CN109560199A - A kind of preparation method of the perovskite thin film photoelectric device based on low pressure flash crystallization - Google Patents
A kind of preparation method of the perovskite thin film photoelectric device based on low pressure flash crystallization Download PDFInfo
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- H—ELECTRICITY
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- 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
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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Abstract
The present invention provides a kind of preparation methods of perovskite thin film photoelectric device based on low pressure flash crystallization, belong to field of photoelectric devices.The present invention is in TiO2Spin coating lead halide on compacted zone carries out flash distillation crystallization after halogenation methylamine solution is added dropwise on halogenation thin film lead, to obtain perovskite thin film under lower pressure.Preparation method of the invention passes through low pressure flash revulsive crystallization, solvent is evaporated rapidly with lower boiling point under low pressure clean, then the various reactants of perovskite are precipitated with controllable rate, make between crystal grain mutual cannibal growth at big crystal grain further according to your moral curing effect of Oswald.Compared with conventional " two-step method ", the perovskite thin film surface that preparation method provided by the invention obtains is more uniform smooth, and entire perovskite thin film layer crystallization degree is higher.
Description
Technical field
The present invention relates to photoelectric device technical field, in particular to a kind of perovskite thin film light based on low pressure flash crystallization
The preparation method of electrical part.
Background technique
Perovskite has been subjected to research in 12 years, photoelectricity from dye-sensitized solar cells is used in for the first time so far
Transformation efficiency has reached 22% or more, and the performance in third generation solar cell is much arresting.
Perovskite material has the high absorption coefficient of wide spectral range, and high carrier mobility and low trap states etc. are all
More advantages, the efficiency of Ca-Ti ore type photoelectric device are somewhat dependent on the variation of film morphology, improve perovskite thin film
Crystallinity, increase its crystallite dimension to reduce crystal boundary, surface is smooth to obtain, the few perovskite thin film of internal flaw
It is the key that obtain high efficiency solar cell.
Currently, the method for preparing perovskite thin film mainly has " one-step method " and " two-step method ", wherein " one-step method " is by halogen
Change lead and halogenation methylamine co-dissolve in a solvent, perovskite thin film, this method then can be obtained by spin coating and annealing
Step is simple, but gained film quality is poor, and crystallization degree is low.
" two-step method " is first halogenation lead solution to be spun in substrate, halogenation thin film lead is formed, on halogenation thin film lead
It anneals in atmospheric conditions after halogenation methylamine solution is added dropwise, forms perovskite thin film.The perovskite thin film that this method obtains
Crystallization degree increases compared with " one-step method ", but film quality is unstable, is unfavorable for the production of efficient stable, and the crystalline substance of film
Change degree is improved with there is still a need for further.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of perovskite thin film photoelectric devices based on low pressure flash crystallization
Preparation method.Preparation method step provided by the invention is simple, at low cost, is easy to carry out the production of efficient stable, and gained calcium
Titanium ore film crystal unity is high, crystallite dimension is big.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of preparation method of the perovskite thin film photoelectric device based on low pressure flash crystallization, comprising the following steps:
(1) FTO electro-conductive glass successively performed etching, cleaned, dried up and ozone surface is handled, obtaining pretreated FTO
Electro-conductive glass；
(2) in the etched surface spin coating TiO of the pretreated FTO electro-conductive glass2It anneals, is formed after compacted zone solution
TiO2Compacted zone；
(3) in the TiO2It is dry after fine and close layer surface spin coating halogenation lead solution, form halogenation thin film lead；
(4) be added dropwise on the halogenation thin film lead after halogenation methylamine solution successively stood, whirl coating and low pressure flash it is brilliant
Change, forms perovskite thin film；The pressure of the low pressure flash crystallization is 10~200Pa, and temperature is 90~110 DEG C, the time 10
~25min；
(5) it is sequentially prepared hole transmission layer and metal electrode on the perovskite thin film, obtains perovskite thin film photoelectricity
Device.
Preferably, the TiO in the step (2)2Compacted zone solution is by dehydrated alcohol, acid and TiO2Presoma is prepared to obtain；
The acid includes concentrated hydrochloric acid and/or glacial acetic acid；The TiO2Presoma includes four isopropyl alcohol ester of metatitanic acid and/or butyl titanate；
The dehydrated alcohol, acid and TiO2The amount ratio of presoma is the μ of 3~7mL:5~10 L:0.2~0.5g.
Preferably, the annealing way in the step (2) are as follows: be warming up to 150~200 with the rate of 7.5~10 DEG C/min
DEG C, 20~30 minutes are kept the temperature, is then warming up to 300~350 DEG C with 5~7.5 DEG C/min, keeps the temperature 20~30 minutes, then with 5~
7.5 DEG C/min is warming up to 500 DEG C, keeps the temperature 60~90 minutes.
Preferably, TiO is formed in the step (2)2After compacted zone further include:
There to be TiO2The FTO electro-conductive glass of compacted zone is successively dried and moves back after impregnating in titanium tetrachloride solution
Fire；The mode of the annealing are as follows: be warming up to 150~200 DEG C with the rate of 7.5~10 DEG C/min, keep the temperature 20~30 minutes, then
300~350 DEG C are warming up to 5~7.5 DEG C/min, keeps the temperature 20~30 minutes, then is warming up to 500 DEG C with 5~7.5 DEG C/min, is protected
Temperature 30~60 minutes.
Preferably, in the step (3) halogenation lead solution solvent be n,N-Dimethylformamide, dimethyl sulfoxide and
One or more of gamma-butyrolacton；The lead halide is lead iodide, lead chloride or lead bromide；
The concentration of the halogenation lead solution is 1~1.2mol/L；
The spin coating amount of the halogenation lead solution is 20~50 μ L/7.5cm2。
Preferably, the solvent of halogenation methylamine solution is alcohols solvent in the step (4)；The alcohols solvent includes second
One or more of alcohol, ethylene glycol and isopropanol；The halogenation methylamine is methylamine iodine, methylamine chlorine or methylamine bromine；
The concentration of the halogenation methylamine solution is 0.044~0.063mol/L.
The spin coating amount of the halogenation methylamine solution is 100~300 μ L/7.5cm2。
Preferably, the time stood in the step (4) is 30~50s；
The revolving speed of the whirl coating is 3500~4500rpm, and the time is 25~35s.
Preferably, step (5) hole-transporting layer the preparation method comprises the following steps: on the perovskite thin film spin coating hole
24~48h is dried after transport layer solution in oxygen atmosphere.
Preferably, the hole transmission layer solution is by solvent, 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) ammonia
Base] two fluorenes of -9,9'- spiral shell, lithium salts and 4- tert .-butylpyridine prepare to obtain；
The solvent, 2,2', two fluorenes of 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, lithium salts and 4-
The amount ratio of tert .-butylpyridine is 1mL:0.15~0.2mol:0.05~0.08mol:0.17~0.22mol；
The solvent is the mixed solvent of chlorobenzene and acetonitrile；The volume ratio of the in the mixed solvent chlorobenzene and acetonitrile is 1:
0.1~0.3.
Preferably, the metal electrode in the step (5) is gold electrode.
The present invention provides a kind of preparation methods of perovskite thin film photoelectric device based on low pressure flash crystallization.The present invention
TiO is prepared after FTO electro-conductive glass is pre-processed2Compacted zone, then in TiO2Spin coating halogenation thin film lead on compacted zone, then
Halogenation methylamine solution is added dropwise on halogenation thin film lead, is flashed under lower pressure after reacting lead halide and halogenation methylamine sufficiently
Crystallization to obtain perovskite thin film, then is sequentially prepared hole transmission layer and metal electrode on perovskite thin film and can be obtained
Perovskite thin film photoelectric device.Preparation method of the invention is by low pressure flash revulsive crystallization, under low pressure with lower boiling point
Solvent is evaporated rapidly completely, then the various reactants of perovskite are precipitated with controllable rate, further according to Oswald that moral
Curing effect makes between crystal grain mutual cannibal growth at big crystal grain.Compared with conventional " two-step method ", preparation provided by the invention
The perovskite thin film surface that method obtains is more uniform smooth, and entire perovskite thin film layer crystallization degree is higher.Embodiment result
Show that the size of perovskite crystal grain in the perovskite thin film of method preparation provided by the invention can reach 500nm, and crystallinity
Height, the photoelectric conversion efficiency of gained perovskite photoelectric device can reach 14.13%, and fill factor can reach 52.31.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of perovskite thin film photoelectric device prepared by the embodiment of the present invention 1；
Fig. 2 is the X-ray diffraction phenogram of perovskite thin film prepared by the embodiment of the present invention 1 and comparative example 1；
Fig. 3 is the scanning electron microscope phenogram of perovskite thin film prepared by the embodiment of the present invention 1；
Fig. 4 is that the current-voltage (I-V) of perovskite thin film photoelectric device prepared by the embodiment of the present invention 1 and comparative example 1 turns
Change efficiency curve diagram.
Specific embodiment
The present invention provides a kind of preparation methods of perovskite thin film photoelectric device based on low pressure flash crystallization, including with
Lower step:
(1) FTO electro-conductive glass successively performed etching, cleaned, dried up and ozone surface is handled, obtaining pretreated FTO
Electro-conductive glass；
(2) in the etched surface spin coating TiO of the pretreated FTO electro-conductive glass2It anneals, is formed after compacted zone solution
TiO2Compacted zone；
(3) in the TiO2It is dry after fine and close layer surface spin coating halogenation lead solution, form halogenation thin film lead；
(4) be added dropwise on the halogenation thin film lead after halogenation methylamine solution successively stood, whirl coating and low pressure flash it is brilliant
Change, forms perovskite thin film；The pressure of the low pressure flash crystallization be 10~200Pa, temperature be 100 DEG C, the time be 5~
15min；
(5) it is sequentially prepared hole transmission layer and metal electrode on the perovskite thin film, obtains perovskite thin film photoelectricity
Device.
The present invention is successively performed etching, cleaned to FTO electro-conductive glass, drying up and ozone surface processing, obtains pretreated
FTO electro-conductive glass.The present invention does not have particular/special requirement to the area of the FTO electro-conductive glass, in a specific embodiment of the present invention,
Can FTO electro-conductive glass determine according to actual needs area；The FTO thickness degree of the FTO electro-conductive glass is preferably 700~
900nm, more preferably 800nm.
In the present invention, the etching preferably includes: the FTO layer of electro-conductive glass is performed etching using zinc powder and hydrochloric acid,
Specifically: it is not required to the part of etching with adhesive tape protection, and reserves etched line, first fills up etched line with zinc powder, then drips upper hydrochloric acid
10~15s is reacted, residue is then wiped and adhesive tape of tearing completes etching；The concentration of etching hydrochloric acid is preferably 3mol/
L；The width of the etched line is preferably 2mm；The present invention preferably passes through etching and forms four active areas；The present invention is real by etching
The electric isolation of existing back electrode and light anode.
After the completion of etching, the present invention cleans the FTO electro-conductive glass after etching.In the present invention, the cleaning tool
Body are as follows: using FTO electro-conductive glass 4 times after deionization ultrasonic cleaning etching, then each 15min is wiped using cleaning solution, and
It is clean with hot water injection, ion ultrasonic cleaning 15min is spent again, it is finally super with ethyl alcohol-isopropanol-acetone mixed organic solvents
Sound cleans 4 times, each 15min.The present invention is cleaned up the remaining impurity of FTO conductive glass surface by cleaning.
After the completion of cleaning, the present invention dries up the FTO electro-conductive glass after cleaning, and present invention preferably uses nitrogen to be blown
It is dry.
After drying, the present invention carries out ozone surface processing to FTO electro-conductive glass, and the time of the ozone surface processing is preferred
For 20min；The concrete operation method that the present invention handles the ozone surface does not have particular/special requirement, uses those skilled in the art
Well known ozone surface processing method.The present invention handles the surface wettability of FTO electro-conductive glass by ozone surface, to mention
High subsequent spin coating effect.
After obtaining pretreated FTO electro-conductive glass, etched surface spin coating of the present invention in the pretreated FTO electro-conductive glass
TiO2It anneals after compacted zone solution, forms TiO2Compacted zone.In the present invention, the TiO2Compacted zone solution is preferably by nothing
Water-ethanol, acid and TiO2Presoma is prepared to obtain；The acid preferably includes concentrated hydrochloric acid and/or glacial acetic acid；The TiO2Presoma is excellent
Choosing includes four isopropyl alcohol ester of metatitanic acid and/or butyl titanate；The dehydrated alcohol, acid and TiO2The amount ratio of presoma is preferably
μ L:0.2~the 0.5g of 3~7mL:5~10, more preferably 5mL:8 μ L:0.37g；The present invention preferably first closes dehydrated alcohol and acid-mixed
Ultrasound 1min afterwards, then by TiO2Ultrasound 10min in the mixed solution of dehydrated alcohol and acid is added in presoma；The present invention is to described super
The power of sound does not have particular/special requirement, can above-mentioned substance is completely dissolved and is uniformly mixed.
In the present invention, the spin coating TiO2Compacted zone solution preferably includes the low speed spin coating successively carried out and high speed is revolved
It applies；The revolving speed of the low speed spin coating is preferably 1000rpm, and the time is preferably 5s, and the revolving speed of high speed spin coating is preferably 3000rpm,
Time is preferably 20s；Elder generation's low speed of the present invention evenly spreads out solution, then high speed spin-coated thin film again, covers to improve film
Lid rate and uniformity.
In the present invention, the spin coating TiO2The mode annealed after compacted zone solution is preferred are as follows: with 7.5~10 DEG C/
The rate of min is warming up to 150~200 DEG C, keeps the temperature 20~30 minutes, is then warming up to 300~350 DEG C with 5~7.5 DEG C/min,
Heat preservation 20~30 minutes, then 500 DEG C are warming up to 5~7.5 DEG C/min, 60~90 minutes are kept the temperature, more preferably with 10 DEG C/min
Rate be warming up to 200 DEG C, keep the temperature 20 minutes, be then warming up to 350 DEG C with 7.5 DEG C/min, keep the temperature 20 minutes, then with 7.5 DEG C/
Min is warming up to 500 DEG C, keeps the temperature 30~60 minutes.The present invention preferably anneals in sintering furnace；The present invention is obtained by annealing
The TiO of rutile-type2Compacted zone.
In the present invention, the TiO2The thickness of compacted zone is preferably 30~100nm, more preferably 50~80nm.
In the present invention, the formation TiO2After compacted zone further include: will have TiO2The FTO electro-conductive glass of compacted zone exists
It is successively dried and anneals after being impregnated in titanium tetrachloride solution.In the present invention, the titanium tetrachloride solution is preferably by tetrachloro
Change titanium and deionized water is formulated under the conditions of ice-water bath, the volume ratio of the titanium tetrachloride and water is preferably 200~400 μ
L:100mL, more preferably 220 μ L:100mL；The temperature of the immersion is preferably 65~75 DEG C, and more preferably 70 DEG C, the time is excellent
It is selected as 30~60min, more preferably 30~40min；The present invention is preferably stirred in soaking process, to enhance electro-conductive glass
Contact with titanium tetrachloride solution.
After the completion of immersion, the present invention rinses after preferably taking out electro-conductive glass, is then successively dried and anneals.This hair
The bright temperature and time to the drying does not have particular/special requirement, can be completely dried electro-conductive glass；In the present invention, institute
The mode for stating annealing is preferred are as follows: is warming up to 150~200 DEG C with the rate of 7.5~10 DEG C/min, keeps the temperature 20~30 minutes, then
300~350 DEG C are warming up to 5~7.5 DEG C/min, keeps the temperature 20~30 minutes, then is warming up to 500 DEG C with 5~7.5 DEG C/min, is protected
Temperature 30~60 minutes is more preferably warming up to 200 DEG C with the rate of 10 DEG C/min, 20 minutes is kept the temperature, then with 7.5 DEG C/min liter
Temperature keeps the temperature 20 minutes to 350 DEG C, then is warming up to 500 DEG C with 7.5 DEG C/min, keeps the temperature 30~60 minutes.The present invention is by impregnating four
The step of titanium chloride solution and annealing, generates a part of lesser titanium dioxide nano-particle in titanium dioxide dense layer surface, mentions
The specific surface area of high light anode.
Obtain TiO2After compacted zone, the present invention is in the TiO2It is dry after fine and close layer surface spin coating halogenation lead solution, form halogen
Change thin film lead.In the present invention, the solvent of the halogenation lead solution be preferably n,N-Dimethylformamide, dimethyl sulfoxide and
One or more of gamma-butyrolacton；The lead halide is preferably lead iodide, lead chloride or lead bromide；The halogenation lead solution
Concentration be preferably 1~1.2mol/L, more preferably 1.1mol/L；The spin coating amount of the halogenation lead solution is preferably 20~50 μ
L/7.5cm2, more preferably 30~40 μ L/7.5cm2。
In the present invention, the spin coating halogenation lead solution preferably includes the low speed spin coating and high speed spin coating successively carried out；Institute
The revolving speed for stating low speed spin coating is preferably 1000~3000rpm, and the time is preferably 5s, and the revolving speed of high speed spin coating is preferably 3000~
5000rpm, time are preferably 10s；The temperature of the drying is preferably 70~100 DEG C, and more preferably 75~80 DEG C；The drying
Time be preferably 20~40min, more preferably 30min.
After obtaining halogenation thin film lead, the present invention be added dropwise on the halogenation thin film lead after halogenation methylamine solution successively carry out it is quiet
It sets, whirl coating and low pressure flash crystallization, forms perovskite thin film.In the present invention, the solvent of the halogenation methylamine solution is preferably
Alcohols solvent；The alcohols solvent preferably includes one or more of ethyl alcohol, ethylene glycol and isopropanol；The halogenation methylamine is excellent
It is selected as methylamine iodine, methylamine chlorine or methylamine bromine；The concentration of the halogenation methylamine solution is preferably 0.044~0.063mol/L, more excellent
It is selected as 0.05~0.06mol/L；The spin coating amount of the halogenation methylamine solution is preferably 100~300 μ L/7.5cm2, more preferably
150~200 μ L/7.5cm2。
In the present invention, the time of the standing is preferably 30~50s, more preferably 40s.It is added dropwise on halogenation thin film lead
After halogenation methylamine solution, exchange and self assembly occur immediately for halogenation methylamine and lead halide, form perovskite (CH3NH3PbX3, X is
Halogen), halogenation thin film lead becomes dark brown from yellow, and the present invention makes lead halide and halogenation methylamine fully reacting by standing.
In the present invention, the revolving speed of the whirl coating is preferably 3500~4500rpm, more preferably 4000rpm, and the time is preferred
For 25~35s, more preferably 30s；The present invention gets rid of extra solution by whirl coating, to form the film of uniform ground.
In the present invention, the process of above-mentioned dropwise addition halogenation methylamine solution, standing and whirl coating carries out preferably in glove box.
In the present invention, the pressure of the low pressure flash crystallization is 10~200Pa, preferably 50~150Pa, temperature 90
~110 DEG C, preferably 100 DEG C, time are 10~25min, preferably 15~18min.The present invention is to the low pressure flash crystallization
Specific device there is no particular/special requirement, as long as can be realized above-mentioned low pressure flash crystallization condition, in specific reality of the invention
Apply in example, installed additional preferably on sol evenning machine pallet one can heated for controlling temperature heating plate, then install a vacuum-pumping system additional
Photoelectric device semi-finished product to crystallization are placed in heating plate, to realize low pressure flash crystallization by pallet cover.
The present invention can be improved the crystallinity of perovskite thin film, increase its crystallite dimension by low pressure flash revulsive crystallization
To reduce crystal boundary, to obtain the perovskite thin film absorbed layer that internal flaw is few, surface is smooth；And low pressure flash method
Cost is relatively low, simple process, is conducive to the production application of efficient stable.
In the present invention, the thickness of the perovskite thin film is preferably 450~550nm, more preferably 500nm.
After obtaining perovskite thin film, the present invention is sequentially prepared hole transmission layer and metal electricity on the perovskite thin film
Pole obtains perovskite thin film photoelectric device.In the present invention, the preparation method of the hole transmission layer is preferred are as follows: in the calcium
Dry 24~48h on titanium ore film after spin coating hole transmission layer solution in oxygen atmosphere；The hole transmission layer solution is preferred
By solvent, 2,2', two fluorenes of 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, lithium salts and 4- tert .-butylpyridine
Preparation obtains；The solvent, 2,2', two fluorenes of 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, lithium salts and 4-
The amount ratio of tert .-butylpyridine is preferably 1mL:0.15~0.2mol:0.05~0.08mol:0.17~0.22mol, more preferably
1mL:0.17mol:0.067mol:0.198mol；In the present invention, the solvent is preferably the mixed solvent of chlorobenzene and acetonitrile；
The volume ratio of the in the mixed solvent chlorobenzene and acetonitrile is preferably 1:0.1~0.3, more preferably 1:0.2；The lithium salts is preferably
Double trifluoromethanesulfonimide lithiums (Li-TFSI)；The lithium salts can be improved the electric conductivity of hole transmission layer, the 4- tert-butyl
Pyridine can be improved the open-circuit voltage of photoelectric device.
In the present invention, the thickness of the hole transmission layer is preferably 150~250nm, more preferably 200nm.
In the present invention, the metal electrode is preferably gold electrode, and the thickness of the metal electrode is preferably 70~90nm,
More preferably 80nm.The present invention preferably passes through vapor deposition and prepares metal electrode；The present invention is to the actual conditions of the vapor deposition without spy
It is different to require, as long as the metal electrode of thickness can be obtained requiring.
Below with reference to embodiment to the system of the perovskite thin film photoelectric device provided by the invention based on low pressure flash crystallization
Preparation Method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
1, the preparation of required various spin coating solutions:
(1) titanium dioxide (TiO2) preparation of compacted zone solution:
Measurement 5mL dehydrated alcohol, 8 μ L hydrochloric acid (37% concentration), ultrasonic dissolution 1 minute；Weigh four isopropanol of 0.37g metatitanic acid
Ester (TTIP) is added in above-mentioned solution, and ultrasonic disperse 10 minutes.
(2) 1mol/L lead iodide (PbI2) solution preparation:
Weigh the PbI of 0.461g2, the mixed solvent of 600mg DMF and 78mg DMSO is then added, being made into molar ratio is
The solution of 1:1:1 stirs 12 hours to clarification in 70 DEG C of heating plates.
(3) 0.063mol/L methylamine iodine (CH3NH3I) the preparation of solution
Weigh 50mg CH3NH3I is added in the isopropanol of 5ml, and room temperature is protected from light stirring and dissolving.
(4) two fluorenes of 0.17mol/mL 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell
(Spiro-OMeTAD) preparation of solution:
Weigh chlorobenzene: the solution 1ml of acetonitrile=1:0.1 (volume ratio)；0.17M is added into chlorobenzene-acetonitrile mixed solution
Spiro-OMeTAD, 0.064M lithium salts (Li-TFSI), 0.198M 4- tert .-butylpyridine (TBP), are sufficiently stirred dissolution.
2, the preparation of perovskite thin film photoelectric device
(1) fluorine-doped tin oxide (FTO) electro-conductive glass is etched with zinc powder and dilute hydrochloric acid (3mol/L), to realize back electrode and light
Anode electric isolation.The size of FTO electro-conductive glass is 3cm × 2.5cm, and etching line width is 2mm, is divided into four active areas；
FTO electro-conductive glass after etching is cleaned: being first cleaned by ultrasonic the FTO electro-conductive glass etched with deionized water
Four times, every time 15 minutes.Then FTO electro-conductive glass is wiped with cleaning solution, it is clean with hot water injection.It is clear with deionized water ultrasound again
Wash FTO electro-conductive glass 15 minutes.The ethyl alcohol for being finally 1:1:1 with volume ratio: isopropanol: acetone mixes organic liquor ultrasonic cleaning
FTO electro-conductive glass four times, every time 15 minutes.
By cleaned FTO electro-conductive glass with after being dried with nitrogen, using ozone surface handle 20 minutes it is spare.
(2) spin coating TiO on FTO electro-conductive glass after the pre-treatment2Compacted zone solution, revolving speed are that 1000rpm is for 5 seconds,
3000rpm is for 20 seconds；It then puts into a sintering furnace and anneals, annealing temperature curve are as follows: rise to 200 DEG C for 20 minutes, heat preservation
20 minutes, 350 DEG C then were risen to by 20 minutes, keeps the temperature 20 minutes, finally rose to 500 DEG C using 20 minutes, heat preservation 1 is small
When, form rutile TiO2Compacted zone is cooled to room temperature after annealing.
(3) titanium tetrachloride of 220 μ l is added dropwise in 100ml deionized water with liquid-transfering gun, the sample that step (3) obtains is set
In titanium tetrachloride solution, constant temperature is stirred 30 minutes under 70 DEG C of water bath conditions, is rinsed with deionized water rapidly after taking out substrate,
It is put into baking oven drying；It is then placed in sintering furnace to anneal, the temperature curve of annealing are as follows: rise within 20 minutes 200 DEG C, keep the temperature 20 points
Then clock rose to 350 DEG C by 20 minutes, keep the temperature 20 minutes, finally rose to 500 DEG C using 20 minutes, keeps the temperature 30 minutes, moves back
It is cooled to room temperature after fire.
(4) in TiO2The PbI of 20 μ L of spin coating on compacted zone2Solution, revolving speed are that 3000rpm is for 5 seconds, and 5000rpm continues 10
Second, 70 DEG C drying 30 minutes in baking oven are then placed in, then cools to room temperature and is put into glove box.
(5) PbI after the cooling period2200 μ l CH are added dropwise with liquid-transfering gun on film3NH3I solution, film color is at once by Huang
Discoloration is dark brown, stand 40 seconds, continue whirl coating 30 seconds with the revolving speed of 4000rpm, be then placed in autonomous Design heating plate (
On sol evenning machine pallet install additional one can heated for controlling temperature heating plate, then install the pallet cover of a vacuum-pumping system additional) on carry out
Low pressure flash crystallization, the pressure of the low pressure flash crystallization are 80Pa, and temperature is 100 DEG C, and the time is 15 minutes.
(6) spin coating Spiro-OMeTAD solution, revolving speed are that 4000rpm continues 30 on perovskite thin film after being cooled to room temperature
Second, it is then placed in drying basin oxygen atmosphere 24 hours.
(7) gold electrode is deposited on Spiro-OMeTAD layers, obtains perovskite thin film photoelectric device.
Wherein, the FTO layer of gained perovskite thin film photoelectric device is with a thickness of 800nm, TiO2Dense layer thickness is 100nm,
Perovskite thin film layer with a thickness of 500nm, Spiro-OMeTAD layers with a thickness of 200nm, gold electrode is with a thickness of 80nm, structure such as Fig. 1
It is shown.
Comparative example 1
Perovskite thin film photoelectric device is prepared using routine " two-step method ", specifically:
Other steps and embodiment 1 are identical, only are changed to move back under atmospheric conditions by the annealing conditions after whirl coating in step (4)
Fire.
X-ray diffraction characterization is carried out to embodiment 1 and 1 gained perovskite thin film of comparative example, acquired results as shown in Fig. 2,
According to fig. 2 as can be seen that perovskite thin film prepared by embodiment 1 is compared with comparative example 1, there is higher diffracted intensity, explanation
Perovskite thin film crystallinity prepared by the embodiment of the present invention 1 is high.
Electronic Speculum observation is scanned to perovskite thin film prepared by embodiment 1, acquired results are as shown in figure 3, can according to Fig. 3
To find out, the crystallite dimension for the perovskite thin film that embodiment 1 obtains is larger, about 500nm.
The current-voltage transformation curve of photoelectric device prepared by testing example 1 and comparative example 1, acquired results such as Fig. 4 institute
Show, according to Fig. 4 as can be seen that the photoelectric conversion efficiency of photoelectric device prepared by the embodiment of the present invention 1 is higher than comparative example 1.
Embodiment 2
Other conditions and embodiment 1 are identical, are only changed to the condition of the low pressure flash crystallization in step (4): pressure 10Pa,
Temperature is 90 DEG C, and the time is 15 minutes.
Embodiment 3
Other conditions and embodiment 1 are identical, are only changed to the condition of the low pressure flash crystallization in step (4): pressure
150Pa, temperature are 110 DEG C, and the time is 10 minutes.
Embodiment 4
Other conditions and embodiment 1 are identical, are only changed to the condition of the low pressure flash crystallization in step (4): pressure
200Pa, temperature are 100 DEG C, and the time is 25 minutes.
Embodiment 5
Other conditions and embodiment 1 are identical, only change the concentration of required various spin coating solutions:
(1) titanium dioxide (TiO2) preparation of compacted zone solution:
Measurement 7ml dehydrated alcohol, 5 μ l hydrochloric acid (37% concentration), ultrasonic dissolution 1 minute；Weigh four isopropanol of 0.25g metatitanic acid
Ester (TTIP) is added in above-mentioned solution, and ultrasonic disperse 10 minutes.
(2) 1.2mol/L lead iodide (PbI2) solution preparation:
Weigh the PbI of 0.553g2, 1ml n,N-Dimethylformamide is then added, it is small that 12 are stirred in 70 DEG C of heating plates
Up to clarification.
(3) 0.044mol/L methylamine iodine (CH3NH3I) the preparation of solution
Weigh 35mg CH3NH3I is added in the isopropanol of 5ml, and room temperature is protected from light stirring and dissolving.
(4) two fluorenes of 0.2mol/mL 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell
(Spiro-OMeTAD) preparation of solution:
Weigh chlorobenzene: the solution 1ml of acetonitrile=1:0.2 (volume ratio)；0.2M is added into chlorobenzene-acetonitrile mixed solution
Spiro-OMeTAD, 0.05M lithium salts (Li-TFSI), 0.17M 4- tert .-butylpyridine (TBP), are sufficiently stirred dissolution.
The resulting perovskite thin film of embodiment 2~5 is characterized according to the method in embodiment 1, it is known that gained film
Crystallinity it is higher, crystallite dimension can reach 500nm；The current-voltage of gained perovskite thin film photoelectric device is converted bent
Line is tested, and acquired results and embodiment 1 are similar.
As can be seen from the above embodiments, preparation method of the invention is available by low pressure flash revulsive crystallization
Perovskite thin film surface is more uniform smooth, and entire perovskite thin film layer crystallization degree is higher, thus gained perovskite thin film light
The photoelectric conversion efficiency of electrical part is higher, and preparation method of the present invention is simple, at low cost, has broad application prospects.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the perovskite thin film photoelectric device based on low pressure flash crystallization, which is characterized in that including following
Step:
(1) FTO electro-conductive glass successively performed etching, cleaned, dried up and ozone surface is handled, it is conductive to obtain pretreated FTO
Glass；
(2) in the etched surface spin coating TiO of the pretreated FTO electro-conductive glass2It anneals after compacted zone solution, forms TiO2
Compacted zone；
(3) in the TiO2It is dry after fine and close layer surface spin coating halogenation lead solution, form halogenation thin film lead；
(4) be added dropwise on the halogenation thin film lead after halogenation methylamine solution successively stood, whirl coating and low pressure flash crystallization, shape
At perovskite thin film；The pressure of the low pressure flash crystallization be 10~200Pa, temperature be 90~110 DEG C, the time be 10~
25min；
(5) it is sequentially prepared hole transmission layer and metal electrode on the perovskite thin film, obtains perovskite thin film photoelectric device.
2. preparation method according to claim 1, which is characterized in that the TiO in the step (2)2Compacted zone solution is by nothing
Water-ethanol, acid and TiO2Presoma is prepared to obtain；The acid includes concentrated hydrochloric acid and/or glacial acetic acid；The TiO2Presoma includes titanium
Sour four isopropyl alcohol esters and/or butyl titanate；
The dehydrated alcohol, acid and TiO2The amount ratio of presoma is the μ of 3~7mL:5~10 L:0.2~0.5g.
3. preparation method according to claim 1, which is characterized in that the annealing way in the step (2) are as follows: with 7.5
The rate of~10 DEG C/min is warming up to 150~200 DEG C, keeps the temperature 20~30 minutes, then 300 are warming up to 5~7.5 DEG C/min~
350 DEG C, 20~30 minutes are kept the temperature, then is warming up to 500 DEG C with 5~7.5 DEG C/min, keeps the temperature 60~90 minutes.
4. preparation method according to claim 1, which is characterized in that form TiO in the step (2)2It is also wrapped after compacted zone
It includes:
There to be TiO2The FTO electro-conductive glass of compacted zone is successively dried and anneals after impregnating in titanium tetrachloride solution；It is described
The mode of annealing are as follows: be warming up to 150~200 DEG C with the rate of 7.5~10 DEG C/min, keep the temperature 20~30 minutes, then with 5~
7.5 DEG C/min is warming up to 300~350 DEG C, keeps the temperature 20~30 minutes, then is warming up to 500 DEG C with 5~7.5 DEG C/min, and heat preservation 30~
60 minutes.
5. preparation method according to claim 1, which is characterized in that the solvent of halogenation lead solution is in the step (3)
One or more of N,N-dimethylformamide, dimethyl sulfoxide and gamma-butyrolacton；The lead halide is lead iodide, chlorination
Lead or lead bromide；
The concentration of the halogenation lead solution is 1~1.2mol/L；
The spin coating amount of the halogenation lead solution is 20~50 μ L/7.5cm2。
6. preparation method according to claim 1, which is characterized in that the solvent of halogenation methylamine solution in the step (4)
For alcohols solvent；The alcohols solvent includes one or more of ethyl alcohol, ethylene glycol and isopropanol；The halogenation methylamine is first
Amine iodine, methylamine chlorine or methylamine bromine；
The concentration of the halogenation methylamine solution is 0.044~0.063mol/L；
The spin coating amount of the halogenation methylamine solution is 100~300 μ L/7.5cm2。
7. preparation method according to claim 1, which is characterized in that the time stood in the step (4) is 30~
50s；
The revolving speed of the whirl coating is 3500~4500rpm, and the time is 25~35s.
8. preparation method according to claim 1, which is characterized in that the preparation side of step (5) hole-transporting layer
Method are as follows: 24~48 hours dry in oxygen atmosphere after spin coating hole transmission layer solution on the perovskite thin film.
9. preparation method according to claim 8, which is characterized in that the hole transmission layer solution is by solvent, 2,2', and 7,
Two fluorenes of 7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, lithium salts and 4- tert .-butylpyridine are prepared to obtain；
The solvent, 2,2', two fluorenes of 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, lithium salts and the tertiary fourth of 4-
The amount ratio of yl pyridines is 1mL:0.15~0.2mol:0.05~0.08mol:0.17~0.22mol；
The solvent is the mixed solvent of chlorobenzene and acetonitrile；The volume ratio of the in the mixed solvent chlorobenzene and acetonitrile be 1:0.1~
0.3。
10. preparation method according to claim 1, which is characterized in that the metal electrode in the step (5) is gold electricity
Pole.
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