CN109423286B - Preparation method of indium phosphide nanocrystal - Google Patents

Preparation method of indium phosphide nanocrystal Download PDF

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CN109423286B
CN109423286B CN201710729253.6A CN201710729253A CN109423286B CN 109423286 B CN109423286 B CN 109423286B CN 201710729253 A CN201710729253 A CN 201710729253A CN 109423286 B CN109423286 B CN 109423286B
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张卫
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Suzhou Xingshuo Nanotech Co Ltd
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Abstract

The invention provides a preparation method of indium phosphide nanocrystalline, which comprises the following steps: providing a first indium precursor comprising a source of indium, a source of zinc, and a first ligand; providing a second indium precursor comprising a source of indium, a source of zinc, and a second ligand; providing a phosphorus precursor, the phosphorus precursor comprising a phosphorus source; and mixing the first indium precursor and the second indium precursor, heating to a preset temperature, adding a phosphorus precursor, and reacting to generate the indium phosphide nanocrystal. In the process of forming the nanocrystal, the invention reduces the surface defect of the indium phosphide nanocrystal by adding two different indium precursors, and the obtained indium phosphide nanocrystal has small half-peak width and high quantum yield.

Description

Preparation method of indium phosphide nanocrystal
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a preparation method of semiconductor nanocrystals.
Background
Quantum dots, also called fluorescent semiconductor nanocrystals, are inorganic semiconductor luminescent materials with physical diameters in the range of 1-20nm, and have obvious quantum size effect and unique optical properties. In recent years, quantum dots are widely applied to the fields of illumination, display, biological marking and the like due to the characteristics of wide excitation wavelength range, narrow emission peak, large silox displacement, controllable particle size, strong photochemical stability and the like, and gradually become a nano material with important development prospect.
The quantum dots are used as basic materials at the front end of an industrial chain, and need to have the characteristics of good luminescence property, high stability, environmental friendliness and the like. The III-V group compound quantum dots are represented by indium phosphide quantum dots, do not contain heavy metal elements, have no inherent toxicity, are green and environment-friendly, meet the environment-friendly standard, and are more suitable for industrial production, popularization and application.
In the prior art, the preparation method of the indium phosphide quantum dot is generally to mix a phosphorus source and an indium source by a hot injection method, and then coat a shell layer with a wide band gap such as zinc sulfide to form the core-shell quantum dot with a structure such as indium phosphide/zinc sulfide. However, the quantum dots have more surface defects, large half-peak width of emission peak, generally more than 50nm, low quantum yield and poor luminescence property. These problems have largely limited the application of indium phosphide quantum dots.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of an indium phosphide nanocrystal, and aims to solve the problems of large half-peak width of an emission peak and low quantum yield caused by more surface defects of the indium phosphide nanocrystal in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing indium phosphide nanocrystals, comprising the steps of: providing a first indium precursor comprising a source of indium, a source of zinc, and a first ligand; providing a second indium precursor comprising a source of indium, a source of zinc, and a second ligand; providing a phosphorus precursor, the phosphorus precursor comprising a phosphorus source; and mixing the first indium precursor and the second indium precursor, heating to a preset temperature, adding the phosphorus precursor, and reacting to generate the indium phosphide nanocrystal.
Further, the indium source is selected from at least one of indium acetate, indium chloride, indium carbonate, indium iodide, indium nitrate, indium bromide, indium perchlorate, indium myristate, and indium stearate.
Further, the zinc source is selected from at least one of zinc nitrate, zinc sulfate, zinc carbonate, zinc perchlorate, zinc fluoride, zinc chloride, zinc iodide, zinc bromide, zinc acetate, zinc carboxylate, dimethyl zinc, diethyl zinc, zinc acetylacetonate, zinc stearate, zinc oleate, zinc decate, zinc undecylenate, zinc myristate, zinc palmitate, and zinc diethyl dithiocarbamate.
Further, the first ligand and the second ligand are selected from at least one of saturated or unsaturated amine and saturated or unsaturated acid with the carbon number being more than or equal to 6.
Further, the first ligand is not the same as the second ligand.
Further, the phosphorus source is selected from at least one of tris (dimethylamino) phosphine, tris (diethylamino) phosphine, tris (trimethylsilyl) phosphine, tris (triethylsilyl) phosphine, and phosphine.
Further, the phosphine is added to the solution system after the first indium precursor and the second indium precursor are mixed in the form of gas or gas solution.
Further, the predetermined temperature is in the range of 180-.
Further, the first indium precursor and/or the second indium precursor and/or the phosphorus precursor further include a non-coordinating solvent.
Further, the non-coordination solvent is at least one selected from alkanes, alkenes, halogenated hydrocarbons, aromatic hydrocarbons, ethers, amines, ketones and esters with the number of carbon atoms being not less than 10 and not more than 22.
Further, a shell layer is further coated on the surface of the indium phosphide nanocrystal.
Further, the shell layer includes at least one of ZnS, ZnSe, or ZnSeS s.
According to another aspect of the invention, an indium phosphide nanocrystal prepared by any one of the preparation methods is provided.
By applying the technical scheme of the invention, two different indium precursors are added in the forming process of the nanocrystalline, so that the surface defect of the nanocrystalline can be reduced, and the obtained indium phosphide nanocrystalline has uniform size, small half-peak width of an emission peak and high quantum yield. In addition, the preparation method is simple to operate, green and environment-friendly, is easy to repeat and amplify, and meets the requirement of industrial production.
Drawings
The accompanying drawings, which form a part of the specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a UV-visible absorption and fluorescence emission spectrum of an indium phosphide nanocrystal sample 1 prepared in example 1 of the present invention;
FIG. 2 is a UV-visible absorption and fluorescence emission spectrum of sample 2 of indium phosphide nanocrystal prepared in example 2 of the present invention;
FIG. 3 is a UV-visible absorption and fluorescence emission spectrum of sample 3 of indium phosphide nanocrystal prepared in example 3 of the present invention;
FIG. 4 is a UV-visible absorption and fluorescence emission spectrum of sample 4 of indium phosphide nanocrystal prepared in example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described in detail below with reference to specific embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
It should be understood that the preparation method of the present invention is the same as the reaction environment required for preparing the nanocrystal in the prior art unless otherwise specified. Before the reaction, moisture and oxygen in the reaction vessel were removed using an inert gas atmosphere or an air atmosphere from which moisture and oxygen had been removed, and each reaction process in the experiment was carried out under the protection of an inert gas atmosphere. Wherein the inert gas atmosphere comprises at least one of nitrogen, argon, or a rare gas.
In order to solve the problems of uneven grain diameter, large half-peak width and low quantum yield caused by more surface defects of the existing indium phosphide nanocrystal, the invention discloses a preparation method of the indium phosphide nanocrystal, which comprises the following steps: providing a first indium precursor comprising a source of indium, a source of zinc, and a first ligand; providing a second indium precursor comprising a source of indium, a source of zinc, and a second ligand; providing a phosphorus precursor, the phosphorus precursor comprising a phosphorus source; and mixing the first indium precursor and the second indium precursor, heating to a preset temperature, adding a phosphorus precursor, and reacting to generate the indium phosphide nanocrystal.
In the process of preparing the indium phosphide nanocrystal, the first indium precursor and the second indium precursor containing different ligands react with the phosphorus precursor to generate the indium phosphide nanocrystal with uniform particle size. Wherein the indium source is at least one selected from the group consisting of indium acetate, indium chloride, indium carbonate, indium iodide, indium nitrate, indium bromide, indium perchlorate, indium myristate and indium stearate; the zinc source is at least one selected from zinc nitrate, zinc sulfate, zinc carbonate, zinc perchlorate, zinc fluoride, zinc chloride, zinc iodide, zinc bromide, zinc acetate, zinc carboxylate, dimethyl zinc, diethyl zinc, zinc acetylacetonate, zinc stearate, zinc oleate, zinc decate, zinc undecylenate, zinc tetradecate, zinc hexadecate and zinc diethyldithiocarbamate; the first ligand and the second ligand are selected from at least one of saturated or unsaturated amine and saturated or unsaturated acid with the carbon number being more than or equal to 6. The first ligand is different from the second ligand.
Further, the first ligand and the second ligand are selected from at least one of the following compounds: hexylamine, heptylamine, octylamine, trioctylamine, nonylamine, decylamine, undecylamine, undecylylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, oleylamine, hexanoic acid, heptanoic acid, octanoic acid, tricaprylic acid, nonanoic acid, decanoic acid, decenoic acid, undecylenic acid, dodecanoic acid, dodecenoic acid, tridecenoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexadecenoic acid, heptadecanoic acid, octadecanoic acid, octadecenoic acid, and oleic acid.
In the present invention, the phosphorus source is at least one selected from the group consisting of an organic aminophosphine, an organosilicon-based phosphorus, and phosphine. According to a preferred embodiment of the invention, the phosphorus source is selected from at least one of tris (dimethylamino) phosphine, tris (diethylamino) phosphine, tris (trimethylsilyl) phosphine, tris (triethylsilyl) phosphine. According to another preferred embodiment of the present invention, the phosphorus source is phosphine, wherein the phosphine is added in the form of a gas or a gas solution to a solution system in which the first indium precursor and the second indium precursor are mixed.
According to a preferred embodiment of the present invention, the first indium precursor and/or the second indium precursor and/or the phosphorus precursor further comprises a non-coordinating solvent. Wherein the non-coordination solvent is at least one of alkane, olefin, halogenated hydrocarbon, aromatic hydrocarbon, ether, amine, ketone and ester with the carbon number of less than or equal to 10 and less than or equal to 22. Further, the alkane is selected from at least one of the following: 1-octadecane, 1-heptadecane, 1-hexadecane, 1-dodecane, 1-tetradecane, 1-tridecane, 1-pristane, 1-phytane, 1-pentadecane, paraffin, 1-eicosane, 1-octacosane and 1-tetracosane; the olefin is selected from at least one of the following substances: 1-octadecene, 1-dodecene, 1-hexadecene, 1-tetradecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 1-tridecene, 1-pentadecene; the amine is selected from at least one of the following: hexadecylamine, octadecylamine, tetradecylamine, decylamine, dodecylamine, undecylamine, tridecylamine, 1, 12-diaminododecane, 1, 18-diaminooctadecane, 1, 16-diaminohexadecane, 1, 14-diaminotetradecylamine, oleylamine; the lipid is selected from at least one of the following substances: stearyl ester, lauryl acetate, cetyl acetate, eicosyl acetate, pentadecyl, heptadecyl acetate.
In the present invention, the first indium precursor is obtained by adding an indium source and a zinc source to a non-coordinating solvent containing a first ligand, and the second indium precursor is obtained by adding an indium source and a zinc source to a non-coordinating solvent containing a second ligand. And mixing the first indium precursor and the second indium precursor which are respectively obtained, and adding a phosphorus precursor to form the indium phosphide nanocrystal of the invention. According to a preferred embodiment of the present invention, the phosphorus precursor further comprises a first ligand or a second ligand, and a non-coordinating solvent.
In a preferred embodiment of the present invention, the first indium precursor and the second indium precursor are added to a non-coordinating solvent, heated to dissolve, and incubated for 1-120 minutes. This operation is intended to sufficiently dissolve the first indium precursor and the second indium precursor in the non-coordinating solvent to obtain a uniform indium mixed precursor solution. And then, heating the reaction to 260 ℃ and further to 240 ℃ and 200 ℃, adding a phosphorus precursor, and reacting for 1-120 minutes to ensure that the indium mixed precursor and the phosphorus precursor fully react to form the indium phosphide nanocrystal. To avoid the introduction of moisture or oxygen into the reaction, the indium source, zinc source, first ligand, phosphorus source, and non-coordinating solvent used in the present invention are all subjected to water removal and drying prior to participating in the reaction.
According to a preferred embodiment of the present invention, the surface of the indium phosphide nanocrystal is further coated with a shell layer. Further, the shell layer comprises ZnSexS1-x、ZnSeyS1-y/ZnS、ZnSe/ZnSezS1-zWherein x is more than or equal to 0 and less than 1, y is more than 0 and less than or equal to 1, and z is more than 0 and less than 1. The inorganic shell layers grow on the surface of the nanocrystal through a continuous ion adsorption method, and the luminous efficiency and photochemical stability of the nanocrystal can be improved. In addition, the shell layer is ZnSexS1-xWhen the precursor is added with Se and S precursors in different proportions and coated with one or more layers of ZnSexS1-xA shell layer; the shell layer is ZnSeyS1-y/ZnS or ZnSe/ZnSezS1-zWhen it is used, it means that one or more layers of ZnSe are first coatedyS1-yOr a ZnSe shell layer, and then coating one or more layers of ZnS or ZnSezS1-zAnd (4) shell layer. According to actual needs, the shell layer is repeatedly coated for many times, so that the shell layer can better cover the surface of the indium phosphide nanocrystal, and the optical stability of the indium phosphide nanocrystal is further improved.
In the invention, an optional zinc source, a sulfur source and/or a selenium source are added into the solution containing the indium phosphide nanocrystal to further coat the shell layer. Further, the zinc source is also selected from at least one of zinc nitrate, zinc sulfate, zinc carbonate, zinc perchlorate, zinc fluoride, zinc chloride, zinc iodide, zinc bromide, zinc acetate, zinc carboxylate, dimethyl zinc, diethyl zinc, zinc acetylacetonate, zinc stearate, zinc oleate, zinc decate, zinc undecylenate, zinc myristate, zinc palmitate and zinc diethyl dithiocarbamate; the sulfur source is at least one selected from elemental sulfur, alkyl mercaptan, trialkylphosphine sulfide, trienylphosphine sulfide, alkyl aminosulfide, alkenyl aminosulfide and hydrogen sulfide; the selenium source is at least one selected from elemental selenium, trialkylphosphine selenide, alkylamino selenide, alkenylamino selenide and hydrogen selenide. According to a preferred embodiment of the present invention, the shell layer of the indium phosphide nanocrystal is obtained by alternately adding the zinc source, the sulfur source and/or the selenium source a plurality of times. Compared with the method of directly coating the shell layer at one time, the method of alternately adsorbing and gradually forming the shell layer enables the shell layer to better coat the indium phosphide nanocrystal,
in the present invention, the first indium precursor and the second indium precursor contain a zinc source, and the zinc source provides a part of the zinc source for the step of coating the shell layer on the surface of the indium phosphide nanocrystal. In a specific embodiment of the invention, at least one of a sulfur source and/or a selenium source required for synthesizing a shell is added to a solution containing the indium phosphide nanocrystal to obtain the shell-coated indium phosphide nanocrystal. In another embodiment of the invention, at least one of a zinc source and a sulfur source and/or a selenium source required for synthesizing the shell is added into the solution containing the indium phosphide nanocrystal to obtain the shell-coated indium phosphide nanocrystal.
According to a preferred embodiment of the present invention, the shell coating of the indium phosphide nanocrystal is performed while gradually increasing the amount of raw material to be charged and gradually increasing the cladding temperature. Because the nanocrystals grow continuously, in the subsequent step of coating the shell layer, more raw materials than before need to be provided to obtain the nanocrystals with better appearance sphericity and uniformity. In addition, the formation process of the outer shell layer is also facilitated by increasing the temperature.
The invention also comprises the process of separating and purifying the directly obtained reaction liquid with the indium phosphide nanocrystalline or the reaction liquid with the indium phosphide nanocrystalline with the coating shell. And cooling the obtained reaction liquid to room temperature, adding an extracting agent, separating to obtain an extract, and adding acetone for precipitation to obtain the indium phosphide nanocrystal with high purity.
According to another aspect of the invention, an indium phosphide nanocrystal is provided, the half-peak width of which is less than or equal to 50nm, and the quantum yield can reach 60%.
The invention will be further illustrated with reference to the attached drawings and in connection with specific embodiments, which are intended only for a better understanding of the content of the invention and do not limit the scope of protection of the invention. Unless otherwise specified, the technical means used in the embodiments of the present invention are conventional means well known to those skilled in the art. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
Preparation of indium phosphide nanocrystalline sample with Shell coating 1
S1, first indium precursor (In-Z)n-OA) preparation: mixing indium acetate (in (OAc)33g), zinc chloride (ZnCl)24g), oleic acid (OA, 30mL) and 1-octadecene (ODE, 80mL) were mixed and heated to dissolve to give an In-Zn-OA first indium precursor solution, which was left for use.
S2, preparation of a second indium precursor (In-Zn-STA): mixing indium acetate (in (OAc)33g), zinc chloride (ZnCl)24g), stearic acid (STA, 12g) and 1-octadecene (ODE, 80mL) are mixed and heated to be dissolved, so as to obtain an In-Zn-St second indium precursor solution, and the solution is reserved for later use;
s3 phosphorus Precursor (PH)3Preparation of ODE): to adjust the pH3Introducing gas into the 1-Octadecene (ODE) solution after water and oxygen removal treatment to obtain PH3A saturated solution of gas is reserved for standby;
s4, preparation of indium phosphide nanocrystal cores: adding the In-Zn-OA prepared In the step S1 and the In-Zn-STA prepared In the step S2 into a three-neck flask respectively, heating and stirring until the mixture is uniformly mixed, vacuumizing or introducing N2The reaction was maintained for 30min to obtain a homogeneous indium precursor mixture. Next, the heating was continued and the temperature was raised to 240 ℃ to which the pH prepared in the step S3 was slowly injected31mL of ODE solution is reacted for 30min to obtain mixed liquid with indium phosphide nanocrystal cores;
s5, preparing the indium phosphide nanocrystal coated with the shell layer: trioctylphosphine selenide (0.5M, 0.2mL) and trialkylphosphine sulfide (2M, 0.5mL) were added to the mixed solution having the indium phosphide nanocrystal core prepared in step S4, respectively, and reacted for 20 min. Then, zinc stearate (Zn (STA) is added20.5g) and oleylamine (OLAM, 1mL) for 20 min. Finally, DDT (n-dodecyl mercaptan, 2mL) was added and the incubation continued for 60 min. The heating was stopped and the reaction was completed.
FIG. 1 is a spectrum of UV-visible absorption and fluorescence emission spectra of sample 1 of indium phosphide nanocrystal prepared in example 1, and it can be seen from FIG. 1 that the fluorescence emission peak is 543nm and the half-peak width is 49 nm. The quantum yield of this sample was measured using an integrating sphere and was 40%.
Example 2
Preparation of indium phosphide nanocrystalline sample with Shell coating 2
The first indium precursor (In-Zn-OA) and the second indium precursor (In-Zn-St) were prepared In the same manner as In example 1.
S3, preparation of indium phosphide nanocrystal cores: adding the In-Zn-OA prepared In the step S1 and the In-Zn-St prepared In the step S2 into a three-neck flask respectively, heating and stirring until the mixture is uniformly mixed, vacuumizing or introducing N2The reaction was maintained for 30min to obtain a homogeneous indium precursor mixture. Then, the temperature is increased to 240 ℃ by continuing heating, and a certain amount of PH is slowly pumped into the solution3Reacting for 30min to obtain a mixed solution with indium phosphide nanocrystal cores;
s4, preparing the indium phosphide nanocrystal coated with the shell layer: trioctylphosphine selenide (0.5M, 0.2mL) and trialkylphosphine sulfide (2M, 0.5mL) were added to the mixed solution prepared in the above step S3, respectively, and reacted for 20 min. Then, zinc stearate (Zn (STA) is added20.5g) and oleylamine (OLAM, 1mL) for 20 min. Finally, DDT (n-dodecyl mercaptan, 2mL) was added and the incubation continued for 60 min. The heating was stopped and the reaction was completed.
FIG. 2 is a spectrum of UV-visible absorption and fluorescence emission spectra of sample 2 of indium phosphide nanocrystal prepared in example 2, and it can be seen from FIG. 2 that the fluorescence emission peak is 539nm and the half-width is 46 nm. The quantum yield of this sample was tested using an integrating sphere and was 60%.
Example 3
Preparation of indium phosphide nanocrystalline sample with Shell coating 3
S1, preparation of first indium precursor (In-Zn-OA): mixing indium acetate (in (OAc)32g), zinc chloride (ZnCl)23g), oleic acid (OA, 10mL) and 1-octadecene (ODE, 100mL) are mixed and heated to be dissolved to obtain an In-Zn-OA first indium precursor solution, and the solution is reserved for standby;
s2, preparation of a second indium precursor (In-Zn-St): mixing indium acetate (in (OAc)32g), zinc chloride (ZnCl)23g) and oleylamine (OLAM, 8mL), heating until the mixture is dissolved to obtain a second indium precursor solution of In-Zn-OLAM, and reserving for later use;
s3, phosphorus precursor ((EDA)3Preparation of P-OLAM): reacting tris (diethylamino) phosphine ((EDA)3P, 2g) was mixed with oleylamine (OLAM, 1mL) and heated to dissolve to give (EDA)3P-OLAM phosphorus precursor solution, and reserving for later use;
s4, preparation of indium phosphide nanocrystal cores: adding the In-Zn-OA prepared In the step S1 and the In-Zn-OLAM prepared In the step S2 into a three-neck flask respectively, heating and stirring until the mixture is uniformly mixed, vacuumizing or introducing N2The reaction was maintained for 30min to obtain a homogeneous indium precursor mixture. Next, heating was continued and the temperature was raised to 220 ℃ to which (EDA) prepared in step S3 was added31mL of P-OLAM solution is reacted for 30min to obtain mixed liquid with indium phosphide nanocrystal cores.
S5, preparing the indium phosphide nanocrystal coated with the shell layer: trioctylphosphine selenide (0.5M, 0.2mL) and DDT (n-dodecyl mercaptan, 2mL) were added to the mixed solution having the indium phosphide nanocrystal cores prepared in step S4, respectively, and reacted for 20 min. Adding zinc stearate (Zn (STA)20.5g) and oleylamine (OLAM, 1mL) for 60 min. The heating was stopped and the reaction was completed.
FIG. 3 is a spectrum of UV-visible absorption and fluorescence emission spectra of sample 3 of indium phosphide nanocrystal prepared in example 3, and it can be seen from FIG. 3 that the fluorescence emission peak is 518nm and the half-width is 48 nm. The quantum yield of this sample was measured using an integrating sphere and was 53%.
Example 4
Preparation of InP nanocrystalline sample 4 with Shell coating
S1, preparation of first indium precursor (In-Zn-OA): mixing indium acetate (in (OAc)32g), Zinc acetate (Zn (OAc)24g) and oleic acid (OA, 10mL) are mixed and heated to be dissolved to obtain an In-Zn-OA first indium precursor solution, and the solution is reserved for later use;
s2, preparation of a second indium precursor (In-Zn-OLAM): mixing indium acetate (in (OAc)32g), Zinc stearate (Zn (STA)212g), oleylamine (OLAM, 10mL) and 1-octadecene (ODE, 80mL) are mixed and heated to be dissolved to obtain a second indium precursor solution of In-Zn-OLAM, and the solution is kept for later use;
s3 phosphorus precursor ((EMA)3Preparation of P-OLAM-ODE): reacting tris (diethylamino) phosphine ((EMA)3P, 2g), oleylamine (OLAM, 1mL) and 1-octadecene (ODE, 10mL) were mixed and heated to dissolve to give (EMA)3P-OLAM-ODE phosphorus precursor solution, and reserving for later use;
s4, preparation of indium phosphide nanocrystal cores: adding the In-Zn-OA prepared In the step S1 and the In-Zn-OLAM prepared In the step S2 into a three-neck flask respectively, heating and stirring until the mixture is uniformly mixed, vacuumizing or introducing N2The reaction was maintained for 30min to obtain a homogeneous indium precursor mixture. Next, the heating was continued and the temperature was raised to 260 ℃ to which (EMA) prepared in step S3 was added31mL of P-OLAM-ODE solution is reacted for 30min to obtain mixed liquid with indium phosphide nanocrystal cores.
S5, preparing the indium phosphide nanocrystal coated with the shell layer: trioctylphosphine selenide (0.5M, 0.2mL) and trialkylphosphine sulfide (2M, 0.5mL) were added to the mixed solution having the indium phosphide nanocrystal core prepared in step S4, respectively, and reacted for 20 min. Then, zinc stearate (Zn (STA) is added20.5g) and oleylamine (OLAM, 1mL) for 20 min. The reaction temperature was raised, trioctylphosphine selenide (0.5M, 0.3mL) and trialkylphosphine sulfide (2M, 0.6mL) were added continuously, the reaction was carried out for 30min, and zinc stearate (Zn (STA) was added20.6g) and oleylamine (OLAM, 2mL) for 20 min. The temperature was again raised and DDT (n-dodecyl mercaptan, 4mL) was added and the incubation continued for 120 min. The heating was stopped and the reaction was completed.
FIG. 4 is a spectrum of UV-visible absorption and fluorescence emission spectra of the indium phosphide nanocrystal sample 4 prepared in example 4, and it can be seen from FIG. 4 that the fluorescence emission peak is 550nm and the half-width is 47 nm. The sample was tested for quantum yield using an integrating sphere, which was 50%.
Sample 1 Sample 2 Sample 3 Sample No. 4
Peak of fluorescence emission 543nm 539nm 518nm 550nm
Half peak width 49nm 46nm 48nm 47nm
Quantum yield 40％ 60％ 53％ 50％
In conclusion, the invention provides a preparation method of indium phosphide nanocrystal. By adding two different indium precursors in the process of forming the nanocrystal, the surface defect of the nanocrystal is reduced, and the obtained indium phosphide nanocrystal has uniform size, small half-peak width of an emission peak and high quantum yield.
In addition, the nanocrystalline obtained by the preparation method does not contain heavy metal elements, is green and environment-friendly, can be widely applied to the application fields of illumination, display, biology and the like, and meets the requirement of industrial production.
Although the invention has been described and illustrated in greater detail by the inventor, it should be understood that modifications and/or alterations to the above-described embodiments, or equivalent substitutions, will be apparent to those skilled in the art without departing from the spirit of the invention, and it is intended that all such modifications and alterations that fall within the true spirit and scope of the invention are to be embraced therein. Furthermore, the terms used in the following description and drawings are not intended to be construed as limiting the invention in any way.

Claims (10)

1. A preparation method of indium phosphide nanocrystal is characterized by comprising the following steps:
providing a first indium precursor comprising a source of indium, a source of zinc, and a first ligand;
providing a second indium precursor comprising a source of indium, a source of zinc, and a second ligand;
providing a phosphorus precursor, the phosphorus precursor comprising a phosphorus source;
and mixing the first indium precursor and the second indium precursor, heating to a preset temperature, adding the phosphorus precursor, and reacting to generate the indium phosphide nanocrystal.
2. The method of claim 1, wherein: the indium source is selected from at least one of indium acetate, indium chloride, indium carbonate, indium iodide, indium nitrate, indium bromide, indium perchlorate, indium myristate and indium stearate; the zinc source is selected from at least one of zinc nitrate, zinc sulfate, zinc carbonate, zinc perchlorate, zinc fluoride, zinc chloride, zinc iodide, zinc bromide, zinc acetate, zinc carboxylate, dimethyl zinc, diethyl zinc, zinc acetylacetonate, zinc stearate, zinc oleate, zinc decate, zinc undecylenate, zinc tetradecate, zinc palmitate and zinc diethyl dithiocarbamate; the first ligand and the second ligand are selected from at least one of saturated or unsaturated amine and saturated or unsaturated acid with the carbon atom number being more than or equal to 6.
3. The method of claim 1, wherein: the first ligand is not the same as the second ligand.
4. The method of claim 1, wherein: the phosphorus source is selected from at least one of tris (dimethylamino) phosphine, tris (diethylamino) phosphine, tris (trimethylsilyl) phosphine, tris (triethylsilyl) phosphine, and phosphine.
5. The method of claim 4, wherein: the phosphine is added into a solution system formed by mixing the first indium precursor and the second indium precursor in the form of gas or gas solution.
6. The method of claim 1, wherein: the predetermined temperature is in the range of 180 ℃ and 260 ℃.
7. The method of claim 1, wherein: the first indium precursor and/or the second indium precursor and/or the phosphorus precursor further include a non-coordinating solvent, and the non-coordinating solvent is at least one selected from alkanes, alkenes, halogenated hydrocarbons, aromatic hydrocarbons, ethers, amines, ketones, and esters having 10 or more carbon atoms and 22 or less carbon atoms.
8. The method of claim 1, wherein: and further coating a shell layer on the surface of the indium phosphide nanocrystal.
9. The method of claim 8, wherein: the shell layer comprises ZnSexS1-x、ZnSeyS1-y/ZnS、ZnSe/ZnSezS1-zWherein x is more than or equal to 0 and less than 1, y is more than 0 and less than or equal to 1, and z is more than 0 and less than 1.
10. An indium phosphide nanocrystal characterized by: prepared by the preparation method of any one of claims 1 to 9.
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