CN102856498B - Parallel type polymer solar cell and preparation method thereof - Google Patents
Parallel type polymer solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of solar cells, and discloses a parallel type polymer solar cell. The parallel type polymer solar cell comprises an anode substrate, a first hole buffering layer, a first active layer, an n-type doped layer, a second active layer, a second hole buffering layer and an anode layer which are stacked sequentially. The active layers of two cell units can capture sunlight as much as possible, so that large quantities of electrons and holes are formed, a connecting layer for connecting two cells is the n-type doped layer capable of increasing conductivity of the cells, and hole and electron injection efficiency is improved.
Description
Technical field
The present invention relates to area of solar cell, particularly relate to a kind of parallel polymer solar battery and preparation method thereof.
Background technology
Nineteen eighty-two, Weinberger etc. have studied the Photovoltaic Properties of polyacetylene, produced first solar cell had truly, but photoelectric conversion efficiency are at that time extremely low by (10
-3%).And then, Glenis etc. have made the solar cell of various polythiophene, and all problems faced was extremely low open circuit voltage and photoelectric conversion efficiency at that time.Until 1986, p-type semiconductor and n-type semiconductor are incorporated in double-deck device by C.W.Tang etc. first, just make photoelectric current obtain the raising of high degree, from then on this work for milestone, organic polymer solar cell is flourish.
Sariciftci in 1992 etc. find 2-methoxyl group-5-(2-ethyl-own oxygen base)-1, fast light photoinduced electron transfer phenomena is there is in 4-benzene second (MEH-PPV) and compound system, cause the great interest of people, and in nineteen ninety-five, MEH-PPV and the C such as Yu
60the derivative PCBM mixing of (i.e. 60 carbon atom organic substances) has prepared organic polymer bulk heterojunction solar cell as active layer.Device is at 20mW/cm
2under the monochromatic light exposure of 430nm, energy conversion efficiency is 2.9%.This is the first bulk heteroj joint solar cell prepared based on polymeric material and PCBM acceptor, and proposes the concept of inierpeneirating network structure in composite membrane.So far, the application of bulk heteroj unction structure in polymer solar battery obtains and develops rapidly.This structure also becomes the organic polymer solar cell structure that current people generally adopt.
The operation principle of polymer solar battery is mainly divided into four parts: the formation of (1) optical excitation and exciton; (2) diffusion of exciton; (3) division of exciton; (4) transmission of electric charge and collection.First, conjugated polymer is absorb photons under incident light irradiates, electronics transits to lowest unoccupied molecular orbital (LUMO) from polymer highest occupied molecular orbital (HOMO), form exciton, exciton is diffused into and is separated into the electronics and hole that move freely to body/acceptor interface place under the effect of internal electric field, then electronics acceptor mutually in transmit and by cathode collector, hole is then by being collected by anode to body phase, thus generation photoelectric current, which forms an effective photoelectric conversion process.
Current polymer solar battery is all generally single battery cellular construction, and photoelectric conversion efficiency is not high, and the absorption of active layer to sunlight is limited, fundamentally can not improve the utilization of device to sunlight, constrain the raising of efficiency.
Summary of the invention
The object of the present invention is to provide the parallel polymer solar battery that a kind of energy conversion rate is high.
Technical scheme of the present invention is as follows:
A kind of parallel polymer solar battery, this parallel polymer solar battery comprises the anode substrate, the first Hole-injecting Buffer Layer for Improvement, the first active layer, N-shaped doped layer, the second active layer, the second Hole-injecting Buffer Layer for Improvement, the anode layer that stack gradually, and namely the structure of this battery is followed successively by: anode substrate/the first Hole-injecting Buffer Layer for Improvement/the first active layer/N-shaped doped layer/the second active layer/the second Hole-injecting Buffer Layer for Improvement/anode layer.
This parallel polymer solar is divided into two battery units by described N-shaped doped layer, namely anode substrate, the first Hole-injecting Buffer Layer for Improvement, the first active layer and N-shaped doped layer form and are just putting type first battery unit, and anode layer in anode substrate and N-shaped doped layer are respectively as the anode of this first battery unit and negative electrode; N-shaped doped layer, the second active layer, electron buffer layer and anode layer form inversion type second battery unit, and anode layer and N-shaped doped layer are respectively as the anode of this second battery unit and negative electrode; Wherein, N-shaped doped layer is the negative electrode simultaneously as the first battery unit and the second battery unit, and such first battery unit and the second battery unit form parallel polymer solar battery by N-shaped doped layer.
In this parallel polymer solar battery, each functional layer material used is as follows:
Conductive anode substrate is indium tin oxide glass (ITO), mix indium zinc oxide glass (IZO), fluorine doped tin oxide glass (FTO) or mix the change zinc glass (AZO) of aluminium;
The material of the first Hole-injecting Buffer Layer for Improvement and the second Hole-injecting Buffer Layer for Improvement is the mixture of poly-3,4-ethylenedioxy thiophenes (PEDOT) and kayexalate (PSS), i.e. PEDOT:PSS mixture;
The material of the first active layer and the second active layer is poly-3-hexyl thiophene (P3HT), poly-[2-methoxyl group-5-(3,7. dimethyl octyloxy) phenylenevinylene] (MDMO-PPV) or poly-[2-methoxyl group-5-(2 '-vinyl-own oxygen base) is poly-to styrene support] (MEH-PPV) and [6,6] mixture formed after-phenyl-C61-methyl butyrate (PCBM) mixing, i.e. P3HT:PCBM, MDMO-PPV:PCBM or MEH-PPV:PCBM mixture; Wherein, the mass ratio of P3HT: PCBM controls the scope 1: 1 ~ 1: 0.8, and the mass ratio of MODO-PPV: PCBM and MEH-PPV: PCBM controls the scope 1: 4 ~ 1: 1 respectively;
The dopant mixture that the material of described N-shaped doped layer is formed for electron injection material doping electron transport material; Wherein,
Electron injection material is lithium fluoride (LiF), lithium carbonate (Li
2cO
3), cesium carbonate (Cs
2cO
3), cesium azide (CsN
3) or cesium fluoride (CsF);
Electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI);
The material of anode layer is aluminium (Al), silver (Ag), gold (Au) or platinum (Pt).
Another object of the present invention is to the preparation method providing above-mentioned parallel polymer solar battery, its processing step is as follows:
S1, by anode substrate successively at liquid detergent, deionized water, acetone, ethanol, ultrasonic cleaning in isopropyl alcohol, remove surface organic pollution;
S2, anode surface spin coating first Hole-injecting Buffer Layer for Improvement in anode substrate, again in the first Hole-injecting Buffer Layer for Improvement surface spin coating first active layer, then dry process after drying;
S3, at the first active layer surface evaporating n type doped layer;
S4, in N-shaped doped layer surface spin coating second active layer, then dry process; Then in two active layer surface spin coating second Hole-injecting Buffer Layer for Improvement, then dry process;
S5, at the second Hole-injecting Buffer Layer for Improvement surface evaporation anode layer, finally obtained parallel polymer solar battery.
In the step S1 of above-mentioned preparation method, also comprise the steps:
By anode substrate successively at liquid detergent, deionized water, acetone, ethanol, ultrasonic cleaning in isopropyl alcohol.
Parallel polymer solar battery of the present invention, the active layer of two battery units can catch more sunlight as much as possible, thus produce more electronics and hole, and the articulamentum connecting two batteries is the conductivity that n doped layer can improve battery, the injection efficiency of hole and electronics is improved.
Accompanying drawing explanation
Fig. 1 is the parallel polymer solar battery structural representation of the present invention;
Fig. 2 is preparation technology's flow chart of the parallel polymer solar battery of the present invention;
Fig. 3 is the parallel polymer solar battery of embodiment 1: ITO substrate/PEDOT:PSS/P3HT:PCBM/CsN
3: Bphen/P3HT:PCBM/PEDOT:PSS/Al and comparative example battery: the current density of ITO substrate/PEDOT:PSS/P3HT:PCBM/LiF/Al and voltage relationship figure; Wherein, curve 1 is the curve of embodiment 1, and curve 2 is the curve of comparative example.
Embodiment
The parallel polymer solar battery of one provided by the invention, as shown in Figure 1, this parallel polymer solar battery is layer structure, and this layer structure comprises successively: anode substrate 11, first Hole-injecting Buffer Layer for Improvement 12, first active layer 13, N-shaped doped layer 14, second active layer 15, second Hole-injecting Buffer Layer for Improvement 16, anode layer 17, namely the structure of this battery is: anode substrate 11/ first Hole-injecting Buffer Layer for Improvement 12/ first active layer 13/n type doped layer 14/ second active layer 15/ second Hole-injecting Buffer Layer for Improvement 16/ anode layer 17.
This parallel polymer solar battery is divided into two battery units by described N-shaped doped layer 14, namely anode substrate 11, first Hole-injecting Buffer Layer for Improvement 12, first active layer 13 and N-shaped doped layer 14 form and just put type first battery unit, and the anode layer of anode substrate 11 and N-shaped doped layer 14 are respectively as the anode of this first battery unit and negative electrode; N-shaped doped layer 14, second active layer 15, electron buffer layer 16 and anode layer 17 form inversion type second battery unit, and anode layer 17 and N-shaped doped layer 14 are respectively as the anode of this second battery unit and negative electrode; Wherein, N-shaped doped layer 14 is the negative electrode simultaneously as the first battery unit and the second battery unit, and such first battery unit and the second battery unit form parallel polymer solar battery by N-shaped doped layer 14.
In this parallel polymer solar battery, each functional layer material used is as follows:
Conductive anode substrate is indium tin oxide glass (ITO), mixes indium zinc oxide glass (IZO), fluorine doped tin oxide glass (FTO) or Al-Doped ZnO glass (AZO);
The material of the first Hole-injecting Buffer Layer for Improvement and the second Hole-injecting Buffer Layer for Improvement is respectively the mixture of poly-3,4-ethylenedioxy thiophenes (PEDOT) and kayexalate (PSS), i.e. PEDOT:PSS mixture;
The material of the first active layer and the second active layer is poly-3-hexyl thiophene (P3HT), poly-[2-methoxyl group-5-(3,7. dimethyl octyloxy) phenylenevinylene] (MDMO-PPV) or poly-[2-methoxyl group-5-(2 '-vinyl-own oxygen base) is poly-to styrene support] (MEH-PPV) form mixture after mixing with [6,6]-phenyl-C61-methyl butyrate (PCBM); I.e. P3HT:PCBM, MDMO-PPV:PCBM or MEH-PPV:PCBM mixture; Wherein, the mass ratio of P3HT: PCBM controls the scope 1: 1 ~ 1: 0.8, and the mass ratio of MODO-PPV: PCBM and MEH-PPV: PCBM controls the scope 1: 4 ~ 1: 1 respectively;
The dopant mixture that the material of described N-shaped doped layer is formed for electron injection material doping electron transport material, and electron transport material is main body, electron injection material is object (i.e. dopant material), the dopant ratio of guest materials is 10-60wt% (mass percent, lower same); Wherein,
Electron injection material is lithium fluoride (LiF), lithium carbonate (Li
2cO
3), cesium carbonate (Cs
2cO
3), cesium azide (CsN
3) or cesium fluoride (CsF);
Electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI);
The material of anode layer is metal material, and e.g., aluminium (Al), silver (Ag), gold (Au) or platinum (Pt), be preferably Al; The thickness of this anode layer is 20 ~ 250nm, and preferred thickness is 150nm.
The preparation method of above-mentioned parallel polymer solar battery, as shown in Figure 2, its processing step is as follows:
S1, by anode substrate successively at liquid detergent, deionized water, acetone, ethanol, ultrasonic cleaning in isopropyl alcohol, remove surface organic pollution; After cleaning up under power 10 ~ 50W, oxygen plasma treatment 5 ~ 15min is carried out to it, or UV-ozone treatment 5 ~ 20min;
S2, be first Hole-injecting Buffer Layer for Improvement of 20 ~ 80nm at the anode layer surface spin coating thickness of anode substrate, again at the first active layer that the first Hole-injecting Buffer Layer for Improvement surface spin coating thickness is 80 ~ 300nm after drying, then dry process;
S3, be the N-shaped doped layer of 10 ~ 150nm at the first active layer surface evaporation thickness;
S4, to be coated with thickness on N-shaped doped layer surface be second active layer of 80 ~ 300nm, then dry process; Then at second Hole-injecting Buffer Layer for Improvement of two active layer surface spin coating thickness 20 ~ 80nm, then dry process;
S5, be the anode layer of 20 ~ 250nm at the second Hole-injecting Buffer Layer for Improvement surface evaporation thickness, finally obtained parallel polymer solar battery.
In the step S2 of above-mentioned preparation method and S5, first Hole-injecting Buffer Layer for Improvement and the second Hole-injecting Buffer Layer for Improvement employing mass ratio are the aqueous solution of 6: 1 PEDOT: PSS, the mass percent of PEDOT: PSS is 1.5wt%, after first Hole-injecting Buffer Layer for Improvement, the second Hole-injecting Buffer Layer for Improvement spin coating terminate, bake drying, THICKNESS CONTROL is at 20 ~ 80nm; Preferred Hole-injecting Buffer Layer for Improvement thickness is 40nm.
In the step S2 of above-mentioned preparation method and S4, the material of the first active layer and the second active layer is solution system, its solvent is one or both mixed solvents in toluene, dimethylbenzene, chlorobenzene or chloroform, and solute is P3HT:PCBM, MDMO-PPV:PCBM or MEH-PPV:PCBM.The total concentration of often kind of system controls at 8-30mg/ml, and the mass ratio of P3HT: PCBM controls the scope 1: 1 ~ 1: 0.8; The mass ratio of MDMO-PPV: PCBM and MEH-PPV: PCBM controls the scope 1: 4 ~ 1: 1; Then in the glove box being full of inert gas, carry out spin coating, finally anneal 10 ~ 100min at 50 ~ 200 DEG C, or at room temperature place 24 ~ 48h, and THICKNESS CONTROL is at 80 ~ 300nm; Preferred total concentration is the P3HT:PCBM chlorobenzene solution system of 15mg/ml, and the mass ratio of preferred P3HT: PCBM is 1: 0.8, and anneal at being preferably 120 DEG C 10min, and preferred active layer thickness is 200nm.
Parallel polymer solar battery of the present invention, the active layer of two battery units can catch more sunlight as much as possible, thus produce more electronics and hole, and the articulamentum connecting two batteries is the conductivity that n doped layer can improve battery, the injection efficiency of hole and electronics is improved.
Below preferred embodiment of the present invention is described in further detail.
Embodiment 1
In the present embodiment, the structure of parallel polymer solar battery is: ITO substrate/PEDOT:PSS/P3HT:PCBM/CsN
3: Bphen/P3HT:PCBM/PEDOT:PSS/Al.
The preparation technology of this parallel polymer solar battery is as follows:
1, by ITO substrate (wherein, ITO is anode layer) use liquid detergent successively, deionized water, acetone, ethanol, isopropyl alcohol cleans, and each ultrasonic 15min during cleaning, remove the organic pollution of glass surface, clean up the rear ITO layer to ITO substrate oxygen plasma surface treatment 15min under power is 10W condition;
2, by the PEDOT:PSS aqueous solution, (wherein, PEDOT: PSS mass ratio is 6: 1; The gross mass percentage of PEDOT and PSS is 1.5wt%) by the mode of spin coating be prepared in ITO substrate ITO layer surface; Bake drying, obtained thickness is first Hole-injecting Buffer Layer for Improvement of 40nm;
3, P3HT:PCBM chlorobenzene solution system is spin-coated on the first Hole-injecting Buffer Layer for Improvement surface, after spin coating is complete, anneal 10min at 120 DEG C, and obtained thickness is first active layer of 200nm; Wherein, in P3HT:PCBM chlorobenzene solution system, solvent is chlorobenzene, and the total concentration of P3HT and PCBM is the mass ratio of 14mg/ml, P3HT: PCBM is 1: 0.8;
4, be the N-shaped doped layer of 50nm at the first active layer surface evaporation thickness, material is CsN
3: Bphen, and Bphen is material of main part, CsN
3for dopant material, and doping ratio is 20wt%;
5, spin coating second active layer again on N-shaped doped layer surface: be spin-coated on N-shaped doped layer surface by P3HT:PCBM chlorobenzene solution system, after spin coating is complete, anneal 10min at 120 DEG C, and obtained thickness is second active layer of 200nm; Wherein, in P3HT:PCBM chlorobenzene solution system, solvent is chlorobenzene, and the total concentration of P3HT and PCBM is the mass ratio of 15mg/ml, P3HT: PCBM is 1: 0.8;
6, by the PEDOT:PSS aqueous solution, (wherein, PEDOT: PSS mass ratio is 6: 1; The gross mass percentage of PEDOT and PSS is 1.5wt%) be prepared in N-shaped doped layer surface by the mode of spin coating; Spin coating post-drying, obtained thickness is second Hole-injecting Buffer Layer for Improvement of 40nm;
7, at the second Hole-injecting Buffer Layer for Improvement surface evaporation anode layer, material is Al, and thickness is 150nm;
8, after above-mentioned preparation technology completes, required parallel polymer solar battery is obtained.
Accompanying drawing 3 is that (structure is: ITO substrate/PEDOT:PSS/P3HT:PCBM/CsN for the parallel polymer solar battery of preparation of embodiment 1
3: Bphen/P3HT:PCBM/PEDOT:PSS/Al) with the current density of comparative example battery (structure is: ITO substrate/PEDOT:PSS/P3HT:PCBM/LiF/Al) and voltage relationship.
The test of above-mentioned current density and voltage, the model adopting U.S. Keithly company to generate is that 2602 current-voltage testers carry out, and test technology is: be the white light source of simulated solar irradiation with the filter set cooperation of 500W xenon lamp (Osram) and AM 1.5.
As can see from Figure 3, the current density of comparative example solar cell is 5.11mA/cm
2, and the current density of solar cell in the present embodiment has brought up to 7.57mA/cm
2; This explanation, the resistance of the solar cell of this parallel-connection structure reduces, make that two active layers are more effective absorbs sunlight, and the efficiency that n doping makes the efficiency of transmission electrode of electronics collect electronics is obtained for raising, the energy conversion efficiency of solar cell is finally made to obtain enhancing, the energy conversion efficiency of comparative example solar cell is only 1.19%, and the energy conversion efficiency of the present embodiment 1 has brought up to 1.86%.
Table 1 is the corresponding concrete data of curve 1 and curve 2; Wherein curve 1 is the curve of embodiment 1, and curve 2 is the curve of comparative example;
Table 1
| Current density (mA cm-2) | Voltage (V) | η(％) | Fill factor, curve factor | |
| Curve 1 | 7.57 | 0.74 | 1.86 | 0.33 |
| Curve 2 | 5.11 | 0.65 | 1.19 | 0.35 |
Embodiment 2
In the present embodiment, the structure of parallel polymer solar battery is: IZO substrate/PEDOT:PSS/P3HT:PCBM/CsF:PBD/MDMO-PPV:PCBM/PEDOT:PSS/Ag.
The preparation technology of this parallel polymer solar battery is as follows:
1, by IZO substrate (wherein, IZO is anode layer) use liquid detergent successively, deionized water, acetone, ethanol, isopropyl alcohol cleans, and each ultrasonic 15min during cleaning, remove the organic pollution of glass surface, clean up the rear IZO to IZO substrate surface oxygen plasma surface treatment 10min under power is 30W condition;
2, the PEDOT:PSS aqueous solution is prepared in the IZO surface of IZO substrate by the mode of spin coating; Bake drying, obtained thickness is first Hole-injecting Buffer Layer for Improvement of 20nm;
3, P3HT:PCBM toluene solution system is spin-coated on the first Hole-injecting Buffer Layer for Improvement surface, after spin coating is complete, anneal 80min at 200 DEG C, and obtained thickness is first active layer of 300nm; Wherein, in P3HT:PCBM toluene solution system, solvent is toluene, and the total concentration of P3HT and PCBM is the mass ratio of 8mg/ml, P3HT: PCBM is 1: 0.8;
4, be the N-shaped doped layer of 150nm at the first active layer surface evaporation thickness, material is CsF:PBD, and PBD is material of main part, and CsF is dopant material, and doping ratio is 60wt%;
5, spin coating second active layer again on N-shaped doped layer surface: MDMO-PPV:PCBM chloroformic solution system is spin-coated on N-shaped doped layer surface, after spin coating is complete, anneal 5min at 200 DEG C, and obtained thickness is second active layer of 300nm; Wherein, in MDMO-PPV:PCBM chloroformic solution system, solvent is chloroform, and the total concentration of MDMO-PPV and PCBM is the mass ratio of 24mg/ml, P3HT: PCBM is 1: 4;
6, the PEDOT:PSS aqueous solution is prepared in N-shaped doped layer surface by the mode of spin coating; Spin coating post-drying, obtained thickness is second Hole-injecting Buffer Layer for Improvement of 20nm;
7, at the second Hole-injecting Buffer Layer for Improvement surface evaporation anode layer, material is Ag, and thickness is 20nm;
8, after above-mentioned preparation technology completes, required parallel polymer solar battery is obtained.
Embodiment 3
In the present embodiment, the structure of parallel polymer solar battery is:
FTO substrate/PEDOT:PSS/MDMO-PPV:PCBM/LiF:TPBi/MEH-PPV:PCBM/PEDOT:PSS/ Au.
The preparation technology of this parallel polymer solar battery is as follows:
1, by FTO substrate (wherein, FTO is anode layer) use liquid detergent successively, deionized water, acetone, ethanol, isopropyl alcohol cleans, and each ultrasonic 15min during cleaning, remove the organic pollution of glass surface, clean up the rear FTO to FTO substrate surface oxygen plasma surface treatment 5min under power is 50W condition;
2, the PEDOT:PSS aqueous solution is prepared in the FTO surface of FTO substrate by the mode of spin coating; Bake drying, obtained thickness is first Hole-injecting Buffer Layer for Improvement of 80nm;
3, MDMO-PPV:PCBM chlorobenzene solution system is spin-coated on the first Hole-injecting Buffer Layer for Improvement surface, after spin coating is complete, anneal 100min at 50 DEG C, and obtained thickness is first active layer of 120nm; Wherein, in MDMO-PPV:PCBM chlorobenzene solution system, solvent is chlorobenzene, and the total concentration of MDMO-PPV and PCBM is the mass ratio of 30mg/ml, MDMO-PPV: PCBM is 1: 1;
4, be the N-shaped doped layer of 10nm at the first active layer surface evaporation thickness, material is LiF:TPBi, and TPBi is material of main part, and LiF is dopant material, and doping ratio is 10wt%;
5, spin coating second active layer again on N-shaped doped layer surface: be spin-coated on N-shaped doped layer surface by MEH-PPV:PCBM xylene solution system, after spin coating is complete, anneal 100min at 180 DEG C, and obtained thickness is second active layer of 150nm; Wherein, in MEH-PPV:PCBM xylene solution system, solvent is dimethylbenzene, and the total concentration of MEH-PPV and PCBM is the mass ratio of 26mg/ml, MEH-PPV: PCBM is 1: 2;
6, the PEDOT:PSS aqueous solution is prepared in N-shaped doped layer surface by the mode of spin coating; Spin coating post-drying, obtained thickness is second Hole-injecting Buffer Layer for Improvement of 60nm;
7, at the second Hole-injecting Buffer Layer for Improvement surface evaporation anode layer, material is Au, and thickness is 180nm;
8, after above-mentioned preparation technology completes, required parallel polymer solar battery is obtained.
Embodiment 4
In the present embodiment, the structure of parallel polymer solar battery is: AZO substrate/PEDOT:PSS/MEH-PPV:PCBM/Li
2cO
3: TAZ/MEH-PPV:PCBM/PEDOT:PSS/Pt.
The preparation technology of this parallel polymer solar battery is as follows:
1, AZO substrate is used liquid detergent successively, deionized water, acetone, ethanol, isopropyl alcohol cleans, and each ultrasonic 15min during cleaning, remove the organic pollution of glass surface, clean up the rear AZO to AZO substrate surface in UV-ozone treatment 5min;
2, the PEDOT:PSS aqueous solution is prepared in the AZO surface of AZO substrate by the mode of spin coating; Bake drying, obtained thickness is first Hole-injecting Buffer Layer for Improvement of 70nm, then dry process;
3, MEH-PPV:PCBM toluene and xylene solution system are spin-coated on the first Hole-injecting Buffer Layer for Improvement surface, after spin coating is complete, at 25 DEG C, leave standstill 24h, obtained thickness is first active layer of 250nm; Wherein, in MEH-PPV:PCBM toluene and xylene solution system, solvent is toluene and dimethylbenzene, and the total concentration of MEH-PPV and PCBM is the mass ratio of 10mg/ml, MEH-PPV:PCBM is 1: 1;
4, be the N-shaped doped layer of 100nm at the first active layer surface evaporation thickness, material is Li
2cO
3: TAZ, and TAZ is material of main part, Li
2cO
3for dopant material, and doping ratio is 30wt%;
5, spin coating second active layer again on N-shaped doped layer surface: be spin-coated on N-shaped doped layer surface by MEH-PPV:PCBM xylene solution system, after spin coating is complete, anneal 20min at 200 DEG C, and obtained thickness is second active layer of 160nm; Wherein, in MEH-PPV:PCBM xylene solution system, solvent is dimethylbenzene, and the total concentration of MEH-PPV and PCBM is the mass ratio of 15mg/ml, MEH-PPV: PCBM is 1: 3;
6, the PEDOT:PSS aqueous solution is prepared in N-shaped doped layer surface by the mode of spin coating; Spin coating post-drying, obtained thickness is second Hole-injecting Buffer Layer for Improvement of 30nm;
7, at the second Hole-injecting Buffer Layer for Improvement surface evaporation anode layer, material is Pt, and thickness is 50nm;
8, after above-mentioned preparation technology completes, required parallel polymer solar battery is obtained.
Embodiment 5
In the present embodiment, the structure of parallel polymer solar battery is:
ITO substrate/PEDOT:PSS/MDMO-PPV:PCBM/Cs
2cO
3: PBD/MEH-PPV:PCBM/PEDOT:PSS/Al.
The preparation technology of this parallel polymer solar battery is as follows:
1, ITO substrate is used liquid detergent successively, deionized water, acetone, ethanol, isopropyl alcohol cleans, and each ultrasonic 15min during cleaning, remove the organic pollution of glass surface, clean up the rear ITO layer to ITO substrate in UV-ozone treatment 20min;
2, the PEDOT:PSS aqueous solution is prepared in the ITO layer surface of ITO substrate by the mode of spin coating; Bake drying, obtained thickness is first Hole-injecting Buffer Layer for Improvement of 20nm;
3, MDMO-PPV:PCBM chlorobenzene solution system is spin-coated on the first Hole-injecting Buffer Layer for Improvement surface, after spin coating is complete, at 25 DEG C, leave standstill 48h, obtained thickness is first active layer of 100nm; Wherein, in MDMO-PPV:PCBM chlorobenzene solution system, solvent is chlorobenzene, and the total concentration of MDMO-PPV and PCBM is the mass ratio of 8mg/ml, MDMO-PPV: PCBM is 1: 3;
4, be the N-shaped doped layer of 80nm at the first active layer surface evaporation thickness, material is Cs
2cO
3: PBD, and PBD is material of main part, Cs
2cO
3for dopant material, and doping ratio is 50wt%;
5, spin coating second active layer again on N-shaped doped layer surface: be spin-coated on N-shaped doped layer surface by MEH-PPV:PCBM chlorobenzene solution system, after spin coating is complete, anneal 50min at 70 DEG C, and obtained thickness is second active layer of 200nm; Wherein, in MEH-PPV:PCBM chlorobenzene solution system, solvent is chlorobenzene, and the total concentration of MEH-PPV and PCBM is the mass ratio of 24mg/ml, MEH-PPV: PCBM is 1: 4;
6, the PEDOT:PSS aqueous solution is prepared in N-shaped doped layer surface by the mode of spin coating; Spin coating post-drying, obtained thickness is second Hole-injecting Buffer Layer for Improvement of 30nm;
7, at the second Hole-injecting Buffer Layer for Improvement surface evaporation anode layer, material is Ag, and thickness is 250nm;
8, after above-mentioned preparation technology completes, required parallel polymer solar battery is obtained.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. a parallel polymer solar battery, it is characterized in that, this parallel polymer solar battery comprises the anode substrate, the first Hole-injecting Buffer Layer for Improvement, the first active layer, N-shaped doped layer, the second active layer, the second Hole-injecting Buffer Layer for Improvement, the anode layer that stack gradually;
The dopant mixture that the material of described N-shaped doped layer is formed for electron injection material doping electron transport material.
2. parallel polymer solar battery according to claim 1, is characterized in that, described anode substrate is indium tin oxide glass, mixes indium zinc oxide glass, fluorine doped tin oxide glass or Al-Doped ZnO glass.
3. parallel polymer solar battery according to claim 1, is characterized in that, the material of described first Hole-injecting Buffer Layer for Improvement and the second Hole-injecting Buffer Layer for Improvement is respectively the mixture of poly-3,4-ethylenedioxy thiophenes and kayexalate.
4. parallel polymer solar battery according to claim 1, it is characterized in that, the material of described first active layer and the second active layer is poly-3-hexyl thiophene, poly-[2-methoxyl group-5-(3,7. dimethyl octyloxy) phenylenevinylene] or gather the mixture formed after [2-methoxyl group-5-(2 '-vinyl-own oxygen base) is poly-to styrene support] mixes with [6,6]-phenyl-C61-methyl butyrate.
5. parallel polymer solar battery according to claim 4, it is characterized in that, described poly-3-hexyl thiophene and [6,6] in the mixture that-phenyl-C61-methyl butyrate is formed, poly-3-hexyl thiophene is 1:1 ~ 1:0.8 with the mass ratio of [6,6]-phenyl-C61-methyl butyrate;
Described poly-[2-methoxyl group-5-(3,7. dimethyl octyloxy) phenylenevinylene] with [6,6] in the mixture that-phenyl-C61-methyl butyrate is formed, poly-[2-methoxyl group-5-(3,7. dimethyl octyloxy) phenylenevinylene] be 1:4 ~ 1:1 with the mass ratio of [6,6]-phenyl-C61-methyl butyrate;
Described poly-[2-methoxyl group-5-(2 '-vinyl-own oxygen base) is poly-to styrene support] is with [6,6] in the mixture that-phenyl-C61-methyl butyrate is formed, poly-[2-methoxyl group-5-(2 '-vinyl-own oxygen base) is poly-to styrene support] is 1:4 ~ 1:1 with the mass ratio of [6,6]-phenyl-C61-methyl butyrate.
6. parallel polymer solar battery according to claim 1, it is characterized in that, described electron transport material is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, 4,7-diphenyl-1,10-phenanthrolines, 1,2,4-triazole derivative or N-aryl benzimidazole;
Described electron injection material is lithium fluoride, lithium carbonate, cesium carbonate, cesium azide or cesium fluoride.
7. parallel polymer solar battery according to claim 1, is characterized in that, the material of described anode layer is aluminium, silver, gold or platinum.
8. a preparation method for parallel polymer solar battery as claimed in claim 1, is characterized in that, this preparation method comprises the steps:
S1, antianode substrate surface are for subsequent use after carrying out clean, drying;
S2, anode layer surface spin coating first Hole-injecting Buffer Layer for Improvement in anode substrate, again in this Hole-injecting Buffer Layer for Improvement surface spin coating first active layer, subsequently dry process after drying;
S3, the first active layer surface evaporating n type doped layer in drying;
S4, surperficial spin coating second active layer at N-shaped doped layer, subsequently dry process; Then in the second active layer surface spin coating second Hole-injecting Buffer Layer for Improvement, then dry process;
S5, surperficial evaporation anode layer at the second Hole-injecting Buffer Layer for Improvement, obtained described parallel polymer solar battery.
9. the preparation method of parallel polymer solar battery according to claim 8, is characterized in that, the clean in described step S1 comprises:
By anode substrate successively at liquid detergent, deionized water, acetone, ethanol, ultrasonic cleaning in isopropyl alcohol.
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| CN104253214A (en) * | 2013-06-27 | 2014-12-31 | 海洋王照明科技股份有限公司 | Solar cell device and production method thereof |
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| CN108832007B (en) * | 2018-07-04 | 2021-11-02 | 河南师范大学 | Preparation method of perovskite and semiconductor type silicon hybrid solar cell |
| CN110931657A (en) * | 2019-12-06 | 2020-03-27 | 中国乐凯集团有限公司 | Flexible composite substrate for perovskite thin-film solar cell and preparation method thereof |
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