CN108470852A - A kind of preparation method of modifying interface perovskite solar cell - Google Patents
A kind of preparation method of modifying interface perovskite solar cell Download PDFInfo
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- CN108470852A CN108470852A CN201810314370.0A CN201810314370A CN108470852A CN 108470852 A CN108470852 A CN 108470852A CN 201810314370 A CN201810314370 A CN 201810314370A CN 108470852 A CN108470852 A CN 108470852A
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- solar cell
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Abstract
The invention discloses a kind of preparation methods of modifying interface perovskite solar cell, including step：Transparent electrode substrate is sequentially placed into deionized water, acetone, ethyl alcohol and carries out ultrasonic cleaning, is cleaned again by ozone plasma after dry；The solution coating of hole transmission layer will be prepared on the substrate after cleaned and drying according to default spin speed, and is made annealing treatment at a set temperature；The polar solvent with high coordination ability of spin coating set amount on the hole transmission layer of formation；The mode for passing sequentially through spin coating prepares light-absorption layer and electron transfer layer, and is made annealing treatment respectively；Finally, in high vacuum plates chamber, top electrode is deposited on the electron transport layer by way of thermal evaporation.The present invention by using polar solvent to improve the surface roughness and grain size dimensional homogeneity of light-absorption layer by the interaction of polar solvent and extinction layer material, improve the performance of perovskite solar cell on the hole transport layer.
Description
Technical field
The present invention relates to perovskite solar cell preparation field more particularly to a kind of modifying interface perovskite solar-electricities
The preparation method in pond.
Background technology
With flourishing for photoelectric field, so far, various photovoltaic technologies, such as the sun based on Si have been developed
Energy battery, using copper indium gallium selenide as the thin-film solar cells of representative, dye-sensitized solar cells, organic solar batteries and calcium
Titanium ore solar cell（PSC, Perovskite Solar Cells）.The commercialization of solar cell often requires that energy is converted
Efficiency（PCE）With low cost manufacturing technique and with the compatibility of Technology of Flexibility.Since perovskite solar cell complies fully with
Commercial requirements, therefore attracted global concern, and caused many research interests.Perovskite solar cell in recent years
Energy conversion efficiency has been promoted to more than 20 %, close to the energy conversion efficiency of commercialization silica-based solar cell.This can return
Because in the peculiar property of perovskite, such as large charge carrier mobility and long charge carriers carrier diffusion length.
Since PSC devices are that perovskite light-absorption layer is clipped in the sandwich between ETL and htl layer, the property of ETL and htl layer
Matter largely affects the device performance of PSC.It can effectively improve device performance by optimizing ETL and htl layer,
In, it is a kind of effective approach to carry out surface solvent processing to htl layer surface.
Invention content
It is an object of the invention to for the technical problems in the prior art, provide a kind of modifying interface perovskite too
The preparation method of positive energy battery, specific technical solution are as follows：
A kind of preparation method of modifying interface perovskite solar cell, the method includes the steps：
Transparent electrode substrate is sequentially placed into deionized water, acetone, ethyl alcohol and carries out ultrasonic cleaning, again by smelly after drying
Oxygen plasma cleans；
The solution coating of hole transmission layer will be prepared on the substrate after cleaned and drying according to default spin speed, and
It is made annealing treatment at a set temperature；
The polar solvent with high coordination ability of spin coating set amount on the hole transmission layer of formation；
Light-absorption layer is prepared using different spin speed spin coatings stage by stage on the hole transmission layer after polar solvent is processed
Precursor solution, and made annealing treatment after the completion of spin coating；
The solution of spin coating electron transfer layer on light-absorption layer, is then placed in the thermal station of set temperature and is made annealing treatment；
In high vacuum plates chamber, top electrode is deposited on the electron transport layer by way of thermal evaporation.
Further, the substrate respectively carries out the ultrasound of the min of 10 min ~ 20 in the deionized water, acetone, ethyl alcohol
Wave cleans, and 3 ~ 5 min are cleaned in the ozone plasma.
Further, the transparent electrode is indium tin oxide（ITO）, fluorine tin-oxide（FTO）, aluminium zinc oxide
（AZO）Or one kind in other transparent conductive materials.
Further, the hole transmission layer is formed by the material preparation with higher hole mobility.
Further, the polar solvent is dimethyl sulfoxide (DMSO)（DMSO）, ethyl alcohol or DMSO and ethyl alcohol mixed solution.
Further, the light-absorption layer is made of the compact-grain of perovskite material.
Further, the top electrode is the material with higher work-functions.
Modifying interface perovskite preparation method of solar battery provided by the invention during preparing solar cell,
Spin coating has the polar solvent of high coordination ability on the hole transport layer, passes through high ligand solvent and perovskite precursor solution point
Interaction between son improves the pattern of perovskite thin film；Compared with prior art, beneficial effects of the present invention are：Improve
The surface roughness and even grain size of light-absorption layer so that the film of light-absorption layer is more flat in perovskite solar cell
It is sliding, be conducive to the transmission of carrier, improve the short circuit current and energy conversion efficiency of perovskite solar cell.
Description of the drawings
Fig. 1 is modifying interface perovskite solar cell preparation process flow block diagram of the present invention；
Fig. 2 is the SEM pattern comparison diagrams on the surface of light-absorption layer perovskite thin film and traditional light-absorption layer perovskite thin film in the present invention；
Fig. 3 is the voltage-current density of modifying interface perovskite solar cell of the present invention and traditional perovskite solar cell
Test curve；
Fig. 4 is the structural schematic diagram of modifying interface perovskite solar cell of the present invention.
Specific implementation mode
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention
Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described.Obviously, described embodiment is only this
Invention a part of the embodiment gives presently preferred embodiments of the present invention instead of all the embodiments in attached drawing.The present invention can be with
It realizes in many different forms, however it is not limited to embodiment described herein, on the contrary, provide the purpose of these embodiments
It is to make the disclosure of the present invention more thorough and comprehensive.Based on the embodiments of the present invention, ordinary skill
The every other embodiment that personnel are obtained without making creative work, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation methods of modifying interface perovskite solar cell, wherein the solar-electricity
Pond includes substrate 1, transparent electrode layer 2, hole transmission layer 3, light-absorption layer 4, electron transfer layer 5 and the top electrode 6 of lamination successively,
The concrete structure of modifying interface perovskite solar cell sees Fig. 4.
Refering to fig. 1, in embodiments of the present invention, the preparation method of modifying interface perovskite solar cell includes step：
S1：It will be sequentially placed by transparent electrode substrate in deionized water, acetone, ethyl alcohol and carry out ultrasonic cleaning, after drying again
It is cleaned by ozone plasma；
In embodiments of the present invention, it in order to ensure that the perovskite solar cell prepared is with good performance, needs to transparent
Electrode substrate is cleaned, and substrate is sequentially placed into cleaning solution and carries out ultrasonic cleaning, and cleaning solution includes deionized water, acetone
And ethyl alcohol；Specifically, respectively needing the cleaning of progress 10 min ~ 20 min in each cleaning solution, scavenging period can be according to reality
Situation is selected；In the present embodiment, excellent to take scavenging period for 20 min.Processing is dried in substrate after the completion of cleaning,
For example, passing through N2The surface of pneumatic conveying drying device；Finally, the cleaning operation for carrying out 3 min again by ozone plasma, with
Remove the organic impurities on surface；After being dried the processing with ozone plasma, be conducive to subsequently carry out hole transport
The preparation of layer.
In embodiments of the present invention, transparent electrode is by indium tin oxide（ITO）, fluorine tin-oxide（FTO）, aluminium zinc oxidation
Object（AZO）Or other transparent conductive materials are prepared into.
S2：Described after cleaned and dry of the solution coating of hole transmission layer transparent is led according to default spin speed
In electric layer, and made annealing treatment at a set temperature；And spin coating has high coordination ability on the hole transmission layer of formation
Polar solvent；
In embodiments of the present invention, excellent to take PEDOT：PSS is hole transmission layer, and PEDOT is prepared by way of spin coating：PSS layer；
In the present embodiment, spin speed is 2000 rpm, in practical applications, can be carried out carrying out spin speed according to actual conditions
Adjustment；Then, it puts it into vacuum environment and is made annealing treatment, control 100 DEG C of temperature；Wherein, the time of annealing is
20 min ultimately form the hole transport layer film that thickness is 20 nm.
In embodiments of the present invention, in order to improve the pattern of extinction layer film, there is height in hole transport layer surface spin coating
The polar solvent of coordination property；When subsequently carrying out the preparation of light-absorption layer, polar solvent will influence the pattern of light-absorption layer, make shape
At light-absorption layer grain size is uniform, surface is smooth.
In embodiments of the present invention, hole transmission layer is made of the material with higher hole mobility, can be organic
Material can also be inorganic material, wherein organic material can be Spiro-MeOTAD, P3HT, PTAA, NPB etc., inorganic material
Material can be copper oxide, cuprous oxide, nickel oxide etc.；Polar solvent can be ethyl alcohol, DSMO or ethyl alcohol and the mixing of DSMO
Liquid can specifically be selected according to actual conditions, and the present invention is limited and fixed not to this.
S3：The precursor solution of spin coating light-absorption layer on the hole transmission layer after polar solvent is processed, and in spin coating
It is made annealing treatment after the completion；
In the present embodiment, the specific preparation method of light-absorption layer is：First, the MAPbI of predetermined amount is taken3Precursor solution, with
On the hole transport layer, after 15s, adjustment spin speed is 4000 rpm, is instilled after 14 s for the speed spin coating of 1000 rpm
Anti-solvent toluene carries out washing operation, wherein the toluene amount of instillation is 400 μ L；After the completion of spin coating operation, it is placed on 100 DEG C of heat
Anneal 10 min on platform, forms the light-absorption layer that thickness is 320 nm.
Preferably, in embodiments of the present invention, light-absorption layer is made of perovskite structure photovoltaic material, perovskite structure photovoltaic
Material is with ABX3The organic inorganic hybridization perovskite material of type crystal structure is thickness between the nm of 200 nm ~ 400
Film layer；Anti-solvent can be toluene, chlorobenzene, ether etc., and the present invention is not limited and fixed to this, can be according to reality
Situation is selected.
Referring to Fig.2, the perovskite solar cell prepared compared to the prior art, modifying interface calcium titanium provided by the invention
Mine solar cell, which prepares the battery light-absorption layer to be formed, has more smooth surface, the Size Distribution of crystal grain more uniform.
S4：Use the solution of different spin speed spin coating electron transfer layers at film-form stage by stage on light-absorption layer, so
It is placed in the thermal station of set temperature and is made annealing treatment afterwards；
In the present embodiment, PC is selected61BM prepares material as electron transfer layer, and a film is formed by way of spin coating
Layer, specifically, first with the rotating speed spin coating PC of 3000 rpm61Then 20 s of BM solution regulates the speed to 6000 rpm spin coatings 20
S is placed in the thermal station that set temperature is 70 DEG C and is made annealing treatment, annealing time is 60 min, is eventually formed after the completion
The electron-transport layer film of 40 nm of thickness.
In embodiments of the present invention, electron-transport can also be selected by metal oxide or C60Deng with the conduction of excellent electronics
The material of effect forms film layer of the thickness between the nm of 10 nm ~ 100.
In addition, in other embodiments, electron transfer layer can also be prepared by way of vapor deposition, specifically how to select,
It can be decided according to actual conditions.
S5：Top electrode is deposited on the electron transport layer by way of thermal evaporation in high vacuum plates chamber.
After the completion of hole transmission layer, light-absorption layer, electron transfer layer are sequentially prepared, the preparation of top electrode is finally carried out,
In the embodiment of the present invention, top electrode is formed by the material preparation with higher work-functions.Concrete operations are：3 need to be placed it in
×10-4 The vacuum environment of Pa, the Ag of BCP and 150 the nm thickness of 10 nm of thermal evaporation thickness successively, forming effective area is
0.096cm2The top electrode of size.
Refering to Fig. 3, it is illustrated that for modifying interface perovskite solar cell of the present invention and traditional perovskite solar cell
Voltage-current density test curve, therefrom it is clear that compared to existing perovskite solar cell, the present invention carries
After polar solvent modification of the perovskite solar cell of confession by hole transport layer surface, the short circuit electricity of device is effectively increased
Stream and energy conversion efficiency.
Modifying interface perovskite preparation method of solar battery provided by the invention during preparing solar cell,
There is the polar solvent of high coordination ability in hole transport layer surface spin coating, polar solvent molecule can be with perovskite precursor solution
Molecule interacts；Compared with prior art, beneficial effects of the present invention are：Improve light-absorption layer surface roughness and
Even grain size is conducive to the transmission of carrier, improves the short circuit current and energy conversion effect of perovskite solar cell
Rate.
The foregoing is merely a prefered embodiment of the invention, the scope of the claims of the present invention is not intended to limit, although with reference to aforementioned reality
Applying example, invention is explained in detail, still can be to aforementioned each tool for those skilled in the art comes
Technical solution recorded in body embodiment is modified, or carries out equivalence replacement to which part technical characteristic.Every profit
The equivalent structure made of description of the invention and accompanying drawing content is directly or indirectly used in other related technical areas,
Similarly within scope of patent protection of the present invention.
Claims (7)
1. a kind of preparation method of modifying interface perovskite solar cell, which is characterized in that the method includes the steps：
Transparent electrode substrate is sequentially placed into deionized water, acetone, ethyl alcohol and carries out ultrasonic cleaning, again by smelly after drying
Oxygen plasma cleans；
The solution coating of hole transmission layer will be prepared on the substrate after cleaned and drying according to default spin speed, and
It is made annealing treatment at a set temperature；
The polar solvent with high coordination ability of spin coating set amount on the hole transmission layer of formation；
Light-absorption layer is prepared using different spin speed spin coatings stage by stage on the hole transmission layer after polar solvent is processed
Precursor solution, and made annealing treatment after the completion of spin coating；
Spin coating prepares the solution of electron transfer layer on light-absorption layer, forms film layer, is then placed in the thermal station of set temperature
It is made annealing treatment；
In high vacuum plates chamber, top electrode is deposited on the electron transport layer by way of thermal evaporation.
2. a kind of preparation method of modifying interface perovskite solar cell according to claim 1, which is characterized in that institute
The ultrasonic cleaning that substrate respectively carries out the min of 10 min ~ 20 in the deionized water, acetone, ethyl alcohol is stated, in described ozone etc.
Gas ions clean 3 ~ 5 min.
3. a kind of preparation method of modifying interface perovskite solar cell according to claim 1, which is characterized in that institute
Transparent electrode is stated by indium tin oxide（ITO）, fluorine tin-oxide（FTO）, aluminium zinc oxide（AZO）Or other electrically conducting transparent materials
Material.
4. a kind of preparation method of modifying interface perovskite solar cell according to claim 1, which is characterized in that institute
Hole transmission layer is stated to be made of the material with higher hole mobility.
5. a kind of preparation method of modifying interface perovskite solar cell according to claim 1, which is characterized in that institute
It is dimethyl sulfoxide (DMSO) to state polar solvent（DMSO）, ethyl alcohol or dimethyl sulfoxide (DMSO) and ethyl alcohol mixed solution.
6. a kind of preparation method of modifying interface perovskite solar cell according to claim 1, which is characterized in that institute
Light-absorption layer is stated to be made of the compact-grain of perovskite material.
7. a kind of preparation method of modifying interface perovskite solar cell according to claim 1, which is characterized in that institute
It is the material with higher work-functions to state top electrode.
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Cited By (6)
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| CN109904334A (en) * | 2019-03-13 | 2019-06-18 | 湖北工业大学 | Multilayer hybrid inorganic-organic perovskite light emitting diode and preparation method thereof |
| CN110003450A (en) * | 2019-04-06 | 2019-07-12 | 苏州和颂生化科技有限公司 | Boundary material: the amphoteric ion conjugated polyelectrolytes with amino acid group |
| CN111223988A (en) * | 2018-11-23 | 2020-06-02 | 国家纳米科学中心 | Perovskite photovoltaic device modified by phosphate molecules and preparation method and application thereof |
| CN111403615A (en) * | 2020-03-27 | 2020-07-10 | 深圳市华星光电半导体显示技术有限公司 | Organic light emitting device and method of manufacturing the same |
| CN111740019A (en) * | 2020-06-05 | 2020-10-02 | 浙江大学 | Halide perovskite photoelectric device based on polar interface |
| CN113258024A (en) * | 2021-04-13 | 2021-08-13 | 泰山学院 | ITO electrode modification method of inverted bottom-emitting OLED |
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