JPH06177410A - Manufacture of photovoltaic element and its manufacture - Google Patents
Manufacture of photovoltaic element and its manufactureInfo
- Publication number
- JPH06177410A JPH06177410A JP43A JP32673392A JPH06177410A JP H06177410 A JPH06177410 A JP H06177410A JP 43 A JP43 A JP 43A JP 32673392 A JP32673392 A JP 32673392A JP H06177410 A JPH06177410 A JP H06177410A
- Authority
- JP
- Japan
- Prior art keywords
- electron
- phthalocyanine
- donating
- metal
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000126 substance Substances 0.000 claims description 54
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 49
- 239000011368 organic material Substances 0.000 claims description 39
- 239000000049 pigment Substances 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 150000002894 organic compounds Chemical class 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 25
- 238000007740 vapor deposition Methods 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 50
- 238000013086 organic photovoltaic Methods 0.000 abstract description 11
- 239000007772 electrode material Substances 0.000 abstract description 5
- 239000005416 organic matter Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 99
- 239000004065 semiconductor Substances 0.000 description 24
- 230000005684 electric field Effects 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 12
- 230000035945 sensitivity Effects 0.000 description 12
- 230000003595 spectral effect Effects 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 9
- 238000001771 vacuum deposition Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 239000010931 gold Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 6
- SJHHDDDGXWOYOE-UHFFFAOYSA-N oxytitamium phthalocyanine Chemical compound [Ti+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 SJHHDDDGXWOYOE-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- -1 polycyclic aromatic compounds Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 4
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 3
- 229940107698 malachite green Drugs 0.000 description 3
- JFTBTTPUYRGXDG-UHFFFAOYSA-N methyl violet Chemical compound Cl.C1=CC(=NC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JFTBTTPUYRGXDG-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010549 co-Evaporation Methods 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 229930192419 itoside Natural products 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- YLGQLQSDQXOIBI-UHFFFAOYSA-N (29h,31h-phthalocyaninato(2-)-n29,n30,n31,n32)platinum Chemical compound [Pt+2].[N-]1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)[N-]3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 YLGQLQSDQXOIBI-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical class [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- RPQOZSKWYNULKS-UHFFFAOYSA-N 1,2-dicarbamoylperylene-3,4-dicarboxylic acid Chemical compound C1=C(C(O)=O)C2=C(C(O)=O)C(C(=N)O)=C(C(O)=N)C(C=3C4=C5C=CC=C4C=CC=3)=C2C5=C1 RPQOZSKWYNULKS-UHFFFAOYSA-N 0.000 description 1
- DKZYLXIFCGMAOV-UHFFFAOYSA-N 1h-imidazole;naphthalene-1,2,3,4-tetracarboxylic acid Chemical compound C1=CNC=N1.C1=CNC=N1.C1=CC=CC2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 DKZYLXIFCGMAOV-UHFFFAOYSA-N 0.000 description 1
- SRRFBOZZGCGKQP-UHFFFAOYSA-N 1h-imidazole;perylene-1,2,3,4-tetracarboxylic acid Chemical compound C1=CNC=N1.C1=CNC=N1.C=12C3=CC=CC2=CC=CC=1C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C2=C1C3=CC=C2C(=O)O SRRFBOZZGCGKQP-UHFFFAOYSA-N 0.000 description 1
- VHQGURIJMFPBKS-UHFFFAOYSA-N 2,4,7-trinitrofluoren-9-one Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=O)C2=C1 VHQGURIJMFPBKS-UHFFFAOYSA-N 0.000 description 1
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- XPZQBGDNVOHQIS-UHFFFAOYSA-N 2,9-dichloro-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione Chemical compound N1C2=CC=C(Cl)C=C2C(=O)C2=C1C=C(C(=O)C=1C(=CC=C(C=1)Cl)N1)C1=C2 XPZQBGDNVOHQIS-UHFFFAOYSA-N 0.000 description 1
- WKLOSXKZASUWLB-UHFFFAOYSA-N 2,9-dimethoxy-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione Chemical compound N1C2=CC=C(OC)C=C2C(=O)C2=C1C=C(C(=O)C=1C(=CC=C(C=1)OC)N1)C1=C2 WKLOSXKZASUWLB-UHFFFAOYSA-N 0.000 description 1
- TXWSZJSDZKWQAU-UHFFFAOYSA-N 2,9-dimethyl-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione Chemical compound N1C2=CC=C(C)C=C2C(=O)C2=C1C=C(C(=O)C=1C(=CC=C(C=1)C)N1)C1=C2 TXWSZJSDZKWQAU-UHFFFAOYSA-N 0.000 description 1
- BFEJTCHFLJECJN-UHFFFAOYSA-N 4,11-Dichloro-5,12-dihydroquino[2,3-b]acridine-7,14-dione Chemical compound N1C2=C(Cl)C=CC=C2C(=O)C2=C1C=C(C(C=1C=CC=C(C=1N1)Cl)=O)C1=C2 BFEJTCHFLJECJN-UHFFFAOYSA-N 0.000 description 1
- DGWVTMBLTSNMFN-UHFFFAOYSA-N 4,11-dimethyl-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione Chemical compound N1C2=C(C)C=CC=C2C(=O)C2=C1C=C(C(C=1C=CC=C(C=1N1)C)=O)C1=C2 DGWVTMBLTSNMFN-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
- GDALETGZDYOOGB-UHFFFAOYSA-N Acridone Natural products C1=C(O)C=C2N(C)C3=CC=CC=C3C(=O)C2=C1O GDALETGZDYOOGB-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- FZEYVTFCMJSGMP-UHFFFAOYSA-N acridone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3NC2=C1 FZEYVTFCMJSGMP-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 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
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- LBAIJNRSTQHDMR-UHFFFAOYSA-N magnesium phthalocyanine Chemical compound [Mg].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 LBAIJNRSTQHDMR-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YRZZLAGRKZIJJI-UHFFFAOYSA-N oxyvanadium phthalocyanine Chemical compound [V+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 YRZZLAGRKZIJJI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光センサ等にも有用な
光起電力素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photovoltaic element which is also useful as an optical sensor or the like.
【０００２】[0002]
【従来の技術】有機物を能動材料として用いた光起電力
素子が多く研究されている。その目的は、単結晶、多結
晶、アモルファスのＳｉでは達成が困難とされている安
価で毒性のない光起電力素子を開発するためである。2. Description of the Related Art A lot of research has been conducted on photovoltaic devices using organic materials as active materials. The purpose is to develop an inexpensive and non-toxic photovoltaic element, which is difficult to achieve with single crystal, polycrystal, and amorphous Si.
【０００３】光起電力素子は、光エネルギを電気エネル
ギ（電圧×電流）に変換する素子であるため、変換効率
がその主要な評価対象となる。光電流の生成には内部電
界の存在が必要であるが、内部電界を生成する方法とし
ていくつかの素子構成が知られている。能動材料として
有機物を用いた場合、各々の既知の構成での変換効率の
ベストデータは以下の通りである。Since a photovoltaic element is an element that converts light energy into electric energy (voltage × current), its conversion efficiency is a main evaluation target. The generation of photocurrent requires the presence of an internal electric field, but several device configurations are known as methods for generating an internal electric field. When organic substances are used as the active material, the best data of conversion efficiency in each known constitution are as follows.
【０００４】１）ショットキー接合またはＭＩＳ型接合 金属／半導体接合で生じる内部電界を利用したもの。有
機半導体材料としてメロシアニン染料、フタロシアニン
顔料等が報告されている。Ａｌ／メロシアニン／Ａｇ素
子に対する７８ｍＷ／ｃｍ2の白色光照射で変換効率
０．７％（ＶOC＝１．２Ｖ、ＪSC＝１．８ｍＡ／ｃ
ｍ2、ｆｆ＝０．２５）が報告されている。｛Ａ．Ｋ．
ＧｈｏｓｈらＪ．Ａｐｐｌ．Ｐｈｙｓ．４９，５９８２
（１９７８）｝。このタイプの素子に用いられている有
機半導体で変換効率の高いものはｐ型に限定されてい
る。従って、電極材料もＡｌ，Ｉｎ，Ｍｇ等の仕事関数
が低いものが使用される。これらは容易に酸化される。1) Schottky junction or MIS type junction A method utilizing an internal electric field generated in a metal / semiconductor junction. As organic semiconductor materials, merocyanine dyes, phthalocyanine pigments, etc. have been reported. Conversion efficiency of 0.7% (V OC = 1.2 V, J SC = 1.8 mA / c) when white light of 78 mW / cm 2 was irradiated to the Al / merocyanine / Ag element.
m 2 , ff = 0.25) has been reported. {A. K.
Ghosh et al. Appl. Phys. 49,5982
(1978)}. Among the organic semiconductors used in this type of device, those having high conversion efficiency are limited to p-type. Therefore, an electrode material having a low work function such as Al, In, or Mg is used. These are easily oxidized.
【０００５】２）ｎ型無機半導体／ｐ型有機半導体接合
を利用したヘテロｐｎ接合 ｎ型無機半導体／ｐ型有機半導体を接合したときに生じ
る内部電界を利用したもの。ｎ型材料としてＣｄＳ、Ｚ
ｎＯ等が用いられる。ｐ型有機半導体材料としてメロシ
アニン染料、フタロシアニン等が報告されている。ＩＴ
Ｏ／電着ＣｄＳ／塩素化アルミニウムクロルフタロシア
ニン／Ａｕ素子に対する７５ｍＷ／ｃｍ2のＡＭ−２光
照射で変換効率０．２２％（ＶOC＝０．６９Ｖ，ＪSC＝
０．８９ｍＡ／ｃｍ2、ｆｆ＝．０２９）がベストであ
る｛Ａ．ＨｏｒらＡｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，４
２，１５（１９８３）｝。2) Hetero pn junction using n-type inorganic semiconductor / p-type organic semiconductor junction One utilizing an internal electric field generated when n-type inorganic semiconductor / p-type organic semiconductor is joined. CdS, Z as n-type material
nO or the like is used. Merocyanine dyes and phthalocyanines have been reported as p-type organic semiconductor materials. IT
O / electrodeposited CdS / chlorinated aluminum chlorophthalocyanine / Au device irradiated with 75 mW / cm 2 of AM-2 light had a conversion efficiency of 0.22% (V OC = 0.69 V, J SC =
0.89 mA / cm 2 , ff =. 029) is the best {A. Hor et al. Appl. Phys. Lett. , 4
2, 15 (1983)}.
【０００６】３）有機／有機ヘテロｐｎ接合を利用した
もの 電子受容性の有機物と電子供与性の有機物を接合したと
きに生じる電界を利用したもの。3) Utilizing organic / organic hetero pn junction A technique utilizing an electric field generated when an electron-accepting organic substance and an electron-donating organic substance are bonded.
【０００７】前者の有機物としてマラカイトグリーン、
メチルバイオレット、ピリリウム等の染料、フラバンス
ロン、ペリレン顔料等の縮合多環芳香族化合物が報告さ
れており、後者の例として、フタロシアニン顔料、メロ
シアニン染料等が報告されている。Malachite green as the former organic matter,
Dyes such as methyl violet and pyrylium, condensed polycyclic aromatic compounds such as flavanthuron and perylene pigments have been reported, and examples of the latter include phthalocyanine pigments and merocyanine dyes.
【０００８】ＩＴＯ／銅フタロシアニン／ペリレン顔料
／Ａｇ素子に対する７５ｍＷ／ｃｍ2のＡＭ−２光照射
で変換効率０．９５％（ＶOC＝０．４５Ｖ，ＪSC＝２．
３ｍＡ／ｃｍ2，ｆｆ＝０．６５）が報告されている
｛Ｃ．Ｔａｎｇ ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，４
８，１８３（１９８６）｝。この値は有機物を用いた光
起電力素子では最高のものである。また、同じ発明者に
よる特公昭６２−４８７１には、本素子構成で別種のペ
リレン顔料に対して変換効率１％（ＶOC＝０．４４Ｖ，
ＪSC＝３．０ｍＡ／ｃｍ2，ｆｆ＝０．６）が報告され
ている。Conversion efficiency of 0.95% (V OC = 0.45 V, J SC = 2.V) when irradiated with 75 mW / cm 2 of AM-2 light on ITO / copper phthalocyanine / perylene pigment / Ag element.
3 mA / cm 2 , ff = 0.65) has been reported {C. Tang appl. Phys. Lett. , 4
8, 183 (1986)}. This value is the highest in a photovoltaic device using an organic material. Further, Japanese Patent Publication No. 62-4871 by the same inventor discloses that a conversion efficiency of 1% (V OC = 0.44 V,
J SC = 3.0 mA / cm 2 , ff = 0.6) has been reported.
【０００９】有機物を用いた光起電力素子の変換効率
は、無機半導体を用いたものより低い。この要因として
最大のものは短絡光電流（ＪSC）に低さである。変換効
率５％の素子では７５ｍＷ／ｃｍ2の白色光照射に対
し、少なくとも１０ｍＡ／ｃｍ2のＪSCが必要である。
前述のＪSCはそれよりもはるかに低い。この原因は、量
子効率の低さと、分光感度波長域の狭さにある。分光感
度波長は、４００ｎｍからなるべく長波長まで広がって
いることが望ましいが、従来の例は特定波長域に限定さ
れている例が多い。The conversion efficiency of a photovoltaic element using an organic substance is lower than that using an inorganic semiconductor. The biggest cause of this is low short circuit photocurrent (J SC ). A device having a conversion efficiency of 5% requires a J SC of at least 10 mA / cm 2 for 75 mW / cm 2 of white light irradiation.
The aforementioned J SC is much lower than that. The causes are low quantum efficiency and narrow spectral sensitivity wavelength range. The spectral sensitivity wavelength is preferably extended from 400 nm to as long a wavelength as possible, but many conventional examples are limited to a specific wavelength range.
【００１０】また、ｆｆが小さい例が多い。ｆｆの低さ
の原因の一つは有機半導体の示す量子効率が、低電界で
急激に低下することにあるといわれている。従って、こ
の様な低下を来さないような強い内部電界が生成する構
成がｆｆの向上に好ましい。さらに、生成電界がエネル
ギ的な障壁無しにスムーズに電極に到達できる素子構成
がｆｆを大きくする。これらの達成によりＶOCの向上も
図られるが、従来はこれらの点で十分な考慮がなされて
いない例が多かった。In many cases, ff is small. It is said that one of the causes of the low ff is that the quantum efficiency exhibited by the organic semiconductor sharply decreases in a low electric field. Therefore, a configuration in which a strong internal electric field that does not cause such a decrease is generated is preferable for improving ff. Furthermore, an element configuration in which the generated electric field can smoothly reach the electrode without an energy barrier increases ff. Although V OC can be improved by achieving these, in the past, in many cases, sufficient consideration has not been given to these points.
【００１１】更に加えると、報告されている有機光起電
力素子では、電極材料の化学的安定性の点でも問題があ
るものが多い。In addition, most of the reported organic photovoltaic devices also have a problem in terms of chemical stability of electrode materials.
【００１２】以上のような観点から前述の従来技術を眺
める。From the above viewpoint, the above-mentioned prior art is viewed.
【００１３】１）ショットキー接合またはＭＩＳ型接合 ＶOCは大きくとれるが、電極として金属材料が用いられ
ているため、電極の光透過率が低くなる。実際の光透過
率は、よくても３０％、通常は１０％前後である。ま
た、これらの材料は耐酸化性に乏しい。従って、この素
子形態では高い変換効率と、安定した特性を作り出すこ
とは望めない。1) Schottky junction or MIS type junction V OC can be made large, but since a metal material is used for the electrode, the light transmittance of the electrode becomes low. The actual light transmittance is at most 30%, usually around 10%. Also, these materials have poor oxidation resistance. Therefore, it is not possible to expect high conversion efficiency and stable characteristics with this device form.
【００１４】２）無機半導体／有機半導体ヘテロｐｎ接
合 電荷生成は主として有機層でなされるため、分光感度の
制限を受ける。通常、有機層は単一の材料から形成され
るが、４００から例えば８００ｎｍまで強い光吸収をも
つ有機半導体は現在存在しないからである。従って、こ
の素子構成では光入射電極の光透過性や、電極の安定性
の問題はクリアできるが、分光感度領域が狭いため、高
い変換効率は望めない。2) Inorganic semiconductor / organic semiconductor hetero pn junction Since the charge generation is mainly performed in the organic layer, the spectral sensitivity is limited. This is because the organic layer is usually formed of a single material, but there is currently no organic semiconductor having strong light absorption from 400 to 800 nm, for example. Therefore, with this element structure, although the problems of the light transmittance of the light incident electrode and the stability of the electrode can be solved, a high conversion efficiency cannot be expected because the spectral sensitivity region is narrow.
【００１５】３）有機／有機ヘテロｐｎ接合 上記２種の構成と較べ、現在のところ最も望ましいもの
である。透明電極からの光照射が行え、また、２種の材
料で光電荷生成が可能であるため、分光感度も広げるこ
とができる。実際、前述のＴａｎｇによる報告では４５
０〜５５０ｎｍではペリレン系顔料、５５０〜７００ｎ
ｍでは銅フタロシアニンで電荷が生成していることが伺
える。また、ｆｆが他の素子構成と較べ大きいことは、
生成している内部電界が大きいと推定される。しかし、
Ｔａｎｇ氏の技術は次の欠点を有している。3) Organic / organic hetero pn junction Compared to the above two types of structures, it is the most desirable one at present. Light can be irradiated from the transparent electrode, and since photocharges can be generated with two kinds of materials, the spectral sensitivity can be expanded. In fact, the Tang report mentioned above was 45
At 0 to 550 nm, perylene pigment, 550 to 700 n
It can be seen that electric charge is generated by copper phthalocyanine at m. Also, the fact that ff is larger than other element configurations means that
It is estimated that the generated internal electric field is large. But,
Tang's technology has the following drawbacks.
【００１６】１つめは有機層の厚さが薄いため（３００
〜５００Åが望ましいことが特許に記載されている）、
ピンホールの確率が高いことである。我々の実験では、
ピンホールによると思われる２つの電極間の短絡が比較
的高い確率で認められる。Ｔａｎｇ氏の論文の電極面積
は０．１ｃｍ2となっており、実使用での面積（１ｃｍ2
以上が必要）となれば歩留まりの向上が大問題となる。The first is that the organic layer is thin (300
It is stated in the patent that ~ 500Å is desirable),
The probability of pinholes is high. In our experiment,
A relatively high probability of a short circuit between the two electrodes, possibly due to a pinhole, is observed. The electrode area in Mr. Tang's paper is 0.1 cm 2 , which is the actual area (1 cm 2
If the above is required), the improvement of yield becomes a big problem.
【００１７】２つめは電極材料の問題である。彼の発明
では、電極は各々の有機物層とオーミック接触する必要
がある。前述の論文には、有機層を逆転した素子構成で
はＶOCが低下すると書かれている。これはオーミック接
触が損なわれたためと推定される。ところが、オーミッ
ク接触を達成した構成では、金属材料の安定性が問題と
なる。それは、電子受容性の有機物とこの様な接触しう
る金属は仕事関数が低い必要があるからである。実際、
特許中にはＩｎ，Ａｇ，Ｓｎ，Ａｌが例示されている。
これらはすべて酸化され易いものである。The second problem is the electrode material. In his invention, the electrodes need to make ohmic contact with each organic layer. In the above-mentioned paper, it is written that V OC decreases in a device structure in which the organic layer is inverted. This is presumably because the ohmic contact was damaged. However, the stability of the metal material becomes a problem in the configuration in which the ohmic contact is achieved. This is because a metal that can make contact with an electron-accepting organic substance needs to have a low work function. In fact
In the patent, In, Ag, Sn, and Al are exemplified.
All of these are easily oxidized.
【００１８】３つめとして、この電子受容性有機物とし
てはマラカイトグリーン、メチルバイオレット、ピリリ
ウム等の染料、フラバンスロン、ペリレン顔料等の縮合
多環芳香族化合物が報告されており、電子供与性有機物
としてはフタロシアニン顔料、メロシアニン染料等が報
告されている。記されている材料が電子受容性有機物は
短波長領域に分光感度を有し、電子供与性有機物は長波
長領域に分光感度を有しているため積層する組み合わせ
が限定されてしまう。また、前記２種の電子受容性有機
物、電子供与性有機物で光電荷生成が可能であるが、太
陽光に対しては未だ分光感度域が十分とは言えない。Third, as the electron-accepting organic substance, dyes such as malachite green, methyl violet and pyrylium, and condensed polycyclic aromatic compounds such as flavanthrone and perylene pigment have been reported, and as the electron-donating organic substance. Phthalocyanine pigments and merocyanine dyes have been reported. As for the materials described, the electron-accepting organic substance has a spectral sensitivity in the short wavelength region, and the electron-donating organic substance has a spectral sensitivity in the long wavelength region. Further, although photocharges can be generated with the above-mentioned two kinds of electron-accepting organic substances and electron-donating organic substances, it cannot be said that the spectral sensitivity region for sunlight is still sufficient.
【００１９】[0019]
【発明が解決しようとする課題】本発明の目的は、透光
性の高い電極を入射側に使用し、安定性の高い電極材料
を使用することができ、さらに、有機光起電力素子とし
ては分光感度域が広くかつ高い変換効率を与える素子を
提供することにある。The object of the present invention is to use an electrode having a high light-transmitting property on the incident side, and to use an electrode material having a high stability. Furthermore, as an organic photovoltaic element, An object is to provide an element having a wide spectral sensitivity range and high conversion efficiency.
【００２０】[0020]
【課題を解決するための手段】上記目的を達成するた
め、鋭意検討した結果、入射光側が少なくとも一方が透
光性である２つの電極の間に、電子受容性有機物層と電
子供与性有機物層の連続した２つの層からなる部分を含
む光起電力素子、または電子受容性有機物層と電子供与
性有機物層（Ｉ）と前記とは異なる電子供与性有機物層
（II）の連続した３つの層からなる部分を含む光起電力
素子において、この電子供与性有機物層および電子供与
性有機物層（Ｉ）または電子供与性有機物層（II）が、
２種以上の異なる電子供与性物質を含有していることに
より目的が達成できることを見出した。更にこの２種以
上の異なる電子供与性物質の組合せが、フタロシアニン
顔料とキナクリドン顔料または異種のフタロシアニン顔
料同志が好ましく、また更に前記異種のフタロシアニン
顔料の組合せとして、無金属のフタロシアニンまたは
中心金属として２価の金属を有するフタロシアニンと中
心金属として３価の金属を有するフタロシアニン、無
金属のフタロシアニンまたは中心金属として２価の金属
を有するフタロシアニンと中心金属として４価の金属を
有するフタロシアニン、フタロシアニン顔料が中心金
属として３価の金属を有するフタロシアニンと中心金属
として４価の金属を有するフタロシアニンが特に好まし
いことを見出した。加えてこれらの２種以上の異なる電
子供与性物質からなる電子供与性有機物層の形成法とし
て、混合状態からの真空蒸着、それぞれ単独状態からの
真空共蒸着、混晶状態からの真空蒸着が有効であること
を見出し本発明に至った。以下本発明の重要な構成要素
である素子構成、使用材料、作製法等について説明す
る。In order to achieve the above object, as a result of extensive studies, an electron-accepting organic material layer and an electron-donating organic material layer are provided between two electrodes, at least one of which is transparent on the incident light side. Or a photovoltaic device including a portion consisting of two consecutive layers of, or three consecutive layers of an electron-accepting organic compound layer, an electron-donating organic compound layer (I) and an electron-donating organic compound layer (II) different from the above. In the photovoltaic device including the part consisting of, the electron donating organic compound layer and the electron donating organic compound layer (I) or the electron donating organic compound layer (II) are
It has been found that the purpose can be achieved by containing two or more different electron donating substances. Further, the combination of two or more different electron-donating substances is preferably a phthalocyanine pigment and a quinacridone pigment or different phthalocyanine pigments. Further, as a combination of the different phthalocyanine pigments, a metal-free phthalocyanine or a divalent central metal is used. A phthalocyanine having a metal of 3 and a phthalocyanine having a trivalent metal as a central metal, a phthalocyanine having no metal or a phthalocyanine having a divalent metal as a central metal and a phthalocyanine having a tetravalent metal as a central metal, and a phthalocyanine pigment as a central metal It has been found that a phthalocyanine having a trivalent metal and a phthalocyanine having a tetravalent metal as a central metal are particularly preferable. In addition, vacuum deposition from mixed state, vacuum co-deposition from individual state, and vacuum deposition from mixed crystal state are effective methods for forming an electron donating organic material layer composed of two or more different electron donating substances. Therefore, the present invention has been completed. The element structure, materials used, manufacturing method, and the like, which are important constituent elements of the present invention, will be described below.
【００２１】（素子構成）本発明の光起電力素子の１つ
の構成は図１のとおりである。(Element Configuration) One configuration of the photovoltaic element of the present invention is as shown in FIG.
【００２２】ここで支持体は背面電極側にあってもよ
い。また、電子受容性層と電子供与性層の順が逆であっ
てもよい。しかし、好ましいのは図１の態様である。Here, the support may be on the back electrode side. Further, the order of the electron-accepting layer and the electron-donating layer may be reversed. However, the embodiment of FIG. 1 is preferred.
【００２３】また、本発明の別の更に好ましい構成とし
て図２のものが挙げられる。Further, another preferable structure of the present invention is shown in FIG.
【００２４】この構成の特徴は透光性ｎ型無機半導体層
が挿入されたことにある。本層は背面電極側にあっても
よく、この場合には、透光性である必要はなく、また図
１の場合と同様に有機物層の順も反対となる。図２の方
が図１よりも良好な特性を与える。The feature of this structure is that a transparent n-type inorganic semiconductor layer is inserted. This layer may be on the back electrode side, and in this case, it does not need to be translucent, and the order of the organic material layers is opposite as in the case of FIG. FIG. 2 gives better characteristics than FIG.
【００２５】また、本発明の別の態様として図３のもの
が挙げられる。Another embodiment of the present invention is shown in FIG.
【００２６】ここで支持体は背面電極側にあってもよ
い。また、電子受容性層と電子供与性層の順が逆であっ
てもよく、その場合は電子供与性有機物層（II）、電子
供与性有機物層（Ｉ）、電子受容性有機物層の順とな
る。Here, the support may be on the back electrode side. The order of the electron-accepting layer and the electron-donating layer may be reversed, and in that case, the order of the electron-donating organic compound layer (II), the electron-donating organic compound layer (I), and the electron-accepting organic compound layer may be reversed. Become.
【００２７】また、本発明の別の更に好ましい態様とし
て下図のものが挙げられる。Further, another more preferable embodiment of the present invention is shown in the following figure.
【００２８】この構成は図３の素子に透光性ｎ型無機半
導体層が挿入されたものである。本層は背面電極側にあ
ってもよく、この場合には、透光性である必要はなく、
また、図２と同様に有機物層の順も反対となる。In this structure, a translucent n-type inorganic semiconductor layer is inserted in the device shown in FIG. This layer may be on the back electrode side, in which case it need not be translucent,
Further, as in FIG. 2, the order of the organic material layers is opposite.
【００２９】（動作）上記、図１から図４の本素子が光
起電力能を有する理由は、電子受容性有機物層と電子供
与有機物層の界面で両層のフェルミレベルの違いによっ
て生ずる局所的な内部電界に起因している。この内部電
界が働いている部分に光が吸収されることにより電子、
正孔が発生し、それぞれが両電極まで移動し最終的に外
部に電流として取り出される。従って、この界面にいか
に多くの光が到達し吸収されるか、電子受容性有機物層
と電子供与有機物層の間に生ずる内部電界の大きさ等の
キャリア発生能と電子受容性有機物層、電子供与有機物
層の電子及び正孔の移動能及び注入性等が光起電力素子
の変換効率の大きな因子となる。これらは電子受容性有
機物層、電子供与有機物層に使用される材料及びその形
態に大きく左右されるものであるが、現在のところそれ
ぞれの層に適切な材料及び材料の凝集状態、結晶粒径、
膜質等の形態は明確になっていない。(Operation) The reason why the present device shown in FIGS. 1 to 4 has the photovoltaic function is that the local difference is caused by the difference in Fermi level between the electron-accepting organic material layer and the electron-donating organic material layer. Due to a strong internal electric field. The light is absorbed in the part where this internal electric field is working, so that electrons,
Holes are generated, move to both electrodes, and are finally taken out as a current. Therefore, how much light reaches and is absorbed at this interface, the carrier generating ability such as the magnitude of the internal electric field generated between the electron-accepting organic material layer and the electron-donating organic material layer, the electron-accepting organic material layer, and the electron-donating organic material layer. Electron and hole transferability and injection property of the organic material layer are major factors for the conversion efficiency of the photovoltaic device. These are largely dependent on the materials used for the electron-accepting organic material layer and the electron-donating organic material layer and their forms, but at present, suitable materials for each layer and the aggregation state of the materials, crystal grain size,
The morphology such as film quality is not clear.
【００３０】光起電力素子の変換効率（η）は次式によ
って表される。The conversion efficiency (η) of the photovoltaic element is expressed by the following equation.
【００３１】[0031]
【数１】 [Equation 1]
【００３２】上式において、ＶOCは開放時の電圧、ＪSC
は短絡時の電流、ｆｆはフィルファクターと呼ばれる光
照射時の電圧−電流曲線の因子を示す値である。Ｐｉｎ
は入射光エネルギーである。In the above equation, V OC is the voltage when open, J SC
Is a current at the time of short circuit, and ff is a value indicating a factor of a voltage-current curve at the time of light irradiation called a fill factor. Pin
Is the incident light energy.
【００３３】本素子における変換効率の向上は、ＶOC、
ＪSC、ｆｆのそれぞれが増加したことによるものである
が、その理由は現在のところ明らかになっていない。例
えば次のような要因が考えられる。The improvement of the conversion efficiency in the present device, V OC,
This is due to the increase in each of J SC and ff, but the reason for this is not clear at present. For example, the following factors can be considered.
【００３４】１．電子受容性有機物層と連続する電子供
与性有機物層または電子供与性有機物層（Ｉ）として２
種以上の電子供与性有機物を用いた効果、 （ａ）２種の異なる吸収を有する電子供与性有機物によ
り、電子供与性有機物層の光吸収領域が拡大し、これに
ともない分光感度域が広がりキャリア生成量の増加につ
ながった。1. 2 as an electron-donating organic compound layer or an electron-donating organic compound layer (I) continuous with the electron-accepting organic compound layer
Effect of using one or more types of electron-donating organic substances, (a) The electron-donating organic substance having two different kinds of absorption expands the light absorption region of the electron-donating organic substance layer, and the spectral sensitivity region widens accordingly. This led to an increase in production.
【００３５】（ｂ）２種の異なるエネルギーレベルを有
する電子供与性有機物により、１つの電子供与性有機物
が主にキャリア発生を受持ち、他の電子供与性有機物が
キャリア移動を行う機能分離が達成された。これにより
電子供与性有機物層のキャリア分離効率が向上しキャリ
ア生成量の増加につながった。また、キャリア移動能が
上がりキャリアの失活が低減した。(B) By the two electron donating organic substances having different energy levels, one electron donating organic substance mainly takes charge of carrier generation, and another electron donating organic substance carries out carrier separation to achieve the function separation. It was As a result, the carrier separation efficiency of the electron-donating organic layer was improved, leading to an increase in the amount of carriers generated. In addition, carrier mobility was increased and carrier deactivation was reduced.
【００３６】（ｃ）２種の形態が異なる電子供与性有機
物により、電子供与性有機物層の結晶粒径が小さくな
り、膜質が向上し短絡が低減された。(C) The two types of electron-donating organic substances having different morphologies reduced the crystal grain size of the electron-donating organic substance layer, improving the film quality and reducing short circuits.
【００３７】（ｄ）２種の配向性が異なる電子供与性有
機物により、電子供与性有機物層の配向性が変化し、光
の吸収量の増加、移動度の向上がもたらされた。(D) The two types of electron-donating organic materials having different orientations changed the orientation of the electron-donating organic material layer, resulting in an increase in light absorption and an improvement in mobility.
【００３８】（ｅ）２種の結晶形が異なる電子供与性有
機物により、電子供与性有機物層が他の新たな結晶形に
変化し、キャリア生成能が向上した。(E) The two electron-donating organic substances having different crystal forms changed the electron-donating organic substance layer to another new crystal form, and the carrier-forming ability was improved.
【００３９】（ｆ）２種の異なるエネルギーレベルを有
する電子供与性有機物により、２種の電子供与性有機物
間にエネルギー異動が生じ、キャリア生成能が向上し
た。(F) Due to the electron donating organic substances having two different energy levels, energy transfer occurs between the two electron donating organic substances, and the carrier generation ability is improved.
【００４０】２．電気供与性有機物層（II）として２種
以上の電子供与性有機物を用いた効果（ａ）、電子供与
性有機物層（Ｉ）の電子供与性有機物と他の高移動度電
子供与性有機物の２種を用いることで、材料間の接触面
積を拡大し電子供与性有機物層（Ｉ）で発生したキャリ
アを効率よく高移動度電子供与性有機物に注入する。 （ｂ）２種の形態が異なる電子供与性有機物により、電
子供与性有機物層の結晶粒径が小さくなり、膜質が向上
し短絡が低減された。2. Effect of using two or more kinds of electron-donating organic materials as the electron-donating organic material layer (II) (a), electron-donating organic material of the electron-donating organic material layer (I) and other high mobility electron-donating organic material 2 By using the seed, the contact area between the materials is expanded, and the carriers generated in the electron donating organic material layer (I) are efficiently injected into the high mobility electron donating organic material. (B) The two types of electron-donating organic substances having different forms reduced the crystal grain size of the electron-donating organic substance layer, improving the film quality and reducing short circuits.
【００４１】（ｃ）２種の配向性が異なる電子供与性有
機物により、電子供与性有機物層の配向性が変化し、移
動度の向上がもたらされた。(C) The two types of electron-donating organic substances having different orientations changed the orientation of the electron-donating organic substance layer, resulting in improvement of mobility.
【００４２】次に上記電子供与性物質層に用いられる２
種以上の異なる電子供与性物質の組合せ材料について
は、フタロシアニン顔料とキナクリドン顔料が好まし
い。この理由としては以下のことが推測される。Next, 2 used for the above-mentioned electron donating material layer
As the combination material of two or more different electron donating substances, a phthalocyanine pigment and a quinacridone pigment are preferable. The reason for this is presumed to be as follows.
【００４３】フタロシアニン顔料とキナクリドン顔料
は、いずれも高い光導電性を有しており、また正孔移動
度も高い。加えて異なる領域に吸収を有し、分光感度域
の拡大されている可能性が強い。また、アルミニウムク
ロロフタロシアニン、無金属フタロシアニン、銅フタロ
シアニンなど様々なフタロシアニンにおいて、フタロシ
アニンで発生した正孔が障壁なくキナクリドン顔料に注
入されることが確認されており、前記のキャリア発生と
異動の機能分離が達成されている可能性がある。また。
異種のフタロシアニン顔料同志の組合せが好ましい理由
としては、高い光導電性、高移動度以外に、中心金属に
より膜の光吸収波長、結晶粒径、結晶形などの性質が違
っており、組合せにより分光感度域、凝集状態、膜の形
態などの調節が可能であるためと推測される。また、中
心金属の価数が異なる組合せで特に好ましい結果が得ら
れたのは、前記性質がほぼ中心金属の価数により分類さ
れるためであると考えられる。例えば中心金属の価数に
より下記のような性質の違いがある。吸収波長について
は、無金属のフタロシアニン及び銅フタロシアニンなど
の２価のフタロシアニンでは主たる吸収が５７０〜７２
０ｎｍであるのに対し、アルミニウムクロロフタロシア
ニンなどの３価のフタロシアニン及びチタニルフタロシ
アニンなどの４価のフタロシアニンでは６３０〜８５０
ｎｍである。結晶粒径に関しては、銅フタロシアニンな
どの２価のフタロシアニンは、室温の蒸着成膜で柱状の
かなり大きな結晶がみられるのに対し、アルミニウムク
ロロフタロシアニンなどの３価のフタロシアニンでは微
結晶の緻密な膜が得られる。結晶形に関しては、無金属
のフタロシアニン及び銅フタロシアニンなどの２価のフ
タロシアニンは、α型、β型などの分子が揃って凝集し
ているのに対し、アルミニウムクロロフタロシアニンな
どの３価のフタロシアニンでは分子が少しずれて凝集し
ている。Both the phthalocyanine pigment and the quinacridone pigment have high photoconductivity and high hole mobility. In addition, it has absorption in different regions, and there is a strong possibility that the spectral sensitivity region is expanded. Further, it has been confirmed that in various phthalocyanines such as aluminum chlorophthalocyanine, metal-free phthalocyanine, and copper phthalocyanine, holes generated in phthalocyanine are injected into the quinacridone pigment without a barrier, and the above-described carrier generation and transfer functional separation are performed. It may have been achieved. Also.
The reason why the combination of different phthalocyanine pigments is preferable is that, in addition to high photoconductivity and high mobility, the properties such as the light absorption wavelength, crystal grain size, and crystal form of the film differ depending on the central metal. It is presumed that it is possible to control the sensitivity range, aggregation state, film morphology, and the like. Further, it is considered that the reason why particularly preferable results were obtained with the combinations having different valences of the central metal is that the above properties are classified almost by the valence of the central metal. For example, the following properties differ depending on the valence of the central metal. Regarding the absorption wavelength, the main absorption is 570 to 72 for divalent phthalocyanines such as metal-free phthalocyanine and copper phthalocyanine.
While it is 0 nm, it is 630 to 850 for trivalent phthalocyanines such as aluminum chlorophthalocyanine and tetravalent phthalocyanines such as titanyl phthalocyanine.
nm. Regarding the crystal grain size, divalent phthalocyanines such as copper phthalocyanine show columnar fairly large crystals when deposited at room temperature by vapor deposition, whereas trivalent phthalocyanines such as aluminum chlorophthalocyanine give a fine crystalline dense film. Is obtained. Regarding the crystal form, divalent phthalocyanines such as metal-free phthalocyanine and copper phthalocyanine are aggregated with α-type and β-type molecules, whereas trivalent phthalocyanine such as aluminum chlorophthalocyanine is a molecule. Are slightly displaced and aggregated.
【００４４】本発明の前記キナクリドン化合物として
は、無置換キナクリドン、２，９−ジクロルキナクリド
ン、３，１０−ジクロルキナクリドン、４，１１−ジク
ロルキナクリドン、３，４，１０，１１−テトラクロル
キナクリドン、２，４，９，１１−テトラクロルキナク
リドン、１，２，８，９−テトラクロルキナクリドン、
１，２，４，８，９，１１−ヘキサクロルキナクリド
ン、２，４，９，１１−テトラブロムキナクリドン、
２，３，９，１０−テトラブロムキナクリドン、１，
４，８，１１−テトラブロムキナクリドン、２，４，
９，１１−テトラフルオロキナクリドン、１，４，８，
１１−テトラフルオロキナクリドン、２，４，９，１１
−テトラヨードキナクリドン、２，９−ジメチルキナク
リドン、３，１０−ジメチルキナクリドン、４，１１−
ジメチルキナクリドン、３，４，１０，１１−テトラメ
チルキナクリドン、２，４，９，１１−テトラメチルキ
ナクリドン、１，２，８，９−テトラメチルキナクリド
ン、１，４，８，１１−テトラメチルキナクリドン、
２，９−ジメトキシキナクリドン、３，１０−ジメトキ
シキナクリドン、４，１１−ジメトキシキナクリドン、
２，４，９，１１−テトラメトキシキナクリドン、１，
４，８，１１−テトラメトキシキナクリドン等が挙げら
れる。Examples of the quinacridone compound of the present invention include unsubstituted quinacridone, 2,9-dichloroquinacridone, 3,10-dichloroquinacridone, 4,11-dichloroquinacridone, 3,4,10,11-tetrachloro. Quinacridone, 2,4,9,11-tetrachloroquinacridone, 1,2,8,9-tetrachloroquinacridone,
1,2,4,8,9,11-hexachlorquinacridone, 2,4,9,11-tetrabromoquinacridone,
2,3,9,10-tetrabromoquinacridone, 1,
4,8,11-Tetrabromoquinacridone, 2,4
9,11-tetrafluoroquinacridone, 1,4,8,
11-tetrafluoroquinacridone, 2,4,9,11
-Tetraiodoquinacridone, 2,9-dimethylquinacridone, 3,10-dimethylquinacridone, 4,11-
Dimethylquinacridone, 3,4,10,11-tetramethylquinacridone, 2,4,9,11-tetramethylquinacridone, 1,2,8,9-tetramethylquinacridone, 1,4,8,11-tetramethylquinacridone ,
2,9-dimethoxyquinacridone, 3,10-dimethoxyquinacridone, 4,11-dimethoxyquinacridone,
2,4,9,11-tetramethoxyquinacridone, 1,
4,8,11-tetramethoxyquinacridone and the like can be mentioned.
【００４５】本発明の前記フタロシアニン顔料のうち、
中心金属が２価のフタロシアニンとしては、銅フタロシ
アニン、亜鉛フタロシアニン、ニッケルフタロシアニ
ン、白金フタロシアニン、マグネシウムフタロシアニ
ン、塩素化銅フタロシアニン、塩素化亜鉛フタロシアニ
ン、鉄フタロシアニン等がある。中心金属が３価のフタ
ロシアニンとしては、アルミニウムクロロフタロシアニ
ン、アルミニウムフルオロフタロシアニン、アルミニウ
ムブロムフタロシアニン、インジウムクロルフタロシア
ニン、インジウムブロムフタロシアニン、ガリウムクロ
ロフタロシアニン、塩素化アルミニウムクロロフタロシ
アニン等が、また中心金属が４価のフタロシアニンとし
ては、バナジルフタロシアニン、チタニルフタロシアニ
ン等が挙げられる。Among the phthalocyanine pigments of the present invention,
Examples of the phthalocyanine having a divalent central metal include copper phthalocyanine, zinc phthalocyanine, nickel phthalocyanine, platinum phthalocyanine, magnesium phthalocyanine, chlorinated copper phthalocyanine, chlorinated zinc phthalocyanine and iron phthalocyanine. Examples of the phthalocyanine having a trivalent central metal include aluminum chlorophthalocyanine, aluminum fluorophthalocyanine, aluminum bromophthalocyanine, indium chlorophthalocyanine, indium bromophthalocyanine, gallium chlorophthalocyanine, and chlorinated aluminum chlorophthalocyanine, and phthalocyanine having a tetravalent central metal. Examples thereof include vanadyl phthalocyanine and titanyl phthalocyanine.
【００４６】次に上記２種以上の異なる電子供与性物質
からなる電子供与性物質層の形成方法に関しては、混合
状態からの真空蒸着、それぞれ単独状態からの真空共蒸
着、混晶状態からの真空蒸着の３法が特に有効である。
真空蒸着法は、ピンホールのない有機薄膜作製法として
有効であることは既に周知のことである。材料の混合状
態からの真空蒸着法は、蒸着における制御箇所が少なく
操作が簡便で、安価に製造が可能であるという利点を有
している。しかし、蒸発温度の差が大きい場合（例えば
トリフェニルアミン等の低分子電子供与性物質とフタロ
シアニン顔料）、加熱蒸発時に反応が起こる場合（キナ
クリドン顔料とアルミニウムクロロフタロシアニン）は
適していない。それに対し、材料それぞれ単独状態から
の真空共蒸着法は、前記の欠点を克服できるが、蒸着に
おける制御箇所が多く操作が複雑でありコスト的にも前
法を上回ってしまう。一方、混晶状態からの真空蒸着法
は、２種の分子がそのまま一緒に蒸着される可能性があ
り、より分子状に分散された膜形成が可能である。混晶
の作製方法としては、例えば２種の顔料を強酸または強
塩基溶媒に溶解、混合し水に滴下する。混合状態の材料
から昇華精製するなどがある。Next, regarding the method for forming the electron-donating substance layer composed of two or more different electron-donating substances, the vacuum deposition from the mixed state, the vacuum co-deposition from each individual state, and the vacuum from the mixed crystal state are performed. The three methods of vapor deposition are particularly effective.
It is already known that the vacuum vapor deposition method is effective as a method for producing an organic thin film without pinholes. The vacuum vapor deposition method from the mixed state of materials has the advantages that there are few control points in vapor deposition, the operation is simple, and the manufacturing is possible at low cost. However, when the difference in evaporation temperature is large (for example, a low molecular weight electron-donating substance such as triphenylamine and a phthalocyanine pigment), a reaction occurs during heating and evaporation (quinacridone pigment and aluminum chlorophthalocyanine), which is not suitable. On the other hand, the vacuum co-evaporation method from each material alone can overcome the above-mentioned drawbacks, but there are many control points in vapor deposition, the operation is complicated, and the cost exceeds the previous method. On the other hand, in the vacuum vapor deposition method from the mixed crystal state, there is a possibility that two kinds of molecules are vapor-deposited together as they are, and it is possible to form a more molecularly dispersed film. As a method for producing a mixed crystal, for example, two types of pigments are dissolved in a strong acid or strong base solvent, mixed, and added dropwise to water. For example, sublimation purification from materials in a mixed state.
【００４７】さらに、ｎ型無機半導体層の存在により、
ＶOC，ＪSC，ｆｆの改善による変換効率の向上と短絡の
低減が達成される。この様な効果が生じる理由について
は正確には不明であるが以下のことが考えられる。Further, due to the presence of the n-type inorganic semiconductor layer,
By improving V OC , J SC and ff, the conversion efficiency is improved and the short circuit is reduced. The reason why such an effect occurs is not exactly known, but the following may be considered.
【００４８】１）変換効率の向上 ａ）透明電極としては、通常ＩＴＯの様なフェルミレベ
ルが低い材料が用いられる。このため、ｎ型無機半導体
層がない場合、電子受容性有機物層と透明電極との間で
ショットキー接合が形成される。この接合は、電子受容
性有機物層から透明電極へ電子が移動する際にエネルギ
障壁として作用する。ｎ型無機半導体層が存在すると、
透明電極／ｎ型無機半導体層、ｎ型無機半導体層／電子
受容性有機物層の接触は、各々、オーミック接触を達成
し、電子の移動がスムーズになる。1) Improvement of conversion efficiency a) For the transparent electrode, a material having a low Fermi level such as ITO is usually used. Therefore, when there is no n-type inorganic semiconductor layer, a Schottky junction is formed between the electron-accepting organic material layer and the transparent electrode. This junction acts as an energy barrier when electrons move from the electron-accepting organic layer to the transparent electrode. When the n-type inorganic semiconductor layer is present,
The contact between the transparent electrode / n-type inorganic semiconductor layer and the n-type inorganic semiconductor layer / electron-accepting organic material layer achieves ohmic contact, respectively, and the movement of electrons becomes smooth.
【００４９】ｂ）短絡の確率を低くすることができるた
め、有機層の薄膜化が達成され量子効率の向上につなが
る。B) Since the probability of short circuit can be lowered, the organic layer can be made thin, which leads to an improvement in quantum efficiency.
【００５０】ｃ）ｎ型無機半導体層から電子受容性有機
物層へ暗時に電子が供給され、電子受容性有機物層と電
子供与性有機物層の界面に生成する内部電界強度が強化
される。C) Electrons are supplied from the n-type inorganic semiconductor layer to the electron-accepting organic compound layer in the dark, and the internal electric field strength generated at the interface between the electron-accepting organic compound layer and the electron-donating organic compound layer is enhanced.
【００５１】２）短絡の低減 ａ）透明電極層のエッジ部の段差（ＩＴＯを用いると１
０００Å程度以上が普通）がｎ型無機半導体層の存在で
ゆるやかとなり、この部分での両電極間の短絡の確率が
低減する。2) Reduction of short circuit a) Step difference at the edge of the transparent electrode layer (1 when ITO is used)
However, the presence of the n-type inorganic semiconductor layer becomes gradual, and the probability of short circuit between both electrodes at this portion is reduced.
【００５２】ｂ）例えば電子受容性有機物層にピンホー
ルが存在しても、それと接した電子供与性有機物層がｎ
型無機半導体層とｐｎ接合を形成し、電子受容性有機物
層のピンホールの影響を消失させる形となる。電子供与
性有機物層にピンホールが存在する場合も同様の効果
が、背面電極と電子受容性有機物層の間で生じる。この
ため、短絡が観測されづらくなる。B) For example, even if a pinhole is present in the electron-accepting organic compound layer, the electron-donating organic compound layer in contact with the pinhole is n
A pn junction is formed with the type inorganic semiconductor layer to eliminate the effect of pinholes in the electron-accepting organic material layer. Similar effects occur between the back electrode and the electron-accepting organic material layer when pinholes are present in the electron-donating organic material layer. Therefore, it becomes difficult to observe a short circuit.
【００５３】（その他の材料、製法、膜厚） １）透明絶縁支持体 ガラス、プラスチックフィルム等が用いられる。(Other Materials, Manufacturing Method, Film Thickness) 1) Transparent Insulating Support Glass or plastic film is used.
【００５４】２）透明電極 酸化スズインジウム（ＩＴＯ）、酸化スズ、酸化インジ
ウム等が用いられる。好ましい厚さは１００〜１０００
０Å ３）ｎ型半導体層 酸化亜鉛、３価の金属がドープされた酸化亜鉛、Ｃｄ
Ｓ、酸化チタン、リンをドープしたアモルファスシリコ
ン等で酸化亜鉛、ＣｄＳ等が好ましい。厚さは１０〜１
００００Å ４）電子受容性有機物層 ペリレンテトラカルボン酸ジイミド顔料、ペリレンテト
ラカルボン酸ジイミダゾール顔料、多環キノン顔料、ア
ントラキノンアクリドン顔料、ナフタレンテトラカルボ
ン酸ジイミダゾール顔料等の有機顔料、クリスタルバイ
オレット、メチルバイオレット、マラカイトグリーン等
の染料２，４，７−トリニトロフルオレノン、テトラシ
アノキノジメタン、テトラシアノエチレン、ジフェノキ
ノン等のアクセプター これらは蒸着、スピンコート、ディッピングにて製膜さ
れる。薄膜化、均一化には蒸着が好ましい。電子受容性
有機物層では適当な膜厚は５０〜３０００Åである。2) Transparent electrode Indium tin oxide (ITO), tin oxide, indium oxide or the like is used. Preferred thickness is 100-1000
0Å 3) n-type semiconductor layer zinc oxide, zinc oxide doped with trivalent metal, Cd
Amorphous silicon doped with S, titanium oxide, phosphorus, etc., such as zinc oxide and CdS are preferable. Thickness is 10-1
0000Å 4) Electron-accepting organic compound layer Perylene tetracarboxylic acid diimide pigment, perylene tetracarboxylic acid diimidazole pigment, polycyclic quinone pigment, anthraquinone acridone pigment, naphthalene tetracarboxylic acid diimidazole pigment, and other organic pigments, crystal violet, methyl violet , Dyes such as malachite green, 2,4,7-trinitrofluorenone, tetracyanoquinodimethane, tetracyanoethylene, diphenoquinone and the like acceptors. These are formed by vapor deposition, spin coating or dipping. Vapor deposition is preferred for thinning and uniforming. A suitable film thickness for the electron-accepting organic material layer is 50 to 3000Å.
【００５５】５）電子供与性有機物層（Ｉ），（II） 前記のフタロシアニン顔料、キナクリドン顔料以外に以
下のものが挙げられる。希土類ジフタロシアニン、ナフ
タロシアニン顔料、インジゴ、チオインジゴ系顔料（Ｐ
ｉｇｍｅｎｔ Ｂｌｕｅ ６６，Ｐｉｇｍｅｎｔ Ｖｉ
ｏｌｅｔ ３６等）、メロシアニン化合物、シアニン化
合物、スクアリウム化合物等の染料、有機電子写真感光
体で用いられる電荷移動剤（ヒドラゾン化合物、ピラゾ
リン化合物、トリフェニルメタン化合物、トリフェニル
アミン化合物等）、ポリピロール、ポリアニリン、ポリ
チオフェン等の共役系導電性高分子。これらの層は蒸
着、スピンコート、ディッピング等での方法で製膜され
る。この中で、薄膜化、均一化には蒸着が好ましい。膜
厚は電子供与性有機物層が１層の場合５０〜３０００Å
が適当で、２層の場合電子供与性有機物層（Ｉ）では３
０〜３００Åが適当である。厚くなるとＪSCの増大がみ
られず、又薄くなるとその層自体の光吸収効率が落ち、
ＪSCが低下する。電子供与性有機物層（II）では適当な
膜厚は５０〜３０００Åである。5) Electron-donating organic compound layers (I) and (II) In addition to the above-mentioned phthalocyanine pigment and quinacridone pigment, the following are listed. Rare earth diphthalocyanine, naphthalocyanine pigment, indigo, thioindigo pigment (P
igment Blue 66, Pigment Vi
36), dyes such as merocyanine compounds, cyanine compounds, squarylium compounds, charge transfer agents used in organic electrophotographic photoreceptors (hydrazone compounds, pyrazoline compounds, triphenylmethane compounds, triphenylamine compounds, etc.), polypyrrole, polyaniline Conductive polymers such as polythiophene. These layers are formed by a method such as vapor deposition, spin coating and dipping. Among these, vapor deposition is preferable for thinning and uniforming. The film thickness is 50 to 3000 Å when the electron-donating organic layer is one layer.
Is appropriate, and in the case of two layers, it is 3 in the electron-donating organic compound layer (I).
0 to 300Å is suitable. As the thickness increases, J SC does not increase, and as the thickness decreases, the light absorption efficiency of the layer itself decreases.
J SC decreases. In the electron donating organic compound layer (II), a suitable film thickness is 50 to 3000 Å.
【００５６】６）背面電極 Ａｕ，Ｐｔ，Ｎｉ，Ｐｄ，Ｃｕ，Ｃｒ，Ａｇ等の仕事関
数の高い金属、特にＡｕは安定で好ましい。この金属の
膜厚は５０〜３０００Åが好ましい。6) Back electrode A metal having a high work function such as Au, Pt, Ni, Pd, Cu, Cr and Ag, especially Au is stable and preferable. The film thickness of this metal is preferably 50 to 3000 Å.
【００５７】[0057]
【実施例】以下、本発明を実施例によって具体的に説明
する。EXAMPLES The present invention will be specifically described below with reference to examples.
【００５８】実施例１ よく洗浄したＩＴＯガラス（松崎真空製、３０Ω／□）
上に、電子受容性物質であるペリレンテトラカルボン酸
ジメチルイミド顔料（ＰＬ−ＭＥ）を約４００Åの厚さ
で真空蒸着し、次いで電子供与性物質である無金属のフ
タロシアニン（Ｈ2Ｐｃ）３０ｍｇとキナクリドン（Ｑ
Ａ）３０ｍｇを粉末で混合した後モリブデンボートを用
い約４００Åの厚さで真空蒸着により設け、その上に金
を真空蒸着した。ＩＴＯと金がなす面積は０．２５ｃｍ
2とした。２つの電極に銀ペーストにてリード線を取り
付けた。Example 1 Well-cleaned ITO glass (Matsuzaki Vacuum, 30Ω / □)
An electron-accepting substance, perylene tetracarboxylic acid dimethylimide pigment (PL-ME), was vacuum-deposited to a thickness of about 400 Å, and then 30 mg of an electron-donating substance, metal-free phthalocyanine (H 2 Pc) was added. Quinacridone (Q
A) After mixing 30 mg of the powder with a powder, a molybdenum boat was used to provide a thickness of about 400 Å by vacuum vapor deposition, and gold was vacuum vapor deposited thereon. The area formed by ITO and gold is 0.25 cm
2 Lead wires were attached to the two electrodes with silver paste.
【００５９】この素子のＩＴＯ側に、７５ｍＷ／ｃｍ2
の白色光を照射しながら、６ｍＶ／ｓで掃引される電圧
を印加して変換効率を測定したところＶOC＝０．３１
Ｖ，ＪSC＝０．８７ｍＡ／ｃｍ2，ｆｆ＝０．２５とな
り変換効率０．０９０％が得られた。この値は有機光起
電力素子としては大きなものである。また、同様な素子
を１０個作製し特性を測定したところ、７個でこれと同
等の特性が観測された。 比較例１（実施例１に対するもの） 実施例１の電子供与性物質層を無金属のフタロシアニン
（Ｈ2Ｐｃ）単独で約４００Å真空蒸着で設けた以外は
実施例１と同様に素子を作製し、変換効率を測定した。
その結果、ＶOC＝０．１８Ｖ，ＪSC＝０．８５ｍＡ／ｃ
ｍ2，ｆｆ＝０．２２となり変換効率０．０４５％で実
施例１に比べ明らかに低い値であった。また、同様な素
子を１０個作製し特性を測定したところ、７個でＶOCが
０．１Ｖ以下で多くの短絡が観測された。On the ITO side of this element, 75 mW / cm 2
The conversion efficiency was measured by applying a voltage swept at 6 mV / s while irradiating the white light of V oc = 0.31.
V, J SC = 0.87 mA / cm 2 , ff = 0.25, and a conversion efficiency of 0.090% was obtained. This value is large for an organic photovoltaic element. Moreover, when 10 similar devices were manufactured and the characteristics were measured, the same characteristics were observed for 7 of them. Comparative Example 1 (Compared to Example 1) A device was prepared in the same manner as in Example 1 except that the electron donating material layer of Example 1 was provided by vacuum deposition of metal-free phthalocyanine (H 2 Pc) alone at about 400 Å. , The conversion efficiency was measured.
As a result, V OC = 0.18 V, J SC = 0.85 mA / c
Since m 2 and ff = 0.22, the conversion efficiency was 0.045%, which was clearly lower than that in Example 1. Moreover, when 10 similar devices were manufactured and the characteristics were measured, many short circuits were observed when V OC was 0.1 V or less in 7 devices.
【００６０】比較例２（実施例１に対するもの） 実施例１の電子供与性物質層をキナクリドン（ＱＡ）単
独で約４００Å真空蒸着で設けた以外は実施例１と同様
に素子を作製し、変換効率を測定した。その結果、ＶOC
＝０．２９Ｖ，ＪSC＝０．４７ｍＡ／ｃｍ2，ｆｆ＝
０．２６となり変換効率０．０４７％で実施例１に比べ
明らかに低い値であった。また、同様な素子を１０個作
製し特性を測定したところ、５個でＶOCが０．１Ｖ以下
で多くの短絡が観測された。Comparative Example 2 (Compared to Example 1) A device was prepared and converted in the same manner as in Example 1 except that the electron donating material layer of Example 1 was provided by quinacridone (QA) alone by about 400 Å vacuum deposition. The efficiency was measured. As a result, V OC
= 0.29 V, J SC = 0.47 mA / cm 2 , ff =
The value was 0.26 and the conversion efficiency was 0.047%, which was clearly lower than that in Example 1. Moreover, when 10 similar devices were produced and the characteristics were measured, many short circuits were observed when V OC was 0.1 V or less with 5 devices.
【００６１】実施例２ よく洗浄したＩＴＯガラス（松崎真空製、３０Ω／□）
上に基板温度約２５０℃で、導入ガスとしてアルゴンを
用い、ＲＦマグネトロンスパッタ法で、酸化亜鉛を約１
５００Åの厚さで設けた。その上に、電子受容性物質で
あるペリレンテトラカルボン酸ジメチルイミド顔料（Ｐ
Ｌ−ＭＥ）を約４００Åの厚さで真空蒸着し、次いで電
子供与性物質である銅フタロシアニン（ＣｕＰｃ）３０
ｍｇとアルミニウムクロロフタロシアニン（ＡｌＣｌＰ
ｃ）３０ｍｇを粉末で混合した後モリブデンボートを用
い約４００Åの厚さで真空蒸着により設け、その上に金
を真空蒸着した。ＩＴＯと金がなす面積は０．２５ｃｍ
2とした。２つの電極に銀ペーストにてリード線を取り
付けた。Example 2 Well-cleaned ITO glass (Matsuzaki Vacuum, 30Ω / □)
When the substrate temperature is about 250 ° C., argon is used as an introduction gas, and the zinc oxide is about 1 by the RF magnetron sputtering method.
It was provided with a thickness of 500Å. In addition, a perylene tetracarboxylic acid dimethylimide pigment (P
L-ME) is vacuum-deposited to a thickness of about 400Å, and then copper phthalocyanine (CuPc) 30 which is an electron-donating substance is deposited.
mg and aluminum chlorophthalocyanine (AlClP
c) 30 mg of the powder was mixed and then provided by vacuum vapor deposition using a molybdenum boat to a thickness of about 400 Å, and gold was vacuum vapor deposited thereon. The area formed by ITO and gold is 0.25 cm
2 Lead wires were attached to the two electrodes with silver paste.
【００６２】この素子のＩＴＯ側に、７５ｍＷ／ｃｍ2
の白色光を照射しながら、６ｍＶ／ｓで掃引される電圧
を印加して変換効率を測定したところＶOC＝０．４８
Ｖ，ＪSC＝１．９９ｍＡ／ｃｍ2，ｆｆ＝０．４８とな
り変換効率０．６１％が得られた。この値は有機光起電
力素子としては大きなものである。On the ITO side of this element, 75 mW / cm 2
The conversion efficiency was measured by applying a voltage swept at 6 mV / s while irradiating the white light of V oc = 0.48
V, J SC = 1.99 mA / cm 2 , ff = 0.48, and a conversion efficiency of 0.61% was obtained. This value is large for an organic photovoltaic element.
【００６３】比較例３（実施例２に対するもの） 実施例２の電子供与性物質層を銅フタロシアニン（Ｃｕ
Ｐｃ）単独で約４００Å真空蒸着で設けた以外は実施例
２と同様に素子を作製し、変換効率を測定した。その結
果、ＶOC＝０．３１Ｖ，ＪSC＝１．２７ｍＡ／ｃｍ2，
ｆｆ＝０．４７となり変換効率０．２５％で実施例２に
比べ明らかに低い値であった。Comparative Example 3 (Compared to Example 2) The electron donating material layer of Example 2 was replaced with copper phthalocyanine (Cu).
Pc) A device was prepared in the same manner as in Example 2 except that it was provided by vacuum vapor deposition of about 400 Å alone, and the conversion efficiency was measured. As a result, V OC = 0.31 V, J SC = 1.27 mA / cm 2 ,
ff = 0.47, which was a conversion efficiency of 0.25%, which was clearly lower than that of Example 2.
【００６４】比較例４（実施例２に対するもの） 実施例２の電子供与性物質層をアルミニウムクロロフタ
ロシアニン（ＡｌＣｌＰｃ）単独で約４００Å設けた以
外は実施例２と同様に素子を作製し、変換効率を測定し
た。その結果、ＶOC＝０．３９Ｖ，ＪSC＝１．９０ｍＡ
／ｃｍ2，ｆｆ＝０．４０となり、変換効率０．４０％
で実施例２に比べ明らかに低い値であった。Comparative Example 4 (Compared to Example 2) A device was prepared in the same manner as in Example 2 except that the electron donating material layer of Example 2 was provided with about 400 Å of aluminum chlorophthalocyanine (AlClPc) alone, and the conversion efficiency was obtained. Was measured. As a result, V OC = 0.39 V, J SC = 1.90 mA
/ Cm 2 , ff = 0.40, conversion efficiency 0.40%
The value was obviously lower than that in Example 2.
【００６５】実施例３ 実施例１の電子供与性物質層として無金属のフタロシア
ニン（Ｈ2Ｐｃ）１５ｍｇと２，７−ジメチルキナクリ
ドン（ＱＡ−ＭＥ）１５ｍｇを粉末で混合した後モリブ
デンボートを用い約２００Å真空蒸着で設け、続いてそ
の上に２，７−ジメチルキナクリドン（ＱＡ−ＭＥ）を
真空蒸着で約４００Å設けた以外は実施例１と同様に素
子を作製し、変換効率を測定した。その結果、ＶOC＝
０．３６Ｖ，ＪSC＝１．６２ｍＡ／ｃｍ2，ｆｆ＝０．
３８となり変換効率０．３０％が得られた。この値は有
機光起電力素子としては大きなものである。また、同様
な素子を１０個作製し特性を測定したところ、９個でこ
れと同等の特性が観測された。Example 3 As the electron-donating substance layer of Example 1, 15 mg of metal-free phthalocyanine (H 2 Pc) and 15 mg of 2,7-dimethylquinacridone (QA-ME) were mixed in a powder form, and a molybdenum boat was used to mix them. A device was prepared in the same manner as in Example 1 except that 200Å was formed by vacuum vapor deposition, and subsequently, about 400Å of 2,7-dimethylquinacridone (QA-ME) was provided by vacuum vapor deposition, and the conversion efficiency was measured. As a result, V OC =
0.36 V, J SC = 1.62 mA / cm 2 , ff = 0.
38, a conversion efficiency of 0.30% was obtained. This value is large for an organic photovoltaic element. Further, when 10 similar devices were manufactured and the characteristics were measured, the same characteristics were observed in 9 of them.
【００６６】比較例５（実施例３に対するもの） 実施例３の電子供与性物質層として無金属のフタロシア
ニン（Ｈ2Ｐｃ）単独で約２００Å真空蒸着で設け、続
いてその上に２，７−ジメチルキナクリドン（ＱＡ−Ｍ
Ｅ）を真空蒸着で約４００Å設けた以外は実施例１と同
様に素子を作製し、変換効率を測定した。その結果、Ｖ
OC＝０．２５Ｖ，ＪSC＝１．１１ｍＡ／ｃｍ2，ｆｆ＝
０．３５となり変換効率０．１３％で実施例３に比べ明
らかに低い値であった。また、同様な素子を１０個作製
し特性を測定したところ、４個でＶOCが０．１Ｖ以下で
多くの短絡が観測された。Comparative Example 5 (Compared to Example 3) As an electron-donating substance layer of Example 3, metal-free phthalocyanine (H 2 Pc) alone was provided by about 200Å vacuum deposition, and then 2,7- Dimethylquinacridone (QA-M
A device was prepared in the same manner as in Example 1 except that E) was provided by vacuum evaporation to about 400Å, and the conversion efficiency was measured. As a result, V
OC = 0.25V, J SC = 1.11mA / cm 2, ff =
The value was 0.35, and the conversion efficiency was 0.13%, which was clearly lower than that in Example 3. Moreover, when 10 similar devices were manufactured and the characteristics were measured, many short circuits were observed when V OC was 0.1 V or less with 4 devices.
【００６７】実施例４ 実施例２の電子供与性物質層として無金属のフタロシア
ニン（Ｈ2Ｐｃ）と２，７−ジメチルキナクリドン（Ｑ
Ａ−ＭＥ）の同量混合したものを昇華精製して得られた
混晶３０ｍｇをモリブデンボートを用い真空蒸着で約２
００Åの厚さ設け、続いてその上に２，７−ジメチルキ
ナクリドン（ＱＡ−ＭＥ）を真空蒸着で約４００Å設け
た以外は実施例２と同様に素子を作製し、変換効率を測
定した。その結果、ＶOC＝０．５２Ｖ，ＪSC＝１．８８
ｍＡ／ｃｍ2，ｆｆ＝０．５５となり変換効率０．７２
％が得られた。この値は有機光起電力素子としては大き
なものである。Example 4 Metal-free phthalocyanine (H 2 Pc) and 2,7-dimethylquinacridone (Q) were used as the electron-donating substance layer of Example 2.
30 mg of a mixed crystal obtained by sublimation purification of a mixture of the same amount of A-ME) was vacuum-deposited with a molybdenum boat to about 2
A device was prepared in the same manner as in Example 2 except that a thickness of 00Å was provided, and subsequently, about 400Å of 2,7-dimethylquinacridone (QA-ME) was provided by vacuum vapor deposition, and the conversion efficiency was measured. As a result, V OC = 0.52V, J SC = 1.88
mA / cm 2 , ff = 0.55 and conversion efficiency 0.72
%was gotten. This value is large for an organic photovoltaic element.
【００６８】比較例６（実施例４に対するもの） 実施例４の電子供与性物質層として無金属のフタロシア
ニン（Ｈ2Ｐｃ）単独で約２００Å真空蒸着で設け、続
いてその上に２，７−ジメチルキナクリドン（ＱＡ−Ｍ
Ｅ）を真空蒸着で約４００Å設けた以外は実施例２と同
様に素子を作製し、変換効率を測定した。その結果、Ｖ
OC＝０．３７Ｖ，ＪSC＝１．６０ｍＡ／ｃｍ2，ｆｆ＝
０．５２となり変換効率０．４１％で実施例４に比べ明
らかに低い値であった。Comparative Example 6 (Compared to Example 4) As an electron-donating substance layer of Example 4, metal-free phthalocyanine (H 2 Pc) alone was provided by about 200Å vacuum deposition, and then 2,7- Dimethylquinacridone (QA-M
A device was prepared in the same manner as in Example 2 except that E) was provided by vacuum evaporation to about 400Å, and the conversion efficiency was measured. As a result, V
OC = 0.37V, J SC = 1.60mA / cm 2, ff =
The conversion efficiency was 0.52 and the conversion efficiency was 0.41%, which was clearly lower than that in Example 4.
【００６９】実施例５ 実施例２の電子供与性物質層としてチタニルフタロシア
ニン（ＴｉＯＰｃ）１５ｍｇと銅フタロシアニン（Ｃｕ
Ｐｃ）１５ｍｇを粉末で混合した後モリブデンボートを
用い約２００Å真空蒸着で設け、続いてその上に２，７
−ジメチルキナクリドン（ＱＡ−ＭＥ）を真空蒸着で約
４００Å設けた以外は実施例２と同様に素子を作製し、
変換効率を測定した。その結果、ＶOC＝０．５１Ｖ，Ｊ
SC＝２．５０ｍＡ／ｃｍ2，ｆｆ＝０．５３となり変換
効率０．９０％が得られた。この値は有機光起電力素子
としては大きなものである。Example 5 As the electron-donating substance layer of Example 2, 15 mg of titanyl phthalocyanine (TiOPc) and copper phthalocyanine (Cu) were used.
Pc) 15 mg was mixed with the powder, and then about 200Å vacuum deposition was performed using a molybdenum boat, and then 2,7 on it.
-A device was prepared in the same manner as in Example 2 except that about 400 Å of dimethylquinacridone (QA-ME) was formed by vacuum evaporation.
The conversion efficiency was measured. As a result, V OC = 0.51V, J
SC = 2.50 mA / cm 2 , ff = 0.53, and a conversion efficiency of 0.90% was obtained. This value is large for an organic photovoltaic element.
【００７０】比較例７（実施例５に対するもの） 実施例５の電子供与性物質層として銅フタロシアニン
（ＣｕＰｃ）単独で約２００Å真空蒸着で設け、続いて
その上に２，７−ジメチルキナクリドン（ＱＡ−ＭＥ）
を真空蒸着で約４００Å設けた以外は実施例２と同様に
素子を作製し、変換効率を測定した。その結果、ＶOC＝
０．３９Ｖ，ＪSC＝１．６６ｍＡ／ｃｍ2，ｆｆ＝０．
４７となり変換効率０．４１％で実施例５に比べ明らか
に低い値であった。Comparative Example 7 (Compared to Example 5) The electron-donating substance layer of Example 5 was provided by vacuum vapor deposition of copper phthalocyanine (CuPc) alone at about 200Å, and then 2,7-dimethylquinacridone (QA) was formed thereon. -ME)
A device was manufactured in the same manner as in Example 2 except that about 400 Å was formed by vacuum evaporation, and the conversion efficiency was measured. As a result, V OC =
0.39 V, J SC = 1.66 mA / cm 2 , ff = 0.
The conversion efficiency was 47 and the conversion efficiency was 0.41%, which was clearly lower than that in Example 5.
【００７１】実施例６ 実施例２の電子供与性物質層としてチタニルフタロシア
ニン（ＴｉＯＰｃ）を約２００Å真空蒸着で設け、続い
てその上にチタニルフタロシアニン（ＴｉＯＰｃ）と
２，７−ジメチルキナクリドン（ＱＡ−ＭＥ）を別の蒸
発源から同時に蒸発させ、共蒸着により約４００Å設け
た以外は実施例２と同様に素子を作製し、変換効率を測
定した。その結果、ＶOC＝０．４６Ｖ，ＪSC＝２．４６
ｍＡ／ｃｍ2，ｆｆ＝０．５１となり変換効率０．７７
％が得られた。この値は有機光起電力素子としては大き
なものである。Example 6 Titanyl phthalocyanine (TiOPc) was provided as an electron-donating substance layer of Example 2 by vacuum vapor deposition of about 200Å, and then titanyl phthalocyanine (TiOPc) and 2,7-dimethylquinacridone (QA-ME) were formed thereon. 2) was simultaneously evaporated from another evaporation source, and a device was prepared in the same manner as in Example 2 except that about 400 Å was provided by co-evaporation, and the conversion efficiency was measured. As a result, V OC = 0.46 V, J SC = 2.46
mA / cm 2 , ff = 0.51 and conversion efficiency 0.77
%was gotten. This value is large for an organic photovoltaic element.
【００７２】比較例８（実施例５，６に対するもの） 実施例５の電子供与性物質層としてチタニルフタロシア
ニン（ＴｉＯＰｃ）単独で約２００Å真空蒸着で設け、
続いてその上に２，７−ジメチルキナクリドン（ＱＡ−
ＭＥ）を真空蒸着で約４００Å設けた以外は実施例２と
同様に素子を作製し、変換効率を測定した。その結果、
ＶOC＝０．４１Ｖ，ＪSC＝１．８７ｍＡ／ｃｍ2，ｆｆ
＝０．４３となり変換効率０．４４％で実施例５及び６
に比べ明らかに低い値であった。Comparative Example 8 (Compared with Examples 5 and 6) Titanyl phthalocyanine (TiOPc) alone was provided as an electron-donating substance layer of Example 5 by vacuum deposition of about 200Å,
Subsequently, 2,7-dimethylquinacridone (QA-
A device was prepared in the same manner as in Example 2 except that (ME) was provided by vacuum evaporation to about 400Å, and the conversion efficiency was measured. as a result,
V OC = 0.41 V, J SC = 1.87 mA / cm 2 , ff
= 0.43, and the conversion efficiency is 0.44%.
It was clearly lower than
【００７３】[0073]
【発明の効果】以上説明した本発明の光起電力素子の効
果を要約すると以下のとおりである。 １．電子受容性有機物層と電子供与性有機物層の連続し
た２つの層からなる部分を含む光起電力素子において、
電子供与性有機物層が２種以上の異なる電子供与性物質
を含有することにより、ＶOC，ＪSC，ｆｆとして高い値
が得られ、有機光起電力素子としては高い変換効率が達
成され、且つ短絡の低減により歩留りが向上した。The effects of the photovoltaic device of the present invention described above are summarized as follows. 1. In a photovoltaic device including a part composed of two consecutive layers of an electron-accepting organic compound layer and an electron-donating organic compound layer,
By containing two or more different electron-donating substances in the electron-donating organic material layer, high values of V OC , J SC , and ff are obtained, and high conversion efficiency is achieved as an organic photovoltaic element, and Yield has been improved by reducing short circuits.
【００７４】２．電子受容性有機物層と電子供与性有機
物層（Ｉ）と前記とは異なる電子供与性有機物層（II）
の連続した３つの層からなる部分を含む光起電力素子に
おいて、電子供与性有機物層（Ｉ）または電子供与性有
機物層（II）が、２種以上の異なる電子供与性物質を含
有することにより、ＶOC，ＪSC，ｆｆとして高い値が得
られ、有機光起電力素子としては高い変換効率が達成さ
れ、且つ短絡の低減により歩留りが向上した。2. Electron-accepting organic compound layer, electron-donating organic compound layer (I) and electron-donating organic compound layer (II) different from the above
In a photovoltaic device including a part consisting of three consecutive layers of, the electron donating organic compound layer (I) or the electron donating organic compound layer (II) contains two or more different electron donating substances. , V OC , J SC , ff, high values were obtained, high conversion efficiency was achieved for the organic photovoltaic element, and the yield was improved by reducing short circuits.
【図１】本発明の光起電力素子の一具体例の説明図、FIG. 1 is an explanatory view of a specific example of the photovoltaic element of the present invention,
【図２】同上[Fig. 2] Same as above
【図３】同上[FIG. 3] Same as above
【図４】同上[Fig. 4] Same as above
Claims (7)
極の間に、電子受容性有機物層と電子供与性有機物層の
連続した２つの層からなる部分を含む光起電力素子にお
いて、この電子供与性有機物層が２種以上の異なる電子
供与性物質を含有していることを特徴とする光起電力素
子。1. A photovoltaic device comprising a portion composed of two consecutive layers of an electron-accepting organic material layer and an electron-donating organic material layer between two electrodes, at least one of which is translucent, wherein the electrons are A photovoltaic device, wherein the donative organic material layer contains two or more different electron donating substances.
極の間に、電子受容性有機物層と電子供与性有機物層
（Ｉ）と前記とは異なる電子供与性有機物層（II）の連
続した３つの層からなる部分を含む光起電力素子におい
て、この電子供与性有機物層（Ｉ）が２種以上の異なる
電子供与性物質を含有していることを特徴とする光起電
力素子。2. An electron-accepting organic compound layer, an electron-donating organic compound layer (I), and an electron-donating organic compound layer (II) different from the above are consecutively provided between two electrodes, at least one of which is transparent. A photovoltaic element comprising a part composed of three layers, wherein the electron donating organic compound layer (I) contains two or more different electron donating substances.
極の間に、電子受容性有機物層と電子供与性有機物層
（Ｉ）と前記とは異なる電子供与性有機物層（II）の連
続した３つの層からなる部分を含む光起電力素子におい
て、この電子供与性有機物層（II）が２種以上の異なる
電子供与性物質を含有していることを特徴とする光起電
力素子。3. An electron-accepting organic material layer, an electron-donating organic material layer (I), and an electron-donating organic material layer (II) different from the above are continuously provided between two electrodes, at least one of which is transparent. A photovoltaic element comprising a portion composed of three layers, wherein the electron donating organic compound layer (II) contains two or more different electron donating substances.
ロシアニン顔料とキナクリドン顔料からなることを特徴
とする請求項１ないし請求項３の何れかに記載の光起電
力素子。4. The photovoltaic element according to claim 1, wherein the two or more different electron donating substances are a phthalocyanine pigment and a quinacridone pigment.
のフタロシアニン顔料からなることを特徴とする請求項
１ないし請求項３の何れかに記載の光起電力素子。5. The photovoltaic element according to claim 1, wherein the two or more different electron donating substances are different phthalocyanine pigments.
フタロシアニンまたは中心金属として２価の金属を有す
るフタロシアニンと中心金属として３価の金属を有する
フタロシアニンとの混合物、無金属のフタロシアニンま
たは中心金属として２価の金属を有するフタロシアニン
と中心金属として４価の金属を有するフタロシアニンと
の混合物、中心金属として３価の金属を有するフタロシ
アニンと４価の金属を有するフタロシアニンとの混合物
のうち何れかの混合物であることを特徴とする請求項５
記載の光起電力素子。6. The heterogeneous phthalocyanine pigment comprises a metal-free phthalocyanine or a mixture of a phthalocyanine having a divalent metal as a central metal and a phthalocyanine having a trivalent metal as a central metal, a metal-free phthalocyanine or a phthalocyanine having a central metal of 2. It is a mixture of a phthalocyanine having a valent metal and a phthalocyanine having a tetravalent metal as a central metal, and a mixture of a phthalocyanine having a trivalent metal as a central metal and a phthalocyanine having a tetravalent metal. 6. The method according to claim 5, wherein
The photovoltaic element described.
極の間に、電子受容性有機物層と電子供与性有機物層の
連続した２つの層からなる部分を含み、この電子供与性
有機物層が２種以上の異なる電子供与性物質を含有して
いる光起電力素子の製造方法において、真空蒸着法によ
って電子供与性有機物層を形成する場合に、蒸着原料と
して別個に配置された各別の電子供与性物質、それ等の
混合物または混晶のうち何れかの状態のものを用いるこ
とを特徴とする光起電力素子の製造方法。7. An electron-donating organic compound layer comprising a portion composed of two consecutive layers of an electron-accepting organic compound layer and an electron-donating organic compound layer between two electrodes, at least one of which is transparent. In a method for manufacturing a photovoltaic device containing two or more different electron donating substances, when the electron donating organic material layer is formed by a vacuum vapor deposition method, each electron separately arranged as a vapor deposition material. A method of manufacturing a photovoltaic element, comprising using a donor material, a mixture thereof, or a mixed crystal in any state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP43A JPH06177410A (en) | 1992-12-07 | 1992-12-07 | Manufacture of photovoltaic element and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP43A JPH06177410A (en) | 1992-12-07 | 1992-12-07 | Manufacture of photovoltaic element and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06177410A true JPH06177410A (en) | 1994-06-24 |
Family
ID=18191076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP43A Pending JPH06177410A (en) | 1992-12-07 | 1992-12-07 | Manufacture of photovoltaic element and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06177410A (en) |
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| JPH0974217A (en) * | 1995-09-07 | 1997-03-18 | Nippon Shokubai Co Ltd | Organic solar battery |
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1992
- 1992-12-07 JP JP43A patent/JPH06177410A/en active Pending
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