CN110504367A - A kind of organic solar batteries preparation method based on infrared radiation processing active layer - Google Patents
A kind of organic solar batteries preparation method based on infrared radiation processing active layer Download PDFInfo
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- CN110504367A CN110504367A CN201910815941.3A CN201910815941A CN110504367A CN 110504367 A CN110504367 A CN 110504367A CN 201910815941 A CN201910815941 A CN 201910815941A CN 110504367 A CN110504367 A CN 110504367A
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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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/152—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising zinc oxide, e.g. ZnO
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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Abstract
A kind of organic solar batteries preparation method based on infrared radiation processing active layer, including step 3, step 3 prepare PTB7:PC while carrying out step 271BM active layer solution, after sufficiently being dissolved in thermal station, active layer solution is spin-coated on by ZnO cathode buffer layer surface using spin coating proceeding, after the good active layer of spin coating, substrate is transferred under infrared light, Infrared irradiation power power is 150W, Infrared irradiation wavelength is 900~1400nm, irradiating height is 50cm, irradiation time is 5~30min, finally obtain active layer, pass through the processing of Infrared irradiation annealing process, it can obtain in lower temperature and in the shorter time the preferably active layer film of film forming, optimize active layer pattern, reduce surface roughness, contact of the active layer with charge transport layer is improved simultaneously, reduce interface contact resistance, greatly improve the efficiency of transmission of photo-generated carrier, improve short circuit current, it finally improves entire organic The performance of solar battery.
Description
Technical field
The present invention relates to organic semiconductor thin-film technical field of solar batteries, more particularly to one kind is based at infrared radiation
Manage the organic solar batteries preparation method of active layer.
Background technique
Currently, the energy plays a crucial role the development of human society, the effective exploitation and utilization to the energy
The always target constantly pursued of the mankind, but most of energy used in the world is from the exploitation of fossil fuel, wherein
Mineral material mainly includes petroleum, natural gas and coal etc..However, on the one hand these resources be it is non-renewable, limited, it is another
The use of aspect fossil energy will cause very big environmental pollution, just urgently solve at the mankind so finding new fungible energy source
Certainly the problem of, it is contemplated that solar energy has the characteristics that and do not pollute that scientists from all over the world are by the sun inexhaustible, nexhaustible
The development and utilization of energy is as the breach for solving mankind energy problem.
Currently, the solar battery used is divided into the inorganic sun by the mankind according to the difference of device active layers material properties
Energy battery and organic solar batteries, inorganic solar cell is since development starting is early, and research is than wide, in solar-electricity
Leading position is occupied in the application in pond, has been realized in commercialization in recent years.But inorganic solar cell itself has it
Shortcoming, for example processing technology is extremely complex, material requirements is harsh, is not easy to carry out large area flexible processing, certain materials tool
Toxic etc., these disadvantages limit the further development of inorganic solar cell.Compared with inorganic solar cell, based on organic
The organic solar batteries of semiconductor material not only have highest theory photoelectric conversion identical with inorganic solar cell effect
Rate, but also have light weight, can water-laid film, be capable of processing into specific character, be easily made flexible device, even may be implemented it is complete
The significant advantage such as plastic, oneself becomes one of the hot spot studied both at home and abroad at present.
Existing organic solar batteries generally use reciprocal form structure, as shown in Figure 1, from top to bottom successively are as follows: substrate,
Transparent conductive cathode, cathode buffer layer, active layer, anode buffer layer and metal anode layer.Wherein in research organic solar
In numerous experiments of cell photoelectric efficiency, suitable heat can be selected when preparing active layer according to the property difference of used material
Annealing process technique.For example, for traditional PTB7:PC71BM system, can be by the good active layer of spin coating when preparing active layer
Substrate is placed on progress thermal anneal process 40min in 70 DEG C of thermal station, finally obtains active layer, but uses the above conventional method system
It is standby at active layer there are some defects: carry out long term annealing due to needing for substrate to be placed directly on high-temperature stage, this work
Skill process will be unfavorable for the contact between ito transparent electrode and active layer, also be unfavorable for the subsequent work of organic solar batteries
Industryization preparation；Simultaneously as the hysteresis quality and inhomogeneities and device annealing process of thermal station heat supplying process need exposure for a long time
In antivacuum environment, active layer film-formation result defect easy to form, when further influencing vapor deposition anode buffer layer therewith
Interfacial contact.These all greatly reduce device capture sunlight, separation exciton, the ability for transmitting charge, it is suppressed that entire device
The performance of part.
Therefore, optimization prepares the process flow of organic solar batteries photoactive layer, so high efficiency, low cost prepare
Even, fine and close active layer film is one of emphasis and difficult point of current organic solar batteries area research.
Summary of the invention
It is an object of the invention to: it is directly put for present in existing organic solar batteries preparation method because of substrate
Contact caused by long term annealing on high-temperature stage between ito transparent electrode and active layer is in bad order, because of thermal station
The hysteresis quality and inhomogeneities and device of heat supplying process are exposed to activity caused by antivacuum environment in annealing process for a long time
Layer film-formation result defect easy to form, and because the reduction of device capture sunlight, separation exciton, the ability for transmitting charge causes
To the reduction of entire device performance, the present invention provides a kind of organic solar batteries preparation based on infrared radiation processing active layer
Method replaces traditional thermal anneal process at room temperature, and the substrate that active layer film is got well in spin coating is placed under infrared lamp and is irradiated, benefit
With the fuel factor and strong permeability of infrared light, infrared light action time is controlled, makes active layer film in the atmosphere of uniform illumination
Middle film forming obtains active layer by the irradiation of short period.
The technical solution adopted by the invention is as follows: a kind of organic solar batteries system based on infrared radiation processing active layer
Preparation Method, specific step is as follows for preparation method:
Step 1: the ito substrate as composed by transparent substrates and transparent conductive cathode being cleaned, nitrogen is used after cleaning
Air-blowing is dry；
Step 2: by zinc acetate (Zn (CH3COO)2) and ethanol amine (C2H7NO) it is added to dimethoxy-ethanol (C3H8O2) molten
In agent, it is stirred at room temperature after sufficiently dissolution by 2 hours and obtains ZnO precursor solution, then by ZnO precursor solution spin coating
Ito substrate surface in step 1 obtains ZnO cathode buffer layer after carrying out thermal anneal process；
Step 3: while carrying out step 2, preparing PTB7:PC71BM active layer solution, sufficiently dissolves it in thermal station
Afterwards, active layer solution is spin-coated on by ZnO cathode buffer layer surface using spin coating proceeding, after the good active layer of spin coating, by substrate
It is transferred under infrared light (light direct irradiation active layer), Infrared irradiation power power is 150W, and Infrared irradiation wavelength is 900
~1400nm, irradiation height are 50cm, and irradiation time is 5~30min, finally obtain active layer.
Step 4: being 3 × 10 in vacuum degree3Under conditions of Pa, MoO is deposited in active layer surface3, obtain anode buffer layer；
Step 5: in anode buffer layer surface evaporation metal anode material, obtaining metal anode layer, complete.
Further, the PTB7:PC in the step 371BM active layer solution by electron donor material PTB7 and electronics by
Body material PC71BM is mixed by the mass percent of 1:5~5:1, is dissolved in 1ml chlorobenzene, and concentration is 10~30mg/ml.
Further, the PTB7:PC71BM active layer solution is by electron donor material PTB7 and electron acceptor material
PC71BM is mixed by the mass percent of 1:1, is dissolved in 1ml chlorobenzene, concentration 10mg/ml, and is added in mixed solution
The DIO of 30ul.
Further, the metal anode material in the step 5 is one of Ag, Al, Au or a variety of.
Further, the active layer thickness that the step 3 obtains is 50~250nm.
Further, the anode buffer layer that the step 4 obtains is with a thickness of 10~20nm.
Further, the metal anode layer that the step 5 obtains is with a thickness of 100~200nm.
Compared to the prior art, the beneficial effects of the present invention are:
1. a kind of organic solar batteries preparation method based on infrared radiation processing active layer, by using infrared radiation
Annealing process prepares the photoactive layer of organic solar batteries, high temperature needed for avoiding active layer annealing due to this process flow
In heating environment, so as to obtain the better active layer of film forming within the shorter time, be conducive to subsequent solar battery
Preparation of industrialization.
2. the step of replacing thermal station annealing in traditional handicraft in the present invention, avoiding the hysteresis quality and not of thermal station heat supplying process
The influence that uniformity forms a film to active layer takes full advantage of the fuel factor and permeability of infrared light, enables active layer equal
It is even it is heated under conditions of homogeneous film formation, while also avoiding annealing process substrate and being exposed in antivacuum environment for a long time, lead to
Entire process flow is crossed, the pattern of active layer is improved, reduces surface roughness；It is caught to further substantially increase device
The ability for obtaining sunlight, separating exciton, improves the performance of entire device.
3. preparing resulting photolytic activity and charge transport layer circle by heretofore described step compared to conventional preparation techniques
Face contact is more preferable, and the transmission for being conducive to photogenerated charge inhibits the compound of carrier, is conducive to the preparation of high performance device.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of organic solar batteries according to the present invention；
Fig. 2 is the structural schematic diagram that infrared lamp involved in the present invention irradiates substrate.
In the figure, it is marked as 1- substrate, 2- infrared lamp, 3- substrate, 4-ITO transparent conductive cathode, 5-ZnO cathode buffer layer,
6- activity layer film, 7- anode buffer layer, 8- metal anode layer, 9-ITO substrate, 10-PBT7:PC71BM active layer.
Specific embodiment
All features disclosed in this specification can be with any other than mutually exclusive feature and/or step
Mode combines.
It elaborates below with reference to Fig. 1 and Fig. 2 to the present invention.
A kind of organic solar batteries preparation method based on infrared radiation processing active layer provided in this embodiment, in room
Under temperature, replace traditional thermal anneal process, the substrate 1 that active layer film 6 is got well in spin coating is placed under infrared lamp 2 and is irradiated, utilization is red
The fuel factor of outer light and strong permeability, control infrared light action time, make active layer film 6 in the atmosphere of uniform illumination at
Film obtains active layer film 6 by the irradiation of short period, and specific step is as follows for the preparation method:
Step 1: being less than the ITO base as composed by transparent substrates 3 and transparent conductive cathode 4 of 1nm to surface roughness
Plate 9 is cleaned, with being dried with nitrogen after cleaning；
Step 2: by zinc acetate (Zn (CH3COO)2) and ethanol amine (C2H7NO) dimethoxy-ethanol (C3H8O2) in solvent,
It is stirred at room temperature after sufficiently dissolution by 2 hours and obtains ZnO precursor solution, ZnO precursor solution is spin-coated on step 1
9 surface of ito substrate obtains ZnO cathode buffer layer 5 after carrying out thermal anneal process；
Step 3: while carrying out step 2, the PBT7 of 90 DEG C, 800r processed 6 hours will be passed through in thermal station:
10 solution of PC71BM active layer is spin-coated on 5 surface of ZnO cathode buffer layer (1200rpm, 90s).It, will after the good active layer of spin coating
Substrate 1 is transferred under infrared light, the model CHF-XM35 of the infrared lamp 2 of this example transmission infrared light, and visible light is cooperated to cut
It is 150W that only filter plate, which uses (light direct irradiation active layer) Infrared irradiation power power, Infrared irradiation wavelength is 900~
1400nm, irradiation height are 50cm, and irradiation time is 5~30min, are finally obtained with a thickness of 120nm active layer, PTB7:PC71BM
Active layer solution is by electron donor material PTB7 and electron acceptor material PC71BM is mixed by the mass percent of 1:1, is dissolved in
In 1ml chlorobenzene, concentration 10mg/ml, and plus the DIO of 30ul in mixed solution；
Step 4: being 3 × 10 in vacuum degree3Under conditions of Pa, MoO is deposited in active layer surface3, obtain with a thickness of 15nm's
Anode buffer layer 7；
Step 5: in 7 surface evaporation metal anode material Ag of anode buffer layer, obtaining the metal anode layer with a thickness of 100nm
8, it completes.
The present invention is according to circumstances respectively provided with 5min, 10min, 15min, 20min, 25min, 30min six in step 3
Kind irradiation time, and performance detection has been carried out to six kinds of organic solar batteries being prepared under six kinds of irradiation times,
Under standard test condition (AM 1.5,100mW/cm2), matched according to two kinds of solvents in 5 solution of collosol and gel ZnO cathode buffer layer
The difference of ratio measures the open-circuit voltage (VOC), short circuit current (JSC), fill factor (FF), photoelectric conversion efficiency (PCE) of device
Different, the data measured are as shown in table 1.
Solar cell properties parameter under the different Infrared irradiation times of table 1
As shown in table 1, the organic solar batteries produced by existing thermal anneal process preparation method are surveyed in standard
(AM 1.5,100mW/cm2) is detected under the conditions of examination, measures open-circuit voltage (VOC)=0.75V of device, short circuit current
(JSC)=13.27mA/cm2, fill factor (FF)=0.61, photoelectric conversion efficiency (PCE)=6.07%.
It can be seen that in summary, by using the organic solar batteries of infrared radiation annealing active layer, infrared
In the suitable situation of light irradiation time, compared to the organic solar batteries device of existing method preparation, photovoltaic performance parameter is equal
Be substantially improved, in a word active layer film forming of the invention uniformly, be convenient for industrialized production, photolytic activity and charge transport layer interface
Contact is good and prepares the advantages of device performance increases substantially.
The foregoing is merely illustrative of the preferred embodiments of the present invention, the protection scope being not intended to limit the invention, any
Those skilled in the art within the spirit and principles in the present invention made by any modifications, equivalent replacements, and improvements etc.,
It should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of organic solar batteries preparation method based on infrared radiation processing active layer, it is characterised in that:
Step 1: the ito substrate as composed by transparent substrates and transparent conductive cathode being cleaned, is blown after cleaning with nitrogen
It is dry；
Step 2: by zinc acetate (Zn (CH3COO)2) and ethanol amine (C2H7NO dimethoxy-ethanol (C) is added3H8O2) in solvent, warp
Spending 2 hours is stirred at room temperature after sufficiently dissolution and obtains ZnO precursor solution.ZnO precursor solution is spin-coated on step 1
Ito substrate surface obtains ZnO cathode buffer layer after carrying out thermal anneal process；
Step 3: while carrying out step 2, preparing PTB7:PC71BM active layer solution is adopted after sufficiently dissolving in thermal station
Active layer solution is spin-coated on ZnO cathode buffer layer surface with spin coating proceeding.After the good active layer of spin coating, substrate is transferred to
Under infrared light, Infrared irradiation power power is 150W, and Infrared irradiation wavelength is 900~1400nm, and irradiation height is 50cm,
Irradiation time is 5~30min, finally obtains active layer.
Step 4: being 3 × 10 in vacuum degree3Under conditions of Pa, MoO is deposited in active layer surface3, obtain anode buffer layer；
Step 5: in anode buffer layer surface evaporation metal anode material, obtaining metal anode layer, complete.
2. a kind of organic solar batteries preparation method based on infrared radiation processing active layer as described in claim 1,
It is characterized in that: the PTB7:PC in the step 371BM active layer solution is by electron donor material PTB7 and electron acceptor material
PC71BM is mixed by the mass percent of 1:5~5:1, is dissolved in 1ml chlorobenzene, and concentration is 10~30mg/ml.
3. a kind of organic solar batteries preparation method based on infrared radiation processing active layer as described in claim 1,
It is characterized in that: the PTB7:PC71BM active layer solution is by electron donor material PTB7 and electron acceptor material PC71BM presses 1:1
Mass percent mix, be dissolved in 1ml chlorobenzene, concentration 10mg/ml, and in mixed solution add 30ul DIO.
4. a kind of as claimed in claim 1 organic solar batteries preparation method based on infrared radiation processing active layer,
Be characterized in that: the metal anode material in the step 5 is one of Ag, Al, Au or a variety of.
5. a kind of as claimed in claim 1 organic solar batteries preparation method based on infrared radiation processing active layer,
Be characterized in that: the active layer thickness that the step 3 obtains is 50~250nm.
6. a kind of as claimed in claim 1 organic solar batteries preparation method based on infrared radiation processing active layer,
Be characterized in that: the anode buffer layer that the step 4 obtains is with a thickness of 10~20nm.
7. a kind of as claimed in claim 1 organic solar batteries preparation method based on infrared radiation processing active layer,
Be characterized in that: the metal anode layer that the step 5 obtains is with a thickness of 100~200nm.
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2019
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