CN100544055C - A kind of preparation method of novel mutual-leakage type polymer solar battery - Google Patents
A kind of preparation method of novel mutual-leakage type polymer solar battery Download PDFInfo
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- CN100544055C CN100544055C CN 200810051147 CN200810051147A CN100544055C CN 100544055 C CN100544055 C CN 100544055C CN 200810051147 CN200810051147 CN 200810051147 CN 200810051147 A CN200810051147 A CN 200810051147A CN 100544055 C CN100544055 C CN 100544055C
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Abstract
The present invention relates to a kind of by the method for solvent penetration mode preparation based on conjugated polymer/fullerene derivate solar cell.At ambient temperature, conjugated polymer is dissolved in its good solvent, PCBM is dissolved in its good solvent again; Conjugated polymer solution is spun on the ITO or FTO electro-conductive glass of clean, after treating that solvent volatilizees fully, again PCBM solution is spin-coated on the conjugated polymer thin films, by solvent action the PCBM molecule infiltration is given in the body layer to conjugated polymer, formed conjugated polymer and PCBM and ooze the active layer of structure mutually; After treating that solvent volatilizees fully, evaporation one deck electrode promptly obtains mutual-leakage type polymer solar battery on PCBM.The mutual-leakage type heterojunction solar battery of preparation can provide bigger to being subjected to body interface for the separation of exciton, and for the transmission of charge carrier provides continuous passage, avoid the loss of charge carrier in transmission course, thereby help improving the efficient of solar cell.
Description
Technical field
The invention belongs to technical field of solar batteries, be specifically related to a kind of by the method for solvent penetration mode preparation based on conjugated polymer/fullerene derivate solar cell.
Background technology
In recent years, organic polymer solar cell is cheap with it, manufacture craft is simple, can prepare advantage such as large area flexible device, becomes the focus of regenerative resource area research.C.W.Tang in 1986 designs first and has prepared with phthalocyanine bronze for being the double-deck organic solar batteries of receptive layers to body layer ， Yi perylene derivative, and its energy conversion efficiency reaches 1%.In double-deck organic solar batteries, though charge carrier can be in main body separately effectively transmission, exciton dissociation only occurs in and limited is subjected to body interface, so solar energy converting efficient is relatively low.People such as nineteen ninety-five Yu Gang are being dissolved in altogether in the same solvent as the conjugated polymer MEH-PPV of electron donor with as the C60 of electron acceptor, pass through spin coating method, prepared the blend film of mixing and forming inierpeneirating network structure mutually for body and acceptor, i.e. the organic solar batteries of so-called bulk heterojunction.This bulk heterojunction has increased considerably the interface of giving acceptor, has realized exciton dissociation effectively and has produced free carrier.But in actual film forming procedure, can not form inierpeneirating network structure completely for acceptor, but form discrete network-like body phase, and occur for the acceptor two-phase easily simultaneously at film surface, thereby cause directly contacting mutually to body in the active layer with negative electrode, increase the free carrier recombination probability, reduced the collection efficiency of charge carrier, and then reduced the efficient of battery.Therefore, in order to increase to being subjected to body interface, improve exciton dissociation efficient, be beneficial to simultaneously the transmission and the collection of free carrier again, we are in conjunction with the exciton dissociation efficient advantages of higher of double-deck heterojunction solar battery carrier transport and collection and bulk heterojunction solar cell, utilize solvent corrosion method to design organic solar batteries with interpenetrative double-deck heterojunction structure, be the mutual-leakage type heterojunction solar battery, for preparation high-performance polymer fullerene solar cell provides a short-cut method.At present, the method that adopts solwution method to prepare the conjugated polymer fullerene derivate solar cell of mutual-leakage type structure is not appeared in the newspapers as yet.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of new polymers solar cell, it is a method of utilizing the solvent corrosion, preparation has the solar cell of interpenetrative double-deck heterojunction structure.Wherein giving the body layer is conjugated polymer, as poly-3 hexane thiophene (P3HT), poly-(2-methoxyl group-5-(2 '-ethyl hexyl oxy)-1,4-is to phenylacetylene) (MEH-PPV), poly-[2-methoxyl group-5 (3 ', 7 '-dimethyl octyloxy)-1,4-is to phenylacetylene] (MDMO-PPV) etc., receptive layers is fullerene derivate [6.6]-C61-phenylbutyric acid methyl esters (PCBM).
In order to increase the contact interface of giving between the acceptor effectively, can improve the transmission and the collection efficiency of charge carrier when guaranteeing exciton dissociation efficient again, we are beneficial to the advantage that carrier transport and bulk heterojunction solar cell are beneficial to exciton dissociation in conjunction with double-deck heterojunction solar battery, interpenetrate effect by solvent, designed the mutual-leakage type organic polymer solar cell.By interpenetrating to receptive layers, ensure to acceptor and have abundant contact interface, simultaneously at the body layer that exists between infiltration layer and the electrode mutually separately, can guarantee that like this photoproduction exciton separates effectively, the free carrier of separation is transmitted in main body separately, thereby can improve the efficiency of transmission and the collection efficiency of charge carrier, and then improve the energy conversion efficiency of solar cell.
The solar cell of this method preparation as giving body and acceptor material, and utilizes the solvent permeating method to be subjected to the body interface realization to ooze network configuration mutually giving with conjugated polymer and fullerene derivate PCBM, need not any subsequent treatment.The more double-deck solar cell of its photoelectric conversion efficiency improves a lot under white light, and increases than the efficient of bulk heterojunction solar cell.Thereby adopt this method to be easier to prepare high performance solar cells, simplified the preparation process of polymer solar battery, more avoid the influence that utilizes modes such as thermal anneal process or solvent annealing in process to bring, eliminated the risk of device easily oxidation, degraded in reprocessing to solar cell.
The preparation method of polymer solar battery of the present invention is as follows:
A: under the room temperature condition, conjugated polymer is dissolved in its good solvent, under the mixing speed of 200～1200RPM, stirred 6～10 hours as o-dichlorohenzene (ODCB), chlorobenzene (CB), chloroform (CF) or oxolane (THF), to guarantee that conjugated polymer fully dissolves, be mixed with the solution of 5～20 mg/ml;
B: PCBM is dissolved in its good solvent, this solvent also is in the good solvent of conjugated polymer simultaneously, as chloroform (CF), chlorobenzene (CB), oxolane (THF) or their mixed solvent (as mixed solvent of mixed solvent, chlorobenzene and the oxolane of chloroform and chlorobenzene etc.), be mixed with 5～20 mg/ml solution;
C: be spun to conjugated polymer solution on the ITO electro-conductive glass of clean with the rotating speed of 700～2000rpm, obtain the thick thin polymer film of 100～200nm, after treating that solvent volatilizees fully, again the rotating speed of PCBM solution with 2000～4000rpm is spin-coated on the conjugated polymer thin films, make in the middle of the PCBM molecule infiltration gives the body layer to conjugated polymer by solvent action, final form have conjugated polymer and PCBM ooze mutually structure, thickness is the active layer of 80～150nm;
D: after treating that solvent volatilizees fully, evaporation one deck electrode promptly obtains mutual-leakage type polymer solar battery on PCBM.
Remove the ITO electro-conductive glass, can also adopt the FTO electro-conductive glass; The electrode of evaporation can adopt Mg/Ag, Ca/Al or LiF/Al electrode etc. on PCBM.
The polymer solar battery schematic diagram that the present invention is prepared, as shown in Figure 1.As can be seen, by method of the present invention, can prepare the active layer that interpenetrates to receptive layers, than the double-decker solar cell, increased effectively to give and be subjected to body interface, and can control length of penetration and active layer thickness by evaporation rate (promptly selecting solvent such as chloroform, the chlorobenzene etc. of different boiling for use) and the time of penetration (being PCBM drips of solution quiescent time on thin polymer film) of control solvent, and acceptor is direct mutually and electrode is in contact with one another and the charge carrier that causes loses mutually thereby avoid in the heterogeneous solar cell of body giving body.Therefore, the mutual-leakage type heterojunction solar battery of the present invention's preparation, can provide bigger for the separation of exciton to being subjected to body interface, and provide continuous passage for the transmission of charge carrier, avoid the loss of charge carrier in transmission course, thereby help improving the efficient of solar cell, and preparation process is simple, easily control.
Description of drawings
Fig. 1: the device architecture schematic diagram that adopts method preparation of the present invention;
Wherein, 1 is clear glass, and 2 is the translucent ITO layer that uses as anode, and 3 is the PEDOT:PSS layer, and 4 is conjugated polymer layer, and 5 is the PCBM layer, and 6 is negative electrode.Form the prepared active layer of the present invention in conjugated polymer layer 4 and 5 on PCBM layer with mutual-leakage type structure.
Fig. 2: the UV, visible light absorption spectra of the permeable membrane of pure MEH-PPV film, pure PCBM film, the inventive method preparation;
As seen from the figure, near the absworption peak in the permeable membrane 495nm shows as the absworption peak of MEH-PPV, and near the absworption peak 270nm and the 340nm all shows as the absworption peak of PCBM.
Fig. 3: the fluorescence spectrum of the permeable membrane of pure MEH-PPV film, the inventive method preparation;
As seen from the figure, along with the infiltration of PCBM to the MEH-PPV layer, the fluorescent quenching of MEH-PPV is obvious.Than the fluorescence intensity of pure MEH-PPV film, 100% quencher has taken place in the fluorescence of MEH-PPV in the permeable membrane.This result shows that the PCBM molecule can be penetrated in the MEH-PPV thin layer, when under the optical excitation condition, effective separation of charge can take place, the fluorescence of cancellation MEH-PPV.
Fig. 4: the atomic force electron micrograph of the film surface of different condition preparation;
Wherein (a) is pure MEH-PPV film surface appearance; (b) be the permeable membrane surface topography; (c) remove PCBM molecule rear film surface topography for permeable membrane.As can be seen from the figure, the surface of pure MEH-PPV film is comparatively smooth, do not occur being separated, and the surface of permeable membrane is comparatively coarse.Adopt solvent method, be about to 1min in the cyclohexane that permeable membrane is dipped into and indissoluble MEH-PPV easily molten to PCBM, permeable membrane surface after the PCBM molecule removed as scheme shown in (c), as can be known in the MEH-PPV body layer, formed the defective that more size differs, and these defectives are removed and form just by being penetrated into PCBM in the MEH-PPV body layer.This shows that in permeable membrane the inner boundary of MEH-PPV and PCBM is PCBM and the interpenetrative structure of MEH-PPV.
Embodiment
Embodiment 1:
MEH-PPV is dissolved in the chloroformic solution, is mixed with 5 mg/ml solution, stirred 6 hours under the 700rpm condition; PCBM is dissolved in the chloroformic solution, is mixed with 5 mg/ml solution.Ito glass usefulness acetone, isopropyl alcohol, deionized water are distinguished ultrasonic cleaning 15 minutes, and then with rotating speed 3000RPM spin coating, obtaining a layer thickness is the PEDOT:PSS layer of 40nm, to modify the work function on ITO surface.Put into vacuum drying oven 120 degree dry 1 hour.Again the MEH-PPV chloroformic solution that the prepares rotating speed with 2000rpm is spin-coated on the ito glass sheet of having modified, obtains the polymer foil that a layer thickness is about 150nm.After treating that solvent volatilizees fully, the PCBM chloroformic solution for preparing is dripped on the MEH-PPV of bone dry film, and immediately with the speed spin-coating film of 3000rpm, then PCBM will be penetrated in the MEH-PPV film under solvent action.The final active layer thickness that obtains is about 100nm.Method evaporation one layer thickness by vacuum evaporation is the LiF/Al electrode of 100nm at last, promptly prepares polymer solar battery.
Use the prepared polymer solar battery of method of the present invention, do not passing through under the condition of any reprocessing, its energy conversion efficiency has reached 2.68%, energy conversion efficiency than the bi-layer devices that adopts the same material preparation obviously improves, and (polymer and PCBM mass ratio are MEH-PPV: PCBM=1: the energy conversion efficiency of bulk heterojunction device 4) also increases, and in detail relatively sees Table 1 than the system that adopts same material.In addition, studies show that: the active layer of using the present invention's preparation, owing to have the mutual-leakage type structure, the inner boundary that MEH-PPV contacts with PCBM is the formula interface of interpenetrating, increased the interfacial area of giving acceptor, improved well double-deck heterojunction solar battery the active layer midplane give the acceptor contact interface, improved the separative efficiency of photoproduction exciton effectively, make the short circuit current of battery obtain bigger raising; On the other hand, give acceptor body layer separately owing to exist in the active layer of mutual-leakage type solar cell, guaranteed that inner boundary that the active layer of battery contacts with electrode is for to acceptor contacting of body layer and electrode separately, thereby effectively reduce the recombination probability of charge carrier in being transferred to the process of electrode, simultaneously in the mixed layer of oozing for acceptor mutually, the photo-generated carrier that has separated again can transmission effectively in each autonomous agent, improved the transmission and the collection efficiency of electric charge, thereby the energy conversion efficiency of battery is significantly improved.Therefore, utilize method of the present invention can prepare the high performance polymer solar cell.
Table 1: utilize the polymer solar battery performance of distinct methods preparation to compare
(light intensity is 100mW/cm
2Measure under the white light condition, adopt JY Triax 320 monochromators and xenon lamp)
Claims (2)
1, a kind of preparation method of novel mutual-leakage type polymer solar battery, its step is as follows:
A: under the room temperature condition, conjugated polymer is dissolved in its good solvent, under the mixing speed of 200～1200RPM, stirred 6～10 hours, be mixed with the solution of 5～20 mg/ml;
B: [6.6]-C61-phenylbutyric acid methyl esters is dissolved in its good solvent, is mixed with 5～20 mg/ml solution;
C: be spun to conjugated polymer solution on the ITO or FTO electro-conductive glass of clean with the rotating speed of 700～2000rpm, after treating that solvent volatilizees fully, again the rotating speed of [6.6]-C61-phenylbutyric acid methyl ester solution with 2000～4000rpm is spin-coated on the conjugated polymer thin films, make [6.6]-C61-phenylbutyric acid methyl esters molecule infiltration in the middle of conjugated polymer thin films by solvent action, form conjugated polymer and ooze the active layer of structure mutually with [6.6]-C61-phenylbutyric acid methyl esters;
D: after treating that solvent volatilizees fully, evaporation one deck electrode on [6.6]-C61-phenylbutyric acid methyl esters promptly obtains mutual-leakage type polymer solar battery;
Conjugated polymer is poly-3 hexane thiophene, poly-(2-methoxyl group-5-(2 '-ethyl hexyl oxy)-1,4-is to phenylacetylene) or poly-[2-methoxyl group-5 (3 ', 7 '-dimethyl octyloxy)-1,4-is to phenylacetylene]; The good solvent of conjugated polymer is o-dichlorohenzene, chlorobenzene, chloroform or oxolane; [6.6]-good solvent of C61-phenylbutyric acid methyl esters is chloroform, chlorobenzene, oxolane or their mixed solvent.
2, the preparation method of novel mutual-leakage type polymer solar battery as claimed in claim 1 is characterized in that: the electrode of evaporation is Mg/Ag, Ca/Al or LiF/Al electrode on [6.6]-C61-phenylbutyric acid methyl esters.
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| CN101826599B (en) * | 2010-04-23 | 2012-05-23 | 浙江大学 | Polymer solar battery with high open-circuit voltage |
| CN102270745B (en) * | 2011-08-08 | 2012-12-12 | 华南师范大学 | Method for preparing polymer solar cell in air |
| US20130247993A1 (en) * | 2012-03-23 | 2013-09-26 | Xiong Gong | Enhanced Efficiency Polymer Solar Cells Using Aligned Magnetic Nanoparticles |
| CN110392939B (en) * | 2017-04-25 | 2023-04-04 | 香港科技大学 | Sequential processing and manufacturing process of high-efficiency organic solar cell based on conjugated polymer with temperature-dependent aggregation |
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