CN102315392A - Polymer solar battery without PEDOT and preparation method thereof - Google Patents
Polymer solar battery without PEDOT and preparation method thereof Download PDFInfo
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- CN102315392A CN102315392A CN201110289068A CN201110289068A CN102315392A CN 102315392 A CN102315392 A CN 102315392A CN 201110289068 A CN201110289068 A CN 201110289068A CN 201110289068 A CN201110289068 A CN 201110289068A CN 102315392 A CN102315392 A CN 102315392A
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Abstract
The invention, which belongs to the polymer solar battery technology field, relates to a polymer solar battery without PEDOT and a preparation method thereof. The polymer solar battery comprises a substrate, a transparent conductive metal oxide electrode layer, an anode modification layer, a photoelectric active layer, a cathode modification layer and a low work content cathode layer, wherein the above-mentioned components are stacked successively, the battery possibly does not contain the cathode modification layer and the anode modification layer is a vanadium dioxide ( acetylacetone ) film. A transparent conductive metal oxide electrode layer is prepared on a substrate and is utilized as an anode of a battery; a mixing solution with vanadium dioxide ( acetylacetone ) and a solvent are spiningly coated on the transparent conductive anode; after baking, an anode modification layer is obtained; and then a photoelectric active layer, a cathode modification layer and a low work content cathode layer are successively prepared on the anode modification layer. According to the invention, the vanadium dioxide ( acetylacetone ) film is utilized as an anode modification layer, so that collection on cavities can be effectively realized and a work content of an anode and especially of ITO can be improved; and thus excellent performances on the polymer solar battery can be displayed.
Description
Technical field
The present invention relates to a kind of no PEDOT polymer solar battery and preparation method thereof, belong to the polymer solar battery technical field.
Background technology
Along with the aggravation gradually of energy crisis and environmental pollution in recent years, more and more big to the demand of regenerative resource.As a kind of regenerative resource of cleaning, the research of solar cell and be applied in decades in the past and obtained huge development.Polymer solar battery generally is clipped between transparent positive pole of ITO and the metal negative pole for the blend film of body and fullerene derivate acceptor by conjugated polymer to form, have structure and preparation technology simple, in light weight, cheap, prepare advantage such as large area flexible device easily and receive extensive concern.Gather (3-hexyl) thiophene (P3HT) and the solubility C60 derivative PCBM of compound with regular structure are the most representative body and the receptor photovoltaic materials given.Polymer donor material through the optimal design synthesizing new and fullerene derivative receptor material and optimize the micro phase separation structure of giving acceptor in the active layer; Make body heterojunction polymer solar battery electricity conversion surpass 8%, near the level of amorphous silicon battery.In traditional body heterojunction polymer solar battery; Because the work content lower (4.7eV) of anode ITO; Can not mate with the highest occupied molecular orbital energy level (about 5.0eV) of most of conjugated polymer photovoltaic materials; PEDOT:PSS commonly used is as the work content of anode modification layer with the raising anode, thus the capacity gauge in increase hole.But PEDOT:PSS itself has certain acidity, and long-term the use can be corroded anode ITO, thereby causes the instability of anodic interface, finally influences the long-time stability of solar cell.Therefore prepare the anode modification layer with the neutral solution of high work content and more and more cause people's attention.Like Fig. 1; Polymer solar battery mainly comprises the substrate 1 that stacks gradually, transparent conductive metal oxide electrode layer 2, anode modification layer 3; Photoelectric active layer 4; Cathodic modification layer (also can not having) 5 and low work function 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.
Two (acetylacetone,2,4-pentanedione) vanadium oxide is blue to the blue-green crystal, chemical formula VO (C
5H
7O
2)
2, its structure is suc as formula shown in 1.Molecular weight 265.16, fusing point 256-259 ℃, boiling point: 187.6 ℃ (760mmHg), and flash-point: 71.9 ℃, decompose before the fusing, in benzene monomer.In sodium carbonate liquor, react and get by vanadium sulfate acyl, acetylacetone,2,4-pentanedione, mainly as catalyst.
(formula 1)
Summary of the invention
The purpose of this invention is to provide a kind of polymer solar battery and preparation method thereof.The present invention is applied to two (acetylacetone,2,4-pentanedione) vanadium oxide in the polymer solar battery as the anode modification material first.
Polymer solar battery provided by the present invention; Comprise the substrate, transparent conductive metal oxide electrode layer, anode modification layer, photoelectric active layer, cathodic modification layer (also can not having) and the low work function cathode layer that stack gradually; Wherein, said anode modification layer is two (acetylacetone,2,4-pentanedione) vanadium oxide membrane.
In the present invention, the preferred thickness of two (acetylacetone,2,4-pentanedione) vanadium oxide membrane is
Wherein, the substrate of polymer solar battery of the present invention can be selected glass or polyester film for use;
The transparent conductive metal oxide electrode layer is oxide or its composite multi-component oxide of In, Sn, Zn, Cd;
Photoelectric active layer is electron donor and electron acceptor blend film; Wherein said electron donor material is selected from: gather (to the inferior ethene of phenylene) type, gather (arlydene ethenylidene) type, gather (to phenylene) type, gather (arlydene) class, polythiophene class, poly quinoline class, porphyrin class, phthalocyanines or be selected from by electrophilic conjugate unit such as pyrrolopyrrole diketone (DPP), diazosulfide (BT), Thienopyrroles diketone (TP) and the copolymer of forming for electron conjugated unit such as carbazole (Cz), fluorenes (F), benzo two thiophene (BDT), two thiophene acene (BDP) couplings etc. etc., electron acceptor material is selected from: fullerene or derivatives thereof, perylene or derivatives thereof, naphthalene or derivatives thereof, quinones perhaps are selected from III-V family and II-VI family semiconductor nano etc.;
The oxide of fluoride, Ti or Zn that said cathodic modification layer is alkali-metal fluoride, alkaline-earth metal or its composite multi-component oxide;
Said low work function cathode layer is Ca, Mg, Cs, Al or its combination electrode.
The preparation method of above-mentioned polymer solar battery comprises the steps:
(1) preparation transparent conductive metal oxide electrode layer on substrate is as the anode of polymer solar battery;
(2) two (acetylacetone,2,4-pentanedione) vanadium oxides and solvent form mixed solution, and the above-mentioned mixed solution of spin coating on transparent conductive anode through baking, obtains two (acetylacetone,2,4-pentanedione) vanadium oxide membrane as the anode modification layer;
(3) on the anode modification layer, prepare photoelectric active layer and low work function cathode layer successively, perhaps on the anode modification layer, prepare photoelectric active layer, cathodic modification layer and low work function cathode layer successively, obtain said polymer solar battery.
In the preparation process, mainly utilize the rotating speed of spin coating to control the thickness of two (acetylacetone,2,4-pentanedione) vanadium oxide membrane, the preferred 1000-5000rpm of rotating speed.
In the step (2), the preferred 2-10mg/mL of concentration of two (acetylacetone,2,4-pentanedione) vanadium oxide in the mixed solution.The temperature of baking can be 20-250 ℃, and the time can be 1 minute to 48 hours.
In the step (2), said solvent is any one or a few in isopropyl alcohol, isooctanol, ethanol, ethyl acetate or the benzinum.
Beneficial effect of the present invention is: the anode modification layer is two (acetylacetone,2,4-pentanedione) vanadium oxide membrane, and two (acetylacetone,2,4-pentanedione) vanadium oxide is introduced in the polymer solar battery as the anode modification material, has realized the efficient collection in hole; And EDOT:PSS compares with existing P, and the present invention also has decorative layer and do not corrode that anode, photoelectric conversion efficiency are high, technology is simple, with low cost, and experimental repeatability is good, be suitable for characteristics such as large-scale industrial production.
The present invention uses two (acetylacetone,2,4-pentanedione) vanadium oxide membrane as the anode modification layer, can effectively realize the collection in hole, improves the especially work content of ITO of anode, in polymer solar battery, shows excellent performance.
Description of drawings
Fig. 1 is the polymer solar battery structural representation;
Fig. 2 is ITO/ two (acetylacetone,2,4-pentanedione) vanadium oxide/P3HT:PC
60The current-voltage characteristic curve of BM/Ca/Al;
Fig. 3 is ITO/ two (acetylacetone,2,4-pentanedione) vanadium oxide/P3HT:PC
70The current-voltage characteristic curve of BM/Ca/Al;
Fig. 4 is ITO/ two (acetylacetone,2,4-pentanedione) vanadium oxide/P3HT:IC
60The current-voltage characteristic curve of BA/Ca/Al;
Fig. 5 is ITO/ two (acetylacetone,2,4-pentanedione) vanadium oxide/P3HT:IC
70The current-voltage characteristic curve of BA/Ca/Al
Label among the figure:
The 1-substrate; 2-transparent conductive metal oxide skin(coating); 3-anode modification layer; The 4-photoelectric active layer; 5-cathodic modification layer; 6-low work function cathode layer; 7-load or testing apparatus; The 8-plain conductor; The 9-incident light.
Embodiment
There is the transparent conducting glass of tin indium oxide (ITO) to use liquid detergent, running water, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively 2 times sputter; Nitrogen dries up; Two of spin coating 2.5mg/mL (acetylacetone,2,4-pentanedione) vanadium oxide aqueous isopropanol under the rotating speed of 5000rpm; 150 ℃ were toasted 10 minutes, and natural cooling obtains the anode modification layer.Then with P3HT and the PC of 20mg/mL
60The mixed solution of BM 1: 1 (mass ratio) directly is being spun under the rotating speed of 800rpm on the above-mentioned anode modification layer, as photoelectric active layer.At last, 5 * 10
-5The calcium of vacuum evaporation 20 nanometers and the aluminium of 100nm are made negative electrode under the handkerchief.In the polymer solar battery of gained; The thickness of two (acetylacetone,2,4-pentanedione) vanadium oxide membrane is 0.58 volt for
prepared device open circuit voltage under the simulated solar rayed of every square centimeter of 100 milliwatt; Short circuit current is 10.97 milliamperes every square centimeter; Fill factor, curve factor is 63.8%, and conversion efficiency is 4.06%.
There is the transparent conducting glass of tin indium oxide (ITO) to use liquid detergent, running water, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively 2 times sputter; Nitrogen dries up; Two of spin coating 2.5mg/mL (acetylacetone,2,4-pentanedione) vanadium oxide aqueous isopropanol under the rotating speed of 4000rpm; 130 ℃ were toasted 10 minutes, and natural cooling obtains the anode modification layer.Then with P3HT and the PC of 20mg/mL
60The mixed solution of BM 1: 1 (mass ratio) directly is being spun under the rotating speed of 800rpm on the above-mentioned anode modification layer, as photoelectric active layer.At last, 5 * 10
-5The calcium of vacuum evaporation 20 nanometers and the aluminium of 100nm are made negative electrode under the handkerchief.In the polymer solar battery of gained; The thickness of two (acetylacetone,2,4-pentanedione) vanadium oxide membrane is 0.58 volt for
prepared device open circuit voltage under the simulated solar rayed of every square centimeter of 100 milliwatt; Short circuit current is 11.32 milliamperes every square centimeter; Fill factor, curve factor is 66.8%, and conversion efficiency is 4.38%.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.
There is the transparent conducting glass of tin indium oxide (ITO) to use liquid detergent, running water, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively 2 times sputter; Nitrogen dries up; Two of spin coating 5mg/mL (acetylacetone,2,4-pentanedione) vanadium oxide aqueous isopropanol under the rotating speed of 1000rpm; 150 ℃ were toasted 10 minutes, and natural cooling obtains the anode modification layer.Then with P3HT and the PC of 20mg/mL
70The mixed solution of BM 1: 1 (mass ratio) directly is being spun under the rotating speed of 800rpm on the above-mentioned anode modification layer, as photoelectric active layer.5 * 10
-5The lithium fluoride cathodic modification layer of vacuum evaporation 1 nanometer under the handkerchief, last, 5 * 10
-5The calcium of vacuum evaporation 20 nanometers and the aluminium of 100nm are made negative electrode under the handkerchief.In the polymer solar battery of gained; The thickness of two (acetylacetone,2,4-pentanedione) vanadium oxide membrane is 0.58 volt for
prepared device open circuit voltage under the simulated solar rayed of every square centimeter of 100 milliwatt; Short circuit current is 11.14 milliamperes every square centimeter; Fill factor, curve factor is 65.5%, and conversion efficiency is 4.23%.
Embodiment 4
There is the transparent conducting glass of tin indium oxide (ITO) to use liquid detergent, running water, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively 2 times sputter; Nitrogen dries up; Two of spin coating 2.5mg/mL (acetylacetone,2,4-pentanedione) vanadium oxide aqueous isopropanol under the rotating speed of 3000rpm; 140 ℃ were toasted 10 minutes, and natural cooling obtains the anode modification layer.Then with P3HT and the PC of 20mg/mL
70The mixed solution of BM 1: 1 (mass ratio) directly is being spun under the rotating speed of 800rpm on the above-mentioned anode modification layer, as photoelectric active layer.At last, 5 * 10
-5The calcium of vacuum evaporation 20 nanometers and the aluminium of 100nm are made negative electrode under the handkerchief.In the polymer solar battery of gained; The thickness of two (acetylacetone,2,4-pentanedione) vanadium oxide membrane is 0.58 volt for
prepared device open circuit voltage under the simulated solar rayed of every square centimeter of 100 milliwatt; Short circuit current is 11.74 milliamperes every square centimeter; Fill factor, curve factor is 66.9%, and conversion efficiency is 4.55%.Fig. 3 has provided this device without rayed and the current-voltage curve under the simulated solar rayed of every square centimeter of 100 milliwatt.
Embodiment 5
There is the transparent conducting glass of tin indium oxide (ITO) to use liquid detergent, running water, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively 2 times sputter; Nitrogen dries up; Two of spin coating 2.5mg/mL (acetylacetone,2,4-pentanedione) vanadium oxide aqueous isopropanol under the rotating speed of 4000rpm; 140 ℃ were toasted 10 minutes, and natural cooling obtains the anode modification layer.Then with P3HT and the IC of 17mg/mL
60The mixed solution of BA 1: 1 (mass ratio) directly is being spun under the rotating speed of 800rpm on the above-mentioned anode modification layer, as photoelectric active layer.At last, 5 * 10
-5The aluminium of the calcium of vacuum evaporation 20nm and 100nm is made negative electrode under the handkerchief.In the polymer solar battery of gained; The thickness of two (acetylacetone,2,4-pentanedione) vanadium oxide membrane is 0.85 volt for
prepared device open circuit voltage under the simulated solar rayed of every square centimeter of 100 milliwatt; Short circuit current is 10.23 milliamperes every square centimeter; Fill factor, curve factor is 71.3%, and conversion efficiency is 6.20%.Fig. 4 has provided this device without rayed and the current-voltage curve under the simulated solar rayed of every square centimeter of 100 milliwatt.
There is the transparent conducting glass of tin indium oxide (ITO) to use liquid detergent, running water, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively 2 times sputter; Nitrogen dries up; Two of spin coating 2.5mg/mL (acetylacetone,2,4-pentanedione) vanadium oxide aqueous isopropanol under the rotating speed of 4000rpm; 140 ℃ were toasted 10 minutes, and natural cooling obtains the anode modification layer.Then with P3HT and the IC of 20mg/mL
70The mixed solution of BA 1: 1 (mass ratio) directly is being spun under the rotating speed of 800rpm on the above-mentioned anode modification layer, as photoelectric active layer.At last, 5 * 10
-5The aluminium of the calcium of vacuum evaporation 20nm and 100nm is made negative electrode under the handkerchief.In the polymer solar battery of gained; The thickness of two (acetylacetone,2,4-pentanedione) vanadium oxide membrane is 0.85 volt for
prepared device open circuit voltage under the simulated solar rayed of every square centimeter of 100 milliwatt; Short circuit current is 10.62 milliamperes every square centimeter; Fill factor, curve factor is 70.3%, and conversion efficiency is 6.35%.Fig. 5 has provided this device without rayed and the current-voltage curve under the simulated solar rayed of every square centimeter of 100 milliwatt.
The above; Be merely the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technical staff who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claim.
Claims (10)
1. polymer solar battery; Comprise the substrate, transparent conductive metal oxide electrode layer, anode modification layer and the photoelectric active layer that stack gradually; After low work function cathode layer or photoelectric active layer laminated cathodic modification layer are set on the photoelectric active layer low work function cathode layer is set again, it is characterized in that: said anode modification layer is two (acetylacetone,2,4-pentanedione) vanadium oxide membrane.
2. polymer solar battery according to claim 1 is characterized in that: two (acetylacetone,2,4-pentanedione) vanadium oxide membrane thickness is
3. polymer solar battery according to claim 1 is characterized in that: said substrate is selected glass or polyester film for use;
The transparent conductive metal oxide electrode layer is oxide or its composite multi-component oxide of In, Sn, Zn, Cd;
Photoelectric active layer is electron donor and electron acceptor blend film;
The oxide of fluoride, Ti or Zn that said cathodic modification layer is alkali-metal fluoride, alkaline-earth metal or its composite multi-component oxide;
Said low work function cathode layer is Ca, Mg, Cs, Al or its combination electrode.
4. polymer solar battery according to claim 3; It is characterized in that: in the said photoelectric active layer; Described electron donor material is selected from: gather (to the inferior ethene of phenylene) type, gather (arlydene ethenylidene) type, gather (to phenylene) type, gather (arlydene) class, polythiophene class, poly quinoline class, porphyrin class, phthalocyanines or be selected from by electrophilic conjugate unit and the copolymer of forming for the coupling of electron conjugated unit, electron acceptor material is selected from: fullerene or derivatives thereof 、 perylene or derivatives thereof, naphthalene or derivatives thereof, quinones perhaps are selected from III-V family and II-VI family semiconductor nano.
5. polymer solar battery according to claim 4; It is characterized in that: said electrophilic conjugate unit is pyrrolopyrrole diketone, diazosulfide or Thienopyrroles diketone, and said is carbazole, fluorenes, benzo two thiophene or two thiophene acenes to electron conjugated unit.
6. the preparation method of any described polymer solar battery of claim of claim 1 to 5 is characterized in that: comprise the steps:
(1) preparation transparent conductive metal oxide electrode layer on substrate is as the anode of polymer solar battery;
(2) two (acetylacetone,2,4-pentanedione) vanadium oxides and solvent form mixed solution, and the above-mentioned mixed solution of spin coating on transparent conductive anode through baking, obtains two (acetylacetone,2,4-pentanedione) vanadium oxide membrane as the anode modification layer;
(3) on the anode modification layer, prepare photoelectric active layer and low work function cathode layer successively, perhaps on the anode modification layer, prepare photoelectric active layer, cathodic modification layer and low work function cathode layer successively, obtain said polymer solar battery.
7. method according to claim 6 is characterized in that: in the preparation process, mainly utilize the rotating speed of spin coating to control the thickness of two (acetylacetone,2,4-pentanedione) vanadium oxide membrane, rotating speed is 1000-5000rpm.
8. method according to claim 6 is characterized in that: in the step (2), the concentration of two (acetylacetone,2,4-pentanedione) vanadium oxide is 2-10mg/mL in the mixed solution, and the temperature of baking is 20-250 ℃, and the time is 1 minute to 48 hours.
9. method according to claim 6 is characterized in that: in the step (2), said solvent be in isopropyl alcohol, isooctanol, ethanol, ethyl acetate or the benzinum any one or a few.
10. two (acetylacetone,2,4-pentanedione) vanadium oxide is as the application of anode modification material in polymer solar battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104022228A (en) * | 2014-06-17 | 2014-09-03 | 华北电力大学 | Non-conjugate ionic polymer solar batteries and preparation method thereof |
| CN110504366A (en) * | 2019-08-30 | 2019-11-26 | 湘潭大学 | A kind of vanadium copper composite oxide film and its preparation method and application and a kind of organic solar batteries |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101123296A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院化学研究所 | A polymer solar battery and its making method |
| US20110220853A1 (en) * | 2008-11-19 | 2011-09-15 | Takuji Yoshimoto | Charge-transporting material and charge-transporting varnish |
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- 2011-09-26 CN CN201110289068A patent/CN102315392A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101123296A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院化学研究所 | A polymer solar battery and its making method |
| US20110220853A1 (en) * | 2008-11-19 | 2011-09-15 | Takuji Yoshimoto | Charge-transporting material and charge-transporting varnish |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104022228A (en) * | 2014-06-17 | 2014-09-03 | 华北电力大学 | Non-conjugate ionic polymer solar batteries and preparation method thereof |
| CN110504366A (en) * | 2019-08-30 | 2019-11-26 | 湘潭大学 | A kind of vanadium copper composite oxide film and its preparation method and application and a kind of organic solar batteries |
| CN110504366B (en) * | 2019-08-30 | 2022-08-16 | 湘潭大学 | Vanadium-copper composite oxide film, preparation method and application thereof, and organic solar cell |
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Application publication date: 20120111 |