CN103236503B - Polymer solar battery and preparation method thereof - Google Patents

Polymer solar battery and preparation method thereof Download PDF

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CN103236503B
CN103236503B CN201310142156.9A CN201310142156A CN103236503B CN 103236503 B CN103236503 B CN 103236503B CN 201310142156 A CN201310142156 A CN 201310142156A CN 103236503 B CN103236503 B CN 103236503B
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annealing
methods
pcbm
atmosphere
solar battery
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CN103236503A (en
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李灯华
闫晗
杨延莲
王琛
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National Center for Nanosccience and Technology China
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National Center for Nanosccience and Technology China
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a post-processing method capable of remarkably improving the photoelectrical conversion efficiency of a polymer solar battery. According to the method, by adopting the method of self-atmosphere dissolvent annealing and high-temperature annealing, the photoelectrical conversion efficiency of the polymer solar battery can be greatly improved. The experimental result finds that by the adoption of the method, the efficiency of the polymer solar battery can be improved to above three times that of the polymer solar battery not subjected to annealing treatment, and the efficiency is the highest reported conversion efficiency of the material so far. According to the method, a complex annealing process after inletting dissolvent and air can be omitted, the process is simplified, great operability in the production and practice can be realized, and the production efficiency is improved.

Description

A kind of polymer solar battery and preparation method thereof
Technical field
The present invention relates to polymer solar battery field, particularly, the present invention relates to a kind of polymer solar battery and preparation method thereof.
Background technology
Along with petering out of fossil energy (oil, coal, natural gas etc.), finding the green regenerative energy sources that can substitute fossil energy is one of focus of whole world research.In recent years, particularly rapid to the research of the development and utilization of solar energy.Photovoltaic solar cell refers to the device utilizing photovoltaic effect solar energy to be converted into electric energy.Organic photovoltaic solar cell (Organic Photovoltaic, OPV), especially polymer solar battery (Polymer Solar Cell, PSC) because of its cheapness, lightweight, flexibility, easily processing, large area the concern that advantage causes increasing researcher such as can to prepare.
1992, Heeger has found that quantity of photogenerated charge is from the polymer as electron donor (Donor or D) to the rush transfer process of the fullerene derivate as electron acceptor (Acceptor or A), and nineteen ninety-five reported first based on body heterojunction (Bulk Heterojunction, BHJ) photovoltaic cell, polymer solar battery field obtains and develops rapidly afterwards.So-called body heterojunction refers in body phase film, and electron donor and acceptor form the inierpeneirating network structure of many contact points, and each D/A contact point is a heterojunction, and whole film is bulk heteroj unction structure.BHJ film is generally electron donor and electron acceptor are dissolved in altogether in organic solvent, then be prepared into D phase by the method for rotary coating to interpenetrate and the film of each self-forming interpenetrating networks shape two-arch tunnel with A phase, this film is the active layer of polymer solar battery.
Scientific circles and industrial quarters are devoted to new electron donor, the design and synthesis of electron acceptor material mostly in recent years, the optimization of active layer membrance casting condition, and the aspect such as the optimization of device preparation technology.In polymer solar battery, the links of separation of charge and transmission all can affect the electricity conversion of battery.The exciton diffusion length of conjugated polymer only has about 10nm, but the light absorption length of organic material is approximately about 100nm, if the yardstick of D, A two-phase is far longer than 10nm, the electronics then dissociated at boundary and hole will in diffusion process compound again, cause the decline of separation of charge efficiency.In order to meet the condition of good spectral absorption and efficient exciton dissociation simultaneously, the two-phase of body heterojunction must mix in the size of exciton diffusion length.The continuity of network that formed of D, A two-phase and the farmland district size of D, A two-phase all can have influence on the mobility of charge carrier, the i.e. efficiency of transmission of charge carrier in D, A two-phase in addition.Therefore, need the thickness of adjustment active layer film, microscopic appearance and electron donor electron acceptor two-phase inierpeneirating network structure, thus reach the object regulating the generation of charge carrier, separation and transmission finally to improve polymer solar battery transformation efficiency.But electricity conversion of the prior art is still too low.
CN101022153A discloses a kind of solvent processing method improving polymer thin-film solar cell efficiency.This polymer solar cell device adopts transparent indium-tin-oxide (ITO) as anode, and metallic aluminium is negative electrode.Anode adopts polythiofuran derivative polystyrene doped sulfonic acid (PEDOT:PSS) to modify, and active layer is the mixture of P3HT:PCBM.After active layer spin-coating film, put into the container filling chlorobenzene or dichloro-benzenes, solvent molecule infiltrates induction P3HT in active layer and self assembly occurs, and improves the order of P3HT, thus improves the mobility in film extinction and hole.Carry out high-temperature thermal annealing process to device after having steamed Al electrode, device performance is significantly improved.But the electricity conversion of this polymer thin-film solar cell is lower, can not satisfy the demand; Further, chlorobenzene or dichloro-benzenes are toxic solvent, are unfavorable for environmental protection; Chlorobenzene or dichloro-benzenes are be liquid condition under room temperature, and the solvent gas phase pressure in molten device is difficult to control; In addition, the introducing of extraneous solvent atmosphere is difficult to evaporate by making the residual solvent of film inside, and the inner heterojunction structure of heavy damage film, affects the photoelectric conversion efficiency of device; Need after active layer spin-coating film to proceed in another solvent atmosphere to carry out solvent annealing, therefore, operation is comparatively complicated.
Therefore, develop a kind of technique simple, and the preparation method with the polymer solar battery of high light electricity transformation efficiency is the technical barrier in affiliated field.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is the preparation method providing a kind of polymer solar battery, and it is simple and efficient.
The preparation method of described polymer solar battery comprises: carry out from atmosphere annealing in process after coating active layer, and after deposit metal electrodes, heat-treat annealing at 70-160 DEG C, by adopting the method for solvent annealing+high annealing, the photoelectric conversion efficiency of polymer solar battery greatly can be improved.
In the present invention, describedly to refer to from atmosphere annealing in process: after active layer coating is complete, the container with opening is adopted to be covered, owing to just applying complete lamella inside containing a large amount of solvents, in sub-closed container, form solvent atmosphere after solvent slowly volatilizees, make active layer under solvent atmosphere is closed in Asia, carry out solvent annealing (as shown in Figure 3 a).The method can remove the Complicated Flow passing into solvent atmosphere from, simplifies technical process, can in production practices, have great operability and improve production efficiency.
Preferably, the preparation method of described polymer solar battery comprises the following steps:
(1) anode preliminary treatment;
(2) hole transmission layer is applied;
(3) apply active layer, and carry out from atmosphere annealing in process;
(4) deposit metal electrodes;
(5) heat-treat annealing at 70-160 DEG C, obtain polymer solar battery.
Preferably, described anode is a kind in ITO transparent flexible plastic sheet (as PEN/ITO), FTO transparent flexible plastic sheet (as PEN/FTO), ito glass or FTO glass, is particularly preferably ito glass.
Preferably, described anode preliminary treatment comprises and etches successively, cleans and plasma surface treatment; Preferably, described cleaning comprises and adopts cleaning agent, deionized water, acetone and isopropyl alcohol to clean successively; Described cleaning agent is the micro level solution of 1%; Preferably, described cleaning adopts ultrasonic cleaning; Described micro level solution is known product, obtains by commercially available, the M-9051 such as produced by the green laboratory apparatus Co., Ltd in upper sea.
Preferably, the coating of described hole transmission layer adopts spin-coating method.
Preferably, annealing in process is carried out after coating hole transmission layer, the effect selection that described annealing temperature reaches according to the material of the hole transmission layer selected and needs; Preferably, the annealing in process temperature of described hole transmission layer is 110-150 DEG C, is particularly preferably 140 DEG C.
Preferably, described hole transmission layer is vanadic oxide, cuprous nano crystalline substance, CuPc, molybdenum trioxide, tungstic acid and poly-3,4-ethylenedioxy thiophene: a kind in sulfonated polystyrene (PEDOT:PSS) or the combination of at least 2 kinds, be particularly preferably PEDOT:PSS.
Preferably, the coating of described active layer adopts spin-coating method; Preferably, in spin coating process, the rotary speed of sol evenning machine is 500-1200 revolutions per second, more preferably 600-800 revolutions per second, is particularly preferably 700 revolutions per seconds.
Preferably, the described pressure from atmosphere annealing in process is 0.01-1MPa, more preferably 0.05-0.5MPa, is particularly preferably 0.1MPa; By regulating the openings of sizes of the container covering active layer, regulate the pressure from atmosphere annealing in process.
Preferably, described is 1-60min, more preferably 20-50min from the atmosphere annealing in process time, is particularly preferably 30min.
Preferably, described active layer is a kind in MEH-PPV:PCBM, MDMO-PPV:PCBM, P3HT:PCBM, PCDTBT:PCBM or PBTTT:PCBM, is particularly preferably P3HT:PCBM; Preferably, the mass ratio of P3HT and PCBM is 1:0.8 ~ 1:1.1, is particularly preferably 1:1.
The solvent adopted in the coating of described active layer is according to the different choice of active layer material.Such as, when active layer is P3HT:PCBM, solvent is o-dichlorohenzene, chloroform or chlorobenzene, is particularly preferably o-dichlorohenzene; Wherein, the concentration of P3HT is preferably 12-20mg mL -1, more preferably 15-18mg mL -1, be particularly preferably 17mg mL -1; The concentration of PCBM is preferably 12-20mg mL -1, more preferably 15-18mgmL -1, be particularly preferably 17mg mL -1.
MEH-PPV is poly-(2-methoxyl group-5-(2 '-vinyl-own oxygen base) is poly-to styrene support); MDMO-PPV is poly-(2-methoxyl group-5-(3,7-dimethyl octyloxy) phenylenevinylene); P3HT is poly-3-hexyl thiophene; PCDTBT is poly-[[9-(1-octyl group nonyl)-9H-carbazole-2,7-bis-base]-2,5-thiophene two base-2,1,3-diazosulfide-4,7-bis-base-2,5-thiophene two base]; PBTTT is poly-(2,5-two (3-heneicosyl thiophene-2-base) thieno [3,2-b]) thiophene); PCBM is [6,6]-C61-phenylbutyric acid methyl esters.
Preferably, the deposition of described metal electrode adopts vapour deposition method.
Preferably, described metal electrode is made up of calcium film and aluminium film.
Preferably, described thermal anneal temperature is 120 ~ 155 DEG C, is particularly preferably 150 DEG C.
Preferably, the described heat-treatment of annealing time is at least 10 minutes, such as 11 minutes, 12 minutes, 13 minutes, 15 minutes, 20 minutes, 25 minutes, 29 minutes, 31 minutes, 35 minutes, 40 minutes, 50 minutes, 59 minutes, 61 minutes, 65 minutes, 70 minutes etc., more preferably 10-60 minute, is particularly preferably 30 minutes.
Described heat-treatment of annealing makes active layer film form inierpeneirating network structure; All there are significant impact heat treatment temperature and time to the inierpeneirating network structure of active layer film.
Preferably, the preparation method of described polymer solar battery comprises the following steps:
(1) adopt ito glass to be anode, it is etched successively, cleans and plasma surface treatment;
(2) spin coating hole transmission layer PEDOT:PSS on ito glass, carries out annealing in process at 110-150 DEG C after spin coating;
(3) spin coating active layer P3HT:PCBM, and carry out from atmosphere annealing in process, namely, be that the o-dichlorobenzene solution of 1:0.8 ~ 1:1.1 is with the speed spin coating of 500-1200 revolutions per second by the mass ratio of P3HT and PCBM, then covered with the container with opening, control openings of sizes, make in container from the pressure of atmosphere annealing in process be 0.01-1MPa;
(4) evaporation calcium film and aluminium film successively, obtains metal electrode;
(5) heat-treat annealing at least 10 minutes at 70-160 DEG C, obtain polymer solar battery.
An object of the present invention is also the polymer solar battery providing a kind of described method to prepare.The photoelectric conversion efficiency of polymer solar battery prepared by the method can bring up to more than three times of unannealed process.
Compared with prior art, the advantage of the method for the invention is:
(1) employing can remove from atmosphere solvent method for annealing the complicated annealing process passing into extraneous solvent atmosphere from, simplifies technical process, can in production practices, have great operability and improve production efficiency;
(2) photoelectric conversion efficiency of the polymer solar battery adopting the method for the invention to prepare can bring up to more than three times of unannealed process; Such as, with poly-(3-hexyl) thiophene) with [6,6]-C61-phenylbutyric acid methyl esters (P3HT:PCBM) blended photovoltaic material is example, the inierpeneirating network structure of body heterojunction is regulated by the method for high annealing after solvent annealing+electrode evaporation before electrode evaporation, making the transformation efficiency of material bring up to 4.6% after annealing in process from 1.3% before annealing in process, is the highest transformation efficiency reported of this material so far;
(3) through the battery of the method for the invention process, its photovoltaic active layers pattern produces obvious inierpeneirating network structure and phase separation, is conducive to charge carrier and arrives corresponding electrode efficiency in each phase;
(4) through the battery of the method for the invention process, its photovoltaic active layers degree of crystallinity significantly promotes, and contributes to charge carrier in material internal mobility;
(5) through the battery of the technology of the present invention process, it significantly strengthens in the light absorbing ability in region of ultra-red place, and its Carrier recombination probability reduces greatly.
Accompanying drawing explanation
Fig. 1 a is the structure of the polymer solar battery of one embodiment of the invention, and Fig. 1 b is schematic arrangement.
Fig. 2 is the scale diagrams of battery described in embodiment 1.
Fig. 3 be the polymer solar battery of one embodiment of the invention prepare treatment process process; Wherein Fig. 3 a is the installation drawing from the annealing of atmosphere solvent, and Fig. 3 b is the metal electrode evaporation after solvent annealing, and Fig. 3 c is the high annealing of completed device.
Fig. 4 a is the untreated and I-V curve after this method 150 DEG C of different time annealing in process of polymer solar battery, and Fig. 4 b is the untreated and I-V curve after this method different temperatures annealing in process 30min of polymer solar battery.
Fig. 5 shows the regulating and controlling effect for the treatment of method to polymer solar battery photovoltaic active layers film morphology and inierpeneirating network structure; Fig. 5 a is undressed atomic force microscope schematic diagram, and Fig. 5 b is through the atomic force microscope schematic diagram after solvent of the present invention annealing+150 DEG C of 30min the high temperature anneal.
Fig. 6 be polymer solar battery photovoltaic active layers unprocessed and through the method for the invention solvent annealing+150 DEG C of 30min the high temperature anneal after X-ray diffraction degree of crystallinity resolution chart.
Fig. 7 a be polymer solar battery photovoltaic active layers untreated and through this method solvent annealing+150 DEG C of 30min the high temperature anneal after uv absorption spectra, show the humidification of described method to film absorption photon ability; Fig. 7 b is the untreated and fluorescence spectrum resolution chart after this method solvent annealing+150 DEG C of 30min the high temperature anneal of polymer solar battery photovoltaic active layers, shows that described method reduces the effect of the inner carrier electric charge compound of film.
Reference numeral is as follows:
1—Al/Ca； 2—P3HT/PCBM； 3—PEDOT/PSS；
4-ITO; 5-glass; 6-battery thin film;
7-small ventilating holes, 8-small plastic culture dish; 9-substrate.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
1, the etching of ito glass, cleaning and preliminary treatment
The etching of 1.1 substrate ITO and process
15mm × 15mm regular square ito glass that cutting is complete touch with insulating cement the part of central 2mm × 15mm, and relative dimensions as shown in Figure 2, is guaranteed not stay bubble between glass and adhesive tape, especially marginal portion.The ito glass posted is put into the H that concentration is 37% is housed 2sO 4with the glass container of deionized water (volume ratio is 1:1) solution, after about 1min, take out ito glass, clean in deionized water several times, remove the acid remained on glass, complete the etching of ITO.
The cleaning of 1.2ITO sheet
The ITO sheet of lable number is placed on film hanger, follows these steps to carry out surface clean:
(1) cleaning agent cleaning: micro level solution (upper marine green laboratory apparatus Co., Ltd, the M-9051) ultrasonic cleaning with 1% 10 minutes, to wash away the inorganic and organic remains on ITO slide.
(2) washed with de-ionized water: with deionized water ultrasonic cleaning 2 times, each 5 minutes, mainly in order to wash away the micro level washing agent (upper marine green laboratory apparatus Co., Ltd, M-9051) on ITO slide.
(3) acetone cleaning: with acetone soln ultrasonic cleaning 10 minutes, object was for washing away organic dirt that ITO slide may remain.
(4) isopropyl alcohol cleaning: with isopropyl alcohol ultrasonic cleaning 10 minutes, to wash the organic impurities that still possibility is remaining off, nitrogen dries up for subsequent use.
(5) before preparing battery device, ITO surface will through UV ozone plasma surface treatment.Processing time is 10 minutes.The effect of plasma surface treatment is the organic substance thoroughly removing ITO sheet remained on surface, and the surface contact angle of ITO sheet can be diminished, be conducive to water miscible PEDOT:PSS layer tack and moulding property, reduce the contact resistance between this ito glass and organic semiconductor.
2, the spin coating of PEDOT:PSS, annealing
The PEDOT:PSS solution that we use buys (model Baytron PAL4083, HC Stark) from Bayer A.G.PEDOT:PSS is a kind of novel organic conductive material, because it has the advantages such as high conductivity, good stability, dopant states be transparent, has a wide range of applications in the devices such as organic electroluminescence device, organic solar batteries, capacitor.Usual PEDOT:PSS, as the hole transmission layer of organic electro-optic device, can improve the performance of organic electro-optic device significantly.
With sol evenning machine, PEDOT:PSS solution is spin-coated on film forming on ITO sheet with the speed of 4000 revolutions per seconds, the thickness of film is controlled by the spin coating rotating speed of sol evenning machine, measures the thickness of film with surface profile calibrator, the thickness required for being obtained by adjustment sol evenning machine rotating speed.The thickness recorded with step instrument is about 40 nanometers.Finally, the ITO sheet of PEDOT:PSS layer by spin coating, puts into constant temperature 140 DEG C heating 10 minutes, evaporating the solvent of the remnants of PEDOT:PSS layer completely.
3, the preparation of organic photovoltaic active layer
Adopt rotary coating method preparation, spin coating preparation mainly comprise solution allocation, spin-coating film, solvent evaporates anneal three parts composition.In the wherein solution allocation stage, the selection of solution concentration and solvent is larger on device efficiency impact.We adopt o-dichlorohenzene to be solvent, and concentration is P3HT (17mg mL -1): PCBM (17mgmL -1).Being spin-coated in semiconductor test arm casing of P3HT:PCBM polyblend layer is carried out.The rotary speed of sol evenning machine is 700 revolutions per seconds.Be high pure nitrogen filling in semiconductor test arm casing, oxygen content is less than 5ppm, and relative humidity is less than 1ppm, to be formed with the hypoxemia low humidified state being beneficial to protection device.The ITO sheet scribbling PEDOT:PSS layer after drying is put into glove box.
4, organic photovoltaic active layer from atmosphere solvent annealing in process
With the method passing into solvent atmosphere adopted before unlike, what we adopted is from atmosphere solvent method for annealing, namely photovoltaic active layers spin coating complete after, the culture dish of a mini zone opening is adopted to cover ITO sheet, and the size of culture dish opening can be controlled, a large amount of solvents is contained in the lamella inside complete due to firm spin coating, in sub-closed petridish, solvent atmosphere is formed after solvent slowly volatilizees, make its internal pressure remain on 0.01-1MPa, under solvent atmosphere is closed in Asia, carry out solvent annealing to allow photovoltaic active layers.
5, the evaporation of metal electrode
The metal electrode of battery is chosen as the combination of calcium (Ca)+aluminium (Al), and electrode high temperature deposition in vacuum coating equipment obtains, first evaporation one deck calcium film in electric shock, then evaporation one deck aluminium film on this basis.The vacuum coating equipment that the present embodiment uses mainly comprises the parts such as coating chamber, extract system, control panel, and coating chamber is built with three critical pieces such as heater, baffle plate, support of evaporation source.The general flow of evaporation calcium is: first put on the sample stage of vacuum chamber to the cell substrate scribbling active layer material, fixes its position with specimen holder, faces down towards electrode material source by one of active layer; Then recirculated water is opened, start extracting vacuum, be first pumped into elementary vacuum with mechanical pump, then take out higher vacuum with diffusion pump, when chamber pressure is less than 2 × 10 -6during mbar vacuum degree, first baffle plate is covered plated substrate, carry out fritting and evaporate a period of time.This processing method both can make the impure part of electrode surface evaporate and not be deposited on sample, can start evaporation again when electrode evaporation rate and thickness are stablized, ensure that quality and the uniformity of electrode metallizations.When electrode prevapourising 5nm thickness, remove baffle plate and start formal evaporation.Due to electrode and battery active layer material between contact and evaporate process in before film in 10nm thickness in close relations, so, usually in the beginning of electrode evaporation, controlling electric current makes the speed of evaporation slow, after thickness is more than 10nm, slowly improve electric current, accelerate its evaporation rate, complete whole evaporate process at leisure.After the complete calcium film of evaporation, turn off the evaporation source of calcium, open the evaporation source of aluminium, use the same method and carry out the evaporation of aluminium film.The thickness of calcium film is 20nm, and the thickness of aluminium film is 80nm.
6, heat-treatment of annealing
The device of complete for evaporation metal electrode is carried out high annealing heat treatment.All there are significant impact heat treatment temperature and time to the inierpeneirating network structure of active layer film, and heat-treat condition is 150 DEG C, 30min.
7, device photovoltaic efficiency test
With adding an AMO filter plate before the light neon source of 100W with simulated solar irradiation.After light intensity calibration, adopt 100mW/cm 2the light of radiant illumination irradiates, its energy conversion efficiency its can calculate by defining:
η = P max P in = ( IV ) max / S P in × 100 .
Wherein P maxfor peak power output (unit: mW), P infor radiant illumination (unit: mW/cm 2), S is the effective area (unit: cm of device 2).
Test result:
(1) the device architecture schematic diagram in the present embodiment as shown in Figure 1a, spin coating PEDOT:PSS electron transfer layer, P3HT:PCBM photovoltaic active layer on ito glass successively, evaporation Ca/Al negative electrode.P3HT:PCBM structural representation as shown in Figure 1 b.
(2) battery prepared of the present embodiment method, namely from the battery of atmosphere solvent annealing+high-temperature heat treatment annealing, open circuit voltage is 0.60V, and short circuit current is 11.6mA/cm 2, fill factor, curve factor is 61.0%, and photoelectric conversion efficiency is for 4.6%(is as shown in table 1 and Fig. 4).
(3) through battery prepared by the present embodiment method, its photovoltaic active layer pattern characterizes through atomic force microscope, produces obvious inierpeneirating network structure and phase separation, is conducive to charge carrier and arrives corresponding electrode efficiency (Fig. 5) in each phase.
(4) through battery prepared by the present embodiment method, its photovoltaic active layer degree of crystallinity significantly promotes, and contributes to charge carrier at material internal mobility (Fig. 6).
(5) through battery prepared by the present embodiment method, (Fig. 7 a), and its Carrier recombination probability reduces (Fig. 7 b) greatly it significantly strengthen in the light absorbing ability in region of ultra-red (500-615nm) place.
Embodiment 2
1, the etching of FTO glass, cleaning and preliminary treatment
Identical with embodiment 1.
2, the spin coating of tungstic acid, annealing
Substantially the same manner as Example 1, difference is, spin coating rotating speed is 3600 revolutions per seconds, and thickness is about 45 nanometers, and annealing conditions is: 135 DEG C, 20 minutes.
3, the preparation of organic photovoltaic active layer
Substantially the same manner as Example 1, difference is, active layer adopts MEH-PPV:PCBM, and solvent is chlorobenzene, and MEH-PPV and PCBM mass ratio is 1:4, and spin coating rotating speed is 1200 revolutions per seconds.
4, organic photovoltaic active layer from atmosphere solvent annealing in process
Substantially the same manner as Example 1, the container internal pressure when atmosphere is annealed remains on 0.01-1MPa.
5, the evaporation of metal electrode
Identical with embodiment 1.
6, heat-treatment of annealing
Heat-treat condition is 70 DEG C, 100min.
Test the battery that the present embodiment obtains, test condition is as embodiment 1.
Test result:
Battery prepared by the present embodiment method, open circuit voltage is 0.82V, and short circuit current is 5.1mA/cm 2, fill factor, curve factor is 54.1%, and photoelectric conversion efficiency is 3.9%.
Embodiment 3
1, the etching of ito glass, cleaning and preliminary treatment
Identical with embodiment 1.
2, the spin coating of cuprous oxide, annealing
Substantially the same manner as Example 1, difference is, spin coating rotating speed is 4100 revolutions per seconds, and thickness is about 38 nanometers, and annealing conditions is: 145 DEG C, 10 minutes.
3, the preparation of organic photovoltaic active layer
Substantially the same manner as Example 1, difference is, active layer adopts MDMO-PPV:PCBM, and solvent is dimethylbenzene, and MDMO-PPV and PCBM mass ratio is 1:2, and spin coating rotating speed is 500 revolutions per seconds.
4, organic photovoltaic active layer from atmosphere solvent annealing in process
Substantially the same manner as Example 1, the container internal pressure when atmosphere is annealed remains on 0.01-1MPa.
5, the evaporation of metal electrode
Identical with embodiment 1.
6, heat-treatment of annealing
Heat-treat condition is 160 DEG C, 10min.
Test the battery that the present embodiment obtains, test condition is as embodiment 1.
Test result:
Battery prepared by the present embodiment method, open circuit voltage is 0.85V, and short circuit current is 5.6mA/cm 2, fill factor, curve factor is 53.4%, and photoelectric conversion efficiency is 3.3%.
Embodiment 4
1, the etching of ito glass, cleaning and preliminary treatment
Identical with embodiment 1.
2, the spin coating of vanadic oxide, annealing
Substantially the same manner as Example 1, difference is, spin coating rotating speed is 4050 revolutions per seconds, and thickness is about 40 nanometers, and annealing conditions is: 85 DEG C, 20 minutes.
3, the preparation of organic photovoltaic active layer
Substantially the same manner as Example 1, difference is, solvent is chlorobenzene, and P3HT and PCBM mass ratio is 1:0.8, and spin coating rotating speed is 550 revolutions per seconds.
4, organic photovoltaic active layer from atmosphere solvent annealing in process
Substantially the same manner as Example 1, the container internal pressure when atmosphere is annealed remains on 0.01-1MPa.
5, the evaporation of metal electrode
Identical with embodiment 1.
6, heat-treatment of annealing
Heat-treat condition is 100 DEG C, 70min.
Test the battery that the present embodiment obtains, test condition is as embodiment 1.
Test result:
Battery prepared by the present embodiment method, open circuit voltage is 0.61V, and short circuit current is 10.6mA/cm 2, fill factor, curve factor is 63.5%, and photoelectric conversion efficiency is 4.5%.
Embodiment 5
1, the etching of ito glass, cleaning and preliminary treatment
Identical with embodiment 1.
2, the spin coating of PEDOT:PSS, annealing
Substantially the same manner as Example 1, difference is, spin coating rotating speed is 3900 revolutions per seconds, and thickness is about 42 nanometers, and annealing conditions is: 130 DEG C, 20 minutes.
3, the preparation of organic photovoltaic active layer
Substantially the same manner as Example 1, difference is, P3HT and PCBM mass ratio is 1:1.1, and spin coating rotating speed is 600 revolutions per seconds.
4, organic photovoltaic active layer from atmosphere solvent annealing in process
Substantially the same manner as Example 1, the container internal pressure when atmosphere is annealed remains on 0.01-1MPa.
5, the evaporation of metal electrode
Identical with embodiment 1.
6, heat-treatment of annealing
Heat-treat condition is 155 DEG C, 10min.
Test the battery that the present embodiment obtains, test condition is as embodiment 1.
Test result:
Battery prepared by the present embodiment method, open circuit voltage is 0.61V, and short circuit current is 11.5mA/cm 2, fill factor, curve factor is 58.2%, and photoelectric conversion efficiency is 4.4%.
Comparative example 1
Substantially the same manner as Example 1, difference is, this comparative example do not carry out organic photovoltaic active layer from atmosphere solvent annealing in process and heat-treatment of annealing.
Test the battery that this comparative example obtains, test condition is as embodiment 1.
Test result is in table 1.
Battery prepared by this comparative example method, open circuit voltage is 0.63V, and short circuit current is 3.87mA/cm 2, fill factor, curve factor is 49.5%, and photoelectric conversion efficiency is 1.3%.
Comparative example 2
This comparative example adopts embodiment 1 disclosed in CN101022153A.Experiment condition is as follows:
First the ITO on ito glass is photo-etched into the electrode of 4 mm wides, 30 millimeters long, the fine strip shape ITO electro-conductive glass with one fixed width etched is cleaned up and dries, clean ito glass is placed on the bracket of spin coater, the PEDOT:PSS dissolution homogeneity filtered is filled whole slice, thin piece, control rotating speed and time chien shih PEDOT:PSS form the film of uniform 30 nanometers of one deck on ito glass surface, then the baking oven putting into 120 DEG C heats 30 minutes.
The refining organic solvent chlorobenzene of P3HT and PCBM weighed up is made into the solution that mass percent concentration is 2% and 1.6% respectively in nitrogen glove box, then, stirs both by identical volume mixture together.The ito glass scribbling PEDOT:PSS film is transferred in glove box, be placed on the bracket of spin coater, again the mixed solution dissolved evenly is filled after 0.45 micron filter whole PEDOT:PSS film surface, control rotating speed and time chien shih mixture form uniform 150 nano thin-films of one deck on ito glass surface.Then sample is placed on the support in the wide-mouth bottle that o-dichlorohenzene solvent is housed, makes solvent not flood sample, then drive air in bottle away with nitrogen, good seal container, allow 30 minutes, solvent gas effect film surface, to transfer in glove box room temperature and place solvent flashing.And then put in vacuum coating equipment and start to vacuumize steaming metal aluminium electrode.5 × 10 are respectively in vacuum degree 1the metal aluminium electrode of evaporation thick layer 100 nanometer under Pascal, battery effectively and to amass be 12 square millimeters, make the polymer solar battery that structure is ITO/PEDOT:PSS (30nm)/P3HT:PCBM (150nm)/Al (100nm).The 150 degree of high-temperature thermal annealings 1 minute in glove box of the completed device after electrode are steamed.
After tested, battery prepared by this comparative example method, open circuit voltage is 0.7V, and short circuit current is 10.01mA/cm 2, fill factor, curve factor is 52.8%, and photoelectric conversion efficiency is 3.7%.
Table 1
Device V oc(V) J sc(mA/cm 2) FF(%) PCE(%)
Untreated 0.63 3.87 49.5 1.3
150℃/30min 0.60 11.6 61.0 4.6
From above embodiment and comparative example, polymer solar battery prepared by the method for the invention compared with prior art, has more excellent photoelectric conversion performance.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (33)

1. the preparation method of a polymer solar battery, comprise: carry out from atmosphere annealing in process after coating active layer, and heat-treat annealing at 70-160 DEG C after deposit metal electrodes, the described pressure from atmosphere annealing in process is 0.01-1Mpa, and the heat-treatment of annealing time is at least 10 minutes; Wherein saidly to refer to from atmosphere annealing in process: after active layer coating is complete, the container with opening is adopted to be covered, owing to just applying complete lamella inside containing a large amount of solvents, in sub-closed container, form solvent atmosphere after solvent slowly volatilizees, make active layer carry out solvent annealing under solvent atmosphere is closed in Asia.
2. the method for claim 1, is characterized in that, the preparation method of described polymer solar battery comprises the following steps:
(1) anode preliminary treatment;
(2) hole transmission layer is applied;
(3) apply active layer, and carry out from atmosphere annealing in process;
(4) deposit metal electrodes;
(5) heat-treat annealing at 70-160 DEG C, obtain polymer solar battery.
3. method as claimed in claim 2, it is characterized in that, described anode is a kind in ITO transparent flexible plastic sheet, FTO transparent flexible plastic sheet, ito glass or FTO glass, and described anode preliminary treatment comprises and etches successively, cleans and plasma surface treatment.
4. method as claimed in claim 3, it is characterized in that, described anode is ito glass.
5. method as claimed in claim 3, is characterized in that, described cleaning comprises and adopts cleaning agent, deionized water, acetone and isopropyl alcohol to clean successively; Described cleaning agent is the micro level solution of 1%.
6. method as claimed in claim 5, is characterized in that, described cleaning adopts ultrasonic cleaning.
7. method as claimed in claim 2, is characterized in that, the coating of described hole transmission layer adopts spin-coating method.
8. method as claimed in claim 7, is characterized in that, carries out annealing in process after coating hole transmission layer.
9. method as claimed in claim 8, it is characterized in that, the annealing in process temperature of described hole transmission layer is 110-150 DEG C.
10. method as claimed in claim 9, it is characterized in that, the annealing in process temperature of described hole transmission layer is 140 DEG C.
11. methods as described in claim 2 or any one of 7-10, it is characterized in that, described hole transmission layer is vanadic oxide, cuprous nano crystalline substance, CuPc, molybdenum trioxide, tungstic acid and poly-3,4-ethylene dioxythiophene: a kind in sulfonated polystyrene or the combination of at least 2 kinds.
12. methods as claimed in claim 11, it is characterized in that, described hole transmission layer is PEDOT:PSS.
13. methods as claimed in claim 2, is characterized in that, the coating of described active layer adopts spin-coating method.
14. methods as claimed in claim 13, it is characterized in that, in spin coating process, the rotary speed of sol evenning machine is 500-1200 revolutions per second.
15. methods as claimed in claim 14, it is characterized in that, in spin coating process, the rotary speed of sol evenning machine is 600-800 revolutions per second.
16. methods as claimed in claim 15, it is characterized in that, in spin coating process, the rotary speed of sol evenning machine is 700 revolutions per seconds.
17. methods as claimed in claim 1 or 2, is characterized in that, the described pressure from atmosphere annealing in process is 0.05-0.5MPa.
18. methods as claimed in claim 17, is characterized in that, the described pressure from atmosphere annealing in process is 0.1MPa.
19. methods as claimed in claim 1 or 2, is characterized in that, described is 1-60min from the atmosphere annealing in process time.
20. methods as claimed in claim 19, is characterized in that, described is 20-50min from the atmosphere annealing in process time.
21. methods as claimed in claim 20, is characterized in that, described is 30min from the atmosphere annealing in process time.
22. methods as claimed in claim 1 or 2, is characterized in that, described active layer is a kind in MEH-PPV:PCBM, MDMO-PPV:PCBM, P3HT:PCBM, PCDTBT:PCBM or PBTTT:PCBM.
23. methods as claimed in claim 22, it is characterized in that, described active layer is P3HT:PCBM.
24. methods as claimed in claim 23, is characterized in that, the mass ratio of described P3HT and PCBM is 1:0.8 ~ 1:1.1.
25. methods as claimed in claim 24, is characterized in that, the mass ratio of described P3HT and PCBM is 1:1.
26. methods as claimed in claim 2, is characterized in that, the deposition of described metal electrode adopts vapour deposition method.
27. methods as claimed in claim 26, it is characterized in that, described metal electrode is made up of calcium film and aluminium film.
28. methods as claimed in claim 1 or 2, it is characterized in that, described thermal anneal temperature is 120 ~ 155 DEG C.
29. methods as claimed in claim 28, it is characterized in that, described thermal anneal temperature is 150 DEG C.
30. methods as claimed in claim 1 or 2, it is characterized in that, the described heat-treatment of annealing time is 10-60 minute.
31. methods as claimed in claim 30, it is characterized in that, the described heat-treatment of annealing time is 30 minutes.
32. methods as claimed in claim 1 or 2, it is characterized in that, the preparation method of described polymer solar battery comprises the following steps:
(1) adopt ito glass to be anode, it is etched successively, cleans and plasma surface treatment;
(2) spin coating hole transmission layer PEDOT:PSS on ito glass, carries out annealing in process at 110-150 DEG C after spin coating;
(3) spin coating active layer P3HT:PCBM, and carry out from atmosphere annealing in process, namely, be that the o-dichlorobenzene solution of 1:0.8 ~ 1:1.1 is with the speed spin coating of 500-1200 revolutions per second by the mass ratio of P3HT and PCBM, then covered with the container with opening, control openings of sizes, make in container from the pressure of atmosphere annealing in process be 0.01-1MPa;
(4) evaporation calcium film and aluminium film successively, obtains metal electrode;
(5) heat-treat annealing at least 10 minutes at 70-160 DEG C, obtain polymer solar battery.
33. 1 kinds of polymer solar batteries, is characterized in that, described polymer solar battery is prepared by the method described in claim 1 or 2.
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