CN103700772A - Polymer solar cell and preparation method thereof - Google Patents

Polymer solar cell and preparation method thereof Download PDF

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Publication number
CN103700772A
CN103700772A CN201210367663.8A CN201210367663A CN103700772A CN 103700772 A CN103700772 A CN 103700772A CN 201210367663 A CN201210367663 A CN 201210367663A CN 103700772 A CN103700772 A CN 103700772A
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polymer solar
solar battery
spin coating
buffer layer
fullerene
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周明杰
王平
黄辉
陈吉星
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/87—Light-trapping means
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention provides a polymer solar cell and a preparation method of the polymer solar cell. The polymer solar cell comprises an anode substrate, a hole buffer layer, an active layer, a reflecting layer, an electronic buffer layer and a cathode which are stacked in sequence, wherein the material of the reflecting layer comprises fullerene or a derivative thereof and titanium dioxide, and fullerene or the fullerene derivative is C60, (6, 6)-phenyl-C61-butyric acid methyl ester, C70, or 6, 6-phenyl-C71-butyric acid methyl ester. The reflecting layer having high reflection efficiency for sunlight is prepared to improve the capture rate of the active layer for the sunlight and the photoelectric conversion efficiency of the polymer solar cell, the preparation method is simple, and the polymer solar cell has industrialization prospect.

Description

A kind of polymer solar battery and preparation method thereof
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.
Double-deck polymer solar battery comprises positive and negative electrode and has photoactive thin layer therebetween, i.e. active layer, and active layer generally has by the bulk heterojunction structure forming to body (D) and acceptor (A), and acceptor material mainly contains CdSe, n-polymer and C 60and derivative PCBM etc., the both positive and negative polarity of PCBM type solar cell can be respectively indium tin oxide (ITO) and has the metal compared with low work function, active layer is generally mixed to get by conjugated polymer and PCBM, when the transparent ITO of light transmission is irradiated on conjugated polymer molecule, when being greater than polymer band gap, photon energy will inspire exciton, exciton is to D/A Interface Moving, because D/A energy level difference is greater than exciton binding energy, cause exciton separated on interface, electronics is delivered to negative pole by PCBM, thereby hole is delivered to anodal ITO by polymer and produces photoelectric current and photovoltage.
Often by changing the structure of active layer material, strengthen its absorptivity to sunlight at present, thereby improve energy conversion efficiency, but the method exists R&D costs high, the shortcoming that the time is long.And the part proportion that solar irradiation can be absorbed and used while being mapped on active layer is low, major part is not used through battery, thereby by improving composition or the structure of battery, improving solar cell is also an important channel of improving energy conversion efficiency to the utilance of sunlight, and at present relevant technology is less.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of polymer solar battery.Between the active layer of described polymer solar battery and electron buffer layer, comprising material is the reflector of fullerene and derivative and metal oxide titanium dioxide, fullerene crystal in this reflector and there is the titanium dioxide of tridimensional network, can carry out scattering and reflection to the sunlight through active layer, make it to get back to active layer and be again absorbed and used, improve the absorption rate of sunlight and the photoelectric conversion efficiency of battery.
The present invention also provides the preparation method of above-mentioned polymer solar battery.
The invention provides a kind of polymer solar battery, comprise the anode substrate, Hole-injecting Buffer Layer for Improvement, active layer, reflector, electron buffer layer and the negative electrode that stack gradually, the material in described reflector comprises fullerene or derivatives thereof and titanium dioxide, and described fullerene or derivatives thereof is C 60, (6,6)-phenyl-C61-methyl butyrate (PC 61bM), C 70or 6,6-phenyl-C71-methyl butyrate (PC 71bM).
Preferably, the particle diameter of described titanium dioxide is 20 ~ 200nm.
Preferably, the quality of described titanium dioxide is 5 ~ 15% of fullerene or derivatives thereof quality.
Preferably, the thickness in described reflector is 5 ~ 40nm.
The material of described active layer is MDMO-PPV and PC 61the mixture of BM, or MEH-PPV and PC 61the mixture of BM.MDMO-PPV is poly-[2-methoxyl group, 5-(3 ', 7 ' dimethoxy-octyloxy)]-to phenylacetylene, and MEH-PPV, for poly-(2-methoxyl group, 5-(2-ethyl-ethyoxyl)-to phenylacetylene), is all the conventional electron donor materials in this area, PC 61bM is (6,6)-phenyl-C61-methyl butyrate, and molecular formula is C 72h 14o 2, be C 60derivative, be conventional electron transport material.Active layer of the present invention adopts the fullerene or derivatives thereof similar to reflector as main active material, makes not have energy barrier between two structure sheafs, promotes electric transmission.
Preferably, described MDMO-PPV:PC 61the weight ratio of BM is 1:1 ~ 1:4.More preferably, described MDMO-PPV:PC 61the weight ratio of BM is 1:3.
Preferably, described MEH-PPV:PC 61weight ratio 1:1 ~ 1:4 of BM.More preferably, described MEH-PPV:PC 61the weight ratio of BM is 1:3.
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 ~ 250nm.More preferably, described cathode thickness is 150nm.
Preferably, the material of described Hole-injecting Buffer Layer for Improvement is 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 3:1.
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, 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 120nm.
The preparation method who the present invention further provides a kind 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 reflector: fullerene or derivatives thereof and titanium dioxide are added in solvent, obtain mixture, mixture described in spin coating on active layer, then, at 25 ~ 100 ℃ of annealing 5 ~ 30min, prepares reflector;
On reflector, evaporation is prepared electron buffer layer and negative electrode successively, obtains polymer solar battery; Described fullerene or derivatives thereof is C 60, (6,6)-phenyl-C61-methyl butyrate, C 70or 6,6-phenyl-C71-methyl butyrate.
The material in described reflector comprises fullerene or derivatives thereof and titanium dioxide.In above preparation process, when preparation reflector, the mixture of fullerene or derivatives thereof and titania additive is after annealing, fullerene or derivatives thereof forms crystallization, (titanium dioxide becomes aggregating state to the dispersion suspension liquid of titanium dioxide in raw material simultaneously, in solvent, be dispersed) after solvent is removed, titanium dioxide forms uniform particles and distributes and interconnective tridimensional network, together with fullerene derivate crystallization, sunlight is reflected, improve the utilance of sunlight and the energy conversion efficiency of battery.
Preferably, the particle diameter of described titanium dioxide is 20 ~ 200nm.
Preferably, the quality of described titanium dioxide is 5 ~ 15% of fullerene or derivatives thereof quality, and in described mixture, the mass fraction of fullerene or derivatives thereof is 5 ~ 40%.
Preferably, the thickness in described reflector is 5 ~ 40nm.
Preferably, described solvent is chlorobenzene, chloroform, carrene or toluene.
Preferably, in the preparation in described reflector, the rotating speed of spin coating is 4000 ~ 6000 revs/min, and the time is 10 ~ 60s.
Preferably, described anode substrate is the glass with anode functional layer, for indium tin oxide glass (ito glass), fluorine doped tin oxide glass (FTO glass), mix the zinc oxide glass (AZO glass) of aluminium or mix the zinc oxide glass (IZO glass) of indium.Anode substrate is to buy on market, uniform specification, and anode function layer thickness is 120nm.
Preferably, preliminary treatment comprises oxygen plasma treatment or UV-ozone treatment.Wherein, the described oxygen plasma treatment time is 5 ~ 15min, and power is 10 ~ 50W; The described UV-ozone treatment time is 5 ~ 20min.Pretreated object is to improve the performance of anode substrate.
Preferably, the material of described Hole-injecting Buffer Layer for Improvement is PEDOT and PSS.
Preferably, the weight ratio of described PEDOT:PSS is 2:1 ~ 6:1.More preferably, the weight ratio of described PEDOT:PSS is 3:1.
The concrete operations that Hole-injecting Buffer Layer for Improvement is prepared in described spin coating are: PEDOT and PSS is water-soluble, obtain the PEDOT/PSS aqueous solution, and in anode substrate, after the spin coating PEDOT/PSS aqueous solution, at 100 ~ 200 ℃, heat 15 ~ 60min, obtain Hole-injecting Buffer Layer for Improvement.
Preferably, after the described spin coating PEDOT/PSS aqueous solution, at 200 ℃, heat 30min.
Preferably, in the described PEDOT/PSS aqueous solution, the gross mass mark of PEDOT and PSS is 1% ~ 5%.More preferably, the gross mass mark of described PEDOT and PSS is 4%.
Preferably, the THICKNESS CONTROL of described Hole-injecting Buffer Layer for Improvement is at 20 ~ 80nm.More preferably, the thickness of described Hole-injecting Buffer Layer for Improvement is 40nm.
Preferably, speed during the described spin coating PEDOT/PSS aqueous solution is 4000 ~ 6000 revs/min, and the time is 10 ~ 30s.
The material of described active layer is MDMO-PPV and PC 61the mixture of BM, or MEH-PPV and PC 61the mixture of BM.
Preferably, the material of described active layer is MDMO-PPV and PC 61the mixture of BM.
Preferably, described MDMO-PPV:PC 61the weight ratio of BM is 1:1 ~ 1:4.More preferably, described MDMO-PPV:PC 61the weight ratio of BM is 1:3.
Preferably, described MEH-PPV:PC 61weight ratio 1:1 ~ 1:4 of BM.More preferably, described MEH-PPV:PC 61the weight ratio of BM is 1:3.
The process that active layer is prepared in described spin coating is specially: by described MDMO-PPV and PC 61bM adds in organic solvent, obtains mixed solution, in inert gas on Hole-injecting Buffer Layer for Improvement mixed solution described in spin coating, the 5 ~ 100min that then anneals at 50 ~ 200 ℃, or at room temperature place 24 ~ 48h, prepares active layer, or by MEH-PPV and PC 61bM adds in solvent and obtains mixed solution, in inert gas on Hole-injecting Buffer Layer for Improvement mixed solution described in spin coating, the 5 ~ 100min that then anneals at 50 ~ 200 ℃, or at room temperature place 24 ~ 48h, prepares active layer.
Preferably, after mixed solution, 5min anneals at 200 ℃ described in spin coating.
Preferably, described organic solvent is toluene, dimethylbenzene, chlorobenzene or chloroform.More preferably, described organic solvent is chlorobenzene.
Preferably, the solute total mass concentration of described mixed solution is 8 ~ 30mg/ml.More preferably, the solute total mass concentration of described mixed solution is 18mg/ml.
Preferably, the thickness of described active layer is 80 ~ 300nm.More preferably, the thickness of described active layer is 200nm.
Preferably, while preparing active layer, the speed of described spin coating is 2000 ~ 6000 revs/min, and the time is 10 ~ 30s.
Preferably, the material of described electron buffer layer is LiF, Li 2cO 3or 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 adopts vacuum evaporation while preparing electron buffer layer, and vacuum degree during evaporation is 5 * 10 -5~ 2 * 10 -3pa, evaporation speed is 0.1 ~ 1nm/s.
Preferably, the material of described negative electrode is Al, Ag, Au or Pt.More preferably, the material of described negative electrode is Al.
Preferably, the thickness of described negative electrode is 80 ~ 250nm.More preferably, described cathode thickness is 150nm.
Preferably, described evaporation adopts vacuum evaporation while preparing negative electrode, and vacuum degree during evaporation is 5 * 10 -5~ 2 * 10 -3pa, evaporation speed is 1 ~ 10nm/s.
Solar cell is an important factor that affects energy conversion efficiency on the utilization of sunlight, and conventional method is that the structure that changes active layer material strengthens its absorptivity to sunlight at present.
Polymer solar battery of the present invention is prepared the reflector that one deck is formed by fullerene and titania additive between active layer and electron buffer layer.Wherein, the easy crystallization of fullerene, in preparation process, the fullerene in reflector forms crystal structure, and light is had to scattering and reflex, can concentrate light intensity, and make light reflect back into active layer, is absorbed once again by active layer.Meanwhile, fullerene is electron transport material, and active layer also adopts fullerene derivate as main active material, similar to reflector, makes both not have energy barrier, can make electric transmission speed be strengthened.In addition, the metal oxide titania nanoparticles material adulterating in reflector, it is strong reflection material, less to visible absorption, can further strengthen scattering of light and reflection, and in preparation process at spin coating after annealing reasonable time, make titanium dioxide sufficient crystallising, the tridimensional network forming is also conducive to improve the transmission rate of electronics and the scattering of light absorbs, thereby improve photoelectric conversion efficiency, and the titanium dioxide that adds stable chemical nature can improve the stability of device, add that preparation method of the present invention is easy to control, simple to operate, make polymer solar battery of preparing fullerene and titania additive of the present invention and preparation method thereof there is the prospect of commercial application.
The invention provides a kind of polymer solar battery and preparation method thereof, have following beneficial effect:
(1) fullerene and titanium dioxide crystal are contained in the reflector in polymer solar battery of the present invention, and the sunlight through active layer is had to scattering and reflex, make sunlight get back to active layer, are absorbed once again by active layer, improve photoelectric conversion efficiency;
(2) in polymer solar battery of the present invention, reflector adopts similar fullerene-based material to active layer, can improve electric transmission speed, is beneficial to raising photoelectric conversion efficiency;
(3) polymer solar battery of the present invention has higher photoelectric conversion efficiency, and preparation method is simple, is suitable for commercial Application.
Accompanying drawing explanation
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, reflector 4, electron buffer layer 5 and the negative electrode 6 that stack gradually.
Fig. 2 is the polymer solar battery of embodiment mono-preparation and the current density voltage curve of Common Polymers solar cell, respectively corresponding curve 1 and curve 2.
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 polymer solar battery, preparation method comprises the following steps:
(1) first by ito glass, the thickness of ITO functional layer is 120nm, carries out photoetching treatment, and by size, 2 * 2cm cuts out, illuminating area is 0.3 * 0.3cm, uses successively liquid detergent, deionized water, acetone, ethanol, 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, processing time is 10min, power is 25W, then the PEDOT/PSS aqueous solution that the weight ratio of speed spin coating PEDOT:PSS of 5000 revs/min of take is 4% as 3:1, mass fraction, the spin coating time is 15s, then at 200 ℃, heat 30min, prepare Hole-injecting Buffer Layer for Improvement, thickness is 40nm;
(2) in being full of the glove box of inert gas, on Hole-injecting Buffer Layer for Improvement with speed spin coating MDMO-PPV and the PC of 4000 revs/min 61the chlorobenzene solution of BM, the spin coating time is 20s, solute total mass concentration is 18mg/ml, MDMO-PPV:PC 61the weight ratio of BM is 1:3, and the 5min that anneals at 200 ℃ after spin coating, prepares active layer, and thickness is 200nm;
(3) by PC 61bM adds in chlorobenzene and mixes with titania additive, obtains mixture, TiO 2particle diameter be 20nm, PC in mixture 61the mass fraction of BM is 30%, TiO 2quality account for PC 6110% of BM quality, then, with mixture described in the speed spin coating of 5000 revs/min, the time is 30s, after spin coating completes, at 70 ℃ of annealing 15min, prepares reflector, thickness is 30nm, can be observed titanium dioxide three-dimensional crystalline structure on this reflector;
(4) finally adopt high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure <1 * 10 -3pa, lower same) vacuum evaporation electron buffer layer Cs 2cO 3, evaporation pressure is 2 * 10 -4pa, evaporation speed is 0.2nm/s, thickness is 5nm; Then vacuum evaporation negative electrode Al, evaporation pressure is 2 * 10 -4pa, evaporation speed is 5nm/s, thickness is 150nm, obtains polymer solar battery.
Polymer solar battery prepared by the present embodiment, comprises the anode substrate 1, Hole-injecting Buffer Layer for Improvement 2, active layer 3, reflector 4, electron buffer layer 5 and the negative electrode 6 that stack gradually, and structure is specially: ITO/ (PEDOT:PSS)/(MDMO-PPV:PC 61bM)/(PC 61bM:TiO 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/MDMO-PPV:PC 61bM/Cs 2cO 3/ 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 lacked reflector, the composition of other each layers, thickness and preparation method are all consistent, for the polymer solar battery of common structure, be called for short control cell.
Embodiment bis-
A polymer solar battery, preparation method comprises the following steps:
(1) first IZO glass is carried out to photoetching treatment, the thickness of IZO functional layer is 120nm, and by size, 2 * 2cm cuts out, and illuminating area is 0.3 * 0.3cm, use successively liquid detergent, deionized water, acetone, ethanol, 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, processing time is 5min, power is 50W, then the PEDOT/PSS aqueous solution that the weight ratio of speed spin coating PEDOT:PSS of 6000 revs/min of take is 5% as 2:1, mass fraction, the spin coating time is 30s, then at 200 ℃, heat 15min, prepare Hole-injecting Buffer Layer for Improvement, thickness is 80nm;
(2) in being full of the glove box of inert gas, on Hole-injecting Buffer Layer for Improvement with speed spin coating MEH-PPV and the PC of 2000 revs/min 61the chloroformic solution of BM, the spin coating time is 10s, solute total mass concentration is 24mg/ml, MEH-PPV:PC 61the weight ratio of BM is 1:4, and the 20min that anneals at 100 ℃ after spin coating, prepares active layer, and thickness is 160nm;
(3) by C 60add in chloroform and mix with titania additive, obtain mixture, TiO 2particle diameter be 200nm, C in mixture 60mass fraction be 5%, TiO 2quality account for C 6015% of quality, then, with mixture described in the speed spin coating of 4000 revs/min, the time is 60s, after spin coating completes, at 25 ℃ of annealing 30min, prepares reflector, thickness is 40nm, can be observed titanium dioxide three-dimensional crystalline structure on this reflector;
(4) finally adopt high vacuum coating equipment vacuum evaporation electron buffer layer LiF, evaporation pressure is 5 * 10 -5pa, evaporation speed is 0.1nm/s, thickness is 0.5nm; Then vacuum evaporation negative electrode Ag, evaporation pressure is 5 * 10 -5pa, evaporation speed is 1nm/s, thickness is 80nm, obtains polymer solar battery.
Polymer solar battery prepared by the present embodiment, comprises the anode substrate, Hole-injecting Buffer Layer for Improvement, active layer, reflector, electron buffer layer and the negative electrode that stack gradually, and structure is specially: ITO/ (PEDOT:PSS)/(MDMO-PPV:PC 61bM)/(C 60: TiO 2)/LiF/Ag.
Embodiment tri-
A polymer solar battery, preparation method comprises the following steps:
(1) first FTO glass is carried out to photoetching treatment, the thickness of FTO functional layer is 120nm, and by size, 2 * 2cm cuts out, and illuminating area is 0.3 * 0.3cm, use successively liquid detergent, deionized water, acetone, ethanol, 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, processing time is 15min, power is 10W, then the PEDOT/PSS aqueous solution that the weight ratio of speed spin coating PEDOT:PSS of 4000 revs/min of take is 1% as 5:1, mass fraction, the spin coating time is 10s, then at 100 ℃, heat 60min, prepare Hole-injecting Buffer Layer for Improvement, thickness is 20nm;
(2) in being full of the glove box of inert gas, on Hole-injecting Buffer Layer for Improvement with speed spin coating MEH-PPV and the PC of 6000 revs/min 61the xylene solution of BM, the spin coating time is 30s, solute total mass concentration is 16mg/ml, MEH-PPV:PC 61the weight ratio of BM is 1:3, and the 100min that anneals at 100 ℃ after spin coating, prepares active layer, and thickness is 80nm;
(3) by C 70add in chloroform and mix with titania additive, obtain mixture, TiO 2particle diameter be 100nm, C in mixture 70mass fraction be 40%, TiO 2quality account for C 705% of quality, then, with mixture described in the speed spin coating of 6000 revs/min, the time is 10s, after spin coating completes, at 100 ℃ of annealing 5min, prepares reflector, thickness is 5nm, can be observed titanium dioxide three-dimensional crystalline structure on this reflector;
(4) finally adopt high vacuum coating equipment vacuum evaporation electron buffer layer Li 2cO 3, evaporation pressure is 2 * 10 -3pa, evaporation speed is 1nm/s, thickness is 5nm; Then vacuum evaporation negative electrode Au, evaporation pressure is 2 * 10 -3pa, evaporation speed is 10nm/s, thickness is 180nm, obtains polymer solar battery.
Polymer solar battery prepared by the present embodiment, comprises the anode substrate, Hole-injecting Buffer Layer for Improvement, active layer, reflector, electron buffer layer and the negative electrode that stack gradually, and structure is specially: ITO/ (PEDOT:PSS)/(MDMO-PPV:PC 61bM)/(C 70: TiO 2)/Li 2cO 3/ Au.
Embodiment tetra-
A polymer solar battery, preparation method comprises the following steps:
(1) first ito glass is carried out to photoetching treatment, the thickness of ITO functional layer is 120nm, and by size, 2 * 2cm cuts out, and illuminating area is 0.3 * 0.3cm, use successively liquid detergent, deionized water, acetone, ethanol, 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, processing time is 10min, power is 20W, then the PEDOT/PSS aqueous solution that the weight ratio of speed spin coating PEDOT:PSS of 4500 revs/min of take is 2% as 6:1, mass fraction, the spin coating time is 15s, then at 150 ℃, heat 40min, prepare Hole-injecting Buffer Layer for Improvement, thickness is 70nm;
(2) in being full of the glove box of inert gas, on Hole-injecting Buffer Layer for Improvement with speed spin coating MDMO-PPV and the PC of 5500 revs/min 61the toluene solution of BM, the spin coating time is 25s, solute total mass concentration is 8mg/ml, MEH-PPV:PC 61the weight ratio of BM is 1:2, and the 100min that anneals at 70 ℃ after spin coating, prepares active layer, and thickness is 300nm;
(3) by PC 71bM adds in chloroform and mixes with titania additive, obtains mixture, TiO 2particle diameter be 40nm, PC in mixture 71the mass fraction of BM is 10%, TiO 2quality account for PC 7120% of BM quality, then, with mixture described in the speed spin coating of 5000 revs/min, the time is 50s, after spin coating completes, at 40 ℃ of annealing 20min, prepares reflector, thickness is 25nm, can be observed titanium dioxide three-dimensional crystalline structure on this reflector;
(4) finally adopt high vacuum coating equipment vacuum evaporation electron buffer layer Cs 2cO 3, evaporation pressure is 2 * 10 -4pa, evaporation speed is 0.5nm/s, thickness is 10nm; Then vacuum evaporation negative electrode Al, evaporation pressure is 2 * 10 -4pa, evaporation speed is 2nm/s, thickness is 250nm, obtains polymer solar battery.
Polymer solar battery prepared by the present embodiment, comprises the anode substrate, Hole-injecting Buffer Layer for Improvement, active layer, reflector, electron buffer layer and the negative electrode that stack gradually, and structure is specially: ITO/ (PEDOT:PSS)/(MDMO-PPV:PC 61bM)/(PC 71bM:TiO 2)/Cs 2cO 3/ Al.
Effect embodiment
Adopt current-voltage tester (U.S. Keithly company, 2602) and the filter set cooperation of 500W xenon lamp (Osram) and AM 1.5 white light source that is simulated solar irradiation model:, 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, the polymer solar battery of embodiment mono-preparation 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
Figure BDA00002205412900141
From Fig. 1 and table 1, the short-circuit current density of control cell is 9.93mA/cm 2, and the current density of the polymer solar battery in reflector that adds of the present invention is increased to 11.70 ~ 12.85mA/cm 2, energy conversion efficiency is also increased to 2.41 ~ 3.14% by 2.30% simultaneously, and the performance of polymer solar battery of the present invention and control cell are relatively significantly increased.Show that the present invention by preparing the reflector that material is fullerene and derivative and titanium dioxide between active layer and electron buffer layer, because fullerene and derivative thereof form crystal structure in preparation process, metal oxide titania nanoparticles forms tridimensional network, jointly light is formed to scattering and reflection effect, the photoelectric conversion efficiency of polymer solar battery is effectively improved.
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, reflector, electron buffer layer and the negative electrode that stack gradually, the material in described reflector comprises fullerene or derivatives thereof and titanium dioxide, and described fullerene or derivatives thereof is C 60, (6,6)-phenyl-C61-methyl butyrate, C 70or 6,6-phenyl-C71-methyl butyrate.
2. polymer solar battery as claimed in claim 1, is characterized in that, the particle diameter of described titanium dioxide is 20 ~ 200nm.
3. polymer solar battery as claimed in claim 1, is characterized in that, the quality of described titanium dioxide is 5 ~ 15% of fullerene or derivatives thereof quality.
4. polymer solar battery as claimed in claim 1, is characterized in that, the thickness in described reflector is 5 ~ 40nm.
5. polymer solar battery as claimed in claim 1, is characterized in that, the material of described active layer is MDMO-PPV and PC 61the mixture of BM or MEH-PPV and PC 61the mixture of BM.
6. 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 reflector: fullerene or derivatives thereof and titanium dioxide are added in solvent, obtain mixture, mixture described in spin coating on active layer, then, at 25 ~ 100 ℃ of annealing 5 ~ 30min, prepares reflector;
On reflector, evaporation is prepared electron buffer layer and negative electrode successively, obtains polymer solar battery, and described fullerene or derivatives thereof is C 60, (6,6)-phenyl-C61-methyl butyrate, C 70or 6,6-phenyl-C71-methyl butyrate.
7. the preparation method of polymer solar battery as claimed in claim 6, is characterized in that, the quality of described titanium dioxide is 5 ~ 15% of fullerene or derivatives thereof quality, and in described mixture, the mass fraction of fullerene or derivatives thereof is 5 ~ 40%.
8. the preparation method of polymer solar battery as claimed in claim 6, it is characterized in that, the concrete operations that Hole-injecting Buffer Layer for Improvement is prepared in described spin coating are: PEDOT and PSS is water-soluble, obtain the PEDOT/PSS aqueous solution, in anode substrate, after the spin coating PEDOT/PSS aqueous solution, at 100 ~ 200 ℃, heat 15 ~ 60min, obtain Hole-injecting Buffer Layer for Improvement, the weight ratio of described PEDOT:PSS is 2:1 ~ 6:1, and the speed of described spin coating is 4000 ~ 6000 revs/min, and the time is 10 ~ 30s.
9. the preparation method of polymer solar battery as claimed in claim 6, is characterized in that, the process that active layer is prepared in described spin coating is specially: by MDMO-PPV and PC 61bM or MEH-PPV and PC 61bM adds in organic solvent, obtain mixed solution, in inert gas on Hole-injecting Buffer Layer for Improvement mixed solution described in spin coating, then 5 ~ 100min anneals at 50 ~ 200 ℃, or at room temperature place 24 ~ 48h, prepare active layer, the speed of described spin coating is 2000 ~ 6000 revs/min, and the time is 10 ~ 30s.
10. the preparation method of polymer solar battery as claimed in claim 6, is characterized in that, in the preparation in described reflector, the rotating speed of spin coating is 4000 ~ 6000 revs/min, and the time is 10 ~ 60s.
CN201210367663.8A 2012-09-28 2012-09-28 Polymer solar cell and preparation method thereof Pending CN103700772A (en)

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CN201210367663.8A CN103700772A (en) 2012-09-28 2012-09-28 Polymer solar cell and preparation method thereof

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Application Number Priority Date Filing Date Title
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CN103700772A true CN103700772A (en) 2014-04-02

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Application publication date: 20140402