WO2013162334A1

WO2013162334A1 - Light-emitting nanoparticles having improved light emission characteristics and having zinc-silver-indium-sulfide composition and method for preparing same using combinatorial chemistry

Info

Publication number: WO2013162334A1
Application number: PCT/KR2013/003650
Authority: WO
Inventors: 박정규; 이승재; 김미애; 정종진
Original assignee: 한국화학연구원
Priority date: 2012-04-27
Filing date: 2013-04-26
Publication date: 2013-10-31

Abstract

The present invention relates to light-emitting nanoparticles having improved light emission characteristics and having a zinc-silver-indium-sulfide composition and to a method for preparing same using combinatorial chemistry. To this end, the present invention provides light-emitting nanoparticles having improved light emission characteristics and having a zinc-silver-indium-sulfide ((ZnxAgyInz)S2)(0≤x≤1, 0≤y≤1, 0.1≤z≤1, x+y+z=1) composition. Furthermore, the present invention provides a method for preparing the light-emitting nanoparticles, comprising: a step (step 1) of constructing a library for a zinc-silver-indium composition; a step (step 2) of introducing a zinc precursor, a silver precursor and an indium precursor and a vulcanizing agent based on the library constructed in step 1 to each of different reactors including a solvent to prepare a metal precursor solution; a step (step 3) of irradiating the metal precursor solution with ultrasonic waves in each reactor prepared by step 2; a step (step 4) of adding an alcohol-based solvent, a hydrocarbon-based solvent or a mixture solvent thereof to the metal precursor solution after the ultrasonic wave irradiation of step 3 so as to precipitate zinc-silver-indium-sulfide particles; a step (step 5) of removing supernatant after the precipitation of the particles in step 4; and a step (step 6) of checking the light emission characteristics of the zinc-silver-indium-sulfide nanoparticles from which the supernatant is removed in step 5. According to the present invention, light-emitting nanoparticles having various compositions can be quickly prepared, and light emission characteristics are checked to find light-emitting nanoparticles optimized to a desired composition.

Description

[Specifications

[Name of invention]

Light-emitting nanoparticles with improved composition of zinc-silver-indium-sulfide and their preparation method using combinatorial chemistry

Technical Field

The present invention relates to luminescent nanoparticles having an improved composition of zinc-silver-indium-sulfide, and a method for preparing the same using combination chemistry.

<2>

Background Art

In general, methods for producing light emitting nanoparticles include pyrolysis and ultrasonic irradiation. In the early stages, the synthesis of luminescent nanoparticles was carried out mainly by pyrolysis, and is still mainly used. The method for preparing nanoparticles by pyrolysis is a hot organic solvent containing alkylphosphine, alkylphosphine oxide, alkylamine, etc. having a long chain.

It is prepared by quickly adding a metal precursor to (150-350).

<4>

According to Korean Patent Laid-Open Publication No. 10-2007—0068492 ^, a thermal decomposition synthesis method of copper nanoparticles using a surfactant is disclosed. Specifically, a method of forming copper-oleate complexes through ionic bonds and using them to thermally synthesize copper nanoparticles in large quantities is described.

<6>

According to Korean Patent Laid-Open Publication No. 10-2004-0084241, in the preparation of nano-phosphor powder by spray pyrolysis, a spray solution containing the agent is used, or the agent is added to the phosphor particles prepared by the spray pyrolysis process. A method for producing a nanophosphor having a uniform shape by controlling heat treatment conditions is described.

<8>-

In addition, a method of forming a metal complex by reacting metal raw materials with water to form a metal complex, rather than adding a metal raw material directly to an organic solvent, and then synthesizing by thermal decomposition by adding the metal complex compound to an organic solvent is also used. .

<10>

<π> However, the synthesis of light emitting nanoparticles by pyrolysis proceeds at high temperature, requires reaction to block water or oxygen, and requires a long reaction time. In addition However, pyrolysis is not easy to synthesize a large amount of samples because only one light emitting nanoparticle can be synthesized in one reaction. According to the ultrasonic irradiation method, another method for synthesizing light emitting nanoparticles, It is economical in terms of process energy since it does not need to be heated to high temperatures. In the ultrasonic irradiation method, metal acetate and metal chloride are used as a metal raw material in a solvent such as alcohol, water, and amine, and sulfur, thioacetamide, and thiourea are dissolved as a raw material of sulfur and irradiated with ultrasonic waves. For example, metal and sulfur raw materials may be dissolved in a solvent, and then light emitting nanoparticles may be synthesized by ultrasonic irradiation. On the other hand, in combinatorial chemistry, when a compound composing a plurality of components is synthesized, a method is used to create a library using various combinations of components, and to select a compound having excellent functions according to the purpose in the process. It has been widely used for a long time. Due to the advantage that a large number of structurally similar compounds can be synthesized in a short time, it is possible to minimize the time required for new drug development and new material development by adopting combinatorial chemistry as an effective strategy to secure a library of leading materials with excellent properties. Research is being conducted. Thus, the inventors of the present invention have found that by using the combination chemistry, the composition of the material can be optimized in a short time to produce light emitting nanoparticles having desired characteristics, thereby completing the present invention.

[Detailed Description of the Invention]

[Technical problem]

Disclosure of Invention An object of the present invention is to provide a light emitting nanoparticle having a composition of zinc-silver-indium-sulfide and a method of manufacturing the same using light emitting nanoparticles and combination chemistry.

Technical Solution

To this end, the present invention

Light emission with a composition of zinc-silver-indium-sulfide ((Zn _x Ag _y In _z ) S ₂ ) (0≤x≤l, 0 <y <l, 0.1 <ζ <1, x + y + z = l) It provides light emitting nanoparticles with improved properties (first light emitting nanoparticles). In addition, the present invention

： 24> Zinc-Silver-Indium-Sulfide ((Zn _x Ag _y In _z ) S ₂ ) (The above x, y, z is 0 <x <0.4, 0.1 <y <

0.9, 0.1 <ζ <0 · 9, x + y + z = l; x = 0.5, 0.1 <y <0.3, 0.2 <z <0.4, x + y + z = l; And x = 0.6, y = 0.1, and z = 0.3; and light emitting nanoparticles having improved composition (light emitting nanoparticles) having a composition (second light emitting nanoparticle).

In addition, the present invention provides zinc-silver-sulphur-sulfide ((Zn _x Ag _y In _z ) ¾) (0.15≤x≤0.25,

Provided is light emission or no-particles with improved light emission characteristics having a composition of 0.35 <y <0.45, 0.35 <z <0.45, x + y + z = l) (third light emitting nanoparticle).

26> Furthermore, the present invention

: 27> constructing a library ^ for the composition of zinc-silver-indium (step 1);

: 28) preparing a metal precursor solution by introducing a zinc precursor silver precursor, an indium precursor and a vulcanizing agent according to the library configured in step 1 into each of the different reactors containing a solvent (step 2);

: Irradiating ultrasonic waves to the metal precursor solution in each reactor prepared in step 2 (step 3);

30> In the step 3 to the ultrasonic irradiation alcohol-based solvent, a hydrocarbon solvent or zinc by the addition of these solvents heunhap-silver-indium-sulfonic step of ^3} precipitate Id particles (step 4); : 31> removing the supernatant after the particles precipitate in step 4 (step 5) and

: 32> confirming the luminescence properties of the zinc-silver-indium-sulfide nanoparticles from which the supernatant was removed in step 5 (step 6);

It provides a method for producing the first light-emitting nanoparticles with improved luminescence properties using a combination chemistry characterized in that it comprises a.

: 34>

Advantageous Effects

35. According to the present invention, zinc-silver-indium-sulfide ((Z Ag _y In _z ) S ₂ ) (0 ≦ x ≦ l, 0 <y <

1, 0.1 <ζ <1, x + y + z = l) light emitting nanoparticles have various light emission characteristics and light emission intensity. In addition, zinc-sylvindium-sulfide ((Z Ag _y In _z ) S ₂ ) (where x, y, z is 0 <x <0.4, 0.1 <y <0.9, 0.1 <z <0.9, x + y + z = l; x = 0.5, 0.1 <y <0.3, 0.2 <z <0.4, x + y + z = l; and x = 0.6, y = 0.1, z = 0.3; one kind selected from the group consisting of The light emitting nanoparticles having the composition have relatively higher emission intensity. Luminous properties are improved. ᅳ Zinc-Silver-Indium-Sulfide ((Zn _x Ag _y In _z ) S ₂ ) (0.15 <x≤

The light emitting nanoparticles having the composition of 0.25, 0.35 <y <0.45, 0.35 <z <0.45, x + y + z = l) have the characteristic that the luminous efficiency increases as the excitation wavelength of the long wavelength region of 400 nm or more increases. Since the energy of the light source can prevent a phenomenon of directly damaging the cell, it can be applied to a bio area such as bio-optical imaging. In addition, by providing a library according to the composition of the light emitting nanoparticles using a combination chemistry and by emitting ultrasonic waves to the light emitting nanoparticles according to the library to quickly produce light emitting nanoparticles having a variety of compositions, the light emission characteristics of the various light emitting nanoparticles produced In a short time, the optimized light emitting nanoparticles can be found.

6>

[Brief Description of Drawings]

7> Figure 1 is a schematic diagram of the composition of the library according to the composition;

8> FIG. 2 is a schematic diagram illustrating a process of synthesizing luminescent nanoparticles by irradiating ultrasonic waves to each reactor manufactured according to a library;

9 (a) is a graph showing the light emission characteristics of the light emitting nanoparticles prepared in Examples 1 to 8 and Comparative Examples 1 to 11 of the present invention; 3 (b) is a graph showing the light emission characteristics of the light emitting nanoparticles prepared in Examples 9 to 55 of the present invention; (4) Figure 4 is a light emitting nanoparticles prepared in Examples 30 and 35 of the present invention An image of the particles observed with a transmission electron microscope;

i> FIG. 5 is an X-ray diffraction image of luminescent nanoparticles prepared in Examples 30, 35, and 36;

2> FIG. 6 is an energy equity X-ray spectrometer analysis image of luminescent nanoparticles prepared in Examples 30 and 35 of the present invention; FIG.

3> FIG. 7 is a graph comparing light emission characteristics according to changes in excitation wavelengths of light emitting nanoparticles prepared in Examples 30 and 35 of the present invention.

4>

Best Mode for Implementation of the Invention

5> An object of the present invention is to provide a light emitting nanoparticles with improved luminescent properties and a method of manufacturing the same using combination chemistry.

6>

7> Hereinafter, the present invention will be described in detail.

8> ^■ 9> The present invention provides zinc-silver-indium-sulfide ((Zn _x Ag _y In _z ) S ₂ ) (0 ≦ x <l, 0 <y <l, 0.1 < _z ≦ l, x + y + A light emitting nanoparticle having a light emitting property having a composition of z ^ l) is flavored ¹ (first light emitting nanoparticle).

o> The light emitting nanoparticles have the light emission intensity and light emission wavelength due to the composition range. Thus, appropriately selected within the composition range can be useful for light-emitting nanoparticles exhibit the desired emission ^{characteristics.}

; 2> In addition, the present invention is a zinc-silver-indium-sulfide ((Zn _x Ag _y In ₂ ) ¾) (where x, y, z is 0≤x

<0.4, 0.1 <y <0.9, 0.1 <z <0.9, x + y + z = l; x = 0.5, 0.1 <y <0.3, 0.2 <z <0.4, x + y + z = l; And x = 0.6, y = 0.1, and z = 0.3; and a light emitting nanoparticle having an improved light emitting characteristic having a composition (second light emitting nanoparticle).

The light emitting nanoparticles have a composition of ((Zn _x Ag _y In _z ) S ₂ ) (0 <x <l, 0 <y <l, 0.1 <ζ <1, x + y + z = l) It has relatively better luminescent properties than luminescent nanoparticles. Specifically, the light emitting nanoparticles have light emission characteristics up to 700 times the light emission intensity at the light emission wavelength of 500 nm to 750 nm. Therefore, the light emitting nanoparticles having appropriately selected light emission characteristics within the composition range may be useful.

55>,

56> In addition, the ^'present invention is a zinc-silver-indium-sulfide _{_{_{((Zn x Ag y In z}}} ) S 2) having improved light emission characteristics nanoparticles to light having a composition of (0.15≤x≤0.25, 0.35 <y <0.45 , 0.35 <z <0.45, x + y + z = l) (third luminescent nanoparticle).

The luminescent nanoparticles can be applied to bio-regions such as bio-optical imaging. For this purpose, the luminescent nanoparticles must have an effective luminescence in a long wavelength light source that does not directly damage cells. However, conventional light emitting particles have a problem of directly damaging cells by emitting light from an excitation wavelength having a short wavelength having high energy. Zinc-Silver-Indium-Sulfide ((Zn _x Ag _y In _z ) S ₂ ) provided by the present invention (0.15≤x≤0.25, 0.35 <y <0.45,

The light emitting nanoparticles having the luminescence properties having the composition of 0.35 <z <0.45, x + y + z = l) have the characteristic that the luminescence efficiency increases as the excitation wavelength of the long wavelength region of 400 nm or more is used in the bio region. Can be. ,

58>

59> In addition, the present invention ro> constructing a library for the composition of zinc-silver-indium (step 1);

r> i> introducing a zinc precursor, a silver precursor, an indium precursor, and a vulcanizing agent according to the library configured in step 1 to each of the different reaction groups including the solvent, thereby preparing a metal whole solution (step 2);

62> irradiating ultrasonic waves to the metal precursor solution in each reactor prepared in step 2 (step 3);

63) precipitating zinc-silver-rhythm-sulfide particles by adding an alcohol solvent, a hydrocarbon solvent or a mixed solvent thereof after ultrasonication in step 3 (step 4); 64> removing the supernatant after the particles are precipitated in step 4 (step 5)

Checking the luminescence properties of the zinc-silver-indium-sulfide nanoparticles from which the supernatant was removed in step 5 (step 6);

It provides a method for producing the first light-emitting nanoparticles with improved light emission characteristics using a combination chemistry comprising a. ·

67>

68> Hereinafter, a method of manufacturing light emitting nanoparticles according to the present invention will be described in detail for each step.

6>

In the manufacturing method of the present invention, step Ί is a step of constructing a library for the composition of zinc-silver-rhythm. Increase zinc and silver from 0 to 1 in 0.1 increments, and increase indium from 1 to 1 in 0.1 increments. The schematic of the structure of the library which concerns on the said composition is shown in FIG.

: 71>

In the manufacturing method of the present invention, the step 2 is a metal precursor solution by introducing a zinc precursor, a silver precursor, an indium precursor and a vulcanizing agent according to the library configured in the step 1 to each of the different reactors containing a solvent. To prepare. The metal precursors are, for example, zinc nitrate hydrate as the zinc precursor, silver nitrate as the silver precursor, indium nitrate hydrate as the rhythm precursor, and dimethyldiocarbamate as the vulcanizing agent. (diniethyldithiocarbamate) may be used and dodecylamine may be used as a solvent, but is not necessarily limited to the above content as long as it meets the object of the present invention. is.

In the manufacturing method according to the present invention, the solvent of step 2 is preferably at least one selected from ether-based, hydrocarbon-based, alcohol-based, and amine-based solutions.

75>

In the preparation method according to the present invention, the ether-based solution is preferably at least one selected from the group consisting of octyl ether, butyl ether, nuclear chamber ether, benzyl ether, phenyl ether and decyl ether. The solutions are high boiling point solvents to increase the reaction temperature in a short time during ultrasonic irradiation, and also has the advantage of maintaining a high temperature state.

77>

In the preparation method according to the present invention, the hydrocarbon-based solution is preferably at least one selected from the group consisting of nucleic acid, toluene, xylene, chlorobenzoic acid, benzene, nucleodesine, tetradecine and octadecine. The solutions are high boiling point solvents to increase the reaction temperature in a short time when the ultrasonic irradiation, and also has the advantage of maintaining a high temperature state.

79>

8 ()> In the preparation method according to the present invention, the alcohol-based solution is octyl alcohol, decanol, nuxadecanol, ethylene glycol, 1,2-octanediol, 1,2-dodecanediol and 1, It is preferable that it is at least 1 type selected from the group which consists of 2-nuxadecane diol. The solutions have the advantage of stabilizing the nanoparticles formed by having a hydroxyl group at the end of the long alkyl chain.

: 81>

In the production method according to the present invention, the amine solution is at least one member selected from the group consisting of dodecylamine, nucleated decylamine, octylamine, trioctylamine, dimethyloctylamine and dimethyldodecylamine. It is desirable. The solutions have the advantage of stabilizing the nanoparticles formed by having an amine group at the end of the long alkyl phosphorus.

: 83>

In the manufacturing method according to the present invention, step 3 is a step of irradiating ultrasonic waves to the metal precursor solution in each semi-unggi prepared in step 2. Ultrasonic irradiation produces fine cavitation inside the solution due to the ultrasonic waves. Energy is transferred in the process of destruction, and there is a catalytic effect on the light emitting nanoparticles. All. 2 is a schematic diagram illustrating a process of synthesizing light emitting nanoparticles by irradiating ultrasonic waves to each reactor manufactured according to a library.

In the manufacturing method according to the present invention, the ultrasonic irradiation in the step 3 is preferably performed for 1 minute to 12 hours in the range of 2 200 kHz. If the frequency is less than 2 kHz, there is a problem that the generation of light emitting nanoparticles is poor because the energy is not supplied through the ultrasonic waves, and if the frequency is more than 200 kHz, the energy supplied to generate the nanoparticles is excessive and suitable for producing the nanoparticles. There is a problem that it is difficult to adjust. In addition, ultrasonic irradiation was performed for 1 minute _; If it is performed less than the ultrasonic irradiation is not made enough due to poorly synthesized light emitting nanoparticles, there is a problem that the bulk particles, not nanoparticles are formed due to excessive energy supply over 12 hours There is this. 8> In the manufacturing method according to the present invention, the step 4 is a step of precipitating the zinc-silver-indium-sulfide particles by adding an alcohol solvent, a hydrocarbon solvent or a mixed solvent thereof after ultrasonic irradiation in the step 3 As such, the alcohol-based solution of step 4 is preferably at least one selected from the group consisting of ethanol, methanol and octyl alcohol. The solution has an advantage that it is easy to separate the nanoparticles prepared by inducing precipitation of nanoparticles dispersed in a nonpolar solvent as a polar solvent.

89>

In the preparation method according to the present invention, the hydrocarbon-based solution of step 4 is preferably at least one selected from the group consisting of nucleic acid, toluene and chloroform. The solution has the advantage of being able to uniformly disperse the nanoparticles stabilized by the alkyl chain as a nonpolar solvent.

91>

In the manufacturing method according to the present invention, step 5 is a step of removing the supernatant after the particles are precipitated in step 4, the method of removing the supernatant is preferably centrifugation. Centrifugal separation allows the separation of undissolved light emitting nanomaterials mixed with solvents in the reaction vessel using the difference in centrifugal force and specific gravity.

: 3>

: 4> In the manufacturing method according to the present invention, step 6 is a step of checking the luminescence properties of the zinc-silver-indium-sulfide nanoparticles from which the supernatant was removed in step 5. bracket By transmitting light sources of different wavelengths and confirming the light emission characteristics thereof, it is possible to find nanoparticles with high luminous efficiency in long wavelength bands.

5>

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for the description of the present invention and the scope of the present invention is not limited by the following examples.

97>

[Form for implementation of invention]

Example 1-55 Preparation of light emitting nanoparticles having a composition of zinc silver indium sulfide

9> Step 1: The ternary library was fabricated in 0.1 increments from 0 to 1 for zinc, 0 to 1 for silver and 0.1 to 1 for indium.

oo> Step 2: According to the composition of the library prepared in step 1, 0.7 g of zinc nitrate hydrate, silver nitrate and indium nitrate hydrate and the vulcanizing agent solid dimethyl diocarbamate 10 ml of dodecylamine It was put in each flask containing.

() |> Step 3: The ultrasonic wave was irradiated to the metal precursor solution in each flask prepared in Step 2 using a sonic dismembrator at 20 kHz for 10 minutes.

Step 4> 5 ml of chloroform and 5 ml of methanol were added to the reaction solution to induce precipitation of nanoparticles. -

Step 5: After the particles of zinc-silver-sulphur-sulfide were precipitated in step 4, centrifugation was performed using a centrifuge for 10 minutes to remove the supernatant and zinc of various compositions as shown in Table 1 below. Light-emitting nanoparticles having a composition of silver-indium-sulfide were prepared.

Step 6> The emission spectra of the various composition zinc-silver-indium-sulfide particles prepared in step 5 were changed by 365 nm, 405 nra, 450 nm, 465 nm ^ with a fluorescence spectrometer (PerkinElmer LS50B). The characteristics were confirmed, and the composition of the light emitting nanoparticles having excellent luminescent properties was confirmed therefrom.

05>

06> [Table 1]

07>

() 8> ■

o ^y ><Comparative Example 1-11> Preparation of zinc silver indium sulfide (Zn _x Ag _y In _z ) S ₂ luminescent nanoparticles ιο> In the step 1 of Example 1 according to the present invention, ^0-1 , About silver

0-1, except that the composition of the luminescent nanoparticles prepared by fabricating a ternary library with an increment of 0.1 to 0 with respect to indium is shown in Table 2 below.

The light emitting nanoparticles were prepared in the same manner as in Example 1, and the light emission characteristics of the prepared light emitting nanoparticles were confirmed.

12> [Table 2]

Experimental Example 1 Emission Curve of Light Emitting Nanoparticles

The emission intensity according to the wavelength measured by using a fluorescence spectrometer (PerkinElnier LS50B) in step 6 of Examples 1 to 55 and Comparative Examples 1 to 11 according to the present invention is shown in FIGS. It is shown to 3 (b).

3 (a) and 3 (b), the zinc-silver-sulphur-sulfide light emitting nanoparticles prepared according to Examples 1 to 55 of the present invention emit light with different emission intensities at different wavelength bands. You can see that. Experimental Example 2 Investment Microscopy

Transmission electron microscope analysis of Examples 30 and 35 according to the present invention was performed using a transmission electron microscope (JEM-2100F), and the results are shown in FIG. 4.

4, the zinc-silver-sulphur-sulfide light emitting nanoparticles prepared according to Example 30 of the present invention are spherical particles having an average size of 4.1 nm, and zinc-silver-indium- according to Example 36. It can be seen that the sulfide light emitting nanoparticles are spherical particles having an average size of 3.9 nm. ^'' Experimental Example 3 X-ray Diffraction Analysis

X-ray diffraction analysis of Examples 30, 35 and 36 according to the present invention was performed using an X-ray diffractometer (Rigaku D / MAX-2200V), and the results are shown in FIG. It was. ᅳ

5, zinc-silver-indium-sulfide prepared according to Example 35

_{_{_{(. Zn 0 Ag 0 5 In}}} 0.5) because S _2, zinc as that of example composition 112, 204, the silver having a crystal plane of a 312-indium-one match exactly sulfide composition of the present invention In the case of zinc-silver-indium-sulfide prepared according to Example 1 and Example 36, the composition containing zinc can be confirmed to be different from the position of the peak of Example 36. Through this, it can be seen that zinc-silver-sulphur-sulfide light emitting nanoparticles having different compositions were prepared.

>

Experimental Example 4 Analysis of Energy Dispersive X-ray Spectrometer

> Example 30 and according to the present invention _. The energy dispersive X-ray spectrometer analysis of Example 35 was performed using an energy dispersive X-ray spectrometer (Quantax 200), and the results are shown in FIG. 6.

> According to Figure 6, Zn element is present in the zinc-silver-indium-sulfide light emitting nanoparticles prepared according to Example 30 according to the present invention, the zinc-silver-indium-sulfide light emitting nanoparticles of Example 35 Zn does not exist. Through this embodiment the zinc produced according to (1) according to the present invention silver-indium-composition of the sulfide luminescent nanoparticles comprising zinc _{_{_{(. Zn 0.2 Ag 0 4 In}}} 0.4) S 2 can verify that, in Example 35 the zinc prepared in accordance with the-silver-indium composition of the light-emitting eu sulfide nanoparticles that do not contain zinc _{_{_{(.. 5 in 0 Zn 0}}} Ag 0 5) is able to confirm that S _2. Experimental Example 5 Comparison of Excitation Curves by Maximum Emission Wavelength

i> In Example 30 and Example 35 of the present invention, the emission intensity was measured while gradually increasing the excitation wavelength, and the results are shown in FIG. 7.

> According to FIG. 7, the emission wavelength was measured by increasing the excitation wavelength to 365 nm, 405 nm, 450 nm, and 465 nm in the zinc-silver-sulphur-sulfide light emitting nanoparticles prepared according to Example 30 of the present invention. As a result, the luminescence intensity gradually increased. In the zinc-silver-indium-sulfide light emitting nanoparticles prepared according to Example 35, the excitation wavelength was increased to 405 nm, 450 nm, and 465 nni, and the emission intensity was gradually decreased. Through this, it can be confirmed that the zinc-silver-indium-sulfide luminescent nanoparticles herbicided according to Example 30 of the present invention have more effective luminescence in a long wavelength light source ^.

3>

Claims

[Range of request]

[Claim 1]

Luminescent nanoparticles having improved luminescence properties having a composition of zinc-silver-indium-sulfide ((Zn _x Ag _y In _z ) S ₂ ):

(In the above, 0 <x <l, 0 <y ≦ l, 0.1 <ζ <1, x + y + z = l).

[Claim 2] '^'

Luminescent nanoparticles with improved luminescence properties having a composition of zinc-silver-indium-sulfide ((Z Ag _y In _z ) S ₂ ):

(Where x, y, z is 0 <x <(). 4, 0.1 <y <0.9, 0.1 <z <0.9, x + y + z = l);

x = 0.5, 0.1 <y <0.3, 0.2 <z <0.4, x + y + z = l; And

x = 0.6, y = 0.1, z = 0.3; 1 type selected from the group consisting of.

[Claim 3]

Luminescent nanoparticles with improved luminescence properties having a composition of zinc-silver-sulphur-sulfide ((Zn _x Ag _y In _z ) S ₂ ):

(In the above, 0.15 <x <0.25, 0.35 <y <0.45, 0.35 <z <0.45, x + y + z = l). [Claim 4]

Constructing a library for the composition of zinc-silver-indium (step 1);

Preparing a metal precursor solution by introducing zinc precursor, silver precursor, indium precursor, and a vulcanizing agent according to the library configured in Step 1 into each of the different reactors including the solvent (step 2);

Irradiating ultrasonic waves to the metal precursor solution in each reactor prepared in step 2 (step 3); .

Ultrasonic irradiation in step 3 to the step of precipitating the zinc-silver-indium-sulfide particles by adding an alcohol solvent, a hydrocarbon solvent or a mixed solvent thereof

(Step 4); Removing the supernatant after the particles are precipitated in step 4 (step 5) checking the luminescence properties of the zinc-silver-indium-sulfide nanoparticles from which the supernatant is removed in step 5 (step 6); Method for producing a light emitting nanoparticles according to claim 1, wherein the light emission characteristics are improved using a combination chemistry comprising a.

[Claim 5] ^' ;

The method of claim 4,

The solvent of step 2 is a method for producing the light-emitting nanoparticles according to claim 1, wherein the luminescent properties are improved using a combination chemistry, characterized in that at least one selected from ether hydrocarbon-based, alcohol-based and amine-based solution.

[Claim 6]

_. The method of claim 5,

. According to claim 1, wherein the ether solution is at least one selected from the group consisting of octyl ether, butyl ether, nuclear chamber ether, benzyl ether, phenyl ether and decyl ether. Manufacturing Method of Light Emitting Nanoparticles.

[Claim 7]

The method of claim 5,

The hydrocarbon solution is a light-emitting characteristics using combinatorial chemistry, characterized in that at least one member selected from hexane, toluene, xylene, chloro-benzo acid, benzene, hex decyne, tetra-decyne and octanoyl group consisting of decyne _incense, corrupt the Method for producing light emitting nanoparticles according to claim 1.

[Claim 8]

The method of claim 5,

The alcoholic solution is at least one selected from the group consisting of octyl alcohol, decanol, nuxadecanol, ethylene glycol, 1,2-octeindiol, 1,2-dodecanediol and 12-nuxadecanediol A method of manufacturing the light emitting nanoparticles according to claim 1, wherein the luminescence properties are improved by using combinatorial chemistry.

[Claim 9]

The method of claim 5 The amine-based solution is dodecylamine, nucleodecyl ' ^: amine, octylamine, trioctylamine, dimethyloctylamine and dimethyldodecylamine using at least one selected from the group consisting of combinatorial chemistry, characterized in that Method of manufacturing light emission or old particles according to claim 1 with improved light emission characteristics

[Claim 10]

The method of claim 4,

Ultrasonic irradiation of step 3 is a method for producing light-emitting nanoparticles according to claim 1, wherein the luminescence properties are improved using combination chemistry, characterized in that performed for 1 minute to 12 hours in the range of 2-200 kHz.

[Claim 11]

The method of claim 4,

The alcohol-based solution of step 4 is a method for producing the light-emitting nanoparticles according to claim 1, wherein the luminescent properties are improved by using a combination chemistry, characterized in that at least one selected from the group consisting of ethane, methanol and octyl alcohol.

【Claim 12】,

The method of claim 4,

The method of claim 4, wherein the hydrocarbon-based solution of step 4 is one or more selected from the group consisting of nucleic acid, toluene and chloroform. ―