CN101179109B - 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 using a three-layer organic heterojunction thin film as an intermediate electrode. The advantage of using the organic heterojunction thin film as an intermediate electrode is to avoid the quenching of photogenerated excitons caused by the introduction of metal particles. At the interface of the heterojunction, the electron-holes are effectively recombined with almost no energy loss, and have better electrical contact with the organic photoactive layer to reduce the internal resistance and improve the device efficiency.

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, MYChan, MKFung, CSLee, STLee, Journal of Applied Physics 101, 014509 (2007) ) reported that the double-layer heterojunction of copper phthalocyanine and copper fluorophthalocyanine was used as the intermediate electrode of stacked organic light-emitting diodes, and 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, first intermediate electrode layer 5, second intermediate electrode layer 6, third intermediate electrode layer 7, first semiconductor layer 8 of the second cell, first intermediate electrode layer of the second cell Second semiconductor layer 9 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, first intermediate electrode layer 5, second intermediate electrode layer 6 , the third 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 are connected in sequence; wherein, the first semiconductor layer 3 of the first battery and the first battery The second semiconductor layer 4 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 intermediate electrode layer 5, the second intermediate electrode layer 6 and the second intermediate electrode layer Three intermediate electrode layers 7 constitute the intermediate electrodes 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 first 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 second intermediate electrode layer 6 is tin phthalocyanine oxide (SnOPc), tin phthalocyanine dichloride (SnCl ₂ Pc), hexadecylchloroaluminum phthalocyanine (Cl ₁₆ AlClPc), hexadecafluorophthalocyanine oxygen Titanium (F ₁₆ TiOPc), vanadyl hexadecafluorophthalocyanine (F ₁₆ VOPc), indium chloride hexadecafluorophthalocyanine (F ₁₆ InClPc), manganese chloride hexadecafluorophthalocyanine (F ₁₆ MnClPc), deca Tin dichlorohexafluorophthalocyanine (F ₁₆ SnCl ₂ Pc), titanium dichlorohexafluorophthalocyanine (F ₁₆ TiCl ₂ Pc), aluminum chloride hexafluorophthalocyanine (F ₁₆ AlClPc), hexadecylchlorophthalocyanine Tin cyanine dichloride (Cl ₁₆ SnCl ₂ Pc), hexadecyl chlorotitanium phthalocyanine (Cl ₁₆ TiOPc), hexadecyl chlorovanadyl phthalocyanine (Cl ₁₆ VOPc), hexadecyl chloroindium phthalocyanine chloride (Cl 16 TiOPc) Any one of 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 third 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 phthalocyanine oxide (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 phthalocyanine Any one of cyanine germanium dichloride (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 cell, first intermediate electrode layer 5, second intermediate electrode layer 6, third intermediate electrode layer 7, 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, first intermediate electrode layer 5, second intermediate electrode layer 6, third intermediate electrode layer 7, second The second semiconductor layer 9 of the battery is connected to the metal electrode 10 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, the first intermediate electrode layer 5, the second The intermediate electrode layer 6 and the third intermediate electrode layer 7 constitute the intermediate electrode connecting the first battery and the second battery, and the third intermediate electrode layer 7 serves as the first semiconductor layer of the second battery at the same time, and the third intermediate electrode layer 7 and the second The second semiconducting layer 9 of the 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 first 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 second intermediate electrode layer 6 is tin phthalocyanine oxide (SnOPc), tin phthalocyanine dichloride (SnCl ₂ Pc), hexadecylchloroaluminum phthalocyanine (Cl ₁₆ AlClPc), hexadecafluorophthalocyanine oxygen Titanium (F ₁₆ TiOPc), vanadyl hexadecafluorophthalocyanine (F ₁₆ VOPc), indium chloride hexadecafluorophthalocyanine (F ₁₆ InClPc), manganese chloride hexadecafluorophthalocyanine (F ₁₆ MnClPc), deca Tin dichlorohexafluorophthalocyanine (F ₁₆ SnCl ₂ Pc), titanium dichlorohexafluorophthalocyanine (F ₁₆ TiCl ₂ Pc), aluminum chloride hexafluorophthalocyanine (F ₁₆ AlClPc), hexadecylchlorophthalocyanine Tin cyanine dichloride (Cl ₁₆ SnCl ₂ Pc), hexadecyl chlorotitanium phthalocyanine (Cl ₁₆ TiOPc), hexadecyl chlorovanadyl phthalocyanine (Cl ₁₆ VOPc), hexadecyl chloroindium phthalocyanine chloride (Cl 16 TiOPc) One of 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 third 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 phthalocyanine oxide (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 phthalocyanine One of cyanine germanium dichloride (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 third 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, first intermediate electrode layer 5, second intermediate electrode layer 6, third 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, first intermediate electrode layer 5, second intermediate electrode layer 6, third intermediate electrode layer 7, first semiconductor layer 8 of the second battery, second The second semiconductor layer 9 of the battery is connected to the metal electrode 10 in sequence; wherein, the first intermediate electrode layer 5, the second intermediate electrode layer 6 and the third intermediate electrode layer 7 form an intermediate electrode connecting the first battery and the second battery, Meanwhile, the first intermediate electrode layer 5 forms the first battery as the second semiconductor of the first battery and the first semiconductor layer 3 of the first battery; the first semiconductor layer 8 of the second battery and the second semiconductor layer 9 of the second battery forming a 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 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;

The first 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 second intermediate electrode layer 6 is tin phthalocyanine oxide (SnOPc), tin phthalocyanine dichloride (SnCl ₂ Pc), hexadecylchloroaluminum phthalocyanine (Cl ₁₆ AlClPc), hexadecafluorophthalocyanine oxygen Titanium (F ₁₆ TiOPc), vanadyl hexadecafluorophthalocyanine (F ₁₆ VOPc), indium chloride hexadecafluorophthalocyanine (F ₁₆ InClPc), manganese chloride hexadecafluorophthalocyanine (F ₁₆ MnClPc), deca Tin dichlorohexafluorophthalocyanine (F ₁₆ SnCl ₂ Pc), titanium dichlorohexafluorophthalocyanine (F ₁₆ TiCl ₂ Pc), aluminum chloride hexafluorophthalocyanine (F ₁₆ AlClPc), hexadecylchlorophthalocyanine Tin cyanine dichloride (Cl ₁₆ SnCl ₂ Pc), hexadecyl chlorotitanium phthalocyanine (Cl ₁₆ TiOPc), hexadecyl chlorovanadyl phthalocyanine (Cl ₁₆ VOPc), hexadecyl chloroindium phthalocyanine chloride (Cl 16 TiOPc) One of 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 third 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 phthalocyanine oxide (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 phthalocyanine One of cyanine germanium dichloride (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 first 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, and its thickness is greater than or equal to 20 nanometers and less than or equal to 60 nanometers, and the second semiconductor layer 4 that constitutes the intermediate electrode is sequentially deposited on the second semiconductor layer 4 of the first battery by vacuum evaporation. An intermediate electrode layer 5, a second intermediate electrode layer 6, and a third intermediate electrode layer 7 are three layers of organic heterojunction thin films, each layer having a thickness greater than or equal to 2 nanometers and less than or equal to 30 nanometers; in the third intermediate electrode layer 7 The first semiconductor layer 8 of the second battery is deposited by vacuum evaporation, and its thickness is greater than or equal to 10 nanometers and less than or equal to 50 nanometers; the first semiconductor layer 8 of the second battery is deposited by vacuum evaporation The thickness of the second semiconductor layer 9 of the second battery 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 first intermediate electrode layer 5, the second intermediate electrode layer 6, and the third intermediate electrode layer 7 are three layers of organic heterojunction thin films, each layer having a thickness greater than or equal to 2 nanometers and less than or equal to 30 nanometers; in the third intermediate electrode layer The second semiconductor layer 9 of the second battery is deposited by vacuum evaporation on 7, and its thickness is greater than or equal to 20 nanometers and less than or equal to 100 nanometers; the method of vacuum evaporation is adopted on the second semiconductor layer 9 of the second battery A metal electrode 10 is prepared.

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 the middle first electrode layer 5, the second middle electrode layer 6, and the third middle electrode layer 7 three-layer organic heterojunction thin film forming the middle electrode, each layer thickness is greater than or equal to 2 nanometers, less than or equal to 30 Nanometer; the 3rd on the intermediate electrode layer 7, adopt the method for vacuum evaporation to deposit the first semiconductor layer 8 of the second battery, its thickness is greater than or equal to 10 nanometers, less than or equal to 50 nanometers; On the first semiconductor layer of the second battery 8, the second semiconductor layer 9 of the second battery is deposited by vacuum evaporation, 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, the method of vacuum evaporation is adopted A metal electrode 10 is prepared.

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. Wherein, 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 first intermediate electrode layer, 6 is the second intermediate electrode layer, 7 is the third intermediate electrode layer, 8 is the first semiconductor layer of the second battery, 9 is the second semiconductor layer of the second battery, 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 . Among them, the transparent anode is ITO, the first semiconductor layer of the first and second batteries is zinc phthalocyanine (ZnPc), the second semiconductor layer of the first and second batteries is fullerene (C60), and the first intermediate electrode layer 5 is tin dichloride phthalocyanine (SnCl ₂ Pc), the second intermediate electrode layer 6 is copper phthalocyanine (F ₁₆ CuPc), the third intermediate 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. Wherein, 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 first intermediate electrode layer, 6 is the second intermediate electrode layer, 7 is the third intermediate electrode layer, 9 is the second semiconductor layer of the second battery, 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 cell is CuPc, the second semiconductor layer of the first and second cells is C60, the first intermediate electrode layer 5 is SnOPc, and the second intermediate electrode layer 6 is _F16 AlClPc, the third intermediate 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 battery, 5 is the first intermediate electrode layer, 6 is the second intermediate electrode layer, 7 is the third intermediate electrode layer, and 8 is the second intermediate electrode layer. The first semiconductor layer of the second battery, 9 is the second semiconductor layer of the second battery, 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), and the first intermediate electrode layer 5 is SnCl ₂ Pc, which also has the function of the second semiconductor layer of the first battery , the second intermediate electrode layer 6 is Cl ₁₆ CuPc, the third 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 sequentially deposits the first intermediate electrode layer 5, the second intermediate electrode layer 6, and the third intermediate electrode layer 7; on the third intermediate electrode layer 7, the first semiconductor layer 8 and the 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 the aluminum (Al) with an area of 3.14 square centimeters and a thickness of 100 nanometers is deposited as a metal cathode 10 by drain plate. A laminated battery with the structure shown in Figure 1 is formed.

Among them, the background vacuum is 8x10 ^-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 The second semiconductor layer 4 of a battery is fullerene (C60), with a thickness of 20 nanometers; the first intermediate electrode layer 5 is tin phthalocyanine dichloride (SnCl ₂ Pc), with a thickness of 2 nanometers; Copper phthalocyanine (F ₁₆ CuPc) with a thickness of 3 nanometers; the third 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, and the second semiconductor layer 9 of the second battery 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 first intermediate electrode layer 5, and F ₁₆ CuPc on the surface of ITO glass. is the second intermediate electrode layer 6, CuPc is the third intermediate electrode layer 7, and Al is the current-voltage curve of the laminated organic photovoltaic cell in the dark state and under the irradiation of the 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

Continued Table 1

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 first intermediate electrode layer 5, the second intermediate electrode layer 6, and the third intermediate electrode layer 7 are sequentially deposited by vacuum evaporation, wherein the third intermediate electrode layer 7 is simultaneously used as the first semiconductor of the second battery; The second semiconductor layer 9 of the second battery is followed by vacuum evaporation on the intermediate electrode layer 7; the vacuum evaporation method is used on the second semiconductor layer 9 of the second battery, and a layer of area 3.14 square centimeters is deposited by a drain plate Aluminum (Al) with a thickness of 100 nanometers was used as the metal cathode 10 to form a stacked organic photovoltaic cell with the structure shown in FIG. 3 .

Among them, the background vacuum is 8x10 ^-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. And the second semiconductor layer of the second battery is C60, the thickness is 20 nanometers and 30 nanometers respectively, the first intermediate electrode layer 5 is SnOPc, thickness 5 nanometers, the second intermediate electrode layer 6 is F ₁₆ AlClPc, thickness 2 nanometers; The third intermediate electrode layer 7 is ZnPc with a thickness of 30 nanometers and also functions as 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 prepared according to Example 2 and using a three-layer organic heterojunction thin film as an intermediate electrode 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

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 cell is deposited on the ITO glass 2 by vacuum evaporation; the first intermediate layer is sequentially deposited on the first semiconductor layer 3 of the first cell by vacuum evaporation. Electrode layer 5, the second intermediate electrode layer 6, the third intermediate electrode layer 7; wherein, the first intermediate electrode layer 5 simultaneously serves as the second semiconductor layer of the first battery; on the third intermediate electrode 7, vacuum-evaporated Method Deposit the first semiconductor layer 8 of the second battery and the second semiconductor layer 9 of the second battery in sequence; on the second semiconductor layer 9 of the second battery, vacuum evaporation is used to deposit a layer with an area of 3.14 square meters using a drain plate Aluminum (Al) with a thickness of 100 nanometers per centimeter is used as the metal cathode 10 to form a stacked organic photovoltaic cell with a structure as shown in FIG. 5 .

Among them, the background vacuum is 8x10 ^-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; the first intermediate electrode layer 5 is SnCl ₂ Pc and has the function of the second semiconductor layer of the first battery, and the thickness is 30 nanometers; the second intermediate electrode layer 6 is Cl ₁₆ CuPc, and the thickness is 2 nanometers; The third intermediate electrode layer 7 is CoPc with a thickness of 5 nanometers; the second semiconductor layer of the second cell 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

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. A stacked organic photovoltaic cell using three layers of organic heterojunction thin films as an intermediate electrode, characterized in that it consists of: a transparent substrate (1), a transparent electrode (2), a first semiconductor layer (3) of the first cell ), the second semiconductor layer (4) of the first battery, the first intermediate electrode layer (5), the second intermediate electrode layer (6), the third intermediate electrode layer (7), the first semiconductor layer of the second battery ( 8), the second semiconductor layer (9) and the metal electrode (10) of the second battery; the transparent substrate (1), the transparent electrode (2), the first semiconductor layer (3) of the first battery, the first semiconductor layer of the first battery The second semiconductor layer (4), the first intermediate electrode layer (5), the second intermediate electrode layer (6), the third intermediate electrode layer (7), the first semiconductor layer (8) of the second battery, the second battery The second semiconductor layer (9) 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 second battery The first semiconductor layer (8) of the second battery and the second semiconductor layer (9) of the second battery constitute the second battery, the first intermediate electrode layer (5), the second intermediate electrode layer (6) and the third intermediate electrode layer (7 ) constitutes an intermediate electrode connecting the first cell and the second cell; The first semiconductor layer (3) of the first battery is nickel phthalocyanine, ferrous phthalocyanine, tin phthalocyanine, copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, lead phthalocyanine, vanadyl phthalocyanine, phthalocyanine Titanium oxycyanine, iron chloride phthalocyanine, titanium dichloride phthalocyanine, indium phthalocyanine chloride, manganese phthalocyanine chloride, gallium phthalocyanine chloride, titanium difluoride phthalocyanine, tin difluoride phthalocyanine, indium phthalocyanine fluoride and germanium phthalocyanine Any of dichloro; 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, dibenzimidazole perylene, oxytin phthalocyanine and tin phthalocyanine dichloride; its thickness is greater than or equal to 20 nanometers, less than or equal to 60 nanometers; The first semiconductor layer (8) of the second battery is nickel phthalocyanine, ferrous phthalocyanine, tin phthalocyanine, copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, lead phthalocyanine, vanadyl phthalocyanine, phthalocyanine Oxytitanium, iron chloride phthalocyanine, titanium dichloride phthalocyanine, indium phthalocyanine chloride, manganese chloride phthalocyanine, gallium phthalocyanine chloride, titanium difluoride phthalocyanine, tin difluoride phthalocyanine, indium phthalocyanine fluoride and germanium phthalocyanine A species of chlorine; 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, dibenzimidazole perylene, oxytin phthalocyanine and tin phthalocyanine dichloride, and its thickness is greater than or equal to 20 nanometers and less than or equal to 100 nanometers; The first intermediate electrode layer (5) is one of oxytin phthalocyanine and tin phthalocyanine dichloride, and its thickness is greater than or equal to 2 nanometers and less than or equal to 30 nanometers; The second intermediate electrode layer (6) is oxytin phthalocyanine, tin phthalocyanine dichloride, hexadecylchloroaluminum phthalocyanine, hexadecafluorotitanium phthalocyanine, hexadecafluorovanadyl phthalocyanine, Hexadecafluorophthalocyanine indium chloride, hexadecafluorophthalocyanine manganese chloride, hexadecafluorophthalocyanine tin dichloride, hexadecafluorophthalocyanine titanium dichloride, hexadecafluorophthalocyanine aluminum chloride, hexadecylchlorophthalocyanine Any of tin dichloride cyanine, titanyl hexadecylchlorophthalocyanine, vanadyl hexadecylchlorophthalocyanine, indium chloride hexadecylchlorophthalocyanine and copper hexadecafluorophthalocyanine; its thickness is greater than or equal to 2 nanometers, less than or equal to 30 nanometers; The third intermediate electrode layer (7) is nickel phthalocyanine, ferrous phthalocyanine, tin phthalocyanine, copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, lead phthalocyanine, vanadyl phthalocyanine, titanium phthalocyanine , iron chloride phthalocyanine, titanium dichloride phthalocyanine, indium phthalocyanine chloride, manganese chloride phthalocyanine, gallium phthalocyanine chloride, titanium difluoride phthalocyanine, tin difluoride phthalocyanine, indium phthalocyanine fluoride and germanium phthalocyanine dichloride Any of the above; its thickness is greater than or equal to 2 nanometers and less than or equal to 30 nanometers. 2. A stacked organic photovoltaic cell using three layers of organic heterojunction thin films as an intermediate electrode, characterized in that it consists of: a transparent substrate (1), a transparent electrode (2), the first semiconductor layer of the first cell (3 ), the second semiconductor layer (4) of the first battery, the first intermediate electrode layer (5), the second intermediate electrode layer (6), the third intermediate electrode layer (7), the second semiconductor layer of the second battery ( 9) 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, first intermediate electrode layer (5), the second intermediate electrode layer (6), the third intermediate electrode layer (7), the second semiconductor layer (9) of the second battery and the metal electrode (10) are connected in sequence; wherein, the first battery of the first battery A semiconductor layer (3) and the second semiconductor layer (4) of the first battery form the first battery, and the first intermediate electrode layer (5), the second intermediate electrode layer (6) and the third intermediate electrode layer 7 form the connecting second electrode layer. The intermediate electrode of a battery and the second battery, the third intermediate electrode layer (7) simultaneously serves as the first semiconductor layer of the second battery, the third intermediate electrode layer (7) and the second semiconductor layer (9) of the second battery constitute second battery; The first semiconductor layer (3) of the first battery is nickel phthalocyanine, ferrous phthalocyanine, tin phthalocyanine, copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, lead phthalocyanine, vanadyl phthalocyanine, phthalocyanine Oxytitanium, iron chloride phthalocyanine, titanium dichloride phthalocyanine, indium phthalocyanine chloride, manganese chloride phthalocyanine, gallium phthalocyanine chloride, titanium difluoride phthalocyanine, tin difluoride phthalocyanine, indium phthalocyanine fluoride and germanium phthalocyanine A species of chlorine; 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, dibenzimidazole perylene, oxytin phthalocyanine and tin phthalocyanine dichloride; its thickness is greater than or equal to 20 nanometers, less than or equal to 60 nanometers; The first intermediate electrode layer (5) is one of oxytin phthalocyanine and tin phthalocyanine dichloride; its thickness is greater than or equal to 2 nanometers and less than or equal to 30 nanometers; The second intermediate electrode layer (6) is oxytin phthalocyanine, tin phthalocyanine dichloride, hexadecylchloroaluminum phthalocyanine, hexadecafluorotitanium phthalocyanine, hexadecafluorovanadyl phthalocyanine, Hexadecafluorophthalocyanine indium chloride, hexadecafluorophthalocyanine manganese chloride, hexadecafluorophthalocyanine tin dichloride, hexadecafluorophthalocyanine titanium dichloride, hexadecafluorophthalocyanine aluminum chloride, hexadecylchlorophthalocyanine One of tin dichloride cyanine, titanyl hexadecylchlorophthalocyanine, vanadyl hexadecylchlorophthalocyanine, indium chloride hexadecylchlorophthalocyanine and copper hexadecafluorophthalocyanine; its thickness is greater than or equal to 2 nanometer, less than or equal to 30 nanometers; The third intermediate electrode layer (7) is nickel phthalocyanine, ferrous phthalocyanine, tin phthalocyanine, copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, lead phthalocyanine, vanadyl phthalocyanine, titanium phthalocyanine , iron chloride phthalocyanine, titanium dichloride phthalocyanine, indium phthalocyanine chloride, manganese chloride phthalocyanine, gallium phthalocyanine chloride, titanium difluoride phthalocyanine, tin difluoride phthalocyanine, indium phthalocyanine fluoride and germanium phthalocyanine dichloride A type; 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, dibenzimidazole perylene, tin oxytin phthalocyanine (SnOPc) and tin phthalocyanine dichloride; its thickness is greater than or equal to 20 Nanometer, less than or equal to 100 nanometers. 3. A stacked organic photovoltaic cell using three layers of organic heterojunction thin films as an intermediate electrode, characterized in that it consists of: a transparent substrate (1), a transparent electrode (2), the first semiconductor layer of the first cell (3 ), the first intermediate electrode layer (5), the second intermediate electrode layer (6), the third intermediate electrode layer (7), the first semiconductor layer (8) of the second battery, the second semiconductor layer of the second battery ( 9) and metal electrode (10); transparent substrate (1), transparent electrode (2), first semiconductor layer (3) of the first cell, first intermediate electrode layer (5), second intermediate electrode layer (6) , the third 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) are connected in sequence; wherein, the first intermediate electrode layer (5), the second intermediate electrode layer (6) and the third intermediate electrode layer (7) form the intermediate electrode connecting the first battery and the second battery, and at the same time, the first intermediate electrode layer (5) serves as the first intermediate electrode layer of the first battery The second semiconductor and the first semiconductor layer (3) of the first battery form 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, ferrous phthalocyanine, tin phthalocyanine, copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, lead phthalocyanine, vanadyl phthalocyanine, phthalocyanine Oxytitanium, iron chloride phthalocyanine, titanium dichloride phthalocyanine, indium phthalocyanine chloride, manganese chloride phthalocyanine, gallium phthalocyanine chloride, titanium difluoride phthalocyanine, tin difluoride phthalocyanine, indium phthalocyanine fluoride and germanium phthalocyanine A species of chlorine; 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, ferrous phthalocyanine, tin phthalocyanine, copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, lead phthalocyanine, vanadyl phthalocyanine, phthalocyanine Oxytitanium chloride, iron chloride phthalocyanine, titanium dichloride phthalocyanine, indium phthalocyanine, manganese chloride phthalocyanine, gallium chloride phthalocyanine, titanium difluoride phthalocyanine, tin difluoride phthalocyanine, indium phthalocyanine fluoride, and germanium phthalocyanine dichloride One of: its thickness is greater than or equal to 10 nanometers and less than or equal to 50 nanometers; The second semiconductor layer (9) of the second battery is any one of fullerene, dibenzimidazole perylene, oxytin phthalocyanine and tin phthalocyanine dichloride; its thickness is greater than or equal to 20 nanometers, less than or equal to 100 nanometers; The first intermediate electrode layer (5) is one of oxytin phthalocyanine and tin phthalocyanine dichloride; its thickness should be greater than or equal to 2 nanometers and less than or equal to 30 nanometers; The second intermediate electrode layer (6) is oxytin phthalocyanine, tin phthalocyanine dichloride, hexadecylchloroaluminum phthalocyanine, hexadecafluorotitanium phthalocyanine, hexadecafluorovanadyl phthalocyanine, Hexadecafluorophthalocyanine indium chloride, hexadecafluorophthalocyanine manganese chloride, hexadecafluorophthalocyanine tin dichloride, hexadecafluorophthalocyanine titanium dichloride, hexadecafluorophthalocyanine aluminum chloride, hexadecylchlorophthalocyanine One of tin dichloride cyanine, titanyl hexadecylchlorophthalocyanine, vanadyl hexadecylchlorophthalocyanine, indium chloride hexadecylchlorophthalocyanine and copper hexadecafluorophthalocyanine; its thickness is greater than or equal to 2 nanometer, less than or equal to 30 nanometers; The third intermediate electrode layer (7) is nickel phthalocyanine, ferrous phthalocyanine, tin phthalocyanine, copper phthalocyanine, cobalt phthalocyanine, zinc phthalocyanine, lead phthalocyanine, vanadyl phthalocyanine, titanium phthalocyanine , iron chloride phthalocyanine, titanium dichloride phthalocyanine, indium phthalocyanine chloride, manganese chloride phthalocyanine, gallium phthalocyanine chloride, titanium difluoride phthalocyanine, tin difluoride phthalocyanine, indium phthalocyanine fluoride and germanium phthalocyanine dichloride A species; its thickness is greater than or equal to 2 nanometers and less than or equal to 30 nanometers.

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