CN103824940A - Solar cell device and preparation method thereof - Google Patents
Solar cell device and preparation method thereof Download PDFInfo
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- CN103824940A CN103824940A CN201210468579.5A CN201210468579A CN103824940A CN 103824940 A CN103824940 A CN 103824940A CN 201210468579 A CN201210468579 A CN 201210468579A CN 103824940 A CN103824940 A CN 103824940A
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
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Abstract
The invention provides a solar cell device comprising an anode, a hole buffer layer, a first active layer, a first intermediate layer, a connecting layer, a second intermediate layer, a second active layer, an electron buffer layer and a cathode which are laminated in turn. The material of the first active layer and the second active layer is mixture of poly 3-hexyl thiophene and 6,6-phenyl-C61-methyl butyrate. The material of the first intermediate layer comprises hole buffer materials and fullerene derivatives. The fullerene derivatives are selected from at least one of C60, C70, 6,6-phenyl-C61-butyl acid methyl esters and 6,6-phenyl-C71-butyl acid methyl esters. The material of the connecting layer is mixture of poly 3,4-ethylene dioxythiophene and polyphenyl sulfonate. The material of the second intermediate layer comprises oxides of rhenium and the hole buffer materials. The solar cell device is relatively high in energy conversion efficiency. Besides, the invention also provides a preparation method of the solar cell device.
Description
[technical field]
The present invention relates to a kind of solar cell device and preparation method thereof.
[background technology]
Solar cell device owing to thering is cheapness, the advantage such as clean, renewable is widely used.Conventional solar cell device structure comprises the anode, Hole-injecting Buffer Layer for Improvement, the first active layer, electron buffer layer and the negative electrode that stack gradually at present.The exciton dissociation of the first active layer produces after hole and electronics, and hole arrives anode, and electronics arrives negative electrode, thereby 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, comprises the anode, Hole-injecting Buffer Layer for Improvement, the first active layer, the first intermediate layer, articulamentum, the second intermediate layer, the second active layer, electron buffer layer and the negative electrode that stack gradually; The material of described the first active layer is poly-3-hexyl thiophene and 6,6-phenyl-C
61the mixture of-methyl butyrate, the material in described the first intermediate layer comprises hole padded coaming and fullerene derivate, and described hole padded coaming is the mixture of poly-3,4-dioxy ethene thiophene and polyphenyl sulfonate, and described fullerene derivate is selected from C
60, C
70, 6,6-phenyl-C
61-butyl acid methyl esters and 6,6-phenyl-C
71at least one in-butyl acid methyl esters, the material of described articulamentum is poly-3, the mixture of 4-dioxy ethene thiophene and polyphenyl sulfonate, the material in described the second intermediate layer comprises oxide and the hole padded coaming of rhenium, the oxide of described rhenium is selected from least one in rhenium dioxide, rhenium heptoxide, rhenium sesquioxide and oxidation two rheniums, the poly-3-hexyl thiophene of material and 6, the 6-phenyl-C of described the second active layer
61the mixture of-methyl butyrate.
In a preferred embodiment, the thickness in described the first intermediate layer is 10nm ~ 30nm, and the thickness of described articulamentum is 10nm ~ 30nm, and the thickness in described the second intermediate layer is 10nm ~ 40nm.
In a preferred embodiment, the mass ratio of fullerene derivate described in described the first intermediate layer and described hole padded coaming is 20:1 ~ 1:1.
In a preferred embodiment, the mass ratio of the oxide of rhenium described in described the second intermediate layer and described hole padded coaming is 10:1 ~ 1:5.
In a preferred embodiment, the material of described electron buffer layer is selected from least one in cesium azide, lithium fluoride, lithium carbonate and cesium carbonate.
A preparation method for solar cell device, comprises the following steps:
On anode surface, Hole-injecting Buffer Layer for Improvement and the first active layer are prepared in spin coating successively, and the material of described the first active layer is poly-3-hexyl thiophene and 6,6-phenyl-C
61the mixture of-methyl butyrate;
The first suspension that contains hole padded coaming and fullerene derivate is spin-coated on to described first preparation the first intermediate layer, active layer surface, described hole padded coaming is poly-3, the mixture of 4-dioxy ethene thiophene and polyphenyl sulfonate, described fullerene derivate is selected from C
60, C
70, 6,6-phenyl-C
61-butyl acid methyl esters and 6,6-phenyl-C
71at least one in-butyl acid methyl esters;
The aqueous solution that will gather 3,4-dioxy ethene thiophene and polyphenyl sulfonate is spin-coated on described the first interlayer surfaces and prepares articulamentum;
The second intermediate layer is prepared on the surface that the second suspension of the oxide that contains rhenium and hole padded coaming is spin-coated on to described articulamentum, and the oxide of described rhenium is selected from least one in rhenium dioxide, rhenium heptoxide, rhenium sesquioxide and oxidation two rheniums;
Prepare the second active layer in described the second interlayer surfaces spin coating, the material of described the second active layer is poly-3-hexyl thiophene and 6,6-phenyl-C
61the mixture of-methyl butyrate; And
On the surface of described the second active layer, evaporation is prepared electron buffer layer and negative electrode successively.
In a preferred embodiment, described in described the first intermediate layer, the mass ratio of fullerene derivate and described electronics padded coaming is 20:1 ~ 1:1.
In a preferred embodiment, the mass ratio of the oxide of rhenium described in described the second intermediate layer and described hole padded coaming is 10:1 ~ 1:5.
In a preferred embodiment, when the first intermediate layer is prepared in spin coating, rotating speed is 3000rpm ~ 5000rpm, and the time is 10 seconds ~ 30 seconds.
In a preferred embodiment, when articulamentum is prepared in spin coating, rotating speed is 6000rpm ~ 8000rpm, and the time is 10 seconds ~ 30 seconds.
Above-mentioned solar cell device and preparation method thereof, by prepare the first intermediate layer, articulamentum and the second intermediate layer between the first active layer and the second active layer, improve the first active layer of solar cell device and the efficiency of light absorption of the second active layer, thereby improve photoelectric conversion efficiency; Hole padded coaming and fullerene derivate are mixed with to the first intermediate layer, fullerene derivate has very strong electron transport ability, can improve injection efficiency and the efficiency of transmission of electronics, the oxide of rhenium and hole padded coaming are mixed with to the second intermediate layer, in the padded coaming of hole poly-3,4-dioxy ethene thiophene has very strong conductivity and hole injectability, the oxide work function of rhenium is lower (approximately-5.8eV is following) all, be conducive to hole and inject, can improve the efficiency of solar cell device collection hole and electronics; And the oxide of rhenium is crystal structure, and light is had to scattering process, can make the light scattering that is transmitted into the second intermediate layer be absorbed by the second active layer in the second active layer, thereby the energy conversion efficiency of solar cell device is higher; Poly-3,4-dioxy ethene thiophene, poly-3 are all contained in the first intermediate layer, articulamentum and the second intermediate layer, the easy crystallization of 4-dioxy ethene thiophene, can carry out scattering to light fully by crystallization, improve the absorptivity of the first active layer and the second active layer, the connectivity between three layers is better simultaneously.
[accompanying drawing explanation]
By the more specifically explanation of the preferred embodiments of the present invention shown in accompanying drawing, above-mentioned and other object of the present invention, Characteristics and advantages will be more clear.In whole accompanying drawings, identical Reference numeral is indicated identical part.Deliberately do not draw accompanying drawing by actual size equal proportion convergent-divergent, focus on illustrating purport of the present invention.
Fig. 1 is the structural representation of the solar cell device of an embodiment;
Fig. 2 is the preparation method's of the solar cell device of an embodiment flow chart;
Fig. 3 is the solar cell device of embodiment 1 and current density and the voltage relationship figure of traditional solar cell device.
[embodiment]
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar popularization without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the solar cell device 100 of an embodiment comprises the anode 10, Hole-injecting Buffer Layer for Improvement 20, the first active layer 30, the first intermediate layer 40, articulamentum 50, the second intermediate layer 60, the second active layer 70, electron buffer layer 80 and the negative electrode 90 that stack gradually.
Hole-injecting Buffer Layer for Improvement 20 is formed at anode 10 surfaces.The material of Hole-injecting Buffer Layer for Improvement 20 is poly-3,4-dioxy ethene thiophene (PEDOT) and the mixture of 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 40nm.
The first active layer 30 is formed at Hole-injecting Buffer Layer for Improvement 20 surfaces.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:PC
61the quality of BM is that 1:0.5 ~ 1:4 is preferably 1:0.8.The thickness of the first active layer 30 is 80nm ~ 300nm, is preferably 140nm.
The first intermediate layer 40 is formed at the surface of the first active layer 30.The material in the first intermediate layer 40 comprises hole padded coaming and fullerene derivate.Hole padded coaming is poly-3,4-dioxy ethene thiophene (PEDOT) and the mixture of polyphenyl sodium sulfonate (PSS).Wherein the mass ratio of PEDOT and PSS is 2:1 ~ 6:1, is preferably 3:1.Fullerene derivate is selected from C
60, C
70, 6,6-phenyl-C
61-methyl butyrate (PC
61and 6,6-phenyl-C BM)
71-methyl butyrate (PC
71bM) at least one in.Preferably, the mass ratio of fullerene derivate and hole padded coaming is 20:1 ~ 1: 1.The thickness in the first intermediate layer 40 is 10nm ~ 30nm.
The second intermediate layer 60 is formed at the surface of articulamentum 50.The material in the second intermediate layer 60 comprises oxide and the hole padded coaming of rhenium.The oxide of rhenium is selected from rhenium dioxide (ReO
2), rhenium heptoxide (Re
2o
7), rhenium sesquioxide (Re
2o
3) and oxidation two rhenium (Re
2o) at least one in.Hole padded coaming is poly-3,4-dioxy ethene thiophene (PEDOT) and the mixture of polyphenyl sodium sulfonate (PSS).Wherein the mass ratio of PEDOT and PSS is 2:1 ~ 6:1, is preferably 3:1.In the second intermediate layer, the mass ratio of the oxide of rhenium and hole padded coaming is 10:1 ~ 1:5.The thickness in the second intermediate layer 60 is 10nm ~ 40nm.
The second active layer 70 is formed at the surface in the second intermediate layer 60.The material of the second active layer 70 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 that 1:0.5 ~ 1:4 is preferably 1:0.8.The thickness of the second active layer 70 is 80nm ~ 300nm, is preferably 140nm.
This solar cell device 100, by prepare the first intermediate layer 40, articulamentum 50 and the second intermediate layer 60 between the first active layer 30 and the second active layer 70, improve the first active layer 30 of solar cell device and the efficiency of light absorption of the second active layer 70, thereby improve photoelectric conversion efficiency; Hole padded coaming and fullerene derivate are mixed with to the first intermediate layer 40, fullerene derivate has very strong electron transport ability, can improve injection efficiency and the efficiency of transmission of electronics, the oxide of rhenium and hole padded coaming are mixed with to the second intermediate layer 60, in the padded coaming of hole poly-3,4-dioxy ethene thiophene has very strong conductivity and hole injectability, the oxide work function of rhenium is lower (approximately-5.8eV is following) all, be conducive to hole and inject, the efficiency that can improve solar cell device 100 and collect hole and electronics; And the oxide of rhenium is crystal structure, and light is had to scattering process, can make the light scattering that is transmitted into the second intermediate layer 60 be absorbed by the second active layer 70 in the second active layer 70, thereby the energy conversion efficiency of solar cell device 100 is higher; The first intermediate layer 40, articulamentum 50 and the second intermediate layer 60 all contain poly-3,4-dioxy ethene thiophene, poly-3, the easy crystallization of 4-dioxy ethene thiophene, can carry out scattering to light fully by crystallization, improve the absorptivity of the first active layer 30 and the second active layer 70, the connectivity between three layers is better simultaneously.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, on anode 10 surfaces, Hole-injecting Buffer Layer for Improvement 20 and the first active layer 30 are prepared in spin coating successively.
In present embodiment, antianode 10 pre-treatments comprise that organic pollution and the antianode 10 of removing anode 10 surfaces wait oxonium ion processing.Anode 10 is adopted to liquid detergent, deionized water, acetone, ethanol, the each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution on substrate 10 surfaces; It is 5min ~ 15min that antianode 10 waits the oxonium ion processing time, and power is 10 ~ 50W.
Hole-injecting Buffer Layer for Improvement 20 is by the solution preparation that contains 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.Layer hole padded coaming is poly-3,4-dioxy ethene thiophene (PEDOT) and the mixture of polyphenyl sodium sulfonate (PSS).Wherein the mass ratio of PEDOT and PSS is 2:1 ~ 6:1, is preferably 3:1.In the solution that contains hole padded coaming, the mass concentration of hole padded coaming is 1% ~ 5%, is preferably 4%, and solvent is water.After spin coating, at 100 ℃ ~ 200 ℃, add 15 minutes ~ 60 minutes, preferably at 200 ℃, heat 30 minutes.The thickness of Hole-injecting Buffer Layer for Improvement 20 is 20nm ~ 80nm, is preferably 40nm.
The first active layer 30 is spin-coated on Hole-injecting Buffer Layer for Improvement 20 surfaces by the first active layer solution and makes.The rotating speed of spin coating is 4000rpm ~ 6000rpm, and the time is 10s ~ 30s.In the first active layer solution, the concentration of the first active layer material is 8mg/ml ~ 30mg/ml, is preferably 12mg/ml.The solvent of the first active layer solution is selected from least one in toluene, dimethylbenzene, chlorobenzene and chloroform, is preferably chlorobenzene.The 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 that 1:0.5～1:4 is preferably 1:0.8.Spin coating the first active layer 30 carries out in the glove box that is full of inert gas, anneals 5 minutes ~ 100 minutes afterwards, or at room temperature place 24 ~ 48 hours at 50 ℃ ~ 200 ℃, preferably at 200 ℃, anneals 5 minutes.The thickness of the first active layer 30 is 80nm ~ 300nm, is preferably 140nm.
Step S120, the first suspension that contains hole padded coaming and fullerene derivate is spin-coated on to first preparation the first intermediate layers 40, active layer 30 surface.
Hole padded coaming is poly-3,4-dioxy ethene thiophene (PEDOT) and the mixture of polyphenyl sodium sulfonate (PSS).Wherein the mass ratio of PEDOT and PSS is 2:1 ~ 6:1, is preferably 3:1.Fullerene derivate is selected from C
60, C
70, 6,6-phenyl-C
61-methyl butyrate (PC
61and 6,6-phenyl-C BM)
71-methyl butyrate (PC
71bM) at least one in.Preferably, the mass ratio of fullerene derivate and hole padded coaming is 20:1 ~ 1:1.
In the first suspension that contains hole padded coaming and fullerene derivate, the mass concentration of hole padded coaming is 1% ~ 5%, and the mass concentration of fullerene derivate is 5% ~ 20%.Solvent is for being water.。The rotating speed of spin coating is 3000rpm ~ 5000rpm, and the time is 10 seconds ~ 30 seconds.Dry after spin coating, the thickness in the first intermediate layer 40 obtaining is 10nm ~ 30nm.
Step S130, the aqueous solution that will gather 3,4-dioxy ethene thiophene (PEDOT) and polyphenyl sodium sulfonate (PSS) are spin-coated on the surface in the first intermediate layer 40 and prepare articulamentum 50.
The rotating speed of spin coating is 6000rpm ~ 8000rpm, and the time is 10s ~ 30s.Wherein the mass ratio of PEDOT and PSS is 2:1 ~ 6:1, is preferably 3:1.The mass concentration of hole padded coaming in the aqueous solution (i.e. the mixture of poly-3,4-dioxy ethene thiophene and polyphenyl sodium sulfonate) is 1% ~ 5%, is preferably 4%.After spin coating, at 100 ℃ ~ 200 ℃, add 15 minutes ~ 60 minutes, preferably at 200 ℃, heat 30 minutes.The thickness of articulamentum is 10nm ~ 30nm.
The oxide of rhenium is selected from rhenium dioxide (ReO
2), rhenium heptoxide (Re
2o
7), rhenium sesquioxide (Re
2o
3) and oxidation two rhenium (Re
2o) at least one in.Hole padded coaming is poly-3,4-dioxy ethene thiophene (PEDOT) and the mixture of polyphenyl sodium sulfonate (PSS).Wherein the mass ratio of PEDOT and PSS is 2:1 ~ 6:1, is preferably 3:1.In the second intermediate layer, the mass ratio of the oxide of rhenium and hole padded coaming is 10:1 ~ 1:5
In the second suspension of the oxide that contains rhenium and hole padded coaming, the mass concentration of the oxide of rhenium is 1% ~ 10%, and the mass concentration of hole padded coaming is 1% ~ 5%.Solvent is water.The rotating speed of spin coating is 4000rpm ~ 6000rpm, and the time is 10 seconds ~ 30 seconds.Dry after spin coating, the thickness in the second intermediate layer 60 obtaining is 10nm ~ 40nm.
Step S150, prepare the second active layer 70 in the second surperficial spin coating in intermediate layer 60.
The second active layer 70 is spin-coated on 60 surfaces, the second intermediate layer by the second active layer solution and makes.The rotating speed of spin coating is 4000rpm ~ 6000rpm, and the time is 10s ~ 30s.In the second active layer solution, the concentration of the second active layer material is 8mg/ml ~ 30mg/ml, is preferably 12mg/ml.The solvent of the second active layer solution is selected from least one in toluene, dimethylbenzene, chlorobenzene and chloroform, is preferably chlorobenzene.The 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 that 1:0.5～1:4 is preferably 1:0.8.Spin coating the second active layer 70 carries out in the glove box that is full of inert gas, anneals 5 minutes ~ 100 minutes afterwards, or at room temperature place 24 ~ 48 hours at 50 ℃ ~ 200 ℃, preferably at 200 ℃, anneals 5 minutes.The thickness of the second active layer 70 is 80nm ~ 300nm, is preferably 140nm.
Step S160, on the surface of the second active layer 70, evaporation is prepared electron buffer layer 80 and negative electrode 90 successively.
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 of solar cell device provided by the invention is elaborated.
The preparation used of the embodiment of the present invention and comparative example and tester are: high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure <1 × 10
-32602), the white light source that is simulated solar irradiation with the filter set cooperation of 500W xenon lamp (Osram) and AM 1.5 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/PC
61bM:PEDOT:PSS/PEDOT:PSS/PEDOT:PSS:Re
2o
7/ P3HT:PC
61the solar cell device of BM/LiF/Al.
First ITO is carried out to photoetching treatment, be cut into needed size, use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface; Clean up and rear conductive substrates is carried out to oxygen plasma treatment, the processing time is 5-15min, and power is 10-50W; Hole-injecting Buffer Layer for Improvement is prepared in spin coating, and the mass ratio of PEDOT and PSS is 3:1, and the mass fraction of PEDOT:PSS is 4%, and the rotating speed of spin coating is 4000rpm, and the time is 15s, after spin coating, at 200 ℃, heats 30min, and thickness is 40nm; Spin coating the first active layer, the P3HT:PC that the first active layer is 12mg/ml by concentration
61the spin coating of BM solution forms, and solvent is chlorobenzene, P3HT and PC
61the mass ratio of BM is 1:0.8, and the rotating speed of spin coating is 5000rpm, and the time is 20s, after spin coating, anneals 5 minutes at 200 ℃, and THICKNESS CONTROL is at 140nm.Spin coating the first intermediate layer, the material of suspension is PEDOT:PSS and PC
61bM composition, solvent is benzene, and the mass ratio of PEDOT and PSS is 3:1, and the mass fraction of PEDOT and PSS is 3.5%, PC
61the mass fraction of BM is 15%, and the rotating speed of spin coating is 4000rpm, and the time is 15s, dries, and thickness is 15nm.The aqueous solution of spin coating PEDOT:PSS is prepared articulamentum, and the mass ratio of PEDOT and PSS is 3:1, and the mass fraction of PEDOT:PSS is 3%, and the rotating speed of spin coating is 5000rpm, and the time is 15s, after spin coating, at 100 ℃, heats 30min, and thickness is 10nm; Spin coating the second intermediate layer, the material of suspension is Re
2o
7and PEDOT:PSS, solvent is water, and the weight ratio of PEDOT and PSS is 3:1, and the mass fraction of PEDOT:PSS is 2.5%, Re
2o
7mass fraction is 5%, and rotating speed is 4500rpm, and the time is 20s, and after drying, thickness is 15nm.Then spin coating the second active layer, material is P3HT:PC
61bM, P3HT and PC
61bM mass ratio is 1:0.8, P3HT:PC in suspension
61the mass fraction of BM is 12mg/L, and the rotating speed of spin coating is 5000rpm, and the time is 15s, after spin coating, anneals 5 minutes at 200 ℃, and THICKNESS CONTROL is at 140nm.Then evaporation is prepared electron buffer layer, and material is LiF, and thickness is 1nm, and evaporation is 5 × 10 at vacuum pressure
-4under Pa, carry out, evaporation speed is 0.2nm/s; Evaporation negative electrode, material is Al, and thickness is 150nm, and evaporation is 5 × 10 at vacuum pressure
-4under Pa, carry out, evaporation speed is 3nm/s.Finally obtain desired polymer solar cell device.
Refer to Fig. 3, the structure that is depicted as preparation in embodiment 1 is ITO/PEDOT:PSS/P3HT:PC
61bM/PC
61bM:PEDOT:PSS/PEDOT:PSS/PEDOT:PSS:Re
2o
7/ P3HT:PC
61the solar cell device (curve 1) of BM/LiF/Al is ITO/PEDOT:PSS/P3HT:PC with traditional structure
61current density and the voltage relationship of BM/LiF/Al solar cell device (curve 2), the structure that table 1 is depicted as preparation in embodiment 1 is ITO/PEDOT:PSS/P3HT:PC
61bM/PC
61bM:PEDOT:PSS/PEDOT:PSS/PEDOT:PSS:Re
2o
7/ P3HT:PC
61the solar cell device of BM/LiF/Al and traditional structure are ITO/PEDOT:PSS/P3HT:PC
61current density, voltage, energy conversion efficiency (η) and the fill factor, curve factor data of BM/LiF/Al solar cell device.In the solar cell device that in traditional solar cell device, each layer thickness is prepared with embodiment 1, each layer thickness is identical.
Table 1
| ? | Current density (mA/cm 2） | Voltage (V) | η（%） | Fill factor, curve factor |
| Curve 1 | 13.08 | 0.73 | 3.28 | 0.34 |
| |
12.23 | 0.72 | 2.96 | 0.34 |
Can see from table 1 and Fig. 3, conventional solar cell device current density is 12.23mA/cm
2, and solar cell device current density prepared by embodiment 1 has been brought up to 13.08mA/cm
2, this explanation, the present invention can improve injection and the transmission performance of electronics by preparing the first intermediate layer, articulamentum and the second intermediate layer, being conducive to hole injects, make fully light carry out scattering, improve the efficiency of light absorption of active layer, thereby can improve photoelectric conversion efficiency.The energy conversion efficiency of traditional solar cell device is 2.96%, and the energy conversion efficiency of solar cell device prepared by embodiment 1 is 3.28%.
The current density of each embodiment and voltage curve, current density, voltage, energy conversion efficiency and fill factor, curve factor are all similar with embodiment 1 below, and each solar cell device also has similar energy conversion efficiency, repeats no more below.
Structure prepared by the present embodiment is IZO/PEDOT:PSS/P3HT:PC
61bM/C
60: PEDOT:PSS/PEDOT:PSS/PEDOT:PSS:ReO
2/ P3HT:PC
61bM/Cs
2cO
3the solar cell device of/Au.
First IZO is carried out to photoetching treatment, be cut into needed size, use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface; Clean up and rear conductive substrates is carried out to oxygen plasma treatment, the processing time is 5-15min, and power is 10-50W; Hole-injecting Buffer Layer for Improvement is prepared in spin coating, and the mass ratio of PEDOT:PSS is 2:1, and the mass fraction of PEDOT:PSS is 5%, and the rotating speed of spin coating is 6000rpm, and the time is 30s, after spin coating, at 100 ℃, heats 60min, and thickness is 20nm; Spin coating the first active layer, the P3HT:PC that the first active layer is 8mg/ml by concentration
61the spin coating of BM solution forms, and solvent is chlorobenzene, 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, the 100min that anneals at 50 ℃ after spin coating, and THICKNESS CONTROL is at 300nm.Spin coating the first intermediate layer, the material of suspension is PEDOT:PSS and C
60composition, solvent is water, and the mass ratio of PEDOT and PSS is 6:1, and the mass fraction of PEDOT and PSS is 1%, C
60mass fraction be 50%, the rotating speed of spin coating is 3000rpm, the time is 30s, dry, thickness is 30nm.The aqueous solution of spin coating PEDOT:PSS is prepared articulamentum, and the mass ratio of PEDOT and PSS is 2:1, and the mass fraction of PEDOT:PSS is 5%, and the rotating speed of spin coating is 8000rpm, and the time is 30s, after spin coating, at 200 ℃, heats 15min, and thickness is 10nm; Spin coating the second intermediate layer, the material of suspension is ReO
2and PEDOT:PSS, solvent is water, and the weight ratio of PEDOT and PSS is 2:1, and the mass fraction of PEDOT:PSS is 1%, ReO
2mass fraction is 1%, and rotating speed is 6000rpm, and the time is 10s, and after drying, thickness is 10nm.Then spin coating the second active layer, material is P3HT:PC
61bM, P3HT and PC
61bM mass ratio is 1:4, P3HT:PC in suspension
61the mass fraction of BM is 24mg/L, and the rotating speed of spin coating is 4000rpm, and the time is 10s, at room temperature places 48 hours after spin coating, and THICKNESS CONTROL is at 300nm.Then evaporation is prepared electron buffer layer, and material is Cs
2cO
3, thickness is 5nm, evaporation is 3 × 10 at vacuum pressure
-4under Pa, carry out, evaporation speed is 0.1nm/s; Evaporation negative electrode, material is Au, and thickness is 300nm, and evaporation is 3 × 10 at vacuum pressure
-4under Pa, carry out, evaporation speed 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/C
70: PEDOT:PSS/PEDOT:PSS/PEDOT:PSS:Re
2o
3/ P3HT:PC
61bM/CsN
3the solar cell device of/Ag.
First FTO is carried out to photoetching treatment, be cut into needed size, use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface; Clean up and rear conductive substrates is carried out to oxygen plasma treatment, the processing time is 5-15min, and power is 10-50W; Hole-injecting Buffer Layer for Improvement is prepared in spin coating, and the mass ratio of PEDOT:PSS is 6:1, and the mass fraction of PEDOT:PSS is 1%, and the rotating speed of spin coating is 5000rpm, and the time is 20s, after spin coating, at 200 ℃, heats 15min, and thickness is 20nm; Spin coating the first active layer, the P3HT:PC that the first active layer is 18mg/ml by concentration
61the spin coating of BM solution forms, and solvent is chlorobenzene, P3HT and PC
61the mass ratio of BM is 1:2, and the rotating speed of spin coating is 6000rpm, and the time is 10s, the 5min that anneals at 200 ℃ after spin coating, and THICKNESS CONTROL is at 80nm.Spin coating the first intermediate layer, the material of suspension is PEDOT:PSS and C
70composition, solvent is water, and the mass ratio of PEDOT and PSS is 2:1, and the shared mass fraction of PEDOT and PSS is 5%, C
70shared mass fraction is 20%, and the rotating speed of spin coating is 5000rpm, and the time is 10s, dries, and thickness is 10nm.The aqueous solution of spin coating PEDOT:PSS is prepared articulamentum, and the mass ratio of PEDOT and PSS is 6:1, and the mass fraction of PEDOT:PSS is 1%, and the rotating speed of spin coating is 6000rpm, and the time is 10s, after spin coating, at 100 ℃, heats 60min, and thickness is 30nm; Spin coating the second intermediate layer, the material of suspension is Re
2o
3and PEDOT:PSS, solvent is water, and the weight ratio of PEDOT:PSS is 6:1, and the mass fraction of PEDOT:PSS is 5%, Re
2o
3mass fraction is 10%, and rotating speed is 4000rpm, and the time is 10s, and after drying, thickness is 40nm.Then spin coating the second active layer, material is P3HT:PC
61bM, P3HT and PC
61bM mass ratio is 1:0.8, P3HT:PC in suspension
61the mass fraction of BM is 16mg/L, and the rotating speed of spin coating is 4500rpm, and the time is 10s, the 15min that anneals at 150 ℃ after spin coating, and, THICKNESS CONTROL is at 120nm.Then evaporation is prepared electron buffer layer, and material is CsN
3, thickness is 10nm, evaporation is 3 × 10 at vacuum pressure
-3under Pa, carry out, evaporation speed is 1nm/s; Evaporation negative electrode, material is Ag, and thickness is 80nm, and evaporation is 3 × 10 at vacuum pressure
-3under Pa, carry out, evaporation speed is 10nm/s.Finally obtain desired polymer solar cell device.
Structure prepared by the present embodiment is ITO/PEDOT:PSS/P3HT:PC
61bM/PC
71bM:PEDOT:PSS/PEDOT:PSS/PEDOT:PSS:Re
2o/P3HT:PC
61bM/Li
2cO
3the solar cell device of/Pt.
First ITO is carried out to photoetching treatment, be cut into needed size, use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface; Clean up and rear conductive substrates is carried out to oxygen plasma treatment, the processing time is 5-15min, and power is 10-50W; Hole-injecting Buffer Layer for Improvement is prepared in spin coating, and the mass ratio of PEDOT:PSS is 3.5:1, and the mass fraction of PEDOT:PSS is 3.5%, and the rotating speed of spin coating is 2000rpm, and the time is 10s, after spin coating, at 150 ℃, heats 20min, and thickness is 80nm; Spin coating the first active layer, the P3HT:PC that the first active layer is 10mg/ml by concentration
61the spin coating of BM solution forms, and solvent is chloroform, P3HT and PC
61the mass ratio of BM is 1:1, and the rotating speed of spin coating is 5500rpm, and the time is 30s, the 30min that anneals at 100 ℃ after spin coating, and THICKNESS CONTROL is at 200nm.Spin coating the first intermediate layer, the material of suspension is PEDOT:PSS and PC
71bM composition, solvent is water, and the mass ratio of PEDOT and PSS is 3:1, and the shared mass fraction of PEDOT:PSS is 1.5%, PC
71the shared mass fraction of BM is 8%, and the rotating speed of spin coating is 3500rpm, and the time is 10s, dries, and thickness is 12nm.The aqueous solution of spin coating PEDOT:PSS is prepared articulamentum, and the mass ratio of PEDOT and PSS is 2.5:1, and the mass fraction of PEDOT:PSS is 1.5%, and the rotating speed of spin coating is 7000rpm, and the time is 15s, after spin coating, at 150 ℃, heats 20min, and thickness is 25nm; Spin coating the second intermediate layer, the material of suspension is Re
2o and PEDOT:PSS, solvent is water, and the weight ratio of PEDOT:PSS is 4:1, and the mass fraction of PEDOT:PSS is 3%, Re
2o mass fraction is 6%, and rotating speed is 5500rpm, and the time is 15s, and after drying, thickness is 30nm.Then spin coating the second active layer, material is P3HT:PC
61bM, P3HT and PC
61bM mass ratio is 1:3, P3HT:PC in suspension
61the mass fraction of BM is 30mg/L, and the rotating speed of spin coating is 5500rpm, and the time is 30s, the 10min that anneals at 150 ℃ after spin coating, and THICKNESS CONTROL is at 80nm.Then evaporation is prepared electron buffer layer, and material is Li
2cO
3, thickness is 1nm, evaporation is 8 × 10 at vacuum pressure
-4under Pa, carry out, evaporation speed is 0.2nm/s; Evaporation negative electrode, material is Pt, and thickness is 100nm, and evaporation is 8 × 10 at vacuum pressure
-4under Pa, carry out, evaporation speed is 5nm/s.Finally obtain desired polymer solar cell device.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore 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, is characterized in that, comprises the anode, Hole-injecting Buffer Layer for Improvement, the first active layer, the first intermediate layer, articulamentum, the second intermediate layer, the second active layer, electron buffer layer and the negative electrode that stack gradually; The material of described the first active layer is poly-3-hexyl thiophene and 6,6-phenyl-C
61the mixture of-methyl butyrate, the material in described the first intermediate layer comprises hole padded coaming and fullerene derivate, and described hole padded coaming is the mixture of poly-3,4-dioxy ethene thiophene and polyphenyl sulfonate, and described fullerene derivate is selected from C
60, C
70, 6,6-phenyl-C
61-butyl acid methyl esters and 6,6-phenyl-C
71at least one in-butyl acid methyl esters, the material of described articulamentum is poly-3, the mixture of 4-dioxy ethene thiophene and polyphenyl sulfonate, the material in described the second intermediate layer comprises oxide and the hole padded coaming of rhenium, the oxide of described rhenium is selected from least one in rhenium dioxide, rhenium heptoxide, rhenium sesquioxide and oxidation two rheniums, the poly-3-hexyl thiophene of material and 6, the 6-phenyl-C of described the second active layer
61the mixture of-methyl butyrate.
2. solar cell device according to claim 1, is characterized in that: the thickness in described the first intermediate layer is 10nm ~ 30nm, and the thickness of described articulamentum is 10nm ~ 30nm, and the thickness in described the second intermediate layer is 10nm ~ 40nm.
3. solar cell device according to claim 1, is characterized in that: the mass ratio of fullerene derivate described in described the first intermediate layer and described hole padded coaming is 20:1 ~ 1:1.
4. solar cell device according to claim 1, is characterized in that: the mass ratio of the oxide of rhenium described in described the second intermediate layer and described hole padded coaming is 10:1 ~ 1:5.
5. solar cell device according to claim 1, is characterized in that: the material of described electron buffer layer is selected from least one in cesium azide, lithium fluoride, lithium carbonate and cesium carbonate.
6. a preparation method for solar cell device, is characterized in that, comprises the following steps:
On anode surface, Hole-injecting Buffer Layer for Improvement and the first active layer are prepared in spin coating successively, and the material of described the first active layer is poly-3-hexyl thiophene and 6,6-phenyl-C
61the mixture of-methyl butyrate;
The first suspension that contains hole padded coaming and fullerene derivate is spin-coated on to described first preparation the first intermediate layer, active layer surface, described hole padded coaming is poly-3, the mixture of 4-dioxy ethene thiophene and polyphenyl sulfonate, described fullerene derivate is selected from C
60, C
70, 6,6-phenyl-C
61-butyl acid methyl esters and 6,6-phenyl-C
71at least one in-butyl acid methyl esters;
The aqueous solution that will gather 3,4-dioxy ethene thiophene and polyphenyl sulfonate is spin-coated on described the first interlayer surfaces and prepares articulamentum;
The second intermediate layer is prepared on the surface that the second suspension of the oxide that contains rhenium and hole padded coaming is spin-coated on to described articulamentum, and the oxide of described rhenium is selected from least one in rhenium dioxide, rhenium heptoxide, rhenium sesquioxide and oxidation two rheniums;
Prepare the second active layer in described the second interlayer surfaces spin coating, the material of described the second active layer is poly-3-hexyl thiophene and 6,6-phenyl-C
61the mixture of-methyl butyrate; And
On the surface of described the second active layer, evaporation is prepared electron buffer layer and negative electrode successively.
7. the preparation method of solar cell device according to claim 6, is characterized in that: described in described the first intermediate layer, the mass ratio of fullerene derivate and described electronics padded coaming is 20:1 ~ 1:1.
8. the preparation method of solar cell device according to claim 6, is characterized in that: the mass ratio of the oxide of rhenium described in described the second intermediate layer and described hole padded coaming is 10:1 ~ 1:5.
9. the preparation method of solar cell device according to claim 6, is characterized in that: when the first intermediate layer is prepared in spin coating, rotating speed is 3000rpm ~ 5000rpm, and the time is 10 seconds ~ 30 seconds.
10. the preparation method of solar cell device according to claim 6, is characterized in that: when articulamentum is prepared in spin coating, rotating speed is 6000rpm ~ 8000rpm, and the time is 10 seconds ~ 30 seconds.
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