CN115433562B - Method for improving particle size dispersity of quantum dots based on solvothermal method - Google Patents
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Abstract
The invention discloses a method for improving the dispersion degree of particle diameters of quantum dots based on a solvothermal method, which comprises the following steps: first, the precursor of partial elements in the quantum dot component is encapsulated in an organic polymer carrier to form a precursor carrier, and then the precursor carrier is combined with other reactants to perform solvothermal synthesis of the quantum dot. According to the invention, a new quantum dot preparation thought based on a solvothermal method and capable of improving the particle size dispersity of the quantum dots is obtained, and the organic polymer carrier is introduced to enable the precursor with local high concentration to appear in the reaction process, so that the local rapid centralized nucleation process of the quantum dots is realized, the purpose of improving the particle size dispersity of the synthesized quantum dots is realized, and the method has important value for realizing mass production of the quantum dots.
Description
Technical Field
The invention belongs to the field of material synthesis, and particularly relates to a method for improving the particle size dispersity of quantum dots based on a solvothermal method.
Background
Quantum Dots (QDs), also known as semiconductor nanocrystals (semiconductor nanocrystal, NC), are semiconductor nanoparticles composed of a small number of atoms. The three dimensions of the quantum dot are all in the nanometer level, the movement of the carrier in all directions is restrained, and the quantum confinement effect is obvious. Thus, quantum dots also have the following unique physical properties: quantum size effects, quantum tunneling effects, coulomb blockade effects, surface effects, dielectric confinement effects, and the like. The quantum dot material also has the characteristics of high quantum yield, narrow light-emitting spectrum, adjustable light-emitting wavelength, high photochemical stability, long fluorescence life, multiple synthesis methods and the like, and can cover the whole visible light range. Due to their unique optical properties, quantum dots are widely used in the fields of medical imaging and bioluminescence labeling, fluorescence sensing and electrochemiluminescence analysis, photocatalysis, solar cells, LEDs, and the like. Currently, the quantum dots that are widely studied are: II-VI group quantum dots (represented by CdSe), III-V group quantum dots (represented by InP), graphene quantum dots, I-III-VI group quantum dots (represented by AgInGaS), perovskite quantum dots, and the like.
The synthesis method of quantum dots can be classified into a physical preparation method and a chemical preparation method. The physical preparation method comprises a molecular beam epitaxy method, a vapor deposition method, a laser sputtering deposition method, an ion implantation method, a vapor condensation method, a mechanical crushing method and the like. The chemical preparation method comprises a metal organic synthesis method, a sol-gel method, a supersaturation crystallization method, a microemulsion method, a hot injection method, a hydrothermal method, a solvothermal method and the like.
The quantum dots prepared by the physical preparation method have high purity and excellent performance, but the preparation method needs to be carried out under high vacuum or ultrahigh vacuum, has extremely high requirements on the preparation environment, and has extremely high preparation cost due to expensive preparation equipment. The chemical preparation method has the advantages of relatively simple preparation flow, no need of complex instruments and equipment, low cost, mass preparation, high yield and high luminous efficiency of the prepared quantum dot.
The chemical synthesis method has relatively low preparation cost and is safe and reliable. The main representative method is as follows: microemulsion, hot injection, solvothermal. The solvothermal method has the advantages of easy operation of the reaction process, relatively simple reaction conditions and capability of preparing a large amount of quantum dot materials, but also has the defect of larger dispersion degree of the prepared particle size.
Disclosure of Invention
The solvothermal method has the advantage of preparing a large number of quantum dots at a time, but the quantum dots prepared by the solvothermal method have poor particle size dispersity, so that the yield of the target product of the method cannot reach the theoretical highest value. The invention provides a synthesis method capable of improving the particle size dispersity of prepared quantum dots based on a solvothermal method so as to improve the feasibility of the solvothermal method in large-scale synthesis of the quantum dots. According to the invention, the preparation method of the quantum dots is improved to be a rapid concentrated nucleation quantum dot preparation method by improving the preparation method of the quantum dots which are randomly and spontaneously nucleated in a large range in an integral reaction vessel by a traditional solvothermal method, so that the reaction precursor of the quantum dots reaches a high concentration state in a local area in the reaction vessel, and the particle size dispersity of the prepared quantum dots is improved by realizing a local high concentration concentrated nucleation process. Due to the quantum size effect of the quantum dots, the better the dispersion of the particle size of the quantum dots is manifested in the photoelectric performance as a smaller light emitting full width at half maximum (FWHM), and the larger the size of the quantum dots is manifested in the photoelectric performance as a larger red shift of the light emitting peak.
The technical scheme of the invention is as follows: the method for improving the particle size dispersity of the quantum dots based on the solvothermal method is characterized by comprising the following steps of:
(1) The precursor of part of elements in the quantum dot component is encapsulated in an organic polymer in a wrapping, dispersing and other modes to obtain an organic polymer carrier (hereinafter simply referred to as carrier) containing the precursor, and the carrier is kept stable at normal temperature and normal pressure so that the precursor is not contacted with the external environment; the selection of partial elements in the quantum dot component is that certain elements in the II-VI group quantum dot are II-group or VI-group elements in the quantum dot component, certain elements in the III-V group quantum dot are III-group or V-group elements in the quantum dot component, certain elements in the I-III-VI group quantum dot are VI-group elements or the combination of I-group and III-group elements, and certain elements in the perovskite quantum dot (ABX 3) are A-bit elements or the combination of B-bit and X-bit elements;
(2) Transferring the carrier and other reactants (other reaction precursors, organic ligands and solvents) required by synthesizing the quantum dots into a reaction vessel, heating the reaction vessel to the temperature required by the synthesis reaction for carrying out the synthesis reaction, wherein the reaction process can be divided into three stages, namely a stable heating stage, wherein the carrier is kept stable in the stage before the reaction environment is heated from room temperature to temperature T1; the second stage is a stage of intensively releasing and nucleating the precursor from the carrier, in the stage, the reaction environment is heated to the temperature T1, the precursor is intensively released from the carrier, the precursor reaches a high concentration state in a region near the carrier, the high concentration precursor contacts with other reactants and rapidly completes the region centralized nucleating process of the quantum dots, so as to form crystal nuclei; thirdly, in the growth stage of the quantum dots, the temperature of a reaction environment is T2, and quantum dot crystal nuclei generated by concentrated nucleation are dispersed in a reaction vessel solvent to continuously complete the growth of the quantum dots. After the reaction is completed, products with different sizes are separated in a centrifugal mode to obtain the quantum dots with the target sizes.
The II-VI group quantum dots, the II-VI group quantum dots and the I-III-VI group quantum dots and the perovskite quantum dots in the step (1) are respectively as follows: the II-VI group quantum dot can be binary or multi-element combination of II group elements Zn, cd and VI group elements O, S, se, te; the III-V quantum dots may be binary or multi-element combinations of III-element Al, ga, in, tl and V-element N, P, as; the I-III-VI group quantum dots can be ternary or multi-element combinations of I group elements Cu, ag and Au, III group elements Al, ga, in, tl and VI group elements O, S, se, te; perovskite quantum dots are a generic term for a class of materials having ABX 3 crystal structure, wherein the a-position can be one or more combinations of methylamine ion, formamidine ion, cesium ion, the B-position can be one or more combinations of divalent lead ion, tin ion, manganese ion, and the X-position can be one or more combinations of halogen anions. The quantum dots described in step (1) above are selected from the group consisting of: for II-VI group quantum dots, the selected precursor is a precursor of Cd and Zn elements or a precursor of O, S, se, te elements; for III-V quantum dots, the precursor selected is Al, ga, in, tl precursor or N, P, as precursor; for the I-III-VI quantum dots, the precursor is O, S, se, te element precursor or Cu, ag, au, al, ga, in, tl element precursor; for perovskite quantum dots, the precursors selected are precursors of methylamine ions, formamidine ions, cesium ions, or precursors of lead ions, tin ions, manganese ions, halogen ions.
The organic polymer used for encapsulating the precursor in the step can be one or more of polyvinyl acetate, polymethyl oxide, polystyrene, polyethylene, polyvinyl chloride, polypropylene, polyacrylate, acrylic resin, cyanoacrylate and silica gel, and the materials are selected so that the synthesis reaction of the quantum dots does not involve the components of the selected organic polymer.
The method of encapsulating the precursor into the organic polymer in step (1) above comprises: and (3) wrapping, dispersing and wrapping. Wherein the encapsulation is a packaging method in which the precursor is placed in a closed space formed by the organic polymer; the dispersion is a packaging method for uniformly dispersing the precursor in the organic polymer by a melting method, a solvent-melting method, a grinding method, an ultraviolet light curing method and an oxidation curing method, wherein the melting method is to uniformly mix the precursor and the organic polymer, heat the precursor to melt, and rapidly cool the melt into solid under stirring to obtain a carrier; the solvent method is to dissolve the precursor and the organic polymer in the organic solvent together, and remove the solvent by evaporation, cooling and drying to obtain a carrier; the solvent-melting method is to dissolve one of the precursor or the organic polymer in a small amount of organic solvent, then directly add the solution into the melted other material, uniformly mix, evaporate and remove the solvent to obtain the carrier; the grinding method is to mix the precursor and the organic polymer, grind for a period of time and obtain the carrier; the ultraviolet curing method is to uniformly disperse the precursor in an ultraviolet curing material, then cure the precursor under the irradiation of ultraviolet light, and stably disperse the precursor in the cured mixture to obtain a carrier; the oxidation curing method is to uniformly disperse the precursor in a substance which is easy to cause oxidation reaction in air and generates stable solid substances, and after the oxidation reaction is completely carried out, the precursor is stably dispersed in the solid substances generated by the oxidation reaction to obtain the carrier. Specific encapsulation will employ a combination of one or more of the above encapsulation methods depending on the nature of the precursor and the organic polymer.
After the precursor for encapsulation in the carrier is encapsulated by using the organic polymer and the encapsulation method, the obtained carrier needs to meet the following requirements: (1) For the temperature T1 of the precursor released from the carrier (namely, the organic polymer carrier keeps a stable state before the temperature of the reaction environment reaches T1) and the lowest temperature T3 of the quantum dot generating nuclear reaction, T3 is less than or equal to T1, and the T1 of the carrier can be regulated by adjusting the material and packaging mode of the organic polymer; (2) Before the reaction environment temperature reaches T1, the carrier keeps a stable state, so that the internal precursor does not contact with the external environment (other reaction raw materials in the reaction vessel) of the carrier, the precursor does not generate any chemical reaction in the carrier, and the carrier has an isolation effect on the packaged precursor; (3) When the temperature of the carrier reaches T1, the carrier should be cracked, decomposed, dissolved, hydrolyzed or decomposed to quickly release the precursor, wherein if the carrier needs to be added with other reactants or catalysts and the reaction vessel is airtight in the above reaction, the relevant reaction raw materials should be added together when being transferred to the reaction vessel in the step (2); (4) The carrier and other reactants or components of the catalyst required for the reaction do not participate in the synthesis of the quantum dots. The external environment of the carrier in the requirement (2) refers to other reaction precursors, organic ligands, solvents, other reactants or catalysts added according to the reaction requirement and gas environment in a reaction vessel; the reaction environment described in the claim (2) means a reaction vessel, a precursor carrier in the reaction vessel, and the carrier external environment described above.
The solvothermal method is a synthetic method which takes organic matters or water as a solvent and reacts original reactants in the solvent under certain temperature and pressure. The solvothermal method comprises a solvothermal method, a hydrothermal method and an LSS three-phase method which take organic matters as solvents, and the pressure in a reaction vessel can be high pressure or normal pressure.
The three stages of the reaction in the step (2) are specifically: a stable heating stage, in which the precursor carrier is kept in a stable state before the reaction environment is heated from room temperature to temperature T1, and the precursor is kept in the carrier stably and does not contact with the external environment, and the precursor in the carrier does not undergo any chemical reaction; secondly, the precursor is intensively released from the carrier and intensively nucleated, the reaction environment is heated to the temperature T1, the precursor carrier is subjected to reactions such as cracking, decomposition, dissolution or hydrolysis, the precursor is intensively released from the carrier and reaches a high concentration state in a region near the carrier, even a local supersaturation state of the precursor occurs, the precursor with local high concentration contacts with other reactants and rapidly completes the centralized nucleation process of the quantum dots, a batch of crystal nuclei with high size uniformity is generated, and the nucleation reaction is rapidly and intensively performed due to the high temperature of the reaction environment and the high concentration of the precursor in the local region near the carrier; thirdly, in the growth stage of the quantum dot, the temperature of the reaction environment is T2, crystal nuclei generated by concentrated nucleation are dispersed in a solvent and continue to complete the growth of the quantum dot, and the temperature T2 for continuing to grow after the nucleation of the quantum dot can be equal to, higher than or lower than the nucleation temperature T3 of the quantum dot, but the temperature T2 is in a temperature range in which the growth of the quantum dot can continue after the nucleation of the quantum dot, namely the continuous growth speed of the quantum dot can be controlled by regulating and controlling different growth temperatures.
The specific steps of separating the products with different sizes by centrifugation in the step (2) are as follows: dispersing the product in polar solvent, adding a small amount of nonpolar solvent, mixing the product, polar solvent and nonpolar solvent thoroughly and uniformly by shaking, ultrasonic vibration and the like, and separating the products with different sizes by centrifugation. Wherein, the greater the proportion of polar solvent and nonpolar solvent, the higher the separation precision; the higher the rotational speed of the centrifugation, the poorer the accuracy of the separation.
The invention relates to a method for improving the dispersion degree of particle size of quantum dots based on a solvothermal method, which is characterized in that the size of the prepared quantum dots is controllable, and the control method comprises the following steps: (1) The growth of the quantum dots is controlled by changing the reaction time, namely, the longer the time of the growth stage of the quantum dots, the closer the probability of collision among various particles in a reaction vessel is to the theoretical maximum value, and the closer the growth size of the quantum dots is to the theoretical maximum value, so that the longer the reaction time is, the larger the size of the prepared quantum dots is; (2) The growth of the quantum dots is controlled by changing the temperature T2 for continuing to grow after the nucleation of the quantum dots, the higher the reaction temperature is in a temperature range suitable for continuing to grow after the nucleation of the quantum dots, the higher the energy of various particles in a reaction vessel is, the more intense the convection motion in the reaction vessel is, the higher the probability of collision of various particles in the same time is, and the higher the theoretical maximum value of collision among various particles is, so that the higher the reaction temperature is in a temperature range suitable for the nucleation and growth of the quantum dots, the larger the size of the prepared quantum dots is; (3) After the quantum dots are prepared according to the steps, precursors and organic ligands required by synthesizing the quantum dots are continuously added into a reaction vessel, and solvothermal reaction is performed again, so that the continuous growth of the quantum dots can be realized, and the mechanism is as follows: after the preparation step is finished by the method for improving the particle size dispersity of the quantum dots based on the solvothermal method for the first time, a batch of quantum dots are generated in the reaction vessel, the concentration of reactants in the reaction vessel is reduced to be low enough, the growth speed of the residual reactants continuously surrounding the quantum dots is very slow by increasing the temperature and prolonging the reaction time, after precursors and organic ligands required for synthesizing the quantum dots are continuously added, the concentration of the reactants in the reaction vessel is increased, the newly added reactants mainly grow around the quantum dots in the next solvothermal reaction, so that the quantum dots continuously grow, even if a very small amount of reactants possibly spontaneously nucleate due to the excessive concentration of the local reactants, the newly nucleated small-size quantum dots are also "swallowed" by the existing large-size quantum dots according to the Ostwald Ripening theory, and the particle size dispersity of the prepared quantum dots is ensured.
Drawings
Fig. 1 is a simplified schematic diagram of a reaction process of a method for improving dispersion of particle size of quantum dots based on a solvothermal method according to the present invention, wherein a is a precursor encapsulated in an organic polymer carrier, B is other precursors in a reaction vessel, 1 is the organic polymer carrier, 2 is the precursor a and the precursor B perform concentrated nucleation reaction, 3 is the quantum dot nuclei continue to grow, and an organic ligand, a solvent, other reactants or catalysts added according to the reaction requirement, and a gas environment in the reaction vessel are omitted in the figure. The stage 1 is a stable heating stage, the precursor A is kept stable in the carrier, and the precursor A and the precursor B are not contacted due to the isolation effect of the carrier, so that chemical reaction does not occur to any extent; stage 2 and stage 3 are stages of centralized release and centralized nucleation of the precursor from the carrier, stage 2 is rapid centralized release of the precursor A from the carrier, and reaches a high concentration, even supersaturated state in the vicinity of the carrier, stage 3 is rapid centralized nucleation of the quantum dots, and the precursor A with local high concentration is contacted with the precursor B in the reaction vessel to generate a nuclear reaction (as shown in the position 2 in the figure); the stage 4 is a growth stage of the quantum dots, and quantum dot crystal nuclei generated by rapid concentrated nucleation in the stage 3 are dispersed in a solvent and continue to react to realize the growth of the quantum dots (as shown at 3 in the figure).
Detailed Description
The invention is further described below in connection with the following examples:
Example 1
Dissolving cadmium acetate in a small amount of water, and transferring the solution into a closed polyethylene container to obtain a precursor carrier; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in a photoelectric oven with the set temperature of 140 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 553nm under the excitation of light with the wavelength of 380nm, and the FWHM is 36nm.
Example 2
Dissolving cadmium acetate in a small amount of water, and transferring the solution into a closed polyethylene container to obtain a precursor carrier; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 150 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 569nm and the FWHM is 30nm under the excitation of light with the wavelength of 380 nm.
Example 3
Dissolving cadmium acetate in a small amount of water, and transferring the solution into a closed polyethylene container to obtain a precursor carrier; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in a photoelectric oven with the set temperature of 160 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 583nm and FWHM is 28nm under the excitation of light with the wavelength of 380 nm.
Example 4
Dissolving cadmium acetate in a small amount of water, and transferring the solution into a closed polyethylene container to obtain a precursor carrier; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in a photoelectric oven with the set temperature of 170 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 591nm and FWHM is 28nm under the excitation of light with the wavelength of 380 nm.
Example 5
Dissolving cadmium acetate in a small amount of water, and transferring the solution into a closed polyethylene container to obtain a precursor carrier; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 608nm under the excitation of light with the wavelength of 380nm, and the FWHM is 31nm.
Example 6
Dissolving cadmium acetate in a small amount of water, and transferring the solution into a closed polyethylene container to obtain a precursor carrier; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 160 ℃ for 6 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 598nm and the FWHM is 27nm under the excitation of light with the wavelength of 380 nm.
Example 7
Dissolving cadmium acetate in a small amount of water, and transferring the solution into a closed polyethylene container to obtain a precursor carrier; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the reaction kettle in a photoelectric oven with the set temperature of 160 ℃ for 8 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 611nm and FWHM is 33nm under the excitation of light with the wavelength of 380 nm.
Example 8
Dissolving cadmium acetate in a small amount of water, and transferring the solution into a closed polyethylene container to obtain a precursor carrier; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in a photoelectric oven with the set temperature of 160 ℃ for 10 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 617nm and FWHM is 28nm under the excitation of light with the wavelength of 380 nm.
Example 9
Dissolving cadmium acetate in a small amount of water, and transferring the solution into a closed polyethylene container to obtain a precursor carrier; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 6 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 624nm under the excitation of light with the wavelength of 380nm, and the FWHM is 34nm.
Example 10
Dissolving cadmium acetate in a small amount of water, and transferring the solution into a closed polyethylene container to obtain a precursor carrier; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 8 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 632nm and the FWHM is 35nm under the excitation of light with the wavelength of 380 nm.
Example 11
Dissolving cadmium acetate in a small amount of water, and transferring the solution into a closed polyethylene container to obtain a precursor carrier; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 10 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 640 nm and the FWHM is 35nm under the excitation of light with the wavelength of 380 nm.
Example 12
Injecting cyanoacrylate into a mould, waiting for the cyanoacrylate to be oxidized with air to obtain a carrier container, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container by cyanoacrylate, and obtaining a precursor carrier after the cyanoacrylate is completely oxidized; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in a photoelectric oven with the set temperature of 140 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 547nm and FWHM is 28nm under the excitation of light with the wavelength of 380 nm.
Example 13
Injecting cyanoacrylate into a mould, waiting for the cyanoacrylate to be oxidized with air to obtain a carrier container, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container by cyanoacrylate, and obtaining a precursor carrier after the cyanoacrylate is completely oxidized; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 150 ℃ for 4 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 573nm under the excitation of light with the wavelength of 380nm, and the FWHM is 30nm.
Example 14
Injecting cyanoacrylate into a mould, waiting for the cyanoacrylate to be oxidized with air to obtain a carrier container, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container by cyanoacrylate, and obtaining a precursor carrier after the cyanoacrylate is completely oxidized; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the reaction kettle in a photoelectric oven with the set temperature of 160 ℃ for 4 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 589nm and FWHM is 36nm under the excitation of light with the wavelength of 380 nm.
Example 15
Injecting cyanoacrylate into a mould, waiting for the cyanoacrylate to be oxidized with air to obtain a carrier container, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container by cyanoacrylate, and obtaining a precursor carrier after the cyanoacrylate is completely oxidized; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in a photoelectric oven with the set temperature of 170 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminous peak of the quantum dot is 598nm and FWHM is 33nm under the excitation of light with the wavelength of 380 nm.
Example 16
Injecting cyanoacrylate into a mould, waiting for the cyanoacrylate to be oxidized with air to obtain a carrier container, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container by cyanoacrylate, and obtaining a precursor carrier after the cyanoacrylate is completely oxidized; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 603nm under the excitation of light with the wavelength of 380nm, and the FWHM is 35nm.
Example 17
Injecting cyanoacrylate into a mould, waiting for the cyanoacrylate to be oxidized with air to obtain a carrier container, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container by cyanoacrylate, and obtaining a precursor carrier after the cyanoacrylate is completely oxidized; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 160 ℃ for 6 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 597nm and the FWHM is 27nm under the excitation of light with the wavelength of 380 nm.
Example 18
Injecting cyanoacrylate into a mould, waiting for the cyanoacrylate to be oxidized with air to obtain a carrier container, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container by cyanoacrylate, and obtaining a precursor carrier after the cyanoacrylate is completely oxidized; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the reaction kettle in a photoelectric oven with the set temperature of 160 ℃ for 8 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 614nm and FWHM is 36nm under the excitation of light with the wavelength of 380 nm.
Example 19
Injecting cyanoacrylate into a mould, waiting for the cyanoacrylate to be oxidized with air to obtain a carrier container, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container by cyanoacrylate, and obtaining a precursor carrier after the cyanoacrylate is completely oxidized; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in a photoelectric oven with the set temperature of 160 ℃ for 10 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminous peak of the quantum dot is 621nm and FWHM is 31nm under the excitation of light with the wavelength of 380 nm.
Example 20
Injecting cyanoacrylate into a mould, waiting for the cyanoacrylate to be oxidized with air to obtain a carrier container, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container by cyanoacrylate, and obtaining a precursor carrier after the cyanoacrylate is completely oxidized; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 6 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 605nm under the excitation of light with the wavelength of 380nm, and the FWHM is 37nm.
Example 21
Injecting cyanoacrylate into a mould, waiting for the cyanoacrylate to be oxidized with air to obtain a carrier container, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container by cyanoacrylate, and obtaining a precursor carrier after the cyanoacrylate is completely oxidized; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 8 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 616nm and the FWHM is 27nm under the excitation of light with the wavelength of 380 nm.
Example 22
Injecting cyanoacrylate into a mould, waiting for the cyanoacrylate to be oxidized with air to obtain a carrier container, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container by cyanoacrylate, and obtaining a precursor carrier after the cyanoacrylate is completely oxidized; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 10 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 631nm and FWHM is 28nm under the excitation of light with the wavelength of 380 nm.
Example 23
Injecting acrylic resin into a mold, irradiating with an ultraviolet lamp to obtain a carrier container after curing, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container with the acrylic resin, and irradiating with the ultraviolet lamp to obtain a precursor carrier after curing the whole container; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in a photoelectric oven with the set temperature of 140 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 543nm and the FWHM is 32nm under the excitation of light with the wavelength of 380 nm.
Example 24
Injecting acrylic resin into a mold, irradiating with an ultraviolet lamp to obtain a carrier container after curing, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container with the acrylic resin, and irradiating with the ultraviolet lamp to obtain a precursor carrier after curing the whole container; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 150 ℃ for 4 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 560 nm under the excitation of light with the wavelength of 380nm, and the FWHM is 31nm.
Example 25
Injecting acrylic resin into a mold, irradiating with an ultraviolet lamp to obtain a carrier container after curing, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container with the acrylic resin, and irradiating with the ultraviolet lamp to obtain a precursor carrier after curing the whole container; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in a photoelectric oven with the set temperature of 160 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 577nm and FWHM is 35nm under the excitation of light with the wavelength of 380 nm.
Example 26
Injecting acrylic resin into a mold, irradiating with an ultraviolet lamp to obtain a carrier container after curing, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container with the acrylic resin, and irradiating with the ultraviolet lamp to obtain a precursor carrier after curing the whole container; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in a photoelectric oven with the set temperature of 170 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminous peak of the quantum dot is 592nm and FWHM is 28nm under the excitation of light with the wavelength of 380 nm.
Example 27
Injecting acrylic resin into a mold, irradiating with an ultraviolet lamp to obtain a carrier container after curing, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container with the acrylic resin, and irradiating with the ultraviolet lamp to obtain a precursor carrier after curing the whole container; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 4 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 608nm under the excitation of light with the wavelength of 380nm, and the FWHM is 32nm.
Example 28
Injecting acrylic resin into a mold, irradiating with an ultraviolet lamp to obtain a carrier container after curing, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container with the acrylic resin, and irradiating with the ultraviolet lamp to obtain a precursor carrier after curing the whole container; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 160 ℃ for 6 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 284 nm under the excitation of light with the wavelength of 380nm, and the FWHM is 32nm.
Example 29
Injecting acrylic resin into a mold, irradiating with an ultraviolet lamp to obtain a carrier container after curing, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container with the acrylic resin, and irradiating with the ultraviolet lamp to obtain a precursor carrier after curing the whole container; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in a photoelectric oven with the set temperature of 160 ℃ for 8 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 603nm and FWHM is 35nm under the excitation of light with the wavelength of 380 nm.
Example 30
Injecting acrylic resin into a mold, irradiating with an ultraviolet lamp to obtain a carrier container after curing, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container with the acrylic resin, and irradiating with the ultraviolet lamp to obtain a precursor carrier after curing the whole container; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the reaction kettle in a photoelectric oven with the set temperature of 160 ℃ for 10 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the photoelectric oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining a product CdSe/ZnS quantum dot after centrifugal separation size, wherein the luminescence peak of the quantum dot is 615nm and FWHM is 31nm under the excitation of light with the wavelength of 380 nm.
Example 31
Injecting acrylic resin into a mold, irradiating with an ultraviolet lamp to obtain a carrier container after curing, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container with the acrylic resin, and irradiating with the ultraviolet lamp to obtain a precursor carrier after curing the whole container; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 6 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 625nm under the excitation of light with the wavelength of 380nm, and the FWHM is 35nm.
Example 32
Injecting acrylic resin into a mold, irradiating with an ultraviolet lamp to obtain a carrier container after curing, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container with the acrylic resin, and irradiating with the ultraviolet lamp to obtain a precursor carrier after curing the whole container; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 8 hours, after the reaction kettle is cooled to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 634nm under the excitation of light with the wavelength of 380nm, and the FWHM is 35nm.
Example 33
Injecting acrylic resin into a mold, irradiating with an ultraviolet lamp to obtain a carrier container after curing, dissolving cadmium acetate in a small amount of water, transferring the solution into the carrier container, sealing the carrier container with the acrylic resin, and irradiating with the ultraviolet lamp to obtain a precursor carrier after curing the whole container; transferring water, sodium oleate, absolute ethyl alcohol, oleic acid and selenium powder into a polytetrafluoroethylene reaction kettle in turn under the stirring condition, stirring until the solutions are uniformly mixed, transferring a precursor carrier into the reaction kettle, placing the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, heating the high-pressure reaction kettle in an optoelectronic oven with the set temperature of 180 ℃ for 10 hours, after the heating is completed, cooling the reaction kettle to room temperature, sequentially adding zinc acetate and sodium sulfide into the reaction kettle under the stirring condition, then placing the reaction kettle into the optoelectronic oven with the set temperature of 180 ℃ for heating for 8 hours, after the heating is completed, dispersing a product precipitate in the reaction kettle into cyclohexane, adding a small amount of absolute ethyl alcohol, and obtaining the product CdSe/ZnS quantum dots after centrifugal separation size, wherein the luminescence peak of the quantum dots is 641nm and the FWHM is 27nm under the excitation of light with the wavelength of 380 nm.
Claims (6)
1. The method for improving the particle size dispersity of the quantum dots based on the solvothermal method is characterized by comprising the following steps of:
(1) The precursor of part of elements in the quantum dot component is encapsulated in an organic polymer through encapsulation, dispersion or a combination of dispersion and encapsulation to obtain an organic polymer carrier containing the precursor, which is hereinafter referred to as carrier for short, and the carrier is kept stable at normal temperature and normal pressure so that the precursor is not contacted with the external environment; the selection of certain elements in the quantum dot component is that certain elements in the II-VI group quantum dot are II-group or VI-group elements in the quantum dot component, certain elements in the III-V group quantum dot are III-group or V-group elements in the quantum dot component, certain elements in the I-III-VI group quantum dot are VI-group elements or a combination of I-group and III-group elements, and certain elements in the perovskite quantum dot ABX 3 are A-bit elements or a combination of B-bit and X-bit elements;
(2) Transferring other precursors, organic ligands, solvents and carriers required by synthesizing the quantum dots into a reaction vessel, heating the reaction vessel to the temperature required by the synthesis reaction to perform the synthesis reaction, wherein the reaction process can be divided into three stages, namely a stable heating stage, wherein the reaction environment is heated from room temperature to a temperature T1 before the precursors are released from the carriers, and the carriers are kept stable in the stage; the second stage is a stage of intensively releasing and nucleating the precursor from the carrier, in the stage, the reaction environment is heated to the temperature T1, the precursor is intensively released from the carrier, the precursor reaches a high concentration state in a region near the carrier, the high concentration precursor contacts with other reactants and rapidly completes the region centralized nucleating process of the quantum dots, so as to form crystal nuclei; thirdly, in the growth stage of the quantum dots, the temperature of a reaction environment is T2, and quantum dot crystal nuclei generated by concentrated nucleation are dispersed in a reaction vessel solvent to continuously complete the growth of the quantum dots.
2. The method for improving the dispersion degree of the particle size of the quantum dots based on the solvothermal method according to claim 1, wherein the quantum dots in the step (1) are: the II-VI group quantum dot is binary or multi-element combination of II group elements Zn, cd and VI group elements O, S, se, te; the III-V group quantum dot is a binary or multi-element combination of III group element Al, ga, in, tl and V group element N, P, as; the I-III-VI group quantum dots are ternary or multi-component combinations of I group elements Cu, ag and Au, III group elements Al, ga, in, tl and VI group elements O, S, se, te; perovskite quantum dots are a generic name of a class of materials with ABX 3 crystal structure, wherein the a-position is one or more combinations of methylamine ion, formamidine ion, cesium ion, the B-position is one or more combinations of divalent lead ion, tin ion, manganese ion, and the X-position is one or more combinations of halogen anions; the quantum dots described in the step (1) are selected as precursors for encapsulation in an organic polymer carrier: for II-VI group quantum dots, the selected precursor is a precursor of Cd and Zn elements or a precursor of O, S, se, te elements; for III-V quantum dots, the precursor selected is Al, ga, in, tl precursor or N, P, as precursor; for the I-III-VI quantum dots, the precursor is O, S, se, te element precursor or Cu, ag, au, al, ga, in, tl element precursor; for perovskite quantum dots, the precursors selected are precursors of methylamine ions, formamidine ions, cesium ions, or precursors of lead ions, tin ions, manganese ions, halogen ions.
3. The method for improving the dispersion degree of the particle size of the quantum dots according to claim 1, wherein the organic polymer used for encapsulating the precursor in the step (1) is one or more selected from the group consisting of polyvinyl acetate, polymethyl oxide, polystyrene, polyethylene, polyvinyl chloride, polypropylene, polyacrylate, acrylic resin, cyanoacrylate and silica gel, and the synthesis reaction of the quantum dots is not involved in the selection of the materials.
4. The method for improving the dispersion degree of the particle size of the quantum dots based on the solvothermal method according to claim 1, wherein the precursor-containing organic polymer carrier in the step (1) is selected according to claim 2, the precursor-containing organic polymer carrier is selected according to claim 3, and the obtained precursor-containing organic polymer carrier meets the following requirements:
(1) Before the reaction environment temperature reaches T1, the carrier keeps a stable state, so that the precursor in the carrier is not contacted with other reaction raw materials in the reaction vessel;
(2) The carrier should undergo cracking, decomposition, dissolution, hydrolysis or decomposition reaction at the reaction environment temperature of T1 to release the precursor rapidly, wherein if the carrier needs to add other reactants or catalysts and the reaction vessel is airtight, the relevant reaction raw materials should be added together when transferring the relevant reaction raw materials to the reaction vessel in the step (2) of claim 1;
(3) The carrier and other reactants or components of the catalyst required for the reaction do not participate in the synthesis of the quantum dots.
5. The method for improving the dispersion degree of the particle size of the quantum dots based on the solvothermal method according to claim 1, wherein the solvothermal method is carried out under high pressure or normal pressure, and the reaction vessel is closed or open.
6. The method for improving the dispersion degree of the particle size of the quantum dots based on the solvothermal method according to claim 1, wherein the solvent in the step (2) is an organic solvent or water.
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