CN116607200A - Halogen perovskite single crystal material and preparation method and application thereof - Google Patents
Halogen perovskite single crystal material and preparation method and application thereof Download PDFInfo
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- CN116607200A CN116607200A CN202310568273.5A CN202310568273A CN116607200A CN 116607200 A CN116607200 A CN 116607200A CN 202310568273 A CN202310568273 A CN 202310568273A CN 116607200 A CN116607200 A CN 116607200A
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- 239000013078 crystal Substances 0.000 title claims abstract description 90
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 28
- 150000002367 halogens Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000012258 culturing Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- -1 halogen salt Chemical class 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 description 7
- 238000011218 seed culture Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001161 time-correlated single photon counting Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- 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
- H10K30/50—Photovoltaic [PV] devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- 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
Abstract
The application provides a halogen perovskite single crystal material, a preparation method and application thereof. The preparation method of the halogen perovskite single crystal material comprises the following steps: s1: dissolving halogen salt in solvent, heating, cooling, crystallizing, and growing small blocks of FAPbBr in solution (3‑X) I (X) Single crystal, x=0-2; s2: removal of FAPbBr from solution (3‑X) I (X) Single crystal, filtering the solution, adding 1-2 FAPbBr into the filtered solution (3‑X) I (X) And (3) culturing the single crystal until the single crystal grows to a preset size, and taking out to obtain the halogen perovskite single crystal material. The halogen perovskite single crystal material of the application has large single crystal size,The monocrystal quality is good, the luminous intensity is high, and the practical application value is high.
Description
Technical Field
The application relates to the technical field of perovskite, in particular to a halogen perovskite single crystal material, a preparation method and application thereof.
Background
Halogen perovskite is a semiconductor material with excellent performance, has the advantages of large light absorption coefficient, adjustable direct band gap, high carrier mobility, high defect tolerance, simple preparation and the like, and is widely applied to solar cells, lasers, light-emitting diodes, photodetectors, hydrogen production and the like. The perovskite materials are regulated and controlled by adopting different kinds of ions, so that the band gap of the perovskite materials can be effectively regulated and controlled, the absorption and luminous characteristics of the materials are affected, and the perovskite materials have important application in the fields of solar cells and luminous devices.
The perovskite single crystal surface is easily influenced by a preparation method or a working environment, so that various defects, such as vacancy defects, doping defects and other structural point defects, appear; meanwhile, perovskite single crystals are also easily affected by oxygen, water vapor and solar light in the air, so that the surface structure of the single crystals is changed, and the performance of devices is further affected. Therefore, there is a need to develop a method for growing high quality single crystals to minimize various defects of the single crystals and adverse effects caused by oxygen, water vapor, and the like.
In view of this, the present application has been made.
Disclosure of Invention
The application aims to provide a halogen perovskite single crystal material, a preparation method and application thereof, and the halogen perovskite single crystal material has the advantages of large single crystal size, good single crystal quality, high luminous intensity and stronger practical application value.
The application provides a preparation method of a halogen perovskite single crystal material, which comprises the following steps:
s1: dissolving halogen salt in solvent, heating, cooling, crystallizing, and growing small blocks of FAPbBr in solution (3-X) I (X) Single crystal, x=0-2;
s2: removal of FAPbBr from solution (3-X) I (X) Single crystal, filtering the solution, adding 1-2 FAPbBr into the filtered solution (3-X) I (X) And (3) culturing the single crystal until the single crystal grows to a preset size, and taking out to obtain the halogen perovskite single crystal material.
In the present application, FAPbBr (3-X) I (X) The single crystal may be FAPbBr 3 Single crystal, FAPbBr 2 I single crystal or FAPbBrI 2 A single crystal; the solvent can be GBL or a mixed solvent of GBL and DMF, and the volume ratio of GBL to DMF in the mixed solvent is (3-5): 1, a step of; the heating temperature is 55-65 ℃, and the heating time is 1-10d; the concentration of the halogen salt in the solution is 0.6-1mol/L.
In the preparation of FAPbBr 3 In the case of single crystals, step S1 comprises: FABr and PbI 2 According to the mole ratio of 1:1 is dissolved in GBL, heated at 55-65 ℃ for 1-3d, then cooled for crystallization, and small blocks of FAPbBr are grown in the solution 3 And (3) single crystals.
In the preparation of FAPbBr 2 In the case of I single crystal, step S1 includes: FAI, pbI 2 、FABr、PbBr 2 According to the mole ratio of 1:1:2:2 dissolving in a mixed solvent of GBL and DMF, heating at 55-65deg.C for 4-6d, cooling for crystallization, and growing small blocks of FAPbBr in the solution 2 I single crystal.
In the preparation of FAPbBrI 2 In the case of single crystals, step S1 comprises: FAI, pbI 2 、FABr、PbBr 2 According to the mole ratio of 2:2:1:1 is dissolved in GBL, heated at 55-65deg.C for 8-10d, then cooled to crystallize, and small pieces of FAPbBri are grown in the solution 2 And (3) single crystals.
In step S2, the single crystal material of halogen perovskite may be stored in a nitrogen atmosphere after being taken out.
The application also provides a halogen perovskite single crystal material which is prepared according to the preparation method.
The application also provides application of the halogen perovskite single crystal material in a solar cell.
According to the preparation method, the small perovskite single crystal is separated out by a method of increasing the solution temperature to reduce the solubility through the reverse temperature crystallization method and the seed culture method, and then the large perovskite single crystal is grown by the seed culture method, so that the prepared halogen perovskite single crystal material has large single crystal size, good single crystal quality and high luminous intensity, various defects of the single crystal and adverse effects caused by oxygen, water vapor and the like can be reduced, and the preparation method has a relatively high practical application value.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a morphology of the single crystal of halogen perovskite prepared in examples 1-3; wherein: a is FAPbBr 3 Single crystal, b is FAPbBr 2 I single crystal, c is FAPbBrI 2 A single crystal;
FIG. 2 is a TRPL spectrum of the halogen perovskite single crystal prepared in example 1-3; wherein: a is FAPbBr 3 TRPL spectrum of single crystal, b is FAPbBr 2 TRPL spectrum of 605nm peak position of I single crystal, c is FAPbBr 2 TRPL spectrum of 750nm peak position of I single crystal, d is FAPbBrI 2 TRPL spectrum of single crystal 750nm peak position.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular forms also include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present application will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The preparation method of the halogen perovskite single crystal material comprises the following steps:
s1: crystallization at reverse temperature
FABr and PbI 2 According to the mole ratio of 1:1 is dissolved in GBL, the molar concentration of the solution is controlled to be 0.8mol/L, the mixture is heated for 2d at 60 ℃, then cooled and crystallized, and small blocks of FAPbBr are grown in the solution 3 And (3) single crystals.
S2: seed culture
Removing FAPbBr from the solution crystallized in step S1 3 Single crystal, then filtering the solution, adding 1 FAPbBr into the filtered solution 3 Culturing the single crystal, and taking out the single crystal to obtain square regular brown red FAPbBr with the thickness of about 5mm multiplied by 5mm 3 Single crystals (see a of fig. 1).
Example 2
The preparation method of the halogen perovskite single crystal material comprises the following steps:
s1: crystallization at reverse temperature
FAI, pbI 2 、FABr、PbBr 2 According to the mole ratio of 1:1:2:2 is dissolved in a mixed solvent of GBL and DMF, wherein the volume ratio of GBL to DMF in the mixed solvent is 4:1, controlling the molar concentration of the solution to be 0.8mol/L, heating for 5d at 60 ℃, then cooling and crystallizing to grow small blocks of FAPbBr in the solution 2 I single crystal.
S2: seed culture
Removing FAPbBr from the solution crystallized in step S1 2 I single crystal, then filtering the solution, adding 1 FAPbBr into the filtered solution 2 Culturing the I single crystal, and taking out the single crystal after culturing to obtain the square red brown FAPbBr with the thickness of about 3mm multiplied by 3mm 2 I single crystal (see b of FIG. 1).
Example 3
The preparation method of the halogen perovskite single crystal material comprises the following steps:
s1: crystallization at reverse temperature
FAI, pbI 2 、FABr、PbBr 2 According to the mole ratio of 2:2:1:1 in GBL, controlling the molar concentration of the solution to be 0.8mol/L, heating at 60 ℃ for 9d, cooling and crystallizing to grow small blocks of FAPbBri in the solution 2 And (3) single crystals.
S2: seed culture
Removing FAPbBri from the solution crystallized in step S1 2 Single crystals, followed by filtering the solution, adding 1 FAPbBri to the filtered solution 2 Culturing the single crystal, and taking out the single crystal to obtain black irregular FAPbBri with a thickness of about 2mm×2mm 2 Single crystals (see c of fig. 1).
Test example 1
Transient fluorescence lifetimes of FAPbBr3, FAPbBr2I and FAPbBrI2 single crystals prepared in examples 1-3 were tested using TCSPC method and the results are shown in fig. 2.
As can be seen from FIG. 2, FAPbBr 3 Has a fluorescence lifetime of 426.41ns, FAPbBr 2 The fluorescence lifetime of the 605nm peak position of I is 15.61ns, FAPbBr 2 The fluorescence lifetime of the peak position of I at 750nm is 86.14ns, FAPbBrI 2 The fluorescence lifetime at the 750nm peak position of (2) was 447.74ns.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (10)
1. The preparation method of the halogen perovskite single crystal material is characterized by comprising the following steps of:
s1: dissolving halogen salt in solvent, heating, cooling, crystallizing, and growing small blocks of FAPbBr in solution (3-X) I (X) Single crystal, X＝0-2；
S2: removal of FAPbBr from solution (3-X) I (X) Single crystal, filtering the solution, adding 1-2 FAPbBr into the filtered solution (3-X) I (X) And (3) culturing the single crystal until the single crystal grows to a preset size, and taking out to obtain the halogen perovskite single crystal material.
2. The method of claim 1, wherein FAPbBr (3-X) I (X) Single crystal of FAPbBr 3 Single crystal, FAPbBr 2 I single crystal or FAPbBrI 2 And (3) single crystals.
3. The preparation method according to claim 1, wherein the solvent is GBL or a mixed solvent of GBL and DMF, and the volume ratio of GBL to DMF in the mixed solvent is (3-5): 1.
4. the preparation method according to claim 1, wherein the heating temperature is 55-65 ℃ and the heating time is 1-10d; the concentration of the halogen salt in the solution is 0.6-1mol/L.
5. The method of claim 1, wherein step S1 comprises: FABr and PbI 2 According to the mole ratio of 1:1 is dissolved in GBL, heated at 55-65 ℃ for 1-3d, then cooled for crystallization, and small blocks of FAPbBr are grown in the solution 3 And (3) single crystals.
6. The method of claim 1, wherein step S1 comprises: FAI, pbI 2 、FABr、PbBr 2 According to the mole ratio of 1:1:2:2 dissolving in a mixed solvent of GBL and DMF, heating at 55-65deg.C for 4-6d, cooling for crystallization, and growing small blocks of FAPbBr in the solution 2 I single crystal.
7. The method of claim 1, wherein step S1 comprises: FAI, pbI 2 、FABr、PbBr 2 According to the mole ratio of 2:2:1:1 dissolution in GBLHeating at 55-65deg.C for 8-10d, cooling and crystallizing to grow small pieces of FAPbBri in solution 2 And (3) single crystals.
8. The method according to claim 1, wherein in step S2, the single crystal material of halogen perovskite is stored in a nitrogen atmosphere after being taken out.
9. A halogen perovskite single crystal material, characterized by being produced according to the production method as claimed in any one of claims 1 to 8.
10. Use of the halogen perovskite single crystal material as claimed in claim 9 in solar cells.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310568273.5A CN116607200A (en) | 2023-05-18 | 2023-05-18 | Halogen perovskite single crystal material and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310568273.5A CN116607200A (en) | 2023-05-18 | 2023-05-18 | Halogen perovskite single crystal material and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN116607200A true CN116607200A (en) | 2023-08-18 |
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| CN202310568273.5A Pending CN116607200A (en) | 2023-05-18 | 2023-05-18 | Halogen perovskite single crystal material and preparation method and application thereof |
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- 2023-05-18 CN CN202310568273.5A patent/CN116607200A/en active Pending
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