Abstract:
Provided are a polymer solar cell ( 100 ) and a method for preparing the same. The solar cell ( 100 ) comprises the following structures: a conductive anode substrate ( 10 ), a hole buffer layer ( 20 ), an active layer ( 30 ), an electron transportation layer ( 40 ) and a cathode ( 50 ); and the material for the electron transportation layer ( 40 ) is an electron transportation material doped with a cerium salt and metal particles. The solar cell ( 100 ) effectively increases the rate of electron transportation, and decreases the potential barrier between the electron transportation layer ( 40 ) and the cathode ( 50 ).

Description:
FIELD OF THE INVENTION 
       [0001]    The present disclosure relates to a field of solar cell, and more particularly relates to a polymer solar cell device and a method for preparing the same. 
       BACKGROUND OF THE INVENTION 
       [0002]    In 1982, Weinberger et al. researched the photovoltaic properties of polyacetylene and prepared the first true sense of solar cell, while the energy conversion efficiency of the solar cell is very low (10 −3 %). Subsequently, Glenis et al. prepared a variety of solar cells of polythiophene, but these solar cells had problems of very low open circuit voltage and photoelectric conversion efficiency. Until 1986, C. W. Tang et al. introduced the p-type semiconductor and the n-type semiconductor into devices of bilayer structure for the first time, the level of the photocurrent had been improved greatly, and the organic polymer solar cells had flourished since this work which is regarded as a milestone. 
         [0003]    In 1992, Sariciftci et al. found that there was a phenomenon of rapid light-induced electron transfer in the composite system of 2-methoxy-5-(2-ethyl-hexyloxy)-1,4-styrene (MEH-PPV) and C60 derivatives, which aroused great interest. In 1995, Yu et al. prepared an organic polymer bulk-heterojunction solar cell by mixing MEH-PPV and C60 derivatives PCBM as an active layer. The energy conversion efficiency of the device was 2.9% under the monochromatic light of 20 mW/cm 2  430 nm, this was the first bulk-heterojunction solar cell based on polymer materials and PCBM acceptor, and the concept of composite membrane interpenetrating with network structure was proposed. So far the application of the bulk-heterojunction structure in the polymer solar cell has been rapidly developed; this structure has been widely used in the organic polymer solar cell currently. 
         [0004]    The working principle of the polymer solar cell mainly includes four parts: (1) the formation of light excitation and excitons; (2) the diffusion of the excitons; (3) the splitting of the excitons; (4) the transmission and collection of the charges. First, the conjugated polymer absorbs photons under the incident light, the electrons transit from the highest occupied orbital (HOMO) to the lowest empty track (LUMO) to form the excitons; the excitons diffuse to the intersurface of the donor/acceptor under the influence of the built-in electric field and separate into free electrons and holes, and the electrons transfer in the receptor and are collected by the cathode, the holes are collected by the anode via the donor, thereby generating photocurrent. Accordingly, an effective photoelectric conversion process is formed. 
         [0005]    The conventional polymer solar cell has a structure of conductive anode/hole buffer layer/active layer/electron buffer layer/cathode. While the electron buffer layer is usually made of lithium fluoride (LiF) with a much small thickness of about 0.7 nm, which can help to improve the electron injecting ability. However, if the thickness of this material is too great (more than 1 nm), the series resistance of the device will rise steeply, and most of the voltage falls within this region, thus ultimately affecting the photoelectric conversion efficiency; while if the thickness is too small, it will result in poor film formation, cause electron traps, lead to electronic quenching, and ultimately affect the energy conversion efficiency; thus a severer control of the thickness of the buffer layer is needed, and the production difficulty is increased. In the solar cells, the electron transport rate is often lower than the hole transport rate with two orders of magnitude, the electron transport rate already becomes an important reason for restricting the development of solar cells. 
       SUMMARY OF THE INVENTION 
       [0006]    Accordingly, it is necessary to provide a polymer solar cell device which is capable of improving the electron transport rate. 
         [0007]    A polymer solar cell device includes a conductive anode substrate, a hole buffer layer, an active layer, an electron transporting layer, and a cathode, which are laminated in that order. The electron transporting layer is made of electron transporting material doped with cesium salt and metal particle. The metal particle has a particle size of from 1 nm to 50 nm; the metal particle is made of a material selected from the group consisting of aluminum, silver, gold, and platinum. 
         [0008]    Preferably, a mass ratio of the cesium salt to the electron transporting layer is in a range of from 5% to 20%. 
         [0009]    Preferably, a mass ratio of the metal particle to the electron transporting layer is in a range of from 0.5% to 5%. 
         [0010]    Preferably, the electron transporting layer is made of a material selected from the group consisting of 2-(4-biphenyl)-5-(4-tert-butyl) phenyl-1,3,4-oxadiazole; 4,7-diphenyl-1,10-phenanthroline; 1,2,4-triazole derivant; and N-aryl benzimidazole. 
         [0011]    Preferably, the cesium salt is selected from the group consisting of cesium carbonate, cesium azide, cesium fluoride, and cesium chloride. 
         [0012]    Preferably, a thickness of the electron transporting layer is in a range of from 5 nm to 40 nm. 
         [0013]    Preferably, the hole buffer layer is made of a mixture of poly 3,4-ethylenedioxythiophene and polystyrene sulfonate with a mass ratio of 2:1 to 6:1. 
         [0014]    Preferably, the active layer is made of a mixture of poly (3-hexylthiophene) and butyrate derivative of fullerene with a mass ratio of 1:0.8 to 1:1; 
         [0015]    or, the active layer is made of a mixture of poly[2-methoxy-5-(3,7-dimethyloctyl)oxy)phenylene vinylene] and butyrate derivative of fullerene with a mass ratio of 1:1 to 1:4; 
         [0016]    or, the active layer is made of a mixture of poly[2-methoxy-5-(2′-vinyl-hexyloxy) poly phenylene vinylene] and butyrate derivative of fullerene with a mass ratio of 1:1 to 1:4. 
         [0017]    Preferably, the conductive anode substrate is made of a material selected from the group consisting of indium tin oxide glass, fluorine-doped tin oxide glass, aluminum-doped zinc oxide glass, and indium-doped zinc oxide glass; 
         [0018]    the cathode is made of a material selected from the group consisting of aluminum, silver, gold, and platinum. 
         [0019]    A method for preparing a polymer solar cell device includes steps of: 
         [0020]    preprocessing a conductive anode substrate; 
         [0021]    forming a hole buffer layer on the conductive anode substrate by spin-coating; 
         [0022]    forming an active layer on the hole buffer layer by spin-coating; 
         [0023]    depositing an electron transporting material doped with cesium salt and metal particle on the active layer to form an electron transporting layer; and 
         [0024]    forming a cathode on the electron transporting layer, and obtaining the polymer solar cell device. 
         [0025]    In the polymer solar cell device, the electron transporting layer is made of electron transporting material doped with cesium salt and metal particle. An n-doping is formed by doping cesium salt to the electron transporting material, which improves the electron transport rate effectively, and the energy band between the electron transporting layer and the active layer is bended, the injection barrier of the electrons on this interface is reduced; it is conducive to the injection of the electrons. Furthermore, the barrier between the electron transporting layer and the cathode is reduced due to the doping of metal particle; it is conducive to the collection of the electrons injected in the electron; thus an effective photoelectric conversion is formed. Further still, the film quality of the electron transporting layer formed by ternary doping is improved greatly due to the presence of the metal particle, the roughness of the film is reduced, the film is much more smoother; thus reducing the probability of the generation of the electron traps in the electron transport, and it is conducive to the transport of electrons, the energy conversion efficiency of the polymer solar cell device is finally improved. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0026]      FIG. 1  is a schematic, cross-sectional view of an embodiment of a polymer solar cell device; 
           [0027]      FIG. 2  is a flow chart of an embodiment of a method of preparing the polymer solar cell device shown in  FIG. 1 ; and 
           [0028]      FIG. 3  is a graph illustrating a relationship of current density and voltage between the conventional polymer solar cell device and the polymer solar cell device of Example 1. 
       
    
    
     DETAILED DESCRIPTION OF THE EMBODIMENTS 
       [0029]    A more detailed description of the polymer solar cell device and a method of preparing the polymer solar cell device will be illustrated by reference to specific embodiments and drawings. 
         [0030]    Referring to  FIG. 1 , an embodiment of a polymer solar cell device  100  includes a conductive anode substrate  10 , a hole buffer layer  20 , an active layer  30 , an electron transporting layer  40 , and a cathode  50 , which are laminated in that order. 
         [0031]    The conductive anode substrate  10  is made of a material selected from the group consisting of indium tin oxide glass (ITO), fluorine-doped tin oxide glass (FTO), aluminum-doped zinc oxide glass (AZO), and indium-doped zinc oxide glass (IZO). 
         [0032]    The hole buffer layer  20  is made of a mixture of poly 3,4-ethylenedioxythiophene (PEDOT) and polystyrene sulfonate (PSS) with a mass ratio of 2:1 to 6:1. A thickness of the hole buffer layer  20  is controlled to be in a range of from 20 nm to 80 nm. The hole buffer layer  20  can be formed by following steps: a solution of poly 3,4-ethylenedioxythiophene (PEDOT) and polystyrene sulfonate (PSS) is spin-coated on the conductive anode substrate  10 , a mass ratio of PEDOT to PSS is in a range of from 2:1 to 6:1, a mass percent of the solution is in a range of from 1% to 5%; and then the solution is dried at a temperature from 100° C. to 200° C. for 15 minutes to 60 minutes. Preferably, a solution of PEDOT and PSS is spin-coated, the mass ratio of PEDOT to PSS is 6:1, the mass percent of the solution is 1.3%, and then dried at a temperature of 200° C. for 30 minutes. The thickness of the hole buffer layer is 40 nm. 
         [0033]    The active layer  30  is made of a mixture using butyrate derivatives of fullerene (PCBM) as acceptor; the thickness of the active layer  30  can be in a range of from 80 nm to 300 nm. 
         [0034]    Specifically, the active layer  30  is made of a mixture composed of poly (3-hexylthiophene) (P3HT) and butyrate derivative of fullerene (PCBM) with a mass ratio of 1:0.8 to 1:1. 
         [0035]    Or, the active layer  30  is made of a mixture composed of poly[2-methoxy-5-(3,7-dimethyloctyl)oxy)phenylenevinylene] (MDMO-PPV) and butyrate derivative of fullerene (PCBM) with a mass ratio of 1:1 to 1:4. 
         [0036]    Or, the active layer is made of a mixture composed of poly[2-methoxy-5-(2′-vinyl-hexyloxy) poly phenylenevinylene] (MEH-PPV) and butyrate derivative of fullerene (PCBM) with a mass ratio of 1:1 to 1:4. 
         [0037]    Preferably, the active layer  30  is made composed of MEH-PPV:PCBM with a mass ratio of 1:3. The thickness of the active layer  30  is 200 nm. 
         [0038]    The electron transporting layer  40  is made of electron transporting material doped with cesium salt and metal particle. 
         [0039]    A mass ratio of the cesium salt to the electron transporting layer is in a range of from 5% to 20%. 
         [0040]    The cesium salt can be selected from the group consisting of cesium carbonate, cesium azide, cesium fluoride, and cesium chloride. 
         [0041]    A mass ratio of the metal particle to the electron transporting layer is in a range of from 0.5% to 5%. 
         [0042]    A particle size of the metal particle is in a range of from 1 nm to 50 nm. Preferably, the particle size of the metal particle is in a range of from 10 nm to 30 nm. 
         [0043]    The metal particle is made of metal with a high conductivity, a work function beyond 4.2 eV, and a melting point below 2000° C. When a film with a thickness 10 nm is made of the metal, the visible light transmittance of the metal is needed to be greater than 90%. Specifically, the metal can be selected from the group consisting of the aluminum (Al), silver (Ag), gold (Au), and platinum (Pt). 
         [0044]    The electron transporting material can be selected from the group consisting of 2-(4-biphenyl)-5-(4-tert-butyl) phenyl-1,3,4-oxadiazole (PBD); 4,7-diphenyl-1,10-phenanthroline (Bphen); 1,2,4-triazole derivant (such as TAZ); and N-aryl benzimidazole (TPBI). 
         [0045]    The thickness of the electron transporting layer  40  is in a range of from 5 nm to 40 nm. 
         [0046]    The cathode  50  is made of material selected from the group consisting of aluminum (Al), silver (Ag), gold (Au), and platinum (Pt). 
         [0047]    The thickness of the cathode  50  is in a range of from 80 nm to 250 nm. 
         [0048]    Preferably, the cathode  50  is made of Al; the thickness of the cathode  50  is 150 nm. 
         [0049]    In the polymer solar cell device  100 , the electron transporting layer  40  is made of electron transporting material doped with cesium salt and metal particle. An n-doping is formed by doping cesium salt to the electron transporting material, which improves the electron transport rate effectively, and the energy band between the electron transporting layer  40  and the active layer  30  is bend, the injection barrier of the electrons on this interface is reduced, it is conducive to the injection of the electrons. Furthermore, the electron transporting layer  40  is also doped with metal particle, which reduces the barrier between the electron transporting layer  40  and the cathode  50 , it is conducive to collection of the electrons injected in the electron; thus an effective photoelectric conversion is obtained. Further still, the film quality of the electron transporting layer  40  formed by ternary doping is improved greatly due to the presence of the metal particle, the roughness of the film is reduced, the film is much more smoother, thus reducing the probability of the generation of the electron traps of the electron transport, and it is conducive to the transport of electrons; the energy conversion efficiency of the polymer solar cell device  100  is finally improved. 
         [0050]    Referring to  FIG. 2 , an embodiment of a method for preparing a polymer solar cell device  100  is provided, which includes the steps of: 
         [0051]    Step S 10 , a conductive anode substrate  10  is preprocessed. 
         [0052]    The conductive anode substrate  10  is made of material selected from the group consisting of indium tin oxide glass (ITO), fluorine-doped tin oxide glass (FTO), aluminum-doped zinc oxide glass (AZO), and indium-doped zinc oxide glass (IZO). 
         [0053]    The pretreatment process includes the following steps: the conductive anode substrate  10  is cleaned, then the conductive anode substrate  10  is treated with oxygen plasma or a UV-ozone. 
         [0054]    Specifically, the conductive anode substrate  10  is photoetched and cut into pieces with required size, the conductive anode substrate  10  is then treated using ultrasonic sequentially in detergent, deionized water, acetone, ethanol, and isopropyl alcohol each for 15 minutes to remove organic pollutants on the surface of the glass. The conductive anode substrate  10  is surface-treated using oxygen plasma for 5 minutes to 15 minutes after cleaning; the power is 10 W to 50 W. The UV-ozone treatment can be performed for 5 minutes to 20 minutes. 
         [0055]    Step S 20 , a hole buffer layer  20  is formed on the surface of the conductive anode substrate  10  by spin-coating. 
         [0056]    The hole buffer layer  20  is made of a mixture of poly 3,4-ethylenedioxythiophene (PEDOT) and polystyrene sulfonate (PSS) with a mass ratio of 2:1 to 6:1. A solution of poly 3,4-ethylenedioxythiophene (PEDOT) and polystyrene sulfonate (PSS) is spin-coated on the conductive anode substrate  10 , a mass ratio of PEDOT to PSS is in a range of from 2:1 to 6:1, a mass percent of the solution is in a range of from 1% to 5%, and then dried at a temperature from 100° C. to 200° C. for 15 minutes to 60 minutes. 
         [0057]    The thickness of the hole buffer layer  20  is in a range of from 20 nm to 80 nm. 
         [0058]    Preferably, the solution of PEDOT and PSS is spin-coated, the mass ratio of PEDOT to PSS is 6:1, the mass percent of the solution is 1.3%; and then the solution is dried at a temperature of 200° C. for 30 minutes. The thickness of the hole buffer layer  20  is 40 nm. 
         [0059]    Step S 30 , an active layer  30  is formed on the hole buffer layer  20  by spin-coating. 
         [0060]    An active material is dissolved in an organic solvent to form an active material solution. Under an atmosphere of the protective gas, the active material solution is spin-coated on the surface of the hole buffer layer  20 , and then dried to obtain the active layer  30 . 
         [0061]    In the active material solution, the total concentration of the active material is in a range of from 8 mg/L to 30 mg/L. 
         [0062]    When the active material solution is spin-coated to form the active layer  30 , the active material is a system using butyrate derivative of fullerene (PCBM) as an acceptor. 
         [0063]    Specifically, the active material can be a mixture composed of poly (3-hexylthiophene) and butyrate derivative of fullerene (PCBM) with a mass ratio of 1:0.8 to 1:1 
         [0064]    Or, the active material can be a mixture composed of poly[2-methoxy-5-(3,7-dimethyloctyl)oxy)phenylene vinylene] (MDMO-PPV) and butyrate derivative of fullerene (PCBM) with a mass ratio of 1:1 to 1:4. 
         [0065]    Or, the active material can be a mixture composed of poly[2-methoxy-5-(2′-vinyl-hexyloxy) poly phenylene vinylene] (MEH-PPV) and butyrate derivative of fullerene (PCBM) with a mass ratio of 1:1 to 1:4. 
         [0066]    The organic solvent can be one or two selected from the group consisting of toluene, xylene, chlorobenzene, and chloroform. 
         [0067]    Preferably, the active material solution can be a chlorobenzene solution of MEH-PPV and PCBM with a mass ratio of 1:3 and a total concentration of 24 mg/mL. 
         [0068]    The protective gas atmosphere can be a nitrogen atmosphere or an inert gas atmosphere. 
         [0069]    The thickness of the active layer  30  can be in a range of from 80 nm to 300 nm. Preferably, the thickness of the active layer  30  is 200 nm. 
         [0070]    The active layer  30  can be dried at a room temperature for 24 hours to 48 hours, or annealed at a temperature from 50° C. to 100° C. for 10 minutes to 100 minutes. Preferably, the active layer  30  is annealed at a temperature 100° C. for 45 min. 
         [0071]    Step S 40 , an electron transporting material doped with cesium salt and metal particle is deposited on the active layer  30  to form an electron transporting layer  40 . 
         [0072]    A mass ratio of the cesium salt to the electron transporting layer is in a range of from 5% to 20%. 
         [0073]    The cesium salt is selected from the group consisting of cesium carbonate (Cs 2 CO 3 ), cesium azide (CsN 3 ), cesium fluoride (CsF), and cesium chloride (CsCl). 
         [0074]    A mass ratio of the metal particle to the electron transporting layer is in a range of from 0.5% to 5%. 
         [0075]    The particle size of the metal particle is in a range of from 1 nm to 50 nm. Preferably, the particle size of the metal particle is in a range of from 10 m to 30 nm. 
         [0076]    The metal particle is made of metal with a high conductivity, a work function beyond 4.2 eV, and a melting point below 2000° C. When a film with a thickness 10 nm is made of the metal, the visible light transmittance of the metal is needed to be greater than 90%. Specifically, the electron transporting material can be selected from the group consisting of 2-(4-biphenyl)-5-(4-tert-butyl) phenyl-1,3,4-oxadiazole (PBD); 4,7-diphenyl-1,10-phenanthroline (Bphen); 1,2,4-triazole derivant (such as TAZ); and N-aryl benzimidazole (TPBI). 
         [0077]    The thickness of the electron transporting layer  40  is in a range of 5 nm to 40 nm. 
         [0078]    Step S 50 , a cathode  50  is formed on the electron transporting layer  40 ; and the polymer solar cell device  100  is obtained. 
         [0079]    The cathode  50  is made of material selected from the group consisting of aluminum (Al), silver (Ag), gold(Au), and platinum (Pt). 
         [0080]    The thickness of the cathode  50  is in a range of 80 nm to 250 nm. 
         [0081]    Preferably, the cathode  50  is made of Al; the thickness of the cathode  50  is 150 nm. 
         [0082]    The specific examples are further described as follows: 
         [0083]    The test instruments used in each example are: a high vacuum coating equipment (Shenyang scientific instruments Center Ltd. pressure&lt;1×10 −3  Pa), a current-voltage tester (U.S. Keithly Corporation, Model: 2602), a 500 W xenon lamp (Osram) combined with filter of AM 1.5 are used as white light source for simulating sunlight. 
       Example 1 
       [0084]    The embodiment of the polymer solar cell device has a structure of ITO/(PEDOT:PSS)/(MEH-PPV:PCBM)/(Bhpen:Cs 2 CO 3 :Ag)/Al. 
         [0085]    The preparation process of the polymer solar cell device is described as follows: 
         [0086]    The ITO was photoetched and cut into pieces with required size, the ITO was then treated using ultrasonic sequentially in detergent, deionized water, acetone, ethanol, and isopropyl alcohol each for 15 minutes to remove organic pollutants on the surface of the glass. The ITO was treated with oxygen plasma for 5 minutes after cleaning; the power was 30 W. A solution of PEDOT and PSS was spin-coated on the ITO, a mass ratio of PEDOT to PSS was 6:1, a mass percent of the solution was 1.3%; and then heated at a temperature of 200° C. for 30 minutes, a hole buffer layer with a thickness of 40 nm was formed. Then, under a nitrogen atmosphere, a chlorobenzene solution of MEH-PPV and PCBM was spin-coated on the hole buffer layer, a mass ratio of MEH-PPV to PCBM was 1:3, a total concentration of the chlorobenzene solution was 24 mg/mL, and then placed at a room temperature for 48 hours to form an active layer with a thickness of 200 nm. Then, a material of Bhpen:Cs 2 CO 3 :Ag (Cs 2 CO 3  and Ag were used as doping material, a mass ratio of Cs 2 CO 3  was 10%, a particle size of Ag was 30 nm, a mass ratio of Ag was 1%) was deposited to form an electron transporting layer with a thickness of 25 nm. Finally, a cathode was formed by depositing, the cathode was made of Al, the thickness of that was 150 nm, and a required polymer solar cell device was formed. 
         [0087]      FIG. 3  was a graph illustrating a relationship of current density and voltage between the conventional polymer solar cell device and the polymer solar cell device of example 1. 
         [0088]    Curve 1 was a graph illustrating a relationship of current density and voltage of the polymer solar cell device of example 1; curve 2 was a graph illustrating a relationship of current density and voltage of the conventional polymer solar cell device. 
         [0089]    The difference between the polymer solar cell device of example 1 and the conventional polymer solar cell device was only about the electron transporting layer. The electron transporting layer of the conventional polymer solar cell device was made of LiF with a thickness of 0.7 nm. 
         [0090]    Referring to  FIG. 3 , the polymer solar cell device was subjected to a photocurrent test (in the atmosphere, with a light intensity of 100 mW/cm 2  and an irradiation area of 0.09 mm 2 ); the specific data was shown as the following table. 
         [0000]    
       
         
               
               
               
               
               
             
           
               
                   
               
               
                   
                 Current density (mA cm −2 ) 
                 voltage (V) 
                 η (%) 
                 fill factor 
               
               
                   
               
             
             
               
                 Curve 1 
                 6.48 
                 0.66 
                 1.38 
                 0.32 
               
               
                 Curve 2 
                 5.21 
                 0.63 
                 1.02 
                 0.31 
               
               
                   
               
             
          
         
       
     
         [0091]    It can be seen that, the current density of the conventional polymer solar cell device is 5.21 mA/cm 2 , while the current density of the polymer solar cell device of Example one is increased to 6.48 mA/cm 2 . The results illustrate that the electron transferring rate of the polymer solar cell device is effectively improved by using a ternary doped electron transporting layer, which reduces the barriers between the active layer, the electron transporting layer, and the cathode; the efficiency of electron injection and electron transport is effectively increased; finally, the energy conversion efficiency of the device is improved. The energy conversion efficiency of conventional polymer solar cell device is 1.02%, while the energy conversion efficiency of the polymer solar cell device of Example one is 1.38%. 
       Example 2 
       [0092]    The embodiment of the polymer solar cell device has a structure of IZO/(PEDOT:PSS)/(MDMO-PPV:PCBM)/(PBD:CsF:Al)/Ag. 
         [0093]    The preparation process is described as follows: 
         [0094]    The IZO was photoetched and cut into pieces with required size, the IZO was then treated using ultrasonic sequentially in detergent, deionized water, acetone, ethanol, and isopropyl alcohol each for 15 minutes to remove organic pollutants on the surface of the glass, respectively. The IZO was treated with oxygen plasma for 5 minutes after cleaning; the power was 30 W. A solution of PEDOT and PSS was spin-coated on the IZO, a mass ratio of PEDOT to PSS was 2:1, a mass percent of the solution was 5%; and then heated at a temperature of 100° C. for 60 minutes, a hole buffer layer with a thickness of 20 nm was formed. Then, under an argon atmosphere, an xylene solution of MEH-PPV and PCBM was spin-coated on the hole buffer layer, a mass ratio of MEH-PPV to PCBM was 1:4, a total concentration of the xylene solution was 8 mg/mL, and annealed at a temperature of 200° C. for 5 min to form an active layer with a thickness of 300 nm. Then, a material of PBD:CsF:Al (CsF and Al were used as doping material, a mass ratio of CsF was 20%, a particle size of Al was 10 nm, a mass ratio of Al was 0.5%) was deposited to form an electron transporting layer with a thickness of 5 nm. Finally, a cathode was formed by depositing, the cathode was made of Ag, the thickness of that was 80 nm, and a required polymer solar cell device was formed. 
       Example 3 
       [0095]    The embodiment of the polymer solar cell device has a structure of AZO/(PEDOT:PSS)/(P3HT:PCBM)/(TPBi:CsCl:Au)/Pt. 
         [0096]    The preparation process is described as follows: 
         [0097]    The AZO was photoetched and cut into pieces with required size, the AZO was then treated using ultrasonic sequentially in detergent, deionized water, acetone, ethanol, and isopropyl alcohol each for 15 minutes to remove organic pollutants on the surface of the glass, respectively. The AZO was treated with UV-ozone treatment for 15 minutes after cleaning. A solution of PEDOT and PSS was spin-coated on the AZO, a mass ratio of PEDOT to PSS was 4:1, a mass percent of the solution was 1%; and then heated at a temperature of 200° C. for 15 minutes, a hole buffer layer with a thickness of 80 nm was formed. Then, under a helium atmosphere, an xylene solution of P3HT and PCBM was spin-coated on the hole buffer layer, a mass ratio of P3HT to PCBM was 1:0.8, a total concentration of the xylene solution was 30 mg/mL, and annealed at a temperature of 100° C. for 30 minutes to form an active layer with a thickness of 100 nm. Then, a material of TPBi:CsCl:Au (CsCl and Au were used as doping material, a mass ratio of CsCl was 5%, a particle size of Au was 1 nm, a mass ratio of Au was 5%) was deposited to form an electron transporting layer with a thickness of 40 nm. Finally, a cathode was formed by depositing, the cathode was made of Pt, the thickness of that was 250 nm, and a required polymer solar cell device was formed. 
       Example 4 
       [0098]    The embodiment of the polymer solar cell device has a structure of FTO/(PEDOT:PSS)/(P3HT:PCBM)/(TAZ: CsN 3 :Pt)/Au. 
         [0099]    The preparation process is described as follows: 
         [0100]    The FZO was photoetched and cut into pieces with required size, the FZO was then treated using ultrasonic sequentially in detergent, deionized water, acetone, ethanol, and isopropyl alcohol each for 15 minutes to remove organic pollutants on the surface of the glass, respectively. The FZO was treated with oxygen plasma for 5 minutes after cleaning; the power was 30 W. A solution of PEDOT and PSS was spin-coated on the FZO, a mass ratio of PEDOT to PSS was 5:1, a mass percent of the solution was 2%; and then heated at a temperature of 100° C. for 45 minutes, a hole buffer layer with a thickness of 60 nm was formed. Then, under a nitrogen atmosphere, a chlorobenzene solution of P3HT and PCBM was spin-coated on the hole buffer layer, a mass ratio of MEH-PPV to PCBM was 1:1, a total concentration of the chlorobenzene solution was 20 mg/mL, and annealed at a temperature of 50° C. for 10 minutes to form an active layer with a thickness of 80 nm. Then, a material of TAZ:CsN 3 :Pt (CsN 3  and Pt were used as doping material, a mass ratio of CsN 3  was 10%, a particle size of Pt was 20 nm, a mass ratio of Pt was 2%) was deposited to form an electron transporting layer with a thickness of 20 nm. Finally, a cathode was formed by depositing, the cathode was made of Au, the thickness of that was 100 nm, and a required polymer solar cell device was formed. 
       Example 5 
       [0101]    The embodiment of the polymer solar cell device has a structure of IZO/(PEDOT:PSS)/(MEH-PPV:PCBM)/(Bphen:CsF:Ag)/Al. 
         [0102]    The preparation process of the polymer solar cell device is described as follows: 
         [0103]    The ITO was photoetched and cut into pieces with required size, the ITO was then treated using ultrasonic sequentially in detergent, deionized water, acetone, ethanol, and isopropyl alcohol each for 15 minutes to remove organic pollutants on the surface of the glass, respectively. The ITO was treated with oxygen plasma for 5 minutes after cleaning; the power was 30 W. A solution of PEDOT and PSS was spin-coated on the ITO, a mass ratio of PEDOT to PSS was 6:1, a mass percent of the solution was 5%; and then heated at a temperature of 200° C. for 15 minutes, a hole buffer layer with a thickness of 40 nm was formed. Then, under a nitrogen atmosphere, a mixed solution of chloroform and chlorobenzene of MEH-PPV and PCBM was spin-coated on the hole buffer layer, a mass ratio of MEH-PPV to PCBM was 1:2, a total concentration of the mixed solution was 16 mg/mL, and annealed at a temperature of 150° C. for 60 minutes to form an active layer with a thickness of 160 nm. Then, a material of Bhpen:CsF:Ag (CsF and Ag were used as doping material, a mass ratio of CsF was 15%, a particle size of Ag was 50 nm, a mass ratio of Ag was 2%) was deposited to form an electron transporting layer with a thickness of 25 nm. Finally, a cathode was formed by depositing, the cathode was made of Al, the thickness of that was 150 nm, and a required polymer solar cell device was formed. 
         [0104]    Although the invention has been described in language specific to structural features and/or methodological acts, it is to be understood that the invention defined in the appended claims is not necessarily limited to the specific features or acts described. Rather, the specific features and acts are disclosed as sample forms of implementing the claimed invention.