CN113684024B - Composite metal halide modified halogen perovskite quantum dot and preparation method thereof - Google Patents
Composite metal halide modified halogen perovskite quantum dot and preparation method thereof Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 118
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 94
- 150000002367 halogens Chemical class 0.000 title claims abstract description 94
- 229910001507 metal halide Inorganic materials 0.000 title claims abstract description 48
- 150000005309 metal halides Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 23
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 12
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 230000001737 promoting effect Effects 0.000 claims description 3
- -1 aluminum halide Chemical class 0.000 abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 abstract description 27
- 239000013110 organic ligand Substances 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 66
- 238000000034 method Methods 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- WLCFKPHMRNPAFZ-UHFFFAOYSA-M didodecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC WLCFKPHMRNPAFZ-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- WQSSOMOMZAESQE-UHFFFAOYSA-M CC1=CC=CC=C1.[Br-].C(CCCCCCCCCCC)[N+](C)(C)CCCCCCCCCCCC Chemical compound CC1=CC=CC=C1.[Br-].C(CCCCCCCCCCC)[N+](C)(C)CCCCCCCCCCCC WQSSOMOMZAESQE-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical compound [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
Abstract
The invention discloses a composite metal halide modified halogen perovskite quantum dot and a preparation method thereof, wherein the preparation method comprises the following steps: providing a halogen perovskite quantum dot solution, an organic ligand solution, aluminum halide and divalent metal halide; adding the organic ligand solution, aluminum halide and divalent metal halide into the halogen perovskite quantum dot solution, and stirring for reaction to obtain the composite metal halide modified halogen perovskite quantum dot. According to the invention, the original ligand of the halogen perovskite quantum dot is replaced by the organic ligand, and meanwhile, the pure-color halogen perovskite quantum dot with excellent optical performance and good stability, in particular the blue light-emitting halogen perovskite quantum dot, is realized by the aluminum halide and the divalent metal halide, and the halogen perovskite quantum dot can be applied to preparing high-efficiency stable photoelectric devices.
Description
Technical Field
The invention relates to the field of quantum dots, in particular to a composite metal halide modified halogen perovskite quantum dot and a preparation method thereof.
Background
The halogen perovskite quantum dot has various excellent performances, such as direct band gap, high fluorescence quantum efficiency, high luminous color purity, adjustable luminous color, large light absorption coefficient, large carrier mobility, high defect tolerance, convenience in synthesis and the like, so that the halogen perovskite quantum dot has great potential in practical applications of photoelectric devices such as displays, photoluminescence diodes, electroluminescent diodes, solar cells, photodetectors, semiconductor lasers and the like.
The synthesis method of the halogen perovskite quantum dot comprises a hot injection method, a ligand-assisted coprecipitation method and a ball milling method. In general, organic ligands such as oleic acid, oleylamine, etc. are added in the synthesis of halogen perovskite quantum dots, on the one hand, for passivating the surface defects of the quantum dots and, on the other hand, for avoiding the agglomeration of the quantum dots. However, the organic ligands used in these syntheses are poor in conductivity on the one hand and unstable in binding on the surface of the halogen perovskite quantum dots on the other hand, so that the stability of the halogen perovskite quantum dots is poor, and particularly the stability of the blue light halogen perovskite quantum dots of pure chlorine-based or chlorine-bromine mixed halogen is worse, which is unfavorable for preparing efficient and stable photoelectric devices. Therefore, further modification treatment such as cleaning, ligand replacement, surface passivation and the like is generally required for synthesizing the halogen perovskite quantum dots, so that the halogen perovskite quantum dots with higher fluorescence quantum yield, better conductivity and better stability are obtained.
The halogen substitution can change the green light-emitting halogen perovskite quantum dot which is relatively easy to synthesize into a quantum dot which emits blue light or red light in the post-treatment of the quantum dot, but the commonly obtained mixed halogen perovskite quantum dot has poor stability and is easy to split phases when being used for photoelectric devices. The doped metal element can enhance the stability of the halogen perovskite quantum dot, for example, when the bromine perovskite quantum dot is synthesized by adopting a thermal injection method, aluminum bromide is added to partially replace lead ions, so that the halogen perovskite quantum dot with improved thermal stability is obtained, but the synthesis method cannot obtain the pure-color perovskite quantum dot. The pure-color halogen perovskite quantum dots with excellent optical performance and good stability, in particular to blue light-emitting halogen perovskite quantum dots, have quite great difficulty. Accordingly, the prior art is still in need of improvement.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a composite metal halide modified halogen perovskite quantum dot and a preparation method thereof, which aims to solve the problems set forth in the above-mentioned background art.
The technical scheme of the invention is as follows:
the preparation method of the composite metal halide modified halogen perovskite quantum dot comprises the following steps:
providing a halogen perovskite quantum dot solution, an organic ligand solution, aluminum halide and divalent metal halide;
adding the organic ligand solution, aluminum halide and divalent metal halide into the halogen perovskite quantum dot solution, and stirring for reaction to obtain the composite metal halide modified halogen perovskite quantum dot.
Further, the halogen in the halogen perovskite quantum dot, the halogen in the aluminum halide, and the halogen in the divalent metal halide may be the same or different.
Further, the metal element in the divalent metal halide contains Zn 2+ 、Mg 2+ 、Mn 2+ 、Cu 2+ 、Cd 2+ Or Ni 2 + 。
Further, the molar ratio of the aluminum halide to the divalent metal element in the halogen perovskite quantum dot is 0.02 to 1.
Further, the ratio of the molar amount of the metal element in the divalent metal halide to the molar amount of the divalent metal element in the halogen perovskite quantum dot is 0.02 to 0.7.
Further, the organic ligand in the organic ligand solution is one or more organic molecules different from the perovskite quantum dot original ligand, including but not limited to one or more of an ammonium halide group, a sulfonic acid group, a phosphoric acid group, including but not limited to didodecyl dimethyl ammonium bromide or didodecyl dimethyl ammonium chloride.
Further, the aluminum halide and the divalent metal halide may be partially or completely dissolved in the organic ligand solution.
Further, the stirring reaction time after the organic ligand solution, aluminum halide and divalent metal halide are added to the halogen perovskite quantum dot solution is not less than 2 minutes.
Further, the molecular formula of the perovskite quantum dot is ABX 3 Wherein A includes but is not limited to CH 3 NH 3+ 、HC(NH 2 ) 2+ Or Cs + One or more of Pb or Sn, and one or two of Cl, br or I.
The beneficial effects are that: the invention provides a composite metal halide modified halogen perovskite quantum dot and a preparation method thereof, which are based on the existing halogen perovskite quantum dot and are modified and optimized through simple and easy-to-operate post-treatment. The original ligand of the halogen perovskite quantum dot is replaced by the organic ligand, and meanwhile, pure-color halogen perovskite quantum dot with excellent optical performance and good stability, in particular blue light-emitting halogen perovskite quantum dot, is realized by aluminum halide and divalent metal halide, and the halogen perovskite quantum dot can be applied to preparation of efficient and stable photoelectric devices.
Drawings
FIG. 1 is a flow chart of a method for preparing a complex metal halide modified halogen perovskite quantum dot of the present invention.
Fig. 2 is a luminescence spectrum of the modified halogen perovskite quantum dot obtained in example 2 of the present invention.
Detailed Description
The invention provides a composite metal halide modified halogen perovskite quantum dot and a preparation method thereof, which are used for making the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the detailed description is presented by way of example only and is not intended to limit the invention.
FIG. 1 is a flow chart showing a method for preparing a composite metal halide modified halogen perovskite quantum dot according to the invention, wherein the method comprises the following steps:
s10, providing a halogen perovskite quantum dot solution, an organic ligand solution, aluminum halide and divalent metal halide;
and S20, adding the organic ligand solution and the divalent metal halide into the halogen perovskite quantum dot solution, and stirring for reaction to obtain the composite metal halide modified halogen perovskite quantum dot.
In some embodiments, the halogen perovskite quantum dot solution may be a quantum dot solution synthesized by methods including, but not limited to, thermal injection methods, ligand-assisted co-precipitation methods, ball milling methods, and the like. The solvent of the halogen perovskite quantum dot solution may include, but is not limited to, non-polar organic solvents such as toluene, hexane, octane, and the like. The halogen perovskite quantum dots in the halogen perovskite quantum dot solution can be all-inorganic halogen perovskite quantum dots or organic-inorganic hybrid halogen perovskite quantum dots. For example, the halogen perovskite quantum dot solution can be CH (NH) synthesized by a hot injection method and taking octane as a solvent 2 ) 2 PbBr 3 Quantum dot solution. For another example, the halogen perovskite quantum dot solution may be synthesized by ligand-assisted co-precipitation method using toluene as solvent (CH 3 NH 3 ) x Cs 1-x PbBr1 .5 Cl 1.5 Quantum dot solution.
In some embodiments, the halogen in the halogen perovskite quantum dot, the halogen in the aluminum halide, and the halogen in the divalent metal halide may be the same or different. The aluminum halide is AlBr 3 、AlCl 3 、AlI 3 One or two of them. For example, the halogen perovskite quantum dot is CsPbCl 3 The aluminum halide is AlCl 3 The divalent metal halide is a divalent metal chloride. For another example, the halogen perovskite quantum dot is CH 3 NH 3 PbBr 3 The aluminum halide is AlBr 3 The divalent metal halide may be a divalent metal chloride or a divalent metal bromide.
In some embodiments, the metal element in the divalent metal halide comprises Zn 2+ 、Mg 2+ 、Mn 2+ 、Cu 2+ 、Cd 2 + Or Ni 2+ . For example, the divalent metal halide may include, but is not limited to, znBr 2 、ZnCl 2 、MgBr 2 、MgCl 2 、MgI 2 、MnBr 2 、MnCl 2 、MnI 2 、CuBr 2 、CuCl 2 、CdBr 2 、CdCl 2 、NiBr 2 、NiCl 2 Etc.
In some embodiments, the molar amount of aluminum halide to the molar amount of divalent metal element in the halogen perovskite quantum dot is 0.02 to 1. For example, the halogen perovskite quantum dot is CsPbBr 1.5 Cl 1.5 The aluminum halide is AlBr 3 Then AlBr 3 The molar amount of (C) may be CsPbBr 1.5 Cl 1.5 Or synthesizing CsPbBr 1.5 Cl 1.5 50% of the molar amount of the lead element used. For another example, the halogen perovskite quantum dot is CH 3 NH 3 PbBr 3 The aluminum halide is AlCl 3 Then AlCl 3 The molar amount of (2) may be (CH (NH) 2 ) 2 ) x Cs 1-x Br 3 Or synthesis (CH (NH) 2 ) 2 ) x Cs 1-x Br 3 90% of the molar amount of the lead element used. For another example, the halogen perovskite quantum dot is CH 3 NH 3 PbI 3 The aluminum halide is AlBr 3 And AlCl 3 AlBr, then 3 And AlCl 3 The total molar amount may be CH 3 NH 3 PbI 3 Or synthesizing CH 3 NH 3 PbI 3 The molar amount of lead element used was 0.5%.
In some embodiments, the molar ratio of the metal element in the divalent metal halide to the molar amount of the divalent metal element in the halogen perovskite quantum dot is 0.02 to 0.7. For example, the halogen perovskite quantum dot is CsPbBr 1.5 Cl 1.5 The divalent metal halide is ZnBr 2 Then ZnBr 2 The molar amount of (C) may be CsPbBr 1.5 Cl 1.5 Or synthesizing CsPbBr 1.5 Cl 1.5 The molar amount of lead element used was 10%. For another example, the halogen perovskite quantum dot is CH 3 NH 3 PbBr 3 The divalent metal halide is CuCl 2 Then CuCl 2 The molar amount of (2) may be (CH (NH) 2 ) 2 ) x Cs 1-x Br 3 Or synthesis (CH (NH) 2 ) 2 ) x Cs 1-x Br 3 60% of the molar amount of the lead element used. For another example, the halogen perovskite quantum dot is CH 3 NH 3 PbI 3 The divalent metal halide is MnI 2 Then MnI 2 The molar quantity of (C) can be CH 3 NH 3 PbI 3 Or synthesizing CH 3 NH 3 PbI 3 The molar amount of the lead element used was 0.1%.
In some embodiments, the molar amount of aluminum halide may be less than, equal to, or greater than the molar amount of metal element in the divalent metal halide.
In some embodiments, the organic ligand in the organic ligand solution is one or more organic molecules that are different from the perovskite quantum dot original ligand. The organic molecules include, but are not limited to, one or more of ammonium halide groups, sulfonic acid groups, and phosphoric acid groups. The ammonium halide groups include, but are not limited to, didodecyl dimethyl ammonium bromide or didodecyl dimethyl ammonium chloride. Solvents for the organic ligand solution include, but are not limited to, toluene, hexane, octane, and the like. For example, the original ligands of the perovskite quantum dots are oleic acid molecules and oleylamine molecules, and the organic ligand solution may be a toluene solution in which didodecyl dimethyl ammonium bromide and didodecyl dimethyl ammonium chloride are dissolved. For another example, the original ligand of the perovskite quantum dot is oleic acid molecules, and the organic ligand solution may be a toluene solution in which sodium benzenesulfonate or sodium alkylbenzenesulfonate is dissolved.
In some embodiments, the aluminum halide and the divalent metal halide may be partially or fully dissolved in the organic ligand solution, and the organic ligand solution and the aluminum halide and the divalent metal halide may be added to the halogen perovskite quantum dot solution simultaneously or after mixing. For example, the aluminum halide and divalent metal halide may be added to the didodecyl dimethyl ammonium bromide solution to form a clear solution or suspension, which is then added to the halogen perovskite quantum dot solution.
In some embodiments, the organic ligand solution may be added to the halogen perovskite quantum dot solution prior to the aluminum halide and the divalent metal halide. For example, an octylphosphonic acid solution containing phosphorus-oxygen groups may be added to the halogen perovskite quantum dot solution first, and then the aluminum halide and the divalent metal halide powder or organic solution may be added to the halogen perovskite quantum dot solution.
In some embodiments, the organic ligand solution and the aluminum halide and the divalent metal halide are stirred for a reaction time of not less than 2 minutes after being added to the perovskite quantum dot solution. The stirring rate is not less than 2000 revolutions per minute. For example, the reaction system may be stirred at a stirring speed of 8000 rpm, and the stirring may be stopped after 2 minutes from the start of adding the organic ligand solution. For another example, the reaction system may be stirred at a stirring speed of 4000 rpm, and the stirring may be stopped after 4 minutes from the start of adding the organic ligand solution.
In some embodiments, the perovskite quantum dots have a molecular formula of ABX 3 Wherein A contains CH 3 NH 3 + 、HC(NH 2 ) 2 + Or Cs + One or more of Pb or Sn, and one or two of Cl, br or I. For example, the perovskite quantum dot may have the formula (CH 3 NH 3 ) x (HC(NH 2 ) 2 ) y Cs 1-x-y PbBr 3 . For another example, the perovskite quantum dot may have a molecular formula of CsSnBr X I 3-X 。
In some embodiments, the modifications include, but are not limited to, surface passivation, metal doping, band gap adjustment, stability enhancement, and the like.
In some embodiments, the preparation method of the complex metal halide modified halogen perovskite quantum dot can be performed in air or under vacuum.
In some embodiments, the preparation method of the complex metal halide modified halogen perovskite quantum dot can be performed at normal temperature or under heating condition.
In some embodiments, the resulting composite metal halide modified halogen perovskite quantum dots may be washed or purified one or more times.
The invention is illustrated in further detail by the following examples:
example 1
Taking 20mL of CsPbBr with concentration of 10mg/mL and synthesized by adopting a hot injection method x Cl 3-x Putting the quantum dot solution into a 40mL glass bottle, and putting the ceramic tiles into the glass bottle to be stirred in the air, wherein the stirring speed is 4000 rpm; preparing 3mL of octyl phosphonic acid toluene solution with the concentration of 10 mg/mL; preparation of 0.3mmol AlBr 3 Powder; preparation of 0.015mmolNiCl 2 Powder; subjecting the AlBr to 3 Powder and the CuCl 2 Adding the powder into the octyl phosphonic acid toluene solution, and ultrasonically promoting AlBr 3 Powder and NiCl 2 Dissolving powder; the AlBr is contained in 3 And NiCl 2 Toluene octylphosphinate solution containing CsPbBr is poured into x Cl 3-x A glass bottle of the quantum dot solution starts timing, and stirring is stopped after 3 minutes; after the obtained quantum dot solution is cleaned, the blue halogen perovskite quantum dot solution with better luminous performance is obtained.
Example 2
Preparing 2.5mL of toluene solution of didodecyl dimethyl ammonium bromide with the concentration of 10 mg/mL; preparation of 0.08mmol AlCl 3 Powder; preparation of 0.08 mmole of CuCl 2 Powder; the AlCl is subjected to 3 Powder and the CuCl 2 Adding the powder into the toluene solution of the didodecyl dimethyl ammonium bromide, and promoting AlCl by ultrasonic waves 3 Powder and CuCl 2 Dissolving powder; 15mL of the solution having a concentration of 10mg/mL was taken and synthesized by ligand-assisted coprecipitation (CH (NH) 2 ) 2 ) x Cs 1-x PbBr 3 Putting the quantum dot solution into a 25mL glass bottle, and putting the ceramic tiles into the glass bottle to be stirred in the air, wherein the stirring speed is 8000 revolutions per minute; the AlCl-containing solution is prepared 3 And CuCl 2 Is poured into the toluene solution containing (CH (NH) 2 ) 2 ) x Cs 1-x PbBr 3 A glass bottle of the quantum dot solution starts timing, and stirring is stopped after 2 minutes; after the obtained quantum dot solution is washed, a halogen perovskite quantum dot solution with blue luminescence color and stable in air is obtained, and the fluorescence spectrum is shown in figure 2.
Example 3
Taking 20mL of CH synthesized by adopting a hot injection method and with the concentration of 10mg/mL 3 NH 3 PbI 3 Putting the quantum dot solution into a 40mL glass bottle, and putting the ceramic tiles into a glove box for stirring at the stirring speed of 6000 rpm; 1.5mL of a toluene solution of didodecyl dimethyl ammonium bromide with a concentration of 10mg/mL and 1.5mL of a toluene solution of didodecyl dimethyl ammonium chloride with a concentration of 10mg/mL are prepared; preparation of 0.15mmol AlCl 3 Powder; preparation of 0.18mmolZnBr 2 Powder; pouring said didodecyl dimethyl ammonium bromide toluene solution and said didodecyl dimethyl ammonium chloride toluene solution into said container containing CH 3 NH 3 PbI 3 A glass bottle of the quantum dot solution starts timing; rapidly bringing said AlCl into contact with 3 Powder and ZnBr 2 Pouring the powder into a reaction bottle; stopping stirring after 3 minutes; after the obtained quantum dot solution is cleaned, the quantum dot solution with blue shift of luminescence peak and remarkably enhanced luminescence brightness is obtained.
In summary, the invention provides a composite metal halide modified halogen perovskite quantum dot and a preparation method thereof, and the halogen perovskite quantum dot is optimized by simple and easy-to-operate post-treatment modification based on the existing halogen perovskite quantum dot. The original ligand of the halogen perovskite quantum dot is replaced by the organic ligand, and meanwhile, pure-color halogen perovskite quantum dot with excellent optical performance and good stability, in particular blue light-emitting halogen perovskite quantum dot, is realized by aluminum halide and divalent metal halide, and the halogen perovskite quantum dot can be applied to preparation of efficient and stable photoelectric devices.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (1)
1. The preparation method of the composite metal halide modified halogen perovskite quantum dot is characterized by comprising the following steps of:
preparing 2.5mL of toluene solution of didodecyl dimethyl ammonium bromide with the concentration of 10 mg/mL; preparation of 0.08mmolAlCl 3 Powder; preparation of 0.08 mmole of CuCl 2 Powder; the AlCl is subjected to 3 Powder and the CuCl 2 Adding the powder into the toluene solution of the didodecyl dimethyl ammonium bromide, and promoting AlCl by ultrasonic waves 3 Powder and CuCl 2 Dissolving powder; 15mL of the solution having a concentration of 10mg/mL was taken and synthesized by ligand-assisted coprecipitation (CH (NH) 2 ) 2 ) x Cs 1-x PbBr 3 Putting the quantum dot solution into a 25mL glass bottle, and putting a magnetic rotor into the glass bottle to stir in the air at 8000 rpm; will contain AlCl 3 And CuCl 2 Is poured into a toluene solution containing (CH (NH) 2 ) 2 ) x Cs 1-x PbBr 3 A glass bottle of the quantum dot solution starts timing, and stirring is stopped after 2 minutes; and after the obtained quantum dot solution is cleaned, obtaining the halogen perovskite quantum dot solution with blue luminescent color.
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| CN110922968A (en) * | 2019-12-23 | 2020-03-27 | 宁波大学 | Preparation method of all-inorganic perovskite quantum dot used as blue-violet light source |
| CN112442359A (en) * | 2019-09-05 | 2021-03-05 | Tcl集团股份有限公司 | Modified perovskite quantum dot and preparation method thereof |
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| CN112442359A (en) * | 2019-09-05 | 2021-03-05 | Tcl集团股份有限公司 | Modified perovskite quantum dot and preparation method thereof |
| CN110922968A (en) * | 2019-12-23 | 2020-03-27 | 宁波大学 | Preparation method of all-inorganic perovskite quantum dot used as blue-violet light source |
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