CN105070839B - A kind of polymer solar battery and preparation method thereof - Google Patents
A kind of polymer solar battery and preparation method thereof Download PDFInfo
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- CN105070839B CN105070839B CN201510404590.9A CN201510404590A CN105070839B CN 105070839 B CN105070839 B CN 105070839B CN 201510404590 A CN201510404590 A CN 201510404590A CN 105070839 B CN105070839 B CN 105070839B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title description 14
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 39
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims abstract description 31
- 239000002086 nanomaterial Substances 0.000 claims abstract description 26
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011521 glass Substances 0.000 claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 8
- -1 C60 phenylbutyric acids methyl esters Chemical class 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 47
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 34
- 238000000137 annealing Methods 0.000 claims description 30
- 238000004528 spin coating Methods 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 18
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 14
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 12
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000007740 vapor deposition Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229920000954 Polyglycolide Polymers 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 3
- 229940059939 kayexalate Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004633 polyglycolic acid Substances 0.000 claims description 3
- 238000002207 thermal evaporation Methods 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 2
- 239000010408 film Substances 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 229930192474 thiophene Natural products 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 230000000295 complement effect Effects 0.000 abstract description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000011056 performance test Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
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- 239000013078 crystal Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
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- 238000001771 vacuum deposition Methods 0.000 description 4
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- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- DSCFFEYYQKSRSV-KLJZZCKASA-N D-pinitol Chemical compound CO[C@@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-KLJZZCKASA-N 0.000 description 1
- 238000000637 aluminium metallisation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
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Classifications
-
- 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
- H10K30/81—Electrodes
-
- 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
- H10K71/621—Providing a shape to conductive layers, e.g. patterning or selective deposition
-
- 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
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
- Polyethers (AREA)
Abstract
The present invention provides a kind of polymer solar battery, the polymer solar battery includes the glass substrate, anode layer, anode modification layer, active layer and the cathode layer that are sequentially overlapped from bottom to top, it is characterized in that, interface between the active layer and cathode layer is in complementary peak valley shape micro-nano structure, the peak width of the peak valley shape micro-nano structure is 300~400 μm, peak height is 20~30nm, and the active layer includes poly- 3 hexyl thiophene (P3HT):[6.6] C60 phenylbutyric acids methyl esters (PCBM) and propylene glycol methyl ether acetate (PGMEA).The present invention also provides a kind of straightforward procedures for preparing polymer solar battery.The micro-nano structure expands cathode and the contact interface of active layer material, improves the collection efficiency of electrode pair charge, improves the efficiency of polymer solar battery.
Description
Technical field
The invention belongs to photovoltaic materials and device preparation field, and particularly the present invention relates to a kind of polymer solar batteries
And preparation method thereof.
Background technology
The exhaust gas generated when the increasingly depleted of traditional fossil energy (coal, oil, natural gas) and burning is caused by environment
Pollution allows it was recognized that finding the urgency of regenerative resource.The energy of low-carbon environment-friendly mainly has waterpower, solar energy, wind at present
Can wait, wherein solar energy due to have many advantages, such as it is inexhaustible, with it not to the utmost, and not can cause environmental pollution, receive
The more and more extensive attention of people.
Silica-based solar cell commercially achieves huge success at present, but due to complex manufacturing technology, cost
It is high, and noxious material can be generated in the production purification process of silicon, there are certain safety and pollution hidden trouble, development
It is restricted.Polymer solar battery is because its raw material sources is wide, and cheap, preparation process is simple, can pass through rotation
The methods of coating, spraying, printing, forms a film on flexible substrates, this not only greatly reduces manufacture cost, but also can be with large area
Film forming, this photovoltaic cell for allowing for preparing low-cost large-area are possibly realized.By the development of more than 20 years, the polymer sun
The efficiency of energy battery has had significant raising, but compared with ripe inorganic solar cell, polymer solar battery
Efficiency also than relatively low.Restrict the spectral response range and solar spectrum that an important factor for efficiency improves is organic semiconducting materials
It mismatches, the factors such as exciton diffusion length is short, carrier mobility is low and the collection efficiency of electrode pair charge is low.
Widely used micro-nano structure electrode in inorganic solar cell is introduced organic sun by Recent study personnel
In energy battery, it is found that micro-nano structure electrode can improve efficiency of transmission and electrode pair charge of the electric charge carrier in active layer
Collection efficiency.Micro-nano structure cathode is prepared often by means of template (such as silicon template, porous alumina formwork), is pressed by nanometer
The method of print makes active layer material have micro-nano structure, and in electrode evaporation, electrode material can form mutually nested with active layer
Complementary structure, so as to prepare the cathode of micro-nano structure.Although this method can prepare having with micro-nano structure electrode
Machine solar cell, but preparation process is cumbersome, nano impression is of high cost, and during the experiment, in order to make template from active layer
Sur-face peeling will usually use releasing agent, and releasing agent not easy cleaning can pollute active layer surface, influence the performance of photovoltaic device.
The content of the invention
In order to solve the problems in the existing technology, the present invention provides a kind of polymer solar battery and offers one
The method that kind prepares the polymer solar battery.In the case of not by template so that polymer solar battery
Active layer can spontaneously form micro-nano structure, so that the cathode of surface vapor deposition is with nested against one another with active layer on it
Peak valley shape micro-nano structure, so as to improve the efficiency of polymer solar battery.
On the one hand, the present invention provides a kind of polymer solar battery, the polymer solar battery is included under
Glass substrate, anode layer, anode modification layer, active layer and the cathode layer being sequentially overlapped on and, which is characterized in that the photolytic activity
Interface between layer and cathode layer in complementary peak valley shape micro-nano structure, the peak width of the peak valley shape micro-nano structure for 300~
400nm, peak height are 20~30nm, and the active layer includes poly- 3- hexyl thiophenes (P3HT):[6.6]-C60- phenylbutyric acids methyl esters
(PCBM) and propylene glycol methyl ether acetate (PGMEA).
Preferably, the active layer is use by P3HT：The active layer solution of PCBM and PGMEA compositions is prepared by spin coating
's.
Preferably, the active layer solution is by the way that PGMEA is mixed P3HT：It is prepared in PCBM mixed solutions,
In by volume, the PGMEA accounts for P3HT：The 1%~4% of PCBM mixed solutions is preferably 2%.
Preferably, the thickness of the active layer is 80~120nm, is preferably 100nm.
Preferably, the substrate is glass substrate, and the anode layer is tin indium oxide (ITO)；The anode modification layer is
Polyglycolic acid fibre:Kayexalate (PEDOT：PSS) film, it is preferable that the thickness of the anode modification layer for 30~
50nm；And/or the cathode layer is aluminium electrode, the thickness of preferably described cathode layer is 100nm.
On the other hand, the present invention provides a kind of method for preparing polymer solar battery as described above, the method
Comprise the following steps：
(1) UV ozone processing is carried out to the anode layer after cleaning, it is preferable that the time of the UV ozone processing is 8-
15min, more preferably 10min；
(2) with sol evenning machine by PEDOT：PSS aqueous solutions are spin-coated on the anode layer handled through UV ozone described in step (1)
On, to prepare PEDOT：PSS films；Then the dry PEDOT of annealing：PSS films, to form PEDOT：PSS anode modifications
Layer, it is preferable that the dry annealing is the dry 30min that anneals at a temperature of 150 DEG C；
(3) active layer 5~30min of solution is ultrasonically treated, is preferably 15min, then with sol evenning machine by processed activity
Layer solution is spin-coated on the PEDOT formed in step (2)：Above PSS anode modification layers, to prepare active layer, wherein the work
Property layer solution is by the way that PGMEA is mixed P3HT：It is prepared in PCBM mixed solutions, and wherein by volume, it is described
PGMEA accounts for P3HT：The 1%~4% of PCBM mixed solutions is preferably 2%；
(4) negative electrode is deposited by the method for thermal evaporation on the active layer prepared by step (3), it then will be obtained
Device carries out after annealing processing at a temperature of 120-160 DEG C, so as to be spontaneously formed between the active layer and cathode layer mutually
The peak valley shape micro-nano structure of benefit, the peak width of the peak valley shape micro-nano structure is 300~400nm, peak height is 20~30nm, after described
The time of annealing is 10-80min.
Preferably, in step (2), the rotating speed 3000rps of the sol evenning machine, spin-coating time is 50 seconds.
Preferably, in step (3), the rotating speed of the sol evenning machine is 1500rpm, spin-coating time 45s.
Preferably, in step (4), the rate of the vapor deposition isPreferably
Preferably, in step (5), the temperature of the after annealing processing is 150 DEG C, and the time of after annealing processing is 30-
80min is preferably 50min.
Propylene glycol methyl ether acetate (PGMEA) is mixed into P3HT in the present invention：Active layer is prepared in PCBM mixed solutions
Solution, by being ultrasonically treated to active layer solution and being carried out to polymer solar cell device obtained at after annealing
Reason, PGMEA can crystallize P3HT so that complementary peak valley shape micro-nano structure, institute are spontaneously formed between active layer and cathode layer
The peak width for stating peak valley shape micro-nano structure is 300~400nm, peak height is 20~30nm (Fig. 1).The AM aluminum metallization in the activity layer surface
Electrode, then aluminium (Al) atom be gradually deposited at active layer surface, formed with active layer pattern it is nested against one another there is micro-nano structure
Cathode layer, so as to be made with micro-nano structure cathode layer polymer solar cell device.On the one hand, the micro-nano structure
Cathode interts mutually with active layer material, shortens transmission path of the electric charge carrier in active layer, is conducive to carrier
Transmission.On the other hand, the micro-nano structure expands cathode and the contact interface of active layer material, improves electrode pair charge
Collection efficiency improves the efficiency of polymer solar battery.The present invention by the reunion of P3HT, the upper surface of active layer from
It forms micro-nano structure hair, is prepared on the premise of additional process (such as nano impression) is not increased with micro-nano structure cathode
Polymer solar battery, improve the energy conversion efficiency of polymer solar battery.Meanwhile the present invention also provides one
Kind prepares the straightforward procedure of polymer solar battery.
Description of the drawings
Fig. 1 is atomic force microscope (AFM) shape appearance figure of active layer surface；
Fig. 2 is the structure diagram of polymer solar battery；
Fig. 3 shows that the Current density-voltage of polymer solar battery prepared by 2-6 according to an embodiment of the invention is special
Linearity curve；
Fig. 4 shows that the Current density-voltage of polymer solar battery prepared by 7-8 according to an embodiment of the invention is special
Linearity curve；
Fig. 5 shows the Current density-voltage of polymer solar battery prepared by 9-11 according to an embodiment of the invention
Characteristic curve.
Reference sign
Glass substrate：1；Anode：2；Anode modification layer：3；Active layer：4；Cathode：5.
Specific embodiment
For a better understanding of the present invention, with reference to the accompanying drawings and embodiments, the present invention will be described in further detail.
It should be appreciated that implementation column described herein is only to explain the purpose of the present invention, protection scope of the present invention is not limited.
Experimental method used in the present invention is conventional method unless otherwise specified.
Material, reagent used in the present invention etc. unless otherwise specified, are obtained by commercial sources.
Abbreviation
AFM represents atomic force microscope；
ITO represents tin indium oxide；
PEDOT：PSS represents Polyglycolic acid fibre：Kayexalate；
P3HT represents poly- 3- hexyl thiophenes；
PCBM represents [6.6]-C60- phenylbutyric acid methyl esters；
PGMEA represents propylene glycol methyl ether acetate.
Definition
As used in the present disclosure, P3HT：PCBM mixed solutions are by by the PCBM of the P3HT of 15mg and 12mg
It is dissolved in the chlorobenzene solution of P3HT prepared in the chlorobenzene of 1ml and PCBM.
Experiment reagent and instrument used in the present invention：
Propylene glycol methyl ether acetate (purity 99%) is purchased from lark prestige Science and Technology Ltd.；
Poly- 3- hexyl thiophenes (P3HT) and [6.6]-C60- phenylbutyric acids methyl esters (PCBM) are purchased from the limited public affairs of machine light science and technology
Department；
PEDOT:PSS (Clevios P VPA14083), is the PEDOT with 1.3wt% purchased from H.C.Starck companies：
PSS is dissolved in water the conductive aqueous solution to be formed；
Chlorobenzene is bought from Sigma-Aldrich companies；
Acetone (concentration 99.5%), alcohol (concentration 99.5%)；
For the high-purity aluminium wire (purity of plated electrode>99.999%) buy from Zhong Nuo green woods company.
Ito glass substrate used in the present invention is purchased from Zhuhai Kaivo Optoelectronic Technology Co., Ltd., square resistance 15
Ω/□。
Sol evenning machine is purchased from the desk-top sol evenning machine of KW-4A types that Microelectronics Institute of the Chinese Academy of Sciences manufactures and designs.
The photovoltaic performance parameter of polymer solar battery, using 4200 digital sourcemeters of Keithley in 100mW/cm2's
Current density-voltage characteristic curve is measured under standard analog sunlight (AM 1.5G), and is calculated.
PEDOT：The thickness of PSS layer and active layer by German Brooker company Dektak XT type probe-type surface profiles
Instrument measurement obtains.
The AFM shape appearance figures of active layer surface are that the JEOL JSPM-5400 types produced with Jeol Ltd. scan spy
Pin microscope is tested to obtain.
Ultrasound Instrument used in supersound process is purchased from Kunshan ultrasonic instrument Co., Ltd, model KQ-300DV.
Embodiment 1
Mixed with the pattern test of the active layer film surface of PGMEA
The preparation of active layer solution is using chlorobenzene as solvent, in mass/volume (w/v) than being 15mg/ml:12mg/ml's
P3HT:It is mixed in PCBM mixed solutions and accounts for P3HT by volume：2% PGMEA of PCBM mixed solutions prepares active layer solution,
It preserves at room temperature.
Dipping the wiping sputtering of ITO washing lotions with swab stick has the transparent conductive glass surface of ITO, until glass surface has continuously
Ito glass is successively put into deionized water, acetone (concentration 99.5%) and alcohol (concentration 99.5%), by suitable by moisture film afterwards
Sequence is 30 minutes ultrasonic respectively successively.UV ozone processing, time 10min are carried out to ito anode layer.By PEDOT：PSS solution
Filtered with 0.45 μm of filtering head, afterwards with sol evenning machine with the rotating speed of 3000rpm by PEDOT：PSS solution is spun to ITO surfaces,
Spin-coating time is 50 seconds to prepare PEDOT：PSS films so that film thickness is about 40nm.Afterwards by PEDOT：PSS films are at 150 DEG C
At a temperature of drying and annealing 30 minutes to form PEDOT：PSS anode modification layers.By active layer solution be ultrasonically treated 15 minutes, then
Processed active layer solution is spin-coated on PEDOT with sol evenning machine：To prepare active layer above PSS films, spin coating machine speed is
1500rpm, spin-coating time 45s.Active layer film obtained is annealed 15 minutes at a temperature of 150 DEG C.
The JEOL JSPM-5400 types that obtained active layer film is produced with Jeol Ltd. are scanned into probe
Microscope tests its AFM surface topography.
Fig. 1 is the AFM surface topography maps of the active layer film that PGMEA contents are 2% by volume.As seen from Figure 1,
Occurs the peak valley shape micro-nano structure that peak width is 300~400nm, peak height is 20~30nm on the surface of active layer film.
Embodiment 2
The preparation and performance test of polymer solar battery undoped with PGMEA
Mass ratio is 15mg/ml using chlorobenzene as solvent by the preparation of active layer solution:The P3HT of 12mg/ml:PCBM is dissolved in
Chlorobenzene solution prepares active layer solution, preserves at room temperature.
Dipping the wiping sputtering of ITO washing lotions with swab stick has the transparent conductive glass surface of ITO, until glass surface has continuously
Ito glass is successively put into deionized water, acetone (concentration 99.5%) and alcohol (concentration 99.5%), by suitable by moisture film afterwards
Sequence is 30 minutes ultrasonic respectively successively.UV ozone processing, time 10min are carried out to ito anode layer.By PEDOT：PSS solution
Filtered with 0.45 μm of filtering head, afterwards with sol evenning machine with the rotating speed of 3000rpm by PEDOT：PSS solution is spun to ITO surfaces,
Spin-coating time is 50 seconds to prepare PEDOT：PSS films so that film thickness is about 40nm.Afterwards by PEDOT：PSS films are at 150 DEG C
At a temperature of drying and annealing 30 minutes to form PEDOT：PSS anode modification layers.By active layer solution be ultrasonically treated 15 minutes, then
Processed active layer solution is spin-coated on PEDOT with sol evenning machine：To prepare active layer above PSS films, spin coating machine speed is
1500rpm, spin-coating time 45s.Then aluminium electrode is deposited into Vacuum Deposition membrane cavity in active layer film transfer obtained, intracavitary
Vacuum degree is maintained at 5 × 10-4Pa or so, evaporation rate and film thickness are monitored in real time by quartz crystal oscillator, to ensure the equal of evaporated film
Even property.After the completion of plated film, solar cell is obtained, anneals 30 at a temperature of 150 DEG C to polymer solar battery obtained
Minute.
With 4200 digital sourcemeters of Keithley in 100mW/cm2Standard analog sunlight (AM1.5G) under measure polymerization
The Current density-voltage characteristic curve of object solar cell.The Current density-voltage of obtained polymer solar battery is special
Linearity curve according to the photovoltaic performance of Current density-voltage characteristic curve calculating polymer solar battery as shown in figure 3, and join
Number：Open-circuit voltage (Uoc), short-circuit current density (Jsc), fill factor, curve factor (FF) and power conversion efficiency (PCE).Open-circuit voltage is
Refer to when there is no current loop, the voltage that device generates after illumination；Short-circuit current density refers to when applied voltage is zero,
The current density that can be generated by the device of illumination in forming circuit；Fill factor, curve factor refers to the peak power output of battery
(UmJm) ratio with open-circuit voltage and short-circuit current density product, i.e.,：
Power conversion efficiency refers to peak power output PmWith irradiation power PinThe ratio between, i.e.,
In formula, JSCIt is short-circuit current density, unit mA/cm2；PinIt is irradiation power, unit mW/cm2。
Embodiment 3
Adulterate the preparation and performance test of the polymer solar battery of PGMEA
Dipping the wiping sputtering of ITO washing lotions with swab stick has the transparent conductive glass surface of ITO, until glass surface has continuously
Ito glass is successively put into deionized water, acetone (concentration 99.5%) and alcohol (concentration 99.5%), by suitable by moisture film afterwards
Sequence is 30 minutes ultrasonic respectively successively.UV ozone processing, time 10min are carried out to ito anode layer.By PEDOT：PSS solution
Filtered with 0.45 μm of filtering head, afterwards with sol evenning machine with the rotating speed of 3000rpm by PEDOT：PSS solution is spun to ITO surfaces,
Spin-coating time is 50 seconds to prepare PEDOT：PSS films so that film thickness is about 40nm.Afterwards by PEDOT：PSS films are at 150 DEG C
At a temperature of drying and annealing 30 minutes to form PEDOT：PSS anode modification layers.It is 15mg/ml in mass ratio using chlorobenzene as solvent:
The P3HT of 12mg/ml:The PGMEA that volume is 1% is mixed in PCBM solution and prepares active layer solution, by active layer solution ultrasound 15
Minute, it is then spin coated onto in PEDOT：Active layer, spin coating machine speed 1500rpm, spin-coating time 45s are prepared above PSS films.Then will
The film prepared is transferred to evaporating Al electrode in Vacuum Deposition membrane cavity, and the vacuum degree of intracavitary is maintained at 5 × 10-4Pa or so, vapor deposition
Rate and film thickness are monitored in real time by quartz crystal oscillator, to ensure the uniformity of evaporated film.After the completion of plated film, exist to device obtained
It anneals 30 minutes at a temperature of 150 DEG C, obtains the polymer solar battery of the present invention.Method according to embodiment 2 is surveyed
The performance of weight polymers solar cell, the results are shown in Table 1.The Current density-voltage of obtained polymer solar battery is special
Linearity curve is as shown in Figure 3.
Embodiment 4
Adulterate the preparation and performance test of the polymer solar battery of PGMEA
Except in photoactive layer solution, the content of PGMEA is beyond 2% by volume, remaining operation is complete with embodiment 3
It is exactly the same.The performance of method measurement polymer solar battery according to embodiment 2, the results are shown in Table 1.Obtained polymerization
The Current density-voltage characteristic curve of object solar cell is as shown in Figure 3.
Embodiment 5
Adulterate the preparation and performance test of the polymer solar battery of PGMEA
Except in photoactive layer solution, the content of PGMEA is beyond 3% by volume, remaining operation is complete with embodiment 3
It is exactly the same.The performance of method measurement polymer solar battery according to embodiment 2, the results are shown in Table 1.Obtained polymerization
The Current density-voltage characteristic curve of object solar cell is as shown in Figure 3.
Embodiment 6
Adulterate the preparation and performance test of the polymer solar battery of PGMEA
Except in photoactive layer solution, the content of PGMEA is beyond 4% by volume, remaining operation is complete with embodiment 3
It is exactly the same.The performance of method measurement polymer solar battery according to embodiment 2, the results are shown in Table 1.Obtained polymerization
The Current density-voltage characteristic curve of object solar cell is as shown in Figure 3.
Embodiment 7
The polymer solar battery prepared using different ultrasonic times and performance test
Dipping the wiping sputtering of ITO washing lotions with swab stick has the transparent conductive glass surface of ITO, until glass surface has continuously
Ito glass is successively put into deionized water, acetone (concentration 99.5%) and alcohol (concentration 99.5%), by suitable by moisture film afterwards
Sequence is 30 minutes ultrasonic respectively successively.UV ozone processing, time 10min are carried out to ito anode layer.By PEDOT：PSS solution
Filtered with 0.45 μm of filtering head, afterwards with sol evenning machine with the rotating speed of 3000rpm by PEDOT：PSS solution is spun to ITO surfaces,
Spin-coating time is 50 seconds to prepare PEDOT：PSS films so that film thickness is about 40nm.Afterwards by PEDOT：PSS films are at 150 DEG C
At a temperature of drying and annealing 30 minutes to form PEDOT：PSS anode modification layers.It is 15mg/ml in mass ratio using chlorobenzene as solvent:
The P3HT of 12mg/ml:The PGMEA that volume is 2% is mixed in PCBM solution and prepares active layer solution, by active layer solution ultrasound 5
Minute, it is then spin coated onto in PEDOT：Active layer, spin coating machine speed 1500rpm, spin-coating time 45s are prepared above PSS films.Then will
The film prepared is transferred to evaporating Al electrode in Vacuum Deposition membrane cavity, and the vacuum degree of intracavitary is maintained at 5 × 10-4Pa or so, vapor deposition
Rate and film thickness are monitored in real time by quartz crystal oscillator, to ensure the uniformity of evaporated film.After the completion of plated film, exist to device obtained
It anneals 30 minutes at a temperature of 150 DEG C, obtains the polymer solar battery of the present invention.Method according to embodiment 2 is surveyed
The performance of weight polymers solar cell, the results are shown in Table 1.The Current density-voltage of obtained polymer solar battery is special
Linearity curve is as shown in Figure 4.
Embodiment 8
The polymer solar battery prepared using different ultrasonic times and performance test
In addition to active layer solution ultrasound 30 minutes, remaining operation is same as Example 7.According to embodiment 2
Method measures the performance of polymer solar battery, the results are shown in Table 1.The current density of obtained polymer solar battery-
Voltage response is as shown in Figure 4.
Embodiment 9
The polymer solar battery prepared using the different after annealing times and performance test
Dipping the wiping sputtering of ITO washing lotions with swab stick has the transparent conductive glass surface of ITO, until glass surface has continuously
Ito glass is successively put into deionized water, acetone (concentration 99.5%) and alcohol (concentration 99.5%), by suitable by moisture film afterwards
Sequence is 30 minutes ultrasonic respectively successively.UV ozone processing, time 10min are carried out to ito anode layer.By PEDOT：PSS solution
Filtered with 0.45 μm of filtering head, afterwards with sol evenning machine with the rotating speed of 3000rpm by PEDOT：PSS solution is spun to ITO surfaces,
Spin-coating time is 50 seconds to prepare PEDOT：PSS films so that film thickness is about 40nm.Afterwards by PEDOT：PSS films are at 150 DEG C
At a temperature of drying and annealing 30 minutes to form PEDOT：PSS anode modification layers.It is 15mg/ml in mass ratio using chlorobenzene as solvent:
The P3HT of 12mg/ml:The PGMEA that volume is 2% is mixed in PCBM solution and prepares active layer solution, by active layer solution ultrasound 15
Minute, it is then spin coated onto in PEDOT：Active layer, spin coating machine speed 1500rpm, spin-coating time 45s are prepared above PSS films.Then will
The film prepared is transferred to evaporating Al electrode in Vacuum Deposition membrane cavity, and the vacuum degree of intracavitary is maintained at 5 × 10-4Pa or so, vapor deposition
Rate and film thickness are monitored in real time by quartz crystal oscillator, to ensure the uniformity of evaporated film.After the completion of plated film, exist to device obtained
After annealing 15 minutes at a temperature of 150 DEG C obtain the polymer solar battery of the present invention.According to the method described in embodiment 2
The performance of polymer solar battery is measured, the results are shown in Table 1.The Current density-voltage of obtained polymer solar battery
Characteristic curve is as shown in Figure 5.
Embodiment 10
The polymer solar battery prepared using the different after annealing times and performance test
Except to polymer solar battery obtained at 150 DEG C at a temperature of in addition to after annealing 50 minutes, remaining operation
It is same as Example 9.The performance of method measurement polymer solar battery according to embodiment 2, the results are shown in Table 1.It is made
The Current density-voltage characteristic curve of the polymer solar battery obtained is as shown in Figure 5.
Embodiment 11
The polymer solar battery prepared using the different after annealing times and performance test
Except to polymer solar battery obtained at 150 DEG C at a temperature of in addition to after annealing 80 minutes, remaining operation
It is same as Example 9.The performance of method measurement polymer solar battery according to embodiment 2, the results are shown in Table 1.It is made
The Current density-voltage characteristic curve of the polymer solar battery obtained is as shown in Figure 5..
Polymer solar battery of the table 1 prepared by embodiment 2-11 is in 100mW/cm2Standard analog sunlight (AM
The photovoltaic performance parameter measured under 1.5G).
Table 1：PGMEA contents, ultrasonic time and after annealing time are to current density, open-circuit voltage, fill factor, curve factor and power
The influence of transfer efficiency
Annotation："-" expression does not mix PGMEA.
As shown in Table 1, P3HT:The polymer sun prepared by the PGMEA that volume ratio is 1%~4% is mixed in PCBM solution
It can polymer solar battery (embodiment of the battery (embodiment 3, embodiment 4, embodiment 5, embodiment 6) than being not incorporated into PGMEA
2) power-conversion efficiencies are significantly improved, especially, P3HT:When the PGMEA that volume ratio is 2% is mixed in PCBM solution
The polymer solar battery (embodiment 4) of preparation, power conversion efficiency improvement is the most apparent, than the polymerization for being not incorporated into PGMEA
The power-conversion efficiencies of object solar cell (embodiment 2) improve 17%；
Embodiment 4, embodiment 7, embodiment 8 compared the active layer solvent supersonic time to polymer solar battery power
The influence of transfer efficiency, it can be seen that ultrasound can obtain maximum power conversion efficiency for 15 minutes；
Embodiment 4, embodiment 9, embodiment 10, embodiment 11 compared after annealing to polymer solar battery performance
It influences, it can be seen that 30~80 minutes obtained polymer solar batteries of annealing time are than 15 minutes obtained polymer of annealing
The power conversion efficiency of solar cell is significantly improved, especially, the polymer that the after annealing time obtains when being 50 minutes
The power conversion efficiency highest of solar cell.
Claims (17)
1. a kind of method for preparing polymer solar battery, the polymer solar battery includes being sequentially overlapped from bottom to top
Glass substrate, anode layer, anode modification layer, active layer and cathode layer, which is characterized in that the described method comprises the following steps：
(1) UV ozone processing is carried out to the anode layer after cleaning；
(2) with sol evenning machine by Polyglycolic acid fibre:Kayexalate, that is, PEDOT：PSS aqueous solutions are spin-coated on step (1)
In through UV ozone handle anode layer on, to prepare PEDOT：PSS films；Then the dry PEDOT of annealing：PSS is thin
Film, to form PEDOT：PSS anode modification layers；
(3) active layer solution 5-30min is ultrasonically treated, processed active layer solution is then spin-coated on step with sol evenning machine
(2) PEDOT formed in：Above PSS anode modification layers, to prepare active layer, wherein the active layer solution by poly- 3- oneself
Base thiophene, that is, P3HT:[6.6]-C60- phenylbutyric acids methyl esters, that is, PCBM and propylene glycol methyl ether acetate, that is, PGMEA compositions, and it is described
Active layer solution is by the way that PGMEA is mixed P3HT：It is prepared in PCBM mixed solutions, by volume, the PGMEA is accounted for
P3HT：The 1%~4% of PCBM mixed solutions；
(4) negative electrode is deposited by the method for thermal evaporation on the active layer prepared by step (3), then by obtained device
After annealing processing is carried out at a temperature of 120-160 DEG C, so as to spontaneously form complementation between the active layer and cathode layer
Peak valley shape micro-nano structure, the peak width of the peak valley shape micro-nano structure is 300~400nm, peak height is 20~30nm, the after annealing
The time of processing is 10-80min.
2. according to the method described in claim 1, it is characterized in that, in step (1), the time of the UV ozone processing is
8-15min。
3. according to the method described in claim 2, it is characterized in that, in step (1), the time of the UV ozone processing is
10min。
4. according to the method described in claim 1, it is characterized in that, in step (2), the dry annealing is at 150 DEG C
At a temperature of anneal dry 30min.
5. according to the method described in claim 1, it is characterized in that, in step (3), by volume, the PGMEA is accounted for
P3HT：PCBM mixed solutions are 2%.
6. according to the method described in claim 1, it is characterized in that, in step (3), active layer solution 15min is ultrasonically treated.
7. according to the method described in claim 1, it is characterized in that, in step (2), the rotating speed 3000rps of the sol evenning machine,
Spin-coating time is 50 seconds.
8. according to the method described in claim 1, it is characterized in that, in step (3), the rotating speed of the sol evenning machine is
1500rpm, spin-coating time 45s.
9. according to the method described in claim 1, it is characterized in that, in step (4), the rate of the vapor deposition is
10. according to the method described in claim 9, it is characterized in that, in step (4), the rate of the vapor deposition is
11. according to the method described in claim 1, it is characterized in that, in step (5), the temperature of the after annealing processing is
150 DEG C, the time of after annealing processing is 30-80min.
12. according to the method for claim 11, which is characterized in that in step (5), the time of the after annealing processing is
50min。
13. according to the method described in claim 1, it is characterized in that, the thickness of the active layer is 80~120nm.
14. according to the method for claim 13, which is characterized in that the thickness of the active layer is 100nm.
15. according to the method described in claim 1, it is characterized in that, the thickness of the anode modification layer is 30~50nm.
16. according to the method described in claim 1, it is characterized in that, the thickness of the cathode layer is 100nm.
17. according to the method any one of claim 1-16, which is characterized in that the anode layer is for tin indium oxide
ITO, the cathode layer are aluminium electrode.
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| Improvement of the power conversion efficiency of organic photovoltaic cells with a P3HT layer fabricated by using a sonication process and having a vertically modulated nanoscale morphology;Lee Y H;《Applied Surface Science》;20121219;第268卷;第156-162页 * |
| Significant enhancement of the power conversion efficiency for organic photovoltaic cells due to a P3HT pillar layer containing ZnSe quantum dots;Kim D H;《Optics Express》;20120320;第20卷(第10期);第10476页 * |
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