CN102983276A - Polymer solar cell and production method thereof - Google Patents
Polymer solar cell and production method thereof Download PDFInfo
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- CN102983276A CN102983276A CN2011102641425A CN201110264142A CN102983276A CN 102983276 A CN102983276 A CN 102983276A CN 2011102641425 A CN2011102641425 A CN 2011102641425A CN 201110264142 A CN201110264142 A CN 201110264142A CN 102983276 A CN102983276 A CN 102983276A
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Abstract
The invention belongs to the field of solar cells, and discloses a polymer solar cell and a production method of the polymer solar cell. The polymer solar cell comprises an anode substrate, an anode protective layer, a hole buffer layer, an active layer, an electronic buffer layer and a cathode layer, wherein the anode substrate, the anode protective layer, the hole buffer layer, the active layer, the electronic buffer layer and the cathode layer are stacked in sequence. According to the polymer solar cell, the anode protective layer is additionally arranged to isolate the hole buffer layer from an anode layer on the anode substrate. The addition of the anode protective layer can greatly promote flatness of the anode layer and enable distribution of current to be evener, and thus dark spots are prevented from occurring on the anode layer with a rough surface because hole traps occur, and the function of protecting the anode layer is achieved. Meanwhile, metal fluoride can further reduce injection barriers of holes, and therefore injection efficiency of the holes is promoted and attenuation of photoelectric conversion efficiency is effectively reduced.
Description
Technical field
The present invention relates to area of solar cell, relate in particular to a kind of polymer solar battery and preparation side thereof.
Background technology
Nineteen eighty-two, Weinberger etc. have studied the Photovoltaic Properties of polyacetylene, produced first and had truly solar cell, but photoelectric conversion efficiency at that time is extremely low by (10
-3%).And then, Glenis etc. have made the solar cell of various polythiophenes, and the problem that all faced at that time is extremely low open circuit voltage and photoelectric conversion efficiency.Until 1986, C.W.Tang etc. are incorporated into p-type semiconductor and N-shaped semiconductor in the double-deck device first, and just so that photoelectric current has obtained the raising of very big degree, from then on take this work as milestone, organic polymer solar cell is flourish.
Sariciftci in 1992 etc. find 2-methoxyl group-5-(2-ethyl-own oxygen base)-1, there is quick Photoinduced Electron transfer phenomena in 4-benzene second (MEH-PPV) and the compound system, caused people's very big interest, and in nineteen ninety-five, the usefulness MEH-PPV such as Yu mix as active layer with C60 derivative PCBM and have prepared organic polymer bulk heterojunction solar cell.Solar cell is at 20mW/cm
2, 430nm monochromatic light irradiation lower, energy conversion efficiency is 2.9%.This is first body heterojunction solar cell based on polymeric material and the preparation of PCBM acceptor, and has proposed the concept of inierpeneirating network structure in the composite membrane.So far, the application of body heterojunction structure in polymer solar battery obtained rapidly development.This structure also becomes the organic polymer solar cell structure that present people generally adopt.
The operation principle of polymer solar battery mainly is 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.At first, conjugated polymer absorbs photon under the incident light irradiation, electronics transits to lowest unoccupied molecular orbital (LUMO) from polymer highest occupied molecular orbital (HOMO), form exciton, exciton is diffused under the effect of internal electric field to body/acceptor and is separated at the interface electronics and the hole that moves freely, then electronics transmits and is collected by negative electrode in mutually at acceptor, and the hole is then by collecting to the body phase and by anode, thereby produces photoelectric current; This has just formed an effective photoelectric conversion process.
In polymer solar battery, inject and transmittability in order to improve the hole, often achieve the goal at the upper spin coating one deck Hole-injecting Buffer Layer for Improvement of anode conducting film substrate (common used material is ito glass), the material of this Hole-injecting Buffer Layer for Improvement is often by poly-3, the composite material that 4-dioxy ethene thiophene (PEDOT) and poly-P-TOLUENE SULFO ACID 99's salt (PSS) form, the energy level of this material and stability all relatively are suitable as hole-injecting material, can reduce the hole and be injected into the HOMO energy level potential barrier (hole is to inject and transmit by the HOMO energy level) of ITO at active layer, be conducive to improve the photoelectric conversion efficiency of polymer solar battery.But it is acid that the composite material that this PEDOT:PSS forms is, and the antianode conductive film has certain corrosiveness, thereby affects the stability of polymer solar battery, accelerates the photoelectric conversion efficiency decay of polymer solar battery.
Summary of the invention
The object of the present invention is to provide a kind of polymer solar battery that can protect anode layer, reduce the photoelectric conversion efficiency decay.
A kind of polymer solar battery, it comprises anode substrate, anodic coating, Hole-injecting Buffer Layer for Improvement, active layer, electron buffer layer and the cathode layer that stacks gradually.
In the described polymer solar battery, the material of each functional layer is as follows:
Described anode substrate is selected from indium tin oxide glass (ITO), fluorine doped tin oxide glass (FTO), Al-Doped ZnO glass (AZO) or mixes indium zinc oxide glass (IZO);
The material of described anodic coating is selected from magnesium fluoride (MgF
2), calcirm-fluoride (CaF
2), cesium fluoride (CsF), aluminum fluoride (AlF
3) and sodium fluoride (NaF) at least a;
The material of described Hole-injecting Buffer Layer for Improvement is that weight ratio is 2: 1～6: 1 poly-3,4-dioxy ethene thiophene (PEDOT) and the composite material of poly-P-TOLUENE SULFO ACID 99's salt (PSS) composition, i.e. PEDOT:PSS;
The material of described active layer is selected from P3HT:PCBM, MDMO-PPV:PCBM or MEH-PPV:PCBM;
The material of described electron buffer layer is selected from lithium fluoride (LiF), lithium carbonate (Li
2CO
3), cesium carbonate (Cs
2CO
3), nitrogenize caesium (CsN
3), at least a in lithium chloride (LiCl), lithium iodide (LiI) and the lithium bromide (LiBr);
The material of described cathode layer is selected from least a in aluminium (Al), silver (Ag), calcium (Ca), copper (Cu), gold (Au) and the platinum (Pt).
Another object of the present invention is to provide the preparation method of above-mentioned polymer solar battery, comprise the steps:
S1, anode purge substrate are carried out surface treatment to the anode layer surface of described anode substrate subsequently;
S2, through surface-treated described anode layer surface evaporation anodic coating; Wherein, the material of described anodic coating is metal fluoride;
S3, at described anodic coating surface spin coating Hole-injecting Buffer Layer for Improvement, carry out subsequently drying and processing;
S4, at described Hole-injecting Buffer Layer for Improvement surface spin coating active layer, carry out subsequently drying processing;
S5, in the surperficial evaporation electron buffer layer of described active layer;
S6, at described electron buffer layer surface evaporation cathode layer;
After above-mentioned processing step is finished, make described polymer solar battery.
Among the above-mentioned preparation method, among the step S1, the clean of anode substrate comprises: use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol, remove the organic pollution of glass surface.
Among the above-mentioned preparation method, among the step S4, described dry the processing comprises: in the inert atmosphere, under 50～200 ℃, described active layer is carried out annealing in process 10～100min; Perhaps under the room temperature 24～48h is processed in described active layer placement.
Polymer solar battery of the present invention by increasing anodic coating, is isolated the anode layer on Hole-injecting Buffer Layer for Improvement and the anode substrate; The adding of this anodic coating can greatly improve the evenness of anode layer, makes being more evenly distributed of electric current, thereby can avoid shaggy anode layer to produce dim spot because hole trap occurring, reaches the effect of protection anode layer; Simultaneously, anodic coating can further reduce the injection barrier in hole, and the injection efficiency in hole is improved, and has effectively reduced the decay of photoelectric conversion efficiency.
Description of drawings
Fig. 1 is the structural representation of polymer solar battery of the present invention;
Fig. 2 is preparation technology's flow chart of polymer solar battery of the present invention;
Fig. 3 is current density and the voltage curve figure that does not add the polymer solar battery of anodic coating in the polymer solar battery of embodiment 1 and the Comparative Examples.
Embodiment
A kind of polymer solar battery provided by the invention, as shown in Figure 1, it comprises anode substrate 11, anodic coating 12, Hole-injecting Buffer Layer for Improvement 13, active layer 14, electron buffer layer 15 and the cathode layer 16 that stacks gradually.
In the described polymer solar battery:
11 ends of described anode base, are selected from indium tin oxide glass (ITO), fluorine doped tin oxide glass (FTO), Al-Doped ZnO glass (AZO) or mix indium zinc oxide glass (IZO); In these anode substrate, substrate is glass, and anode layer is respectively indium tin oxide, fluorine doped tin oxide, Al-Doped ZnO, mixes indium zinc oxide;
The material of described anodic coating 12 is metal fluoride, as, magnesium fluoride (MgF
2), calcirm-fluoride (CaF
2), cesium fluoride (CsF), aluminum fluoride (AlF
3) and sodium fluoride (NaF) at least a; The thickness of described anodic coating 12 is 0.4～5nm;
The material of described Hole-injecting Buffer Layer for Improvement 13 is that weight ratio is 2: 1～6: 1 PEDOT: PSS; The thickness of described Hole-injecting Buffer Layer for Improvement is 20～80nm; Wherein, PEDOT is poly-3,4-ethylenedioxy thiophene, and PSS is kayexalate;
The material of described active layer 14 is selected from P3HT:PCBM, MDMO-PPV:PCBM or MEH-PPV:PCBM; The thickness of described active layer is 80～300nm; Wherein, [2-methoxyl group-5-(3 in order to gather for poly-3-hexyl thiophene, MDMO-PPV for P3HT, 7. dimethyl octyloxy) phenylenevinylene], MEH-PPV is poly-[2-methoxyl group-5-(2 '-vinyl-own oxygen base) is poly-to the styrene support], and PCBM is [6,6]-phenyl-C61-methyl butyrate;
The material of described electron buffer layer 15 is selected from lithium fluoride (LiF), lithium carbonate (Li
2CO
3), cesium carbonate (Cs
2CO
3), nitrogenize caesium (CsN
3), at least a in lithium chloride (LiCl), lithium iodide (LiI) and the lithium bromide (LiBr); The thickness of described electron buffer layer is 0.5～10nm; In the described electron buffer layer, the preferred LiF of material, the preferred 0.7nm of thickness;
The material of described cathode layer 16 is selected from least a in aluminium (Al), silver (Ag), calcium (Ca), copper (Cu), gold (Au) and the platinum (Pt); The thickness of described cathode layer is 80～200nm; In the described cathode layer, the preferred Al of material, the preferred 150nm of thickness.
The preparation method of above-mentioned polymer solar battery as shown in Figure 2, comprises the steps:
S1, first anode substrate is carried out photoetching treatment, be cut into needed size;
S2, use liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning anode substrate 15min of isopropyl alcohol successively, remove the organic pollution of glass surface;
S3, surface treatment is carried out on the anode layer surface of described anode substrate, as, power is oxygen plasma treatment 5～15min under 10～50W condition; Perhaps UV-ozone treatment 5～20min;
S4, through the described anode layer of step S3 surface-treated surface evaporation anodic coating; Wherein, the material of described anodic coating is metal fluoride;
S5, revolve the surface at anodic coating and be coated with Hole-injecting Buffer Layer for Improvement, carry out subsequently drying and processing;
S6, at the surperficial spin coating active layer of described Hole-injecting Buffer Layer for Improvement, carry out subsequently drying and process;
S7, stack gradually the evaporation electron buffer layer on the surface of described active layer;
S8, at electron buffer layer surface evaporation cathode layer;
After above-mentioned processing step is finished, make described polymer solar battery.
Among the above-mentioned preparation method, among the step S5, in the spin coating proceeding of described Hole-injecting Buffer Layer for Improvement:
The mode of the PEDOT:PSS aqueous solution by spin coating prepared anode layer surface in anode substrate, and control thickness makes Hole-injecting Buffer Layer for Improvement at 20～80nm; After the Hole-injecting Buffer Layer for Improvement spin coating is complete, process 15～60min at 100～200 ℃ of lower heating, dryings; Preferably, 200 ℃ of heating, drying treatment temperatures, heating, drying processing time 30min; Wherein, in the PEDOT:PSS aqueous solution, PEDOT:PSS is solute, and its mass percent is 1～5%, and the weight ratio of PEDOT: PSS is 2: 1～6: 1; Preferably, the weight ratio of PEDOT: PSS is 6: 1, and the mass percent of PEDOT: PSS is 1.3%, and thickness is 40nm.
Among the above-mentioned preparation method, among the step S6, in the spin coating proceeding of described active layer:
P3HT:PCBM, MDMO-PPV:PCBM or MEH-PPV:PCBM solution system are spin-coated on the surface of described Hole-injecting Buffer Layer for Improvement; Subsequently, in the inert atmosphere, under 50～200 ℃, described active layer is carried out annealing in process 10～100min, perhaps under the room temperature described active layer is placed processing 24～48h, make dry active layer; Wherein:
In P3HT:PCBM, MDMO-PPV:PCBM or MEH-PPV:PCBM solution system, solute is respectively P3HT:PCBM, MDMO-PPV:PCBM or MEH-PPV:PCBM, solvent is one or both mixed solvents of toluene, dimethylbenzene, chlorobenzene or chloroform, and the total concentration of solute P3HT:PCBM, MDMO-PPV:PCBM or MEH-PPV:PCBM is controlled at 8～30mg/ml;
When the material of active layer is selected from the P3HT:PCBM solution system, the mass ratio of P3HT: PCBM is controlled at 1: 0.8～1: 1 scope;
When the material of active layer is selected from MDMO-PPV:PCBM or MEH-PPV:PCBM solution system, the mass ratio of MDMO-PPV:PCBM or MEH-PPV: PCBM is controlled at 1: 1～1: 4 scope.
Polymer solar battery of the present invention by increasing the anodic coating of metal fluoride, is isolated the anode layer on Hole-injecting Buffer Layer for Improvement and the anode substrate; The adding of this anodic coating can greatly improve the evenness of anode layer, makes being more evenly distributed of electric current, thereby can avoid shaggy anode layer to produce dim spot because hole trap occurring, reaches the effect of protection anode layer; Simultaneously, this metal fluoride can further reduce the injection barrier in hole, and the injection efficiency in hole is improved, and has effectively reduced the decay of photoelectric conversion efficiency.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The structure of the polymer solar battery in the present embodiment 1 is: ITO/MgF/PEDOT:PSS/P3HT:PCBM/LiF/Al.
The step of preparation process of this polymer solar battery is as follows:
1, first ITO is carried out photoetching treatment, be cut into needed size;
2, the ITO that step 1 is obtained uses liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol successively, removes the organic pollution of glass surface;
3, be under the 30W condition at power, the surface treatment of oxygen plasma 5min is carried out on the anode layer surface of the ITO that cleans up;
4, through surface-treated anode layer surface evaporation anodic coating: material is MgF, and thickness is 1.5nm;
5, at described anodic coating surface spin coating Hole-injecting Buffer Layer for Improvement: material is the PEDOT:PSS aqueous solution, the weight ratio of PEDOT: PSS is 6: 1, the mass percent of PEDOT: PSS is 1.3%, behind the spin coating PEDOT:PSS aqueous solution, in 200 ℃ of lower heating 30min, the thickness of control Hole-injecting Buffer Layer for Improvement is 40nm;
6, at the surperficial spin coating active layer of Hole-injecting Buffer Layer for Improvement: material is the toluene solution system of P3HT:PCBM, P3HT: the PCBM mass ratio is 1: 1, and the total concentration of P3HT:PCBM is 24mg/ml; Active layer is to carry out spin coating to finish in being full of the glove box of inert gas, and after spin coating finished, active layer needed at 150 ℃ of lower annealing 15min, and control active layer thickness is 140nm;
7, in described active layer surface evaporation electron buffer layer: material is LiF, and thickness is 0.7nm;
8, then at electron buffer layer surface evaporation cathode layer: material is Al, and thickness is 150nm;
Above-mentioned technique obtains needed polymer solar battery after finishing.
Fig. 3 is current density and the voltage curve figure that does not add the polymer solar battery of anodic coating in the polymer solar battery of embodiment 1 and the Comparative Examples; Wherein, curve 1 is the current density voltage curve of the polymer solar battery of embodiment 1, and (its structure is curve 2: current density voltage curve ITO/PEDOT:PSS/P3HT:PCBM/LiF/A) for the polymer solar battery that does not add anodic coating in the Comparative Examples.As shown in Figure 3, under different voltages, all than the height of Comparative Examples, under the voltage of 0.6V, the current density of embodiment 1 is 3.19mAcm to the current density of embodiment 1
-2, and Comparative Examples only is 1.35mAcm
-2, under the voltage of 0.3V, the current density of embodiment is increased to 6.17mAcm
-2, and that Comparative Examples only is 3.89mAcm
-2Therefore, polymer solar battery has added after metal fluoride (MgF) anodic coating, and metal fluoride can make hole injection barrier reduce, and the short circuit current of polymer solar battery increases.
The photoelectric current test data of embodiment 1 and Comparative Examples, as shown in table 1
Table 1
| Current density (mAcm -2) | Voltage (V) | Efficient (%) | Fill factor, curve factor | |
| Embodiment 1 | 8.00 | 0.73 | 2.10 | 0.36 |
| Comparative Examples | 6.32 | 0.70 | 1.43 | 0.32 |
The polymer solar battery that adds metal fluoride has improved the stability of polymer solar battery, has reduced simultaneously the trap in hole, and electric charge and hole are more collected by electrode, has improved current density, and current density is from 6.32mAcm
-2Brought up to 8mAcm
-2, also reduced the potential barrier of hole transport, finally make the energy conversion efficiency of polymer solar battery obtain enhancing, the efficient of device has reached 2.1%.
Polymer solar battery structure in the present embodiment 2 is: ITO/MgF/PEDOT:PSS/P3HT:PCBM/Li
2CO
3/ Ag.
The step of preparation process of this polymer solar battery is as follows:
1, first ITO is carried out photoetching treatment, be cut into needed size;
2, the ITO that step 1 is obtained uses liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol successively, removes the organic pollution of glass surface;
3, be under the 15W condition at power, the surface treatment of oxygen plasma 5min is carried out on the anode layer surface of the ITO that cleans up;
4, through surface-treated anode layer surface evaporation anodic coating: material is MgF, and thickness is 0.4nm;
5, at described anodic coating surface spin coating Hole-injecting Buffer Layer for Improvement: material is the PEDOT:PSS aqueous solution, the weight ratio of PEDOT: PSS is 2: 1, the mass percent of PEDOT: PSS is 5%, behind the spin coating PEDOT:PSS aqueous solution, in 200 ℃ of lower heating 30min, the thickness of control Hole-injecting Buffer Layer for Improvement is 60nm;
6, at the surperficial spin coating active layer of Hole-injecting Buffer Layer for Improvement: material is toluene and the chloroformic solution system of MEH-PPV:PCBM, and MEH-PPV: the PCBM mass ratio is 1: 1, and the total concentration of MEH-PPV:PCBM is 30mg/ml; Active layer is to carry out spin coating to finish in being full of the glove box of inert gas, and after spin coating finished, active layer needed at 200 ℃ of lower annealing 10min, and control active layer thickness is 300nm;
7, in described active layer surface evaporation electron buffer layer: material is Li
2CO
3, thickness is 10nm;
8, then at electron buffer layer surface evaporation cathode layer: material is Ag, and thickness is 150nm;
Above-mentioned technique obtains needed polymer solar battery after finishing.
Embodiment 3
Polymer solar battery structure in the present embodiment 3 is: AZO/CaF
2/ PEDOT:PSS/P3HT:PCBM/CsF/Ag.
The step of preparation process of this polymer solar battery is as follows:
1, first AZO is carried out photoetching treatment, be cut into needed size;
2, the AZO that step 1 is obtained uses liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol successively, removes the organic pollution of glass surface;
3, carry out the UV-ozone surface treatment of 10min on the anode layer surface of the AZO that cleans up;
4, through surface-treated anode layer surface evaporation anodic coating: material is CaF
2, thickness is 0.4nm;
5, at described anodic coating surface spin coating Hole-injecting Buffer Layer for Improvement: material is the PEDOT:PSS aqueous solution, the weight ratio of PEDOT: PSS is 3: 1, the mass percent of PEDOT: PSS is 1%, behind the spin coating PEDOT:PSS aqueous solution, in 120 ℃ of lower heating 50min, the thickness of control Hole-injecting Buffer Layer for Improvement is 20nm;
6, at the surperficial spin coating active layer of Hole-injecting Buffer Layer for Improvement: material is the chloroformic solution system of P3HT:PCBM, P3HT: the PCBM mass ratio is 1: 4, and the total concentration of P3HT:PCBM is 8mg/ml; Active layer is to carry out spin coating to finish in being full of the glove box of inert gas, and after spin coating finished, active layer needed at 50 ℃ of lower annealing 100min, and control active layer thickness is 80nm;
7, in described active layer surface evaporation electron buffer layer: material is CsF, and thickness is 7nm;
8, then at electron buffer layer surface evaporation cathode layer: material is Ag, and thickness is 80nm;
Above-mentioned technique obtains needed polymer solar battery after finishing.
Embodiment 4
Polymer solar battery structure in the present embodiment 4 is: ITO/CsF/PEDOT:PSS/P3HT:PCBM/LiCl/Au.
The step of preparation process of this polymer solar battery is as follows:
1, first ITO is carried out photoetching treatment, be cut into needed size;
2, the ITO that step 1 is obtained uses liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol successively, removes the organic pollution of glass surface;
3, be under the 10W condition at power, the surface treatment of oxygen plasma 15min is carried out on the anode layer surface of the ITO that cleans up;
4, through surface-treated anode layer surface evaporation anodic coating: material is CsF, and thickness is 0.4nm;
5, at described anodic coating surface spin coating Hole-injecting Buffer Layer for Improvement: material is the PEDOT:PSS aqueous solution, the weight ratio of PEDOT: PSS is 4: 1, the mass percent of PEDOT: PSS is 2.5%, behind the spin coating PEDOT:PSS aqueous solution, in 180 ℃ of lower heating 25min, the thickness of control Hole-injecting Buffer Layer for Improvement is 80nm;
6, at the surperficial spin coating active layer of Hole-injecting Buffer Layer for Improvement: material is the xylene solution system of MDMO-PPV:PCBM, MDMO-PPV: the PCBM mass ratio is 1: 1, and the total concentration of MDMO-PPV:PCBM is 12mg/ml; Active layer is to carry out spin coating to finish in being full of the glove box of inert gas, and after spin coating finished, active layer needed at 150 ℃ of lower annealing 50min, and control active layer thickness is 100nm;
7, in described active layer surface evaporation electron buffer layer: material is LiCl, and thickness is 5nm;
8, then at electron buffer layer surface evaporation cathode layer: material is Au, and thickness is 200nm;
Above-mentioned technique obtains needed polymer solar battery after finishing.
Embodiment 5
Polymer solar battery structure in the present embodiment 5 is: IZO/NaF/PEDOT:PSS/MDMO-PPV:PCBM/LiCl/Au.
The step of preparation process of this polymer solar battery is as follows:
1, first IZO is carried out photoetching treatment, be cut into needed size;
2, the IZO that step 1 is obtained uses liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol successively, removes the organic pollution of glass surface;
3, carry out the UV-ozone surface treatment of 15min on the anode layer surface of the IZO that cleans up;
4, through surface-treated anode layer surface evaporation anodic coating: material is NaF, and thickness is 5nm;
5, at described anodic coating surface spin coating Hole-injecting Buffer Layer for Improvement: material is the PEDOT:PSS aqueous solution, the weight ratio of PEDOT: PSS is 5: 1, the mass percent of PEDOT: PSS is 5%, behind the spin coating PEDOT:PSS aqueous solution, in 150 ℃ of lower heating 30min, the thickness of control Hole-injecting Buffer Layer for Improvement is 60nm;
6, at the surperficial spin coating active layer of Hole-injecting Buffer Layer for Improvement: material is the chlorobenzene solution system of MDMO-PPV:PCBM, MDMO-PPV: the PCBM mass ratio is 1: 4, and the total concentration of MDMO-PPV:PCBM is 24mg/ml; Active layer is to carry out spin coating to finish in being full of the glove box of inert gas, and after spin coating finished, active layer needed at 70 ℃ of lower annealing 30min, and control active layer thickness is 150nm;
7, in described active layer surface evaporation electron buffer layer: material is LiCl, and thickness is 5nm;
8, then at electron buffer layer surface evaporation cathode layer: material is Au, and thickness is 200nm;
Above-mentioned technique obtains needed polymer solar battery after finishing.
Polymer solar battery structure in the present embodiment 6 is: FTO/AlF
3/ PEDOT:PSS/MEH-PPV:PCBM/LiI/Pt.
The step of preparation process of this polymer solar battery is as follows:
1, first FTO is carried out photoetching treatment, be cut into needed size;
2, the FTO that step 1 is obtained uses liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol successively, removes the organic pollution of glass surface;
3, be 10W at power, the surface treatment of oxygen plasma 15min is carried out on the anode layer surface of the FTO that cleans up;
4, through surface-treated anode layer surface evaporation anodic coating: material is AlF
3, thickness is 2nm;
5, at described anodic coating surface spin coating Hole-injecting Buffer Layer for Improvement: material is the PEDOT:PSS aqueous solution, the weight ratio of PEDOT: PSS is 2: 1, the mass percent of PEDOT: PSS is 1.5%, behind the spin coating PEDOT:PSS aqueous solution, in 200 ℃ of lower heating 15min, the thickness of control Hole-injecting Buffer Layer for Improvement is 70nm;
6, at the surperficial spin coating active layer of Hole-injecting Buffer Layer for Improvement: material is the chlorobenzene solution system of MEH-PPV:PCBM, MEH-PPV: the PCBM mass ratio is 1: 4, and the total concentration of MEH-PPV:PCBM is 12mg/ml; Active layer is to carry out spin coating to finish in being full of the glove box of inert gas, and after spin coating finished, active layer needs at room temperature to place processed 48h, and control active layer thickness is 200nm;
7, in described active layer surface evaporation electron buffer layer: material is LiI, and thickness is 0.7nm;
8, then at electron buffer layer surface evaporation cathode layer: material is Pt, and thickness is 100nm;
Above-mentioned technique obtains needed polymer solar battery after finishing.
Embodiment 7
Polymer solar battery structure in the present embodiment 7 is: ITO/NaF/PEDOT:PSS/MDMO-PPV:PCBM/LiBr/Cu.
The step of preparation process of this polymer solar battery is as follows:
1, first ITO is carried out photoetching treatment, be cut into needed size;
2, the ITO that step 1 is obtained uses liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol successively, removes the organic pollution of glass surface;
3, carry out the UV-ozone surface treatment of 15min on the anode layer surface of the ITO that cleans up;
4, the surface of the anode layer after described surface treatment evaporation anodic coating: material is NaF, and thickness is 2nm;
5, at described anodic coating surface spin coating Hole-injecting Buffer Layer for Improvement: material is the PEDOT:PSS aqueous solution, the weight ratio of PEDOT: PSS is 2: 1, the mass percent of PEDOT: PSS is 5%, behind the spin coating PEDOT:PSS aqueous solution, in 100 ℃ of lower heating 60min, the thickness of control Hole-injecting Buffer Layer for Improvement is 60nm;
6, at the surperficial spin coating active layer of Hole-injecting Buffer Layer for Improvement: material is chlorobenzene and the xylene solution system of MDMO-PPV:PCBM, and MDMO-PPV: the PCBM mass ratio is 1: 1, and the total concentration of MDMO-PPV:PCBM is 10mg/ml; Active layer is to carry out spin coating to finish in being full of the glove box of inert gas, and after spin coating finished, active layer needs at room temperature to place processed 24h, and control active layer thickness is 80nm;
7, in described active layer surface evaporation electron buffer layer: material is LiBr, and thickness is 8nm;
8, then at electron buffer layer surface evaporation cathode layer: material is Cu, and thickness is 100nm;
Above-mentioned technique obtains needed polymer solar battery after finishing.
Should be understood that above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore 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 (10)
1. a polymer solar battery is characterized in that, it comprises anode substrate, anodic coating, Hole-injecting Buffer Layer for Improvement, active layer, electron buffer layer and the cathode layer that stacks gradually.
2. polymer solar battery according to claim 1 is characterized in that, described anode substrate is selected from indium tin oxide glass, fluorine doped tin oxide glass, Al-Doped ZnO glass or mixes indium zinc oxide glass.
3. polymer solar battery according to claim 1 is characterized in that, the material of described anodic coating is selected from least a in magnesium fluoride, calcirm-fluoride, cesium fluoride, aluminum fluoride and the sodium fluoride.
4. polymer solar battery according to claim 1 is characterized in that, the material of described Hole-injecting Buffer Layer for Improvement is that weight ratio is 2: 1～6: 1 poly-3,4-dioxy ethene thiophene and the composite material of poly-P-TOLUENE SULFO ACID 99's salt composition.
5. polymer solar battery according to claim 1 is characterized in that, the material of described active layer is selected from P3HT:PCBM, MDMO-PPV:PCBM or MEH-PPV:PCBM.
6. polymer solar battery according to claim 1 is characterized in that, the material of described electron buffer layer is selected from least a in lithium fluoride, lithium carbonate, cesium carbonate, nitrogenize caesium, lithium chloride, lithium iodide and the lithium bromide.
7. polymer solar battery according to claim 1 is characterized in that, the material of described cathode layer is selected from least a in aluminium, silver, calcium, copper, gold and the platinum.
8. the preparation method of a polymer solar battery is characterized in that, comprises the steps:
S1, anode purge substrate are carried out surface treatment to the anode layer surface of described anode substrate subsequently;
S2, through surface-treated described anode layer surface evaporation anodic coating;
S3, at described anodic coating surface spin coating Hole-injecting Buffer Layer for Improvement, carry out subsequently drying and processing;
S4, at described Hole-injecting Buffer Layer for Improvement surface spin coating active layer, carry out subsequently drying processing;
S5, in the surperficial evaporation electron buffer layer of described active layer;
S6, at described electron buffer layer surface evaporation cathode layer;
After above-mentioned processing step is finished, make described polymer solar battery.
9. the preparation method of polymer solar battery according to claim 8 is characterized in that, among the described step S1, the clean of described anode substrate comprises: use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic cleaning 15min of isopropyl alcohol.
10. the preparation method of polymer solar battery according to claim 8 is characterized in that, among the described step S4, described dry the processing comprises: in the inert atmosphere, under 50～200 ℃, described active layer is carried out annealing in process 10～100min; Perhaps under the room temperature 24～48h is processed in described active layer placement.
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| CN109148691A (en) * | 2018-09-06 | 2019-01-04 | 西安理工大学 | A kind of low-voltage multiplication type colour organic photodetector and preparation method thereof |
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