KR20200088710A - A quantum dot, a quantum dot light-emitting diode and a quantum dot film and a light converting resin composition comprising the quantum dot, a color filter and a light converting laminated base material manufactured by the composition and a display device comprising the same - Google Patents

Abstract

The present invention relates to a quantum dot having a ligand layer on a surface, wherein the ligand layer comprises a compound having a specific chemical structure. The quantum dot according to the present invention has excellent oxidation stability and can be effectively applied to various applications such as quantum dot films, quantum dot light-emitting diodes, color filters, and light conversion lamination substrates.

Description

A quantum dot, a quantum dot light emitting diode including the same, a quantum dot film, a light conversion resin composition, a color filter formed using the light conversion resin composition, a light conversion laminated substrate and an image display device including the color filter or the light conversion laminated substrate {A QUANTUM DOT, A QUANTUM DOT LIGHT-EMITTING DIODE AND A QUANTUM DOT FILM AND A LIGHT CONVERTING RESIN COMPOSITION COMPRISING THE QUANTUM DOT, A COLOR FILTER AND A LIGHT CONVERTING LAMINATED BASE MATERIAL MANUFACTURED BY THE COMPOSITION AND A DISPLAY DEICE

The present invention includes a quantum dot, a quantum dot light emitting diode comprising the same, a quantum dot film, a light conversion resin composition, a color filter formed using the light conversion resin composition, a light conversion laminated base material and the color filter or the light conversion laminated base material It relates to an image display device.

Since quantum dots have high luminescence and a narrow emission spectrum, the emission wavelength can be controlled by a single excitation wavelength, and they have a unique characteristic of stable quantum dots for light. Many studies have been conducted for use in the same important application field.

The quantum dot is a material that is very sensitive to the state of the surface, and oxidation occurs from the surface depending on the dispersed solvent or the surrounding environment, resulting in a rapid decrease in luminous efficiency. For various applications of quantum dots, it must be dispersed in various solvents in addition to the organic solvent that was initially dispersed, or a specific functional group must be formed on the surface, and these processes damage the surface of the quantum dots and eventually lead to a decrease in luminous efficiency. There is this.

Many attempts have been made to overcome this problem, and various methods are currently being proposed. One of them is a ligand exchange method in which organic substances present on the surface of a quantum dot are replaced with molecules having a desired functional group. This method is intended to apply an organic molecule existing on the surface of the quantum dot, but is a method of substituting with a suitable organic molecule, but has a disadvantage of causing a fatal problem in luminous efficiency because it directly affects the quantum dot surface.

Republic of Korea Patent Publication No. 10-2018-0002716 and Republic of Korea Patent Registration No. 10-1628065 discloses a quantum dot containing a ligand disposed on the surface, but the compatibility is low, the dispersibility is low, stability and reliability are reduced, It is a situation that does not solve the problem that the light resistance decreases over time.

Republic of Korea Patent Publication No. 10-2018-0002716 Republic of Korea Registered Patent No. 10-1628065

One object of the present invention is to provide a quantum dot excellent in oxidation stability and reliability.

In addition, an object of the present invention is to provide a quantum dot film including the quantum dots, a light conversion resin composition and a quantum dot light emitting diode (Quantum Dot Light-Emitting Diode, QLED).

In addition, an object of the present invention is to provide an image display device comprising a color filter, a light conversion laminated base material and the color filter or the light conversion laminated base material formed using the light conversion resin composition.

The present invention is a quantum dot having a ligand layer on the surface,

The ligand layer provides a quantum dot comprising a compound represented by Formula 1 below.

[Formula 1]

(In the formula 1,

R ₁ is a group represented by the following formula (2), a group represented by the following formula (3) or a group represented by the following formula (4),

R ₂ is a straight or branched alkylene group having 1 to 30 carbon atoms,

n is an integer from 1 to 250.)

[Formula 2]

[Formula 3]

[Formula 4]

(In the formulas 2 to 4, * is a bond with an oxygen atom.)

In addition, the present invention provides a quantum dot light emitting diode, a quantum dot film and a light conversion resin composition comprising the quantum dots.

In addition, the present invention provides an image display device including a color filter, a light conversion laminated base material and the color filter or the light conversion laminated base material formed using the light conversion resin composition.

The quantum dot according to the present invention includes a compound represented by a specific chemical structure as a ligand layer, and thus the surface of the quantum dot is protected, thereby providing excellent oxidation stability and preventing quantum efficiency degradation.

Accordingly, the quantum dot can provide an effect of improving luminance and reliability, and thus can be effectively applied to various uses such as a quantum dot film, a quantum dot light emitting diode, a color filter, and a light conversion laminated substrate.

Hereinafter, the present invention will be described in detail.

The present invention provides a quantum dot having a ligand layer on its surface, wherein the ligand layer comprises a compound represented by the following Chemical Formula 1.

[Formula 1]

(In the formula 1,

R ₁ is a group represented by the following formula (2), a group represented by the following formula (3) or a group represented by the following formula (4),

R ₂ is a straight or branched alkylene group having 1 to 30 carbon atoms,

n is an integer from 1 to 250.)

[Formula 2]

[Formula 3]

[Formula 4]

(In the formulas 2 to 4, * is a bond with an oxygen atom.)

In addition, the present invention provides a quantum dot light-emitting diode (Quantum Dot Light-Emitting Diode, QLED), a quantum dot film or light conversion resin composition containing the quantum dots.

In addition, the present invention provides an image display device including a color filter, a light conversion laminated base material and the color filter or the light conversion laminated base material formed using the light conversion resin composition.

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

<quantum shop>

In the present invention, the quantum dots self-emission by the light source may be used to generate light in the visible and infrared regions. A quantum dot is a material having a crystal structure of several nanometers, and may be composed of hundreds to thousands of atoms. The atoms form a molecule, and the molecule forms a collection of small molecules called clusters to form nanoparticles. Usually, these nanoparticles are called quantum dots, especially when they have semiconductor properties. The quantum dot of the present invention is not particularly limited as long as it conforms to this concept. When an object becomes smaller than a nano size, a quantum confinement effect, which is a phenomenon in which the energy band gap of the object increases, appears, and when the quantum dot receives energy from the outside and reaches an excited state, the energy band itself It releases energy corresponding to the gap and can self-emit.

The quantum dot according to the present invention has a ligand layer on the surface, and the ligand layer is characterized by including a compound represented by the following Chemical Formula 1. Accordingly, the surface of the quantum dots is protected, oxidation stability is improved, a decrease in quantum efficiency is prevented, and reliability can be improved.

[Formula 1]

In Chemical Formula 1, R ₁ may be a group represented by Chemical Formula 2, a group represented by Chemical Formula 3 or a group represented by Chemical Formula 4 below.

[Formula 2]

[Formula 3]

[Formula 4]

In the above formulas 2 to 4, * is a bond with an oxygen atom.

In addition, in Chemical Formula 1, R ₂ may be a straight chain or branched alkylene group having 1 to 30 carbon atoms, preferably a straight chain or branched chain alkylene group having 1 to 20 carbon atoms.

In addition, in Chemical Formula 1, n may be an integer of 1 to 250, preferably 1 to 100.

In one embodiment of the present invention, the compound represented by Formula 1 may be a compound represented by any one of the following Formulas 1-1 to 1-14.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

The compound represented by Chemical Formula 1 of the present invention is an organic ligand and may coordinately bind to the surface of the quantum dot to perform a role of stabilizing the quantum dot.

It is common for quantum dots to be prepared to have a ligand layer on the surface, and immediately after production, the ligand layer is oleic acid, lauric acid, 2-(2-methoxyethoxy)acetic acid, 2 -[2-(2-methoxyethoxy)ethoxy]acetic acid, and succinic acid mono-[2-(2-methoxy-ethoxy)-ethyl] ester. In this case, compared to the quantum dots of the present invention comprising the compound represented by the formula (1) as a ligand layer, due to the weaker binding force between the ligand layer and the quantum dots, the surface protection effect may be reduced due to non-bonding defects on the surface of the quantum dots. have. Also, in the case of oleic acid, it is well dispersed in an unsaturated hydrocarbon solvent such as n-hexane, which is a volatile organic compound (VOC), and an aromatic solvent such as chloroform and benzene, but has poor dispersibility in a solvent such as PGMEA. .

The quantum dots according to the present invention include a compound represented by Chemical Formula 1 in the ligand layer, and as the surface of the quantum dots is protected, it can exhibit excellent oxidation stability compared to conventional quantum dots, and dispersibility in solvents such as PGMEA. It is very excellent and has an effect of improving light characteristics.

In some embodiments, the quantum dot according to the present invention includes a compound represented by Formula 1 in the ligand layer, oleic acid, lauric acid, 2-(2-methoxyethoxy ) Acetic acid, 2-[2-(2-methoxyethoxy)ethoxy]acetic acid, and succinic acid mono-[2-(2-methoxy-ethoxy)-ethyl] ester.

The quantum dot is not particularly limited as long as it is a quantum dot particle that can emit light by stimulation by light or electricity. For example, II-VI semiconductor compound; III-V semiconductor compound; IV-VI semiconductor compound; A group IV element or a compound containing the same; And it may be selected from the group consisting of a combination thereof, these may be used alone or in combination of two or more.

For example, the II-VI semiconductor compound may be a binary compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, selected from HgZnS, HgZnT And CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe and mixtures thereof, but are not limited thereto.

The group III-V semiconductor compound is a binary element selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; A ternary compound selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP and mixtures thereof; And GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. It is not limited.

The group IV-VI semiconductor compound is a binary element selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; Ternary compounds selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe and mixtures thereof; And SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof, but may be one or more selected from the group consisting of tetrahydrogen compounds.

Although not limited thereto, the group IV element or a compound containing the same may be selected from the group consisting of Si, Ge and mixtures thereof; And a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

Quantum dots are homogeneous single structures; Dual structures such as a core-shell structure and a gradient structure; Or it may be a mixed structure of these, and in the present invention, the quantum dot is not particularly limited as long as it can emit light by stimulation by light.

According to one embodiment, the quantum dot has a core-shell structure, the core is InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, Contains one or more selected from the group consisting of HgS, HgSe, HgTe, GaN, GaP, GaAs, InGaN, InAs, and ZnO, and the shell is ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, InP , InS, GaP, GaN, GaO, InZnP, InGaP, InGaN, InZnSCdSe, PbS, TiO, SrSe and may include one or more selected from the group consisting of HgSe, preferably, InP/ZnS, InP/ZnSe , InP/GaP/ZnS, InP/ZnSe/ZnS, InP/ZnSeTe/ZnS, and one or more selected from the group consisting of InP/MnSe/ZnS.

In general, quantum dots may be prepared by a wet chemical process, a metal organic chemical vapor deposition (MOCVD), or a molecular beam epitaxy (MBE).

Quantum dots according to the present invention can be synthesized by a wet chemical process.

The wet chemical process is a method of growing particles by adding a precursor material to an organic solvent. When the crystal grows, the organic solvent is naturally coordinated to the surface of the quantum dot crystal to act as a dispersant to control the growth of the crystal. It is possible to control the size growth of quantum dot particles through an easier and cheaper process than vapor deposition methods such as molecular beam epitaxy.

When a quantum dot is prepared by a wet chemical process, an organic ligand is used to prevent agglomeration of the quantum dots and control the particle size of the quantum dots to the nano level. Oleic acid may be generally used as the organic ligand.

In one embodiment of the present invention, oleic acid used in the manufacturing process of the quantum dots is replaced by a ligand exchange method by the compound represented by the formula (1).

For the ligand exchange, an organic ligand to be exchanged, that is, a compound represented by the formula (1) is added to the dispersion containing the original organic ligand, that is, a quantum dot with oleic acid, and stirred for 30 minutes to 3 hours at room temperature to 200°C. Thus, it can be carried out by obtaining a quantum dot to which the compound represented by Formula 1 is bonded. If necessary, the process of separating and purifying the quantum dots to which the compound of Formula 1 is bound may be further performed.

The quantum dot according to an embodiment of the present invention has the advantage that it can be produced by an organic ligand exchange method under a simple stirring treatment at room temperature as described above, so that mass production is possible.

In addition, the quantum dot according to an embodiment of the present invention can maintain a quantum efficiency of about 90% or more compared to the initial quantum efficiency even after 15 days, so it can be stably stored for a long period of time and commercialized for various uses.

<quantum dot light emitting diode>

The quantum dot light-emitting diode (QLED) according to an embodiment of the present invention may include the quantum dots described above.

The quantum dot light emitting diode is an element of an electroluminescence (EL) method that electrically excites quantum dots to emit light.

The electrons and holes injected from both electrodes form excitons in the quantum dot light emitting layer, and emit light through radiative recombination of the excitons. Since it has the same operating principle as an organic light-emitting diode (OLED), it is constructed by replacing only the light-emitting layer with a quantum dot instead of an organic light-emitting material in a multi-layer device structure that uses the electron/hole injection layer and transport layer of a conventional OLED as it is. Can be.

The manufacturing method of the quantum dot light emitting diode of the present invention is not particularly limited, and a method known in the art can be used.

For example, a method of manufacturing a quantum dot light emitting diode may be manufactured by sequentially stacking an anode, a cathode, an electron injection/transport layer, a light emitting layer, a hole transport layer, and a hole injection layer.

For another embodiment, a method of manufacturing a quantum dot light emitting diode may be manufactured by sequentially stacking a cathode, an electron injection/transport layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode. The method of manufacturing a diode may be produced by sequentially laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron injection and transport layer, and a cathode.

In this case, the light emitting layer may include the quantum dots described above.

<quantum dot film>

The quantum dot film according to an embodiment of the present invention may include the quantum dots described above.

The quantum dot film includes a polymer resin and a quantum dot dispersion layer including the above-described quantum dots dispersed in the polymer resin.

Examples of the polymer resin include epoxy, epoxy acrylate, lauryl acrylate, norbornene, polyethylene, polystyrene, ethylene-styrene copolymer, acrylate containing bisphenol A and bisphenol A derivatives, and fluorene derivatives Acrylate, isobornyl acrylate, polyphenylalkylsiloxane, polydiphenylsiloxane, polydialkylsiloxane, silsesquioxane, silicone fluoride, and vinyl and hydride substituted silicones can be used. Or it can be used by mixing two or more.

The quantum dot film may further include a barrier layer on at least one surface of the quantum dot dispersion layer.

The barrier layer may have an oxygen permeability of 0.001 cm 3 /m 2 ·day·bar or less and a water permeability of 0.001 g/m 2 ·day or less, such as polyester, polycarbonate, polyolefin, cyclic olefin polymer, or polyimide. can do.

The thickness of the quantum dot dispersion layer may be 10 μm to 100 μm, and the thickness of the barrier layer may be 50 μm to 70 μm.

The method for producing the quantum dot film of the present invention is not particularly limited, and methods known in the art can be used.

For one embodiment, a method of manufacturing a quantum dot film,

a) preparing a lower transparent substrate;

b) forming a quantum dot thin film by applying a quantum dot dispersion to the lower transparent substrate; And

c) manufacturing a quantum dot film by laminating an upper transparent substrate on the quantum dot thin film.

<Light conversion resin composition>

The method for producing the light conversion resin composition of the present invention is not particularly limited, and methods known in the art can be used.

For example, the light conversion resin may include the above-described quantum dots, binder resins, photopolymerizable compounds, thermopolymerizable compounds, photopolymerization initiators, and solvents, in addition to coloring agents including pigments and dyes, scattering particles, etc. Accordingly, it may further include a configuration known in the art.

The thus prepared light conversion resin composition can be preferably used for the production of color filters and image display devices including the same.

<Light conversion laminated base material>

The light conversion laminated base material according to the present invention includes a cured product of the light conversion resin composition. The light conversion laminated base material may include a light conversion resin composition that can be coated on a glass substrate, so that a solvent that does not correspond to a human harmful substance can be used, thereby improving worker safety and product productivity.

The photo-conversion laminating substrate may be silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The photo-conversion laminated substrate may be formed by applying the photo-conversion resin composition and thermal curing.

<Color filter>

The pattern forming method for forming the color filter of the present invention can use a method known in the art.

In one embodiment, the pattern forming method,

a) applying a light conversion resin composition to the substrate;

b) a prebaking step of drying the solvent;

c) placing a photo mask on the resulting film to irradiate active light to cure the exposed portion;

d) performing a developing process of dissolving the unexposed portion using an aqueous alkali solution; And

e) drying and post-baking.

The substrate may be a glass substrate or a polymer substrate, but is not limited thereto. As the glass substrate, in particular, soda-lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, or the like can be preferably used. Further, examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and poly sulfone substrates.

At this time, the coating may be performed by a known wet coating method using a coating device such as a roll coater, spin coater, slit-and-spin coater, slit coater (sometimes also referred to as a die coater), inkjet, etc. to obtain a desired thickness .

Pre-baking is performed by heating with an oven, a hot plate, or the like. At this time, the heating temperature and the heating time in the pre-baking are appropriately selected depending on the solvent used, and for example, it may be performed at a temperature of 80 to 150°C for 1 to 30 minutes.

In addition, exposure performed after pre-baking is performed by an exposure machine and exposed through a photo mask, whereby only the portion corresponding to the pattern is exposed. At this time, for the light to be irradiated, for example, visible light, ultraviolet light, X-rays, and electron beams may be used.

The developing step of dissolving the unexposed portion using an aqueous alkali solution after exposure is performed for the purpose of removing the photosensitive resin composition of the unexposed portion and the desired pattern is formed. As a developing solution suitable for development using this aqueous alkali solution, for example, an aqueous solution of carbonate of an alkali metal or alkaline earth metal can be used. In particular, using a developing solution or an ultrasonic cleaner or the like at a temperature of 10 to 50°C, preferably 20 to 40°C, using a less alkaline aqueous solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate and lithium carbonate. Can be done.

Post-baking is performed to increase the adhesion between the patterned film and the substrate, and may be performed through heat treatment at 80 to 250° C. for 10 to 120 minutes, for example. Post-baking, like pre-baking, can be performed using an oven, hot plate, or the like.

<Image display device>

The image display apparatus according to the present invention includes the above-described color filter or light conversion laminated base material. Specifically, the image display device includes a liquid crystal display (liquid crystal display; LCD), an organic EL display (organic EL display), a liquid crystal projector, a display device for a game machine, a display device for a mobile terminal such as a mobile phone, and a display for a digital camera. And a display device such as a device or a display device for car navigation, and a color display device is particularly suitable.

The image display device includes a configuration known to those skilled in the art in the art of the present invention, except that the color filter or the light conversion laminated substrate is provided, that is, the present invention is a color filter or light. And an image display device to which a converted laminated base material can be applied.

The image display device including the color filter according to the present invention may have excellent characteristics in color reproducibility, luminance, light resistance and reliability.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples.

Synthesis Example 1: InP/ZnS core-shell quantum dot synthesis

In a 3-neck flask, 0.05839 g of indium acetate, 0.12019 g of oleic acid and 10 mL of 1-octadecene (ODE) were added. After the flask was stirred and degassed for 30 minutes at 110°C and 100 mTorr, the solution was heated to a temperature of 270°C under an inert gas until the solution became transparent.

Tris(trimethylsilyl)phosphine as a phosphorus (P) precursor was prepared at 0.025054g, placed in 0.5 mL of 1-octadecene and 0.5 mL of tri-n-octylphosphine and stirred to heat the flask to 270°C under inert gas. Was injected quickly. After reacting for 1 hour, the reaction was terminated by rapid cooling. Then, when the temperature of the flask reached 100°C, 10 mL of toluene was injected and then transferred to a 50 mL centrifuge tube. After adding 10 mL of ethanol, it was purified twice using a precipitation and redispersion method. The purified InP core nanoparticles were dispersed in 1-octadecene and stored.

In a three-necked flask, 3.669 g of zinc acetate, 20 mL of oleic acid and 20 mL of 1-octadecene were added, and after degassing for 30 minutes at 110°C and 100 mTorr with stirring, an inert gas was obtained until the solution became clear. The mixture was heated to a temperature of 270° C. and then cooled to 60° C. to obtain a transparent zinc oleate precursor solution.

In a three-necked flask, 0.6412 g of sulfur and 10 mL of tri-n-octylphosphine are added and heated to a temperature of 80° C. while stirring in an inert gas atmosphere until the solution becomes transparent, and then cooled to room temperature to form a TOP:S type S precursor solution. Got

In a separate three-necked flask, the nanoparticle solution of the prepared InP core was put in advance, the temperature of the flask was adjusted to 300°C, and 0.6 mL of the pre-prepared zinc precursor solution was rapidly injected using a syringe. Thereafter, 0.3 mL of the prepared S precursor solution was injected into the flask at a rate of 2 mL/hr using a syringe pump. After the injection was completed, the reaction was further performed for 3 hours, and the reaction was terminated by cooling rapidly. When the temperature of the flask reached 100°C, 10 mL of toluene was injected, and then transferred to a 50 mL centrifuge tube. After adding 10 mL of ethanol, it was purified twice using a precipitation and redispersion method. The purified InP/ZnS core-shell nanoparticles were dispersed in n-chloroform and stored. The solid content was adjusted to 10%. The maximum emission wavelength was 525 nm.

Synthesis Example 2: InP/ZnSe/ZnS core-shell quantum dot synthesis

Indium acetate (Indium acetate) 0.4mmol (0.058g), palmitic acid (palmitic acid) 0.6mmol (0.15g) and 1-octadecene (octadecene) 20mL was placed in a reactor and heated to 120 ℃ under vacuum. After 1 hour, the atmosphere in the reactor was converted to nitrogen. After heating to 280° C., a mixed solution of 0.2 mmol (58 μl) of tris(trimethylsilyl)phosphine (TMS 3 P) and 1.0 mL of trioctylphosphine was rapidly injected and reacted for 0.5 minute.

Subsequently, 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was converted to nitrogen and the reactor was heated to 280°C. 2 mL of the previously synthesized InP core solution was added, and then 4.8 mmol of selenium (Se/TOP) in trioctylphosphine was added, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution rapidly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and then dried under reduced pressure to form an InP/ZnSe core-shell.

Subsequently, 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was converted to nitrogen and the reactor was heated to 280°C. 2 mL of the previously synthesized InP core solution was added, and then 4.8 mmol of sulfur (S/TOP) in trioctylphosphine was added, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution rapidly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and then dried under reduced pressure to obtain quantum dots of an InP/ZnSe/ZnS core-shell structure and then dispersed in chloroform. The solid content was adjusted to 10%. The maximum emission wavelength was 520 nm.

Preparation of quantum dots according to Examples and Comparative Examples

Example 1: Ligand Substitution Reaction 1 (LE-1)

5 mL of the quantum dot solution obtained in Synthesis Example 1 was placed in a centrifuge tube, and 20 mL of ethanol was added to precipitate. The supernatant was discarded through centrifugation, and 3 mL of chloroform was added to the precipitate to disperse quantum dots, followed by 1.0 g of 8-[(9H-Fluoren-9-ylmethoxy)carbonylamino]-3,6- Dioxa-n-octanoic acid (TCI) was added and reacted for 1 hour while heating to 60° C. under a nitrogen atmosphere.

[Formula 1-1]

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate quantum dots, followed by centrifugation to separate the precipitate, followed by dispersing by adding PGMEA to a solid content of 10%. The maximum emission wavelength was 520 nm.

Example 2. Ligand Substitution Reaction 2 (LE-2)

Example 1 except that instead of the ligand used in Example 1, 9-[(9H-Fluoren-9-ylmethoxy)carbonylamino]-4,7-dioxanonanoic acid (TCI) represented by Chemical Formula 1-2 was used. The same was done.

[Formula 1-2]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 520 nm.

Example 3. Ligand Substitution Reaction 3 (LE-3)

The same procedure as in Example 1 was performed except that Fmoc-NH-PEG ₈ -CH ₂ CH ₂ COOH (FutureChem) represented by Chemical Formula 1-3 was used instead of the ligand used in Example 1.

[Formula 1-3]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 521 nm.

Example 4. Ligand Substitution Reaction 4 (LE-4)

The same procedure as in Example 1 was performed except that Fmoc-NH-PEG ₁₆ -CH ₂ CH ₂ COOH (Future Chem Co.) represented by Chemical Formula 1-4 was used instead of the ligand used in Example 1.

[Formula 1-4]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 522 nm.

Example 5 Ligand Substitution Reaction 5 (LE-5)

Except for using the Fmoc-NH-PEG _36- CH ₂ CH ₂ COOH (Future Chem Co.) represented by the following Chemical Formula 1-5 instead of the ligand used in Example 1, the procedure was the same as in Example 1.

[Formula 1-5]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 522 nm.

Example 6 Ligand Substitution Reaction 6 (LE-6)

5 mL of the quantum dot solution obtained in Synthesis Example 2 was placed in a centrifuge tube, and 20 mL of ethanol was added to precipitate. After discarding the supernatant through centrifugation, 3 mL of chloroform was added to the precipitate to disperse quantum dots, and then 1.0 g of Boc-NH-PEG ₂ -CH ₂ COOH (Future Chem Co.) represented by the following Chemical Formula 1-6 was added to the nitrogen atmosphere. The reaction was carried out for 1 hour while heating to 60°C.

[Formula 1-6]

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate quantum dots, followed by centrifugation to separate the precipitate, and then PGMEA was added to a solid content of 10% for dispersion. The maximum emission wavelength was 520 nm.

Example 7 Ligand Substitution Reaction 7 (LE-7)

The procedure was carried out in the same manner as in Example 6, except that Boc-NH-PEG ₁₁ -CH ₂ COOH (FutureChem) represented by Chemical Formula 1-7 was used instead of the ligand used in Example 6.

[Formula 1-7]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 521 nm.

Example 8. Ligand substitution reaction 8 (LE-8)

Except for using the 21-[(tert-Butoxycarbonyl)amino]-4,7,10,13,16,19-hexaoxaheneicosanoic acid (TCI Co.) represented by the following Chemical Formula 1-8 instead of the ligand used in Example 6, The procedure was the same as in Example 6.

[Formula 1-8]

Subsequently, 25 mL of n-hexane was added to the reactant to precipitate quantum dots, followed by centrifugation to separate the precipitate, followed by dispersing by adding PGMEA to a solid content of 10%. The maximum emission wavelength was 520 nm.

Example 9 Ligand Substitution Reaction 9 (LE-9)

The procedure was carried out in the same manner as in Example 6, except that Boc-NH-PEG ₁₂ -CH ₂ CH ₂ COOH (FutureChem) represented by the following Chemical Formula 1-9 was used instead of the ligand used in Example 6.

[Formula 1-9]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 521 nm.

Example 10. Ligand Substitution Reaction 10 (LE-10)

The procedure was carried out in the same manner as in Example 6, except that Boc-NH-PEG ₃₆ -CH ₂ CH ₂ COOH (FutureChem) represented by the following Chemical Formula 1-10 was used instead of the ligand used in Example 6.

[Formula 1-10]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 522 nm.

Example 11. Ligand Substitution Reaction 11 (LE-11)

The procedure was carried out in the same manner as in Example 6, except that CBZ-NH-PEG ₂ -CH ₂ COOH (Future Chem Co., Ltd.) represented by the following Chemical Formula 1-11 was used instead of the ligand used in Example 6.

[Formula 1-11]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 520 nm.

Example 12. Ligand Substitution Reaction 12 (LE-12)

It was carried out in the same manner as in Example 6, except that CBZ-NH-PEG ₁₀ -CH ₂ COOH (FutureChem) represented by Chemical Formula 1-12 was used instead of the ligand used in Example 6.

[Formula 1-12]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 521 nm.

Example 13. Ligand substitution reaction 13 (LE-13)

It was carried out in the same manner as in Example 6, except that CBZ-NH-PEG ₂ -CH ₂ CH ₂ COOH (FutureChem) represented by the following Chemical Formula 1-13 was used instead of the ligand used in Example 6.

[Formula 1-13]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 520 nm.

Example 14. Ligand substitution reaction 14 (LE-14)

BZ-NH-PEG _10- CH ₂ CH ₂ COOH represented by the following Chemical Formula 1-14 was used instead of the ligand used in Example 6 (Future Chem Co.), and the same procedure as Example 6 was performed.

[Formula 1-14]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 521 nm.

Comparative Example 1: Preparation of quantum dots of InP/ZnS core alone without ligand exchange reaction

The quantum dots of Synthesis Example 1 in which oleic acid was bonded to the surface were dispersed in chloroform at a concentration of 10%.

Comparative Example 2: InP/ZnSe/ZnS core-shell quantum dot preparation without ligand exchange reaction

The quantum dots of Synthesis Example 2 in which oleic acid was bonded to the surface were dispersed in chloroform at a concentration of 10%.

Comparative Example 3: Ligand Substitution Reaction 15 (LE-15)

The same procedure as in Example 6 was performed except that Fmoc-GABA-OH (Sigma-Aldrich Co., Ltd.) represented by the following Chemical Formula 1-15 was used instead of the ligand used in Example 6.

[Formula 1-15]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 520 nm.

Comparative Example 4: Ligand Substitution Reaction 16 (LE-16)

The procedure was carried out in the same manner as in Example 6, except that Boc-GABA-OH (Sigma-Aldrich Co.) represented by the following Chemical Formula 1-16 was used instead of the ligand used in Example 6.

[Formula 1-16]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 520 nm.

Comparative Example 5: Ligand Substitution Reaction 17 (LE-17)

It was carried out in the same manner as in Example 6, except that 4-Benzyloxycarbonylamino butyric acid (Sigma-Aldrich Co., Ltd.) represented by the following Chemical Formula 1-17 was used instead of the ligand used in Example 6.

[Formula 1-17]

The solid content was adjusted to 10% with PGMEA. The maximum emission wavelength was 520 nm.

Experimental Example

(1) Quantum efficiency

The quantum efficiency (QY%) at the beginning of the preparation of the quantum dot dispersions of Examples 1 to 14 and Comparative Examples 1 and 5 and absolute quantum efficiency (QY%) after 15 days of standing at room temperature were measured using QE-2100 (Otsuka Co.). Did.

Since quantum efficiency is reduced by quantum dot surface oxidation, it is possible to confirm oxidation stability by measuring a decrease in quantum efficiency. That is, oxidative stability can be confirmed by measuring ΔQY%.

The measurement results are shown in Table 1 below.

Initial QY (%) QY (%) after 15 days of neglect Δ QY (%) Example 1 79 70 9 Example 2 80 71 9 Example 3 78 70 8 Example 4 79 70 9 Example 5 78 69 9 Example 6 82 70 12 Example 7 81 77 12 Example 8 81 71 10 Example 9 81 70 11 Example 10 80 72 8 Example 11 80 72 8 Example 12 82 70 12 Example 13 81 70 11 Example 14 82 72 10 Comparative Example 1 80 25 55 Comparative Example 2 83 27 56 Comparative Example 3 81 31 50 Comparative Example 4 82 30 52 Comparative Example 5 80 30 50

(2) Light resistance

The quantum efficiency of the initial production of the quantum dot dispersions of Examples 1 to 14 and Comparative Examples 1 and 5 and absolute quantum efficiency after 7 days of standing in a blue LED light source at room temperature were measured using QE-2100 (Otsuka Co.).

When the surface of the quantum dot is oxidized with a defect that is not protected by a ligand, the quantum efficiency decreases. Reliability can be confirmed by measuring the amount of reduction in absolute quantum efficiency.

The measurement results are shown in Table 2 below.

Initial QY (%) QY(%) after 7 days of neglect Δ QY (%) Example 1 78 70 8 Example 2 77 70 7 Example 3 77 70 7 Example 4 78 70 8 Example 5 78 69 9 Example 6 80 70 10 Example 7 81 70 9 Example 8 80 73 7 Example 9 80 70 10 Example 10 81 70 9 Example 11 82 70 12 Example 12 81 70 9 Example 13 82 70 12 Example 14 80 71 9 Comparative Example 1 78 24 54 Comparative Example 2 81 22 59 Comparative Example 3 80 28 52 Comparative Example 4 81 30 51 Comparative Example 5 80 31 49

As shown in Tables 1 and 2, the quantum dots of Examples 1 to 14 according to the present invention containing a ligand represented by Chemical Formula 1 on the surface are confirmed to be inhibited from quantum efficiency degradation as oxidation of the quantum dot surface is prevented. Could. On the other hand, it was confirmed that the quantum dots of Comparative Examples 1 to 5 significantly reduced the quantum efficiency.

Specifically, the quantum dots of Examples 1 to 14 maintain a quantum efficiency of about 90% or more compared to the initial quantum efficiency even after leaving for 15 days at room temperature, and about 80% of the initial quantum efficiency even after leaving the blue LED light source at room temperature for 7 days Through maintaining the above quantum efficiency, it was found that the oxidation stability and light resistance were excellent.

On the other hand, it was confirmed that the quantum dots of Comparative Examples 1 to 5 had reduced quantum efficiency and light resistance. In particular, the quantum dots of Comparative Examples 1 to 5 have a quantum efficiency of about 50% or less compared to the initial quantum efficiency after 15 days at room temperature, and after leaving the blue LED light source for 7 days, they are also about 50% or less of the initial quantum efficiency. , Remarkably reduced quantum efficiency and light resistance.

As described above, when the compound represented by Chemical Formula 1 is included as a ligand on the surface of the quantum dot, the surface of the quantum dot is protected to have excellent oxidation stability, to prevent quantum efficiency degradation, and thus to improve reliability.

Claims (13)

As a quantum dot having a ligand layer on the surface,
The ligand layer includes a compound represented by the following formula (1):
[Formula 1]

(In the formula 1,
R ₁ is a group represented by the following formula (2), a group represented by the following formula (3) or a group represented by the following formula (4),
R ₂ is a straight or branched alkylene group having 1 to 30 carbon atoms,
n is an integer from 1 to 250.)
[Formula 2]

[Formula 3]

[Formula 4]

(In the formulas 2 to 4, * is a bond with an oxygen atom.) The quantum dot according to claim 1, wherein R ₂ is a straight or branched alkylene group having 1 to 20 carbon atoms, and n is an integer from 1 to 100. The method according to claim 1, wherein the ligand layer comprises at least one selected from compounds represented by the following formulas 1-1 to 1-14, quantum dots:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

The method according to claim 1,
The ligand layer includes oleic aicd, lauric acid, 2-(2-methoxyethoxy)acetic acid, 2-[2-(2-methoxyethoxy)ethoxy]acetic acid and A quantum dot further comprising at least one member selected from the group consisting of succinic acid mono-[2-(2-methoxy-ethoxy)-ethyl] ester. The method according to claim 1, The quantum dot has a core-shell structure comprising a core and a shell covering the core,
The cores are InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, HgS, HgSe, HgTe, GaN, GaP, GaP Contains one or more of ZnO,
The shell includes at least one of ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, InP, InS, GaP, GaN, GaO, InZnP, InGaP, InGaN, InZnSCdSe, PbS, TiO, SrSe and HgSe Quantum dots. The method according to claim 1,
The quantum dot is characterized in that it comprises one or more selected from the group consisting of InP/ZnS, InP/ZnSe, InP/GaP/ZnS, InP/ZnSe/ZnS, InP/ZnSeTe/ZnS and InP/MnSe/ZnS. Quantum dots. Quantum dot light-emitting diode (QLED) comprising a quantum dot according to any one of claims 1 to 6. Quantum dot film comprising a quantum dot according to any one of claims 1 to 6. A light conversion resin composition comprising the quantum dots according to claim 1. A color filter formed using the light conversion resin composition according to claim 9. A light conversion laminated base material formed using the light conversion resin composition according to claim 9. An image display device comprising the color filter according to claim 10. An image display device comprising the light conversion laminated base according to claim 11.