CN110137361A - Non-stoichiometric perovskite thin film and its preparation method and application - Google Patents
Non-stoichiometric perovskite thin film and its preparation method and application Download PDFInfo
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- CN110137361A CN110137361A CN201810134925.3A CN201810134925A CN110137361A CN 110137361 A CN110137361 A CN 110137361A CN 201810134925 A CN201810134925 A CN 201810134925A CN 110137361 A CN110137361 A CN 110137361A
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- 239000010409 thin film Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 230000026030 halogenation Effects 0.000 claims abstract description 96
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 96
- -1 amine compounds Chemical class 0.000 claims abstract description 55
- 150000002611 lead compounds Chemical class 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000010408 film Substances 0.000 claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 94
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 12
- 238000004528 spin coating Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- 229940050176 methyl chloride Drugs 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 53
- 238000002156 mixing Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- 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
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- 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
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
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- 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
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
-
- 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
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- Engineering & Computer Science (AREA)
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- Chemical & Material Sciences (AREA)
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to perovskite area of solar cell, disclose a kind of preparation method of non-stoichiometric perovskite thin film, this method comprises: the solution containing halogenation amine compounds and halogenation lead compound is coated on substrate, and are heat-treated;Wherein, in the solution containing halogenation amine compounds and halogenation lead compound, the molar ratio of the halogenation amine compounds and the halogenation lead compound is 1:x, wherein 1 < x < 2.The preparation method of non-stoichiometric perovskite thin film of the invention is simple, and solution composition is easy to control, and raw material types and dosage are few, and the film preparation period is short, reduces preparation cost and improves preparation efficiency.
Description
Technical field
The present invention relates to perovskite area of solar cell, and in particular to a kind of non-stoichiometric perovskite thin film and its
Preparation method and application.
Background technique
In recent years, perovskite (perovskite) solar battery is looked steadily due to its high-effect, cheap manufacturing cost
Mesh.And active material of the perovskite thin film as perovskite solar battery, performance are to influence the pass of solar cell properties
Key factor.
(the Iodide management in formamidinium-lead-halide-based such as Yang
perovskite layers for efficient solar cells,Yang et al.,Science 356,1376-
1379,2017) a kind of method that successive sedimentation method prepares perovskite thin film is disclosed.By I2It is added IPA stirring and dissolving 7 days, adds
Enter FAI/MABr stirring preparation FAI/MABr/IPA dropping liquid.By PbI2/PbBr2DMF/DMSO heating stirring is added and prepares PbI2
(PbBr2)-DMSO mixed solution.Spin coating prepares PbI on substrate2(PbBr2)-DMSO film, spin coating again after dropping liquid is added dropwise,
It is cleaned after baking with IPA, i.e. the preparation of completion perovskite thin film.Using the film of the method preparation as absorbed layer, calcium titanium is made
Mine solar battery, energy conversion efficiency reach 22.1%.
For perovskite solar battery, continuous, fine and close, smooth perovskite thin film to the contribution of energy conversion efficiency extremely
Close important, miscellaneous phase, hole and point defect all can seriously damage perovskite solar battery.This method preparation containing there are many sun from
During the carbonamidine lead halide of son and mixed halogen anion, excess I ion is introduced in FAI/MABr/IPA dropping liquid, to promote
It is exchanged into molecule, reduces defect, successfully prepare the good perovskite thin film of pattern.But this method uses raw material types
More, dropping liquid long preparation period, film spin coating preparation process is cumbersome to be difficult to control.
Summary of the invention
The purpose of the invention is to overcome, perovskite thin film preparation method of the existing technology is cumbersome, the period long asks
Topic provides a kind of non-stoichiometric perovskite thin film and its preparation method and application, the non-stoichiometric perovskite thin film
Preparation method it is simple, solution composition is easy to control, and raw material types and dosage are few, and the film preparation period is short, reduces and is prepared into
Originally preparation efficiency is improved.
To achieve the goals above, one aspect of the present invention provides a kind of preparation side of non-stoichiometric perovskite thin film
Method, wherein this method comprises: the solution containing halogenation amine compounds and halogenation lead compound is coated on substrate, and carry out
Heat treatment;Wherein, in the solution containing halogenation amine compounds and halogenation lead compound, the halogenation amine compounds and the halogen
The molar ratio for changing lead compound is 1:x, wherein 1 < x < 2.
Preferably, x 1.01-1.9, preferably 1.1-1.75, more preferably 1.2-1.5.
Preferably, the halogenation amine compounds are one of methylpyridinium iodide amine, carbonamidine iodine and methyl chloride amine or a variety of.
Preferably, the halogenation lead compound is one of lead iodide, lead bromide and lead chloride or a variety of;More preferably
Ground, the halogenation lead compound are lead iodide.
Preferably, the solvent in the solution containing halogenation amine compounds and halogenation lead compound is dimethyl formyl
One of amine, dimethyl sulfoxide and isopropanol are a variety of.
Preferably, it by mixing the solution of halogenation amine compounds with the solution of halogenation lead compound, is made described and contains
The solution of halogenation amine compounds and halogenation lead compound.
It is highly preferred that the solvent in the solution of the halogenation amine compounds is dimethylformamide, dimethyl sulfoxide and isopropyl
One of alcohol is a variety of.
It is highly preferred that the solvent in the solution of the halogenation lead compound is dimethylformamide and/or dimethyl sulfoxide.
Preferably, the solution of the halogenation amine compounds is identical as the solvent in the solution of the halogenation lead compound.
Preferably, the concentration of halogenation amine compounds is 0.01-1mol/L in the solution of the halogenation amine compounds;More preferably
Ground, the concentration of halogenation amine compounds is 0.05-0.5mol/L in the solution of the halogenation amine compounds.
Preferably, the concentration of halogenation lead compound is 0.01-1mol/L in the solution of the halogenation lead compound;More preferably
Ground, the concentration of halogenation lead compound is 0.05-0.5mol/L in the solution of the halogenation lead compound.
Preferably, the solution containing halogenation amine compounds and halogenation lead compound is coated in the method on substrate is spin coating
Or silk-screen printing, preferably spin coating.
It is highly preferred that it is 1000-6000r/min, time 10-60s that the condition of the spin coating, which includes: speed,.
Preferably, it is 60 DEG C -120 DEG C that the condition of the heat treatment, which includes: temperature, time 1-60min.
Preferably, the substrate is glass, preferably FTO glass or TiO2Film glass.
Second aspect of the present invention provides the non-stoichiometric perovskite thin film that above-mentioned preparation method is prepared.
Third aspect present invention provides the application of above-mentioned non-stoichiometric perovskite thin film in solar cells.
Through the above technical solutions, preparation method of the invention is simple, solution composition is easy to control, raw material types and dosage
Few, the film preparation period is short, and film-forming process simply easily manipulates, and reduces perovskite thin film preparation cost, convenient for industrialization system
Standby perovskite thin film.Perovskite thin film phase structure prepared by the present invention is controllable, film continuous formation and morphology controllable, has good
Physical property, can satisfy the needs of solar battery.
Detailed description of the invention
Fig. 1 is the XRD diagram for the perovskite thin film that the embodiment of the present invention 1 is prepared.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The preparation method of non-stoichiometric perovskite thin film provided by the invention, this method comprises: halogeno-amine will be contained
The solution of compound and halogenation lead compound is coated on substrate, and is heat-treated;Wherein, containing halogenation amine compounds and
In the solution of halogenation lead compound, the molar ratio of the halogenation amine compounds and the halogenation lead compound is 1:x, wherein 1 < x
< 2.
Preferably, x 1.01-1.9, preferably 1.1-1.75, more preferably 1.2-1.5, further preferably 1.25-
1.5。
In the present invention, by using the excessive solution containing halogenation amine compounds and halogenation lead compound of halogeno-amine,
The preparation process of perovskite thin film is simplified, raw material types and dosage are few, short preparation period, and can prepare continuous formation
And the perovskite thin film of morphology controllable.
In the present invention, the halogenation amine compounds can be methylpyridinium iodide amine (MAI), carbonamidine iodine (FAI) and methyl chloride
Change one of ammonium (MACl) or a variety of.From the viewpoint of the performance for improving the perovskite thin film being prepared, the halogenation
Amine compounds are preferably methylpyridinium iodide amine.
In the present invention, the halogenation lead compound can be one of lead iodide, lead bromide and lead chloride or a variety of.
From the viewpoint of the performance for improving the perovskite thin film being prepared, the halogenation lead compound is preferably lead iodide.
In the present invention, as long as the solvent in the solution containing halogenation amine compounds and halogenation lead compound can be molten
Solve halogenation amine compounds and halogenation lead compound, and perovskite thin film can be prepared, can be used it is existing can
Various solvents for perovskite thin film preparation.For example, in the solution containing halogenation amine compounds and halogenation lead compound
Solvent can be one of dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and isopropanol (IPA) or a variety of, wherein
Preferably dimethylformamide.
According to the present invention, the method for preparing the above-mentioned solution containing halogenation amine compounds and halogenation lead compound is not special
Restriction be made described preferably by mixing the solution of halogenation amine compounds with the solution of halogenation lead compound and contain halogenation
The solution of amine compounds and halogenation lead compound.It wherein, can be two as the solvent in the solution of the halogenation amine compounds
One of methylformamide, dimethyl sulfoxide and isopropanol are a variety of;As the solvent in the solution of the halogenation lead compound,
It can be dimethylformamide and/or dimethyl sulfoxide.From convenient for from the viewpoint of solution hybrid manipulation, it is preferable that the halogenation
The solution of amine compounds is identical as the solvent in the solution of the halogenation lead compound.
The method of solution as the solution and halogenation lead compound for preparing above-mentioned halogenation amine compounds, as long as solute is molten
Solution, can be by the way of the acceleration such as stirring dissolution.It in order to accelerate to dissolve, can be heated simultaneously, the temperature of heating
It such as can be 50-150 DEG C, preferably 60-100 DEG C.
A preferred embodiment according to the present invention, halogenation amine compounds in the solution of the halogenation amine compounds
Concentration is 0.01-1mol/L, preferably 0.05-0.5mol/L.
A preferred embodiment according to the present invention, halogenation lead compound in the solution of the halogenation lead compound
Concentration is 0.01-1mol/L, preferably 0.05-0.5mol/L.
According to the present invention, the method that the solution containing halogenation amine compounds and halogenation lead compound is coated on substrate is not had
There is special restriction, obtains the film of required thickness as long as above-mentioned solution uniformly can be coated on substrate, such as
It can be spin coating or silk-screen printing, wherein preferably spin coating.
In the present invention, it is 1000-6000r/min, time 10-60s that the condition of the spin coating, which includes: speed,;It is preferred that
Ground, speed 2000-4000r/min, time 20-40s.
According to the present invention, the thickness of the non-stoichiometric perovskite thin film, which can according to need, is prepared, such as
It is 50nm-1 μm, preferably 200nm-500nm.The non-stoichiometric perovskite thin film of above-mentioned thickness in order to obtain, it is coated
The dosage of solution containing halogenation amine compounds and halogenation lead compound in journey is preferably 20-100 μ L/cm2, preferably 30-50 μ
L/cm2。
In the present invention, as long as the heat-treating methods obtain perovskite thin film, for example, the item of the heat treatment
Part may include: that temperature is 60 DEG C -120 DEG C, time 1-60min;Preferably, temperature is 70 DEG C -100 DEG C, time 5-
20min.By above-mentioned heat treatment, not needing any cleaning operation can be obtained perovskite thin film.
In the present invention, the substrate can use the existing various substrates that can be used as perovskite thin film substrate, example
It can be such as glass, wherein preferably FTO (stannic oxide of fluorine doped) glass or TiO2Film glass.
In order to which the better perovskite thin film of performance is prepared, it is preferable that before carrying out above-mentioned coating, first to the substrate
It is cleaned.As above-mentioned cleaning, preferably ultrasonic cleaning.It is described cleaning specifically can using aqueous slkali, acetone, ethyl alcohol,
One or more of water carries out.A preferred embodiment according to the present invention, to the substrate successively use aqueous slkali,
Acetone, ethyl alcohol, water are cleaned.
The present invention also provides the non-stoichiometric perovskite thin films that above-mentioned preparation method is prepared.
The present invention also provides the application of above-mentioned non-stoichiometric perovskite thin film in solar cells.
The present invention will be described in detail by way of examples below.In following embodiment, glass substrate is Yingkou U.S. shield
Company, the photoelectric material Co., Ltd trade mark is the commercially available product of TEC15.
Embodiment 1
1, by 0.1mmol PbI2Be dissolved in 1mL DMF, 80 DEG C heating stirring 4 hours, prepare the PbI of 0.1mol/L2/DMF
Solution.
2,0.1mmol MAI is dissolved in 1mL DMF, stirs 0.5 hour, prepares the MAI/DMF solution of 0.1mol/L.
3, by the volume ratio of 1:1.25 by PbI2The mixing of/DMF and MAI/DMF solution, prepares PbI2/MAI1.25/ DMF mixing
Solution.
4, glass substrate is successively used to aqueous slkali, acetone, ethyl alcohol, ultrapure water ultrasonic cleaning 30min.
5, PbI is added dropwise on substrate2/MAI1.25/ DMF mixed solution, dosage are 30 μ L/cm2, revolved by 3000r/min speed
30s is applied, 80 DEG C of heating 10min, obtain the MA of non-stoichiometric on hot plate1.25PbI3.25Perovskite thin film A1, thickness
For 500nm.
The XRD spectrum of the perovskite thin film is measured with X-ray diffractometer (Bruker company, D8ADVANCE model), is such as schemed
Shown in 1.As shown in Figure 1, perovskite thin film A1 continuous uniform manufactured in the present embodiment does not contain PbI2With MAI miscellaneous phase.
Embodiment 2
1, by 0.1mmol PbI2Be dissolved in 1mLDMF, 80 DEG C heating stirring 4 hours, prepare the PbI of 0.1mol/L2/DMF
Solution.
2,0.1mmol MAI is dissolved in 1mLDMF, stirs 0.5 hour, prepares the MAI/DMF solution of 0.1mol/L.
3, by by the volume ratio of 1:1.5 by PbI2The mixing of/DMF and MAI/DMF solution, prepares PbI2/MAI1.5/ DMF mixing
Solution.
4, glass substrate is successively used to aqueous slkali, acetone, ethyl alcohol, ultrapure water ultrasonic cleaning 30min.
5, PbI is added dropwise on substrate2/MAI1.5/ DMF mixed solution, dosage are 30 μ L/cm2, revolved by 3000r/min speed
30s is applied, 80 DEG C of heating 10min, obtain the MA of non-stoichiometric on hot plate1.5PbI3.5Perovskite thin film A2, thickness
For 450nm.
By measurement XRD spectrum it is found that the perovskite thin film A2 continuous uniform of embodiment preparation, does not contain PbI2With
MAI miscellaneous phase.
Embodiment 3
Perovskite thin film is prepared according to the method for embodiment 1, unlike, it will by the volume ratio of 1:1.1 in step 3
PbI2The mixing of/DMF and MAI/DMF solution.Obtain the MA of non-stoichiometric1.1PbI3.1Perovskite thin film A3, with a thickness of
510nm。
By measurement XRD spectrum it is found that the perovskite thin film A3 continuous uniform of embodiment preparation, contains a small amount of PbI2It is miscellaneous
Phase does not contain MAI miscellaneous phase.
Embodiment 4
Perovskite thin film is prepared according to the method for embodiment 1, unlike, it will by the volume ratio of 1:1.75 in step 3
PbI2The mixing of/DMF and MAI/DMF solution.Obtain the MA of non-stoichiometric1.75PbI3.75Perovskite thin film A4, with a thickness of
400nm。
By measurement XRD spectrum it is found that the perovskite thin film A4 continuous uniform of embodiment preparation, does not contain PbI2It is miscellaneous
Phase contains a small amount of MAI miscellaneous phase.
Comparative example 1
Perovskite thin film is prepared according to the method for embodiment 1, unlike, the volume ratio in step 3 by 1:1 is by PbI2/
The mixing of DMF and MAI/DMF solution.Perovskite thin film D1 is obtained, with a thickness of 520nm.
By measurement XRD spectrum it is found that the perovskite thin film D1 continuous uniform of comparative example preparation, contains a large amount of PbI2It is miscellaneous
Phase does not contain MAI miscellaneous phase.
Comparative example 2
Perovskite thin film is prepared according to the method for embodiment 1, unlike, the volume ratio in step 3 by 1:2 is by PbI2/
The mixing of DMF and MAI/DMF solution.Perovskite thin film D2 is obtained, with a thickness of 350nm.
By measurement XRD spectrum it is found that the perovskite thin film D2 continuous uniform of comparative example preparation, does not contain PbI2It is miscellaneous
Phase contains a large amount of MAI miscellaneous phases.
It can be seen that the embodiment 1-4 using preparation method of the invention with the result of comparative example through the foregoing embodiment
Obtained perovskite thin film performance is better than comparative example 1-2, and the perovskite thin film in embodiment 1-2 does not contain PbI2And MAI
Miscellaneous phase is very beneficial for application in solar cells.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (12)
1. a kind of preparation method of non-stoichiometric perovskite thin film, which is characterized in that this method comprises: halogeno-amine will be contained
The solution of compound and halogenation lead compound is coated on substrate, and is heat-treated;
Wherein, in the solution containing halogenation amine compounds and halogenation lead compound, the halogenation amine compounds and the halogenation
The molar ratio of lead compound is 1:x, wherein 1 < x < 2.
2. the preparation method of non-stoichiometric perovskite thin film according to claim 1, wherein x 1.01-1.9, it is excellent
It is selected as 1.1-1.75, more preferably 1.2-1.5.
3. the preparation method of non-stoichiometric perovskite thin film according to claim 1 or 2, wherein the halogeno-amine
Compound is one of methylpyridinium iodide amine, carbonamidine iodine and methyl chloride amine or a variety of.
4. the preparation method of non-stoichiometric perovskite thin film according to claim 1 or 2, wherein the lead halide
Compound is one of lead iodide, lead bromide and lead chloride or a variety of;
Preferably, the halogenation lead compound is lead iodide.
5. the preparation method of non-stoichiometric perovskite thin film according to claim 1 or 2, wherein described to contain halogen
Changing the solvent in the solution of amine compounds and halogenation lead compound is one of dimethylformamide, dimethyl sulfoxide and isopropanol
Or it is a variety of.
6. the preparation method of non-stoichiometric perovskite thin film described in any one of -5 according to claim 1, wherein logical
It crosses and mixes the solution of halogenation amine compounds with the solution of halogenation lead compound, be made described and contain halogenation amine compounds and halogenation
The solution of lead compound;
Preferably, the solvent in the solution of the halogenation amine compounds is in dimethylformamide, dimethyl sulfoxide and isopropanol
It is one or more;
Preferably, the solvent in the solution of the halogenation lead compound is dimethylformamide and/or dimethyl sulfoxide;
Preferably, the solution of the halogenation amine compounds is identical as the solvent in the solution of the halogenation lead compound.
7. the preparation method of non-stoichiometric perovskite thin film according to claim 6, wherein the halogenation amine compounds
The concentration of halogenation amine compounds is 0.01-1mol/L in the solution of object,
Preferably, the concentration of halogenation amine compounds is 0.05-0.5mol/L in the solution of the halogenation amine compounds;
Preferably, the concentration of halogenation lead compound is 0.01-1mol/L in the solution of the halogenation lead compound,
Preferably, the concentration of halogenation lead compound is 0.05-0.5mol/L in the solution of the halogenation lead compound.
8. the preparation method of non-stoichiometric perovskite thin film described in any one of -5 according to claim 1, wherein will
Solution containing halogenation amine compounds and halogenation lead compound is coated in the method on substrate for spin coating or silk-screen printing, preferably
For spin coating;
Preferably, it is 1000-6000r/min, time 10-60s that the condition of the spin coating, which includes: speed,.
9. the preparation method of non-stoichiometric perovskite thin film described in any one of -5 according to claim 1, wherein institute
It is 60 DEG C -120 DEG C that the condition for stating heat treatment, which includes: temperature, time 1-60min.
10. the preparation method of non-stoichiometric perovskite thin film described in any one of -5 according to claim 1, wherein
The substrate is glass, preferably FTO glass or TiO2Film glass.
11. the non-stoichiometric perovskite that preparation method described in any one of -10 is prepared according to claim 1 is thin
Film.
12. the application of non-stoichiometric perovskite thin film in solar cells described in claim 11.
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