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KR101665450B1 - A light emitting element having quantum dot of indium-gallium metal nitride and a manufacturing method of the same, and a light emitting device using the same - Google Patents

A light emitting element having quantum dot of indium-gallium metal nitride and a manufacturing method of the same, and a light emitting device using the same Download PDF

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KR101665450B1
KR101665450B1 KR1020150076292A KR20150076292A KR101665450B1 KR 101665450 B1 KR101665450 B1 KR 101665450B1 KR 1020150076292 A KR1020150076292 A KR 1020150076292A KR 20150076292 A KR20150076292 A KR 20150076292A KR 101665450 B1 KR101665450 B1 KR 101665450B1
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South Korea
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light emitting
emitting device
quantum dot
indium
electrode
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KR1020150076292A
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Korean (ko)
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박종남
서요한
주진환
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울산과학기술원
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0062—Processes for devices with an active region comprising only III-V compounds
    • H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
    • H01L2924/12041—LED

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention relates to a light emitting device comprising a quantum dot of indium gallium metal nitride represented by the following Chemical Formula 1, a method for producing the same, and a light emitting device using the same. More specifically, the present invention relates to a light emitting device having excellent light- To a light emitting device including a quantum dot of indium gallium metal nitride formed by incorporating a quantum dot which can be used in the form of a dispersion into an emitting layer, a method of manufacturing the same, and a light emitting device using the same. Since the quantum dots of the indium gallium nitride contained in the quantum dot light emitting device according to the present invention have high stability and excellent luminescence efficiency without toxicity, the quantum dot light emitting device of the present invention including the quantum dots can pass various environmental regulations In addition, it can be used in the form of a colloidal dispersion, and can be formed on a substrate by an ink process without a conventional high-temperature deposition process. Accordingly, the present invention can be applied also to a flexible substrate having low heat resistance, so that a light emitting device having flexibility can be manufactured by a relatively simple process.
[Chemical Formula 1]
In x Ga 1 - x N
(In the above formula (1), x has a range of 0? X? 1.)

Description

FIELD OF THE INVENTION [0001] The present invention relates to a light emitting device comprising a quantum dot of indium gallium-based metal nitride, a method of manufacturing the same, and a light emitting device using the same. BACKGROUND ART THE SAME}

The present invention relates to a light emitting device comprising a quantum dot of indium gallium metal nitride, a method of manufacturing the same, and a light emitting device using the same, and more particularly, to a light emitting device having excellent light emitting properties without toxicity, A quantum dot of indium gallium-based metal nitride, a method of manufacturing the same, and a light emitting device using the same.

A quantum dot is a semiconductor crystal material having a diameter of several to several tens of nanometers or less. It can control various colors of light emitted according to the size of a quantum dot, and an absorption wavelength is in a very wide range from a short wavelength to a long wavelength , The emission wavelength has a narrow range and has a higher color index than that of the organic material. Particularly, many researchers are actively researching in the display field.

The method of applying such a quantum dot to a display or illumination can be roughly classified into a fluorescence (PL) method which emits light by LED and an electroluminescence (EL) method which emits light by electrically exciting. ) Method is referred to as a quantum dot light emitting element (QD-LED). Since the quantum dot light emitting device (QD-LED) basically operates in the same way as the organic light emitting device OLED, only the material of the light emitting layer can be replaced with a quantum dot in place of the organic light emitting material. In view of the advantage of being able to use it as it is, it is getting attention as a next generation technology.

However, the cadmium-based quantum dot light-emitting device (Korean Patent Laid-Open No. 2006-0101184) using the currently used cadmium-based quantum dots has a very low utility in accordance with the global trend in which various environmental regulations are strengthened due to toxicity due to cadmium, In fact, it is not meaningful as a next-generation technology that replaces the conventional OLED. In addition, the InP quantum dot light emitting device using InP quantum dots has a considerably low stability of the InP quantum dots itself, and therefore it is necessary to add coating or doping of the shell to the surface of the quantum dots. Therefore, There is a drawback that it costs a lot.

Meanwhile, in recent years, demand for a flexible display has increased rapidly. In order to manufacture a flexible display, a process of forming a light emitting device on a flexible substrate must be accompanied. However, since the flexible substrate is a plastic material having poor heat resistance, it is difficult to apply the conventional high-temperature deposition process, which has been a major obstacle to manufacturing a flexible display.

Therefore, there is an urgent need to develop a light emitting device using quantum dots capable of being formed on a flexible substrate without toxicity, high stability and excellent luminous efficiency, simple manufacturing process, and high-temperature deposition process.

Korea Patent Publication No. 2006-0101184

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems occurring in the prior art,

Indium gallium nitride, which can be formed on a flexible substrate without a high temperature deposition process, can be applied in the form of a colloidal dispersion due to its high stability and excellent luminous efficiency without toxicity, simple manufacturing process and excellent dispersibility. And to provide a light emitting device using the quantum dot, a method of manufacturing the same, and a light emitting device using the light emitting device.

In order to achieve the object of the present invention, the present invention provides a quantum dot light emitting device comprising a light emitting layer containing a quantum dot of a metal nitride represented by the following Chemical Formula 1 between an anode and a cathode.

[Chemical Formula 1]

In x Ga 1-x N

(In the above formula (1), x has a range of 0? X? 1.)

The light emitting layer may contain the quantum dot in the form of a colloidal dispersion.

The solvent of the colloidal dispersion is not limited thereto, but it may be an organic solvent, and the organic solvent may be hexane, toluene, benzene, octane, chloroform, chlorobenzene, tetrahydrofuran (THF). At least one selected from the group consisting of pentane, heptane, decane, methylene chloride, 1,4-dioxane, diethyl ether, cyclohexane and dichlorobenzene But are not limited thereto.

X in the above formula (1) may have a range of 0.01? X? 0.5.

The cathode or the anode may be laminated on a flexible substrate and the flexible substrate may be formed of a material selected from the group consisting of polyethylene terephthalate (PET), polyisoprene (PI), polyethylene naphthalate (PEN), poly Polyether sulfone (PES), and polycarbonate (PC, PolyCarbonate).

And at least one selected from the group consisting of an electron injection layer, an electron transport layer, and a hole blocking layer may further be interposed between the cathode and the light emitting layer.

A hole injecting layer, a hole transporting layer, and an electron blocking layer may be additionally provided between the anode and the light emitting layer.

According to another aspect of the present invention, there is provided a light emitting device including the quantum dot light emitting device.

According to another aspect of the present invention, there is provided a method of manufacturing a light emitting device, comprising: forming a first electrode on a substrate; forming a light emitting layer containing quantum dots of the metal nitride represented by Formula 1 on the first electrode; And forming a second electrode on the light emitting layer.

The light emitting layer may be formed by a method such as a drop-coating method, a spin coating method, a die coating method, a blade coating method, a roll coating method, an inkjet printing method, a printing method, a spray coating method, May be formed on the first electrode by one or more methods selected from the group consisting of transfer printing and curtain coating.

The substrate is made of polyethylene terephthalate (PET), polyisoprene (PI), polyethylene naphthalate (PEN), polyether sulfone (PES), and polycarbonate And may be one or more flexible substrates selected from the group.

Since the quantum dots of the indium gallium nitride contained in the quantum dot light emitting device according to the present invention have high stability and excellent luminescence efficiency without toxicity, the quantum dot light emitting device of the present invention including the quantum dots can pass various environmental regulations In addition, it can be used in the form of a colloidal dispersion, and can be formed on a substrate by an ink process without a conventional high-temperature deposition process. Accordingly, the present invention can be applied also to a flexible substrate having low heat resistance, so that a light emitting device having flexibility can be manufactured by a relatively simple process.

1 is a graph showing XRD characteristics of In x Ga 1 - x N quantum dots (CQDs) prepared in the present invention.
FIG. 2 is a graph showing bandgap characteristics of In x Ga 1 - x N quantum dots (CQDs) prepared in the present invention.
FIG. 3 is a graph showing the characteristics of PL (Photoluminescence) according to the composition and temperature of In x Ga 1 - x N prepared in the present invention.
4 is a graph showing X-ray absorption spectroscopy (XAFS) measurement results of the In x Ga 1 - x N quantum dots (CQDs) prepared in the present invention.
FIG. 5 is a graph showing the metal quantity characteristics of the present invention. FIG.
6 is a graph showing XPS In3d binding spectra characteristics of In x Ga 1 - x N prepared in the present invention.
7 is a TEM image of In x Ga 1 - x N quantum dots (CQDs) prepared in the present invention.
8 is a graph showing PL-QY (Photoluminescence Quantum yield) characteristics of In x Ga 1 - x N prepared in the present invention.
9 is a graph showing the characteristics of PL (Photoluminescence) according to the amount of oleic acid of In x Ga 1 - x N prepared in the present invention.
10 is a graph showing the characteristics of PL (Photoluminescence) according to the output of In x Ga 1 - x N produced in the present invention.
11 is a graph showing reduction characteristics of PL (Photoluminescence) according to the decay time of In x Ga 1 - x N prepared in the present invention.
12 is a graph showing X-ray absorption spectroscopy (XAS) characteristics of In x Ga 1 - x N prepared in the present invention.
13 is a graph showing energy level characteristics of In x Ga 1 - x N according to the ultraviolet electron spectroscopy (UPS) analysis of the present invention.
14 is a graph comparing PL-QY (Photoluminescence Quantum yield) characteristics of In x Ga 1 - x N quantum dots (CQDs) prepared in the present invention.
Fig. 15 is a photograph showing the difference in solubility between the In x Ga 1 - x N quantum dots produced in the present invention and the commercially available comparative example.
16 is a photograph showing the difference in luminescence characteristics between the In x Ga 1 - x N quantum dots produced in the present invention and the commercially available comparative example.
17 is a graph showing bandgap characteristics of another In x Ga 1 - x N quantum dot prepared in the present invention.
18 is a schematic cross-sectional view of a layered structure of a quantum dot light emitting device according to an embodiment of the present invention.
19 is a schematic cross-sectional view of a layered structure of a quantum dot light emitting device according to another embodiment of the present invention.
20 is a schematic cross-sectional view of a layered structure of a quantum dot light emitting device according to another embodiment of the present invention.
21 shows energy diagrams of the electron injection layer (ZnO), the light emitting layer (InGaN CQD) and the hole injection layer (HIL) materials of Production Examples 1 to 3 of the present invention (Device A: Production Example 1, Device B: 2, Device C: Production Example 3).
22 (a) shows current intensities according to the voltages of Production Examples 1 to 3 of the present invention (Device A: Production Example 1, Device B: Production Example 2, Device C: Production Example 3).
22 (b) shows the luminance according to the voltages of Production Examples 1 to 3 of the present invention (Device A: Production Example 1, Device B: Production Example 2, Device C: Production Example 3).
23 shows the spectra of EL (electroluminescence) and PL (photoluminescence) according to the wavelength of the light emitting device manufactured in the present invention.
Fig. 24 is a photograph showing whether or not the light emitting device manufactured in the present invention actually emits light when mounted on a light emitting device. Fig.

The present invention provides a quantum dot light emitting device comprising a light emitting layer containing a quantum dot of a metal nitride represented by the following Chemical Formula 1 between an anode and a cathode.

[Chemical Formula 1]

In x Ga 1-x N

(In the above formula (1), x has a range of 0? X? 1.)

The light emitting layer may contain the quantum dot in the form of a colloidal dispersion. This is because the dispersibility of the quantum dots represented by Formula 1 is excellent. When the quantum dots are dispersed in the organic solvent, the dispersion state can be maintained for at least 3 months.

The organic solvent of the colloidal dispersion of the quantum dots represented by Formula 1 may be hexane, toluene, benzene, octane, chloroform, chlorobenzene, tetrahydrofuran (THF). At least one selected from the group consisting of pentane, heptane, decane, methylene chloride, 1,4-dioxane, diethyl ether, cyclohexane and dichlorobenzene But are not limited to,

The quantum dot according to the present invention can be produced by adding a precursor of indium, a precursor of gallium and a surfactant to a solvent to prepare a mixture, and then introducing a nitrogen source thereto to cause a thermal decomposition reaction. The composition of the quantum dots of the In x Ga 1 - x N metal nitride can be controlled by controlling the reaction mole number of the indium precursor, the gallium precursor, the surfactant and the solvent.

The indium precursor may be an organic indium compound, but is not limited to indium (III) acetylacetonate, indium (III) chloride, indium (III) acetate, Indium Myristate, Indium Myristate Acetate, and Indium Myristate 2, which are known to those skilled in the art, such as indium myristate acetate, indium myristate acetate, Acetate (Indium (III) Myristate 2 Acetate).

The gallium precursor may be an organic gallium compound, but is not limited to gallium (III) acetylacetonate, Gallium (III) acetate, Gallium (III) chloride, , Triethyl gallium, trimethyl gallium, Alkyl Gallium, Aryl Gallium, Gallium (III) Myristate, Gallium (III) Myristate Acetate) and gallium myristate 2 acetate (Gallium (III) Myristate 2 Acetate).

The surfactant may be, but is not limited to, a carboxylic acid-based compound, a phosphonic acid-based compound, or a mixture of the two compounds, and the carboxylic acid-based compound may be selected from the group consisting of oleic acid, The phosphonic acid-based compound may be at least one selected from the group consisting of palmitic acid, paletic acid, stearic acid, linoleic acid, myristic aicd and lauric acid, Hexylphosphonic acid, octadecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, decylphosphonic acid, octylphosphonic acid, octadecylphosphonic acid, octadecylphosphonic acid, octadecylphosphonic acid, And Butylphosphonic acid. [0033] The term " anionic surfactant "

Such solvents include, but are not limited to, 2,6,10,15,19,23-hexamethyltetracosane (Squalane), 1-octadecene (ODE), trioctylamine (TOA), tributylphosphine oxide, octadecene, octadecylamine, hexane, octane, trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO), or a mixture of two or more thereof.

The solvent may be 2 to 10 mL per mol of the sum of the molar number of the indium precursor and the molar amount of the gallium precursor. If the content of the solvent is less than the above range, there is a problem in the stability of the precursor solution, and if it is more than the above range, the reaction does not proceed properly.

The pyrolysis reaction is not limited thereto, but may be a hot injection method or a heating up method. The high-temperature injection and heating method has the advantage that the quantum dot can be manufactured at a high temperature in a short time.

Specifically, the hot injection may be performed by heating the mixture of the indium precursor, gallium precursor, surfactant, and solvent in an argon, nitrogen, ammonia, or vacuum atmosphere to a temperature of 150 to 400 ° C., And then pyrolysis is carried out by hot injection at a temperature of 400 ° C.

When the nitrogen source is injected at a high temperature, it may be mixed with a solvent and injected. The solvent may include, but is not limited to, 2,6,10,15,19,23-hexamethyltetracosane (Squalane), octadecene (ODE), trioctylamine TOA), tributylphosphine, tributylphosphine oxide, trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO), or a mixture of two or more thereof.

Specifically, the heating up method is a method in which a nitrogen source is added to a mixture of the indium precursor, the gallium precursor, the surfactant, and the solvent, and then pyrolysis is performed at a temperature of 150 to 400 ° C in an argon, nitrogen, ammonia, It will proceed.

After the quantum dot is prepared by the above-described method, an anti-solvent may be added to precipitate the quantum dot. As the anti-solvent, any one or more selected from the group consisting of methanol, ethanol, propanol, butanol, and acetone may be used.

Further, by dispersing the precipitated quantum dots in an organic solvent, quantum dots of a colloid can be produced.

Since the quantum dot of the present invention can be used in the form of a colloidal dispersion, it is possible to use inkjet printing (Inkjet printing) or transfer printing ) Method and a pixel pattern of 1 or less can be formed in the case of the transfer printing, it is possible to realize an ultra-high resolution display which is difficult to achieve with the conventional display. In addition, since the quantum dots in the form of a colloidal dispersion can be formed on a substrate without a high-temperature deposition process, they can be easily applied onto a flexible substrate having low heat resistance. In addition, since the colloidal mass production method can produce quantum dots at a low cost, the cost can be reduced by using the quantum dots according to the present invention. That is, the quantum dot of the present invention, which can be used in the form of a colloidal dispersion, can achieve both softening, thinning, lightening, high resolution and low cost of a light emitting device or a light emitting device.

The quantum dots of the metal nitride can be relatively easily changed in composition (In x Ga 1 - x N, where x is 0? X? 1) by controlling the input ratio of the metal precursor used in the manufacturing process. Similarly, since the light emitting layer has various light emitting properties depending on the composition, a light emitting device having various colors and brightness can be manufactured by using such properties. In addition, since the quantum dots of the metal nitride are not toxic because a heavy metal is not used, they can pass various environmental regulations.

In the above formula (1), x is preferably, but not limited to, in the range of 0.01? X? 0.5. The smaller the proportion of indium in the composition ratio of indium and gallium, the lower the defect level of the quantum dots and the higher the luminous efficiency.

Further, the cathode 20 or the anode 30 may be laminated on a glass substrate, a transparent substrate, or a flexible substrate. As described above, the quantum dots represented by Formula 1 contained in the light emitting layer 10 can be applied in the form of a colloidal dispersion and thus can be applied to a flexible substrate because a high temperature deposition process is not required. The material of the flexible substrate may include, but is not limited to, polyethylene terephthalate (PET), polyisoprene (PI), polyethylene naphthalate (PEN), polyether sulfone (PES) And may be made of at least one selected from the group consisting of polycarbonate (PC) and poly carbonate, preferably polyethylene terephthalate (PET).

Hereinafter, the structure of the light emitting device of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 18 is a schematic cross-sectional view of a layered structure of a quantum dot light emitting device according to an embodiment of the present invention, FIG. 19 is a schematic sectional view of a layered structure of a quantum dot light emitting device according to another embodiment of the present invention, Sectional view of a layered structure of a quantum dot light emitting device according to another embodiment.

18, the quantum dot light emitting device of the present invention includes a cathode 20 formed on a substrate 40, a quantum dot light emitting layer 10 formed on the cathode 20, and a cathode 30 formed on the quantum dot light emitting layer 10 .

The quantum dot light emitting layer 10 of the present invention is a layer in which electrons and holes are recombined to emit light, and the light emitting portion may be within the layer of the light emitting layer or may be the interface with the adjacent layer.

The thickness of the quantum dot light-emitting layer 10 can be controlled in consideration of the uniformity of the film, the prevention of application of unnecessary high voltage in light emission, or the improvement of the stability of the luminescent color with respect to the driving current, and the like. Mu] m, preferably in the range of 2 nm to 200 nm, more preferably in the range of 5 nm to 100 nm.

In addition, the quantum dot luminescent layer 10 may be formed by coating the quantum dots represented by the above formula (1) on the adjacent layer. Any method that can be used for forming the layer may be used, and the vacuum evaporation method, A coating method such as a drop coating method, a spin coating method, a casting method, a die coating method, a blade coating method, a roll coating method, an inkjet printing method, a printing method, a spray coating method, a curtain coating method, a knife coating, And a Langmuir Blodgett method may be used. Preferably, a method such as a drop coating method, a spin coating method, a die coating method, a blade coating method, a roll coating method, an inkjet printing method, a printing method, Coating method, transfer printing or curtain coating method may be used.

The cathode 20 may be formed of a material selected from the group consisting of ITO, Ca, Ba, Ca / Al, LiF / Ca, LiF / Al, BaF 2 / Al, BaF 2 / Ca / Al, Al, Mg, CsF / 3 / Al, Au / Mg, or Ag / Mg.

The anode 30 is made of indium tin oxide (ITO), indium zinc oxide (IZO), indium copper oxide (ICO), Cd / ZnO, SnO 2 , In 2 O 3 , F / SnO 2 , In / SnO 2 , Ga / ZnO, MoO 3 , Ag / MoO 3 (Ni), platinum (Pt), gold (Au), silver (Ag), iridium (Ir), or carbon nanotubes Or a metal layer. In addition, the anode 30 can be a continuous film, or it can be composed of microwires or nanowires that can be patterned or distributed in any manner.

The quantum dot light emitting device 10 of the present invention may include an electron injection layer 50 (EIL: Electron Injection Layer) between the cathode 20 and the quantum dot light emitting layer 10 as shown in FIG. 18 And a hole injection layer 60 between the anode 30 and the quantum dot luminescent layer 10.

19, the quantum dot light emitting device of the present invention includes an electron injection layer 50 and an electron transport layer 51 (ETL) between the cathode 20 and the quantum dot luminescent layer 10, An electron transport layer 51 and a hole blocking layer 52 may be formed on the cathode 20 in this order. In this case, the electron injection layer 50, the electron transport layer 51, and the hole blocking layer 52 .

However, the light emitting device of the present invention is formed by stacking only one layer of the electron injecting layer 50, the electron transporting layer 51 and the hole blocking layer 52 on the cathode 20, Or a structure in which two layers are stacked. It is preferable that the electron injection layer 50 and the electron transport layer 51 are stacked in this order on the cathode 20 in the structure in which the electron injection layer 50 and the electron transport layer 51 are laminated. When the hole blocking layer 52 is laminated together with the electron injecting layer 50 or the electron transporting layer 51, the hole blocking layer 52 is laminated on the electron injecting layer 50 or the electron transporting layer 51, .

19, a quantum dot light emitting device according to the present invention includes a hole injection layer 60 (HIL: Hole Injection Layer), a hole injection layer A hole transport layer 61 and an electron blocking layer 62. The electron blocking layer 62 and the hole transporting layer 62 may be formed on the quantum dot light emitting layer 10, 61 and the hole injection layer 60 may be stacked in this order.

However, FIG. 19 shows only one embodiment. In the light emitting device of the present invention, only one of the electron blocking layer 62, the hole transport layer 61, and the hole injection layer 60 is formed on the quantum dot light emitting layer 10 Or may have a structure in which two layers are stacked. It is preferable that the hole transport layer 61 and the hole injection layer 60 are stacked in this order on the quantum dot light emitting layer 10 in the structure in which the hole injection layer 60 and the hole transport layer 61 are laminated. When the electron blocking layer 62 is laminated together with the hole injecting layer 60 or the hole transporting layer 61, the electron blocking layer 62 is laminated on the bottom of the hole injecting layer 60 or the hole transporting layer 61, May be desirable.

18 and 19, the cathode 20 may be formed on the substrate 40 to form the light emitting device. However, as shown in FIG. 20, the anode 40 may be formed on the substrate 40, 30 to form the light emitting device of the present invention. In this case, a light emitting element having a reverse structure to the light emitting element forming the cathode 20 is formed on the substrate 40.

The electron injection layer 50 serves to facilitate electron injection from the cathode 20 toward the quantum dot luminescent layer 10 and the electron transport layer 50 transmits electrons from the cathode 20 to the quantum dot luminescent layer 10. [ It plays a role. In addition, the hole blocking layer 50 serves to prevent diffusion of holes to the electron transport layer 51 or the electron injection layer 50 without interfering with the flow of electrons.

The electron transport layer 51 or the electron injection layer 50 may be formed of a material selected from the group consisting of TiO 2 , ZnO, SiO 2 , SnO 2 , WO 3 , Ta 2 O 3 , BaTiO 3 , BaZrO 3 , ZrO 2 , HfO 2 , Al 2 O 3 , Y 2 O 3 , ZrSiO 4 , SnO 2 , TPBI or TAZ, preferably ZnO.

The material of the hole blocking layer 52 may be any material that can block holes without interrupting the flow of electrons. Examples of the material include (8-hydroxyquinolinolato) lithium (Liq), bis (BAlq), bathocuproine (BCP), LiF, or any combination of these. ≪ RTI ID = 0.0 > In addition, the hole blocking layer 52 may be formed by a conventional film forming method, and may be formed by a spin-coating method or the like, although it is not limited thereto.

The hole injection layer 50 facilitates injection of holes from the anode 30 toward the quantum dot light emitting layer 10 and the hole transport layer 61 transmits holes from the anode 30 to the quantum dot light emitting layer 10. [ . The electron blocking layer 62 serves to prevent electrons from diffusing into the hole transport layer 61 or the hole injection layer 60 without interfering with the flow of the holes.

Materials constituting the hole injection layer (HIL) or the hole transport layer (HTL) include, but are not limited to, poly (3,4-ethylenedioxythiophene) (PEDOT: PSS), poly- Poly (9,9-octylfluorene), poly (spiro-fluorene), TPD, NPB, CBP, HAT-CN, tris (3-methylphenyl) (4-methylphenyl) phenylamine) triphenylamine (m-MTDATA), poly (9,9'-dioctylfluorene- (MEH-PPV), poly [2-methoxy-5- (3 ', 7'-dimethyloctyloxy) -1,4- phenylenevinylene] (MDMO-PPV), tetrafluoroethylene-tetrahydro-dicyano-quinolyl nodi methane (F4-TCNQ), arylamine (arylamine), NiO, MoO 3 , Cr 2 O 3, Bi 2 O 3, ZnO, MoS 2 , GaN, or any combination thereof.

The present invention provides a light emitting device comprising the quantum dot light emitting element. The light-emitting device is an all-in-one device including the light-emitting device according to the present invention, and may be any electronic device or a lighting device that uses a light-emitting device such as an image display device (display device).

The present invention also provides a method of manufacturing a light emitting device, comprising the steps of forming a first electrode on a substrate upper portion 40, forming a light emitting layer 10 containing a quantum dot of a metal nitride represented by the following Chemical Formula 1 on the first electrode, And forming a second electrode on the first electrode (10).

[Chemical Formula 1]

In x Ga 1 - x N

(In the above formula (1), x has a range of 0? X? 1.)

When the light emitting layer 10 is prepared in the form of a colloidal dispersion, the light emitting layer may be formed by a spin coating method, a die coating method, a blade coating method, a roll coating method, May be formed on the first electrode by one or more methods selected from the group consisting of an ink jet printing method, a printing method, a spray coating method, a knife coating method, a transfer printing method and a curtain coating method.

The methods listed above are suitable for forming a film on a liquid substrate without a heating process, and are suitable for manufacturing a light emitting layer on a flexible substrate having low heat resistance. Accordingly, the indium gallium-based quantum dots according to the present invention having excellent dispersibility can be prepared in the form of a liquid colloidal dispersion. However, in the case of a quantum dot having a low dispersibility, a powder not in the form of a colloidal dispersion It is very difficult to coat with the above methods, and a high temperature deposition process is essential.

The first electrode may be a cathode 20 or an anode 30 and when the first electrode is a cathode 20, the second electrode is preferably an anode 30, In the case of the anode 30, the second electrode is preferably the cathode 20.

Further layers may be formed between the first electrode and the light emitting layer 10 and between the light emitting layer 10 and the second electrode in relation to the injection, transport and blocking of electrons or holes, The order of the layers and constituent materials are the same as those described for the light emitting element.

Further, in the above manufacturing method, the substrate 40 may be a commonly used glass substrate, a transparent substrate, or a flexible substrate, and the description of the flexible substrate is the same as that described for the light emitting device.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are on a mass basis unless otherwise specified.

< Example  - Quantum dot  Synthesis>

1. Reagents used

In the examples of the present invention, a mixture of 1-octadecene (ODE, 90%), oleic acid (OA, 90%), Indium (III) acetylacetonate (In (acac) 3 , 99.99%), Gallium (III) acetylacetonate acac) 3, 99.99%), hexamethyldisilazane (HMDS, 99.9%), Tris (trimethylsilyl) amine (TMSA, 99.9%), N, N-Bis (trimethylsilyl) methylamine (TMSMA, 99.9%) , and Ammonia (99.9%) a And all reagents were purchased from Sigma-aldrich

2. Hot Injection  Method Qdot  synthesis( Example  1 to 15)

Synthesis was carried out based on pyrolysis synthesis method using hot injection method and Schlenk line was used to block and remove water and oxygen.

In order to gallium precursors Ga (acac) 3, was used for In (acac) 3 as indium precursor, to adjust the x of the In x Ga 1-x N In (acac) 3 to the x mol, Ga (acac) 3 (1-x) mol, 4.52 mL of ODE, and 0.6 to 2.2 mmol of OA to synthesize a metal oleate solution. The reaction temperature was 300 ° C and the temperature was increased by 10 ° C per minute.

When the temperature of the metal olefinsate solution reached 300 ° C, a solution containing 0.9 mL of TOP and a nitrogen source was rapidly injected into the metal olefinsate solution using a syringe (hot injection), and the reaction was continued for 30 minutes The synthesis of the quantum dots ends.

After the temperature of the solution was lowered, the quantum dots were precipitated using methanol as an antisolvent, and the quantum dots were dispersed in hexane.

Examples of the quantum dots of various indium gallium metal nitrides according to the above manufacturing method are shown in Table 1 below by adjusting the composition ratios of indium and gallium (In x Ga 1 - x N), types of nitrogen source and their amounts, and amounts of OA input Respectively. Examples 14 and 15 use ammonia gas bubbled as a nitrogen source.

Quantum dot composition (x) value (1-x) value Type of nitrogen source and input (mmol) OA input
(mmol) Example 1 GaN 0 One HMDS, 0.5 1.2 Example 2 In 0 .25 Ga 0 .75 N 0.25 0.75 HMDS, 0.5 1.2 Example 3 In 0 .5 Ga 0 .5 N 0.5 0.5 HMDS, 0.5 1.2 Example 4 In 0 .75 Ga 0 .25 N 0.75 0.25 HMDS, 0.5 1.2 Example 5 InN One 0 HMDS, 0.5 1.2 Example 6 In 0 .25 Ga 0 .75 N 0.25 0.75 HMDS, 0.5 0.6 Example 7 In 0 .25 Ga 0 .75 N 0.25 0.75 HMDS, 0.5 2.2 Example 8 In 0 .25 Ga 0 .75 N 0.25 0.75 TMSA, 0.5 0.6 Example 9 In 0 .25 Ga 0 .75 N 0.25 0.75 TMSA, 0.5 1.2 Example 10 In 0 .25 Ga 0 .75 N 0.25 0.75 TMSA, 0.5 2.2 Example 11 In 0 .25 Ga 0 .75 N 0.25 0.75 TMS, 0.25 1.2 Example 12 In 0 .25 Ga 0 .75 N 0.25 0.75 TMSMA, 0.5 1.2 Example 13 In 0 .25 Ga 0 .75 N 0.25 0.75 TMS, 1.0 1.2 Example 14 In 0 .35 Ga 0 .75 N 0.35 0.75 Ammonia, 1 1.2 Example 15 In 0 .35 Ga 0 .75 N 0.35 0.75 Ammonia, 1 1.2

3. Heating up  Method Qdot  synthesis( Example  16-22)

Synthesis was carried out based on pyrolysis synthesis method using heating up method. Schlenk line was used to block and remove water and oxygen.

In order to gallium precursors Ga (acac) 3, was used for In (acac) 3 as indium precursor, to adjust the x of the In x Ga 1-x N In (acac) 3 to the x mol, Ga (acac) 3 (1-x) mol, ODE of 4.52 mL, and OA of 0.6 ~ 2.2 mmol. To this solution, 0.9 mL of TOP and 0.5 mmol of HMDS, which is a nitrogen source, were mixed together and the temperature of the solution was raised to 300 ° C. The synthesis of the quantum dots ends.

Thereafter, the temperature of the solution was lowered, the quantum dots were precipitated using methanol as an anti-solvent, and the quantum dots were dispersed in hexane.

Examples of quantum dots of various indium gallium metal nitride according to the above manufacturing method were prepared by controlling the composition ratio of indium and gallium (In x Ga 1 - x N) as shown in Table 2 below.

Quantum dot composition (x) value (1-x) value Type of nitrogen source and input (mmol) OA input
(mmol) Example 16 GaN 0 One HMDS, 0.5 1.2 Example 17 In 0 .25 Ga 0 .75 N 0.25 0.75 HMDS, 0.5 1.2 Example 18 In 0 .5 Ga 0 .5 N 0.5 0.5 HMDS, 0.5 1.2 Example 19 In 0 .75 Ga 0 .25 N 0.75 0.25 HMDS, 0.5 1.2 Example 20 InN One 0 HMDS, 0.5 1.2 Example 21 In 0 .25 Ga 0 .75 N 0.25 0.75 HMDS, 0.5 0.6 Example 22 In 0 .25 Ga 0 .75 N 0.25 0.75 HMDS, 0.5 2.2

< Manufacturing example  - Production of light emitting device>

The light emitting device including the In 0.25 Ga 0.75 N quantum dot was fabricated as in the following Production Examples 1 to 3, and a schematic cross-sectional view showing the quantum dot light emitting device of this production example is shown in FIG. 18, and the electron injection layer, The energy diagram of the injection layer is shown in Fig.

Production Example 1. Using CBP as a hole injecting material (DEVICE A)

In the quantum dot light emitting device (QD-LED) production example 1 of the present invention, ITO / ZnO (40 nm) / In 0.25 Ga 0.75 N CQDs (10 nm) / HTL (60-80 nm) / MoO 3 (10 nm) . The ITO thin film coated on the flexible PET film was washed with an organic solvent and then subjected to oxygen (O 2 ) plasma treatment for 10 minutes. Thereafter, a ZnO nanoparticle solution (solvent: butanol) having a concentration of 45 mg / mL was coated on the ITO substrate by spin coating until the thickness became 40 nm and then dried at 150 ° C. for 30 minutes to form an electron injection layer Respectively.

In order to fabricate the light emitting layer, the In 0.25 Ga 0.75 N colloid quantum dot prepared in the above example was dissolved in octane at a concentration of 7.5 mg / mL, and then, by spin coating until the thickness became 10 nm, And the hole injecting material CBP was deposited on the thus formed light emitting layer by thermal deposition at a rate of 1 to 1.5 [A / s] until the thickness of the CBP layer became 60 nm. Respectively. The anode was deposited by thermal evaporation until MoO 3 and Ag (Ag) were deposited on the hole injection layer to a thickness of 10 nm and 100 nm, respectively.

Production Example 2. Using CBP and TPBi as a hole injecting material (DEVICE B)

In the above Production Example 1, TPBi having a thickness of 5 nm was inserted between the light emitting layer and CBP (60 nm), and TPBi was deposited by thermal evaporation.

Production Example 3. Use of CBP and HAT-CN as a hole injecting material (DEVICE C)

In Production Example 1, HAT-CN having a thickness of 20 nm was inserted between the anode and CBP (60 nm), and HAT-CN was deposited by thermal evaporation.

Production Example 4. Production on a flexible substrate

Except that the substrate was replaced with a flexible substrate (ITO coated PET, Sigma-Aldrich, 60 OMEGA) to prepare a light emitting device.

< Experimental Example  >

Experimental Example  One. Of quantum dots (CQDs) XRD  characteristic

The XRD characteristics of the quantum dots of the present invention were measured using Rigaku, D.MAZX 2500V / PC.

XRD results of In x Ga 1 - x N prepared in Example 1 (x = 0), Example 2 (x = 0.25) and Example 3 (x = 0.5) are shown in FIG. XRD results of In x Ga 1-x N prepared in Example 4 (x = 0.5) and Example 4 (x = 0.75) are shown in FIG. 1 (b). 1 (c) shows the Ga3d binding position of In x Ga 1 - x N prepared in Example 2 (x = 0.25), Example 3 (x = 0.5) and Example 4 (x = 0.75) The N1s binding position is shown in Figure 1 (d).

From the above results, it was confirmed that InN has a cubic structure and GaN has a hexagonal structure. The crystal structure of each quantum dot was identified and the change of crystal structure according to the ratio of each metal was found.

Experimental Example  2. Of quantum dots (CQDs)  Band gap characteristics

The bandgap characteristics of the quantum dots of the present invention were measured using a Cary Eclipse device manufactured by Varian, and the quantum dots were dispersed in organic solvent hexane and the band gap was measured.

UV-vis absorption spectra of In x Ga 1 - x N prepared in Example 2 (x = 0.25), Example 3 (x = 0.5) and Example 4 (x = 0.75) The PL spectra is shown in Fig. 2 (b). The PL spectra and the UV-vis absorption spectra of In x Ga 1 - x N according to the amount of oleic acid (OA) are shown in FIG. 2 (c) and FIG. 2 (d)

The amount of oleic acid (OA) of InxGa1-xN prepared in Example 8 (OA = 0.6 mmol), Example 9 (OA = 1.2 mmol) and Example 10 (OA = 2.2 mmol) Vis absorption spectra are shown in Fig. 2 (e), and PL spectra are shown in Fig. 2 (f).

The UV-vis absorption spectra of the InxGa1-xN prepared according to Example 11 (TMSMA = 0.25 mmol), Example 12 (TMSMA = 0.5 mmol) and Example 13 (TMSMA = 1 mmol) (g), and the PL spectra is shown in Fig. 2 (h).

Example 14 (x = 0), Example 15 (x = 0.5) of In x Ga 1 manufactured by - x N of the UV-vis absorption 17 to the spectra of 17 (a) also, PL spectra of (b) and 17 (c).

From the above results, it was found that quantum dots can be prepared using HMDS, TMSA, TMSMA and ammonia as N-sources.

From the above results, it was found that the reactivity was the best when HMDS was used as an N-source, and the reactivity was better in the order of TMSA and TMSMA.

From the above results, it can be seen from the above results that Examples 2 to 4 using HMDS as an N-source were effective in increasing the particle size of the quantum dots, followed by band gap control in the order of TMSA and TMSMA .

The difference in PL-QY is also shown in Fig. HMDS is the most frequently used, and it can be seen that when TMSMA is used, PL-QY is about 8% lower than that of other N-sources.

Experimental Example  3. Depending on composition and temperature PL ( Photoluminescence ) Characteristics

The PL characteristics of the In x Ga 1 - x N quantum dots of the present invention were measured using an MIRA laser (λ = 375 nm, Exc power: 1.1 mW).

(X = 0.2) (Fig. 3 (b)), Example 3 (x = 0.5) (Fig. 3 (c) The variation of peak intensity with temperature in each composition was investigated by using Si substrate coated with In x Ga 1 - x N quantum dots prepared in Example 4 (x = 0.75) (Fig. 3 (d) Respectively. It can be seen that the emission wavelength and the intensity of the peak change depending on the metal composition, and the peak intensity decreases as the temperature increases.

Experimental Example  4. Of quantum dots (CQDs)  X-ray absorption spectroscopy ( XAFS ) Characteristics

The X-ray absorption spectroscopic characteristics of the quantum dots of the present invention were measured using a Pohang radiation accelerator (belonging to POSTECH). At this time, indium acetylacetonate was used as a reference for calibrate.

The measured values of In x Ga 1 - x N quantum dots prepared in Example 2 (x = 0.25), Example 3 (x = 0.5), Example 4 (x = 0.75) and Example 5 For comparison, the values are converted into Fourier function values and shown in Fig. 4 (a). The converted value ranged from 2.2 to 3.4 Å. FIG. 4 (b) is a graph comparing the results converted into the Fourier function values at phases A, B, and C in FIG. 4 (a).

From the above results, it can be shown that the quantum dots synthesized by the present method have a multi-phase shape rather than a single phase, and the results show that the reason why a single peak does not appear in the PL spectra.

Experimental Example  5. Metal amount ( quantity ).

Example 2 (x = 0.25), Example 3 (x = 0.5) and Example 4 (x = 0.75) were prepared in order to examine the characteristics of the In x Ga 1 - x N of the present invention, ) Was measured using ICP-MS, and the result is shown in FIG. 5. As shown in FIG.

From the above results, it was found that the metal ratio of the generated In x Ga 1 - x N quantum dots is controlled by controlling the ratio of the metal (In, Ga) introduced during the production.

Experimental Example  6. XPS In3d binding Spectra  characteristic

XPS In3d binding spectra results were obtained from various compositions of In x Ga 1 -x N prepared in Example 2 (x = 0.25), Example 3 (x = 0.5) and Example 4 (x = 0.75) 6.

From the above results, it can be seen that when the metal composition of In and Ga is changed, the chemical bonding state of the quantum dots changes at a certain rate. Thus, when the metal nitride is synthesized using the present method, Can be freely adjusted.

Experimental Example  7. Of quantum dots (CQDs) TEM  image

Example 2 (OA = 1.2 mmol) TEM image of Green condition of quantum dot is shown in FIG. 7 (a), and TEM image of Blue condition of quantum dot of Example 7 (OA = 2.2 mmol) is shown in FIG. 7 (b). As shown in the above results, it can be seen that the color changes to Green or Blue depending on the amount of O.A., and it is found that the color has a size of about 2.5 to 4 nm as shown in the photograph.

The single component images of Example 5 (x = 1) and Example 1 (x = 0) are shown in Figs. 7 (c) and 7 (d), respectively. From the above results, it can be seen that even a single component can be synthesized as spherical particles.

Experimental Example  8. PL - QY ( Photoluminescence Quantum yield ) Characteristics

PL-QY (Photoluminescence Quantum Yield) of In x Ga 1 - x N prepared in Example 2 (x = 0.25), Example 3 (x = 0.5) and Example 4 (x = 0.75) 8.

From the above results, it can be seen that the ratio of Green Pl-QY increases as the ratio of In decreases.

Experimental Example  9. Depending on the amount of oleic acid PL ( Photoluminescence ) Characteristics

The PL spectra of In x Ga 1 - x N prepared in Example 6 (OA = 0.6 mmol), Example 2 (OA = 1.2 mmol) and Example 7 (OA = 2.2 mmol) Respectively.

PL spectra of In x Ga 1 - x N prepared in Example 8 (OA = 0.6 mmol), Example 9 (OA = 1.2 mmol) and Example 10 (OA = 2.2 mmol) b).

As shown in FIGS. 9 (a) and 9 (b), when the amount of OA is small, it has a yellowish green color. When the amount of OA is increased, it is changed to Green. When the amount of OA is increased, As shown in FIG.

Experimental Example  10. Depending on output PL ( Photoluminescence ) Characteristics

10 (b)), Example 3 (x = 0.5) (Fig. 10 (c)) and Example (x = 0) 4 (x = 0.75) (Fig. 10 (d)) prepared in the in x Ga 1 - shows the result of the PL is output from x N in Figure 10 is measured.

MIRA laser (? = 375 nm, T = 20 K) was used for the PL measurement.

From the above results, it can be seen that as the output increases, the intensity of the peak becomes stronger. From this, the luminescence characteristics of the quantum dots are affected by surface defects or defects in the crystal, The recombination of electrons and holes in the luminescence of quantum dots is the main characteristic of quantum dot luminescence.

Experimental Example  11. Decay time ( decay time )In accordance PL ( Photoluminescence ) Reduction characteristics

The decay time measured from In x Ga 1 - x N produced in Example 1 (x = 0), Example 2 (x = 0.25), Example 3 (x = 0.5) and Example 4 Fig. 11 shows PL reduction characteristics according to the present invention. First, FIG. 11 (a) shows the result of calculation of time correlated single photon counting (TCSPC) at 520 nm. Fig. 11 (b) shows the results of TCSPC calculation at 550 nm. In addition, the average decay time at 520 nm and 550 nm is shown in Fig. 11 (c).

From the above results, it is possible to quantify the change of the decay time according to the mixing ratio of In and Ga metal. As a result, it can be understood that the PL intensity in the solution state decreases as the proportion of In metal increases.

Experimental Example  12. X-ray absorption spectroscopy ( XAS ) Characteristics

XANES measured from In x Ga 1 - x N prepared in Example 2 (x = 0.25), Example 3 (x = 0.5), Example 4 (x = 0.75) and Example 5 XAFS results are shown in Figs. 12 (a) and 12 (b), respectively. From the above results, it can be seen that the InGaN quantum dots synthesized through the present method are in a multi-phase state rather than a single phase state, and the results show that the PL peak is not a single peak type.

Experimental Example  13. Ultraviolet Electron Spectroscopy ( UPS ) Energy level characteristics by analysis

Example 2 (x = 0.25) of In x Ga 1 prepared in-was from x N measured energy levels characteristic of the ultraviolet ray electron spectroscopy, was also shown in 13 (a) to High binding energy cut-off region, valence band The region is shown in Fig. 13 (b). The valence band level was determined to be 7.24 eV.

From the above results, the band state of the InGaN quantum dots synthesized by the present method was found, and the energy level required for various electro-electronic devices was found.

Experimental Example  14. Of quantum dots (CQDs) colloidal stability  compare

The solubility of the GaN particles prepared in Example 1 and the GaN powder (Sigma-Aldrich, Aldrich 481769) purchased as a conventionally used product were compared as Comparative Example 1.

0.05 g of GaN was added to 50 ml of hexane and shaken sufficiently. Then, the change with time (0 hours, 0.5 hours, 2 hours, 3.5 hours and 5 hours) was photographed and shown in FIG.

The GaN of Example 1 tends to be stably dissolved even after a lapse of time. However, in the case of GaN of Comparative Example 1, there is a tendency that the GaN is not dissolved from the beginning (meaning that the cloudy solution is not dissolved) But, as time went on, it seemed to settled.

Experimental Example  15. Of quantum dots (CQDs)  Luminescence characteristic

GaN particles prepared in Example 1 and GaN powder (Sigma-Aldrich, Aldrich 481769) purchased as a conventionally used product were set as Comparative Example 1, and their luminescent characteristics were compared.

0.05 g of GaN was added to 50 ml of hexane and sufficiently shaken to confirm the luminescence characteristics using a UV lamp.

It can be confirmed that the GaN produced in Example 1 emits light under the UV lamp condition, but it can be confirmed that the light emitting characteristic in Comparative Example 1 does not exist at all.

When GaN was synthesized by a conventional method as in the case of the GaN powder used in Comparative Example 1, a thin film was formed on a substrate by a chemical vapor deposition method, and then a thin film was scratched off or a solvothermal The synthesis should be carried out using the method. However, these methods are problematic in that when the GaN growth occurs, the defects are formed too much to cause luminescence (no substrate), and when the GaN grown on the substrate is scraped off, The broken site acts as a defect site (in the case of a substrate) and loses its luminescent characteristics.

Due to such a difference, there is a difference in light emission characteristics as shown in FIG.

Experimental Example  16. Voltage-current vs. luminance comparison of luminous elements

The current-voltage-luminance characteristics of Manufacturing Examples 1 to 3 were measured using a SMU (source measurement unit, Keithley Instruments, Inc.) and a luminance meter (Minolta, CS-100A) 22.

In FIG. 22, it can be seen that, in comparison with the device 1 (Device A) and device 2 (Device B), it is necessary to apply a larger voltage to the device of Production Example 3. This is presumably because the energy level of the HAT-CN used as the hole injecting material of Production Example 3 was significantly different from that of other materials, which interfered with the flow of holes.

Experimental Example  17. Measurement of luminescence spectrum and observation of luminescence

The emission spectrum of Production Example 1 (Device A) was measured with an optical fiber spectrometer (K-Mac, SV 2100), and the results are shown in Fig.

In FIG. 23, it can be seen that electroluminescence and photoluminescence occur at the wavelengths of various regions, and it is understood that the quantum dots manufactured in the embodiment of the present invention are suitable for various colors.

In addition, when a voltage of 18 V was applied to Production Example 4 produced on a flexible substrate, it was confirmed that light emission actually occurred as shown in Fig.

10: light emitting layer 20: cathode
30: anode 40: substrate
50: electron injection layer 51: electron transport layer
52: hole blocking layer 60: hole injection layer
61: hole transport layer 62: electron blocking layer

Claims (16)

a) adding an indium precursor, a gallium precursor and a surfactant to a solvent and mixing;
b) pyrolyzing the mixture prepared in step a) and the nitrogen source;
c) dispersing the quantum dots in an organic solvent by adding an anti-solvent to the pyrolysis reaction in the step b) to prepare quantum dots of colloid-like metal nitride represented by the following formula (1) step;
[Chemical Formula 1]
In x Ga 1-x N
(In the above formula (1), x has a range of 0? X? 1.)
d) forming a first electrode on the substrate, and applying a quantum dot of the following colloid on the first electrode to form a light emitting layer; And
and e) forming a second electrode on the light emitting layer.
The method according to claim 1,
The pyrolysis reaction in the step b)
Heating the mixture to a temperature of 150 to 400 ° C. in an argon, nitrogen, ammonia, or vacuum atmosphere, and then hot injecting the nitrogen source at a temperature of 100 to 400 ° C., or
And heating the mixture at a temperature of 150 to 400 DEG C in an argon, nitrogen, ammonia, or vacuum atmosphere after the nitrogen source is added to the mixture.
The method according to claim 1,
The organic solvent in step c) is selected from the group consisting of hexane, toluene, benzene, octane, chloroform, chlorobenzene, tetrahydrofuran (THF). At least one selected from the group consisting of pentane, heptane, decane, methylene chloride, 1,4-dioxane, diethyl ether, cyclohexane and dichlorobenzene Emitting device.
The method according to claim 1,
Wherein x in the above formula (1) has a range of 0.01? X? 0.5.
The method according to claim 1,
Wherein the first electrode or the second electrode is laminated on a flexible substrate.
6. The method of claim 5,
The flexible substrate may be formed of a material selected from the group consisting of polyethylene terephthalate (PET), polyisoprene (PI), polyethylene naphthalate (PEN), polyether sulfone (PES), and polycarbonate Wherein the quantum dot light emitting device is one or more selected from the group consisting of
The method according to claim 1,
Wherein the first electrode or the second electrode further comprises at least one selected from the group consisting of an electron injection layer, an electron transport layer and a hole blocking layer between an electrode serving as a cathode of the first electrode or the second electrode and the light emitting layer.
The method according to claim 1,
Wherein at least one selected from the group consisting of a hole injecting layer, a hole transporting layer, and an electron blocking layer is additionally disposed between the anode and the light emitting layer of the first electrode or the second electrode.
delete delete The method according to claim 1,
The light emitting layer in step d) may be selected from the group consisting of spin coating, die coating, blade coating, roll coating, inkjet printing, printing, spray coating, knife coating, transfer printing and curtain coating Wherein the quantum dot light emitting device is formed on the first electrode in at least one manner.
The method according to claim 1,
The substrate in the step d) may be at least one selected from the group consisting of polyethylene terephthalate (PET), polyisoprene (PI), polyethylene naphthalate (PEN), polyether sulfone (PES), and polycarbonate Wherein the substrate is at least one flexible substrate selected from the group consisting of polyesters, polyesters, polyesters, and polycarbonates.
The method according to claim 1,
The solvent of step a) may be selected from the group consisting of 2,6,10,15,19,23-hexamethyltetracosane (Squalane), 1-octadecene (ODE), trioctylamine (TOA), tributylphosphine oxide, octadecene, octadecylamine, hexane, octane, trioctylphosphine ) And trioctylphosphine oxide (TOPO), or a mixed solution of two or more thereof.
The method according to claim 1,
The indium precursor in step a) may be at least one selected from the group consisting of indium (III) acetylacetonate, indium (III) chloride, indium (III) acetate, trimethyl indium, (III) Myristate 2 Acetate and Indium (III) Myristate Acetate), indium (III) myristate acetate, indium myristate acetate, Wherein the quantum dot light emitting device is one selected from the group consisting of a quantum dot light emitting device and a quantum dot light emitting device.
The method according to claim 1,
The gallium precursor in step a) is selected from the group consisting of gallium (III) acetylacetonate, gallium (III) acetate, gallium (III) chloride, triethyl gallium, Gallium myristate acetate and Gallium myristate 2 acetate, such as Gallium (III) Myristate, Gallium (III) Myristate Acetate, (III) Myristate 2 Acetate). &Lt; / RTI &gt;
The method according to claim 1,
The nitrogen source in step b) may be selected from the group consisting of hexamethyldisilazane, tris (trimethylsilyl) amine, N, N-bis (trimethylsilyl) ) methylamine), and ammonia (Ammonia). &lt; / RTI &gt;




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US10581008B2 (en) 2017-06-22 2020-03-03 Daegu Gyeongbuk Institute Of Science & Technology Method of manufacturing quantum dot having tunable and narrow light emission wavelength for achieving high color purity and a method of manufacturing film
CN109929330A (en) * 2017-12-15 2019-06-25 Tcl集团股份有限公司 Inorganic nano material prints ink and its preparation method and application
WO2019190147A1 (en) 2018-03-28 2019-10-03 재단법인대구경북과학기술원 Red-emitting quantum dots having narrow full width at half maximum and emission wavelength for application to high-color-purity display, and preparation method therefor
KR20190113323A (en) 2018-03-28 2019-10-08 재단법인대구경북과학기술원 Red light emitting quantumdot having a light emitting wavelength and a narrow half-value width for high color puritydisplay application and a method for manufacturing the same
WO2020075946A1 (en) * 2018-10-12 2020-04-16 고려대학교 산학협력단 Method for manufacturing gallium nitride quantum dots doped with metal ions
KR20200042041A (en) * 2018-10-12 2020-04-23 고려대학교 산학협력단 Method for preparing metal ion doped gallium nitride quantum dot
KR102350250B1 (en) * 2018-10-12 2022-01-14 고려대학교 산학협력단 Method for preparing metal ion doped gallium nitride quantum dot

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