CN100563043C - 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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Abstract
The invention discloses a kind of polymer solar battery and preparation method thereof.Polymer solar battery provided by the present invention comprises: the substrate that is connected successively in twos, anode layer, anode modification layer, photoelectric active layer, cathodic modification layer and cathode layer, wherein, the cathodic modification layer is that dialkoxy two (acetylacetone,2,4-pentanedione) closes titanium film.The present invention uses diisopropoxy two (acetylacetone,2,4-pentanedione) and closes titanium as the cathodic modification layer material, is introduced in the polymer solar battery, has increased the photoelectric conversion efficiency of solar cell; And, with existing be that the battery of cathodic modification layer material is compared with the lithium fluoride, it is simple that the present invention also has technology, with low cost, characteristics such as experiment favorable reproducibility.And, adopt very mode such as simple spin-coating diisopropoxy two (acetylacetone,2,4-pentanedione) can be closed titanium and film on photoelectric active layer, preparation process is simple, and thickness is controlled easily, and to the photoelectric active layer of lower floor without any destruction, be suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of polymer solar battery and preparation method thereof.
Background technology
Along with the aggravation gradually of energy crisis and environmental pollution in recent years, also increasing to the demand of regenerative resource.As a kind of regenerative resource of cleaning, the research of solar cell and application have obtained huge development in the past few decades.Organic/polymer solar battery owing to have preparation technology simple, in light weight, cheap, prepare advantages such as large area flexible device easily and paid close attention to (1:Tang widely, C.W.Appl.Phys.Lett., 1986,48,183.2:Brabec, C.J.; Sariciftci, N.S.; Hummelen, J.C.Adv.Funct.Mater.2001,11,15).
In the past few years, increasing research work concentrates on and improves organic/polymer solar battery (1:Hasobe, T. on the collection efficiency of yin, yang the two poles of the earth electric charge; Imahori, H.; Kamat, P.V.; Fukuzumi, S.J.Am.Chem.Soc.2003,125,14962.2:Zhang, F.L.; Gadisa, A.; Inganas, O.Appl.Phys.Lett.2004,84,3906.3:Tetsuya, T.; Masayuki, C.; Yuji, Y.Kazuhiro, S.; Kiyoshi, Y.Appl.Phys.Lett.2004,85,1832.4:Shrotriya, V.; Li, G.; Yao, Y.; Chu, C.W.; Yang, Y.Appl.Phys.Lett.2006,88,073508.5:Brabec, C.J.; Shaheen, S.E.; Winder, C.; Sariciftci, S.; Denk, P.Appl.Phys.Lett.2002,80,1288.5:Kim, J.Y.; Kim, S.H.; Lee, H.H.; Lee, K.Ma, W.; Gong, X.; Heeger, A.J.Adv.Mater.2006,18,572.).As Fig. 1, organic/polymer solar battery mainly comprises in twos connection successively: substrate 1 (common used material is glass or polyester film etc.), (common used material is ITO to high work content transparent anode 2, gold film etc.), (common used material is poly-enedioxy thiophene (PEDOT) to anode modification layer 3: the composite membrane of kayexalate (PSS) etc.), photoelectric active layer 4 (organic/polymeric donor/the acceptor composite bed), cathodic modification layer 5 and cathode layer 6 etc., battery is connected with load or testing apparatus 7 with plain conductor 8, and incident light 9 is injected from substrate 1 direction.In photoelectric active layer 4, contain electron donor material and electron acceptor material, electron donor material commonly used can be selected from: poly-(to the inferior ethene of phenylene) class, poly-(arlydene ethenylidene) class, poly-(to phenylene) class, poly-(arlydene) class, polythiophene class, poly quinoline class, porphyrin class, phthalocyanines etc.; Electron acceptor material can be selected from fullerene and derivative, perylene and derivative thereof, naphthalene and derivative thereof, quinones and III-V family and II-VI family semiconductor nano etc.Cathode layer 6 comprises alkali metal, alkaline-earth metal that has than low work function or the covering that contains aluminium, silver or copper.At present, cathodic modification layer 5 material commonly used are lithium fluoride, after modifying, device performance is improved significantly, but its mechanism is not very clear that still present explanation mainly contains: 1) lithium fluoride and aluminium interact and generate the lithium of low work content, thereby reduce the potential barrier at interface; 2) introduce lithium fluoride and can effectively stop of the doping of the metallic atom of evaporation, thereby improve the stability of device active layer.But because that the thickness of the performance of device and lithium fluoride has is very big according to patience, obtain perfect performance must be with THICKNESS CONTROL between 5～15 dusts, and this is very high to technological requirement, is difficult to accurately control, and also is unfavorable for large-scale industrial production.
It is the pale red transparency liquid that diisopropoxy two (acetylacetone,2,4-pentanedione) closes titanium, and its structure is suc as formula shown in the I, and relative molecular weight or atomic weight are 364.31; Density is 1.01 grams per milliliters; Fusing point is 10 ℃; Viscosity in the time of 25 ℃ is 10.0mPas.This material is dissolved in isopropyl alcohol, also is dissolved in benzene, toluene and chloroform, and the energy hydrolysis decomposites two mol of alcohol when having water to exist during hydrolysis.At air drying, then dehydration becomes insoluble hydroxy compounds.To this material heating, become compound with chelating ability.This material mainly is used as the modifier of coating, printing ink, varnish etc.; The tackifier of curing accelerator, surface conditioning agent etc.
(formula I)
Summary of the invention
The purpose of this invention is to provide a kind of polymer solar battery and preparation method thereof.
Polymer solar battery provided by the present invention comprises: the substrate that is connected successively in twos, anode layer, anode modification layer, photoelectric active layer, cathodic modification layer and cathode layer, wherein, the cathodic modification layer is that dialkoxy two (acetylacetone,2,4-pentanedione) closes titanium film.
In the present invention, dialkoxy two (acetylacetone,2,4-pentanediones) thickness that closes titanium film is preferably 5-500
Wherein, the substrate of solar cell of the present invention can be selected glass or polyester film for use; Anode layer is ITO or golden film; Described anode modification layer is poly-enedioxy thiophene: the composite membrane of kayexalate; Described photoelectric active layer is the composite membrane of PPV derivative and PCBM; Described negative electrode is alkali metal, alkaline-earth metal or the covering that contains aluminium, silver or copper.
The preparation method of polymer solar battery comprises the steps:
1) on substrate, prepares anode layer, anode modification layer and photoelectric active layer successively continuously;
2) dialkoxy two (acetylacetone,2,4-pentanedione) closes titanium solution in spin coating on the photoelectric active layer, and vacuumize obtains the cathodic modification layer;
3) on the cathodic modification layer, prepare cathode layer, obtain described polymer solar battery.
Wherein, the solvent that available dialkoxy two (acetylacetone,2,4-pentanedione) closes titanium solution closes titanium for dissolving dialkoxy two (acetylacetone,2,4-pentanedione), do not have an effect with the photoelectric active layer of lower floor again, commonly used have isopropyl alcohol, isooctanol, ethanol, ethyl acetate, a benzinum; Be preferably isopropyl alcohol, isooctanol, ethanol.
In preparation process, mainly utilize the rotating speed of spin coating to control the thickness that dialkoxy two (acetylacetone,2,4-pentanedione) closes titanium film, the fast more film thickness of rotating speed is thin more; Rotating speed is slow more, and film thickness is big more; Rotating speed during spin coating is 1000rpm-5000rpm.Vacuum drying temperature is a room temperature-250 ℃, and the time is 5 minutes to 48 hours.
The present invention uses diisopropoxy two (acetylacetone,2,4-pentanedione) and closes titanium as the cathodic modification layer material, be introduced in the polymer solar battery, compare with polymer solar battery with cathodic modification, not only improved polymer solar battery open circuit voltage of the present invention, increase short circuit current, simultaneously also improve fill factor, curve factor, and then increased the photoelectric conversion efficiency of solar cell; And, with existing be that the battery of cathodic modification layer material is compared with the lithium fluoride, it is simple that the present invention also has technology, with low cost, characteristics such as experiment favorable reproducibility.And, adopt very mode such as simple spin-coating diisopropoxy two (acetylacetone,2,4-pentanedione) can be closed titanium and film on photoelectric active layer, preparation process is simple, and thickness is controlled easily, and to the photoelectric active layer of lower floor without any destruction, be suitable for large-scale industrial production.
Description of drawings
Fig. 1 is the structural representation of polymer solar battery;
Fig. 2 is the dark current and the photoelectric current curve of the polymer solar battery (ITO/PEDOT:PSS/MEH-PPV+PCBM/Al) without cathodic modification;
Fig. 3 is not for modified and make the cathodic modification material and the current-voltage curve of the polymer solar battery that obtained in 30 minutes 80 ℃ of vacuum drying treatment at the 1000rpm spin-coating;
Fig. 4 is not for modified and make the cathodic modification material and the current-voltage curve of the polymer solar battery that obtained in 30 minutes 80 ℃ of vacuum drying treatment at the 4000rpm spin-coating;
Fig. 5 is not for modified and make the cathodic modification material and the current-voltage curve of the polymer solar battery that obtained in 30 minutes 110 ℃ of vacuum drying treatment at the 3000rpm spin-coating;
Fig. 6 is not for modified and make the cathodic modification material and the current-voltage curve of the polymer solar battery that obtained in 30 minutes 50 ℃ of vacuum drying treatment at the 2500rpm spin-coating.
Embodiment
Embodiment 1 (Comparative Examples), with the preparation of the solar cell of cathodic modification layer
There is the transparent conducting glass of ITO (anode) to use detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter, use the ozone treatment substrate surface then, again rotation coat 30 nanometer thickness PEDOT:PSS as the anode modification film, 150 ℃ of dryings 10 minutes.Under the rotating speed of 1600 commentaries on classics per minutes (rpm), directly be spun on the mixed solution of 3 milligrams every milliliter MEH-PPV and PCBM 1: 4 (mass ratio) above-mentioned on the substrate of anode modification, as photoelectric active layer, 50 ℃ of dryings are 30 minutes then, naturally cool to room temperature; At last, 5 * 10
-5The aluminium of vacuum evaporation 150 nanometers is made negative electrode under the handkerchief.
Fig. 2 has provided this device without rayed and the current-voltage curve under the simulated solar rayed of every square centimeter of 100 milliwatt.Prepared device open circuit voltage under the simulated solar rayed of every square centimeter of 100 milliwatt is 0.78 volt, and short circuit current is 4.39 milliamperes every square centimeter, and fill factor, curve factor is 0.39, and conversion efficiency is 1.34%.
The preparation of embodiment 2, solar cell of the present invention
The diisopropoxy two (acetylacetone,2,4-pentanedione) of accurately measuring 50 microlitres 70% closes the aqueous isopropanol (available from U.S. Alfa Aesar company) of titanium, it is joined in the isopropyl alcohol of anhydrous and oxygen-free of 1000 microlitres, fully stir, leave standstill, and filter with 5 microns filter, stand-by.
There is the transparent conducting glass of ITO (anode) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter, use the ozone treatment substrate surface then, again rotation coat 30 nanometer thickness PEDOT:PSS as the anode modification film, 150 ℃ of dryings 10 minutes.Under the rotating speed of 1600 commentaries on classics per minutes (rpm), directly be spun on the mixed solution of 3 milligrams every milliliter MEH-PPV and PCBM 1: 4 (mass ratio) above-mentioned on the substrate of anode modification, as photoelectric active layer, 50 ℃ of dryings are 30 minutes then, naturally cool to room temperature.The aqueous isopropanol that prepared diisopropoxy two (acetylacetone,2,4-pentanedione) is closed titanium directly is spin-coated on above the photoelectric active layer under the rotating speed of 1000rpm, and at 80 ℃ of vacuumizes 30 minutes, natural cooling; At last, 5 * 10
-5The aluminium of vacuum evaporation 150 nanometers is made negative electrode under the handkerchief.
To close titanium film thickness be 250 to diisopropoxy two (acetylacetone,2,4-pentanediones) in the gained battery
About, and in preparation process, photoelectric active layer is not produced destruction; Fig. 3 has provided comparative device and this device without rayed and the current-voltage curve under the simulated solar rayed of every square centimeter of 100 milliwatt.Prepared device open circuit voltage under the simulated solar rayed of every square centimeter of 100 milliwatt is 0.81 volt, and short circuit current is 5.83 milliamperes every square centimeter, and fill factor, curve factor is 0.48, and conversion efficiency is 2.29%.Compare with not modified battery, open circuit voltage improves 0.03 volt, and short circuit current improves 33%, and fill factor, curve factor improves 23%, and efficient improves 71%.
There is the transparent conducting glass of ITO (anode) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter, use the ozone treatment substrate surface then, again rotation coat 30 nanometer thickness PEDOT:PSS as the anode modification film, 150 ℃ of dryings 10 minutes.Under the rotating speed of 1600 commentaries on classics per minutes (rpm), directly be spun on the mixed solution of 3 milligrams every milliliter MEH-PPV and PCBM 1: 4 (mass ratio) above-mentioned on the substrate of anode modification, as photoelectric active layer, 50 ℃ of dryings are 30 minutes then, naturally cool to room temperature.The aqueous isopropanol that prepared diisopropoxy two (acetylacetone,2,4-pentanedione) is closed titanium directly is spin-coated on above the photoelectric active layer under the rotating speed of 4000rpm, and at 80 ℃ of vacuumizes 30 minutes, natural cooling; At last, 5 * 10
-5The aluminium of vacuum evaporation 150 nanometers is made negative electrode under the handkerchief.
To close titanium film thickness be 70-80 to diisopropoxy two (acetylacetone,2,4-pentanediones) in the gained battery
About, and in preparation process, photoelectric active layer is not produced destruction; Fig. 4 has provided comparative device and this device without rayed and the current-voltage curve under the simulated solar rayed of every square centimeter of 100 milliwatt.Prepared device open circuit voltage under the simulated solar rayed of every square centimeter of 100 milliwatt is 0.81 volt, and short circuit current is 5.81 milliamperes every square centimeter, and fill factor, curve factor is 0.52, and conversion efficiency is 2.47%.Compare with not modified battery, open circuit voltage improves 0.03 volt, and short circuit current improves 32%, and fill factor, curve factor improves 33%, and efficient improves 84%.
Embodiment 4,
There is the transparent conducting glass of ITO (anode) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter, use the ozone treatment substrate surface then, again rotation coat 30 nanometer thickness PEDOT:PSS as the anode modification film, 150 ℃ of dryings 10 minutes.Under the rotating speed of 1600 commentaries on classics per minutes (rpm), directly be spun on the mixed solution of 3 milligrams every milliliter MEH-PPV and PCBM 1: 4 (mass ratio) above-mentioned on the substrate of anode modification, as photoelectric active layer, 50 ℃ of dryings are 30 minutes then, naturally cool to room temperature.The aqueous isopropanol that prepared diisopropoxy two (acetylacetone,2,4-pentanedione) is closed titanium directly is spin-coated on above the photoelectric active layer under the rotating speed of 3000rpm, and at 110 ℃ of vacuumizes 30 minutes, natural cooling; At last, 5 * 10
-5The aluminium of vacuum evaporation 150 nanometers is made negative electrode under the handkerchief.
To close titanium film thickness be 150 to diisopropoxy two (acetylacetone,2,4-pentanediones) in the gained battery
About, and in preparation process, photoelectric active layer is not produced destruction; Fig. 5 has provided comparative device and this device without rayed and the current-voltage curve under the simulated solar rayed of every square centimeter of 100 milliwatt.Prepared device open circuit voltage under the simulated solar rayed of every square centimeter of 100 milliwatt is 0.81 volt, and short circuit current is 5.88 milliamperes every square centimeter, and fill factor, curve factor is 0.46, and conversion efficiency is 2.17%.Compare with not modified battery, open circuit voltage improves 0.03 volt, and short circuit current improves 34%, and fill factor, curve factor improves 18%, and efficient improves 62%.
There is the transparent conducting glass of ITO (anode) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter, use the ozone treatment substrate surface then, again rotation coat 30 nanometer thickness PEDOT:PSS as the anode modification film, 150 ℃ of dryings 10 minutes.Under the rotating speed of 1600 commentaries on classics per minutes (rpm), directly be spun on the mixed solution of 3 milligrams every milliliter MEH-PPV and PCBM 1: 4 (mass ratio) above-mentioned on the substrate of anode modification, as photoelectric active layer, 50 ℃ of dryings are 30 minutes then, naturally cool to room temperature.The aqueous isopropanol that prepared diisopropoxy two (acetylacetone,2,4-pentanedione) is closed titanium directly is spin-coated on above the photoelectric active layer under the rotating speed of 2500rpm, and at 200 ℃ of vacuumizes 30 minutes, natural cooling; At last, 5 * 10
-5The aluminium of vacuum evaporation 150 nanometers is made negative electrode under the handkerchief.
To close titanium film thickness be 180 to diisopropoxy two (acetylacetone,2,4-pentanediones) in the gained battery
About, and in preparation process, photoelectric active layer is not produced destruction; Fig. 6 has provided comparative device and this device without rayed and the current-voltage curve under the simulated solar rayed of every square centimeter of 100 milliwatt.Prepared device open circuit voltage under the simulated solar rayed of every square centimeter of 100 milliwatt is 0.81 volt, and short circuit current is 6.04 milliamperes every square centimeter, and fill factor, curve factor is 0.45, and conversion efficiency is 2.18%.Compare with not modified battery, open circuit voltage improves 0.03 volt, and short circuit current improves 38%, and fill factor, curve factor improves 15%, and efficient improves 63%.
Other solvent all can be used as the solvent that diisopropoxy two (acetylacetone,2,4-pentanedione) close titanium as isooctanol, ethanol, ethyl acetate, benzinum etc., and can not have an effect with photoelectric active layer, and the polymer solar battery of gained also has identical performance.
Claims (9)
1, a kind of polymer solar battery, comprise: the substrate that is connected successively in twos, anode layer, anode modification layer, photoelectric active layer, cathodic modification layer and cathode layer is characterized in that: described cathodic modification layer is that diisopropoxy two (acetylacetone,2,4-pentanedione) closes titanium film.
2, polymer solar battery according to claim 1 is characterized in that: the thickness that described diisopropoxy two (acetylacetone,2,4-pentanedione) closes titanium film is 5
-500
3, polymer solar battery according to claim 1 and 2 is characterized in that: described substrate is glass or polyester film; Described anode layer is ITO or golden film; Described anode modification layer is poly-enedioxy thiophene: the composite membrane of kayexalate; Described photoelectric active layer is the composite membrane of PPV derivative and PCBM; Described negative electrode is alkali metal, alkaline-earth metal or the covering that contains aluminium, silver or copper.
4, the preparation method of the described polymer solar battery of claim 1 comprises the steps:
1) on substrate, prepares anode layer, anode modification layer and photoelectric active layer successively continuously;
2) diisopropoxy two (acetylacetone,2,4-pentanedione) closes titanium solution in spin coating on the photoelectric active layer, and vacuumize obtains the cathodic modification layer;
3) on the cathodic modification layer, prepare cathode layer, obtain described polymer solar battery.
5, preparation method according to claim 4 is characterized in that: the solvent that described diisopropoxy two (acetylacetone,2,4-pentanedione) closes titanium solution is isopropyl alcohol, isooctanol, ethanol, ethyl acetate or benzinum.
6, preparation method according to claim 5 is characterized in that: described solvent is isopropyl alcohol, isooctanol or ethanol.
7, preparation method according to claim 4 is characterized in that: the rotating speed during spin coating is 1000rpm-5000rpm.
8, preparation method according to claim 4 is characterized in that: vacuum drying temperature is a room temperature-250 ℃, and the time is 5 minutes to 48 hours.
9, preparation method according to claim 4 is characterized in that: described substrate is glass or polyester film; Described anode layer is ITO or golden film; Described anode modification layer is poly-enedioxy thiophene: the composite membrane of kayexalate; Described photoelectric active layer is the composite membrane of PPV derivative and PCBM; Described negative electrode is alkali metal, alkaline-earth metal or the covering that contains aluminium, silver or copper.
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| CN102646794A (en) * | 2012-04-23 | 2012-08-22 | 华北电力大学 | P-I-N type polymer solar cell and preparation method thereof |
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