CN112126430A - Indium phosphide core-shell structure quantum dot and preparation method and application thereof - Google Patents
Indium phosphide core-shell structure quantum dot and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an indium phosphide core-shell structure quantum dot and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing an indium precursor solution and a phosphorus precursor solution; adjusting the indium precursor solution to a first temperature, adding a phosphorus precursor solution, and mixing to form a first mixed solution containing indium phosphide nanocrystal cores; the first temperature is 60-120 ℃; heating the first mixed solution to a second temperature and preserving the heat for 30-50 min; the second temperature is 200-300 ℃; after preserving heat at the second temperature, cooling to a third temperature, and adding fatty acid, fatty amine, a non-coordinating solvent and a zinc oxide precursor to form a second mixed solution; the third temperature is 40-100 ℃; and heating the second mixed solution to a fourth temperature, and keeping the temperature for 20-30 min, wherein the fourth temperature is 250-320 ℃, so as to form the zinc oxide shell-coated indium phosphide core-shell structure quantum dot. By controlling the precursor, the temperature, the reaction time and the like, the prepared indium phosphide core-shell structure quantum dot has smaller half-peak width and higher quantum efficiency.
Description
Technical Field
The invention relates to the technical field of quantum dots, in particular to an indium phosphide core-shell structure quantum dot and a preparation method and application thereof.
Background
Because the semiconductor quantum dots have outstanding absorption and luminescence characteristics, the materials have attracted extensive research interests of researchers at home and abroad in the fields of photoelectric devices, biomedicine, fluorescent markers and the like, and have made outstanding progress in the fields of luminescent devices, solar cells, biomarkers and the like. However, the quantum dot materials in the current market generally have the problems of 'high-performance quantum dots containing heavy metal elements of cadmium, poor performance of green environment-friendly cadmium-free quantum dots', high raw material cost, harsh preparation conditions and the like, and limit the application and popularization of quantum dot luminescent materials.
The III-V group element quantum dots represented by indium phosphide 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. However, the indium phosphide nuclear quantum dot has low fluorescence quantum yield and poor stability, which is far lower than the performance of cadmium selenide quantum dot. At present, a shell layer grows on the surface of the indium phosphide nuclear quantum dot in a main mode for improving the performance of the indium phosphide nuclear quantum dot, but the prepared nuclear shell structure quantum dot has large half-peak width of an emission peak, generally more than 45nm, low quantum yield and poor luminous performance. These problems have largely limited the application of indium phosphide quantum dots.
Disclosure of Invention
Therefore, it is necessary to provide an indium phosphide core-shell structure quantum dot with a narrow emission peak half-peak width and a high quantum yield, and a preparation method and an application thereof.
A preparation method of an indium phosphide core-shell structure quantum dot comprises the following steps.
Preparing an indium precursor solution and a phosphorus precursor solution;
adjusting the indium precursor solution to a first temperature and adding the phosphorus precursor solution for mixing to form a first mixed solution containing indium phosphide nanocrystal cores; the first temperature is 60-120 ℃;
heating the first mixed solution to a second temperature and preserving the heat for 30-50 min; the second temperature is 200-300 ℃;
after preserving heat at the second temperature, cooling to a third temperature, and adding fatty acid, fatty amine, a non-coordinating solvent and a zinc oxide precursor to form a second mixed solution; the third temperature is 40-100 ℃; and
and heating the second mixed solution to a fourth temperature, and keeping the temperature for 20-30 min, wherein the fourth temperature is 250-320 ℃, so as to form the zinc oxide shell layer coated indium phosphide core-shell structure quantum dots.
According to the preparation method of the indium phosphide core-shell structure quantum dot, the indium phosphide core is synthesized by mixing and controlling the nucleation of the indium phosphide nanocrystal core at the low temperature of the first temperature and preserving heat at the high temperature of the second temperature so as to be beneficial to the growth of the nanocrystal core, so that the size distribution of the synthesized quantum dot becomes uniform and the half-peak width becomes narrow. In addition, control is gone on at first temperature and second temperature substep, still can effectively avoid indium phosphide nanocrystal core surface to oxidize the risk, and then be favorable to free monomer reactant to grow on the seed crystal surface, promotes indium phosphide quantum dot's optical property to a certain extent. In the process of forming the zinc oxide cladding, the zinc oxide precursor is controlled to be injected at a lower third temperature, so that the reaction activity can be reduced to a certain degree, and the zinc oxide precursor is uniformly dispersed in the first mixed solution to promote uniform reaction; and raising the temperature to enable the shell layer to uniformly grow on the surface of the core, thereby reducing the surface defects, narrowing the half-peak width of the emission peak of the indium phosphide core-shell structure quantum dot, and improving the quantum yield and the luminous efficiency.
According to the preparation method of the indium phosphide core-shell structure quantum dot, the emission wavelength of the obtained indium phosphide core-shell structure quantum dot is easy to control by controlling the precursor, the temperature, the reaction time and the like, and the prepared indium phosphide core-shell structure quantum dot is small in half-peak width and high in quantum efficiency.
The indium phosphide core-shell structure quantum dot is of a type II core-shell structure, and the growth of a shell layer is controlled to cause obvious spectral red shift, so that the fluorescent spectral interval can be controlled by adjusting the thickness of the shell layer.
In some of these embodiments, the first temperature is 60 to 80 ℃; and/or
The second temperature is 250-300 ℃; and/or
The third temperature is 40-70 ℃; and/or
The fourth temperature is 270-310 ℃.
In some of these embodiments, the first temperature is 60 ℃; the second temperature is 250 ℃; the third temperature is 60 ℃; the fourth temperature is 300 ℃.
In some of these embodiments, the step of preparing the indium precursor solution comprises the steps of:
mixing an indium precursor, fatty acid and a non-coordination solvent, heating to 90-120 ℃, and keeping the temperature for 60-90 min to form a uniform indium precursor solution.
In some of these embodiments, the indium precursor is selected from at least one of indium acetate, indium carbonate, indium nitrate, indium chloride, indium iodide, indium bromide, indium stearate, and indium myristate; and/or
In the indium precursor solution, the fatty acid is selected from at least one of saturated or unsaturated fatty acid with the carbon atom number being more than or equal to 6; and/or
In the indium precursor solution, the non-coordinating solvent is at least one selected from the group consisting of alkanes, alkenes, ethers, and aromatic compounds having 10 or more carbon atoms or less and 22 or less.
In some of these embodiments, the step of preparing the phosphorus precursor solution comprises the steps of:
mixing a phosphorus precursor and a non-coordination solvent to prepare a phosphorus precursor solution;
wherein the phosphorus precursor is selected from at least one of tris (dimethylamino) phosphine, tris (diethylamino) phosphine, tris (trimethylsilyl) phosphine, tris (triethylsilyl) phosphine, trioctylphosphine, tributylphosphine, and phosphine;
in the phosphorus precursor solution, the non-coordinating solvent is at least one selected from the group consisting of 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene.
In some of these embodiments, in the second mixed solution,
the fatty acid is selected from at least one of myristic acid, palmitic acid, stearic acid and oleic acid; and/or
The fatty amine is selected from at least one of dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and oleylamine; and/or
The non-coordination solvent is selected from at least one of 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene; and/or
The zinc precursor is at least one selected from zinc adipate, zinc caprylate, zinc laurate, zinc myristate, zinc palmitate, zinc dithiocarbamate, diethyl zinc, dimethyl zinc, zinc acetate, zinc acetylacetonate and zinc diethyl dithiocarbamate.
In some of the embodiments, the indium precursor solution is mixed with the phosphorus precursor solution, and the phosphorus precursor solution is added in such an amount that the ratio of the amount of the substance of phosphorus atoms in the phosphorus precursor solution to the amount of the substance of indium atoms in the indium precursor solution is 1 (2-4).
An indium phosphide core-shell structure quantum dot prepared by the preparation method.
The indium phosphide core-shell structure quantum dot is applied to the preparation of luminescent devices, solar cells or biomarkers.
Drawings
FIG. 1 is a schematic diagram of two types of core-shell quantum dots;
FIG. 2 is a schematic view of a core-shell structure of an indium phosphide core-shell structure quantum dot in the present invention;
FIG. 3 is an emission spectrum of a green-light InP/ZnO quantum dot with a core-shell structure prepared in example 1 of the present invention;
FIG. 4 is an emission spectrum of a red-light InP/ZnO quantum dot with a core-shell structure prepared in example 2 of the present invention;
FIG. 5 is an emission spectrum of green-light InP/ZnO quantum dots with core-shell structure prepared in example 3 of the present invention;
FIG. 6 is an emission spectrum of a green-light InP/ZnO quantum dot with a core-shell structure prepared in comparative example 1;
FIG. 7 is an emission spectrum of the red-light InP/ZnO quantum dot with core-shell structure prepared in comparative example 2.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, a core-shell structure of a conventional indium phosphide quantum dot is mainly of type i, a valence band of an indium phosphide core of the indium phosphide quantum dot of the core-shell structure is higher than a valence band of a shell, and a conduction band of the indium phosphide quantum dot is lower than a conduction band of the shell; the emission peak half-peak width of the quantum dots is large and generally more than 45nm, and the quantum dots have low quantum yield and poor luminescence property. These problems have largely limited the application of indium phosphide quantum dots. Researchers of the invention prepare the indium phosphide quantum dot with the type II core-shell structure, wherein the valence band of an indium phosphide core is higher than that of a shell layer, and the conduction band is also higher than that of the shell layer.
Based on the above, the invention provides an indium phosphide (InP) core-shell structure quantum dot coated by a zinc oxide (ZnO) shell layer, the valence band and conduction band distribution of which is shown in figure 2, wherein the unit of ordinate is eV.
An embodiment of the invention provides a preparation method of an indium phosphide core-shell structure quantum dot, which comprises the following steps of S110-S150.
Step S110: an indium precursor solution and a phosphorus precursor solution are prepared.
In some of these embodiments, the step of preparing the indium precursor solution comprises the steps of: mixing an indium precursor, fatty acid and a non-coordination solvent, heating to 90-120 ℃, and keeping the temperature for 60-90 min to remove water and oxygen to form a uniform indium precursor solution.
Further, the indium precursor is at least one selected from the group consisting of indium acetate, indium carbonate, indium nitrate, indium chloride, indium iodide, indium bromide, indium stearate, and indium myristate. In one embodiment, the indium precursor is selected from indium acetate.
Further, in the indium precursor solution, the fatty acid is at least one selected from saturated or unsaturated fatty acids having 6 or more carbon atoms.
Further, in the indium precursor solution, the non-coordinating solvent is at least one selected from the group consisting of alkanes, alkenes, ethers, and aromatic compounds having 10 or more carbon atoms and 22 or less carbon atoms. Further, the alkane may be at least one selected from the group consisting of 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. Further, the olefin may be selected from at least one of 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene. Further, the ether may be at least one selected from the group consisting of phenyl ether and benzyl ether.
In some of these embodiments, the step of preparing the phosphorus precursor solution comprises the steps of: and mixing the phosphorus precursor and the non-coordination solvent to prepare a phosphorus precursor solution.
Further, the phosphorus precursor is at least one selected from the group consisting of tris (dimethylamino) phosphine, tris (diethylamino) phosphine, tris (trimethylsilyl) phosphine, tris (triethylsilyl) phosphine, trioctylphosphine, tributylphosphine, and phosphine.
Further, in the phosphorus precursor solution, the non-coordinating solvent is at least one selected from the group consisting of 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene.
Step S120: adjusting the indium precursor solution to a first temperature, adding a phosphorus precursor solution, and mixing to form a first mixed solution containing indium phosphide nanocrystal cores; the first temperature is 60-120 ℃.
Further, the first temperature is preferably 60 to 80 ℃. Thus controlling the nucleation of the indium precursor solution and the phosphorus precursor solution at the lower first temperature allows the nucleation of the indium phosphide nanocrystal core to be controlled.
In some of the embodiments, the phosphorus precursor solution is added in an amount such that the ratio of the amount of the substance of phosphorus atoms to the amount of indium atoms in the indium precursor solution is 1 (2-4), and the ratio of the amounts of the substance is more preferably 1 (2.2-3).
Step S130: heating the first mixed solution to a second temperature and preserving the heat for 30-50 min; the second temperature is 200-300 ℃.
And controlling the temperature of the first mixed solution to rise to a second temperature and preserving the heat for 30-50 min to promote the uniform growth of the indium phosphide nanocrystal core, so that the size distribution of the synthesized quantum dots becomes uniform and the half-peak width becomes narrow. In addition, control is carried out in first temperature and second temperature substep and still can effectively avoid the risk that indium phosphide nanocrystal core surface is oxidized, and then is favorable to free monomer reactant to grow on the seed crystal surface, promotes indium phosphide quantum dot's optical property to a certain extent. Further, the second temperature is preferably 250 to 300 ℃.
Step S140: after preserving heat at the second temperature, cooling to a third temperature, and adding fatty acid, fatty amine, a non-coordinating solvent and a zinc oxide precursor to form a second mixed solution; the third temperature is 40-100 ℃.
Research finds that particularly when the zinc oxide shell layer is prepared, the injection of the fatty acid, the fatty amine, the non-coordinating solvent and the zinc oxide precursor is controlled at a lower third temperature, so that the initial reaction activity can be reduced to a certain degree, and the initial reaction activity can be uniformly dispersed in the first mixed solution to promote uniform reaction. It is understood that in some examples, the third temperature can be 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃. Preferably, the third temperature may be 40 to 70 ℃, and more preferably, the third temperature may be 50 to 65 ℃.
Further, in the second mixed solution of step S140, the fatty acid is selected from at least one of myristic acid, palmitic acid, stearic acid, and oleic acid.
Further, the fatty amine is at least one selected from the group consisting of dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and oleylamine.
Further, the non-coordinating solvent is at least one selected from the group consisting of 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene.
Further, the zinc precursor is selected from at least one of zinc adipate, zinc caprylate, zinc laurate, zinc myristate, zinc palmitate, zinc dithiocarbamate, diethyl zinc, dimethyl zinc, zinc acetate, zinc acetylacetonate, and zinc diethyl dithiocarbamate.
Step S150: and heating the second mixed solution to a fourth temperature, and keeping the temperature for 20-30 min, wherein the fourth temperature is 250-320 ℃, so as to form the zinc oxide shell layer coated indium phosphide core-shell structure quantum dot.
And 150, raising the temperature to enable a zinc oxide shell layer to uniformly grow on the surface of the indium phosphide core, so that the surface defects are reduced, and the luminous efficiency of the core is improved. Further, the fourth temperature is preferably 270 to 310 ℃.
Further, the first temperature is 60 ℃; the second temperature is 250 ℃; the third temperature is 60 ℃; the fourth temperature was 300 ℃.
In some specific examples, the indium precursor is indium acetate; the phosphorus precursor is tris (trimethylsilyl) phosphine; the zinc oxide precursor is zinc acetylacetonate.
According to the preparation method of the indium phosphide core-shell structure quantum dot, the indium phosphide core is synthesized by mixing and controlling the nucleation of the indium phosphide nanocrystal core at the low temperature of the first temperature and preserving heat at the high temperature of the second temperature so as to be beneficial to the growth of the nanocrystal core, so that the size distribution of the synthesized quantum dot becomes uniform and the half-peak width becomes narrow. In addition, control is carried out in first temperature and second temperature substep and still can effectively avoid the risk that indium phosphide nanocrystal core surface is oxidized, and then is favorable to free monomer reactant to grow on the seed crystal surface, promotes indium phosphide quantum dot's optical property to a certain extent. In the process of forming the zinc oxide cladding, the zinc oxide precursor is controlled to be injected at a lower third temperature, so that the reaction activity can be reduced to a certain degree, and the zinc oxide precursor is uniformly dispersed in the first mixed solution to promote uniform reaction; and raising the temperature to enable the shell layer to uniformly grow on the surface of the core, thereby reducing the surface defects, narrowing the half-peak width of the emission peak of the indium phosphide core-shell structure quantum dot, and improving the quantum yield and the luminous efficiency.
According to the preparation method of the indium phosphide core-shell structure quantum dot, the emission wavelength of the obtained indium phosphide core-shell structure quantum dot is easy to control by controlling the precursor, the temperature, the reaction time and the like, and the prepared indium phosphide core-shell structure quantum dot is small in half-peak width and high in quantum efficiency.
The indium phosphide core-shell structure quantum dot is of a type II core-shell structure, and the growth of a shell layer is controlled to cause obvious spectral red shift, so that the fluorescent spectral interval can be controlled by adjusting the thickness of the shell layer.
The invention also provides an indium phosphide core-shell structure quantum dot prepared by adopting any one of the preparation methods.
Furthermore, the fluorescence emission peak of the indium phosphide core-shell structure quantum dot is within the range of 500-640 nm, the half-peak width is less than 40nm, and the quantum efficiency is greater than or equal to 70%.
The invention also provides application of the indium phosphide core-shell structure quantum dot in preparation of a luminescent device, a solar cell or a biomarker.
Correspondingly, the invention also provides a luminescent device, a solar cell or a biomarker, which contains the indium phosphide core-shell structure quantum dot.
The following are specific examples.
Example 1
And (3) preparing the green light indium phosphide/zinc oxide core-shell structure quantum dot.
Step one, preparing indium precursor solution and phosphorus precursor solution
(1) 0.515g of indium acetate, 1.693g of oleic acid and 26.513g of 1-octadecene are mixed in a 250mL conical flask at normal temperature, magnetic stirring is carried out, the rotating speed is 600rpm, the temperature is raised to 90 ℃, the system is vacuumized and kept for 90min at 200mTorr, and a uniform indium precursor solution is formed.
(2) 0.221g of tris (trimethylsilyl) phosphine was mixed with 2.607g of 1-octadecene at room temperature, magnetically stirred at 600rpm for 10min to form a uniform phosphorus precursor solution.
Step two, preparing indium phosphide nuclear quantum dots
And filling inert gas into the indium precursor solution, adjusting the temperature to 60 ℃, adding the phosphorus precursor solution into the indium precursor solution, raising the temperature of the system to 250 ℃, and keeping the temperature for 30min to obtain the indium phosphide nuclear quantum dot.
Step three, preparing the indium phosphide/zinc oxide core-shell structure quantum dot
And adjusting the temperature of the indium phosphide core quantum dot solution to 60 ℃, adding 1.303g of zinc acetylacetonate, 2.373g of oleic acid, 6mL of oleylamine and 12mL of 1-octadecene, heating to 300 ℃, and stirring for 30min to obtain the indium phosphide/zinc oxide core-shell structure quantum dot.
The indium phosphide/zinc oxide core-shell structure quantum dot prepared in example 1 is a red light emitting quantum dot, and as shown in fig. 3, the fluorescence emission peak is 524nm, the half-peak width is 38nm, the quantum efficiency is 75%, and the fluorescence property is good.
Example 2
And (3) preparing the red-light indium phosphide/zinc oxide core-shell structure quantum dot.
Step one, preparing indium precursor solution and phosphorus precursor solution
(1) 0.618g of indium acetate, 2.0316g of oleic acid and 31.8156g of 1-octadecene are mixed in a 250mL conical flask at normal temperature, magnetic stirring is carried out, the rotating speed is 600rpm, the temperature is increased to 90 ℃, the system is vacuumized and kept for 60min at 200mTorr, and a uniform indium precursor solution is formed.
(2) 0.2652g of tris (trimethylsilyl) phosphine and 3.1284g of 1-octadecene were mixed at room temperature, magnetically stirred at 600rpm for 10min to form a uniform phosphorus precursor solution.
Step two, preparing indium phosphide nuclear quantum dots
And filling inert gas into the indium precursor solution, adjusting the temperature to 80 ℃, adding the phosphorus precursor solution into the indium precursor solution, raising the temperature of the system to 300 ℃, and keeping the temperature for 30min to obtain the indium phosphide nuclear quantum dot.
Step three, preparing the indium phosphide/zinc oxide core-shell structure quantum dot
And (3) adjusting the temperature of the indium phosphide core quantum dot solution to 60 ℃, adding 1.9545g of zinc acetylacetonate, 3.5595g of oleic acid, 9mL of oleylamine and 18mL of 1-octadecene, heating to 300 ℃, and stirring for 30min to obtain the indium phosphide/zinc oxide core-shell structure quantum dot.
The indium phosphide/zinc oxide core-shell structure quantum dot prepared in example 2 is a red light emitting quantum dot, and as shown in fig. 4, the fluorescence emission peak is 616nm, the half-peak width is 36nm, the quantum efficiency is 72%, and the fluorescence property is good.
Example 3
Preparation of green light indium phosphide/zinc oxide core-shell structure quantum dot
Step one, preparing indium precursor solution and phosphorus precursor solution
(1) 0.515g of indium acetate, 1.693g of oleic acid and 26.513g of 1-octadecene are mixed in a 250mL conical flask at normal temperature, magnetic stirring is carried out, the rotating speed is 600rpm, the temperature is raised to 90 ℃, the system is vacuumized and kept for 90min at 200mTorr, and a uniform indium precursor solution is formed.
(2) 0.221g of tris (trimethylsilyl) phosphine was mixed with 2.607g of 1-octadecene at room temperature, magnetically stirred at 600rpm for 10min to form a uniform phosphorus precursor solution.
Step two, preparing indium phosphide nuclear quantum dots
And filling inert gas into the indium precursor solution, adjusting the temperature to 60 ℃, adding the phosphorus precursor solution into the indium precursor solution, raising the temperature of the system to 250 ℃, and keeping the temperature for 30min to obtain the indium phosphide nuclear quantum dot.
Step three, preparing the indium phosphide/zinc oxide core-shell structure quantum dot
And adjusting the temperature of the indium phosphide core quantum dot solution to 100 ℃, adding 1.303g of zinc acetylacetonate, 2.373g of oleic acid, 6mL of oleylamine and 12mL of 1-octadecene, heating to 300 ℃, and stirring for 30min to obtain the indium phosphide/zinc oxide core-shell structure quantum dot.
The indium phosphide/zinc oxide core-shell structure quantum dot prepared in example 3 is a green light-emitting quantum dot, and as shown in fig. 5, the fluorescence emission peak is 528nm, the half-peak width is 40nm, the quantum efficiency is 68%, and the fluorescence performance is good.
Comparative example 1
And preparing the green light indium phosphide/zinc oxide core-shell structure quantum dot.
Step one, preparing indium precursor solution and phosphorus precursor solution
(1) 0.515g of indium acetate, 1.693g of oleic acid and 26.513g of 1-octadecene are mixed in a 250mL conical flask at normal temperature, magnetic stirring is carried out, the rotating speed is 600rpm, the temperature is raised to 90 ℃, the system is vacuumized and kept for 90min at 200mTorr, and a uniform indium precursor solution is formed.
(2) 0.221g of tris (trimethylsilyl) phosphine was mixed with 2.607g of 1-octadecene at room temperature, magnetically stirred at 600rpm for 10min to form a uniform phosphorus precursor solution.
Step two, preparing indium phosphide nuclear quantum dots
And filling inert gas into the indium precursor solution, adjusting the temperature to 60 ℃, adding the phosphorus precursor solution into the indium precursor solution, raising the temperature of the system to 250 ℃, and keeping the temperature for 30min to obtain the indium phosphide nuclear quantum dot.
Step three, preparing the indium phosphide/zinc oxide core-shell structure quantum dot
And adjusting the temperature of the indium phosphide core quantum dot solution to 120 ℃, adding 1.303g of zinc acetylacetonate, 2.373g of oleic acid, 6mL of oleylamine and 12mL of 1-octadecene, heating to 300 ℃, and stirring for 30min to obtain the indium phosphide/zinc oxide core-shell structure quantum dot.
The indium phosphide/zinc oxide core-shell structure quantum dot prepared in comparative example 1 is a red light emitting quantum dot, and as shown in fig. 6, the fluorescence emission peak is 530nm, the half-peak width is 42nm, the quantum efficiency is 50%, and the fluorescence performance is poor.
Comparative example 2
And (3) preparing the red-light indium phosphide/zinc oxide core-shell structure quantum dot.
Step one, preparing indium precursor solution and phosphorus precursor solution
(1) 0.618g of indium acetate, 2.0316g of oleic acid and 31.8156g of 1-octadecene are mixed in a 250mL conical flask at normal temperature, magnetic stirring is carried out, the rotating speed is 600rpm, the temperature is increased to 90 ℃, the system is vacuumized and kept for 60min at 200mTorr, and a uniform indium precursor solution is formed.
(2) 0.2652g of tris (trimethylsilyl) phosphine and 3.1284g of 1-octadecene were mixed at room temperature, magnetically stirred at 600rpm for 10min to form a uniform phosphorus precursor solution.
Step two, preparing indium phosphide nuclear quantum dots
And filling inert gas into the indium precursor solution, adjusting the temperature to 60 ℃, adding the phosphorus precursor solution into the indium precursor solution, raising the temperature of the system to 300 ℃, and keeping the temperature for 30min to obtain the indium phosphide nuclear quantum dot.
Step three, preparing the indium phosphide/zinc oxide core-shell structure quantum dot
And (3) adjusting the temperature of the indium phosphide core quantum dot solution to 120 ℃, adding 1.9545g of zinc acetylacetonate, 3.5595g of oleic acid, 9mL of oleylamine and 18mL of 1-octadecene, heating to 300 ℃, and stirring for 30min to obtain the indium phosphide/zinc oxide core-shell structure quantum dot.
The indium phosphide/zinc oxide core-shell structure quantum dot prepared in comparative example 2 is a red light emitting quantum dot, and as shown in fig. 7, the fluorescence emission peak is 623nm, the half-peak width is 43nm, the quantum efficiency is 45%, and the fluorescence performance is poor.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of an indium phosphide core-shell structure quantum dot is characterized by comprising the following steps:
preparing an indium precursor solution and a phosphorus precursor solution;
adjusting the indium precursor solution to a first temperature and adding the phosphorus precursor solution for mixing to form a first mixed solution containing indium phosphide nanocrystal cores; the first temperature is 60-120 ℃;
heating the first mixed solution to a second temperature and preserving the heat for 30-50 min; the second temperature is 200-300 ℃;
after preserving heat at the second temperature, cooling to a third temperature, and adding fatty acid, fatty amine, a non-coordinating solvent and a zinc oxide precursor to form a second mixed solution; the third temperature is 40-100 ℃; and
and heating the second mixed solution to a fourth temperature, and keeping the temperature for 20-30 min, wherein the fourth temperature is 250-320 ℃, so as to form the zinc oxide shell layer coated indium phosphide core-shell structure quantum dots.
2. The method of claim 1, wherein the first temperature is 60 to 80 ℃; and/or
The second temperature is 250-300 ℃; and/or
The third temperature is 40-70 ℃; and/or
The fourth temperature is 270-310 ℃.
3. The method of claim 2, wherein the first temperature is 60 ℃; the second temperature is 250 ℃; the third temperature is 60 ℃; the fourth temperature is 300 ℃.
4. The production method according to claim 1, wherein the step of preparing the indium precursor solution includes the steps of:
mixing an indium precursor, fatty acid and a non-coordination solvent, heating to 90-120 ℃, and keeping the temperature for 60-90 min to form a uniform indium precursor solution.
5. The method according to claim 4, wherein the indium precursor is at least one selected from the group consisting of indium acetate, indium carbonate, indium nitrate, indium chloride, indium iodide, indium bromide, indium stearate, and indium myristate; and/or
In the indium precursor solution, the fatty acid is selected from at least one of saturated or unsaturated fatty acid with the carbon atom number being more than or equal to 6; and/or
In the indium precursor solution, the non-coordinating solvent is at least one selected from the group consisting of alkanes, alkenes, ethers, and aromatic compounds having 10 or more carbon atoms or less and 22 or less.
6. The production method according to any one of claims 1 to 5, wherein the step of preparing the phosphorus precursor solution comprises the steps of:
mixing a phosphorus precursor and a non-coordination solvent to prepare a phosphorus precursor solution;
wherein the phosphorus precursor is selected from at least one of tris (dimethylamino) phosphine, tris (diethylamino) phosphine, tris (trimethylsilyl) phosphine, tris (triethylsilyl) phosphine, trioctylphosphine, tributylphosphine, and phosphine;
in the phosphorus precursor solution, the non-coordinating solvent is at least one selected from the group consisting of 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene.
7. The production method according to any one of claims 1 to 5, wherein, in the second mixed solution,
the fatty acid is selected from at least one of myristic acid, palmitic acid, stearic acid and oleic acid; and/or
The fatty amine is selected from at least one of dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and oleylamine; and/or
The non-coordination solvent is selected from at least one of 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene; and/or
The zinc precursor is at least one selected from zinc adipate, zinc caprylate, zinc laurate, zinc myristate, zinc palmitate, zinc dithiocarbamate, diethyl zinc, dimethyl zinc, zinc acetate, zinc acetylacetonate and zinc diethyl dithiocarbamate.
8. The production method according to any one of claims 1 to 5, wherein the phosphorus precursor solution is added in such an amount that the ratio of the amount of the phosphorus atoms to the amount of the indium atoms in the indium precursor solution is 1 (2-4) when the indium precursor solution is mixed with the phosphorus precursor solution.
9. An indium phosphide core-shell structure quantum dot, characterized by being produced by the production method according to any one of claims 1 to 8.
10. The use of the indium phosphide core-shell structure quantum dot as defined in claim 9 in the preparation of a light-emitting device, a solar cell or a biomarker.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105887A (en) * | 2021-04-29 | 2021-07-13 | 合肥福纳科技有限公司 | Quantum dot and preparation method thereof |
| WO2023134300A1 (en) * | 2022-01-12 | 2023-07-20 | 广东粤港澳大湾区国家纳米科技创新研究院 | Method for preparing quantum dot material from precursor capsule, quantum dot material, quantum dot composition, and quantum dot device |
| CN118165730A (en) * | 2024-05-13 | 2024-06-11 | 北京北达聚邦科技有限公司 | Indium phosphide quantum dot and preparation method thereof |
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2020
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105887A (en) * | 2021-04-29 | 2021-07-13 | 合肥福纳科技有限公司 | Quantum dot and preparation method thereof |
| CN113105887B (en) * | 2021-04-29 | 2024-04-19 | 湖州鑫成新材料科技有限公司 | Quantum dot and preparation method thereof |
| WO2023134300A1 (en) * | 2022-01-12 | 2023-07-20 | 广东粤港澳大湾区国家纳米科技创新研究院 | Method for preparing quantum dot material from precursor capsule, quantum dot material, quantum dot composition, and quantum dot device |
| CN118165730A (en) * | 2024-05-13 | 2024-06-11 | 北京北达聚邦科技有限公司 | Indium phosphide quantum dot and preparation method thereof |
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