CN103515536B - A kind of simple method for preparing of transoid organic solar batteries - Google Patents

A kind of simple method for preparing of transoid organic solar batteries Download PDF

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Publication number
CN103515536B
CN103515536B CN201310270925.3A CN201310270925A CN103515536B CN 103515536 B CN103515536 B CN 103515536B CN 201310270925 A CN201310270925 A CN 201310270925A CN 103515536 B CN103515536 B CN 103515536B
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solar batteries
organic solar
preparation
volume
film
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CN103515536A (en
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阳仁强
包西昌
孙亮
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a kind of simple method for preparing of transoid organic solar batteries device.The structure of the transoid organic solar batteries is followed successively by transparent conductive substrate, cathodic modification layer, organic active layer, anode modification layer and anode electrode from bottom to top.Wherein cathodic modification layer is the fine and close amorphous TiO prepared using one-step method2Film.The simple method for preparing of transoid organic solar batteries disclosed by the invention, compared to physical preparation process such as magnetron sputtering, pulsed laser depositions, with preparation process is simple, is conducive to being greatly lowered the cost of organic solar batteries；Compared to first synthesizing TiO2, ZnO nano particle, redisperse revolves the preparation method of film, has the advantages that film forming is rapid, fine and close, is adapted to the large area preparation of industrialization of quick low cost.The present invention is more suitable for large-scale volume to volume printing and prepares flexible solar battery.

Description

A kind of simple method for preparing of transoid organic solar batteries
Technical field
The present invention relates to area of solar cell, and in particular to a kind of simple preparation side of transoid organic solar batteries Method.
Background technology
The energy is that the mankind originate for the energy of the activity of surviving.With the development of social economy, people are to the energy Demand is increasing, and the storage of conventional fossil energy is limited, and increasingly exhausted.Therefore except increasing income and decreasing expenditure fossil resource Outward, it is badly in need of exploitation and substitutes new energy, wherein solar energy is most important renewable resource and inexhaustible clean energy resource, will too The solar cell that sun can be converted to electric energy causes the extensive concern of people.
It is the most ripe with monocrystalline silicon and polycrystalline silicon technology in the solar cell of numerous kinds, but due to its high cost, work The problems such as skill is complicated, environmental pollution is big, limits the large-scale application of such solar cell.Therefore, for solar power generation is obtained To large-scale promotion, efficiency, the reduces cost of solar cell must be just improved.
Organic solar batteries technology is considered as one of most attractive, cheap solar battery technology.One is electricity The preparation cost of organic active layer material used in pond is low, structure is easy to cut, pliability is good, extinction coefficient is high, film forming The advantages of property is all good.Two is that the preparation technology of organic solar batteries need not be related to inorganic matter sputtering, chemical vapor deposition, height The expensive thin-film process such as purity crystal growth, doping, it is possible to use the system such as spin coating, inkjet printing or volume to volume printing Standby technology, large area manufacture, process is simple, usable flexible substrate, environment-friendly, light portable, making are realized with easy The features such as low cost.
In recent years, with the continuous exploration to organic solar battery material and device architecture, organic solar batteries Efficiency has reached 8%~10%.But the high-performance organic solar batteries device reported at present, mostly using the eurymeric sun Energy battery, while anode buffer layer uses PEDOT:PSS, and PEDOT:PSS materials have very strong corrosivity to ITO electrode, separately Outward, oxidizable low work function metal material that eurymeric solar cell cathode electrode is used etc. greatly reduces solar cell The life-span of device and stability.
In organic solar batteries, it is followed successively by from bottom to top as the structure of the transoid organic solar batteries of study hotspot Transparent conductive substrate, cathodic modification layer, organic active layer, anode modification layer and anode electrode.Transoid battery avoids PEDOT: The use of PSS and low-work-function material, can greatly improve the stability of organic solar batteries device.Transoid organic solar One of key of battery is to prepare the transparent oxide that level structure is suitable, work function is matched, conductance is high（Usually TiO2 Or ZnO）Decorative layer is used to modify ITO electrode as electronics collecting layer and hole blocking layer.Development can industrialize extensive life The low temperature preparation technique of product meets the TiO of above-mentioned requirements to obtain2Or ZnO or other decorative layers are transoid organic solar batteries An important technology bottleneck of urgent need to resolve in research and development field.
TiO is prepared at present2Or ZnO film, a kind of method be using the complex process such as magnetron sputtering, pulsed laser deposition, The physical method of high cost, limits large-scale production.Another method is first to synthesize TiO2Or ZnO nano particle, redisperse Wiring solution-forming, but the method not only increases the complexity of technique, and also the uniformity of the nano particle of synthesis is difficult control, into Film is poor.Other Physical prepares film and substrate there are certain requirements, it is difficult to realize the production of flexible device.These problems are limited Its large-scale application is made.
The content of the invention
The present invention provides and a kind of can realize process is simple, low temperature, low cost, can industrialize the transoid of large-scale production too The preparation method of positive energy battery device.
To reach above-mentioned purpose, from bottom to top specific features include transoid organic solar batteries device described in this patent： Transparent conductive substrate, this substrate is high transmittance conductive material that a class etches figure as cathode layer.
Cathodic modification layer, is to use tetraethyl titanate, or isopropyl titanate, or the alcoholic solution of butyl titanate is spun on In bright conductive substrates, post processing obtains fine and close amorphous TiO in air2Film.Alcoholic solution of the present invention is ethanol, isopropyl Alcohol, butanol.
Organic active layer, is the blend of one layer of conjugated conductive polymer or small molecule and fullerene derivate.
Anode modification layer, is one layer of molybdenum oxide, tungsten oxide, nickel oxide or vanadium oxide material.
Anode electrode, is gold, silver, copper or the aluminium of a floor height work function.
The specific preparation process of the transoid organic solar batteries described in this patent is as follows.
Step 1, carries out cleaning, drying standby to transparent conductive substrate.
Step 2, spin coating prepares one layer of amorphous TiO of densification in the transparent conductive substrate that step 1 is washed2Film.This is thin The specific preparation process of film includes.
2.1, titanate esters are configured to alcoholic solution in atmosphere of inert gases, described titanate esters are tetraethyl titanate, metatitanic acid Isopropyl ester, or butyl titanate, solution concentration volume ratio is in 1-60 v/v%.
2.2, the titanate esters alcoholic solution that 2.1 prepare stir for a period of time in atmosphere of inert gases, the time is 0.1-200 hours.
2.3, the metatitanic acid ester solution that 2.2 are stirred spin coating, inkjet printing or volume to volume printing in atmosphere of inert gases In on substrate prepared by step 1.
2.4, by the TiO of 2.3 spin coatings2Precursor thin-film is post-processed in being transferred to air, fine and close non-needed for obtaining Brilliant TiO2Film., from room temperature to 300 degree, described thickness is between 2-200 nm for described post-processing temperature.
2.5, the fine and close amorphous TiO that 2.4 are prepared2Film is transferred to standby in atmosphere of inert gases.
Step 3, in fine and close amorphous TiO2Preparing one layer using spin coating, inkjet printing or volume to volume printing technology on film has Machine active layer, this active layer is the mixture of conjugated polymer or small molecule and fullerene derivate.
Step 4, is prepared on organic active layer using hot evaporation, sputtering, spin coating, inkjet printing or volume to volume printing technology Anode modification layer, this decorative layer is molybdenum oxide, tungsten oxide, nickel oxide or vanadium oxide.
Step 5, prepares anode electrode layer, institute using hot evaporation, sputtering, spin coating, inkjet printing or volume to volume printing technology It is silver, gold, aluminium or copper to state anode electrode material.
Compared with prior art, it is of the invention in cathodic modification layer, by preparing titanate esters alcoholic solution, using improved preparation Technique, one-step method is prepared for high-performance densification amorphous TiO2The performances such as film, battery device open-circuit voltage, the fill factor, curve factor of preparation Parameter constant, but technique is simpler, and cost is lower, is adapted to the extensive preparation of organic solar batteries.
Brief description of the drawings
In order to illustrate more clearly of embodiments of the invention, the accompanying drawing for being used embodiment below is clearly and succinctly situated between Continue, the accompanying drawing in being described herein as is directed to embodiments of the invention.
Fig. 1 is transoid organic solar batteries schematic diagram；1 is ito glass in figure, and 2 is TiO2Film, 3 is organic active Layer P3HT:PC61The blend of BM, 4 is molybdenum oxide, and 5 is silver electrode.
Fig. 2 be isopropyl titanate aqueous isopropanol on ito glass spin-coating film, be empty in gas light and handy after 60 minutes Atomic force exterior view under pattern.
Fig. 3 be isopropyl titanate aqueous isopropanol on ito glass spin-coating film, be empty saturating after 60 minutes in gas The comparison diagram of rate and ito glass transmitance is crossed, back end, fine and close amorphous TiO are done with air2The thickness of film is 30 nm.
Fig. 4 be isopropyl titanate aqueous isopropanol on ito glass spin-coating film, be empty conduct after 60 minutes in gas The transoid organic solar batteries device of cathodic modification layer is AM 1.5G in intensity of illumination（100 mW/cm2）Under simulated solar irradiation Current density voltage curve.
Specific embodiment
A kind of simple method for preparing of transoid organic solar batteries of this patent, with reference to Figure of description, with P3HT： PC60BM is as follows for the specific preparation process of the transoid organic solar batteries of active layer.
First, by patterned ito glass 1, after being cleaned by ultrasonic through acetone, ITO cleaning agents, deionized water, isopropanol, dry It is dry standby.
Compound concentration is the aqueous isopropanol of the isopropyl titanate of 20 v/v% in the glove box of pure nitrogen gas atmosphere, and Stirred 30 minutes in pure nitrogen gas atmosphere glove box.
Then in the glove box of pure nitrogen gas atmosphere, using 20 v/v% isopropyl titanate aqueous isopropanol in ITO Glass one layer of isopropyl titanate film of quick spin coating.
The ito glass that spin coating has isopropyl titanate film is transferred in air and is placed 60 minutes.One layer of cause of hydrolysis generation Close amorphous TiO2Film 2, such as Fig. 2.Fig. 3 is its transmittance curve, the nm of thickness about 30.
Then will be covered with fine and close amorphous TiO2The ITO of film is transferred in the glove box of nitrogen atmosphere, thereon spin coating Organic active layer 3.Described active layer is P3HT and PC60The weight ratio of BM is 1：1 chlorobenzene solution（Total concentration is 30mg/ ml）；Described rotating speed is 500 turns per minute.
Active layer is made annealing treatment 10 minutes at 150 DEG C then.
The sample that active layer will be scribbled is transferred in evaporated device, and 5nm molybdenum trioxides 4 are deposited with successively（Evaporation rate is 0.1nm/s）, 100nm metals silver electrode 5（Evaporation rate 0.5nm/s）.
The transoid organic solar batteries are AM1.5G in intensity of illumination（100mW/cm2）Test result under simulated solar irradiation As shown in figure 4, its performance is as follows：Open-circuit voltage is 0.62V, short circuit current 10.7mA/cm2, fill factor, curve factor 63%, energy conversion Efficiency reaches 4.18%.

Claims (8)

1. a kind of transoid organic solar batteries are followed successively by transparent conductive substrate (1), cathodic modification layer (2), organic from bottom to top Active layer (3), anode modification layer (4) and anode electrode (5), it is characterised in that preparation is comprised the following steps：
1) in pure nitrogen gas or pure argon atmosphere of inert gases, phthalate ester is configured to certain density alcoholic solution；
2) the titanate esters alcoholic solution prepared is stirred into a period of time in atmosphere of inert gases；
3) the titanate esters alcoholic solution that will be stirred spin coating, inkjet printing or volume to volume in atmosphere of inert gases are printed in transparent leading On electric substrate；
4) titanium dioxide (TiO will be printed with2) precursor thin-film substrate be transferred to air in post-processed, obtain required thickness The fine and close amorphous TiO of degree2Film；
5) the fine and close amorphous TiO that will be prepared2Film-substrate is transferred in atmosphere of inert gases；
6) in fine and close amorphous TiO2Organic active layer is prepared using spin coating, inkjet printing or volume to volume printing process on film；
7) anode modification layer is prepared using the printing of evaporation, spin coating, inkjet printing or volume to volume on organic active layer；
8) anode electrode is prepared using evaporation, spin coating, inkjet printing or volume to volume printing in anode modification layer.
2. the preparation method of transoid organic solar batteries according to claim 1, it is characterised in that described transparent to lead Electric substrate is transparent ito glass, transparent FTO glass or transparent polyester ito thin film.
3. the preparation method of transoid organic solar batteries according to claim 1, it is characterised in that described titanate esters It is tetraethyl titanate, isopropyl titanate or butyl titanate, its alcoholic solution is ethanol, isopropanol, butanol, and concentration volume ratio is 1- 60v/v%.
4. the preparation method of transoid organic solar batteries according to claim 1, it is characterised in that described post processing Temperature is room temperature to 300 DEG C.
5. the preparation method of transoid organic solar batteries according to claim 1, it is characterised in that described is fine and close non- Brilliant TiO2The thickness of film is 2-200nm.
6. the preparation method of transoid organic solar batteries according to claim 1, it is characterised in that described organic work Property layer be conjugated conductive polymer or small molecule and fullerene derivate mixture.
7. the preparation method of transoid organic solar batteries according to claim 1, it is characterised in that described anode is repaiied Decorations layer is molybdenum oxide, tungsten oxide, nickel oxide or vanadium oxide, and thickness is 2-50nm.
8. the preparation method of transoid organic solar batteries according to claim 1, it is characterised in that described anode electricity Extremely silver-colored, gold, aluminium or copper electrode, thickness is 10-200nm.
CN201310270925.3A 2013-07-01 2013-07-01 A kind of simple method for preparing of transoid organic solar batteries Expired - Fee Related CN103515536B (en)

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CN103887432A (en) * 2014-03-28 2014-06-25 电子科技大学 Inversion type organic thin-film solar cell decorated by polar solvent and preparation method there of
CN104505423A (en) * 2014-11-18 2015-04-08 华南理工大学 Inverted-structure CdTe nanocrystalline heterojunction high-efficiency solar cell processed by solution method, and preparation method of solar cell
TWI629810B (en) * 2015-10-20 2018-07-11 行政院原子能委員會核能研究所 Method for improving mass-production yield of large-area organic solar cells
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101577313A (en) * 2009-06-19 2009-11-11 吉林大学 Reciprocal form structure polymer solar cell and preparation method thereof
CN101593812A (en) * 2009-07-02 2009-12-02 吉林大学 A kind of semitransparent inverse organic solar cell and preparation method thereof
CN102201539A (en) * 2011-04-22 2011-09-28 华北电力大学 Polymer solar battery with inverted structure and fabrication method thereof
CN102983277A (en) * 2012-12-10 2013-03-20 吉林大学 Inverted polymer solar cell of Ag nano particle compounded cavity transmission layer and fabrication method
CN103000811A (en) * 2012-12-14 2013-03-27 吉林大学 One-dimensional photonic crystal back reflecting mirror based inverted semitransparent polymer solar cell and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101577313A (en) * 2009-06-19 2009-11-11 吉林大学 Reciprocal form structure polymer solar cell and preparation method thereof
CN101593812A (en) * 2009-07-02 2009-12-02 吉林大学 A kind of semitransparent inverse organic solar cell and preparation method thereof
CN102201539A (en) * 2011-04-22 2011-09-28 华北电力大学 Polymer solar battery with inverted structure and fabrication method thereof
CN102983277A (en) * 2012-12-10 2013-03-20 吉林大学 Inverted polymer solar cell of Ag nano particle compounded cavity transmission layer and fabrication method
CN103000811A (en) * 2012-12-14 2013-03-27 吉林大学 One-dimensional photonic crystal back reflecting mirror based inverted semitransparent polymer solar cell and preparation method thereof

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