CN102569656A - Polymer bulk-heterojunction organic solar cell with cathode buffer layer - Google Patents

Polymer bulk-heterojunction organic solar cell with cathode buffer layer Download PDF

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CN102569656A
CN102569656A CN2012100276135A CN201210027613A CN102569656A CN 102569656 A CN102569656 A CN 102569656A CN 2012100276135 A CN2012100276135 A CN 2012100276135A CN 201210027613 A CN201210027613 A CN 201210027613A CN 102569656 A CN102569656 A CN 102569656A
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buffer layer
cathode buffer
anode
cathode
organic solar
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高志强
密保秀
黄维
赵新彦
王海珊
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Nanjing Post and Telecommunication University
Nanjing University of Posts and Telecommunications
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Nanjing Post and Telecommunication University
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Abstract

The invention discloses an organic polymer bulk-heterojunction organic solar cell structure with a hexa-7-azaindole zinc tetroxide complex [Zn4O(AID)6] material serving as a cathode buffer layer. The structure sequentially comprises a substrate, an anode, an anode buffer layer, a bulk-heterojunction active layer, the cathode buffer layer and a cathode from bottom to top, wherein the substrate is made of a quartz plate, a glass sheet, polystyrene or polyethylene and other transparent materials; the anode is made of metal of which a work function is higher than that of the cathode, metal oxide, carbon black or conductive polymer; the bulk-heterojunction active layer is formed by mixing an electron donor material and an electron acceptor material; the electron donor layer is made of poly(3-hexylthiophene) (P3HT) or other polymer donor materials; the electron acceptor layer is made of a fullerene derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM) or other electron acceptor materials; the cathode buffer layer is Zn4O(AID)6; and the cathode is made of metal of which a work function is relatively lower than that of the anode or a metal alloy. Except the anode, various layers can be prepared by various methods for depositing organic films by vacuum evaporation, spin coating, spraying, printing and the like.

Description

Polymeric acceptor heterojunction organic solar batteries with cathode buffer layer
Technical field
The present invention relates to the organic electro-optic device technical field, be specifically related to a kind of employing six-7-azaindole four zinc and close oxygen complex [Zn 4O (AID) 6] do the polymeric acceptor heterojunction organic solar batteries of cathode buffer layer.This battery structure is through adopting Zn 4O (AID) 6Material has been prepared the high organic solar batteries of power conversion efficiency as the cathode buffer layer of polymeric acceptor heterojunction organic solar batteries.
Background technology
Along with the mankind to energy demand increase day by day and to the attention day by day of environmental problem, solar energy is following global optimal energy mode as not receiving the region restriction, not producing greenhouse effect, inexhaustible clean energy resource.Utilizing the solar energy storage and the energy is provided, is crucial the principles of science and technical application problem that current academia pays close attention to.The expensive cost and the serious photoetch of narrow gap semiconductor have limited the practical application of inorganic solar cell, and meanwhile, organic solar batteries is expected to become rising solar powered technology because of its unique excellent properties comes into one's own day by day.Its advantage is mainly reflected in: organic material has the very high absorption coefficient of light; It is better that the synthetic cost of organic material is low, function is easy to modulation, pliability and film forming; But the simple low-temperature operation of the organic solar batteries course of processing, element manufacturing cost be low, can use flexible substrate, can realize the large tracts of land manufacturing.
In recent years, the power conversion efficiency of bulk heterojunction organic solar batteries has reached about 9%, yet the peak power conversion efficiency of organic solar batteries does not reach application level (power conversion efficiency is greater than 10%) as yet at present.Key constraints comprises following three aspects: the absorption spectrum of organic material is narrower, and is limited to the absorption of sunlight, causes power conversion efficiency not high; Photic exciton is when heterojunction boundary dissociates, and the energy level difference when shifting between to body and acceptor owing to electronics is big, and energy loss is bigger, causes the device open circuit voltage less; The organic material carrier mobility is lower, and charge carrier loss in transition process is bigger, causes short circuit current less.Research shows, through the suitable resilient coating of adding between active layer and metal interface electrode interface is modified and can be significantly improved charge transfer and collection efficiency, thereby improve the power conversion efficiency of battery.Among the present invention through in the bulk heterojunction organic solar batteries, introducing Zn 4O (AID) 6Material make organic solar batteries open circuit voltage, short circuit current, fill factor, curve factor, and power conversion efficiency is greatly improved as cathode buffer layer.
Summary of the invention
Technical problem:The purpose of this invention is to provide a kind of employing six-7-azaindole four zinc and close oxygen complex [Zn 4O (AID) 6] as the bulk heterojunction organic polymer solar cell of cathode buffer layer.Utilize the present invention, can improve the power conversion efficiency of bulk heterojunction organic solar batteries.
Technical scheme:The polymeric acceptor heterojunction organic solar batteries that the present invention has cathode buffer layer adopts six-7-azaindole, four zinc to close the polymeric acceptor heterojunction of oxygen complex material as cathode buffer layer, and the structure of this solar cell is followed successively by from down to up: substrate, anode, anode buffer layer, bulk heterojunction active layer, cathode buffer layer, negative electrode.
Described substrate adopts quartz plate, sheet glass, polystyrene or polyethylene.
Described anode adopts metal, metal oxide, carbon black or the conducting polymer of work function greater than negative electrode.
The bulk heterojunction active layer is mixed with by electron donor material and electron acceptor material and forms, and wherein the electron donor layer adopts P3HT or other polymer donor materials, and the electron acceptor layer adopts PCBM or other electron acceptor materials.
Cathode buffer layer is Zn 4O (AID) 6
Negative electrode adopts the work function metal or metal alloy lower than anode.
Described bulk heterojunction, the thickness of its active layer are 600-3000, and the thickness of cathode buffer layer is 20-200, and cathode thickness is 500-2000.
The preparation method of anode and negative electrode is vacuum evaporation or sputter, if material is very thin particle, can obtain through the spin coating or the spraying of solution, and the method for electrochemical deposition also can make corresponding electrode in addition.
Anode buffer layer, bulk heterojunction active layer and cathode buffer layer are with the method preparation of vacuum evaporation, spin coating, printing or spraying.
Beneficial effect:Can find out that from technique scheme the present invention has following beneficial effect:
Employing six-7-azaindole four zinc provided by the invention close oxygen complex [Zn 4O (AID) 6] material is as the bulk heterojunction organic solar batteries of cathode buffer layer, through between bulk heterojunction active layer and cathode interface, introducing Zn 4O (AID) 6As resilient coating, help charge transfer, eliminate the exciton cancellation that negative electrode causes, improve the utilance of exciton; Avoided simultaneously because the infringement that vapor deposition causes the organic receptor layer; And then can improve the power conversion efficiency of organic solar batteries.
Description of drawings
Fig. 1 is employing Zn provided by the invention 4O (AID) 6Material is as the organic sun of the bulk heterojunction of cathode buffer layer
The sketch map of ability battery structure;
Fig. 2 is Zn 4O (AID) 6Molecular structure;
Fig. 3 does not adopt the normal component of cathode buffer layer and the I-V curve of device of the present invention.This I-V curve be
100 mW/cm 2The irradiation of AM1.5 solar simulator under measure;
Fig. 4 is that the power conversion efficiency of device of the present invention is with Zn 4O (AID) 6The varied in thickness curve.
Embodiment
Below in conjunction with embodiment the present invention is specifically described, but the present invention is not limited only to cited embodiment.
Described employing six-7-azaindole four zinc close the oxygen complex material and may further comprise the steps as the preparation method of the bulk heterojunction organic solar energy cell structure of cathode buffer layer:
A. on substrate, prepare anode;
B. on anode, prepare anode buffer layer;
C. on anode buffer layer, prepare the bulk heterojunction active layer;
D. on the bulk heterojunction active layer, prepare cathode buffer layer;
E. vapor deposition negative electrode on cathode buffer layer.
The preparation method of anode and negative electrode is vacuum evaporation or sputter; If material is very thin particle; Like metal, carbon black, metal oxide, conducting polymer etc., then can obtain through the spin coating or the spraying of solution, the method for electrochemical deposition also can make corresponding electrode in addition.Anode buffer layer, bulk heterojunction active layer and cathode buffer layer are organic layer, can adopt the method preparation of various deposition of organic thin film such as vacuum evaporation, spraying, spin coating, printing.
Bulk heterojunction active layer as embodiments of the invention adopts most effective organic solar batteries active layer structure at present, and electron donor material adopts P3HT among the embodiment.P3HT is a kind of polymer of 3-hexyl thiophene; Be mainly used in OTFT and organic solar batteries; This polymer develops very fastly after being synthesized the eighties, is reached more than 5% by the common organic solar batteries efficient of forming of P3HT and PCBM at present.But the band gap broad of P3HT; Less to red light absorption; Be unfavorable for absorbing to solar spectrum; It is higher to have developed some spectrum utilances at present, is suitable as the polymer of organic solar batteries donor material, and these polymer all can be used as the donor material of bulk heterojunction solar cell proposed by the invention.The acceptor material of bulk heterojunction active layer adopts PCBM in the embodiment of the invention, and PCBM is a fullerene derivate, comprises C 60Derivative and C 70Derivative.Because PCBM has good dissolubility, very high electron mobility etc. are usually used in the electron acceptor reference material of organic solar batteries.The bulk heterojunction active layer forms the interpenetrating networks of donor-receiver material mixing generally through the preparation of solwution methods such as spraying, spin coating, printing, helps improving the exciton dissociation efficiency.
After choosing suitable organic layer material and device architecture, be the better device of obtained performance, we introduce Zn between bulk heterojunction active layer and negative electrode 4O (AID) 6Material is as cathode buffer layer.This cathode buffer layer can prepare through vacuum evaporation.With Zn 4O (AID) 6After material is dissolved in the solvent, also can prepare through solwution methods such as spraying, spin coating, printings.The introducing of this cathode buffer layer can be eliminated the exciton cancellation that negative electrode causes, has improved the utilance of exciton; When stopping the vapor deposition negative electrode to the destruction of organic layer; Can also stop simultaneously extraneous intrusion, improve the stability of device like materials such as water, oxygen.
Embodiment 1
(square resistance is that 15 Ω/) go up the preparation organic solar batteries, and the ito glass substrate was washed agent, acetone, isopropyl alcohol and washed with de-ionized water 30 minutes successively, then 120 ℃ of oven dry at least 10 minutes down at the ito glass substrate that cleans up.Before the spin coating anode buffer layer, use O again 2Cement Composite Treated by Plasma 50 seconds.Anode buffer layer adopts PEDOT:PSS, prepares film forming with spin-coating method, and rotating speed is 4000 rpm, and the time is 60 s.After spin coating obtains PEDOT:PSS, be placed on the hot plate of 120 ° of C heating 15 minutes, make wherein excessive moisture volatilization.Then the baking after PEDOT:PSS film above-prepared bulk heterojunction active layer.P3HT and PCBM are dissolved in chlorobenzene with 2% mass ratio, mixed solution 50 degree heated and stirred 12 hours after with the mixed of 1:0.8.Active layer adopts spin-coating method to prepare film forming, and rotating speed is 1000 rpm, and the time is 60 s.Spin coating obtains after the active tunic, is placed on the hot plate of 120 ° of C heating 15 minutes, makes wherein unnecessary solvent evaporates and improves appearance structure.Cathode buffer layer Zn 4O (AID) 6With negative electrode Al be vacuum evaporation, during vapor deposition vacuum for the degree be 8 * 10 -4Pa.The ITO substrate is a room temperature during vapor deposition, Zn 4O (AID) 6Purified by distillation before use.Zn 4O (AID) 6Vapor deposition speed be about 0.2/s, thickness is 1.2 nm; The vapor deposition speed of Al is about 10/s, and the thickness of Al is 100 nm.The effective area of the device for preparing (negative electrode and anode lap) is 0.1 cm 2Each layer thickness of vacuum evaporation detects with quartz crystal oscillator thickness monitor appearance.Measurement is (100 mW/cm under the illumination of the AM 1.5 that solar simulator produces 2) carry out.Current density-voltage (J-V) curve is measured by Keithley 2400.Device does not encapsulate, and all measurements are all accomplished under atmospheric environment.Device architecture of the present invention is as shown in Figure 1; Do not adopt the normal component and the I-V curve of structure devices of the present invention under light conditions of cathode buffer layer as shown in Figure 2.
Do not adopt the normal component of cathode buffer layer: glass substrate/ITO/PEDOT:PSS (400)/P3HT:PCBM (1000)/Al (1000);
Device of the present invention: glass substrate/ITO/PEDOT:PSS (400)/P3HT:PCBM (1000)/Zn 4O (AID) 6(12)/Al (1000).
Table 1 is not for adopting the normal component of cathode buffer layer and the contrast of device of the present invention.The performance test of normal component and device of the present invention of not adopting cathode buffer layer is all at 100 mW/cm 2The simulated light of AM 1.5 according to down recording.The result shows that open circuit voltage, short circuit current, fill factor, curve factor and the power conversion efficiency of device of the present invention all are higher than normal component.
 
Table 1 does not adopt the normal component of cathode buffer layer and the comparison of device of the present invention
? J SC (mA/cm 2) V OC (V) FF (%) PCE (%)
Normal component 9.6 0.53 0.40 2.04
Device of the present invention 11.41 0.58 0.52 3.46
Embodiment 2
This embodiment has showed different-thickness Zn 4O (AID) 6Short circuit current, open circuit voltage, fill factor, curve factor and the power conversion efficiency of material device of the present invention during as cathode buffer layer change.Device architecture: glass substrate/ITO/PEDOT:PSS (400)/P3HT:PCBM (1000)/Zn 4O (AID) 6(5 ~ 90)/Al (1000).Table 2 is based on different Zn 4O (AID) 6The short circuit current of the device of the present invention of thickness, open circuit voltage, power conversion efficiency and fill factor, curve factor relevant numerical.Can find out at device of the present invention in cathode buffer layer thickness 5 ~ 20 scopes that by table 2 short circuit current, fill factor, curve factor and power conversion efficiency all increase with respect to the normal component that does not adopt cathode buffer layer to some extent.Along with Zn 4O (AID) 6Thickness increases, and the value of fill factor, curve factor still has obvious raising with respect to the normal component that does not adopt cathode buffer layer, but short circuit current and open circuit voltage descend to some extent.The Zn that device of the present invention adopts is described 4O (AID) 6Cathode buffer layer thickness, under this experiment condition, be controlled within 20 relatively good, the most remarkable to the raising of device performance.Certainly, do not get rid of change experiment condition and post-processing approach after, the situation that optimum thickness will change to some extent.
Table 2 different-thickness Zn 4O (AID) 6Short circuit current, open circuit voltage, fill factor, curve factor and the power conversion efficiency of material device of the present invention during as cathode buffer layer change
The implication of relevant abbreviation title is following among this paper:
ITO: indium tin oxide
PEDOT：PSS?：Poly(3,4-ethylenedioxythiophene)?poly(styrenesulfonate)
P3HT?：poly(3-hexylthiophene)
PCBM：[6,6]-phenyl?C61-butyric?acid?methyl?ester
Zn 4O (AID) 6: six-7-azaindole, four zinc close oxygen complex [tetranucluear zinc (II) oxide compound (AID=7-azaindolate)].

Claims (8)

1. polymeric acceptor heterojunction organic solar batteries with cathode buffer layer; It is characterized in that this solar cell adopts six-7-azaindole, four zinc to close the oxygen complex material as cathode buffer layer, the structure of this solar cell is followed successively by from down to up: substrate, anode, anode buffer layer, bulk heterojunction active layer, cathode buffer layer, negative electrode.
2. according to right 1 described polymeric acceptor heterojunction organic solar batteries, it is characterized in that described substrate adopts quartz plate, sheet glass, polystyrene or polyethylene with cathode buffer layer.
3. according to right 1 described polymeric acceptor heterojunction organic solar batteries, it is characterized in that described anode adopts metal, metal oxide, carbon black or the conducting polymer of work function greater than negative electrode with cathode buffer layer.
4. according to right 1 described polymeric acceptor heterojunction organic solar batteries with cathode buffer layer; It is characterized in that the bulk heterojunction active layer is mixed with by electron donor material and electron acceptor material forms; Wherein the electron donor layer adopts P3HT or other polymer donor materials, and the electron acceptor layer adopts PCBM or other electron acceptor materials.
5. according to right 1 described polymeric acceptor heterojunction organic solar batteries, its spy with cathode buffer layer
Levy and be that cathode buffer layer is Zn 4O (AID) 6
6. according to right 1 described polymeric acceptor heterojunction organic solar batteries, it is characterized in that negative electrode adopts the work function metal or metal alloy lower than anode with cathode buffer layer.
7. the polymeric acceptor heterojunction organic solar batteries with cathode buffer layer according to claim 1; It is characterized in that described bulk heterojunction; The thickness of its active layer is 600-3000, and the thickness of cathode buffer layer is 20-200, and cathode thickness is 500-2000.
8. according to right 1 described polymeric acceptor heterojunction organic solar batteries, it is characterized in that anode buffer layer, bulk heterojunction active layer and cathode buffer layer, with the method preparation of vacuum evaporation, spin coating, printing or spraying with cathode buffer layer.
CN2012100276135A 2012-02-08 2012-02-08 Polymer bulk-heterojunction organic solar cell with cathode buffer layer Pending CN102569656A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109888099A (en) * 2018-12-11 2019-06-14 西安理工大学 High specific detecivity organic photodetector of quaternary wide spectrum and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101022153A (en) * 2006-12-29 2007-08-22 中国科学院长春应用化学研究所 Solvent processing method for raising polymer thin film solar battery effect
CN102244197A (en) * 2011-07-18 2011-11-16 南京邮电大学 Organic solar cell structure based on [Zn4O(AID)6] coordination compound material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101022153A (en) * 2006-12-29 2007-08-22 中国科学院长春应用化学研究所 Solvent processing method for raising polymer thin film solar battery effect
CN102244197A (en) * 2011-07-18 2011-11-16 南京邮电大学 Organic solar cell structure based on [Zn4O(AID)6] coordination compound material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109888099A (en) * 2018-12-11 2019-06-14 西安理工大学 High specific detecivity organic photodetector of quaternary wide spectrum and preparation method thereof

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Application publication date: 20120711