CN104253221A - 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
CN104253221A
CN104253221A CN201310264349.1A CN201310264349A CN104253221A CN 104253221 A CN104253221 A CN 104253221A CN 201310264349 A CN201310264349 A CN 201310264349A CN 104253221 A CN104253221 A CN 104253221A
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solar cell
active layer
cell device
intermediate layer
layer
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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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Publication of CN104253221A publication Critical patent/CN104253221A/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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photovoltaic Devices (AREA)

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 titanium dioxide, phthalocyanine compounds and hole transport materials, the selected phthalocyanine compounds include at least one type of copper phthalocyanine, zinc phthalocyanine, magnesium phthalocyanine and vanadium phthalocyanine, and the selected hole transport materials comprise at least one type of 1,1-di-{4-[N,N'-di-(p-tolyl) amine] phenyl} cyclohexane, 4,4',4''-tri-(carbazole-9-based) triphenylamine and N,N'-(1-naphth)-N,N'-diphenyl-4,4'-benzidine. 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 titanium dioxide, phthalocyanine compound and hole mobile material, described phthalocyanine compound is selected from least one in CuPc, Phthalocyanine Zinc, magnesium phthalocyanine and phthalocyanine vanadium, described hole mobile material is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, at least one in N '-diphenyl-4,4 '-benzidine.
In a preferred embodiment, the thickness in described intermediate layer is 20nm ~ 50nm.
In a preferred embodiment, the mass ratio of titanium dioxide, phthalocyanine compound and hole mobile material described in described intermediate layer is 0.01:1:2 ~ 0.1:1:10.
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 titanium dioxide, phthalocyanine compound and hole mobile material, described phthalocyanine compound is selected from CuPc, Phthalocyanine Zinc, at least one in magnesium phthalocyanine and phthalocyanine vanadium, described hole mobile material is selected from 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4, 4', 4''-tri-(carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine,
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 titanium dioxide, phthalocyanine compound and hole mobile material described in described intermediate layer is 0.01:1:2 ~ 0.1:1:10.
In a preferred embodiment, the thickness in described intermediate layer is 20nm ~ 50nm.
In a preferred embodiment, described containing in the suspension of intermediate layer material, the concentration of described hole mobile material is 10mg/ml ~ 30mg/ml; When intermediate layer is prepared in spin coating, rotating speed is 4000rpm ~ 8000rpm, and the time is 5 seconds ~ 30 seconds.
In a preferred embodiment, the titanium dioxide in described intermediate layer is anatase structured.
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 titanium dioxide, phthalocyanine compound and hole mobile material carry out doping and form intermediate layer, titanium dioxide is anatase structured, specific area is larger, porosity is high, be conducive to the transmission of electronics, there is certain scattering process to light simultaneously, scattering can be carried out to light, make to enter into the second active layer by the light of the first active layer through scattering major part, and the easy crystallization of phthalocyanine compound, also scattering can be carried out to light after crystallization, improve absorption efficiency, simultaneously, phthalocyanine compound is hole mobile material, can further improve hole mobile material, and after adding hole mobile material, the energy level of hole mobile material more mates with the second active layer, the energy level of hole mobile material is about-5.5 ~-6.0eV, the donor material HOMO energy level of active layer is-5.4eV ~-5.8eV, be conducive to the injection in hole, thus enable hole arrive intermediate layer faster, 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 3:1.The thickness of Hole-injecting Buffer Layer for Improvement 20 is 20nm ~ 80nm, is preferably 60nm.
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 130nm.
Intermediate layer 40 is formed at the surface of the first active layer 30.The material in intermediate layer 40 comprises titanium dioxide (TiO 2), phthalocyanine compound and hole mobile material.Titanium dioxide (TiO 2), phthalocyanine compound and hole mobile material Homogeneous phase mixing.Titanium dioxide is anatase structured.Phthalocyanine compound is selected from least one in CuPc (CuPc), Phthalocyanine Zinc (ZnPc), magnesium phthalocyanine (MgPc) and phthalocyanine vanadium (VPc).Hole mobile material is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB).The mass ratio of titanium dioxide, phthalocyanine compound and hole mobile material described in intermediate layer 40 is 0.01:1:2 ~ 0.1:1:10.The thickness in intermediate layer 40 is 20nm ~ 50nm.
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 130nm.
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 titanium dioxide, phthalocyanine compound and hole mobile material carry out doping and form intermediate layer, titanium dioxide is anatase structured, specific area is larger, porosity is high, be conducive to the transmission of electronics, there is certain scattering process to light simultaneously, scattering can be carried out to light, make to enter into the second active layer by the light of the first active layer through scattering major part, and the easy crystallization of phthalocyanine compound, also scattering can be carried out to light after crystallization, improve absorption efficiency, simultaneously, phthalocyanine compound is hole mobile material, can further improve hole mobile material, and after adding hole mobile material, the energy level of hole mobile material more mates with the second active layer, the energy level of hole mobile material is about-5.5 ~-6.0eV, the donor material HOMO energy level of active layer is-5.4eV ~-5.8eV, be conducive to the injection in hole, thus enable hole arrive intermediate layer faster, 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 3000rpm, 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 3:1.In solution containing hole padded coaming, the mass percentage of PEDOT is 1% ~ 5%, and be preferably 3%, 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 60nm.
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 4000rpm ~ 6000rpm, and the time is 10s ~ 30s, and preferably, spin coating rotating speed is 5000rpm, and the time is 10s.In first active layer solution, the concentration of the first active layer material is 8mg/ml ~ 30mg/ml, is preferably 25mg/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 130nm.
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 titanium dioxide (TiO 2), phthalocyanine compound and hole mobile material.Titanium dioxide (TiO 2), phthalocyanine compound and hole mobile material Homogeneous phase mixing.Titanium dioxide is anatase structured.Phthalocyanine compound is selected from least one in CuPc (CuPc), Phthalocyanine Zinc (ZnPc), magnesium phthalocyanine (MgPc) and phthalocyanine vanadium (VPc).Hole mobile material is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB).The mass ratio of titanium dioxide, phthalocyanine compound and hole mobile material described in intermediate layer 40 is 0.01:1:2 ~ 0.1:1:10.
Be chlorobenzene, chloroform, carrene or paraxylene containing the solvent in the suspension of intermediate layer material.In suspension, the concentration of hole mobile material is 10mg/ml ~ 30mg/ml.
The rotating speed of spin coating is 4000rpm ~ 8000rpm, and the time is 5s ~ 30s.Dry 10 minutes ~ 30 minutes at 100 DEG C ~ 200 DEG C after spin coating.The thickness in intermediate layer 40 is 20nm ~ 50nm.
Preferably, titanium dioxide is anatase structured, and particle diameter is 20nm ~ 200nm.In order to obtain anatase structured titanium dioxide, titanium dioxide being placed on temperature is calcine 20 minutes ~ 60 minutes in the Muffle furnace of 400 DEG C ~ 800 DEG C.
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 4000rpm ~ 6000rpm, and the time is 10s ~ 30s, and preferably, spin coating rotating speed is 5000rpm, and the time is 10s.In second active layer solution, the concentration of the second active layer material is 8mg/ml ~ 30mg/ml, is preferably 25mg/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 130nm.
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/TiO 2: CuPc:NPB/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 3:1, PEDOT is 3%, and the rotating speed of spin coating is 3000rpm, and the time is 15s, heats 30min after spin coating at 200 DEG C, and thickness is 60nm; Spin coating first active layer, the first active layer is P3HT and PC of 25mg/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 4500rpm, and the time is 10s, and anneal 30 minutes at 100 DEG C after spin coating, THICKNESS CONTROL is at 130nm.Spin coating intermediate layer, suspension comprises TiO 2, CuPc, NPB and solvent, solvent is chlorobenzene, and the concentration of NPB is 15mg/ml, TiO 2, CuPc, NPB mass ratio be 0.03:1:5, TiO 2for commercially available titanium dioxide, particle diameter is 100nm, is placed in Muffle furnace in advance and calcines, and temperature is 500 DEG C, and the time is that 30min obtains anatase structured titanium dioxide, and the rotating speed of spin coating is 5000rpm, and the time is 10s, and dry 20min for 150 DEG C, thickness is 30nm.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 chlorobenzene, P3HT and PC 61the mass ratio of BM is 1:2, and the rotating speed of spin coating is 5000rpm, and the time is 10s, and anneal 30 minutes at 100 DEG C after spin coating, THICKNESS CONTROL is at 130nm.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/TiO 2: CuPc:NPB/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/TiO 2: CuPc:NPB/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 13.19 0.69 3.46 0.38
Curve 2 7.86 0.67 1.97 0.37
Can see from table 1 and Fig. 3, conventional solar cell device current density is 7.86mA/cm 2, and solar cell device current density prepared by embodiment 1 has brought up to 13.19mA/cm 2, this illustrates, the present invention passes through titanium dioxide (TiO 2), phthalocyanine compound and hole mobile material be mixed with intermediate layer, improve injection and the transmission of electronics, the injection in hole and transmission performance simultaneously, thus can photoelectric conversion efficiency be improved.The energy conversion efficiency of traditional solar cell device is 1.97%, and the energy conversion efficiency of solar cell device prepared by embodiment 1 is 3.46%.
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/TiO 2: ZnPc:TAPC/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 TiO 2, ZnPc, TAPC and solvent, solvent is chloroform, TiO 2for commercially available titanium dioxide, particle diameter is 200nm, is placed in Muffle furnace in advance and calcines, and temperature is 800 DEG C, and the time is that 20min obtains anatase structured titanium dioxide, and the concentration of TAPC is 10mg/ml, TiO 2, ZnPc, TAPC weight ratio be 0.01:1:2, the rotating speed of spin coating is 4000rpm, and the time is 5s, 100 DEG C dry 30 minutes, thickness is 50nm.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/TiO 2: MgPc:TCTA/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 TiO 2, MgPc, TCTA and solvent, solvent is carrene, TiO 2for commercially available titanium dioxide, particle diameter is 20nm, is placed in Muffle furnace in advance and calcines, and temperature is 400 DEG C, and the time is that 60min obtains anatase structured titanium dioxide, and the concentration of TCTA is 30mg/ml, TiO 2, MgPc, TCTA mass ratio be 0.1:1:10, the rotating speed of spin coating is 8000rpm, and the time is 30s, 200 DEG C dry 10 minutes, thickness is 20nm.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/TiO 2: VPc:NPB/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 TiO 2: VPc:NPB and solvent, solvent is paraxylene, TiO 2for commercially available titanium dioxide, particle diameter is 150nm, is placed in Muffle furnace in advance and calcines, and temperature is 600 DEG C, and the time is that 30min obtains anatase structured titanium dioxide, and the concentration of NPB is 20mg/ml, TiO 2, VPc, NPB mass ratio be 0.05:1:8, the rotating speed of spin coating is 6000rpm, and the time is 20s, 120 DEG C dry 20 minutes, thickness is 25nm.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 0.35nm/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 titanium dioxide, phthalocyanine compound and hole mobile material, described phthalocyanine compound is selected from least one in CuPc, Phthalocyanine Zinc, magnesium phthalocyanine and phthalocyanine vanadium, described hole mobile material is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, at least one in N '-diphenyl-4,4 '-benzidine.
2. solar cell device according to claim 1, is characterized in that: the thickness in described intermediate layer is 20nm ~ 50nm.
3. solar cell device according to claim 1, is characterized in that: the mass ratio of titanium dioxide, phthalocyanine compound and hole mobile material described in described intermediate layer is 0.01:1:2 ~ 0.1:1:10.
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 titanium dioxide, phthalocyanine compound and hole mobile material, described phthalocyanine compound is selected from CuPc, Phthalocyanine Zinc, at least one in magnesium phthalocyanine and phthalocyanine vanadium, described hole mobile material is selected from 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4, 4', 4''-tri-(carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine,
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 titanium dioxide, phthalocyanine compound and hole mobile material described in described intermediate layer is 0.01:1:2 ~ 0.1:1:10.
8. the preparation method of solar cell device according to claim 6, is characterized in that: the thickness in described intermediate layer is 20nm ~ 50nm.
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 hole mobile material is 10mg/ml ~ 30mg/ml; When intermediate layer is prepared in spin coating, rotating speed is 4000rpm ~ 8000rpm, and the time is 5 seconds ~ 30 seconds.
10. the preparation method of solar cell device according to claim 6, is characterized in that: the titanium dioxide in described intermediate layer is anatase structured.
CN201310264349.1A 2013-06-27 2013-06-27 Solar cell device and method for manufacturing same Pending CN104253221A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109802040A (en) * 2019-01-26 2019-05-24 中国海洋大学 Inorganic perovskite solar battery and the preparation method and application thereof based on the compound cavitation layer of poly- 3 hexyl thiophenes/Phthalocyanine Zinc

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109802040A (en) * 2019-01-26 2019-05-24 中国海洋大学 Inorganic perovskite solar battery and the preparation method and application thereof based on the compound cavitation layer of poly- 3 hexyl thiophenes/Phthalocyanine Zinc

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