JP6035966B2 - Composite, photoelectrode, dye-sensitized solar cell, and dye-sensitized solar cell module - Google Patents
Composite, photoelectrode, dye-sensitized solar cell, and dye-sensitized solar cell module Download PDFInfo
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- JP6035966B2 JP6035966B2 JP2012172671A JP2012172671A JP6035966B2 JP 6035966 B2 JP6035966 B2 JP 6035966B2 JP 2012172671 A JP2012172671 A JP 2012172671A JP 2012172671 A JP2012172671 A JP 2012172671A JP 6035966 B2 JP6035966 B2 JP 6035966B2
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- 239000002131 composite material Substances 0.000 title claims description 94
- 239000000463 material Substances 0.000 claims description 122
- 239000000758 substrate Substances 0.000 claims description 96
- 239000004065 semiconductor Substances 0.000 claims description 77
- 229910052723 transition metal Inorganic materials 0.000 claims description 69
- 150000003624 transition metals Chemical class 0.000 claims description 69
- 239000007769 metal material Substances 0.000 claims description 50
- 230000005525 hole transport Effects 0.000 claims description 25
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical group O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 11
- 239000004020 conductor Substances 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000975 dye Substances 0.000 description 197
- 229910010413 TiO 2 Inorganic materials 0.000 description 61
- 230000031700 light absorption Effects 0.000 description 45
- 229910052751 metal Inorganic materials 0.000 description 44
- 239000002184 metal Substances 0.000 description 44
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- 230000003993 interaction Effects 0.000 description 19
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 19
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 19
- 239000011521 glass Substances 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000002585 base Substances 0.000 description 7
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012860 organic pigment Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
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- 230000009471 action Effects 0.000 description 2
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- 125000001072 heteroaryl group Chemical group 0.000 description 2
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- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- VASPYXGQVWPGAB-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;thiocyanate Chemical compound [S-]C#N.CCN1C=C[N+](C)=C1 VASPYXGQVWPGAB-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 101000967087 Homo sapiens Metal-response element-binding transcription factor 2 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100040632 Metal-response element-binding transcription factor 2 Human genes 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000005013 aryl ether group Chemical group 0.000 description 1
- 150000004832 aryl thioethers Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- 239000008151 electrolyte solution Substances 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012900 molecular simulation Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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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
-
- 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
本発明は、複合体、光電極、色素増感型太陽電池及び色素増感型太陽電池モジュールに関する。 The present invention relates to a composite, a photoelectrode, a dye-sensitized solar cell, and a dye-sensitized solar cell module.
従来、色素増感型太陽電池としては、ＴｉＯ2上に吸着した有機色素の光吸収特性にしたがって、太陽光を吸収し、光電流が得られるものが提案されている。このような色素増感型太陽電池では、変換効率をより向上させる必要があり、特に光電流を向上させることが重要である。従来、色素増感型太陽電池で用いられている有機色素は、太陽光に対して特に長波長側の分光感度特性が不十分であることから、長波長側の光吸収特性をより拡張した有機色素を用いることによって、光電流をより向上させることが検討されている（例えば、非特許文献１，２参照）。 Conventionally, as a dye-sensitized solar cell, one that absorbs sunlight and obtains a photocurrent according to the light absorption characteristics of an organic dye adsorbed on TiO 2 has been proposed. In such a dye-sensitized solar cell, it is necessary to further improve the conversion efficiency, and it is particularly important to improve the photocurrent. Conventionally, organic dyes used in dye-sensitized solar cells have an extended optical absorption characteristic on the long wavelength side because the spectral sensitivity characteristic on the long wavelength side is particularly insufficient with respect to sunlight. It has been studied to improve the photocurrent by using a dye (for example, see Non-Patent Documents 1 and 2).
また、色素増感型太陽電池としては、電子受容部位を有する有機色素とＣｕを含むＣｕ系材料とを含有した複合体を備えたものが提案されている（例えば、特許文献１参照）。この太陽電池では、有機色素とＣｕイオンとの相互作用により光吸収特性を向上することができる。 In addition, as a dye-sensitized solar cell, a solar cell including a composite containing an organic dye having an electron accepting site and a Cu-based material containing Cu has been proposed (for example, see Patent Document 1). In this solar cell, the light absorption characteristics can be improved by the interaction between the organic dye and Cu ions.
しかしながら、上述の非特許文献１，２では、新規な有機色素を検討しなければならなかった。例えば、新規に有機色素分子を合成するには高度な技術を必要とする上、このような有機色素を合成するには、一般に多段階反応で合成する必要があり、時間がかかることがあった。また、分子シミュレーションなどで予め所望の光吸収特性になるように有機色素分子を設計しても、合成した有機色素が目的通りの光吸収特性を有するものとなるかはわからないことがあった。また、特許文献１では、有機色素とＣｕイオンとの相互作用を用いているが、更なる光吸収特性の向上が望まれていた。このように、有機合成による有機色素分子の構造最適化や、イオンの作用によって光吸収特性の向上が図られているものの、まだ十分でなく、有機色素の光吸収特性を向上することが求められていた。 However, in the above-mentioned Non-Patent Documents 1 and 2, a novel organic dye has to be studied. For example, in order to newly synthesize organic dye molecules, advanced techniques are required, and in order to synthesize such organic dyes, it is generally necessary to synthesize in a multi-step reaction, which may take time. . Further, even when an organic dye molecule is designed in advance so as to have a desired light absorption characteristic by molecular simulation or the like, it may not be known whether the synthesized organic dye has a desired light absorption characteristic. Moreover, in patent document 1, although the interaction of an organic pigment | dye and Cu ion is used, the improvement of the further light absorption characteristic was desired. As described above, the structure of organic dye molecules by organic synthesis is optimized, and the light absorption characteristics are improved by the action of ions, but this is not sufficient, and it is required to improve the light absorption characteristics of organic dyes. It was.
本発明は、このような課題に鑑みなされたものであり、有機色素の光吸収特性をより向上することができる複合体、光電極、色素増感型太陽電池及び色素増感型太陽電池モジュールを提供することを主目的とする。 This invention is made | formed in view of such a subject, The composite body which can improve the light absorption characteristic of an organic pigment | dye more, a photoelectrode, a dye-sensitized solar cell, and a dye-sensitized solar cell module The main purpose is to provide.
上述した目的を達成するために鋭意研究したところ、本発明者らは、有機色素分子と、第１族元素及び第２族元素のうち１以上を含むアルカリ系材料と、１以上の遷移金属を含む遷移金属材料とを含むものとすると、有機色素の光吸収特性をより向上することができることを見いだし、本発明を完成するに至った。 As a result of diligent research to achieve the above-mentioned object, the present inventors have found an organic dye molecule, an alkaline material containing one or more of Group 1 elements and Group 2 elements, and one or more transition metals. It has been found that the light absorption characteristics of the organic dye can be further improved by including the transition metal material, and the present invention has been completed.
即ち、本発明の複合体は、
Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、
第１族元素及び第２族元素のうち１以上を含むアルカリ系材料と、
１以上の遷移金属を含む遷移金属材料と、
を含有したものである。
That is, the complex of the present invention is
An organic dye molecule having an electron accepting site containing at least one of S and N;
An alkaline material containing one or more of Group 1 elements and Group 2 elements;
A transition metal material comprising one or more transition metals;
Is contained.
あるいは、本発明の複合体は、
Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、
Ｆｅを少なくとも含む遷移金属材料と、
を含有したものである。
Alternatively, the complex of the present invention is
An organic dye molecule having an electron accepting site containing at least one of S and N;
A transition metal material containing at least Fe;
Is contained.
あるいは、本発明の複合体は、
Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、
第１族元素及び第２族元素のうち１以上を含むアルカリ系材料と、
を含有したものである。
Alternatively, the complex of the present invention is
An organic dye molecule having an electron accepting site containing at least one of S and N;
An alkaline material containing one or more of Group 1 elements and Group 2 elements;
Is contained.
あるいは、本発明の複合体は、
Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、
Ｃｕを含む半導体及びＣｕを含む導電体のうち少なくとも一方を含むＣｕ系材料とＣｕ以外の遷移金属を含む非Ｃｕ系材料とを含む遷移金属材料と、
を含有したものである。
Alternatively, the complex of the present invention is
An organic dye molecule having an electron accepting site containing at least one of S and N;
A transition metal material including a Cu-based material including at least one of a semiconductor including Cu and a conductor including Cu and a non-Cu-based material including a transition metal other than Cu;
Is contained.
本発明の光電極は、色素増感型太陽電池に用いられる光電極であって、透明導電膜と透明基板とを有する導電性基板と、前記導電性基板に隣接して設けられているｎ型半導体層と、前記ｎ型半導体層に形成されている上述したいずれかの複合体と、を備えたものである。 The photoelectrode of the present invention is a photoelectrode used for a dye-sensitized solar cell, and is a conductive substrate having a transparent conductive film and a transparent substrate, and an n-type provided adjacent to the conductive substrate. A semiconductor layer and any one of the above-described composites formed in the n-type semiconductor layer are provided.
本発明の色素増感型太陽電池は、上述した光電極と、前記光電極に対向して設けられた対極と、を備えたものである。 The dye-sensitized solar cell of the present invention includes the above-described photoelectrode and a counter electrode provided to face the photoelectrode.
本発明の色素増感型太陽電池モジュールは、上述した色素増感型太陽電池を複数備えているものである。 The dye-sensitized solar cell module of the present invention includes a plurality of the dye-sensitized solar cells described above.
本発明は、有機色素の光吸収特性をより向上することができる。このような効果が得られる理由は明らかではないが、以下のように推測される。例えば、有機色素分子内において、電荷移動の相互作用が、色素と金属イオンとの相互作用又は結合などにより変化することによって、光吸収特性が長波長側に拡大するためであると推察される。このような、有機色素分子と金属イオンとの相互作用又は結合が、有機色素分子とアルカリ系金属イオンとの間、及び有機色素分子と遷移金属イオンとの間で重畳的に起きることによって、有機色素の光吸収特性をより向上することができるものと推察される。 The present invention can further improve the light absorption characteristics of organic dyes. The reason why such an effect is obtained is not clear, but is presumed as follows. For example, it is presumed that the charge absorption interaction is expanded in the long wavelength side by changing the interaction of charge transfer in the organic dye molecule due to the interaction or bond between the dye and the metal ion. Such interaction or bonding between the organic dye molecule and the metal ion occurs in an overlapping manner between the organic dye molecule and the alkali metal ion and between the organic dye molecule and the transition metal ion. It is presumed that the light absorption characteristics of the dye can be further improved.
本発明の色素増感型太陽電池モジュールの一実施形態を図面を用いて説明する。図１は、色素増感型太陽電池モジュール１０の構成の概略の一例を示す断面図である。図１に示すように、本実施形態に係る色素増感型太陽電池モジュール１０は、透明導電性基板１４上に複数の色素増感型太陽電池４０（以下セルとも称する）が順次配列した構成となっている。これらのセルは直列に接続されている。この色素増感型太陽電池モジュール１０では、各セルの間を埋めるように、シール材３２が形成されており、透明導電性基板１４とは反対側のシール材３２の面に平板状の保護部材３４が形成されている。この色素増感型太陽電池４０は、透明導電膜１２と透明基板１１とを有する透明導電性基板１４とｎ型半導体を含み下地層２２を介して透明導電性基板１４に隣接して設けられている多孔質半導体層２４と多孔質半導体層２４に形成されている複合体２８とを備えた光電極２０と、光電極２０に対向して設けられた対極３０と、を備えている。また、色素増感型太陽電池４０は、ｐ型半導体を含み光電極２０と対極３０との間に介在する正孔輸送層２６を備えている。本実施形態に係る色素増感型太陽電池４０は、光が透過する透明基板１１の表面に透明導電膜１２が形成されている透明導電性基板１４と、下地層２２を介して透明導電膜１２に形成されている多孔質半導体層２４と、多孔質半導体層２４に対して正孔輸送層２６及びセパレータ２９を介して設けられた対極３０と、を備えている。光電極２０は、透明導電性基板１４と、透明基板１１の受光面１３の反対側の面に分離形成された透明導電膜１２に配設された下地層２２と、下地層２２に配設され受光に伴い電子を放出する多孔質半導体層２４とを備えている。この多孔質半導体層２４には、詳しくは後述する有機色素分子及び金属含有材料を含む複合体２８が形成されている。この色素増感型太陽電池４０では、光電極２０と対極３０とが固体ｐ型半導体層である正孔輸送層２６を介して接続されている、いわゆる全固体型の色素増感型太陽電池として構成されている。 An embodiment of the dye-sensitized solar cell module of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view illustrating an example of a schematic configuration of a dye-sensitized solar cell module 10. As shown in FIG. 1, the dye-sensitized solar cell module 10 according to this embodiment has a configuration in which a plurality of dye-sensitized solar cells 40 (hereinafter also referred to as cells) are sequentially arranged on a transparent conductive substrate 14. It has become. These cells are connected in series. In this dye-sensitized solar cell module 10, a sealing material 32 is formed so as to fill between the cells, and a flat protective member is provided on the surface of the sealing material 32 on the side opposite to the transparent conductive substrate 14. 34 is formed. The dye-sensitized solar cell 40 includes a transparent conductive substrate 14 having a transparent conductive film 12 and a transparent substrate 11 and an n-type semiconductor, and is provided adjacent to the transparent conductive substrate 14 via a base layer 22. A photoelectrode 20 having a porous semiconductor layer 24 and a composite 28 formed on the porous semiconductor layer 24, and a counter electrode 30 provided to face the photoelectrode 20. The dye-sensitized solar cell 40 includes a hole transport layer 26 that includes a p-type semiconductor and is interposed between the photoelectrode 20 and the counter electrode 30. The dye-sensitized solar cell 40 according to this embodiment includes a transparent conductive substrate 12 having a transparent conductive film 12 formed on the surface of a transparent substrate 11 through which light is transmitted, and the transparent conductive film 12 via a base layer 22. And a counter electrode 30 provided to the porous semiconductor layer 24 via a hole transport layer 26 and a separator 29. The photoelectrode 20 is disposed on the transparent conductive substrate 14, the underlying layer 22 disposed on the transparent conductive film 12 formed separately on the surface opposite to the light receiving surface 13 of the transparent substrate 11, and the underlying layer 22. And a porous semiconductor layer 24 that emits electrons upon receiving light. In this porous semiconductor layer 24, a composite 28 containing organic dye molecules and a metal-containing material, which will be described in detail later, is formed. The dye-sensitized solar cell 40 is a so-called all-solid dye-sensitized solar cell in which the photoelectrode 20 and the counter electrode 30 are connected via a hole transport layer 26 that is a solid p-type semiconductor layer. It is configured.
透明導電性基板１４は、透明基板１１と透明導電膜１２とにより構成され、光透過性及び導電性を有するものである。具体的には、フッ素ドープＳｎＯ2コートガラス、ＩＴＯコートガラス、ＺｎＯ：Ａｌコートガラス、アンチモンドープ酸化スズ（ＳｎＯ2−Ｓｂ）コートガラス等が挙げられる。また、酸化スズや酸化インジウムに原子価の異なる陽イオン若しくは陰イオンをドープした透明電極、メッシュ状、ストライプ状など光が透過できる構造にした金属電極をガラス基板等の基板上に設けたものも使用できる。この透明導電性基板１４の透明導電膜１２側の両端には、集電電極１６，１７が設けられており、この集電電極１６，１７を介して色素増感型太陽電池４０で発電した電力を利用することができる。 The transparent conductive substrate 14 is composed of the transparent substrate 11 and the transparent conductive film 12, and has light transmittance and conductivity. Specific examples include fluorine-doped SnO 2 coated glass, ITO coated glass, ZnO: Al coated glass, and antimony-doped tin oxide (SnO 2 —Sb) coated glass. Also, a transparent electrode obtained by doping tin oxide or indium oxide with cations or anions having different valences, or a metal electrode having a structure capable of transmitting light, such as a mesh shape or a stripe shape, provided on a substrate such as a glass substrate. Can be used. Current collecting electrodes 16 and 17 are provided at both ends of the transparent conductive substrate 14 on the transparent conductive film 12 side. Electric power generated by the dye-sensitized solar cell 40 via the current collecting electrodes 16 and 17 is provided. Can be used.
透明基板１１としては、例えば、透明ガラス、透明プラスチック板、透明プラスチック膜、無機物透明結晶体などが挙げられ、このうち、透明ガラスが好ましい。この透明基板１１は、透明なガラス基板、ガラス基板表面を適当に荒らすなどして光の反射を防止したもの、すりガラス状の半透明のガラス基板など光を透過するものなどとしてもよい。透明導電膜１２は、例えば、透明基板１１上に酸化スズを付着させることにより形成することができる。特に、フッ素をドープした酸化スズ（ＦＴＯ）等の金属酸化物を用いれば、好適な透明導電膜１２を形成することができる。透明導電膜１２は、所定の間隔に溝１８が形成されており、この溝１８の幅に相当する間隔を隔てて複数の透明導電膜１２の領域が分離形成されている。 Examples of the transparent substrate 11 include transparent glass, a transparent plastic plate, a transparent plastic film, and an inorganic transparent crystal, and among these, transparent glass is preferable. The transparent substrate 11 may be a transparent glass substrate, a glass substrate whose surface is appropriately roughened to prevent reflection of light, or a transparent glass substrate such as a ground glass-like translucent glass substrate. The transparent conductive film 12 can be formed, for example, by depositing tin oxide on the transparent substrate 11. In particular, if a metal oxide such as tin oxide (FTO) doped with fluorine is used, a suitable transparent conductive film 12 can be formed. In the transparent conductive film 12, grooves 18 are formed at predetermined intervals, and a plurality of regions of the transparent conductive film 12 are separately formed at intervals corresponding to the width of the grooves 18.
下地層２２は、透明導電性基板１４から正孔輸送層２６へのリーク電流（逆電子移動）を抑制もしくは防止する層であり、例えば、透光性及び導電性のある材料が好ましく、例えば、酸化チタンや酸化亜鉛、酸化スズなどのｎ型半導体などが挙げられ、このうち酸化チタンがより好ましい。酸化チタンは、リーク電流を抑制・防止し、且つ多孔質半導体層２４から透明導電性基板１４へ電子を流しやすいからである。下地層２２では、多孔質半導体層２４に比してより緻密な材料とすることが好ましい。なお、この下地層２２を形成しないものとしても色素増感型太陽電池４０として十分機能することから、この下地層２２を省略しても構わない。 The underlayer 22 is a layer that suppresses or prevents leakage current (reverse electron transfer) from the transparent conductive substrate 14 to the hole transport layer 26. For example, a material having translucency and conductivity is preferable. Examples include n-type semiconductors such as titanium oxide, zinc oxide, and tin oxide. Among these, titanium oxide is more preferable. This is because titanium oxide suppresses and prevents leakage current and easily allows electrons to flow from the porous semiconductor layer 24 to the transparent conductive substrate 14. The underlayer 22 is preferably made of a denser material than the porous semiconductor layer 24. Even if the base layer 22 is not formed, the base layer 22 may be omitted because it functions sufficiently as the dye-sensitized solar cell 40.
多孔質半導体層２４は、Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、半導体及び導電体のうち少なくとも一方である金属含有材料と、を含む複合体２８と、この複合体２８の有機色素分子が吸着しているｎ型半導体層とにより形成されている。即ち、この多孔質半導体層２４は、複合体２８とｎ型半導体層とが複合化されている層となっている。有機色素分子は、詳しくは後述するが、受光に伴い電子を放出する色素である。また、金属含有材料は、第１族元素及び第２族元素のうち１以上を含むアルカリ系材料と、１以上の遷移金属を含む遷移金属材料とを含むものである。アルカリ系材料は、例えば、Ｌｉ，Ｎａ，Ｋ，Ｍｇ及びＣａのうち１以上を含むものとしてもよい。また、遷移金属材料は、Ｃｕ，Ｎｉ，Ｃｏ，Ｆｅ及びＣｒのうち１以上の遷移金属を含むものとしてもよい。また、遷移金属材料は、少なくともＣｕを含み、更にＣｕ以外の遷移金属を１以上含むことがより好ましい。こうすれば、光吸収特性を更に向上することができる。この遷移金属材料は、Ｃｕを含む半導体及びＣｕを含む導電体のうち少なくとも一方を含むＣｕ系材料を含むものとしてもよい。このＣｕ系材料は、ＣｕＩ，ＣｕＳＣＮ，ＣｕＯ，Ｃｕ2Ｏ及びＣｕのうちいずれか１以上を含むものとしてもよく、このうちＣｕＩ及びＣｕＳＣＮが好ましい。この複合体２８は、アルカリ系材料と、Ｃｕ系材料と、Ｃｕ以外の遷移金属を含む非Ｃｕ系材料と、の３種を含むものとすることがより好ましい。こうすれば、アルカリ系の金属イオンと有機色素との相互作用、Ｃｕイオンと有機色素との相互作用及び他の遷移金属イオンと有機色素との相互作用が重畳的に起き、光吸収特性をより高く向上することができる。その組み合わせとしては、例えば、ＬｉとＣｕとＦｅとの組み合わせ、ＬｉとＣｕとＣｏとの組み合わせ、Ｌｉ，Ｃｕ及びＮｉの組み合わせなどが好ましい。また、複合体２８に含まれるアニオンとしては、例えば、ビス（トリフルオロメタンスルホニル）イミド（（ＣＦ3ＳＯ2）2Ｎ-，以下ＴＦＳＩとも称する）や、ＳＣＮ-、Ｉ-などが挙げられる。 The porous semiconductor layer 24 includes a composite 28 including an organic dye molecule having an electron accepting site including at least one of S and N, and a metal-containing material that is at least one of a semiconductor and a conductor, and the composite The n-type semiconductor layer to which the organic dye molecules of the body 28 are adsorbed is formed. That is, the porous semiconductor layer 24 is a layer in which the composite 28 and the n-type semiconductor layer are combined. The organic dye molecules are dyes that emit electrons upon receiving light, as will be described in detail later. The metal-containing material includes an alkaline material containing one or more of Group 1 elements and Group 2 elements and a transition metal material containing one or more transition metals. The alkaline material may include, for example, one or more of Li, Na, K, Mg, and Ca. The transition metal material may include one or more transition metals among Cu, Ni, Co, Fe, and Cr. Moreover, it is more preferable that the transition metal material contains at least Cu and further contains one or more transition metals other than Cu. In this way, the light absorption characteristics can be further improved. The transition metal material may include a Cu-based material including at least one of a semiconductor including Cu and a conductor including Cu. The Cu-based material may include one or more of CuI, CuSCN, CuO, Cu 2 O and Cu, and among these, CuI and CuSCN are preferable. More preferably, the composite 28 includes three types of an alkaline material, a Cu-based material, and a non-Cu-based material containing a transition metal other than Cu. In this way, the interaction between alkali metal ions and organic dyes, the interaction between Cu ions and organic dyes, and the interaction between other transition metal ions and organic dyes occur in a superimposed manner, resulting in more light absorption characteristics. It can be improved greatly. As the combination, for example, a combination of Li, Cu, and Fe, a combination of Li, Cu, and Co, and a combination of Li, Cu, and Ni are preferable. Examples of the anion contained in the complex 28 include bis (trifluoromethanesulfonyl) imide ((CF 3 SO 2 ) 2 N − , hereinafter also referred to as TFSI), SCN − , I − and the like.
あるいは、複合体２８は、第１族元素及び第２族元素のうち１以上を含むアルカリ系材料と１以上の遷移金属を含む遷移金属材料とのうち少なくとも一方を含むものとしてもよい。例えば、複合体２８は、Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、アルカリ系材料とを含むものとすれば、それに応じて光吸収特性を向上することができる。また、複合体２８は、Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、Ｆｅを少なくとも含む遷移金属材料とを含むものとすれば、それに応じて光吸収特性を向上することができる。また、複合体２８は、Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、Ｃｕを含むＣｕ系材料とＣｕ以外の遷移金属を含む非Ｃｕ系材料とを含む遷移金属材料と、を含むものとすれば、それに応じて光吸収特性を向上することができる。 Alternatively, the composite 28 may include at least one of an alkaline material including one or more of Group 1 elements and Group 2 elements and a transition metal material including one or more transition metals. For example, if the composite 28 includes an organic dye molecule having an electron accepting site including at least one of S and N, and an alkaline material, the light absorption characteristics can be improved accordingly. Further, if the composite 28 includes an organic dye molecule having an electron accepting site including at least one of S and N and a transition metal material including at least Fe, the light absorption characteristics are improved accordingly. be able to. The composite 28 is a transition metal material including an organic dye molecule having an electron accepting site including at least one of S and N, a Cu-based material including Cu, and a non-Cu-based material including a transition metal other than Cu. Thus, the light absorption characteristics can be improved accordingly.
多孔質半導体層２４に含まれるｎ型半導体としては、金属酸化物半導体や金属硫化物半導体などが適しており、例えば、酸化チタン（ＴｉＯ2）、酸化スズ（ＳｎＯ2）、酸化亜鉛（ＺｎＯ）、硫化カドミウム（ＣｄＳ）、硫化亜鉛（ＺｎＳ）のうち少なくとも１以上であることが好ましく、このうち多孔質の酸化チタンがより好ましい。これらの半導体材料を微結晶又は多結晶状態にして薄膜化することにより、良好な多孔質のｎ型半導体層を形成することができる。特に、多孔質の酸化チタン層は、光電極２０が有するｎ型半導体層として好適である。有機色素は、多孔質のｎ型半導体の表面に吸着させるものとしてもよい。この吸着は、化学吸着や物理吸着等によって行うことができる。具体的には、多孔質半導体層２４は、多孔質のｎ型半導体層を透明導電性基板１４上に形成したのち、このｎ型半導体層へ有機色素を含む溶液を滴下したのち乾燥する方法や、色素溶液にｎ型半導体層を浸漬したのち乾燥する方法などにより作製することができる。同様に、複合体２８は、有機色素が形成されたｎ型半導体層へ金属含有材料を含む溶液を滴下したのち乾燥する方法や、金属含有材料を含む溶液に有機色素が形成されたｎ型半導体層を浸漬したのち乾燥する方法などにより作製することができる。ここで、この光電極２０では、多孔質半導体層２４に含まれる有機色素と金属含有材料に含まれる金属とが相互作用した複合体２８となっている。この相互作用によって、有機色素の光吸収特性が長波長側に拡大し、ひいてはより高い光電変換特性を得ることができると考えられる。この複合体２８は、有機色素分子と金属含有材料に含まれる金属イオンとが複合していると考えられるが、その形態は、例えば、錯体となっていてもよい。この複合体２８について、特に有機色素分子について、以下詳述する。 As the n-type semiconductor contained in the porous semiconductor layer 24, a metal oxide semiconductor or a metal sulfide semiconductor is suitable. For example, titanium oxide (TiO 2 ), tin oxide (SnO 2 ), zinc oxide (ZnO) At least one of cadmium sulfide (CdS) and zinc sulfide (ZnS) is preferable, and among these, porous titanium oxide is more preferable. By thinning these semiconductor materials into a microcrystalline or polycrystalline state, a good porous n-type semiconductor layer can be formed. In particular, the porous titanium oxide layer is suitable as an n-type semiconductor layer included in the photoelectrode 20. The organic dye may be adsorbed on the surface of the porous n-type semiconductor. This adsorption can be performed by chemical adsorption or physical adsorption. Specifically, the porous semiconductor layer 24 is a method in which a porous n-type semiconductor layer is formed on the transparent conductive substrate 14, and then a solution containing an organic dye is dropped on the n-type semiconductor layer and then dried. The n-type semiconductor layer can be dipped in a dye solution and dried. Similarly, the composite 28 includes a method in which a solution containing a metal-containing material is dropped on an n-type semiconductor layer in which an organic dye is formed and then drying, or an n-type semiconductor in which an organic dye is formed in a solution containing a metal-containing material. It can be produced by a method of dipping the layer and then drying it. Here, the photoelectrode 20 is a composite 28 in which the organic dye contained in the porous semiconductor layer 24 interacts with the metal contained in the metal-containing material. By this interaction, it is considered that the light absorption characteristic of the organic dye is expanded to the long wavelength side, and as a result, higher photoelectric conversion characteristics can be obtained. Although this complex 28 is considered to be a complex of organic dye molecules and metal ions contained in the metal-containing material, the form may be a complex, for example. The complex 28, particularly the organic dye molecule, will be described in detail below.
多孔質半導体層２４に含まれる有機色素分子は、Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有している。例えば、有機色素分子は、式（１）に示すロダニン構造を有することが好ましい。このとき、有機色素分子は、式（２）に示す基本構造を有するものとしてもよい。あるいは、有機色素分子は、ＣＮ基を有するものとしてもよいし、式（３）に示す、ＣＮ基を有するエチレン構造が結合したチオフェン構造を有することが好ましい。式（１）〜（３）において、置換基Ｒ1〜Ｒ8は、それぞれ同じでも異なっていてもよく、例えば、水素、アルキル基、シクロアルキル基、複素環基、アルケニル基、シクロアルケニル基、アルキニル基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、ヘテロアリール基、ハロゲン、シアノ基、カルボニル基、カルボキシル基、オキシカルボニル基、カルバモイル基、アミノ基、ホスフィンオキサイド基、隣接置換基との間に形成される縮合環及び硫黄などの中から選ばれるものとしてもよい。これらの置換基のうち、アルキル基とは、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基などの飽和脂肪族炭化水素基を示し、これは置換基を有していても有していなくてもよい。置換されている場合の追加の置換基には特に制限は無く、例えば、アルキル基、アリール基、ヘテロアリール基等を挙げることができ、この点は、他の上記置換基などについても共通する。また、アルキル基など、置換基の炭素数は特に限定されないが、作製の容易性やコストの点から、１以上２０以下、より好ましくは１以上１２以下の範囲であることが好ましい。 The organic dye molecule contained in the porous semiconductor layer 24 has an electron accepting site containing at least one of S and N. For example, the organic dye molecule preferably has a rhodanine structure represented by the formula (1). At this time, the organic dye molecule may have a basic structure represented by Formula (2). Alternatively, the organic dye molecule may have a CN group, and preferably has a thiophene structure to which an ethylene structure having a CN group is bonded as shown in Formula (3). In the formulas (1) to (3), the substituents R 1 to R 8 may be the same or different, for example, hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, Alkynyl group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, phosphine oxide group, adjacent It may be selected from a condensed ring formed between the substituent and sulfur. Among these substituents, the alkyl group is, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. This may or may not have a substituent. There are no particular limitations on the additional substituent when it is substituted, and examples include an alkyl group, an aryl group, a heteroaryl group, and the like, and this point is common to the other substituents. In addition, the number of carbon atoms of the substituent such as an alkyl group is not particularly limited, but is preferably in the range of 1 to 20 and more preferably 1 to 12 from the viewpoint of ease of production and cost.
図２は、ロダニン構造を有する有機色素分子の一例である色素１〜４の説明図であり、図３は、ＣＮ基とエチレン構造及びチオフェン構造を有する有機色素分子の一例である色素５〜１０の説明図である。まず、ロダニン構造を有する有機色素分子について説明する（図２の色素１〜４参照）。この有機色素分子は、式（１）において、ロダニン構造のＮに結合した置換基Ｒ1が、炭素数１以上２０以下であるアルキル基及び炭素数１以上２０以下の炭素鎖に結合したカルボキシル基のうちいずれか一方であることが好ましい。置換基Ｒ1がアルキル基である場合、炭素数１以上では化学的により安定であり好ましく、炭素数２０以下では有機色素分子をより容易に製造可能であり、好ましい。この置換基Ｒ1の炭素数は、２以上１２以下であることがより好ましい。また、有機色素分子は、ロダニン構造の置換基Ｒ2及びＲ3の少なくとも一方が更に同様のロダニン構造を有していることが好ましい。例えば、置換基Ｒ2にロダニン構造を有するものとしては、図２の色素１〜３に示すものなどが挙げられる。また、有機色素分子は、式（１）において、ロダニン構造の置換基Ｒ1〜Ｒ3のうち少なくとも１つが、ＮとＳとの少なくとも一方を含む芳香環及び、ＮとＳとの少なくとも一方が結合した芳香環、のうち少なくとも一方を含んでいることが好ましい。ＮとＳとの少なくとも一方が結合した芳香環としては、例えば図２の色素１〜３に示すものなどが挙げられる。この色素１〜３に示す有機色素分子は、置換基Ｒ3がＳであり、置換基Ｒ2におけるロダニン構造のＮには、酢酸基が結合した構造を有している。また、この有機色素分子は、図２の色素１〜３に示すものなど、ロダニン構造とインドリン構造とを有することが好ましい。これらの構成のうち、いずれかの態様を採用すると、有機色素分子と金属含有材料の金属イオンとの相互作用が惹起され、有機色素の光吸収特性がより向上しやすく、好ましい。 FIG. 2 is an explanatory diagram of dyes 1 to 4 which are examples of organic dye molecules having a rhodanine structure, and FIG. 3 is a dye 5 to 10 which is an example of organic dye molecules having a CN group, an ethylene structure and a thiophene structure. It is explanatory drawing of. First, organic dye molecules having a rhodanine structure will be described (see dyes 1 to 4 in FIG. 2). In the organic dye molecule, the substituent R 1 bonded to N of the rhodanine structure in formula (1) is a carboxyl group bonded to an alkyl group having 1 to 20 carbon atoms and a carbon chain having 1 to 20 carbon atoms. It is preferable that any one of them. In the case where the substituent R 1 is an alkyl group, it is preferable that the number of carbon atoms is 1 or more because it is chemically more stable, and the case where the number of carbon atoms is 20 or less is preferable because an organic dye molecule can be easily produced. The number of carbon atoms of the substituent R 1 is more preferably 2 or more and 12 or less. Further, in the organic dye molecule, it is preferable that at least one of the substituents R 2 and R 3 of the rhodanine structure further has a similar rhodanine structure. For example, examples of the substituent R 2 having a rhodanine structure include those shown in dyes 1 to 3 in FIG. Further, in the organic dye molecule, in the formula (1), at least one of the substituents R 1 to R 3 of the rhodanine structure includes an aromatic ring containing at least one of N and S, and at least one of N and S is It is preferable that at least one of the bonded aromatic rings is included. Examples of the aromatic ring to which at least one of N and S are bonded include those shown in dyes 1 to 3 in FIG. The organic dye molecules shown in these dyes 1 to 3 have a structure in which the substituent R 3 is S and an acetate group is bonded to N of the rhodanine structure in the substituent R 2 . The organic dye molecule preferably has a rhodanine structure and an indoline structure such as those shown in dyes 1 to 3 in FIG. Of these configurations, it is preferable to employ any one of the modes because an interaction between the organic dye molecule and the metal ion of the metal-containing material is induced, and the light absorption property of the organic dye is easily improved.
次に、ＣＮ基を有する有機色素分子について説明する（図３の色素５〜１０参照）。この有機色素分子は、１以上のチオフェン構造（Ｓを含む芳香環）がエチレン構造の二重結合を有する炭素に結合した構造を有する（図３の色素５〜１０参照）。このとき、式（３）に示す置換基Ｒ6が、カルボキシル基であることが好ましい。例えば、酸化チタンのような金属酸化物への固定は、色素のカルボキシル基と金属酸化物の化学吸着によってより強固になり、電子移動の効率も高くなるためである。また、チオフェン構造は、ｎが１以上５以下であることが好ましい。チオフェン構造の末端となる置換基Ｒ8は、例えば、式（４）に示す置換基としてもよいし、式（５）に示す置換基としてもよい。置換基Ｒ8は、例えば、水素、炭素数１以上２０以下のアルキル基のいずれかとしてもよい。また、ＮとＳとの少なくとも一方を含む芳香環及びＮとＳとの少なくとも一方が結合した芳香環としては、式（４）〜（６）に示す置換基などが挙げられる（図３の色素５〜９参照）。ＣＮ基を有する有機色素分子において、２以上のエチレン構造が連なる構成、共役構造、としてもよい。即ち、式（３）の置換基Ｒ5及びＲ6の少なくとも一方にエチレン構造が含まれていることが好ましい。このとき、式（３）の置換基Ｒ7及びＲ8の少なくとも一方の末端には、式（６）に示す置換基が結合していることが好ましい（図３の色素８，９参照）。これらの構成のうち、いずれか１つの態様を採用すると、金属含有材料に含まれる金属イオンとの相互作用が惹起され、有機色素の光吸収特性がより向上しやすく、好ましい。 Next, an organic dye molecule having a CN group will be described (see dyes 5 to 10 in FIG. 3). This organic dye molecule has a structure in which one or more thiophene structures (aromatic rings containing S) are bonded to carbon having a double bond of an ethylene structure (see dyes 5 to 10 in FIG. 3). At this time, the substituent R 6 shown in Formula (3) is preferably a carboxyl group. For example, the fixation to a metal oxide such as titanium oxide becomes stronger due to the chemical adsorption of the carboxyl group of the dye and the metal oxide, and the efficiency of electron transfer is also increased. In the thiophene structure, n is preferably 1 or more and 5 or less. The substituent R 8 serving as the terminal of the thiophene structure may be, for example, a substituent represented by the formula (4) or a substituent represented by the formula (5). The substituent R 8 may be, for example, any one of hydrogen and an alkyl group having 1 to 20 carbon atoms. Examples of the aromatic ring containing at least one of N and S and the aromatic ring to which at least one of N and S are bonded include substituents represented by formulas (4) to (6) (the dye in FIG. 3). 5-9). The organic dye molecule having a CN group may have a structure in which two or more ethylene structures are linked, or a conjugated structure. That is, it is preferable that at least one of the substituents R 5 and R 6 in the formula (3) contains an ethylene structure. At this time, it is preferable that a substituent represented by formula (6) is bonded to at least one terminal of substituents R 7 and R 8 of formula (3) (see dyes 8 and 9 in FIG. 3). Adopting any one of these configurations is preferable because interaction with metal ions contained in the metal-containing material is induced, and the light absorption characteristics of the organic dye are more easily improved.
正孔輸送層２６は、例えば、ｐ型半導体材料が挙げられ、Ｃｕを含む半導体により形成された層としてもよい。このＣｕを含む半導体としては、上記Ｃｕ系材料と同様に、例えば、ＣｕＩ、ＣｕＳＣＮ、ＣｕＯ及びＣｕ2Ｏのうちいずれか１以上を用いることが好ましく、ＣｕＩを用いるのがより好ましい。あるいは、正孔輸送層２６は、Ｃｕを含む導電体により形成された導電体層としてもよい。また、この正孔輸送層２６は、複合体２８にＣｕ系材料が含まれるときには、このＣｕ系材料と異なる材質で作製されていてもよいが、同じ材質で形成されていることが作製が容易であり、より好ましい。複合体２８に少なくともＣｕ系材料が含まれる場合、この正孔輸送層２６に含まれるＣｕ系材料が多孔質半導体層２４に充填されることにより、複合体２８が形成されるものとしてもよい。 The hole transport layer 26 is, for example, a p-type semiconductor material, and may be a layer formed of a semiconductor containing Cu. As the semiconductor containing Cu, for example, one or more of CuI, CuSCN, CuO, and Cu 2 O are preferably used, and CuI is more preferably used, like the Cu-based material. Alternatively, the hole transport layer 26 may be a conductor layer formed of a conductor containing Cu. In addition, when the composite 28 includes a Cu-based material, the hole transport layer 26 may be made of a material different from the Cu-based material. However, the hole transport layer 26 is easily formed by using the same material. It is more preferable. When the composite 28 includes at least a Cu-based material, the composite 28 may be formed by filling the porous semiconductor layer 24 with the Cu-based material included in the hole transport layer 26.
セパレータ２９は、下地層２２、多孔質半導体層２４及び正孔輸送層２６が積層された光電極２０の１つの側面に隣接するように断面Ｉ字状に形成されている。セパレータ２９の一端は透明導電性基板１４上の溝１８と接触している。これにより、光電極２０と対極３０との直接接触が回避される。セパレータ２９は、絶縁性の材料からなり、例えば、ガラスビーズ、二酸化ケイ素（シリカ）及びルチル型の酸化チタンなどで形成されていてもよい。このセパレータ２９としては、シリカ粒子を焼結した絶縁体が好ましい。シリカ粒子は、屈折率が低く光散乱が小さく、良好な透明性を有するため、セパレータに好ましい。このセパレータ２９は、良好な透明性を確保する観点から、平均粒径が５〜２００ｎｍであることが好ましい。 The separator 29 is formed in an I-shaped cross section so as to be adjacent to one side surface of the photoelectrode 20 on which the base layer 22, the porous semiconductor layer 24 and the hole transport layer 26 are laminated. One end of the separator 29 is in contact with the groove 18 on the transparent conductive substrate 14. Thereby, the direct contact with the photoelectrode 20 and the counter electrode 30 is avoided. The separator 29 is made of an insulating material, and may be formed of, for example, glass beads, silicon dioxide (silica), rutile titanium oxide, or the like. The separator 29 is preferably an insulator in which silica particles are sintered. Silica particles are preferable for the separator because they have a low refractive index, low light scattering, and good transparency. The separator 29 preferably has an average particle size of 5 to 200 nm from the viewpoint of ensuring good transparency.
対極３０は、セパレータ２９の外面と正孔輸送層２６の裏面２７とに接触するよう、鍔状の縁部分３１を有する断面Ｌ字状に形成されている。この対極３０は、一端が正孔輸送層２６の裏面２７に接続されていると共に、他端が接続部２１を介して隣側の透明導電膜１２に接続されている。裏面２７と接触する対極３０の面は、光電極２０に対して所定の間隔を隔てて対向している。対極３０としては、導電性及び正孔輸送層２６との接合性を有するものであれば特に限定されず、例えば、Ｐｔ，Ａｕ，カーボンなどが挙げられ、このうちカーボンが好ましい。なお、対極３０は、正孔輸送層２６と同一材料で形成してもよい。即ち、正孔輸送層２６の外表面側の一部を対極３０として用いてもよい。 The counter electrode 30 is formed in an L-shaped cross section having a bowl-shaped edge portion 31 so as to contact the outer surface of the separator 29 and the back surface 27 of the hole transport layer 26. One end of the counter electrode 30 is connected to the back surface 27 of the hole transport layer 26, and the other end is connected to the adjacent transparent conductive film 12 via the connection portion 21. The surface of the counter electrode 30 in contact with the back surface 27 is opposed to the photoelectrode 20 with a predetermined interval. The counter electrode 30 is not particularly limited as long as it has conductivity and bondability with the hole transport layer 26, and examples thereof include Pt, Au, and carbon. Among these, carbon is preferable. The counter electrode 30 may be formed of the same material as the hole transport layer 26. That is, a part of the outer surface side of the hole transport layer 26 may be used as the counter electrode 30.
シール材３２は、絶縁性の部材であれば特に限定されずに用いることができる。このシール材３２としては、例えば、ポリエチレン等の熱可塑性樹脂フィルム、あるいはエポキシ系接着剤を使用することができる。 The sealing material 32 can be used without particular limitation as long as it is an insulating member. As the sealing material 32, for example, a thermoplastic resin film such as polyethylene or an epoxy adhesive can be used.
保護部材３４は、色素増感型太陽電池４０の保護を図る部材であり、例えば、防湿フィルムや保護ガラスなどとすることができる。 The protection member 34 is a member that protects the dye-sensitized solar cell 40, and can be, for example, a moisture-proof film or protective glass.
この色素増感型太陽電池４０に対して、透明基板１１の受光面１３側から光を照射すると、透明導電膜１２の受光面１５及び下地層２２の受光面２３を介して光が多孔質半導体層２４へ到達し、有機色素が光を吸収して電子が発生する。電子は光電極２０から透明導電膜１２、接続部２１を経由して隣の対極３０へ移動する。色素増感型太陽電池４０では、この電子の移動により起電力が発生し、電池の発電作用が得られる。 When this dye-sensitized solar cell 40 is irradiated with light from the light-receiving surface 13 side of the transparent substrate 11, the light is transmitted through the light-receiving surface 15 of the transparent conductive film 12 and the light-receiving surface 23 of the base layer 22 into the porous semiconductor. It reaches the layer 24 and the organic dye absorbs light to generate electrons. Electrons move from the photoelectrode 20 to the adjacent counter electrode 30 via the transparent conductive film 12 and the connection portion 21. In the dye-sensitized solar cell 40, an electromotive force is generated by the movement of the electrons, and the power generation action of the battery is obtained.
次に、色素増感型太陽電池モジュール１０の製造方法について説明する。この色素増感型太陽電池モジュール１０の製造方法には、基板作製工程、多孔質半導体層形成工程（複合体形成工程）、正孔輸送層形成工程、セパレータ形成工程、対極形成工程及び保護部材形成工程を含むものとしてもよい。なお、以下の製造方法において、上述した色素増感型太陽電池４０の各構成を採用することができる。基板作製工程では、複数の透明導電膜１２の間に溝１８を形成しつつ透明導電膜１２を透明基板１１上に形成する。 Next, a method for manufacturing the dye-sensitized solar cell module 10 will be described. The method for producing the dye-sensitized solar cell module 10 includes a substrate manufacturing process, a porous semiconductor layer forming process (composite forming process), a hole transport layer forming process, a separator forming process, a counter electrode forming process, and a protective member forming process. A process may be included. In addition, in the following manufacturing methods, each structure of the dye-sensitized solar cell 40 mentioned above is employable. In the substrate manufacturing process, the transparent conductive film 12 is formed on the transparent substrate 11 while forming the grooves 18 between the plurality of transparent conductive films 12.
多孔質半導体層形成工程では、透明導電膜１２上に下地層２２を介してｎ型半導体層を形成する。次に、有機色素分子をｎ型半導体層へ吸着させたのち、金属含有材料を添加して複合体２８を形成させ、多孔質半導体層２４を形成する。金属含有材料の添加は、例えば、金属含有材料を溶解した溶液をｎ型半導体層へ供給するものとしてもよいし、金属含有材料を溶解した溶液にｎ型半導体層を浸漬させるものとしてもよい。有機色素分子としては、上述した、Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子、例えばＣＮ基やロダニン構造を有するものとすることができる。また、ｎ型半導体層としては、上述したものを用いることができ、多孔質の酸化チタンが好ましい。また、金属含有材料としては、上述したように、アルカリ系材料と、Ｃｕ系材料と、Ｃｕ以外の遷移金属を含む非Ｃｕ系材料と、のうち少なくとも１種以上の材料を含むものとしてもよく、これら３種を含むことがより好ましい。遷移金属材料は、Ｃｕ，Ｎｉ，Ｃｏ，Ｆｅ及びＣｒのうち１以上の遷移金属を含むことが好ましい。Ｃｕ系材料として、Ｃｕを含む半導体（例えばＣｕＩ、ＣｕＳＣＮ、ＣｕＯ及びＣｕ2Ｏのうちいずれか１以上）を用いることが好ましい。このように多孔質半導体層２４を形成すると、多孔質半導体層２４に含まれる有機色素分子と、金属含有材料に含まれる金属イオンとが相互作用し、有機色素の光吸収特性が長波長側に拡大するものと考えられる。この長波長シフトにより、光電変換に利用可能な波長領域が広がることによって、色素増感型太陽電池４０の光電変換特性が向上するものと考えられる。 In the porous semiconductor layer forming step, an n-type semiconductor layer is formed on the transparent conductive film 12 via the base layer 22. Next, after the organic dye molecules are adsorbed to the n-type semiconductor layer, a metal-containing material is added to form the composite 28, and the porous semiconductor layer 24 is formed. The metal-containing material may be added, for example, by supplying a solution in which the metal-containing material is dissolved to the n-type semiconductor layer, or by immersing the n-type semiconductor layer in a solution in which the metal-containing material is dissolved. The organic dye molecule may have the above-described organic dye molecule having an electron accepting site containing at least one of S and N, for example, a CN group or a rhodanine structure. Further, as the n-type semiconductor layer, those described above can be used, and porous titanium oxide is preferable. In addition, as described above, the metal-containing material may include at least one material among an alkali-based material, a Cu-based material, and a non-Cu-based material including a transition metal other than Cu. More preferably, these three types are included. The transition metal material preferably contains one or more transition metals among Cu, Ni, Co, Fe and Cr. As the Cu-based material, a semiconductor containing Cu (for example, any one or more of CuI, CuSCN, CuO, and Cu 2 O) is preferably used. When the porous semiconductor layer 24 is formed in this manner, the organic dye molecules contained in the porous semiconductor layer 24 interact with the metal ions contained in the metal-containing material, so that the light absorption characteristics of the organic dye are on the long wavelength side. It is expected to expand. This long wavelength shift is considered to improve the photoelectric conversion characteristics of the dye-sensitized solar cell 40 by expanding the wavelength region that can be used for photoelectric conversion.
次に、正孔輸送層形成工程では、多孔質半導体層２４の裏面２５へ固体ｐ型半導体を供給し、その後乾燥させて正孔輸送層２６を形成してもよい。固体ｐ型半導体として、Ｃｕを含む半導体（例えば、ＣｕＩ）を用いることが好ましい。このとき、ｐ型半導体を含む溶液を多孔質半導体層２４上に供給することにより、正孔輸送層２６を形成するものとしてもよい。こうすれば、ｐ型半導体材料が多孔質半導体層２４に充填されることにより、正孔輸送層２６のｐ型半導体材料をも含む複合体２８を得ることができる。続いて、セパレータ形成工程では、溝１８に合わせて光電極２０の側面にセパレータ２９を形成する。対極形成工程では、セパレータ２９と正孔輸送層２６とに接するように対極３０を形成する。対極３０は、例えばカーボンとしてもよい。保護部材形成工程では、各セルを覆うようにシール材３２を形成すると共にシール材３２に保護部材３４を形成する。このようにして、発電特性が向上した色素増感型太陽電池４０及び色素増感型太陽電池モジュール１０を作製することができる。 Next, in the hole transport layer forming step, the solid p-type semiconductor may be supplied to the back surface 25 of the porous semiconductor layer 24 and then dried to form the hole transport layer 26. It is preferable to use a semiconductor containing Cu (for example, CuI) as the solid p-type semiconductor. At this time, the hole transport layer 26 may be formed by supplying a solution containing a p-type semiconductor onto the porous semiconductor layer 24. In this way, the composite 28 including the p-type semiconductor material of the hole transport layer 26 can be obtained by filling the porous semiconductor layer 24 with the p-type semiconductor material. Subsequently, in the separator forming step, a separator 29 is formed on the side surface of the photoelectrode 20 in alignment with the groove 18. In the counter electrode forming step, the counter electrode 30 is formed so as to contact the separator 29 and the hole transport layer 26. The counter electrode 30 may be carbon, for example. In the protective member forming step, the sealing material 32 is formed so as to cover each cell, and the protective member 34 is formed on the sealing material 32. In this manner, the dye-sensitized solar cell 40 and the dye-sensitized solar cell module 10 with improved power generation characteristics can be produced.
以上詳述した色素増感型太陽電池モジュール１０では、複合体２８において、有機色素と金属含有材料に含まれる金属イオンとの相互作用が惹起されており、有機色素の光吸収特性がより向上し、より高い光電変換特性を示す。例えば、有機色素分子内において、電荷移動の相互作用が、有機色素分子と金属イオンとの相互作用又は結合などにより変化することによって、光吸収特性が長波長側に拡大するものと考えられる。このような、有機色素分子と金属イオンとの相互作用又は結合が、有機色素分子とアルカリ系イオンとの間、及び有機色素分子と遷移金属イオンとの間で重畳的に起きることによって、有機色素の光吸収特性をより向上することができると考えられる。 In the dye-sensitized solar cell module 10 described in detail above, the interaction between the organic dye and the metal ion contained in the metal-containing material is induced in the composite 28, and the light absorption characteristics of the organic dye are further improved. Higher photoelectric conversion characteristics are shown. For example, in the organic dye molecule, it is considered that the charge transfer interaction changes due to the interaction or bond between the organic dye molecule and the metal ion, thereby expanding the light absorption characteristics to the longer wavelength side. Such an interaction or bond between the organic dye molecule and the metal ion occurs in an overlapping manner between the organic dye molecule and the alkali ion and between the organic dye molecule and the transition metal ion. It is thought that the light absorption characteristics of the can be further improved.
なお、本発明は上述した実施形態に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.
例えば上述した実施形態では、色素増感型太陽電池モジュール１０としたが、特にこれに限定されず、色素増感型太陽電池４０としてもよい。図４は、色素増感型太陽電池４０の構成の概略の一例を示す断面図である。図４では、図１で説明した構成と同様の構成については同じ符号を付してその説明を省略する。図４に示すように、色素増感型太陽電池４０の単体では、対極３０を断面をＬ字状ではなく、鍔状の縁部分を省略して平板状に形成するものとしてもよい。また、図１のセパレータ２９を省略してもよい。また、対極３０は、例えば透明導電性基板１４と同じ構成を有するものを用いるものとしてもよいし、透明導電膜１２に白金を付着させたものや、白金などの金属薄膜などとしてもよい。 For example, in the above-described embodiment, the dye-sensitized solar cell module 10 is used. However, the present invention is not particularly limited thereto, and the dye-sensitized solar cell 40 may be used. FIG. 4 is a cross-sectional view showing an example of a schematic configuration of the dye-sensitized solar cell 40. In FIG. 4, the same components as those described in FIG. 1 are denoted by the same reference numerals, and the description thereof is omitted. As shown in FIG. 4, in the single body of the dye-sensitized solar cell 40, the counter electrode 30 may be formed in a flat plate shape with the cross-section not being L-shaped and omitting the bowl-shaped edge portion. Further, the separator 29 in FIG. 1 may be omitted. The counter electrode 30 may be, for example, one having the same configuration as that of the transparent conductive substrate 14, or may be one in which platinum is attached to the transparent conductive film 12, or a metal thin film such as platinum.
上述した実施形態では、色素増感型太陽電池４０としたが、特にこれに限定されず、透明導電膜１２と透明基板１１とを有する透明導電性基板１４と、透明導電性基板１４に隣接して設けられているｎ型半導体を含む多孔質半導体層２４と、上述した複合体２８とを備えた光電極２０としてもよい。あるいは、Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、金属含有材料と、を含有した複合体２８としてもよい。 In the above-described embodiment, the dye-sensitized solar cell 40 is used. However, the present invention is not particularly limited thereto, and the transparent conductive substrate 14 having the transparent conductive film 12 and the transparent substrate 11 is adjacent to the transparent conductive substrate 14. It is good also as the photoelectrode 20 provided with the porous semiconductor layer 24 containing the n-type semiconductor provided, and the composite 28 mentioned above. Or it is good also as the composite_body | complex 28 containing the organic pigment | dye molecule | numerator which has an electron acceptance part containing at least one among S and N, and a metal containing material.
また、複合体は、金属含有材料として、第１族元素及び第２族元素のうち１以上を含むアルカリ系材料と、Ｃｕを含む半導体及びＣｕを含む導電体のうち少なくとも一方を含む遷移金属材料としてのＣｕ系材料と、Ｃｕ以外の遷移金属を含む遷移金属材料としての非Ｃｕ系材料と、のうち少なくとも１以上を含むものとしてもよい。例えば、複合体は、Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、Ｆｅを少なくとも含む遷移金属材料と、を含有したものとしてもよい。こうしても、有機色素分子とＦｅイオンとが相互作用することにより、有機色素の光吸収特性をより向上することができる。この複合体、及びこの複合体を採用した光電極、色素増感型太陽電池及び色素増感型太陽電池モジュールにおいて、上述した実施形態のいずれかの構成を採用することができる。 The composite includes a transition metal material containing at least one of an alkali-based material containing one or more of Group 1 elements and Group 2 elements as a metal-containing material, a semiconductor containing Cu, and a conductor containing Cu. It is good also as what contains at least 1 or more among Cu-type material as these, and non-Cu-type material as a transition metal material containing transition metals other than Cu. For example, the composite may contain an organic dye molecule having an electron accepting site containing at least one of S and N, and a transition metal material containing at least Fe. Even in this case, the light absorption characteristics of the organic dye can be further improved by the interaction between the organic dye molecules and the Fe ions. In this composite, and a photoelectrode, a dye-sensitized solar cell, and a dye-sensitized solar cell module that employ this composite, any of the configurations of the above-described embodiments can be employed.
あるいは、複合体は、Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、第１族元素及び第２族元素のうち１以上を含むアルカリ系材料と、を含有したものとしてもよい。こうしても、有機色素分子とアルカリ系材料に含まれる金属イオンとが相互作用することにより、有機色素の光吸収特性をより向上することができる。この複合体、及びこの複合体を採用した光電極、色素増感型太陽電池及び色素増感型太陽電池モジュールにおいて、上述した実施形態のいずれかの構成を採用することができる。 Alternatively, the composite contains an organic dye molecule having an electron accepting site containing at least one of S and N, and an alkaline material containing one or more of Group 1 elements and Group 2 elements. Also good. Even in this case, the light absorption characteristics of the organic dye can be further improved by the interaction between the organic dye molecule and the metal ion contained in the alkaline material. In this composite, and a photoelectrode, a dye-sensitized solar cell, and a dye-sensitized solar cell module that employ this composite, any of the configurations of the above-described embodiments can be employed.
あるいは、複合体は、Ｓ及びＮのうち少なくとも一方を含む電子受容部位を有する有機色素分子と、Ｃｕを含む半導体及びＣｕを含む導電体のうち少なくとも一方を含むＣｕ系材料とＣｕ以外の遷移金属を含む非Ｃｕ系材料とを含む遷移金属材料と、を含有したものとしてもよい。こうしても、有機色素分子とＣｕイオンと、遷移金属イオンとが相互作用することにより、有機色素の光吸収特性をより向上することができる。この複合体、及びこの複合体を採用した光電極、色素増感型太陽電池及び色素増感型太陽電池モジュールにおいて、上述した実施形態のいずれかの構成を採用することができる。 Alternatively, the composite includes an organic dye molecule having an electron accepting site containing at least one of S and N, a Cu-based material containing at least one of a semiconductor containing Cu and a conductor containing Cu, and a transition metal other than Cu. And a transition metal material containing a non-Cu-based material containing. Even in this case, the light absorption characteristics of the organic dye can be further improved by the interaction between the organic dye molecule, the Cu ion, and the transition metal ion. In this composite, and a photoelectrode, a dye-sensitized solar cell, and a dye-sensitized solar cell module that employ this composite, any of the configurations of the above-described embodiments can be employed.
上述した実施形態では、ｐ型半導体を含む正孔輸送層２６を備えた全固体型太陽電池として説明したが、特にこれに限定されず、例えば、光電極２０と対極３０との間に電解液を備えた色素増感型太陽電池としてもよい。 In the above-described embodiment, the all-solid-state solar cell including the hole transport layer 26 including the p-type semiconductor has been described. However, the present invention is not particularly limited thereto. For example, the electrolytic solution is provided between the photoelectrode 20 and the counter electrode 30. It is good also as a dye-sensitized solar cell provided with.
以下には、本発明の複合体、光電極及び色素増感型太陽電池を具体的に作製した例を実験例として説明する。 Below, the example which produced the composite_body | complex, photoelectrode, and dye-sensitized solar cell of this invention concretely is demonstrated as an experiment example.
［複合体の光吸収特性評価］
種々の金属含有材料（アルカリ系材料、Ｃｕ系材料及び非Ｃｕ系材料を含む遷移金属材料）を用い、有機色素分子として図２，３に示す色素１（Ｄ１４９とも称する）及び色素５（ＭＫ２とも称する）を用いて、ｎ型半導体層であるＴｉＯ2基板上に本発明の複合体を作製し、光吸収スペクトルを検討した。ここでは、ＴｉＯ2基板のみ、ＴｉＯ2基板に有機色素を形成したもの、ＴｉＯ2基板に有機色素及び金属含有材料を含む複合体を形成したものの３種を測定した。また、有機色素を形成したＴｉＯ2基板の吸収スペクトル、及び複合体の吸収スペクトルからＴｉＯ2基板の吸収スペクトルを差し引き、色素のみで得られる吸収スペクトルと複合体に含まれる色素で得られる吸収スペクトルとの対比を行い、その特性を評価した。吸収スペクトルは、分光光度計（日立製作所社製Ｕ−３４００）により、２９０ｎｍ〜９００ｎｍの波長領域で測定した。なお、この評価では、アルカリ系材料のみを含む複合体、遷移金属材料のみを含む複合体、及び、アルカリ系材料及び遷移金属材料の両方を含む複合体の光吸収特性を検討した。
[Evaluation of light absorption characteristics of composite]
Using various metal-containing materials (transition metal materials including alkali-based materials, Cu-based materials, and non-Cu-based materials), as organic dye molecules, dye 1 (also referred to as D149) and dye 5 (also referred to as MK2) shown in FIGS. The composite of the present invention was fabricated on a TiO 2 substrate which is an n-type semiconductor layer, and the light absorption spectrum was examined. Here, TiO 2 substrate only, that forms the organic dye TiO 2 substrate was measured three but to form a complex containing an organic dye and a metal-containing material to a TiO 2 substrate. In addition, the absorption spectrum of the TiO 2 substrate formed by subtracting the absorption spectrum of the TiO 2 substrate from the absorption spectrum of the TiO 2 substrate on which the organic dye is formed and the absorption spectrum of the composite, and the absorption spectrum obtained with the dye contained in the composite Were compared and their characteristics were evaluated. The absorption spectrum was measured with a spectrophotometer (U-3400 manufactured by Hitachi, Ltd.) in a wavelength region of 290 nm to 900 nm. In this evaluation, the light absorption characteristics of a composite containing only an alkaline material, a composite containing only a transition metal material, and a composite containing both an alkaline material and a transition metal material were examined.
（複合体の作製）
ＴＣＯガラス基板上に、ｎ型半導体層としての多孔質ＴｉＯ2膜をスクリーン印刷法で塗布し、１５０℃で乾燥したのち電気炉内で４５０℃で加熱して、多孔質ＴｉＯ2膜基板を作製した。この多孔質ＴｉＯ2膜基板を複数作製した。次に、有機色素１（Ｄ１４９）及び有機色素５（ＭＫ２）を各々含む色素溶液を調製した。色素溶液は、例えばＤ１４９では、アセトニトリルとｔｅｒｔ−ブチルアルコールとを混合した混合溶液を溶媒として用い、ＭＫ２では、トルエンを溶媒として用いた。続いて、上記作製したいずれかの色素溶液に多孔質ＴｉＯ2膜基板をそれぞれ浸漬し、２５℃の温度条件の下で１５時間放置した。このようにして、有機色素１又は有機色素５を吸着させた多孔質ＴｉＯ2膜基板（ＴｉＯ2／色素基板とも称する）をそれぞれ作製した。その後、金属含有材料（例えば、ＬｉＴＦＳＩやＦｅＩ2など）を所定濃度、溶解したアセトニトリル溶液に、上記ＴｉＯ2／色素基板を３０秒浸漬させた。
(Production of complex)
A porous TiO 2 film as an n-type semiconductor layer is applied on a TCO glass substrate by screen printing, dried at 150 ° C., and then heated at 450 ° C. in an electric furnace to produce a porous TiO 2 film substrate. did. A plurality of porous TiO 2 film substrates were produced. Next, a dye solution containing each of organic dye 1 (D149) and organic dye 5 (MK2) was prepared. As the dye solution, for example, in D149, a mixed solution of acetonitrile and tert-butyl alcohol was used as a solvent, and in MK2, toluene was used as a solvent. Subsequently, the porous TiO 2 film substrate was immersed in any of the dye solutions prepared above, and left for 15 hours under a temperature condition of 25 ° C. In this way, porous TiO 2 film substrates (also referred to as TiO 2 / dye substrate) on which the organic dye 1 or the organic dye 5 was adsorbed were produced. Thereafter, the TiO 2 / dye substrate was immersed in an acetonitrile solution in which a metal-containing material (for example, LiTFSI or FeI 2 ) was dissolved at a predetermined concentration for 30 seconds.
［実験例１〜４（複合体）］
有機色素としてＤ１４９を用い、金属含有材料としてＬｉＩを用い、金属含有材料を０．１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させる上記工程を経て得られた複合体を実験例１とした。また、ＬｉＳＣＮを０．１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例２とした。また、ＬｉＴＦＳＩを０．１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例３とした。また、ＬｉＴＦＳＩを０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例４とした。
[Experimental Examples 1 to 4 (complex)]
The composite obtained through the above-described step of immersing the TiO 2 / dye substrate in a solution containing D149 as the organic dye, LiI as the metal-containing material, and a metal-containing material at a concentration of 0.1 M is referred to as Experimental Example 1 did. In addition, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 2 except that the TiO 2 / dye substrate was immersed in a solution having a LiSCN concentration of 0.1M. Further, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 3, except that the TiO 2 / dye substrate was immersed in a solution having a LiTFSI concentration of 0.1M. In addition, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 4 except that the TiO 2 / dye substrate was immersed in a solution having a LiTFSI concentration of 0.01M.
［実験例５，６（複合体）］
アルカリ系材料としてＬｉＴＦＳＩを０．０１Ｍの濃度とし、移金属材料としてＦｅＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例５とした。また、アルカリ系材料としてＬｉＴＦＳＩを０．０１Ｍの濃度とし、遷移金属材料としてＣｏＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例６とした。
[Experimental Examples 5 and 6 (complex)]
Obtained through the same steps as in Experimental Example 1 except that the TiO 2 / dye substrate was immersed in a solution having a LiTFSI concentration of 0.01M as the alkaline material and a FeI 2 concentration of 0.01M as the transfer metal material. The obtained composite was taken as Experimental Example 5. Further, the same steps as in Experimental Example 1 were performed except that the TiO 2 / dye substrate was immersed in a solution having LiTFSI as a concentration of 0.01M as an alkaline material and CoI 2 as a transition metal material at a concentration of 0.01M. The composite obtained as a result was designated as Experimental Example 6.
［実験例７，８（複合体）］
アルカリ系材料としてＫＩを０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例７とした。また、アルカリ系材料としてＮａＩを０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例８とした。
[Experimental Examples 7 and 8 (complex)]
A composite obtained through the same steps as Experimental Example 1 was used as Experimental Example 7, except that the TiO 2 / dye substrate was immersed in a solution having a KI concentration of 0.01 M as an alkaline material. In addition, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 8, except that the TiO 2 / dye substrate was immersed in a solution having a NaI concentration of 0.01 M as an alkaline material.
［実験例９，１０（複合体）］
アルカリ系材料としてＭｇＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例９とした。また、アルカリ系材料としてＣａＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例１０とした。
[Experimental Examples 9 and 10 (Composite)]
A composite obtained through the same steps as Experimental Example 1 was used as Experimental Example 9, except that the TiO 2 / dye substrate was immersed in a solution containing 0.01 M MgI 2 as an alkaline material. In addition, a composite obtained through the same steps as Experimental Example 1 was used as Experimental Example 10 except that the TiO 2 / dye substrate was immersed in a solution having CaI 2 as a concentration of 0.01 M as an alkaline material.
［実験例１１〜１４（複合体）］
遷移金属材料としてＦｅＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例１１とした。また、遷移金属材料としてＣｏＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例１２とした。また、遷移金属材料としてＮｉＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例１３とした。また、遷移金属材料としてＣｕＩを０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１と同様の工程を経て得られた複合体を実験例１４とした。
[Experimental Examples 11 to 14 (Composite)]
A composite obtained through the same process as Experimental Example 1 was used as Experimental Example 11 except that the TiO 2 / dye substrate was immersed in a solution having a FeI 2 concentration of 0.01 M as a transition metal material. In addition, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 12 except that the TiO 2 / dye substrate was immersed in a solution having CoI 2 concentration of 0.01M as a transition metal material. In addition, a composite obtained through the same process as Experimental Example 1 was used as Experimental Example 13 except that the TiO 2 / dye substrate was immersed in a solution having a NiI 2 concentration of 0.01 M as a transition metal material. In addition, a composite obtained through the same steps as Experimental Example 1 was used as Experimental Example 14, except that the TiO 2 / dye substrate was immersed in a solution having a CuI concentration of 0.01 M as a transition metal material.
［実験例１５，１６（複合体）］
有機色素としてＭＫ２を用い、ＬｉＴＦＳＩを０．１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させる上記工程を経て得られた複合体を実験例１５とした。また、ＬｉＴＦＳＩを０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１５と同様の工程を経て得られた複合体を実験例１６とした。
[Experimental Examples 15 and 16 (complex)]
A composite obtained through the above-described step of immersing the TiO 2 / dye substrate in a solution having MTF2 as the organic dye and a concentration of LiTFSI of 0.1 M was defined as Experimental Example 15. In addition, a composite obtained through the same process as Experimental Example 15 was used as Experimental Example 16, except that the TiO 2 / dye substrate was immersed in a solution having a LiTFSI concentration of 0.01M.
［実験例１７，１８（複合体）］
アルカリ系材料としてＫＩを０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１５と同様の工程を経て得られた複合体を実験例１７とした。また、アルカリ系材料としてＮａＩを０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１５と同様の工程を経て得られた複合体を実験例１８とした。
[Experimental Examples 17 and 18 (complex)]
A composite obtained through the same steps as in Experimental Example 15 was used as Experimental Example 17, except that the TiO 2 / dye substrate was immersed in a solution having a KI concentration of 0.01 M as an alkaline material. In addition, a composite obtained through the same steps as in Experimental Example 15 was used as Experimental Example 18 except that the TiO 2 / dye substrate was immersed in a solution having a NaI concentration of 0.01 M as an alkaline material.
［実験例１９，２０（複合体）］
アルカリ系材料としてＭｇＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１５と同様の工程を経て得られた複合体を実験例１９とした。また、アルカリ系材料としてＣａＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１５と同様の工程を経て得られた複合体を実験例２０とした。
[Experimental Examples 19 and 20 (complex)]
A composite obtained through the same process as Experimental Example 15 was used as Experimental Example 19 except that the TiO 2 / dye substrate was immersed in a solution containing 0.01 M MgI 2 as an alkaline material. In addition, a composite obtained through the same process as Experimental Example 15 was used as Experimental Example 20 except that the TiO 2 / dye substrate was immersed in a solution having CaI 2 as a concentration of 0.01 M as an alkaline material.
［実験例２１〜２４（複合体）］
遷移金属材料としてＦｅＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１５と同様の工程を経て得られた複合体を実験例２１とした。また、遷移金属材料としてＣｏＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１５と同様の工程を経て得られた複合体を実験例２２とした。また、遷移金属材料としてＮｉＩ2を０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１５と同様の工程を経て得られた複合体を実験例２３とした。また、遷移金属材料としてＣｕＩを０．０１Ｍの濃度とした溶液にＴｉＯ2／色素基板を浸漬させた以外、実験例１５と同様の工程を経て得られた複合体を実験例２４とした。
[Experimental Examples 21 to 24 (complex)]
A composite obtained through the same process as Experimental Example 15 was used as Experimental Example 21, except that the TiO 2 / dye substrate was immersed in a solution having a FeI 2 concentration of 0.01 M as a transition metal material. In addition, a composite obtained through the same process as Experimental Example 15 was used as Experimental Example 22 except that the TiO 2 / dye substrate was immersed in a solution having CoI 2 concentration of 0.01M as a transition metal material. In addition, a composite obtained through the same process as Experimental Example 15 was used as Experimental Example 23, except that the TiO 2 / dye substrate was immersed in a solution having a NiI 2 concentration of 0.01 M as a transition metal material. In addition, a composite obtained through the same steps as Experimental Example 15 was used as Experimental Example 24 except that the TiO 2 / dye substrate was immersed in a solution having a CuI concentration of 0.01 M as a transition metal material.
（複合体の実験結果）
実験例１〜１４の複合体の吸収スペクトルの測定結果を、表１及び図５〜８に示し、実験例１５〜２４の複合体の吸収スペクトルの測定結果を、表２及び図９〜１１に示す。なお、図５では、ＴｉＯ2／色素基板の吸収、及び金属含有材料を有するＴｉＯ2／色素基板の吸収から、ＴｉＯ2の吸収を差し引いた結果を示した。また、図６以降では、ＴｉＯ2／色素基板の吸収、及び金属含有材料を有するＴｉＯ2／色素基板の吸収の測定結果を示した。図５，６に示すように、有機色素がＤ１４９であるＴｉＯ2／色素基板に、アルカリ系材料であるＬｉＴＦＳＩ、ＬｉＩ及びＬｉＳＣＮを作用させると、光吸収スペクトルが長波長化することが明らかになった。また、図６に示すように、金属含有材料（ＬｉＴＦＳＩ）の濃度は、０．０１Ｍでも効果があることがわかった。また、金属イオンとしてＬｉ+は効果があり、更にアニオンとして、ＴＦＳＩ-、Ｉ-及びＳＣＮ-などが好ましいことがわかった。また、ＴｉＯ2／色素基板に、アルカリ系材料であるＬｉＴＦＳＩと遷移金属材料であるＦｅＩ2とを作用させると、光吸収スペクトルが更に長波長化することが明らかになった。同様に、ＴｉＯ2／色素基板に、アルカリ系材料であるＬｉＴＦＳＩと遷移金属材料であるＣｏＩ2とを作用させると、光吸収スペクトルが更に長波長化することが明らかになった。したがって、アルカリ系材料と遷移金属材料とは有機色素（Ｄ１４９）の別の部位に作用することが示唆された。また、図７に示すように、有機色素がＤ１４９であるＴｉＯ2／色素基板に、アルカリ系材料であるＫＩ，ＮａＩ，ＭｇＩ2及びＣａＩ2を作用させると、光吸収スペクトルが長波長化することが明らかになった。また、図８に示すように、有機色素がＤ１４９であるＴｉＯ2／色素基板に、遷移金属材料であるＦｅＩ2，ＣｏＩ2，ＮｉＩ2及びＣｕＩを作用させると、光吸収スペクトルが長波長化することが明らかになった。特に、ＦｅＩ2，ＣｏＩ2，及びＮｉＩ2が、ＣｕＩに比して吸収スペクトルがより長波長側にシフトすることがわかった。
(Experimental result of complex)
The measurement results of the absorption spectra of the composites of Experimental Examples 1 to 14 are shown in Table 1 and FIGS. 5 to 8, and the measurement results of the absorption spectra of the composites of Experimental Examples 15 to 24 are shown in Table 2 and FIGS. Show. In FIG. 5, the absorption of TiO 2 / dye substrate, and the absorption of TiO 2 / dye substrate having a metal-containing material, shows the results obtained by subtracting the absorption of TiO 2. Further, in FIG. 6 and subsequent absorption of TiO 2 / dye substrate, and showing the measurement results of the absorption of TiO 2 / dye substrate having a metal-containing material. As shown in FIGS. 5 and 6, when the alkaline materials LiTFSI, LiI and LiSCN are allowed to act on the TiO 2 / dye substrate whose organic dye is D149, it becomes clear that the light absorption spectrum becomes longer. It was. Moreover, as shown in FIG. 6, it turned out that the density | concentration of a metal containing material (LiTFSI) is effective even if it is 0.01M. Further, it was found that Li + is effective as a metal ion, and TFSI − , I − and SCN − are preferable as anions. Further, it was revealed that when the alkaline material LiTFSI and the transition metal material FeI 2 are allowed to act on the TiO 2 / dye substrate, the light absorption spectrum becomes longer. Similarly, when LiTFSI as an alkaline material and CoI 2 as a transition metal material are allowed to act on a TiO 2 / dye substrate, it has been clarified that the light absorption spectrum becomes longer. Therefore, it was suggested that the alkaline material and the transition metal material act on another part of the organic dye (D149). In addition, as shown in FIG. 7, when KI, NaI, MgI 2 and CaI 2 as alkaline materials are allowed to act on a TiO 2 / dye substrate whose organic dye is D149, the light absorption spectrum becomes longer. Became clear. As shown in FIG. 8, when the transition metal materials FeI 2 , CoI 2 , NiI 2 and CuI are allowed to act on a TiO 2 / dye substrate whose organic dye is D149, the light absorption spectrum becomes longer. It became clear. In particular, it was found that the absorption spectrum of FeI 2 , CoI 2 , and NiI 2 shifts to the longer wavelength side compared to CuI.
表２及び図９に示すように、有機色素がＭＫ２である場合でも、金属含有材料（ＬｉＴＦＳＩ）の濃度は、０．０１Ｍや０．１Ｍでも光吸収スペクトルが長波長化する効果があることがわかった。また、図１０に示すように、有機色素がＭＫ２であるＴｉＯ2／色素基板に、アルカリ系材料であるＫＩ，ＮａＩ，ＭｇＩ2及びＣａＩ2を作用させると、光吸収スペクトルが長波長化することが明らかになった。また、図１１に示すように、有機色素がＭＫ２であるＴｉＯ2／色素基板に、遷移金属材料であるＦｅＩ2，ＣｏＩ2，ＮｉＩ2及びＣｕＩを作用させると、光吸収スペクトルが長波長化することが明らかになった。特に、ＦｅＩ2，ＣｏＩ2，及びＮｉＩ2が、ＣｕＩに比して光吸収スペクトルがより長波長側にシフトすることがわかった。 As shown in Table 2 and FIG. 9, even when the organic dye is MK2, even if the concentration of the metal-containing material (LiTFSI) is 0.01M or 0.1M, the light absorption spectrum may have an effect of increasing the wavelength. all right. In addition, as shown in FIG. 10, when alkali materials KI, NaI, MgI 2 and CaI 2 are allowed to act on a TiO 2 / dye substrate whose organic dye is MK2, the light absorption spectrum becomes longer. Became clear. As shown in FIG. 11, when the transition metal materials FeI 2 , CoI 2 , NiI 2 and CuI are allowed to act on a TiO 2 / dye substrate whose organic dye is MK2, the light absorption spectrum becomes longer. It became clear. In particular, it was found that the light absorption spectrum of FeI 2 , CoI 2 , and NiI 2 shifts to the longer wavelength side compared to CuI.
図１２は、有機色素に金属含有材料を作用させたときの光吸収特性の測定結果であり、図１２（ａ）が有機色素をＤ１４９とし、ピーク位置のシフト量を示す図であり、図１２（ｂ）が有機色素をＤ１４９とし、ピーク立ち上がり位置のシフト量を示す図であり、図１２（ｃ）が有機色素をＭＫ２とし、ピーク位置のシフト量を示す図であり、図１２（ｄ）が有機色素をＭＫ２とし、ピーク立ち上がり位置のシフト量を示す図である。図１３に示すように、実験例１〜２４では、いずれの有機色素でも光吸収スペクトルが長波長化することが明らかになった。また、金属イオンを１種類とし、濃度が０．０１Ｍであるものを比較すると、ＬｉＴＦＳＩ、ＦｅＩ2、ＣｏＩ2、ＣａＩ2、ＮｉＩ2及びＭｇＩ2などが、ＣｕＩに比して長波長化する傾向にあることがわかった。 FIG. 12 shows measurement results of light absorption characteristics when a metal-containing material is allowed to act on an organic dye. FIG. 12A shows the shift amount of the peak position with D149 as the organic dye. FIG. 12B is a diagram showing the shift amount of the peak rising position with D149 as the organic dye, and FIG. 12C is a diagram showing the shift amount of the peak position with MK2 as the organic dye. FIG. 4 is a diagram showing the shift amount of the peak rising position when the organic dye is MK2. As shown in FIG. 13, in Experimental Examples 1 to 24, it has been clarified that the light absorption spectrum becomes longer in any organic dye. Further, the metal ions and one, comparing what concentration is 0.01 M, LiTFSI, tend to FeI 2, CoI 2, CaI 2 , NiI 2 and MgI 2 and, to longer wavelength in comparison with CuI I found out.
［色素増感型太陽電池の内部量子効率（ＩＰＣＥ）特性及び太陽電池特性評価］
ＴＣＯガラス基板上に、ｎ型半導体層として多孔質ＴｉＯ2膜をスクリーン印刷法で塗布し、１５０℃で乾燥したのち、電気炉内で４５０℃に加熱して、多孔質ＴｉＯ2膜基板を作製した。次に、有機色素１（Ｄ１４９）及び有機色素５（ＭＫ２）を各々含む色素溶液を調製した。色素溶液は、例えばＤ１４９では、アセトニトリルとｔｅｒｔ−ブチルアルコールとを混合した混合溶液を溶媒として用い、ＭＫ２では、トルエンを溶媒として用いた。続いて、上記作製したいずれかの色素溶液に上記多孔質ＴｉＯ2膜基板をそれぞれ浸漬し、２５℃の温度条件の下で１５時間放置した。このようにして、有機色素１又は有機色素５を吸着させたＴｉＯ2／色素基板をそれぞれ作製した。次に、アセトニトリルにＣｕＩを飽和させ、１−メチル３−エチルイミダゾリウムチオシアネート（ＥＭＩＳＣＮ）を添加してＣｕＩ溶液を調製した。４０℃〜１２０℃のホットプレート上に、上記得られたＴｉＯ2／色素基板をＴｉＯ2膜が上になるように静置した。調製したＣｕＩ溶液をＴｉＯ2／色素基板上に５００μＬ滴下し、ＴｉＯ2膜内の有機色素にＣｕＩを更に吸着させた複合体を形成させた。ＣｕＩ溶液に含まれる溶媒を蒸発させることによりＴｉＯ2膜内にＣｕＩを充填させ、更に、ＴｉＯ2膜上にＣｕＩ層（正孔輸送層）を形成した。そして、このＣｕＩ層の上に、対極としてのＰｔ薄膜を配置し、色素増感型太陽電池を作製した。作製した色素増感型太陽電池は、内部量子効率（Incident Photon to Current Efficiency：ＩＰＣＥ）値により評価した。
[Internal quantum efficiency (IPCE) characteristics and evaluation of solar cell characteristics of dye-sensitized solar cell]
A porous TiO 2 film is applied as a n-type semiconductor layer on a TCO glass substrate by screen printing, dried at 150 ° C., and then heated to 450 ° C. in an electric furnace to produce a porous TiO 2 film substrate. did. Next, a dye solution containing each of organic dye 1 (D149) and organic dye 5 (MK2) was prepared. As the dye solution, for example, in D149, a mixed solution of acetonitrile and tert-butyl alcohol was used as a solvent, and in MK2, toluene was used as a solvent. Subsequently, the porous TiO 2 film substrate was immersed in any one of the prepared dye solutions, and left for 15 hours under a temperature condition of 25 ° C. In this way, a TiO 2 / dye substrate on which the organic dye 1 or the organic dye 5 was adsorbed was produced. Next, CuI was saturated with acetonitrile, and 1-methyl 3-ethylimidazolium thiocyanate (EMISCN) was added to prepare a CuI solution. The obtained TiO 2 / dye substrate was placed on a hot plate at 40 ° C. to 120 ° C. so that the TiO 2 film was on top. 500 μL of the prepared CuI solution was dropped on a TiO 2 / dye substrate to form a complex in which CuI was further adsorbed on the organic dye in the TiO 2 film. The CuI is filled into the TiO 2 film by evaporating the solvent contained in the CuI solution, further, to form CuI layer (hole transport layer) on the TiO 2 film. And the Pt thin film as a counter electrode was arrange | positioned on this CuI layer, and the dye-sensitized solar cell was produced. The produced dye-sensitized solar cell was evaluated by an internal quantum efficiency (IPC) value.
［実験例２５〜２７（色素増感型太陽電池）］
有機色素としてＤ１４９を用い、金属含有材料としてＬｉＴＦＳＩを用い、金属含有材料を１．０Ｍの濃度とした溶液を用いて上記工程を経て得られた色素増感型太陽電池を実験例２５とした。実験例２５は、Ｄ１４９の有機色素と、アルカリ系材料としてＬｉＴＦＳＩ及び遷移金属材料としてＣｕＩを含む金属含有材料と、を有する複合体を備えたものである。また、金属含有材料としてＬｉＩを用いた以外は実験例２５と同様の工程を経て得られた色素増感型太陽電池を実験例２６とした。実験例２６は、Ｄ１４９の有機色素と、アルカリ系材料としてＬｉＩ及び遷移金属材料としてＣｕＩを含む金属含有材料と、を有する複合体を備えたものである。また、金属含有材料としてＬｉＳＣＮを用いた以外は実験例２５と同様の工程を経て得られた色素増感型太陽電池を実験例２７とした。実験例２９は、Ｄ１４９の有機色素と、アルカリ系材料としてＬｉＳＣＮ及び遷移金属材料としてＣｕＩを含む金属含有材料と、を有する複合体を備えたものである。
[Experimental Examples 25 to 27 (Dye-sensitized solar cell)]
A dye-sensitized solar cell obtained through the above steps using a solution in which D149 was used as the organic dye, LiTFSI was used as the metal-containing material, and the metal-containing material had a concentration of 1.0 M was defined as Experimental Example 25. Experimental Example 25 includes a composite having an organic dye of D149 and a metal-containing material containing LiTFSI as an alkaline material and CuI as a transition metal material. In addition, Experimental Example 26 was a dye-sensitized solar cell obtained through the same process as Experimental Example 25 except that LiI was used as the metal-containing material. Experimental Example 26 is provided with a composite having an organic dye of D149 and a metal-containing material containing LiI as an alkaline material and CuI as a transition metal material. Further, a dye-sensitized solar cell obtained through the same steps as in Experimental Example 25 was used as Experimental Example 27 except that LiSCN was used as the metal-containing material. Experimental Example 29 is provided with a composite having an organic dye of D149 and a metal-containing material containing LiSCN as an alkaline material and CuI as a transition metal material.
［実験例２８〜３０（色素増感型太陽電池）］
有機色素としてＤ１４９を用い、金属含有材料としてＬｉＴＦＳＩの代わりにＣｏＩ2を用いた以外は実験例２５と同様の工程を経て得られた色素増感型太陽電池を実験例２８とした。実験例２８は、Ｄ１４９の有機色素と、遷移金属材料としてＣｏＩ2及びＣｕＩを含む金属含有材料と、を有する複合体を備えたものである。また、有機色素としてＭＫ２を用いた以外は実験例２５と同様の工程を経て得られた色素増感型太陽電池を実験例２９とした。実験例２９は、ＭＫ２の有機色素と、アルカリ系材料としてＬｉＴＦＳＩ及び遷移金属材料としてＣｕＩを含む金属含有材料と、を有する複合体を備えたものである。また、有機色素としてＭＫ２を用い、金属含有材料としてＬｉＴＦＳＩの代わりにＣｏＩ2を用いた以外は実験例２５と同様の工程を経て得られた色素増感型太陽電池を実験例３０とした。実験例３０は、ＭＫ２の有機色素と、遷移金属材料としてＣｏＩ2及びＣｕＩを含む金属含有材料と、を有する複合体を備えたものである。
[Experimental Examples 28 to 30 (Dye-sensitized solar cell)]
A dye-sensitized solar cell obtained through the same process as Experimental Example 25 was used as Experimental Example 28 except that D149 was used as the organic dye and CoI 2 was used as the metal-containing material instead of LiTFSI. Experimental Example 28 is provided with a composite having an organic dye of D149 and a metal-containing material containing CoI 2 and CuI as transition metal materials. Further, a dye-sensitized solar cell obtained through the same steps as in Experimental Example 25 except that MK2 was used as the organic dye was used as Experimental Example 29. Experimental Example 29 includes a composite having an organic dye of MK2 and a metal-containing material containing LiTFSI as an alkaline material and CuI as a transition metal material. A dye-sensitized solar cell obtained through the same process as Experimental Example 25 was used as Experimental Example 30 except that MK2 was used as the organic dye and CoI 2 was used as the metal-containing material instead of LiTFSI. Experimental Example 30 is provided with a composite having an organic dye of MK2 and a metal-containing material containing CoI 2 and CuI as transition metal materials.
［ＩＰＣＥ測定］
ＩＰＣＥ測定は、分光計器製、色素増感・有機薄膜太陽電池評価用分光感度測定装置ＣＥＰ−２０００を用い、モノクロメーターにより単色化した光を、作製した色素増感型太陽電池の光電極に照射し、入射光子数に対して得られた電子数を測定することにより行った。
[IPCE measurement]
For the IPCE measurement, a monochromator is used to irradiate the photoelectrode of the prepared dye-sensitized solar cell using a spectral sensitivity measuring device CEP-2000 for dye-sensitized / organic thin-film solar cell evaluation manufactured by Spectrometer Co., Ltd. Then, the number of electrons obtained with respect to the number of incident photons was measured.
（色素増感型太陽電池の実験結果）
実験例２５〜２７のセルの波長に対するＩＰＣＥ測定結果を図１３に示し、実験例２８〜３０のセルの波長に対するＩＰＣＥ測定結果を図１４〜１６に示す。図１４〜１６では、ＩＰＣＥの最大値を「１」に規格化した相対ＩＰＣＥについても示した。図１３、１５に示すように、実験例２５〜２７，２９の複合体を用いたセルでは、アルカリ金属（Ｌｉ）を加えないものに比して、アルカリ金属を加えたものは、ＬｉＴＦＳＩ，ＬｉＩ及びＬｉＳＣＮのいずれもＩＰＣＥが長波長側にシフトした。即ち、色素増感型太陽電池としては有利な方向にシフトした。これらの結果は、複合体での結果を支持するものである。また、図１４、１６に示すように、遷移金属材料としてＣｏＩ2及びＣｕＩを含む、実験例２８，３０の複合体を用いたセルにおいても、ＩＰＣＥが、色素増感型太陽電池としては有利な方向である長波長側にシフトした。
(Experimental result of dye-sensitized solar cell)
The IPCE measurement result with respect to the wavelength of the cell of Experimental Example 25-27 is shown in FIG. 13, and the IPCE measurement result with respect to the wavelength of the cell of Experimental Example 28-30 is shown in FIGS. 14 to 16 also show the relative IPCE in which the maximum IPCE value is normalized to “1”. As shown in FIGS. 13 and 15, in the cells using the composites of Experimental Examples 25 to 27 and 29, the cells added with the alkali metal compared to the cells not added with the alkali metal (Li) were LiTFSI, LiI. And LiSCN both IPCE shifted to the longer wavelength side. That is, it shifted to an advantageous direction as a dye-sensitized solar cell. These results support the results with the complex. In addition, as shown in FIGS. 14 and 16, IPCE is advantageous as a dye-sensitized solar cell even in a cell using the composites of Experimental Examples 28 and 30 containing CoI 2 and CuI as transition metal materials. The direction shifted to the long wavelength side.
以上の測定結果より、電子受容部位を有する有機色素分子と、第１族元素及び第２族元素のうち１以上を含むアルカリ系材料とを備えた複合体は、光吸収特性が向上し好ましいことがわかった。同様に、電子受容部位を有する有機色素分子と、１以上の遷移金属を含む遷移金属材料とを備えた複合体は、光吸収特性が向上し好ましいことがわかった。また、有機色素分子と、アルカリ系材料と、１以上の遷移金属材料とを備えた複合体は、更に光吸収特性が向上し好ましいことがわかった。特に、有機色素分子と、アルカリ系材料と、Ｃｕを含むＣｕ系材料と、Ｃｕ以外の遷移金属を含む遷移金属材料とを備えた複合体は、最も光吸収特性が向上し好ましいことがわかった。 From the above measurement results, a composite comprising an organic dye molecule having an electron-accepting site and an alkaline material containing one or more of Group 1 elements and Group 2 elements is preferably improved in light absorption characteristics. I understood. Similarly, it has been found that a complex including an organic dye molecule having an electron accepting site and a transition metal material containing one or more transition metals has improved light absorption characteristics. Moreover, it turned out that the composite provided with the organic pigment | dye molecule | numerator, an alkaline material, and one or more transition metal materials improves a light absorption characteristic further, and is preferable. In particular, it has been found that a composite comprising an organic dye molecule, an alkaline material, a Cu-based material containing Cu, and a transition metal material containing a transition metal other than Cu has the most improved light absorption characteristics. .
本発明は、色素増感型太陽電池及び色素増感型太陽電池モジュールに好適に利用可能である。 The present invention can be suitably used for a dye-sensitized solar cell and a dye-sensitized solar cell module.
１０ 色素増感型太陽電池モジュール、１１ 透明基板、１２ 透明導電膜、１３ 受光面、１４ 透明導電性基板、１５ 受光面、１６，１７ 集電電極、１８ 溝、２０ 光電極、２１ 接続部、２２ 下地層、２３ 受光面、２４ 多孔質半導体層、２５ 裏面、２６ 正孔輸送層、２７ 裏面、２８ 複合体、２９ セパレータ、３０ 対極、３２ シール材、３４ 保護部材、４０ 色素増感型太陽電池。 10 Dye-sensitized solar cell module, 11 Transparent substrate, 12 Transparent conductive film, 13 Light receiving surface, 14 Transparent conductive substrate, 15 Light receiving surface, 16, 17 Current collecting electrode, 18 Groove, 20 Photo electrode, 21 Connection portion, 22 Underlayer, 23 Light-receiving surface, 24 Porous semiconductor layer, 25 Back surface, 26 Hole transport layer, 27 Back surface, 28 Composite, 29 Separator, 30 Counter electrode, 32 Sealing material, 34 Protection member, 40 Dye-sensitized solar battery.
Claims (14)
第１族元素及び第２族元素のうち１以上を含みアニオンを（ＣＦ3ＳＯ2）2Ｎ-、ＳＣＮ-及びＩ-のうち１以上とするアルカリ系材料（ヒドロキサム酸塩を除く）と、
１以上の遷移金属を含みアニオンを（ＣＦ3ＳＯ2）2Ｎ-、ＳＣＮ-及びＩ-のうち１以上とする遷移金属材料と、
を含有した、複合体。
An alkaline material (excluding hydroxamic acid salt) containing at least one of group 1 elements and group 2 elements and an anion of at least one of (CF 3 SO 2 ) 2 N − , SCN − and I − ;
A transition metal material including one or more transition metals and an anion of one or more of (CF 3 SO 2 ) 2 N − , SCN − and I − ;
A composite containing
第１族元素及び第２族元素のうち１以上を含みアニオンを（ＣＦ An anion containing one or more of group 1 elements and group 2 elements (CF 3Three ＳＯSO 22 ）) 22 ＮN -- 、ＳＣＮ, SCN -- 及びＩAnd I -- のうち１以上とするアルカリ系材料（ヒドロキサム酸塩を除く）と、One or more alkaline materials (excluding hydroxamates),
１以上の遷移金属を含みアニオンを（ＣＦ An anion containing one or more transition metals (CF 3Three ＳＯSO 22 ）) 22 ＮN -- 、ＳＣＮ, SCN -- 及びＩAnd I -- のうち１以上とする遷移金属材料と、One or more transition metal materials,
を含有した、複合体。 A composite containing
第１族元素及び第２族元素のうち１以上を含みアニオンを（ＣＦ An anion containing one or more of group 1 elements and group 2 elements (CF 3Three ＳＯSO 22 ）) 22 ＮN -- 、ＳＣＮ, SCN -- 及びＩAnd I -- のうち１以上とするアルカリ系材料（ヒドロキサム酸塩を除く）と、One or more alkaline materials (excluding hydroxamates),
１以上の遷移金属を含みアニオンを（ＣＦ An anion containing one or more transition metals (CF 3Three ＳＯSO 22 ）) 22 ＮN -- 、ＳＣＮ, SCN -- 及びＩAnd I -- のうち１以上とする遷移金属材料と、One or more transition metal materials,
を含有した、複合体。 A composite containing
透明導電膜と透明基板とを有する導電性基板と、
前記導電性基板に隣接して設けられているｎ型半導体層と、
前記ｎ型半導体層に形成されている請求項１〜９のいずれか１項に記載の複合体と、
を備えた光電極。 A photoelectrode used in a dye-sensitized solar cell,
A conductive substrate having a transparent conductive film and a transparent substrate;
An n-type semiconductor layer provided adjacent to the conductive substrate;
The composite according to any one of claims 1 to 9 , which is formed in the n-type semiconductor layer,
A photoelectrode.
前記光電極に対向して設けられた対極と、
を備えた色素増感型太陽電池。 The photoelectrode according to claim 10 or 11 ,
A counter electrode provided facing the photoelectrode;
A dye-sensitized solar cell comprising:
前記光電極と前記対極との間に介在し、Ｃｕを含む半導体及びＣｕを含む導電体のうち少なくとも一方を含むＣｕ系材料を含む正孔輸送層、を備えた色素増感型太陽電池。 The dye-sensitized solar cell according to claim 12 ,
A dye-sensitized solar cell including a hole transport layer including a Cu-based material including at least one of a semiconductor including Cu and a conductor including Cu interposed between the photoelectrode and the counter electrode.
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| WO2012001628A1 (en) * | 2010-06-29 | 2012-01-05 | Basf Se | Photoelectric conversion device comprising hydroxamic acid derivative or salt thereof as additive and process for producing same |
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| JP5894372B2 (en) * | 2010-11-01 | 2016-03-30 | パナソニック株式会社 | OPTOELECTRIC ELEMENT AND METHOD FOR PRODUCING OPTOELECTRIC ELEMENT |
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