CN103400941A - Organic solar cell based on heteropoly acid anode modifying layer and preparation method of organic solar cell - Google Patents

Organic solar cell based on heteropoly acid anode modifying layer and preparation method of organic solar cell Download PDF

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CN103400941A
CN103400941A CN201310336377XA CN201310336377A CN103400941A CN 103400941 A CN103400941 A CN 103400941A CN 201310336377X A CN201310336377X A CN 201310336377XA CN 201310336377 A CN201310336377 A CN 201310336377A CN 103400941 A CN103400941 A CN 103400941A
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heteropoly acid
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organic solar
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CN103400941B (en
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孙宝全
朱雅文
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Suzhou Inner Electronic Materials Co Ltd
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Suzhou University
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Abstract

The invention discloses an organic solar cell based on a heteropoly acid anode modifying layer and a preparation method of the organic solar cell. Cells are divided into solar cells in a reverse structure and a positive structure, wherein the anode modifying layer is made of heteropoly acid materials. The complete crystal structure characteristics of the heteropoly acid material are utilized, the defect state number of cell devices is reduced, the electric charge transmission is favorably realized, in addition, the cell performance can show better stability in air, in addition, the heteropoly acid can be easily dissolved in solvents such as isopropanol and ethyl alcohol to form uniform and stable solution, a film formed by the solution has higher light transmittance in a visible light region, and the photon absorption is favorably realized. The organic solar cell and the preparation method have the advantages that the preparation process is simple, the preparation temperature is low (room temperature), and the like; and the cost of the organic solar cell is favorably and greatly reduced.

Description

Based on organic solar batteries of heteropoly acid anode modification layer and preparation method thereof
Technical field
The present invention relates to a kind of organic solar batteries, be specifically related to a kind of polymeric acceptor heterojunction organic solar batteries of heteropoly acid as the anode modification layer that adopt, belong to technical field of solar.
Background technology
Along with the fast development of society, a lot of available resources are being faced with depleted danger, find new forms of energy and replace these resources that are about to exhaust and become one of urgent difficult problem that current mankind faces.In numerous new forms of energy, such as nuclear energy, solar energy, biological energy source, water power energy, wind energy, geothermal energy and tidal energy, because solar energy is a kind of pollution-free, effective, renewable and clean energy resource, and its reserves are huge, inexhaustible, utilize cost low, be not subjected to the advantages such as geographical conditions restriction, be full of wide application prospect; And solar power generation possess thermoelectricity, water power, nuclear power spatter property, fail safe, popularity and the abundance of resource that can't compare with it, so solar energy is considered to of greatest concern, the most promising energy of 21st century.
Solar cell is solar energy directly to be converted to the photoelectric device of electric energy, be to utilize solar energy one of the most effective mode, the research of conventional solar cell mainly concentrates on the inorganic photoelectric device take silicon, GaAs, cadmium telluride and lamination GaInP/GaAs/Ge etc. as active material; But the such devices cost of material is high, and the serious photoetch problem of complex manufacturing and narrow gap semiconductor has limited its large-scale practical application.By contrast, organic solar batteries, because its unique excellent properties comes into one's own day by day, is expected to become the solar powered technology that development potentiality is arranged most, and its Heterosis is: the synthetic cost of organic material is low, function and structure is easy to modulation, and is flexible and film forming is all better; The organic solar batteries course of processing is relatively simple, but low-temperature operation, and the element manufacturing cost decreases, and can realize the large tracts of land manufacturing, can use flexible substrate, light portable etc.
Photoelectric conversion efficiency is one of main parameter that determines the solar cell quality.Every kind of solar cell has its limit conversion efficiency.In the making of actual solar cell, there is several factors limiting the performance of device, thereby must consider the impact of these factors at the aspects such as selection of the design of solar cell and material.
In recent years, in order to improve the photoelectric conversion efficiency of organic solar batteries, the researcher is studied it in all its bearings, wherein, increase decorative layer and can reduce the cancellation rate of photoproduction exciton at organic layer and electrode interface place between organic photoactive layer and metal electrode, make the photoproduction exciton can be separated into more fully electronics and hole, be conducive to collection and the transmission of electric charge, thereby can improve the overall efficiency of battery.Usually, the selection of anode modification layer need to be considered the following aspects: (1) must form ohmic contact with acceptor material; (2) can effectively transmit positive charge; (3) can stop negative electrical charge when collecting positive charge; (4) series resistance of device need be stablized and can not be increased to material.Based on these requirements, in organic solar batteries, usually select PEDOT:PSS(poly (3,4-ethylenedioxithiophene) this class conjugation organic polymer and MoO of poly (styrene sulfonic acid) 3, V 2O 5This quasi-metal oxides is as the anode modification layer.But the pattern of PEDOT:PSS film is subjected to many-sided conditionalities such as environment, is difficult to guarantee its reproducibility, and work function is subjected to the impact of moisture very large, and these unfavorable factors all can reduce overall efficiency and the stability of device; And employing MoO 3Although this quasi-metal oxides has stability preferably as the solar cell of anode modification layer, but need the several different methods deposition film forming such as hot evaporation, electron beam evaporation, sputter, these method costs are higher, be not easy to extensive preparation, meanwhile, there is more defect state density in metal oxide, affects separation and the transmission of electric charge.
So, study a kind of new anode modification layer material necessary with the photoelectric conversion efficiency that improves organic solar batteries.
Summary of the invention
The purpose that the present invention relates to is to provide a kind of organic solar batteries based on heteropoly acid anode modification layer and preparation method thereof.
For achieving the above object, the present invention adopts following technical scheme:
A kind of organic solar batteries based on heteropoly acid anode modification layer comprises: cathode substrate, cathodic modification layer, bulk heterojunction active layer, anode modification layer and anode electrode; Described anode modification layer is heteropolyacid material;
Wherein, described cathode substrate is the indium tin oxide transparent substrate; Described cathodic modification layer is zinc-oxide film; Described bulk heterojunction active layer is prepared from by the mixture of the derivative of thiophene compound and fullerene; Described anode electrode is silver or aluminium; Described heteropolyacid material is H x[MM ' 12O 40], M is P or Si; M 'For Mo or W; X is 3 or 4; Described thiophene compound is poly--3 basic thiophene or polyphenyl 1,4-Dithiapentalenes; The derivative of fullerene is PC 61BM or PC 71BM.
In preferred technical scheme, described heteropolyacid material is H 3PMo 12O 40(phosphomolybdic acid) or H 3PW 12O 40(phosphotungstic acid).
The preparation method of above-mentioned solar cell comprises the following steps:
1) cleaning up and spin coating ZnO precursor solution on the indium-tin-oxide substrate that ozone treatment is crossed;
2) indium-tin-oxide substrate that scribbles the ZnO precursor solution in step 1) is carried out annealing in process, at substrate surface, form the uniform ZnO film of a layer thickness, be the cathodic modification layer;
3) spin coating bulk heterojunction active layer solution on ZnO film, annealing is rear at bulk heterojunction active layer surface spin coating heteropoly acid solution;
4) after solvent volatilizees naturally in the heteropoly acid solution of step 3) spin coating, utilize vacuum thermal evaporation to collect hole at its surperficial evaporation metal electrode, namely complete the preparation of described solar cell.
In technique scheme, the concentration of described heteropoly acid solution is 0.5 mg/mL ~ 2 mg/mL; Solvent is preferably isopropyl alcohol.
In above-mentioned solar cell, described cathodic modification layer thickness is 40nm; Described anode modification layer thickness is 5nm; Described bulk heterojunction active layer thickness is 100nm; Described anode electrode thickness is 60～80nm.
Above-mentioned solar cell is the organic solar batteries of reverse geometry.
The invention also discloses a kind of organic solar batteries based on heteropoly acid anode modification layer, comprising: anode substrate, anode modification layer, bulk heterojunction active layer, cathodic modification layer and cathode electrode; Described anode modification layer is heteropolyacid material;
Wherein, described anode substrate is the indium tin oxide transparent substrate; Described cathodic modification layer is the LiF film; Described bulk heterojunction active layer is prepared from by the mixture of the derivative of thiophene compound and fullerene; Described cathode electrode is aluminium; Described heteropolyacid material is H x[MM ' 12O 40], M is P or Si; M 'For Mo or W; X is 3 or 4; Described thiophene compound is poly--3 basic thiophene or polyphenyl 1,4-Dithiapentalenes; The derivative of fullerene is PC 61BM or PC 71BM.
In preferred technical scheme, described heteropolyacid material is H 3PMo 12O 40Perhaps H 3PW 12O 40Be called phosphomolybdic acid, phosphotungstic acid.
The preparation method of above-mentioned solar cell comprises the following steps:
1) cleaning up and spin coating heteropoly acid solution on the indium-tin-oxide substrate that ozone treatment is crossed;
2) after solvent volatilizees naturally in the heteropoly acid solution of step 1) spin coating, spin coating bulk heterojunction active layer and annealing in process on the heteropoly acid film;
3) the bulk heterojunction active layer surface after annealing in process utilizes vacuum thermal evaporation evaporation LiF and metal electrode collection electronics successively, namely completes the preparation of described solar cell.
In technique scheme, the concentration of described heteropoly acid solution is 0.5 mg/mL ~ 2 mg/mL; Solvent is preferably isopropyl alcohol.
In above-mentioned solar cell, described cathodic modification layer thickness is 6; Described anode modification layer thickness is 5nm; Described bulk heterojunction active layer thickness is 100nm; Described cathode electrode thickness is 100nm.
Above-mentioned solar cell is the organic solar batteries of forward structure.
The raw material of making the bulk heterojunction active layer in the present invention is prior art, is preferably the mixture of the derivative of thiophene compound and fullerene, and wherein thiophene compound is poly--3 basic thiophene P3HT or polyphenyl 1,4-Dithiapentalene PTB7; The derivative of fullerene is PC 61BM or PC 71BM.Bulk heterojunction active layer solution can prepare by the following method:
P3HT and PC 61BM is dissolved in dichloro-benzenes after mixing with the ratio of 1:0.8 (W:W), and 40 ℃ of mixed solution add thermal agitation and got final product in 12 hours; Perhaps PTB7 and PC 71BM is dissolved in chlorobenzene after mixing with the ratio of 1:1.5 (W:W), add volume ratio and be 3% 1,8-diiodo-octane (DIO), mixed solution stir and got final product in 3 hours.
Introduce the heteropolyacid material H of tetrahedral coordination in the present invention x[MM ' 12O 40] (M is P or Si; M 'For Mo or W; X is 3 or 4) as the anode modification layer of organic solar batteries, it is a kind ofly by a plurality of oxyacid molecules, by dehydrating condensation, to become the oxyacid cluster compound, soluble in water, ethanol, isopropyl alcohol equal solvent.Materials, by spin-coating film, need not annealed, and the preparation technology of battery is simplified, and production cost reduces; Simultaneously, effect due to the perfect crystal structure of heteropoly acid, reduce the defect state density of active layer and anodic interface, make the defect state decreased number of device, be conducive to transmission and the collection in hole, more be conducive to the transmission of anode electric charge, and utilize this solution to present stability preferably as the organic solar batteries of anode modification layer preparation in air.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1, the present invention utilizes the anode modification layer of heteropolyacid material as organic solar batteries, preparation technology is simple, need not evaporation, it is soluble in water, in the ethanol equal solvent, form homogeneous, stable solution, get final product through normal temperature spin coating, natural solvent flashing, need not annealing in process, be conducive to reduce the cost of organic solar batteries;
2, heteropolyacid material disclosed by the invention has reduced the number of device defects state, be conducive to the electric charge transmission, and its light transmittance in visible region is high, is conducive to the absorption of photon, thereby has improved the photoelectric conversion efficiency of organic solar batteries;
3, preparation technology provided by the invention is simple, and without reprocessing, environmental friendliness, be easy to suitability for industrialized production.
Description of drawings
Fig. 1 is the structural representation of embodiment gained organic solar batteries;
Fig. 2 is the J-V curve of organic solar batteries in embodiment one;
Fig. 3 is the external quantum efficiency curve of organic solar batteries in embodiment one;
Fig. 4 is the aerial stability curve of the photoelectric conversion efficiency of organic solar batteries in embodiment one;
Fig. 5 is the J-V curve of organic solar batteries in embodiment two;
Fig. 6 is the external quantum efficiency curve of organic solar batteries in embodiment two;
Fig. 7 is the aerial stability curve of the photoelectric conversion efficiency of organic solar batteries in embodiment two.
Embodiment
The invention will be further described below in conjunction with drawings and Examples:
Embodiment one
Take isopropyl alcohol as solvent, the preparation phosphorus molybdenum acid solution is standby.P3HT and PC 61BM is dissolved in dichloro-benzenes after mixing with the ratio of 1:0.8 (W:W), and 40 ℃ of mixed solution added thermal agitation 12 hours, and are stand-by.The ITO transparent substrates is used acetone, ethanol, deionized water ultrasonic cleaning 20 min successively, with nitrogen, dry up rear ozone treatment 15 min.Adopt spin-coating method that the ZnO presoma is spin-coated on the ITO substrate, rotating speed is 4000 rpm, and the time is 1min.150 ℃ of annealing 60-90 min, form fine and close ZnO film in air atmosphere.Spin coating bulk heterojunction active layer P3HT:PC on cooled ZnO film 61BM, rotating speed are 700 rpm, and the time is 18 s, 110 ℃ of annealing 10 min in nitrogen atmosphere.Spin coating 1mg/mL phosphorus molybdenum acid solution on active layer, rotating speed is 4000 rpm, time is 1 min, need not heating, after volatilizing naturally, solvent utilizes the approximately Ag electrode of 70 nm of the hot evaporation thickness of high vacuum, namely obtain described organic solar batteries, it has reverse geometry, and the figure in accompanying drawing 1 (a) is its structural representation.
Device need not encapsulation, under room temperature environment, records J-V curve, external quantum efficiency curve and the device efficiency stability curve of device.
Accompanying drawing 2 is that upper organic solar batteries is at 100 mW/cm 2The irradiation of AM1.5 solar simulator under measure the J-V curve; The short circuit current that can find out battery is 8.55 mA/cm 2, open circuit voltage is 0.66 V, and fill factor, curve factor is 0.71, and photoelectric conversion efficiency is 4.01%;
Accompanying drawing 3 is external quantum efficiency curves of above-mentioned organic solar batteries; Can find out its external quantum efficiency〉60%;
Accompanying drawing 4 is the aerial stability curves of the photoelectric conversion efficiency of above-mentioned organic solar batteries; Can find out that it has stability preferably in air, after 60 days, device still remains on more than 90% of optimum efficiency.
Embodiment two
Take isopropyl alcohol as solvent, the preparation phosphorus molybdenum acid solution is standby.PTB7 and PC 71BM is dissolved in chlorobenzene after mixing with the ratio of 1:1.5 (W:W), and the interpolation volume ratio is 3% DIO, and mixed solution stirs half an hour, and is stand-by.The ITO transparent substrates is used acetone, ethanol, deionized water ultrasonic cleaning 20 min successively, with nitrogen, dry up rear ozone treatment 15 min.Adopt spin-coating method that the ZnO presoma is spin-coated on the ITO substrate, rotating speed is 4000 rpm, and the time is 1 min.150 ℃ of annealing 60-90 min, form fine and close ZnO film in air atmosphere.Spin coating bulk heterojunction active layer PTB7:PC on cooled ZnO film 71BM, rotating speed are 1000 rpm, and the time is 1 min.After solution volatilizees naturally, spin coating 2mg/mL phosphorus molybdenum acid solution on active layer, rotating speed is 4000 rpm, time is 1 min, need not heating, utilizes the approximately Ag electrode of 70 nm of the hot evaporation thickness of high vacuum after solvent volatilizees naturally, namely obtain described organic solar batteries, it has reverse geometry.
Device need not encapsulation, under room temperature environment, records J-V curve, external quantum efficiency curve and the device efficiency stability curve of device.
Accompanying drawing 5 is that upper organic solar batteries is at 100 mW/cm 2The irradiation of AM1.5 solar simulator under measure the J-V curve; The short circuit current that can find out battery is 16.20 mA/cm 2, open circuit voltage is 0.70 V, and fill factor, curve factor is 0.68, and photoelectric conversion efficiency is 7.75%;
Accompanying drawing 6 is external quantum efficiency curves of above-mentioned organic solar batteries; Can find out its external quantum efficiency〉80%;
Accompanying drawing 7 is the aerial stability curves of the photoelectric conversion efficiency of above-mentioned organic solar batteries; Can find out that it has stability preferably in air, after 30 days, device still remains on more than 90% of optimum efficiency.
Embodiment three
Take isopropyl alcohol as solvent, the preparation phosphorus molybdenum acid solution is standby.The ITO transparent substrates is used acetone, ethanol, deionized water ultrasonic cleaning 20 min successively, with nitrogen, dry up rear ozone treatment 15 min.Adopt spin-coating method that the 0.5mg/mL phosphorus molybdenum acid solution is spin-coated on the ITO substrate, rotating speed is 4000 rpm, and the time is 1 min, need not annealing, after solvent volatilizees naturally, and spin coating bulk heterojunction active layer P3HT:PC on the phosphomolybdic acid film 61BM, rotating speed are 700 rpm, and the time is 18 s, 110 ℃ of annealing 10 min in nitrogen atmosphere.Utilize the hot evaporation of high vacuum approximately 6 LiF and the about Al electrode of 100 nm of evaporation thickness successively, namely obtain described organic solar batteries, it has forward structure.Figure in accompanying drawing 1 (b) is its structural representation.Device need not encapsulation, and under room temperature environment, the short circuit current that records device is 7.04 mA/cm 2, open circuit voltage is 0.58V, and fill factor, curve factor is 0.50, and photoelectric conversion efficiency is 2.06 %.
Embodiment four
Take isopropyl alcohol as solvent, the preparation phosphorus molybdenum acid solution is standby.The ITO transparent substrates is used acetone, ethanol, deionized water ultrasonic cleaning 20 min successively, with nitrogen, dry up rear ozone treatment 15 min.Adopt spin-coating method that the 1mg/mL phosphorus molybdenum acid solution is spin-coated on the ITO substrate, rotating speed is 4000 rpm, and the time is 1min, need not annealing.After solvent volatilizees naturally, spin coating bulk heterojunction active layer PTB7:PC on the phosphomolybdic acid film 71BM, rotating speed are 1000 rpm, and the time is 1 min, after solvent volatilizees naturally, utilize the hot evaporation of high vacuum approximately 6 LiF and the about Al electrode of 100 nm of evaporation thickness successively, namely obtain described organic solar batteries, and it has forward structure.Device need not encapsulation, and under room temperature environment, the short circuit current that records device is 15.79 mA/cm 2, open circuit voltage is 0.72V, and fill factor, curve factor is 0.62, and photoelectric conversion efficiency is 7.01 %.
Embodiment five
Take isopropyl alcohol as solvent, the preparation Salkowski's solution is standby.The ITO transparent substrates is used acetone, ethanol, deionized water ultrasonic cleaning 20 min successively, with nitrogen, dry up rear ozone treatment 15 min.Adopt spin-coating method that the ZnO presoma is spin-coated on the ITO substrate, rotating speed is 4000 rpm, and the time is 1min.150 ℃ of annealing 60-90 min, form fine and close ZnO film in air atmosphere.Spin coating bulk heterojunction active layer P3HT:PC on cooled ZnO film 61BM, rotating speed are 700 rpm, and the time is 18 s, 110 ℃ of annealing 10 min in nitrogen atmosphere.Spin coating 0.5mg/mL Salkowski's solution on active layer, rotating speed is 4000 rpm, the time is 1 min, need not heating, utilize the approximately Ag electrode of 70 nm of the hot evaporation thickness of high vacuum after solvent volatilizees naturally, namely obtain described organic solar batteries, it has reverse geometry.Device need not encapsulation, and under room temperature environment, the short circuit current that records device is 8.95 mA/cm 2, open circuit voltage is 0.64V, and fill factor, curve factor is 0.66, and photoelectric conversion efficiency is 3.80 %.
Embodiment six
Take isopropyl alcohol as solvent, the preparation Salkowski's solution is standby.The ITO transparent substrates is used acetone, ethanol, deionized water ultrasonic cleaning 20 min successively, with nitrogen, dry up rear ozone treatment 15 min.Adopt spin-coating method that the ZnO presoma is spin-coated on the ITO substrate, rotating speed is 4000 rpm, and the time is 1 min.150 ℃ of annealing 60-90 min, form fine and close ZnO film in air atmosphere.Spin coating bulk heterojunction active layer PTB7:PC on cooled ZnO film 71BM, rotating speed are 1000 rpm, and the time is 1 min.After solution volatilizees naturally, spin coating 2mg/mL Salkowski's solution on active layer, rotating speed is 4000 rpm, time is 1 min, need not heating, utilizes the approximately Ag electrode of 70 nm of the hot evaporation thickness of high vacuum after solvent volatilizees naturally, namely obtain described organic solar batteries, it has reverse geometry.Device need not encapsulation, and under room temperature environment, the short circuit current that records device is 16.36mA/cm 2, open circuit voltage is 0.68V, and fill factor, curve factor is 0.65, and photoelectric conversion efficiency is 7.20 %.

Claims (10)

1. the organic solar batteries based on heteropoly acid anode modification layer, comprising: cathode substrate, cathodic modification layer, bulk heterojunction active layer, anode modification layer and anode electrode; It is characterized in that, described anode modification layer is heteropolyacid material;
Wherein, described cathode substrate is the indium tin oxide transparent substrate; Described cathodic modification layer is zinc-oxide film; Described bulk heterojunction active layer is prepared from by the mixture of the derivative of thiophene compound and fullerene; Described anode electrode is silver or aluminium; Described heteropolyacid material is H x[MM ' 12O 40], M is P or Si; M 'For Mo or W; X is 3 or 4;
Described thiophene compound is poly--3 basic thiophene or polyphenyl 1,4-Dithiapentalenes; The derivative of fullerene is PC 61BM or PC 71BM.
2. solar cell according to claim 1, it is characterized in that: described heteropolyacid material is H 3PMo 12O 40Perhaps H 3PW 12O 40
3. the preparation method of claim 1 or 2 described solar cells, is characterized in that, comprises the following steps:
1) cleaning up and spin coating ZnO precursor solution on the indium-tin-oxide substrate that ozone treatment is crossed;
2) indium-tin-oxide substrate that scribbles the ZnO precursor solution in step 1) is carried out annealing in process, at substrate surface, form the uniform ZnO film of a layer thickness, be the cathodic modification layer;
3) spin coating bulk heterojunction active layer solution on ZnO film, annealing is rear at bulk heterojunction active layer surface spin coating heteropoly acid solution;
4) after solvent volatilizees naturally in heteropoly acid solution, utilize vacuum thermal evaporation to collect hole at its surperficial evaporation metal electrode, namely complete the preparation of described solar cell.
4. preparation method according to claim 3, it is characterized in that: the concentration of described heteropoly acid solution is 0.5 mg/mL ~ 2 mg/mL.
5. preparation method according to claim 3, it is characterized in that: described cathodic modification layer thickness is 40nm; Described anode modification layer thickness is 5nm; Described bulk heterojunction active layer thickness is 100nm; Described anode electrode thickness is 60～80nm.
6. the organic solar batteries based on heteropoly acid anode modification layer, comprising: anode substrate, anode modification layer, bulk heterojunction active layer, cathodic modification layer and cathode electrode; It is characterized in that, described anode modification layer is heteropolyacid material;
Wherein, described anode substrate is the indium tin oxide transparent substrate; Described cathodic modification layer is the LiF film; Described bulk heterojunction active layer is prepared from by the mixture of the derivative of thiophene compound and fullerene; Described cathode electrode is aluminium; Described heteropolyacid material is H x[MM ' 12O 40], M is P or Si; M 'For Mo or W; X is 3 or 4;
Described thiophene compound is poly--3 basic thiophene or polyphenyl 1,4-Dithiapentalenes; The derivative of fullerene is PC 61BM or PC 71BM.
7. solar cell according to claim 6, it is characterized in that: described heteropolyacid material is H 3PMo 12O 40Perhaps H 3PW 12O 40
8. the preparation method of claim 6 or 7 described solar cells, is characterized in that, comprises the following steps:
1) cleaning up and spin coating heteropoly acid solution on the indium-tin-oxide substrate that ozone treatment is crossed;
2) after solvent volatilizees naturally in the heteropoly acid solution of step 1) spin coating, spin coating bulk heterojunction active layer solution and annealing in process on the heteropoly acid film;
3) the bulk heterojunction active layer surface after annealing in process utilizes vacuum thermal evaporation evaporation LiF and metal electrode collection electronics successively, namely completes the preparation of described solar cell.
9. preparation method according to claim 8, it is characterized in that: the concentration of described heteropoly acid solution is 0.5 mg/mL ~ 2 mg/mL.
10. preparation method according to claim 8, it is characterized in that: described cathodic modification layer thickness is 6; Described anode modification layer thickness is 5nm; Described bulk heterojunction active layer thickness is 100nm; Described cathode electrode thickness is 100nm.
CN201310336377.XA 2013-08-05 2013-08-05 Based on the organic solar batteries and preparation method thereof of heteropoly acid anode modification layer Active CN103400941B (en)

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CN110268538A (en) * 2016-12-27 2019-09-20 埃尼股份公司 Hole mobile material and the photovoltaic devices for using the hole mobile material
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US11795092B2 (en) 2018-10-19 2023-10-24 Bottero S.P.A. Plunger assembly for forming ribbons of molten glass

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