KR20180105500A - Complex comprising quantum dot and method for manufacturing the same - Google Patents

Abstract

The present invention provides a quantum dot containing complex and a method for manufacturing the same. The quantum dot containing complex according to an embodiment of the present invention includes inorganic particles including a thiol group (-SH) and at least one quantum dot bonded to the inorganic particle surface. In the quantum dot containing complex according to an embodiment of the present invention, the thermal stability and the light stability of the quantum dot can be enhanced by chemical bonding between the quantum dot and the inorganic particle.

Description

TECHNICAL FIELD [0001] The present invention relates to a quantum dot-containing complex and a method for producing the same,

TECHNICAL FIELD The present invention relates to a quantum dot-containing complex and a method for producing the same, and more particularly to a quantum dot-containing complex having excellent thermal stability and light stability, and a method for producing the same.

The quantum dot is a semiconductor material having a nano-sized crystal structure, and has high color purity, excellent optical stability compared with organic materials, thermal stability, and ease of band gap control. Since the quantum dots have a small surface area per unit volume and a quantum confinement effect due to their small size, they have physicochemical properties different from those of the semiconductor material itself. The quantum dots absorb the light from the excitation source, enter the energy excited state, and emit energy corresponding to the energy band gap of the quantum dots. Since quantum dots can control the energy bandgap by controlling the size and composition of the nanocrystals and have high luminescence characteristics with high color purity, various applications to display devices, energy devices, and bioluminescent devices have been developed.

Conventional quantum dots generally referred to herein refer to quantum dots of a core-shell structure in which a shell is coated on the surface of a spherical core. The constituent elements include Group II, III Group IV, Group V, and Group VI are used. The shell may typically consist of one or more layers and may be referred to as a multi-shell quantum dot when the shell is composed of multiple layers. The quantum dot may be a nano- Size crystalline structure, which is a material having high color purity, excellent light stability compared with organic materials, thermal stability, and ease of band gap control. Since the quantum dots have a small surface area per unit volume and a quantum confinement effect due to their small size, they have physicochemical properties different from those of the semiconductor material itself. The quantum dots absorb the light from the excitation source, enter the energy excited state, and emit energy corresponding to the energy band gap of the quantum dots. Since quantum dots can control the energy bandgap by controlling the size and composition of the nanocrystals and have high luminescence characteristics with high color purity, various applications to display devices, energy devices, and bioluminescent devices have been developed.

Conventional quantum dots generally referred to herein refer to quantum dots of a core-shell structure in which a shell is coated on the surface of a spherical core. The constituent elements include Group II, III Group IV, Group V, and Group VI are used. The shell may typically consist of one or more layers and may also be referred to as a multi-shell quantum dot if the shell is composed of multiple layers. The quantum dots of the core-shell structure can control the optical and electrical properties of the quantum dots by controlling the relative bandgap between the core and the shell. The quantum dot of the core-shell structure has an advantage of having high luminescence.

However, since the quantum dot generally has a small size, there is a problem that the thermal stability is poor. In order to solve this problem, attempts have been made to improve the thermal stability by reducing the surface energy of the quantum dots by coating the quantum dots on a porous support such as silica or zeolite. However, bonding between the quantum dots and the porous support is not sufficient, and there is a problem that the thermal stability of the quantum dots decreases again with time.

DISCLOSURE OF THE INVENTION Problems to be solved by the present invention are to provide a quantum dot-containing complex comprising inorganic particles containing a thiol group (-SH) and at least one quantum dot bonded to the surface of the inorganic particles.

Another object to be solved by the present invention is to provide a complex containing a quantum dot having excellent optical stability and thermal stability.

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

In order to solve the above-mentioned problems, the quantum dot containing complex according to an embodiment of the present invention includes inorganic particles including a thiol group (-SH) and at least one quantum dot bonded to the surface of an inorganic particle. In the quantum dot containing complex according to an embodiment of the present invention, the thermal stability and the light stability of the quantum dot can be improved by the chemical bonding between the quantum dot and the inorganic particle.

According to another aspect of the present invention, the inorganic particles may be at least one selected from the group consisting of silica, alumina (Al2O3, AlO2), titanium dioxide, and zinc dioxide.

According to another aspect of the present invention, the quantum dot may comprise a Group II element.

According to another aspect of the present invention, the quantum dot may comprise zinc (Zn).

According to another aspect of the present invention, sulfur of the inorganic particle and zinc of the quantum dot can be combined.

According to another feature of the invention, the diameter of the inorganic particles may be between 50 nm and 10 um, and the diameter of the quantum dot may be between 1 nm and 20 nm.

According to another aspect of the present invention, a quantum dot is formed of two or more selected from the group consisting of zinc (Zn), cadmium (Cd), mercury (Hg), indium (In), magnesium (Mg) P), arsenic (As), nitrogen (N), sulfur (S), selenium (Se) and tellurium (Te).

According to another aspect of the present invention, the quantum dot may be in the form of an alloy composed of four-component elements.

According to an aspect of the present invention, there is provided a method for preparing a quantum dot-containing complex, the method comprising: preparing a first mixed solution including at least one cation precursor and at least one anion precursor; And injecting the solvent into a solution comprising inorganic particles comprising a thiol group to form a complex.

According to another feature of the present invention, the cation precursor is selected from the group consisting of Zn, Cd, Hg, In, Mg, Al, Cu, And the anion precursor may include sulfur (S), selenium (Se), phosphorus (P), tellurium (Te), arsenic (As), nitrogen (N) or antimony (Sb).

According to another aspect of the present invention, each of the first solution and the second solution may each include at least one precursor.

According to still another aspect of the present invention, the step of preparing the first mixed solution includes the steps of: providing a second solution including a first solution containing at least one cation precursor and at least one anion precursor; And mixing the second solution at 25 占 폚 to 120 占 폚.

According to another feature of the present invention, the first solution comprises zinc oriate and cadmium oleate, and the second solution may comprise trioctylphosphine sulphide and trioctylphosphine selenide.

The step of forming the composite comprises reacting the reactive compound containing a thiol group with at least one inorganic particle selected from the group consisting of silica, alumina (Al ₂ O ₃ , AlO ₂ ), titanium dioxide and zinc dioxide to modify the inorganic particles, Preparing an inorganic particle containing a thiol group, mixing the inorganic particles containing a thiol group with an organic solvent to prepare a second mixed solution, gradually heating the second mixed solution to 250 to 350 ° C And injecting the first mixed solution into the heated second mixed solution for 1 minute to 20 minutes.

The details of other embodiments are included in the detailed description and drawings.

The present invention can provide a quantum dot containing complex comprising inorganic particles comprising a thiol group and at least one quantum dot bonded to the surface of an inorganic particle.

INDUSTRIAL APPLICABILITY The present invention can provide a quantum dot-containing complex which forms a chemical bond between an inorganic particle and a quantum dot and is excellent in light stability and thermal stability.

The effects according to the present invention are not limited by the contents exemplified above, and more various effects are included in the specification.

1A and 1B are schematic diagrams showing the structure of a quantum dot containing complex according to an embodiment of the present invention.
2 is a flowchart schematically showing a method for producing a quantum dot containing complex according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Further, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other features and advantages of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. In addition, the size and thickness of each component shown in the drawings are shown for convenience of explanation, and the present invention is not necessarily limited to the size and thickness of the components shown in the drawings.

Where the terms "comprises", "having", "done", and the like are used in this specification, other portions may be added unless "only" is used. Unless the context clearly dictates otherwise, including the plural unless the context clearly dictates otherwise.

In interpreting the constituent elements, it is construed to include the error range even if there is no separate description.

In the case of a description of the positional relationship, for example, if the positional relationship between two parts is described as 'on', 'on top', 'under', and 'next to' Or " direct " is not used, one or more other portions may be located between the two portions.

It will be understood that when an element or layer is referred to as being on another element or layer, it encompasses the case where it is directly on or intervening another element or intervening another element or element.

Although the first, second, etc. are used to describe various components, these components are not limited by these terms. These terms are used only to distinguish one component from another. Therefore, the first component mentioned below may be the second component within the technical spirit of the present invention.

It is to be understood that each of the features of the various embodiments of the present invention may be combined or combined with each other partially or entirely and technically various interlocking and driving is possible as will be appreciated by those skilled in the art, It may be possible to cooperate with each other in association.

1A and 1B are schematic diagrams showing the structure of a quantum dot containing complex according to an embodiment of the present invention.

1A and 1B, a quantum dot containing complex 100 includes inorganic particles 110 including a thiol group and at least one quantum dot 120. At this time, the quantum dots 120 are bonded to the surface of the inorganic particles 110 and attached. The number of quantum dots 120 introduced into the surface of the quantum dot containing complex 100 is not limited thereto but may be 1 to several million, more preferably 10 to several hundred thousand.

Inorganic particles 110 may be selected from silica, alumina (Al ₂ O _3, AlO _2), titanium dioxide, and the group consisting of zinc dioxide. The inorganic particles 110 are combined with the quantum dots 120 in the production of quantum dots to help the quantum dots 120 to be stably formed. At this time, the inorganic particles 110 can improve the heat resistance of the quantum dot 120 to minimize the surface energy of the quantum dot 120.

The diameter of the inorganic particles 110 may be between 20 nm and 50 um, and more preferably between 50 nm and 20 um, but is not limited thereto.

The inorganic particles 110 include a thiol group (-SH). As a functional group of the inorganic particle 110, a part of the thiol group forms a chemical bond with the quantum dot 120. More specifically, referring to FIG. 1B, the thiol group of the inorganic particle 110 combines with Group II elements of the quantum dot 120, more preferably zinc, to form a "-S-Zn-" bond . As a result, the bonding force between the inorganic particle 110 and the quantum dot 120 can be improved.

The inorganic particles 110 having a thiol group can be prepared by reacting a silica, alumina, titanium dioxide, or zinc dioxide with a reactive compound containing a thiol group to modify the surface of the inorganic particle 110. A specific method for producing the inorganic particles 110 having a thiol group will be described later.

The quantum dot 120 is a nanoparticle containing at least four component elements. Specifically, the quantum dots 120 may be in the form of an alloy made of II-VI group semiconductors. More specifically, the quantum dot 120 may include at least two elements selected from Group II elements and Group III elements, and at least two elements selected from Group V elements and Group VI elements. At this time, the Group II element may be zinc (Zn), cadmium (Cd) or mercury (Hg), and the Group III element may be indium (In), magnesium (Mg) or aluminum (Al). The Group V element may be phosphorus (P), arsenic (As) or nitrogen (N), and the Group VI element may be sulfur (S), selenium (Se), or tellurium (Te).

At this time, the quantum dot 120 preferably includes a group II element so as to facilitate chemical bonding with the thiol group of the inorganic particle 110, and more preferably includes zinc. Although not limited thereto, for example, the quantum dot 120 manufactured by a manufacturing method according to an embodiment of the present invention may have a single core shape including a quaternary element such as Zn-Cd-S-Se have.

The diameter of the quantum dot 120 may be 1 nm to 50 nm, and may be 1 nm to 20 nm, but is not limited thereto.

1A-1B, the quantum dot 120 may further include an organic ligand or an inorganic ligand on its surface.

The quantum dot containing complex 100 according to an embodiment of the present invention includes inorganic particles 110 including a thiol group and at least one quantum dot 120 bonded to a surface of the inorganic particle 110. Some of the thiol groups of the inorganic particles 110 may form chemical bonds with the semiconductor elements constituting the quantum dots 120. For example, referring to FIG. 1B, the thiol group is bonded to the zinc of the quantum dot 120 to form a "-Zn-S-" bond. As a result, the bonding strength between the quantum dot 120 and the inorganic particles 110 is improved, so that the thermal stability of the quantum dot containing composite 100 can be greatly improved.

Hereinafter, a method for producing a quantum dot-containing complex according to an embodiment of the present invention will be described.

2 is a flowchart schematically showing a method for producing a quantum dot containing complex according to an embodiment of the present invention.

The method for preparing a quantum dot containing complex according to an embodiment of the present invention includes the steps of preparing a first mixed solution containing at least one cation precursor and at least one anion precursor and mixing the first mixed solvent with an inorganic particle ≪ / RTI > to form a complex.

More specifically, referring to FIG. 2, a method for preparing a quantum dot containing complex according to an embodiment of the present invention includes preparing a first solution containing at least one cation precursor and a second solution containing at least one anion precursor (S120) mixing the first solution and the second solution to prepare a first mixed solution (S120), and reacting the reactive compound containing a thiol group with the inorganic particles to modify the inorganic particles to obtain a thiol group (S140), mixing the inorganic particles including the thiol group with an organic solvent to prepare a second mixed solution (S140), and gradually mixing the second mixed solution at 250 to 350 DEG C (S150), and injecting the first mixed solution into the heated second mixed solution (S160).

Hereinafter, each step will be described in detail.

A first solution including at least one cation precursor and a second solution including at least one anion precursor are prepared (S110). Wherein the first solution and the second solution each comprise two or more precursors. For example, the first solution may comprise two cationic precursors and the second solution may also comprise two anionic precursors, but is not limited thereto.

The cation precursor may be a compound comprising a Group II element or a Group III element. Specifically, the Group II element may be zinc (Zn), cadmium (Cd) or mercury (Hg), and the Group III element may be indium (In), magnesium (Mg) or aluminum (Al). Although not limited thereto, the cation precursor may be a compound comprising copper (Cu) or gallium (Ga).

More specifically, a Group II precursor containing a Group II element is selected from the group consisting of zinc acetate, dimethyl zinc, diethyl zinc, zinc carboxylate, zinc acetylacetonate < RTI ID = 0.0 > zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, Zinc nitrate, zinc oxide, zinc peroxide, zinc perchlorate, zinc sulfate, zinc oleate, dimethyl cadmium, and the like. ), Diethyl cadmium, cadmium oxide, cadmium carbonate, cadmium acetate dihydrate, cadmium oxide Cadmium bromide, cadmium perchlorate, cadmium phosphate, cadmium bromide, cadmium bromide, cadmium bromide, cadmium bromide, cadmium bromide, cadmium bromide, cadmium bromide, cadmium bromide, cadmium bromide, cadmium fluoride, cadmium chloride, cadmium iodide, cadmium phosphide, cadmium nitrate, cadmium sulfate, cadmium carboxylate, cadmium oleate, mercury iodide, mercury bromide, ), Mercury fluoride, mercury cyanide, mercury nitrate, mercury perchlorate, mercury sulfate, mercury oxide, mercuric carbonate ( mercury carbonate, mercury carboxylate and a light bulb based on the precursors And compounds of the formula (I).

Group III precursors containing group III elements may be selected from the group consisting of aluminum phosphate, aluminum acetylacetonate, aluminum chloride, aluminum fluoride, aluminum oxide, aluminum nitride Aluminum nitrate, aluminum sulfate, gallium acetylacetonate, gallium chloride, gallium fluoride, gallium oxide, gallium nitrate, ), Gallium sulfate, indium chloride, indium oxide, indium nitrate, indium sulfate, indium carboxylate, and the precursors, ≪ / RTI > and < RTI ID = 0.0 > .

The anion precursor may be a compound comprising a Group V element or a Group VI element. Specifically, the Group V element may be phosphorus (P), arsenic (As), or nitrogen (N), and the Group VI element may be sulfur (S), selenium (Se), or tellurium (Te).

More specifically, a Group V precursor comprising a Group V element can be selected from the group consisting of alkyl phosphine, tris (trialkylsilyl phosphine), tris (dialkylsilyl phosphine) Tris (dialkylamino phosphine), arsenic oxide, arsenic chloride, arsenic sulfate, arsenic bromide, And may be at least one selected from the group consisting of arsenic iodide, nitric oxide, nitric acid, and ammonium nitrate.

More specifically, a Group VI precursor comprising a Group VI element is selected from the group consisting of sulfur, trialkylphosphine sulfide, trialkenylphosphine sulfide, alkylaminosulfide, alkenyl But are not limited to, alkenylamino sulfide, alkylthiol, trialkylphosphine selenide, trialkenylphosphine selenide, alkylamino selenide, Alkenylamino selenide, trialkylphosphine telluride, trialkenylphosphine telluride, alkylamino telluride, alkenylamino telluride, and the precursor < RTI ID = 0.0 > Based precursor compounds. ≪ RTI ID = 0.0 > [0040] < / RTI >

The first solution includes, but is not limited to, zinc oleate and cadmium oleate, and the second solution may include trioctylphosphine sulfide and trioctylphosphine selenide.

On the other hand, the step of preparing the first solution may further include mixing the first cation precursor, the second cation precursor and the unsaturated fatty acid to form an appropriate cation precursor and then raising the temperature. For example, in order to prepare a first solution containing zinc oleate and cadmium oleate, a step of mixing zinc acetate, cadmium oxide and oleic acid and then raising the temperature to 100 ° C to 150 ° C may be additionally carried out.

Next, the first solution and the second solution are mixed to prepare a first mixed solution (S120).

 Specifically, the first solution containing the cation precursor and the second solution containing the anion precursor may be mixed at a relatively low temperature of 25 ° C to 120 ° C, more preferably 80 ° C to 120 ° C . At this time, by mixing the first solution and the second solution at a relatively low temperature, the chemical reaction between the cation precursor and the anion precursor can be suppressed.

The composition ratio of the first solution and the second solution in the mixed solution can be appropriately adjusted according to the emission wavelength of the finally formed quantum dot. For example, the molar ratio of the first solution to the second solution may be 1: 4 to 4: 1, but is not limited thereto.

Next, inorganic particles containing a thiol group are prepared (S130).

Specifically, a reactive compound containing a thiol group is reacted with at least one inorganic particle selected from the group consisting of silica, alumina (Al ₂ O ₃ , AlO ₂ ), titanium dioxide and zinc dioxide. That is, by modifying the inorganic particles, inorganic particles containing a thiol group can be produced. Although not limited thereto, the reactive compound comprising a thiol group may be 3-mercaptopropyl trimethoxysilane. Inorganic particles containing a thiol group may be formed and then washed using an alcohol.

Next, the second mixed solution is prepared by mixing the inorganic particles including the thiol group and the organic solvent (S140).

Examples of the organic solvent include primary alkylamines having 6 to 22 carbon atoms such as hexadecylamine, secondary alkylamines having 6 to 22 carbon atoms such as dioctylamine, tertiary alkylamines having 6 to 40 carbon atoms such as trioctylamine, (Alkane, alkene, alkyne, etc.) having 6 to 40 carbon atoms such as hexadecane, octadecane, octadecene and squalane, phenyldodecane, phenyltetradecane, phenylhexadecane and the like Phosphines substituted with an alkyl group having 6 to 22 carbon atoms such as an aromatic hydrocarbon having 6 to 30 carbon atoms, trioctylphosphine, phosphine oxide substituted with an alkyl group having 6 to 22 carbon atoms such as trioctylphosphine oxide, Benzyl ether, and aromatic ether having 12 to 22 carbon atoms, and combinations thereof. However, the present invention is not limited thereto.

The organic solvent is subjected to a water removal process at about 100 캜, and then mixed with inorganic particles containing the produced thiol group to form a second mixed solution.

The second mixed solution is gradually heated at 250 ° C to 350 ° C (S150).

The second mixed solution is heated to 250 캜 to 350 캜 though not limited thereto.

The first mixed solution is injected into the heated second mixed solution for 1 minute to 20 minutes (S160). The time for injecting the mixed solution can be appropriately controlled in consideration of the amount of the quantum dot containing complex to be produced and the number of quantum dots bonded to the surface of the inorganic particle. For example, the injection time of the first mixed solution may be 1 minute to 20 minutes, more preferably 1 minute to 10 minutes, but is not limited thereto. At this time, care should be taken not to inject water and oxygen into the reactor.

At this time, the cation precursor of the first solution and the anion precursor of the second solution react rapidly on the surface of the inorganic particle. The cation precursor and the anion precursor are simultaneously injected and reacted in a high temperature environment to form quantum dots having an alloy form by bonding the elements of the cation precursor and the anion precursor.

At this time, the quantum dots are formed in a form combined with inorganic particles. More specifically, in the process of forming the quantum dot, an element of the cation precursor, for example, a zinc element, directly bonds with sulfur of the thiol group. Thus, the quantum dots can be firmly formed on the surface of the inorganic particles by bonding the cation element (for example, zinc element) with the sulfur of the inorganic particle.

Finally, the product formed with the quantum dots can be cooled. The solution containing the quantum dot-containing complex prepared through step S160 can be easily obtained without cooling the solution to room temperature and then performing a separate purification process such as centrifugation. Since the quantum dot containing complex has a size of several to several tens of um, the quantum dot containing complex according to one embodiment of the present invention is advantageous in terms of the productivity of the quantum dot, since it can be easily purified through a filter.

The method for preparing a quantum dot containing complex according to an embodiment of the present invention includes mixing a first solution containing a cation precursor and a second solution containing an anion precursor at a low temperature first and then adding an inorganic particle containing a thiol group By reacting with the solution at a high temperature, a quantum dot is formed which chemically bonds with the inorganic particles. At this time, the quantum dot may be in the form of an alloy composed of four or more elements and can be stably formed through chemical bonding with the thiol group of the inorganic particle.

Particularly, since the bond between the formed quantum dots and the inorganic particles is strong, the surface energy of the particles constituting the quantum dots can be minimized, and quantum dots having greatly improved thermal stability and optical stability can be realized.

Hereinafter, embodiments of the present invention will be described in detail.

Example

4 mmol of zinc acetate, 1 mmol of cadmium oxide and 10 ml of oleic acid were placed in a reactor and reacted at 150 ° C for 1 hour to obtain a solution containing cadmium oleate (Cd-OA) and zinc oleate (Zn-OA) 1 solution was prepared and stored at 100 ° C.

Selenium (0.5 mmol), sulfur (4 mmol) and trioctylphosphine (2 mmol) were placed in a reactor and reacted at 100 ° C for 1 hour to obtain sulfur trioctylphosphine selenide (Se-TOP) and trioctylphosphine A second solution containing sulfur trioctylphosphine sulfide (S-TOP) was prepared and stored at 100 ° C.

Then, the first solution and the second solution were mixed in a reactor to prepare a first mixed solution, which was then stored at 100 ° C.

10 mL of silica particles having a size of 10 mu m were mixed with 2 mL of 3-mercaptopropyltrimethoxysilane (MPTS), 20 mL of cyclohexane, and 1 mL of methanol, followed by stirring at room temperature for 24 hours. Thereafter, the silica particles were washed with an alcohol to prepare a silica particle containing a thiol group.

400 ml of 1-octadecene (1-ODE), an organic solvent, was first subjected to water removal at 100 ° C for 30 minutes, and then mixed with inorganic particles containing the produced thiol group to prepare a second mixed solution . Thereafter, the second mixed solution was heated to 320 캜.

The first mixed solution prepared in the heated second mixed solution was injected at 320 DEG C for 10 minutes to form a quantum dot and a quantum dot containing complex.

Comparative Example

4 mmol of zinc acetate, 1 mmol of cadmium oxide and 10 ml of oleic acid were placed in a reactor and reacted at 150 ° C for 1 hour to obtain a solution containing cadmium oleate (Cd-OA) and zinc oleate (Zn-OA) 1 solution.

Selenium (0.5 mmol), sulfur (4 mmol) and trioctylphosphine (2 mmol) were placed in a reactor and reacted at 100 ° C for 1 hour to obtain sulfur trioctylphosphine selenide (Se-TOP) and trioctylphosphine A second solution containing sulfur trioctylphosphine sulfide (S-TOP) was prepared and stored at 100 ° C.

4 mmol of selenium and 2 mmol of trioctylphosphine were placed in a reactor and reacted at 100 ° C for 1 hour to obtain a third solution containing shell of trioctylphosphine selenide (Se-TOP) Solution) was prepared and stored at 100 ° C.

400 mL of an organic solvent 1-octadecene was dehydrated at 100 DEG C for 30 minutes, and then mixed with the first solution. Thereafter, the temperature of the mixed solution was raised to 320 DEG C, and then the second solution was injected into the mixed solution at 300 DEG C for 10 minutes for reaction. Thereafter, the third solution was further injected for 10 minutes to react.

Thereafter, the solution was cooled to room temperature and precipitated with acetone, followed by centrifugation using a complex solvent containing hexane and ethanol to obtain quantum dots of a core-shell structure.

100 g of the 0.1 wt% solution in which the quantum dots of the prepared core-shell structure were dispersed in 1-chloroform and 10 g of the silica particles of 10 mu m were mixed and reacted at 50 DEG C for 1 hour and then dried to form a quantum dot complex structure .

Experimental Example 1 - Evaluation of thermal stability

The quantum dots according to the examples and the quantum dot complex structures according to the comparative examples were stored at a high temperature of 150 ° C. for 100 hours, and the rate of change in luminance intensity at 530 nm was measured using C11347-11 (Hamamatsu).

As a result of the measurement, the luminance change rate of the quantum dot complex structure according to the embodiment was 1.7%, and the luminance change rate of the quantum dot complex structure according to the comparative example was 55%. Therefore, it can be confirmed that the quantum dot-containing complex produced by the production method according to an embodiment of the present invention has excellent thermal stability as compared with a complex of a quantum dot containing a ligand and a silica support.

EXPERIMENTAL EXAMPLE 2 - Evaluation of light stability

The quantum dot according to the embodiment and the quantum dot complex structure according to the comparative example were subjected to light of 38 W / m ² intensity for 1000 hours at a temperature of 40 캜. Then, the rate of change of the luminance intensity at 530 nm was measured using (C11347-11, Hamamatsu Co.).

As a result of measurement, the luminance change rate of the quantum dot complex structure according to the embodiment was 0.7%, and the luminance change rate of the quantum dot complex structure according to the comparative example was 3.6%. Therefore, it was confirmed that the quantum dot-containing complex produced by the production method according to an embodiment of the present invention has excellent optical stability as compared with a complex of a quantum dot containing a ligand and a silica support.

Although the embodiments of the present invention have been described in detail with reference to the accompanying drawings, it is to be understood that the present invention is not limited to those embodiments and various changes and modifications may be made without departing from the scope of the present invention. . Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. Therefore, it should be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

Claims (14)

Inorganic particles comprising a thiol group (-SH); And
And at least one quantum dot bonded to the surface of the inorganic particle. The method according to claim 1,
Wherein the inorganic particles are at least one selected from the group consisting of silica, alumina (Al ₂ O ₃ , AlO ₂ ), titanium dioxide, and zinc dioxide. The method according to claim 1,
Wherein the quantum dot comprises a Group II element. The method of claim 3,
Wherein the quantum dot comprises zinc (Zn). 5. The method of claim 4,
Wherein the sulfur of the inorganic particles is bonded to the zinc of the quantum dot. The method according to claim 1,
Wherein the diameter of the inorganic particles is 50 nm to 10 mu m and the diameter of the quantum dots is 1 nm to 20 nm. The method according to claim 1,
The quantum dot may include at least two selected from the group consisting of zinc (Zn), cadmium (Cd), mercury (Hg), indium (In), magnesium (Mg) Wherein the quantum dot-containing complex comprises at least two selected from the group consisting of nitrogen (N), sulfur (S), selenium (Se) and tellurium (Te). 8. The method of claim 7,
Wherein the quantum dot is in the form of an alloy consisting of four component elements. Preparing a first mixed solution comprising at least one cation precursor and at least one anion precursor; And
And injecting the first mixed solvent into a solution containing inorganic particles comprising a thiol group to form a complex. 10. The method of claim 9,
Wherein the cation precursor comprises zinc (Zn), cadmium (Cd), mercury (Hg, In, magnesium, aluminum, copper or gallium) A method for producing a quantum dot-containing complex comprising sulfur (S), selenium (Se), phosphorus (P), tellurium (Te), arsenic (As), nitrogen (N) or antimony (Sb). 10. The method of claim 9,
Wherein the step of preparing the first mixed solution comprises:
Providing a first solution comprising said at least one cation precursor and a second solution comprising said at least one anion precursor; And
And mixing the first solution and the second solution at 25 占 폚 to 120 占 폚. 12. The method of claim 11,
Wherein the first solution and the second solution each comprise at least two precursors. 13. The method of claim 12,
Wherein the first solution comprises zinc oleate and cadmium oleate, and the second solution comprises trioctylphosphine sulfide and trioctylphosphine selenide. 10. The method of claim 9,
The step of forming the composite
By reacting the reactive compound containing a thiol group with at least one inorganic particle selected from the group consisting of silica, alumina (Al ₂ O ₃ , AlO ₂ ), titanium dioxide and zinc dioxide to modify the inorganic particles, Producing inorganic particles;
Mixing the inorganic particles containing the thiol group with an organic solvent to prepare a second mixed solution;
Gradually heating the second mixed solution to 250 ° C to 350 ° C; And
And injecting the first mixed solution into the heated second mixed solution for 1 minute to 20 minutes.

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