JP2007013115A - Photoelectric conversion element and its manufacturing method, and solar cell using the same - Google Patents
Photoelectric conversion element and its manufacturing method, and solar cell using the same Download PDFInfo
- Publication number
- JP2007013115A JP2007013115A JP2006146555A JP2006146555A JP2007013115A JP 2007013115 A JP2007013115 A JP 2007013115A JP 2006146555 A JP2006146555 A JP 2006146555A JP 2006146555 A JP2006146555 A JP 2006146555A JP 2007013115 A JP2007013115 A JP 2007013115A
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- general formula
- photoelectric conversion
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 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
- 150000002476 indolines Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 125000000346 malonyl group Chemical group C(CC(=O)*)(=O)* 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MGJXBDMLVWIYOQ-UHFFFAOYSA-N methylazanide Chemical compound [NH-]C MGJXBDMLVWIYOQ-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- DXYYLUGHPCHMRQ-UHFFFAOYSA-N n,n-diphenyl-4-(2-phenylethenyl)aniline Chemical compound C=1C=CC=CC=1C=CC(C=C1)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 DXYYLUGHPCHMRQ-UHFFFAOYSA-N 0.000 description 1
- WHIQECICUOFHPL-UHFFFAOYSA-N n-[4-(dibenzo[1,2-a:1',2'-e][7]annulen-11-ylidenemethyl)phenyl]-4-methyl-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(C=C2C3=CC=CC=C3C=CC3=CC=CC=C32)=CC=1)C1=CC=C(C)C=C1 WHIQECICUOFHPL-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class 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
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
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- 239000004431 polycarbonate resin Substances 0.000 description 1
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- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 description 1
- BJDYCCHRZIFCGN-UHFFFAOYSA-N pyridin-1-ium;iodide Chemical compound I.C1=CC=NC=C1 BJDYCCHRZIFCGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000005839 radical cations Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GGYFMLJDMAMTAB-UHFFFAOYSA-N selanylidenelead Chemical compound [Pb]=[Se] GGYFMLJDMAMTAB-UHFFFAOYSA-N 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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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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- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
Description
本発明は、光電変換素子とその製造方法及び光電変換素子を用いた太陽電池に関するものである。 The present invention relates to a photoelectric conversion element, a method for producing the same, and a solar cell using the photoelectric conversion element.
太陽電池にはいくつかの種類があるが、実用化されているものはシリコン半導体の接合を利用したダイオード型のものがほとんどである。これらの太陽電池は現状では製造コストが高く、このことが普及を妨げる要因となっている。 There are several types of solar cells, but most of them are diode type using silicon semiconductor junctions. These solar cells are currently expensive to manufacture, which is a factor that hinders their spread.
最近、低コスト化の可能性としてスイスローザンヌ工科大学のGraetzelらが高効率の太陽電池を発表したことにより、実用化への期待が高まっている(例えば、特許文献1、非特許文献1、2参照)。
この高効率太陽電池の構造は、透明導電性ガラス基板上に多孔質な金属酸化物半導体を設け、その表面に吸着した色素と、酸化還元対を有する電解質と、対向電極とからなる。Graetzelらは酸化チタン等の金属酸化物半導体電極を多孔質化して表面積を大きくしたこと、並びに色素としてルテニウム錯体を単分子吸着させたことにより光電変換効率を著しく向上させた。
Recently, Graetzel et al. Of Swiss Lausanne University of Technology announced the possibility of cost reduction, and the expectation for practical use has increased (for example, Patent Document 1, Non-Patent Documents 1 and 2). reference).
The structure of this high-efficiency solar cell includes a porous metal oxide semiconductor provided on a transparent conductive glass substrate, a dye adsorbed on the surface thereof, an electrolyte having a redox pair, and a counter electrode. Graetzel et al. Significantly improved the photoelectric conversion efficiency by making the metal oxide semiconductor electrode such as titanium oxide porous to increase the surface area and adsorbing a ruthenium complex as a dye with a single molecule.
しかしながら、これらの太陽電池はアセトニトリル等の蒸気圧の高い電解液を用いているため、電解液の揮発や漏れに問題があった。この欠点を補うものとして、次に示されるような完全固体型色素増感型太陽電池の発表が行われている。
(1)無機半導体を用いたもの(例えば、非特許文献3、4参照)
(2)低分子有機ホール輸送材料を用いたもの(例えば、特許文献2、非特許文献5、6参照)
(3)導電性高分子を用いたもの(例えば、特許文献3、非特許文献7参照)
However, since these solar cells use an electrolytic solution having a high vapor pressure such as acetonitrile, there is a problem in volatilization and leakage of the electrolytic solution. In order to compensate for this drawback, the following completely solid dye-sensitized solar cell has been announced.
(1) Using an inorganic semiconductor (for example, see Non-Patent Documents 3 and 4)
(2) A material using a low-molecular organic hole transport material (see, for example, Patent Document 2, Non-Patent Documents 5 and 6)
(3) Using conductive polymer (for example, see Patent Document 3 and Non-Patent Document 7)
非特許文献3の太陽電池では、p型半導体層の構成材料としてヨウ化銅が用いられている。しかしながら、ヨウ化銅の結晶粒の増大等を理由とする劣化により、発生電流が低下する問題があった。そこで、非特許文献4においては、イミダゾリニウム塩を加えることによってヨウ化銅の結晶化を抑制しているが、長期安定性に欠け、更なる耐久性向上が求められている。
In the solar cell of Non-Patent Document 3, copper iodide is used as a constituent material of the p-type semiconductor layer. However, there is a problem that the generated current is reduced due to deterioration due to an increase in crystal grains of copper iodide. Therefore, in
非特許文献5記載の有機ホール輸送材料を用いたタイプの固体型太陽電池はHagenらによって報告され、Graetzelらによって改良されている(非特許文献6)。
しかしながら、液体電解質に比べて変換効率は非常に低く、また、特許文献2記載のトリフェニルアミン化合物を用いた固体型太陽電池は、トリフェニルアミン化合物を真空蒸着して電荷輸送層を形成している。そのため、多孔質半導体の内部空孔へトリフェニルアミン化合物が到達出来ず、やはり低い変換効率しか得られていない。
A solid type solar cell using the organic hole transport material described in Non-Patent Document 5 was reported by Hagen et al. And improved by Graetzel et al. (Non-Patent Document 6).
However, the conversion efficiency is very low as compared with the liquid electrolyte, and the solid-type solar cell using the triphenylamine compound described in Patent Document 2 forms a charge transport layer by vacuum-depositing the triphenylamine compound. Yes. Therefore, the triphenylamine compound cannot reach the internal pores of the porous semiconductor, and only low conversion efficiency is obtained.
導電性高分子を用いたタイプの固体型太陽電池として、大阪大学柳田らがポリピロールを用いたもの(非特許文献7)を報告している。
しかしながら、これらにおいても変換効率は低く、特許文献3記載のポリチオフェン誘導体を用いた固体型太陽電池は、色素を吸着した多孔質酸化チタン電極上で、電解重合法を用いて電荷移動層を設けているが、色素が酸化チタンから脱着したり、あるいは色素の分解が生じたりする問題がある。また、ポリチオフェン誘導体は耐久性に非常に問題がある。
以上、これまでに検討されてきた完全固体型の光電変換素子は、何れも満足いく特性のものが得られていないのが現状である。
なお、本出願人は先に特定の構造を有する高分子材料を含有する光起電力素子及びこれを備えた光センサーを提案した(例えば、特許文献4参照。)が、本発明の光電変換素子とは動作原理及び構成材料の異なるものである。
As a solid-state solar cell of a type using a conductive polymer, Osaka University Yanagida et al. Have reported a polypyrrole (Non-patent Document 7).
However, even in these cases, the conversion efficiency is low, and the solid-type solar cell using the polythiophene derivative described in Patent Document 3 is provided with a charge transfer layer using an electrolytic polymerization method on a porous titanium oxide electrode adsorbed with a dye. However, there is a problem that the pigment is desorbed from titanium oxide or the pigment is decomposed. Further, the polythiophene derivative has a very problem in durability.
As described above, none of the perfect solid-state photoelectric conversion elements that have been studied so far have been obtained with satisfactory characteristics.
The present applicant has previously proposed a photovoltaic element containing a polymer material having a specific structure and an optical sensor provided with the photovoltaic element (see, for example, Patent Document 4), but the photoelectric conversion element of the present invention. Is different in operating principle and constituent materials.
本発明は、上記問題点を解決し、従来と比較して良好な光電変換特性を示すと共に長期安定性に優れ、更に生産性にも優れた完全固体型の光電変換素子とその製造方法を提供することを目的とする。また、上記光電変換素子を用いた太陽電池を提供することを目的とする。 The present invention solves the above-mentioned problems, and provides a completely solid-state photoelectric conversion element that exhibits excellent photoelectric conversion characteristics as compared with the prior art, has excellent long-term stability, and also has excellent productivity, and a method for manufacturing the same. The purpose is to do. Moreover, it aims at providing the solar cell using the said photoelectric conversion element.
上記課題を解決するために鋭意検討した結果、以下に記載する〔1〕〜〔22〕の発明により、上記課題が解決されて高性能な光電変換素子を提供できることを見出し本発明に到達した。以下、本発明について具体的に説明する。 As a result of intensive studies to solve the above problems, the inventors have found that the above problems can be solved by the inventions [1] to [22] described below, and that a high-performance photoelectric conversion element can be provided, thereby reaching the present invention. Hereinafter, the present invention will be specifically described.
〔1〕:少なくとも一方が透明な電子集電電極とホール集電電極間に、電子輸送層とホール輸送層が設けられた光電変換素子において、
前記ホール輸送層が、下記一般式(1)で表される高分子材料と、少なくとも1種以上の下記一般式(1B)、一般式(2)、一般式(3)、一般式(4)、一般式(5)で表される化合物を含有することを特徴とする光電変換素子である。
[1]: In a photoelectric conversion element in which an electron transport layer and a hole transport layer are provided between an electron collector electrode and a hole current collector electrode, at least one of which is transparent,
The hole transport layer includes a polymer material represented by the following general formula (1), and at least one or more of the following general formula (1B), general formula (2), general formula (3), and general formula (4). The photoelectric conversion element characterized by containing the compound represented by General formula (5).
[(1)式中、Ar1は置換もしくは無置換の芳香族炭化水素基を表し、Ar2、Ar3はそれぞれ独立に置換もしくは無置換の2価の単環式、非縮合多環式または縮合多環式芳香族炭化水素基を表す。Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。] [In the formula (1), Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, and Ar 2 and Ar 3 are each independently substituted or unsubstituted divalent monocyclic, non-condensed polycyclic or Represents a condensed polycyclic aromatic hydrocarbon group. Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. ]
[式中、nは0または1の整数を表し、Ar’は置換もしくは無置換のアリール基を表し、R5は水素原子、置換アルキル基を含むアルキル基あるいは置換もしくは無置換のアリール基を表し、R6は水素原子、置換アルキル基を含むアルキル基あるいは置換もしくは無置換のアリール基を表し、Ar’とR5は互いに結合して環を形成してもよい。Aは9−アントリル基または置換もしくは無置換のカルバゾリル基あるいは下記一般式(1B−1)または(1B−2): [Wherein n represents an integer of 0 or 1, Ar ′ represents a substituted or unsubstituted aryl group, R 5 represents a hydrogen atom, an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group. , R 6 represents a hydrogen atom, an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and Ar ′ and R 5 may be bonded to each other to form a ring. A is a 9-anthryl group, a substituted or unsubstituted carbazolyl group, or the following general formula (1B-1) or (1B-2):
〔式中、R50及びR51は水素原子、アルキル基、アルコキシル基、ハロゲン原子または下記一般式(1B−3): [Wherein, R 50 and R 51 are a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom or the following general formula (1B-3):
(式中、R52及びR53は置換アルキル基を含むアルキル基、置換または無置換のアリール基を表し、R52及びR53は同一でも別異でもよく、R52及びR53は互いに結合して環を形成してもよい。)で表される基を表す。〕で表される基を表す。] (Wherein R 52 and R 53 represent an alkyl group containing a substituted alkyl group, a substituted or unsubstituted aryl group, R 52 and R 53 may be the same or different, and R 52 and R 53 are bonded to each other. And may form a ring). Represents a group represented by the formula: ]
[(2)式中、R1、R2は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R3は置換もしくは無置換のアルキレン基、置換もしくは無置換の2価の芳香族炭化水素基を表す。R1とR2、R1とR3、あるいはR2とR3は共同で環を形成してもよい。R4は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表す。R5、R6は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R5とR6は共同で環を形成してもよい。] [In the formula (2), R 1 and R 2 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. , R 3 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted divalent aromatic hydrocarbon group. R 1 and R 2 , R 1 and R 3 , or R 2 and R 3 may jointly form a ring. R 4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group. R 5 and R 6 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group, and R 5 and R 6 represent You may form a ring jointly. ]
[(3)式中、R7は置換もしくは無置換のアルキレン基、置換もしくは無置換の2価の芳香族炭化水素基を表す。R8、R9、R10、R11は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R8とR9、R10とR11は共同で環を形成してもよい。] [In the formula (3), R 7 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted divalent aromatic hydrocarbon group. R 8 , R 9 , R 10 and R 11 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, R 8 and R 9 , and R 10 and R 11 may form a ring together. ]
[(4)式中、R12、R13、R14は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R12とR13、R13とR14、R12とR14は共同で環を形成してもよい。R15は窒素原子、ホウ素原子、アルキリジン基、置換もしくは無置換の3価の芳香族炭化水素基を表す。] [In the formula (4), R 12 , R 13 and R 14 are substituted or unsubstituted alkyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heterocyclic rings. Represents a group, and R 12 and R 13 , R 13 and R 14 , and R 12 and R 14 may form a ring together. R 15 represents a nitrogen atom, a boron atom, an alkylidine group, or a substituted or unsubstituted trivalent aromatic hydrocarbon group. ]
[(5)式中、R16は置換もしくは無置換の4価の芳香族炭化水素基を表す。R17〜R24は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R17とR18、R19とR20、R21とR22、R23とR24は共同で環を形成してもよい。] [In the formula (5), R 16 represents a substituted or unsubstituted tetravalent aromatic hydrocarbon group. R 17 to R 24 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, R 17 and R 18 , R 19 and R 20 , R 21 and R 22 , and R 23 and R 24 may form a ring together. ]
〔2〕:前記ホール輸送層が、上記一般式(1)で表される高分子材料と、少なくとも1種以上の上記一般式(1B)、一般式(2)、一般式(3)、一般式(4)、一般式(5)で表される化合物を含有し、かつ、一般式(1)で表される高分子材料を前記ホール集電電極として兼用するように構成したことを特徴とする〔1〕に記載の光電変換素子である。 [2]: The hole transport layer is composed of the polymer material represented by the general formula (1) and at least one of the general formula (1B), the general formula (2), the general formula (3), and the general formula. It comprises a compound represented by the formula (4) and the general formula (5), and the polymer material represented by the general formula (1) is also used as the hole collecting electrode. The photoelectric conversion element according to [1].
〔3〕:前記電子輸送層が酸化物半導体からなることを特徴とする〔1〕または〔2〕に記載の光電変換素子である。 [3] The photoelectric conversion element according to [1] or [2], wherein the electron transport layer is made of an oxide semiconductor.
〔4〕:前記電子輸送層が酸化物半導体からなり、ホール輸送層が上記一般式(1)で表される高分子材料、少なくとも1種以上の上記一般式(1B)、一般式(2)、一般式(3)、一般式(4)、一般式(5)で表される化合物、及び金属化合物を含有することを特徴とする〔3〕に記載の光電変換素子である。 [4]: The electron transport layer is made of an oxide semiconductor, and the hole transport layer is a polymer material represented by the general formula (1), at least one of the general formula (1B), and the general formula (2). The photoelectric conversion device according to [3], comprising a compound represented by general formula (3), general formula (4), and general formula (5), and a metal compound.
〔5〕:前記金属化合物が、ハロゲン化金属、チオシアン化金属、アミド化金属の何れか1種以上であることを特徴とする〔4〕に記載の光電変換素子である。 [5] The photoelectric conversion element according to [4], wherein the metal compound is one or more of a metal halide, a metal thiocyanide, and an amidated metal.
〔6〕:前記電子輸送層が酸化物半導体からなり、ホール輸送層が上記一般式(1)で表される高分子材料、少なくとも1種以上の上記一般式(1B)、一般式(2)、一般式(3)、一般式(4)、一般式(5)で表される化合物、及びイオン性液体の混合物を含有することを特徴とする〔3〕に記載の光電変換素子である。 [6]: The electron transport layer is made of an oxide semiconductor, and the hole transport layer is a polymer material represented by the general formula (1), at least one of the general formula (1B), and the general formula (2). The photoelectric conversion device according to [3], comprising a mixture of a compound represented by general formula (3), general formula (4), and general formula (5), and an ionic liquid.
〔7〕:前記イオン性液体がイミダゾリニウム化合物であることを特徴とする〔6〕に記載の光電変換素子である。 [7] The photoelectric conversion element according to [6], wherein the ionic liquid is an imidazolinium compound.
〔8〕:前記電子輸送層が酸化物半導体からなり、該電子輸送層上に光増感化合物が吸着されていることを特徴とする〔3〕〜〔7〕の何れかに記載の光電変換素子である。 [8] The photoelectric conversion according to any one of [3] to [7], wherein the electron transport layer is made of an oxide semiconductor, and a photosensitizing compound is adsorbed on the electron transport layer. It is an element.
〔9〕:前記光増感化合物が、下記一般式(6)〜(10)の少なくとも1種以上から選ばれる化合物であることを特徴とする〔8〕に記載の光電変換素子である。 [9] The photoelectric conversion device according to [8], wherein the photosensitizing compound is a compound selected from at least one of the following general formulas (6) to (10).
[(6)、(7)式中、R25〜R31は、水素原子、カルボキシル基、アルコキシカルボキシル基、アリールオキシカルボキシル基、カルボキシル基の4級アンモニウム塩、カルボキシル基の金属塩、スルホン酸、スルホン酸の4級アンモニウム塩、スルホン酸の金属塩、ホスホン酸、ホスホン酸の4級アンモニウム塩、ホスホン酸の金属塩、酸性基を有するアルキル基、酸性基を有するアルケニル基、置換基を有していてもよいアルキル基を表し、同一であっても異なっていてもよい。X1はハロゲン原子、シアノ基、チオシアン酸基、イソシアン酸基を表す。
(8)式中、R32〜R35は、水素原子、アルキル基を表す。Ar7は、2価のビニレン基、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の複素環基を表す。X2は、シアノ基、ニトロ基、ハロゲン原子、置換基を有していてもよいアルキルスルホニル基、置換基を有していてもよいアリールスルホニル基を表す。R36は、水素原子、4級アンモニウム塩を表す。
(9)式中、R37、R38は置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族炭化水素ル基、置換基を有していてもよい複素環基を表す。R38とベンゼン環は共同で環を形成してもよい。R39は、水素原子、4級アンモニウム塩を表す。X3は、シアノ基、ニトロ基、ハロゲン原子、置換基を有していてもよいアルキルスルホニル基、置換基を有していてもよいアリールスルホニル基を表す。sは0〜2の整数を表す。
(10)式中、R40、R41は置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい複素環基を表す。R41とベンゼン環は共同で環を形成してもよい。X4は酸素原子、硫黄原子、セレン原子を表す。X5は酸素原子、硫黄原子、置換基を有していてもよいローダニン環を表す。]
[In the formulas (6) and (7), R 25 to R 31 are hydrogen atom, carboxyl group, alkoxycarboxyl group, aryloxycarboxyl group, quaternary ammonium salt of carboxyl group, metal salt of carboxyl group, sulfonic acid, Quaternary ammonium salt of sulfonic acid, metal salt of sulfonic acid, phosphonic acid, quaternary ammonium salt of phosphonic acid, metal salt of phosphonic acid, alkyl group having acidic group, alkenyl group having acidic group, substituent Represents an optionally substituted alkyl group, which may be the same or different. X 1 represents a halogen atom, a cyano group, a thiocyanate group, or an isocyanate group.
In (8), R 32 to R 35 represents a hydrogen atom, an alkyl group. Ar 7 represents a divalent vinylene group, a divalent aromatic hydrocarbon group which may have a substituent, or a divalent heterocyclic group which may have a substituent. X 2 represents a cyano group, a nitro group, a halogen atom, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent. R 36 represents a hydrogen atom or a quaternary ammonium salt.
(9) In the formula, R 37 and R 38 are an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a heterocycle which may have a substituent. Represents a cyclic group. R 38 and the benzene ring may form a ring together. R 39 represents a hydrogen atom or a quaternary ammonium salt. X 3 represents a cyano group, a nitro group, a halogen atom, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent. s represents the integer of 0-2.
(10) In the formula, R 40 and R 41 are an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a heterocyclic ring which may have a substituent. Represents a group. R 41 and the benzene ring may form a ring together. X 4 represents an oxygen atom, a sulfur atom, or a selenium atom. X 5 represents an oxygen atom, a sulfur atom, or a rhodanine ring which may have a substituent. ]
〔10〕:前記電子輸送層をなす酸化物半導体のラフネスファクターが20以上であることを特徴とする〔3〕〜〔9〕の何れかに記載の光電変換素子である。 [10] The photoelectric conversion element according to any one of [3] to [9], wherein the oxide semiconductor constituting the electron transport layer has a roughness factor of 20 or more.
〔11〕:前記電子輸送層の膜厚が100nm以上であることを特徴とする〔3〕〜〔10〕の何れかに記載の光電変換素子である。 [11] The photoelectric conversion element according to any one of [3] to [10], wherein the electron transport layer has a thickness of 100 nm or more.
〔12〕:前記電子輸送層をなす酸化物半導体が、酸化チタン、酸化亜鉛、酸化スズ、酸化ニオブ、酸化ニッケルの少なくとも1種以上から選ばれることを特徴とする〔3〕〜〔11〕の何れかに記載の光電変換素子である。 [12]: The oxide semiconductor forming the electron transport layer is selected from at least one of titanium oxide, zinc oxide, tin oxide, niobium oxide, and nickel oxide. [3] to [11] It is a photoelectric conversion element in any one.
〔13〕:前記電子輸送層が、非多孔質構造からなる層と多孔質構造からなる層の多層構造であることを特徴とする〔1〕〜〔12〕の何れかに記載の光電変換素子である。 [13]: The photoelectric conversion element according to any one of [1] to [12], wherein the electron transport layer has a multilayer structure of a layer having a non-porous structure and a layer having a porous structure. It is.
〔14〕:前記電子輸送層が酸化物半導体からなり、該電子輸送層上に光増感化合物が吸着されており、かつ、ホール輸送層が上記一般式(1)で表される高分子材料、及び少なくとも1種以上の上記一般式(1B)、一般式(2)、一般式(3)、一般式(4)、一般式(5)で表される化合物を含有する溶液を湿式製膜法により塗布形成されたものであることを特徴とする〔1〕〜〔13〕の何れかに記載の光電変換素子である。 [14]: A polymer material in which the electron transport layer is made of an oxide semiconductor, a photosensitizing compound is adsorbed on the electron transport layer, and the hole transport layer is represented by the general formula (1) And a solution containing at least one compound represented by the general formula (1B), the general formula (2), the general formula (3), the general formula (4), and the general formula (5). The photoelectric conversion element according to any one of [1] to [13], wherein the photoelectric conversion element is applied and formed by a method.
〔15〕:前記ホール輸送層が、400mmHg以下の真空中で湿式製膜法により塗布形成されたものであることを特徴とする〔14〕に記載の光電変換素子である。 [15] The photoelectric conversion element according to [14], wherein the hole transport layer is formed by a wet film forming method in a vacuum of 400 mmHg or less.
〔16〕:上記一般式(1)で表される高分子材料が、下記一般式(11)で表される高分子材料であることを特徴とする〔1〕〜〔15〕の何れかに記載の光電変換素子である。 [16]: The polymer material represented by the general formula (1) is a polymer material represented by the following general formula (11), and any one of [1] to [15] It is a photoelectric conversion element of description.
[(11)式中、Ar1は置換もしくは無置換の芳香族炭化水素基を表し、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R44、R45はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、x、yはそれぞれ独立に0〜4の整数を表し、R44、R45が各々複数存在する場合には、同一でも別異でもよい。] [In the formula (11), Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these have a substituent. May be. R 44 and R 45 each independently represents a halogen atom, a substituted or unsubstituted alkyl group, or an alkoxy group or an alkylthio group, x and y each independently represents an integer of 0 to 4; When a plurality of 44 and R 45 are present, they may be the same or different. ]
〔17〕:上記一般式(1)で表される高分子材料が、下記一般式(12)で表される高分子材料であることを特徴とする〔1〕〜〔15〕の何れかに記載の光電変換素子である。 [17]: Any one of [1] to [15], wherein the polymer material represented by the general formula (1) is a polymer material represented by the following general formula (12) It is a photoelectric conversion element of description.
[(12)式中、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R44、R45はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、R46はハロゲン原子、置換もしくは無置換の、アルキル基、アルコキシ基、アルキルチオ基、芳香族炭化水素基から選択される基を表す。zは0〜5の整数を表し、x、yはそれぞれ独立に0〜4の整数を表し、R44、R45、R46が各々複数存在する場合には、同一でも別異でもよい。] [In the formula (12), Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. R 44 and R 45 each independently represents a halogen atom, a substituted or unsubstituted alkyl group or a group selected from an alkoxy group or an alkylthio group, and R 46 represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group. Represents a group selected from a group, an alkylthio group, and an aromatic hydrocarbon group. z represents an integer of 0 to 5, x and y each independently represents an integer of 0 to 4, and when a plurality of R 44 , R 45 and R 46 are present, they may be the same or different. ]
〔18〕:上記一般式(1)で表される高分子材料が、下記一般式(13)で表される高分子材料であることを特徴とする〔1〕〜〔15〕の何れかに記載の光電変換素子である。 [18] The polymer material represented by the general formula (1) is a polymer material represented by the following general formula (13), wherein any one of [1] to [15] It is a photoelectric conversion element of description.
[(13)式中、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R44、R45、R46、R47、R48、R49はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表す。vは0〜3の整数を表し、w、x、yはそれぞれ独立に0〜4の整数を表し、R44、R45、R46、R47が各々複数存在する場合には、同一でも別異でもよい。] [In the formula (13), Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. R 44 , R 45 , R 46 , R 47 , R 48 and R 49 each independently represent a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group. v represents an integer of 0 to 3, w, x and y each independently represents an integer of 0 to 4, and when there are a plurality of R 44 , R 45 , R 46 and R 47 , they may be the same or different. It may be different. ]
〔19〕:上記一般式(1)で表される高分子材料が、下記一般式(14)で表される高分子材料であることを特徴とする〔1〕〜〔15〕の何れかに記載の光電変換素子である。 [19] Any one of [1] to [15], wherein the polymer material represented by the general formula (1) is a polymer material represented by the following general formula (14): It is a photoelectric conversion element of description.
[(14)式中、Ar1は置換もしくは無置換の芳香族炭化水素基を表し、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R50、R51、R52、R53はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、r、s、t、uはそれぞれ独立に0 〜4の整数を表し、R50、R51、R52、R53が各々複数存在する場合には、同一でも別異でもよい。] [In the formula (14), Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these have a substituent. May be. R 50 , R 51 , R 52 and R 53 each independently represent a halogen atom, a substituted or unsubstituted alkyl group or a group selected from an alkoxy group or an alkylthio group, and r, s, t and u are each independently selected. Represents an integer of 0 to 4, and when there are a plurality of R 50 , R 51 , R 52 and R 53 , they may be the same or different. ]
〔20〕:上記一般式(1)で表される高分子材料が、下記一般式(15)で表される高分子材料であることを特徴とする〔1〕〜〔15〕の何れかに記載の光電変換素子である。 [20]: Any one of [1] to [15], wherein the polymer material represented by the general formula (1) is a polymer material represented by the following general formula (15): It is a photoelectric conversion element of description.
[(15)式中、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R50、R51、R52、R53、R54はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、qは0〜5の整数を表し、r、s、t、uはそれぞれ独立に0〜4の整数を表し、R50、R51、R52、R53、R54が各々複数存在する場合には、同一でも別異でもよい。] [In the formula (15), Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. R 50 , R 51 , R 52 , R 53 and R 54 each independently represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group, and q is an integer of 0 to 5 R, s, t and u each independently represents an integer of 0 to 4, and when there are a plurality of R 50 , R 51 , R 52 , R 53 and R 54 , they may be the same or different. Good. ]
〔21〕:〔1〕〜〔20〕の何れかに記載の光電変換素子を用いたことを特徴とする太陽電池である。 [21]: A solar cell using the photoelectric conversion element according to any one of [1] to [20].
〔22〕:少なくとも一方が透明な電子集電電極とホール集電電極間に、電子輸送層とホール輸送層を設けてなる光電変換素子の製造方法において、
前記電子集電電極上に電子輸送層を形成し、該電子輸送層に光増感化合物を担持させ、次いで下記一般式(1)で表される高分子材料及び少なくとも1種以上の下記一般式(1B)、一般式(2)、一般式(3)、一般式(4)、一般式(5)で表される化合物を含有する溶液を用いて湿式製膜法によりホール輸送層を塗布積層し、多孔化処理を施した後に該ホール輸送層に接してホール集電電極を形成することを特徴とする光電変換素子の製造方法である。
[22]: In the method for producing a photoelectric conversion element in which an electron transport layer and a hole transport layer are provided between an electron collector electrode and a hole current collector electrode, at least one of which is transparent,
An electron transport layer is formed on the electron current collecting electrode, a photosensitizing compound is supported on the electron transport layer, and then a polymer material represented by the following general formula (1) and at least one of the following general formulas ( 1B), a hole transport layer is applied and laminated by a wet film-forming method using a solution containing a compound represented by general formula (2), general formula (3), general formula (4), or general formula (5). The method for producing a photoelectric conversion element is characterized by forming a hole current collecting electrode in contact with the hole transport layer after performing a porous treatment.
[(1)式中、Ar1は置換もしくは無置換の芳香族炭化水素基を表し、Ar2、Ar3はそれぞれ独立に置換もしくは無置換の2価の単環式、非縮合多環式または縮合多環式芳香族炭化水素基を表す。Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。] [In the formula (1), Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, and Ar 2 and Ar 3 are each independently substituted or unsubstituted divalent monocyclic, non-condensed polycyclic or Represents a condensed polycyclic aromatic hydrocarbon group. Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. ]
[式中、nは0または1の整数を表し、Ar’ は置換もしくは無置換のアリール基を表し、R5は水素原子、置換アルキル基を含むアルキル基あるいは置換もしくは無置換のアリール基を表し、R6は水素原子、置換アルキル基を含むアルキル基あるいは置換もしくは無置換のアリール基を表し、Ar’とR5は互いに結合して環を形成してもよい。Aは9−アントリル基または置換もしくは無置換のカルバゾリル基あるいは下記一般式(1B−1)または(1B−2): [Wherein n represents an integer of 0 or 1, Ar ′ represents a substituted or unsubstituted aryl group, R 5 represents a hydrogen atom, an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group. , R 6 represents a hydrogen atom, an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and Ar ′ and R 5 may be bonded to each other to form a ring. A is a 9-anthryl group, a substituted or unsubstituted carbazolyl group, or the following general formula (1B-1) or (1B-2):
〔式中、R50及びR51は水素原子、アルキル基、アルコキシル基、ハロゲン原子または下記一般式(1B−3): [Wherein, R 50 and R 51 are a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom or the following general formula (1B-3):
(式中、R52及びR53は置換アルキル基を含むアルキル基、置換または無置換のアリール基を表し、R52及びR53は同一でも別異でもよく、R52及びR53は互いに結合して環を形成してもよい。)で表される基を表す。〕で表される基を表す。] (Wherein R 52 and R 53 represent an alkyl group containing a substituted alkyl group, a substituted or unsubstituted aryl group, R 52 and R 53 may be the same or different, and R 52 and R 53 are bonded to each other. And may form a ring). Represents a group represented by the formula: ]
[(2)式中、R1、R2は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R3は置換もしくは無置換のアルキレン基、置換もしくは無置換の2価の芳香族炭化水素基を表す。R1とR2、R1とR3、あるいはR2とR3は共同で環を形成してもよい。R4は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表す。R5、R6は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R5とR6は共同で環を形成してもよい。] [In the formula (2), R 1 and R 2 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. , R 3 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted divalent aromatic hydrocarbon group. R 1 and R 2 , R 1 and R 3 , or R 2 and R 3 may jointly form a ring. R 4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group. R 5 and R 6 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group, and R 5 and R 6 represent You may form a ring jointly. ]
[(3)式中、R7は置換もしくは無置換のアルキレン基、置換もしくは無置換の2価の芳香族炭化水素基を表す。R8、R9、R10、R11は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R8とR9、R10とR11は共同で環を形成してもよい。] [In the formula (3), R 7 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted divalent aromatic hydrocarbon group. R 8 , R 9 , R 10 and R 11 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, R 8 and R 9 , and R 10 and R 11 may form a ring together. ]
[(4)式中、R12、R13、R14は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R12とR13、R13とR14、R12とR14は共同で環を形成してもよい。R15は窒素原子、ホウ素原子、アルキリジン基、置換もしくは無置換の3価の芳香族炭化水素基を表す。] [In the formula (4), R 12 , R 13 and R 14 are substituted or unsubstituted alkyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heterocyclic rings. Represents a group, and R 12 and R 13 , R 13 and R 14 , and R 12 and R 14 may form a ring together. R 15 represents a nitrogen atom, a boron atom, an alkylidine group, or a substituted or unsubstituted trivalent aromatic hydrocarbon group. ]
[(5)式中、R16は置換もしくは無置換の4価の芳香族炭化水素基を表す。R17〜R24は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R17とR18、R19とR20、R21とR22、R23とR24は共同で環を形成してもよい。] [In the formula (5), R 16 represents a substituted or unsubstituted tetravalent aromatic hydrocarbon group. R 17 to R 24 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, R 17 and R 18 , R 19 and R 20 , R 21 and R 22 , and R 23 and R 24 may form a ring together. ]
本発明の〔1〕、〔2〕の構成により、コストパフォーマンスに優れ、良好な変換効率を示す完全固体型の光電変換素子が提供される。
〔3〕〜〔7〕の電子輸送層に酸化物半導体を用いる構成により、電子移動が効率的となり、更に優れた変換効率を示す光電変換素子が提供される。
〔8〕、〔9〕の電子輸送層上に光増感化合物を吸着させる構成により、光吸収効率が増し、より高い変換効率を示す光電変換素子が提供される。
〔10〕〜〔20〕における構成により、電子輸送層、ホール輸送層に用いる高分子材料が適切に選択されることで、コストパフォーマンスに優れ、かつ良好な変換効率を示す、優れた光電変換素子が提供される。
上記〔1〕〜〔19〕の光電変換素子を用いた構成〔21〕により、優れた変換効率を示す太陽電池が提供される。このような太陽電池は、携帯電話、電子手帳、電子ペーパー等各種電子装置の電源や、充電式あるいは乾電池式の各種電気器具の補助電源として用いることができる。また、上記〔22〕の製造方法によれば、光電変換特性の優れた完全固体型の光電変換素子を生産性良く製造することができる。
With the configurations [1] and [2] of the present invention, a complete solid-state photoelectric conversion element having excellent cost performance and good conversion efficiency is provided.
With the configuration using the oxide semiconductor in the electron transport layer of [3] to [7], electron transfer becomes efficient, and a photoelectric conversion element exhibiting further excellent conversion efficiency is provided.
[8], [9] The structure in which the photosensitizing compound is adsorbed on the electron transport layer increases the light absorption efficiency, and provides a photoelectric conversion element exhibiting higher conversion efficiency.
[10]-[20] Excellent photoelectric conversion element which is excellent in cost performance and shows good conversion efficiency by appropriately selecting a polymer material used for the electron transport layer and the hole transport layer according to the configuration in [20] Is provided.
With the configuration [21] using the photoelectric conversion elements [1] to [19], a solar cell exhibiting excellent conversion efficiency is provided. Such a solar cell can be used as a power source for various electronic devices such as a mobile phone, an electronic notebook, and electronic paper, and as an auxiliary power source for various rechargeable or dry cell type electric appliances. In addition, according to the production method [22], a complete solid-state photoelectric conversion element having excellent photoelectric conversion characteristics can be produced with high productivity.
以下本発明を詳細に説明する。
光電変換素子は一般に電子集電電極、電子受容体兼電子輸送層(以下単に電子輸送層と称す)、電子供与体兼ホール輸送層(以下単にホール輸送層と称す)、ホール集電電極から構成される。
本発明の光電変換素子は、電子集電電極とホール集電電極間に、電子輸送層とホール輸送層が設けられた光電変換素子において、前記ホール輸送層が、特定の高分子材料と、特定の化合物をホール輸送層に用いることを特徴としている。また、特徴の一つとして、必要によりホール輸送層の構成材料成分である高分子材料を、ホール集電電極にも兼用して用いることができる。
The present invention will be described in detail below.
A photoelectric conversion element generally comprises an electron collector electrode, an electron acceptor / electron transport layer (hereinafter simply referred to as an electron transport layer), an electron donor / hole transport layer (hereinafter simply referred to as a hole transport layer), and a hole current collector electrode. Is done.
The photoelectric conversion element of the present invention is a photoelectric conversion element in which an electron transport layer and a hole transport layer are provided between an electron collector electrode and a hole collector electrode, wherein the hole transport layer is a specific polymer material and a specific polymer material. These compounds are used for the hole transport layer. In addition, as one of the features, a polymer material that is a constituent material component of the hole transport layer can be used also for the hole collector electrode if necessary.
以下、本発明の好適な実施の形態について図を参照して説明する。
本発明における光電変換素子は、例えば、図1の概略図に示すような構造を有する。
図1の光電変換素子では、透明な支持体(基板)(1a)に支持された透明な電子集電電極(2a)上に緻密構造からなる電子輸送層(3a)と、光増感化合物(5)を吸着した多孔質構造からなる粒状の電子輸送層(3b)、ホール輸送層(4)、ホール集電電極(2b)、支持体である基板(1b)が積層されている。(3a)と(3b)により電子輸送層(3)が構成されている。なお、図1の構成図は本発明に係る光電変換素子の一構成例を示すものであり、本発明はこれに限定されるものではない。
Preferred embodiments of the present invention will be described below with reference to the drawings.
The photoelectric conversion element in the present invention has, for example, a structure as shown in the schematic diagram of FIG.
In the photoelectric conversion element of FIG. 1, an electron transport layer (3a) having a dense structure on a transparent electron collecting electrode (2a) supported by a transparent support (substrate) (1a), a photosensitizing compound ( A granular electron transport layer (3b) having a porous structure adsorbing 5), a hole transport layer (4), a hole collecting electrode (2b), and a substrate (1b) as a support are laminated. The electron transport layer (3) is constituted by (3a) and (3b). In addition, the block diagram of FIG. 1 shows one structural example of the photoelectric conversion element according to the present invention, and the present invention is not limited to this.
以下に説明する本発明のホール輸送層とすることにより、変換効率など光電変換特性特が良好で長期安定性にも優れた完全固体型の光電変換素子が得られる。また、生産性が良好であるためコストパフォーマンスの良い光電変換素子とすることができる。 By using the hole transport layer of the present invention described below, a completely solid photoelectric conversion element having excellent photoelectric conversion characteristics such as conversion efficiency and excellent long-term stability can be obtained. In addition, since the productivity is good, a photoelectric conversion element with good cost performance can be obtained.
ここで、本発明におけるホール輸送層は、少なくとも下記一般式(1)で表される高分子材料を成分の一つとして含有することを特徴としている。 Here, the hole transport layer in the present invention is characterized by containing at least a polymer material represented by the following general formula (1) as one of the components.
[(1)式中、Ar1は置換もしくは無置換の芳香族炭化水素基を表し、Ar2、Ar3はそれぞれ独立に置換もしくは無置換の2価の単環式、非縮合多環式または縮合多環式芳香族炭化水素基を表す。Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。] [In the formula (1), Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, and Ar 2 and Ar 3 are each independently substituted or unsubstituted divalent monocyclic, non-condensed polycyclic or Represents a condensed polycyclic aromatic hydrocarbon group. Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. ]
上記高分子材料は、芳香環上に置換基を有していてもよく、置換基としては溶解性向上の観点から、アルキル基、アルコキシ基あるいはアルキルチオ基などが挙げられる。
これら置換基の炭素数が増加すれば溶解性はより向上する。好適な置換基の例としては炭素数が1〜25のアルキル基、アルコキシ基及びアルキルチオ基が挙げられる。更に好適には、炭素数が2〜18のアルキル基、アルコキシ基及びアルキルチオ基が挙げられる。これら置換基は同一のものを複数導入してもよいし、異なるものを複数導入してもよい。また、これらのアルキル基、アルコキシ基及びアルキルチオ基は、さらにハロゲン原子、シアノ基、フェニル基、ヒドロキシル基、カルボキシル基または炭素数1〜12の直鎖、分岐鎖もしくは環状のアルキル基やアルコキシ基、アルキルチオ基で置換されたフェニル基を含有していてもよい。
The polymer material may have a substituent on the aromatic ring, and examples of the substituent include an alkyl group, an alkoxy group, and an alkylthio group from the viewpoint of improving solubility.
If the carbon number of these substituents increases, the solubility is further improved. Examples of suitable substituents include alkyl groups having 1 to 25 carbon atoms, alkoxy groups, and alkylthio groups. More preferable examples include an alkyl group having 2 to 18 carbon atoms, an alkoxy group, and an alkylthio group. A plurality of the same substituents may be introduced, or a plurality of different substituents may be introduced. In addition, these alkyl groups, alkoxy groups and alkylthio groups are further halogen atoms, cyano groups, phenyl groups, hydroxyl groups, carboxyl groups, or linear, branched or cyclic alkyl groups or alkoxy groups having 1 to 12 carbon atoms, It may contain a phenyl group substituted with an alkylthio group.
アルキル基として具体的には、メチル基、エチル基、n−プロピル基、i−プロピル基、t−ブチル基、s−ブチル基、n−ブチル基、i−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、3,7−ジメチルオクチル基、2−エチルヘキシル基、トリフルオロメチル基、2−シアノエチル基、ベンジル基、4−クロロベンジル基、4−メチルベンジル基、シクロペンチル基、シクロヘキシル基等を一例として挙げることができ、アルコキシ基、アルキルチオ基としては上記アルキル基の結合位に酸素原子または硫黄原子を挿入してアルコキシ基、アルキルチオ基としたものが一例として挙げられる。 Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, pentyl group, hexyl group, Heptyl, octyl, nonyl, decyl, 3,7-dimethyloctyl, 2-ethylhexyl, trifluoromethyl, 2-cyanoethyl, benzyl, 4-chlorobenzyl, 4-methylbenzyl, A cyclopentyl group, a cyclohexyl group, etc. can be mentioned as an example, As an alkoxy group and an alkylthio group, what made the alkoxy group and the alkylthio group by inserting an oxygen atom or a sulfur atom in the bond position of the said alkyl group is mentioned as an example. .
前記一般式(1)における置換もしくは無置換の芳香族炭化水素基Ar1としては、単環基、多環基(縮合多環基、非縮合多環基)の何れでもよく、一例として以下のものを挙げることができる。例えば、フェニル基、ナフチル基、ピレニル基、フルオレニル基、アズレニル基、アントリル基、トリフェニレニル基、クリセニル基、ビフェニル基、ターフェニル基などが挙げられる。置換もしくは無置換の2価の、単環式、非縮合多環式または縮合多環式芳香族炭化水素基Ar2、Ar3としては、一例として上記芳香族基の2価基が挙げられる。 The substituted or unsubstituted aromatic hydrocarbon group Ar 1 in the general formula (1) may be a monocyclic group or a polycyclic group (a condensed polycyclic group or a non-condensed polycyclic group). Things can be mentioned. Examples include a phenyl group, a naphthyl group, a pyrenyl group, a fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrycenyl group, a biphenyl group, and a terphenyl group. Examples of the substituted or unsubstituted divalent, monocyclic, non-condensed polycyclic or condensed polycyclic aromatic hydrocarbon groups Ar 2 and Ar 3 include the divalent groups of the above aromatic groups.
また、これら芳香族炭化水素基は以下に示す置換基を有していてもよい。
(1)ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基。
(2)炭素数1〜25の直鎖または分岐鎖の、アルキル基またはアルコキシ基。これらはさらにハロゲン原子、シアノ基、フェニル基、ヒドロキシル基、カルボキシル基、アルコキシ基、アルキルチオ基で置換されていてもよい。
(3)アリールオキシ基。(アリール基としてフェニル基、ナフチル基を有するアリールオキシ基が挙げられる。これらは、ハロゲン原子を置換基として含有してもよく、炭素数1〜25の直鎖または分岐鎖の、アルキル基またはアルコキシ基あるいはアルキルチオ基を含有してもよい。具体的には、フェノキシ基、1−ナフチルオキシ基、2−ナフチルオキシ基、4−メチルフェノキシ基、4−メトキシフェノキシ基、4−クロロフェノキシ基、6−メチル−2−ナフチルオキシ基等が挙げられる。)
(4)アルキルチオ基又はアリールチオ基。(アルキルチオ基又はアリールチオ基としては、具体的にはメチルチオ基、エチルチオ基、フェニルチオ基、p−メチルフェニルチオ基等が挙げられる。)
(5)アルキル置換アミノ基。(具体的には、ジエチルアミノ基、N−メチル−N−フェニルアミノ基、N,N−ジフェニルアミノ基、N,N−ジ(p−トリル)アミノ基、ジベンジルアミノ基、ピペリジノ基、モルホリノ基、ユロリジル基等が挙げられる。)
(6)アシル基。(アシル基としては、具体的にはアセチル基、プロピオニル基、ブチリル基、マロニル基、ベンゾイル基等が挙げられる。)
Moreover, these aromatic hydrocarbon groups may have a substituent shown below.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) A linear or branched alkyl group or alkoxy group having 1 to 25 carbon atoms. These may be further substituted with a halogen atom, a cyano group, a phenyl group, a hydroxyl group, a carboxyl group, an alkoxy group, or an alkylthio group.
(3) Aryloxy group. (Examples include aryloxy groups having a phenyl group or a naphthyl group as the aryl group. These may contain a halogen atom as a substituent, and are a linear or branched alkyl group or alkoxy having 1 to 25 carbon atoms. A phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group, 6 -A methyl-2-naphthyloxy group etc. are mentioned.
(4) An alkylthio group or an arylthio group. (Specific examples of the alkylthio group or arylthio group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.)
(5) An alkyl-substituted amino group. (Specifically, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group, dibenzylamino group, piperidino group, morpholino group And a urolidyl group.)
(6) Acyl group. (Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.)
上記一般式(1)に示されるくり返し単位を含む重合体のうち、更に好ましい態様は下記一般式(11)で表される。 Among the polymers containing repeating units represented by the general formula (1), a more preferred embodiment is represented by the following general formula (11).
[(11)式中、Ar1は置換もしくは無置換の芳香族炭化水素基を表し、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R44、R45はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、x、yはそれぞれ独立に0〜4の整数を表し、R44、R45が各々複数存在する場合には、同一でも別異でもよい。] [In the formula (11), Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these have a substituent. May be. R 44 and R 45 each independently represents a halogen atom, a substituted or unsubstituted alkyl group, or an alkoxy group or an alkylthio group, x and y each independently represents an integer of 0 to 4; When a plurality of 44 and R 45 are present, they may be the same or different. ]
上記一般式(1)に示されるくり返し単位を含む重合体のうち、更に好ましい態様は下記一般式(12)で表される。 Of the polymers containing repeating units represented by the general formula (1), a more preferred embodiment is represented by the following general formula (12).
[(12)式中、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R44、R45はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、R46はハロゲン原子、置換もしくは無置換の、アルキル基、アルコキシ基、アルキルチオ基、芳香族炭化水素基から選択される基を表す。zは0〜5の整数を表し、x、yはそれぞれ独立に0〜4の整数を表し、R44、R45、R46が各々複数存在する場合には、同一でも別異でもよい。]
アルキル基またはアルコキシ基もしくはアルキルチオ基への置換基については前記一般式(1)と同様である。
[In the formula (12), Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. R 44 and R 45 each independently represents a halogen atom, a substituted or unsubstituted alkyl group or a group selected from an alkoxy group or an alkylthio group, and R 46 represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group. Represents a group selected from a group, an alkylthio group, and an aromatic hydrocarbon group. z represents an integer of 0 to 5, x and y each independently represents an integer of 0 to 4, and when a plurality of R 44 , R 45 and R 46 are present, they may be the same or different. ]
The substituent on the alkyl group, alkoxy group or alkylthio group is the same as in the general formula (1).
上記一般式(1)に示されるくり返し単位を含む重合体のうち、更に好ましい態様は下記一般式(13)で表わされる。 Of the polymers containing repeating units represented by the general formula (1), a more preferred embodiment is represented by the following general formula (13).
[(13)式中、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R44、R45、R46、R47、R48、R49はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表す。vは0〜3の整数を表し、w、x、yはそれぞれ独立に0〜4の整数を表し、R44、R45、R46、R47が各々複数存在する場合には、同一でも別異でもよい。]
アルキル基またはアルコキシ基もしくはアルキルチオ基への置換基については前記一般式(1)と同様である。
[In the formula (13), Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. R 44 , R 45 , R 46 , R 47 , R 48 and R 49 each independently represent a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group. v represents an integer of 0 to 3, w, x and y each independently represents an integer of 0 to 4, and when there are a plurality of R 44 , R 45 , R 46 and R 47 , they may be the same or different. It may be different. ]
The substituent on the alkyl group, alkoxy group or alkylthio group is the same as in the general formula (1).
上記一般式(1)に示されるくり返し単位を含む重合体のうち、更に好ましい態様は下記一般式(14)で表される。 Of the polymers containing repeating units represented by the general formula (1), a more preferred embodiment is represented by the following general formula (14).
[(14)式中、Ar1は置換もしくは無置換の芳香族炭化水素基を表し、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R50、R51、R52、R53はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、r、s、t、uはそれぞれ独立に0 〜4の整数を表し、R50、R51、R52、R53が各々複数存在する場合には、同一でも別異でもよい。]
アルキル基またはアルコキシ基もしくはアルキルチオ基への置換基については前記一般式(1)と同様である。
[In the formula (14), Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these have a substituent. May be. R 50 , R 51 , R 52 and R 53 each independently represent a halogen atom, a substituted or unsubstituted alkyl group or a group selected from an alkoxy group or an alkylthio group, and r, s, t and u are each independently selected. Represents an integer of 0 to 4, and when there are a plurality of R 50 , R 51 , R 52 and R 53 , they may be the same or different. ]
The substituent on the alkyl group, alkoxy group or alkylthio group is the same as in the general formula (1).
上記一般式(1)に示されるくり返し単位を含む重合体のうち、更に好ましい態様は下記一般式(15)で表わされる。 Of the polymers containing repeating units represented by the general formula (1), a more preferred embodiment is represented by the following general formula (15).
[(15)式中、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R50、R51、R52、R53、R54はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、qは0〜5の整数を表し、r、s、t、uはそれぞれ独立に0〜4の整数を表し、R50、R51、R52、R53、R54が各々複数存在する場合には、同一でも別異でもよい。]
アルキル基またはアルコキシ基もしくはアルキルチオ基への置換基については前記一般式(1)と同様である。
[In the formula (15), Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. R 50 , R 51 , R 52 , R 53 and R 54 each independently represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group, and q is an integer of 0 to 5 R, s, t and u each independently represents an integer of 0 to 4, and when there are a plurality of R 50 , R 51 , R 52 , R 53 and R 54 , they may be the same or different. Good. ]
The substituent on the alkyl group, alkoxy group or alkylthio group is the same as in the general formula (1).
以下に、本発明で用いられる一般式(1)で表される高分子材料の具体例を下記構造式(A−01)〜(A−19)に列挙するが、これら具体例は本発明を制限的に提示しているものでも、限定する意図で開示しているものでもない。 Specific examples of the polymer material represented by the general formula (1) used in the present invention are listed in the following structural formulas (A-01) to (A-19). It is not intended to be limiting or disclosed with the intention of limiting.
上記(A−01)、(A−07)、(A−08)、(A−09)、(A−10)、(A−11)に示される高分子材料の製造方法は、例えばアルデヒドとホスホネートを用いたWittig−Horner反応、アルデヒドとホスホニウム塩を用いたWittig反応、ビニル置換体とハロゲン化物を用いたHeck反応、アミンとハロゲン化物を用いたUllmann反応などを用いることができ、公知の方法により製造可能である。特に、Wittig−Horner反応およびWittig反応は反応操作の簡便さから有効である。 The method for producing the polymer material represented by (A-01), (A-07), (A-08), (A-09), (A-10), or (A-11) includes, for example, aldehyde and Wittig-Horner reaction using phosphonate, Wittig reaction using aldehyde and phosphonium salt, Heck reaction using vinyl substituent and halide, Ullmann reaction using amine and halide, etc. can be used. Can be manufactured. In particular, the Wittig-Horner reaction and the Wittig reaction are effective because of the simplicity of the reaction operation.
一例としてWittig−Horner反応を用いた本発明における高分子材料の製造方法について説明する。
本発明で用いられる高分子材料は、下記の反応式(F1)で示されるように、ホスホン酸エステル化合物及びアルデヒド化合物が化学量論的に等しく存在する溶液と、その2倍モル量以上の塩基を混合させることにより重合反応が進行し、得ることができる。
As an example, a method for producing a polymer material in the present invention using a Wittig-Horner reaction will be described.
As shown in the following reaction formula (F1), the polymer material used in the present invention includes a solution in which the phosphonic acid ester compound and the aldehyde compound are present stoichiometrically, and a base more than twice the molar amount thereof. By mixing these, the polymerization reaction proceeds and can be obtained.
本発明で用いられる高分子材料を製造する場合には、例えば、Aとしてアリールアミン部位、BとしてAr4の組み合わせのモノマーを用いるか、またはAとしてAr4、Bとしてアリールアミン部位の組み合わせのモノマーを用いればよい。 In the production of polymeric materials used in the present invention, for example, an aryl amine moiety as A, or using a monomer combination of Ar 4 as B, or A as Ar 4, B as monomers a combination of aryl amine sites May be used.
上記ジアルデヒド化合物は、公知の種々の反応により合成することが可能である。例として下記反応式(F2)で示されるVilsmeier反応; The dialdehyde compound can be synthesized by various known reactions. As an example, a Vilsmeier reaction represented by the following reaction formula (F2);
あるいは、下記反応式(F3)で示される、アリールリチウム化合物と、DMF、N−ホルミルモルホリン、N−ホルミルピペリジン等をはじめとするホルミル化剤との反応; Alternatively, the reaction of an aryllithium compound represented by the following reaction formula (F3) with a formylating agent such as DMF, N-formylmorpholine, N-formylpiperidine and the like;
あるいは、下記反応式(F4)で示されるGatterman反応; Alternatively, a Gatterman reaction represented by the following reaction formula (F4);
あるいは、下記反応式(F5)で示されるヒドロキシメチル化合物の各種酸化反応; Alternatively, various oxidation reactions of a hydroxymethyl compound represented by the following reaction formula (F5);
等を一例として挙げることができ、これら反応を用いてジアルデヒド化合物を合成することができる。 Can be cited as examples, and dialdehyde compounds can be synthesized using these reactions.
また、上記ホスホン酸ジエステル化合物についても、公知の種々の反応により合成することが可能であるが、下記反応式(F6)で示されるMichaelis−Arbuzov反応が特に容易である。 The phosphonic acid diester compound can also be synthesized by various known reactions, but the Michaelis-Arbuzov reaction represented by the following reaction formula (F6) is particularly easy.
なお、本発明で用いられる上記高分子材料の具体的な製造方法は、特開2004−18831号公報にその詳細が記載されている。 In addition, the specific manufacturing method of the said polymer material used by this invention is described in the Unexamined-Japanese-Patent No. 2004-18831.
さらに、本発明におけるホール輸送層は、少なくとも下記一般式(1B)、一般式(2)〜(5)で表される化合物を第二の成分として含有することを特徴としている。
先ず、下記一般式(1B)で表される化合物について説明する。
Furthermore, the hole transport layer in the present invention is characterized by containing at least a compound represented by the following general formula (1B) and general formulas (2) to (5) as the second component.
First, the compound represented by the following general formula (1B) will be described.
[式中nは0または1の整数を表し、Ar’ は置換もしくは無置換のアリール基を表し、R5は水素原子、置換アルキル基を含むアルキル基あるいは置換もしくは無置換のアリール基を表し、R6は水素原子、置換アルキル基を含むアルキル基あるいは置換もしくは無置換のアリール基を表し、Ar’とR5は互いに結合して環を形成してもよい。Aは9−アントリル基または置換もしくは無置換のカルバゾリル基あるいは下記一般式(1B−1)または(1B−2): [Wherein n represents an integer of 0 or 1, Ar ′ represents a substituted or unsubstituted aryl group, R 5 represents a hydrogen atom, an alkyl group containing a substituted alkyl group or a substituted or unsubstituted aryl group, R 6 represents a hydrogen atom, an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and Ar ′ and R 5 may be bonded to each other to form a ring. A is a 9-anthryl group, a substituted or unsubstituted carbazolyl group, or the following general formula (1B-1) or (1B-2):
〔式中、R50及びR51は水素原子、アルキル基、アルコキシル基、ハロゲン原子または下記一般式(1B−3): [Wherein, R 50 and R 51 are a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom or the following general formula (1B-3):
(式中、R52及びR53は置換アルキル基を含むアルキル基、置換または無置換のアリール基を表し、R52及びR53は同一でも別異でもよく、R52及びR53は互いに結合して環を形成してもよい。)で表される基を表す。〕で表される基を表す。] (Wherein R 52 and R 53 represent an alkyl group containing a substituted alkyl group, a substituted or unsubstituted aryl group, R 52 and R 53 may be the same or different, and R 52 and R 53 are bonded to each other. And may form a ring). Represents a group represented by the formula: ]
一般式(1B)の具体例としては、4−ジフェニルアミノスチルベン、4−ジ−p−トリルアミノスチルベン、4’−ジフェニルアミノ−α−フェニルスチルベン、4’−ジ−p−トリルアミノ−α−フェニルスチルベン、9−スチリルアントラセン、3−スチリル−9−エチルカルバゾール、1,1−ジフェニル−4―ジエチルアミノフェニル−1,3−ブタジエン、5−[4−(ジ−p−トリルアミノ)ベンジリデン]−5H−ジベンゾ[a,d]シクロヘプタン、5−[4−(ジ−p−トリルアミノ)ベンジリデン]−5H−ジベンゾ[a,d]シクロヘプテン等が挙げられるが、これらの列挙は本発明に用いられる化合物を制限的に提示している訳でも、これらに限定する意図で開示している訳でもない。
なお、本発明で用いられる一般式(1B)で表される化合物の具体例は、特公平2−24864号公報、特公平3−39306号公報、特公平4−66023号公報にその詳細が記載されている。
Specific examples of the general formula (1B) include 4-diphenylaminostilbene, 4-di-p-tolylaminostilbene, 4′-diphenylamino-α-phenylstilbene, 4′-di-p-tolylamino-α-phenyl. Stilbene, 9-styrylanthracene, 3-styryl-9-ethylcarbazole, 1,1-diphenyl-4-diethylaminophenyl-1,3-butadiene, 5- [4- (di-p-tolylamino) benzylidene] -5H- And dibenzo [a, d] cycloheptane, 5- [4- (di-p-tolylamino) benzylidene] -5H-dibenzo [a, d] cycloheptene, and the like. These enumerations show compounds used in the present invention. It is not intended to be limiting or disclosed with the intention of limiting it.
Specific examples of the compound represented by the general formula (1B) used in the present invention are described in detail in JP-B-2-24864, JP-B-3-39306, and JP-B-4-66023. Has been.
前記高分子材料と上記一般式(1B)の化合物は種々の一般的有機溶媒、例えばジクロロメタン、テトラヒドロフラン、クロロホルム、トルエン、ジクロロベンゼン及びキシレン等に対し良好な溶解性を示す。このため、これら高分子材料と低分子化合物を適当な濃度の溶液に作製して用いれば湿式成膜法によりホール輸送層を形成することができる。
次に、一般式(2)〜(5)で表される化合物について説明する。
The polymer material and the compound of the above general formula (1B) exhibit good solubility in various general organic solvents such as dichloromethane, tetrahydrofuran, chloroform, toluene, dichlorobenzene and xylene. For this reason, if these high molecular materials and low molecular weight compounds are prepared and used in a solution having an appropriate concentration, a hole transport layer can be formed by a wet film formation method.
Next, the compounds represented by the general formulas (2) to (5) will be described.
[(2)式中、R1、R2は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R3は置換もしくは無置換のアルキレン基、置換もしくは無置換の2価の芳香族炭化水素基を表す。R1とR2、R1とR3、あるいはR2とR3は共同で環を形成してもよい。R4は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表す。R5、R6は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R5とR6は共同で環を形成してもよい。] [In the formula (2), R 1 and R 2 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. , R 3 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted divalent aromatic hydrocarbon group. R 1 and R 2 , R 1 and R 3 , or R 2 and R 3 may jointly form a ring. R 4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group. R 5 and R 6 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group, and R 5 and R 6 represent You may form a ring jointly. ]
[(3)式中、R7は置換もしくは無置換のアルキレン基、置換もしくは無置換の2価の芳香族炭化水素基を表す。R8、R9、R10、R11は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R8とR9、R10とR11は共同で環を形成してもよい。] [In the formula (3), R 7 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted divalent aromatic hydrocarbon group. R 8 , R 9 , R 10 and R 11 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, R 8 and R 9 , and R 10 and R 11 may form a ring together. ]
[(4)式中、R12、R13、R14は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R12とR13、R13とR14、R12とR14は共同で環を形成してもよい。R15は窒素原子、ホウ素原子、アルキリジン基、置換もしくは無置換の3価の芳香族炭化水素基を表す。] [In the formula (4), R 12 , R 13 and R 14 are substituted or unsubstituted alkyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heterocyclic rings. Represents a group, and R 12 and R 13 , R 13 and R 14 , and R 12 and R 14 may form a ring together. R 15 represents a nitrogen atom, a boron atom, an alkylidine group, or a substituted or unsubstituted trivalent aromatic hydrocarbon group. ]
[(5)式中、R16は置換もしくは無置換の4価の芳香族炭化水素基を表す。R17〜R24は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R17とR18、R19とR20、R21とR22、R23とR24は共同で環を形成してもよい。] [In the formula (5), R 16 represents a substituted or unsubstituted tetravalent aromatic hydrocarbon group. R 17 to R 24 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, R 17 and R 18 , R 19 and R 20 , R 21 and R 22 , and R 23 and R 24 may form a ring together. ]
以下に、本発明で用いられる一般式(2)の具体例を下記構造式(B−01)〜(B−26)に、一般式(3)の具体例を下記構造式(B−27)〜(B−50)に、一般式(4)の具体例を下記構造式(B−51)〜(B−56)に、一般式(5)の具体例を下記構造式(B−57)〜(B−60)に列挙するが、これら具体例は本発明を制限的に提示しているものでも、限定する意図で開示しているものでもない。 Specific examples of general formula (2) used in the present invention are shown in the following structural formulas (B-01) to (B-26), and specific examples of general formula (3) are shown in the following structural formula (B-27). To (B-50), specific examples of the general formula (4) in the following structural formulas (B-51) to (B-56), specific examples of the general formula (5) in the following structural formula (B-57) Although listed in (B-60), these specific examples are not intended to limit the present invention, nor are they intended to limit the present invention.
前記高分子材料と上記(B−01)〜(B−60)で示される化合物は、種々の一般的有機溶媒、例えば、アセトン、メチルエチルケトン、あるいはメチルイソブチルケトン等のケトン系溶媒、ギ酸エチル、酢酸エチル、あるいは酢酸n−ブチル等のエステル系溶媒、ジイソプロピルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキソラン、あるいはジオキサン等のエーテル系溶媒、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、あるいはN−メチル−2−ピロリドン等のアミド系溶媒、ジクロロメタン、クロロホルム、ブロモホルム、ヨウ化メチル、ジクロロエタン、トリクロロエタン、トリクロロエチレン、クロロベンゼン、o−ジクロロベンゼン、フルオロベンゼン、ブロモベンゼン、ヨードベンゼン、あるいは1−クロロナフタレン等のハロゲン化炭化水素系溶媒、n−ペンタン、n−ヘキサン、n−オクタン、1,5−ヘキサジエン、シクロヘキサン、メチルシクロヘキサン、シクロヘキサジエン、ベンゼン、トルエン、o−キシレン、m−キシレン、p−キシレン、エチルベンゼン、あるいはクメン等の炭化水素系溶媒に溶解し、これを用いて湿式成膜法によりホール輸送層を形成することができる。溶剤は単独、あるいは2種以上の混合として用いることができる。 The polymer material and the compounds represented by the above (B-01) to (B-60) are various general organic solvents, for example, ketone solvents such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, ethyl formate, acetic acid. Ester solvents such as ethyl or n-butyl acetate, ether solvents such as diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, or N-methyl- Amide solvents such as 2-pyrrolidone, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, Or halogenated hydrocarbon solvents such as 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m A hole transport layer can be formed by a wet film formation method by dissolving in a hydrocarbon solvent such as -xylene, p-xylene, ethylbenzene, or cumene. A solvent can be used individually or in mixture of 2 or more types.
また、前記一般式(1B)で示される化合物(低分子化合物)や上記(B−01)〜(B−60)に示される化合物以外の公知のホール輸送物質を併せて添加することも可能である。他のホール輸送物質の具体例としては、特公昭34−5466号公報等に示されているオキサジアゾール化合物、特公昭45−555号公報等に示されているトリフェニルメタン化合物、特公昭52−4188号公報等に示されているピラゾリン化合物、特公昭55−42380号公報等に示されているヒドラゾン化合物、特開昭56−123544号公報等に示されているオキサジアゾール化合物、特開昭54−58445号公報に示されているテトラアリールベンジジン化合物、特開昭58−65440号公報あるいは特開昭60−98437号公報に示されているスチルベン化合物等を挙げることができる。 It is also possible to add a known hole transporting material other than the compound represented by the general formula (1B) (low molecular weight compound) or the compounds represented by the above (B-01) to (B-60). is there. Specific examples of other hole transport materials include oxadiazole compounds disclosed in Japanese Patent Publication No. 34-5466, triphenylmethane compounds shown in Japanese Patent Publication No. 45-555, and Japanese Patent Publication No. 52. Pyrazoline compounds shown in JP-4188, hydrazone compounds shown in JP-B-55-42380, oxadiazole compounds shown in JP-A-56-123544, etc. Examples thereof include tetraarylbenzidine compounds disclosed in JP-A-54-58445, stilbene compounds disclosed in JP-A-58-65440, and JP-A-60-98437.
また、本発明の光電変換素子においては、上記に示した高分子材料に各種添加剤を加えても構わない。添加剤としては、ヨウ素、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化セシウム、ヨウ化カルシウム、ヨウ化銅、ヨウ化鉄、ヨウ化銀等の金属ヨウ化物、ヨウ化テトラアルキルアンモニウム、ヨウ化ピリジニウム等の4級アンモニウム塩、臭化リチウム、臭化ナトリウム、臭化カリウム、臭化セシウム、臭化カルシウム等の金属臭化物、臭化テトラアルキルアンモニウム、臭化ピリジニウム等の4級アンモニウム化合物の臭素塩、塩化銅、塩化銀等の金属塩化物、酢酸銅、酢酸銀、酢酸パラジウム等の酢酸金属塩、硫酸銅、硫酸亜鉛等の金属硫化物、フェロシアン酸塩−フェリシアン酸塩、フェロセン−フェリシニウムイオン等の金属錯体、ポリ硫化ナトリウム、アルキルチオール−アルキルジスルフィド等のイオウ化合物、ビオロゲン色素、ヒドロキノン等、ヨウ化1,2−ジメチル−3−n−プロピルイミダゾイニウム塩、ヨウ化1−メチル−3−n−ヘキシルイミダゾリニウム塩等のInorg. Chem. 35 (1996) 1168に記載の常温溶融塩(イオン性液体)、ピリジン、4−t−ブチルピリジン、ベンズイミダゾール等の塩基性化合物、リチウムトリフルオロメタンスルホニルイミド、リチウムジイソプロピルイミド等のリチウム化合物を挙げることができる。
上記において好ましいものは金属化合物や常温溶融塩からなるイオン性液体である。特に好ましい金属化合物としては、ハロゲン化金属、チオシアン化金属もしくはアミド化金属が挙げられる。また、特に好ましい常温溶融塩からなるイオン性液体としてはイミダゾリニウム化合物が挙げられる。
このような金属化合物もしくは常温溶融塩からなるイオン性液体を加えることにより、電子移動が効率的となり更に優れた光電変換特性を示す光電変換素子とすることができる。
Moreover, in the photoelectric conversion element of this invention, you may add various additives to the polymeric material shown above. Additives include iodine, lithium iodide, sodium iodide, potassium iodide, cesium iodide, calcium iodide, copper iodide, iron iodide, silver iodide and other metal iodides, tetraalkylammonium iodide, Quaternary ammonium salts such as pyridinium iodide, metal bromides such as lithium bromide, sodium bromide, potassium bromide, cesium bromide and calcium bromide, quaternary ammonium compounds such as tetraalkylammonium bromide and pyridinium bromide Metal chlorides such as bromine salts, copper chloride and silver chloride, metal acetates such as copper acetate, silver acetate and palladium acetate, metal sulfides such as copper sulfate and zinc sulfate, ferrocyanate-ferricyanate, ferrocene -Sulfur compounds such as metal complexes such as ferricinium ions, sodium polysulfide, alkylthiol-alkyl disulfides Inorg. Chem. 35 (1996) 1168 such as viologen dye, hydroquinone, 1,2-dimethyl-3-n-propylimidazolinium iodide, 1-methyl-3-n-hexylimidazolinium iodide, etc. And normal compounds such as pyridine, 4-t-butylpyridine and benzimidazole, and lithium compounds such as lithium trifluoromethanesulfonylimide and lithium diisopropylimide.
Preferred in the above is an ionic liquid composed of a metal compound or a room temperature molten salt. Particularly preferred metal compounds include metal halides, thiocyanides or amidated metals. Moreover, an imidazolinium compound is mentioned as an ionic liquid which consists of especially preferable normal temperature molten salt.
By adding such an ionic liquid composed of a metal compound or a room temperature molten salt, the electron transfer becomes efficient, and a photoelectric conversion element exhibiting further excellent photoelectric conversion characteristics can be obtained.
また、導電性を向上させる目的で、高分子材料の一部をラジカルカチオンにするための酸化剤を添加しても構わない。その酸化剤としては、ヘキサクロロアンチモン酸トリス(4−ブロモフェニル)アミニウム、ヘキサフルオロアンチモネート銀、ニトロソニウムテトラフルオボラート等が好ましい。この酸化剤の添加によって全ての高分子が酸化される必要はなく、一部のみが酸化されていれば良い。また添加した酸化剤は添加した後、系外に取り出しても、取り出さなくてもよい。 Moreover, you may add the oxidizing agent for making a part of polymer material into a radical cation for the purpose of improving electroconductivity. As the oxidizing agent, tris (4-bromophenyl) aminium hexachloroantimonate, silver hexafluoroantimonate, nitrosonium tetrafluorate and the like are preferable. It is not necessary for all the polymers to be oxidized by the addition of the oxidizing agent, and only a part of the polymer needs to be oxidized. The added oxidizing agent may be taken out of the system after the addition or may not be taken out.
ホール輸送層は、後述する光増感化合物を担持(吸着)した電子輸送層の上に直接形成される。ホール輸送層の作製方法には特に制限は無く、スパッタリング等の真空中で薄膜を形成する方法や湿式製膜法が挙げられる。製造コスト等を考慮した場合、特に湿式製膜法が好ましく、電子輸送層上に塗布する方法が好ましい。この湿式製膜法を用いた場合、塗布方法は特に制限はなく、公知の方法に従って行うことができる。例えば、ディップ法、スプレー法、ワイヤーバー法、スピンコート法、ローラーコート法、ブレードコート法、グラビアコート法、また、湿式印刷方法として、凸版、オフセット、グラビア、凹版、ゴム版、スクリーン印刷等様々な方法を用いることができる。 The hole transport layer is directly formed on the electron transport layer carrying (adsorbing) a photosensitizing compound described later. There is no restriction | limiting in particular in the preparation methods of a hole transport layer, The method of forming a thin film in vacuum, such as sputtering, and the wet film forming method are mentioned. In consideration of the manufacturing cost and the like, a wet film forming method is particularly preferable, and a method of coating on the electron transport layer is preferable. When this wet film-forming method is used, the coating method is not particularly limited and can be performed according to a known method. For example, dip method, spray method, wire bar method, spin coating method, roller coating method, blade coating method, gravure coating method, and wet printing methods such as relief printing, offset, gravure, intaglio printing, rubber printing, screen printing, etc. Can be used.
ホール集電電極は、ホール輸送層形成後に新たに付与するか、あるいは本発明の高分子材料をホール集電電極として兼用してもよい。また、ホール集電電極は通常前述の電子集電電極と同様のものを用いることができ、強度や密封性が十分に保たれるような構成では支持体(図1に示した基板(1b))は必ずしも必要ではない。
ホール集電電極材料の具体例としては、白金、金、銀、銅、アルミニウム等の金属、グラファイト、フラーレン、カーボンナノチューブ等の炭素系化合物、インジウム・スズ酸化物(以下、ITOと称す)、フッ素ドープ酸化スズ(以下、FTOと称す)等の導電性金属酸化物、ポリチオフェン、ポリアニリン等の導電性高分子が挙げられる。ホール集電電極層の膜厚には特に制限はなく、また単独あるいは2種以上の混合で用いても構わない。ホール集電電極の塗設については、用いられる材料の種類やホール輸送層の種類により、適宜ホール輸送層上に塗布、ラミネート、蒸着、CVD、貼り合わせ等の手法により形成可能である。
The hole collecting electrode may be newly added after the hole transport layer is formed, or the polymer material of the present invention may be used as the hole collecting electrode. In addition, the hole collecting electrode can usually be the same as the above-described electron collecting electrode, and in a configuration in which the strength and the sealing performance are sufficiently maintained, the support (the substrate (1b) shown in FIG. 1). ) Is not always necessary.
Specific examples of hole collecting electrode materials include metals such as platinum, gold, silver, copper, and aluminum, carbon compounds such as graphite, fullerene, and carbon nanotubes, indium tin oxide (hereinafter referred to as ITO), fluorine Examples thereof include conductive metal oxides such as doped tin oxide (hereinafter referred to as FTO), and conductive polymers such as polythiophene and polyaniline. There is no restriction | limiting in particular in the film thickness of a hole current collection electrode layer, and you may use individually or in mixture of 2 or more types. The hole collecting electrode can be applied by a method such as coating, laminating, vapor deposition, CVD, and bonding on the hole transport layer as appropriate depending on the type of material used and the type of hole transport layer.
光電変換素子として動作するためには、電子集電電極とホール集電電極の少なくとも一方は実質的に透明でなければならない。本発明の光電変換素子においては、電子集電電極側が透明であり、太陽光を電子集電電極側から入射させる方法が好ましい。この場合、ホール集電電極側には光を反射させる材料を使用することが好ましく、金属、導電性酸化物を蒸着したガラス、プラスチック、あるいは金属薄膜が好ましい。また、太陽光の入射側に反射防止層を設けることも有効な手段である。 In order to operate as a photoelectric conversion element, at least one of the electron collector electrode and the hole collector electrode must be substantially transparent. In the photoelectric conversion element of the present invention, a method in which the electron collecting electrode side is transparent and sunlight is incident from the electron collecting electrode side is preferable. In this case, it is preferable to use a material that reflects light on the side of the hole collecting electrode, and a metal, glass, plastic, or metal thin film on which a conductive oxide is deposited is preferable. It is also effective to provide an antireflection layer on the sunlight incident side.
本発明に用いられる電子集電電極としては、可視光に対して透明な導電性物質であれば特に限定されるものではなく、通常の光電変換素子、あるいは液晶パネル等に用いられる公知のものを使用できる。例えば、インジウム・スズ酸化物(ITO)、フッ素ドープ酸化スズ(FTO)等が挙げられる。これらの内、FTOが好ましい。電子集電電極の厚さは5nm〜1μmが好ましく、10〜100nmが更に好ましい。また電子集電電極は一定の硬性を維持するため、可視光に透明な材質からなる基板上に設けることが好ましく、例えば、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用いられる。 The electron collector electrode used in the present invention is not particularly limited as long as it is a conductive material transparent to visible light, and a known one used for ordinary photoelectric conversion elements, liquid crystal panels, or the like. Can be used. For example, indium tin oxide (ITO), fluorine-doped tin oxide (FTO), and the like can be given. Of these, FTO is preferred. The thickness of the electron current collecting electrode is preferably 5 nm to 1 μm, more preferably 10 to 100 nm. In addition, the electron collector electrode is preferably provided on a substrate made of a material transparent to visible light in order to maintain a certain hardness. For example, glass, a transparent plastic plate, a transparent plastic film, an inorganic transparent crystal, or the like is used. .
電子集電電極と基板が一体となっている公知のものを用いることもでき、例えば、FTOコートガラス、ITOコートガラス、酸化亜鉛:アルミニウムコートガラス、FTOコート透明プラスチック膜、ITOコート透明プラスチック膜等が挙げられる。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でもよい。これらは単独あるいは2種以上の混合、または積層したものでも構わない。 For example, FTO coated glass, ITO coated glass, zinc oxide: aluminum coated glass, FTO coated transparent plastic film, ITO coated transparent plastic film, etc. can be used. Is mentioned. In addition, a transparent electrode obtained by doping cations or anions with different valences into tin oxide or indium oxide, 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 Good. These may be used singly or as a mixture of two or more kinds or laminated ones.
また、基板の抵抗を下げる目的で、金属リード線等を用いてもよい。金属リード線の材質はアルミニウム、銅、銀、金、白金、ニッケル等の金属が挙げられる。金属リード線は、基板に蒸着、スパッタリング、圧着等で設置し、その上にITOやFTOを設ける方法が挙げられる。 Moreover, a metal lead wire or the like may be used for the purpose of reducing the resistance of the substrate. Examples of the material of the metal lead wire include metals such as aluminum, copper, silver, gold, platinum, and nickel. For example, the metal lead wire may be provided on the substrate by vapor deposition, sputtering, pressure bonding, or the like, and ITO or FTO may be provided thereon.
本発明の光電変換素子は、上記の電子集電電極上に、電子輸送層として、半導体からなる薄膜を形成する。この電子輸送層は、電子集電電極上に緻密な電子輸送層を形成し、更にその上に多孔質状の電子輸送層を形成する積層構造であることが好ましい。この緻密な電子輸送層は、電子集電電極とホール輸送層との電子的コンタクトを防ぐ目的で形成するものである。従って、電子終電電極とホール輸送層が物理的に接触しなければ、ピンホールやクラック等が形成されていても構わない。また、この緻密な電子輸送層の膜厚に制限はないが、10nm〜1μmが好ましく、20nm〜700nmがより好ましい。 The photoelectric conversion element of this invention forms the thin film which consists of semiconductors as an electron carrying layer on said electron current collection electrode. This electron transport layer preferably has a laminated structure in which a dense electron transport layer is formed on an electron current collecting electrode, and a porous electron transport layer is further formed thereon. This dense electron transport layer is formed for the purpose of preventing electronic contact between the electron collector electrode and the hole transport layer. Therefore, if the electron final electrode and the hole transport layer are not in physical contact, pinholes, cracks, or the like may be formed. Moreover, although there is no restriction | limiting in the film thickness of this precise | minute electron carrying layer, 10 nm-1 micrometer are preferable and 20 nm-700 nm are more preferable.
緻密な電子輸送層上に形成する多孔質状の電子輸送層は、単層であっても多層であってもよい。多層の場合、粒径の異なる半導体微粒子の分散液を多層塗布することも、種類の異なる半導体や、樹脂、添加剤の組成が異なる塗布層を多層塗布することもできる。一度の塗布で膜厚が不足する場合には多層塗布は有効な手段である。一般的に、電子輸送層の膜厚が増大するほど単位投影面積当たりの担持光増感化合物量も増えるため光の捕獲率が高くなるが、注入された電子の拡散距離も増えるため電荷の再結合によるロスも大きくなってしまう。従って、電子輸送層の膜厚は100nm〜100μmが好ましい。 The porous electron transport layer formed on the dense electron transport layer may be a single layer or multiple layers. In the case of multiple layers, a dispersion of semiconductor fine particles having different particle diameters can be applied in multiple layers, or different types of semiconductors, and application layers having different compositions of resins and additives can be applied in multiple layers. Multi-layer coating is an effective means when the film thickness is insufficient with a single coating. In general, as the film thickness of the electron transport layer increases, the amount of the photosensitized compound carried per unit projected area increases, so that the light capture rate increases. Loss due to coupling also increases. Therefore, the thickness of the electron transport layer is preferably 100 nm to 100 μm.
半導体としては特に限定されるものではなく、公知のものを使用することができる。
具体的には、シリコン、ゲルマニウムのような単体半導体、あるいは金属のカルコゲニドに代表される化合物半導体、またはペロブスカイト構造を有する化合物等を挙げることができる。
The semiconductor is not particularly limited, and a known semiconductor can be used.
Specifically, a single semiconductor such as silicon or germanium, a compound semiconductor typified by a metal chalcogenide, a compound having a perovskite structure, or the like can be given.
金属のカルコゲニドとしては、チタン、スズ、亜鉛、鉄、タングステン、ジルコニウム、ハフニウム、ストロンチウム、インジウム、セリウム、イットリウム、ランタン、バナジウム、ニオブ、あるいはタンタルの酸化物、カドミウム、亜鉛、鉛、銀、アンチモン、ビスマスの硫化物、カドミウム、鉛のセレン化物、カドミウムのテルル化物等が挙げられる。他の化合物半導体としては亜鉛、ガリウム、インジウム、カドミウム、等のリン化物、ガリウム砒素、銅−インジウム−セレン化物、銅−インジウム−硫化物等が好ましい。また、ペロブスカイト構造を有する化合物としては、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸ナトリウム、チタン酸バリウム、ニオブ酸カリウム等が好ましい。これらの中でも酸化物半導体が好ましく、特に酸化チタン、酸化亜鉛、酸化スズ、酸化ニオブ、酸化ニッケルが好ましく、単独、あるいは2種以上の混合で使用しても構わない。これらの半導体の結晶型は特に限定されるものではなく、単結晶でも多結晶でも、あるいは非晶質でも構わない。 Metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, or tantalum oxide, cadmium, zinc, lead, silver, antimony, Bismuth sulfide, cadmium, lead selenide, cadmium telluride and the like. Other compound semiconductors are preferably phosphides such as zinc, gallium, indium, cadmium, gallium arsenide, copper-indium-selenide, copper-indium-sulfide, and the like. As the compound having a perovskite structure, strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate and the like are preferable. Among these, an oxide semiconductor is preferable, and titanium oxide, zinc oxide, tin oxide, niobium oxide, and nickel oxide are particularly preferable, and they may be used alone or in combination of two or more. The crystal type of these semiconductors is not particularly limited, and may be single crystal, polycrystal, or amorphous.
半導体微粒子のサイズに特に制限は無いが、一次粒子の平均粒径は1〜100nmが好ましく、5〜50nmがより好ましい。また、より大きい平均粒径の半導体微粒子を混合し、入射光を散乱させる効果により、効率を向上させることも可能である。この場合の半導体の平均粒径は50〜500nmが好ましい。 Although there is no restriction | limiting in particular in the size of a semiconductor fine particle, 1-100 nm is preferable and, as for the average particle diameter of a primary particle, 5-50 nm is more preferable. It is also possible to improve efficiency by mixing semiconductor fine particles having a larger average particle diameter and scattering incident light. In this case, the average particle size of the semiconductor is preferably 50 to 500 nm.
電子輸送層の作製方法には特に制限は無く、スパッタリング等の真空中で薄膜を形成する方法や湿式製膜法が挙げられる。製造コスト等を考慮した場合、特に湿式製膜法が好ましく、半導体微粒子の粉末あるいはゾルを分散したペーストを調製し、電子集電電極基板上に塗布する方法が好ましい。この湿式製膜法を用いた場合、塗布方法は特に制限はなく、公知の方法に従って行うことができる。例えば、ディップ法、スプレー法、ワイヤーバー法、スピンコート法、ローラーコート法、ブレードコート法、グラビアコート法、また、湿式印刷方法として、凸版、オフセット、グラビア、凹版、ゴム版、スクリーン印刷等様々な方法を用いることができる。 There is no restriction | limiting in particular in the preparation methods of an electron carrying layer, The method of forming a thin film in vacuum, such as sputtering, and the wet film forming method are mentioned. In view of the manufacturing cost and the like, a wet film forming method is particularly preferable, and a method in which a paste in which semiconductor fine particle powder or sol is dispersed is prepared and applied onto an electron collecting electrode substrate is preferable. When this wet film-forming method is used, the coating method is not particularly limited and can be performed according to a known method. For example, dip method, spray method, wire bar method, spin coating method, roller coating method, blade coating method, gravure coating method, and wet printing methods such as relief printing, offset, gravure, intaglio printing, rubber printing, screen printing, etc. Can be used.
機械的粉砕、あるいはミルを使用して分散液を作製する場合、少なくとも半導体微粒子単独、あるいは半導体微粒子と樹脂の混合物を水あるいは有機溶剤に分散して形成される。この時に使用される樹脂としては、スチレン、酢酸ビニル、アクリル酸エステル、メタクリル酸エステル等によるビニル化合物の重合体や共重合体、シリコン樹脂、フェノキシ樹脂、ポリスルホン樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、ポリエステル樹脂、セルロースエステル樹脂、セルロースエーテル樹脂、ウレタン樹脂、フェノール樹脂、エポキシ樹脂、ポリカーボネート樹脂、ポリアリレート樹脂、ポリアミド樹脂、ポリイミド樹脂等が挙げられる。 When a dispersion is prepared by mechanical pulverization or using a mill, it is formed by dispersing at least semiconductor fine particles alone or a mixture of semiconductor fine particles and a resin in water or an organic solvent. As the resin used at this time, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, acrylic acid ester, methacrylic acid ester, silicon resin, phenoxy resin, polysulfone resin, polyvinyl butyral resin, polyvinyl formal resin, Examples include polyester resin, cellulose ester resin, cellulose ether resin, urethane resin, phenol resin, epoxy resin, polycarbonate resin, polyarylate resin, polyamide resin, polyimide resin, and the like.
半導体微粒子を分散する溶媒としては、水、メタノール、エタノール、あるいはイソプロピルアルコール等のアルコール系溶媒、アセトン、メチルエチルケトン、あるいはメチルイソブチルケトン等のケトン系溶媒、ギ酸エチル、酢酸エチル、あるいは酢酸n−ブチル等のエステル系溶媒、ジエチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキソラン、あるいはジオキサン等のエーテル系溶媒、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、あるいはN−メチル−2−ピロリドン等のアミド系溶媒、ジクロロメタン、クロロホルム、ブロモホルム、ヨウ化メチル、ジクロロエタン、トリクロロエタン、トリクロロエチレン、クロロベンゼン、o−ジクロロベンゼン、フルオロベンゼン、ブロモベンゼン、ヨードベンゼン、あるいは1−クロロナフタレン等のハロゲン化炭化水素系溶媒、n−ペンタン、n−ヘキサン、n−オクタン、1,5−ヘキサジエン、シクロヘキサン、メチルシクロヘキサン、シクロヘキサジエン、ベンゼン、トルエン、o−キシレン、m−キシレン、p−キシレン、エチルベンゼン、あるいはクメン等の炭化水素系溶媒を挙げることができる。これらは単独、あるいは2種以上の混合溶媒として用いることができる。 Solvents for dispersing the semiconductor fine particles include alcohol solvents such as water, methanol, ethanol, and isopropyl alcohol, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl formate, ethyl acetate, and n-butyl acetate. Ester solvents, diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or ether solvents such as dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, or amide solvents such as N-methyl-2-pyrrolidone , Dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodine Halogenated hydrocarbon solvents such as debenzene or 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, Examples thereof include hydrocarbon solvents such as m-xylene, p-xylene, ethylbenzene, and cumene. These can be used alone or as a mixed solvent of two or more.
半導体微粒子の分散液、あるいはゾル−ゲル法等によって得られた半導体微粒子のペーストは、粒子の再凝集を防ぐため、アセチルアセトン、塩酸、硝酸、酢酸等の酸、トリトンX−100等の界面活性剤、キレート剤等を添加することができる。また、製膜性を向上させる目的で増粘剤を添加することも有効な手段である。この時加える増粘剤としては、ポリエチレングリコール、ポリビニルアルコール等の高分子、エチルセルロース等の増粘剤等が挙げられる。 In order to prevent re-aggregation of particles, a dispersion of semiconductor particles or a paste of semiconductor particles obtained by a sol-gel method or the like, an acid such as acetylacetone, hydrochloric acid, nitric acid or acetic acid, or a surfactant such as Triton X-100 Chelating agents and the like can be added. It is also an effective means to add a thickener for the purpose of improving the film forming property. Examples of the thickener added at this time include polymers such as polyethylene glycol and polyvinyl alcohol, and thickeners such as ethyl cellulose.
半導体微粒子は、塗布した後に粒子同士を電子的にコンタクトさせ、膜強度の向上や基板との密着性を向上させるために焼成、マイクロ波照射、電子線照射、レーザー光照射、あるいはプレス処理を行うことが好ましい。これらの処理は単独で行ってもあるいは二種類以上組み合わせて行ってもよい。焼成する場合、焼成温度の範囲に特に制限は無いが、温度を上げ過ぎると基板の抵抗が高くなったり、溶融することもあるため、30〜700℃が好ましく、100〜600℃がより好ましい。また、焼成時間にも特に制限は無いが、10分〜10時間が好ましい。焼成後、半導体微粒子の表面積の増大や、光増感化合物から半導体微粒子への電子注入効率を高める目的で、例えば四塩化チタン水溶液を用いた化学メッキや三塩化チタン水溶液を用いた電気化学的メッキ処理を行っても良い。 Semiconductor fine particles are subjected to baking, microwave irradiation, electron beam irradiation, laser light irradiation, or press treatment in order to bring the particles into electronic contact with each other after coating and to improve film strength and adhesion to the substrate. It is preferable. These treatments may be performed alone or in combination of two or more. When firing, the range of the firing temperature is not particularly limited, but if the temperature is raised too much, the resistance of the substrate may be increased or the substrate may be melted, so 30 to 700 ° C is preferable, and 100 to 600 ° C is more preferable. Moreover, although there is no restriction | limiting in particular also in baking time, 10 minutes-10 hours are preferable. After firing, for example, chemical plating using titanium tetrachloride aqueous solution or electrochemical plating using titanium trichloride aqueous solution for the purpose of increasing the surface area of semiconductor fine particles or increasing the efficiency of electron injection from the photosensitizing compound to the semiconductor fine particles. Processing may be performed.
直径が数十nmの半導体微粒子を焼結等によって積層した膜は、多孔質状態を形成する。このナノ多孔構造は、非常に高い表面積を持ち、その表面積はラフネスファクターを用いて表すことが出来る。このラフネスファクターは、基板に塗布した半導体微粒子の面積に対する多孔質内部の実面積を表す数値である。従って、ラフネスファクターは大きいほど好ましいが、電子輸送層の膜厚との関係もあり、本発明においては20以上であることが好ましい。 A film in which semiconductor fine particles having a diameter of several tens of nanometers are stacked by sintering or the like forms a porous state. This nanoporous structure has a very high surface area, which can be expressed using a roughness factor. This roughness factor is a numerical value representing the actual area inside the porous body relative to the area of the semiconductor fine particles applied to the substrate. Accordingly, the roughness factor is preferably as large as possible, but is also preferably 20 or more in the present invention because of the relationship with the film thickness of the electron transport layer.
また、電子輸送層のインピーダンスを低減させる目的で導電助剤を添加しても良い。マイクロ波照射は、電子輸送層形成側から照射しても、裏側から照射しても構わない。照射時間には特に制限が無いが、1時間以内で行うことが好ましい。プレス処理は、100kg/cm2以上が好ましく、1000kg/cm2が更に好ましい。プレスする時間は特に制限が無いが、1時間以内で行うことが好ましい。また、プレス処理時に熱を加えても構わない。 Moreover, you may add a conductive support agent in order to reduce the impedance of an electron carrying layer. Microwave irradiation may be performed from the electron transport layer forming side or from the back side. Although there is no restriction | limiting in particular in irradiation time, It is preferable to carry out within 1 hour. The press treatment is preferably 100 kg / cm 2 or more, more preferably 1000 kg / cm 2 . There is no particular limitation on the pressing time, but it is preferably performed within 1 hour. Further, heat may be applied during the pressing process.
光変換効率のさらなる向上のため、電子輸送層に重ねて光増感化合物を吸着させてもよい。光増感化合物は使用される励起光により光励起される化合物であれば特に限定されないが、具体的には以下の化合物が挙げられる。
特表平7−500630号公報、特開平10−233238号公報、特開2000−26487号公報、特開2000−323191号公報、特開2001−59062号公報等に記載の金属錯体化合物、特開平10−93118号公報、特開2002−164089号公報、特開2004−95450号公報に記載のクマリン化合物、同特開2004−95450号公報に記載のポリエン化合物、特開2003−264010号公報、特開2004−63274号公報、特開2004−115636号公報、特開2004−200068号、特開2004−235052号公報に記載のインドリン型化合物、特開平11−86916号公報、特開平11−214730号公報、特開2000−106224号公報、特開2001−76773号公報、特開2003−7359号公報等に記載のシアニン色素、特開平11−214731号公報、特開平11−238905号公報、特開2001−52766号公報、特開2001−76775号公報、特開2003−7360号等に記載メロシアニン色素、特開平10−92477号公報、特開平11−273754号公報、特開平11−273755号公報、特開2003−31273号等に記載の9−アリールキサンテン化合物、特開平10−93118号公報、特開2003−31273号等に記載のトリアリールメタン化合物、特開平9−199744号公報、特開平10−233238号公報、特開平11−204821号公報、特開平11−265738号公報等に記載のフタロシアニン化合物、ポルフィリン化合物等を挙げることができる。特にこの中で、金属錯体化合物、クマリン化合物、ポリエン化合物、インドリン化合物を用いることが好ましく、さらには前記一般式(6)〜(10)の光増感化合物がより好ましい。
In order to further improve the light conversion efficiency, a photosensitizing compound may be adsorbed on the electron transport layer. The photosensitizing compound is not particularly limited as long as it is a compound that is photoexcited by the excitation light used, and specific examples thereof include the following compounds.
The metal complex compounds described in JP 7-500630 A, JP 10-233238 A, JP 2000-26487 A, JP 2000-323191 A, JP 2001-59062 A, etc. JP-A-10-93118, JP-A-2002-164089, JP-A-2004-95450, Coumarin compounds described in JP-A-2004-95450, polyene compounds described in JP-A-2003-264010, JP Indoline type compounds described in JP-A-2004-63274, JP-A-2004-115636, JP-A-2004-200068, and JP-A-2004-235052, JP-A-11-86916, JP-A-11-214730 JP, 2000-106224, JP 2001-7777 Cyanine dyes described in JP-A No. 2003-7359, JP-A No. 11-214731, JP-A No. 11-238905, JP-A No. 2001-52766, JP-A No. 2001-76775, 9-arylxanthene compounds described in JP 2003-7360 A, JP-A-10-92477, JP-A-11-273754, JP-A-11-273755, JP-A 2003-31273, etc. , JP-A-10-93118, JP-A-2003-31273, etc., triarylmethane compounds, JP-A-9-199744, JP-A-10-233238, JP-A-11-204821, The phthalocyanine compounds and porphyrin compounds described in JP-A-11-265738 It can be mentioned. In particular, it is preferable to use a metal complex compound, a coumarin compound, a polyene compound, and an indoline compound, and more preferable are the photosensitizing compounds represented by the general formulas (6) to (10).
前記一般式(6)〜(10)の光増感化合物の具体例は、下記構造式(16)〜(58)に挙げることができ、具体例中の炭素−炭素二重結合は、E体、Z体の何れであっても構わない。また、これらの色素は少なくとも1種、または2種以上の混合として用いることができる。 Specific examples of the photosensitizing compounds of the general formulas (6) to (10) can be listed in the following structural formulas (16) to (58), and the carbon-carbon double bond in the specific examples is an E-form. Any of the Z bodies may be used. Moreover, these pigment | dyes can be used as at least 1 type, or 2 or more types of mixture.
電子輸送層に光増感化合物を吸着させる方法としては、光増感化合物溶液中あるいは分散液中に半導体微粒子を含有する電子集電電極を浸漬する方法、溶液あるいは分散液を電子輸送層に塗布して吸着させる方法を用いることができる。前者の場合、浸漬法、ディップ法、ローラ法、エアーナイフ法等を用いることができ、後者の場合は、ワイヤーバー法、スライドホッパー法、エクストルージョン法、カーテン法、スピン法、スプレー法等を用いることができる。 As a method of adsorbing the photosensitizing compound to the electron transport layer, a method of immersing an electron current collecting electrode containing semiconductor fine particles in a photosensitizing compound solution or dispersion, or applying a solution or dispersion to the electron transport layer Then, a method of adsorbing can be used. In the former case, dipping method, dipping method, roller method, air knife method, etc. can be used, and in the latter case, wire bar method, slide hopper method, extrusion method, curtain method, spin method, spray method, etc. Can be used.
光増感化合物を吸着させる際、縮合剤を併用してもよい。縮合剤は、無機物表面に物理的あるいは化学的に光増感化合物を結合すると思われる触媒的作用をするもの、または化学量論的に作用し、化学平衡を有利に移動させるものの何れであってもよい。更に、縮合助剤としてチオール、あるいはヒドロキシ化合物を添加してもよい。 When adsorbing the photosensitizing compound, a condensing agent may be used in combination. The condensing agent is either a catalytic agent that seems to physically or chemically bind the photosensitizing compound to the inorganic surface, or a stoichiometric agent that favorably moves the chemical equilibrium. Also good. Furthermore, a thiol or a hydroxy compound may be added as a condensation aid.
光増感化合物を溶解、あるいは分散する溶媒は、水、メタノール、エタノール、あるいはイソプロピルアルコール等のアルコール系溶媒、アセトン、メチルエチルケトン、あるいはメチルイソブチルケトン等のケトン系溶媒、ギ酸エチル、酢酸エチル、あるいは酢酸n−ブチル等のエステル系溶媒、ジエチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキソラン、あるいはジオキサン等のエーテル系溶媒、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、あるいはN−メチル−2−ピロリドン等のアミド系溶媒、ジクロロメタン、クロロホルム、ブロモホルム、ヨウ化メチル、ジクロロエタン、トリクロロエタン、トリクロロエチレン、クロロベンゼン、o−ジクロロベンゼン、フルオロベンゼン、ブロモベンゼン、ヨードベンゼン、あるいは1−クロロナフタレン等のハロゲン化炭化水素系溶媒、n−ペンタン、n−ヘキサン、n−オクタン、1,5−ヘキサジエン、シクロヘキサン、メチルシクロヘキサン、シクロヘキサジエン、ベンゼン、トルエン、o−キシレン、m−キシレン、p−キシレン、エチルベンゼン、あるいはクメン等の炭化水素系溶媒を挙げることができ、これらは単独、あるいは2種以上の混合として用いることができる。 Solvents for dissolving or dispersing the photosensitizing compound are water, methanol, ethanol, alcohol solvents such as isopropyl alcohol, ketone solvents such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, ethyl formate, ethyl acetate, or acetic acid. Ester solvents such as n-butyl, ether solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, or N-methyl-2-pyrrolidone Amido solvents, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromoben Halogenated hydrocarbon solvents such as ethylene, iodobenzene or 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o Examples include hydrocarbon solvents such as -xylene, m-xylene, p-xylene, ethylbenzene, and cumene, and these can be used alone or as a mixture of two or more.
これらを用い、光増感化合物を吸着する際の温度としては、−50℃以上、200℃以下が好ましい。また、この吸着は攪拌しながら行っても構わない。攪拌する場合の方法としては、スターラー、ボールミル、ペイントコンディショナー、サンドミル、アトライター、ディスパーザー、あるいは超音波分散等が挙げられるが、これらに限定されるものではない。吸着に要する時間は、5秒以上、1000時間以下が好ましく、10秒以上、500時間以下がより好ましく、1分以上、150時間が更に好ましい。 The temperature at which the photosensitizing compound is adsorbed using these is preferably −50 ° C. or higher and 200 ° C. or lower. Further, this adsorption may be performed while stirring. Examples of the stirring method include, but are not limited to, a stirrer, a ball mill, a paint conditioner, a sand mill, an attritor, a disperser, and ultrasonic dispersion. The time required for adsorption is preferably 5 seconds or more and 1000 hours or less, more preferably 10 seconds or more and 500 hours or less, and further preferably 1 minute or more and 150 hours.
前述のように本発明の光電変換素子は、例えば、電子輸送層が酸化物半導体からなり、該電子輸送層上に光増感化合物を吸着(担持)させ、かつ、ホール輸送層が前記一般式(1)で表される高分子材料、及び少なくとも1種以上の前記一般式(1B)、一般式(2)、一般式(3)、一般式(4)、一般式(5)で表される化合物を含有する溶液を湿式製膜法により塗布形成して構成することができる。 As described above, in the photoelectric conversion element of the present invention, for example, the electron transport layer is made of an oxide semiconductor, the photosensitizing compound is adsorbed (supported) on the electron transport layer, and the hole transport layer has the general formula. The polymer material represented by (1) and at least one of the general formula (1B), general formula (2), general formula (3), general formula (4), and general formula (5) A solution containing the above compound can be applied and formed by a wet film forming method.
すなわち、本発明の光電変換素子は、前記電子集電電極上に電子輸送層を形成し、該電子輸送層に光増感化合物を担持させ、次いで前記一般式(1)で表される高分子材料及び少なくとも1種以上の前記一般式(1B)、一般式(2)、一般式(3)、一般式(4)、一般式(5)で表される化合物を含有する溶液を用いて湿式製膜法によりホール輸送層を塗布積層し、多孔化処理を施した後に該ホール輸送層に接してホール集電電極を形成することにより製造することができる。 That is, in the photoelectric conversion element of the present invention, an electron transport layer is formed on the electron collecting electrode, a photosensitizing compound is supported on the electron transport layer, and then the polymer material represented by the general formula (1) And at least one kind of the general formula (1B), the general formula (2), the general formula (3), the general formula (4), and a solution containing a compound represented by the general formula (5) It can be manufactured by coating and laminating a hole transport layer by a film method, forming a hole collecting electrode in contact with the hole transport layer after performing a porous treatment.
本発明の光電変換素子は、例えば、太陽電池及び太陽電池を用いた電源装置に応用できる。応用例としては従来から太陽電池やそれを用いた電源装置を利用している機器類であれば、いずれのものでも可能である。例えば電子卓上計算機や腕時計用の太陽電池に用いてもよいが、本発明の光電変換素子の特徴を活用する一例として、携帯電話、電子手帳、電子ペーパー等の電源装置が挙げられる。また充電式や乾電池式の電気器具の連続使用時間を長くするための補助電源として用いることもできる。 The photoelectric conversion element of this invention is applicable to the power supply device using a solar cell and a solar cell, for example. As an application example, any device can be used as long as it has conventionally used a solar cell or a power supply device using the solar cell. For example, although it may be used for an electronic desk calculator or a solar cell for a wristwatch, examples of utilizing the characteristics of the photoelectric conversion element of the present invention include power supply devices such as a mobile phone, an electronic notebook, and electronic paper. It can also be used as an auxiliary power source for extending the continuous use time of a rechargeable or dry battery type electric appliance.
以下、実施例により本発明を具体的に説明するが、本発明の実施の形態はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, embodiment of this invention is not limited to these Examples.
(実施例1)
以下の条件で、高分子材料(重合体1)の合成、酸化チタン半導体電極の作製、光電変換素子の作製を行い、評価した。
Example 1
Under the following conditions, synthesis of a polymer material (polymer 1), production of a titanium oxide semiconductor electrode, and production of a photoelectric conversion element were performed and evaluated.
[重合体1の合成]
下記反応式(F7)により高分子化合物(重合体1)を合成した。
[Synthesis of Polymer 1]
A polymer compound (polymer 1) was synthesized according to the following reaction formula (F7).
すなわち、100ml四つ口フラスコに、上記のジアルデヒド0.852g(2.70mmol)及びジホスホネート1.525g(2.70mmol)を入れ、窒素置換してテトラヒドロフラン75mlを加えた。この溶液にカリウムt−ブトキシドの1.0mol dm−3テトラヒドロフラン溶液6.75ml(6.75mmol)を滴下し室温で2時間撹拌した後、ベンジルホスホン酸ジエチル及びベンズアルデヒドを順次加え、さらに2時間撹拌した。酢酸およそ1mlを加えて反応を終了し、溶液を水洗した。溶媒を減圧留去した後、テトラヒドロフラン及びメタノールを用いて再沈澱による精製を行ない、重合体1を1.07g得た。収率73%であった。元素分析値(計算値);C:84.25%(84.02%)、H:8.20%(7.93%)、N:2.33%(2.45%)。
示差走査熱量測定から求めたガラス転移温度は116.9℃であった。ゲルろ過クロマトグラフィー(GPC)により測定したポリスチレン換算の数平均分子量は8500、重量平均分子量は20000であった。
That is, 0.852 g (2.70 mmol) of the above dialdehyde and 1.525 g (2.70 mmol) of diphosphonate were placed in a 100 ml four-necked flask, and nitrogen substitution was performed and 75 ml of tetrahydrofuran was added. To this solution, 6.75 ml (6.75 mmol) of a 1.0 mol dm -3 tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred at room temperature for 2 hours, and then diethyl benzylphosphonate and benzaldehyde were sequentially added, followed by further stirring for 2 hours. . About 1 ml of acetic acid was added to terminate the reaction, and the solution was washed with water. After the solvent was distilled off under reduced pressure, purification by reprecipitation was performed using tetrahydrofuran and methanol to obtain 1.07 g of polymer 1. The yield was 73%. Elemental analysis value (calculated value); C: 84.25% (84.02%), H: 8.20% (7.93%), N: 2.33% (2.45%).
The glass transition temperature determined from differential scanning calorimetry was 116.9 ° C. The number average molecular weight in terms of polystyrene measured by gel filtration chromatography (GPC) was 8500, and the weight average molecular weight was 20000.
[酸化チタン半導体電極の作製]
チタニウムテトラ−n−プロポキシド2ml、酢酸4ml、イオン交換水1ml、ポリビニルピロリン0.8g、2−プロパノール40mlを混合し、FTOガラス基板上にスピンコートし、室温で乾燥後、空気中、450℃で1時間焼成した。焼成して得た電極上に再度、同一溶液を用いてスピンコートし、空気中、450℃で1時間焼成した。
次いで、酸化チタン(日本アエロジル社製P−25)3g、アセチルアセトン0.2g、界面活性剤(和光純薬製ポリオキシエチレンオクチルフェニルエーテル)0.3gを水5.5g、エタノール1.0gと共にビーズミル処理により12時間分散を施した。得られた分散液にポリエチレングリコール(#20,000)1.2gを加えてペーストを作製した。このペーストを、上記で得た電極上に膜厚3μmになるように塗布し、室温で乾燥後、空気中、500℃で1時間焼成した。
[Production of titanium oxide semiconductor electrode]
Titanium tetra-n-propoxide 2 ml,
Next, 3 g of titanium oxide (P-25 manufactured by Nippon Aerosil Co., Ltd.), 0.2 g of acetylacetone, and 0.3 g of surfactant (polyoxyethylene octylphenyl ether manufactured by Wako Pure Chemical Industries, Ltd.) together with 5.5 g of water and 1.0 g of ethanol are bead milled. Dispersion was carried out for 12 hours by treatment. 1.2 g of polyethylene glycol (# 20,000) was added to the obtained dispersion to prepare a paste. This paste was applied on the electrode obtained above so as to have a film thickness of 3 μm, dried at room temperature, and then fired in air at 500 ° C. for 1 hour.
[光電変換素子の作製]
上記酸化チタン半導体電極を、ルテニウム錯体であるN719色素[シス−ビス(イソチオシアナート)ビス(2,2‘−ビピリジル−4,4’−ジカルボキシレート)ルテニウム(II)−ビス−テトラ−n−ブチルアンモニウム]のアセトニトリル/t−ブタノール(体積比1:1)混合溶液中に室温で2日間、暗所にて静置して色素を吸着させた。
高分子化合物(重合体1)90重量部、及び下記構造式(a)の化合物10重量部からなる混合物の塩化メチレン溶液(固形分濃度10%)にトリフルオロメタンスルホニルイミドリチウム(27mM)、トリス(4−ブロモフェニル)アミニウム(0.2mM)、4−t−ブチルピリジン(0.11M)を加え、得られた溶液をキャスト法により、先に作製した電極付の光増感化合物を担持した酸化チタン半導体上に導入した。室温で30分、次いで温風乾燥機で80℃、30分乾燥させた。この上に、対極として金を真空蒸着して光電変換素子を作製した。
[Production of photoelectric conversion element]
The titanium oxide semiconductor electrode was replaced with an N719 dye [cis-bis (isothiocyanato) bis (2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium (II) -bis-tetra-n which is a ruthenium complex. -Butylammonium] in an acetonitrile / t-butanol (volume ratio 1: 1) mixed solution was allowed to stand in the dark at room temperature for 2 days to adsorb the dye.
To a methylene chloride solution (solid content concentration 10%) of a mixture comprising 90 parts by weight of a polymer compound (Polymer 1) and 10 parts by weight of the compound of the following structural formula (a), trifluoromethanesulfonylimide lithium (27 mM), Tris ( 4-Bromophenyl) aminium (0.2 mM), 4-t-butylpyridine (0.11 M) was added, and the resulting solution was oxidized by the cast method to carry the photosensitized compound with an electrode prepared earlier. Introduced on titanium semiconductor. It was dried at room temperature for 30 minutes and then with a hot air dryer at 80 ° C. for 30 minutes. On top of this, gold was vacuum-deposited as a counter electrode to produce a photoelectric conversion element.
〔評価〕
上記により作製した光電変換素子について疑似太陽光照射下(AM1.5、100mW/cm2)で光電変換特性を評価した。その結果、光電変換特性は;開放電圧=0.82V、短絡電流密度3.1mA/cm2、形状因子=0.62、変換効率=1.58%という優れた特性を示した。
[Evaluation]
The photoelectric conversion characteristics of the photoelectric conversion element produced as described above were evaluated under simulated sunlight irradiation (AM1.5, 100 mW / cm 2 ). As a result, the photoelectric conversion characteristics were as follows: open circuit voltage = 0.82 V, short circuit current density 3.1 mA / cm 2 , form factor = 0.62, conversion efficiency = 1.58%.
(実施例2)
実施例1の重合体1に代えて、具体例(A−03)に示した構造式の高分子材料80重量部とし、構造式(a)の化合物を20重量部に変えて、混合物として用いた以外は、実施例1と同様の方法により、光電変換素子を作製した。
作製した光電変換素子の疑似太陽光照射下(AM1.5、100mW/cm2)における光電変換特性を実施例1と同様に評価した。その結果、光電変換特性は;開放電圧=0.85V、短絡電流密度3.9mA/cm2、形状因子=0.59、変換効率=1.96%という優れた特性を示した。
(Example 2)
Instead of the polymer 1 of Example 1, 80 parts by weight of the polymer material having the structural formula shown in the specific example (A-03) was used, and the compound of the structural formula (a) was changed to 20 parts by weight to be used as a mixture. A photoelectric conversion element was produced in the same manner as in Example 1 except that.
The photoelectric conversion characteristics of the produced photoelectric conversion element under pseudo-sunlight irradiation (AM1.5, 100 mW / cm 2 ) were evaluated in the same manner as in Example 1. As a result, the photoelectric conversion characteristics were as follows: open circuit voltage = 0.85V, short circuit current density 3.9 mA / cm 2 , form factor = 0.59, conversion efficiency = 1.96%.
(実施例3)
実施例1の重合体1に代えて、具体例(A−07)に示した構造式の高分子材料70重量部とし、構造式(a)の化合物を30重量部に変えて、混合物として用いた以外は、実施例1と同様の方法により、光電変換素子を作製した。
作製した光電変換素子の疑似太陽光照射下(AM1.5、100mW/cm2)における光電変換特性を実施例1と同様に評価した。その結果、光電変換特性は;開放電圧=0.90V、短絡電流密度3.8mA/cm2、形状因子=0.60、変換効率=2.05%という優れた特性を示した。
(Example 3)
Instead of the polymer 1 of Example 1, 70 parts by weight of the polymer material having the structural formula shown in the specific example (A-07) is used, and the compound of the structural formula (a) is changed to 30 parts by weight to be used as a mixture. A photoelectric conversion element was produced in the same manner as in Example 1 except that.
The photoelectric conversion characteristics of the produced photoelectric conversion element under pseudo-sunlight irradiation (AM1.5, 100 mW / cm 2 ) were evaluated in the same manner as in Example 1. As a result, the photoelectric conversion characteristics were as follows; open circuit voltage = 0.90 V, short circuit current density 3.8 mA / cm 2 , form factor = 0.60, conversion efficiency = 2.05%.
(実施例4)
実施例1の重合体1に代えて、具体例(A−12)に示した構造式の高分子材料70重量部とし、構造式(a)の化合物を30重量部に変えて、混合物として用いた以外は、実施例1と同様の方法により、光電変換素子を作製した。
作製した光電変換素子の疑似太陽光照射下(AM1.5、100mW/cm2)における光電変換特性を実施例1と同様に評価した。その結果、光電変換特性は;開放電圧=0.81V、短絡電流密度3.9mA/cm2、形状因子=0.58、変換効率=1.83%という優れた特性を示した。
Example 4
Instead of the polymer 1 of Example 1, 70 parts by weight of the polymer material having the structural formula shown in the specific example (A-12) is used, and the compound of the structural formula (a) is changed to 30 parts by weight to be used as a mixture. A photoelectric conversion element was produced in the same manner as in Example 1 except that.
The photoelectric conversion characteristics of the produced photoelectric conversion element under pseudo-sunlight irradiation (AM1.5, 100 mW / cm 2 ) were evaluated in the same manner as in Example 1. As a result, the photoelectric conversion characteristics were as follows: open circuit voltage = 0.81V, short circuit current density 3.9 mA / cm 2 , form factor = 0.58, conversion efficiency = 1.83%.
(実施例5)
実施例1の重合体1に代えて、具体例(A−14)に示した構造式の高分子材料60重量部とし、構造式(a)の化合物を40重量部に変えて、混合物として用いた以外は、実施例1と同様の方法により、光電変換素子を作製した。
作製した光電変換素子の疑似太陽光照射下(AM1.5、100mW/cm2)における光電変換特性を実施例1と同様に評価した。その結果、光電変換特性は;開放電圧=0.82V、短絡電流密度3.6mA/cm2、形状因子=0.59、変換効率=1.74%という優れた特性を示した。
(Example 5)
Instead of the polymer 1 of Example 1, 60 parts by weight of the polymer material having the structural formula shown in the specific example (A-14) was used, and the compound of the structural formula (a) was changed to 40 parts by weight to be used as a mixture. A photoelectric conversion element was produced in the same manner as in Example 1 except that.
The photoelectric conversion characteristics of the produced photoelectric conversion element under pseudo-sunlight irradiation (AM1.5, 100 mW / cm 2 ) were evaluated in the same manner as in Example 1. As a result, the photoelectric conversion characteristics were as follows: open circuit voltage = 0.82 V, short circuit current density 3.6 mA / cm 2 , form factor = 0.59, conversion efficiency = 1.74%.
(比較例1)
実施例1の重合体1に代えて、PEDOT−PSSを用いた以外は、実施例1と同様の方法により、光電変換素子を作製した。
作製した光電変換素子の疑似太陽光照射下(AM1.5、100mW/cm2)における光電変換特性を実施例1と同様に評価した。その結果、光電変換特性は;開放電圧=0.45V、短絡電流密度1.1mA/cm2、形状因子=0.48、変換効率=0.24%という結果であった。
(Comparative Example 1)
A photoelectric conversion element was produced in the same manner as in Example 1 except that PEDOT-PSS was used in place of the polymer 1 in Example 1.
The photoelectric conversion characteristics of the produced photoelectric conversion element under pseudo-sunlight irradiation (AM1.5, 100 mW / cm 2 ) were evaluated in the same manner as in Example 1. As a result, the photoelectric conversion characteristics were as follows: open circuit voltage = 0.45V, short circuit current density 1.1 mA / cm 2 , form factor = 0.48, conversion efficiency = 0.24%.
実施例1〜実施例5の結果から明らかなように、ホール輸送層の構成物質として上記高分子材料と一般式(1B)で表される化合物(低分子化合物)を含有する本発明の光電変換素子は、比較例に比べていずれも優れた光電変換特性を示す。そして、本発明の光電変換素子は、生産性にも優れ、完全固体型で高性能の光電変換特性を示すことから、太陽電池として用いることが可能でる。 As is clear from the results of Examples 1 to 5, the photoelectric conversion of the present invention containing the above-described polymer material and the compound represented by the general formula (1B) (low molecular compound) as the constituent material of the hole transport layer All of the elements exhibit excellent photoelectric conversion characteristics as compared with the comparative example. And since the photoelectric conversion element of this invention is excellent also in productivity, and shows a high-performance photoelectric conversion characteristic with a complete solid type, it can be used as a solar cell.
(実施例6)
実施例1で合成した重合体1を用い、以下の条件で酸化チタン半導体電極の作製、光電変換素子の作製を行い評価した。
[酸化チタン半導体電極の作製]
チタニウムテトラ−n−プロポキシド2ml、酢酸4ml、イオン交換水1ml、2−プロパノール40mlを混合し、FTOガラス基板上にスピンコートし、室温で乾燥後、空気中450℃で30分間焼成した。再度同一溶液を用いて、得た電極上にスピンコートし、空気中450℃で30分間焼成し、緻密な電子輸送層を形成した。
酸化チタン(石原産業製ST−21)3g、アセチルアセトン0.2g、界面活性剤(和光純薬製ポリオキシエチレンオクチルフェニルエーテル)0.3gを水5.5g、エタノール1.0gと共にビーズミル処理を12時間施した。得られた分散液にポリエチレングリコール(#20,000)0.9gを加えてペーストを作製した。このペーストを、上記緻密な電子輸送層上に膜厚3μmになるように塗布し、室温で乾燥後、空気中450℃で30分間焼成し、多孔質状の電子輸送層を形成した。
(Example 6)
Using the polymer 1 synthesized in Example 1, a titanium oxide semiconductor electrode and a photoelectric conversion element were prepared and evaluated under the following conditions.
[Production of titanium oxide semiconductor electrode]
Titanium tetra-n-propoxide (2 ml), acetic acid (4 ml), ion exchange water (1 ml), and 2-propanol (40 ml) were mixed, spin-coated on an FTO glass substrate, dried at room temperature, and baked at 450 ° C. for 30 minutes in air. Using the same solution again, the obtained electrode was spin-coated and baked in air at 450 ° C. for 30 minutes to form a dense electron transport layer.
Titanium oxide (ST-21 manufactured by Ishihara Sangyo) 3 g, 0.2 g acetylacetone, 0.3 g surfactant (polyoxyethylene octylphenyl ether manufactured by Wako Pure Chemical Industries) 0.3 g water and 1.0 g ethanol were subjected to bead mill treatment 12 Time was given. 0.9 g of polyethylene glycol (# 20,000) was added to the resulting dispersion to prepare a paste. This paste was applied on the dense electron transport layer so as to have a film thickness of 3 μm, dried at room temperature, and then baked in air at 450 ° C. for 30 minutes to form a porous electron transport layer.
[光電変換素子の作製]
上記酸化チタン半導体電極を、ルテニウム錯体として0.5mMに調整したN719色素[シス−ビス(イソチオシアナート)ビス(2,2’−ビピリジル−4,4’−ジカルボキシレート)ルテニウム(II)−ビス−テトラ−n−ブチルアンモニウム]のアセトニトリル/t−ブタノール(体積比1:1)混合溶液中に室温で2日間、暗所にて静置して光増感化合物を吸着させた。
重合体1、90重量部、および例示化合物(B−05)10重量部からなる混合物のクロロベンゼン溶液(固形分濃度10%)にトリフルオロメタンスルホニルイミドリチウム(27mM)、ヘキサクロロアンチモン酸トリス(4−ブロモフェニル)アミニウム(0.2mM)、4−t−ブチルピリジン(0.11M)を加え、得られた溶液は室温、大気圧下でキャスト法を用いて上記電極上に導入した。室温で3時間、次いで温風乾燥機で80℃、1.5時間乾燥させ、ホール輸送層を形成した。この上に、対極として金を真空蒸着して光電変換素子を作製した。
[Production of photoelectric conversion element]
N719 dye [cis-bis (isothiocyanato) bis (2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium (II) −] prepared by adjusting the titanium oxide semiconductor electrode to 0.5 mM as a ruthenium complex. The photosensitized compound was adsorbed in a mixed solution of bis-tetra-n-butylammonium] in acetonitrile / t-butanol (volume ratio 1: 1) at room temperature for 2 days in the dark.
To a chlorobenzene solution (solid concentration 10%) of a mixture consisting of 90 parts by weight of polymer 1 and 10 parts by weight of exemplary compound (B-05), lithium trifluoromethanesulfonylimide (27 mM), tris (4-bromohexachloroantimonate) Phenyl) aminium (0.2 mM) and 4-t-butylpyridine (0.11 M) were added, and the resulting solution was introduced onto the electrode using a casting method at room temperature and atmospheric pressure. It was dried at room temperature for 3 hours and then with a hot air dryer at 80 ° C. for 1.5 hours to form a hole transport layer. On top of this, gold was vacuum-deposited as a counter electrode to produce a photoelectric conversion element.
〔評価〕
上記光電変換素子の疑似太陽光照射下(AM1.5、100mW/cm2)における光電変換効率は、開放電圧=0.85V、短絡電流密度3.2mA/cm2、形状因子=0.58、変換効率=1.58%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
[Evaluation]
The photoelectric conversion efficiency of the photoelectric conversion element under pseudo-sunlight irradiation (AM1.5, 100 mW / cm 2 ) is as follows: open-circuit voltage = 0.85 V, short-circuit current density 3.2 mA / cm 2 , form factor = 0.58, conversion efficiency = 1.58 % Excellent characteristics. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例7)
実施例6における重合体1の代りに、具体例(A−03)に示した構造式の高分子材料80重量部、および例示化合物(B−05)20重量部からなる混合物を用いた以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.85V、短絡電流密度3.3mA/cm2、形状因子=0.58、変換効率=1.62%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 7)
Instead of the polymer 1 in Example 6, a mixture comprising 80 parts by weight of the polymer material having the structural formula shown in the specific example (A-03) and 20 parts by weight of the exemplary compound (B-05) was used. A photoelectric conversion element was produced in the same manner as in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.85 V, the short-circuit current density was 3.3 mA / cm 2 , the form factor was 0.58, and the conversion efficiency was 1.62%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例8)
実施例6における重合体1の代りに、具体例(A−07)に示した構造式の高分子材料70重量部、および例示化合物(B−05)30重量部からなる混合物を用いた以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.85V、短絡電流密度3.3mA/cm2、形状因子=0.58、変換効率=1.62%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 8)
Instead of the polymer 1 in Example 6, a mixture comprising 70 parts by weight of the polymer material having the structural formula shown in the specific example (A-07) and 30 parts by weight of the exemplary compound (B-05) was used. A photoelectric conversion element was produced in the same manner as in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.85 V, the short-circuit current density was 3.3 mA / cm 2 , the form factor was 0.58, and the conversion efficiency was 1.62%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例9)
実施例6における重合体1の代りに、具体例(A−12)に示した構造式の高分子材料70重量部、および例示化合物(B−05)30重量部からなる混合物を用いた以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.84V、短絡電流密度3.4mA/cm2、形状因子=0.59、変換効率=1.69%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
Example 9
Instead of the polymer 1 in Example 6, a mixture composed of 70 parts by weight of the polymer material having the structural formula shown in the specific example (A-12) and 30 parts by weight of the exemplary compound (B-05) was used. A photoelectric conversion element was produced in the same manner as in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.84 V, the short-circuit current density was 3.4 mA / cm 2 , the form factor was 0.59, and the conversion efficiency was 1.69%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例10)
実施例6における重合体1の代りに、具体例(A−14)に示した構造式の高分子材料60重量部、および例示化合物(B−05)40重量部からなる混合物を用いた以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.80V、短絡電流密度3.6mA/cm2、形状因子=0.58、変換効率=1.67%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 10)
Instead of the polymer 1 in Example 6, a mixture composed of 60 parts by weight of the polymer material having the structural formula shown in the specific example (A-14) and 40 parts by weight of the exemplary compound (B-05) was used. A photoelectric conversion element was produced in the same manner as in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.80 V, the short-circuit current density was 3.6 mA / cm 2 , the form factor was 0.58, and the conversion efficiency was 1.67%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例11)
実施例6における重合体1の代りに、具体例(A−18)に示した構造式の高分子材料60重量部、および例示化合物(B−05)40重量部からなる混合物を用いた以外は、実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.83V、短絡電流密度3.8mA/cm2、形状因子=0.56、変換効率=1.77%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 11)
Instead of the polymer 1 in Example 6, a mixture composed of 60 parts by weight of the polymer material having the structural formula shown in the specific example (A-18) and 40 parts by weight of the exemplary compound (B-05) was used. A photoelectric conversion element was produced by the same method as in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.83 V, the short-circuit current density was 3.8 mA / cm 2 , the form factor was 0.56, and the conversion efficiency was 1.77%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例12)
実施例6における例示化合物(B−05)の代りに、例示化合物(B−33)40重量部、および重合体1の代りに、具体例(A−14)に示した構造式の高分子材料60重量部からなる混合物を用いた以外は、実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.83V、短絡電流密度3.5mA/cm2、形状因子=0.58、変換効率=1.68%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 12)
In place of the exemplified compound (B-05) in Example 6, 40 parts by weight of the exemplified compound (B-33) and a polymer material having the structural formula shown in the specific example (A-14) in place of the polymer 1 A photoelectric conversion element was produced in the same manner as in Example 6 except that a mixture composed of 60 parts by weight was used.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.83 V, the short-circuit current density was 3.5 mA / cm 2 , the form factor was 0.58, and the conversion efficiency was 1.68%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例13)
実施例6における例示化合物(B−05)の代りに、例示化合物(B−51)40重量部、および重合体1の代りに、具体例(A−14)に示した構造式の高分子材料60重量部からなる混合物を用いた以外は、実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.83V、短絡電流密度3.5mA/cm2、形状因子=0.58、変換効率=1.68%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 13)
Instead of Exemplified Compound (B-05) in Example 6, 40 parts by weight of Exemplified Compound (B-51) and the polymer material having the structural formula shown in Specific Example (A-14) instead of Polymer 1 A photoelectric conversion element was produced in the same manner as in Example 6 except that a mixture composed of 60 parts by weight was used.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.83 V, the short-circuit current density was 3.5 mA / cm 2 , the form factor was 0.58, and the conversion efficiency was 1.68%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例14)
実施例6における例示化合物(B−05)の代りに、例示化合物(B−59)40重量部、および重合体1の代りに、具体例(A−14)に示した構造式の高分子材料60重量部からなる混合物を用いた以外は、実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.80V、短絡電流密度3.3mA/cm2、形状因子=0.59、変換効率=1.56%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 14)
Instead of the exemplified compound (B-05) in Example 6, 40 parts by weight of the exemplified compound (B-59), and a polymer material having the structural formula shown in the specific example (A-14) instead of the polymer 1 A photoelectric conversion element was produced in the same manner as in Example 6 except that a mixture composed of 60 parts by weight was used.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.80 V, the short-circuit current density was 3.3 mA / cm 2 , the form factor was 0.59, and the conversion efficiency was 1.56%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例15)
実施例6におけるN719色素の吸着を行わなかった以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.88V、短絡電流密度1.6mA/cm2、形状因子=0.55、変換効率=0.77%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 15)
A photoelectric conversion element was produced in the same manner as in Example 6 except that N719 dye was not adsorbed in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.88 V, the short-circuit current density was 1.6 mA / cm 2 , the form factor was 0.55, and the conversion efficiency was 0.77%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例16)
実施例6におけるトリフルオロメタンスルホニルイミドリチウム、ヘキサクロロアンチモン酸トリス(4−ブロモフェニル)アミニウム、4−t−ブチルピリジンを加えなかった以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.82V、短絡電流密度3.3mA/cm2、形状因子=0.59、変換効率=1.60%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 16)
A photoelectric conversion element was produced in the same manner as in Example 6 except that trifluoromethanesulfonylimide lithium, tris (4-bromophenyl) aminium hexachloroantimonate, and 4-t-butylpyridine in Example 6 were not added.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.82 V, the short-circuit current density was 3.3 mA / cm 2 , the form factor was 0.59, and the conversion efficiency was 1.60%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例17)
実施例6におけるトリフルオロメタンスルホニルイミドリチウム(27mM)の代りに、ヨウ化リチウム(27mM)を加えた以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.82V、短絡電流密度3.5mA/cm2、形状因子=0.59、変換効率=1.69%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 17)
A photoelectric conversion device was produced in the same manner as in Example 6 except that lithium iodide (27 mM) was added instead of trifluoromethanesulfonylimide lithium (27 mM) in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.82 V, the short-circuit current density was 3.5 mA / cm 2 , the form factor was 0.59, and the conversion efficiency was 1.69%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例18)
実施例6におけるヘキサクロロアンチモン酸トリス(4−ブロモフェニル)アミニウム(0.2mM)のかわりに、ヨウ素(0.2mM)を加えた以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.75V、短絡電流密度3.8mA/cm2、形状因子=0.58、変換効率=1.65%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 18)
A photoelectric conversion element was produced in the same manner as in Example 6 except that iodine (0.2 mM) was added instead of tris (4-bromophenyl) aminium (0.2 mM) hexachloroantimonate in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.75 V, the short-circuit current density was 3.8 mA / cm 2 , the form factor was 0.58, and the conversion efficiency was 1.65%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例19)
実施例6におけるトリフルオロメタンスルホニルイミドリチウム(27mM)の代りに、ヨウ化1,2−ジメチル−3−n−プロピルイミダゾリニウム(27mM)を加えた以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.80V、短絡電流密度3.7mA/cm2、形状因子=0.56、変換効率=1.66%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
Example 19
In the same manner as in Example 6 except that 1,2-dimethyl-3-n-propylimidazolinium iodide (27 mM) was added instead of trifluoromethanesulfonylimide lithium (27 mM) in Example 6, A conversion element was produced.
The obtained photoelectric conversion device was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.80 V, the short-circuit current density was 3.7 mA / cm 2 , the form factor was 0.56, and the conversion efficiency was 1.66%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例20)
実施例6におけるN719色素の代りに、例示化合物(25)で示した光増感化合物を用いた以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.78V、短絡電流密度4.1mA/cm2、形状因子=0.58、変換効率=1.85%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 20)
A photoelectric conversion element was produced in the same manner as in Example 6 except that the photosensitizing compound shown as the exemplary compound (25) was used instead of the N719 dye in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.78 V, the short-circuit current density was 4.1 mA / cm 2 , the form factor was 0.58, and the conversion efficiency was 1.85%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例21)
実施例6におけるN719色素の代りに、例示化合物(32)で示した光増感化合物を用いた以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.75V、短絡電流密度2.7mA/cm2、形状因子=0.55、変換効率=1.11%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 21)
A photoelectric conversion element was produced in the same manner as in Example 6 except that the photosensitizing compound shown as the exemplary compound (32) was used instead of the N719 dye in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.75 V, the short-circuit current density was 2.7 mA / cm 2 , the form factor was 0.55, and the conversion efficiency was 1.11%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例22)
実施例6におけるN719色素の代りに、例示化合物(40)で示した光増感化合物を用いた以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.89V、短絡電流密度2.7mA/cm2、形状因子=0.60、変換効率=1.44%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 22)
A photoelectric conversion element was produced in the same manner as in Example 6 except that the photosensitizing compound shown by the exemplary compound (40) was used instead of the N719 dye in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.89 V, the short-circuit current density was 2.7 mA / cm 2 , the form factor was 0.60, and the conversion efficiency was 1.44%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例23)
実施例6におけるN719色素の代りに、例示化合物(49)で示した光増感化合物を用いた以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.80V、短絡電流密度3.1mA/cm2、形状因子=0.57、変換効率=1.41%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 23)
A photoelectric conversion element was produced in the same manner as in Example 6 except that the photosensitizing compound shown in the exemplified compound (49) was used instead of the N719 dye in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.80 V, the short-circuit current density was 3.1 mA / cm 2 , the form factor was 0.57, and the conversion efficiency was 1.41%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例24)
実施例6においてホール輸送層上に、対極として金蒸着を行わなかった以外は実施例6と同様の方法により、光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.86V、短絡電流密度2.8mA/cm2、形状因子=0.56、変換効率=1.35%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 24)
A photoelectric conversion element was produced in the same manner as in Example 6 except that gold deposition was not performed as a counter electrode on the hole transport layer in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 1. As a result, it was shown that the open circuit voltage was 0.86 V, the short-circuit current density was 2.8 mA / cm 2 , the form factor was 0.56, and the conversion efficiency was 1.35%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例25)
実施例6における室温、大気圧下での条件に代えて、室温、50mmHgの真空下でキャスト法を用いた以外は実施例6と同様の方法により光電変換素子を作製した。
得られた光電変換素子を実施例1と同様に評価したところ、開放電圧=0.89V、短絡電流密度4.1mA/cm2、形状因子=0.59、変換効率=2.15%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 25)
A photoelectric conversion element was produced in the same manner as in Example 6 except that the casting method was used under a vacuum of room temperature and 50 mmHg instead of the conditions at room temperature and atmospheric pressure in Example 6.
When the obtained photoelectric conversion element was evaluated in the same manner as in Example 1, it exhibited excellent characteristics of an open circuit voltage = 0.89 V, a short-circuit current density of 4.1 mA / cm 2 , a form factor = 0.59, and a conversion efficiency = 2.15%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例26)
実施例6における室温、大気圧下での条件に代えて、室温、100mmHgの真空下でキャスト法を用いた以外は実施例6と同様の方法により光電変換素子を作製した。
得られた光電変換素子を実施例6と同様に評価したところ、開放電圧=0.89V、短絡電流密度4.0mA/cm2、形状因子=0.59、変換効率=2.10%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 26)
A photoelectric conversion element was produced in the same manner as in Example 6 except that the casting method was used under a vacuum of room temperature and 100 mmHg instead of the conditions at room temperature and atmospheric pressure in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 6. As a result, it was shown that the open circuit voltage was 0.89 V, the short-circuit current density was 4.0 mA / cm 2 , the form factor was 0.59, and the conversion efficiency was 2.10%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例27)
実施例6における室温、大気圧下での条件に代えて、室温、350mmHgの真空下でキャスト法を用いた以外は実施例6と同様の方法により光電変換素子を作製した。
得られた光電変換素子を実施例6と同様に評価したところ、開放電圧=0.89V、短絡電流密度3.9mA/cm2、形状因子=0.59、変換効率=2.05%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 27)
A photoelectric conversion element was produced in the same manner as in Example 6 except that the casting method was used at room temperature under a vacuum of 350 mmHg instead of the conditions at room temperature and atmospheric pressure in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 6. As a result, it was shown that the open circuit voltage was 0.89 V, the short-circuit current density was 3.9 mA / cm 2 , the form factor was 0.59, and the conversion efficiency was 2.05%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例28)
実施例6における室温、大気圧下での条件に代えて、室温、450mmHgの真空下でキャスト法を用いた以外は実施例6と同様の方法により光電変換素子を作製した。
得られた光電変換素子を実施例6と同様に評価したところ、開放電圧=0.85V、短絡電流密度3.2mA/cm2、形状因子=0.58、変換効率=1.58%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 28)
A photoelectric conversion element was produced in the same manner as in Example 6 except that the casting method was used under a vacuum of 450 mmHg at room temperature instead of the conditions at room temperature and atmospheric pressure in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 6. As a result, it was shown that the open circuit voltage was 0.85 V, the short-circuit current density was 3.2 mA / cm 2 , the form factor was 0.58, and the conversion efficiency was 1.58%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(実施例29)
実施例6における酸化チタン3gの代りに、酸化チタン2.9gとジルコニアテトラ−n−ブトキシド0.1gの混合を用いた以外は実施例6と同様にして光電変換素子を作製した。
得られた光電変換素子を実施例6と同様に評価したところ、開放電圧=0.87V、短絡電流密度3.3mA/cm2、形状因子=0.58、変換効率=1.67%という優れた特性を示した。この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、特性の変化は見出されなかった。
(Example 29)
A photoelectric conversion element was produced in the same manner as in Example 6 except that instead of 3 g of titanium oxide in Example 6, a mixture of 2.9 g of titanium oxide and 0.1 g of zirconia tetra-n-butoxide was used.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 6. As a result, it was shown that the open circuit voltage was 0.87 V, the short-circuit current density was 3.3 mA / cm 2 , the form factor was 0.58, and the conversion efficiency was 1.67%. After this photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, no change in the characteristics was found.
(比較例2)
実施例6における重合体1の代りに、PEDOT−PSSを用いて実施例6と同様に光電変換素子を作製した。
得られた光電変換素子を実施例6と同様に評価したところ、開放電圧=0.45V、短絡電流密度1.1mA/cm2、形状因子=0.48、変換効率=0.24%という結果であり、本発明に比較して劣っていることが明らかである。また、この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、開放電圧=0.41V、短絡電流密度0.3mA/cm2、形状因子=0.27、変換効率=0.033%と特性の劣化が観測された。
(Comparative Example 2)
A photoelectric conversion element was produced in the same manner as in Example 6 using PEDOT-PSS instead of the polymer 1 in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 6. As a result, the open circuit voltage was 0.45 V, the short-circuit current density was 1.1 mA / cm 2 , the form factor was 0.48, and the conversion efficiency was 0.24%. It is clear that it is inferior in comparison. Moreover, this after the photoelectric conversion element 24 hours left in the dark, as a result of measuring photoelectric conversion characteristics under the same conditions, the open-circuit voltage = 0.41 V, the short-circuit current density 0.3 mA / cm 2, the shape factor = 0.27 , Conversion efficiency = 0.033%, characteristic degradation was observed.
(比較例3)
実施例6における重合体1の代りに、ポリ(3−n−ヘキシルチオフェン)(Aldrich製)を用いて実施例6と同様に光電変換素子を作製した。
得られた光電変換素子を実施例6と同様に評価したところ、開放電圧=0.58V、短絡電流密度1.8mA/cm2、形状因子=0.44、変換効率=0.46%という結果であり、本発明に比較して劣っていることが明らかである。また、この光電変換素子を暗所にて24時間静置した後、同様の条件にて光電変換特性を測定した結果、開放電圧=0.52V、短絡電流密度0.02mA/cm2、形状因子=0.22、変換効率=0.0023%と特性の劣化が観測された。
(Comparative Example 3)
A photoelectric conversion element was produced in the same manner as in Example 6 by using poly (3-n-hexylthiophene) (manufactured by Aldrich) instead of the polymer 1 in Example 6.
The obtained photoelectric conversion element was evaluated in the same manner as in Example 6. As a result, the open circuit voltage was 0.58 V, the short-circuit current density was 1.8 mA / cm 2 , the form factor was 0.44, and the conversion efficiency was 0.46%. It is clear that it is inferior in comparison. Further, after the photoelectric conversion element was allowed to stand for 24 hours in a dark place, the photoelectric conversion characteristics were measured under the same conditions. As a result, the open circuit voltage = 0.52 V, the short-circuit current density 0.02 mA / cm 2 , and the form factor = 0.22. , Conversion efficiency = 0.0023%, characteristic degradation was observed.
実施例6〜29の結果から明らかなように、本発明の光電変換素子は、高い変換効率を示す。また、実施例15に示されるように光増感剤が無くても高い変換効率を示すが、光増感剤を吸着することでさらに高い変換効率が得られる。実施例16に示されるようにホール輸送材への添加剤が無い場合でも高い効率を示すが、実施例6に示されるようにホール輸送材に添加することでより高い変換効率が得られる。また、実施例24の結果から明らかなように、本願発明品は対極として金を用いなくても高い効率を得ることが可能であるが、実施例6の結果から明らかなように、金を対極として設けることでより高い変換効率を得ることが可能である。また、本発明の光電変換素子は、実施例6〜29の結果より明らかなように高い耐久性を有していることが分かる。
そして、実施例25〜28の結果に示されるように、本発明の光電変換素子は、大気圧下で製造しても良好な特性を示すが、400mmHg以下の真空下にすることでより高性能な光電変換素子とすることができる。
As is clear from the results of Examples 6 to 29, the photoelectric conversion element of the present invention exhibits high conversion efficiency. Further, as shown in Example 15, high conversion efficiency is exhibited even without a photosensitizer, but higher conversion efficiency can be obtained by adsorbing the photosensitizer. As shown in Example 16, even when there is no additive to the hole transport material, high efficiency is exhibited. However, by adding to the hole transport material as shown in Example 6, higher conversion efficiency can be obtained. As is clear from the results of Example 24, the present invention product can obtain high efficiency without using gold as a counter electrode. However, as is clear from the results of Example 6, the counter electrode of gold is used. It is possible to obtain higher conversion efficiency. Moreover, it turns out that the photoelectric conversion element of this invention has high durability evidently from the result of Examples 6-29.
As shown in the results of Examples 25 to 28, the photoelectric conversion element of the present invention shows good characteristics even when manufactured under atmospheric pressure, but it has higher performance by being under a vacuum of 400 mmHg or less. It can be set as a photoelectric conversion element.
すなわち、本発明の光電変換素子は、生産性にも優れ、完全固体型で高性能の光電変換特性を示すことから、太陽電池として用いることが可能である。この太陽電池は、例えば、携帯電話、電子手帳、電子ペーパー等の電子機器の電源や、充電式あるいは乾電池式の電気器具の補助電源として応用することができる。 That is, the photoelectric conversion element of the present invention is excellent in productivity and exhibits a high-performance photoelectric conversion characteristic with a complete solid type, and thus can be used as a solar cell. This solar cell can be applied, for example, as a power source for electronic devices such as mobile phones, electronic notebooks, and electronic papers, and as an auxiliary power source for rechargeable or dry battery type electric appliances.
1a 基板
1b 基板
2a 電子集電電極
2b ホール集電電極
3 電子輸送層
3a 緻密構造からなる電子輸送層
3b 多孔質構造からなる粒状の電子輸送層
4 ホール輸送層
5 光増感化合物
DESCRIPTION OF SYMBOLS 1a board | substrate 1b board | substrate 2a electron current collection electrode 2b hole current collection electrode 3 electron transport layer 3a electron transport layer which consists of dense structure 3b granular electron transport layer which consists of
Claims (22)
前記ホール輸送層が、下記一般式(1)で表される高分子材料と、少なくとも1種以上の下記一般式(1B)、一般式(2)、一般式(3)、一般式(4)、一般式(5)で表される化合物を含有することを特徴とする光電変換素子。
[(1)式中、Ar1は置換もしくは無置換の芳香族炭化水素基を表し、Ar2、Ar3はそれぞれ独立に置換もしくは無置換の2価の単環式、非縮合多環式または縮合多環式芳香族炭化水素基を表す。Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。]
[式中、nは0または1の整数を表し、Ar’ は置換もしくは無置換のアリール基を表し、R5は水素原子、置換アルキル基を含むアルキル基あるいは置換もしくは無置換のアリール基を表し、R6は水素原子、置換アルキル基を含むアルキル基あるいは置換もしくは無置換のアリール基を表し、Ar’とR5は互いに結合して環を形成してもよい。Aは9−アントリル基または置換もしくは無置換のカルバゾリル基あるいは下記一般式(1B−1)または(1B−2):
〔式中、R50及びR51は水素原子、アルキル基、アルコキシル基、ハロゲン原子または下記一般式(1B−3):
(式中、R52及びR53は置換アルキル基を含むアルキル基、置換または無置換のアリール基を表し、R52及びR53は同一でも別異でもよく、R52及びR53は互いに結合して環を形成してもよい。)で表される基を表す。〕で表される基を表す。]
[(2)式中、R1、R2は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R3は置換もしくは無置換のアルキレン基、置換もしくは無置換の2価の芳香族炭化水素基を表す。R1とR2、R1とR3、あるいはR2とR3は共同で環を形成してもよい。R4は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表す。R5、R6は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R5とR6は共同で環を形成してもよい。]
[(3)式中、R7は置換もしくは無置換のアルキレン基、置換もしくは無置換の2価の芳香族炭化水素基を表す。R8、R9、R10、R11は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R8とR9、R10とR11は共同で環を形成してもよい。]
[(4)式中、R12、R13、R14は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R12とR13、R13とR14、R12とR14は共同で環を形成してもよい。R15は窒素原子、ホウ素原子、アルキリジン基、置換もしくは無置換の3価の芳香族炭化水素基を表す。]
[(5)式中、R16は置換もしくは無置換の4価の芳香族炭化水素基を表す。R17〜R24は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R17とR18、R19とR20、R21とR22、R23とR24は共同で環を形成してもよい。] In a photoelectric conversion element in which an electron transport layer and a hole transport layer are provided between an electron collector electrode and a hole current collector electrode, at least one of which is transparent,
The hole transport layer includes a polymer material represented by the following general formula (1), and at least one or more of the following general formula (1B), general formula (2), general formula (3), and general formula (4). The photoelectric conversion element characterized by containing the compound represented by General formula (5).
[In the formula (1), Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, and Ar 2 and Ar 3 are each independently substituted or unsubstituted divalent monocyclic, non-condensed polycyclic or Represents a condensed polycyclic aromatic hydrocarbon group. Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. ]
[Wherein n represents an integer of 0 or 1, Ar ′ represents a substituted or unsubstituted aryl group, R 5 represents a hydrogen atom, an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group. , R 6 represents a hydrogen atom, an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and Ar ′ and R 5 may be bonded to each other to form a ring. A is a 9-anthryl group, a substituted or unsubstituted carbazolyl group, or the following general formula (1B-1) or (1B-2):
[Wherein, R 50 and R 51 are a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom or the following general formula (1B-3):
(Wherein R 52 and R 53 represent an alkyl group containing a substituted alkyl group, a substituted or unsubstituted aryl group, R 52 and R 53 may be the same or different, and R 52 and R 53 are bonded to each other. And may form a ring). Represents a group represented by the formula: ]
[In the formula (2), R 1 and R 2 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. , R 3 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted divalent aromatic hydrocarbon group. R 1 and R 2 , R 1 and R 3 , or R 2 and R 3 may jointly form a ring. R 4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group. R 5 and R 6 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group, and R 5 and R 6 represent You may form a ring jointly. ]
[In the formula (3), R 7 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted divalent aromatic hydrocarbon group. R 8 , R 9 , R 10 and R 11 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, R 8 and R 9 , and R 10 and R 11 may form a ring together. ]
[In the formula (4), R 12 , R 13 and R 14 are substituted or unsubstituted alkyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heterocyclic rings. Represents a group, and R 12 and R 13 , R 13 and R 14 , and R 12 and R 14 may form a ring together. R 15 represents a nitrogen atom, a boron atom, an alkylidine group, or a substituted or unsubstituted trivalent aromatic hydrocarbon group. ]
[In the formula (5), R 16 represents a substituted or unsubstituted tetravalent aromatic hydrocarbon group. R 17 to R 24 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, R 17 and R 18 , R 19 and R 20 , R 21 and R 22 , and R 23 and R 24 may form a ring together. ]
[(6)、(7)式中、R25〜R31は、水素原子、カルボキシル基、アルコキシカルボキシル基、アリールオキシカルボキシル基、カルボキシル基の4級アンモニウム塩、カルボキシル基の金属塩、スルホン酸、スルホン酸の4級アンモニウム塩、スルホン酸の金属塩、ホスホン酸、ホスホン酸の4級アンモニウム塩、ホスホン酸の金属塩、酸性基を有するアルキル基、酸性基を有するアルケニル基、置換基を有していてもよいアルキル基を表し、同一であっても異なっていてもよい。X1はハロゲン原子、シアノ基、チオシアン酸基、イソシアン酸基を表す。
(8)式中、R32〜R35は、水素原子、アルキル基を表す。Ar7は、2価のビニレン基、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の複素環基を表す。X2は、シアノ基、ニトロ基、ハロゲン原子、置換基を有していてもよいアルキルスルホニル基、置換基を有していてもよいアリールスルホニル基を表す。R36は、水素原子、4級アンモニウム塩を表す。
(9)式中、R37、R38は置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族炭化水素ル基、置換基を有していてもよい複素環基を表す。R38とベンゼン環は共同で環を形成してもよい。R39は、水素原子、4級アンモニウム塩を表す。X3は、シアノ基、ニトロ基、ハロゲン原子、置換基を有していてもよいアルキルスルホニル基、置換基を有していてもよいアリールスルホニル基を表す。sは0〜2の整数を表す。
(10)式中、R40、R41は置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい複素環基を表す。R41とベンゼン環は共同で環を形成してもよい。X4は酸素原子、硫黄原子、セレン原子を表す。X5は酸素原子、硫黄原子、置換基を有していてもよいローダニン環を表す。] The photoelectric conversion element according to claim 8, wherein the photosensitizing compound is a compound selected from at least one of the following general formulas (6) to (10).
[In the formulas (6) and (7), R 25 to R 31 are hydrogen atom, carboxyl group, alkoxycarboxyl group, aryloxycarboxyl group, quaternary ammonium salt of carboxyl group, metal salt of carboxyl group, sulfonic acid, Quaternary ammonium salt of sulfonic acid, metal salt of sulfonic acid, phosphonic acid, quaternary ammonium salt of phosphonic acid, metal salt of phosphonic acid, alkyl group having acidic group, alkenyl group having acidic group, substituent Represents an optionally substituted alkyl group, which may be the same or different. X 1 represents a halogen atom, a cyano group, a thiocyanate group, or an isocyanate group.
In (8), R 32 to R 35 represents a hydrogen atom, an alkyl group. Ar 7 represents a divalent vinylene group, a divalent aromatic hydrocarbon group which may have a substituent, or a divalent heterocyclic group which may have a substituent. X 2 represents a cyano group, a nitro group, a halogen atom, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent. R 36 represents a hydrogen atom or a quaternary ammonium salt.
(9) In the formula, R 37 and R 38 are an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a heterocycle which may have a substituent. Represents a cyclic group. R 38 and the benzene ring may form a ring together. R 39 represents a hydrogen atom or a quaternary ammonium salt. X 3 represents a cyano group, a nitro group, a halogen atom, an alkylsulfonyl group which may have a substituent, or an arylsulfonyl group which may have a substituent. s represents the integer of 0-2.
(10) In the formula, R 40 and R 41 are an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a heterocyclic ring which may have a substituent. Represents a group. R 41 and the benzene ring may form a ring together. X 4 represents an oxygen atom, a sulfur atom, or a selenium atom. X 5 represents an oxygen atom, a sulfur atom, or a rhodanine ring which may have a substituent. ]
[(11)式中、Ar1は置換もしくは無置換の芳香族炭化水素基を表し、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R44、R45はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、x、yはそれぞれ独立に0〜4の整数を表し、R44、R45が各々複数存在する場合には、同一でも別異でもよい。] 16. The photoelectric conversion element according to claim 1, wherein the polymer material represented by the general formula (1) is a polymer material represented by the following general formula (11).
[In the formula (11), Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these have a substituent. May be. R 44 and R 45 each independently represents a halogen atom, a substituted or unsubstituted alkyl group, or an alkoxy group or an alkylthio group, x and y each independently represents an integer of 0 to 4; When a plurality of 44 and R 45 are present, they may be the same or different. ]
[(12)式中、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R44、R45はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、R46はハロゲン原子、置換もしくは無置換の、アルキル基、アルコキシ基、アルキルチオ基、芳香族炭化水素基から選択される基を表す。zは0〜5の整数を表し、x、yはそれぞれ独立に0〜4の整数を表し、R44、R45、R46が各々複数存在する場合には、同一でも別異でもよい。] 16. The photoelectric conversion device according to claim 1, wherein the polymer material represented by the general formula (1) is a polymer material represented by the following general formula (12).
[In the formula (12), Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. R 44 and R 45 each independently represents a halogen atom, a substituted or unsubstituted alkyl group or a group selected from an alkoxy group or an alkylthio group, and R 46 represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group. Represents a group selected from a group, an alkylthio group, and an aromatic hydrocarbon group. z represents an integer of 0 to 5, x and y each independently represents an integer of 0 to 4, and when a plurality of R 44 , R 45 and R 46 are present, they may be the same or different. ]
[(13)式中、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R44、R45、R46、R47、R48、R49はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表す。vは0〜3の整数を表し、w、x、yはそれぞれ独立に0〜4の整数を表し、R44、R45、R46、R47が各々複数存在する場合には、同一でも別異でもよい。] 16. The photoelectric conversion element according to claim 1, wherein the polymer material represented by the general formula (1) is a polymer material represented by the following general formula (13).
[In the formula (13), Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. R 44 , R 45 , R 46 , R 47 , R 48 and R 49 each independently represent a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group. v represents an integer of 0 to 3, w, x and y each independently represents an integer of 0 to 4, and when there are a plurality of R 44 , R 45 , R 46 and R 47 , they may be the same or different. It may be different. ]
[(14)式中、Ar1は置換もしくは無置換の芳香族炭化水素基を表し、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R50、R51、R52、R53はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、r、s、t、uはそれぞれ独立に0 〜4の整数を表し、R50、R51、R52、R53が各々複数存在する場合には、同一でも別異でもよい。] 16. The photoelectric conversion element according to claim 1, wherein the polymer material represented by the general formula (1) is a polymer material represented by the following general formula (14).
[In the formula (14), Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these have a substituent. May be. R 50 , R 51 , R 52 and R 53 each independently represent a halogen atom, a substituted or unsubstituted alkyl group or a group selected from an alkoxy group or an alkylthio group, and r, s, t and u are each independently selected. Represents an integer of 0 to 4, and when there are a plurality of R 50 , R 51 , R 52 and R 53 , they may be the same or different. ]
[(15)式中、Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。R50、R51、R52、R53、R54はそれぞれ独立にハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基から選択される基を表し、qは0〜5の整数を表し、r、s、t、uはそれぞれ独立に0〜4の整数を表し、R50、R51、R52、R53、R54が各々複数存在する場合には、同一でも別異でもよい。] 16. The photoelectric conversion element according to claim 1, wherein the polymer material represented by the general formula (1) is a polymer material represented by the following general formula (15).
[In the formula (15), Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. R 50 , R 51 , R 52 , R 53 and R 54 each independently represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group, and q is an integer of 0 to 5 R, s, t and u each independently represents an integer of 0 to 4, and when there are a plurality of R 50 , R 51 , R 52 , R 53 and R 54 , they may be the same or different. Good. ]
前記電子集電電極上に電子輸送層を形成し、該電子輸送層に光増感化合物を担持させ、次いで下記一般式(1)で表される高分子材料及び少なくとも1種以上の下記一般式(1B)、一般式(2)、一般式(3)、一般式(4)、一般式(5)で表される化合物を含有する溶液を用いて湿式製膜法によりホール輸送層を塗布積層し、多孔化処理を施した後に該ホール輸送層に接してホール集電電極を形成することを特徴とする光電変換素子の製造方法。
[(1)式中、Ar1は置換もしくは無置換の芳香族炭化水素基を表し、Ar2、Ar3はそれぞれ独立に置換もしくは無置換の2価の単環式、非縮合多環式または縮合多環式芳香族炭化水素基を表す。Ar4はベンゼン、チオフェン、ビフェニル、アントラセン、ナフタレンの2価基を表し、これらは置換基を有していてもよい。]
[式中、nは0または1の整数を表し、Ar’ は置換もしくは無置換のアリール基を表し、R5は水素原子、置換アルキル基を含むアルキル基あるいは置換もしくは無置換のアリール基を表し、R6は水素原子、置換アルキル基を含むアルキル基あるいは置換もしくは無置換のアリール基を表し、Ar’とR5は互いに結合して環を形成してもよい。Aは9−アントリル基または置換もしくは無置換のカルバゾリル基あるいは下記一般式(1B−1)または(1B−2):
〔式中、R50及びR51は水素原子、アルキル基、アルコキシル基、ハロゲン原子または下記一般式(1B−3):
(式中、R52及びR53は置換アルキル基を含むアルキル基、置換または無置換のアリール基を表し、R52及びR53は同一でも別異でもよく、R52及びR53は互いに結合して環を形成してもよい。)で表される基を表す。〕で表される基を表す。]
[(2)式中、R1、R2は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R3は置換もしくは無置換のアルキレン基、置換もしくは無置換の2価の芳香族炭化水素基を表す。R1とR2、R1とR3、あるいはR2とR3は共同で環を形成してもよい。R4は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基を表す。R5、R6は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R5とR6は共同で環を形成してもよい。]
[(3)式中、R7は置換もしくは無置換のアルキレン基、置換もしくは無置換の2価の芳香族炭化水素基を表す。R8、R9、R10、R11は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R8とR9、R10とR11は共同で環を形成してもよい。]
[(4)式中、R12、R13、R14は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R12とR13、R13とR14、R12とR14は共同で環を形成してもよい。R15は窒素原子、ホウ素原子、アルキリジン基、置換もしくは無置換の3価の芳香族炭化水素基を表す。]
[(5)式中、R16は置換もしくは無置換の4価の芳香族炭化水素基を表す。R17〜R24は置換もしくは無置換のアルキル基、置換もしくは無置換のアラルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の複素環基を表し、R17とR18、R19とR20、R21とR22、R23とR24は共同で環を形成してもよい。]
In the method for producing a photoelectric conversion element in which an electron transport layer and a hole transport layer are provided between an electron collector electrode and a hole current collector electrode, at least one of which is transparent,
An electron transport layer is formed on the electron current collecting electrode, a photosensitizing compound is supported on the electron transport layer, and then a polymer material represented by the following general formula (1) and at least one of the following general formulas ( 1B), a hole transport layer is applied and laminated by a wet film-forming method using a solution containing a compound represented by general formula (2), general formula (3), general formula (4), or general formula (5). A method for producing a photoelectric conversion element comprising: forming a hole collecting electrode in contact with the hole transport layer after performing a porous treatment.
[In the formula (1), Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group, and Ar 2 and Ar 3 are each independently substituted or unsubstituted divalent monocyclic, non-condensed polycyclic or Represents a condensed polycyclic aromatic hydrocarbon group. Ar 4 represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, and these may have a substituent. ]
[Wherein n represents an integer of 0 or 1, Ar ′ represents a substituted or unsubstituted aryl group, R 5 represents a hydrogen atom, an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group. , R 6 represents a hydrogen atom, an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and Ar ′ and R 5 may be bonded to each other to form a ring. A is a 9-anthryl group, a substituted or unsubstituted carbazolyl group, or the following general formula (1B-1) or (1B-2):
[Wherein, R 50 and R 51 are a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom or the following general formula (1B-3):
(Wherein R 52 and R 53 represent an alkyl group containing a substituted alkyl group, a substituted or unsubstituted aryl group, R 52 and R 53 may be the same or different, and R 52 and R 53 are bonded to each other. And may form a ring). Represents a group represented by the formula: ]
[In the formula (2), R 1 and R 2 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. , R 3 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted divalent aromatic hydrocarbon group. R 1 and R 2 , R 1 and R 3 , or R 2 and R 3 may jointly form a ring. R 4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group. R 5 and R 6 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group, and R 5 and R 6 represent You may form a ring jointly. ]
[In the formula (3), R 7 represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted divalent aromatic hydrocarbon group. R 8 , R 9 , R 10 and R 11 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, R 8 and R 9 , and R 10 and R 11 may form a ring together. ]
[In the formula (4), R 12 , R 13 and R 14 are substituted or unsubstituted alkyl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heterocyclic rings. Represents a group, and R 12 and R 13 , R 13 and R 14 , and R 12 and R 14 may form a ring together. R 15 represents a nitrogen atom, a boron atom, an alkylidine group, or a substituted or unsubstituted trivalent aromatic hydrocarbon group. ]
[In the formula (5), R 16 represents a substituted or unsubstituted tetravalent aromatic hydrocarbon group. R 17 to R 24 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group, R 17 and R 18 , R 19 and R 20 , R 21 and R 22 , and R 23 and R 24 may form a ring together. ]
Priority Applications (1)
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