CN106340587B - The preparation method and perovskite solar battery of perovskite film - Google Patents
The preparation method and perovskite solar battery of perovskite film Download PDFInfo
- Publication number
- CN106340587B CN106340587B CN201510400368.1A CN201510400368A CN106340587B CN 106340587 B CN106340587 B CN 106340587B CN 201510400368 A CN201510400368 A CN 201510400368A CN 106340587 B CN106340587 B CN 106340587B
- Authority
- CN
- China
- Prior art keywords
- perovskite
- solvent
- spin coating
- precursor solution
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- 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
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a kind of preparation methods of perovskite film, comprising the following steps: by AX and PbX2It is dissolved in a presoma solvent according to certain stoichiometric ratio, is heated to solid and is completely dissolved, and stirred and form perovskite precursor solution；The perovskite precursor solution is spun on a substrate, starting to instill a secondary solvent in the certain time after spin coating perovskite precursor solution, and continue perovskite precursor solution described in spin coating, the secondary solvent and the presoma solvent are immiscible, and the boiling point of secondary solvent is lower than the boiling point of the presoma solvent；After spin coating, the presoma solvent is removed, obtains the pin-free perovskite film of pattern uniform compact.The invention further relates to a kind of perovskite solar battery, calcium titanium ore bed used in the perovskite solar battery is prepared by the preparation method using the perovskite film.
Description
Technical field
The invention belongs to perovskite material fields, and in particular to a kind of preparation method and perovskite solar energy of perovskite film
Battery.
Background technique
Since two thousand nine, hybrid inorganic-organic perovskite material (APbX3, A CH3NH3Etc. organic ammonium ion, X is
The halide ions such as Cl, Br, I) with the higher absorption coefficient of light, excellent carrier separation, good carrier transport ability,
The advantages such as lower cost and the preparation of wettable method cause extensive concern in area of solar cell.Currently, being based on calcium titanium
The battery efficiency of mine profile material from 3.8% in 2009 risen to 2015 20.4%, it is most heavy to become current photovoltaic art
One of research hotspot wanted.Other than high efficiency, Ca-Ti ore type solar battery have can solution preparation, convenient for using being not required to
The characteristics of wanting the roll-to-roll technology of vacuum condition to prepare, this is provided for extensive, the low cost manufacturing of perovskite solar battery
It may.
The method of the perovskite film of solwution method preparation at present mainly includes a step solwution method and two step solwution methods.One step solwution method
It is the preparation method being most widely used at present.With CH3NH3PbI3For, first by CH3NH3I and PbI2According to certain chemistry
Metering is stirred in dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or gamma-butyrolacton solvent to clear than mixed dissolution
It is clear to form precursor solution, and film will be formed on liquid deposition to substrate in a manner of spin coating.Heat then is carried out to the film
Processing, can form perovskite film.And two step solwution methods are first by PbI2Powder is dissolved in DMF solution, spin coating after stirring clarification
To porous TiO2On film, it is dipped in after drying containing CH3NH3In the aqueous isopropanol of I, then heat treatment can be prepared by calcium
Titanium ore film.
Compared with two step solwution methods, a step solwution method is more convenient simple, but the perovskite film of step solwution method preparation
Modification of surface morphology it is big, it is often more difficult to control, and surface is easy to appear pin hole, especially for CH3NH3PbI3For.And it grinds
Study carefully and shows that the pattern of perovskite film is an important factor for influencing perovskite solar battery.
Summary of the invention
In view of this, it is necessory to provide the preparation method and calcium of a kind of uniform, the fine and close pin-free perovskite film of pattern
Titanium ore solar battery.
A kind of preparation method of perovskite film, comprising the following steps: by AX and PbX2It is molten according to certain stoichiometric ratio
In a presoma solvent, be heated to solid and be completely dissolved, and stir form perovskite precursor solution, wherein A be sun from
Son, X are halide ion；The perovskite precursor solution is spun on a substrate, starting, spin coating perovskite presoma is molten
Instill a secondary solvent in certain time after liquid, and continue perovskite precursor solution described in spin coating, the secondary solvent with
The presoma solvent is immiscible, and the boiling point of secondary solvent is lower than the boiling point of the presoma solvent；And after spin coating,
Remove the presoma solvent.
A kind of preparation method of perovskite film, comprising the following steps: by AX and PbX2It is molten according to certain stoichiometric ratio
In a presoma solvent, be heated to solid and be completely dissolved, and stir form perovskite precursor solution, wherein A be sun from
Son, X are halide ion, and the presoma solvent is dimethylformamide, dimethyl sulfoxide or gamma-butyrolacton；By the calcium titanium
Mine precursor solution is spun on a substrate, is starting to instill in the 6th second ~ 20 seconds after perovskite precursor solution described in spin coating
N-hexane, one of hexamethylene and normal heptane or a variety of, while continuing perovskite precursor solution described in spin coating；And rotation
After painting, the presoma solvent is removed.
A kind of perovskite solar battery, including a perovskite film, the perovskite film utilize the perovskite film
Prepared by preparation method.
Compared with prior art, the present invention adds secondary solvent in solwution method, which on the one hand can be effective
The nucleation and crystallization for accelerating perovskite material, improves the crystallinity of perovskite, prepares that pattern is uniform, smooth densification is pin-free, light
The good perovskite film of absorbent properties；On the other hand, presoma solvent can be completely removed, the stability of perovskite film is improved.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of perovskite film provided by the invention.
Fig. 2 is the SEM figure of perovskite film prepared by the embodiment of the present invention 1 and reference examples 1.
Fig. 3 is the abosrption spectrogram of perovskite film prepared by the embodiment of the present invention 1 and reference examples 1.
Fig. 4 is the XRD diagram before the perovskite film heat treatment of the embodiment of the present invention 1 and reference examples 1.
Fig. 5 is the XRD diagram after the perovskite film heat treatment of the embodiment of the present invention 1 and reference examples 1.
Fig. 6 is the structural schematic diagram of perovskite solar battery provided by the invention.
Fig. 7 is the VA characteristic curve of Cell-1 and control Cell-1 under AM 1.5G illumination.
Main element symbol description
| Perovskite solar battery | 10 |
| Electrode composite layer | 12 |
| Lower electrode | 120 |
| Electron transfer layer | 122 |
| Porous layer | 124 |
| Calcium titanium ore bed | 126 |
| Hole transmission layer | 14 |
| Top electrode | 16 |
The present invention that the following detailed description will be further explained with reference to the above drawings.
Specific embodiment
The preparation method of perovskite film provided by the invention is done further below in conjunction with the accompanying drawings and the specific embodiments
It is described in detail.
Referring to Figure 1, the present invention provides a kind of preparation method of perovskite film, comprising the following steps:
S1, by AX and PbX2It is dissolved in a presoma solvent according to certain stoichiometric ratio, it is completely molten to be heated to solid
Solution, and stir and form perovskite precursor solution；
The perovskite precursor solution is spun on a substrate by S2, after starting spin coating perovskite precursor solution
Certain time in instill a secondary solvent, and continue perovskite precursor solution described in spin coating, the secondary solvent with it is described
Presoma solvent is immiscible, and the boiling point of secondary solvent is lower than the boiling point of the presoma solvent；And
S3 after spin coating, removes the presoma solvent, obtains the pin-free perovskite film of pattern uniform compact.
In step S1, the AX and PbX2It is dissolved in presoma solvent according to the ratio of stoichiometric ratio 3:1 ~ 1:1, forms matter
The solution that concentration is 20 ~ 50 % is measured, for example mass concentration is 25%, 40%.Preferably, the AX and PbX2According to stoichiometric ratio
The ratio of 1:1 is dissolved in presoma solvent, forms the solution that mass concentration is 40 %.Wherein, A is a cation, cation choosing
From CH3NH3、NH2CHNH2Etc. organic amino；X is identical I(iodine), Br(bromine) or halide ions such as different I, Br, Cl.
The presoma solvent is the high boiling polar solvent that can dissolve perovskite material, such as DMF, DMSO and gamma-butyrolacton.Add
Heat and is stirred overnight to 65 DEG C ~ 70 DEG C until solid is completely dissolved and to form transparent uniform perovskite precursor solution.This implementation
In example, 70 DEG C are heated to until solid is completely dissolved.
In step S2, the substrate, which can be, is coated with compact titanium dioxide (c-TiO2) or the fluorine of zinc oxide (ZnO) mix
Miscellaneous tin-oxide (FTO) substrate of glass (FTO/c-TiO2, FTO/c-ZnO) or compacted zone above be also coated with porous material, such as
Poriferous titanium dioxide (m-TiO2) FTO/c-TiO2Substrate (FTO/c-TiO2/m-TiO2) or porous Al2O3、SiO2、
ZrO2、ZnO、SnO2Deng.
The secondary solvent can be 6s(seconds after starting to deposit perovskite precursor solution) ~ 20s quickly instills.
The time for adding of the secondary solvent changes according to the condition of spin coating and is changed, when the revolving speed of spin coating perovskite precursor solution is
When 4000 ~ 6000rpm/s, 6s ~ 10s after spin coating perovskite precursor solution starts quickly instills the secondary solvent；When
When the revolving speed of spin coating perovskite precursor solution is 2000 ~ 3000rpm/s, spin coating perovskite precursor solution start after the
10s ~ 20s quickly instills the secondary solvent.The amount of the dropwise addition of the secondary solvent and the size of substrate are related, such as when substrate is big
Small when being 1cm × 1cm ~ 2.5cm × 2.5cm, the secondary solvent of dropwise addition is 150 ~ 400 μ L.Preferably, the substrate size is
1cm × 1cm, the secondary solvent are 150 μ L.The secondary solvent is saturated with the immiscible low boiling point height of the presoma solvent
Vapor pressure solvents, including n-hexane, hexamethylene, one of normal heptane or a variety of.
Since secondary solvent and the presoma solvent are immiscible, so secondary solvent is dropped in the forerunner on substrate
The surface of liquid solution；And since the boiling point of secondary solvent is very low, during continuing spin coating precursor solution, the auxiliary is molten
Agent has been evaporated completely.
In step S3, the method for removing remaining presoma solvent and secondary solvent is unlimited, and in the present embodiment, substrate is put
It is placed on one 80 DEG C ~ 100 DEG C of hot plate 15min(minutes dry) ~ 60min.In the present embodiment, by substrate as 100 DEG C of heat
Dry 15min removes the presoma solvent and secondary solvent on plate.Due to the effect of secondary solvent in step 2, the presoma
Solvent can be removed completely.
The structural formula of the perovskite film are as follows: ABX3, wherein A is a cation, which is selected from CH3NH3、
NH2CHNH2Etc. organic amino；B is Pb2+；X is the halide ion of the halide ions such as I, Br, Cl or hydridization, such as I2Cl、I2Br
Deng.
Further, the spin coating hole mobile material in the perovskite film, and electrode is set, the perovskite sun can be obtained
It can battery.Specifically, the substrate removes remaining presoma solvent and secondary solvent on hot plate, and it is completely cooling after, in
In glove box, the spin coating hole mobile material in the perovskite film, such as 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl)
Amino] two fluorenes (SpiroOMeTAD) of -9,9'- spiral shell, Polyglycolic acid fibre, polyphenyl sulfonic acid (PEDOT:PSS), poly- 3- hexyl thiophene
Pheno (P3HT), poly- three fragrant ammonia (PTAA) etc., and using the method electrode evaporation of vacuum thermal evaporation, as electrode under Au is deposited
Prepare perovskite solar battery.
In addition to this, it can also be introduced directly into the perovskite film to electrode, such as gold, silver metal, conductive carbon paste,
Low-dimensional materials etc. by taking graphene as an example prepare the perovskite solar battery without hole transmission layer.
Embodiment one
In the present embodiment, the preparation method of perovskite film the following steps are included:
1, by CH3NH3I and PbI2It is dissolved in anhydrous DMF according to the ratio of stoichiometric ratio 1:1, forming mass concentration is 40
The solution of %.It is heated to 70 DEG C to be completely dissolved to solid, is stirred overnight to form transparent uniform perovskite precursor solution；
2, take the drop of perovskite precursor solution described in 50 μ L in the FTO/c-TiO of 1cm × 1cm2Substrate on, spin coating turn
Speed is 2500rpm, total time 60s.10s ~ 15s after starting spin coating quickly instills the secondary solvent n-hexane of 150 μ L.
After spin coating, substrate is removed into remaining solvent as 15min dry on 100 DEG C of hot plate, it can obtain uniform compact
Perovskite film.
Reference examples one
In this reference examples, the preparation method of perovskite film the following steps are included:
1, by CH3NH3I and PbI2It is dissolved in anhydrous DMF according to the ratio of stoichiometric ratio 1:1, forming mass concentration is 40
The solution of %.It is heated to 70 DEG C to be completely dissolved to solid, is stirred overnight to form transparent uniform perovskite precursor solution.
2, take the drop of perovskite precursor solution described in 50 μ L in the FTO/c-TiO of 1cm × 1cm2Substrate on, spin coating revolving speed
For 2500rpm, total time 60s.It is after spin coating, substrate is remaining as 15min removal dry on 100 DEG C of hot plate
Solvent obtains perovskite film.
Embodiment two
Step such as embodiment one, is changed to hexamethylene for secondary solvent, other conditions are constant.
Embodiment three
Step such as embodiment one, is changed to normal heptane for secondary solvent, other conditions are constant.
Example IV
In the present embodiment, the preparation method of perovskite film the following steps are included:
1, by NH2CHNH2I and PbI2It is dissolved in anhydrous DMF according to the ratio of stoichiometric ratio 1:1, forming mass concentration is
The solution of 40 %.It is heated to 70 DEG C to be completely dissolved to solid, is stirred overnight to form transparent uniform perovskite precursor solution.
2, take the drop of perovskite precursor solution described in 50 μ L in the FTO/c-TiO of 1cm × 1cm2Substrate on, spin coating turn
Speed is 2500rpm, total time 60s.10s ~ 15s after starting spin coating quickly instills the secondary solvent n-hexane of 150 μ L.
After spin coating, substrate is removed into remaining solvent as 15min dry on 100 DEG C of hot plate, it can obtain uniform compact
Perovskite film.
Embodiment five
Secondary solvent is changed to hexamethylene by step such as example IV, and other conditions are constant.
Embodiment six
Secondary solvent is changed to normal heptane by step such as example IV, and other conditions are constant.
Embodiment seven
In the present embodiment, the preparation method of perovskite film the following steps are included:
1, by CH3NH3Br and PbBr2It is dissolved in anhydrous DMF according to the ratio of stoichiometric ratio 1:1, forming mass concentration is
The solution of 40 %.It is heated to 70 DEG C to be completely dissolved to solid, is stirred overnight to form transparent uniform perovskite precursor solution.
2, take 50 μ L perovskite precursor solutions drop in the FTO/c-TiO of 1cm × 1cm2Substrate on, spin coating revolving speed is
2500rpm, total time 60s.10s ~ 15s after starting spin coating quickly instills the secondary solvent normal heptane of 150 μ L.Spin coating
After, substrate is removed into remaining solvent as 15min dry on 100 DEG C of hot plate, it can obtain the calcium of uniform compact
Titanium ore film.
Embodiment eight
Step such as embodiment seven, is changed to hexamethylene for secondary solvent, other conditions are constant.
Embodiment nine
Step such as embodiment seven, is changed to normal heptane for secondary solvent, other conditions are constant.
Embodiment ten is to embodiment 18
Presoma solvent is changed to DMSO, other conditions are constant to embodiment nine to step by such as embodiment one respectively.
Embodiment 19 is to embodiment 27
Presoma solvent is changed to gamma-butyrolacton, other conditions are constant to embodiment nine by step such as embodiment one.
Embodiment 28
In the present embodiment, the preparation method of perovskite film the following steps are included:
1, by CH3NH3I and PbI2It is dissolved in anhydrous DMF according to the ratio of stoichiometric ratio 1:1, forming mass concentration is 40
The solution of %.It is heated to 70 DEG C to be completely dissolved to solid, is stirred overnight to form transparent uniform perovskite precursor solution.
2, the above-mentioned precursor solution of 50 μ L is taken to drip in the FTO/c-TiO of 1cm × 1cm2/m-TiO2Substrate on, spin coating
Revolving speed is 2500rpm, total time 60s.10s ~ 15s after starting spin coating quickly instill the secondary solvent of 150 μ L just oneself
Alkane.After spin coating, substrate is removed into remaining solvent as 15min dry on 100 DEG C of hot plate, it can obtain uniform
Fine and close perovskite film.
Embodiment 29
Step such as embodiment 28, is changed to hexamethylene for secondary solvent, other conditions are constant.
Embodiment 30
Step such as embodiment 28, is changed to normal heptane for secondary solvent, other conditions are constant.
Embodiment 31
In the present embodiment, the preparation method of perovskite film the following steps are included:
1, by NH2CHNH2I and PbI2It is dissolved in anhydrous DMF according to the ratio of stoichiometric ratio 1:1, forming mass concentration is
The solution of 40 %.It is heated to 70 DEG C to be completely dissolved to solid, is stirred overnight to form transparent uniform perovskite precursor solution.
2, take 50 μ L perovskite precursor solutions drop in the FTO/c-TiO of 1cm × 1cm2/m-TiO2Substrate on, spin coating turn
Speed is 2500rpm, total time 60s.10s ~ 15s after starting spin coating quickly instills the secondary solvent n-hexane of 150 μ L.
After spin coating, substrate is removed into remaining solvent as 15min dry on 100 DEG C of hot plate, it can obtain uniform compact
Perovskite film.
Embodiment 32
Step such as embodiment 31, is changed to hexamethylene for secondary solvent, other conditions are constant.
Embodiment 33
Step such as embodiment 31, is changed to normal heptane for secondary solvent, other conditions are constant.
Embodiment 34
In the present embodiment, the preparation method of perovskite film the following steps are included:
1, by CH2NH2Br and PbBr2It is dissolved in anhydrous DMF according to the ratio of stoichiometric ratio 1:1, forming mass concentration is
The solution of 40 %.It is heated to 70 DEG C to be completely dissolved to solid, is stirred overnight to form transparent uniform perovskite precursor solution.
2, take 50 μ L perovskite precursor solutions drop in the FTO/c-TiO of 1cm × 1cm2/m-TiO2Substrate on, spin coating turn
Speed is 2500rpm, total time 60s.10s ~ 15s after starting spin coating quickly instills the secondary solvent n-hexane of 150 μ L.
After spin coating, substrate is removed into remaining solvent as 15min dry on 100 DEG C of hot plate, it can obtain uniform compact
Perovskite film.
Embodiment 35
Step such as embodiment 34, is changed to hexamethylene for secondary solvent, other conditions are constant.
Embodiment 36
Step such as embodiment 34, is changed to normal heptane for secondary solvent, other conditions are constant.
Embodiment 37 is to example IV 15
Presoma solvent is changed to DMSO, other conditions are not to embodiment 36 to step by such as embodiment 28 respectively
Become.
16 ~ embodiment of example IV 54
Presoma solvent is changed to gamma-butyrolacton, other conditions are not to embodiment 36 by step such as embodiment 28
Become.
The present invention is tested and is characterized to the pattern of the perovskite film using scanning electron microscope (SEM).It please join
The SEM of the perovskite film of embodiment one and reference examples one as shown in Figure 2 schemes, wherein Fig. 2 a, Fig. 2 b are calcium titanium in reference examples one
The SEM of mine film schemes；Fig. 2 c, Fig. 2 d are the SEM figure of perovskite film in embodiment one.The crystal grain of the perovskite film of reference examples one is at orphan
Island forms a film not fine and close, and gap is uneven；And the crystallization for the perovskite film for being handled and being prepared with n-hexane in embodiment one is advised
It is whole, film is fine and close, smooth uniform, seamless.As it can be seen that compared with the perovskite film for not utilizing secondary solvent processing, it is molten with assisting
The perovskite film compact crystallization of agent processing is seamless, and perovskite film is smooth uniform.
The present invention is tested and is characterized using absorption spectrum of the UV-Visible absorption instrument to the perovskite film.Please
The abosrption spectrogram of the perovskite film of embodiment one and reference examples one shown in Figure 3, with do not utilize secondary solvent processing and
The perovskite film of preparation is compared, handled with secondary solvent n-hexane and the perovskite film for preparing to the absorption band gap of sunlight not
Become, and the influx and translocation in long-wavelength region.This is because more being caused with the perovskite film that secondary solvent n-hexane is handled and prepared
It is close, the transmission to light can be reduced to enhance the absorption to sunlight.As it can be seen that being prepared with secondary solvent not being utilized to handle
Perovskite film compare, significant change does not occur for the Absorption edge of perovskite film for being handled and being prepared with secondary solvent, illustrates this
The preparation method that invention provides does not influence the band gap of perovskite film material, and absorbance is improved under the same conditions.
The present invention has carried out X-ray diffraction test to the perovskite film.The test is by polycrystalline x-ray diffractometer
(XRD) it is detected at normal temperature, angular range is 5 ° ~ 40 °.Calcium in embodiment one and reference examples one shown in Figure 4
The XRD diagram of titanium ore film is handled without any secondary solvent with the sum that n-hexane is handled and prepares perovskite film at 14.21 °
(110), 28.49 ° (220), 31.95 ° (310) and 43.25 ° (330) have appearance, are typical CH3NH3PbI3's
Peak.But with n-hexane handle and prepare perovskite film 28.49 ° and 31.95 ° relative intensity and without any auxiliary
Solvent handles and prepares perovskite film difference, and explanation is handled with n-hexane and the perovskite film of preparation, takes the crystallization of perovskite
To being changed, promote the nucleation and crystallization of perovskite.As it can be seen that having centainly with the perovskite film that secondary solvent is handled and prepared
Crystalline orientation, illustrate that secondary solvent can promote the nucleation and crystallization of perovskite.
In addition, the present invention compared the thermal stability of the perovskite film.Embodiment one and control shown in Figure 5
XRD comparison diagram after perovskite film heats 24 hours at 100 DEG C under nitrogen atmosphere in example one, it is found that compared to not
The perovskite film for handling and preparing through any secondary solvent, handled with secondary solvent and the perovskite film for preparing after heat treatment only
There is a small amount of PbI2It decomposes.As it can be seen that the thermal decomposition degree of the perovskite film for being handled and being prepared with assisted solution under the same conditions
It decreases, i.e., thermal stability is improved.
Fig. 6 is referred to, the present invention further provides a kind of perovskite solar battery 10, the perovskite solar batteries 10
Including an electrode composite layer 12, a hole transmission layer 14 and the top electrode 16 being cascading.Wherein, the electrode is compound
Layer 12 includes electrode 120, an electron transfer layer 122, a porous layer 124 and a calcium titanium ore bed 126, and the lower electrode
120, electron transfer layer 122, porous layer 124 and calcium titanium ore bed 126 are cascading.The porous layer 124 is optional element,
The i.e. described electrode composite layer 12 can also be made of lower electrode 120, electron transfer layer 122 and the calcium titanium ore bed 126.
The electrode composite layer 12 is transmitted to external circuit for collecting electronics.The material of the lower electrode 120 is not
Limit can be the metal or metal alloy such as gold, platinum.To guarantee translucency, the lower electrode 120 can also be a transparent electrode.This reality
It applies in example, the lower electrode 120 is transparent electrode made of a Fluorin doped tin-oxide (FTO).
The electron transfer layer 122 is used as n-type semiconductor, usually selects fine and close TiO2 Or ZnO layers, it uses
In transmission electronics.In the present embodiment, the electron transfer layer 122 selects fine and close TiO2。
The porous layer 124 is used to support the calcium titanium ore bed 126.The porous layer 124 with a thickness of 200nm(nanometers)
~600nm.The material of the porous layer 124 can be TiO2、ZnO、 SnO2、 Al2O3、 ZrO2、 SiO2Deng.In the present embodiment,
The material of the porous layer 124 is TiO2。
The calcium titanium ore bed 126 can generate electrons and holes after absorbing sunlight, which passes through porous layer 124, electronics
Transport layer 122 is transmitted to lower electrode 120, and is collected by lower electrode 120；It conducts through hole transmission layer 14 to top electrode in the hole
16, and collected by the top electrode 16, to realize the conversion of sunlight to electric energy.The calcium titanium ore bed 126 is exactly to utilize institute
State perovskite film prepared by the preparation method of perovskite film.
The hole transmission layer 14 uses common hole mobile material, such as Polyglycolic acid fibre: polyphenyl sulfonic acid
(PEDOT:PSS), 2,2,7,7 '-four [N, N- bis- (4- methoxyphenyl) amino] -9,9 '-spiral shells two
Fragrant ammonia (PTAA) of fluorenes (Spiro-OMeTAD), poly- 3- hexyl thiophene (P3HT) poly- three etc..The preferred Spiro- of the present embodiment
OMeTAD is the material of hole transmission layer 14.
The top electrode 16 is identical as 120 structure and material of lower electrode in the electrode composite layer 12.In the present embodiment,
The material of the top electrode 16 is gold, and thickness is about 20 nm ~ 100nm.
The perovskite solar battery 10 can be prepared in accordance with the following methods: use cleaning agent, deionized water and ultraviolet
Light irradiation and etc. cleaning have top electrode 16 FTO glass substrate；Densification is prepared using the method for atomic vapor deposition
TiO2；124 TiO of porous layer is prepared using the mode that spin coating is sintered2；Calcium titanium ore bed 126 is prepared using method of the invention；Solution
Spin-coating method prepares hole transmission layer 14；Vacuum evaporation top electrode 16.
The preparation control of embodiment 55 perovskite solar battery 10(compares Cell-1) ~ perovskite solar battery
10(Cell-1 ~ Cell-9)
The detailed process of preparation control Cell-1 and Cell-1 ~ Cell-9 are as follows: the glass of FTO transparency conducting layer will be coated with
Plate is ultrasonically treated in commercial detergent, is rinsed in deionized water, the ultrasonic oil removing in isopropanol solvent, under clean environment
It is baked to and completely removes moisture content, with ultraviolet light and ozone clean.It is heavy using atom gas phase in the above-mentioned substrate of glass with FTO
The fine and close TiO of area method preparation2Layer, with a thickness of 30nm.In fine and close TiO2On layer, nanometer is coated in substrate using spin-coating method
TiO2The precursor solution of particle colloid is put into 500 DEG C of high temperature sintering 30min ~ 90min in Muffle furnace, and it is more to form nanoscale
Aperture layer 124, with a thickness of the nm of 200nm ~ 600.
The preparation of perovskite film: control Cell-1 prepares perovskite film using common solwution method, as described in reference examples one
The preparation method of perovskite film；And 1 ~ cell of cell 9 is using the above embodiment of the present invention 28 to embodiment 36
Method preparation.Being coated with upper hole mobile material spiro-OMeTAD(concentration with solution spin-coating method in perovskite film is 0.17M,
Solvent uses chlorobenzene), obtain the hole transmission layer 14 that thickness is about 40nm.The Au layers of work in vacuum evaporation on hole transmission layer 14
For the lower electrode 120 of device, wherein the evaporation rate of Au is 0.1nm/s, with a thickness of 60nm.
Control Cell-1 and Cell-1 ~ Cell-9 is prepared according to the method described above.Cell-1 and Cell-1 ~ Cell-9 will be compareed
It is placed under standard solar simulator, see Table 1 for details for correlation performance parameters.
The performance of the control of table 1 Cell-1 and Cell-1 ~ Cell-9
(JscRepresent current density；VocRepresent voltage；FF represents fill factor；PCE represents photoelectric conversion efficiency)
| Embodiment | Perovskite film chemical formula | Perovskite film preparation process | Jsc(mA/cm2) | Voc(V) | FF | PCE(%) |
| Compare Cell-1 | CH3NH3PbI3 | Regular solution method | 12.7 | 0.81 | 0.65 | 6.7 |
| Cell-1 | CH3NH3PbI3 | Add n-hexane | 18.8 | 0.93 | 0.65 | 11.3 |
| Cell-2 | CH3NH3PbI3 | Add hexamethylene | 18.5 | 0.93 | 0.66 | 11.3 |
| Cell-3 | CH3NH3PbI3 | Add normal heptane | 18.0 | 0.93 | 0.65 | 11.0 |
| Cell-4 | CH3NH3PbBr3 | Add n-hexane | 18.6 | 0.91 | 0.63 | 10.7 |
| Cell-5 | CH3NH3PbBr3 | Add hexamethylene | 18.6 | 0.91 | 0.62 | 10.5 |
| Cell-6 | CH3NH3PbBr3 | Add normal heptane | 18.4 | 0.90 | 0.62 | 10.3 |
| Cell-7 | NH2CHNH3PbI3 | Add n-hexane | 18.3 | 0.90 | 0.63 | 10.4 |
| Cell-8 | NH2CHNH3PbI3 | Add hexamethylene | 18.5 | 0.91 | 0.63 | 10.6 |
| Cell-9 | NH2CHNH3PbI3 | Add normal heptane | 18.3 | 0.90 | 0.60 | 9.9 |
By perovskite battery solar cell comparison handled without secondary solvent and by secondary solvent processing, Ke Yifa
It is existing, it is molten using assisting relative to the perovskite solar battery 10 for being used without the perovskite film prepared by any processing
Agent is handled and the photoelectric conversion efficiency of the perovskite solar battery 10 of the perovskite film of preparation is high.Specifically, Cell's -1 is short
Road current density is 18.8 mA/cm2, open-circuit voltage is 0.93 V, and fill factor is 0. 65, and photoelectric conversion efficiency is
11.3%.And the short-circuit current density for compareing Cell-1 is 12.7 mA/cm2, open-circuit voltage is 0.81 V, and fill factor is
0. 65, photoelectric conversion efficiency is only 6.7%, as shown in Figure 7.That is, preparing 10 phase of perovskite solar battery with conventional method
Than CH prepared by the present invention3NH3PbI3The short circuit current of perovskite solar battery 10 is from 12.7 mA/cm2Increase 18.8
mA/cm2, open-circuit voltage has been increased to 0.93 V from 0.81 V, and therefore the photoelectric conversion efficiency of battery has been increased to 11.3%, increase
Add 168%.As it can be seen that the short circuit current and photoelectricity of the perovskite solar battery 10 using the present invention by secondary solvent processing
Transfer efficiency is significantly improved relative to untreated solar battery.This is because suitable improve perovskite
The pattern of film enhances the optical absorption intensity of perovskite film, while the reduction of the defect of perovskite film is more advantageous to electron-hole
Pair separation, the compound of light-generated excitons is reduced, to improve the photoelectric conversion efficiency of perovskite solar battery 10.
The preparation control of embodiment 56 perovskite solar battery 10(compares Cell-2) ~ perovskite solar battery
10(Cell-10 ~ Cell-18)
The present embodiment is with the difference of embodiment 55: compareing Cell-2 and Cell-10 ~ Cell- in the present embodiment
18 without porous layer 124, remaining step, material etc. are all the same.
Control Cell-2 and Cell-10 ~ Cell-18 is placed under standard solar simulator, correlation performance parameters are detailed in
Table 2.
The performance of the control of table 2 Cell-2 and Cell-10 ~ Cell-18
(Jsc represents current density；Voc represents voltage；FF represents fill factor；PCE represents photoelectric conversion efficiency)
| Embodiment | Perovskite film chemical formula | Perovskite film preparation process | Jsc(mA/cm2) | Voc(V) | FF | PCE(%) |
| Compare Cell-2 | CH3NH3PbI3 | Regular solution method | 10.0 | 0.80 | 0.55 | 4.4 |
| Cell-10 | CH3NH3PbI3 | Add n-hexane | 17.5 | 0.92 | 0.64 | 10.3 |
| Cell-11 | CH3NH3PbI3 | Add hexamethylene | 17.3 | 0.93 | 0.63 | 10.1 |
| Cell-12 | CH3NH3PbI3 | Add normal heptane | 17.4 | 0.92 | 0.63 | 10.1 |
| Cell-13 | CH3NH3PbBr3 | Add n-hexane | 17.5 | 0.91 | 0.64 | 10.2 |
| Cell-14 | CH3NH3PbBr3 | Add hexamethylene | 17.3 | 0.92 | 0.62 | 9.9 |
| Cell-15 | CH3NH3PbBr3 | Add normal heptane | 17.0 | 0.91 | 0.63 | 9.7 |
| Cell-16 | NH2CHNH3PbI3 | Add n-hexane | 17.6 | 0.91 | 0.63 | 10.1 |
| Cell-17 | NH2CHNH3PbI3 | Add hexamethylene | 17.3 | 0.91 | 0.62 | 9.8 |
| Cell-18 | NH2CHNH3PbI3 | Add normal heptane | 17.2 | 0.90 | 0.60 | 9.3 |
As known from Table 2, even if in no porous layer 124, the processing for carrying out secondary solvent to perovskite film be can also be improved
The photoelectric conversion efficiency of perovskite solar battery 10.
The preparation method of perovskite film provided by the invention has the advantage that first, addition auxiliary is molten in solwution method
Agent, the secondary solvent can effectively accelerate the crystallization of perovskite material, improve the crystallinity of perovskite, and it is equal can to prepare pattern
One, the perovskite film that smooth densification is pin-free, absorbing properties are good；The second, the described secondary solvent can effectively accelerate presoma
The volatilization of solvent, so as to completely remove the higher boiling presoma solvent in perovskite film, therefore prepared perovskite film
Thermal stability it is high；Third, the perovskite solar battery prepared using the perovskite film, photoproduction, which carries exciton, to be had
Effect separation effectively inhibits the compound of exciton, charge transfer efficiency improves, and photoelectric conversion efficiency and repeatability are substantially changed
It is kind.
In addition, those skilled in the art can also do other variations in spirit of that invention, certainly, these are smart according to the present invention
The variation that mind is done, all should be comprising within scope of the present invention.
Claims (10)
1. a kind of preparation method of perovskite film, comprising the following steps:
By AX and PbX2It is dissolved in a presoma solvent according to certain stoichiometric ratio, is heated to solid and is completely dissolved, and stir
Form perovskite precursor solution, wherein A is cation, and X is halide ion；
The perovskite precursor solution is spun on a substrate, the timing after starting spin coating perovskite precursor solution
One secondary solvent of interior instillation, while continuing perovskite precursor solution described in spin coating, the secondary solvent and the presoma
Solvent is immiscible, and the boiling point of secondary solvent is lower than the boiling point of the presoma solvent；And
After spin coating, the presoma solvent is removed.
2. the preparation method of perovskite film as described in claim 1, which is characterized in that the secondary solvent is n-hexane, ring
One of hexane and normal heptane are a variety of.
3. the preparation method of perovskite film as described in claim 1, which is characterized in that starting, spin coating perovskite presoma is molten
Instill the secondary solvent within the 6th second~20 seconds after liquid.
4. the preparation method of perovskite film as claimed in claim 3, which is characterized in that the perovskite presoma described in the spin coating is molten
When the revolving speed of liquid is 4000~6000rpm, the auxiliary is instilled within the 6th second~10 seconds after starting spin coating perovskite precursor solution
Solvent.
5. the preparation method of perovskite film as claimed in claim 3, which is characterized in that when spin coating perovskite precursor solution
When revolving speed is 2000~3000rpm, it is molten to instill the auxiliary within the 10th second~20 seconds after starting spin coating perovskite precursor solution
Agent.
6. the preparation method of perovskite film as described in claim 1, which is characterized in that the cation is selected from CH3NH3、
NH2CHNH2, the X is the halide ion of iodide ion, bromide ion, chloride ion or hydridization.
7. the preparation method of perovskite film as described in claim 1, which is characterized in that the AX and PbX2According to stoichiometry
It is dissolved in presoma solvent than the ratio for 3:1~1:1 and forms the perovskite precursor solution that mass concentration is 20~50%.
8. the preparation method of perovskite film as described in claim 1, which is characterized in that the substrate size be 1cm × 1cm~
2.5cm × 2.5cm, the secondary solvent are 150 μ of μ L~400 L.
9. a kind of preparation method of perovskite film, comprising the following steps:
By AX and PbX2It is dissolved in a presoma solvent according to certain stoichiometric ratio, is heated to solid and is completely dissolved, and stir
Formed perovskite precursor solution, wherein A be cation, X is halide ion, the presoma solvent be dimethylformamide,
Dimethyl sulfoxide or gamma-butyrolacton；
The perovskite precursor solution is spun on a substrate, is starting described in spin coating the after perovskite precursor solution
N-hexane, one of hexamethylene and normal heptane or a variety of are instilled in 6 seconds~20 seconds, while before continuing perovskite described in spin coating
Drive liquid solution；And
After spin coating, the presoma solvent is removed.
10. a kind of perovskite solar battery, including a perovskite film, which is characterized in that the perovskite film is using as weighed
Benefit requires prepared by 1 preparation method to the perovskite film described in any one of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510400368.1A CN106340587B (en) | 2015-07-09 | 2015-07-09 | The preparation method and perovskite solar battery of perovskite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510400368.1A CN106340587B (en) | 2015-07-09 | 2015-07-09 | The preparation method and perovskite solar battery of perovskite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106340587A CN106340587A (en) | 2017-01-18 |
| CN106340587B true CN106340587B (en) | 2019-01-29 |
Family
ID=57827144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510400368.1A Active CN106340587B (en) | 2015-07-09 | 2015-07-09 | The preparation method and perovskite solar battery of perovskite film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106340587B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654020B (en) * | 2017-01-24 | 2019-01-08 | 中国科学院上海硅酸盐研究所 | Bulk heterojunction perovskite thin film and preparation method thereof and solar battery |
| CN108970913B (en) * | 2017-06-02 | 2023-09-01 | 杭州纤纳光电科技有限公司 | Perovskite film coating equipment, use method and application |
| CN107394045B (en) * | 2017-07-21 | 2019-09-20 | 中国乐凯集团有限公司 | Organic inorganic hybridization perovskite thin film solar battery |
| CN107591486B (en) * | 2017-08-18 | 2019-07-19 | 华中科技大学 | A kind of organic inorganic hybridization perovskite semiconductor material and preparation method thereof |
| CN108807144B (en) * | 2018-06-05 | 2020-06-09 | 合肥工业大学 | Method for preparing inorganic perovskite film with assistance of crown ether and application of method |
| CN108987588A (en) * | 2018-07-24 | 2018-12-11 | 南京信息工程大学 | Multiple groups part perovskite absorbed layer precursor solution and preparation method thereof |
| CN109037456A (en) * | 2018-08-10 | 2018-12-18 | 南京邮电大学 | A kind of preparation method of zero sluggish efficiently perovskite solar battery |
| CN110699745B (en) * | 2019-10-31 | 2021-08-06 | 东南大学 | Preparation method of perovskite single crystal |
| CN112142100A (en) * | 2020-09-29 | 2020-12-29 | 陕西师范大学 | Perovskite polycrystalline thin sheet and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103440988A (en) * | 2013-07-22 | 2013-12-11 | 华侨大学 | Preparation method of hybridization solar battery for perovskite-like sensitized photoanode |
| CN105226196A (en) * | 2015-10-20 | 2016-01-06 | 上海交通大学 | A kind of hydrochloric acid assists the method preparing organic inorganic hybridization perovskite material |
-
2015
- 2015-07-09 CN CN201510400368.1A patent/CN106340587B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103440988A (en) * | 2013-07-22 | 2013-12-11 | 华侨大学 | Preparation method of hybridization solar battery for perovskite-like sensitized photoanode |
| CN105226196A (en) * | 2015-10-20 | 2016-01-06 | 上海交通大学 | A kind of hydrochloric acid assists the method preparing organic inorganic hybridization perovskite material |
Non-Patent Citations (1)
| Title |
|---|
| Highly Reproducible Perovskite Solar Cells with Average Efficiency of 18.3% and Best Efficiency of 19.7% Fabricated via Lewis Base Adduct of Lead(II) Iodide;Namyoung Ahn等;《Journal of the American Chemical Society》;20150630;第137卷(第27期);Supporting Information的Solar cell farbrication部分 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106340587A (en) | 2017-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106340587B (en) | The preparation method and perovskite solar battery of perovskite film | |
| Shen et al. | Graphene quantum dots decorated TiO2 mesoporous film as an efficient electron transport layer for high-performance perovskite solar cells | |
| Lu et al. | Identifying the optimum thickness of electron transport layers for highly efficient perovskite planar solar cells | |
| Shi et al. | Effects of 4-tert-butylpyridine on perovskite formation and performance of solution-processed perovskite solar cells | |
| Tang et al. | Vacuum assisted solution processing for highly efficient Sb 2 S 3 solar cells | |
| Mali et al. | Synthesis of SnO 2 nanofibers and nanobelts electron transporting layer for efficient perovskite solar cells | |
| Wang et al. | Enhanced performance of CH 3 NH 3 PbI 3− x Cl x perovskite solar cells by CH 3 NH 3 I modification of TiO 2-perovskite layer interface | |
| US10840030B2 (en) | Organolead halide perovskite film and the method of making the same | |
| Liu et al. | Sequentially vacuum evaporated high-quality CsPbBr3 films for efficient carbon-based planar heterojunction perovskite solar cells | |
| Chu et al. | Screen printing large-area organometal halide perovskite thin films for efficient photodetectors | |
| Jiang et al. | Improvement of CH3NH3PbI3 formation for efficient and better reproducible mesoscopic perovskite solar cells | |
| Numata et al. | Impacts of heterogeneous TiO2 and Al2O3 composite mesoporous scaffold on formamidinium lead trihalide perovskite solar cells | |
| Ren et al. | An Er-doped TiO 2 phase junction as an electron transport layer for efficient perovskite solar cells fabricated in air | |
| CN106457063A (en) | Improved precipitation process for producing perovskite-based solar cells | |
| Khan et al. | Multi-dimensional anatase TiO2 materials: Synthesis and their application as efficient charge transporter in perovskite solar cells | |
| US20200313093A1 (en) | Method for Manufacturing Perovskite Solar Cells and Multijunction Photovoltaics | |
| CN105702864A (en) | High quality perovskite thin film, solar cell and preparation method thereof | |
| Gao et al. | Anti-solvent surface engineering via diethyl ether to enhance the photovoltaic conversion efficiency of perovskite solar cells to 18.76% | |
| Liu et al. | An effective TiO2 blocking layer for hole-conductor-free perovskite solar cells based on carbon counter electrode | |
| Li et al. | Preheating-assisted deposition of solution-processed perovskite layer for an efficiency-improved inverted planar composite heterojunction solar cell | |
| Wu et al. | Solvent-mediated intragranular-coarsening of CH3NH3PbI3 thin films toward high-performance perovskite photovoltaics | |
| Jiang et al. | Efficiency enhancement of perovskite solar cells by fabricating as-prepared film before sequential spin-coating procedure | |
| Huang et al. | Improvement on performance of hybrid CH3NH3PbI3− xClx perovskite solar cells induced sequential deposition by low pressure assisted solution processing | |
| Wei et al. | Importance of PbI2 morphology in two-step deposition of CH3NH3PbI3 for high-performance perovskite solar cells | |
| Pang et al. | UV–O 3 treated annealing-free cerium oxide as electron transport layers in flexible planar perovskite solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |