CN101179109A - Tandem organic photovoltaic cells using three layers of organic heterojunction thin films as intermediate electrodes - Google Patents

Abstract

The invention discloses a laminated organic photovoltaic cell which takes three kind triple layer organic heterojunction film as the middle electrode. The advantages of taking organic heterojunction film as the middle electrode are as follows: avoid photo production exaction quenching caused by introduction of metal particle; lost nearly no energy from the effective recombination of electrons and holes at the heterojunction interface; reduce internal resistance because of good electric contact with organic optical activity layer; thereby increasing the efficiency of device.

Description

Tandem organic photovoltaic cells using three layers of organic heterojunction thin films as intermediate electrodes

technical field

The invention relates to a laminated organic photovoltaic cell using an organic heterojunction thin film as an intermediate electrode.

Background technique

In recent years, organic photovoltaic devices have shown application potential in cheap photovoltaic cells, and energy conversion efficiency is an important indicator for the practical application of photovoltaic cells. In 1986, the American Applied Physics Letters (CWTang, Applied Physics Letters 48, 183 (1986)) reported an organic photovoltaic cell with a double-layer organic thin film structure, and the energy conversion efficiency was close to 1%. After nearly a decade of hard work, it has been recognized that the main reason for limiting the further improvement of the efficiency of organic photovoltaic devices is that the exciton diffusion length of organic materials (generally not higher than 10nm) is much smaller than the light absorption length of materials (generally around 100nm). In 1995, the American Journal of Science (G.Yu, J.Gao, JCHummelen, F.Wudl, AJHeeger, Sciences 270, 1789 (1995)) reported a method of blending two kinds of organic materials to overcome the above-mentioned contradictions and realize Photovoltaic cells with energy conversion efficiency exceeding 2% under monochromatic light. This method is to control the two materials to achieve nanoscale two-phase separation in a relatively thick film, forming a bulk heterojunction in which the two materials are continuous in phase and interpenetrating with each other, which greatly increases the interface area of the two phases. The distance from excitons to the two-phase interface is shortened, thereby improving the conversion efficiency of the battery. Another way to solve the above contradiction is to connect multiple cells in series or in parallel. The light that is not fully absorbed by the upper cell can be continuously used by the lower cell. This is a tandem photovoltaic cell. In 1990, Japan's Chemical Letters (M. Hiramoto, M. Suezaki, M. Yokoyama, Chemistry Letters, 1990, 327) first reported the first tandem organic photovoltaic cell prepared using Au as an intermediate electrode. At present, tandem organic photovoltaic cells generally use metal or metal oxide as the intermediate layer, resulting in poor light transmission and quenching of photogenerated excitons near the metal, which limits the further improvement of device efficiency. In 2006, the U.S. Applied Physics Letters (XJYan, J.Wang, HBWang, H.Wang, DHYan, Applied Physics Letters 89, 053510 (2006)) reported the use of copper phthalocyanine (CuPc) and copper phthalocyanine (F ₁₆ The high conductivity characteristic of CuPc) heterojunction effect improves the metal-semiconductor electrical contact properties of organic thin film transistors, the Journal of Applied Physics of the United States in 2007 (SLLai, MY Chan, MKFung, CSLee, STLee, Journal of Applied Physics 101, 014509 (2007 )) reported that using this double-layer heterojunction of copper phthalocyanine and copper fluorophthalocyanine as the intermediate electrode of stacked organic light-emitting diodes, the current luminous efficiency of stacked light-emitting diodes was significantly improved. However, the direct application of copper phthalocyanine and copper fluorophthalocyanine heterojunction bilayer films to metal phthalocyanine-fullerene (C60) stacked organic photovoltaic cells generally leads to a significant decrease in the open circuit voltage and fill factor of the battery, and cannot exert its full potential. Advantages of tandem organic photovoltaic cells.

Contents of the invention

The object of the present invention is to provide a stacked organic photovoltaic cell using a three-layer organic heterojunction thin film as an intermediate electrode, which overcomes the poor light transmission properties, photogenerated excitons quenching near the intermediate layer, and open circuit voltage and The problem of fill factor loss can be significantly improved at the same time.

The stacked organic photovoltaic cells provided by the present invention using three layers of organic heterojunction thin films as intermediate electrodes have three types.

As shown in Figure 1, the first type of laminated organic photovoltaic cell using three-layer organic heterojunction thin film as the intermediate electrode provided by the present invention is composed of: a transparent substrate 1, a transparent electrode 2, the first cell of the first cell Semiconductor layer 3, second semiconductor layer 4 of the first cell, intermediate electrode layer 5, intermediate electrode layer 6, intermediate electrode layer 7, first semiconductor layer 8 of the second cell, second semiconductor layer 9 of the second cell and metal Electrode 10; transparent substrate 1, transparent electrode 2, first semiconductor layer 3 of the first battery, second semiconductor layer 4 of the first battery, intermediate electrode layer 5, intermediate electrode layer 6, intermediate electrode layer 7, and second semiconductor layer of the second battery The first semiconductor layer 8, the second semiconductor layer 9 of the second battery and the metal electrode 10 are connected in sequence; wherein, the first semiconductor layer 3 of the first battery and the second semiconductor layer 4 of the first battery constitute the first battery, and The first semiconductor layer 8 of the second battery and the second semiconductor layer 9 of the second battery form the second battery, and the intermediate electrode layer 5, the intermediate electrode layer 6 and the intermediate electrode layer 7 constitute the intermediate electrode connecting the first battery and the second battery;

The first semiconductor layer 3 of the first battery is nickel phthalocyanine (NiPc), ferrous phthalocyanine (FePc), tin phthalocyanine (SnPc), copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), phthalocyanine Zinc cyanine (ZnPc), lead phthalocyanine (PbPc), vanadyl phthalocyanine (VOPc), titanium oxyphthalocyanine (TiOPc), iron chloride phthalocyanine (FeClPc), titanium dichloride phthalocyanine (TiCl ₂ Pc), phthalocyanine Indium chloride (InClPc), manganese chloride phthalocyanine (MnClPc), gallium chloride phthalocyanine (GaClPc), titanium difluoride phthalocyanine (TiF ₂ Pc), tin difluoride phthalocyanine (SnF ₂ Pc), indium fluorine phthalocyanine (InFPc ) and germanium phthalocyanine dichloride (GeCl ₂ Pc); its thickness is greater than or equal to 10 nanometers and less than or equal to 30 nanometers;

The second semiconductor layer 4 of the first battery is any one of fullerene (C60), dibenzimidazole perylene (PTCBI), tin oxytin phthalocyanine (SnOPc) and tin dichloride phthalocyanine (SnCl ₂ Pc). One; its thickness is greater than or equal to 20 nanometers and less than or equal to 60 nanometers;

The first semiconductor layer 8 of the second battery is nickel phthalocyanine (NiPc), ferrous phthalocyanine (FePc), tin phthalocyanine (SnPc), copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), phthalocyanine Zinc (ZnPc), lead phthalocyanine (PbPc), vanadyl phthalocyanine (VOPc), titanium oxyphthalocyanine (TiOPc), iron chloride phthalocyanine (FeClPc), titanium dichloride phthalocyanine (TiCl ₂ Pc), indium phthalocyanine Chlorine (InClPc), manganese chloride phthalocyanine (MnClPc), gallium chloride phthalocyanine (GaClPc), titanium difluoride phthalocyanine (TiF ₂ Pc), tin difluoride phthalocyanine (SnF ₂ Pc), indium fluorine phthalocyanine (InFPc) and one of germanium dichloride phthalocyanine (GeCl ₂ Pc); its thickness is greater than or equal to 10 nm and less than or equal to 50 nm;

The second semiconductor layer 9 of the second battery is any one of fullerene (C60), dibenzimidazole perylene (PTCBI), tin oxytin phthalocyanine (SnOPc) and tin dichloride phthalocyanine (SnCl ₂ Pc). One, the thickness of which is greater than or equal to 20 nanometers and less than or equal to 100 nanometers;

The intermediate electrode layer 5 is one of oxytin phthalocyanine (SnOPc) and tin dichloride phthalocyanine (SnCl ₂ Pc), the thickness of which is greater than or equal to 2 nanometers and less than or equal to 30 nanometers;

The intermediate electrode layer 6 is tin oxyphthalocyanine (SnOPc), tin phthalocyanine dichloride (SnCl ₂ Pc), hexadecylchloroaluminum phthalocyanine (Cl ₁₆ AlClPc), hexadecafluorotitanium phthalocyanine ( F ₁₆ TiOPc), hexadecafluorovanadyl phthalocyanine (F ₁₆ VOPc), hexadecafluoroindium phthalocyanine chloride (F ₁₆ InClPc), hexadexadecafluoromanganese phthalocyanine chloride (F ₁₆ MnClPc), hexadecafluoro Tin dichloride phthalocyanine (F ₁₆ SnCl ₂ Pc), titanium dichloride hexadecafluoride (F ₁₆ TiCl ₂ Pc), aluminum chloride hexafluorophthalocyanine (F ₁₆ AlClPc), tin hexadecyl chlorophthalocyanine Dichloro (Cl ₁₆ SnCl ₂ Pc), hexadecyl chlorotitanium phthalocyanine (Cl ₁₆ TiOPc), hexadecyl chlorovanadyl phthalocyanine (Cl ₁₆ VOPc), hexadecyl chloroindium phthalocyanine chloride (Cl ₁₆ InClPc ) and copper hexadecafluorophthalocyanine (F ₁₆ CuPc); its thickness is greater than or equal to 2 nanometers and less than or equal to 30 nanometers;

The intermediate electrode layer 7 is nickel phthalocyanine (NiPc), ferrous phthalocyanine (FePc), tin phthalocyanine (SnPc), copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), zinc phthalocyanine (ZnPc) , lead phthalocyanine (PbPc), vanadyl phthalocyanine (VOPc), titanium oxyphthalocyanine (TiOPc), iron chloride phthalocyanine (FeClPc), titanium dichloride phthalocyanine (TiCl ₂ Pc), indium chloride phthalocyanine (InClPc) , manganese chloride phthalocyanine (MnClPc), gallium chloride phthalocyanine (GaClPc), titanium difluoride phthalocyanine (TiF ₂ Pc), tin difluoride phthalocyanine (SnF ₂ Pc), indium fluoride phthalocyanine (InFPc) and germanium phthalocyanine Any of dichloro (GeCl ₂ Pc); its thickness is greater than or equal to 2 nanometers and less than or equal to 30 nanometers.

As shown in Figure 3, the second type of laminated organic photovoltaic cell using three-layer organic heterojunction thin film as the intermediate electrode provided by the present invention consists of: a transparent substrate 1, a transparent electrode 2, the first cell of the first cell Semiconductor layer 3, second semiconductor layer 4 of the first battery, intermediate electrode layer 5, intermediate electrode layer 6, intermediate electrode layer 7, second semiconductor layer 9 of the second battery and metal electrode 10; transparent substrate 1, transparent electrode 2 , the first semiconductor layer 3 of the first battery, the second semiconductor layer 4 of the first battery, the intermediate electrode layer 5, the intermediate electrode layer 6, the intermediate electrode layer 7, the second semiconductor layer 9 of the second battery and the metal electrode 10 along Secondary connection; Wherein, the first semiconductor layer 3 of the first battery and the second semiconductor layer 4 of the first battery form the first battery, and the intermediate electrode layer 5, the intermediate electrode layer 6 and the intermediate electrode layer 7 form the connection between the first battery and the second electrode layer. The middle electrode of the second battery, the middle electrode layer 7 is simultaneously used as the first semiconductor layer of the second battery, and the second semiconductor layer 9 of the middle electrode layer 7 and the second battery constitutes the second battery;

The first semiconductor layer 3 of the first battery is nickel phthalocyanine (NiPc), ferrous phthalocyanine (FePc), tin phthalocyanine (SnPc), copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), phthalocyanine Zinc (ZnPc), lead phthalocyanine (PbPc), vanadyl phthalocyanine (VOPc), titanium oxyphthalocyanine (TiOPc), iron chloride phthalocyanine (FeClPc), titanium dichloride phthalocyanine (TiCl ₂ Pc), indium phthalocyanine Chlorine (InClPc), manganese chloride phthalocyanine (MnClPc), gallium chloride phthalocyanine (GaClPc), titanium difluoride phthalocyanine (TiF ₂ Pc), tin difluoride phthalocyanine (SnF ₂ Pc), indium fluorine phthalocyanine (InFPc) and one of germanium phthalocyanine dichloride (GeCl ₂ Pc); its thickness is greater than or equal to 10 nm and less than or equal to 30 nm;

The second semiconductor layer 4 of the first battery is any one of fullerene (C60), dibenzimidazole perylene (PTCBI), tin oxytin phthalocyanine (SnOPc) and tin dichloride phthalocyanine (SnCl ₂ Pc). One; its thickness is greater than or equal to 20 nanometers and less than or equal to 60 nanometers;

The intermediate electrode layer 5 is one of oxytin phthalocyanine (SnOPc) and tin dichloride phthalocyanine (SnCl ₂ Pc); its thickness is greater than or equal to 2 nanometers and less than or equal to 30 nanometers;

The intermediate electrode layer 6 is tin oxyphthalocyanine (SnOPc), tin phthalocyanine dichloride (SnCl ₂ Pc), hexadecylchloroaluminum phthalocyanine (Cl ₁₆ AlClPc), hexadecafluorotitanium phthalocyanine ( F ₁₆ TiOPc), hexadecafluorovanadyl phthalocyanine (F ₁₆ VOPc), hexadecafluoroindium phthalocyanine chloride (F ₁₆ InClPc), hexadexadecafluoromanganese phthalocyanine chloride (F ₁₆ MnClPc), hexadecafluoro Tin dichloride phthalocyanine (F ₁₆ SnCl ₂ Pc), titanium dichloride hexadecafluoride (F ₁₆ TiCl ₂ Pc), aluminum chloride hexafluorophthalocyanine (F ₁₆ AlClPc), tin hexadecyl chlorophthalocyanine Dichloro (Cl ₁₆ SnCl ₂ Pc), hexadecyl chlorotitanium phthalocyanine (Cl ₁₆ TiOPc), hexadecyl chlorovanadyl phthalocyanine (Cl ₁₆ VOPc), hexadecyl chlorinated sodium phthalocyanine chloride (Cl ₁₆ InClPc ) and copper hexadecafluorophthalocyanine (F ₁₆ CuPc); its thickness is greater than or equal to 2 nanometers and less than or equal to 30 nanometers;

The intermediate electrode layer 7 is nickel phthalocyanine (NiPc), ferrous phthalocyanine (FePc), tin phthalocyanine (SnPc), copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), zinc phthalocyanine (ZnPc) , lead phthalocyanine (PbPc), vanadyl phthalocyanine (VOPc), titanium oxyphthalocyanine (TiOPc), iron chloride phthalocyanine (FeClPc), titanium dichloride phthalocyanine (TiCl ₂ Pc), indium chloride phthalocyanine (InClPc) , manganese chloride phthalocyanine (MnClPc), gallium chloride phthalocyanine (GaClPc), titanium difluoride phthalocyanine (TiF ₂ Pc), tin difluoride phthalocyanine (SnF ₂ Pc), indium fluoride phthalocyanine (InFPc) and germanium phthalocyanine One of dichloro (GeCl ₂ Pc); its thickness is greater than or equal to 2 nanometers and less than or equal to 30 nanometers;

The second semiconductor layer 9 of the second battery is any one of fullerene (C60), dibenzimidazole perylene (PTCBI), tin oxytin phthalocyanine (SnOPc) and tin dichloride phthalocyanine (SnCl ₂ Pc). One; its thickness is greater than or equal to 20 nanometers and less than or equal to 100 nanometers.

Compared with the first configuration of the present invention, the second configuration uses the intermediate electrode layer 7 for the first semiconductor of the second battery at the same time, which simplifies the manufacturing process.

As shown in Figure 5, the third type of stacked organic photovoltaic cell using three-layer organic heterojunction thin film as the intermediate electrode provided by the present invention is composed of: transparent substrate 1, transparent electrode 2, the first cell of the first cell Semiconductor layer 3, intermediate electrode layer 5, intermediate electrode layer 6, intermediate electrode layer 7, first semiconductor layer 8 of the second cell, second semiconductor layer 9 of the second cell, and metal electrode 10; transparent substrate 1, transparent electrode 2 , the first semiconductor layer 3 of the first battery, the intermediate electrode layer 5, the intermediate electrode layer 6, the intermediate electrode layer 7, the first semiconductor layer 8 of the second battery, the second semiconductor layer 9 of the second battery and the metal electrode 10 along secondary connection; wherein, the intermediate electrode layer 5, the intermediate electrode layer 6 and the intermediate electrode layer 7 constitute the intermediate electrode connecting the first battery and the second battery, and meanwhile, the intermediate electrode layer 5 is as the second semiconductor of the first battery and the first battery The first semiconductor layer 3 of the second battery constitutes the first battery; the first semiconductor layer 8 of the second battery and the second semiconductor layer 9 of the second battery form the second battery;

The first semiconductor layer 3 of the first battery is nickel phthalocyanine (NiPc), ferrous phthalocyanine (FePc), tin phthalocyanine (SnPc), copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), phthalocyanine Zinc (ZnPc), lead phthalocyanine (PbPc), vanadyl phthalocyanine (VOPc), titanium oxyphthalocyanine (TiOPc), iron chloride phthalocyanine (FeClPc), titanium dichloride phthalocyanine (TiCl ₂ Pc), indium phthalocyanine Chlorine (InClPc), manganese chloride phthalocyanine (MnClPc), gallium chloride phthalocyanine (GaClPc), titanium difluoride phthalocyanine (TiF ₂ Pc), tin difluoride phthalocyanine (SnF ₂ Pc), indium fluorine phthalocyanine (InFPc) and one of germanium phthalocyanine dichloride (GeCl ₂ Pc); its thickness is greater than or equal to 10 nm and less than or equal to 30 nm;

The first semiconductor layer 8 of the second battery is nickel phthalocyanine (NiPc), ferrous phthalocyanine (FePc), tin phthalocyanine (SnPc), copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), phthalocyanine Zinc (ZnPc), lead phthalocyanine (PbPc), vanadyl phthalocyanine (VOPc), titanium oxyphthalocyanine (TiOPc), iron chloride phthalocyanine (FeClPc), titanium dichloride phthalocyanine (TiCl ₂ Pc), indium phthalocyanine Chlorine (InClPc), manganese chloride phthalocyanine (MnClPc), gallium chloride phthalocyanine (GaClPc), titanium difluoride phthalocyanine (TiF ₂ Pc), tin difluoride phthalocyanine (SnF ₂ Pc), indium fluorine phthalocyanine (InFPc) and one of germanium dichloride phthalocyanine (GeCl ₂ Pc); its thickness is greater than or equal to 10 nm and less than or equal to 50 nm;

The second semiconductor layer 9 of the second battery is any one of fullerene (C60), dibenzimidazole flower (PTCBI), tin oxytin phthalocyanine (SnOPc) and tin dichloride phthalocyanine (SnCl ₂ Pc). One; its thickness is greater than or equal to 20 nanometers and less than or equal to 100 nanometers;

The intermediate electrode layer 5 is one of oxytin phthalocyanine (SnOPc) and tin dichloride phthalocyanine (SnCl ₂ Pc); its thickness should be greater than or equal to 2 nanometers and less than or equal to 30 nanometers;

The intermediate electrode layer 6 is tin oxyphthalocyanine (SnOPc), tin phthalocyanine dichloride (SnCl ₂ Pc), hexadecylchloroaluminum phthalocyanine (Cl ₁₆ AlClPc), hexadecafluorotitanium phthalocyanine ( F ₁₆ TiOPc), hexadecafluorovanadyl phthalocyanine (F ₁₆ VOPc), hexadecafluoroindium phthalocyanine chloride (F ₁₆ InClPc), hexadexadecafluoromanganese phthalocyanine chloride (F ₁₆ MnClPc), hexadecafluoro Tin dichloride phthalocyanine (F ₁₆ SnCl ₂ Pc), titanium dichloride hexadecafluoride (F ₁₆ TiCl ₂ Pc), aluminum chloride hexafluorophthalocyanine (F ₁₆ AlClPc), tin hexadecyl chlorophthalocyanine Dichloro (Cl ₁₆ SnCl ₂ Pc), hexadecyl chlorotitanium phthalocyanine (Cl ₁₆ TiOPc), hexadecyl chlorovanadyl phthalocyanine (Cl ₁₆ VOPc), hexadecyl chloroindium phthalocyanine chloride (Cl ₁₆ InClPc ) and copper hexadecafluorophthalocyanine (F ₁₆ CuPc); its thickness is greater than or equal to 2 nanometers and less than or equal to 30 nanometers;

The intermediate electrode layer 7 is nickel phthalocyanine (NiPc), ferrous phthalocyanine (FePc), tin phthalocyanine (SnPc), copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), zinc phthalocyanine (ZnPc) , lead phthalocyanine (PbPc), vanadyl phthalocyanine (VOPc), titanium oxyphthalocyanine (TiOPc), iron chloride phthalocyanine (FeClPc), titanium dichloride phthalocyanine (TiCl ₂ Pc), indium chloride phthalocyanine (InClPc) , manganese chloride phthalocyanine (MnClPc), gallium chloride phthalocyanine (GaClPc), titanium difluoride phthalocyanine (TiF ₂ Pc), tin difluoride phthalocyanine (SnF ₂ Pc), indium fluoride phthalocyanine (InFPc) and germanium phthalocyanine One of dichloro (GeCl ₂ Pc); its thickness is greater than or equal to 2 nanometers and less than or equal to 30 nanometers.

Compared with the first configuration of the present invention, the third configuration uses the intermediate electrode layer 5 as the second semiconductor of the first battery, which simplifies the manufacturing process.

Another object of the present invention is to provide a method for preparing a stacked organic photovoltaic cell using a three-layer organic heterojunction thin film as an intermediate electrode.

1) The steps and conditions of the preparation method of the stacked organic photovoltaic cell using the first structure of the three-layer organic heterojunction thin film as the intermediate electrode are as follows:

According to the materials given for each layer, the vacuum deposition equipment used has a vacuum chamber background vacuum of 8.0×10 ^-4 , the substrate temperature is between room temperature and 120 degrees, and the deposition rate is 10 nanometers per minute. The first semiconductor layer 3 of the first battery is deposited on the electrode 2 by vacuum evaporation, and its thickness is greater than or equal to 10 nanometers and less than or equal to 30 nanometers; The method deposits the second semiconductor layer 4 of the first battery, whose thickness is greater than or equal to 20 nanometers and less than or equal to 60 nanometers, and adopts the method of vacuum evaporation on the second semiconductor layer 4 of the first battery to sequentially deposit the middle electrode that constitutes the middle electrode. Electrode layer 5, intermediate electrode layer 6, and intermediate electrode layer 7 are three layers of organic heterojunction films, each layer having a thickness greater than or equal to 2 nanometers and less than or equal to 30 nanometers; the intermediate electrode layer 7 is deposited by vacuum evaporation The first semiconductor layer 8 of the second battery has a thickness greater than or equal to 10 nanometers and less than or equal to 50 nanometers; the second semiconductor layer of the second battery is deposited on the first semiconductor layer 8 of the second battery by vacuum evaporation 9, the thickness of which is greater than or equal to 20 nanometers and less than or equal to 100 nanometers; the metal electrode 10 is prepared on the second semiconductor layer 9 of the second battery by vacuum evaporation.

2) The steps and conditions of the preparation method of the stacked organic photovoltaic cell using the second structure of the three-layer organic heterojunction thin film as the intermediate electrode are as follows:

According to the given materials for each layer, the vacuum deposition equipment used has a vacuum chamber background vacuum of 8.0×10 ^-4 Pa, a substrate temperature between room temperature and 120 degrees, and a deposition rate of 10 nanometers per minute. The first semiconductor layer 3 of the first battery is deposited on the transparent electrode 2 by vacuum evaporation, and its thickness is greater than or equal to 10 nanometers and less than or equal to 30 nanometers; on the first semiconductor layer 3 of the first battery, vacuum evaporation is used The method for depositing the second semiconductor layer 4 of the first battery has a thickness greater than or equal to 20 nanometers and less than or equal to 60 nanometers, and the second semiconductor layer 4 of the first battery is sequentially deposited on the second semiconductor layer 4 of the first battery to form the intermediate electrode. The middle electrode layer 5, the middle electrode layer 6, and the middle electrode layer 7 are three-layer organic heterojunction thin films, each of which has a thickness greater than or equal to 2 nanometers and less than or equal to 30 nanometers; the method of vacuum evaporation is adopted on the middle electrode layer 7 The second semiconductor layer 9 of the second battery is deposited, and its thickness is greater than or equal to 20 nanometers and less than or equal to 100 nanometers; on the second semiconductor layer 9 of the second battery, a metal electrode 10 is prepared by vacuum evaporation.

3) The steps and conditions of the preparation method of the stacked organic photovoltaic cell using the third structure of the three-layer organic heterojunction thin film as the intermediate electrode are as follows:

According to the given materials for each layer, the vacuum deposition equipment used has a vacuum chamber background vacuum of 8.0×10 ^-4 Pa, a substrate temperature between room temperature and 120 degrees, and a deposition rate of 10 nanometers per minute. The first semiconductor layer 3 of the first battery is deposited on the transparent electrode 2 by vacuum evaporation, and its thickness is greater than or equal to 10 nanometers and less than or equal to 30 nanometers; on the first semiconductor layer 3 of the first battery, vacuum evaporation is used The method of sequentially depositing three layers of organic heterojunction films, the intermediate electrode layer 5, the intermediate electrode layer 6, and the intermediate electrode layer 7, which constitute the intermediate electrode, each layer has a thickness greater than or equal to 2 nanometers and less than or equal to 30 nanometers; on the intermediate electrode layer The first semiconductor layer 8 of the second battery is deposited by vacuum evaporation on 7, and its thickness is greater than or equal to 10 nanometers and less than or equal to 50 nanometers; the method of vacuum evaporation is used on the first semiconductor layer 8 of the second battery The second semiconductor layer 9 of the second battery is deposited, and its thickness is greater than or equal to 20 nanometers and less than or equal to 100 nanometers; on the second semiconductor layer 9 of the second battery, a metal electrode 10 is prepared by vacuum evaporation.

Beneficial effects of the present invention: the organic heterojunction thin film is used as the intermediate electrode. Since the organic heterojunction thin film has the characteristics of separate transmission of electrons and holes, the recombination of electrons and holes can be effectively carried out at the heterojunction interface and almost There is no energy loss, and at the same time, it has relatively good electrical contact with the organic active layer, which is beneficial to the improvement of the performance of the laminated organic photovoltaic cell.

The invention has the advantages of remarkably improved battery performance and simple preparation process. The device can be widely used in low-cost and high-efficiency photovoltaic cells and wide-spectrum sensitive sensors and other fields.

Description of drawings

Figure 1 is a schematic diagram of the structure of a stacked organic photovoltaic cell using a three-layer organic semiconductor heterojunction as an intermediate electrode. Among them, 1 is the transparent substrate, 2 is the transparent anode, 3 is the first semiconductor layer of the first battery, 4 is the second semiconductor layer of the first battery, 5 is the intermediate electrode layer, 6 is the intermediate electrode layer, and 7 is the intermediate electrode Layer, 8 is the first semiconductor layer of the second cell, 9 is the second semiconductor layer of the second cell, and 10 is the metal cathode. Figure 1 is also an abstract drawing.

Fig. 2 is a current-voltage characteristic curve of the stacked organic photovoltaic cell adopting the structure of Fig. 1 . Wherein, the transparent anode is ITO, the first semiconductor layer of the first and second cells is zinc phthalocyanine (ZnPc), the second semiconductor layer of the first and second cells is fullerene (C60), and the intermediate electrode layer 5 is Tin phthalocyanine dichloride (SnCl ₂ Pc), the middle electrode layer 6 is hexadecafluorocopper phthalocyanine (F ₁₆ CuPc), the middle electrode layer 7 is copper phthalocyanine (CuPc), and the metal cathode is Al.

Fig. 3 is a schematic diagram of a second structure of a stacked organic photovoltaic cell using a three-layer organic semiconductor heterojunction as an intermediate electrode. Among them, 1 is the transparent substrate, 2 is the transparent anode, 3 is the first semiconductor layer of the first battery, 4 is the second semiconductor layer of the first battery, 5 is the intermediate electrode layer, 6 is the intermediate electrode layer, and 7 is the intermediate electrode Layer 9 is the second semiconductor layer of the second cell and 10 is the metal cathode.

Fig. 4 is a current-voltage characteristic curve of the stacked organic photovoltaic cell adopting the structure of Fig. 3 . Among them, the transparent anode is ITO, the first semiconductor layer of the first battery is CuPc, the second semiconductor layer of the first and second batteries is C60, the middle electrode layer 5 is SnOPc, the middle electrode layer 6 is F ₁₆ AlClPc, and the middle electrode Layer 7 is ZnPc which also functions as the first semiconductor layer of the second battery, and the metal cathode is Al.

Fig. 5 is a schematic diagram of a third structure of a stacked organic battery using a three-layer organic semiconductor heterojunction as an intermediate electrode. Among them, 1 is the transparent substrate, 2 is the transparent anode, 3 is the first semiconductor layer of the first cell, 5 is the intermediate electrode layer, 6 is the intermediate electrode layer, 7 is the intermediate electrode layer, 8 is the first semiconductor layer of the second cell Layer 9 is the second semiconductor layer of the second cell and 10 is the metal cathode.

Fig. 6 is a current-voltage characteristic curve of the stacked organic photovoltaic cell adopting the structure of Fig. 5 . Wherein, the transparent anode is ITO, the first semiconductor layer of the first battery and the second battery is nickel phthalocyanine (NiPc), the middle electrode layer 5 is SnCl ₂ Pc which also has the function of the second semiconductor layer of the first battery, and the middle The electrode layer 6 is Cl ₁₆ CuPc, the intermediate electrode layer 7 is CoPc, and the second semiconductor layer of the second cell is SnCl ₂ Pc.

Example 1

Nickel phthalocyanine (NiPc), tin phthalocyanine (SnPc), copper phthalocyanine (CuPc), cobalt phthalocyanine (CoPc), zinc phthalocyanine (ZnPc), lead phthalocyanine (PbPc), vanadyl phthalocyanine (VOPc) used , titanium oxyphthalocyanine (TiOPc), iron chloride phthalocyanine (FeClPc), titanium dichloride phthalocyanine (TiCl ₂ Pc), tin dichloride phthalocyanine (SnCl ₂ Pc), indium chloride phthalocyanine (InClPc), hexadecyl chloride Aluminum chloride phthalocyanine (Cl ₁₆ AlClPc), manganese chloride phthalocyanine (MnClPc), gallium chloride phthalocyanine (GaClPc), tin oxytin phthalocyanine (SnOPc), titanium difluoride phthalocyanine (TiF ₂ Pc), tin difluoride phthalocyanine Fluorine (SnF ₂ Pc), indium fluorine phthalocyanine (InFPc), germanium phthalocyanine dichloride (GeCl ₂ Pc), hexadecafluorotitanyl phthalocyanine (F ₁₆ TiOPc), hexadecafluorovanadyl phthalocyanine (F ₁₆ VOPc), hexadecafluorophthalocyanine indium chloride (F ₁₆ InClPc), hexadecafluorophthalocyanine manganese chloride (F ₁₆ MnClPc), hexadecafluorophthalocyanine tin dichloride (F ₁₆ SnCl ₂ Pc), ten Titanium dichloride hexafluorophthalocyanine (F ₁₆ TiCl ₂ Pc), Aluminum chloride hexafluorophthalocyanine (F ₁₆ AlClPc), Tin dichloride hexachlorophthalocyanine (Cl ₁₆ SnCl ₂ Pc), Hexadecyl chloride Titanium oxyphthalocyanine (Cl ₁₆ TiOPc), vanadyl phthalocyanine hexadecyl chloride (Cl ₁₆ VOPc), indium chloride phthalocyanine hexadecyl chloride (Cl ₁₆ InClPc), copper hexadecafluorophthalocyanine (F ₁₆ CuPc ), fullerene (C60) and perylene dibenzimidazole (PTCBI) are commercial products, which are used after secondary sublimation purification. ITO glass is a commercial product and is used after cleaning. Metal aluminum is a commercial product and is used directly.

The device structure adopts the first type of composition of the laminated organic photovoltaic cell using three layers of organic heterojunction thin films as intermediate electrodes provided by the present invention.

The specific processing method of the device is as follows:

On the ITO glass 2, the first semiconductor layer 3 of the first battery and the second semiconductor layer 4 of the first battery are sequentially deposited by vacuum evaporation; The method deposits the intermediate electrode layer 5, the intermediate electrode layer 6, and the intermediate electrode layer 7 in sequence; the first semiconductor layer 8 of the second battery and the second semiconductor layer of the second battery are sequentially deposited on the intermediate electrode layer 7 by vacuum evaporation 9; on the second semiconductor layer 9 of the second battery, adopt the method of vacuum evaporation, utilize the drain plate to deposit one layer of aluminum (Al) with an area of 3.14 square centimeters and 100 nanometers thick as the metal cathode 10 to form the structure shown in Figure 1 Laminated battery.

Among them, the background vacuum is 8×10 ^-4 Pa, the substrate temperature is from room temperature to 120°C, and the evaporation rate is 10 nanometers per minute; the first semiconductor layer 3 of the first battery is zinc phthalocyanine (ZnPc) with a thickness of 10 nanometers The second semiconductor layer 4 of the first cell is fullerene (C60), with a thickness of 20 nanometers; the middle electrode layer 5 is tin phthalocyanine dichloride (SnCl ₂ Pc), with a thickness of 2 nanometers; the middle electrode layer 6 is hexadecanofluorine Copper phthalocyanine (F ₁₆ CuPc) with a thickness of 3 nanometers; the intermediate electrode layer 7 is copper phthalocyanine (CuPc) with a thickness of 5 nanometers; the first semiconductor layer 8 of the second battery is zinc phthalocyanine (ZnPc) with a thickness of 10 nanometers , the second semiconductor layer 9 of the second cell is fullerene (C60) with a thickness of 20 nanometers.

For the convenience of comparison, a single cell using ZnPc as the first semiconductor layer, C60 as the second semiconductor layer, and Al as the metal cathode was prepared on the surface of ITO glass under the same conditions.

Figure 2 shows the use of ZnPc as the first semiconductor layer of the first and second cells, C60 as the second semiconductor layer of the first and second cells, SnCl ₂ Pc as the middle electrode layer 5, and F ₁₆ CuPc as the middle electrode layer 5 on the surface of the ITO glass. The current-voltage curves of the stacked organic photovoltaic cell with the electrode layer 6, CuPc as the intermediate electrode layer 7, and Al as the metal cathode in the dark state and under the irradiation of a simulated solar light source. Under the atmosphere mass (AM) 1.5, light intensity 100mW/cm ² simulated solar light source, the open circuit voltage of the device is 1.02V, the short circuit current density is 3.0mA/cm ² , the fill factor is 0.5, and the energy conversion efficiency is 1.53%. Compared with single cells, the open circuit voltage is 0.54V, the short circuit current density is 3.9mA/cm ² , the filling factor is 0.53, the energy conversion efficiency is 1.1%, and the efficiency is increased by more than 40%. Therefore, the intermediate electrode composed of three layers of organic heterojunction films can overcome the problems of poor light transmission properties, quenching of photogenerated excitons near the intermediate layer, and loss of open circuit voltage and fill factor in the prior art, and can significantly improve cell efficiency. .

Table 1 shows the structure and performance of the device of the first configuration of the stacked organic photovoltaic cell using the three-layer organic heterojunction thin film as the intermediate electrode prepared according to Example 1 provided by the present invention, as can be seen from Table 1 , the intermediate electrode composed of three layers of organic heterojunction thin films can realize high-efficiency stacked organic photovoltaic cells.

Table 1: Structure and performance of tandem organic photovoltaic cells using three-layer organic heterojunction thin films as intermediate electrodes

battery material and First battery first semiconductor layer 3 ZnPc ZnPc CuPc CuPc Thickness (nanometer) 10 30 30 20

thickness The first battery second semiconductor layer 4 C60 PTCBI C60 SnOPc Thickness (nanometer) 20 30 60 40 The second battery first semiconductor layer 8 ZnPc CuPc CuPc TiOPc Thickness (nanometer) 10 50 30 45 The second battery second semiconductor layer 9 C60 PTCBI PTCBI C60 Thickness (nanometer) 20 100 70 80 Middle electrode material and thickness Middle electrode layer 5 SnCl ₂ Pc SnOPc SnCl ₂ Pc SnCl ₂ Pc Thickness (nanometer) 2 30 5 15 Middle electrode layer 6 F ₁₆ CuPc F ₁₆ VOPc Cl ₁₆ AlClPc F ₁₆ AlClPc Thickness (nanometer) 3 15 30 13 Middle electrode layer 7 CuPc CoPc NiPc FePc Thickness (nanometer) 5 30 15 20 Device performance Open circuit voltage (volts) 1.02 1.02 1.06 1.04 Short circuit current density (mA/cm2) 3.0 4.8 3.5 5.0 fill factor 0.5 0.48 0.52 0.47  Energy Conversion Efficiency 1.53% 2.35% 1.92% 2.44%

Continued Table 1

Battery material and thickness First Battery First Semiconductor 3 NiPc CoPc FePc VOPc Thickness (nanometer) 10 25 20 30 1st battery 2nd semiconductor 4 PTCBI C60 SnOPc C60 Thickness (nanometer) 20 40 30 60 Second battery First semiconductor 8 TiOPc PbPc SnPc CuPc Thickness (nanometer) 20 10 30 50 Second battery Second semiconductor 9 C60 SnCl ₂ Pc PTCBI C60 Thickness (nanometer) 40 20 50 100 Intermediate electrode material and thickness Intermediate electrode layer 5 SnCl ₂ Pc SnOPc SnCl ₂ Pc SnOPc Thickness (nanometer) 12 7 10 2 Middle layer 6 F ₁₆ InClPc F ₁₆ MnClPc F ₁₆ TiCl ₂ Pc Cl ₁₆ TiOPc Thickness (nanometer) 8 15 20 2 Middle layer 7 CuPc CoPc NiPc FePc Thickness (nanometer) 10 20 5 2 Device performance Open circuit voltage (volts) 1.03 1.05 1.05 1.04 Short circuit current density (mA/cm2) 2.8 3.4 2.7 3.1 fill factor 0.48 0.51 0.49 0.47 Energy conversion efficiency 1.38% 1.82% 1.39% 1.52%

Example 2

Materials used are the same as in Example 1.

The device structure adopts the second structure of the laminated organic photovoltaic cell using three layers of organic heterojunction thin films as the intermediate electrodes provided by the present invention.

The specific processing method of the device is as follows: the first semiconductor layer 3 of the first battery and the second semiconductor layer 4 of the first battery are sequentially deposited on the ITO glass 2 by vacuum evaporation; The method of vacuum evaporation is adopted to successively deposit the intermediate electrode layer 5, the intermediate electrode layer 6, and the intermediate electrode layer 7, wherein the intermediate electrode layer 7 is simultaneously used as the first semiconductor of the second battery; The method is followed by the second semiconductor layer 9 of the second battery; on the second semiconductor layer 9 of the second battery, the method of vacuum evaporation is adopted, and aluminum (Al) with an area of 3.14 square centimeters and a thickness of 100 nanometers is deposited on a drain plate as a metal The cathode 10 forms a stacked organic photovoltaic cell with the structure shown in FIG. 3 .

Among them, the background vacuum is 8×10 ^-4 Pa, the substrate temperature is from room temperature to 120°C, and the evaporation rate is 10 nanometers per minute; the transparent anode is ITO, and the first semiconductor layer of the first cell is CuPc with a thickness of 10 nanometers. The second semiconductor layer of the first and second cells is C60, the thickness is 20 nanometers and 30 nanometers respectively, the middle electrode layer 5 is SnOPc, the thickness is 5 nanometers, the middle electrode layer 6 is F ₁₆ AlClPc, the thickness is 2 nanometers; the middle electrode layer 7 is ZnPc, with a thickness of 30 nanometers and the function of the first semiconductor layer of the second battery.

Fig. 4 is the current-voltage curve of the stacked organic photovoltaic cell corresponding to Example 2 in the dark state and under the irradiation of a simulated solar light source. Under the simulated light source with air mass (AM) of 1.5 and light intensity of 100mW/cm ² , the open circuit voltage of the device is 1.04V, the short circuit current density is 3.65mA/cm ² , the fill factor is 0.48, and the energy conversion efficiency is 1.8%.

Table 2 shows the structure and performance of the device of the second configuration of the stacked organic photovoltaic cell using the three-layer organic heterojunction thin film as the intermediate electrode prepared according to Example 2 provided by the present invention.

Table 2: Structure and performance of tandem organic photovoltaic cells using three-layer organic heterojunction thin films as intermediate electrodes

Battery material and thickness First battery first semiconductor layer 3 CuPc GaCl ₂ Pc InClPc TiCl ₂ Pc Thickness (nanometer) 10 30 30 20 First battery second semiconductor layer 4 C60 PTCBI C60 SnOPc Thickness (nanometer) 20 40 60 30 Second battery second semiconductor layer 9 C60 C60 PTCBI C60 Thickness (nanometer) 30 20 100 50 Intermediate electrode material and thickness middle electrode layer 5 SnOPc SnOPc SnCl ₂ Pc SnCl ₂ Pc Thickness (nanometer) 5 8 2 30 Middle electrode layer 6 F ₁₆ AlClPc F ₁₆ VOPc Cl ₁₆ AlClPc F ₁₆ AlClPc Thickness (nanometer) 2 30 10 15 middle electrode layer 7 ZnPc VOPc TiOPc PbPc Thickness (nanometer) 30 2 15 20 Device performance Open Circuit Voltage (Volts) 1.04 1.02 1.03 1.02 Short circuit current density (mA/cm2) 3.7 3 5 4.2 3.9 fill factor 0.48 0.51 0.46 0.52 energy conversion efficiency 1.8% 1.82% 1.99% 2.07%

Example 3

Materials used are the same as in Example 1.

The device structure adopts the third structure of the laminated organic photovoltaic cell using three-layer organic heterojunction thin film as the intermediate electrode provided by the present invention.

The specific processing method of the device is as follows: the first semiconductor layer 3 of the first battery is deposited on the ITO glass 2 by vacuum evaporation; the intermediate electrode layer is sequentially deposited on the first semiconductor layer 3 of the first battery by vacuum evaporation 5. Intermediate electrode layer 6, intermediate electrode layer 7; wherein, the intermediate electrode layer 5 serves as the second semiconductor layer of the first battery at the same time; the first semiconductor of the second battery is sequentially deposited on the intermediate electrode 7 by vacuum evaporation Layer 8 and the second semiconductor layer 9 of the second battery; on the second semiconductor layer 9 of the second battery, the method of vacuum evaporation is adopted, and a drain plate is utilized to deposit one layer of aluminum (Al) with an area of 3.14 square centimeters and a thickness of 100 nanometers as The metal cathode 10 forms a stacked organic photovoltaic cell with the structure shown in FIG. 5 .

Among them, the background vacuum is 8×10 ^-4 Pa, the substrate temperature is from room temperature to 120°C, and the evaporation rate is 10 nanometers per minute; the transparent anode is ITO, and the first semiconductor layer of the first and second cells is NiPc, with a thickness of 20 nanometers and 35 nanometers respectively; the middle electrode layer 5 is SnCl ₂ Pc which also has the function of the second semiconductor layer of the first battery, and the thickness is 30 nanometers; the middle electrode layer 6 is Cl ₁₆ CuPc, and the thickness is 2 nanometers; the middle electrode layer 7 is CoPc with a thickness of 5 nanometers; the second semiconductor layer of the second battery is SnCl ₂ Pc with a thickness of 50 nanometers.

Fig. 6 is the current-voltage curve of the stacked organic photovoltaic cell corresponding to Example 3 in the dark state and under the irradiation of a simulated solar light source. Under the atmosphere mass (AM) 1.5, light intensity 100mW/cm ² simulated solar light source, the open circuit voltage of the device is 0.62V, the short circuit current density is 1.2mA/cm ² , the fill factor is 0.37, and the energy conversion efficiency is 0.28%.

Table 3 shows the structure and performance of the device of the third configuration of the tandem organic photovoltaic cell prepared according to Example 3 and using the three-layer organic heterojunction thin film as the intermediate electrode provided by the present invention.

Table 3: Structure and performance of tandem organic photovoltaic cells using three-layer organic heterojunction thin films as intermediate electrodes

Battery material and thickness The first battery first semiconductor layer 3 NiPc CuPc ZnPc SnPc Thickness (nanometer) 20 10 30 15 The second battery first semiconductor layer 8 NiPc PbPc FePc VOPc Thickness (nanometer) 35 10 50 20 The second battery second semiconductor layer 9 SnCl ₂ Pc C60 PTCBI SnOPc Thickness (nanometer) 50 20 100 40 Intermediate electrode material and thickness Middle electrode layer 5 SnCl ₂ Pc SnOPc SnOPc SnCl ₂ Pc Thickness (nanometer) 30 2 30 20 Middle electrode layer 6 Cl ₁₆ CuPc F ₁₆ VOPc Cl ₁₆ AlClPc F ₁₆ AlClPc Thickness (nanometer) 2 30 10 20 Middle electrode layer 7 CoPc VOPc TiOPc PbPc Thickness (nanometer) 5 2 10 30 Device performance Open circuit voltage (volts) 0.62 0.76 0.84 0.94 Short circuit current density (mA/cm2) 1.2 1.8 2.1 1.7

Fill factor 0.37 0.42 0.39 0.45   Energy Conversion Efficiency 0.28% 0.57% 0.69% 0.72%

The present invention is not limited to the above-described embodiments. In general, the stacked organic photovoltaic cells disclosed in the present invention can be processed to form two or more organic cells connected in series or in parallel. The tandem organic photovoltaic cells based on the present invention can be processed in the range of room temperature to 120°C.

Claims (3)

1. adopt the stacking organic photovoltaic power cell of three layers of organic heterojunction film as target, it is characterized in that it constitutes: first semiconductor layer (8) of first semiconductor layer (3) of transparency carrier (1), transparency electrode (2), first battery, second semiconductor layer (4) of first battery, intermediate electrode layer (5), intermediate electrode layer (6), intermediate electrode layer (7), second battery, second semiconductor layer (9) and the metal electrode (10) of second battery; First semiconductor layer (8) of first semiconductor layer (3) of transparency carrier (1), transparency electrode (2), first battery, second semiconductor layer (4) of first battery, intermediate electrode layer (5), intermediate electrode layer (6), intermediate electrode layer (7), second battery, second semiconductor layer (9) of second battery are connected in turn with metal electrode (10); Wherein, first semiconductor layer (3) of first battery and second semiconductor layer (4) of first battery constitute first battery, first semiconductor layer (8) of second battery and second semiconductor layer (9) of second battery constitute second battery, and intermediate electrode layer (5), intermediate electrode layer (6) and intermediate electrode layer (7) constitute the target that is connected first battery and second battery;

First semiconductor layer (3) of described first battery is any one in phthalocyanine nickel, ferrous phthalocyanine, phthalocyanine tin, CuPc, phthalocyanine cobalt, Phthalocyanine Zinc, phthalocyanine lead, ranadylic phthalocyanine, TiOPc, FePC chlorine, phthalocyanine titanium dichloro phthalocyanine indium chlorine, manganese phthalocyanine chlorine, phthalocyanine gallium chlorine, phthalocyanine titanium difluoro, phthalocyanine tin difluoro, phthalocyanine indium fluorine and the phthalocyanine germanium dichloro; Its thickness is less than or equal to 30 nanometers more than or equal to 10 nanometers;

Second semiconductor layer (4) of described first battery be in fullerene, dibenzo Mi Zuo perylene, phthalocyanine oxygen tin and the phthalocyanine tin dichloro any one; Its thickness is less than or equal to 60 nanometers more than or equal to 20 nanometers;

First semiconductor layer (8) of described second battery is phthalocyanine nickel, ferrous phthalocyanine, phthalocyanine tin, CuPc, phthalocyanine cobalt, Phthalocyanine Zinc, phthalocyanine lead, ranadylic phthalocyanine, TiOPc, FePC chlorine), a kind of in phthalocyanine titanium dichloro, phthalocyanine indium chlorine, manganese phthalocyanine chlorine, phthalocyanine gallium chlorine, phthalocyanine titanium difluoro, phthalocyanine tin difluoro, phthalocyanine indium fluorine and the phthalocyanine germanium dichloro; Its thickness is less than or equal to 50 nanometers more than or equal to 10 nanometers;

Second semiconductor layer 9 of described second battery be in fullerene, dibenzo Mi Zuo perylene, phthalocyanine oxygen tin and the phthalocyanine tin dichloro any one, its thickness is less than or equal to 100 nanometers more than or equal to 20 nanometers;

Described intermediate electrode layer (5) is a kind of in phthalocyanine oxygen tin and the phthalocyanine tin dichloro, and its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers;

Described intermediate electrode layer (6) is phthalocyanine oxygen tin, phthalocyanine tin dichloro, ten hexachloro phthalocyanine chlorine aluminium, ten hexafluoro TiOPcs, ten hexafluoro ranadylic phthalocyanines, ten hexafluoro phthalocyanine indium chlorine, ten hexafluoro manganese phthalocyanine chlorine, ten hexafluoro phthalocyanine tin dichloros, ten hexafluoro titanium dichloros, ten hexafluoro aluminum phthalocyanine chlorine), in ten hexachloro phthalocyanine tin dichloros, ten hexachloro TiOPcs, ten hexachloro ranadylic phthalocyanines, ten hexachloro phthalocyanine indium chlorine and the ten hexafluoro CuPcs any one; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers;

Described intermediate electrode layer (7) is any one in phthalocyanine nickel, ferrous phthalocyanine, phthalocyanine tin, CuPc, phthalocyanine cobalt, Phthalocyanine Zinc, phthalocyanine lead, ranadylic phthalocyanine, TiOPc, FePC chlorine, phthalocyanine titanium dichloro, phthalocyanine indium chlorine, manganese phthalocyanine chlorine, phthalocyanine gallium chlorine, phthalocyanine titanium difluoro, phthalocyanine tin difluoro, phthalocyanine indium fluorine and the phthalocyanine germanium dichloro; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers.

2. adopt the stacking organic photovoltaic power cell of three layers of organic heterojunction film as target, it is characterized in that it constitutes: first semiconductor layer (3) of transparency carrier (1), transparency electrode (2), first battery, second semiconductor layer (4) of first battery, intermediate electrode layer (5), intermediate electrode layer) second semiconductor layer (9) and the metal electrode (10) of (6), intermediate electrode layer (7), second battery; First semiconductor layer (3) of transparency carrier (1), transparency electrode (2), first battery, second semiconductor layer (4) of first battery, intermediate electrode layer (5), intermediate electrode layer) second semiconductor layer (9) of (6), intermediate electrode layer (7), second battery is connected in turn with metal electrode (10); Wherein, first semiconductor layer (3) of first battery and second semiconductor layer (4) of first battery constitute first battery, intermediate electrode layer (5), intermediate electrode layer (6) and intermediate electrode layer 7 constitute the target that is connected first battery and second battery, as first semiconductor layer of second battery, second semiconductor layer (9) of the intermediate electrode layer (7) and second battery constitutes second battery to intermediate electrode layer (7) simultaneously;

First semiconductor layer (3) of described first battery is a kind of in phthalocyanine nickel, ferrous phthalocyanine, phthalocyanine tin, CuPc, phthalocyanine cobalt, Phthalocyanine Zinc, phthalocyanine lead, ranadylic phthalocyanine, TiOPc, FePC chlorine, phthalocyanine titanium dichloro, phthalocyanine indium chlorine, manganese phthalocyanine chlorine, phthalocyanine gallium chlorine, phthalocyanine titanium difluoro, phthalocyanine tin difluoro, phthalocyanine indium fluorine and the phthalocyanine germanium dichloro; Its thickness is less than or equal to 30 nanometers more than or equal to 10 nanometers;

Second semiconductor layer (4) of described first battery be in fullerene, dibenzo Mi Zuo perylene, phthalocyanine oxygen tin and the phthalocyanine tin dichloro any one; Its thickness is less than or equal to 60 nanometers more than or equal to 20 nanometers;

Described intermediate electrode layer (5) is a kind of in phthalocyanine oxygen tin and the phthalocyanine tin dichloro; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers;

Described intermediate electrode layer (6) is phthalocyanine oxygen tin, phthalocyanine tin dichloro, ten hexachloro phthalocyanine chlorine aluminium, ten hexafluoro TiOPcs), a kind of in ten hexafluoro ranadylic phthalocyanines, ten hexafluoro phthalocyanine indium chlorine, ten hexafluoro manganese phthalocyanine chlorine, ten hexafluoro phthalocyanine tin dichloros, ten hexafluoro titanium dichloros, ten hexafluoro aluminum phthalocyanine chlorine, ten hexachloro phthalocyanine tin dichloros, ten hexachloro TiOPcs, ten hexachloro ranadylic phthalocyanines, ten hexachloro phthalocyanine indium chlorine and the ten hexafluoro CuPcs; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers;

Described intermediate electrode layer (7) is a kind of in phthalocyanine nickel, ferrous phthalocyanine, phthalocyanine tin, CuPc, phthalocyanine cobalt, Phthalocyanine Zinc, phthalocyanine lead, ranadylic phthalocyanine, TiOPc, FePC chlorine, phthalocyanine titanium dichloro, phthalocyanine indium chlorine, manganese phthalocyanine chlorine, phthalocyanine gallium chlorine, phthalocyanine titanium difluoro, phthalocyanine tin difluoro, phthalocyanine indium fluorine and the phthalocyanine germanium dichloro; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers;

Second semiconductor layer (9) of described second battery be in fullerene, dibenzo Mi Zuo perylene, phthalocyanine oxygen tin (SnOPc) and the phthalocyanine tin dichloro any one; Its thickness is less than or equal to 100 nanometers more than or equal to 20 nanometers.

3. adopt the stacking organic photovoltaic power cell of three layers of organic heterojunction film as target, it is characterized in that it constitutes: first semiconductor layer (8) of first semiconductor layer (3) of transparency carrier (1), transparency electrode (2), first battery, intermediate electrode layer (5), intermediate electrode layer (6), intermediate electrode layer (7), second battery, second semiconductor layer (9) of second battery and metal electrode (10); First semiconductor layer (8) of first semiconductor layer (3) of transparency carrier (1), transparency electrode (2), first battery, intermediate electrode layer (5), intermediate electrode layer (6), intermediate electrode layer (7), second battery, second semiconductor layer (9) of second battery are connected in turn with metal electrode (10); Wherein, intermediate electrode layer (5), intermediate electrode layer (6) and intermediate electrode layer (7) constitute the target that is connected first battery and second battery, simultaneously, intermediate electrode layer (5) constitutes first battery as second semiconductor of first battery and first semiconductor layer (3) of first battery; First semiconductor layer (8) of second battery and second semiconductor layer (9) of second battery constitute second battery;

First semiconductor layer (3) of described first battery is a kind of in phthalocyanine nickel, ferrous phthalocyanine, phthalocyanine tin, CuPc, phthalocyanine cobalt, Phthalocyanine Zinc, phthalocyanine lead, ranadylic phthalocyanine, TiOPc, FePC chlorine, phthalocyanine titanium dichloro, phthalocyanine indium chlorine, manganese phthalocyanine chlorine, phthalocyanine gallium chlorine, phthalocyanine titanium difluoro, phthalocyanine tin difluoro, phthalocyanine indium fluorine and the phthalocyanine germanium dichloro; Its thickness is less than or equal to 30 nanometers more than or equal to 10 nanometers;

First semiconductor layer (8) of described second battery is a kind of in phthalocyanine nickel, ferrous phthalocyanine, phthalocyanine tin, CuPc, phthalocyanine cobalt, Phthalocyanine Zinc, phthalocyanine lead, ranadylic phthalocyanine, TiOPc, FePC chlorine, phthalocyanine titanium dichloro, phthalocyanine indium, manganese phthalocyanine chlorine, phthalocyanine gallium chlorine, phthalocyanine titanium difluoro, phthalocyanine tin difluoro, phthalocyanine indium fluorine and the phthalocyanine germanium dichloro; Its thickness is less than or equal to 50 nanometers more than or equal to 10 nanometers;

Second semiconductor layer (9) of described second battery be in fullerene, dibenzo Mi Zuo perylene, phthalocyanine oxygen tin and the phthalocyanine tin dichloro any one; Its thickness is less than or equal to 100 nanometers more than or equal to 20 nanometers;

Described intermediate electrode layer (5) is a kind of in phthalocyanine oxygen tin and the phthalocyanine tin dichloro; Its thickness should be less than or equal to 30 nanometers more than or equal to 2 nanometers;

Described intermediate electrode layer (6) is a kind of in phthalocyanine oxygen tin, phthalocyanine tin dichloro, ten hexachloro phthalocyanine chlorine aluminium, ten hexafluoro TiOPcs, ten hexafluoro ranadylic phthalocyanines, ten hexafluoro phthalocyanine indium chlorine, ten hexafluoro manganese phthalocyanine chlorine, ten hexafluoro phthalocyanine tin dichloros, ten hexafluoro titanium dichloros, ten hexafluoro aluminum phthalocyanine chlorine, ten hexachloro phthalocyanine tin dichloros, ten hexachloro TiOPcs, ten hexachloro ranadylic phthalocyanines, ten hexachloro phthalocyanine indium chlorine and the ten hexafluoro CuPcs; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers;

Described intermediate electrode layer (7) is a kind of in phthalocyanine nickel, ferrous phthalocyanine, phthalocyanine tin, CuPc, phthalocyanine cobalt, Phthalocyanine Zinc, phthalocyanine lead, ranadylic phthalocyanine, TiOPc, FePC chlorine, phthalocyanine titanium dichloro, phthalocyanine indium chlorine, manganese phthalocyanine chlorine, phthalocyanine gallium chlorine, phthalocyanine titanium difluoro, phthalocyanine tin difluoro, phthalocyanine indium fluorine and the phthalocyanine germanium dichloro; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers.

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