CN103280532A - Preparation method of polymer solar cell zinc oxide film with inverted structure - Google Patents

Preparation method of polymer solar cell zinc oxide film with inverted structure Download PDF

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CN103280532A
CN103280532A CN2013101900027A CN201310190002A CN103280532A CN 103280532 A CN103280532 A CN 103280532A CN 2013101900027 A CN2013101900027 A CN 2013101900027A CN 201310190002 A CN201310190002 A CN 201310190002A CN 103280532 A CN103280532 A CN 103280532A
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preparation
zinc oxide
oxide film
solar cell
polymer solar
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CN103280532B (en
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谭占鳌
侯旭亮
李玮
林俊
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North China Electric Power University
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North China Electric Power University
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Abstract

The invention discloses a preparation method of a polymer solar cell zinc oxide film with an inverted structure, belonging to the field of polymer solar cell materials. The zinc oxide film is prepared by making a film with zinc acetylacetonate solution through solution processing, then directly heating in air and performing one-step conversion without sol-gel reaction. The zinc oxide prepared by the method is introduced into the polymer solar cell with the inverted structure, so that effective collection of electrons is realized. The preparation method has the characteristics of high photoelectric conversion efficiency, simple process, low cost, good experimental repeatability, suitability for large-scale industrial production and the like.

Description

A kind of preparation method of reverse geometry polymer solar cell Zinc oxide film
Technical field
The invention belongs to polymer solar battery material technology field, particularly a kind of preparation method of reverse geometry polymer solar cell Zinc oxide film.
Background technology
In recent years the organic and polymer thin-film solar cell that rises has that cost is low, in light weight, manufacture craft simple, can be prepared into outstanding advantage such as large area flexible device and receive much concern.Polymer donor material by 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 cell electricity conversion improve significantly to 8-10%, near the level of amorphous silicon battery.But the PEDOT:PSS that traditional body heterojunction polymer solar cell contacts because of positive pole can corrode the easy oxidation of negative pole of ITO, low work content, causes the stability of battery not good, is unfavorable for the stability of device and the raising in life-span.Because the work content of ITO can be regulated by decorative layer, therefore replace PEDOT:PSS to modify ITO with stable low work content decorative layer, replace the active metal with stable high work content decorative layer, can realize the counter-rotating of electron collection direction, prepare stable reverse geometry polymer solar cell.
The structure of reverse geometry polymer solar cell, mainly comprise the substrate that stacks gradually, transparent conductive metal oxide electrode layer (cathode layer), electron collection layer (cathodic modification layer), photoelectric active layer, collecting layer, hole (anode modification layer), and high work content anode layer, battery is connected with load or testing apparatus with plain conductor.
But the cathodic modification layer that is applicable to reverse geometry polymer solar cell at present is very deficient, mainly is titanium oxide and zinc oxide by the sol-gel process preparation.The invention discloses a kind of zinc acetylacetonate that utilizes and be precursor, do not need independent sol gel reaction step, prepare the method for zinc-oxide film, and this film is applied in the reverse geometry polymer solar cell.
Zinc acetylacetonate is a kind of white solid powder, and its molecular formula is C 10H 14ZnO 4, relative molecular weight or atomic weight are 263.6, structure is suc as formula shown in (I).Its fusing point is 200 ℃, and flash-point is 71.9 ℃, and the boiling point under 760mmHg is 187.6 ℃; Vapour pressure is 0.174mmHg in the time of 25 ℃.Water-soluble during 20 ℃ of this materials is 6.6g/L, dissolves in isopropyl alcohol simultaneously, organic solvents such as benzene, toluene and chloroform.This material is mainly as resin cross-linking agent and curing accelerator; Be used as organic catalyst compound etc.
Figure BDA0000322272621
Formula (I)
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of reverse geometry polymer solar cell Zinc oxide film.
A kind of preparation method of reverse geometry polymer solar cell Zinc oxide film, comprise that step is as follows: utilize zinc acetylacetonate to be precursor, zinc acetylacetonate is dissolved in solvent prepares solution, the acetylacetone,2,4-pentanedione zinc solution is spin-coated on the transparent conductive metal oxide coated cathode layer, baking obtains Zinc oxide film, i.e. cathodic modification layer.
The thickness of described Zinc oxide film is 10-500.
Described solvent is one or more in isopropyl alcohol, isooctanol, ethanol, ethyl acetate or the benzinum.
The concentration of described acetylacetone,2,4-pentanedione zinc solution is 1-10mg/mL.
The temperature of baking is 50-250 ℃, and the time is 1 minute to 24 hours.
The speed of described spin coating is 800-5000rpm.
Method of the present invention is passed through solution method for processing film processed by the acetylacetone,2,4-pentanedione zinc solution, then directly in air the heating one the step be transformed, need not sol gel reaction, the zinc oxide that this patent method is prepared is introduced in the preparation reverse geometry polymer solar battery, has realized effective collection of electronics.The Zinc oxide film of the inventive method preparation has the photoelectric conversion efficiency height, technology is simple, and is with low cost, characteristics such as good, the suitable large-scale industrial production of experimental repeatability.
Description of drawings
Fig. 1 is Glass/ITO/PEDOT:PSS/P3HT:PC 60The current-voltage characteristic curve of BM/Ca/Al;
Fig. 2 is ITO/ zinc oxide/P3HT:PC 60BM/MoO 3The current-voltage characteristic curve of/Al;
Fig. 3 is ITO/ zinc oxide/PBDTTT-CT:PC 70The current-voltage characteristic curve of BM/MoO3/Al;
Fig. 4 is ITO/ zinc oxide/PBDTTT-CT:PC 70BM/MoO 3The current-voltage characteristic curve of/Al;
Fig. 5 is ITO/ zinc oxide/PBDTTT-CT:PC 70The current-voltage characteristic curve of BM/MoO3/Al.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1(Comparative Examples)
There is the transparent conducting glass of tin indium oxide (ITO) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter, nitrogen dries up, spin coating PEDOT:PSS solution under the rotating speed of 2000rpm, 150 ℃ were toasted 15 minutes, naturally cooling obtains collecting layer, hole (anode modification layer).P3HT and PC with 20mg/mL 60BM 1:1(mass ratio) mixed solution directly is being spun under the rotating speed of 800 rpm on the collecting layer, above-mentioned hole, as photoelectric active layer.Then 4 * 10 -5The calcium metal of vacuum evaporation 20nm under the Pa obtains the electron collection layer.At last, 4 * 10 -4The aluminium of vacuum evaporation 100nm is made electrode under the handkerchief.Fig. 1 has provided this device and has penetrated without illumination and current-voltage curve under the simulated solar irradiation irradiation of every square centimeter of 100 milliwatt.Prepared device open circuit voltage under the simulated solar irradiation irradiation of every square centimeter of 100 milliwatt is 0.59 volt, and short circuit current is 9.04 milliamperes every square centimeter, and fill factor, curve factor is 0.694, and conversion efficiency is 3.71%.
Embodiment 2
There is the transparent conducting glass of tin indium oxide (ITO) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter, nitrogen dries up, the zinc acetylacetonate aqueous isopropanol of spin coating 3mg/mL under the rotating speed of 1000rpm, 150 ℃ were toasted 15 minutes, naturally cooling, obtain the electron collection layer, i.e. the cathodic modification layer.P3HT and PC with 20mg/mL 60BM 1:1(mass ratio) mixed solution directly is being spun under the rotating speed of 800 rpm on the above-mentioned electron collection layer, as photoelectric active layer.Then 4 * 10 -4The MoO of vacuum evaporation 15nm under the Pa 3, obtain the collecting layer, hole.At last, 4 * 10 -4The aluminium of vacuum evaporation 100nm is made electrode under the handkerchief.In the reverse geometry polymer solar cell of gained, the thickness of Zinc oxide film is 200.Fig. 2 has provided this device and has penetrated without illumination and current-voltage curve under the simulated solar irradiation irradiation of every square centimeter of 100 milliwatt.Prepared device open circuit voltage under the simulated solar irradiation irradiation of every square centimeter of 100 milliwatt is 0.62 volt, and short circuit current is 10.65 milliamperes every square centimeter, and fill factor, curve factor is 0.622, and conversion efficiency is 4.08%.
Embodiment 3
There is the transparent conducting glass of tin indium oxide (ITO) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter, nitrogen dries up, the zinc acetylacetonate aqueous isopropanol of spin coating 3mg/mL under the rotating speed of 1000rpm, 150 ℃ were toasted 15 minutes, naturally cooling obtains the electron collection layer.PBDTTT-CT and PC with 10mg/mL 70BM 1:1.5(mass ratio) the additive diiodo-octane of adding 3% under the rotating speed of 900rpm directly is being spun on this solution on the above-mentioned electron collection layer, as photoelectric active layer then in the mixed solution.The MoO3 of vacuum evaporation 20nm under 4 * 10-4Pa obtains the collecting layer, hole then.At last, the aluminium of vacuum evaporation 100nm is made electrode under 4 * 10-4 handkerchief.In the reverse geometry polymer solar cell of gained, the thickness of Zinc oxide film is 200.Fig. 3 has provided this device and has penetrated without illumination and current-voltage curve under the simulated solar irradiation irradiation of every square centimeter of 100 milliwatt.Prepared device open circuit voltage under the simulated solar irradiation irradiation of every square centimeter of 100 milliwatt is 0.76 volt, and short circuit current is 17.45 milliamperes every square centimeter, and fill factor, curve factor is 0.605, conversion efficiency 7.98%.
Embodiment 4
There is the transparent conducting glass of tin indium oxide (ITO) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter, nitrogen dries up, the zinc acetylacetonate aqueous isopropanol of spin coating 10mg/mL under the rotating speed of 1000rpm, 50 ℃ were toasted 24 hours, and obtained the electron collection layer.PBDTTT-CT and PC with 10mg/mL 70BM 1:1.5(mass ratio) the additive diiodo-octane of adding 3% under the rotating speed of 900rpm directly is being spun on this solution on the above-mentioned electron collection layer, as photoelectric active layer then in the mixed solution.The MoO3 of vacuum evaporation 20nm under 4 * 10-4Pa obtains the collecting layer, hole then.At last, the aluminium of vacuum evaporation 100nm is made electrode under 4 * 10-4 handkerchief.In the reverse geometry polymer solar cell of gained, the thickness of Zinc oxide film is 500.Fig. 4 has provided this device and has penetrated without illumination and current-voltage curve under the simulated solar irradiation irradiation of every square centimeter of 100 milliwatt.Prepared device open circuit voltage under the simulated solar irradiation irradiation of every square centimeter of 100 milliwatt is 0.74 volt, and short circuit current is 17.30 milliamperes every square centimeter, and fill factor, curve factor is 0.592, conversion efficiency 7.54%.
Embodiment 5
There is the transparent conducting glass of tin indium oxide (ITO) to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively sputter, nitrogen dries up, the zinc acetylacetonate aqueous isopropanol of spin coating 1mg/mL under the rotating speed of 1000rpm, 250 ℃ were toasted 1 minute, naturally cooling obtains the electron collection layer.PBDTTT-CT and PC70BM 1:1.5(mass ratio with 10mg/mL) mixed solution in add 3% additive diiodo-octane, then this solution directly is being spun under the rotating speed of 900rpm on the above-mentioned electron collection layer, as photoelectric active layer.The MoO3 of vacuum evaporation 20nm under 4 * 10-4Pa obtains the collecting layer, hole then.At last, the aluminium of vacuum evaporation 100nm is made electrode under 4 * 10-4 handkerchief.In the reverse geometry polymer solar cell of gained, the thickness of Zinc oxide film is 20.Fig. 5 has provided this device and has penetrated without illumination and current-voltage curve under the simulated solar irradiation irradiation of every square centimeter of 100 milliwatt.Prepared device open circuit voltage under the simulated solar irradiation irradiation of every square centimeter of 100 milliwatt is 0.73 volt, and short circuit current is 17.08 milliamperes every square centimeter, and fill factor, curve factor is 0.594, conversion efficiency 7.37%.

Claims (6)

1. the preparation method of a reverse geometry polymer solar cell Zinc oxide film, it is characterized in that, comprise that step is as follows: utilize zinc acetylacetonate to be precursor, zinc acetylacetonate is dissolved in solvent prepares solution, the acetylacetone,2,4-pentanedione zinc solution is spin-coated on the transparent conductive metal oxide coated cathode layer, baking obtains Zinc oxide film, i.e. cathodic modification layer.
2. preparation method according to claim 1, it is characterized in that: the thickness of described Zinc oxide film is 10-500.
3. preparation method according to claim 1, it is characterized in that: described solvent is one or more in isopropyl alcohol, isooctanol, ethanol, ethyl acetate or the benzinum.
4. preparation method according to claim 1, it is characterized in that: the concentration of described acetylacetone,2,4-pentanedione zinc solution is 1-10mg/mL.
5. preparation method according to claim 1, it is characterized in that: the temperature of baking is 50-250 ℃, the time is 1 minute to 24 hours.
6. preparation method according to claim 1, it is characterized in that: the speed of described spin coating is 800-5000rpm.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104134751A (en) * 2014-07-21 2014-11-05 中国科学院化学研究所 Polymer solar cell in symmetrical structure and application of polymer solar cell
CN106654014A (en) * 2016-10-24 2017-05-10 东莞市联洲知识产权运营管理有限公司 Fullerene microcrystalline based conjugated polymer solar cell and preparation method thereof

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US20020122967A1 (en) * 1996-11-11 2002-09-05 Gorina Liliya Fedorovna Method for manufacturing a single high-temperature fuel cell and its components
US20040253386A1 (en) * 2003-06-13 2004-12-16 Sarojini Deevi Preparation of intermetallics by metallo-organic decomposition
CN101428843A (en) * 2008-12-11 2009-05-13 浙江大学 Process for producing ferromagnetic monodisperse nano-zinc oxide at room temperature
CN102101692A (en) * 2010-11-26 2011-06-22 西安理工大学 Chemical synthesis method of zinc oxide nano crystal based on alcohol-water system
CN102544382A (en) * 2012-03-21 2012-07-04 浙江大学 Preparation method for organic solar battery with reverse structure
WO2012103528A2 (en) * 2011-01-28 2012-08-02 Northwestern University Low-temperature fabrication of metal oxide thin films and nanomaterial-derived metal composite thin films

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020122967A1 (en) * 1996-11-11 2002-09-05 Gorina Liliya Fedorovna Method for manufacturing a single high-temperature fuel cell and its components
US20040253386A1 (en) * 2003-06-13 2004-12-16 Sarojini Deevi Preparation of intermetallics by metallo-organic decomposition
CN101428843A (en) * 2008-12-11 2009-05-13 浙江大学 Process for producing ferromagnetic monodisperse nano-zinc oxide at room temperature
CN102101692A (en) * 2010-11-26 2011-06-22 西安理工大学 Chemical synthesis method of zinc oxide nano crystal based on alcohol-water system
WO2012103528A2 (en) * 2011-01-28 2012-08-02 Northwestern University Low-temperature fabrication of metal oxide thin films and nanomaterial-derived metal composite thin films
CN102544382A (en) * 2012-03-21 2012-07-04 浙江大学 Preparation method for organic solar battery with reverse structure

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104134751A (en) * 2014-07-21 2014-11-05 中国科学院化学研究所 Polymer solar cell in symmetrical structure and application of polymer solar cell
CN106654014A (en) * 2016-10-24 2017-05-10 东莞市联洲知识产权运营管理有限公司 Fullerene microcrystalline based conjugated polymer solar cell and preparation method thereof

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