CN103928613A - Polymer solar cell and preparation method thereof - Google Patents
Polymer solar cell and preparation method thereof Download PDFInfo
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- CN103928613A CN103928613A CN201310016144.1A CN201310016144A CN103928613A CN 103928613 A CN103928613 A CN 103928613A CN 201310016144 A CN201310016144 A CN 201310016144A CN 103928613 A CN103928613 A CN 103928613A
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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
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
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- H—ELECTRICITY
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Abstract
The invention provides a polymer solar cell and a preparation method of the polymer solar cell. The polymer solar cell comprises a positive electrode substrate, a hole buffer layer, an active layer, an electrode transfer layer, an electron buffer layer and a negative electrode, wherein the positive electrode substrate, the hole buffer layer, the active layer, the electrode transfer layer, the electron buffer layer and the negative electrode are arranged in a laminated mode in sequence.. The electron transfer layer is made of acetate. The acetate is zinc acetate or lime acetate or sodium acetate or magnesium acetate. The electron transfer layer is of a nanometer net structure. The bore diameter of the nanometer net structure ranges from 100 nm to 150 nm. The electron transfer layer is prepared by mixing acetate and an azo type material. After the azo type material decomposes, the nanometer net structure of the electron transfer layer is formed, so that the contact area between the electron transfer layer and the active layer is increased; in addition, nano-particles are evenly separated out from acetate, so that the electron transfer efficiency and the photoelectric conversion efficiency of the polymer solar cell are improved. The preparation method is simple, easy to implement, and suitable for industrial application.
Description
Technical field
The present invention relates to area of solar cell, particularly relate to a kind of polymer solar battery and preparation method thereof.
Background technology
Nineteen eighty-two, Weinberger etc. have studied the Photovoltaic Properties of polyacetylene, produced first and had solar cell truly, but its photoelectric conversion efficiency is extremely low by (10
-3%).And then, Glenis etc. have made the solar cell of various polythiophenes, also face the extremely low and low problem of photoelectric conversion efficiency of the open circuit voltage of battery.Until 1986, C.W.Tang etc. introduce p-type semiconductor and N-shaped semiconductor in double-deck device first, make photoelectric current obtain the raising of very big degree, and as milestone, organic polymer solar cell is flourish.
The general principle of polymer solar battery is to utilize light to incide near the photovoltaic effect producing semi-conductive heterojunction or metal semiconductor interface, this effect is that the electron hole pair that optical excitation produces is that the electrostatic potential energy that exciton is caused by various factors separates the phenomenon that produces electromotive force, in the time that light incides light-sensitive material, light-sensitive material is excited and produces electronics and hole pair, under the effect of solar cell internal electric field, separate and transmission, then collected by electrode separately, electronics is to movable cathode, hole anode moves, and forms electric current.
At present, the conversion efficiency of polymer solar battery is lower, for improving energy conversion efficiency, the improvement of battery material and the optimization of device architecture are two main paties, be included between electrode and organic layer and increase resilient coating, can reduce the cancellation rate of photoproduction exciton at organic layer and electrode interface place, make photoproduction exciton fully be separated into electronics and hole, and raising transmission rate separately, thereby improve the collection efficiency of electric charge at electrode place, the photoelectric conversion efficiency of polymer solar battery is improved.Wherein, electron buffer layer generally adopts the method preparation of evaporation, thinner thickness, conventionally be less than 1nm, and evaporation speed is calculated with microsecond, if control excessively in technique, make thickness excessive, can cause the impedance of electron buffer layer to increase, electric transmission is obstructed, and if in technique, control not, thickness is excessively thin, almost cannot form film, there is large-area electronic defects in electron buffer layer, does not have barrier effect, and electric transmission efficiency also can reduce, the preparation technology's control difficulty that is electron buffer layer is large, is to cause one of reason that the transformation efficiency of device is low.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of polymer solar battery and preparation method thereof.Polymer solar battery of the present invention comprises the electron transfer layer that material is acetate, by dry after the mixed solution spin coating of acetate and azo material, in dry, azo material decomposes, obtain having the electron transfer layer of Nanostructure Network, effective contact area between this electron transfer layer and active layer increases, can improve electric transmission efficiency, acetate is N-shaped material simultaneously, electric transmission efficiency is high, and its nano particle diameter is larger, light is had to reflex, can improve the extinction efficiency of active layer and the photoelectric conversion efficiency of battery.
First aspect, the invention provides a kind of polymer solar battery, comprise the anode substrate, Hole-injecting Buffer Layer for Improvement, active layer, electron transfer layer, electron buffer layer and the negative electrode that stack gradually, the material of described electron transfer layer is acetate, described acetate is zinc acetate, calcium acetate, sodium acetate or magnesium acetate, described electron transfer layer is Nanostructure Network, and the aperture of described Nanostructure Network is 100nm～150nm.
In described polymer solar battery, the material of electron transfer layer is acetate, by dry after the mixed solution spin coating of acetate and azo material, when dry, azo material decomposes, acetate is separated out simultaneously, make the electron transfer layer obtaining there is Nanostructure Network, can increase the effective contact area between electron transfer layer and active layer, improve electric transmission efficiency, acetate in electron transfer layer is finely dispersed nano particle simultaneously, particle diameter is larger, light is had to reflex, thereby improve the extinction efficiency of active layer and the photoelectric conversion efficiency of battery.
Described acetate is that electron transport material is the salt that metal oxide forms, and the particle diameter of described acetate is 5nm～20nm.
Preferably, described anode substrate is the glass with anode functional layer, for indium tin oxide glass (ITO), fluorine doped tin oxide glass (FTO), mix the zinc oxide glass (AZO) of aluminium or mix the zinc oxide glass (IZO) of indium.Anode substrate is to buy on market, uniform specification, and anode function layer thickness is 80～250nm.
Preferably, the material of described Hole-injecting Buffer Layer for Improvement is the mixture of poly-3,4-dioxy ethene thiophene (PEDOT) and polystyrolsulfon acid (PSS).
Preferably, the weight ratio of described PEDOT:PSS is 2:1 ~ 6:1.More preferably, the weight ratio of described PEDOT:PSS is 6:1.
Preferably, the material of described active layer is poly-3-hexyl thiophene (P3HT) and the mixture of PCBM.P3HT, for poly-3-hexyl thiophene, is conventional hole mobile material, and PCBM is (6,6)-phenyl-C61-methyl butyrate, and molecular formula is C
72h
14o
2, be the derivative of C60, be conventional electron transport material.
Preferably, described poly-3-hexyl thiophene (P3HT): the weight ratio of PCBM is 1:0.5 ~ 1:3.More preferably, described poly-3-hexyl thiophene (P3HT): the weight ratio of PCBM is 1:0.8.
Preferably, the thickness of described active layer is 80 ~ 300nm.More preferably, the thickness of described active layer is 200nm.
Preferably, the material of described electron buffer layer is lithium fluoride (LiF), lithium carbonate (Li
2cO
3) or cesium carbonate (Cs
2cO
3).More preferably, the material of described electron buffer layer is Cs
2cO
3.
Preferably, the thickness of described electron buffer layer is 0.5 ~ 10nm.More preferably, the thickness of described electron buffer layer is 5nm.
Preferably, described negative electrode is aluminium (Al), silver (Ag), gold (Au) or platinum (Pt).More preferably, described negative electrode is aluminium (Al).
Preferably, the thickness of described negative electrode is 80 ~ 200nm.More preferably, described cathode thickness is 150nm.
Second aspect, the invention provides a kind of preparation method of polymer solar battery, comprises the following steps:
Get the anode substrate after cleaning up, carry out after preliminary treatment spin coating in anode substrate and prepare Hole-injecting Buffer Layer for Improvement;
On Hole-injecting Buffer Layer for Improvement, active layer is prepared in spin coating;
Then on active layer, prepare electron transfer layer, concrete operations are: after acetate is added to the water to dissolving, obtain acetate solution, then azo material is mixed with acetate solution, obtain mixed solution, mixed solution described in spin coating on active layer, then at 100～200 DEG C of dry 10～70min, prepare electron transfer layer; Described azo material is azo-bis-isobutyrate hydrochloride (AIBA), azo two isobutyl imidazoline salt hydrochlorates (AIBI) or azo isobutyl cyano group formamide (V30); Described acetate is zinc acetate, calcium acetate, sodium acetate or magnesium acetate; Described electron transfer layer has Nanostructure Network, and the aperture of Nanostructure Network is 100nm～150nm;
On electron transfer layer, evaporation is prepared electron buffer layer and negative electrode successively, obtains polymer solar battery.
The material of described electron transfer layer is acetate, in above preparation process, the solute of mixed solution is acetate and azo material, the decomposition temperature of azo material is low, in dry run, decompose, acetate is separated out with the form of crystalline particle simultaneously, thereby make the electron transfer layer obtaining after being dried form Nanostructure Network, can increase the effective contact area between electron transfer layer and active layer, improve electric transmission efficiency, the acetate of simultaneously separating out is finely dispersed nano particle, particle diameter is larger, light is had to reflex, can improve the extinction efficiency of active layer and the photoelectric conversion efficiency of battery.
Described acetate is that electron transport material is the salt that metal oxide forms, and in electron transfer layer, the particle diameter of acetate particle is 5nm～20nm.
Preferably, the mass fraction of described acetate solution is 9%～38%.
Described azo material is the water-soluble azo class material with low decomposition temperature, is azo-bis-isobutyrate hydrochloride (AIBA), azo two isobutyl imidazoline salt hydrochlorates (AIBI) or azo isobutyl cyano group formamide (V30).Preferably, the weight ratio of described azo material and acetate solution is (0.01～0.3): 1.
Preferably, rotating speed when described spin coating mixed solution is 500～6000rpm, and the time is 5～60s.
Preferably, the thickness of described electron transfer layer is 40～100nm.
Preferably, described anode substrate is the glass with anode functional layer, for indium tin oxide glass (ITO), fluorine doped tin oxide glass (FTO), mix the zinc oxide glass (AZO) of aluminium or mix the zinc oxide glass (IZO) of indium.Anode substrate is to buy on market, uniform specification, and anode function layer thickness is 80～250nm.
Described cleaning is to use successively liquid detergent, deionized water, and acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, removes the organic pollution on anode substrate surface.Described preliminary treatment comprises carries out oxygen plasma treatment, and the processing time is 5～15min, and power is 10～50W.
Preferably, the material of described Hole-injecting Buffer Layer for Improvement is the mixture of poly-3,4-dioxy ethene thiophene (PEDOT) and polystyrolsulfon acid (PSS).
Preferably, the weight ratio of described PEDOT:PSS is 2:1 ~ 6:1.More preferably, the weight ratio of described PEDOT:PSS is 6:1.
Described spin coating is prepared Hole-injecting Buffer Layer for Improvement operation and is specially: will gather 3,4-dioxy ethene thiophene (PEDOT) and polyphenyl sulfonate (PSS) are added to the water, obtain poly-3, the aqueous solution of 4-dioxy ethene thiophene (PEDOT) and polyphenyl sulfonate (PSS), then the aqueous solution described in spin coating in anode substrate, after spin coating, at 100～200 DEG C, heat 15～60min, obtain Hole-injecting Buffer Layer for Improvement.
Preferably, in the described aqueous solution, the mass fraction of poly-3,4-dioxy ethene thiophene (PEDOT) is 1%～5%.More preferably, in the described aqueous solution, the mass fraction of poly-3,4-dioxy ethene thiophene (PEDOT) is 1.3%.
Preferably, rotating speed when described spin coating is 2000～6000rpm, and the time is 10～30s.
More preferably, after described spin coating, at 200 DEG C, heat 30min.
Preferably, the thickness of described Hole-injecting Buffer Layer for Improvement is 20～80nm.More preferably, the thickness of described Hole-injecting Buffer Layer for Improvement is 40nm.
Preferably, the material of described active layer is poly-3-hexyl thiophene (P3HT) and the mixture of PCBM.
Preferably, described poly-3-hexyl thiophene (P3HT): the weight ratio of PCBM is 1:0.5 ~ 1:3.More preferably, described poly-3-hexyl thiophene (P3HT): the weight ratio of PCBM is 1:0.8.
Preferably, the thickness of described active layer is 80 ~ 300nm.More preferably, the thickness of described active layer is 200nm.
Preferably, the concrete operations that active layer is prepared in described spin coating are: will gather 3-hexyl thiophene (P3HT) and add in solvent and dissolve with PCBM, obtain the solution of poly-3-hexyl thiophene (P3HT) and PCBM, in inert atmosphere on Hole-injecting Buffer Layer for Improvement solution described in spin coating, 5～the 100min that anneals at 70～200 DEG C after spin coating, obtains active layer.
Preferably, described solvent is toluene, dimethylbenzene, chlorobenzene or chloroform.
Preferably, described poly-3-hexyl thiophene (P3HT) is 8～24mg/ml with the mass concentration of the solution of PCBM.Poly-3-hexyl thiophene (P3HT) is poly-3-hexyl thiophene (P3HT) and the ratio of the quality sum of PCBM and the volume of solvent with the mass concentration of the solution of PCBM.More preferably, described poly-3-hexyl thiophene (P3HT) is 12mg/ml with the mass concentration of the solution of PCBM.
Preferably, speed when described spin coating is 4000～6000rpm, and the time is 10～30s.
Preferably, the 5min that anneals at 100 DEG C after described spin coating.
Preferably, the material of described electron buffer layer is lithium fluoride (LiF), lithium carbonate (Li
2cO
3) or cesium carbonate (Cs
2cO
3).More preferably, the material of described electron buffer layer is Cs
2cO
3.
Preferably, the thickness of described electron buffer layer is 0.5 ~ 10nm.More preferably, the thickness of described electron buffer layer is 5nm.
Preferably, described evaporation is prepared electron buffer layer and is adopted vacuum evaporation, and vacuum degree is 5 × 10
-3pa ~ 2 × 10
-5pa, evaporation rate is 0.1～1nm/s.
Preferably, described negative electrode is aluminium (Al), silver (Ag), gold (Au) or platinum (Pt).More preferably, described negative electrode is aluminium (Al).
Preferably, the thickness of described negative electrode is 80 ~ 200nm.More preferably, described cathode thickness is 150nm.
Preferably, described evaporation is prepared negative electrode and is adopted vacuum evaporation, and vacuum degree is 5 × 10
-3pa ~ 2 × 10
-5pa, evaporation rate is 1～10nm/s.
The present invention prepares electron transfer layer between active layer and electron buffer layer, and by dry after the mixed solution spin coating of acetate and azo material, when dry, nitrogen class material decomposes, and acetate crystalline particle is separated out simultaneously, obtains electron transfer layer.On the one hand, there is decomposition reaction in azo material in dry run, makes electron transfer layer form Nanostructure Network, can increase the effective contact area between electron transfer layer and active layer, thereby improve electric transmission efficiency.On the other hand, acetate is N-shaped material, is conducive to the transmission of electronics, and traditional polymer solar battery does not comprise electron transfer layer, and the present invention increases after the electron transfer layer that material is acetate, can improve the transmission rate of electronics.Moreover in dry run, azo material can effectively stop the reunion of acetate particle, the acetate particle in electron transfer layer is uniformly dispersed, be conducive to the consistency of transmission and the raising of transmission rate.And acetate grain diameter is larger, light is had to strong reflex, can improve the extinction efficiency of active layer, thereby improve the photoelectric conversion efficiency of battery.
The invention provides a kind of polymer solar battery and preparation method thereof, have following beneficial effect:
(1) the present invention is by dry after the mixed solution spin coating of acetate and azo material, obtain electron transfer layer, in dry run, there is decomposition reaction in azo material, make electron transfer layer form Nanostructure Network, can increase the effective contact area between electron transfer layer and active layer, improve electric transmission efficiency, thereby improve photoelectric conversion efficiency;
(2) material of the electron transfer layer in polymer solar battery of the present invention is acetate, acetate is N-shaped material, electric transmission efficiency is high, and its grain diameter is large and be uniformly dispersed, sunlight through active layer is had to scattering and reflex, can improve the extinction efficiency of active layer and the photoelectric conversion efficiency of battery;
(3) polymer solar battery of the present invention has higher photoelectric conversion efficiency, and preparation method is simple, is suitable for commercial Application.
Brief description of the drawings
Fig. 1 is the structure chart of polymer solar battery of the present invention, comprises the anode substrate 1, Hole-injecting Buffer Layer for Improvement 2, active layer 3, electron transfer layer 4, electron buffer layer 5 and the negative electrode 6 that stack gradually.
Fig. 2 is polymer solar battery and the current density voltage curve of Common Polymers solar cell, respectively corresponding curve 1 and the curve 2 that in effect embodiment prepared by embodiment mono-.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Embodiment mono-
A kind of polymer solar battery, preparation method comprises the following steps:
(1) first ito glass (thickness of ITO functional layer is 180nm) is carried out to photoetching treatment, by size, 2 × 2cm cuts out, and illuminating area is 0.3 × 0.3cm
2, 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 ito glass is carried out to oxygen plasma treatment, the processing time is 10min, and power is 20W;
By PEDOT and PSS by weight being added to the water dissolving for 6:1, the PEDOT that the mass fraction of configuration PEDOT is 1.3% and the aqueous solution of PSS, then on ito glass with the speed spin coating gained solution of 4000rpm, the spin coating time is 15s, at 200 DEG C, heat 30min, prepare Hole-injecting Buffer Layer for Improvement, thickness is 40nm;
(2) P3HT and the PCBM that are 1:0.8 by weight ratio are dissolved in chlorobenzene, configuration quality concentration is the P3HT of 12mg/ml and the solution of PCBM, in being full of the glove box of inert gas, on Hole-injecting Buffer Layer for Improvement with the speed spin coating gained solution of 5500rpm, the spin coating time is 20s, the 5min that anneals at 100 DEG C after spin coating, prepares active layer, and thickness is 200nm;
(3) by 20g zinc acetate (Zn (Ac)
2) add solution in 100g water, configuration quality mark is 16.67% zinc acetate solution, AIBA is mixed according to weight ratio 0.2:1 with zinc acetate solution, obtain mixed solution, then on active layer with mixed solution described in the speed spin coating of 4000rpm, the time is 15s, after spin coating at 100 DEG C of dry 30min, prepare electron transfer layer, thickness is 60nm;
(4) finally adopt high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure <1 × 10
-3pa) vacuum evaporation Cs
2cO
3, obtaining electron buffer layer, evaporation pressure is 5 × 10
-4pa, evaporation speed is 0.2nm/s, thickness is 5nm; Then vacuum evaporation Al, obtains negative electrode, and evaporation pressure is 5 × 10
-4pa, evaporation speed is 2nm/s, thickness is 150nm, obtains polymer solar battery.
Wherein, prepare after electron transfer layer, the scanning electron microscopy equipment that is CX-200TM by model is observed the three-dimensional displaing micro tissue topography of this layer, can observe electron transfer layer and there is Nanostructure Network, the aperture of Nanostructure Network is 100nm～120nm, in electron transfer layer, the particle diameter of zinc acetate particle is 5nm～20nm, and distribution uniform.When not adopting when adding azo material and making the method for its decomposition, the electron transfer layer of gained is the closelypacked plane layer structure of zinc acetate, and the present invention is by adding azo material and making the method for its decomposition, make electron transfer layer present 3 D stereo cage-shaped nano network structure, can increase the contact area between electron transfer layer and active layer, and zinc acetate is separated out as particle diameter particle comparatively uniformly.
Polymer solar battery prepared by the present embodiment, comprise the anode substrate 1, Hole-injecting Buffer Layer for Improvement 2, active layer 3, electron transfer layer 4, electron buffer layer 5 and the negative electrode 6 that stack gradually, structure is specially: ITO/ (PEDOT:PSS)/(P3HT:PCBM)/Zn (Ac)
2/ Cs
2cO
3/ Al, as shown in Figure 1.
For the preparation of the Common Polymers solar cell of contrast, structure can schematic representation be: ITO/PEDOT:PSS/P3HT:PCBM/LiF/Al, corresponding anode substrate, Hole-injecting Buffer Layer for Improvement, active layer, electron buffer layer and negative electrode successively, polymer solar battery comparison with embodiment 1, only lack electron transfer layer, other compositions of each layer, thickness and preparation method are all consistent, are the polymer solar battery of common structure, are called for short control cell.
Embodiment bis-
A kind of polymer solar battery, preparation method comprises the following steps:
(1) first IZO glass (thickness of IZO functional layer is 250nm) is carried out to photoetching treatment, by size, 2 × 2cm cuts out, and illuminating area is 0.3 × 0.3cm
2, 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 IZO glass is carried out to oxygen plasma treatment, the processing time is 15min, and power is 10W;
By PEDOT and PSS by weight being added to the water dissolving for 2:1, the PEDOT that the mass fraction of configuration PEDOT is 5% and the aqueous solution of PSS, then at the IZO speed spin coating gained solution with 2000rpm on glass, the spin coating time is 10s, at 200 DEG C, heat 15min, prepare Hole-injecting Buffer Layer for Improvement, thickness is 80nm;
(2) P3HT and the PCBM that are 1:0.5 by weight ratio are dissolved in chloroform, configuration quality concentration is the P3HT of 24mg/ml and the solution of PCBM, in being full of the glove box of inert gas, on Hole-injecting Buffer Layer for Improvement with the speed spin coating gained solution of 6000rpm, the spin coating time is 10s, the 20min that anneals at 100 DEG C after spin coating, prepares active layer, and thickness is 160nm;
(3) 60g sodium acetate (NaAc) is added in 100g water and dissolved, configuration quality mark is 37.5% SAS, AIBI is mixed according to the weight ratio of 0.3:1 with SAS, obtain mixed solution, then on active layer with mixed solution described in the speed spin coating of 500rpm, the time is 60s, after spin coating at 200 DEG C of dry 70min, prepare electron transfer layer, thickness is 40nm;
(4) finally adopt high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure <1 × 10
-3pa) vacuum evaporation LiF, obtains electron buffer layer, and evaporation pressure is 5 × 10
-3pa, evaporation speed is 0.1nm/s, thickness is 0.5nm; Then vacuum evaporation Ag, obtains negative electrode, and evaporation pressure is 2 × 10
-5pa, evaporation speed is 10nm/s, thickness is 80nm, obtains polymer solar battery.
Wherein, prepare after electron transfer layer, the scanning electron microscopy equipment that is CX-200TM by model is observed the three-dimensional displaing micro tissue topography of this layer, can observe electron transfer layer and there is Nanostructure Network, the aperture of Nanostructure Network is 120nm～130nm, in electron transfer layer, the particle diameter of zinc acetate particle is 5nm～20nm, and distribution uniform.
Polymer solar battery prepared by the present embodiment, comprise the anode substrate, Hole-injecting Buffer Layer for Improvement, active layer, electron transfer layer, electron buffer layer and the negative electrode that stack gradually, structure is specially: IZO/ (PEDOT:PSS)/(P3HT:PCBM)/NaAc/LiF/Ag.
Embodiment tri-
A kind of polymer solar battery, preparation method comprises the following steps:
(1) first FTO glass (thickness of FTO functional layer is 80nm) is carried out to photoetching treatment, by size, 2 × 2cm cuts out, and illuminating area is 0.3 × 0.3cm
2, 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 FTO glass is carried out to oxygen plasma treatment, the processing time is 5min, and power is 50W;
By PEDOT and PSS by weight being added to the water dissolving for 5:1, the PEDOT that the mass fraction of configuration PEDOT is 1% and the aqueous solution of PSS, then at the FTO speed spin coating gained solution with 6000rpm on glass, the spin coating time is 30s, at 100 DEG C, heat 60min, prepare Hole-injecting Buffer Layer for Improvement, thickness is 20nm;
(2) P3HT and the PCBM that are 1:3 by weight ratio are dissolved in dimethylbenzene, configuration quality concentration is the P3HT of 16mg/ml and the solution of PCBM, in being full of the glove box of inert gas, on Hole-injecting Buffer Layer for Improvement with the speed spin coating gained solution of 4000rpm, the spin coating time is 30s, the 100min that anneals at 200 DEG C after spin coating, prepares active layer, and thickness is 80nm;
(3) by 10g calcium acetate (Ca (Ac)
2) add in 100g water and dissolve, configuration quality mark is 9.09% calcium acetate solution, V30 is mixed according to the weight ratio of 0.01:1 with calcium acetate solution, obtain mixed solution, then on active layer with mixed solution described in the speed spin coating of 6000rpm, the time is 5s, after spin coating at 100 DEG C of dry 10min, prepare electron transfer layer, thickness is 100nm;
(4) finally adopt high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure <1 × 10
-3pa) vacuum evaporation Cs
2cO
3, obtaining electron buffer layer, evaporation pressure is 2 × 10
-5pa, evaporation speed is 1nm/s, thickness is 10nm; Then vacuum evaporation Au, obtains negative electrode, and evaporation pressure is 2 × 10
-5pa, evaporation speed is 1nm/s, thickness is 180nm, obtains polymer solar battery.
Wherein, prepare after electron transfer layer, the scanning electron microscopy equipment that is CX-200TM by model is observed the three-dimensional displaing micro tissue topography of this layer, can observe electron transfer layer and there is Nanostructure Network, the aperture of Nanostructure Network is 125nm～140nm, in electron transfer layer, the particle diameter of zinc acetate particle is 5nm～20nm, and distribution uniform.
Polymer solar battery prepared by the present embodiment, comprise the anode substrate, Hole-injecting Buffer Layer for Improvement, active layer, electron transfer layer, electron buffer layer and the negative electrode that stack gradually, structure is specially: FTO/ (PEDOT:PSS)/(P3HT:PCBM)/Ca (Ac)
2/ Cs
2cO
3/ Au.
Embodiment tetra-
A kind of polymer solar battery, preparation method comprises the following steps:
(1) first ito glass (thickness of ITO functional layer is 100nm) is carried out to photoetching treatment, by size, 2 × 2cm cuts out, and illuminating area is 0.3 × 0.3cm
2, 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 ito glass is carried out to oxygen plasma treatment, the processing time is 10min, and power is 30W;
By PEDOT and PSS by weight being added to the water dissolving for 3:1, the PEDOT that the mass fraction of configuration PEDOT is 2% and the aqueous solution of PSS, then on ito glass with the speed spin coating gained solution of 3000rpm, the spin coating time is 12s, at 150 DEG C, heat 40min, prepare Hole-injecting Buffer Layer for Improvement, thickness is 70nm;
(2) P3HT and the PCBM that are 1:1 by weight ratio are dissolved in toluene, configuration quality concentration is the P3HT of 8mg/ml and the solution of PCBM, in being full of the glove box of inert gas, on Hole-injecting Buffer Layer for Improvement with the speed spin coating gained solution of 4000rpm, the spin coating time is 15s, the 100min that anneals at 70 DEG C after spin coating, prepares active layer, and thickness is 300nm;
(3) by 45g magnesium acetate (Mg (Ac)
2) add in 100g water and dissolve, configuration quality mark is 31.03% magnesium acetate solution, AIBA is mixed according to the weight ratio of 0.2:1 with magnesium acetate solution, obtain mixed solution, then on active layer with mixed solution described in the speed spin coating of 3000rpm, the time is 15s, after spin coating at 200 DEG C of dry 30min, prepare electron transfer layer, thickness is 50nm;
(4) finally adopt high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure <1 × 10
-3pa) vacuum evaporation Cs
2cO
3, obtaining electron buffer layer, evaporation pressure is 9 × 10
-5pa, evaporation speed is 0.5nm/s, thickness is 1.5nm; Then vacuum evaporation Pt, obtains negative electrode, and evaporation pressure is 9 × 10
-5pa, evaporation speed is 5nm/s, thickness is 200nm, obtains polymer solar battery.
Wherein, prepare after electron transfer layer, the scanning electron microscopy equipment that is CX-200TM by model is observed the three-dimensional displaing micro tissue topography of this layer, can observe electron transfer layer and there is Nanostructure Network, the aperture of Nanostructure Network is 120nm～150nm, in electron transfer layer, the particle diameter of zinc acetate particle is 5nm～20nm, and distribution uniform.
Polymer solar battery prepared by the present embodiment, comprise the anode substrate, Hole-injecting Buffer Layer for Improvement, active layer, electron transfer layer, electron buffer layer and the negative electrode that stack gradually, structure is specially: ITO/ (PEDOT:PSS)/(P3HT:PCBM)/Mg (Ac)
2/ Cs
2cO
3/ Pt.
Effect embodiment
Adopt current-voltage tester (Keithly company of the U.S., 2602) and the filter set cooperation of 500W xenon lamp (Osram) and AM1.5 be simulated solar irradiation white light source, the polymer solar battery of the test embodiment of the present invention one ~ tetra-preparation and current density and the voltage relationship of control cell model:.Polymer solar battery prepared by embodiment mono-and the current density voltage curve of control cell are shown in Fig. 2, respectively corresponding curve 1 and curve 2.The polymer solar battery of being prepared by each embodiment and the current density of control cell and voltage curve, obtain the performance datas such as short circuit current, open circuit voltage, energy conversion efficiency and fill factor, curve factor and all list in table 1.
The performance data of table 1 polymer solar battery of the present invention and control cell
From Fig. 1 and table 1, the short-circuit current density of control cell is 10.79mA/cm
2, and the current density of the polymer solar battery that adds electron transfer layer of the present invention is increased to 10.80～11.86mA/cm
2, energy conversion efficiency is also increased to 2.43～3.00% by 2.18% simultaneously, and the photoelectric conversion efficiency of polymer solar battery of the present invention and control cell are relatively significantly increased.Show to comprise electron transfer layer in polymer solar battery of the present invention, this electron transfer layer is by dry obtaining after the mixed solution spin coating of acetate and azo material, because decomposition reaction occurs azo material in dry run, make electron transfer layer form Nanostructure Network, increase the effective contact area between electron transfer layer and active layer, can improve electric transmission efficiency and photoelectric conversion efficiency, simultaneously, acetate grain diameter in electron transfer layer is large and be uniformly dispersed, electric transmission efficiency is high, and the sunlight through active layer is had to scattering and reflex, can effectively improve the extinction efficiency of active layer and the photoelectric conversion efficiency of battery.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a polymer solar battery, it is characterized in that, comprise the anode substrate, Hole-injecting Buffer Layer for Improvement, active layer, electron transfer layer, electron buffer layer and the negative electrode that stack gradually, the material of described electron transfer layer is acetate, described acetate is zinc acetate, calcium acetate, sodium acetate or magnesium acetate, described electron transfer layer is Nanostructure Network, and the aperture of described Nanostructure Network is 100nm～150nm.
2. polymer solar battery as claimed in claim 1, is characterized in that, in electron transfer layer, the particle diameter of acetate is 5nm～20nm.
3. polymer solar battery as claimed in claim 1, is characterized in that, the thickness of described electron transfer layer is 40～100nm.
4. polymer solar battery as claimed in claim 1, is characterized in that, the material of described active layer is poly-3-hexyl thiophene and the mixture of (6,6)-phenyl-C61-methyl butyrate.
5. a preparation method for polymer solar battery, is characterized in that, comprises the following steps:
Get the anode substrate after cleaning up, carry out after preliminary treatment spin coating in anode substrate and prepare Hole-injecting Buffer Layer for Improvement;
On Hole-injecting Buffer Layer for Improvement, active layer is prepared in spin coating;
Then on active layer, prepare electron transfer layer, concrete operations are: after acetate is added to the water to dissolving, obtain acetate solution, then azo material is mixed with acetate solution, obtain mixed solution, mixed solution described in spin coating on active layer, then at 100～200 DEG C of dry 10～30min, prepare electron transfer layer, described azo material is azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline salt hydrochlorates or azo isobutyl cyano group formamide; Described acetate is zinc acetate, calcium acetate, sodium acetate or magnesium acetate; Described electron transfer layer is Nanostructure Network, and the aperture of described Nanostructure Network is 100nm～150nm;
On electron transfer layer, evaporation is prepared electron buffer layer and negative electrode successively, obtains polymer solar battery.
6. the preparation method of polymer solar battery as claimed in claim 5, is characterized in that, in described electron transfer layer, the particle diameter of acetate is 5nm～20nm.
7. the preparation method of polymer solar battery as claimed in claim 5, is characterized in that, the mass fraction of described acetate solution is 9%～38%, and the weight ratio of described azo material and acetate solution is (0.01～0.3): 1.
8. the preparation method of polymer solar battery as claimed in claim 5, is characterized in that, the rotating speed described in described spin coating when mixed solution is 500～6000rpm, and the time is 5～60s.
9. the preparation method of polymer solar battery as claimed in claim 5, it is characterized in that, the concrete operations that active layer is prepared in described spin coating are: will gather 3-hexyl thiophene and (6, 6)-phenyl-C61-methyl butyrate adds in solvent and dissolves, obtain poly-3-hexyl thiophene and (6, 6) solution of-phenyl-C61-methyl butyrate, in inert atmosphere on Hole-injecting Buffer Layer for Improvement solution described in spin coating, 5～100min anneals after spin coating at 70～200 DEG C, obtain active layer, described poly-3-hexyl thiophene: (6, 6) weight ratio of-phenyl-C61-methyl butyrate is 1:0.5 ~ 1:3, described poly-3-hexyl thiophene and (6, 6) mass concentration of the solution of-phenyl-C61-methyl butyrate is 10～24mg/ml.
10. the preparation method of polymer solar battery as claimed in claim 9, is characterized in that, speed when described spin coating is 4000～6000rpm, and the time is 10～30s.
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