CN109705844A - It is nanocrystalline and preparation method thereof with core-shell structure - Google Patents
It is nanocrystalline and preparation method thereof with core-shell structure Download PDFInfo
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- CN109705844A CN109705844A CN201910089509.0A CN201910089509A CN109705844A CN 109705844 A CN109705844 A CN 109705844A CN 201910089509 A CN201910089509 A CN 201910089509A CN 109705844 A CN109705844 A CN 109705844A
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Abstract
It is nanocrystalline that this application provides a kind of with core-shell structure and preparation method thereof.Nano-crystal crystalline substance includes nanocrystal, the first subshell being coated in the nanocrystal and the second subshell being coated in first subshell, which is characterized in that first subshell includes Zn, Se and Mn element；Second subshell includes Zn, S and Cu element.High nanocrystalline of luminous efficiency is prepared by successively coating MnZnSe and CuZnS outside nanocrystal in the application.
Description
Technical field
The application belongs to technical field of nano material, and in particular to a kind of nanocrystalline and its preparation side with core-shell structure
Method.
Background technique
It is nanocrystalline to have launch wavelength with size as a kind of semiconductor material of three-dimensional dimension all between 1~20nm
The advantages that adjusting, half-peak width.It is nanocrystalline that there is important application in fields such as illumination, displays due to these excellent performances
Prospect.
Nanocrystalline surface defect increases the probability of nonradiative transition, causes to itself luminous efficiency and stability
Adverse effect.To solve the problems, such as that nanocrystalline luminous efficiency is low and stability is poor, generally in nanocrystal outer cladding shell, with
Enhance its luminous efficiency.However, in the prior art, due to existing crystalline substance between each layer in shell and nanocrystal and shell
The problems such as lattice mismatch, causes nanocrystalline luminous efficiency still not high.
Summary of the invention
In view of the above technical problems, the application provides a kind of with the nanocrystalline of core-shell structure.
It according to the one aspect of the application, provides a kind of with the nanocrystalline of core-shell structure, including nanocrystal, is coated on
The first subshell in the nanocrystal and the second subshell being coated in first subshell, which is characterized in that institute
Stating the first subshell includes Zn, Se and Mn element；Second subshell includes Zn, S and Cu element.
In the application, the constituent material of nanocrystal includes three-five race's semiconductor materials or two-six race's semiconductor materials
Material, the application do not limit this.
In the prior art, it is commonly used for being coated on InP by double shell structurres that ZnSe and ZnS Shuangzi shell is constituted nanocrystalline
On core, but existing lattice difference is still larger between ZnSe and ZnS, and the luminous efficiency for causing InP nanocrystalline is not high.Invention
People's discovery, by the doping metals Mn element into ZnSe layer, to when doping metals Cu element, this shell structurre can in ZnS layers
Effectively improve the nanocrystalline luminous efficiency of InP.
Further, in first subshell, the molar content of Mn is 1%~5%.
Further, the thickness of first subshell is between 1~4nm.
Further, in second subshell, the molar content of Cu is 1%~5%.
Further, the thickness of second subshell is between 1~4nm.
In the first subshell and the second subshell when the content of Mn or Cu is too low or too high, such as less than 1%
Or when being greater than 5%, it is unable to get preferable matching degree, does not effectively improve nanocrystalline luminous efficiency.
Further, the constitution element of the nanocrystal includes In and P.
Further, the constitution element of the nanocrystal further includes Zn or Ga.
According to further aspect of the application, a kind of nanocrystalline preparation method with core-shell structure, feature are provided
It is, comprising: step S1, the first solution system comprising nanocrystal is provided；Step S2, by the temperature of first solution system
Degree is adjusted between 180~240 DEG C, and the solution containing Zn presoma, Se presoma and Mn presoma, reaction 10~120 is added
Minute, the second solution system is obtained, the surface of nanocrystal is coated with the first subshell in second solution system；Step
S3, the temperature of second solution system is adjusted between 240~300 DEG C, is added and contains Zn presoma, S presoma and Cu
The solution of presoma reacts 10~120 minutes, obtains third solution system, the first subshell in the third solution system
Surface is coated with the second subshell.
In the application, Zn presoma include but be not limited to zinc nitrate, zinc fluoride, zinc chloride, zinc bromide, zinc iodide,
Zinc carbonate, zinc sulfate, zinc perchlorate, zinc acetate, zinc polycarboxylate, zinc acetylacetonate, xanthopone, xanthogen zinc, ten
Six alkyl zinc xanthates, zinc diethyl dithiocarbamate, zinc-ethylphenyl dithiocarbamate, aminomethyl phenyl two are thio
One of carbaminate, zinc dibutyl dithiocaarbamate.
Se presoma includes but is not limited to alkyl amino selenides, alkenyl amino selenides, selenol, selenide, seleno
One of acid esters, selenium substituted acid amide.
Mn presoma includes but is not limited to one of manganese chloride, manganese acetate, manganese sulfate, manganese carbonate.
S presoma includes but is not limited to thioacetic acid, mercaptopropionic acid, mercapto glycerol, mercaptoethanol, thioacetyl
One of amine, alkyl amino sulfide, alkenyl amino sulfide, xanthopone.
Cu presoma includes but is not limited to copper chloride, stannous chloride, copper bromide, cuprous bromide, cuprous iodide, acetic acid
One of cuprous, copper acetate, cuprous sulfate.
Above-mentioned forerunner uses after being prepared into carboxylate, and specific preparation method can refer to the prior art.
Further, the constitution element of the nanocrystal includes In and P.
The utility model has the advantages that shell nanocrystalline in the application includes the first shell of the ZnSe of Mn doping, the ZnS's of Cu doping
High nanocrystalline of luminous efficiency is prepared by successively coating MnZnSe and CuZnS outside nanocrystal in second shell.
Specific embodiment
Below in conjunction with the application embodiment, technical solutions in the embodiments of the present application is described in detail.It answers
It is noted that described embodiment is only a part of embodiment of the application, rather than whole embodiments.
Hereinafter, embodiment is described in more detail referring to embodiment.However, they are exemplary implementation of the invention
Mode, and the invention is not limited thereto.
Embodiment 1
Step S1, the first solution system is the octadecene solution containing InP nanocrystal, and the concentration of InP nanocrystal is about
For 1mg/ml, InP nanocrystal uses prior art preparation, and emission peak is in 525nm；
Step S2, the octadecene solution of the InP nanocrystal of step S1 is warming up to 220 DEG C, and be added thereto
0.3mmol zinc stearate, 0.01mmol manganese stearate, 0.6mmol oleic acid, Se-TOP (selenium-tri octyl phosphine, 0.09mmol) reaction
After 10min, the second solution system that InP nanocrystal is coated containing the first subshell of MnZnSe is obtained；
Step S3, the second solution system is warming up to 260 DEG C, add S-TOP (sulphur-tri octyl phosphine, 0.21mmol),
0.01mmol copper stearate, reaction 30min, form third solution system, and it is nanocrystalline to obtain InP/MnZnSe/CuZnS, uses methanol
The product system is extracted three times, obtains extract；With the acetone precipitation extract, and sediment is centrifuged, it then will be after centrifugation
Obtained precipitating is dissolved in toluene, obtains InP/MnZnSe/CuZnS nanocrystal solution.
Comparative example 1
Comparative example 1 provides a kind of preparation method that InP/ZnSe/ZnS is nanocrystalline, and is substantially the same in embodiment 1, and institute is not
Be manganese stearate is added without in step S2, be added without copper stearate in step S3.
Embodiment 2
Step S1, the first solution system is the octadecene solution containing CdSe nanocrystal, the concentration of CdSe nanocrystal
About 1mg/ml, CdSe nanocrystal use prior art preparation, and emission peak is in 530nm；
Step S2, the octadecene solution of the CdSe nanocrystal of step S1 is warming up to 240 DEG C, and be added thereto
0.3mmol zinc stearate, 0.01mmol manganese stearate, 0.6mmol oleic acid, Se-TOP (selenium-tri octyl phosphine, 0.09mmol) reaction
After 30min, the second solution system that CdSe nanocrystal is coated containing the first subshell of MnZnSe is obtained；
Step S3, the second solution system is warming up to 280 DEG C, add S-TOP (sulphur-tri octyl phosphine, 0.21mmol),
0.01mmol copper stearate, reaction 60min, form third solution system, are down to room temperature and obtain CdSe/MnZnSe/CuZnS nanometers
Crystalline substance extracts the product system three times with methanol, obtains extract；With the acetone precipitation extract, and sediment is centrifuged, then
The precipitating obtained after centrifugation is dissolved in toluene, CdSe/MnZnSe/CuZnS nanocrystal solution is obtained.
Comparative example 2
Comparative example 2 provides a kind of preparation method that CdSe/ZnSe/ZnS is nanocrystalline, and is substantially the same in embodiment 2, and institute is not
Be manganese stearate is added without in step S2, be added without copper stearate in step S3.
To the nanocrystalline fluorescence emission peak of above-described embodiment 1, comparative example 1, embodiment 2, comparative example 2, quantum yield into
Row test, the results are shown in Table 1.
Table 1
| Embodiment 1 | Comparative example 1 | Embodiment 2 | Comparative example 2 | |
| Fluorescence emission peak/nm | 527 | 526 | 531 | 530 |
| Quantum yield | 72% | 56% | 85% | 72% |
As shown in Table 1, quantum yield nanocrystalline in embodiment 1 is than improving 16% in comparative example 1, nanometer in embodiment 2
Brilliant quantum yield absolutely proves in the application using the bivalve MnZnSe/CuZnS layer than improving 13% in comparative example 2 for receiving
The beneficial effect of the promotion of meter Jing Fa light efficiency.
Although inventor has done more detailed elaboration to the technical solution of the application and has enumerated, it should be understood that for
For those skilled in the art, above-described embodiment is modified and/or the flexible or equivalent alternative solution of use is obvious
, cannot all be detached from the essence of the application spirit, the term occurred in the application be used for elaboration to technical scheme and
Understand, the limitation to the application can not be constituted.
Claims (9)
1. it is a kind of with the nanocrystalline of core-shell structure, including nanocrystal, the first subshell being coated in the nanocrystal
With the second subshell being coated in first subshell, which is characterized in that
First subshell includes Zn, Se and Mn element；
Second subshell includes Zn, S and Cu element.
2. according to claim 1 nanocrystalline, which is characterized in that in first subshell, the molar content of Mn is 1%
~5%.
3. according to claim 1 nanocrystalline, which is characterized in that the thickness of first subshell is between 1~4nm.
4. according to claim 1 nanocrystalline, which is characterized in that it is characterized in that, Cu's rubs in second subshell
Your content is 1%~5%.
5. according to claim 1 nanocrystalline, which is characterized in that the thickness of second subshell is between 1~4nm.
6. according to claim 1 nanocrystalline, which is characterized in that the constitution element of the nanocrystal includes In and P.
7. according to claim 6 nanocrystalline, which is characterized in that the constitution element of the nanocrystal further include Zn or
Ga。
8. a kind of nanocrystalline preparation method with core-shell structure characterized by comprising
Step S1, the first solution system comprising nanocrystal is provided；
Step S2, the temperature of first solution system is adjusted between 180~240 DEG C, is added containing before Zn presoma, Se
The solution of body and Mn presoma is driven, reacts 10~120 minutes, obtains the second solution system, nanometer in second solution system
The surface of nucleus is coated with the first subshell；
Step S3, the temperature of second solution system is adjusted between 240~300 DEG C, is added containing before Zn presoma, S
The solution of body and Cu presoma is driven, reacts 10~120 minutes, obtains containing nanocrystalline third solution system, it is described nanocrystalline
The surface of the first subshell be coated with the second subshell.
9. preparation method according to claim 8, which is characterized in that the constitution element of the nanocrystal includes In and P.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111450850A (en) * | 2020-03-27 | 2020-07-28 | 肇庆市华师大光电产业研究院 | Quaternary bismuth-based chalcogenide shell-core nanosphere and preparation method and application thereof |
| CN112143481A (en) * | 2019-06-28 | 2020-12-29 | 苏州星烁纳米科技有限公司 | Preparation method of core-shell structure nanocrystal and core-shell structure nanocrystal prepared by same |
-
2019
- 2019-01-30 CN CN201910089509.0A patent/CN109705844B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| CHOI JONGWAN等: "Aqueous-phase synthesis and color-tuning of core/shell/shell inorganic nanocrystals consisting of ZnSe, (Cu,Mn)-doped ZnS, and ZnS", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| GOPI CHANDU V. V. M.等: "Improved photovoltaic performance and stability of quantum dot sensitized solar cells using Mn-ZnSe shell structure with enhanced light absorption and recombination control", 《NANOSCALE》 * |
| WANG CHUNLEI等: "Aqueous synthesis of multilayer Mn:ZnSe/Cu:ZnS quantum dots with white light emission", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143481A (en) * | 2019-06-28 | 2020-12-29 | 苏州星烁纳米科技有限公司 | Preparation method of core-shell structure nanocrystal and core-shell structure nanocrystal prepared by same |
| CN111450850A (en) * | 2020-03-27 | 2020-07-28 | 肇庆市华师大光电产业研究院 | Quaternary bismuth-based chalcogenide shell-core nanosphere and preparation method and application thereof |
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