CN109524551A - The liquid film speed of the uniform perovskite film of flannelette applies the suppression of air knife rapid-curing cutback method and climbs the continuous preparation method of crystallization in situ - Google Patents
The liquid film speed of the uniform perovskite film of flannelette applies the suppression of air knife rapid-curing cutback method and climbs the continuous preparation method of crystallization in situ Download PDFInfo
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Abstract
The liquid film speed that the present invention discloses a kind of uniform perovskite film of flannelette applies the suppression of air knife rapid-curing cutback method and climbs the continuous preparation method of crystallization in situ, comprising: the first step, the uniform coating of perovskite liquid film；The rapid draing of profiling perovskite liquid film: second step completes the drying to profiling perovskite liquid film using 5~20 airflow channels of multithread air knife；Third step, the hot gas of perovskite liquid film makes annealing treatment: using 30~50 airflow channels of multithread air knife, the gas for being 80~160 DEG C with temperature carries out the heat treatment of 10~30min to perovskite thin film, removal residual solvent simultaneously makes crystal grain grow up, and obtains all standing and imitates the uniform perovskite thin film of pyramidal flannelette.The present invention not to silicon pyramid flannelette carry out polishing polish processing under conditions of, the preparation that the uniform profiling perovskite thin film of all standing in the pyramid flannelette substrate that micro-meter scale rises and falls is realized using solution-deposition method, maintains the efficient advantage of silicon solar cell.
Description
Technical field
The invention belongs to silicon-perovskite lamination solar cell preparation technical field, in particular to a kind of perovskite film
Preparation method.
Background technique
The structure of perovskite material is generally ABX3(A is organic cation, such as CH3NH3,CH(NH2)2Deng；B is metal sun
Ion, such as Pb, Sn etc.；X is F, Cl, Br, I).End in November, 2018, the unijunction perovskite solar battery authenticated
Peak efficiency has reached 23.4%.Higher photoelectric conversion efficiency be always photovoltaic cell technology development core objective it
One.However the photoelectric conversion efficiency of unijunction perovskite solar battery can not be more than Xiao Keli-Kui Yise limit theory efficiency.It is more
Joint solar cell, i.e. laminated cell are made of the solar subcells with different band gap, are a kind of mature effective breakthroughs
The mode of Xiao Keli-Kui Yise limit theory efficiency, has been widely used for traditional silicon, gallium arsenide solar cell.Silicon is too
Positive energy battery is to occupy the maximum mainstream photovoltaic technology of the market share at present.The band gap of monocrystalline silicon is about 1.1eV, is ideal narrow
The sub- battery of band gap.Organic inorganic hybridization perovskite material and full-inorganic perovskite material have band gap it is continuously adjustable (1.25~
2.0eV) the characteristics of.Based on These characteristics, silicon-perovskite lamination photovoltaic cell technology, which becomes, realizes ultra high efficiency, low cost optical
Lie prostrate one of the key subjects of generation technology.
High efficiency commercialization silicon solar cell generallys use pyramid flannelette light trapping structure.Silicon pyramid flannelette rises and falls high
Degree is usually at 1~20 μm, it can effectively increase light capture ability, to improve the short-circuit current density of battery.However, at this
The complicated surface texture structure of kind is difficult to the uniform perovskite film of deposition thickness.Calcium titanium with solwution method deposition thickness less than 1 μm
When mine film, solution gathers in the paddy between " pyramid ", so that being not covered with liquid on pyramidal pinnacle of a pagoda, this be will lead to
Pyramidal apex angle and rib can not be completely covered in final perovskite thin film.This phenomenon will lead to battery short circuit, and then reduce
Perovskite/crystal silicon lamination solar cell photoelectric conversion efficiency.In order to avoid this problem, existing technology is to silion cell
Pyramid flannelette has carried out polishing and has polished processing.However, compared with the silion cell with pyramid flannelette light trapping structure, the silicon sun
Photoelectric conversion efficiency after energy battery polishing can be reduced to about the 50% of original value.Therefore, this technical solution exists as follows not
Foot: first, polishing is carried out to silicon pyramid flannelette and polishes the photoelectric conversion efficiency that processing significantly reduces silicon solar cell；The
Two, increased polishing polishes the production cost that processing improves lamination solar cell, increases process and time, reduces life
Produce efficiency.Therefore, how the uniform profiling perovskite thin film of all standing is prepared in the pyramid flannelette substrate that micro-meter scale rises and falls
As realization high-efficiency and low-cost silicon-perovskite both ends lamination photovoltaic cell technology core problem.
Summary of the invention
The suppression of air knife rapid-curing cutback method, which is applied, the purpose of the present invention is to provide a kind of liquid film speed of the uniform perovskite film of flannelette climbs original position
The continuous preparation method of crystallization, to solve the above technical problems.
To achieve the goals above, the present invention adopts the following technical scheme:
The liquid film speed of the uniform perovskite film of flannelette applies the suppression of air knife rapid-curing cutback method and climbs the continuous preparation method of crystallization in situ, including following
Step:
The first step, the uniform coating of perovskite liquid film: perovskite precursor sol or solution, which are coated in, has pyramid
In the substrate of flannelette pattern, the 60% uniform profiling perovskite liquid that a layer thickness is less than pyramid average characteristics height is formed
Film；
The rapid draing of profiling perovskite liquid film: second step is completed using 5~20 airflow channels of multithread air knife to imitative
The drying of shape perovskite liquid film；
The hot gas annealing of perovskite liquid film: third step uses 30~50 airflow channels of multithread air knife, is with temperature
80~160 DEG C of gas carries out the heat treatment of 10~30min to perovskite thin film, removes residual solvent and crystal grain is made to grow up, obtain
The uniform perovskite thin film of pyramidal flannelette is imitated to all standing.
Further, for second step during after perovskite liquid film coats with drying, in edges and corners part, outer normal direction is solid
The ratio between the total amount of solute and design flow can bear minimum thickness not less than the outer normal direction perovskite thin film in edges and corners part in phase and liquid phase
Before the ratio between degree and design thickness, the drying to profiling perovskite liquid film is completed.Design thickness is not less than 50nm；It can bear most
The ratio between small thickness and design thickness are not less than 10%.
Further, the total amount of solute includes in the solid phase perovskite and liquid phase of forming core crystallization in the solid phase and liquid phase
Still uncrystallized perovskite.
Further, the solid phase perovskite of the forming core crystallization includes solid phase perovskite and existing for complex form
Perovskite.
Further, the substrate of the pyramid flannelette pattern is silicon pyramid flannelette.
Further, the substrate of the pyramid flannelette pattern be the silicon pyramid flannelette for being deposited with profiling tunnel layer,
Silicon pyramid flannelette coated with profiling hole transmission layer or the silicon pyramid flannelette coated with profiling electron transfer layer.
Further, in second step, 5~20 gas of multithread air knife are used in multithread air knife liquid film quick drying apparatus
Circulation road completes the drying to profiling perovskite liquid film；When ventilation, ventilated body is the gas not reacted with perovskite liquid film
Body.
Further, the gas not reacted with perovskite liquid film is air, nitrogen or argon gas.
Further, the chemical general formula of solute is ABX in perovskite precursor sol or solution3, wherein A is selected from alkyl
Amine, alkali metal or combinations thereof, B are selected from lead, tin or combinations thereof, and X is selected from Br, Cl, I or combinations thereof.
Further, the thickness of the profiling perovskite liquid film of first step coating is less than pyramid average characteristics height
60%.Pyramid average characteristics altitude range is 5-20 microns.
Further, in second step, creeping in perovskite liquid film in flannelette reduces thickness of liquid film at pyramid rib and angle
To the time corresponding to the 50~95% of original thickness, the drying to liquid film is completed using multithread air knife method.
Further, the quick finger is completed after the completion of first step coating, in 8S at the pumping drying to perovskite liquid film
Reason.After having coated, it is transferred in drying equipment within time-consuming about 5s, in additional dry 3s, total time-consuming about 8s.
Compared with the existing technology, the invention has the following advantages:
(1) for the present invention after perovskite liquid film quickly coats, creeping in perovskite liquid film in flannelette makes pyramid rib and angle
Place's thickness of liquid film was reduced within the time corresponding to the 50~95% of original thickness；Shorten liquid film using multithread air knife method to creep
Time realizes liquid film rapid-curing cutback；The continuous short annealing of perovskite thin film is realized using high temperature multithread gas.
(2) present invention can be existed using solwution method under conditions of not carrying out polishing to silicon pyramid flannelette and polishing processing
The uniform profiling perovskite thin film of all standing is prepared in the pyramid flannelette substrate that micro-meter scale rises and falls, is able to maintain silicon solar
The advantage of battery-efficient rate realizes silicon-perovskite both ends lamination solar cell technology that photoelectric conversion efficiency is greater than 35%；
(3) polishing that the present invention eliminates silicon pyramid flannelette polishes processing, reduces silicon-perovskite laminate solar electricity
The production cost in pond, reduces waste of time, improves actual production speed.
(4) the present invention provides a kind of continuous production manufacturing method, can be completed with serialization perovskite liquid film coating,
Dry and heat treatment, reduces waste of time, improves actual production speed.
Specific embodiment
Implementation method of the present invention is described further combined with specific embodiments below.
Embodiment 1
The preparation method of the uniform perovskite film of flannelette, comprising:
(1) preparation of perovskite precursor sol: using DMF as solvent, PbI2And CH3NH3I is solute, and it is molten to prepare perovskite
Glue, CH in perovskite colloidal sol3NH3PbI3Mass percentage concentration be 40%.
(2) the uniform coating of perovskite liquid film: perovskite precursor sol is coated in by the way of banister brush coating
On silicon solar cell with pyramid flannelette pattern, one layer of flaxen uniform profiling perovskite with a thickness of 2 μm is formed
Liquid film；The thickness of the profiling perovskite liquid film of coating is less than the 60% of pyramid average characteristics height；
(3) multithread air knife perovskite liquid film quick drying apparatus the rapid draing processing of perovskite liquid film: is utilized in 3s
5 airflow channels complete drying process to perovskite liquid film, imitate golden word to obtain with a thickness of the uniform all standing of 400nm
Tower-shaped perovskite thin film；When ventilation, ventilated body is air；
(4) heat treatment of perovskite thin film: multithread air knife method is used, using 30 airflow channels of multithread air knife, with temperature
The heat treatment for carrying out 10min to perovskite thin film for 100 DEG C of gases removes residual solvent and crystal grain is made to grow up, to obtain
Pyramid perovskite thin film is imitated in uniform all standing.
Embodiment 2
The preparation method of the uniform perovskite film of flannelette, comprising:
(1) preparation of perovskite precursor sol: using DMSO as solvent, PbI2And CH3NH3I is solute, prepares perovskite
Colloidal sol, CH in perovskite colloidal sol3NH3PbI3Mass percentage concentration be 35%.
(2) the uniform coating of perovskite liquid film: perovskite precursor sol is coated in by the way of banister brush coating
On silicon solar cell with pyramid flannelette pattern, one layer of flaxen uniform profiling perovskite with a thickness of 1 μm is formed
Liquid film；The thickness of the profiling perovskite liquid film of coating is less than the 60% of pyramid average characteristics height；
(3) multithread air knife perovskite liquid film quick drying apparatus the rapid draing processing of perovskite liquid film: is utilized in 3s
20 airflow channels complete drying process to perovskite liquid film, imitate gold to obtain with a thickness of the uniform all standing of 200nm
The tower-shaped perovskite thin film of word；When ventilation, ventilated body is argon gas；
(4) heat treatment of perovskite thin film: multithread air knife method is used, using 50 airflow channels of multithread air knife, with temperature
The heat treatment for carrying out 30min to perovskite thin film for 120 DEG C of gases removes residual solvent and crystal grain is made to grow up, to obtain
Pyramid perovskite thin film is imitated in uniform all standing.
Embodiment 3
The preparation method of the uniform perovskite film of flannelette, comprising:
(1) preparation of perovskite precursor sol: using DMF as solvent, PbI2And CH3NH3I is solute, and it is molten to prepare perovskite
Glue, CH in perovskite colloidal sol3NH3PbI3Mass percentage concentration be 40%.
(2) the uniform coating of perovskite liquid film: perovskite precursor sol is coated in by the way of banister brush coating
On silicon solar cell with pyramid flannelette pattern, one layer of flaxen uniform profiling perovskite with a thickness of 2 μm is formed
Liquid film；The thickness of the profiling perovskite liquid film of coating is less than the 60% of pyramid average characteristics height；
(3) multithread air knife perovskite liquid film quick drying apparatus the rapid draing processing of perovskite liquid film: is utilized in 3s
15 airflow channels complete drying process to perovskite liquid film, imitate gold to obtain with a thickness of the uniform all standing of 400nm
The tower-shaped perovskite thin film of word；When ventilation, ventilated body is nitrogen；
(4) heat treatment of perovskite thin film: multithread air knife method is used, using 40 airflow channels of multithread air knife, with temperature
The heat treatment for carrying out 20min to perovskite thin film for 160 DEG C of gases removes residual solvent and crystal grain is made to grow up, to obtain
Pyramid perovskite thin film is imitated in uniform all standing.
Embodiment 4
The preparation method of the uniform perovskite film of flannelette, comprising:
(1) preparation of perovskite precursor sol: using DMF as solvent, PbI2And CH3NH3I is solute, and it is molten to prepare perovskite
Glue, CH in perovskite colloidal sol3NH3PbI3Mass percentage concentration be 40%.
(2) the uniform coating of perovskite liquid film: perovskite precursor sol is coated in by the way of banister brush coating
On silicon solar cell with pyramid flannelette pattern, one layer of flaxen uniform profiling perovskite with a thickness of 2 μm is formed
Liquid film；The thickness of the profiling perovskite liquid film of coating is less than the 60% of pyramid average characteristics height；
(3) multithread air knife perovskite liquid film quick drying apparatus the rapid draing processing of perovskite liquid film: is utilized in 3s
10 airflow channels complete drying process to perovskite liquid film, imitate gold to obtain with a thickness of the uniform all standing of 400nm
The tower-shaped perovskite thin film of word；When ventilation, ventilated body is air；
(4) heat treatment of perovskite thin film: multithread air knife method is used, using 45 airflow channels of multithread air knife, with temperature
The heat treatment for carrying out 15min to perovskite thin film for 80 DEG C of gases removes residual solvent and crystal grain is made to grow up, to obtain equal
Pyramid perovskite thin film is imitated in even all standing.
In conclusion the above is only highly preferred embodiment of the present invention, it is all according to claims of the present invention and explanation
Equivalent modifications made by book belong to the range that the invention patent covers.
Claims (10)
1. the liquid film speed of the uniform perovskite film of flannelette applies the suppression of air knife rapid-curing cutback method and climbs the continuous preparation method of crystallization in situ, feature exists
In, comprising the following steps:
The first step, the uniform coating of perovskite liquid film: perovskite precursor sol or solution, which are coated in, has pyramid flannelette
In the substrate of pattern, one layer of uniform profiling perovskite liquid film is formed；
The rapid draing of profiling perovskite liquid film: second step is completed using 5~20 airflow channels of multithread air knife to profiling calcium
The drying of titanium ore liquid film；
Third step, perovskite liquid film hot gas annealing: use 30~50 airflow channels of multithread air knife, with temperature be 80~
160 DEG C of gas carries out the heat treatment of 10~30min to perovskite thin film, removes residual solvent and crystal grain is made to grow up, and obtains complete
The uniform perovskite thin film of pyramidal flannelette is imitated in covering.
2. it is continuous that crystallization in situ is climbed in the liquid film speed painting air knife rapid-curing cutback method suppression of the uniform perovskite film of flannelette according to claim 1
Preparation method, which is characterized in that second step is during after perovskite liquid film coats with drying, in the outer normal direction in edges and corners part
The ratio between the total amount of solute and design flow can bear minimum not less than the outer normal direction perovskite thin film in edges and corners part in solid phase and liquid phase
Before the ratio between thickness and design thickness, the drying to profiling perovskite liquid film is completed.
3. it is continuous that crystallization in situ is climbed in the liquid film speed painting air knife rapid-curing cutback method suppression of the uniform perovskite film of flannelette according to claim 1
Preparation method, which is characterized in that the total amount of solute includes the solid phase perovskite and liquid of forming core crystallization in the solid phase and liquid phase
Still uncrystallized perovskite in phase.
4. it is continuous that crystallization in situ is climbed in the liquid film speed painting air knife rapid-curing cutback method suppression of the uniform perovskite film of flannelette according to claim 3
Preparation method, which is characterized in that the solid phase perovskite of the crystallization of forming core is included solid phase perovskite and deposited with complex form
Perovskite.
5. it is continuous that crystallization in situ is climbed in the liquid film speed painting air knife rapid-curing cutback method suppression of the uniform perovskite film of flannelette according to claim 1
Preparation method, which is characterized in that the substrate of the pyramid flannelette pattern is silicon pyramid flannelette.
6. it is continuous that crystallization in situ is climbed in the liquid film speed painting air knife rapid-curing cutback method suppression of the uniform perovskite film of flannelette according to claim 1
Preparation method, which is characterized in that the substrate of the pyramid flannelette pattern is the silicon pyramid suede for being deposited with profiling tunnel layer
Face, the silicon pyramid flannelette coated with profiling hole transmission layer or the silicon pyramid flannelette coated with profiling electron transfer layer.
7. it is continuous that crystallization in situ is climbed in the liquid film speed painting air knife rapid-curing cutback method suppression of the uniform perovskite film of flannelette according to claim 1
Preparation method, which is characterized in that in second step, the 5~20 of multithread air knife is used in multithread air knife liquid film quick drying apparatus
A airflow channel completes the drying to profiling perovskite liquid film；When ventilation, ventilated body is not react with perovskite liquid film
Gas.
8. it is continuous that crystallization in situ is climbed in the liquid film speed painting air knife rapid-curing cutback method suppression of the uniform perovskite film of flannelette according to claim 7
Preparation method, which is characterized in that the gas not reacted with perovskite liquid film is air, nitrogen or argon gas.
9. it is continuous that crystallization in situ is climbed in the liquid film speed painting air knife rapid-curing cutback method suppression of the uniform perovskite film of flannelette according to claim 1
Preparation method, which is characterized in that the chemical general formula of solute is ABX in perovskite precursor sol or solution3, wherein A is selected from alkane
Base amine, alkali metal or combinations thereof, B are selected from lead, tin or combinations thereof, and X is selected from Br, Cl, I or combinations thereof.
10. the liquid film speed of the uniform perovskite film of flannelette according to claim 1 applies the suppression of air knife rapid-curing cutback method and climbs crystallization company in situ
Continuous preparation, which is characterized in that the thickness of the profiling perovskite liquid film of first step coating is less than pyramid average characteristics height
60%.
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