用いてもよい。
ホール輸送層は限定的ではなく、従来から全固体光増感太陽電池に使用されているものが使用できる。例えば、CuSCN、CuI、P3HT及びSpiro-OMeTADからなる群から選択される少なくとも1種を含むホール輸送層が好ましい。
対極は、導電性材料からなる単層構造でもよいし、導電層と基板とから構成されていてもよい。基板としては、特に限定されず、材質、厚さ、寸法、形状等は目的に応じて適宜選択することができ、例えば、金属、無色又は有色ガラス、網入りガラス、ガラスブロック等が用いられる他、樹脂でもよい。かかる樹脂としては、ポリエチレンテレフタレート等のポリエステル、ポリアミド、ポリスルホン、ポリエーテルサルホン、ポリエーテルエーテルケトン、ポリフェニレンサルファイド、ポリカーボネート、ポリイミド、ポリメチルメタクリレート、ポリスチレン、トリ酢酸セルロース、ポリメチルペンテン等が挙げられる。また、電荷輸送層上に直接導電性材料を塗布、メッキ又は蒸着(PVD、CVD)して対極を形成しても良い。
(1)FTOガラス(基板)の洗浄等
アセトン溶媒で超音波洗浄を15分間行った。
スプレー熱分解法により、基板上にTiO2薄膜層(約150nm)を形成した。
(3)−1
TiO2ペースト用TiO2粒子(粒径約40nm)の水熱合成及びペースト調製
チタンイソプロポキシド(162ml, 0.5mol)を蒸留水(290ml, 15.5mol)に素早く加えて1時間攪拌した。ガラスフリットを使用して濾過した。濾過物質をビーカーに移して50mlの蒸留水とともに攪拌した。この濾過を3回繰り返した。
(3)−2
スクリーン印刷
調製したTiO2ペーストでスクリーン印刷を行い、多孔質酸化チタン膜を作製した。膜厚は2.3〜2.7μm程度とした。
(4)−1 Al2O3膜の作製の場合
0.15M AlCl3・6H2Oをイオン交換水に溶かした。そこに多孔質酸化チタン膜を浸漬した。浸漬後、軽くイオン交換水で洗い余分なイオンを取り除いた。酸素雰囲気下550℃で30分焼結した。
(4)−2 MgO膜の作製の場合
0.15M MgCl2・6H2Oをイオン交換水に溶かした。そこに多孔質酸化チタン膜を浸漬した。浸漬後、軽くイオン交換水で洗い余分なイオンを取り除いた。酸素雰囲気下550℃で30分焼結した。
(4)−3 BaTiO3膜の作製の場合
飽和Ba(NO3)2水溶液を作製した。そこに多孔質酸化チタン膜を浸漬した。浸漬後、軽くイオン交換水で洗い余分なイオンを取り除いた。酸素雰囲気下550℃で30分焼結した。
(4)−4 BaTiO3及びMgOのダブルブロッキング層の作製の場合
(4)−3の手順でBaTiO3膜を積層後、(4)−2の手順でMgO膜を作製した。BaTiO3膜の作製のための溶液浸漬時間30秒に対して、MgO膜の作製のための溶液浸漬時間を最適化した。
以下に示すようにChemical Bath Deposition(CBD, 溶液成長)法でSb2S3層を作製した。
1)1M SbCl3 アセトン溶媒2.5mlと1M Na2S2O3水溶液25ml(溶液温度5〜10℃)を調製した。
2)1M Na2S2O3水溶液25ml(溶液温度5〜10℃)にイオン交換水(水温度5〜10℃)72.5mlを加え、
3)次に1M SbCl3アセトン溶媒2.5mlを加えた。
4)1分間攪拌した後、ブロッキング層を形成した多孔質酸化チタン膜を溶液に浸漬し
5)冷蔵庫(温度5〜10℃)で3時間成膜した。
6)取り出した後、イオン交換水で余分なものを洗い流した。N2雰囲気下320℃で30分アニーリングを行った。
(6)−1 CuSCN層形成の前処理(KSCN処理)
0.5M KSCN水溶液にSb2S3層形成済み電極を5分間浸漬した。取り出した後、エアースプレーガンで余分な溶液を飛ばした。
(6)−2 CuSCNの積層
基板温度65℃で0.05M CuSCN in n-propyl sulfide溶液を滴下した。一滴ずつ滴下しながらガラス棒で電極表面を均した。多孔質酸化チタン膜から0.5〜1μm程度堆積させた。
蒸着法により、金(Au)背面電極を積層した。
(1)各ブロッキング層の最適化
Al2O3、MgO、BaTiO3をそれぞれブロッキング層として形成する際の溶液浸漬時間の最適化を行った。その結果、多孔質酸化チタン電極の最適の溶液浸漬時間はAl2O3が20分、MgOが10分、BaTiO3が30秒であると分かった。
図2に各ブロッキング層の光電流−電圧特性を示す。また、短絡電流密度(Jsc [mAcm-2])、開放電圧(Voc[V])、フィルファクター(FF)及び光電変換効率(η[%])を表1に示す。
BaTiO3膜作製のための溶液浸漬時間30秒に対してのMgO膜作製のための溶液浸漬時間最適化結果を図5に示す。図5よりMgO膜作製のための最適溶液浸漬時間は5分だと分かった。
図6にダブルブロッキング層を用いた太陽電離セルの光電流−電圧特性を示す。また、短絡電流密度(Jsc [mAcm-2])、開放電圧(Voc[V])、フィルファクター(FF)、光電変換効率(η[%])を表3に示す。図6よりブロッキング層を二層化したことで短絡電流密度の増加、開放電圧の増加、フィルファクターの向上が確認できた。その結果、ブロッキング層を用いないセルが光電変換効率2.82%であったのに対して3.98%と1%以上の変換効率の向上が見られた。
Claims (3)
- 基板上に、光吸収体で修飾した多孔質酸化チタン電極、ホール輸送層及び対極が当該順に積層された構造を有する全固体光増感太陽電池であって、
前記光吸収体で修飾した多孔質酸化チタン電極は、多孔質酸化チタンがチタン酸バリウム層及び酸化マグネシウム層の積層体であるブロッキング層により被覆されており、前記ブロッキング層の表面が硫化アンチモン、硫化鉛、Pb-Sn-Se(1-n)、CdS及びPb-Cdn-Se(1-n)からなる群から選択される少なくとも1種の半導体を含有する光吸収体で修飾されていることを特徴とする全固体光増感太陽電池。 - 前記半導体は、さらに、ビスマス、亜鉛及びチタンからなる群から選択される少なくとも一種を有する、請求項1に記載の全固体光増感太陽電池。
- 前記ホール輸送層は、CuSCN、CuI、P3HT及びSpiro-OMeTADからなる群から選択される少なくとも1種を含有する、請求項1又は2に記載の全固体光増感太陽電池。
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