CN101179109A - Stacking organic photovoltaic power cell taking three layers organic hetero-junction thin film as middle electric pole - Google Patents
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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
Technical field
The present invention relates to a kind of stacking organic photovoltaic power cell that adopts the organic heterojunction film as target.
Background technology
In recent years, organic photovoltaic devices is showing application potential aspect the cheap photovoltaic cell, and energy conversion efficiency is an important indicator of photovoltaic cell practical application.The Applied Physics wall bulletin of the U.S. in 1986 (C.W.Tang, Applied Physics Letters 48,183 (1986)) has been reported a kind of organic photovoltaic battery that adopts double-deck organic film structure, and energy conversion efficiency is near 1%.Through the effort in nearly ten years, people recognized that the main cause that restriction organic photovoltaic devices efficient further improves is the light absorption length (generally about 100nm) of the exciton diffusion length (generally not being higher than 10nm) of organic material much smaller than material.Nineteen ninety-five the U.S. science magazine (G.Yu, J.Gao, J.C.Hummelen, F.Wudl, A.J.Heeger, Sciences 270,1789 (1995)) reported that the method for two kinds of organic material blend of a kind of employing overcomes above-mentioned contradiction, has realized that energy conversion efficiency surpasses 2% photovoltaic cell under the monochromatic light.This method is that two kinds of materials of control realize that in thicker film two of nano-scale is separated, it is mutually continuous separately to form two kinds of materials, the bulk heterojunction that runs through mutually each other, greatly improved the interfacial area of two-phase, shorten exciton and arrived the distance of two-phase interface, thereby improved the conversion efficiency of battery.Another method that solves above-mentioned contradiction is to adopt the serial or parallel connection modes to link together on a plurality of batteries, and the upper strata battery does not absorb completely that light can be continued to utilize by lower floor's battery, Here it is lamination photovoltaic cell.The chemical wall bulletin (M.Hiramoto, M.Suezaki, M.Yokoyama, Chemistry Letters, 1990,327) of Japan at first reported and utilized the first piece stacking organic photovoltaic power cell of Au as target preparation nineteen ninety.Stacking organic photovoltaic power cell generally adopts metal or metal oxide as the intermediate layer at present, causes photopermeability poor, and near cancellation metal of photoproduction exciton has limited the further raising of device efficiency.The Applied Physics wall bulletin of the U.S. in 2006 (X.J.Yan, J.Wang, H.B.Wang, H.Wang, D.H.Yan, Applied Physics Letters 89,053510 (2006)) has been reported and has been utilized CuPc (CuPc) and fluoro CuPc (F
16CuPc) the high conductivity characteristic of the Heterojunction Effect metal semiconductor that improves OTFT electrically contacts character, applicating physical magazine (the S.L.Lai of the U.S. in 2007, M.Y Chan, M.K.Fung, C.S.Lee, S.T.Lee, Journal of Applied Physics 101,014509 (2007)) reported and adopted the target of the double-deck heterojunction of this CuPc and fluoro CuPc that the galvanoluminescence efficient of lamination light-emitting diode significantly improves as the lamination Organic Light Emitting Diode.But CuPc and fluoro CuPc heterojunction duplicature are directly used in metal phthalocyanine-fullerene (C60) stacking organic photovoltaic power cell and generally can cause battery open circuit voltage and fill factor, curve factor significantly to reduce, and can not give play to the advantage of stacking organic photovoltaic power cell.
Summary of the invention
The purpose of this invention is to provide a kind of stacking organic photovoltaic power cell that adopts three layers of organic heterojunction film as target, overcome that light percolating property in the prior art is poor, near the problem of photoproduction exciton cancellation and open circuit voltage and fill factor, curve factor loss intermediate layer, can significantly improve battery efficiency simultaneously.
Three layers of organic heterojunction film of employing provided by the invention constitute three kinds as the stacking organic photovoltaic power cell of target.
As shown in Figure 1, three layers of organic heterojunction film of employing provided by the invention are as first kind of the stacking organic photovoltaic power cell of target constitute: 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, first semiconductor layer 8 of second battery, second semiconductor layer 9 and the metal electrode 10 of 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 6, intermediate electrode layer 7, first semiconductor layer 8 of second battery, second semiconductor layer 9 of second battery are connected in turn with metal electrode 10; Wherein, second semiconductor layer 4 of first semiconductor layer 3 of first battery and first battery constitutes first battery, second semiconductor layer 9 of first semiconductor layer 8 of second battery and second battery constitutes 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;
Described intermediate electrode layer 5 is phthalocyanine oxygen tin (SnOPc) and phthalocyanine tin dichloro (SnCl
2Pc) a kind of in, 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 (SnOPc), phthalocyanine tin dichloro (SnCl
2Pc), ten hexachloro phthalocyanine chlorine aluminium (Cl
16AlClPc), ten hexafluoro TiOPc (F
16TiOPc), ten hexafluoro ranadylic phthalocyanine (F
16VOPc), ten hexafluoro phthalocyanine indium chlorine (F
16InClPc), ten hexafluoro manganese phthalocyanine chlorine (F
16MnClPc), ten hexafluoro phthalocyanine tin dichloro (F
16SnCl
2Pc), ten hexafluoro titanium dichloro (F
16TiCl
2Pc), ten hexafluoro aluminum phthalocyanine chlorine (F
16AlClPc), ten hexachloro phthalocyanine tin dichloro (Cl
16SnCl
2Pc), ten hexachloro TiOPc (Cl
16TiOPc), ten hexachloro ranadylic phthalocyanine (Cl
16VOPc), ten hexachloro phthalocyanine indium chlorine (Cl
16InClPc) and ten hexafluoro CuPc (F
16CuPc) any one in; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers;
Described intermediate electrode layer 7 is phthalocyanine nickel (NiPc), ferrous phthalocyanine (FePc), phthalocyanine tin (SnPc), CuPc (CuPc), phthalocyanine cobalt (CoPc), Phthalocyanine Zinc (ZnPc), phthalocyanine lead (PbPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), FePC chlorine (FeClPc), phthalocyanine titanium dichloro (TiCl
2Pc), phthalocyanine indium chlorine (InClPc), manganese phthalocyanine chlorine (MnClPc), phthalocyanine gallium chlorine (GaClPc), phthalocyanine titanium difluoro (TiF
2Pc), phthalocyanine tin difluoro (SnF
2Pc), phthalocyanine indium fluorine (InFPc) and phthalocyanine germanium dichloro (GeCl
2Pc) any one in; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers.
As shown in Figure 3, three layers of organic heterojunction film of employing provided by the invention are as second kind of the stacking organic photovoltaic power cell of target constitute: second semiconductor layer 9 and the metal electrode 10 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 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 is connected in turn with metal electrode 10; Wherein, second semiconductor layer 4 of first semiconductor layer 3 of first battery and first battery constitutes 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;
Described intermediate electrode layer 5 is phthalocyanine oxygen tin (SnOPc) and phthalocyanine tin dichloro (SnCl
2Pc) a kind of in; 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 (SnOPc), phthalocyanine tin dichloro (SnCl
2Pc), ten hexachloro phthalocyanine chlorine aluminium (Cl
16AlClPc), ten hexafluoro TiOPc (F
16TiOPc), ten hexafluoro ranadylic phthalocyanine (F
16VOPc), ten hexafluoro phthalocyanine indium chlorine (F
16InClPc), ten hexafluoro manganese phthalocyanine chlorine (F
16MnClPc), ten hexafluoro phthalocyanine tin dichloro (F
16SnCl
2Pc), ten hexafluoro titanium dichloro (F
16TiCl
2Pc), ten hexafluoro aluminum phthalocyanine chlorine (F
16AlClPc), ten hexachloro phthalocyanine tin dichloro (Cl
16SnCl
2Pc), ten hexachloro TiOPc (Cl
16TiOPc), ten hexachloro ranadylic phthalocyanine (Cl
16VOPc), ten hexachloro phthalocyanine steel chlorine (Cl
16InClPc) and ten hexafluoro CuPc (F
16CuPc) a kind of in; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers;
Described intermediate electrode layer 7 is phthalocyanine nickel (NiPc), ferrous phthalocyanine (FePc), phthalocyanine tin (SnPc), CuPc (CuPc), phthalocyanine cobalt (CoPc), Phthalocyanine Zinc (ZnPc), phthalocyanine lead (PbPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), FePC chlorine (FeClPc), phthalocyanine titanium dichloro (TiCl
2Pc), phthalocyanine indium chlorine (InClPc), manganese phthalocyanine chlorine (MnClPc), phthalocyanine gallium chlorine (GaClPc), phthalocyanine titanium difluoro (TiF
2Pc), phthalocyanine tin difluoro (SnF
2Pc), phthalocyanine indium fluorine (InFPc) and phthalocyanine germanium dichloro (GeCl
2Pc) a kind of in; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers;
Compare with first kind of formation of the present invention, second kind of formation is used for first semiconductor of second battery simultaneously with intermediate electrode layer 7, simplifies preparation technology.
As shown in Figure 5, three layers of organic heterojunction film of employing provided by the invention are as the third constitute of the stacking organic photovoltaic power cell of target: 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 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, 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, and simultaneously, intermediate electrode layer 5 constitutes first battery as second semiconductor of first battery and first semiconductor layer 3 of first battery; Second semiconductor layer 9 of first semiconductor layer 8 of second battery and second battery constitutes second battery;
Described intermediate electrode layer 5 is phthalocyanine oxygen tin (SnOPc) and phthalocyanine tin dichloro (SnCl
2Pc) a kind of in; Its thickness should be less than or equal to 30 nanometers more than or equal to 2 nanometers;
Described intermediate electrode layer 6 is phthalocyanine oxygen tin (SnOPc), phthalocyanine tin dichloro (SnCl
2Pc), ten hexachloro phthalocyanine chlorine aluminium (Cl
16AlClPc), ten hexafluoro TiOPc (F
16TiOPc), ten hexafluoro ranadylic phthalocyanine (F
16VOPc), ten hexafluoro phthalocyanine indium chlorine (F
16InClPc), ten hexafluoro manganese phthalocyanine chlorine (F
16MnClPc), ten hexafluoro phthalocyanine tin dichloro (F
16SnCl
2Pc), ten hexafluoro titanium dichloro (F
16TiCl
2Pc), ten hexafluoro aluminum phthalocyanine chlorine (F
16AlClPc), ten hexachloro phthalocyanine tin dichloro (Cl
16SnCl
2Pc), ten hexachloro TiOPc (Cl
16TiOPc), ten hexachloro ranadylic phthalocyanine (Cl
16VOPc), ten hexachloro phthalocyanine indium chlorine (Cl
16InClPc) and ten hexafluoro CuPc (F
16CuPc) a kind of in; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers;
Described intermediate electrode layer 7 is phthalocyanine nickel (NiPc), ferrous phthalocyanine (FePc), phthalocyanine tin (SnPc), CuPc (CuPc), phthalocyanine cobalt (CoPc), Phthalocyanine Zinc (ZnPc), phthalocyanine lead (PbPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), FePC chlorine (FeClPc), phthalocyanine titanium dichloro (TiCl
2Pc), phthalocyanine indium chlorine (InClPc), manganese phthalocyanine chlorine (MnClPc), phthalocyanine gallium chlorine (GaClPc), phthalocyanine titanium difluoro (TiF
2Pc), phthalocyanine tin difluoro (SnF
2Pc), phthalocyanine indium fluorine (InFPc) and phthalocyanine germanium dichloro (GeCl
2Pc) a kind of in; Its thickness is less than or equal to 30 nanometers more than or equal to 2 nanometers.
Compare with first kind of formation of the present invention, the third constitutes second semiconductor that intermediate electrode layer 5 is used for simultaneously first battery, simplifies preparation technology.
Another purpose of the present invention provides and adopts the preparation method of three layers of organic heterojunction film as the stacking organic photovoltaic power cell of target.
1) adopt three layers of organic heterojunction film as follows as the preparation method's of the stacking organic photovoltaic power cell of first kind structure of target step and condition:
According to the given material of each layer, its vacuum cavity base vacuum 8.0 * 10 of employed vacuum deposition device
-4, underlayer temperature is between room temperature to 120 degree, and deposition rate per minute 10 nanometers adopt the method for vacuum evaporation to deposit first semiconductor layer 3 of first battery on transparency electrode 2, and its thickness is less than or equal to 30 nanometers more than or equal to 10 nanometers; The method of employing vacuum evaporation deposits second semiconductor layer 4 of first battery on first semiconductor layer 3 of first battery, its thickness is more than or equal to 20 nanometers, be less than or equal to 60 nanometers, on second semiconductor layer 4 of first battery, adopt the method for vacuum evaporation to deposit the 7 three layers of organic heterojunction film of intermediate electrode layer 5, intermediate electrode layer 6, intermediate electrode layer that constitute target successively, every layer thickness is less than or equal to 30 nanometers all more than or equal to 2 nanometers; The method of employing vacuum evaporation deposits first semiconductor layer 8 of second battery on intermediate electrode layer 7, and its thickness is less than or equal to 50 nanometers more than or equal to 10 nanometers; The method of employing vacuum evaporation deposits second semiconductor layer 9 of second battery on first semiconductor layer 8 of second battery, and its thickness is less than or equal to 100 nanometers more than or equal to 20 nanometers; On second semiconductor layer 9 of second battery, adopt the method for vacuum evaporation to prepare metal electrode 10.
2) adopt three layers of organic heterojunction film as follows as the preparation method's of the stacking organic photovoltaic power cell of second kind structure of target step and condition:
According to the given material of each layer, its vacuum cavity base vacuum 8.0 * 10 of employed vacuum deposition device
-4Pa, underlayer temperature are between room temperature to 120 degree, and deposition rate per minute 10 nanometers adopt the method for vacuum evaporation to deposit first semiconductor layer 3 of first battery on transparency electrode 2, and its thickness is less than or equal to 30 nanometers more than or equal to 10 nanometers; The method of employing vacuum evaporation deposits second semiconductor layer 4 of first battery on first semiconductor layer 3 of first battery, its thickness is more than or equal to 20 nanometers, be less than or equal to 60 nanometers, on second semiconductor layer 4 of first battery, adopt the method for vacuum evaporation to deposit the 7 three layers of organic heterojunction film of intermediate electrode layer 5, intermediate electrode layer 6, intermediate electrode layer that constitute target successively, every layer thickness is less than or equal to 30 nanometers all more than or equal to 2 nanometers; The method of employing vacuum evaporation deposits second semiconductor layer 9 of second battery on intermediate electrode layer 7, and its thickness is less than or equal to 100 nanometers more than or equal to 20 nanometers; On second semiconductor layer 9 of second battery, adopt the method for vacuum evaporation to prepare metal electrode 10.
3) adopt three layers of organic heterojunction film as follows as the third preparation method's the step and the condition of stacking organic photovoltaic power cell of structure of target:
According to the given material of each layer, its vacuum cavity base vacuum 8.0 * 10 of employed vacuum deposition device
-4Pa, underlayer temperature are between room temperature to 120 degree, and deposition rate per minute 10 nanometers adopt the method for vacuum evaporation to deposit first semiconductor layer 3 of first battery on transparency electrode 2, and its thickness is less than or equal to 30 nanometers more than or equal to 10 nanometers; On first semiconductor layer 3 of first battery, adopt the method for vacuum evaporation to deposit the 7 three layers of organic heterojunction film of intermediate electrode layer 5, intermediate electrode layer 6, intermediate electrode layer that constitute target successively, every layer thickness is less than or equal to 30 nanometers all more than or equal to 2 nanometers; The method of employing vacuum evaporation deposits first semiconductor layer 8 of second battery on intermediate electrode layer 7, and its thickness is less than or equal to 50 nanometers more than or equal to 10 nanometers; The method of employing vacuum evaporation deposits second semiconductor layer 9 of second battery on first semiconductor layer 8 of second battery, and its thickness is less than or equal to 100 nanometers more than or equal to 20 nanometers; On second semiconductor layer 9 of second battery, adopt the method for vacuum evaporation to prepare metal electrode 10.
Beneficial effect of the present invention: adopting the organic heterojunction film is target, because the organic heterojunction film has the characteristics of the discrete transmission of electronics and hole, can carry out the compound of electronics-hole effectively at the heterojunction boundary place and almost not have energy loss, have simultaneously reasonablely to electrically contact, help the raising of stacking organic photovoltaic power cell performance with organic active layer.
Advantage of the present invention is that battery performance significantly improves, and preparation technology is simple.This device can be widely used in the fields such as transducer of low-cost and high efficiency photovoltaic cell and wide spectrum sensitive.
Description of drawings
Fig. 1 adopts the stacking organic photovoltaic power cell structural representation of three layers of organic semiconductor heterojunction as target.Wherein, the 1st, transparency carrier, the 2nd, transparent anode, 3 is first semiconductor layers of first battery, 4 is second semiconductor layers of first battery, the 5th, intermediate electrode layer, the 6th, intermediate electrode layer, the 7th, intermediate electrode layer, 8 is first semiconductor layers of second battery, 9 is second semiconductor layers of second battery, the 10th, and metallic cathode.Fig. 1 also is a Figure of abstract.
Fig. 2 is the current-voltage characteristic curve that adopts the stacking organic photovoltaic power cell of Fig. 1 structure.Wherein, transparent anode is ITO, and first semiconductor layer of first and second batteries is Phthalocyanine Zinc (ZnPc), and second semiconductor layer of first and second batteries is fullerene (C60), and intermediate electrode layer 5 is phthalocyanine tin dichloro (SnCl
2Pc), intermediate electrode layer 6 is ten hexafluoro CuPc (F
16CuPc), intermediate electrode layer 7 is CuPc (CuPc), and metallic cathode is Al.
Fig. 3 adopts three layers of organic semiconductor heterojunction, second kind of structural representation of stacking organic photovoltaic power cell as target.Wherein, the 1st, transparency carrier, the 2nd, transparent anode, 3 is first semiconductor layers of first battery, 4 is second semiconductor layers of first battery, the 5th, and intermediate electrode layer, the 6th, intermediate electrode layer, the 7th, intermediate electrode layer, 9 is second semiconductor layers of second battery, the 10th, metallic cathode.
Fig. 4 is the current-voltage characteristic curve that adopts the stacking organic photovoltaic power cell of Fig. 3 structure.Wherein, transparent anode is ITO, and first semiconductor layer of first battery is CuPc, and second semiconductor layer of first and second batteries is C60, and intermediate electrode layer 5 is SnOPc, and intermediate electrode layer 6 is F
16AlClPc, intermediate electrode layer 7 has the function of first semiconductor layer of second battery concurrently for ZnPc, and metallic cathode is Al.
Fig. 5 adopts three layers of organic semiconductor heterojunction as the lamination of target the third structural representation of machine battery to be arranged.Wherein, the 1st, transparency carrier, the 2nd, transparent anode, 3 is first semiconductor layers of first battery, the 5th, intermediate electrode layer, the 6th, intermediate electrode layer, the 7th, intermediate electrode layer, 8 is first semiconductor layers of second battery, and 9 is second semiconductor layers of second battery, the 10th, and metallic cathode.
Fig. 6 is the current-voltage characteristic curve that adopts the stacking organic photovoltaic power cell of Fig. 5 structure.Wherein, transparent anode is ITO, first battery and second battery first semiconductor layer be phthalocyanine nickel (NiPc), intermediate electrode layer 5 is SnCl
2Pc has the function of second semiconductor layer of first battery concurrently, and intermediate electrode layer 6 is Cl
16CuPc, intermediate electrode layer 7 is CoPc, second semiconductor layer of second battery is SnCl
2Pc.
Used phthalocyanine nickel (NiPc), phthalocyanine tin (SnPc), CuPc (CuPc), phthalocyanine cobalt (CoPc), Phthalocyanine Zinc (ZnPc), phthalocyanine lead (PbPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), FePC chlorine (FeClPc), phthalocyanine titanium dichloro (TiCl
2Pc), phthalocyanine tin dichloro (SnCl
2Pc), phthalocyanine indium chlorine (InClPc), ten hexachloro phthalocyanine chlorine aluminium (Cl
16AlClPc), manganese phthalocyanine chlorine (MnClPc), phthalocyanine gallium chlorine (GaClPc), phthalocyanine oxygen tin (SnOPc), phthalocyanine titanium difluoro (TiF
2Pc), phthalocyanine tin difluoro (SnF
2Pc), phthalocyanine indium fluorine (InFPc), phthalocyanine germanium dichloro (GeCl
2Pc), ten hexafluoro TiOPc (F
16TiOPc), ten hexafluoro ranadylic phthalocyanine (F
16VOPc), ten hexafluoro phthalocyanine indium chlorine (F
16InClPc), ten hexafluoro manganese phthalocyanine chlorine (F
16MnClPc), ten hexafluoro phthalocyanine tin dichloro (F
16SnCl
2Pc), ten hexafluoro phthalocyanine titanium dichloro (F
16TiCl
2Pc), ten hexafluoro aluminum phthalocyanine chlorine (F
16AlClPc), ten hexachloro phthalocyanine tin dichloro (Cl
16SnCl
2Pc), ten hexachloro TiOPc (Cl
16TiOPc), ten hexachloro ranadylic phthalocyanine (Cl
16VOPc), ten hexachloro phthalocyanine indium chlorine (Cl
16InClPc), ten hexafluoro CuPc (F
16CuPc), fullerene (C60) and dibenzo Mi Zuo perylene (PTCBI) be commercial product, use the secondary distillation back of purifying.Ito glass is a commercial product, cleans the back and uses.Metallic aluminium is a commercial product, directly uses.
Device architecture adopts first kind the formation of three layers of organic heterojunction film of employing provided by the invention as the stacking organic photovoltaic power cell of target.
The concrete processing method of device is as follows:
On ito glass 2, adopt the method for vacuum evaporation to deposit first semiconductor layer 3 of first battery, second semiconductor layer 4 of first battery successively; On second semiconductor layer 4 on first battery, adopt the method for vacuum evaporation to deposit intermediate electrode layer 5, intermediate electrode layer 6, intermediate electrode layer 7 successively; On intermediate electrode layer 7, adopt the method for vacuum evaporation to deposit first semiconductor layer 8 of second battery and second semiconductor layer 9 of second battery successively; On second semiconductor layer 9 of second battery, adopt the method for vacuum evaporation, utilize the aluminium (Al) of 3.14 square centimeter of 100 nanometer thickness of bushing deposition one deck area to form the laminated cell of structure as shown in Figure 1 as metallic cathode 10.
Wherein, base vacuum 8 * 10
-4Pa, underlayer temperature is from room temperature to 120 ℃, and evaporation speed is per minute 10 nanometers; First semiconductor layer 3 of first battery is Phthalocyanine Zinc (ZnPc), thickness 10 nanometers; Second semiconductor layer 4 of first battery is fullerene (C60), thickness 20 nanometers; Intermediate electrode layer 5 is phthalocyanine tin dichloro (SnCl
2Pc), thickness 2 nanometers; Intermediate electrode layer 6 is ten hexafluoro CuPc (F
16CuPc), thickness 3 nanometers; Intermediate electrode layer 7 is CuPc (CuPc), thickness 5 nanometers; First semiconductor layer 8 of second battery is Phthalocyanine Zinc (ZnPc), thickness 10 nanometers, and second semiconductor layer 9 of second battery is fullerene (C60), thickness 20 nanometers.
For the ease of comparing, adopt similarity condition to prepare adopting ZnPc on the ito glass surface is that first semiconductor layer, C60 are that second semiconductor layer, Al are the monocell of metallic cathode.
Fig. 2 is that to adopt ZnPc on ito glass surface be first semiconductor layer of first and second batteries, second semiconductor layer, the SnCl that C60 is first and second batteries
2Pc is intermediate electrode layer 5, F
16CuPc is that intermediate electrode layer 6, CuPc are that intermediate electrode layer 7, Al are that the stacking organic photovoltaic power cell of metallic cathode is under the dark attitude and the current-voltage curve under the irradiation of simulated solar light source.At air mass (AM) 1.5, luminous intensity 100mW/cm
2Under the simulated solar light source, the open circuit voltage of device is 1.02V, and short-circuit current density is 3.0mA/cm
2, fill factor, curve factor is 0.5, energy conversion efficiency is 1.53%.Compare open circuit voltage 0.54V, short-circuit current density 3.9mA/cm with monocell
2, fill factor, curve factor 0.53, energy conversion efficiency 1.1%, efficient improves more than 40%.Therefore, the target that three layers of organic heterojunction film constitutes can overcome that light percolating property in the prior art is poor, near the problem of photoproduction exciton cancellation and open circuit voltage and fill factor, curve factor loss intermediate layer, can significantly improve battery efficiency simultaneously.
Table one provides according to three layers of organic heterojunction film of employing provided by the invention of embodiment 1 preparation structure and performance as the device of first kind of formation of the stacking organic photovoltaic power cell of target, as can be seen, the target of three layers of organic heterojunction film formation can be realized high efficiency stacking organic photovoltaic power cell from table one.
Table one: adopt structure and the performance of three layers of organic heterojunction film as the stacking organic photovoltaic power cell of target
| Battery material reaches | First battery, |
ZnPc | ZnPc | CuPc | CuPc |
| Thickness (nanometer) | 10 | 30 | 30 | 20 |
| Thickness | First battery, |
C60 | PTCBI | C60 | SnOPc |
| Thickness (nanometer) | 20 | 30 | 60 | 40 | |
| Second battery, |
ZnPc | CuPc | CuPc | TiOPc | |
| Thickness (nanometer) | 10 | 50 | 30 | 45 | |
| Second battery, |
C60 | PTCBI | PTCBI | C60 | |
| Thickness (nanometer) | 20 | 100 | 70 | 80 | |
| Target material and thickness | |
SnCl 2Pc | SnOPc | SnCl 2Pc | SnCl 2Pc |
| Thickness (nanometer) | 2 | 30 | 5 | 15 | |
| Intermediate electrode layer 6 | F 16CuPc | F 16VOPc | Cl 16AlClPc | F 16AlClPc | |
| Thickness (nanometer) | 3 | 15 | 30 | 13 | |
| |
CuPc | CoPc | NiPc | FePc | |
| Thickness (nanometer) | 5 | 30 | 15 | 20 | |
| Device performance | Open circuit voltage (volt) | 1.02 | 1.02 | 1.06 | 1.04 |
| Short-circuit current density (milliampere/square centimeter) | 3.0 | 4.8 | 3.5 | 5.0 | |
| Fill factor, curve factor | 0.5 | 0.48 | 0.52 | 0.47 | |
| Energy conversion efficiency | 1.53％ | 2.35％ | 1.92％ | 2.44％ |
Continuous table
| Battery material and thickness | First battery, |
NiPc | CoPc | FePc | VOPc |
| Thickness (nanometer) | 10 | 25 | 20 | 30 | |
| First battery, |
PTCBI | C60 | SnOPc | C60 | |
| Thickness (nanometer) | 20 | 40 | 30 | 60 | |
| Second battery, |
TiOPc | PbPc | SnPc | CuPc | |
| Thickness (nanometer) | 20 | 10 | 30 | 50 | |
| Second battery, |
C60 | SnCl 2Pc | PTCBI | C60 | |
| Thickness (nanometer) | 40 | 20 | 50 | 100 | |
| Target material and thickness | |
SnCl 2Pc | SnOPc | SnCl 2Pc | SnOPc |
| Thickness (nanometer) | 12 | 7 | 10 | 2 | |
| Intermediate layer 6 | F 16InClPc | F 16MnClPc | F 16TiCl 2Pc | Cl 16TiOPc | |
| Thickness (nanometer) | 8 | 15 | 20 | 2 | |
| |
CuPc | CoPc | NiPc | FePc | |
| Thickness (nanometer) | 10 | 20 | 5 | 2 | |
| Device performance | Open circuit voltage (volt) | 1.03 | 1.05 | 1.05 | 1.04 |
| Short-circuit current density (milliampere/square centimeter) | 2.8 | 3.4 | 2.7 | 3.1 | |
| Fill factor, curve factor | 0.48 | 0.51 | 0.49 | 0.47 | |
| Energy conversion efficiency | 1.38％ | 1.82％ | 1.39％ | 1.52％ |
Material therefor is with embodiment 1.
Device architecture adopts second kind the formation of three layers of organic heterojunction film of employing provided by the invention as the stacking organic photovoltaic power cell of target.
The concrete processing method of device is as follows: adopt the method for vacuum evaporation to deposit first semiconductor layer 3 of first battery, second semiconductor layer 4 of first battery successively on ito glass 2; Adopt the method for vacuum evaporation to deposit intermediate electrode layer 5, intermediate electrode layer 6, intermediate electrode layer 7 successively on second semiconductor layer 4 of first battery, wherein, 7 whiles of intermediate electrode layer are as first semiconductor of second battery; The method that adopts vacuum evaporation on intermediate electrode layer 7 is second semiconductor layer 9 of second battery successively; On second semiconductor layer 9 of second battery, adopt the method for vacuum evaporation, utilize the aluminium (Al) of 3.14 square centimeter of 100 nanometer thickness of bushing deposition one deck area to form the stacking organic photovoltaic power cell of structure as shown in Figure 3 as metallic cathode 10.
Wherein, base vacuum 8 * 10
-4Pa, underlayer temperature is from room temperature to 120 ℃, and evaporation speed is per minute 10 nanometers; Transparent anode is ITO, and first semiconductor layer of first battery is CuPc, thickness 10 nanometers, and second semiconductor layer of first and second batteries is C60, and thickness is respectively 20 nanometers and 30 nanometers, and intermediate electrode layer 5 is SnOPc, thickness 5 nanometers, intermediate electrode layer 6 is F
16AlClPc, thickness 2 nanometers; Intermediate electrode layer 7 is ZnPc, and thickness 30 nanometers have the function of first semiconductor layer of second battery concurrently.
Fig. 4 is the current-voltage curves of embodiment 2 pairing stacking organic photovoltaic power cells under dark attitude and the irradiation of simulated solar light source.At air mass (AM) 1.5, luminous intensity 100mW/cm
2Under the analog light source, the open circuit voltage of device is 1.04V, and short-circuit current density is 3.65mA/cm
2, fill factor, curve factor is 0.48, energy conversion efficiency is 1.8%.
Table two provides according to three layers of organic heterojunction film of employing provided by the invention of embodiment 2 preparation structure and performance as the device of second kind of formation of the stacking organic photovoltaic power cell of target.
Table two: adopt structure and the performance of three layers of organic heterojunction film as the stacking organic photovoltaic power cell of target
| Battery material and thickness | First battery, |
CuPc | GaCl 2Pc | InClPc | TiCl 2Pc |
| Thickness (nanometer) | 10 | 30 | 30 | 20 | |
| First battery, |
C60 | PTCBI | C60 | SnOPc | |
| Thickness (nanometer) | 20 | 40 | 60 | 30 | |
| Second battery, |
C60 | C60 | PTCBI | C60 | |
| Thickness (nanometer) | 30 | 20 | 100 | 50 | |
| Target material and thickness | |
SnOPc | SnOPc | SnCl 2Pc | SnCl 2Pc |
| Thickness (nanometer) | 5 | 8 | 2 | 30 | |
| Intermediate electrode layer 6 | F 16AlClPc | F 16VOPc | Cl 16AlClPc | F 16AlClPc | |
| Thickness (nanometer) | 2 | 30 | 10 | 15 | |
| |
ZnPc | VOPc | TiOPc | PbPc | |
| Thickness (nanometer) | 30 | 2 | 15 | 20 | |
| Device performance | Open circuit voltage (volt) | 1.04 | 1.02 | 1.03 | 1.02 |
| Short-circuit current density (milliampere/square centimeter) | 3.7 | 3 5 | 4.2 | 3.9 | |
| Fill factor, curve factor | 0.48 | 0.51 | 0.46 | 0.52 | |
| Energy conversion efficiency | 1.8％ | 1.82％ | 1.99％ | 2.07％ |
Material therefor is with embodiment 1.
Device architecture adopts the third the formation of three layers of organic heterojunction film of employing provided by the invention as the stacking organic photovoltaic power cell of target.
The concrete processing method of device is as follows: the method for employing vacuum evaporation deposits first semiconductor layer 3 of first battery on ito glass 2; On first semiconductor layer 3 of first battery, adopt the method for vacuum evaporation to deposit intermediate electrode layer 5, intermediate electrode layer 6, intermediate electrode layer 7 successively; Wherein, 5 whiles of intermediate electrode layer are as second semiconductor layer of first battery; Adopting on 7 the method for vacuum evaporation to deposit first semiconductor layer 8 of second battery and second semiconductor layer 9 of second battery successively on the target; On second semiconductor layer 9 of second battery, adopt the method for vacuum evaporation, utilize the aluminium (Al) of 3.14 square centimeter of 100 nanometer thickness of bushing deposition one deck area to form the stacking organic photovoltaic power cell of structure as shown in Figure 5 as metallic cathode 10.
Wherein, base vacuum 8 * 10
-4Pa, underlayer temperature is from room temperature to 120 ℃, and evaporation speed is per minute 10 nanometers; Transparent anode is ITO, and first semiconductor layer of first and second batteries is NiPc, and thickness is respectively 20 nanometers and 35 nanometers; Intermediate electrode layer 5 is SnCl
2Pc has the function of second semiconductor layer of first battery concurrently, and thickness is 30 nanometers; Intermediate electrode layer 6 is Cl
16CuPc, thickness 2 nanometers; Intermediate electrode layer 7 is CoPc, thickness 5 nanometers; Second semiconductor layer of second battery is SnCl
2Pc, thickness 50 nanometers.
Fig. 6 is the current-voltage curves of embodiment 3 pairing stacking organic photovoltaic power cells under dark attitude and the irradiation of simulated solar light source.At air mass (AM) 1.5, luminous intensity 100mW/cm
2Under the simulated solar light source, the open circuit voltage of device is 0.62V, and short-circuit current density is 1.2mA/cm
2, fill factor, curve factor is 0.37, energy conversion efficiency is 0.28%.
Table three provides according to three layers of organic heterojunction film of employing provided by the invention of embodiment 3 preparation structure and performance as the device of the third formation of the stacking organic photovoltaic power cell of target.
Table three: adopt structure and the performance of three layers of organic heterojunction film as the stacking organic photovoltaic power cell of target
| Battery material and thickness | First battery, |
NiPc | CuPc | ZnPc | SnPc |
| Thickness (nanometer) | 20 | 10 | 30 | 15 | |
| Second battery, |
NiPc | PbPc | FePc | VOPc | |
| Thickness (nanometer) | 35 | 10 | 50 | 20 | |
| Second battery, |
SnCl 2Pc | C60 | PTCBI | SnOPc | |
| Thickness (nanometer) | 50 | 20 | 100 | 40 | |
| Target material and thickness | |
SnCl 2Pc | SnOPc | SnOPc | SnCl 2Pc |
| Thickness (nanometer) | 30 | 2 | 30 | 20 | |
| |
Cl 16CuPc | F 16VOPc | Cl 16AlClPc | F 16AlClPc | |
| Thickness (nanometer) | 2 | 30 | 10 | 20 | |
| |
CoPc | VOPc | TiOPc | PbPc | |
| Thickness (nanometer) | 5 | 2 | 10 | 30 | |
| Device performance | Open circuit voltage (volt) | 0.62 | 0.76 | 0.84 | 0.94 |
| Short-circuit current density (milliampere/square centimeter) | 1.2 | 1.8 | 2.1 | 1.7 |
| Fill factor, curve factor | 0.37 | 0.42 | 0.39 | 0.45 | |
| Energy conversion efficiency | 0.28％ | 0.57％ | 0.69％ | 0.72％ |
The invention is not restricted to the foregoing description.In general, the disclosed stacking organic photovoltaic power cell of the present invention can be processed to form two or more serial or parallel connections that machine battery is arranged.Use can be processed in room temperature to 120 ℃ scope based on stacking organic photovoltaic power cell of the present invention.
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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