CN116606647A - ZnS cladding Mn doped ZCIS five-element quantum dot, method and application - Google Patents
ZnS cladding Mn doped ZCIS five-element quantum dot, method and application Download PDFInfo
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Abstract
The invention discloses a ZnS cladding Mn doped ZCIS five-element quantum dot, a method and application thereof, comprising the following steps: (1) Preparation of In 2 S 3 Quantum dot templates: heating high-concentration sulfur powder and indium acetate in a solvent octadecene and ligand oleylamine to 100 ℃ for dissolution, and deoxidizing after complete dissolution to obtain an indium sulfide mixed solution; (2) drop heating Cu injection; (3) heating and injecting Zn dropwise; (4) ZnS-coated quantum dots; (5) doping a transition metal element Mn. The ZnS cladding and Mn doping not only can keep the advantages of tunable spectrum, high luminous efficiency and the like of the general undoped quantum dots, but also can effectively inhibit the self-absorption effect of luminescence due to large Stokes displacement, avoid self-quenching phenomenon and simultaneously have more advantagesBroad spectrum adjustable range and better photochemical stability. Based on the synthesized quantum dots, a polymer solution is prepared and printed to obtain a fluorescent pattern.
Description
Technical Field
The invention relates to the technical field of new nano materials, in particular to a ZnS cladding Mn-doped ZCIS five-element quantum dot, a method and application.
Background
Nanomaterial is a material that is critical between bulk material and molecules, exhibiting nanoscale dimensions (1-100 nm) in at least one dimension. The quantum dot belongs to a zero-dimensional material in the nano material, shows quantum size effect, surface effect and the like, has the property which is not possessed by a macroscopic material, is a quasi-zero-dimensional inorganic fluorescent nano material, has the advantages of controllable size, high fluorescence quantum yield, good light stability, long fluorescence service life and the like, has great application potential in the aspects of nonlinear optical response, medical drugs, photoelectric materials and the like, stands out in a plurality of nano materials, and becomes one of great discoveries of 20 th century human beings.
Among the many properties of semiconductor nanocrystals, the good photo-induced fluorescence (PL) properties of quantum dots are more of a focus. The semiconductor nanocrystals have the advantages of good fluorescence, such as good light stability, adjustable luminescence color height, wide excitation spectrum range, good symmetry of emission spectrum peak shape, narrow fluorescence emission half-width, high luminescence color purity, etc., so that the research on the semiconductor nanocrystals has been carried out for twenty years, no matter how the experimental method is improved, the growth mechanism and growth dynamics can be regulated by quantum dot size, morphology and optical property, and the surface modification and energy band engineering of ligand surface dynamics semiconductor nanocrystals can be greatly developed. In the aspect of synthesis methods, particularly colloid chemical methods in chemical methods are greatly improved, such as an organometallic pyrolysis method, a single-source precursor aqueous phase method and a hydrothermal synthesis method, wherein a green organic phase hot injection method developed by the Peng group makes a great contribution to synthesizing high-quality quantum dots. Among these, binary semiconductor nanocrystals meet the demands of practical applications in terms of optical properties and stability, but have some defects that make their application prospects very vast, for example, materials for synthesizing II-VI and III-V semiconductor nanocrystals contain heavy metal elements such as Cd, hg and Pb which can cause cancer; meanwhile, the infrared light-emitting diode also contains extremely toxic anionic elements Se, te, P, as and the like, most of anionic precursors required for synthesizing the near infrared III-V quantum dots are expensive and dangerous, the synthesis process is complicated, the production period is prolonged, and the production cost is increased. Therefore, the development of novel quantum dots with green synthesis, low cost, high emission efficiency and high stability becomes a problem to be solved urgently by scientists at present.
Multicomponent semiconductor nanocrystalline (CuInS) 2 ，CuInSe 2 ，CuZnInS 3 ) Is a popular research direction in semiconductor nanocrystals, and has low toxicity of the contained elements, so that compared with the traditional binary nanocrystals, the semiconductor nanocrystals are more environment-friendly, environment-friendly and low-cost, and are beneficial to practical application, and therefore, the semiconductor nanocrystals are widely paid attention in recent years. In addition, it has a large absorption coefficient in the visible spectrum, which makes it an attractive material for solar energy conversion, photodetectors, light emitting devices, photocatalysis, and biomarkers. The multi-element semiconductor nanocrystals can cover a wide range of colors, with high emission intensities from the visible to near infrared region of the spectrum, and are often developed for in vivo biomedical color tunable emitter imaging, illumination and display.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the multi-element semiconductor quantum dot, which has the advantages of simple synthesis process, high efficiency, high quantum yield and high fluorescence intensity, and can be applied on a large scale and has good stability.
The invention adopts the following technical scheme:
a preparation method of ZnS cladding Mn-doped ZCIS five-element quantum dots comprises the following steps:
(1) Preparation of In 2 S 3 Quantum dot templates: heating high-concentration sulfur powder and indium acetate in a solvent octadecene and ligand oleylamine to 100 ℃ for dissolution, and deoxidizing after complete dissolution to obtain an indium sulfide mixed solution;
(2) Drop heating injection of Cu: and (3) dissolving cuprous iodide in the DDT, and carrying out ultrasonic oscillation to obtain a white turbid solution after complete dissolution. Adding the dissolved cuprous iodide solution into the indium sulfide solution obtained in the step (1) heated to 120 ℃, quickly changing the mixed solution into dark red, deoxidizing, and heating to 160 ℃;
(3) Drop heating injection of Zn: heating the mixed solution obtained In the step (2) to 160 ℃, then cooling to 120 ℃, adding the dissolved zinc oxide mixed solution, heating to 250 ℃ and maintaining a nitrogen atmosphere for reacting for a period of time to obtain a Zn-Cu-In-S quantum dot solution;
(4) ZnS coated quantum dot: zinc oxide is dissolved in a solvent of 2-ethylhexanoic acid, and the zinc oxide is heated and dissolved in a solvent of triglyme to obtain a zinc mixed solution; dissolving thiourea in a solvent triglyme, and heating and dissolving in an oil pan to obtain a sulfur mixed solution; mixing a zinc oxide solution and a thiourea solution to obtain ZnS; heating Zn-Cu-In-S quantum dot solution reacted for a certain time, standing, cooling to 100 ℃, keeping nitrogen, adding mixed zinc oxide solution and thiourea solution, and heating to 180 ℃;
(5) Doping transition metal element Mn: dissolving manganese acetate in a solvent octadecene, and carrying out ultrasonic oscillation to completely dissolve; adding the dissolved manganese acetate solution into the solution obtained in the step (4) heated to 200 ℃, and keeping the temperature for reacting for a certain time when the temperature is raised to 250 ℃; cooling to normal temperature after the reaction is completed, adding excessive isopropanol, and centrifuging to obtain the ZnS cladding and Mn-doped Zn-Cu-In-S quantum dot.
In the preparation method, in the step (1), the material consumption proportion relation is as follows: sulfur powder: 0.05-0.3 mmol, 0.1-0.3 mmol of indium acetate, 9-12 ml of octadecene and 5-8 ml of oleylamine are heated to be completely dissolved, and nitrogen is introduced into a test tube to prevent the oxidation of the medicine during heating.
In the preparation method, in the step (2), the copper mixed solution is as follows: 0.15 to 0.3mmol of cuprous iodide is dissolved in 1 to 3ml of DDT, and the ultrasonic oscillation is uniform.
In the preparation method, in the step (3), the zinc oxide mixed solution is as follows: zinc oxide is dissolved in 2-ethylhexanoic acid and octadecene, and is obtained by heating and dissolving; the material consumption proportion relation is as follows: zinc oxide 0.1-0.3 mmol, 2-ethylhexanoic acid 1-3ml, octadecene 1-3ml.
In the preparation method, in the step (4), the zinc mixed solution is as follows: dissolving 0.15-0.3 mmol of zinc oxide in 1-3ml of 2-ethylhexanoic acid and 1-3ml of triglyme, heating and dissolving; the sulfur mixed solution is: 0.2 to 0.4mmol of thiourea is dissolved in 6 to 8ml of triglyme.
In the preparation method, in the step (5), 0.01-0.1 mmol of manganese acetate is dissolved in 1-3ml of octadecene, and the ultrasonic oscillation is sufficient.
The ZnS cladding Mn-doped ZCIS five-element quantum dot prepared according to any preparation method.
The application of the five-membered quantum dot is applied to light quantum information access information.
The ZnS cladding and Mn doped Zn-Cu-In-S five-membered quantum make up for the defects of low luminous efficiency, generally low quantum yield, short fluorescence life, poor chemical stability and the like of the synthesized quantum dots In the prior art. The novel pentaquantum dot not only can keep the advantages of tunable spectrum, high luminous efficiency and the like of the general undoped quantum dot due to the doping of ZnS cladding and Mn, but also can effectively inhibit the self-absorption effect of luminescence due to large Stokes displacement, avoid self-quenching phenomenon, and simultaneously has the excellent properties of wider spectrum adjustable range, better photochemical stability and the like. Based on the synthesized quantum dots, a polymer solution is prepared and printed to obtain a fluorescent pattern. Under natural light, the patterns are colorless, have a hiding effect, and cannot be observed by naked eyes, and the patterns can be seen only under excitation of a certain wavelength.
Drawings
FIG. 1 shows the UV absorption spectra of Mn-doped Zn-Cu-In-S quantum dots used In the preparation stage of the material according to the invention at different synthesis stages.
FIG. 2 shows photoluminescence spectra of Mn-doped Zn-Cu-In-S quantum dots used In the preparation stage of the material according to the invention at different synthesis stages.
FIG. 3 shows the quantum yields of the Mn-doped Zn-Cu-In-S quantum dots used In the preparation stage of the material according to the invention In the synthesis stage In the state of doping with different molMn.
FIG. 4 is a transmission electron microscope image of Mn-doped Zn-Cu-In-S quantum dots used In the preparation stage of the material of the invention.
FIG. 5 is a high resolution graph of Mn-doped Zn-Cu-In-S quantum dots used In the preparation stage of the material of the present invention.
FIG. 6 is a graph of EDX analysis of Mn-doped Zn-Cu-In-S quantum dots at the preparation stage of the material of the present invention.
Fig. 7 is a pattern printed by a quantum dot solution polymer at the preparation stage of the material according to the present invention.
FIG. 8 is a transmission electron microscope image of the Zn-Cu-In-S quantum dot synthesized In example 1 of the present invention.
FIG. 9 is an EDX analysis chart of Zn-Cu-In-S quantum dots synthesized In example 1 of the present invention.
Fig. 10 is a fluorescent plot of the test quantum dots of example 4 of the present invention.
FIG. 11 is a graph showing the excitation, fluorescence and quantum yield of the test quantum dots according to example 4 of the present invention, wherein the fluorescence quantum yield of the Mn-doped five-membered quantum dots is improved from 38% (a) to 68% (b).
FIG. 12 is a graph of fluorescence lifetime of a test quantum dot according to example 4 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1:
the Zn-Cu-In-S quaternary quantum dot is synthesized without adding transition metal element Mn, and is only compared with Mn-doped Zn-Cu-In-S quinary quantum dot.
The preparation method of the quaternary Zn-Cu-In-S quantum dot comprises the following specific steps:
(1) 0.15mmol of S powder, 0.2mmol of indium acetate and 9ml of octadecene and 2ml of oleylamine are added into a three-neck flask; heating to 100 ℃ in a vacuum state to ensure that the mixed solution is completely dissolved, no solid impurities remain, and heating at a speed of 5 ℃/min;
(2) 0.15mmol of cuprous iodide and 1ml of DDT are added into a test tube, the mouth of the test tube is plugged with cotton to prevent oxidization, the test tube is put into an ultrasonic instrument for ultrasonic oscillation, and a white mixed solution is obtained when the test tube is completely dissolved. Heating the three-neck flask to 120 ℃, then adding the cuprous iodide mixed solution in the test tube into the three-neck flask in the step (1), mixing and deoxidizing (degassing), heating to 160 ℃, and heating at a heating rate of 5 ℃/min;
(3) Adding 0.2mmol of zinc oxide, 1ml of 2-ethylhexanoic acid and 2ml of octadecene into a test tube, heating the test tube by an alcohol lamp until the zinc oxide is completely dissolved, and plugging cotton into a test tube port to prevent the oxidation of the medicine during heating; after the step (2) is heated to 160 ℃, cooling to 120 ℃, rapidly adding the zinc mixed solution in the test tube into the three-neck flask at the moment, introducing nitrogen all the time, heating to 250 ℃, heating to the temperature rising rate of 5 ℃/min, heating and reacting for 3 to 5min, and preserving heat for 30min;
(4) After adding excessive isopropanol, centrifuging for 10min under the condition of 12000r/min to obtain the Zn-Cu-In-S doped quantum dot. The transmission electron microscope image is shown in fig. 8. EDX is shown in fig. 9.
Example 2:
the preparation method of the Mn-doped Zn-Cu-In-S five-membered quantum dot comprises the following specific steps:
(1) Preparation of In 2 S 3 Quantum dot templates: 0.15mmol of S powder, 0.2mmol of indium acetate and 9ml of octadecene and 2ml of oleylamine are added into a three-neck flask; heating to 100 ℃ in a vacuum state to ensure that the mixed solution is completely dissolved, no solid impurities remain, and heating at a speed of 5 ℃/min;
(2) Drop heating injection of Cu: 0.15mmol of cuprous iodide and 1ml of DDT are added into a test tube, the mouth of the test tube is plugged with cotton to prevent oxidization, the test tube is put into an ultrasonic instrument for ultrasonic oscillation, and a white mixed solution is obtained when the test tube is completely dissolved. Heating the three-neck flask to 120 ℃, then adding the cuprous iodide mixed solution in the test tube into the three-neck flask in the step (1), mixing and deoxidizing (degassing), heating to 160 ℃, and heating at a heating rate of 5 ℃/min;
(3) Drop heating injection of Zn: adding 0.2mmol of zinc oxide, 1ml of 2-ethylhexanoic acid and 2ml of octadecene into a test tube, heating the test tube by an alcohol lamp until the zinc oxide is completely dissolved, and plugging cotton into a test tube port to prevent the oxidation of the medicine during heating; after the step (2) is heated to 160 ℃, cooling to 120 ℃, rapidly adding the zinc mixed solution in the test tube into the three-neck flask at the moment, introducing nitrogen all the time, heating to 250 ℃, and heating to react for 3 to 5 minutes at a heating rate of 5 ℃/min;
(4) ZnS coated quantum dot: after the reaction, naturally cooling the obtained ZCIS quantum dot solution; during the cooling period, 0.15mmol of zinc oxide and 1ml of solvent 2-ethylhexanoic acid and 3ml of solvent triglyme are added into a test tube, the test tube is heated by an alcohol lamp until the zinc oxide is completely dissolved, and cotton is plugged into the mouth of the test tube during heating to prevent the oxidation of the medicine; during the cooling period, 0.2mmol of thiourea and 6ml of solvent triethylene glycol dimethyl ether are added into a test tube, and the test tube is placed into a constant temperature oil pot at 70 ℃ to be continuously stirred and heated by a glass rod, and cotton is plugged into a test tube port during heating to prevent the oxidation of the medicine; mixing zinc oxide solution and thiourea solution; mixing and stirring the obtained zinc oxide solution and thiourea solution to obtain ZnS, after the ZCIS quantum dot solution is cooled to 100 ℃, adding the mixed zinc oxide solution and thiourea solution, heating to 180 ℃, and introducing nitrogen at a heating rate of 5 ℃/min;
(5) Adding 0.01mmol of manganese acetate and 2ml of octadecene into a test tube, putting into an ultrasonic machine for complete dissolution, and plugging cotton into an ultrasonic middle test tube orifice to prevent the oxidation of the medicine; after the step (4) is heated to 200 ℃, rapidly adding the manganese mixed solution in the test tube into the three-neck flask at the moment, introducing nitrogen all the time, heating to 250 ℃, heating to a heating rate of 5 ℃/min, and reacting for 8-10 min; preserving heat for 30min, cooling to normal temperature, adding excessive isopropanol, and centrifuging for 10min under the condition of 12000r/min to obtain Mn-doped Zn-Cu-In-S quantum dots.
Fig. 1 and fig. 2 are ultraviolet and photoluminescence spectra of synthesized quantum dots, fig. 3 is quantum yield of Zn-Cu-In-S quantum dots doped with different mmolmns, fig. 4 is a transmission electron microscope image of morphology of synthesized quantum dots, and the morphology is observed as regular dots, wherein the first synthesized indium sulfide has no photoluminescence peak, and the spectra are obviously changed with the introduction of copper element and zinc element after the rest. After copper is added, the fluorescence peak is about 680nm, and after zinc element is added, the light intensity is obviously increased, and the peak is blue-shifted to about 630nm, and the whole product shows oil solubility. Then ZnS cladding and Mn doping are carried out, and finally the crystal is stabilized at about 585nm of emission peak to form orange light. Fig. 5 shows that the lattice spacing between black and white of the quantum dots can be clearly seen with good lattice structure by measuring high resolution. Fig. 6EDX analysis shows successful doping of Mn.
And dissolving the obtained quantum dots in 6ml of benzene reagent, and carrying out ultrasonic oscillation uniformly to obtain a quantum dot solution dissolved in the benzene reagent.
Weighing 1g of polystyrene, putting the polystyrene into the quantum dot solution, adding a rotor heating magnetic stirrer for 500r/min, and obtaining the quantum dot solution polymer after the polystyrene is completely dissolved.
And 2ml of the obtained quantum dot solution polymer is placed in an electrospray printing tube, and the printing can be performed after the current pressure is set. Fig. 7 is a pattern printed by a quantum dot solution polymer. Orange light was varied under 365nm excitation.
Example 3:
the method for providing the quantum dot solution polymer single light quantum information access pattern comprises the following specific scheme:
and (3) dissolving the obtained 0.1g quantum dot in 2ml benzene reagent, and carrying out ultrasonic oscillation uniformly to obtain a quantum dot solution dissolved in the benzene reagent.
Weighing 0.5g of polystyrene, putting the polystyrene into the quantum dot solution, adding a rotor heating magnetic stirrer for 500r/min, and obtaining the quantum dot solution polymer after the polystyrene is completely dissolved;
the solution polymer is placed in an electrospray printing tube, the pressure intensity is set, the current is adjusted, and the solution polymer is printed on a template, so that the set pattern can be printed; the printed pattern is not easy to be seen clearly by naked eyes, and the pattern 7 can be seen clearly under the irradiation of an ultraviolet lamp, so that the original quantum dot solution is emitted.
Example 4:
the novel method for synthesizing the five-membered quantum dot is provided, and has the advantages of high luminous efficiency, strong quantum yield, long fluorescence life and good chemical stability, and the analysis is carried out by carrying out tests of fluorescence intensity, life, yield and the like, and the specific scheme is as follows:
obtaining ZnCuInS quaternary quantum dots by the synthesis method of the example 1;
mn-doped ZnCuInS five-element quantum dots are obtained by the synthesis method of the example 2;
sequentially diluting the synthesized quantum dots with trichloroethylene, and extracting quantitative solution for test analysis;
FIG. 10 is a graph showing the fluorescence intensity of the quantum dots, wherein the fluorescence intensity of the five-membered quantum dots doped with Mn is improved.
FIG. 11 is a graph showing the fluorescence intensity, excitation and quantum yield of the tested quantum dots, wherein the fluorescence quantum yield of the Mn-doped five-membered quantum dots is improved from 38% to 68%.
FIG. 12 is a graph showing the fluorescence lifetime of the tested quantum dots, wherein the fluorescence quantum lifetime of the Mn-doped pentaquantum dots is improved from 9ms to 12ms.
It will be understood that modifications and variations will be apparent to those skilled in the art from the foregoing description, and it is intended that all such modifications and variations be included within the scope of the following claims.
Claims (8)
1. The preparation method of the ZnS cladding Mn-doped ZCIS five-element quantum dot is characterized by comprising the following steps of:
(1) Preparation of In 2 S 3 Quantum dot templates: heating high-concentration sulfur powder and indium acetate in a solvent octadecene and ligand oleylamine to 100 ℃ for dissolution, and deoxidizing after complete dissolution to obtain an indium sulfide mixed solution;
(2) Drop heating injection of Cu: and (3) dissolving cuprous iodide in the DDT, and carrying out ultrasonic oscillation to obtain a white turbid solution after complete dissolution. Adding the dissolved cuprous iodide solution into the indium sulfide solution obtained in the step (1) heated to 120 ℃, quickly changing the mixed solution into dark red, deoxidizing, and heating to 160 ℃;
(3) Drop heating injection of Zn: heating the mixed solution obtained In the step (2) to 160 ℃, then cooling to 120 ℃, adding the dissolved zinc oxide mixed solution, heating to 250 ℃ and maintaining a nitrogen atmosphere for reacting for a period of time to obtain a Zn-Cu-In-S quantum dot solution;
(4) ZnS coated quantum dot: zinc oxide is dissolved in a solvent of 2-ethylhexanoic acid, and the zinc oxide is heated and dissolved in a solvent of triglyme to obtain a zinc mixed solution; dissolving thiourea in a solvent triglyme, and heating and dissolving in an oil pan to obtain a sulfur mixed solution; mixing a zinc oxide solution and a thiourea solution to obtain ZnS; heating Zn-Cu-In-S quantum dot solution reacted for a certain time, standing, cooling to 100 ℃, keeping nitrogen, adding mixed zinc oxide solution and thiourea solution, and heating to 180 ℃;
(5) Doping transition metal element Mn: dissolving manganese acetate in a solvent octadecene, and carrying out ultrasonic oscillation to completely dissolve; adding the dissolved manganese acetate solution into the solution obtained in the step (4) heated to 200 ℃, and keeping the temperature for reacting for a certain time when the temperature is raised to 250 ℃; cooling to normal temperature after the reaction is completed, adding excessive isopropanol, and centrifuging to obtain the ZnS cladding and Mn-doped Zn-Cu-In-S quantum dot.
2. The method according to claim 1, wherein in the step (1), the ratio of the amounts of the substances is: sulfur powder: 0.05-0.3 mmol, 0.1-0.3 mmol of indium acetate, 9-12 ml of octadecene and 5-8 ml of oleylamine are heated to be completely dissolved, and nitrogen is introduced into a test tube to prevent the oxidation of the medicine during heating.
3. The method according to claim 1, wherein in the step (2), the copper mixed solution is: 0.15 to 0.3mmol of cuprous iodide is dissolved in 1 to 3ml of DDT, and the ultrasonic oscillation is uniform.
4. The method according to claim 1, wherein in the step (3), the zinc oxide mixed solution is: zinc oxide is dissolved in 2-ethylhexanoic acid and octadecene, and is obtained by heating and dissolving; the material consumption proportion relation is as follows: zinc oxide 0.1-0.3 mmol, 2-ethylhexanoic acid 1-3ml, octadecene 1-3ml.
5. The method according to claim 1, wherein in the step (4), the zinc mixed solution is: dissolving 0.15-0.3 mmol of zinc oxide in 1-3ml of 2-ethylhexanoic acid and 1-3ml of triglyme, heating and dissolving; the sulfur mixed solution is: 0.2 to 0.4mmol of thiourea is dissolved in 6 to 8ml of triglyme.
6. The process according to claim 1, wherein in step (5), manganese acetate of 0.01 to 0.1mmol is dissolved in octadecene of 1 to 3ml and the ultrasonic vibration is sufficient.
7. ZnS cladding Mn-doped zci five-membered quantum dot prepared according to any one of claims 1 to 6.
8. The application of the five-membered quantum dot in claim 7, which is applied to light quantum information access information.
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