KR101897179B1 - Method for manufacturing metal phosphide nanocrystal - Google Patents

Abstract

The present invention relates to a nanocrystal synthesis step of synthesizing nanocrystals by a pyrolysis reaction by mixing a nonpolar solvent, a precursor of a Group III cation, a first ligand and white phosphorus coordinated to a second ligand, The present invention relates to a method for producing a metal-phosphide nanocrystal having a particle size of 1.5 to 2 nm and a magic-sized particle having an emission range of a wavelength of 430 to 550 nm. (FWHM) of the luminescence spectrum is 100 nm or less, and at least 30% of the photoluminescence of the core is a metal phosphide nano-crystal, M _x P _y (x and y are integers of 10 to 100) it is possible to provide a metal-phosphide nano-crystal having photoluminescence quantum yield.

Description

METHOD FOR MANUFACTURING METAL PHOSPHIDE NANOCYSTAL [0001]

The present invention relates to a method of manufacturing a metal-phosphide nanocrystal, and more particularly, to a method of manufacturing a nanocrystal having a magic-sized characteristic and a light-emitting property formed of metal phosphide.

Nanocrystal is a nano-sized crystalline particle, in which nano-sized single crystals themselves or nano-sized single crystals are aggregated. The shape of nanocrystals is largely classified according to the dimension, such as a zero-dimensional point, a single sphere, a one-dimensional nanowire, and a nanorod, which are two-dimensional nanodiscs.

The point that corresponds to the zero dimension is also called a quantum dot (Quantum Dot). It is a form in which nano-sized single crystals are gathered. It emits light when the energy level is increased by the energy of light and the wavelength of light emitted according to the size of the particle There is a feature that can adjust the color because it is different.

Nanocrystals are typically made using a variety of minerals including cadmium (Cd). However, cadmium is harmful to humans and the environment due to its high toxicity, and thus it is in a trend to restrict its use in various regulations.

In this trend, we are trying to develop 3-5 family nano crystals in order to develop eco-friendly nano crystals without cadmium. The most actively studied nano crystals are nano crystals using phosphide.

A variety of phosphorus sources are used to synthesize phosphide nanocrystals, mainly using Tris (trimethylsilyl) phosphine (TMSP) or Tris (dimethylamino) phosphine (TDAP). However, since the above-mentioned human material should be a highly reactive Trimethylsilyl-halide or dimethylamino-halide material, the material itself is liquid and highly reactive, so even TMSP raw material is prohibited from being imported overseas .

In this study, a method for synthesizing nanocrystals using white phophorus as a material is under study. When white phosphorus is used for the synthesis of nanocrystals, the reaction rate is slower than that of the conventional TMSP and TDAP, so that the nanocrystal size is relatively easy to control. As a result, the band gap It is easy to adjust.

Korean Patent No. 10-0675963 and Korean Patent No. 10-0549402 disclose patents relating to a method for producing nanocrystals using white phosphorus. The two patents disclose that the salt is used as a metal salt (Na ₃ P) The coprecipitation method using the phenomenon of precipitation after reaction was used. However, the above-mentioned patents are very good in reactivity with the white lignite itself. Since the nano crystal is synthesized with Na ₃ P having high reactivity by using metal sodium which is difficult to handle, it is difficult to mass-produce Na _x P (X <3) There is a disadvantage that it is accompanied by impurities, and there is a limitation that the size of the nano-crystal can not be controlled.

1. Korean Patent No. 10-0675963 (Jan. 23, 2007) 2. Korean Patent No. 10-0549402 (2006.01.27) 3. Korean Patent Publication No. 10-2014-0075038 (June 19, 2014) 4. US registered patent US 5,505,928 (April 4, 1996)

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method for producing metal-phosphide nanocrystals having a magic size characteristic and a light emission characteristic by reacting stably with whitin.

However, the objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

The present invention relates to a nanocrystal for synthesizing nanocrystals by a pyrolysis reaction by mixing a nonpolar solvent, a precursor of a group III cation, a first ligand of the following general formula (1) and a white phosphorus coordinated to a second ligand of the general formula Synthesis step S1; And a precipitation step (S2) of precipitating the nanocrystals synthesized after the nanocrystal synthesis step (S1). The present invention also provides a method of manufacturing a metal-phosphide nanocrystal.

[Chemical Formula 1] RCOOH

(R is hydrogen, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, a substituted or unsubstituted C ₆ -C ₁₄ aryl group)

[Formula 2] PR _n H _3-n

(R is a C ₁₀ -C ₃₀ alkyl group, and n is an integer of 1 to 3)

The nanocrystal synthesis step (S1) comprises: preparing a first solution (S111) by mixing the precursor of the group III cations to the non-degradable solvent; preparing a second solution containing the first ligand of the general formula (S112) mixing the first solution and the second solution to prepare a third solution containing white phosphorus coordinated to the second ligand of Formula (2), and mixing the second solution (S113) of mixing the first solution and the third solution, and a step (S114) of heating and reacting a mixture of the first solution, the second solution and the third solution (S114) .

Or the nanocrystal synthesis step (S1) comprises: (S121) heating (S121) a first solution prepared by mixing the precursor of the group III cations to the non-dominant solvent, and a second step (S122) mixing the heated first solution with the prepared second solution, preparing a third solution by coordinating white phosphorus with the second ligand of the formula (2) (S123) mixing the heated first solution with the first solution, the second solution, and the third solution, and maintaining the temperature of the mixture of the first solution, the second solution, and the third solution, And synthesizing nanocrystals including step S124.

The present invention also relates to a method for preparing a nanocrystal, comprising: a precipitation step (S2) of precipitating the synthesized nanocrystal after the nanocrystal synthesis step (S1); And dispersing the precipitated nanocrystals in a non-polar solvent (S3).

The present invention also relates to a method for manufacturing a metal foil, comprising the steps of: (S4) mixing and mixing an organic ligand with a prepared metal phosphide nanocrystal colloid solution, and then adding a shell component precursor to form a shell layer on the metal phosphide nano- To provide a method for producing a free core / shell nano crystal.

The present invention can provide a metal-phosphide nanocrystal having a magic-sized characteristic with a uniform size and a good emission characteristic of a light-emitting region having a specific wavelength.

Since the present invention does not use white phosphorus in the form of a metal salt, it is suitable for mass production because the reaction is stable. By adjusting the degassing temperature, the size of the nanocrystal can be easily controlled, and the metal phosphide nano- Can be manufactured.

1 is a schematic diagram of a nanocrystal synthesis step according to an embodiment of the present invention.
FIG. 2 shows UV-vis absorption and PL spectra of nano-crystals synthesized according to Examples and Comparative Examples of the present invention.
FIG. 3 shows UV-vis absorption spectra of mass synthesized nanocrystals synthesized according to Examples and Comparative Examples of the present invention.
FIG. 4 shows UV-vis absorption spectra over time of synthesized nanocrystals according to Examples and Comparative Examples of the present invention. FIG.

Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined solely by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise stated.

Throughout this specification and claims, the word "comprise", "comprises", "comprising" means including a stated article, step or group of articles, and steps, , Step, or group of objects, or a group of steps.

On the contrary, the various embodiments of the present invention can be combined with any other embodiments as long as there is no clear counterpoint. Any feature that is specifically or advantageously indicated as being advantageous may be combined with any other feature or feature that is indicated as being preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.

1. Metal Phosphide Nano-crystal  Manufacturing method

A method of fabricating a metal phosphide nanocrystal according to an embodiment of the present invention includes a step of forming a magic-nitride structure including a phosphide including a group III element (M) sized and luminescence properties of a nanocrystal.

The metal-phosphide nanocrystals produced according to the present invention have a magic-sized characteristic with a certain size and a certain emission wavelength, and have emission characteristics with a specific wavelength.

The metal-phosphide nanocrystals according to the present invention are prepared by mixing a noviro solvent, a precursor of a group III cation, a first ligand represented by the following general formula (1) and a second ligand represented by the following general formula (S1). &Lt; / RTI &gt;

 [Chemical Formula 1] RCOOH

(Wherein R is hydrogen, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, a substituted or unsubstituted C ₆ -C ₁₄ aryl group)

[Formula 2] PR _n H _3-n

(Wherein R is a C ₁₀ -C ₃₀ alkyl group, and n is an integer of 1 to 3)

The nanocrystal synthesis step S1 according to an embodiment of the present invention is divided into a first embodiment of a heat-up method and a second embodiment of a hot injection method. FIG. 1 shows a schematic view of a nanocrystal synthesis step according to an embodiment of the present invention.

The nanocrystal synthesis step S11 according to the first embodiment is a heat-up method suitable for mass production, and includes the steps of preparing a first solution by mixing a precursor of a group III cations to a non-dominant solvent (S111 (S112) mixing the first solution and the second solution containing the first ligand of Formula (1) and preparing a third solution containing white phosphorus coordinated to the second ligand of Formula (2) (S113) of mixing the first solution and the third solution in which the second solution is mixed, and a step (S114) of heating and reacting the mixture of the first solution, the second solution and the third solution (S114) .

The step of preparing the first solution (S111) is a step of mixing the precursor of the Group III cations into the non-polar solvent into the reactor.

The non-sparing solvents are 2,6,10,15,19,23-hexamethyltetracosane (Squalane), 1-octadecene (ODE), trioctylamine (TOA), tributylphosphine oxide, octadecene, octadecylamine, trioctylphosphine (TOP) and trioctylphosphine oxide And the like. Preferably, 1-octadecene (ODE) is used.

The precursors of the Group III cations are selected from the group consisting of acetylacetonate, chloride, acetate, Myristate, Myristate Acetate, Myristate 2 Acetate, ), Trimethyl, alkyl (Alkyl), and aryl (Aryl) compounds. Preferably, the Group III element is indium, and more preferably the indium precursor is an acetylacetonate compound.

In addition, the step (S111) of preparing the first solution includes a step of mixing the precursor of the group III cations into the non-polar solvent, mixing the mixture, and then degassing the precursor. Vacuumization removes moisture from the air inside the reactor, and when the vacuum is carried out at a temperature of 90 to 120 ° C, metal phosphide nano-crystals having excellent light emission characteristics, that is, metal phosphide nano crystals having high light emission intensity can be produced.

Unlike at room temperature, the higher the vacuum temperature, the less the amount of the material bound to the cations in the precursor of the group III cations is reduced, so that nanocrystals of large particle size can be produced. That is, it is possible to control the particle size of nanocrystals produced by adjusting the vacuum temperature. The vacuuming time is preferably 60 minutes or longer.

In addition, the step (S111) of preparing the first solution may be carried out by purging the inside of the reactor with an inert gas after vacuuming, and the inert gas may be selected from the group consisting of helium, neon, argon, krypton, Or more.

In addition, the step (S111) of preparing the first solution may be performed by mixing the second solution and the third solution at room temperature by cooling the vacuumed first solution to room temperature (15 to 25 DEG C).

The step (S112) of mixing the second solution is a step of preparing a second solution containing the first ligand of the formula (1) and mixing with the first solution. That is, the second solution is put into a reactor containing the first solution at room temperature and mixed.

The first ligand may be a carboxylic acid-based compound, a phosphonic acid-based compound, or a mixture of the two compounds. More specifically, the carboxylic acid-based compound is a compound of oleic acid, paletic acid, stearic acid, linoleic acid, myristic aicd and lauric acid. And the phosphonic acid-based compound may be at least one selected from the group consisting of hexylphosphonic acid, octadecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, And may be at least one selected from the group consisting of decylphosphonic acid, octylphosphonic acid and butylphosphonic acid. It is preferable to use oleic acid.

The step (S113) of mixing the first solution and the third solution in which the second solution is mixed is a step of preparing a third solution by coordinating white phosphorus with the second ligand of the formula (2) And mixing the mixture with the mixture of the first solution and the second solution. That is, the third solution is put into a reactor containing a mixture of the first solution and the second solution at room temperature.

The size of nanocrystals produced according to the type of the second ligand can be controlled. The second ligand uses an alkylphosphine-based compound. More specifically, the alkylphosphine-based compounds include triethyl phosphine, tributyl phosphine, trioctyl phosphine, triphenyl phosphine, and tricyclohexyl phosphine (tricyclohexyl phosphine). It is preferable to use trioctyl phosphine.

White phosphorus is added to the second ligand to coordinate the leucine to the second ligand compound. And the second ligand is coordinated with the wax to prepare a third solution. The ratio of the first ligand to the coordinated to the second ligand is such that the molar ratio of the first ligand to the first ligand is within the range of 1: 0.1 to 1:10. If the molar ratio of the first ligand to the phosphorus coordinated to the second ligand is less than 0.1, there is a problem that the precursor of the group III cations in the first solution can not be sufficiently stabilized, The precursor of the group III cations in the first ligand is excessively stabilized and does not react with the white ligand coordinated to the second ligand.

When white is added to the second ligand, the first ligand is coordinated with the first ligand to form a new organic complex, and then mixed with the first solution mixed with the second solution. Make the reaction possible.

The mixing ratio of the first solution to the third solution is such that the molar ratio of the precursor of the group III cations of the first solution and the white solution of the second solution is in the range of 1: 0.1 to 1: 1. When the molar ratio of the precursor to the precursor of the group III cations is less than 0.1, there is a problem that the synthesis efficiency of the nano-crystals is lowered, and when the mole ratio is more than 1, there is a problem that the luminescent properties are remarkably lowered.

The step (S114) of heating and reacting the mixture of the first solution and the third solution in which the second solution is mixed is performed in the first solution and the second solution. And the pyrolysis reaction is caused by heating the mixture of the third solution.

The heating temperature is 250 to 350 占 폚. More specifically, it is heated at a rate of 5 to 10 占 폚 / min to reach a temperature within the above range, thereby causing a pyrolysis reaction. When the heating temperature is lower than 150 ° C., there is a problem that sufficient thermal decomposition reaction does not occur. When the heating temperature is higher than 400 ° C., the reaction rate is improved but the reaction material is deteriorated.

After heating to the above temperature, the metal phosphoride nanocrystals are synthesized by maintaining the heated temperature for 20 minutes or more. Nanocrystals with a magic size characteristic of a certain size are synthesized by maintaining the heated temperature for 20 minutes or more.

The nanocrystal synthesis step S12 according to the second embodiment is a hot injection method suitable for small volume production and includes heating a first solution prepared by mixing a precursor of a Group III cation to a non-conjugated solvent (S121 ), Mixing a second solution containing the first ligand of Formula 1 with a heated first solution (S122), mixing a third solution prepared by coordinating white phosphorus with the second ligand of Formula (2) (S123) mixing the first solution and the third solution in which the heated second solution is mixed, and maintaining the temperature of the mixture of the first solution, the second solution and the third solution, (S124) to synthesize nanocrystals.

The nanocrystal synthesis step S12 according to the second embodiment is different from the nanocrystal synthesis step S11 according to the first embodiment in that the first solution is heated before the first solution, the second solution and the third solution are mixed And then the second solution and the third solution are rapidly injected at a heated temperature in rapid succession to synthesize nanocrystals.

The step of heating the first solution (S121) is a step of mixing the precursor of the group III cations into the non-saturated solvent into the reactor to mix the first solution and then heating the first solution.

The non-sparing solvents are 2,6,10,15,19,23-hexamethyltetracosane (Squalane), 1-octadecene (ODE), trioctylamine (TOA), tributylphosphine oxide, octadecene, octadecylamine, trioctylphosphine (TOP) and trioctylphosphine oxide And the like. Preferably, 1-octadecene (ODE) is used.

The precursors of the Group III cations are selected from the group consisting of acetylacetonate, chloride, acetate, Myristate, Myristate Acetate, Myristate 2 Acetate, ), Trimethyl, alkyl (Alkyl), and aryl (Aryl) compounds. Preferably, the Group III element is indium, and more preferably the indium precursor is an acetylacetonate compound.

In addition, the step of heating the first solution (S121) includes a step of mixing the precursor of the Group III cations into the non-polar solvent and mixing and degassing the mixture. Vacuumization removes moisture contained in the air inside the reactor. Although the temperature during vacuumization is not limited, when the reaction is carried out at 90 to 120 ° C, metal-phosphide nano-crystals having excellent luminescence characteristics, that is, .

Unlike at room temperature, the higher the vacuum temperature, the less the amount of the material bound to the cations in the precursor of the group III cations is reduced, so that nanocrystals of large particle size can be produced. That is, it is possible to control the particle size of nanocrystals produced by adjusting the vacuum temperature. The vacuuming time is preferably 60 minutes or longer.

Further, the step of heating the first solution (S121) may be performed by purging the inside of the reactor with an inert gas after vacuuming, and the inert gas may be selected from the group consisting of helium, neon, argon, krypton, Or more.

The step of heating the first solution (S121) is different from the cooling of the first solution subjected to the vacuumization in the nanocrystal synthesis step (S11) according to the first embodiment to a temperature of 250 to 350 ° C do. More specifically, it is heated at a rate of 10 to 15 DEG C / min to reach the temperature in the above range.

The step of mixing the second solution (S122) is a step of rapidly injecting the second solution containing the first ligand of the formula (1) into the first solution heated to the above-mentioned range and mixing the solution.

The second solution contains the first ligand of the above formula (1). The first ligand is a carboxylic acid-based compound, and specific examples thereof are the same as those described in the first embodiment.

The step of mixing the third solution (S123) comprises adding a white phosphorus to the second ligand to prepare a third solution, and adding a third solution to the first solution mixed with the second solution heated to the temperature within the range This is a step of rapidly injecting the solution. The second ligand uses an alkylphosphine-based compound. Specific examples of the alkylphosphine-based compound are the same as those described in the first embodiment.

The ratio of the first ligand to the coordinated to the second ligand is such that the molar ratio of the first ligand to the first ligand is within the range of 1: 0.1 to 1:10. If the molar ratio of the first ligand to the phosphorus coordinated to the second ligand is less than 0.1, there is a problem that the precursor of the group III cations in the first solution can not be sufficiently stabilized, The precursor of the group III cations in the first ligand is excessively stabilized and does not react with the white ligand coordinated to the second ligand.

When white is added to the second ligand, the first ligand is coordinated with the first ligand to form a new organic complex, and then mixed with the first solution mixed with the second solution. Make the reaction possible.

The mixing ratio of the first solution and the third solution is such that the molar ratio of the precursor of the group III cations of the first solution and the white solution of the third solution is in the range of 1: 0.1 to 1: 1. When the molar ratio of the precursor to the precursor of the group III cations is less than 0.1, there is a problem that the synthesis efficiency of the nano-crystals is lowered, and when the mole ratio is more than 1, there is a problem that the luminescent properties are remarkably lowered.

The pyrolysis reaction (S124) is performed by rapidly introducing the second solution into the first solution heated at 250 to 350 ° C. and maintaining the heated temperature of the mixture in which the third solution is immediately introduced, thereby performing pyrolysis reaction at a high temperature for a short time, Phosphide nanocrystals are synthesized.

The step of performing the thermal decomposition reaction (S124) is carried out by rapidly introducing the second solution into the first solution heated to 250 to 350 ° C, immediately adding the third solution, holding the mixture for 20 to 60 minutes, and synthesizing nanocrystals through pyrolysis . The nanocrystals are synthesized by maintaining the temperature for 20 minutes or more, and within a period of 60 minutes, nanocrystals having a magic size characteristic of a certain size are synthesized.

The method for preparing a metal-phosphide nano-crystal according to the present invention includes a precipitation step (S2) for precipitating the nanocrystals synthesized after the nanocrystal synthesis step (S1) to obtain a precipitated nanocrystal.

In the precipitation step S2 according to an embodiment of the present invention, an anti-solvent is added to a solution containing the synthesized nanocrystal to precipitate the nanocrystal.

The semi-solvent may be any one or more selected from the group consisting of ethanol, methanol, butanol, propanol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide and acetone.

The method for preparing a metal-phosphide nanocrystalline colloid solution according to another embodiment of the present invention includes a dispersing step (S3) of dispersing the precipitated nanocrystals obtained in the precipitation step (S2) according to the present invention into a nonpolar solvent A metal-phosphide nano-crystal colloidal solution is prepared.

More specifically, a method for producing a metal-phosphide nanocrystalline colloid solution includes mixing a non-conjugated solvent, a precursor of a Group III cation, a first ligand of Formula 1, and white phosphorus coordinated to a second ligand of Formula 2, A nanocrystal synthesis step (S1) for synthesizing nanocrystals by a thermal decomposition reaction, a precipitation step (S2) for precipitating the synthesized nanocrystals, and a dispersion step (S3) for dispersing the precipitated nanocrystals in a nonpolar solvent.

The dispersing step S3 according to an embodiment of the present invention is a step of dispersing the precipitated nanocrystals in a non-polar solvent, and can produce colloidal nanocrystals.

Nonpolar solvents include hexane, toluene, benzene, octane, chloroform, chlorobenzene, tetrahydrofuran (THF). Is selected from the group consisting of pentane, heptane, decane, methylene chloride, 1,4-dioxane, diethyl ether, cyclohexane and dichlorobenzene. .

A method of manufacturing a core / shell nanocrystal according to another embodiment of the present invention includes the steps of: (a) forming a metal-nano-crystal nanocrystal Mixing and reacting the colloidal solution with an organic ligand, and then adding a shell component precursor to form a shell layer on the metal-phosphide nanocrystal (S4). By forming the shell layer, the emission intensity of the nanocrystals can be remarkably increased.

The organic ligand may be selected from the group consisting of trioctylphosphine (TOP), trioctylphosphine oxide (TOPO), oleic acid, oleylamine, octylamine, trioctylamine, hexadecylamine, octadecanol, octanethiol, dodecanethiol, hexylphosphonic acid (HPA), tetradecylphosphonic acid (TDPA), and octylphosphinic acid (OPA).

The shell layer is made of ZnS, ZnS, ZnSe, ZnTe, GaAs, GaN, GaP, GaSb, GaS, GaSe, GaTe, CdO, CdS, CdSe, CdTe, InAs, InN, InP, InSb, InS, InSe, InTe, HgO, HgS , HgSe, HgTe, AlAs, AlN, AlP, AlSb, MgO, MgSe, MgTe, CdZnS, CdZnSe, CdSSe, CaO, CaS, CaTe, GaAsP, GaTeSe, GaLnSe, SrO, SrS, SrSe, SrTe, InGaAs , InAsP, InSeTe, BaO, BaS, BaSe, BaTe, and ZnSSe.

For example, when a ZnSSe shell layer is formed, an organic ligand is mixed and reacted with a metal phosphide nanocrystalline colloid solution, and then a zinc precursor and a selenium sulfur precursor are added to form a ZnSSe shell layer on the metal phosphide core.

Zinc precursors include, but are not limited to, dimethyl zinc, diethyl zinc, zinc acetate, zinc acetate dihydrate, zinc acetylacetonate, Zinc acetylacetonate hydrate, Zinc iodide, Zinc bromide, Zinc chloride, Zinc fluoride, Zinc fluoride, Zinc fluoride, tetrahydrate, zinc carbonate, zinc cyanide, zinc nitrate, zinc nitrate hexahydrate, zinc oxide, zinc peroxide ), Zinc perchlorate, zinc perchlorate hexahydrate, zinc sulfate, diphenylsulfate, Open (Diphenyl zinc), may be at least one that is selected from the group consisting of zinc naphthalate (Zinc naphthenate), zinc oleate (Zinc oleate) and zinc stearyl acrylate (Zinc stearate).

The sulfur precursor may be, but is not limited to, one or more selected from the group consisting of sulfur powder, trimethylsilyl sulfur, bis (trimethylsilyl) sulfide, and alkyl thiol.

More specifically, the step (S4) of forming the shell layer is performed by injecting the organic ligand into the metal phosphide nanocrystal colloid solution and then reacting at 150 to 250 for 10 minutes to 1 hour. The shell component precursor and solvent are then slowly added to the solution at the same temperature for 1 to 20 minutes. A semi-solvent may be added to precipitate the core / shell (metal phosphide / ZnS) nanocrystals.

2. Magic Size  metal Phosphide Nano crystal

The nanocrystals fabricated according to one embodiment of the present invention are metal-phosphide nanocrystals having magic-sized and luminescence characteristics. More specifically, the metal-phosphide nanocrystal produced according to the present invention has a magic-sized characteristic with a uniform size and a luminescence characteristic with a light-emitting region of a specific wavelength.

Nanocrystals are particles of 100 nm or less made of monocrystalline or polycrystalline ordered elements and behave as quantum and exhibit optical and electrical properties different from bulk materials made of the same element. As nanoscale particles, the size of the particles is smaller than the Bohr radius, resulting in a discontinuous band gap due to the quantum confinement effect. By controlling the particle size, the optical and electrical characteristics Can be changed.

The metal-phosphide nanocrystals according to the present invention have a magic-sized characteristic within a range of particle sizes of 1.5 to 2 nm. Here, the term &quot; magic size characteristic &quot; means that the nanocrystal grows continuously in size and does not have a continuous size distribution, but is stabilized at a certain size and has a constant size when grown. Here, the predetermined size includes not only a case where only a metalphosphide nano-crystal of a specific size exists but also a case where metal phosphide nano-crystals of a specific size exist in a large amount and a small amount of metal phosphide nano- do.

In another aspect, the nanocrystals according to the present invention include metal phosphide clusters and may refer to an aggregate of metal phosphide clusters. Here, a cluster means a particle in which a single atom, a molecule, or another kind of atom is clustered or bonded within a few hundred to several thousands, and the metal phosphide cluster has a metal atom and a phosphorus atom at a certain ratio Quot; means a particle which is combined and bound within hundreds to several thousands of particles.

The metal-phosphide clusters according to the present invention can be represented by a structural formula of M _x P _y (where x and y are integers between 10 and 100) by combining a metal atom and a phosphorus atom at a specific ratio, , and has a stable structure when y is a specific integer within the above range. Therefore, when growing a metal-phosphide cluster, a metal-phosphate cluster having a specific integer, that is, a specific atom number, is obtained in a uniform size.

The metal-phosphide nano-crystal according to the present invention has a magic-sized characteristic with a uniform size distribution including a metal-phosphide cluster having a specific size within a range of 1.5 to 2 nm.

Here, the uniform size distribution includes not only a case where only metal foam clusters of a certain size exist but also a case where a large amount of metal phosphide clusters of a certain size exists and a small amount of metal phosphide clusters other than the specific size exists It was used as a meaning.

In addition, since the UV-vis absorption spectrum of the nanocrystals according to the present invention grows without continuous growth of the particles, the magic-sized metal-phosphide nano-crystal according to the present invention is stabilized at a specific size and has a constant size, And has the characteristics of growing clusters.

Also, the magic-sized metal-phosphide nano-crystal according to the present invention has a luminescence characteristic with an emission range of 430 to 550 nm. The metal-phosphide nano-crystal according to the present invention has a particle size of 1.5 to 2 nm, which is very small and absorbs energy, becomes an excitation state, emits energy (light) absorbed again and emits light of a specific wavelength (luminescence). At this time, the emission wavelength is in the range of 430 to 550 nm and has a luminescence characteristic of emitting a cyan light.

Further, the metal-phosphide nano-crystal according to the present invention has a full width at half maximum (FWHM) in an emission wavelength region of 100 nm or less and a purity of emission color And light emission under relaxed conditions is possible.

In addition, the metal-phosphide nanocrystals according to the present invention have a photoluminescence quantum yield of 30% or more in a core excluding the shell layer. The quantum yield means the ratio of the number of emitted photons to the number of photons absorbed. The metal-phosphide nano-crystal according to the present invention has a quantum yield of at least 30% in the core even without a shell layer.

Also, the metal-phosphide nanocrystal according to the present invention has a band gap energy (E _g ) of 2.5 to 3.0 eV. The electrons in the nanocrystals form an energy band that is wider than the energy level of the atoms due to the interaction of the metal and the phosphorus atoms constituting the nanocrystal. Since the spacing between atoms and atoms of nano-crystals is very small, the electrons circulating in the atomic orbit are affected by adjacent atoms, and the increase or decrease of the electrons by this influence changes the kinetic energy of electrons. In the nanocrystals, therefore, the range of energy values that electrons can have is broadened to form energy bands having a constant width.

The nanoscale crystals forming the broadened energy band overlap with broader energy bands as the spacing of the atoms becomes closer to each other. The low energy band formed by the valence electron is called the valence band, the high band formed by the vacant electron orbit The energy band is called the conduction band, and the interval between these two bands is called the band gap energy (E _g ).

That is, the metal-phosphide nano-crystal according to the present invention has a magic-sized characteristic with a uniform particle size in the range of 1.5 to 2.0 nm, has a relatively wide band gap energy of 2.5 to 3.0 eV, Area.

The present invention also provides a magic sized metal phosphite core / shell nanocrystal that further comprises a shell layer on the surface of a metal-phosphide cluster core having magic-sized characteristics according to the present invention as core / shell nanocrystals.

The shell layer is made of ZnS, ZnS, ZnSe, ZnTe, GaAs, GaN, GaP, GaSb, GaS, GaSe, GaTe, CdO, CdS, CdSe, CdTe, InAs, InN, InP, InSb, InS, InSe, InTe, HgO, HgS , HgSe, HgTe, AlAs, AlN, AlP, AlSb, MgO, MgSe, MgTe, CdZnS, CdZnSe, CdSSe, CaO, CaS, CaTe, GaAsP, GaTeSe, GaLnSe, SrO, SrS, SrSe, SrTe, InGaAs , InAsP, InSeTe, BaO, BaS, BaSe, BaTe, and ZnSSe.

The present invention also provides a composition comprising a plurality of magically sized clusters, which nanocrystal compositions comprise a magically sized metal phosphide cluster according to the present invention. The nanocrystal composition may be a solution in which metal phosphide clusters having a magic size characteristic are dispersed in a non-polar solvent.

The metal-phosphide nanocrystal composition according to the present invention has a discontinuous size distribution including metal-phosphide clusters having one or more specific sizes within a range of 1.5 to 2 nm.

Here, the discontinuous size distribution refers to not only the case where only metalphosphide clusters having at least one or more specific sizes are present but also metal phosphide clusters having at least one specific size or two or more specific sizes exist in a large amount, Of metal-phosphide clusters were present in a small amount.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention, and it is to be understood by those skilled in the art that the present invention is not limited thereto It will be obvious.

&Lt; Example 1: Heat-up method >

The first solution was prepared by placing 4 ml of 1-octadecene (ODE) and 0.5 mmol of Indium acetylacetonate (In (acac) 3) in a round flask and vacuuming for 1 hour at 110 ° C. The mixture was then cooled to room temperature. 3.0 mmol of the second solution, Oleic acid, was mixed with 0.25 mmol of white phosphorus coordinated to the third solution, trioctylphosphine (TOP), and then heated from room temperature to 275 ° C for 30 minutes in a nitrogen atmosphere Respectively. After maintaining the temperature at 275 ° C for 30 minutes, the temperature was lowered to room temperature again, and the solution was cooled. Nano-crystals synthesized from a mixed solvent of methanol and acetone 10: 1 were precipitated and washed to obtain InP nano-crystals. The obtained InP nanocrystals were dispersed in hexane to prepare an InP nanocrystalline colloidal solution.

&Lt; Example 2: Hot injection method >

4 ml of 1-octadecene (ODE) and 0.5 mmol of Indium acetylacetonate (In (acac) 3) are added to the round flask, and the first solution is prepared and vacuumed at 110 ° C for 1 hour. The prepared first solution was heated to 110 ° C and 275 ° C in 20 minutes under a nitrogen atmosphere. 3.0 mmol of oleic acid as the second solution and 0.25 mmol of white phosphorus coordinated to the third solution of trioctylphosphine (TOP) were mixed with the first solution, and the temperature was maintained at 275 ° C for 30 minutes. The temperature was lowered to cool, the nanocrystals were precipitated with a 10: 1 mixed solvent of methanol and acetone, and then washed to obtain InP nano-crystals. The obtained InP nanocrystals were dispersed in hexane to prepare an InP nanocrystalline colloidal solution.

&Lt; Comparative Example 1 &

0.5 mmol of In (acetylacetonate) 3, 1.25 mmol of oleic acid and 4 mL of ODE were placed in a 3 neck flask and degassed at room temperature (15-25 ° C) followed by Ar purging Respectively. Then, a solution prepared by mixing 2.84 mL of tributylphosphine (TBP) and 0.242 mmol of white phosphorus was added, and the temperature was raised to 300 ° C., and the reaction was continued for 30 minutes. After 30 minutes, the temperature was lowered and the nano-crystals were precipitated with a 3: 1 mixed solvent of butanol and acetone, followed by washing to obtain InP nano-crystals. The obtained InP nanocrystals were dispersed in hexane to prepare an InP nanocrystalline colloidal solution.

&Lt; Comparative Example 2 &

0.5 mmol of In (acetylacetonate) 3, 1.25 mmol of oleic acid and 4 mL of ODE were placed in a 3 neck flask and degassed at room temperature (15-25 ° C) followed by Ar purging And the temperature was raised to 300 ° C.

When the temperature of the solution reached 300 ° C., a solution prepared by mixing 2.84 mL of tributylphosphine (TBP) and 0.242 mmol of white phosphorus was rapidly injected into the solution using a syringe, and the reaction was continued for 30 minutes To synthesize nano crystals. After 30 minutes, the temperature was lowered and the nano-crystals were precipitated with a 3: 1 mixed solvent of butanol and acetone, followed by washing to obtain InP nano-crystals. The obtained InP nanocrystals were dispersed in hexane to prepare an InP nanocrystalline colloidal solution.

&Lt; Experimental Example 1: UV-vis absorption spectrum and PL spectrum measurement >

The UV-vis absorption spectrum and the photoluminescence (PL) spectrum of the synthesized nanocrystals were measured by a spectrophotometer (Cary Eclipse, VARIAN). FIG. 2 shows UV-vis absorption and PL spectra of nanocrystals synthesized according to the above examples. FIG. 3 shows UV-vis absorption of nanocrystals synthesized according to Examples and Comparative Examples of the present invention. Spectrum. As shown in FIG. 3, it can be seen that the size and size distribution of nanocrystals are maintained unchanged even during mass synthesis.

<Experimental Example 2: UV-vis absorption spectrum of nanocrystals over time during synthesis>

The UV-vis absorption spectrum of nanocrystals over time during synthesis according to Example 1 is shown in FIG. As shown in FIG. 4, when the synthesis time is 30 minutes, it is confirmed that particles having a high absorption peak in a specific wavelength range are synthesized.

The features, structures, effects, and the like illustrated in the above-described embodiments can be combined and modified in other embodiments by those skilled in the art to which the embodiments belong. Therefore, it should be understood that the present invention is not limited to these combinations and modifications.

Claims (18)

(S1) a nanocrystal synthesis step (S1) of synthesizing nanocrystals by a thermal decomposition reaction by mixing a nonpolar solvent, a precursor of a Group III cation, a first ligand and white phosphorus coordinated to a second ligand; And
And a precipitation step (S2) of precipitating the synthesized nanocrystal after the nanocrystal synthesis step (S1)
Wherein the first ligand is a carboxylic acid-based compound,
Wherein the second ligand is selected from the group consisting of triethyl phosphine, tributyl phosphine, trioctyl phosphine, triphenyl phosphine, and tricyclohexyl phosphine. Wherein the metal phosphide nanocrystal is at least one selected from the group consisting of alkylphosphine compounds.
The method according to claim 1,
The nanocrystal synthesis step (S1)
A step (S111) of preparing a first solution by mixing the precursor of the Group III cations to the non-deliverable solvent,
Preparing a second solution containing the first ligand, mixing the first solution and the second solution, S112,
Preparing a third solution containing white phosphorus coordinated to the second ligand, mixing the first solution mixed with the second solution and the prepared third solution (S113), and
And a step (S114) of heating and reacting a mixture of the first solution, the second solution and the third solution to synthesize nano-crystals.
3. The method of claim 2,
Wherein the step (S111) of preparing the first solution further comprises a step of evacuating the first solution in the reactor at 90 to 120 ° C.
The method of claim 3,
The step of preparing the first solution S111 may further include cooling the vacuumed first solution to a room temperature so that the first solution and the second solution at room temperature are mixed in the mixing step S112 Wherein the method comprises the steps of:
3. The method of claim 2,
The step of reacting (S114) comprises heating the mixture of the first solution, the second solution and the third solution to 250 to 350 DEG C and maintaining the temperature for 20 to 60 minutes to decompose the metal, &Lt; / RTI &gt;
The method according to claim 1,
The nanocrystal synthesis step (S1)
(S121) heating the first solution prepared by mixing the precursor of the group III cations to the non-saturated solvent,
Preparing a second solution containing the first ligand, mixing the heated first solution with the second solution (S122)
(S123) mixing the heated first solution mixed with the second solution and the prepared third solution to form a third solution by coordinating white phosphorus with the second ligand, and
And a step (S124) of maintaining the temperature of the mixed mixture of the first solution, the second solution and the third solution to perform thermal decomposition reaction, thereby synthesizing the nanocrystals.
The method according to claim 6,
Wherein the step of heating the first solution (S121) further comprises a step of evacuating the produced first solution at 90 to 120 占 폚 in a reactor.
8. The method of claim 7,
The step of heating the first solution (S121) may include heating the vacuumed first solution to a temperature of 250 to 350 DEG C, wherein the heated first solution and the heated solution are mixed in the step (S122) Thereby allowing the second solution to be mixed.
The method according to claim 6,
The step of reacting (S124) comprises a step of subjecting the mixture of the first solution and the third solution mixed with the second solution to a thermal decomposition reaction by maintaining the temperature for 20 minutes to 60 minutes, thereby producing a metal-phosphide nanocrystal .
3. The method of claim 2,
The mixing step (S113) comprises mixing the first solution mixed with the second solution so that the molar ratio of the precursor of the group III cations of the first solution and the white solution of the third solution is in the range of 1: 0.1 to 1: And mixing the prepared third solution with the metal solution.
delete The method according to claim 1,
The non-polar solvents include but are not limited to 2,6,10,15,19,23-hexamethyltetracosane (Squalane), 1-octadecene (ODE), trioctylamine (TOA), tributylphosphine oxide, octadecene, octadecylamine, trioctylphosphine ). &Lt; / RTI &gt;
The method according to claim 1,
The precursor of the Group III cations is selected from the group consisting of acetylacetonate, chloride, acetate, Myristate, Myristate Acetate, Myristate 2 Acetate, ), Trimethyl, alkyl (Alkyl), and aryl (Aryl) compounds.
delete The method according to claim 1,
The precipitation step S2 may be carried out by adding the nanocrystal solution selected from the group consisting of ethanol, methanol, butanol, propanol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide and acetone to the synthesized nanocrystal- And adding an anti-solvent containing at least one of the metals to obtain a precipitated nanocrystal.
(S1) of synthesizing nanocrystals by a pyrolysis reaction by mixing a nonpolar solvent, a precursor of a Group III cation, a first ligand and white phosphors coordinated to a second ligand;
A precipitation step (S2) of precipitating the synthesized nanocrystal after the nanocrystal synthesis step (S1); And
And a dispersing step (S3) of dispersing the precipitated nanocrystals in a nonpolar solvent,
Wherein the first ligand is a carboxylic acid-based compound,
Wherein the second ligand is selected from the group consisting of triethyl phosphine, tributyl phosphine, trioctyl phosphine, triphenyl phosphine, and tricyclohexyl phosphine. Wherein the metal phosphide nanocrystalline colloid solution is at least one selected from the group consisting of alkylphosphine compounds.
17. The method of claim 16,
The nonpolar solvent is hexane, toluene, benzene, octane, chloroform, chlorobenzene, tetrahydrofuran (THF). At least one selected from the group consisting of pentane, heptane, decane, methylene chloride, 1,4-dioxane, diethyl ether, cyclohexane and dichlorobenzene &Lt; / RTI &gt; wherein the method comprises the steps of:
(S1) of synthesizing nanocrystals by a pyrolysis reaction by mixing a nonpolar solvent, a precursor of a Group III cation, a first ligand and white phosphors coordinated to a second ligand;
A precipitation step (S2) of precipitating the synthesized nanocrystal after the nanocrystal synthesis step (S1);
A dispersing step (S3) of dispersing the precipitated nanocrystals in a non-polar solvent to obtain a metal-phosphide nanocrystalline colloid solution; And
(S4) mixing and reacting the metal-phosphide nanocrystal colloid solution with an organic ligand, and then adding a shell component precursor to form a shell layer on the metal-phosphide nanocrystal,
Wherein the first ligand is a carboxylic acid-based compound,
Wherein the second ligand is selected from the group consisting of triethyl phosphine, tributyl phosphine, trioctyl phosphine, triphenyl phosphine, and tricyclohexyl phosphine. Wherein the metal phosphide core / shell nanocrystal is at least one selected from the group consisting of alkylphosphine compounds.

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