JPH05121771A - Organic photovoltaic element - Google Patents
Organic photovoltaic elementInfo
- Publication number
- JPH05121771A JPH05121771A JP3312004A JP31200491A JPH05121771A JP H05121771 A JPH05121771 A JP H05121771A JP 3312004 A JP3312004 A JP 3312004A JP 31200491 A JP31200491 A JP 31200491A JP H05121771 A JPH05121771 A JP H05121771A
- Authority
- JP
- Japan
- Prior art keywords
- organic compound
- compound layer
- type organic
- layer
- type
- 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
- 238000013086 organic photovoltaic Methods 0.000 title claims abstract description 13
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 4
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- -1 phthalocyanine compound Chemical class 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- AHXBXWOHQZBGFT-UHFFFAOYSA-M 19631-19-7 Chemical compound N1=C(C2=CC=CC=C2C2=NC=3C4=CC=CC=C4C(=N4)N=3)N2[In](Cl)N2C4=C(C=CC=C3)C3=C2N=C2C3=CC=CC=C3C1=N2 AHXBXWOHQZBGFT-UHFFFAOYSA-M 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000000034 method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-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
- 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
- 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
- VESMRDNBVZOIEN-UHFFFAOYSA-N 9h-carbazole-1,2-diamine Chemical compound C1=CC=C2C3=CC=C(N)C(N)=C3NC2=C1 VESMRDNBVZOIEN-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 150000000921 Gadolinium Chemical class 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 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
- 125000000217 alkyl group Chemical group 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 229910052738 indium Inorganic materials 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
- 238000011835 investigation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 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 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 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 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
- 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
- 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
-
- 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
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
- Light Receiving Elements (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機化合物を用いた光
電池、太陽電池、光センサー、フォトダイオードなどの
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 such as a photovoltaic cell, a solar cell, an optical sensor, a photodiode, etc., which uses an organic compound.
【０００２】[0002]
【従来の技術】単結晶Ｓｉ、ＧａＡｓ、アモルファスＳ
ｉ、ＣｄＳ／ＣｄＴｅ等の無機半導体を使用した太陽電
池の開発がさかんに行われている。これらは高変換効率
と高耐久性及び低価格を目標としているが、現状では全
てを満足しているとは言い難い。近年、有機半導体を使
用した太陽電池の作製が試みられている。一般に有機化
合物は高純度の無機半導体に比べて安価である事を考慮
すると、大面積化が可能であり、且つプラスチックフィ
ルム上に素子を形成させることも容易で、その上、高フ
レキシブル性、軽量性の利点を有している。2. Description of the Related Art Single crystal Si, GaAs, amorphous S
Solar cells using inorganic semiconductors such as i and CdS / CdTe are being actively developed. These are aimed at high conversion efficiency, high durability and low price, but at present it is hard to say that all of them are satisfied. In recent years, attempts have been made to produce solar cells using organic semiconductors. Considering that organic compounds are generally cheaper than high-purity inorganic semiconductors, it is possible to increase the area, and it is easy to form elements on a plastic film, and in addition, it is highly flexible and lightweight. Has the advantage of sex.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、現在ま
でに提案されている有機光起電力素子は変換効率が低
く、実用化には至っていない。例えば、特開昭５１−１
２２３８９号公報、特開昭５３−１３１７８２号公報で
はメロシアニン染料を使用した有機光起電力素子が開示
され、最高で０．７％程度の変換効率が得られている
が、実用化のためにはさらに大きな変換効率が望まし
く、またこの素子は耐候性に弱いという欠点を有してい
る。However, the organic photovoltaic elements proposed so far have low conversion efficiency and have not been put to practical use. For example, JP-A-51-1
No. 22389 and Japanese Patent Laid-Open No. 53-131782 disclose an organic photovoltaic element using a merocyanine dye, and a conversion efficiency of about 0.7% at the maximum is obtained. Greater conversion efficiencies are desirable and this device has the disadvantage of poor weatherability.
【０００４】さらに、特開昭５４−２７７８７号公報で
は平坦な多環核を含む有機電子供与体化合物と有機電子
受容体化合物とからなる有機光起電力素子が開示されて
いるが、同公報中において好ましいとされる材料系にお
いて素子を作製評価してみたところ０．１〜０．３％程
度の変換効率しか得られないことから実用化のためには
依然として変換効率が小さく、素子の作製上の性能安定
性も極めて不安定な状況にある。Further, Japanese Patent Application Laid-Open No. 54-27787 discloses an organic photovoltaic element comprising an organic electron donor compound containing a flat polycyclic nucleus and an organic electron acceptor compound. When a device was manufactured and evaluated in a material system which is considered to be preferable, a conversion efficiency of 0.1 to 0.3% is only obtained, and therefore the conversion efficiency is still small for practical use. The performance stability of is also in an extremely unstable situation.
【０００５】本発明は以上のような問題点を解決するた
めになされたものであって、安価で大面積のものが容易
に作製でき、高い変換効率を有し、その上、可撓性の付
与も可能で安定した性能を発揮できる有機光起電力素子
を提供することを目的とする。The present invention has been made in order to solve the above-mentioned problems, and it is possible to easily manufacture an inexpensive and large-area one, have a high conversion efficiency, and, in addition, have flexibility. It is an object of the present invention to provide an organic photovoltaic element that can be applied and can exhibit stable performance.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく種々検討の結果、導体間に少なくともＰ型
半導体特性を有する有機化合物層とＮ型半導体特性を有
する有機化合物層からなる光起電力層を狭持してなる有
機光起電力素子において、Ｐ型有機化合物がＮ型有機化
合物層と接する第一のＰ型有機化合物層とそれに続く第
二のＰ型有機化合物からなり、第二のＰ型有機化合物層
がジフタロシアニン化合物からなることを特徴とする有
機光起電力素子によって、良好な変換効率が達成される
事を見出し、本発明を完成するに到った。また、上記構
成においてＮ型有機化合物層と電極となる導体との間に
酸化亜鉛層を設ける事によって、さらに特性の向上した
有機光起電力素子が得られる事を見出した。以下詳述す
る。Means for Solving the Problems As a result of various investigations for achieving the above object, the present inventors have found that an organic compound layer having at least P-type semiconductor characteristics and an organic compound layer having N-type semiconductor characteristics are formed between conductors. In the organic photovoltaic element having the photovoltaic layer sandwiched between, the P-type organic compound comprises a first P-type organic compound layer in contact with the N-type organic compound layer and a second P-type organic compound following the first P-type organic compound layer. The inventors have found that good conversion efficiency can be achieved by an organic photovoltaic device characterized in that the second P-type organic compound layer is composed of a diphthalocyanine compound, and have completed the present invention. Further, it was found that by providing a zinc oxide layer between the N-type organic compound layer and the conductor to be the electrode in the above structure, an organic photovoltaic element having further improved characteristics can be obtained. This will be described in detail below.
【０００７】ここでいう電極とは、酸化スズインジウ
ム、酸化スズ、酸化インジウムなどの透明電極、またＡ
ｕ、Ｐｔ、Ｎｉ、Ｐｄ、Ｃｕ、Ｃｒ、Ａｇ、Ａｌなどの
金属電極である。また上部電極としては、透光性のもの
がよく、下部電極としては、光反射性の良いものが望ま
しい。The term "electrode" as used herein means a transparent electrode made of indium tin oxide, tin oxide, indium oxide, etc.
Metal electrodes of u, Pt, Ni, Pd, Cu, Cr, Ag, Al, etc. Further, it is preferable that the upper electrode has a light-transmitting property, and the lower electrode has a good light-reflecting property.
【０００８】本明細書中でいう第一のＰ型有機化合物層
に使用されるＰ型有機化合物は、フタロシアニン化合物
類、キナクリドン化合物類、ポルフィリン化合物類、ア
ゾ顔料、ジアミノカルバゾール、フェニレンジアミン、
トリフェニルアミン、ピラゾニン、ベンジジン、スクア
リリウム材料、インジゴ顔料、メロシアニン顔料、ピロ
ール誘導体などである。上記のうちフタロシタニン化合
物類としては、中心金属が、Ｈ2、Ｃｕ、Ｚｎ、Ｍｇ、
Ａｇ、ＦｅＣｌ、Ｎｉ、Ｐｂ、ＴｉＯ等で、アルキル基
などで置換されていても良いものが使用される。キナク
リドン化合物類としては、３，１０−ジメチルキナクリ
ドン、４，１１−ジメチルキナクリドン、２，９−ジメ
チルキナクリドン、２，９−ジメチルオキシキナクリド
ン等が使用される。ポルフィリン化合物類としては、中
心金属がＨ2、Ｃｕ、Ｚｎ、Ｍｇ、Ａｇ、ＦｅＣｌ、Ｎ
ｉ、Ｐｂ、ＳｎＣｌ等で、置換基としてフェニル基やポ
リジル基、エチル基を持っていても良いものが使用され
る。The P-type organic compound used in the first P-type organic compound layer in the present specification includes phthalocyanine compounds, quinacridone compounds, porphyrin compounds, azo pigments, diaminocarbazole, phenylenediamine,
Examples include triphenylamine, pyrazonin, benzidine, squarylium materials, indigo pigments, merocyanine pigments, and pyrrole derivatives. Among the above, as the phthalocytanine compounds, the central metal is H 2 , Cu, Zn, Mg,
A material such as Ag, FeCl, Ni, Pb, or TiO which may be substituted with an alkyl group is used. As the quinacridone compounds, 3,10-dimethylquinacridone, 4,11-dimethylquinacridone, 2,9-dimethylquinacridone, 2,9-dimethyloxyquinacridone and the like are used. As the porphyrin compounds, the central metal is H 2 , Cu, Zn, Mg, Ag, FeCl, N.
i, Pb, SnCl or the like, which may have a phenyl group, a polyzyl group or an ethyl group as a substituent, is used.
【０００９】第二のＰ型有機化合物層に使用されるジフ
タロシアニン化合物としては、３ｂ族の金属を中心とし
たジフタロシアニンが使用される。具体的には、ＬｕＰ
ｃ2、ＹｂＰｃ2、ＤｙＰｃ2、ＧｄＰｃ2、ＮｄＰｃ2、
ＴｂＰｃ2等（Ｐｃはフタロシアニン環を示す。）であ
り、またこれらの水素化物例えばＧｄＨＰｃ2、ＤｙＨ
Ｐｃ2、ＬｕＨＰｃ2、ＳｃＨＰｃ2等であっても良い。As the diphthalocyanine compound used in the second P-type organic compound layer, diphthalocyanine mainly containing a metal of Group 3b is used. Specifically, LuP
c 2 , YbPc 2 , DyPc 2 , GdPc 2 , NdPc 2 ,
TbPc 2 and the like (Pc represents a phthalocyanine ring), and their hydrides such as GdHPc 2 and DyH.
It may be Pc 2 , LuHPc 2 , ScHPc 2 or the like.
【００１０】Ｎ型有機化合物としては、ペリレン誘導
体、キノン類、ピリリウム塩、ローダミン色素、フェノ
チアジン色素、フェナジン色素等が用いられる。As the N-type organic compound, perylene derivatives, quinones, pyrylium salts, rhodamine dyes, phenothiazine dyes, phenazine dyes and the like are used.
【００１１】Ｎ型有機化合物であるペリレン誘導体とし
ては、下記化１のような構造をとるものを用いることが
できる。As the perylene derivative which is an N-type organic compound, one having a structure represented by the following chemical formula 1 can be used.
【００１２】[0012]
【化１】 [Chemical 1]
【００１３】本発明で用いられる有機化合物は上記した
ものに限定されず、真空蒸着又はＬＢ法により成膜で
き、光導電性を示すものであれば使用可能である。The organic compound used in the present invention is not limited to the above-mentioned ones, and any organic compound can be used as long as it can be formed into a film by vacuum vapor deposition or LB method and exhibits photoconductivity.
【００１４】次に、本発明の素子構成を図によりさらに
説明する。図１において１は透明電極の基板となるガラ
ス又は高分子フィルムを表わし、２は酸化スズインジウ
ム等の透明電極層を表わし、３はＮ型有機化合物層、４
は第一のＰ型有機化合物層、５は第二のＰ型有機化合物
層をそれぞれ表わし、６は背面電極を表わす。この場
合、背面電極６としては仕事関数の大きな金属、例えば
Ａｕが使用される。Next, the element structure of the present invention will be further described with reference to the drawings. In FIG. 1, reference numeral 1 represents a glass or polymer film which will be a substrate of a transparent electrode, 2 represents a transparent electrode layer of indium tin oxide or the like, 3 represents an N-type organic compound layer, 4
Represents a first P-type organic compound layer, 5 represents a second P-type organic compound layer, and 6 represents a back electrode. In this case, a metal having a large work function, such as Au, is used as the back electrode 6.
【００１５】図２では３、４、５の積層順が図１と逆に
なった構成例を示す。この場合、背面電極６としては仕
事関数の小さい金属が、例えばＡｌ、Ｉｎ、Ｃｒ等が使
用される。FIG. 2 shows a configuration example in which the stacking order of 3, 4, and 5 is the reverse of that in FIG. In this case, a metal having a small work function such as Al, In, or Cr is used for the back electrode 6.
【００１６】図３は請求項２で述べたさらに特性の向上
した素子構成を示す。７はＮ型無機化合物である酸化亜
鉛からなる層を示す。FIG. 3 shows an element structure having further improved characteristics described in claim 2. Reference numeral 7 indicates a layer made of zinc oxide which is an N-type inorganic compound.
【００１７】なお、図１〜３は本発明の最も基本的な構
成を表すもので、もちろん本発明はこれらのみに限定さ
れるものではなく、例えば、これらの構成単位が電極部
を除いて又は含めて積層された素子に対しても本発明は
適用される。又、保護層等が設けられていても良い。1 to 3 show the most basic structure of the present invention, and of course, the present invention is not limited to these. For example, these structural units may be used except for the electrode part or The present invention is also applied to a device including and laminated. Further, a protective layer or the like may be provided.
【００１８】第一のＰ型有機化合物層は数ｎｍ〜５０ｎ
ｍの範囲の膜厚が適当である。厚過ぎると第二のＰ型有
機化合物層を加えた効果がなくなり、短絡電流が低下す
る。薄過ぎるとＮ型有機化合物層と第二のＰ型有機化合
物層間での短絡が増大し、開放電圧が低下する。The first P-type organic compound layer has a thickness of several nm to 50 n.
A film thickness in the range of m is suitable. If it is too thick, the effect of adding the second P-type organic compound layer is lost and the short-circuit current decreases. If it is too thin, short circuits between the N-type organic compound layer and the second P-type organic compound layer increase, and the open circuit voltage decreases.
【００１９】第二のＰ型有機化合物層は１０ｎｍ〜１０
０ｎｍの範囲の膜厚が適当である。厚過ぎると短絡電流
が低下し、薄過ぎるとやはり短絡電流が低下する。The second P-type organic compound layer has a thickness of 10 nm to 10 nm.
A film thickness in the range of 0 nm is suitable. If it is too thick, the short-circuit current will decrease, and if it is too thin, the short-circuit current will also decrease.
【００２０】Ｎ型有機化合物層は５ｎｍ〜１００ｎｍの
範囲の膜厚が適当である。厚過ぎると短絡電流が低下
し、薄過ぎると開放電圧が低下する。The N-type organic compound layer preferably has a film thickness in the range of 5 nm to 100 nm. If it is too thick, the short-circuit current will decrease, and if it is too thin, the open circuit voltage will decrease.
【００２１】酸化亜鉛層は一般に知られているスパッタ
法により作製できる。例えば、酸化亜鉛をターゲットと
し、基板温度を２００℃〜３００℃とし、１〜１０ｍＴ
ｏｒｒの真空下、アルゴンガスを導入したプラズマ中で
スパッタリングする事により固有抵抗０．１Ω・ｃｍ〜
１０5Ω・ｃｍ程度の透明な膜として得られる。The zinc oxide layer can be formed by a generally known sputtering method. For example, using zinc oxide as a target, the substrate temperature is 200 ° C. to 300 ° C., and 1 to 10 mT
Specific resistance of 0.1 Ω · cm by sputtering under plasma of argon gas under orr vacuum
It is obtained as a transparent film of about 10 5 Ω · cm.
【００２２】[0022]
【実施例】以下に実施例により本発明をさらに詳しく説
明する。The present invention will be described in more detail with reference to the following examples.
【００２３】実施例１ 表面抵抗２０Ω／□の酸化スズインジウム（ＩＴＯ）蒸
着ガラス上にＮ型有機化合物層としてペリレンテトラカ
ルボン酸ビスメチルイミドを５×１０-6Ｔｏｒｒ以下の
真空度で３０ｎｍの膜厚に蒸着した。次いで第一のＰ型
有機化合物層としてクロロインジウムフタロシアニンを
１５ｎｍの膜厚で蒸着した。さらに第二のＰ型有機化合
物層として水素化ルテチウムジフタロシアニンを３０ｎ
ｍの膜厚で蒸着した。最後に背面電極としてＡｕを約５
０ｎｍの膜厚で蒸着し、酸化スズインジウム部とＡｕ部
にリード線を取り付け、本発明による有機光起電力素子
を作製した。Example 1 Perylene tetracarboxylic acid bismethylimide was used as an N-type organic compound layer on indium tin oxide (ITO) vapor-deposited glass having a surface resistance of 20 Ω / □, and a film of 30 nm was formed at a vacuum degree of 5 × 10 -6 Torr or less. It was vapor-deposited thickly. Then, chloroindium phthalocyanine was vapor-deposited with a film thickness of 15 nm as a first P-type organic compound layer. Further, 30 n of lutetium diphthalocyanine hydride was used as a second P-type organic compound layer.
It was vapor-deposited in a film thickness of m. Finally, about 5 Au is used as the back electrode.
An organic photovoltaic element according to the present invention was produced by vapor deposition with a film thickness of 0 nm and attaching lead wires to the indium tin oxide portion and the Au portion.
【００２４】実施例２ 表面抵抗２０Ω／□のＩＴＯ蒸着ガラス上に対向ターゲ
ットスパッタ装置を使用し、ＤＣ法により基板温度：３
００℃、導入ガス：アルゴン、真空度：４ｍＴｏｒｒ、
成膜速度：０．３ｎｍ／ｓｅｃの条件下、酸化亜鉛層を
約１５０ｎｍの厚さに作製した。この上に実施例１と同
様にして、各有機化合物層と背面電極を蒸着し、リード
線を取り付けて本発明による素子を作製した。Example 2 On an ITO vapor-deposited glass having a surface resistance of 20 Ω / □, a facing target sputtering apparatus was used, and the substrate temperature was 3 by a DC method.
00 ° C., introduced gas: argon, vacuum degree: 4 mTorr,
A zinc oxide layer was formed to a thickness of about 150 nm under the condition of film forming rate: 0.3 nm / sec. In the same manner as in Example 1, each organic compound layer and the back electrode were vapor-deposited thereon, lead wires were attached, and a device according to the present invention was produced.
【００２５】実施例３ 第二のＰ型有機化合物層として水素化ガドリニウムジフ
タロシアニンを使用した以外は実施例２と同様にして本
発明による素子を作製した。Example 3 A device according to the present invention was produced in the same manner as in Example 2 except that hydrogenated gadolinium diphthalocyanine was used as the second P-type organic compound layer.
【００２６】比較例１ 第二のＰ型有機化合物層を設けないでクロロインジウム
フタロシアニンの膜厚を４５ｎｍに変えた以外は実施例
１と同様にして比較例の素子を作製した。Comparative Example 1 An element of Comparative Example was prepared in the same manner as in Example 1 except that the thickness of chloroindium phthalocyanine was changed to 45 nm without providing the second P-type organic compound layer.
【００２７】比較例２ 第二のＰ型有機化合物層を設けないでクロロインジウム
フタロシアニンの膜厚を４５ｎｍに変えた以外は実施例
２と同様にして比較例の素子を作製した。Comparative Example 2 An element of Comparative Example was prepared in the same manner as in Example 2 except that the film thickness of chloroindium phthalocyanine was changed to 45 nm without providing the second P-type organic compound layer.
【００２８】比較例３ 第二のＰ型有機化合物層を設けないで第一のＰ型有機化
合物層に水素化ルテチウムジフタロシアニン膜（膜厚４
５ｎｍ）を用いた以外は実施例２と同様にして比較例の
素子を作製した。Comparative Example 3 A lutetium diphthalocyanine hydride film (film thickness: 4) was formed on the first P-type organic compound layer without providing the second P-type organic compound layer.
A device of a comparative example was produced in the same manner as in Example 2 except that 5 nm) was used.
【００２９】以上のようにして作成した各素子につい
て、ＩＴＯ蒸着ガラス側から疑似太陽光を照射して変換
効率等を測定した。その結果を表１に示す。With respect to each of the devices produced as described above, the conversion efficiency and the like were measured by irradiating pseudo sunlight from the ITO vapor deposition glass side. The results are shown in Table 1.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】実施例１と比較例１との比較からわかる
様に請求項１の構成をとる事により、開放電圧、短絡電
流が大きくなり、変換効率の高い素子が提供される。実
施例２及び３と比較例２及び３との比較から明らかな様
に請求項２の構成をとる事により、開放電圧と短絡電
流、特に短絡電流が大きくなり、さらに変換効率の高い
素子が提供される。As can be seen from the comparison between Example 1 and Comparative Example 1, by adopting the structure of claim 1, an open circuit voltage and a short circuit current are increased and a device having high conversion efficiency is provided. As is clear from the comparison between Examples 2 and 3 and Comparative Examples 2 and 3, by adopting the configuration of claim 2, an open circuit voltage and a short circuit current, especially a short circuit current are increased, and an element having higher conversion efficiency is provided. To be done.
【図１】本発明による光起電力素子の基本的構成を示す
断面図である。FIG. 1 is a sectional view showing a basic configuration of a photovoltaic element according to the present invention.
【図２】本発明による光起電力素子の別の基本的構成を
示す断面図である。FIG. 2 is a sectional view showing another basic structure of the photovoltaic element according to the present invention.
【図３】本発明による光起電力素子のさらに別の基本的
構成を示す断面図である。FIG. 3 is a sectional view showing still another basic structure of the photovoltaic element according to the present invention.
１ 基板 ２ 透明電極層 ３ Ｎ型有機化合物層 ４ 第一のＰ型有機化合物層 ５ 第二のＰ型有機化合物層 ６ 背面電極 ７ 酸化亜鉛層 1 substrate 2 transparent electrode layer 3 N type organic compound layer 4 first P type organic compound layer 5 second P type organic compound layer 6 back electrode 7 zinc oxide layer
Claims (2)
する有機化合物層とＮ型半導体特性を有する有機化合物
層からなる光起電力層を狭持してなる有機光起電力素子
において、Ｐ型有機化合物層がＮ型有機化合物層と接す
る第一のＰ型有機化合物層とそれに続く第二のＰ型有機
化合物層からなり、第二のＰ型有機化合物層がジフタロ
シアニン化合物からなることを特徴とする有機光起電力
素子。1. An organic photovoltaic element comprising a photovoltaic layer comprising at least an organic compound layer having a P-type semiconductor characteristic and an organic compound layer having an N-type semiconductor characteristic sandwiched between conductors. The compound layer comprises a first P-type organic compound layer in contact with the N-type organic compound layer and a second P-type organic compound layer following the first P-type organic compound layer, and the second P-type organic compound layer comprises a diphthalocyanine compound. Organic photovoltaic device.
間にＮ型無機化合物である酸化亜鉛からなる層を設ける
ことを特徴とする請求項１に記載の有機光起電力素子。2. The organic photovoltaic device according to claim 1, wherein a layer made of zinc oxide, which is an N-type inorganic compound, is provided between the N-type organic compound layer and the conductor that serves as an electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3312004A JPH05121771A (en) | 1991-10-29 | 1991-10-29 | Organic photovoltaic element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3312004A JPH05121771A (en) | 1991-10-29 | 1991-10-29 | Organic photovoltaic element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05121771A true JPH05121771A (en) | 1993-05-18 |
Family
ID=18024049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3312004A Pending JPH05121771A (en) | 1991-10-29 | 1991-10-29 | Organic photovoltaic element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05121771A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0766436A (en) * | 1993-08-24 | 1995-03-10 | Ricoh Co Ltd | Organic photovoltaic element |
| JP2012124264A (en) * | 2010-12-07 | 2012-06-28 | Dainippon Printing Co Ltd | Organic thin film solar cell and production method for the same |
| US10381413B2 (en) | 2017-09-05 | 2019-08-13 | Samsung Electronics Co., Ltd. | Organic photoelectric device and image sensor and electronic device |
-
1991
- 1991-10-29 JP JP3312004A patent/JPH05121771A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0766436A (en) * | 1993-08-24 | 1995-03-10 | Ricoh Co Ltd | Organic photovoltaic element |
| JP2012124264A (en) * | 2010-12-07 | 2012-06-28 | Dainippon Printing Co Ltd | Organic thin film solar cell and production method for the same |
| US10381413B2 (en) | 2017-09-05 | 2019-08-13 | Samsung Electronics Co., Ltd. | Organic photoelectric device and image sensor and electronic device |
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