CN116904193A - Method for passivating surface defects of all-inorganic perovskite quantum dots and application thereof - Google Patents
Method for passivating surface defects of all-inorganic perovskite quantum dots and application thereof Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000007547 defect Effects 0.000 title claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 53
- 229910001419 rubidium ion Inorganic materials 0.000 claims abstract description 53
- 239000000243 solution Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 20
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims abstract description 19
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 16
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 150000003297 rubidium Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 238000007865 diluting Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- JAAGVIUFBAHDMA-UHFFFAOYSA-M rubidium bromide Chemical compound [Br-].[Rb+] JAAGVIUFBAHDMA-UHFFFAOYSA-M 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- GRHQDJDRGZFIPO-UHFFFAOYSA-N 4-bromobutanoic acid Chemical compound OC(=O)CCCBr GRHQDJDRGZFIPO-UHFFFAOYSA-N 0.000 claims description 10
- WNXNUPJZWYOKMW-UHFFFAOYSA-N 5-bromopentanoic acid Chemical compound OC(=O)CCCCBr WNXNUPJZWYOKMW-UHFFFAOYSA-N 0.000 claims description 7
- DHXNZYCXMFBMHE-UHFFFAOYSA-N 3-bromopropanoic acid Chemical compound OC(=O)CCBr DHXNZYCXMFBMHE-UHFFFAOYSA-N 0.000 claims description 3
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- -1 halogen ion Chemical class 0.000 description 5
- 238000006862 quantum yield reaction Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
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Abstract
The application relates to the technical field of perovskite quantum dots, in particular to a method for passivating surface defects of all-inorganic perovskite quantum dots and application thereof; the method comprises the following steps: mixing N, N-dimethylacetamide and N, N-dimethylpropionamide, and then adding PbX 2 Dissolving the CsX bromoacid and the oleylamine in a mixed solvent for reaction to obtain Cs containing the amphoteric ion ligand 4 PbBr 6 A precursor solution; adding rubidium salt into deionized water, stirring, and diluting to obtain rubidium ion aqueous solution; heating the rubidium ion aqueous solution to a preset temperature, and adding Cs into the heated rubidium ion aqueous solution 4 PbBr 6 Precursor solution to form mixed solution, andperforming reaction, and centrifuging to remove precipitate to obtain CsPbX 3 Perovskite quantum dot aqueous solution; wherein PbX 2 CsX and CsPbX 3 X in the perovskite quantum dot aqueous solution comprises Br or I; the method can passivate the surface defects of all-inorganic perovskite quantum dots on the basis of low cost and simple operation.
Description
Technical Field
The application relates to the technical field of perovskite quantum dots, in particular to a method for passivating surface defects of all-inorganic perovskite quantum dots and application thereof.
Background
Because perovskite quantum dots have excellent properties such as high light absorption coefficient, precisely adjustable band gap, long carrier diffusion length, high quantum yield, pure emission spectrum and the like, the perovskite quantum dots are rapidly developed in the fields such as photovoltaics, light-emitting diodes, detectors, lasers and the like. At present, zhu et al (Angew. Chem. Int. Ed.2022,61, e 202116702) propose the preparation of CsPbX in water using perovskite precursors prepared from 4-bromobutyric acid and an oleylamine ligand 3 Perovskite quantum dots. Subsequently, song et al (adv. Funct. Mater.2023,33,2300493) also prepared CsPbX in water by replacing 4-bromobutyric acid with 5-bromopentanoic acid 3 Perovskite quantum dots. However, the perovskite precursor solution is simply added into deionized water during the preparation process, and the obtained perovskite quantum dots are not further passivated, which results in the synthesis of CsPbX by the method 3 The perovskite quantum dots have the defects of low quantum yield, more defects and weak luminous intensity in the process, and seriously hamper practical application.
Current research has shown that metal cations such as potassium (K) + ) And zinc ion (Zn) 2+ ) The doping mode can reduce non-radiative recombination by passivating perovskite crystal surface defects and grain boundaries by metal cations to improve quantum yield. Although Xu et al characterized by theoretical calculations and a series of experiments, it was verified that doped rubidium ions (Rb + ) Crystal junction of three-dimensional perovskite film prepared by traditional one-step processThe spatial distribution in the structure is composed of rubidium ions (Rb + ) The subtle changes in concentration dominate and details the corresponding mechanism of action that enhances the intrinsic stability of perovskite (adv. Mater.2022,34,2109998), but this approach cannot be used in a two-step process for the preparation of zero-dimensional all-inorganic perovskite quantum dots by water-induced crystal phase transformation. Therefore, how to provide a method for passivating the surface defects of all-inorganic perovskite quantum dots with low cost and simple operation is a technical problem to be solved at present.
Disclosure of Invention
The application provides a method for passivating surface defects of all-inorganic perovskite quantum dots and application thereof, and aims to solve the technical problem that the surface defects of all-inorganic perovskite quantum dots are difficult to passivate on the basis of low cost and simple operation in the prior art.
In a first aspect, the present application provides a method of passivating all-inorganic perovskite quantum dot surface defects, the method comprising:
mixing N, N-dimethylacetamide and N, N-dimethylpropionamide, and then adding PbX 2 Dissolving the CsX bromoacid and the oleylamine in a mixed solvent for reaction to obtain Cs containing the amphoteric ion ligand 4 PbBr 6 A precursor solution;
adding rubidium salt into deionized water, stirring, and diluting to obtain rubidium ion aqueous solution;
heating the rubidium ion aqueous solution to a preset temperature, and adding the Cs into the heated rubidium ion aqueous solution 4 PbBr 6 Precursor solution to form mixed solution, and the mixed solution is reacted and centrifuged to remove precipitate to obtain CsPbX 3 Perovskite quantum dot aqueous solution;
wherein the PbX 2 CsX and CsPbX 3 X in the perovskite quantum dot aqueous solution comprises Br or I.
Optionally, the molar ratio of the bromoacid to the oleylamine is 1:1-1:3.
The molar concentration of Pb element in the optional mixed solution is 0.00272 mmol/mL-0.00368 mmol/mL.
Optionally, the molar concentration of rubidium ions in the rubidium ion aqueous solution is 0.00032 mmol/mL-0.00128 mmol/mL.
Optionally, the volume ratio of the N, N-dimethylacetamide to the N, N-dimethylpropionamide is 0:5-5:0.
Optionally, the preferred volume ratio of the N, N-dimethylacetamide to the N, N-dimethylpropionamide is 3:2 to 2:3.
Optionally, the bromoacid includes at least one of 3-bromopropionic acid, 4-bromobutyric acid and 5-bromopentanoic acid.
Optionally, the bromoacid comprises 4-bromobutyric acid or 5-bromovaleric acid.
Optionally, the preset temperature is 55-65 ℃.
Optionally, the rubidium salt comprises RbBr or RbI.
In a second aspect, the application provides an application of a method for passivating surface defects of all-inorganic perovskite quantum dots, which comprises the step of obtaining CsPbX by the method in the first aspect 3 The perovskite quantum dot aqueous solution is used for preparing luminescent materials.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
the embodiment of the application provides a method for passivating surface defects of all-inorganic perovskite quantum dots, which is characterized in that rubidium ions (Rb) are introduced into deionized water in advance + ) As shown in fig. 2, since rubidium ions (Rb + ) Can be applied to CsPbX 3 The perovskite quantum dot is combined with halogen ion X lacking the coordination of the zwitterionic ligand to form a metal ligand during the generation process of the perovskite quantum dot, and the CsPbX can be passivated by using the metal ligand 3 Surface defects of the perovskite quantum dots, thereby improving the quantum yield and the luminous intensity of the perovskite quantum dots. In addition, the method only needs to dissolve rubidium salt with low price, dilute, and reheat and combine with Cs 4 PbBr 6 The precursor solution reacts, and the whole operation is simple and convenient, so that the surface defects of the all-inorganic perovskite quantum dots can be passivated on the basis of low cost and simple operation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic flow chart of a method for passivating all-inorganic perovskite quantum dot surface defects provided by an embodiment of the application;
fig. 2 shows a CsPbX provided by an embodiment of the application 3 Schematic diagram of preparation process principle of quantum dot solution;
FIG. 3 shows CsPbBr provided in examples 1-4 of the present application 3 PL spectra corresponding to quantum dot materials;
FIG. 4 shows CsPbI provided in examples 5-8 of the application 3 PL spectra corresponding to quantum dot materials;
FIG. 5 shows CsPbBr according to example 1 of the present application 3 TEM image of quantum dot material;
FIG. 6 shows CsPbI provided in example 5 of the present application 3 TEM image of quantum dot material;
FIG. 7 shows CsPbBr provided in example 1 and comparative example 1 of the present application 3 Comparing XPS results of quantum dot materials, FIG. 7a is CsPbBr 3 Fig. 7b is a full XPS diagram of the quantum dot material, and fig. 7b is an XPS spectrum of Rb element.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
As shown in fig. 1, an embodiment of the present application provides a method for passivating surface defects of all-inorganic perovskite quantum dots, the method including:
s1, mixing N, N-dimethylacetamide and N, N-dimethylpropionamide, and then adding PbX 2 Dissolving the CsX bromoacid and the oleylamine in a mixed solvent for reaction to obtain Cs containing the amphoteric ion ligand 4 PbBr 6 A precursor solution;
s2, adding rubidium salt into deionized water, stirring, and diluting to obtain rubidium ion aqueous solution;
s3, heating the rubidium ion aqueous solution to a preset temperature, and adding the Cs into the heated rubidium ion aqueous solution 4 PbBr 6 Precursor solution is used for forming mixed solution, and the mixed solution is reacted, and then is centrifuged and sediment is removed to obtain CsPbX 3 Perovskite quantum dot aqueous solution;
wherein the PbX 2 CsX and CsPbX 3 X in the perovskite quantum dot aqueous solution comprises Br or I.
In the embodiment of the application, pbX is controlled 2 CsX and CsPbX 3 The specific category of halide ions in the perovskite quantum dot aqueous solution can reduce Cs due to the large existence amount of Br or I and lower cost 4 PbBr 6 The precursor solution is formed at the required cost.
In some alternative embodiments, the molar ratio of the bromoacid to the oleylamine is 1:1 to 1:3.
In the embodiment of the application, the specific molar ratio of the bromoacid to the oleylamine is controlled, so that the reaction between the bromoacid and the oleylamine can fully obtain the pure zwitterionic ligand with high yield and no byproducts.
In some alternative embodiments, the molar concentration of Pb element in the mixed solution is 0.00272 mmol/mL-0.00368 mmol/mL.
Implementation of the applicationIn the example, cs is added under control 4 PbBr 6 Specific molar concentration of Pb element in mixed solution formed by rubidium ion aqueous solution after precursor solution can be used for determining Cs 4 PbBr 6 The demand of the reaction between the precursor solution and the rubidium ion aqueous solution can be controlled accurately, so that the raw material cost required by the rubidium ion aqueous solution is reduced.
In some alternative embodiments, the molar concentration of rubidium ions in the rubidium ion aqueous solution is between 0.00032mmol/mL and 0.00128mmol/mL.
In the embodiment of the application, the specific molar concentration of the rubidium ions in the rubidium ion aqueous solution is controlled, so that the rubidium ions can be identical with Cs under the premise of low cost 4 PbBr 6 The precursor solution is completely reacted, so that the addition amount of the rubidium ion aqueous solution is accurately controlled, and the cost of raw materials required by the rubidium ion aqueous solution can be reduced.
In some alternative embodiments, the volume ratio of the N, N-dimethylacetamide to the N, N-dimethylpropionamide is from 0:5 to 5:0.
In the embodiment of the application, the specific volume ratio of the N, N-dimethylacetamide to the N, N-dimethylpropionamide is controlled so that the N, N-dimethylacetamide and the N, N-dimethylpropionamide can be mixed to form a uniform solution, thereby obtaining PbX 2 The reaction of CsX, bromoacid and oleylamine provides a place for the reaction between bromoacid and oleylamine to fully yield a zwitterionic ligand.
The volume ratio of N, N-dimethylacetamide to N, N-dimethylpropionamide may be 3:2 to 2:3.
In some alternative embodiments, the bromoacid includes at least one of 3-bromopropionic acid, 4-bromobutyric acid, and 5-bromopentanoic acid.
In some alternative embodiments, the bromoacid comprises 4-bromobutyric acid or 5-bromovaleric acid.
In the embodiment of the application, the specific types of the bromoacid are controlled, so that the bromoacid and the oleylamine can fully react in the mixed solvent of the N, N-dimethylacetamide and the N, N-dimethylpropionamide to obtain enough zwitterionic ligands, and the subsequent lack of the halogen ions coordinated by the zwitterionic ligands is facilitatedX and rubidium ions (Rb) + ) Is combined with each other to form a metal ligand, thereby being capable of passivating CsPbX 3 Surface defects of perovskite quantum dots.
In some alternative embodiments, the predetermined temperature is 55 ℃ to 65 ℃.
In the embodiment of the application, the specific preset temperature is controlled, so that the temperature of the rubidium ion aqueous solution is high enough, and a small amount of rubidium ions (Rb) in the rubidium ion aqueous solution is convenient + ) Reacts with halogen ion X lacking zwitterionic ligand coordination and combines to form enough metal ligand to substantially passivate CsPbX 3 Surface defects of perovskite quantum dots.
In some alternative embodiments, the rubidium salt comprises RbBr or RbI.
In the embodiment of the application, the specific types of rubidium salt are controlled, and the RbBr or RbI has low price due to lower rubidium ion molar concentration of the rubidium ion aqueous solution, so that CsPbX can be effectively prepared in a reduced manner 3 Raw material cost of perovskite quantum dots.
Based on one general inventive concept, the embodiment of the application provides an application of a method for passivating all-inorganic perovskite quantum dot surface defects, wherein the application comprises the step of obtaining CsPbX by the method 3 The perovskite quantum dot aqueous solution is used for preparing luminescent materials.
The application is realized based on the above method, and specific steps of the method can refer to the above embodiment, and because the application adopts some or all of the technical solutions of the above embodiment, at least the application has all the beneficial effects brought by the technical solutions of the above embodiment, and will not be described in detail herein.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
A method of passivating surface defects of an all-inorganic perovskite quantum dot, the method comprising:
s1, 0.2mmol of PbBr 2 Adding 0.2mmol of CsBr, 1mmol of 4-bromobutyric acid, 1mmol of oleylamine, 3mL of N, N-Dimethylacetamide (DMA) and 2mL of N, N-Dimethylpropionamide (DMPA) into a reaction bottle to obtain a mixed solution, and fully stirring the mixed solution at 60 ℃ for 10 hours to prepare the Cs with a large amount of zwitterionic ligands 4 PbBr 6 A precursor solution, in this case a white turbid solution containing a large amount of white precipitate;
s2, adding 0.16mmol of RbBr into 1mL of deionized water, and stirring for 5min to prepare 0.16mmol/mL of rubidium ions (Rb) + ) A primary aqueous solution. Then, 10. Mu.L of rubidium ion (Rb) + ) The primary aqueous solution was added to 2.5mL of deionized water to produce the desired rubidium ion (Rb) at 0.00064mmol/mL + ) An aqueous solution;
S3.Cs 4 PbBr 6 the precursor solution was shaken well before use and 180. Mu.L of Cs was then removed 4 PbBr 6 The precursor solution was added to 2.5mL of rubidium ions (Rb) at 60℃with continuous magnetic stirring + ) In aqueous solution, centrifuging at 4000rpm for 8min, and collecting supernatant to obtain CsPbBr 3 Perovskite quantum dot aqueous solution.
Example 2
Example 2 and example 1 were compared, and the difference between example 2 and example 1 is that:
rubidium ion (Rb) in S2 + ) The molar concentration of the aqueous solution was replaced by 0.00064mmol/mL to 0.00032mmol/mL.
Example 3
Example 3 was compared with example 1, and the difference between example 3 and example 1 was:
rubidium ion (Rb) in S2 + ) The molar concentration of the aqueous solution was replaced by 0.00064mmol/mL to 0.00096mmol/mL.
Example 4
Example 4 and example 1 were compared, and example 4 and example 1 differ in that:
separation of rubidium from S2Son (Rb) + ) The molar concentration of the aqueous solution was replaced by 0.00064mmol/mL and 0.00128mmol/mL.
Example 5
Example 5 was compared with example 1, and the difference between example 5 and example 1 was:
a method of passivating surface defects of an all-inorganic perovskite quantum dot, the method comprising:
s1, 0.2mmol of PbI is added 2 0.2mmol of CsI, 1mmol of 4-bromobutyric acid, 1mmol of oleylamine, 3mL of N, N-Dimethylacetamide (DMA) and 2mL of N, N-Dimethylpropionamide (DMPA) are added into a reaction flask to obtain a mixed solution, and the mixed solution is fully stirred at 60 ℃ for 10 hours to prepare the required Cs with a large amount of zwitterionic ligands 4 PbBr 6 A precursor solution, in this case a yellow turbid solution containing a large amount of white precipitate;
s2, adding 0.16mmol of RbI into 1mL of deionized water, and stirring for 5min to prepare 0.16mmol/mL of rubidium ion (Rb) + ) A primary aqueous solution. Then, 10. Mu.L of rubidium ion (Rb) + ) The primary aqueous solution was added to 2.5mL of deionized water to produce the desired rubidium ion (Rb) at 0.00064mmol/mL + ) An aqueous solution;
S3.Cs 4 PbBr 6 the precursor solution was shaken well before use and 180. Mu.L of Cs was then removed 4 PbBr 6 The precursor solution was added to 2.5mL of rubidium ions (Rb) at 60℃with continuous magnetic stirring + ) In aqueous solution, centrifuging at 4000rpm for 8min, and collecting supernatant to obtain CsPbBr 3 Perovskite quantum dot aqueous solution.
Example 6
Example 6 and example 5 are compared, and example 2 and example 1 differ in that:
rubidium ion (Rb) in S2 + ) The molar concentration of the aqueous solution was replaced by 0.00064mmol/mL to 0.00032mmol/mL.
Example 7
Example 7 was compared with example 5, and example 3 was different from example 1 in that:
rubidium ion (Rb) in S2 + ) Of aqueous solutionsThe molar concentration was replaced by 0.00064mmol/mL to 0.00096mmol/mL.
Example 8
Example 8 and example 5 are compared, and example 4 and example 1 differ in that:
rubidium ion (Rb) in S2 + ) The molar concentration of the aqueous solution was replaced by 0.00064mmol/mL and 0.00128mmol/mL.
Comparative example 1
Comparative example 1 was compared with example 1, and the difference between comparative example 1 and example 1 was that:
rubidium ion (Rb) in S2 + ) The molar concentration of the aqueous solution was replaced by 0.00064 mmol/mL.
Comparative example 2
Comparative example 2 and example 5 were compared, and the difference between comparative example 2 and example 5 is that:
rubidium ion (Rb) in S2 + ) The molar concentration of the aqueous solution was replaced by 0.00064 mmol/mL.
Related experiment and effect data:
CsPbBr obtained in examples 1 to 4, comparative example 1, examples 5 to 8 and comparative example 2, respectively 3 The quantum dot material was tested and its PL spectra are shown in figures 3 and 4.
CsPbBr obtained in example 1 and example 5 simultaneously 3 The quantum dot material was subjected to a transmission electron microscope, and its TEM images are shown in fig. 5 and 6.
CsPbBr obtained in comparative example 1 and comparative example 1 3 The quantum dot material was subjected to X-ray photoelectron spectroscopy, and the result is shown in fig. 7.
From the above results, it can be seen that:
as can be seen from fig. 3 and 4, rb + Doped CsPbX 3 PL enhancement of the Quantum dots and maximum emission intensity at 0.00064mmol/mL demonstrated doped Rb + By CsPbBr 3 The feasibility of forming metal ligands on the surface of the quantum dots to further passivate defects.
As can be seen from fig. 5 and 6, rb + Doped CsPbX 3 The quantum dots have good crystallinity.
As can be seen from FIG. 7, csPbX 3 Detection of Rb element signal in Quantum dots confirmed doped Rb + Has been combined with CsPbX 3 Successful binding of quantum dots is Rb + Effectively passivate CsPbX 3 Strong evidence of surface defects of quantum dots.
In summary, the method for passivating the surface defects of the all-inorganic perovskite quantum dots provided by the embodiment of the application introduces rubidium ions (Rb) into deionized water in advance + ) So that rubidium ions (Rb + ) Can be applied to CsPbX 3 During the production of perovskite quantum dots, the perovskite quantum dots are combined with halogen ions X lacking the coordination of zwitterionic ligands to form metal ligands, thereby passivating CsPbX 3 Surface defects of the perovskite quantum dots improve the quantum yield and the luminous intensity of the perovskite quantum dots. In addition, the method provided by the application has the advantages of simple process, low price of the used rubidium bromide (RbBr) and rubidium iodide (RbI), small use amount and low cost.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2,3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method of passivating surface defects of all-inorganic perovskite quantum dots, the method comprising:
mixing N, N-dimethylacetamide and N, N-dimethylpropionamide, and then adding PbX 2 Dissolving the CsX bromoacid and the oleylamine in a mixed solvent for reaction to obtain Cs containing the amphoteric ion ligand 4 PbBr 6 A precursor solution;
adding rubidium salt into deionized water, stirring, and diluting to obtain rubidium ion aqueous solution;
heating the rubidium ion aqueous solution to a preset temperature, and adding the C into the heated rubidium ion aqueous solutions 4 PbBr 6 Precursor solution to form mixed solution, and the mixed solution is reacted and centrifuged to remove precipitate to obtain CsPbX 3 Perovskite quantum dot aqueous solution;
wherein the PbX 2 CsX and CsPbX 3 X in the perovskite quantum dot aqueous solution comprises Br or I.
2. The method of claim 1, wherein the molar ratio of the bromoacid to the oleylamine is 1:1 to 1:3.
3. The method according to claim 1, wherein the molar concentration of Pb element in the mixed solution is 0.00272 mmol/mL-0.00368 mmol/mL.
4. The method of claim 1, wherein the molar concentration of rubidium ions in the rubidium ion aqueous solution is from 0.00032mmol/mL to 0.00128mmol/mL.
5. The method according to claim 1, wherein the volume ratio of the N, N-dimethylacetamide and the N, N-dimethylpropionamide is 0:5 to 5:0.
6. The method of claim 1, wherein the bromoacid comprises at least one of 3-bromopropionic acid, 4-bromobutyric acid, and 5-bromopentanoic acid.
7. The method of claim 6, wherein the bromoacid comprises 4-bromobutyric acid or 5-bromovaleric acid.
8. The method of claim 1, wherein the predetermined temperature is 55 ℃ to 65 ℃.
9. The method of claim 1, wherein the rubidium salt comprises RbBr or RbI.
10. Use of a method for passivating surface defects of all-inorganic perovskite quantum dots, characterized in that the use comprises CsPbX obtained by the method according to any one of claims 1-9 3 The perovskite quantum dot aqueous solution is used for preparing luminescent materials.
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