CN103280532B - A kind of preparation method of reverse geometry polymer solar cells Zinc oxide film - Google Patents

A kind of preparation method of reverse geometry polymer solar cells Zinc oxide film Download PDF

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CN103280532B
CN103280532B CN201310190002.7A CN201310190002A CN103280532B CN 103280532 B CN103280532 B CN 103280532B CN 201310190002 A CN201310190002 A CN 201310190002A CN 103280532 B CN103280532 B CN 103280532B
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zinc oxide
oxide film
preparation
polymer solar
zinc
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CN103280532A (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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    • 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

Abstract

The invention discloses the preparation method of a kind of reverse geometry polymer solar cells Zinc oxide film belonging to polymer solar battery Material Field.Described Zinc oxide film, the method masking of being processed by solution by acetylacetone,2,4-pentanedione zinc solution, is then directly heated a step in atmosphere and is transformed, without the need to sol gel reaction.Being introduced by zinc oxide prepared by this patent method prepares in reverse geometry polymer solar battery, achieving effective collection of electronics. the present invention has that photoelectric conversion efficiency is high, technique is simple, with low cost, the features such as good, the applicable large-scale industrial production of experimental repeatability.<!--1-->

Description

A kind of preparation method of reverse geometry polymer solar cells Zinc oxide film
Technical field
The invention belongs to polymer solar battery field of material technology, particularly a kind of preparation method of reverse geometry polymer solar cells Zinc oxide film.
Background technology
In recent years the organic and polymer thin-film solar cell risen has that cost is low, lightweight, manufacture craft is simple, can be prepared into the outstanding advantages such as large area flexible device and receive much concern.By the polymer donor material of optimal design synthesizing new and fullerene derivative receptor material and optimize in active layer to the micro phase separation structure of acceptor, body heterojunction polymer solar cells electricity conversion is made to improve significantly to 8-10%, close to the level of amorphous silicon battery.But conventional bulk heterojunction polymer solar cells because of the PEDOT:PSS of positive contact can corrode ITO, low work content negative pole oxidizable, cause the stability of battery not good, be 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 PEDOT:PSS is replaced to modify ITO with stable low work content decorative layer, replace active metal with stable high work content decorative layer, the reversion in electron collection direction can be realized, prepare stable reverse geometry polymer solar cells.
The structure of reverse geometry polymer solar cells, mainly comprise the substrate stacked gradually, transparent conductive metal oxide electrode layer (cathode layer), electron collection layer (cathodic modification layer), photoelectric active layer, hole collection layer (anode modification layer), and high work function anode layer, battery is connected with load or testing apparatus with plain conductor.
But the cathodic modification layer being applicable to reverse geometry polymer solar cells is at present very deficient, the titanium oxide mainly prepared by sol-gel process and zinc oxide.The invention discloses one utilizes zinc acetylacetonate for precursor, does not need independent sol gel reaction step, prepares the method for zinc-oxide film, and be applied in reverse geometry polymer solar cells by this film.
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, and structure is such as formula shown in (I).Its fusing point is 200 DEG C, and flash-point is 71.9 DEG C, and the boiling point under 760mmHg is 187.6 DEG C; When 25 DEG C, vapour pressure is 0.174mmHg.Water-soluble during this material 20 DEG C is 6.6g/L, dissolves in isopropyl alcohol, the organic solvents such as benzene, toluene and chloroform simultaneously.This material is mainly used as resin cross-linking agent and curing accelerator; As organic catalyst compound etc.
Formula (I)
Summary of the invention
The object of this invention is to provide a kind of preparation method of reverse geometry polymer solar cells Zinc oxide film.
A kind of preparation method of reverse geometry polymer solar cells Zinc oxide film, comprise step as follows: utilize zinc acetylacetonate for precursor, zinc acetylacetonate is dissolved in solvent and prepares solution, acetylacetone,2,4-pentanedione zinc solution is spin-coated on 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 benzinum.
The concentration of described acetylacetone,2,4-pentanedione zinc solution is 1-10mg/mL.
The temperature of baking is 50-250 DEG C, and the time is 1 minute to 24 hours.
The speed of described spin coating is 800-5000rpm.
The method masking that method of the present invention is processed by solution by acetylacetone,2,4-pentanedione zinc solution, then directly heat a step to be in atmosphere transformed, without the need to sol gel reaction, zinc oxide prepared by this patent method is introduced and prepares in reverse geometry polymer solar battery, achieve effective collection of electronics.Zinc oxide film prepared by the inventive method has that photoelectric conversion efficiency is high, technique is simple, with low cost, and experimental repeatability is good, be applicable to the features such as large-scale industrial production.
Accompanying drawing explanation
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 example)
The transparent conducting glass of tin indium oxide (ITO) sputtering is had to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively, nitrogen dries up, spin coating PEDOT:PSS solution under the rotating speed of 2000rpm, 150 DEG C are toasted 15 minutes, naturally cool, obtain hole collection layer (anode modification layer).By P3HT and the PC of 20mg/mL 60bM1:1(mass ratio) mixed solution be directly spun on above-mentioned hole collection layer under the rotating speed of 800rpm, as photoelectric active layer.Then 4 × 10 -5the calcium metal of vacuum evaporation 20nm under Pa, obtains electron collection layer.Finally, 4 × 10 -4under handkerchief, the aluminium of vacuum evaporation 100nm makes electrode.Fig. 1 gives the current-voltage curve of this device penetrating without illumination and under the simulated solar irradiation of 100 milliwatt every square centimeter irradiates.Obtained device open circuit voltage under the simulated solar irradiation of 100 milliwatt every square centimeter irradiates 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
The transparent conducting glass of tin indium oxide (ITO) sputtering is had to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively, nitrogen dries up, the zinc acetylacetonate aqueous isopropanol of spin coating 3mg/mL under the rotating speed of 1000rpm, 150 DEG C are toasted 15 minutes, naturally cool, obtain electron collection layer, i.e. cathodic modification layer.By P3HT and the PC of 20mg/mL 60bM1:1(mass ratio) mixed solution be directly spun on above-mentioned electron collection layer under the rotating speed of 800rpm, as photoelectric active layer.Then 4 × 10 -4the MoO of vacuum evaporation 15nm under Pa 3, obtain hole collection layer.Finally, 4 × 10 -4under handkerchief, the aluminium of vacuum evaporation 100nm makes electrode.In the reverse geometry polymer solar cells of gained, the thickness of Zinc oxide film is 200.Fig. 2 gives the current-voltage curve of this device penetrating without illumination and under the simulated solar irradiation of 100 milliwatt every square centimeter irradiates.Obtained device open circuit voltage under the simulated solar irradiation of 100 milliwatt every square centimeter irradiates 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
The transparent conducting glass of tin indium oxide (ITO) sputtering is had to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively, nitrogen dries up, the zinc acetylacetonate aqueous isopropanol of spin coating 3mg/mL under the rotating speed of 1000rpm, 150 DEG C are toasted 15 minutes, naturally cool, obtain electron collection layer.By PBDTTT-CT and the PC of 10mg/mL 70bM1:1.5(mass ratio) mixed solution in add 3% additive diiodo-octane, then this solution is directly spun under the rotating speed of 900rpm on above-mentioned electron collection layer, as photoelectric active layer.Then the MoO3 of vacuum evaporation 20nm under 4 × 10-4Pa, obtains hole collection layer.Finally, under 4 × 10-4 handkerchief, the aluminium of vacuum evaporation 100nm makes electrode.In the reverse geometry polymer solar cells of gained, the thickness of Zinc oxide film is 200.Fig. 3 gives the current-voltage curve of this device penetrating without illumination and under the simulated solar irradiation of 100 milliwatt every square centimeter irradiates.Obtained device open circuit voltage under the simulated solar irradiation of 100 milliwatt every square centimeter irradiates 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
The transparent conducting glass of tin indium oxide (ITO) sputtering is had to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively, nitrogen dries up, the zinc acetylacetonate aqueous isopropanol of spin coating 10mg/mL under the rotating speed of 1000rpm, 50 DEG C are toasted 24 hours, obtain electron collection layer.By PBDTTT-CT and the PC of 10mg/mL 70bM1:1.5(mass ratio) mixed solution in add 3% additive diiodo-octane, then this solution is directly spun under the rotating speed of 900rpm on above-mentioned electron collection layer, as photoelectric active layer.Then the MoO3 of vacuum evaporation 20nm under 4 × 10-4Pa, obtains hole collection layer.Finally, under 4 × 10-4 handkerchief, the aluminium of vacuum evaporation 100nm makes electrode.In the reverse geometry polymer solar cells of gained, the thickness of Zinc oxide film is 500.Fig. 4 gives the current-voltage curve of this device penetrating without illumination and under the simulated solar irradiation of 100 milliwatt every square centimeter irradiates.Obtained device open circuit voltage under the simulated solar irradiation of 100 milliwatt every square centimeter irradiates 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
The transparent conducting glass of tin indium oxide (ITO) sputtering is had to use liquid detergent, deionized water, acetone, isopropyl alcohol ultrasonic cleaning successively, nitrogen dries up, the zinc acetylacetonate aqueous isopropanol of spin coating 1mg/mL under the rotating speed of 1000rpm, 250 DEG C are toasted 1 minute, naturally cool, obtain electron collection layer.By PBDTTT-CT and the PC70BM1:1.5(of 10mg/mL mass ratio) mixed solution in add 3% additive diiodo-octane, then this solution is directly spun under the rotating speed of 900rpm on above-mentioned electron collection layer, as photoelectric active layer.Then the MoO3 of vacuum evaporation 20nm under 4 × 10-4Pa, obtains hole collection layer.Finally, under 4 × 10-4 handkerchief, the aluminium of vacuum evaporation 100nm makes electrode.In the reverse geometry polymer solar cells of gained, the thickness of Zinc oxide film is 20.Fig. 5 gives the current-voltage curve of this device penetrating without illumination and under the simulated solar irradiation of 100 milliwatt every square centimeter irradiates.Obtained device open circuit voltage under the simulated solar irradiation of 100 milliwatt every square centimeter irradiates 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 (4)

1. the preparation method of a reverse geometry polymer solar cells Zinc oxide film, it is characterized in that, comprise step as follows: utilize zinc acetylacetonate for precursor, zinc acetylacetonate is dissolved in solvent and prepares solution, acetylacetone,2,4-pentanedione zinc solution is spin-coated on transparent conductive metal oxide coated cathode layer, baking obtains Zinc oxide film, i.e. cathodic modification layer; Described baking temperature is 50-150 DEG C, and the time is 1 minute to 24 hours;
Described solvent is more than one in isopropyl alcohol, isooctanol, ethanol, ethyl acetate or benzinum.
2. preparation method according to claim 1, is characterized in that: the thickness of described Zinc oxide film is
3. preparation method according to claim 1, is characterized in that: the concentration of described acetylacetone,2,4-pentanedione zinc solution is 1-10mg/mL.
4. preparation method according to claim 1, is characterized in that: the speed of described spin coating is 800-5000rpm.
CN201310190002.7A 2013-05-21 2013-05-21 A kind of preparation method of reverse geometry polymer solar cells Zinc oxide film Expired - Fee Related CN103280532B (en)

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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

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US20040253386A1 (en) * 2003-06-13 2004-12-16 Sarojini Deevi Preparation of intermetallics by metallo-organic decomposition
CN103828018B (en) * 2011-01-28 2017-04-12 西北大学 Low-temperature fabrication of metal oxide thin films and nanomaterial-derived metal composite thin films

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Publication number Priority date Publication date Assignee Title
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

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