KR20160065230A - core/shell structured quantum dot, the nanohybride film containing these and the preparing method thereof - Google Patents

Abstract

The present invention relates to a quantum dot, a nanohybrid thin film containing the same, and a method for manufacturing the same and, more specifically, to a quantum dot combined with a blue light emitting diode so as to be used in emitting white light, a nanohybrid film containing the same, and a method for manufacturing the same. The present invention provides the quantum dot comprising: a core containing a compound represented by AgIn_xS_(3x+1)/2; a shell containing ZnS; and a ligand polymer. With respect to a chemical formula 1, x is a rational number between 3 and 6 (3 <= x <= 6). In addition, the present invention provides the nanohybrid film comprising: the quantum dot; and a thermoplastic resin. According to the present invention, since the quantum dot contains the ligand polymer, the ligand polymer can be dispersed in a polymer matrix solution. In addition, as the matrix solution is coated on the a substrate through an electrospray method, mixing 10-150 parts by weight of the quantum dot per 100 parts by weight of the polymer matrix solution is possible, and so the quantum dot content in the nanohybrid film can be markedly increased, thereby being able to manufacture the nanohybrid film having excellent luminous efficiency and color rendering properties.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a quantum dot of a core / shell structure, a nanohybrid thin film containing the core / shell structure, and a method of manufacturing the core / shell structured quantum dot,

The present invention relates to a quantum dot of a core / shell structure, a nanohybrid thin film containing the same, and more particularly to a quantum dot which can be combined with a blue light emitting diode to emit white light and a nanohybrid And a method for producing the same.

BACKGROUND ART [0002] White light emitting diodes (LEDs) are the most popular light sources for illumination in the next generation light emitting devices that can replace conventional general lighting. Compared with incandescent lamps and fluorescent lamps, which are used as illumination light sources, white light emitting diodes have advantages such that power consumption is much smaller than conventional light sources, high luminous efficiency, high brightness, and long life.

The first method is a method of mixing high brightness blue, green, and red light emitting diodes. When the blue, green, and red LED chips are fabricated in one package structure to realize white light, a high luminance and a high color rendering index can be obtained. However, since the optimum driving currents of the LED chips are different, It has a disadvantage in that it is complicated and has a very high price, so it is more applied to a special purpose such as a display rather than an illumination application.

The second method is a method of coating blue, green and red phosphors on a long wavelength ultraviolet light emitting diode. Techniques for coating blue, green and red luminescent phosphors on long wavelength ultraviolet light emitting diodes are disclosed in International Patent Publication No. W98 / 039805. This method is the most ideal way to transmit ultraviolet rays through a three-primary-color fluorescent substance to produce three-wavelength white light.

The third method is a method of coating a yellow light emitting phosphor on a blue light emitting diode. A technique for manufacturing a white light emitting diode by coating a yellow light emitting phosphor on a blue light emitting diode is currently being studied extensively. This method is advantageous in that the structure is simple and easy to manufacture and a white light of high brightness can be obtained. This is described in detail in International Publication No. WO98 / 005078, and is also described in S. Nakamura, "The Blue Laser Diode ", Springer-Verlag, P. 216-219, 1997 Lt; / RTI &gt;

Particularly, in recent years, a method for manufacturing a white light emitting diode by combining a blue light emitting diode and a yellow wavelength conversion phosphor layer, which is the third method, is being studied. This is because the structure is simple and easy to apply to mass production, so that it has excellent economical efficiency. Therefore, much research is underway to develop a high-efficiency wavelength conversion phosphor layer.

For this purpose, the quantum dots are considered as a light emitting material for wavelength conversion. A quantum dot is a material exhibiting a quantum confinement effect as a nanocrystal of a semiconductor material having a diameter of about 10 nm or less. The quantum dots generate stronger light in a narrow wavelength band than ordinary phosphors. The luminescence of the quantum dots is generated when electrons excited from the conduction band to the valence band are transferred. Even in the case of the same material, the wavelength varies depending on the particle size. As the size of the quantum dots decreases, the light of a short wavelength is emitted, so that light of a desired wavelength range can be obtained by controlling the size.

The reason for this is that quantum dots have advantages of excellent quantum yield of light, broad absorption spectrum, small dispersion effect, and excellent environmental safety. Thus, attempts to replace conventional luminous material using quantum dots are rapidly spreading.

For example, Korean Patent Registration No. 10-0589250 discloses a silicon quantum dot light emitting device using a transparent electrode including a silicon substrate and a silicon light emitting layer formed on the silicon substrate and having silicon quantum dots formed thereon. The light emitting device has an advantage of improving current injection efficiency and improving luminous efficiency by bonding metals having a low work function. However, in the case of a light emitting device in which a quantum dot is directly applied to silicon, it shows low reliability due to deterioration and extinction of quantum dots, and thus it is difficult to commercialize the device.

In addition, studies on wavelength converting phosphors based on quantum dots and polymer complexes are actively underway. In the quantum dot and polymer complex-based wavelength conversion luminous body, as the quantum dots are uniformly dispersed in the polymer matrix, the efficiency is excellent. When the quantum dots aggregate, the light is dispersed and the quantum yield can be remarkably lowered. However, the quantum dots and the polymer do not easily intermix with each other, so that it is difficult to manufacture the quantum dots so that the quantum dots are sufficiently dispersed in the polymer matrix. Solutions containing Qdots can usually be stabilized through ligand molecules linked to the Qd surface. Because the quantum dots are likely to coagulate in solution, the ligand molecules will mix so that the quantum dots can be homogeneously dispersed between the polymeric matrices. In general, quantum dots can be homogeneously mixed only under a special condition with respect to the polymer matrix, and the quantum dots can be mixed up to a maximum of 10% in the polymer matrix.

To solve these problems, the inventors of the present invention provide a quantum dot that can be uniformly distributed in a polymer matrix, a nanohybrid thin film that generates wavelength conversion light by wavelength conversion of excitation light including the quantum dot, and a light emitting diode package .

The quantum dot of the present invention for solving the above-mentioned problems comprises a core comprising a compound satisfying the following formula (1); A shell comprising ZnS; And a ligand polymer.

[Chemical Formula 1]

AgIn _x S _{(3x + 1) / 2}

In Formula 1, x is a rational number satisfying 3? X? 6.

In one preferred embodiment of the present invention, the core may have an average particle diameter of 1 nm to 10 nm.

In one preferred embodiment of the present invention, the shell may have an average thickness of 1 nm to 5 nm.

In a preferred embodiment of the present invention, the ligand polymer is selected from the group consisting of octanethiol, dodecanethiol, heptanethiol, 8- (9H-carbazol-9-yl) (E) -2 - (-) - dicarboxylic acid, bis [2- (dimethylamino) ethyl] -2-mercaptopentadioate, Phenoxy} propyl-4- (1,2-dithiolan-3-yl) butanoate.

In one preferred embodiment of the present invention, the quantum dot has an emission wavelength of 500 nm to 600 nm and an absorption wavelength of 300 nm to 550 nm.

Further, another aspect of the present invention relates to a nanohybrid thin film, wherein the quantum dot; And a thermoplastic resin.

In a preferred embodiment of the present invention, the thermoplastic resin is at least one selected from the group consisting of polymethyl methacrylate (PMMA), methyl methacrylate-styrene-acrylonitrile-butadiene copolymer resin (MABS), polystyrene, polyester and acrylonitrile- Butadiene-styrene copolymer resin (ABS).

In one preferred embodiment of the present invention, the quantum dot may be contained in an amount of 10 to 150 parts by weight based on 100 parts by weight of the thermoplastic resin.

In one preferred embodiment of the present invention, the nanohybrid thin film has an average thickness of 5 to 40 mu m.

In one preferred embodiment of the present invention, when the nano hybrid thin film is introduced into a blue LED light source and measured, the PL wavelength may be 500 to 600 nm.

In one preferred embodiment of the present invention, when the nanohybrid thin film is introduced into a blue LED light source and the transmittance is measured, the transmittance is 50% to 80%, CIE X 0.30 to 0.45 in terms of color coordinates, CIE Y 0.25 to 0.45, The corelated color temperature (CCT) may range from 2500 K to 7000 K.

In one preferred embodiment of the present invention, the color rendering index (CRI) of the nanohybrid thin film may be 50 to 90.

Another aspect of the present invention relates to a method for producing a nanohybrid thin film, comprising the steps of: preparing a substrate including a soluble polymer coating layer; Electrospraying a mixed solution obtained by mixing the quantum dot and a polymer matrix solution on one side of the soluble polymer coating layer to form a nanohybrid coating layer, and then treating the mixture with chloroform vapor for 1 to 5 seconds; And dissolving the soluble polymer coating layer to separate the nanohybrid thin film.

In a preferred embodiment of the present invention, the polymer matrix solution may include a thermoplastic resin and a solvent.

In a preferred embodiment of the present invention, the thermoplastic resin is at least one selected from the group consisting of polymethyl methacrylate (PMMA), methyl methacrylate-styrene-acrylonitrile-butadiene copolymer resin (MABS), polystyrene, polyester and acrylonitrile- Butadiene-styrene copolymer resin (ABS).

In one preferred embodiment of the present invention, the solvent may include at least one selected from water, alcohol, acetone, ethanol, methanol, dimethylformamide, toluene, tetrahydrofuran, n-hexane and DMSO .

In one preferred embodiment of the present invention, the polymer matrix solution may contain 0.5 to 2 parts by weight of a thermoplastic resin per 100 parts by weight of the solvent.

In one preferred embodiment of the present invention, the electrospray is performed by electrospinning at a distance of 15 cm to 25 cm from the surface of the soluble polymer coating layer under an electric field of 12 kV cm ^-1 to 18 kV cm ^-1 have.

In one preferred embodiment of the present invention, the quantum dots are prepared by mixing the silver precursor solution and the indium precursor solution at 1 atm and 10 to 35 ° C, heating the mixture at 80 to 100 ° C in a nitrogen atmosphere where water and oxygen are removed, Forming a core by injecting the sulfur precursor solution at a temperature of 90 to 200 캜; A step 2-2 in which the zinc precursor solution and the sulfur precursor solution are reacted at 150 to 260 ° C for 1 to 3 hours to grow a shell in the mixed solution in which the core is formed in the step 1; And (2) separating the quantum dots from the mixed solution of the two steps.

In one preferred embodiment of the present invention, the silver precursor solution, the indium precursor solution, and the sulfur precursor solution are contained in a molar ratio of 1: 3 to 6: 5 to 9.

In one preferred embodiment of the present invention, the sulfur precursor solution in step 1 comprises sulfur and a solvent, and the solvent is selected from the group consisting of oleic acid, trioctylphosphine oxide (TOPO) And at least one selected from the group consisting of triphenylphosphine (TPP), trioctylphosphine (TOP), and C ₃ to C ₁₈ alkyl amines.

In one preferred embodiment of the present invention, the silver precursor solution, the zinc precursor solution, and the sulfur precursor solution are mixed in a molar ratio of 1: 3 to 5: 3 to 5 in step 2.

In one preferred embodiment of the present invention, the zinc precursor solution may include at least one selected from the group consisting of diethyl zinc, dimethyl zinc, zinc oxide, zinc stearate, and zinc acetate.

Another aspect of the present invention relates to a light emitting device package, comprising: a light emitting element; A package body on which the light emitting device is mounted; And the nanohybrid thin film located on the package body and converting a wavelength of light emitted from the light emitting device.

Another aspect of the present invention may include a white light emitting diode including the nanofiber hybrid thin film.

Another aspect of the present invention relates to an illumination including the nanohybrid thin film.

However, since the quantum dot according to the present invention has excellent dispersibility in a polymer matrix solution, it is difficult to produce an electrodisplaced nanoparticle by an electrospray method, It is possible to produce a nanohybrid thin film containing a quantum dot at a high concentration. In addition, since the content of quantum dots in the thin film can be drastically improved by manufacturing the nanohybrid thin film by the electric spraying method, a nanohybrid thin film excellent in light emitting efficiency and color rendering property can be produced.

FIG. 1 (a) is a graph showing the results of measuring the excitation and emission intensity according to the wavelength change of the quantum dot prepared in Preparation Example 1; FIG. (b) is a graph showing the absorbance according to a change in wavelength; (c) an X-ray diffraction analysis graph; (d) is a transmission electron microscope image.
FIG. 2 (a) is a graph showing transmittance according to quantum dot content of the nanohybrid thin films prepared in Examples 1 to 6; FIG. (b) is a graph in which the PL intensity is measured.
FIG. 3 is a graph showing changes in the PL emission intensity of Examples 1 to 6, which were obtained on the basis that the quantum dots were contained in 10 parts by weight with respect to 100 parts by weight of the polymer matrix in Example 1. FIG.
Fig. 4 is a graph showing the results of measurement of a polymer matrix of 100 parts by weight of the polymer matrix of the nano hybrid thin film prepared in Example 1, Example 3, Example 4 and Example 6, in which 10 parts by weight of quantum dots, 75 parts by weight of quantum dots, (c) is an image of a transmission electron microscope when 100 weight parts of a quantum dot and 150 weight parts of a quantum dot are shown in (d).
FIG. 5 (a) is a graph showing a change in transmittance according to the thickness of the nanofiber hybrid thin films prepared in Examples 7 to 11 and Comparative Example 1; FIG. (b) is a PL intensity graph.
6 is a graph of the PL intensity improvement ratio based on the light emission intensity at a thickness of 2.9 mu m of Comparative Example 1. Fig.
7 (a) is a light emitting device package model image; (b) is the EL spectrum results of Examples 12 to 15; (c) are CIE chromaticity coordinate graphs of Examples 12 to 15. Fig.
FIG. 8 is a transmission electron microscope image of a cross section of the nanohybrid thin films prepared in Examples 12 to 15. FIG.
9 is an image obtained by dividing the nanohybrid thin film prepared in Example 16 into nine equal parts.
10 is a scanning electron microscope image of a section of the nanohybrid thin film prepared in Example 16 divided into nine equal parts.
11 (a) is a graph showing the emission intensity of the nanohybrid thin film prepared in Example 16 divided into nine equal parts; (b) is a graph showing the maximum peak value of each part.
12 (a) is a schematic view of a light emitting device package of Production Example 1; (b) is a schematic diagram of a light emitting device package of Production Example 2.
13 (a) is a graph showing a light emission intensity spectrum according to time in Production Example 1; (b) is a graph showing the emission intensity spectrum according to the preparation example 2 over time.
14 (a) is a graph showing a change in color coordinates over time in Production Example 1; (b) is a graph showing a change in color coordinates with time in Production Example 2. Fig.
15 (a) is a graph showing the luminous efficiency with respect to time in Production Example 1; (b) is a graph showing the luminous efficiency with respect to time in Production Example 2. Fig.
16 is a schematic view showing a method of manufacturing a nanohybrid thin film according to the present invention.
17 is an image showing a method of separating a nanohybrid thin film according to the present invention from a substrate.

Hereinafter, the quantum dots of the present invention, the nanohybrid thin film containing the same, and the method for producing the same will be described in more detail.

The present invention relates to a core comprising a compound satisfying the following formula (1); A shell comprising ZnS; And a ligand polymer. The quantum dot according to the present invention can easily mix with a polymer matrix by including a ligand polymer in a core / shell structure, and can improve dispersibility, It is possible to prevent the problem of aggregation.

[Chemical Formula 1]

AgIn _x S _{(3x + 1) / 2}

In Formula 1, x is a rational number satisfying 3? X? 6.

The quantum dot according to the present invention can be used as a yellow light emitting phosphor to be applied to a blue light emitting source to realize white light emission. The core part satisfying the above formula (1) is non-toxic due to the above composition and has a direct band gap of a large extinction coefficient. In addition, due to the increase of the half-width of the quantum dot through the donor-acceptor pair recombination, blue LED and white LED have a high color rendering index. In addition, when the shell is coated with ZnS in the core portion satisfying Formula 1, the quantum efficiency of the quantum dot can be increased.

The core of the quantum dots of the present invention may be characterized by having an average particle diameter of 1 nm to 10 nm, preferably an average particle diameter of 2 nm to 4 nm, and the size of the quantum dot may be a reaction time at the time of production, Composition ratio and so on. If the average particle diameter of the quantum dot core is less than 1 nm, it is technically difficult to manufacture. If the average particle diameter exceeds 10 nm, there is a problem that the light emitting efficiency is lowered.

In the quantum dot of the present invention, it is preferable that the shell has an average thickness of 1 nm to 5 nm, preferably 1 nm to 3 nm. If the average thickness of the shell is less than 1 nm, there may be a problem that the defect of the surface of the quantum dot core can not be compensated. If the average thickness of the shell is more than 5 nm, It is preferable to have a thickness within the range.

The core of the quantum dot according to the present invention may be prepared by reacting with the ligand polymer to form a core / shell structure including a ligand by growing the shell. Since quantum dots generally have different solubility parameters with respect to the polymer and Hildebrand, it is difficult for them to easily mix with each other, so that the quantum dots can cohere with each other in the polymer matrix supporting the quantum dots. In this case, when a quantum dot / polymer nanohybrid thin film is prepared, scattering of light occurs due to aggregated quantum dots, and therefore, there arises a problem that luminous efficiency is lowered. At this time, the ligand polymer can easily mix with the polymer matrix, thereby helping the quantum dots to be homogeneously distributed in the polymer matrix.

The ligand polymer plays a role of helping the quantum dots according to the present invention to be homogeneously dispersed in the polymer matrix. If the polymer matrix has a similar hildebrand solubility parameter and can easily mix with each other, the ligand polymer can be used . (9H-carbazol-9-yl) dodecane-1-thiol, octane thiol, (E) -2- (4-formyl- (phenyl) ethenyl (meth) acrylate, 3-mercaptopropionic acid, bis [2- ] Phenoxy} propyl-4- (1,2-dithiolan-3-yl) butanoate, and more preferably at least one selected from the group consisting of octanethiol, dodecanethiol, Thiol is good.

In the quantum dot of the present invention, the quantum dot preferably has an emission wavelength of 500 nm to 600 nm and an absorption wavelength of 300 nm to 550 nm. Since the quantum dots have a maximum peak value within a wavelength range of about 500 nm to 600 nm, the quantum dots exhibit luminescence characteristics in the green to amber range, and the absorption wavelength ranges from about 300 nm to 550 nm 1 &lt; / RTI &gt; That is, it can be seen that the quantum dot according to the present invention absorbs blue-based light, excites it, and then emits yellow-based light.

According to another aspect of the present invention, there is provided a quantum dot device comprising: the quantum dot; And a thermoplastic resin. When a nanohybrid thin film in which a quantum dot and a thermoplastic resin are combined is used, a white light emitting diode can be fabricated together with a blue light source. Since the quantum dot according to the present invention absorbs light in the blue region and emits light in the yellow region, the nanohybrid thin film produced therefrom serves to down-convert the frequency of the complementary blue light, It is possible to obtain white light which is broad.

Here, in the nanohybrid thin film of the present invention, the thermoplastic resin may be at least one selected from the group consisting of polymethyl methacrylate (PMMA), methyl methacrylate-styrene-acrylonitrile-butadiene copolymer resin (MABS), polystyrene, Nitrile-butadiene-styrene copolymer resin (ABS), but it is not particularly limited thereto. The thermoplastic resin may be any transparent thermoplastic resin having a Hildebrand solubility parameter similar to that of the ligand polymer introduced on the surface of the quantum dot of the present invention, and which can easily be mixed with the quantum dot.

In the nanohybrid thin film of the present invention, it is preferable that the quantum dot is contained in an amount of 10 to 150 parts by weight based on 100 parts by weight of the thermoplastic resin, more preferably 70 to 130 parts by weight of the quantum dot in 100 parts by weight of the thermoplastic resin It is good to include.

According to the present invention, as the content of the quantum dot in the thermoplastic resin increases, the transmittance is lowered, and the PL emission intensity of the nanohybrid thin film tends to increase. When the quantum dots are contained in an amount of less than 10 parts by weight based on 100 parts by weight of the thermoplastic resin, the content of quantum dots is low and the PL strength is low. When the quantum dots are contained in excess of 150 parts by weight with respect to 100 parts by weight of the thermoplastic resin There is a problem that the quantum dots coagulate and the PL intensity is lowered.

When the PL wavelength of the nanohybrid thin film is measured under a blue LED light source (? _Max = 445 nm), 100 parts by weight of the thermoplastic resin The PL intensity can be about 3 times or more higher than that in the case where the quantum dot is included in 10 parts by weight.

In the nanohybrid thin film of the present invention, the nanohybrid thin film preferably has an average thickness of 5 to 40 mu m, preferably 8 to 15 mu m. The thickness of the nanohybrid thin film is an important factor that may affect the luminous efficiency, the color temperature, and the color rendering index when the thin film is applied to a light source. If the average thickness is less than 5 m, If it is more than 40 탆, the color temperature and the color rendering index may be decreased, which may make it difficult to use as an illumination. In addition, when the thickness of the nanohybrid thin film is in the range of 8 to 15 占 퐉, the PL strength is advantageously about 2 to 3 times better.

At this time, when the nanohybrid thin film of the present invention is introduced into a blue LED light source, it is preferable that the PL wavelength is 500 to 600 nm, preferably 560 to 590 nm. The blue LED light source may be a He-Cd laser (325 nm) or an Xe lamp (350 nm to 450 nm). The wavelength range is a yellow wavelength range. The nanohybrid thin film according to the present invention includes a quantum dot that excites and excites blue light and emits light of a yellow to amber series, thereby down-converting the blue light Since it is produced for obtaining white light, it is preferable that the PL wavelength is included in the above range.

In the nanohybrid thin film of the present invention, the PL wavelength intensity of the nanohybrid thin film having an average thickness of 5 to 40 mu m was measured using a blue LED light source ([lambda] _max = 445 nm) Or more. As the thickness of the nanohybrid thin film of the present invention increases, the content of the quantum dots contained therein increases, so that the luminescence intensity can also be increased. Therefore, as the average thickness of the nanohybrid thin film increases, the PL wavelength intensity also increases proportionally.

In the nanohybrid thin film of the present invention, when the nanohybrid thin film is introduced into a blue LED light source and the transmittance is measured by a UV-visble spectrophotometer, the transmittance is preferably 50% to 80%. The nanohybrid thin film according to the present invention is affected by the thickness of the thin film and the content of the quantum dots. As the thickness of the thin film and the content of the quantum dots increases, the transmittance decreases. As the thickness and the content of the quantum dots decrease, the transmittance tends to decrease . At this time, since it affects not only the transmittance of the thin film but also the luminous efficiency, the intensity, the color rendering index and the correlated color temperature depending on the thickness of the thin film and the content of the quantum dots, it is preferable that the transmittance is made to exhibit a value included in the above range .

In the nanohybrid thin film of the present invention, the nanohybrid thin film is introduced into a blue LED light source, and has a color coordinate of CIE X of 0.30 to 0.45 and a CIE Y of 0.25 to 0.45, preferably CIE X of 0.35 to 0.40 And CIE Y is preferably 0.30 to 0.40. When the range of CIE X and CIE Y on the chromaticity coordinates deviates from the above range, white light is difficult to develop.

In the nanohybrid thin film of the present invention, the nanohybrid thin film may be introduced into a blue LED light source and have a correlated color temperature (CCT) of 2500 K to 7000 K, more preferably 4000 to 6000 K It is good. The correlated color temperature represents the color temperature corresponding to the blackbody locus closest to the point indicating the chromaticity coordinates of the sample light. The higher the temperature, the closer the color to the blue color. When the correlated color temperature is less than 2500K, the light color shows a color close to red. When the correlated color temperature is more than 7000K, the color is close to blue, which is not preferable for producing a white light emitting diode.

In the nanohybrid thin film of the present invention, the color rendering index (CRI) of the nanohybrid thin film is 50 ~ Preferably 90 to 90, and more preferably 60 to 90. The color rendering index is an index indicating the degree of matching with the perception angle when the object light illuminated by the light source is illuminated with a reference light source under a prescribed condition. When the color rendering index is less than 50, it is difficult to use it as illumination. Since the wavelength of the red light is small in the light emission wavelength of the thin film, when it exceeds 90, there is _a problem that it is difficult to achieve the numerical value close to the reference light source 100 R _a .

Another aspect of the present invention relates to a method for producing a nanohybrid thin film, comprising the steps of: preparing a substrate including a soluble polymer coating layer; Electrospraying a mixed solution obtained by mixing the quantum dot and a polymer matrix solution on one side of the soluble polymer coating layer to form a nanohybrid coating layer, and then treating the mixture with chloroform vapor for 1 to 5 seconds; And separating the nanohybrid thin film by dissolving the soluble polymer coating layer therefrom. Hereinafter, the present invention will be described step by step with reference to FIG.

In the method of manufacturing a nanohybrid thin film according to the present invention, the first step is a step of preparing a substrate for forming a nanohybrid thin film, wherein the substrate including the soluble polymer coating layer dissolves the soluble polymer coating layer in a subsequent step, In order to separate the nanohybrid thin film from the substrate, before the thin film is formed.

In the second method of manufacturing a nanohybrid thin film according to the present invention, a mixed solution obtained by mixing a quantum dot and a polymer matrix solution according to the present invention is electrosprayed on one surface of the soluble polymer coating layer to form a nanohybrid coating layer , And the surface is treated with chloroform vapor for 1 to 5 seconds to form a nanohybrid thin film. According to the present invention, by introducing and using a quantum dot including a ligand polymer, it can be uniformly dispersed in a polymer matrix solution, and it is possible to prevent the problem of aggregation between quantum dots. Also, by using the electrospray method for manufacturing the nanohybrid thin film, the nanohybrid thin film improved in luminous efficiency, color rendering and the like can be obtained because quantum dots in the polymer matrix can contain twice as much as the conventional method, A diode can be manufactured.

In the method for producing a nanohybrid thin film according to the present invention, the polymer matrix solution in two stages includes a thermoplastic resin and a solvent, and the thermoplastic resin may be the same as described above. At this time, the polymer matrix solution preferably contains 0.5 to 2 parts by weight of the thermoplastic resin per 100 parts by weight of the solvent. When the thermoplastic resin is contained in an amount of less than 0.5 parts by weight with respect to 100 parts by weight of the solvent, the thin film is not properly formed and the quantum dots aggregate within a short distance to absorb the energy of emitting light, There is a problem that electric injection becomes difficult.

And, the method of manufacturing a nano-hybrid thin film according to the present invention, the electric injection is under a 12 kVcm ^-1 ~ 18 kVcm ^-1 electric field, and more preferably 14 ~ 15 kVcm ^- the surface of the soluble polymer coating layer under an electric field of ¹ At a distance of 15 cm to 25 cm. At this time, the electric field is 12 kVcm ^-1 is less than, and does not include the electric field is not charged enough not the polymer matrix solution sprayed evenly problems, 18 kVcm ^- if it exceeds ^1, there is a problem in that the equipment is overloaded.

In the method of manufacturing a nanohybrid thin film according to the present invention, step 3 is a step of simply dissolving a soluble polymer coating layer coated in step 1 and separating the nanohybrid thin film.

The soluble polymer coating layer may contain polystyrene sulfonic acid (PSA), PEDOT / PSS and methanol in a weight ratio of 1: 0.8-1.2: 0.8-1.2, more preferably 1: 0.9-1.1: 0.9-1.1 By weight, based on the total weight of the composition. When the nanohybrid thin film is formed on the coating layer and then the nanohybrid thin film is loaded on the distilled water, the soluble polymer coating layer (PSA) The nano hybrid thin film can be separated, and a free-standing nanohybrid thin film can be produced.

The quantum dots used in the method for producing a nanohybrid thin film according to the present invention are prepared by mixing a silver precursor solution and an indium precursor solution at 1 atm and 10 to 35 ° C and then heating them to 80 to 100 ° C in a nitrogen atmosphere in which water and oxygen have been removed Reacting with a ligand forming agent, and injecting a sulfur precursor solution at a temperature of 90 to 200 캜 to form a core; Reacting the zinc precursor solution and the sulfur precursor solution at 150 to 260 ° C. for 1 to 3 hours to grow a shell in the mixed solution in which the core is formed in the step 1; And separating the quantum dots from the mixed solution of the two steps. However, it is possible to use a quantum dot prepared by performing the process including the steps of: But is not limited thereto.

The silver precursor solution, the indium precursor solution, and the sulfur precursor solution may be mixed with the solution of the silver precursor solution, the solution of the indium precursor, and the solution of the sulfur precursor in a ratio of 1: 3 to 6: And preferably in a molar ratio of 5: 9 to 1: 3.5: 5.5: 5.5 to 8.5.

[Chemical Formula 1]

AgIn _x S _{(3x + 1) / 2}

The silver precursor solution may be a silver precursor solution that can be reduced to form a core of a quantum dot. The silver precursor solution may be silver nitrate, silver chloride, silver fluoride, silver bromide, silver hydroxide, silver sulfate, silver silver, silver cyanide, silver tetrafluoro It is preferable to include at least one selected from the group consisting of borate, silver sulfide, silver acetate, silver lactate, silver benzoate, silver cyclohexane butyrate, silver diethyldithiocarbamate and silver trifluoromethanesulfonate .

The indium precursor solution may be any indium precursor solution that can be reduced so as to form a core of a quantum dot. Indium chloride, indium chloride tetrahydrate, indium fluoride, Indium fluoride trihydrate, indium hydroxide, indium nitrate hydrate, indium acetate hydrate, indium acetylacetonate and indium acetylacetonate. It is preferable to include one species selected from the group consisting of acetate and indium acetate.

The sulfur precursor solution in Step 1 may be a sulfur precursor solution that can be reduced to form a core of a quantum dot, and preferably includes sulfur and a solvent. The solvent may be oleic acid, May include at least one member selected from the group consisting of trioctylphosphine oxide (TOPO), triphenylphosphine (TPP), trioctylphosphine (TOP) and C ₃ to C ₁₈ alkylamines have. Preferably, C ₃ -C ₁₈ alkylamines are preferred, and more preferably C ₃ -C ₁₈ alkylamines are oleylamine, octylamine, hexadecylamine, octadecylamine octadecylamine and tri-n-octylamine.

In the method for producing a nanohybrid thin film according to the present invention, the silver precursor solution and the ligand forming agent are preferably mixed in a molar ratio of 1:35 to 45, preferably 1:38 to 43. When the molar ratio of the silver precursor solution and the ligand forming agent is less than 1:35, the ligand is not sufficiently formed in the quantum dots. There is a problem that it is difficult to be dispersed in a solution. When it exceeds 1:45, there is a problem that it is difficult to be purified after the synthesis of a quantum dot, and the amount of the ligand remaining in the solution is large, which lowers the permeability of the polymer matrix.

In the case of deviating from the above range, the quantum dots according to the present invention are not uniformly dispersed in the polymer matrix.

At this time, the ligand-forming agent may be used as long as it has a Hildebrand solubility parameter similar to that of the thermoplastic resin in the polymer matrix and allows quantum dots to be homogeneously dispersed in the polymer matrix. Preferably, the ligand-forming agent is octanethiol, dodecanethiol, (9H-carbazol-9-yl) octane-1-thiol, 8- Ethyl] -2-mercaptopentadioate, 3 {2,5-bis [(E) Dithiolan-3-yl) butanoate.

In the method of manufacturing a nanohybrid thin film according to the present invention, it is preferable that the silver precursor solution, the zinc precursor solution and the sulfur precursor solution are mixed at a molar ratio of 1: 3 to 5: 3 to 5. The zinc precursor solution and the sulfur precursor solution are introduced to form a zinc sulfide shell after the cores of the quantum dots are formed, and the zinc precursor solution and the sulfur precursor solution are preferably introduced at the same ratio.

The zinc precursor solution may be any of those selected from the group consisting of diethyl zinc, dimethyl zinc, zinc oxide, zinc stearate, zinc acetate, and mixtures thereof, as long as the zinc precursor solution can be reduced to form a zinc sulfide shell. And the like.

The sulfur precursor solution in the second step may include sulfur and a solvent, and the solvent may be a substance capable of forming a zinc sulfide shell. Preferably, the sulfur precursor solution is selected from the group consisting of oleic acid, trioctylphosphine oxide (TOPO)), triphenylphosphine (TPP), trioctylphosphine (TOP), and C ₃ to C ₁₈ alkyl amines, More preferably, it is trioctylphosphine oxide (TOPO), triphenylphosphine (TPP), and trioctylphosphine (TOP).

In the method for producing a nanohybrid thin film according to the present invention, the quantum dots may be mixed in a weight ratio of 10 to 150, preferably 70 to 130, per 100 parts by weight of the thermoplastic resin and the thermoplastic resin of the solvent . The conventional quantum dot / polymer nanohybrid thin film has a problem that the quantum dots can only be added up to 10% in the polymer mattress. However, in the method for producing a nanohybrid thin film according to the present invention, since the quantum dots contain the ligand polymer and can be uniformly dispersed in the polymer matrix solution and coated on the substrate through the electrospray method, It is possible to mix the quantum dots at a weight ratio of 10 to 150. Therefore, since the content of quantum dots in the nanohybrid thin film can be remarkably improved, a nanohybrid thin film excellent in light emitting efficiency and color rendering property can be produced. More preferably, the quantum dots are mixed at a weight ratio of 70 to 130 with respect to 100 parts by weight of the polymer matrix solution. The nanohybrid thin film prepared within the range of the above mixing ratio can exhibit a PL emission intensity of about 3 times or more as compared with the nanohybrid thin film prepared by mixing the polymer matrix solution at a weight ratio of 10 to 100 parts by weight of the polymer matrix solution.

Another aspect of the present invention is a light emitting device comprising: a light emitting element; A package body on which the light emitting device is mounted; And a nanohybrid thin film disposed on the package body and converting a wavelength of light emitted from the light emitting device.

The nanohybrid thin film manufactured according to the present invention is different from the conventional structure including a quantum dot in a cup-type device, and the nanohybrid thin film is provided on the package body on which the light emitting device is mounted ), There is an advantage that the installation method is simple. Also, since the quantum dots can be prevented from deteriorating or disappearing due to heat generated in the light source, the stability of the luminescence efficiency according to the use time can be maintained unchanged, and the light stability over time is advantageous.

Another aspect of the present invention relates to a white light emitting diode including the nanohybrid thin film, wherein the nanohybrid thin film absorbs light of a blue region and performs down conversion to emit light of a yellow region Therefore, it can be used as a white light emitting diode by being introduced into an LED of a blue light source.

Another aspect of the present invention relates to an illumination including the light emitting device package. When the nanohybrid thin film is manufactured by adjusting the quantum dot content and the thickness of the thin film, the light emitting efficiency, color rendering property, and correlated color temperature It can be manufactured and used for various purposes such as an incandescent lamp, a fluorescent lamp, and the like.

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

[ Example ]

Preparation Example  One. Quantum dot  Produce

(1) Step 1: Formation of cores and ligands

Silver nitrate (AgNO _{3 ,} 99%, Aldrich, 0.10 mmol), indium acetylacetonate (In (acac) _3, 99.99%, aldrich, 0.50 mmol), oleic acid (OA, 90%, aldrich, 1.50 mmol) and 1-octadecene (ODE, 30 90% Aldrich, 25 mmol) were poured into a round neck three neck flask, Purged for 20 minutes. After purging with nitrogen gas, dodecane thiol (DDT, 98%, Aldrich, 4.0 mmol) was injected into the reaction solution heated to 90 ° C. The sulfur precursor solution prepared by dissolving sulfur (S, 99.98%, Aldrich, 0.8 mmol) in oleic amine (OLA, 70%, Aldrich, 4.0 mmol) was rapidly injected into the reaction solution heated to 120 ° C, .

(2) Step 2: Growth of Shell

After 3 minutes, sulfur (S, 0.4 mmol) dissolved in zinc stearate (10-12% An basis, Aldrich, 0.4 mmol) and trioctylphosphine (TOP, 4 mmol) The precursor solution was injected into the reaction solution heated to 180 캜 and reacted for 2 hours to prepare a final reaction solution.

(3) Step 3: Purification and separation of QDs

The final reaction solution was purified through a centrifuge, dissolved in toluene solution and washed to prepare AgIn ₅ S ₈ / ZnS.

Example of comparison preparation  One. Agin ₅ S ₈ of  Produce

Silver nitrate (AgNO _{3 ,} 99%, Aldrich, 0.10 mmol), indium acetylacetonate (In (acac) _3, 99.99%, aldrich, 0.50 mmol), oleic acid (OA, 90%, aldrich, 1.50 mmol) and 1-octadecene (ODE, 30 90% Aldrich, 25 mmol) were poured into a round neck three neck flask, Purged for 20 minutes. The sulfur precursor solution was prepared by dissolving sulfur (S, 99.98%, Aldrich, 0.8 mmol) in oleic amine (OLA, 70%, Aldrich, 4.0 mmol) in a reaction solution heated to 120 ° C after nitrogen gas purging. Solution 1 was prepared. This was purified through a centrifuge and dissolved in a toluene solution to be washed to prepare AgIn ₅ S ₈ Nanohybrid thin films were prepared.

Experimental Example  One. Quantum dot  Characteristic Analysis 1

The excitation and emission intensity of the quantum dots prepared in Preparation Example 1 were measured with a Xe lamp (450 nm) according to the wavelength change, and the results are shown in FIG. 1 (a) The results are shown in Fig. 1 (b). The quantum dots of Preparation Example 1 and Comparative Preparation Example 1 were subjected to X-ray diffraction analysis on a (203) plane using a UV-visible spectrophotometer (SCINCO, S-3100) , And the quantum dots of Preparation Example 1 were observed with a transmission electron microscope. The results are shown in Fig. 1 (d).

According to FIG. 1 (a), it can be seen that the quantum dots prepared in Preparation Example 1 are excited in a wavelength range of about 300 to 500 nm and emitted at a wavelength of about 530 to 560 nm. 1 (b), it can be confirmed that it exhibits the most excellent absorbance at a wavelength of about 350 to 480 nm. Accordingly, it can be seen that the quantum dot according to the present invention absorbs blue light in the range of about 430 to 460 nm and emits yellow light in the range of about 530 to 560 nm.

According to Fig. 1 (c), the quantum dots of Comparative Example 1 in which the quantum dots prepared in Production Example 1 having a core / shell structure have a similar peak but have diffraction intensities different from each other have mostly similar crystal structures, It can be seen that the content and size of the crystals are different.

According to FIG. 1 (d), the size of the quantum dot produced in Production Example 1 of the present invention is confirmed to be about 3.0 nm in diameter.

Example  One. Qdot / Preparation of polymer nanohybrid thin films 1

(1) Step 1: After cleaning the glass substrate coated with indium tin oxide (ITO), it is exposed to ultraviolet radiation and ozone for 20 minutes to be sterilized. Then, a solution prepared by mixing polystyrene sulfonic acid, PEDOT / PSS (Baytron AI 4083, Bayer) and methanol at a ratio of 1: 1: 1 was spin-coated on the ITO / glass substrate at 4000 rpm for 35 seconds.

(2) Step 2: A 1% polymethyl methacrylate solvent prepared by dissolving polymethyl methacrylate (PMMA) in a mixed solvent of dimethylformamide and toluene (dimethylformamide / toluene, 33.3 vol%) Quantum dots prepared in the same manner as in Preparation Example 1 were introduced. At this time, 0.027 g of the quantum dots was introduced in an amount of 10 parts by weight based on 100 parts by weight of polymethylmethacrylate to prepare a quantum dot / polymer mixed solution.

It was injected with ^1-the mixture loaded into the packed syringe pump (kdScientific, KDS100) in 30 ml capacity syringe, and 48 ~ 52 ㎕min. The mixed solution was installed at a distance of about 20 cm between the ITO substrate coated with the PEPOD / PSS of Step 1 and the needle of the syringe pump after about 14 ~ 15 kVcm ^- had an electric field of ^1, and so that the electrical injection 1.2 ㎛ thickness for 160 minutes on the mixed solution to the PEPOD / PSS coated ITO substrate from the needle of a syringe pump. After the electrospinning, the nanohybrid thin film including the quantum dot and the polymer was treated with chloroform vapor for 2 seconds.

(3) Step 3: The quantum dot / polymer nano hybrid thin film coated on PEPOD / PSS coated ITO substrate is immersed in distilled water for about 1 minute to dissolve the PEDOT / PSS layer, The hybrid thin film was picked up with a forceps to prepare a quantum dot / polymer nanohybrid thin film (see FIGS. 16 and 17)

Example  2 to 6. Qdot / Fabrication of polymer nanohybrid thin films 2

A nanohybrid thin film was prepared in the same manner as in Example 1, except that the quantum dots were introduced in a weight ratio of 100 parts by weight of polymethylmethacrylate in the step 2 of Example 1, as shown in Table 1 below. At this time, a nanohybrid thin film having a similar thickness was prepared by controlling the electrospinning time.

Quantum dot (ratio) PMMA (ratio) Electrospinning time
(minute) Thin film thickness
(탆) Example 2 50 100 160 1.54 Example 3 75 100 160 1.61 Example 4 100 100 130 1.08 Example 5 125 100 110 1.20 Example 6 150 100 110 1.46

Example   7-11. Qdot / Fabrication of polymer nanohybrid thin films 3

The same procedure as in Example 4 was carried out except that the mixed solution was electro-sprayed in the step 2 of Example 4 under the conditions shown in Table 2 below.

Quantum dot (ratio) PMMA (ratio) Electrospinning time
(time) Thin film thickness
(탆) Example 7 100 100 12 6.3 Example 8 100 100 14 7.4 Example 9 100 100 24 11.1 Example 10 100 100 26 12.3 Example 11 100 100 28 13.1

Example  12-15. Qdot / Manufacture of polymer nanohybrid thin films 4

The same procedure as in Example 4 was carried out except that the mixed solution was electro-sprayed in the step 2 of Example 4 under the conditions shown in Table 3 below.

Electrospinning time (hours) Thin film thickness (탆) Example 12 12 6.1 Example 13 18 8.7 Example 14 22 10.5 Example 15 32 14.7

Example  16. Qdot / Preparation of polymer nanohybrid thin films 5

In the same manner as in Example 2 except that the mixed solution containing 1.8% of the polymethylmethacrylate solvent was sprayed for 6 hours in the step 2 of Example 2 to form a coating having a thickness of 38 탆, a nanohybrid thin film .

Comparative Example  One. Qdot / Preparation of polymer nanohybrid thin films 6

The nanohybrid thin film was prepared in the same manner as in Example 4 except that the mixed solution was electrodeposited to a thickness of 2.9 mu m for 400 minutes in the step 2 of Example 4. [

Manufacturing example  1. Fabrication of Light Emitting Device Package 1

The nanohybrid thin film prepared in Example 4 of the present invention was installed in a remote type on the top of a light emitting device body having a size of 5.4 mm x 5.0 mm including a blue LED having a luminous efficiency of 14 lm / W at 60 mA Thereby completing the light emitting device package (see Fig. 12 (a)).

Manufacturing example  2. Manufacturing of light emitting device package 2

The quantum dot prepared in Example 1 of the present invention was mixed with a silicon binder and introduced into a blue LED size 5.4 mm x 5.0 mm having a luminous efficiency of 14 lm / W at 60 mA to complete a light emitting device package (See Fig. 12 (b)).

Experimental Example  1. Characterization of nanohybrid thin films 1

The nanohybrid thin films prepared in Examples 1 to 6 were measured for transmittance using a UV-visible spectrophotometer (SCINCO, S-3100). The results are shown in FIG. 2 (a). The PL intensity was measured, and the result was shown in Fig. 2 (b). The PL emission intensity was determined on the basis of the PL emission intensity at the emission maximum peak of the quantum dot prepared in Example 1, .

According to FIG. 2 (a), as the content of quantum dots increases in the nanohybrid thin film, the transmittance is significantly lowered. That is, it can be seen that the transmittance is decreased in proportion to the content of the quantum dots.

According to FIG. 2 (b), it can be seen that all of Examples 1 to 6 have peaks in the region of about 560 to 600 nm, and the quantum dots according to the present invention emit light in the yellow region have. According to FIG. 3, it can be confirmed that the PL intensity is highest when the quantum dot content is 100 parts by weight with respect to 100 parts by weight of the polymer matrix. Thus, when quantum dots are contained at a ratio of 1: 1 in the polymer matrix, It can be seen that it exhibits excellent luminescence intensity.

Experimental Example  2. Characterization of nanohybrid 2

The nanohybrid thin films prepared in Examples 1, 3, 4 and 6 were observed using a transmission electron microscope (TEM, JEM-4010, 400 kV) and the results are shown in FIG. According to FIG. 4, as the content of the quantum dots contained in the polymer matrix increases, the number of quantum dots observable in the transmission electron microscope image increases.

Experimental Example  3. Characterization of nanohybrid thin films 1

The nanohybrid thin films prepared in Examples 7 to 11 and Comparative Example 1 were measured for transmittance change according to wavelength by using a UV-visible spectrophotometer (SCINCO, S-3100). The results are shown in FIG. 5 (a). The PL intensity was measured using a Xe lamp. The result is shown in FIG. 5 (b). Using this, the PL intensity enhancement ratio based on the PL intensity at 550 nm of Comparative Example 1 was calculated, The results are shown in Fig.

As shown in FIG. 5 (a), it can be seen that as the thickness of the thin film becomes thicker, the transmittance decreases proportionally as in the case of Examples 7 to 11 and Comparative Example 1 at 550 nm. According to FIG. 5 (b) and FIG. 6, it can be seen that the PL intensity increases proportionally as the thickness of the nanohybrid thin film increases. That is, the thickness and transmittance of the nanohybrid thin film according to the present invention are inversely proportional, and the thickness of the thin film and the PL intensity are proportional to each other.

Experimental Example  4. Characterization of nanohybrid films 2

The nanohybrid thin films prepared in Examples 12 to 15 were set as a remote type at a distance of about 600 mu m on a blue LED having an emission efficiency of 14 lm / W at 60 mA ). The EL intensity was measured using a spectrophotometer (Darsapro-5000, PSI Co. Ltd), and the EL spectrum results are shown in FIG. 7 (b). In addition, the CIE color coordinates were measured using a spectrophotometer (Darsapro-5000, PSI Co. Ltd), and the results are shown in FIG. 7 (c) and Table 4. At this time, the CIE color coordinates define a color of an object as a chromaticity coordinate, and a chart having a plane in which the brightness of the object is constant (International Commission on Illumination (CIE) 1931 color coordiantes).

Thickness (㎛) CIE x CIE y Example 12 6.1 0.32 0.27 Example 13 8.7 0.35 0.33 Example 14 10.5 0.39 0.37 Example 15 14.7 0.43 0.43

According to Fig. 7 (b), the nanohybrid thin film prepared in Example 12 exhibits a strong peak in the blue light region at about 450 nm and a relatively low EL in the yellow light region in the vicinity of about 560 nm to 600 nm It can be confirmed that it represents the strength. On the contrary, the nanohybrid thin film prepared in Example 15 exhibits low EL intensity in the blue light region, but relatively high EL intensity in the yellow light series region.

As a result, it can be seen that as the thickness of the nanohybrid thin film according to the present invention increases, the absorption rate of blue light increases and light of yellow series is emitted.

According to FIG. 7 (c), as the thickness of the nanohybrid thin film increases, the color coordinate shifts from the blue region to the yellow region. This is because the downward conversion of the quantum dots included in the nanohybrid thin film conversion effect caused the blue light to be absorbed and the yellow light to increase.

Experimental Example  5. Characterization of nanohybrid thin films 3

The nanohybrid thin films prepared in Examples 12 to 15 were set as a remote type at a distance of about 600 mu m on a blue LED having an emission efficiency of 14 lm / W at 60 mA Corelated color temperature (K), luminous efficiency (LE, lm / W) and color rendering index (CRI, R _a ) were measured using a spectrophotometer (Darsapro-5000, PSI Co. Ltd.) And the results are shown in Table 5 below.

Here, the correlated color temperature refers to a color temperature corresponding to a point on the nearest perfect filler body trajectory nearest to a point indicating chromaticity coordinates of the sample light source, and the color rendering index is a value obtained by dividing the reference light source Is an index indicating the degree of fit with the perception of the light when illuminated.

Thickness (㎛) LE (lm / W) CCT (K) CRI (Ra) Example 12 6.1 32 6857 80 Example 13 8.7 40 4610 71 Example 14 10.5 49 3803 64 Example 15 14.7 46 3258 59

According to Table 5, as the thickness of the nanohybrid thin film increases, the correlated color temperature decreases. As a result, as the thickness of the nanohybrid thin film increases, the color of the light passing through the thin film becomes closer to the yellow color . In addition, the color rendering index decreases proportionally with increasing thickness, which shows that the coloring power of the light passing through the thin film becomes lower as the thickness of the thin film becomes thicker. Also, in Table 5, the LE emission intensity is as low as 32 lm / W in the case of Example 12 in which the thickness is thin, and is superior in the case of Example 14 in which the thickness is 10.5 占 퐉.

Experimental Example  6. Uniformity Analysis of Nano Hybrid Thin Films

The nanohybrid thin film in the light emitting device package manufactured in Example 16 was divided into nine equal parts as shown in FIG. 9, and the thickness of the thin film was observed with a field emission scanning electron microscope (FE-SEM, JSM 7401F) And Table 6. The PL wavelength intensity of each thin film was measured, and the results are shown in FIG.

a b c d e f g h i thickness
(탆) 38.1 39.0 38.1 38.4 38.2 38.8 37.1 37.9 38.1

10 and Table 6, it can be seen that the thickness of the nanohybrid thin film according to the present invention is 38 +/- 1 mu m, which is generally uniform throughout the entire portion.

11 (a) and 11 (b), it can be confirmed that the PL emission intensity of the pieces of the nanohybrid thin film exhibits a peak having a similar relative intensity from about 2000 to 2300 at a wavelength of about 580 nm. Thus, it can be seen that the nanohybrid thin film produced according to the present invention exhibits excellent uniformity.

Experimental Example  7. Cross-sectional view of nanohybrid thin film in light emitting device package

In order to observe the cross section of the nanohybrid thin film in the light emitting device package manufactured in Example 16, the cross section of the nanohybrid thin film was measured using a transmission electron microscope (TEM, JEM-4010, 400 kV) 10. 10, the thickness of the nanohybrid thin film was confirmed.

Experimental Example  8. Light emitting device package Light stability  evaluation

In order to evaluate the stability of the light emitting device package prepared in Production Example 1 and Production Example 2, LE emission intensity was measured using a spectrophotometer (Darsapro-5000, PSI Co. Ltd) under a current of 60 mA for 10 minutes The results are shown in FIG. 13, the CIE color coordinates are shown in FIG. 14, and the results are shown in FIG.

13 (a) and 13 (b), it can be seen that the light emitting device package of Production Example 1 exhibits less change in the light emission intensity of the yellow region after lapse of 10 minutes than that of the light emitting device package of Production Example 2. 14 (a) and 14 (b), it can be seen that the degree of movement of the color coordinates after 10 minutes has passed is smaller than that of Production Example 1 in Production Example 1. 15 (a) and 15 (b), it can be seen that the luminous efficiency of the light-emitting device package of Production Example 1 is less changed with time than that of Production Example 2. FIG.

As a result, it can be seen that the remote type light emitting device package exhibits better light stability than the cup type light emitting device package.

Claims (23)

A core comprising a compound satisfying the following formula (1);
A shell comprising ZnS; And
A quantum dot of a core / shell structure characterized by comprising a ligand polymer;
[Chemical Formula 1]
AgIn _x S _{(3x + 1) / 2}
In Formula 1, x is a rational number satisfying 3? X? 6.
The quantum dot of claim 1, wherein the core has an average particle diameter of 1 nm to 10 nm.
The quantum dot of claim 1, wherein the shell has an average thickness of 1 nm to 5 nm.
The method of claim 1, wherein the ligand polymer is selected from the group consisting of octanethiol, dodecanethiol, heptanethiol, 8- (9H-carbazol-9-yl) (E) -2- (4-morpholino) ethyl] -2-mercaptopropanoate and 3 {2,5-bis [ Wherein the core / shell structure comprises at least one member selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, Of the quantum dot.
The quantum dot of claim 1, wherein the quantum dot has an emission wavelength of 500 to 600 nm and an absorption wavelength of 300 to 550 nm.
A quantum dot of the core / shell structure of any one of claims 1 to 5; And a thermoplastic resin.
The thermoplastic resin composition according to claim 6, wherein the thermoplastic resin is selected from the group consisting of polymethyl methacrylate (PMMA), methyl methacrylate-styrene-acrylonitrile-butadiene copolymer resin (MABS), polystyrene, polyester and acrylonitrile-butadiene- And a copolymer resin (ABS).
The nanohybrid thin film according to claim 6, wherein the quantum dot is contained in an amount of 10 to 150 parts by weight based on 100 parts by weight of the thermoplastic resin.
The nanohybrid thin film according to claim 6, wherein the nanohybrid thin film has an average thickness of 5 to 40 mu m.
The nanohybrid thin film according to claim 6, wherein the nanohybrid thin film is introduced into a blue LED light source and has a PL wavelength of 500 to 600 nm.
7. The method according to claim 6, wherein the nanofiber hybrid thin film is introduced into a blue LED light source and has a transmittance of 50% to 80%, a color coordinate CIE X of 0.30 to 0.45, a CIE Y of 0.25 to 0.45, and a corelated color temperature of 2500K to 7000K.
7. The method of claim 6, wherein the nano hybrid thin film has a color rendering index (CRI) 90. &Lt; / RTI &gt;
Preparing a substrate comprising a soluble polymer coating layer;
A mixed solution obtained by mixing a quantum dot of any one of claims 1 to 5 with a polymer matrix solution is electrosprayed on one surface of the soluble polymer coating layer to form a nanohybrid coating layer, Two-step surface treatment; And
A third step of dissolving the soluble polymer coating layer to separate the nanohybrid thin film;
Hybrid thin film according to claim 1,
14. The method of claim 13, wherein the polymer matrix solution comprises a thermoplastic resin and a solvent,
The thermoplastic resin may be selected from the group consisting of polymethylmethacrylate (PMMA), methylmethacrylate-styrene-acrylonitrile-butadiene copolymer resin (MABS), polystyrene, polyester and acrylonitrile-butadiene- , &Lt; / RTI &gt;
Wherein the solvent comprises at least one selected from the group consisting of water, alcohol, acetone, ethanol, methanol, dimethylformamide, toluene, tetrahydrofuran, n-hexane and demethyl sulfoxide (DMSO).
15. The method according to claim 14, wherein the polymer matrix solution comprises 0.5 to 2 parts by weight of the thermoplastic resin per 100 parts by weight of the solvent.
14. The method of claim 13, wherein the electrospray is performed by electrospraying at a distance of 15 cm to 25 cm from the surface of the soluble polymer coating layer under an electric field of 12 to 18 kVcm ^-1 .
14. The method of claim 13, wherein the quantum dots
The precursor solution and the indium precursor solution are mixed at 1 atm and 10 to 35 ° C, heated to 80 to 100 ° C under a nitrogen atmosphere where moisture and oxygen are removed, reacted with a ligand forming agent, 2-1 &lt; / RTI &gt; step of forming the core by injection at a temperature of 200 DEG C;
A step 2-2 in which the zinc precursor solution and the sulfur precursor solution are reacted at 150 to 260 ° C for 1 to 3 hours to grow a shell in the mixed solution in which the core is formed in the step 1; And
Separating the quantum dots in the mixed solution of the two steps;
The method of manufacturing a nanohybrid thin film according to claim 1,
18. The method according to claim 17, wherein the silver precursor solution, the indium precursor solution, and the sulfur precursor solution in the 2-1 step are contained in a molar ratio of 1: 3 to 6: 5 to 9 .
The method of claim 17, wherein the sulfur precursor solution in step 1 comprises sulfur and a solvent, wherein the solvent is selected from the group consisting of oleic acid, trioctylphosphine oxide (TOPO), triphenylphosphine , TPP), trioctylphosphine (TOP), and C ₃ to C ₁₈ alkyl amines.
18. The method of claim 17, wherein the silver precursor solution, the zinc precursor solution, and the sulfur precursor solution in step 2-2 are mixed at a molar ratio of 1: 3 to 6: 5 to 9.
A light emitting element;
A package body on which the light emitting device is mounted; And
The nanohybrid thin film as set forth in claim 17, which is located above the package body and changes the wavelength of light emitted from the light emitting device.
Emitting device package.
A white light emitting diode comprising the nanohybrid thin film of claim 6.
A lighting comprising the nanohybrid thin film of claim 6.

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