JPS6120372A - Photoelectric conversion element - Google Patents
Photoelectric conversion elementInfo
- Publication number
- JPS6120372A JPS6120372A JP59140972A JP14097284A JPS6120372A JP S6120372 A JPS6120372 A JP S6120372A JP 59140972 A JP59140972 A JP 59140972A JP 14097284 A JP14097284 A JP 14097284A JP S6120372 A JPS6120372 A JP S6120372A
- Authority
- JP
- Japan
- Prior art keywords
- organic material
- type organic
- type
- photoelectric conversion
- electrode
- 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
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 34
- 239000011368 organic material Substances 0.000 claims abstract description 71
- 239000004020 conductor Substances 0.000 claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 claims abstract description 7
- 229920000547 conjugated polymer Polymers 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000008774 maternal effect Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000000975 dye Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 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 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- -1 polythenylene Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- WDVSHHCDHLJJJR-UHFFFAOYSA-N Proflavine Chemical compound C1=CC(N)=CC2=NC3=CC(N)=CC=C3C=C21 WDVSHHCDHLJJJR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003984 copper intrauterine device Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- WTOSNONTQZJEBC-UHFFFAOYSA-N erythrosin Chemical compound OC(=O)C1=CC=CC=C1C(C1C(C(=C(O)C(I)=C1)I)O1)=C2C1=C(I)C(=O)C(I)=C2 WTOSNONTQZJEBC-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 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 1
- 239000012528 membrane Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 229960000286 proflavine Drugs 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/30—Doping active layers, e.g. electron transporting layers
-
- 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
- H10K30/211—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions comprising multiple junctions, e.g. double heterojunctions
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- 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
【発明の詳細な説明】 〔発明の技術分野〕 この発明は新規な光電変換素子に関する。[Detailed description of the invention] [Technical field of invention] The present invention relates to a novel photoelectric conversion element.
従来、光電変換素子としては、主としてシリコン半導体
の表面近（Ｋｐ−ｎ接合を作ることにより得られる太陽
電池が考案され、実用化されている。Conventionally, as a photoelectric conversion element, a solar cell obtained mainly by forming a near-surface (Kp-n junction) of a silicon semiconductor has been devised and put into practical use.
しかし、これとは別にもつと安価な有機材料、例えばポ
リアセチレン々どの導電性高分子材料を半導体として利
用したものや、例えばフタロシアニン々どの有機色素の
光増感能を利用したものなどの検討も行われている。However, in addition to this, we are also investigating other inexpensive organic materials, such as those that use conductive polymer materials such as polyacetylene as semiconductors, and those that utilize the photosensitizing ability of organic dyes such as phthalocyanine. It is being said.
これら有機材料を用いたサンドインチタイプの光電変換
素子は主として第１図に示した構造のようなものである
。Sand inch type photoelectric conversion elements using these organic materials mainly have a structure as shown in FIG.
この動作原理は、透明又は半透明電極（１）を透過した
光（８）が、有機化合物層（２）Ｋ入射すると、透明又
は半透明電極（１）と有機化合物層（２）の界面に電位
差が生じ、リード線（５）および（７）の間に光誘起電
力が発生するというものである。なお、 （４） 、
（６）ｔｉリード接続端である。この場合、透明又は半
透明電極（１）と有機化合物層（２）との間には異方接
合（例えばｐ−ｎ接合）やショットキー接合などができ
ていることが必要で、さらに有機化合物Ｍ（２）と電極
（３）は等方接台、例えばオーミック接触例なっている
ことが必要である。さらに詳しく言うと、光照射下での
それ自身の仕事関数（フェルミ準位）の値が透明又は半
透明電極（１）〉有機化合物層（２）二電極（３）、ま
たは透明又は半透明電極（１）〈有機化合物層（２）に
電極（３）となっていることが必要で、リード線（５）
、 （７）間の電力は、通常前者の場合には（５）が
正極、後者の場合には（７）が正極となる。有機光電変
換素子とはこのような動作原理を応用しようとするもの
である。The principle of this operation is that when light (8) transmitted through the transparent or semi-transparent electrode (1) enters the organic compound layer (2), it reaches the interface between the transparent or semi-transparent electrode (1) and the organic compound layer (2). A potential difference is generated, and photo-induced power is generated between the lead wires (5) and (7). In addition, (4),
(6) Ti lead connection end. In this case, it is necessary that an anisotropic junction (for example, a p-n junction) or a Schottky junction be formed between the transparent or semi-transparent electrode (1) and the organic compound layer (2), and that the organic compound layer M(2) and electrode (3) need to be in isotropic contact, for example ohmic contact. More specifically, the value of its own work function (Fermi level) under light irradiation is transparent or semitransparent electrode (1) > organic compound layer (2) two electrodes (3), or transparent or semitransparent electrode (1) It is necessary to have an electrode (3) on the organic compound layer (2), and a lead wire (5)
, (7), in the former case, (5) is normally the positive electrode, and in the latter case, (7) is the positive electrode. Organic photoelectric conversion elements are intended to apply this operating principle.
しかしながら、このような有機材料を用いた光電変換素
子は、いずれも光電変換効率が低く、得られる光起電力
が不安定で、寿命が短いというような欠点があり、実用
化のためには解決すべき問題点が多数残されている。However, all photoelectric conversion elements using such organic materials have drawbacks such as low photoelectric conversion efficiency, unstable photovoltaic force, and short lifespan, which cannot be solved for practical use. Many issues remain to be addressed.
この発明は上記従来のものの欠点を除去するため罠なさ
れたもので、透光性第１導電材料上に第１ｎ型有機材料
層、第１ｎ型有機材料より低エネルギー側に基礎吸収端
を有する有機材料より成る第２ｎ型有機材料層、ｐ型有
機材料層およびＷ、２導電材料を順に設けたものを用い
ることにより、応答波長域が広がると共に、ｎｎｐ接合
による分離作用によりｎｎおよびｐｎ接合のものよりざ
らに光電変換効率が増大し、さらに安価な有機材料を用
いることができる光電変換素子を提供することを目的と
する。The present invention has been made to eliminate the drawbacks of the conventional ones, and includes a first n-type organic material layer on a transparent first conductive material. By using a layer in which a second n-type organic material layer, a p-type organic material layer, and two conductive materials are provided in this order, the response wavelength range is broadened, and the separation effect of the nnp junction allows for nn and pn junctions. It is an object of the present invention to provide a photoelectric conversion element in which the photoelectric conversion efficiency increases more roughly and in which a cheaper organic material can be used.
第２図はこの発明の一実施例の光電変換素子の断面図で
あり、（８）は光、（９）は透明又は半透明電極となる
第１導電材料、００は第１ｎ型有機材料層、Ｑ］）＃−
ｉ第２ｎ型有機材料層、（６）はｐ型有機材料層、（至
）は電極となる第２導電材料、α→、 Ｑ６はリード端
、Ｑ６．Ｑ７）はリード線である。FIG. 2 is a cross-sectional view of a photoelectric conversion element according to an embodiment of the present invention, in which (8) is light, (9) is a first conductive material that becomes a transparent or semi-transparent electrode, and 00 is a first n-type organic material layer. ,Q])#-
i second n-type organic material layer, (6) a p-type organic material layer, (to) a second conductive material that becomes an electrode, α→, Q6 a lead end, Q6. Q7) is the lead wire.
即ち、透明又は半透明電極となる第１導電材料（９）上
に第１ｎ型有機材料層（１０、第２ｎ型有機材料層αυ
およびｐ型有機材料層（６）を順に設け、その上に電極
となる第２導電材料ａ４を被着し、電極（９）。That is, a first n-type organic material layer (10, a second n-type organic material layer αυ
and a p-type organic material layer (6) are sequentially provided, and a second conductive material a4 serving as an electrode is deposited thereon to form an electrode (9).
（至）にリード＃ｌ（ト）、 ａ’ｈを結着し電力を取
り出せるようにして、ｎｎｐ型光電変換素子を構成する
ものである。Leads #l (g) and a'h are connected to (to) so that electric power can be extracted, thereby constructing an nnp type photoelectric conversion element.
なお、第１導電材料を、例えばガラスおよ、びポリエス
テルフィルムなどの透−開基板に導電材料を被着した透
明又は半透明電極としても用いられるが、図は第１導電
材料のみで電極を構成した場合を示す。Note that the first conductive material can also be used as a transparent or semitransparent electrode made by coating a conductive material on a transparent substrate such as glass or polyester film, but the figure shows an electrode made of only the first conductive material. Indicates the case configured.
この発明に係わる第１導電材料としては、ｎ型材料と良
いオーミック接触をとる仕事関数の小さい金属、例えば
Ｉｎ、 Ａ４ Ｇａ、Ｉｎ酸化物、 Ｓｎ酸化物、Ｉｎ
−８ｎ酸化物およびＩｎ −Ｇａ合金等が用いられる。The first conductive material according to the present invention includes a metal with a small work function that makes good ohmic contact with the n-type material, such as In, A4 Ga, In oxide, Sn oxide, In
-8n oxide, In-Ga alloy, etc. are used.
第１導電材料が透明である場合は特に問題は無いが、通
常半透明になるように透明基板に上記金属を真空蒸着、
スパッタリング、ＣＶＤ（ケミカル・ペーパ・デポジシ
ョン）およびメッキ等の方法によって被着させて、透明
又は半透明電極を得る。There is no particular problem if the first conductive material is transparent, but usually the metal is vacuum-deposited on a transparent substrate to make it semi-transparent.
The transparent or translucent electrodes are deposited by methods such as sputtering, CVD (chemical paper deposition) and plating.
この時金属層の光透過率としては、第１ｎ型有機材料と
の接触抵抗や金属自身の抵抗を考慮して決められるが、
通常５チから９０％の間に制御される。At this time, the light transmittance of the metal layer is determined by considering the contact resistance with the first n-type organic material and the resistance of the metal itself.
It is usually controlled between 5% and 90%.
この発明に係わる第１ｎ型有機材料および第２ｎ型有機
材料としては、例えばポリアセチレン。Examples of the first n-type organic material and the second n-type organic material according to the present invention include polyacetylene.
ポリピロール、ポリチェニレン、ポリアニリン。Polypyrrole, polythenylene, polyaniline.
ポリフェニレン、ポリフェニレンスルフィドおよびポリ
フェニレンオキシドなど化学構造の骨格に共役二重結合
を有するπ−共役系高分子が用いられる。通常、π−共
役系高分子はそれ自身では絶縁体であるが、適当な電子
受容体（例えば臭素。π-conjugated polymers having a conjugated double bond in the chemical structure skeleton are used, such as polyphenylene, polyphenylene sulfide, and polyphenylene oxide. Normally, π-conjugated polymers are insulators by themselves, but they have suitable electron acceptors (e.g. bromine).
ヨウ素、ヨウ化臭素、五フッ化ヒ素および過塩菓酸等）
をドーピングすることによってｐ型に、また適当な電子
供与体（例えばＮａ、 Ｌｉ、 Ｋおよびアミン等）を
ドーピングすることによってｎ型の材料圧することがで
き、その電導度も半導体領域から金属鎖＊まで幅広く制
御可能で好ましく用いられる。さらに例えば、ローダミ
ンＢ、マラカイトグリーン、クリスタルバイオレットお
よびビナシアツールなどのｎ型電導を示す有機色素も用
いられる。(Iodine, bromine iodide, arsenic pentafluoride, persalted confectionery acid, etc.)
The material can be made p-type by doping, or n-type by doping with suitable electron donors (e.g. Na, Li, K and amines), and its conductivity can also be changed from the semiconductor region to the metal chain*. It is preferably used because it can be controlled over a wide range of conditions. Furthermore, organic dyes exhibiting n-type conductivity such as, for example, rhodamine B, malachite green, crystal violet and vinacia tool can also be used.
なお、上記π−共役系高分子材料および有機色素を互い
に２種以上組合せて、あるいは重ねて第１および第２ｎ
型有機材料として用いてもよい。Note that two or more of the above π-conjugated polymer materials and organic dyes may be used in combination with each other, or in combination with each other to form the first and second n-conjugated polymer materials.
It may also be used as a type organic material.
上記π−共役系高分子材料および有機色素を第Ｉｎ型有
機材料および第２ｎ型有機材料として用いる場合、第１
ｎ型有機材料とする材料の基礎吸収端ｒＥｇ）が第２ｎ
型有機材料よ）高エネルギー側にあるという条件を満足
する組合せを上記π−共役系高分子材料および有機色素
の中から各々選定する。When using the above-mentioned π-conjugated polymer material and organic dye as the In-type organic material and the second N-type organic material, the first
The basic absorption edge rEg) of the material used as an n-type organic material is the second n-th
(type organic material) A combination satisfying the condition of being on the high energy side is selected from the above-mentioned π-conjugated polymer material and organic dye.
又、第２ｎ型有機材料の電気伝導度は第１ｎ型有機材料
よりも小さいのが望ましいが、上記のようにドーピング
により電気伝導度を制御できることがらπ−共役系高分
子材料が好んで用いられる。Further, it is desirable that the electrical conductivity of the second n-type organic material is lower than that of the first n-type organic material, but a π-conjugated polymer material is preferably used because the electrical conductivity can be controlled by doping as described above. .
第２ｎ型有機材料は第１ｎ型有機材料上に第２図に示す
ように層状に形成される。この形成方法は通常の溶媒キ
ャスト法（スピナーコートおよびスプレーコート法など
も含む）や、蒸着法などでよいが、ピンホールレスであ
ることや、内部インピーダンスが大きくなりすぎないこ
とを考慮すると膜厚２００人〜１μｍの範囲内とするの
が好ましい。The second n-type organic material is formed in a layered manner on the first n-type organic material as shown in FIG. This formation method can be the usual solvent casting method (including spinner coating and spray coating methods) or vapor deposition, but considering that it is pinhole-less and that the internal impedance does not become too large, the film thickness should be It is preferable to set it within the range of 200 people to 1 μm.
又、第２ｎ型有磯材料に゛第２ｎ型有機材料を被着させ
ることは、第１ｎ型有機材料を保護することにもなり、
動作安定性を一段と増す結果につながつてくる。Furthermore, depositing the second n-type organic material on the second n-type organic material also protects the first n-type organic material.
This leads to a further increase in operational stability.
この発明に係わるｐ型有機材料としては、上記のπ−共
役系高分子をｐ型にドープしたものの他に例えは、メロ
シアニンおよびフタロシアニン女どのシアニン系、フェ
ロサフラニンおよびサフラニンＴなどのフェナジン系、
チオニンおよびメチレンブルーなどのフェノチアジン系
、エリスロシン、クロロフィル、プロフラビン並びにウ
ラニンなどの有機色素などが用いられる。In addition to the above p-type doped π-conjugated polymers, p-type organic materials according to the present invention include cyanine-based materials such as merocyanine and phthalocyanine, phenazine-based materials such as ferrosafranin and safranin T,
Phenothiazines such as thionine and methylene blue, organic pigments such as erythrosin, chlorophyll, proflavin, and uranine are used.
この発明に係わる第２導電材料としては、仕事関数の大
きい金属、例えば金、白金、クロム、パラジウム等が用
いられる。勿論、これら材料を２つ以上用いてもよい。As the second conductive material according to the present invention, a metal with a large work function, such as gold, platinum, chromium, palladium, etc., is used. Of course, two or more of these materials may be used.
この発明の光電変換素子の動作原理の詳細は現時点では
不明であるが、この発明者等は以下に述べるような光電
変換機構を考えている。すなわち、基礎吸収端（Ｅｇ：
バンドギャップエネルギー）の異なる２つの半導体を組
み合わせてできるヘテロ接合の界面にできる電位障壁を
利用していると考えられる。第３図に、この発明の光電
変換素子のエネルギーバンド図を示す。図において、（
８）はｈνのエネルギーを有する光、（至）、０嗜、（
１）は各々第１ｎ型有機材料、第２ｎ型有機材料、ｐ型
有機材料の基礎吸収端Ｅｇｌ、 １ｇ２． Ｅｇ３であ
り、Ｅｇｌ 〉１ｇ２となるように構成されている。Although the details of the operating principle of the photoelectric conversion element of this invention are currently unknown, the inventors are considering a photoelectric conversion mechanism as described below. That is, the fundamental absorption edge (Eg:
It is thought that the potential barrier created at the interface of a heterojunction formed by combining two semiconductors with different band gap energies is used. FIG. 3 shows an energy band diagram of the photoelectric conversion element of the present invention. In the figure, (
8) is light with energy of hν, (to), 0, (
1) are the fundamental absorption edges Egl, 1g2. of the first n-type organic material, the second n-type organic material, and the p-type organic material, respectively. Eg3, and is configured so that Egl > 1g2.
即ち、入射した光（８）の内ｈν：）Ｅｇｌの光は第１
ｎ型有機材料で吸収される。さらに第１ｎ型有機材料を
透過した光のうち１ｇ２ （ｈν（Ｅｇｌの光は第２ｎ
型有機材料で吸収される。第１．第２ｎ型有機材料で吸
収された光は電子正孔対を生成し、光電流を生じるが、
ホモ接合に比べて短波長〕光も利用できるので光電流が
大きくなる。す々わち、広帯域特性を実現できる。さら
に、第２ｎ型有機材料とｐ型有機材料の間のｐｎ接合障
壁によって電子正孔対は分離されるが、第１ｎ型有機材
料と第２ｎ型有機材料の境界の伝導帯ではきわたった障
壁はないために接合で分離された電子は効率よく収集さ
れる。境界の伝導帯での障壁は正孔をｐ−ｎ接合側に追
いやる働きをするととＫなる。また、第１ｎ型有機材料
の電気伝導度が第２ｎ型有磯材料の電気伝導度よりも大
きいことも上の働きを助けることに７Ｔｈると考えられ
る。That is, among the incident light (8), the light hν:)Egl is the first
Absorbed by n-type organic materials. Furthermore, 1g2 (hν(Egl) of the light transmitted through the first n-type organic material is
Type is absorbed by organic materials. 1st. The light absorbed by the second n-type organic material generates electron-hole pairs and generates a photocurrent, but
Compared to homojunctions, light with a shorter wavelength can also be used, resulting in a larger photocurrent. In other words, broadband characteristics can be achieved. Furthermore, the electron-hole pairs are separated by the pn junction barrier between the second n-type organic material and the p-type organic material, but the barrier that is severe in the conduction band at the boundary between the first n-type organic material and the second n-type organic material is Therefore, the electrons separated at the junction are efficiently collected. If the barrier in the conduction band at the boundary acts to drive holes toward the pn junction, it becomes K. It is also believed that the fact that the electrical conductivity of the first n-type organic material is greater than that of the second n-type Aiso material also helps the above function.
又、この発明の光電変換素子の片面あるいは全面を光透
過性を損わない材料、又は紫外線のみを遮断する材料、
例えばシリコン樹脂、エポキシ樹脂などで封止してもよ
い。Further, one side or the entire surface of the photoelectric conversion element of the present invention may be made of a material that does not impair light transmittance or a material that blocks only ultraviolet rays.
For example, it may be sealed with silicone resin, epoxy resin, or the like.
以下、実施例により、この発明を具体的に説明するが、
これに限定されるものではない。Hereinafter, this invention will be specifically explained with reference to Examples.
It is not limited to this.
実施例１
３．５ｃｍ Ｘ ７ｃｍのガラス基板の表面Ｋ ＩＴＯ
を被着したものを作用電極（イ）とした。１ｏｏｍｔの
アセトニトリル罠、ビロール（ｏ、ｏ７ｇ） ＋ Ｉｉ
−メチルピロール（０，３５ｇ）およびテトラエチルア
ンモニウムバークロレート（０，７ｇ）を溶解させた液
を反応溶液（イ）とした。対極として白金（ｐｔ）電極
を、参照電極として８０Ｋ （飽和カロメル電極）を使
用し、反応溶液（イ）中に作用電極（イ）と共に浸し、
窒素ガス雰囲気下で、作用電極（イ）を陽極として対極
との間に一定電流（Ｑ、１５ｍＡ）を２０分間流し、作
用電極（イ）上にπ−共役系高分子膜を約４００への厚
さに形成した。その後対極と作用電極（イ）を短絡して
脱ドープを４時間行い、アセトニトリルで洗浄後、Ｌｉ
ＢＦ４を０ 、２８ ｇ溶解したアセトニトリル溶液に
浸し、白金電極を対極として用いて共に浸す。この系を
窒素ガス雰囲気下で作用電極を陰極として対極との間に
一定電流（０，１５ｍＡ） ｔ−９０分間流し、作用電
極（イ）上のπ−共役系高分子にＬ１＋をドープしてｎ
型とする。その後アセトニトリルで洗浄して、真空乾燥
を行い、ｎ型のπ−共役系高分子膜試料（イ）を得た。Example 1 Surface of 3.5cm x 7cm glass substrate K ITO
The working electrode (A) was coated with . 1oomt acetonitrile trap, virol (o, o7g) + Ii
- A solution in which methylpyrrole (0.35 g) and tetraethylammonium verchlorate (0.7 g) were dissolved was used as a reaction solution (a). Using a platinum (PT) electrode as a counter electrode and an 80K (saturated calomel electrode) as a reference electrode, immerse it together with the working electrode (A) in the reaction solution (A),
In a nitrogen gas atmosphere, a constant current (Q, 15 mA) was passed between the working electrode (a) as an anode and the counter electrode for 20 minutes, and a π-conjugated polymer film was deposited on the working electrode (a) to a thickness of about 400 mA. formed to a thickness. After that, the counter electrode and the working electrode (a) were short-circuited, dedoping was performed for 4 hours, and after washing with acetonitrile, Li
It is immersed in an acetonitrile solution in which 0.28 g of BF4 is dissolved, and a platinum electrode is used as a counter electrode. A constant current (0.15 mA) was passed through this system in a nitrogen gas atmosphere between the working electrode as the cathode and the counter electrode for t-90 minutes, and the π-conjugated polymer on the working electrode (a) was doped with L1+. n
Make it into a mold. Thereafter, it was washed with acetonitrile and vacuum dried to obtain an n-type π-conjugated polymer membrane sample (a).
次にπ−共役系高分子膜試料（イ）上にさらに真空蒸着
でクリスタルバイオレット色素を８００Ａの凧さに設け
、さらＫその上にＰ型有機材料であるメロシアニン色素
を２０Ｏｏ人の厚さに真空蒸着した。さらに、この上に
電極としてＡｕを蒸着した。このようにして得た光電変
換素子試料を試料（イ）とする。このときπ−共役系高
分子であるポリピロールのバンドギャップエネルギーは
３ｅＶであり光吸収極大は４００ｍｍ又はそれより短波
長側にある。クリスタルバイオレットのバンドギャップ
エネルギーは１．７ｅＶであり、ポリピロールよりその
光吸収極大は低エネルギー側にある。電気伝導度はポリ
ピロールが〜３０ｓ／Ｃｍであり、クリスタルバイオレ
ットは〜１０ ｓ／Ｃ＞ｍ程度である。Next, on the π-conjugated polymer film sample (a), a crystal violet dye was further applied by vacuum deposition to a thickness of 800A, and then a merocyanine dye, which is a P-type organic material, was applied to a thickness of 200 mm on top of the Kite. Vacuum deposited. Furthermore, Au was vapor-deposited thereon as an electrode. The photoelectric conversion element sample thus obtained is referred to as sample (a). At this time, the band gap energy of polypyrrole, which is a π-conjugated polymer, is 3 eV, and the maximum light absorption is at 400 mm or shorter wavelength side. The band gap energy of crystal violet is 1.7 eV, and its light absorption maximum is on the lower energy side than that of polypyrrole. The electrical conductivity of polypyrrole is ~30 s/Cm, and that of crystal violet is approximately ~10 s/C>m.
実施例２
実施例１にて得たπ−共役系高分子膜試料（イ）上に真
空蒸着でクリスタルバイオレット色素を８００人の厚さ
に設け、さらに、その上Ｋｐ型有機材料である銅フタロ
ンアニンを２０００人の厚さに真空蒸着した。さらＫこ
の上に電極としてＡｕを蒸着した。このようＫして得た
光電変換素子試料を試料（ロ）とする。Example 2 A crystal violet dye was applied to a thickness of 800 mm by vacuum evaporation on the π-conjugated polymer film sample (a) obtained in Example 1, and furthermore, copper phthalonanine, which is a Kp type organic material, was applied. was vacuum deposited to a thickness of 2000 mm. Furthermore, Au was deposited on this as an electrode. The photoelectric conversion element sample thus obtained is referred to as a sample (b).
比較例１
実施例１で得た作用電極（イ）上に真空蒸着でクリスタ
ルバイオレット色素を８００人の厚さに設け、さらにそ
の上にｐ型有機材料であるメロシアニン色素を８０ｏ人
の厚さに設けた。さらに１この上に電極としてＡｕを蒸
着した。このようＫして得た光電変換素子試料を比較試
料（イ）とする。Comparative Example 1 Crystal violet dye was deposited on the working electrode (A) obtained in Example 1 to a thickness of 800 mm by vacuum deposition, and merocyanine dye, which is a p-type organic material, was further applied to a thickness of 80 mm on top of the working electrode (A) obtained in Example 1. Established. Furthermore, Au was vapor-deposited on top of this as an electrode. The photoelectric conversion element sample thus obtained is referred to as a comparative sample (a).
比較例２
実施例１で得た作用電極（イ）上に真空蒸着でクリメタ
ルバイオレット色素を８００人の厚さに設け、さらＫそ
の上Ｖｃｐ型有型付機材料る銅７タロシアニンを２００
０への厚さに真空蒸着した。さらにこの上に電極として
Ａｕを真空蒸着した。このようにして得た光電変換素子
試料を比較試料（ロ）とする。Comparative Example 2 On the working electrode (A) obtained in Example 1, a creametal violet dye was applied to a thickness of 800 mm by vacuum evaporation, and on top of that, copper 7 talocyanine, which is a Vcp type organic material, was applied to a thickness of 200 mm.
Vacuum deposited to a thickness of 0. Further, Au was vacuum-deposited thereon as an electrode. The photoelectric conversion element sample thus obtained is referred to as a comparative sample (b).
上記実施例１，２および比較例１，２で得た試料（イ）
、（ロ）および比較試料（イ）、（ロ）Ｋついて光電変
換特性を、各試料のネサガラス側を正、Ａｕ側を負とし
て以下に示す各試験により調べた。Samples (A) obtained in Examples 1 and 2 and Comparative Examples 1 and 2 above
, (b) and comparative samples (a) and (b) K, the photoelectric conversion characteristics of each sample were investigated by the following tests, with the Nesa glass side of each sample being positive and the Au side being negative.
光起電力試験
２５０Ｗのキセノンランプおよび紫外線カツトフィルタ
ー（東芝製：商品名ＵＶ−３８）、熱線カットフィルタ
ー（保谷ガラス製：商品名ＨＡ−３０）を用いて受光面
で１０ ｍＷ／ｃ ｍ ２の光を各試料のＡｕ電極側か
ら照射した。光照射開始３分後に各試料が発生した開放
端電圧（ｖｏｃ）および短絡電流（工ｓｃ）を表１Ｋま
とめて示す。Photovoltaic power test Using a 250W xenon lamp, an ultraviolet cut filter (manufactured by Toshiba, product name: UV-38), and a heat ray cut filter (manufactured by Hoya Glass, product name: HA-30), a power of 10 mW/cm2 was generated at the light receiving surface. Light was irradiated from the Au electrode side of each sample. The open circuit voltage (voc) and short circuit current (sc) generated in each sample 3 minutes after the start of light irradiation are summarized in Table 1K.
表１ 各試料のＶｏｃおよびＩｓｃ
上表から、この発明の光電変換素子は優れた光起電力を
示し、特に大きな電流密度が得られるのが特徴であると
言える。Table 1 Voc and Isc of each sample From the above table, it can be said that the photoelectric conversion element of the present invention exhibits excellent photovoltaic force and is characterized by being able to obtain a particularly large current density.
波長依存性試験
２５０Ｗのキセノンランプおよびバンドパスフィルター
（東芝干渉フィルター：商品名ＫＬ−４２〜ＫＬ６５）
を用いて、受光面で１ｍＷ／ｃｍ２の光を試料（イ）お
よび比較試料（イ）のＡｕ電極側から照射し、Ｖｏｃ（
ｍＶ）の光波長（ｎｍ）依存性を測定した。湧」定結果
を第４図に示す。図中、Ａは試料（イＬ Ｂは比較試料
（イ）の特性である。この図からこの発明の光電変換素
子は短波長側の元に対しても、長波長側の光に対しても
応答することがわかる。Wavelength dependence test 250W xenon lamp and bandpass filter (Toshiba interference filter: product name KL-42 to KL65)
Using a light-receiving surface, 1 mW/cm2 light was irradiated from the Au electrode side of the sample (a) and comparative sample (a), and Voc (
mV) dependence on light wavelength (nm) was measured. Figure 4 shows the results. In the figure, A is the characteristic of the sample (A), and B is the characteristic of the comparative sample (A).From this figure, the photoelectric conversion element of the present invention is effective both for light on the short wavelength side and for light on the long wavelength side. You can see that it responds.
以上説明したとおり、この発明は透光性第１導電材料上
に第１ｎ型有機材料層、第１ｎ型有機材料より低エネル
ギー側に基礎吸収端を有する有機材料より成る第２ｎ型
有機材料層、ｐ型有機材料層および第２導電材料を順に
設けたものを用いることにより、応答波長域が広がると
共に％ｎｎｐ接合による分離作用によりｎｎ接合単独あ
るいはｐｎ接合単独のものよりさらに光電変換効率が増
大し、さらに安価な有機材料を用いることのできる光電
変換素子を得ることができ、例えば太陽電池、カラーセ
ンサーおよび色彩認職センサーなどに広く適応すること
ができる。As explained above, the present invention includes a first n-type organic material layer on a transparent first conductive material, a second n-type organic material layer made of an organic material having a fundamental absorption edge on the lower energy side than the first n-type organic material, By using a layer in which a p-type organic material layer and a second conductive material are provided in this order, the response wavelength range is broadened, and due to the separation effect of the nnp junction, the photoelectric conversion efficiency is further increased compared to the nn junction alone or the pn junction alone. Furthermore, it is possible to obtain a photoelectric conversion element that can use cheaper organic materials, and it can be widely applied to, for example, solar cells, color sensors, color recognition sensors, and the like.
第１図は従来の光電変換素子の断面図、第２図はこの発
明の一実施例の光電変換素子の断面図、第３図はこの発
明の一実施例の光電変換素子のエネルギーバンド図、Ｍ
４図はこの発明の一実施例の光電変換素子と従来の光電
変換素子の照射波長（ｎｍ）Ｋよる電圧（ｍＶ）特性図
である。
図において、（９）は第１４電材料、Ｃ１Ｏは＠１ｎ１
ｎ型有料層、０１）けＭ２ｎ２ｎ型有料層、（６）はＰ
型有機材料層、（至）は第２４電材料、
なお、各図中、同一符号は同−又は相当部分を示す。FIG. 1 is a cross-sectional view of a conventional photoelectric conversion element, FIG. 2 is a cross-sectional view of a photoelectric conversion element according to an embodiment of the present invention, and FIG. 3 is an energy band diagram of a photoelectric conversion element according to an embodiment of the present invention. M
FIG. 4 is a voltage (mV) characteristic diagram according to the irradiation wavelength (nm) K of a photoelectric conversion element according to an embodiment of the present invention and a conventional photoelectric conversion element. In the figure, (9) is the 14th electric material, C1O is @1n1
n type paid layer, 01) ke M2n2n type paid layer, (6) is P
type organic material layer, (to) is the 24th electric material. In each figure, the same reference numerals indicate the same or corresponding parts.
Claims (2)
られた第１ｎ型有機材料層、この第１ｎ型有機材料層上
に設けられ、第１ｎ型有機材料より低エネルギー側に基
礎吸収端を有する有機材料より成る第２ｎ型有機材料層
、この第２ｎ型有機材料層上に設けられたｐ型有機材料
層、およびこのｐ型有機材料層上に設けられた第２導電
材料を備えた光電変換素子。(1) a translucent first conductive material; a first n-type organic material layer provided on the first conductive material; A second n-type organic material layer made of an organic material having a fundamental absorption edge, a p-type organic material layer provided on the second n-type organic material layer, and a second conductive material provided on the p-type organic material layer. A photoelectric conversion element equipped with
材料の電気伝導度より大きい特許請求の範囲第１項又は
第２項記載の光電変換素子。(2) The photoelectric conversion element according to claim 1 or 2, wherein the electrical conductivity of the first n-type organic material is higher than the electrical conductivity of the second n-type organic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59140972A JPS6120372A (en) | 1984-07-06 | 1984-07-06 | Photoelectric conversion element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59140972A JPS6120372A (en) | 1984-07-06 | 1984-07-06 | Photoelectric conversion element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6120372A true JPS6120372A (en) | 1986-01-29 |
Family
ID=15281119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59140972A Pending JPS6120372A (en) | 1984-07-06 | 1984-07-06 | Photoelectric conversion element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6120372A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61125090A (en) * | 1984-11-21 | 1986-06-12 | Toyota Central Res & Dev Lab Inc | Photoelectric conversion element |
| JPS63174377A (en) * | 1987-01-14 | 1988-07-18 | Mitsubishi Kasei Corp | Photoelectric conversion thin film |
| WO1994017556A1 (en) * | 1993-01-26 | 1994-08-04 | Fci-Fiberchem, Inc. | Optical sensor with electroluminescent light source and polymer light detector |
| JP2005032793A (en) * | 2003-07-08 | 2005-02-03 | Matsushita Electric Ind Co Ltd | Organic photoelectric converter |
| JP2006048946A (en) * | 2004-07-30 | 2006-02-16 | Dainippon Printing Co Ltd | Organic functional element, organic el element, organic semiconductor element, organic tft element, and manufacturing method for them |
| JP2006527491A (en) * | 2003-06-12 | 2006-11-30 | コナルカ テクノロジーズ インコーポレイテッド | Organic solar cells with intermediate layers with asymmetric transport properties |
| JP2007134444A (en) * | 2005-11-09 | 2007-05-31 | Japan Advanced Institute Of Science & Technology Hokuriku | Solar cell |
| JP2010141268A (en) * | 2008-12-15 | 2010-06-24 | Shinshu Univ | Photoelectric conversion device and solar battery |
-
1984
- 1984-07-06 JP JP59140972A patent/JPS6120372A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61125090A (en) * | 1984-11-21 | 1986-06-12 | Toyota Central Res & Dev Lab Inc | Photoelectric conversion element |
| JPS63174377A (en) * | 1987-01-14 | 1988-07-18 | Mitsubishi Kasei Corp | Photoelectric conversion thin film |
| WO1994017556A1 (en) * | 1993-01-26 | 1994-08-04 | Fci-Fiberchem, Inc. | Optical sensor with electroluminescent light source and polymer light detector |
| JP2006527491A (en) * | 2003-06-12 | 2006-11-30 | コナルカ テクノロジーズ インコーポレイテッド | Organic solar cells with intermediate layers with asymmetric transport properties |
| JP2005032793A (en) * | 2003-07-08 | 2005-02-03 | Matsushita Electric Ind Co Ltd | Organic photoelectric converter |
| JP2006048946A (en) * | 2004-07-30 | 2006-02-16 | Dainippon Printing Co Ltd | Organic functional element, organic el element, organic semiconductor element, organic tft element, and manufacturing method for them |
| US7750553B2 (en) | 2004-07-30 | 2010-07-06 | Dai Nippon Printing Co., Ltd. | Organic EL element provided with an electrode in a liquid state and method for producing the same |
| JP4544937B2 (en) * | 2004-07-30 | 2010-09-15 | 大日本印刷株式会社 | Organic functional device, organic EL device, organic semiconductor device, organic TFT device, and manufacturing method thereof |
| JP2007134444A (en) * | 2005-11-09 | 2007-05-31 | Japan Advanced Institute Of Science & Technology Hokuriku | Solar cell |
| JP2010141268A (en) * | 2008-12-15 | 2010-06-24 | Shinshu Univ | Photoelectric conversion device and solar battery |
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