CN104253215A - Solar cell device and method for manufacturing same - Google Patents

Solar cell device and method for manufacturing same Download PDF

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Publication number
CN104253215A
CN104253215A CN201310263523.0A CN201310263523A CN104253215A CN 104253215 A CN104253215 A CN 104253215A CN 201310263523 A CN201310263523 A CN 201310263523A CN 104253215 A CN104253215 A CN 104253215A
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solar cell
active layer
cell device
intermediate layer
phthalocyanine
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周明杰
黄辉
陈吉星
王平
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Priority to CN201310263523.0A priority Critical patent/CN104253215A/en
Publication of CN104253215A publication Critical patent/CN104253215A/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a solar cell device. The solar cell device comprises an anode, a hole buffer layer, a first active layer, an intermediate layer, a second active layer, an electron buffer layer and a cathode which are sequentially stacked on one another. The first active layer and the second active layer are made of mixtures of poly-3-hexyl-thiophene and 6,6-phenyl-C<61>-methyl butyrate, the intermediate layer is made of ferric salt, phthalocyanine compounds and electron transport materials, the selected ferric salt comprises at least one type of ferric chloride, ferric tribromide and ferric sulfid, the selected phthalocyanine compounds comprise at least one type of copper phthalocyanine, zinc phthalocyanine, magnesium phthalocyanine and vanadium phthalocyanine, and the selected electron transport materials comprise at least one type of 4,7-diphenyl-1,10-phenanthroline, 3-(biphenyl-4-based)-5-(4-tertiary butyl phenyl)-4-phenyl-4H-1,2,4-triazole and N-aryl benzimidazole. The solar cell device has the advantage of high energy conversion efficiency. The invention further provides a method for manufacturing the solar cell device.

Description

Solar cell device and preparation method thereof
Technical field
The present invention relates to a kind of solar cell device and preparation method thereof.
Background technology
Solar cell device is owing to having cheapness, the advantage such as clean, renewable and being widely used.Solar cell device structure conventional at present comprises the anode, Hole-injecting Buffer Layer for Improvement, the first active layer, electron buffer layer and the negative electrode that stack gradually.After the exciton dissociation of the first active layer produces hole and electronics, hole arrives anode, and electronics arrives negative electrode, thus is collected by electrode, forms effective power conversion.At present, the energy conversion efficiency of traditional solar cell is lower.
Summary of the invention
Based on this, be necessary to provide solar cell device that a kind of energy conversion efficiency is higher and preparation method thereof.
A kind of solar cell device, comprise stack gradually anode, Hole-injecting Buffer Layer for Improvement, the first active layer, intermediate layer, the second active layer, electron buffer layer and negative electrode, the material of described first active layer and the second active layer is poly-3-hexyl thiophene and 6,6-phenyl-C 61the mixture of-methyl butyrate, the material in described intermediate layer comprises molysite, phthalocyanine compound and electron transport material, molysite is selected from least one in ferric trichloride, ferric bromide and iron sulfide, described phthalocyanine compound is selected from least one in CuPc, Phthalocyanine Zinc, magnesium phthalocyanine and phthalocyanine vanadium, described electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, at least one in 2,4-triazole and N-aryl benzimidazole.
In a preferred embodiment, the thickness in described intermediate layer is 10nm ~ 100nm.
In a preferred embodiment, the mass ratio of electron transport material, molysite and phthalocyanine compound described in described intermediate layer is 10:0.5:2 ~ 10:2:5.
In a preferred embodiment, the material of described Hole-injecting Buffer Layer for Improvement is the mixture of poly-3,4-dioxyethylene thiophene and polyphenyl sulfonate.
In a preferred embodiment, 3-hexyl thiophene and described 6,6-phenyl-C are gathered described in described first active layer and the second active layer 61the mass ratio of-methyl butyrate is 1:0.5 ~ 1:4.
A preparation method for solar cell device, comprises the following steps:
Hole-injecting Buffer Layer for Improvement is prepared in spin coating on the anode surface;
On described Hole-injecting Buffer Layer for Improvement, spin coating contains poly-3-hexyl thiophene and 6,6-phenyl-C 61the solution of-methyl butyrate, forms the first active layer;
Suspension containing intermediate layer material is spin-coated on described first preparation intermediate layer, active layer surface, described intermediate layer material comprises molysite, phthalocyanine compound and electron transport material, molysite is selected from ferric trichloride, at least one in ferric bromide and iron sulfide, described phthalocyanine compound is selected from CuPc, Phthalocyanine Zinc, at least one in magnesium phthalocyanine and phthalocyanine vanadium, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, at least one in 4-triazole and N-aryl benzimidazole,
Poly-3-hexyl thiophene and 6,6-phenyl-C is contained in described interlayer surfaces spin coating 61the solution of-methyl butyrate, forms the second active layer; And
Electron buffer layer and negative electrode is prepared on the surface of described second active layer successively evaporation.
In a preferred embodiment, the mass ratio of electron transport material, molysite and phthalocyanine compound described in described intermediate layer is 10:0.5:2 ~ 10:2:5.
In a preferred embodiment, the thickness in described intermediate layer is 10nm ~ 100nm.
In a preferred embodiment, described containing in the suspension of intermediate layer material, the concentration of described electron transport material is 5mg/ml ~ 50mg/ml.
In a preferred embodiment, when intermediate layer is prepared in spin coating, rotating speed is 2000rpm ~ 8000rpm, and the time is 10 seconds ~ 30 seconds; At 100 DEG C ~ 200 DEG C, 10min ~ 30min is dried after spin coating.
Above-mentioned solar cell device and preparation method thereof, by preparing intermediate layer between the first active layer and the second active layer, improves the first active layer of solar cell device and the efficiency of light absorption of the second active layer, thus improves photoelectric conversion efficiency, by molysite, phthalocyanine compound and electron transport material carry out doping and form intermediate layer, electron transport material can improve the transmission rate of electronics, improve the efficiency that electric charge is collected in intermediate layer, and there is a large amount of free electrons in molysite, a large amount of rooms can be formed, therefore, the transmission rate in hole can be improved, be conducive to the existence avoiding carrier traps, and phthalocyanine compound is crystallizable at a certain temperature, crystallization can carry out scattering to light, make the light scattering do not absorbed by the first active layer in the second active layer, utilized by the light absorption of the second active layer, improve the absorption efficiency of solar energy, improve the hole collection efficiency in intermediate layer, thus raising photoelectric conversion efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the solar cell device of an embodiment;
Fig. 2 is preparation method's flow chart of the solar cell device of an embodiment;
Fig. 3 is the solar cell device of embodiment 1 and the current density of traditional solar cell device and voltage relationship figure.
Embodiment
For the ease of understanding the present invention, below with reference to relevant drawings, the present invention is described more fully.First-selected embodiment of the present invention is given in accompanying drawing.But the present invention can realize in many different forms, is not limited to embodiment described herein.On the contrary, the object of these embodiments is provided to be make to disclosure of the present invention more thoroughly comprehensively.
Refer to Fig. 1, the solar cell device 100 of an embodiment comprises the anode 10, Hole-injecting Buffer Layer for Improvement 20, first active layer 30, intermediate layer 40, second active layer 50, electron buffer layer 60 and the negative electrode 70 that stack gradually.
Anode 10 is indium tin oxide glass (ITO), mixes the tin oxide glass (FTO) of fluorine, mixes the zinc oxide glass (AZO) of aluminium or mixes the zinc oxide glass (IZO) of indium.
Hole-injecting Buffer Layer for Improvement 20 is formed at anode 10 surface.The material of Hole-injecting Buffer Layer for Improvement 20 is the mixture of poly-3,4-dioxyethylene thiophene (PEDOT) and polyphenyl sodium sulfonate (PSS).Wherein the mass ratio of PEDOT and PSS is 2:1 ~ 6:1, is preferably 2:1.The thickness of Hole-injecting Buffer Layer for Improvement 20 is 20nm ~ 80nm, is preferably 70nm.
First active layer 30 is formed at Hole-injecting Buffer Layer for Improvement 20 surface.The material of the first active layer 30 is poly-3-hexyl thiophene (P3HT) and 6,6-phenyl-C 61-methyl butyrate (PC 61bM) mixture.Wherein P3HT and PC 61the quality of BM is 1:0.5 ~ 1:4, is preferably 1:2.The thickness of the first active layer 30 is 100nm ~ 300nm, is preferably 140nm.
Intermediate layer 40 is formed at the surface of the first active layer 30.The material in intermediate layer 40 comprises molysite phthalocyanine compound and electron transport material.Molysite, phthalocyanine compound and electron transport material Homogeneous phase mixing.Molysite is selected from ferric trichloride (FeCl 3), ferric bromide (FeBr 3) and iron sulfide (Fe 2s 3) at least one.Phthalocyanine compound is selected from least one in CuPc (CuPc), Phthalocyanine Zinc (ZnPc), magnesium phthalocyanine (MgPc) and phthalocyanine vanadium (VPc).Electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, at least one in 2,4-triazole (TAZ) and N-aryl benzimidazole (TPBI).The mass ratio of electron transport material, molysite and phthalocyanine compound described in intermediate layer 40 is 10:0.5:2 ~ 10:2:5.The thickness in intermediate layer 40 is 10nm ~ 100nm.
Second active layer 50 is formed at the surface in intermediate layer 40.The material of the second active layer 50 is poly-3-hexyl thiophene (P3HT) and 6,6-phenyl-C 61-methyl butyrate (PC 61bM) mixture.Wherein P3HT and PC 61the quality of BM is that 1:0.5 ~ 1:4 is preferably 1:2.The thickness of the second active layer 50 is 100nm ~ 300nm, is preferably 140nm.
Electron buffer layer 60 is formed at the second active layer 50 surface.The material of electron buffer layer 60 is selected from cesium azide (CsN 3), lithium fluoride (LiF), lithium carbonate (Li 2cO 3) and cesium carbonate (Cs 2cO 3) at least one, be preferably LiF.The thickness of electron buffer layer 60 is 0.5nm ~ 10nm, is preferably 0.7nm.
Negative electrode 70 is formed at electron buffer layer 60 surface.The material of negative electrode 70 is selected from least one in aluminium (Al), silver (Ag), gold (Au) and platinum (Pt), is preferably Al.The thickness of negative electrode 70 is 80nm ~ 300nm, is preferably 150nm.
This solar cell device 100, by preparing intermediate layer 40 between the first active layer 30 and the second active layer 50, improves the first active layer 30 of solar cell device 10 and the efficiency of light absorption of the second active layer 50, thus improves photoelectric conversion efficiency, by molysite, phthalocyanine compound and electron transport material carry out doping and form intermediate layer, electron transport material can improve the transmission rate of electronics, improve the efficiency that electric charge is collected in intermediate layer, and there is a large amount of free electrons in molysite, a large amount of rooms can be formed, therefore, the transmission rate in hole can be improved, be conducive to the existence avoiding carrier traps, and phthalocyanine compound is crystallizable at a certain temperature, crystallization can carry out scattering to light, make the light scattering do not absorbed by the first active layer in the second active layer, utilized by the light absorption of the second active layer, improve the absorption efficiency of solar energy, improve the hole collection efficiency in intermediate layer, thus raising photoelectric conversion efficiency.
It should be noted that, above-mentioned solar cell device 100 can also arrange other functional layers as required.
Please refer to Fig. 2, the preparation method of the solar cell device 100 of an embodiment, it comprises the following steps:
Step S110, prepare Hole-injecting Buffer Layer for Improvement 20 in the surperficial spin coating of anode 10.
Anode 10 is indium tin oxide glass (ITO), mixes the tin oxide glass (FTO) of fluorine, mixes the zinc oxide glass (AZO) of aluminium or mixes the zinc oxide glass (IZO) of indium.
In present embodiment, antianode 10 pre-treatment comprises removes the oxonium ion process such as the organic pollution on anode 10 surface and antianode 10 carry out.Anode 10 is adopted each Ultrasonic Cleaning 15min of liquid detergent, deionized water, acetone, ethanol, isopropyl acetone, to remove the organic pollution on substrate 10 surface; It is 5min ~ 15min that antianode 10 carries out the oxonium ion processing time such as grade, and power is 10 ~ 50W.
Hole-injecting Buffer Layer for Improvement 20 is by containing the solution preparation of hole padded coaming in the surperficial spin coating of anode 10.The rotating speed of spin coating is 2000rpm ~ 6000rpm, and the time is 10s ~ 30s, and preferably, the rotating speed of spin coating is 4000rpm, and the time is 15s.Hole padded coaming is the mixture of poly-3,4-dioxyethylene thiophene (PEDOT) and polyphenyl sodium sulfonate (PSS).Wherein the mass ratio of PEDOT and PSS is 2:1 ~ 6:1, is preferably 2:1.In solution containing hole padded coaming, the mass percentage of PEDOT is 1% ~ 5%, and be preferably 2%, solvent is water.Heat 15 minutes ~ 60 minutes at 100 DEG C ~ 200 DEG C after spin coating, preferably heat 30 minutes at 200 DEG C.The thickness of Hole-injecting Buffer Layer for Improvement 20 is 20nm ~ 80nm, is preferably 70nm.
Step S120, prepare the first active layer 30 in the surperficial spin coating of Hole-injecting Buffer Layer for Improvement 20.
First active layer 30 is spin-coated on Hole-injecting Buffer Layer for Improvement 20 surface by the first active layer solution and makes.The rotating speed of spin coating is 3000rpm ~ 6000rpm, and the time is 10s ~ 30s, and preferably, spin coating rotating speed is 4000rpm, and the time is 15s.In first active layer solution, the concentration of the first active layer material is 8mg/ml ~ 30mg/ml, is preferably 24mg/ml.The solvent of the first active layer solution is selected from least one in toluene, dimethylbenzene, chlorobenzene and chloroform, is preferably chlorobenzene.First active layer material is poly-3-hexyl thiophene (P3HT) and 6,6-phenyl-C 61-methyl butyrate (PC 61bM) mixture.Wherein P3HT:PC 61the quality of BM is 1:0.5 ~ 1:4, is preferably 1:2.Spin coating first active layer 30 carries out in the glove box being full of inert gas, anneals 5 minutes ~ 100 minutes afterwards at 50 DEG C ~ 200 DEG C, preferably anneals 30 minutes at 100 DEG C.The thickness of the first active layer 30 is 100nm ~ 300nm, is preferably 140nm.
Step S130, the suspension containing intermediate layer material is spin-coated on the first preparation intermediate layer 40, active layer 30 surface.
The material in intermediate layer 40 comprises molysite phthalocyanine compound and electron transport material.Molysite, phthalocyanine compound and electron transport material Homogeneous phase mixing.Molysite is selected from ferric trichloride (FeCl 3), ferric bromide (FeBr 3) and iron sulfide (Fe 2s 3) at least one.Phthalocyanine compound is selected from least one in CuPc (CuPc), Phthalocyanine Zinc (ZnPc), magnesium phthalocyanine (MgPc) and phthalocyanine vanadium (VPc).Electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, at least one in 2,4-triazole (TAZ) and N-aryl benzimidazole (TPBI).The mass ratio of electron transport material, molysite and phthalocyanine compound described in intermediate layer 40 is 10:0.5:2 ~ 10:2:5.The thickness in intermediate layer 40 is 10nm ~ 100nm.
Be chlorobenzene, chloroform, carrene or paraxylene containing the solvent in the suspension of intermediate layer material.In suspension, the concentration of electron transport material is 5mg/ml ~ 50mg/ml.
The rotating speed of spin coating is 2000rpm ~ 8000rpm, and the time is 10s ~ 30s.Dry 10 minutes ~ 30 minutes at 100 DEG C ~ 200 DEG C after spin coating.The thickness in intermediate layer 40 is 10nm ~ 100nm.
Step S140, prepare the second active layer 50 in the surperficial spin coating in intermediate layer 40.
Second active layer 50 is spin-coated on surface, intermediate layer 50 by the second active layer solution and makes.The rotating speed of spin coating is 3000rpm ~ 6000rpm, and the time is 10s ~ 30s, and preferably, spin coating rotating speed is 4000rpm, and the time is 15s.In second active layer solution, the concentration of the second active layer material is 8mg/ml ~ 30mg/ml, is preferably 24mg/ml.The solvent of the second active layer solution is selected from least one in toluene, dimethylbenzene, chlorobenzene and chloroform, is preferably chlorobenzene.Second active layer material is poly-3-hexyl thiophene (P3HT) and 6,6-phenyl-C 61-methyl butyrate (PC 61bM) mixture.Wherein P3HT:PC 61the quality of BM is 1:0.5 ~ 1:4, is preferably 1:2.Spin coating second active layer 50 carries out in the glove box being full of inert gas, anneals 5 minutes ~ 100 minutes afterwards at 50 DEG C ~ 200 DEG C, preferably anneals 30 minutes at 100 DEG C.The thickness of the second active layer 50 is 100nm ~ 300nm, is preferably 140nm.
Step S150, prepare electron buffer layer 60 and negative electrode 70 on the surface of the second active layer 50 successively evaporation.
Electron buffer layer 60 is formed at the second active layer 50 surface.The material of electron buffer layer 60 is selected from cesium azide (CsN 3), lithium fluoride (LiF), lithium carbonate (Li 2cO 3) and cesium carbonate (Cs 2cO 3) at least one, be preferably LiF.The thickness of electron buffer layer 60 is 0.5nm ~ 10nm, is preferably 0.7nm.Evaporation is 3 × 10 at vacuum pressure -3~ 2 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Negative electrode 70 is formed at electron buffer layer 60 surface.The material of negative electrode 70 is selected from least one in aluminium (Al), silver (Ag), gold (Au) and platinum (Pt), is preferably Al.The thickness of negative electrode 70 is 80nm ~ 300nm, is preferably 150nm.Evaporation is 3 × 10 at vacuum pressure -3~ 2 × 10 -5carry out under Pa, evaporation rate is 1nm/s ~ 10nm/s.
Above-mentioned solar cell device preparation method, preparation technology is simple, and the energy conversion efficiency of the solar cell device of preparation is higher.
Below in conjunction with specific embodiment, the preparation method to solar cell device provided by the invention is described in detail.
The embodiment of the present invention and the preparation used by comparative example and tester are: high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure <1 × 10 -32602), be the white light source of simulated solar irradiation with the filter set cooperation of 500W xenon lamp (Osram) and AM1.5 Pa), current-voltage tester (Keithly company of the U.S., model:.
Embodiment 1
Structure prepared by the present embodiment is: ITO/PEDOT:PSS/P3HT:PC 61bM/Bphen:FeCl 3: CuPc/P3HT:PC 61the solar cell device of BM/LiF/Al.Wherein, "/" presentation layer stack structure, ": " represents doping or mixing, and following examples are identical.
First ITO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Clean up and carry out oxygen plasma treatment to conductive substrates afterwards, the processing time is 10min, and power is 20W; Hole-injecting Buffer Layer for Improvement is prepared in spin coating, and the mass fraction of material to be the mass ratio of PEDOT:PSS be 2:1, PEDOT is 2%, and the rotating speed of spin coating is 4000rpm, and the time is 15s, heats 30min after spin coating at 200 DEG C, and thickness is 70nm; Spin coating first active layer, the first active layer is P3HT and PC of 24mg/ml by concentration 61the solution spin coating of BM forms, and solvent is chlorobenzene, P3HT and PC 61the mass ratio of BM is 1:2, and the rotating speed of spin coating is 4000rpm, and the time is 15s, and anneal 30 minutes at 100 DEG C after spin coating, THICKNESS CONTROL is at 140nm.Spin coating intermediate layer, suspension comprises Bphen, FeCl 3, CuPc and solvent, solvent is chlorobenzene, and the concentration of Bphen is 30mg/ml, Bphen, FeCl 3, CuPc mass ratio be 10:1.2:3, the rotating speed of spin coating is 4000rpm, and the time is 15s, 150 DEG C dry 20min, thickness is 60nm.Then spin coating second active layer, the second active layer is P3HT and PC of 24mg/ml by concentration 61the solution spin coating of BM forms, and solvent is chlorobenzene, P3HT and PC 61the mass ratio of BM is 1:2, and the rotating speed of spin coating is 4000rpm, and the time is 15s, and anneal 30 minutes at 100 DEG C after spin coating, THICKNESS CONTROL is at 140nm.Then evaporation prepares electron buffer layer, and material is LiF, and thickness is 0.7nm, and evaporation is 5 × 10 at vacuum pressure -4carry out under Pa, evaporation rate is 0.2nm/s; Evaporation negative electrode, material is Al, and thickness is 150nm, and evaporation is 5 × 10 at vacuum pressure -4carry out under Pa, evaporation rate is 4nm/s.Finally obtain desired polymer solar cell device.
Refer to Fig. 3, the structure being depicted as preparation in embodiment 1 is ITO/PEDOT:PSS/P3HT:PC 61bM/Bphen:FeCl 3: CuPc/P3HT:PC 61solar cell device (curve 1) and traditional structure of BM/LiF/Al are current density and the voltage relationship of ITO/PEDOT:PSS/P3HT:PCBM/LiF/Al solar cell device (curve 2), and the structure that table 1 is depicted as preparation in embodiment 1 is ITO/PEDOT:PSS/P3HT:PC 61bM/Bphen:FeCl 3: CuPc/P3HT:PC 61the solar cell device of BM/LiF/Al and traditional structure are the current density of ITO/PEDOT:PSS/P3HT:PCBM/LiF/Al solar cell device, voltage, energy conversion efficiency (η) and fill factor, curve factor data.In traditional solar cell device, each layer thickness is identical with each layer thickness in solar cell device prepared by embodiment 1.
Table 1
? Current density (mA/cm 2） Voltage (V) η（%） Fill factor, curve factor
Curve 1 25.63 0.72 6.48 0.35
Curve 2 17.19 0.74 3.36 0.31
Can see from table 1 and Fig. 3, conventional solar cell device current density is 17.19mA/cm 2, and solar cell device current density prepared by embodiment 1 has brought up to 25.63mA/cm 2this explanation, the present invention forms intermediate layer by carrying out doping by electron transport material and molysite and phthalocyanine compound, electron transport material can improve the efficiency that electric charge is collected in intermediate layer, and molysite can improve the transmission rate in hole, phthalocyanine compound improves the absorption efficiency of solar energy, thus improves the hole collection efficiency in intermediate layer, thus can improve photoelectric conversion efficiency.The energy conversion efficiency of traditional solar cell device is 3.36%, and the energy conversion efficiency of solar cell device prepared by embodiment 1 is 6.48%.
Below the current density of each embodiment and voltage curve, current density, voltage, energy conversion efficiency and fill factor, curve factor all similar with embodiment 1, each solar cell device also has similar energy conversion efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is IZO/PEDOT:PSS/P3HT:PC 61bM/TAZ:FeBr 3: MgPc/P3HT:PC 61bM/Cs 2cO 3the solar cell device of/Au.
First IZO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Clean up and carry out oxygen plasma treatment to conductive substrates afterwards, the processing time is 15min, and power is 10W; Hole-injecting Buffer Layer for Improvement is prepared in spin coating, and the mass fraction of material to be the mass ratio of PEDOT:PSS be 2:1, PEDOT is 5%, and the rotating speed of spin coating is 6000rpm, and the time is 30s, heats 60min after spin coating at 100 DEG C, and thickness is 20nm; Spin coating first active layer, the first active layer is P3HT and PC of 8mg/ml by concentration 61the solution spin coating of BM forms, and solvent is toluene, P3HT and PC 61the mass ratio of BM is 1:0.5, and the rotating speed of spin coating is 4000rpm, and the time is 10s, and anneal 100 minutes at 50 DEG C after spin coating, THICKNESS CONTROL is at 300nm.Spin coating intermediate layer, suspension comprises TAZ, FeBr 3, MgPc and solvent, solvent is chloroform, and the concentration of TAZ is 5mg/ml, TAZ:FeBr 3: the mass ratio of MgPc is 10:0.5:2, and the rotating speed of spin coating is 2000rpm, and the time is 10s, and dry 30 minutes for 100 DEG C, thickness is 100nm.Then spin coating second active layer, the second active layer is P3HT and PC of 30mg/ml by concentration 61the solution spin coating of BM forms, and solvent is chloroform, P3HT and PC 61the mass ratio of BM is 1:4, and the rotating speed of spin coating is 6000rpm, and the time is 10s, and anneal 15 minutes at 150 DEG C after spin coating, THICKNESS CONTROL is at 100nm.Then evaporation prepares electron buffer layer, and material is Cs 2cO 3, thickness is 5nm, and evaporation is 3 × 10 at vacuum pressure -3carry out under Pa, evaporation rate is 0.1nm/s; Evaporation negative electrode, material is Au, and thickness is 300nm, and evaporation is 3 × 10 at vacuum pressure -3carry out under Pa, evaporation rate is 1nm/s.Finally obtain desired polymer solar cell device.
Embodiment 3
Structure prepared by the present embodiment is FTO/PEDOT:PSS/P3HT:PC 61bM/TPBI:Fe 2s 3: ZnPc/P3HT:PC 61bM/CsN 3the solar cell device of/Ag.
First FTO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Clean up and carry out oxygen plasma treatment to conductive substrates afterwards, the processing time is 5min, and power is 50W; Hole-injecting Buffer Layer for Improvement is prepared in spin coating, and the mass fraction of material to be the mass ratio of PEDOT:PSS be 6:1, PEDOT is 1%, and the rotating speed of spin coating is 2000rpm, and the time is 10s, heats 15min after spin coating at 200 DEG C, and thickness is 80nm; Spin coating first active layer, the first active layer is P3HT and PC of 30mg/ml by concentration 61the solution spin coating of BM forms, and solvent is dimethylbenzene, P3HT and PC 61the mass ratio of BM is 1:4, and the rotating speed of spin coating is 6000rpm, and the time is 30s, and anneal 5 minutes at 200 DEG C after spin coating, THICKNESS CONTROL is at 100nm.Spin coating intermediate layer, suspension comprises TPBI, Fe 2s 3, ZnPc and solvent, solvent is carrene, and the concentration of TPBI is 50mg/ml, TPBI:Fe 2s 3: the mass ratio of ZnPc is 10:2:5, and the rotating speed of spin coating is 8000rpm, and the time is 30s, and dry 10 minutes for 200 DEG C, thickness is 10nm.Then spin coating second active layer, the second active layer is P3HT and PC of 8mg/ml by concentration 61the solution spin coating of BM forms, and solvent is dimethylbenzene, P3HT and PC 61the mass ratio of BM is 1:0.5, and the rotating speed of spin coating is 4000rpm, and the time is 10s, and anneal 15 minutes at 150 DEG C after spin coating, THICKNESS CONTROL is at 200nm.Then evaporation prepares electron buffer layer, and material is CsN 3, thickness is 10nm, and evaporation is 2 × 10 at vacuum pressure -5carry out under Pa, evaporation rate is 1nm/s; Evaporation negative electrode, material is Ag, and thickness is 80nm, and evaporation is 2 × 10 at vacuum pressure -5carry out under Pa, evaporation rate is 10nm/s.Finally obtain desired polymer solar cell device.
Embodiment 4
Structure prepared by the present embodiment is ITO/PEDOT:PSS/P3HT:PC 61bM/Bphen:FeCl 3: VPc/P3HT:PC 61bM/Li 2cO 3the solar cell device of/Pt.
First ITO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Clean up and carry out oxygen plasma treatment to conductive substrates afterwards, the processing time is 10min, and power is 25W; Hole-injecting Buffer Layer for Improvement is prepared in spin coating, and the mass fraction of material to be the mass ratio of PEDOT:PSS be 3:1, PEDOT is 3.5%, and the rotating speed of spin coating is 5000rpm, and the time is 20s, heats 20min after spin coating at 150 DEG C, and thickness is 60nm; Spin coating first active layer, the first active layer is P3HT and PC of 10mg/ml by concentration 61the solution spin coating of BM forms, and solvent is chloroform, P3HT and PC 61the mass ratio of BM is 1:3, and the rotating speed of spin coating is 5000rpm, and the time is 20s, and anneal 30 minutes at 100 DEG C after spin coating, THICKNESS CONTROL is at 200nm.Spin coating intermediate layer, suspension comprises Bphen, FeCl 3, VPc and solvent, solvent is paraxylene, and the concentration of Bphen is 15mg/ml, Bphen:FeCl 3: the mass ratio of VPc is 10:1:3.5, and the rotating speed of spin coating is 6000rpm, and the time is 20s, and dry 20 minutes for 120 DEG C, thickness is 45nm.Then spin coating second active layer, the second active layer is P3HT and PC of 25mg/ml by concentration 61the solution spin coating of BM forms, and solvent is toluene, P3HT and PC 61the mass ratio of BM is 1:2, and the rotating speed of spin coating is 4200rpm, and the time is 20s, and anneal 10 minutes at 150 DEG C after spin coating, THICKNESS CONTROL is at 80nm.Then evaporation prepares electron buffer layer, and material is Li 2cO 3, thickness is 1nm, and evaporation is 2 × 10 at vacuum pressure -4carry out under Pa, evaporation rate is 0.15nm/s; Evaporation negative electrode, material is Pt, and thickness is 100nm, and evaporation is 2 × 10 at vacuum pressure -4carry out under Pa, evaporation rate is 3nm/s.Finally obtain desired polymer solar cell device.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a solar cell device, it is characterized in that, comprise stack gradually anode, Hole-injecting Buffer Layer for Improvement, the first active layer, intermediate layer, the second active layer, electron buffer layer and negative electrode, the material of described first active layer and the second active layer is poly-3-hexyl thiophene and 6,6-phenyl-C 61the mixture of-methyl butyrate, the material in described intermediate layer comprises molysite, phthalocyanine compound and electron transport material, molysite is selected from least one in ferric trichloride, ferric bromide and iron sulfide, described phthalocyanine compound is selected from least one in CuPc, Phthalocyanine Zinc, magnesium phthalocyanine and phthalocyanine vanadium, described electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, at least one in 2,4-triazole and N-aryl benzimidazole.
2. solar cell device according to claim 1, is characterized in that: the thickness in described intermediate layer is 10nm ~ 100nm.
3. solar cell device according to claim 1, is characterized in that: the mass ratio of electron transport material, molysite and phthalocyanine compound described in described intermediate layer is 10:0.5:2 ~ 10:2:5.
4. solar cell device according to claim 1, is characterized in that: the material of described Hole-injecting Buffer Layer for Improvement is the mixture of poly-3,4-dioxyethylene thiophene and polyphenyl sulfonate.
5. solar cell device according to claim 1, is characterized in that: gather 3-hexyl thiophene and described 6,6-phenyl-C described in described first active layer and the second active layer 61the mass ratio of-methyl butyrate is 1:0.5 ~ 1:4.
6. a preparation method for solar cell device, is characterized in that, comprises the following steps:
Hole-injecting Buffer Layer for Improvement is prepared in spin coating on the anode surface;
On described Hole-injecting Buffer Layer for Improvement, spin coating contains poly-3-hexyl thiophene and 6,6-phenyl-C 61the solution of-methyl butyrate, forms the first active layer;
Suspension containing intermediate layer material is spin-coated on described first preparation intermediate layer, active layer surface, described intermediate layer material comprises molysite, phthalocyanine compound and electron transport material, molysite is selected from ferric trichloride, at least one in ferric bromide and iron sulfide, described phthalocyanine compound is selected from CuPc, Phthalocyanine Zinc, at least one in magnesium phthalocyanine and phthalocyanine vanadium, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, at least one in 4-triazole and N-aryl benzimidazole,
Poly-3-hexyl thiophene and 6,6-phenyl-C is contained in described interlayer surfaces spin coating 61the solution of-methyl butyrate, forms the second active layer; And
Electron buffer layer and negative electrode is prepared on the surface of described second active layer successively evaporation.
7. the preparation method of solar cell device according to claim 6, is characterized in that: the mass ratio of electron transport material, molysite and phthalocyanine compound described in described intermediate layer is 10:0.5:2 ~ 10:2:5.
8. the preparation method of solar cell device according to claim 6, is characterized in that: the thickness in described intermediate layer is 10nm ~ 100nm.
9. the preparation method of solar cell device according to claim 6, is characterized in that: described containing in the suspension of intermediate layer material, the concentration of described electron transport material is 5mg/ml ~ 50mg/ml.
10. the preparation method of solar cell device according to claim 6, is characterized in that: when intermediate layer is prepared in spin coating, and rotating speed is 2000rpm ~ 8000rpm, and the time is 10 seconds ~ 30 seconds; At 100 DEG C ~ 200 DEG C, 10min ~ 30min is dried after spin coating.
CN201310263523.0A 2013-06-27 2013-06-27 Solar cell device and method for manufacturing same Pending CN104253215A (en)

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Application publication date: 20141231