CN103247760A - Organic solar cell using fluorescent electronic transfer material Zn (BTZ) 2 as cathode buffer layer - Google Patents

Organic solar cell using fluorescent electronic transfer material Zn (BTZ) 2 as cathode buffer layer Download PDF

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CN103247760A
CN103247760A CN2012100296196A CN201210029619A CN103247760A CN 103247760 A CN103247760 A CN 103247760A CN 2012100296196 A CN2012100296196 A CN 2012100296196A CN 201210029619 A CN201210029619 A CN 201210029619A CN 103247760 A CN103247760 A CN 103247760A
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buffer layer
btz
organic solar
cathode
cathode buffer
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刘春波
刘洋
徐占林
苏斌
车广波
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Jilin Normal University
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Jilin Normal 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
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    • Y02E10/549—Organic PV cells

Abstract

The invention belongs to the technical field of organic optoelectronic devices, relates to an organic solar cell using the fluorescent electronic transfer material Zn (BTZ) 2 as the cathode buffer layer. The organic solar cell is characterized in that the Zn (BTZ) 2 is adopted as the cathode buffer layer of the organic solar cell. When the thickness of the buffer layer is small, as the damage caused by the steamed metallized cathode, the electron can be collected by the cathode through the defect mode. And the high electronic mobility, favourable heat stability and the surface morphology of the film of the material enable the photovoltaic property of the cell to be superior to the cell performance utilizing 2, 9-dimethyl-4, the 7-diphenyl-1, and the 10-phenanthroline (Bathocuproine, BCP) as the cathode buffer layer. When the thickness of the buffer layer Zn (BTZ) 2 is large, as the energy level of the highest occupied molecular orbital (HOMO) of the buffer layer is higher than the HOMO energy level of the receptor, so as to be beneficial to the composition of the electron dissociated from the CuPu/C60 planar neterogeny and the hole injected by the cathode, and the energy conversion efficiency of the cell is improved accordingly. The radiation source uses AM 1.5 G solar imitator with the light intensity of 100 mW/cm2, vacuum distillation sedimentary organic membrane preparation method is adopted to each organic layer, and according to the organic solar cell provided by the invention, the photoelectric conversion efficiency of the organic solar cell is greatly improved.

Description

Utilize fluorescence electron transport material Zn (BTZ) 2Organic solar batteries as cathode buffer layer
Technical field
The invention belongs to material and the devices field of organic solar batteries, specifically relate to a kind of fluorescence electron transport material Zn (BTZ) that utilizes 2Organic solar batteries as cathode buffer layer.
Background technology
Current energy problem is subjected to showing great attention to of countries in the world.Solar energy takes up an area of 99% of ball gross energy, is the maximum energy resources of storage on the earth.Conversion of solar energy is electric energy, can be undertaken by photovoltaic generation and photo-thermal power generation mode.Compare with traditional inorganic photovoltaic cell, organic solar batteries preparation technology is simple, has advantages such as the area of manufacturing is big, cheap, simple and easy, flexibility [1-3]Tang had reported the single heterogeneous joint organic photovoltaic battery of acceptor of giving in 1986, and photoelectric conversion efficiency is 0.95% [4]Because it has potential broad prospect of application, after this academia and business circles have just been launched the further investigation to organic photovoltaic battery [5-9]The organic solar batteries basic functional principle is: light shines on the electron donor-acceptor (EDA) material from transparency electrode; Produce photoproduction exciton (i.e. Shu Fu electron hole pair); Exciton begins forming twin electron hole pair at the interface to the transmission of electron donor-acceptor (EDA) interface under the effect of concentration gradient; Be dissociated into the charge carrier that moves freely subsequently under the effect of Offset (namely giving the difference of the LUMO of acceptor), because there are work function difference in negative electrode and anode, electronics is transferred to different electrodes respectively with the hole under this effect, forms electric current [10,11]So the energy conversion efficiency of organic solar batteries is to be determined jointly by four efficient: efficiency of light absorption; The exciton diffuser efficiency; The exciton dissociation efficiency; Carrier collection efficient [12]In this patent with Zn (BTZ) 2Be cathode cushioning layer material, the increase of its thickness can not improve efficiency of light absorption; The exciton diffuser efficiency is only with relevant to acceptor material; The exciton dissociation efficiency determines by the interface of dissociating, so be carrier collection efficient to what device efficiency played a major role in this patent.Cathode buffer layer has four main effects: stop exciton, reduce exciton negative electrode quencher (being also referred to as exciton barrier-layer) [13]Optical interval layer: be used for regulating light field [14]Passivation layer: protection acceptor [15]Carrier blocking layers: transmission charge carrier [16]Use cathode buffer layer can improve carrier transport and collection efficiency, thereby improve energy content of battery conversion efficiency.Cathode buffer layer roughly is divided into three types at present: the evaporation negative electrode causes defect state to material, and the free electron that dissociates jumps in defect state and collected by negative electrode [17]Material HOMO is higher relatively, and electronics and injected hole are compounded to form battery [18]Material LUMO is darker, reduces and collects potential barrier [19]Traditional devices uses BCP as cathode buffer layer usually [17]Though BCP can improve device efficiency, because the influence of itself wide Bands crack and resistance makes that device efficiency only is about 1%; Add the easy crystallization of BCP, vitrification point is lower, and the life-span of device is also lower [20]Zn (BTZ) 2Be generally used for preparing white light OLED [21], still also be not applied to the relevant report in the little molecule organic solar batteries up to now.Related Zn (BTZ) among the application 2Has higher electron mobility [22,23], film forming and stability preferably, and the HOMO energy level is higher than the HOMO energy level of electron acceptor, electronics that electron donor/electron acceptor planar heterojunction place dissociates easily and the negative electrode injected holes carry out compound, thereby energy conversion efficiency and the life-span of improving device.
The organic solar batteries that this application is related, with the blue moral of the BP of Univ Princeton and University of Southern California, SR not the national inventing patent " photovoltaic cell with organic double-heterostructure of reciprocal-carrier exciton blocking layer " declared of people such as Leicester, ME Tang Pusen (application number: difference 200680027818) is that exciton barrier-layer is different, and the metallic cathode material is also different.The used cathode buffer layer of the application is that the exciton barrier-layer material is electron transport material and is fluorescent material, and negative electrode is metal aluminium electrode.Not people such as Leicester, ME Tang Pusen uses is phosphor material Ru (acac) for the blue moral of BP, SR 3, this material is hole mobile material, negative electrode is the argent electrode.This phosphor material only can utilize the HOMO advantage to transmit charge carrier.Metal Ru is noble metal, and reserves are limited, and this just makes the element manufacturing cost uprise.Used in this application be nontoxic, synthetic simple, reserves than horn of plenty, the relatively cheap metallic zinc complex of price, reduce the element manufacturing cost greatly.This material at thickness not simultaneously, the mechanism of action is also different, the electronic transmission performance that it is remarkable and high-quality film surface form, energy conversion efficiency and the life-span that can effectively improve organic solar batteries.
Figure 980053DEST_PATH_IMAGE001
Figure 897194DEST_PATH_IMAGE002
Summary of the invention
For solve inorganic solar cell complicated process of preparation in the background technology, cost height, be not suitable for being applied to large tracts of land and flexible substrate, problems such as energy conversion efficiency that organic solar batteries is low and low life-span.The objective of the invention is to have a fluorescence electron transport material Zn (BTZ) that is higher than the HOMO energy level of acceptor than high electron mobility and HOMO energy level thereof a kind of 2Be applied in the organic solar batteries, improve device energy conversion efficiency and life-span, device is easy to preparation.
The present invention is a kind of fluorescence electron transport material Zn (BTZ) that utilizes that realizes like this 2As the organic solar batteries of cathode buffer layer, the structure of device is successively: ito anode, electron donor layer, electron acceptor layer, cathode buffer layer, negative electrode is characterized in that: cathode cushioning layer material is Zn (BTZ) 2
Described a kind of fluorescence electron transport material Zn (BTZ) that utilizes 2As the organic solar batteries of cathode buffer layer, it is characterized in that the available phthalocyanines complex of electron donor layer such as CuPc, Phthalocyanine Zinc, phthalocyanine lead etc., thickness 15 ~ 20 nm.
Described a kind of fluorescence electron transport material Zn (BTZ) that utilizes 2As the organic solar batteries of cathode buffer layer, it is characterized in that the electron acceptor layer material is to use C 60Perhaps its derivative, thickness is 35 ~ 40 nm.
The described fluorescence electron transport material Zn (BTZ) that utilizes 2As the organic solar batteries of cathode buffer layer, the thickness that it is characterized in that the cathode buffer layer of organic solar batteries is 3 ~ 20 nm.
Described a kind of fluorescence electron transport material Zn (BTZ) that utilizes 2The organic solar batteries of resilient coating is characterized in that Al as negative electrode, thickness 100 ~ 150 nm.
The invention has the advantages that:
1. metallic zinc complex Zn (BTZ) 2
That the present invention adopts is relative low price, nontoxic, the simple metallic zinc complex of synthetic method Zn (BTZ) 2Cathode cushioning layer material for organic solar batteries.This material has higher electron mobility, is higher than common used material Alq 3And BCP etc.; And stability and film forming are better, are difficult for crystallization in air.Do the life-span that efficient that cathode buffer layer not only can improve device also can be improved device with this complex.
2. battery
The battery structure that the present invention adopts is the planar heterojunction structure, and all functions layer material all is to adopt vacuum thermal evaporation film-forming, and battery preparation method is simple than the preparation method of inorganic solar cell, and easy to operate.
3. resilient coating
The present invention adopts Zn (BTZ) 2As cathode buffer layer, when resilient coating was thinner, because the evaporation metal negative electrode is to burning that it causes, electronics can be collected by negative electrode by defect state.When resilient coating is thicker because the HOMO energy level of material is higher than the HOMO energy level of acceptor, the electronics of dissociateing for acceptor planar heterojunction place easily and the negative electrode injected holes carry out compound, thereby improve the energy conversion efficiency of battery.
Description of drawings
Fig. 1 is the used cathode cushioning layer material Zn of the present invention (BTZ) 2Chemical structural formula.
Fig. 2 is the structural representation of organic solar batteries of the present invention.
Fig. 3 is energy level of the present invention and operation principle schematic diagram.
Fig. 4 is the used cathode cushioning layer material Zn of the present invention (BTZ) 2Thermogravimetric curve.
Fig. 5 is the present invention and conventional batteries life-span comparison diagram.
Wherein: ito anode 1, electron donor layer 2, electron acceptor layer 3, cathode buffer layer 4, negative electrode 5.
Embodiment:
The present invention will be further described below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Structure by organic solar batteries of the present invention shown in the accompanying drawing 2 is successively: ito anode 1, electron donor 2, electron acceptor layer 3, cathode buffer layer 4, negative electrode 5.The present invention utilizes vacuum coating technology, vacuum heat deposition electron donor material-phthalocyanines complex such as CuPc (CuPc), Phthalocyanine Zinc (ZnPc), phthalocyanine lead (PbPc) etc. on the ITO electro-conductive glass, the deposition that continues then electron acceptor layer (C 60Perhaps its derivative), cathode buffer layer Zn (BTZ) 2, be the Al cathode material at last.Thickness 15 ~ 20 nm of electron donor material, thickness 35 ~ 40 nm of electron acceptor material, cathode buffer layer Zn (BTZ) 2Thickness be 3 ~ 20 nm, Al thickness is 100 ~ 150 nm, what radiation source was selected for use is that AM 1.5 G light intensity are 100 mW/cm 2Solar simulator, from the irradiation of nesa coating one side of battery, external circuit adopts KEITHLEY2601 to detect the signal of telecommunication that produces when illumination is penetrated, shown in the accompanying drawing 1 is Zn (BTZ) 2Structure, shown in the accompanying drawing 4 is to go out Zn when being higher than 300 ℃ (BTZ) by thermogravimetric analysis 2Just begin to decompose, it has higher thermal stability.
Embodiment 1
By battery structure shown in Figure 2.In the present embodiment, at first on the ITO electro-conductive glass vacuum moulding machine thickness be the electron donor layer CuPc of 20 nm; Then at electron donor layer 2 deposition 40 nm C 60Electron acceptor layer 3, deposition cathode resilient coating 4 Zn (BTZ) on electron acceptor layer 3 again 2, thickness is 3 nm; Be negative electrode at last, adopt metal A l material, thickness 120 nm.Above-mentioned all films all adopt the technique for vacuum coating deposition.The thickness of film uses the film thickness monitoring instrument monitoring, and external circuit adopts KEITHLEY2601 to detect.Conclusion: be 100 mW/cm with light intensity 2Solar simulator irradiation down, the current density that obtains is 6.12 mA/cm 2, open circuit voltage is 0.48 V, and fill factor, curve factor is 0.35, and photoelectric conversion efficiency is 1.03 %.
Embodiment 2
On embodiment 1 basis, other manufacturing conditions are constant, and only the thickness with cathode buffer layer 4 changes 5 nm into.
Conclusion: be 100 mW/cm with light intensity 2Solar simulator irradiation down, the current density that obtains is 6.47 mA/cm 2, open circuit voltage is 0.48 V, and fill factor, curve factor is 0.48, and photoelectric conversion efficiency is 1.48 %.
Embodiment 3
On embodiment 1 basis, other manufacturing conditions are constant, and only the thickness with cathode buffer layer 4 changes 10 nm into.
Conclusion: be 100 mW/cm with light intensity 2Solar simulator irradiation down, the current density that obtains is 6.21 mA/cm 2, open circuit voltage is 0.53 V, and fill factor, curve factor is 0.34, and photoelectric conversion efficiency is 1.14 %.
Embodiment 4
On embodiment 1 basis, other manufacturing conditions are constant, and only the thickness with cathode buffer layer 4 changes 15 nm into.
Conclusion: be 100 mW/cm with light intensity 2Solar simulator irradiation down, the current density that obtains is 6.13 mA/cm 2, open circuit voltage is 0.53 V, and fill factor, curve factor is 0.33, and photoelectric conversion efficiency is 1.07 %.
Embodiment 5
On embodiment 1 basis, other manufacturing conditions are constant, and only the thickness with cathode buffer layer 4 changes 20 nm into.
Conclusion: be 100 mW/cm with light intensity 2Solar simulator irradiation down, the current density that obtains is 4.84 mA/cm 2, open circuit voltage is 0.50 V, and fill factor, curve factor is 0.37, and photoelectric conversion efficiency is 0.90 %.
Embodiment 6
On embodiment 1 basis, other manufacturing conditions are constant, and device is implemented continuous illumination, measure device performance at set intervals one time.
Conclusion: by being 100 mW/cm with light intensity shown in the accompanying drawing 5 2Solar simulator irradiation down, obtain based on Zn (BTZ) 2The life-span of device (life-span is defined as energy conversion efficiency and decays to the original used time of a half) is 1500 min; Not having resilient coating device lifetime is 150 min; Be 600 min with BCP as resilient coating device lifetime.
From above-described embodiment as can be seen, when battery manufacturing conditions such as embodiment 2, the photoelectric conversion efficiency of organic solar batteries is for the highest.

Claims (5)

1. one kind is utilized fluorescence electron transport material Zn (BTZ) 2As the organic solar batteries of cathode buffer layer, the structure of battery is successively: ito anode, electron donor layer, electron acceptor layer, cathode buffer layer, negative electrode is characterized in that: cathode cushioning layer material is Zn (BTZ) 2
2. a kind of fluorescence electron transport material Zn (BTZ) that utilizes according to claim 1 2As the organic solar batteries of cathode buffer layer, it is characterized in that the available phthalocyanines complex of electron donor layer such as CuPc, Phthalocyanine Zinc, phthalocyanine lead etc., thickness 15 ~ 20 nm.
3. a kind of fluorescence electron transport material Zn (BTZ) that utilizes according to claim 1 2As the organic solar batteries of cathode buffer layer, it is characterized in that the electron acceptor layer material is to use C 60Perhaps its derivative, thickness is 35 ~ 40 nm.
4. the fluorescence electron transport material Zn (BTZ) that utilizes according to claim 1 2As the organic solar batteries of cathode buffer layer, the thickness that it is characterized in that the cathode buffer layer of organic solar batteries is 3 ~ 20 nm.
5. a kind of fluorescence electron transport material Zn (BTZ) that utilizes according to claim 1 2The organic solar batteries of resilient coating is characterized in that Al as negative electrode, thickness 100 ~ 150 nm.
CN2012100296196A 2012-02-10 2012-02-10 Organic solar cell using fluorescent electronic transfer material Zn (BTZ) 2 as cathode buffer layer Pending CN103247760A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1617355A (en) * 2004-12-09 2005-05-18 复旦大学 Novel organic solar energy cell structure and its preparing method
CN102263203A (en) * 2011-08-15 2011-11-30 苏州大学 Organic solar battery and manufacturing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1617355A (en) * 2004-12-09 2005-05-18 复旦大学 Novel organic solar energy cell structure and its preparing method
CN102263203A (en) * 2011-08-15 2011-11-30 苏州大学 Organic solar battery and manufacturing method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HAILIANG DU: "The effect of small-molecule electron transporting materials on the performance of polymer solar cells", <THIN SOLID FILMS>, vol. 519, no. 13, 24 February 2011 (2011-02-24), pages 4357 - 4360, XP028189259, DOI: 10.1016/j.tsf.2011.02.049 *
吴空物: "以Zn(BTZ)2:rubrene为发光层的一种新型白色有机电致发光液晶显示背光源", <CHINESE JOURNAL OF LIQIUD CRYSTALS AND DISPLAYS>, vol. 20, no. 5, 26 October 2005 (2005-10-26), pages 17 - 421 *

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Application publication date: 20130814