CN101976727A - Organic photovoltaic cell with active layer doped with antioxidant and preparation method thereof - Google Patents
Organic photovoltaic cell with active layer doped with antioxidant and preparation method thereof Download PDFInfo
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- CN101976727A CN101976727A CN 201010284050 CN201010284050A CN101976727A CN 101976727 A CN101976727 A CN 101976727A CN 201010284050 CN201010284050 CN 201010284050 CN 201010284050 A CN201010284050 A CN 201010284050A CN 101976727 A CN101976727 A CN 101976727A
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Abstract
The invention relates to an organic photovoltaic cell with an active layer doped with antioxidant and a preparation method thereof, belonging to the field of organic optoelectronics. The organic photovoltaic cell comprises a transparent conducting substrate 1, a PEDOT:PSS anode buffer layer 2, an active layer doped with antioxidant, a cathode modifying layer 4 and a metal back electrode layer 5. The preparation method comprises the following steps of: (1) cleaning and drying the transparent conducting substrate; (2) vortically coating the PEDOT:PSS anode buffer layer 2 on the transparent conducting substrate 1 in the air or under the protection of inert gas and drying; (3) vortically coating the active layer 3 doped with the antioxidant on the PEDOT:PSS anode buffer layer 2 and carrying out heat treatment under the protection of the inert gas; (4) depositing the cathode modifying layer 4 on the active layer 3 by a thermal evaporating or solution vertical coating method; and (5) evaporating the metal Al back electrode 5 by adopting a thermal evaporating method. By doping the antioxidant into the active layer structure, the invention greatly improves the environmental stability of a device. Meanwhile, the photoelectric conversion efficiency and stability of an organic photovoltaic cell device are obviously improved.
Description
[technical field]:
The present invention relates to the organic photoelectric field, specifically, relate to a kind of organic photovoltaic battery with active layer of doping antioxidant.
[background technology]:
Along with exhausting of global petroleum resources, the exploitation of new forms of energy seems and becomes more and more important.Solar cell is the device that luminous energy is converted into electric energy.As a feasible method that solves the world energy sources crisis, the utilization of solar energy becomes the frontier nature problem of a broad research.Therefore, greatly develop the solar cell industry, utilize solar power generation to become the new forms of energy strategy of countries in the world sustainable economic development.Scholarly forecast, to the year two thousand thirty photovoltaic generation will account for 50% of world generating total amount.The research and development of solar cell launch around following two key issues all the time: (1) improves photoelectric conversion efficiency and life-span (2) new material prepares to reduce cost.Up to the present, be the conversion efficiency that the photovoltaic cell of representative can reach 10-20% usually with the inorganic silicon material.Yet inorganic photovoltaic cell required high temperature, high vacuum in preparation process makes that the production cost of inorganic photovoltaic cell is very high, and this makes its application be very restricted.
1992, N.Sariciftci etc. found the ultrafast charge transfer phenomenon of the photoinduction between polymer/C60 first.Nineteen ninety-five A.J.Heeger etc. has proposed " body heterojunction " notion (BHJ), and " body heterojunction " type single polymer layer/C60 photovoltaic cell of invention has improved the contact area of D/A heterojunction greatly.And conjugated polymer/C60 body heterojunction solar cell is because simple in structure, easy preparation has caused people's extensive concern.Around the efficient that improves organic photovoltaic battery, the optimization people that leniently absorb, the design of narrow band gap polymer are synthesized to device architecture have carried out a large amount of exploratory developments.To have made energy conversion efficiency (PCE) be 3.3% polymer solar battery to C.J.Brabec in 2002 etc. by insert the LiF material between metal electrode and active layer, again energy conversion efficiency brought up to 3.85% in 2004.Professor A.J.Heeger of University of California at Santa Barbara in 2005 waits and has obtained 5% efficient by heat treatment P3HT:PCBM active layer.K.Lee in 2007 etc. have reported and have adopted transparent TiOx as the heterojunction that the cascade material forms laminated construction machine battery to be arranged that efficient is up to 6.5%.Adding oleic acid (oleic acid) and heat treatment in P3HT:PCBM after, Cao of South China Science ﹠ Engineering University a large bell academician seminar obtained 4.3% electricity conversion.On December 9th, 2008, Konarka company announces that the said firm has cooperated to obtain 6% conversion efficiency with A J Heeger seminar.On August 1st, 2010, Solarmer Energy announces that Li doctor Gang of the said firm leader's seminar has obtained the conversion efficiency of 8.13% organic polymer photovoltaic cell, and passes through the confirmation in American National regenerative resource laboratory (NREL).The efficient of the heterojunction battery that novel receptor the material ICBA and the P3HT of Beijing chemistry Li Yongfang of institute professor seminar of Chinese Academy of Sciences report formed reaches 6.5%.Organic photovoltaic battery with low, nontoxic, the easy preparation of its cost, be easy to the chemical constitution that realizes flexible device, can change organic material easily and effectively with control best can band, charge mobility, solubility even degree of orientation improve the characteristics such as efficient of battery and become hot research in recent years.If the photoelectric conversion efficiency of organic photovoltaic battery reaches 10%, just might realize commercially producing.
Yet photoelectric conversion efficiency just restricts the bottleneck one of organic photovoltaic industrialization road.Organic photovoltaic battery stability, production cost and processing technology aspect still have many basic science problems to need to solve.Particularly for stability that how to improve organic photovoltaic devices and the life-span deep research work of shortage system still.The common starting fund total value of on December 2nd, 2008 declaration of Konarka company and German federal education and scientific research portion (BMBF) is the research topic of " stability of organic photovoltaic " (OPV stability) of 2,500,000 Euros.Device architecture is one of key factor that influences the raising of photocell energy conversion efficiency.The organic photovoltaic battery of research and development new structure, for charge carrier provide continuous effective transmission path, improve its stability and just seem extremely important.
In the organic photovoltaic battery device, back electrode mostly is the less active metal of ionization energy (as calcium, magnesium, aluminium etc.) greatly, thus their very easily oxidized decline that causes device performance in oxygen containing environment; Organic material is very responsive to oxygen, thereby very easily oxidized pollution reduces photoelectric efficiency; Various materials is aging in the further aggravation of the Joule heat meeting device that produces during device work, and then influences the operation lifetime of device.
[summary of the invention]:
The objective of the invention is that electricity conversion at existing organic photovoltaic battery is lower, the problem of poor stability, organic photovoltaic battery of a kind of active layer with doping antioxidant and preparation method thereof is provided.
The present invention has the organic photovoltaic battery of the active layer of doping antioxidant, and concrete structure comprises as shown in Figure 1 successively:
1), electrically conducting transparent substrate (1);
2), be positioned at anode buffer layer PEDOT:PSS (2) on the above-mentioned electrically conducting transparent substrate (1);
3), be positioned at the active layer that is doped with antioxidant (3) on the above-mentioned anode buffer layer PEDOT:PSS (2);
4), be positioned at cathodic modification layer (4) on the above-mentioned active layer (3) with cross-linked structure;
5), be positioned at metal back electrode (5) on the above-mentioned cathodic modification layer (4);
Above-mentioned electrically conducting transparent substrate is glass or the flexible substrate that has ITO, FTO, AZO conductive layer.Spin coating contains the active layer of antioxidant.Antioxidant be hydroquinones, 2,6 di tert butyl 4 methyl phenol or 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol).The antioxidant ratio accounts for the 0.1%-0.5% of active layer quality.The employed solvent of spin coating is ether, toluene, chlorobenzene, o-dichlorohenzene, paracide, m-dichlorobenzene, oxolane, dimethylbenzene, chloroform or acetone.
The preparation method of above-mentioned organic photovoltaic battery may further comprise the steps:
A) clean electrically conducting transparent substrate (1) and oven dry;
B) in air or under inert gas shielding, go up spin coating PEDOT:PSS anode buffer layer (2), drying in bright conductive substrates (1);
C) go up the active layer (3) that spin coating is doped with antioxidant, heat treatment under nitrogen protection at PEDOT:PSS anode buffer layer (2);
D) method by hot evaporation or solution spin coating is deposited on cathodic modification layer (4) on the active layer (3);
E) go up the way evaporation metal Al back electrode (5) that adopts hot evaporation at cathodic modification layer (4).
Advantage of the present invention and good effect:
The invention provides a kind of method that in active layer structure, adds antioxidant, improved the environmental stability of device greatly.Simultaneously, utilize antioxidant in bad solution, to form the characteristics of acicular crystal, make the conjugated polymer oriented crystalline, the transmission path of continuous effective is provided for charge carrier.Thereby the electricity conversion and the stability of organic photovoltaic battery device have been improved significantly.Cost is low, preparation condition is simple, favorable reproducibility.Adopt solution processing not need the preparation condition of high vacuum, be applicable to following large-scale drum-type (roll-to-roll) suitability for industrialized production organic solar batteries and assembly thereof.
[description of drawings]:
Fig. 1 is the device architecture schematic diagram;
[embodiment]:
(1) ito glass of 3mm * 3mm is cleaned in cleaning agent repeatedly after, soak and ultrasonic cleaning, dried for standby in IR bake at last through isopropyl alcohol, acetone and chloroformic solution respectively again;
(2) in air or under inert gas shielding, spin coating PEDOT:PSS anode buffer layer on the transparent conducting glass substrate, drying is 10 minutes under 120 degree;
(3) spin coating contains the organic active layer P3HT:PCBM (P3HT: benzenediol=100: 0.1, mass ratio) of hydroquinones antioxidant on the PEDOT:PSS anode buffer layer, heat treatment 20min under 160 degree.
(4) utilize vacuum vapour deposition that the thick cathode buffer layer LiF of 1.0nm is deposited on the active layer.
(5) by the bar shaped mask plate, the Al of vacuum evaporation 100nm does back electrode, thereby makes the organic photovoltaic battery device.Prepare comparative device with similar way.
(6) after the device preparation is finished, with all bar shaped ito anode one termination ammeter positive poles, all bar shaped Al negative electrode one termination ammeter negative poles.Test result shows: the device with cross-linked structure active layer is at AM1.5G (100mW/cm
2) under the illumination, Jsc, Voc, FF, PCE are respectively 10.95mA/cm
2, 0.61V, 49.1%, 3.28%.Comparative device under the same conditions, Jsc, Voc, FF, PCE are respectively 10.5mA/cm
2, 0.63V, 38.7%, 2.57%.Device with cross-linked structure active layer is compared with comparative device, and the device decay obviously slows down.Through 340h, the PCE of device drops to 78% of initial value; And comparative device process 140h, the PCE of device just drops to 31% of initial value.
(1) ito glass of 3mm * 3mm is cleaned in cleaning agent repeatedly after, soak and ultrasonic cleaning, dried for standby in IR bake at last through isopropyl alcohol, acetone and chloroformic solution respectively again;
(2) in air or under inert gas shielding, spin coating PEDOT:PSS anode buffer layer on the transparent conducting glass substrate, drying is 10 minutes under 120 degree;
(3) spin coating contains the organic active layer P3HT:PCBM (P3HT: benzenediol=100: 0.5, mass ratio) of hydroquinones antioxidant on the PEDOT:PSS anode buffer layer, heat treatment 20min under 160 degree.。
(4) utilize vacuum vapour deposition that the thick cathode buffer layer LiF of 1.0nm is deposited on the active layer.
(5) Al of vacuum evaporation 100nm does back electrode, thereby makes the organic photovoltaic battery device.With the normal not crosslinked comparative device of similar way preparation.
(6) test result shows: the device with cross-linked structure active layer is at AM1.5G (100mW/cm
2) under the illumination, Jsc, Voc, FF, PCE are respectively 10.47mA/cm
2, 0.62V, 46.1%, 2.99%.
Claims (6)
1. the organic photovoltaic battery with active layer of doping antioxidant is characterized in that, this organic photovoltaic battery comprises successively:
1), electrically conducting transparent substrate (1);
2), be positioned at anode buffer layer PEDOT:PSS (2) on the above-mentioned electrically conducting transparent substrate (1);
3), be positioned at the active layer that is doped with antioxidant (3) on the above-mentioned anode buffer layer PEDOT:PSS (2);
4), be positioned at cathodic modification layer (4) on the above-mentioned active layer (3) with cross-linked structure;
5), be positioned at metal back electrode (5) on the above-mentioned cathodic modification layer (4).
2. the organic photovoltaic battery with active layer of doping antioxidant according to claim 1 is characterized in that, described electrically conducting transparent substrate (1) is glass or the flexible substrate that has ITO, FTO, AZO conductive layer.
3. the organic photovoltaic battery with active layer of doping antioxidant according to claim 1, it is characterized in that, the described antioxidant of step 3) be hydroquinones, 2,6 di tert butyl 4 methyl phenol or 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl 6-tert-butyl phenol).
4. the organic photovoltaic battery with active layer of doping antioxidant according to claim 3, it is characterized in that the solvent of antioxidant activity layer is ether, toluene, chlorobenzene, o-dichlorohenzene, paracide, m-dichlorobenzene, oxolane, dimethylbenzene, chloroform or acetone.
5. the organic photovoltaic battery with active layer of doping antioxidant according to claim 3 is characterized in that, add the 0.1%-0.5% that the antioxidant ratio accounts for the active layer quality.
6. the preparation method of the organic photovoltaic battery of the described a kind of active layer with doping antioxidant of a claim 1 is characterized in that this method may further comprise the steps:
A) clean electrically conducting transparent substrate (1) and oven dry;
B) in air or under inert gas shielding, go up spin coating PEDOT:PSS anode buffer layer (2) in bright conductive substrates (1), in drying;
C) go up the active layer (3) that spin coating is doped with antioxidant, heat treatment under nitrogen protection at PEDOT:PSS anode buffer layer (2);
D) method by hot evaporation or solution spin coating is deposited on cathodic modification layer (4) on the active layer (3);
E) go up the way evaporation metal Al back electrode (5) that adopts hot evaporation at cathodic modification layer (4).
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| CN108574045A (en) * | 2018-05-07 | 2018-09-25 | 太原理工大学 | A kind of organic photovoltaic battery of high-photoelectric transformation efficiency |
| EP3447836A1 (en) * | 2017-08-25 | 2019-02-27 | RISE Acreo AB | Electrode system with polymer electrode |
| WO2019206053A1 (en) * | 2018-04-25 | 2019-10-31 | 杭州纤纳光电科技有限公司 | Antioxidant-doped perovskite film, preparation method for same, and applications thereof |
| CN111384275A (en) * | 2018-12-29 | 2020-07-07 | Tcl集团股份有限公司 | Thin film, preparation method thereof and light-emitting diode |
| CN111446375A (en) * | 2020-03-09 | 2020-07-24 | 浙江师范大学 | Perovskite solar cell modified by benzenediol and preparation method thereof |
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2010
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| 《光电子﹒激光》 20100630 田慧等 PEO作阴极修饰层提高有机光伏电池的稳定性 第887页，附图1 1-6 第21卷, 第6期 2 * |
Cited By (9)
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|---|---|---|---|---|
| EP3447836A1 (en) * | 2017-08-25 | 2019-02-27 | RISE Acreo AB | Electrode system with polymer electrode |
| WO2019206053A1 (en) * | 2018-04-25 | 2019-10-31 | 杭州纤纳光电科技有限公司 | Antioxidant-doped perovskite film, preparation method for same, and applications thereof |
| CN110400876A (en) * | 2018-04-25 | 2019-11-01 | 杭州纤纳光电科技有限公司 | A kind of perovskite thin film and its preparation method and application adulterating antioxidant |
| CN108574045A (en) * | 2018-05-07 | 2018-09-25 | 太原理工大学 | A kind of organic photovoltaic battery of high-photoelectric transformation efficiency |
| CN108574045B (en) * | 2018-05-07 | 2021-10-26 | 太原理工大学 | Organic photovoltaic cell with high photoelectric conversion efficiency |
| CN111384275A (en) * | 2018-12-29 | 2020-07-07 | Tcl集团股份有限公司 | Thin film, preparation method thereof and light-emitting diode |
| CN111384275B (en) * | 2018-12-29 | 2021-08-10 | Tcl科技集团股份有限公司 | Thin film, preparation method thereof and light-emitting diode |
| CN111446375A (en) * | 2020-03-09 | 2020-07-24 | 浙江师范大学 | Perovskite solar cell modified by benzenediol and preparation method thereof |
| CN111446375B (en) * | 2020-03-09 | 2023-05-23 | 浙江师范大学 | Phenyldiphenol modified perovskite solar cell and preparation method thereof |
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