CN115197692A - Surface-treated perovskite nanocrystal and preparation method and application thereof - Google Patents
Surface-treated perovskite nanocrystal and preparation method and application thereof Download PDFInfo
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- CN115197692A CN115197692A CN202210977414.4A CN202210977414A CN115197692A CN 115197692 A CN115197692 A CN 115197692A CN 202210977414 A CN202210977414 A CN 202210977414A CN 115197692 A CN115197692 A CN 115197692A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003446 ligand Substances 0.000 claims abstract description 97
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 76
- 239000002253 acid Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 46
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
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- 239000002243 precursor Substances 0.000 claims description 34
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- 150000001768 cations Chemical class 0.000 claims description 12
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- 239000000203 mixture Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
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- 238000001816 cooling Methods 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
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- 229910001432 tin ion Inorganic materials 0.000 claims description 3
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- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 claims description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
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- 230000000052 comparative effect Effects 0.000 description 16
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 12
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- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 12
- 239000005642 Oleic acid Substances 0.000 description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 11
- 238000005119 centrifugation Methods 0.000 description 9
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- 239000007924 injection Substances 0.000 description 7
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- 238000012360 testing method Methods 0.000 description 6
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- 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 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
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- 239000006185 dispersion Substances 0.000 description 4
- 229940046892 lead acetate Drugs 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YYYDBBHCPOWPBT-UPHRSURJSA-N NCCCCCCCC/C=C\CCCCCCCCBr Chemical compound NCCCCCCCC/C=C\CCCCCCCCBr YYYDBBHCPOWPBT-UPHRSURJSA-N 0.000 description 3
- VDFAFONHYZMTOX-UHFFFAOYSA-N [Sn].[Cs] Chemical compound [Sn].[Cs] VDFAFONHYZMTOX-UHFFFAOYSA-N 0.000 description 3
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- YMXAAHCOIDAUGW-KTKRTIGZSA-N (z)-2-chlorooctadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCC(Cl)C(N)=O YMXAAHCOIDAUGW-KTKRTIGZSA-N 0.000 description 2
- AQQPJNOXVZFTGE-UHFFFAOYSA-N 2-octadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O AQQPJNOXVZFTGE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XPOLVIIHTDKJRY-UHFFFAOYSA-N acetic acid;methanimidamide Chemical compound NC=N.CC(O)=O XPOLVIIHTDKJRY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- XSANTACXJWELAR-UPHRSURJSA-N (z)-18-chlorooctadec-9-en-1-amine Chemical compound NCCCCCCCC\C=C/CCCCCCCCCl XSANTACXJWELAR-UPHRSURJSA-N 0.000 description 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- CTIFKKWVNGEOBU-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O CTIFKKWVNGEOBU-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- IHLDFUILQQSDCQ-UHFFFAOYSA-L C(C)(=O)[O-].[Ge+2].C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[Ge+2].C(C)(=O)[O-] IHLDFUILQQSDCQ-UHFFFAOYSA-L 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- 101100080112 Parietaria judaica PMAI gene Proteins 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- DDQAGDLHARKUFX-UHFFFAOYSA-N acetic acid;methanamine Chemical compound [NH3+]C.CC([O-])=O DDQAGDLHARKUFX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- FFINMCNLQNTKLU-UHFFFAOYSA-N adipiodone Chemical compound OC(=O)C1=C(I)C=C(I)C(NC(=O)CCCCC(=O)NC=2C(=C(C(O)=O)C(I)=CC=2I)I)=C1I FFINMCNLQNTKLU-UHFFFAOYSA-N 0.000 description 1
- UVEJSODIJSXVQE-UHFFFAOYSA-N amino hypoiodite Chemical compound NOI UVEJSODIJSXVQE-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 description 1
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229940029355 iodipamide Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
Abstract
The invention provides a surface-treated perovskite nanocrystal and a preparation method and application thereof. The preparation method comprises the following steps: mixing the perovskite nanocrystalline with a ligand at room temperature, and carrying out ligand exchange reaction to obtain the surface-treated perovskite nanocrystalline; the ligand includes a salt having a sulfonic acid group, or a combination of an acid having a sulfonic acid group and an amine-based compound. The method for preparing the perovskite nanocrystalline is combined with ligand exchange, the amino compound is used for neutralizing the sulfonic acid group-containing acid or the high-stability sulfonic acid group ligand formed by the sulfonic acid group-containing salt is directly used for replacing the original ligand on the surface of the nanocrystalline, so that the lattice binding force between the ligand and the perovskite nanocrystalline can be greatly enhanced, meanwhile, the high-temperature and inert atmosphere environment is not needed in the whole process, the reaction can be carried out at room temperature, the toxic solvent is not needed, and the cost is saved. The perovskite nanocrystal prepared by the method has high stability and strong repeatability, is green and environment-friendly, and can be produced in an enlarged manner.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a surface-treated perovskite nanocrystal and a preparation method and application thereof.
Background
All-inorganic CsPbX 3 The perovskite quantum dots (X = Cl, br, I) have attracted extensive attention due to their advantages of high quantum efficiency, adjustable wavelength, simple synthesis method, high repeatability, and the like. However, perovskite halide materials have poor stability and are particularly sensitive to high temperature environments, which severely limits their applications.
At present, the perovskite nanocrystalline is mostly prepared by a hot injection method, the growth of the perovskite can be controlled by changing the crystal growth direction and the concentration of reactants in the hot injection method, but the reaction is carried out at high temperature, so that high requirements are provided for the uniformity of temperature control, the uniformity of injection reaction and energy consumption, long-chain organic ligands such as oleic acid and oleylamine are required to be used in the process, the long-chain organic ligands are easy to separate from the surface of the perovskite, the quantum efficiency is reduced, and the stability is poor. Therefore, it is difficult to scale up the thermal injection process to obtain high quality products beyond the gram scale for perovskites. In addition, many process strategies for preparing the high-stability perovskite nanocrystalline at normal temperature are developed at present, the normal temperature method is low in cost and high in yield, but most of normal temperature preparation methods still adopt traditional ligands such as oleic acid and oleylamine, the binding force of the ligands and the perovskite lattices is weak, the ligands can fall off after long-time high-temperature environment action, and the stability cannot meet the commercial requirement.
CN110144208A discloses a method for improving APbI 3 A method of perovskite quantum dot efficiency comprising the steps of: APbI prepared by high-temperature thermal injection method 3 Adding a first purification solvent into the quantum dot solution for first purification, and centrifuging to obtain a first precipitate; dispersing the first precipitate in a first organic solvent, addingAdding a second purification solvent and a ligand, and centrifuging again to obtain a second precipitate; re-dispersing the second precipitate in a second organic solvent to obtain purified APbI 3 And (4) quantum dots. The ligand is any one of oleic acid, DDAI, NMAI, PMAI and oleylamine iodide. Although the method passivates defects and improves quantum efficiency, the reaction temperature is required to be above 120 ℃ by a high-temperature thermal injection method, and nitrogen protection is required, so that the method is difficult to amplify and has low yield.
CN 1146569661A discloses a method for preparing perovskite quantum dots by using ricinoleic acid as a solvent and a ligand, which comprises the following steps: dissolving cesium bromide and bismuth bromide in ricinoleic acid, adding octylamine, stirring at normal temperature to form a precursor solution, injecting the precursor solution into an anti-solvent ethanol to obtain Cs 3 Bi 2 Br 9 A quantum dot solution. The method employs oleic acid ligand, and Cs 3 Bi 2 Br 9 The quantum dots have weak bonding force and the stability can not meet the commercial requirement.
Therefore, how to provide a preparation method of the perovskite nanocrystalline at room temperature, which avoids using a heat injection method with high cost and obtains the perovskite nanocrystalline with high stability is a problem to be solved urgently at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a surface-treated perovskite nanocrystal and a preparation method and application thereof. According to the invention, the method for preparing the perovskite nanocrystalline is combined with ligand exchange, the amino compound is used for neutralizing the sulfonic acid group-containing acid or the high-stability sulfonic acid group ligand formed by the sulfonic acid group-containing salt is directly used for replacing the original ligand on the surface of the nanocrystalline, the high-temperature and inert atmosphere environment is not needed in the whole process, the toxic solvent is not needed, the cost is saved, and the prepared perovskite nanocrystalline is high in stability, strong in repeatability, green, environment-friendly and capable of being produced in an enlarged mode.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a surface-treated perovskite nanocrystal, the method comprising:
mixing the perovskite nanocrystalline with a ligand at room temperature, and carrying out ligand exchange reaction to obtain the surface-treated perovskite nanocrystalline;
the ligand includes a salt having a sulfonic acid group, or a combination of an acid having a sulfonic acid group and an amine-based compound.
According to the invention, the perovskite nanocrystal and a specific ligand are mixed, and the perovskite nanocrystal with high stability is prepared through ligand exchange reaction. Wherein, the ligand existing on the surface of the perovskite nanocrystalline can generate ligand exchange reaction with the compound containing sulfonic group in the mixing process; compared with the original ligand on the surface of the perovskite nanocrystal, such as oleic acid or oleylamine and other ligands, the sulfonic acid group adopted by the invention has stronger bonding property with B site ions (such as Pb ions) on the surface of the perovskite nanocrystal, so that a more stable sulfonic acid group ligand can be bonded on the surface of the perovskite nanocrystal. Therefore, the perovskite nanocrystalline prepared by the method has high stability and strong repeatability.
In the invention, the ligand is a sulfonic acid group-containing salt, the sulfonic acid group-containing salt does not need acidic neutralization due to the neutral property, the sulfonic acid group with stronger binding capacity with lead can replace the position of oleic acid to coordinate with lead after ligand exchange reaction, and meanwhile, oleate is generated, and the exchanged sulfonic acid group ligand can improve the stability of the perovskite nanocrystal.
In the invention, for the ligand comprising the combination of the acid containing the sulfonic acid group and the amine compound, the amine compound can perform acid neutralization on the acid containing the sulfonic acid group, so as to prevent the perovskite nanocrystal structure from being damaged due to etching caused by too strong acid and excessive bonding of the sulfonic acid group and the surface atoms of the perovskite nanocrystal.
The method can be carried out at room temperature (25 +/-5 ℃), does not need high temperature, inert gas environment and toxic solvent, so that the cost can be reduced, the effect can be improved, and the method is green, environment-friendly and capable of realizing large-scale production; meanwhile, compared with the method of singly adopting ligands such as oleylamine or oleic acid, the method provided by the invention can also enable the prepared perovskite nanocrystalline to have higher stability.
In the present invention, if the acid containing a sulfonic acid group is not neutralized with an amine compound, the acid will destroy the surface of the perovskite nanocrystal, change the surface structure of the perovskite nanocrystal, and gradually peel off and disintegrate the perovskite nanocrystal from the surface.
Preferably, the sulfonic acid group-containing salt includes a sodium salt and/or a potassium salt containing a sulfonic acid group, preferably sodium dodecylbenzenesulfonate and/or potassium dodecylbenzenesulfonate.
Preferably, the sulfonic acid group-containing acid includes a compound represented by the formula (I):
wherein R is at least one alkyl substituent on the phenyl ring, said alkyl substituent having the general formula C n H 2n+1 N is not greater than 18, e.g., n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17, etc.
Preferably, the amine-based compound includes any one of oleylamine, octylamine, ethylenediamine, or didodecylamine, or a combination of at least two thereof.
Preferably, a combination of an acid having a sulfonic acid group and an amine-based compound is used as a ligand, and the mixing is performed in one or two of the following ways:
the first method is as follows: and respectively adding the acid containing the sulfonic group and the amino compound into the solution of the perovskite nanocrystal, preferably adding the acid containing the sulfonic group into the solution of the perovskite nanocrystal, stirring at 500-1000rpm for 3-15s, and then adding the amino compound.
Preferably, the stirring time for adding the sulfonic acid group-containing acid is 3 to 7 seconds.
Wherein, for example, the stirring rate can be 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, or the like; the stirring time may be 3s, 4s, 5s, 6s, 7s, 8s, 9s, 10s, 11s, 12s, 13s, 14s, 15s, or the like, preferably 3 to 7s.
In the invention, acid containing sulfonic acid group and amino compound are respectively added into the solution of perovskite nanocrystalline, wherein the aim of stirring at 500-1000rpm after adding acid containing sulfonic acid group is to help the acid containing sulfonic acid group and oleic acid ligand on the surface of perovskite nanocrystalline to perform more sufficient replacement reaction through violent stirring, and too large or too small stirring speed can cause insufficient reaction and influence the conversion degree of ligand exchange reaction. Stirring for 3-15s can enable the compound containing sulfonic groups to completely react with the oleic acid ligand on the surface of the perovskite nanocrystal, too little stirring time can cause that the acid containing sulfonic groups does not fully react with the oleic acid ligand on the surface of the perovskite nanocrystal, and too long stirring time can cause that the surface structure of the perovskite nanocrystal is damaged. The acid can be neutralized in time by adding the amino compound after stirring, so that the perovskite nano-crystal is prevented from being damaged.
The second method is as follows: an acid containing a sulfonic acid group and an amine-based compound are mixed, and the resulting mixture is added to a solution of perovskite nanocrystals.
In the invention, in the second mode, the acid containing sulfonic acid groups and the amino compound are mixed in advance, and acid neutralization is carried out firstly, so that the damage of the perovskite nanocrystalline structure caused by over-strong acidity is prevented in advance.
Preferably, a sulfonic acid group-containing salt is used as a ligand, and the mixing is performed in the following manner: the sulfonic acid group-containing salt is directly added to the solution of the perovskite nanocrystal.
In the present invention, a salt having a sulfonic acid group is used as a ligand, since the salt solution contains a cation (e.g., pb) at the B-position 2+ ) The sulfonic acid group ligand with stronger binding capacity can be directly coordinated with the B site cation on the surface of the nanocrystal to replace the original ligand.
Preferably, the solvent in the solution of the perovskite nanocrystal is an organic solvent, preferably any one or a combination of at least two of n-hexane, ethanol, acetone or chloroform.
In the present invention, the type of the solvent in the solution of the perovskite nanocrystal is not limited, and other organic solvents commonly used in the art for preparing perovskite nanocrystals are also suitable for the present invention.
Preferably, the ligand exchange reaction is accompanied by stirring during a period of 0.5 to 5h, preferably 1 to 3h, such as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, or 5h, etc.
In the invention, too short stirring time after the ligand is completely added can cause insufficient ligand exchange reaction, and too long stirring time can finish the reaction, thereby wasting time and causing cost rise.
Preferably, the mass ratio of the perovskite nanocrystal to the sulfonic acid group-containing acid is 1 (0.5-20), preferably 1 (3-10), such as 1.
In the invention, the mass ratio of the perovskite nanocrystal to the sulfonic acid group-containing acid is too large, that is, the perovskite nanocrystal is more, so that oleic acid or oleylamine ligand on the surface of the perovskite nanocrystal is remained, and the stability is influenced; and the mass ratio is too small, so that the sulfonic acid group-containing acid is more, the perovskite nanocrystalline solution contains free sulfonic acid group ligands, and the perovskite nanocrystalline solution can be applied to products only by later cleaning and removal, so that the cost is increased.
Preferably, the molar ratio of the acid containing sulfonic acid groups to the amine-based compound is 1 (0.5-3), such as 1.
In the invention, the molar ratio of the sulfonic acid group-containing acid to the amino compound is too small, the amino compound is remained, and the perovskite nanocrystal is less combined with the stable sulfonic ligand, so that the perovskite nanocrystal is not beneficial to the stability; and when the molar ratio is too large, the excessive acidity is not neutralized, and the crystal structure of the perovskite nanocrystal can be damaged.
Preferably, the perovskite nanocrystal has the general formula ABX 3 。
Preferably, said ABX 3 The cation at position a in (b) includes any one of cesium ion, formamidine ion, or methylamine ion, or a combination of at least two thereof.
Preferably, said ABX 3 The B site cation in (A) includes any one of lead ion, tin ion, bismuth ion or germanium ion or the combination of at least two of the lead ion, the tin ion, the bismuth ion or the germanium ion.
Preferably, said ABX 3 Wherein X is halogen anion, and the halogen anion comprises any one or the combination of at least two of Cl-Br-I.
In the present invention, ABX 3 The perovskite nanocrystal may be, for example, csPbBr 3 、CsPbCl 3 、CsSnCl 3 、CsPbI 3 Or FAPBBr 3 And the like.
As a preferred technical scheme, the preparation method comprises the following steps:
mixing salt containing A site cation, acetate, long-chain organic acid, hexane and propanol to obtain a first precursor solution;
(II) mixing alkylamine compound, halogen acid and propanol, and cooling to room temperature to obtain a second precursor solution;
(III) mixing the first precursor solution and the second precursor solution under the condition of stirring to obtain ABX 3 Perovskite nanocrystals of type;
(IV) dispersing the obtained perovskite nanocrystalline in a solvent, adding an acid containing sulfonic acid groups, stirring for 3-7s at 500-1000rpm, adding an amino compound in 3-10s, continuously stirring for 0.5-3h, and performing centrifugal purification to obtain surface-treated perovskite nanocrystalline, or,
(IV') dispersing the obtained perovskite nano-crystal in a solvent, adding a pre-mixed mixture of an acid containing sulfonic acid groups and an amino compound, continuously stirring for 0.5-5h, and carrying out centrifugal purification to obtain a surface-treated perovskite nano-crystal, or,
(IV') dispersing the obtained perovskite nanocrystal in a solvent, adding a salt containing a sulfonic acid group, continuing stirring for 0.5-5h, and performing centrifugal purification to obtain a surface-treated perovskite nanocrystal.
In the present invention, a salt of a cation at position a such as cesium acetate, formamidine acetate, methylamine acetate or the like, an acetate salt such as lead acetate, tin acetate, bismuth acetate, germanium acetate or the like, a long-chain organic acid such as octanoic acid, heptanoic acid, nonanoic acid or the like, an alkylamine compound such as oleylamine or the like, a hydrohalic acid such as hydrobromic acid, hydrochloric acid, hydroiodic acid or the like, or the like.
In a second aspect, the present invention provides a surface-treated perovskite nanocrystal prepared by the method for preparing a perovskite nanocrystal of the first aspect, wherein the perovskite nanocrystal comprises a perovskite nanocrystal core and a sulfonic ligand;
wherein the sulfonic acid group ligand is coordinated with a B site cation on the surface of the perovskite nanocrystal core, preferably Pb 2+ 。
In a third aspect, the present invention also provides a display device comprising the perovskite nanocrystal of the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the method for preparing the perovskite nanocrystalline is combined with the specific ligand exchange to prepare the surface-treated perovskite nanocrystalline, on one hand, the method can react at room temperature without high temperature and inert gas environment, does not need toxic solvent, saves cost, is green and environment-friendly, and can be used for large-scale production; on the other hand, through ligand exchange reaction, the original ligand on the surface of the nano-crystalline is replaced by the more stable sulfonic ligand, and the lattice binding force between the ligand and the perovskite nano-crystalline is greatly enhanced, so that the stability of the perovskite nano-crystalline is improved, and the repeatability is strong.
(2) After the perovskite nanocrystalline prepared by the method is aged for 13 days at 85 ℃, the quantum efficiency is attenuated to 61% from the initial 83%, and the initial 70% or more can still be retained, namely the retention value is 70% or more.
Drawings
FIG. 1 shows CsPbBr prepared before and after ligand exchange in example 1 3 Perovskite nanocrystal steady state spectroscopy.
FIG. 2 shows CsPbBr before and after ligand exchange provided in example 1 and comparative example 1 3 Aging diagram of perovskite nanocrystal at 85 ℃.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of perovskite nanocrystal, which comprises the following steps:
(1) Preparation of cesium-lead precursor: putting 40mL of isopropanol and 25mL of n-hexane in a conical flask, adding 0.96g (5 mmol) of cesium acetate and 1.90g (5 mmol) of lead acetate trihydrate, then adding 4.75mL of octanoic acid (30 mmol), and stirring until precursor salts are completely dissolved to obtain a cesium-lead precursor solution;
(2) Preparing bromine oleylamine: adding 9.87mL (30 mmol) of oleylamine into 10mL of isopropanol, slowly adding 3.46mL of hydrobromic acid aqueous solution with the purity of 48% (30 mmol) under the condition of stirring, and cooling the mixture to room temperature to obtain bromooleylamine precursor solution;
(3) In the cesium-lead precursor solution, under the condition of rapid stirring (1000 rpm), the bromine oleylamine precursor solution is poured, the mixed solution immediately turns green under room light, which marks the generation of quantum dots, and the reaction is finished after stirring for one minute;
(4) Directly centrifuging the solution after reaction (rotating speed of 7000rpm, time of 10 min); after the centrifugation is finished, removing supernatant, adding the supernatant into the quantum dot precipitate into 50mL of n-hexane, and centrifuging again (rotating speed of 10000rpm, time of 10 min); after the centrifugation, the precipitate was discarded to obtain 50mL of CsPbBr 3 Quantum dot ink dispersion (concentration 20 mg/mL);
(5) To 50mL CsPbBr 3 4.89g (15 mmol) of dodecylbenzene sulfonic acid is added into the quantum dot solution, wherein CsPbBr 3 The mass ratio of the quantum dots to the dodecylbenzene sulfonic acid is 1.89, stirring at 750rpm for 5s, adding 3.65mL (15 mmol) of oleylamine, wherein the molar ratio of the dodecylbenzene sulfonic acid to the oleylamine is 1, and continuing stirring for 2h;
(6) And (3) directly centrifuging the solution after ligand exchange (rotating speed of 10000rpm, time of 10 min) to obtain the perovskite nanocrystalline after ligand exchange.
Example 2
The embodiment provides a preparation method of perovskite nanocrystal, which comprises the following steps:
(1) Preparation of cesium-tin precursor: putting 40mL of isopropanol and 25mL of n-hexane in a conical flask, adding 0.96g (5 mmol) of cesium acetate and 1.90g (5 mmol) of tin acetate trihydrate, then adding 4.75mL of heptanoic acid (30 mmol), and stirring until precursor salts are completely dissolved to obtain a cesium-tin precursor solution;
(2) Preparing chlorooleamide: adding 9.87mL (30 mmol) of oleylamine into 10mL of isopropanol, slowly adding 3.46mL of hydrochloric acid aqueous solution with the purity of 48% (30 mmol) under the condition of stirring, and cooling the mixture to room temperature to obtain chlorooleylamine precursor;
(3) In the cesium-tin precursor solution, under the condition of rapid stirring (800 rpm), chlorooleamide precursor solution is poured, the mixed solution immediately turns green under room light, which marks the generation of quantum dots, and the reaction is finished after stirring for one minute;
(4) Directly centrifuging the solution after reaction (rotating speed of 7000rpm for 10 min); after the centrifugation is finished, discarding supernatant, adding the supernatant into 50mL of ethanol to the quantum dot precipitate, and performing centrifugation again (rotating speed of 10000rpm, time of 10 min); after the centrifugation, the precipitate was discarded to give 50mL of CsSnCl 3 Quantum dot ink dispersion (concentration 20 mg/mL);
(5) To 50mL CsSnCl 3 Adding 1.83mL (7.5 mmol) of octylamine into the quantum dot solution, stirring at 500rpm for 15s, adding 6.15g (15 mmol) of octadecylbenzene sulfonic acid, wherein the molar ratio of the octadecylbenzene sulfonic acid to the octylamine is 1.5, and continuing stirring for 5h;
(6) And (4) directly centrifuging the solution after ligand exchange (the rotating speed is 8000rpm, and the time is 15 min) to obtain the perovskite nanocrystalline after ligand exchange.
Example 3
The embodiment provides a preparation method of perovskite nanocrystals, which comprises the following steps:
(1) Preparation of cesium-lead precursor: putting 40mL of isopropanol and 25mL of n-hexane in a conical flask, adding 0.96g (5 mmol) of cesium acetate and 1.90g (5 mmol) of lead acetate trihydrate, then adding 4.75mL of octanoic acid (30 mmol), and stirring until precursor salts are completely dissolved to obtain a cesium-lead precursor solution;
(2) Preparation of iodipamide: adding 9.87mL (30 mmol) of oleylamine into 10mL of isopropanol, slowly adding 3.46mL of hydriodic acid aqueous solution with the purity of 48% (30 mmol) under the condition of stirring, and cooling the mixture to room temperature to obtain an iodooleylamine precursor solution;
(3) In the cesium-lead precursor solution, under the condition of rapid stirring (1000 rpm), the iodoxylamine precursor solution is poured, the mixed solution immediately turns green under room light, which marks the generation of quantum dots, and the reaction is finished after stirring for one minute;
(4) Directly centrifuging the solution after reaction (rotating speed of 7000rpm for 10 min); after the centrifugation is finished, removing supernatant, adding the supernatant into the quantum dot precipitate into 50mL of acetone, and centrifuging again (rotating speed of 10000rpm, time of 10 min); after the centrifugation, the precipitate was discarded to obtain 50mL of CsPbI 3 Quantum dot ink dispersion (concentration 20 mg/mL);
(5) To 50mL CsPbI 3 11.46g (30 mmol) of dodecylbenzene sulfonic acid is added into the quantum dot solution, wherein CsPbBr is added 3 The mass ratio of the quantum dot to the hexadecyl benzene sulfonic acid is 1.46, stirring at 850rpm for 7s, adding 10.95mL (1545 mmol) of didodecylamine, wherein the molar ratio of the dodecylbenzene sulfonic acid to the didodecylamine is 1.5, and continuing stirring for 3h;
(6) And (4) directly centrifuging the solution after ligand exchange (rotating speed of 5000rpm, time of 20 min) to obtain the perovskite nanocrystalline after ligand exchange.
Example 4
The embodiment provides a preparation method of perovskite nanocrystal, which comprises the following steps:
(1) Preparing a lead formamidine precursor: putting 40mL of isopropanol and 25mL of n-hexane into a conical flask, adding 0.96g (5 mmol) of formamidine acetate and 1.90g (5 mmol) of lead acetate trihydrate, then adding 4.75mL of octanoic acid (30 mmol), and stirring until precursor salt is completely dissolved to obtain a formamidine lead precursor solution;
(2) Preparing bromine oleylamine: adding 9.87mL (30 mmol) of oleylamine into 10mL of isopropanol, slowly adding 3.46mL of hydrobromic acid aqueous solution with the purity of 48% (30 mmol) under the condition of stirring, and cooling the mixture to room temperature to obtain bromooleylamine precursor solution;
(3) In the formamidine lead precursor solution, under the condition of rapid stirring (1500 rpm), the bromooleylamine precursor solution is poured, the mixed solution immediately turns green under room light, which marks the generation of quantum dots, and the reaction is finished after stirring for one minute;
(4) The solution after the reaction was directly centrifuged (7000 rpm, time 10 min). After the centrifugation, the supernatant was discarded, and the quantum dot pellet was added to 50mL of chloroform and centrifuged again (rotation speed 10000rpm, time 10 min). Discarding the precipitate after the centrifugation to obtain 50mL FAPBBr 3 Quantum dot ink dispersion (concentration 20 mg/mL);
(5) To 50mL FAPBR 3 2.45g (7.5 mmol) of dodecyl benzene sulfonic acid is added into the quantum dot solution, wherein CsPbBr 3 The mass ratio of the quantum dot to the dodecylbenzene sulfonic acid is 1.45, stirring at 1000rpm for 3s, adding 3.65mL (15 mmol) of ethylenediamine, wherein the molar ratio of the dodecylbenzene sulfonic acid to the ethylenediamine is 1;
(6) And (4) directly centrifuging the solution after ligand exchange (rotating speed of 3000rpm, time of 30 min) to obtain the perovskite nanocrystalline after ligand exchange.
Example 5
This example differs from example 1 in that, in step (5), 4.89g (15 mmol) of dodecylbenzenesulfonic acid was premixed with 3.65mL of oleylamine (15 mmol), which was then added to 50mL of CsPbBr 3 And stirring the quantum dot solution for 2 hours.
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
This example differs from example 1 in that, in step (5), only 5.22g (15 mmol) of sodium dodecylbenzenesulfonate are added to 50mL of CsPbBr 3 And (4) continuously stirring the quantum dot solution for 2 hours, and centrifuging to obtain a supernatant.
The remaining preparation methods and parameters were in accordance with example 1.
Example 7
This example is different from example 1 in that 4.89g (15 mmol) of dodecylbenzenesulfonic acid was added in step (5) for 1s of stirring.
The remaining preparation methods and parameters were in accordance with example 1.
Example 8
This example is different from example 1 in that 4.89g (15 mmol) of dodecylbenzenesulfonic acid was added in step (5) for 20 seconds.
The remaining preparation methods and parameters were in accordance with example 1.
Example 9
This example differs from example 1 in that in step (5), 0.5g (1.5 mmol) dodecylbenzene sulfonic acid was added to 50mL quantum dot solution, stirring was carried out at 750rpm for 5s, then 0.37mL (1.5 mmol) oleylamine was added, and stirring was continued for 2h. Wherein the mass ratio of the quantum dots to the dodecylbenzene sulfonic acid is 1.
The remaining preparation methods and parameters were in accordance with example 1.
Example 10
This example differs from example 1 in that in step (5) 20g (61 mmol) dodecylbenzene sulphonic acid is added to 50mL quantum dot solution, after stirring for 5s at 750rpm 14.84mL (61 mmol) oleylamine is added and stirring is continued for 2h. Wherein the mass ratio of the quantum dots to the dodecylbenzene sulfonic acid is 1.
The remaining preparation methods and parameters were in accordance with example 1.
Example 11
This example differs from example 1 in that in step (5), 4.89g (15 mmol) of dodecylbenzenesulfonic acid was added to 50mL of quantum dot solution, and after stirring at 750rpm for 5s, 0.37mL (1.5 mmol) of oleylamine was added, and stirring was continued for 2h. Wherein, the mol ratio of the dodecylbenzene sulfonic acid to the oleylamine is 1.
The remaining preparation methods and parameters were in accordance with example 1.
Example 12
This example differs from example 1 in that in step (5) 4.89g (15 mmol) dodecylbenzene sulphonic acid is added to 50mL quantum dot solution, stirring is carried out at 750rpm for 5s, 18.25mL (75 mmol) oleylamine is added and stirring is continued for 2h. Wherein, the mol ratio of the dodecylbenzene sulfonic acid to the oleylamine is 1.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
This comparative example differs from example 1 in that, in step (5), only 3.75mL (15 mmol) of oleylamine was added.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 2
This comparative example differs from example 1 in that, in step (5), only 4.89g (15 mmol) of dodecylbenzenesulfonic acid were added.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 3
The comparative example is different from example 1 in that in step (5), dodecylbenzene sulfonic acid and oleylamine were added and then stirred for 5min.
The remaining preparation methods and parameters were in accordance with example 1.
FIG. 1 shows CsPbBr after ligand exchange provided in example 1 3 The method for testing the quantum efficiency of the perovskite nanocrystal comprises the steps of calibrating an integrating sphere by using a standard luminescent sample rhodamine B before testing, respectively testing a blank control and an emission spectrum of a sample under the 420nm excitation light condition, and calculating the ratio of the number of photons emitted by the sample to the number of photons absorbed by the sample to test the quantum efficiency of the sample.
As can be seen from FIG. 1, the perovskite nanocrystal before ligand exchange had a luminescence peak position of 512nm and a half-peak width of 22nm. The luminescence peak position of the perovskite nanocrystalline after ligand exchange is 511nm, the half-peak width is 21nm, and the luminescence peak position, the half-peak width and the luminescence intensity are not obviously changed, which indicates that the ligand exchange process does not influence the crystal structure of the nanocrystalline. FIG. 2 shows CsPbBr before and after ligand exchange provided in example 1 and comparative example 1 3 The aging data of perovskite nanocrystal at 85 ℃ can show CsPbBr before and after ligand exchange reaction 3 The initial values of the quantum efficiencies of the perovskite nanocrystals were all 83%, the quantum efficiency decreased only to about 61% after aging for 13 days in example 1, and the quantum efficiency decreased to about 30% after aging for 2 days in comparative example 1. With reference to fig. 1 and 2, it can be seen that the stability of the perovskite nanocrystal after ligand exchange is significantly improved.
And (3) performance testing:
the perovskite nanocrystals provided in examples 1 to 12 and comparative examples 1 to 3 were subjected to an aging test at 85 c, and the results are shown in table 1.
TABLE 1
| Retention value of quantum efficiency after aging at 85 ℃ for 13 days (%) | |
| Example 1 | 73.5 |
| Example 2 | 72.7％ |
| Example 3 | 71.2％ |
| Example 4 | 73.4％ |
| Example 5 | 73.4％ |
| Example 6 | 73.6％ |
| Example 7 | 71.8％ |
| Example 8 | 41.2％ |
| Example 9 | 43.2％ |
| Example 10 | 71.5％ |
| Example 11 | 39.5％ |
| Example 12 | 35.1％ |
| Comparative example 1 | Fail after aging |
| Comparative example 2 | Failure in the preparation process |
| Comparative example 3 | 25.2％ |
And (3) analysis:
the data results of examples 1-12 show that the stability of the perovskite nanocrystal can be improved by performing surface treatment on the perovskite nanocrystal by using the sulfonic acid group ligand.
Compared with the data results of the embodiment 1 and the embodiments 5 and 6, the premixing can neutralize the acidity of DBSA in advance, protect the perovskite structure from being damaged, successfully perform ligand exchange, and improve the stability; only the salt containing sulfonic acid group is added, so that the salt can react with the perovskite nanocrystal in the solution, and the stability is improved.
Compared with the data results of the embodiment 7 and the embodiment 8, the data result of the embodiment 1 shows that the stirring time after the sulfonic acid group-containing acid is added is too short, so that the stirring is not uniform, the ligand exchange reaction is not sufficient at the beginning, but the oleylamine is added in time, the stirring is carried out for a long time to create an exchange environment, the original ligand can be successfully replaced, and the stability is improved; and the stirring time is too long, the acidity of the acid containing sulfonic acid groups is not as good as the acidity of the acid containing sulfonic acid groups to be neutralized by the amino compound, so that the surface structure of the nano-crystal is damaged, and the stability of the perovskite nano-crystal is poor.
Compared with the data results of the embodiment 1 and the embodiments 9 and 10, it can be seen that too little acid containing sulfonic acid groups is added, and an effective concentration difference cannot be formed between the added acid groups and the original ligand, so that the sulfonic acid groups cannot effectively act on the surface of the nanocrystal to replace the oleic acid or the oleylamine ligand, and the stability is not obviously improved; and excessive addition of sulfonic acid group-containing acids improves stability, but the excessive free sulfonic acid group ligands in the solution of the nanocrystal need to be removed later to be applied to products, thereby increasing the cost.
Comparing the data of example 1 with those of examples 11 and 12, it can be seen that the addition of too much amine compound leaves amine residue in the solution, which is not favorable for the stability of perovskite nanocrystals; when the amount of the added amine compound is too small, the excess acidity in the sulfonic acid group-containing acid is hardly neutralized, and the structure of the perovskite nanocrystal is destroyed, thereby lowering the stability.
Comparing the data results of example 1 and comparative example 1, it can be seen that the perovskite nanocrystal is poor in stability and fails in luminescence due to the weak binding capacity of the oleylamine ligand, which is obtained by adding only the same amount of oleylamine without performing ligand exchange with the more stable sulfonic acid group ligand.
Comparing the data results of example 1 and comparative example 2, it can be seen that only the acid containing sulfonic acid group is added, and the amine compound is not added to neutralize the acidity, and the stronger acidity can damage the structure of the perovskite nanocrystal, resulting in failure of the perovskite nanocrystal.
Comparing the data of example 1 with the data of comparative example 3, it can be seen that too short stirring time may result in insufficient ligand exchange time and incomplete exchange, and thus may not improve the stability of the perovskite nanocrystal.
In conclusion, the invention combines the method for preparing the perovskite nanocrystal with the exchange of specific ligands to obtain the perovskite nanocrystal with surface treatment, on one hand, the method can react at room temperature,the environment of high temperature and inert gas is not needed, toxic solvent is not needed, the cost is saved, and the environment is protected, and the scale-up production can be realized; on the other hand, through ligand exchange reaction, the original ligand on the surface of the nanocrystalline is replaced by the more stable sulfonic acid group ligand, so that the bonding between the sulfonic acid group ligand and the B site cation on the surface of the nanocrystalline, such as Pb ion, is firmer, the stability of the perovskite nanocrystalline is improved, and the repeatability is strong. Compared with the perovskite nanocrystalline which is not subjected to ligand exchange, the perovskite nanocrystalline with the surface treatment provided by the invention has the advantages that the emission peak position slightly shifts, the emission peak position, the half-peak width and the emission intensity are not obviously changed, and the ligand exchange process does not influence the crystal structure of the nanocrystalline. Further, when dodecylbenzenesulfonic acid and oleylamine were added in this order, the resulting surface-treated CsPbBr was obtained 3 The efficiency of the perovskite nanocrystalline can still be kept above 70% after being aged for 13 days at 85 ℃, and the quantum efficiency is reduced by about 60% after only adding oleylamine and being aged for 2 days. Therefore, the stability of the surface-treated perovskite nanocrystal provided by the invention is obviously improved.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing a surface-treated perovskite nanocrystal, characterized by comprising:
mixing the perovskite nanocrystalline with a ligand at room temperature, and carrying out ligand exchange reaction to obtain the surface-treated perovskite nanocrystalline;
the ligand includes a salt having a sulfonic acid group, or a combination of an acid having a sulfonic acid group and an amine-based compound.
2. The method for producing a perovskite nanocrystal according to claim 1, wherein the salt having a sulfonic acid group comprises a sodium salt and/or a potassium salt having a sulfonic acid group, preferably sodium dodecylbenzenesulfonate and/or potassium dodecylbenzenesulfonate;
preferably, the sulfonic acid group-containing acid includes a compound represented by the formula (I):
wherein R is at least one alkyl substituent on the benzene ring, the alkyl substituent has a general formula C n H 2n+1 N is not greater than 18;
preferably, the amine-based compound includes any one of oleylamine, octylamine, ethylenediamine, or didodecylamine, or a combination of at least two thereof.
3. The production method of a perovskite nanocrystal as claimed in claim 1 or 2, characterized in that a combination of an acid containing a sulfonic acid group and an amine-based compound is used as a ligand, and the mixing is performed in one or two of the following ways:
the first method is as follows: respectively adding an acid containing sulfonic acid groups and an amino compound into the solution of the perovskite nanocrystalline, preferably adding the acid containing the sulfonic acid groups into the solution of the perovskite nanocrystalline, stirring at the rotating speed of 500-1000rpm for 3-15s, and then adding the amino compound;
preferably, the stirring time for adding the sulfonic acid group-containing acid is 3 to 7s;
the second method is as follows: an acid containing a sulfonic acid group and an amine-based compound were mixed, and the resulting mixture was added to a solution of perovskite nanocrystals.
4. A process for the preparation of perovskite nanocrystals according to any one of claims 1 to 3, characterized in that salts containing sulfonic acid groups are used as ligands and the mixing is carried out in the following way:
the sulfonic acid group-containing salt is directly added to the solution of the perovskite nanocrystal.
5. The production method according to any one of claims 1 to 4, wherein the solvent in the solution of the perovskite nanocrystal is an organic solvent, preferably any one or a combination of at least two of n-hexane, ethanol, acetone or chloroform;
preferably, the ligand exchange reaction is accompanied by stirring, and the stirring time is 0.5-5h, preferably 1-3h.
6. The production method of perovskite nanocrystals according to any one of claims 1 to 5, characterized in that the mass ratio of the perovskite nanocrystals to the sulfonic acid group-containing acid is 1 (0.5 to 20), preferably 1 (3 to 10);
preferably, the molar ratio of the acid containing the sulfonic acid group to the amine-based compound is 1 (0.5-3).
7. The perovskite nanocrystal prepared by the preparation method according to any one of claims 1 to 6, wherein the perovskite nanocrystal has a general formula ABX 3 ；
Preferably, said ABX 3 The cation at the A position in (a) comprises any one or a combination of at least two of cesium ion, formamidine ion or methylamine ion;
preferably, said ABX 3 The B site cation in (A) comprises any one or the combination of at least two of lead ion, tin ion, bismuth ion or germanium ion;
preferably, said ABX 3 Wherein X is halogen anion, and the halogen anion comprises any one or the combination of at least two of Cl-Br-I.
8. The method of any one of claims 1 to 7, comprising the steps of:
mixing salt containing A site cations, acetate, long-chain organic acid, hexane and propanol to obtain a first precursor solution;
(II) mixing alkylamine compound, halogen acid and propanol, and cooling to room temperature to obtain a second precursor solution;
(III) mixing the first precursor solution and the second precursor solution under the stirring condition to obtain ABX 3 Perovskite nanocrystals of type;
(IV) dispersing the obtained perovskite nanocrystalline in a solvent, adding an acid containing sulfonic acid groups, stirring at the rotating speed of 500-1000rpm for 3-15s, adding an amino compound, continuously stirring for 0.5-5h, centrifuging and purifying to obtain surface-treated perovskite nanocrystalline, or,
(IV') dispersing the obtained perovskite nanocrystalline in a solvent, adding a pre-mixed mixture of acid containing sulfonic acid groups and amino compounds, continuously stirring for 0.5-5h, and carrying out centrifugal purification to obtain surface-treated perovskite nanocrystalline, or,
(IV') dispersing the obtained perovskite nanocrystal in a solvent, adding a salt containing a sulfonic acid group, continuing stirring for 0.5-5h, and performing centrifugal purification to obtain a surface-treated perovskite nanocrystal.
9. A perovskite nanocrystal produced by the production method according to any one of claims 1 to 8, comprising a perovskite nanocrystal core and a sulfonic ligand;
wherein the sulfonic acid group ligand is coordinated with the B site cation on the surface of the perovskite nanocrystal core, preferably Pb 2+ 。
10. A display device, characterized in that the display device comprises the perovskite nanocrystal of claim 9.
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| CN114410292A (en) * | 2022-01-11 | 2022-04-29 | 北京交通大学 | Preparation method of passivated inorganic perovskite nanocrystalline |
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