TWI753119B - Quantum dot having organic ligand and use thereof - Google Patents

Abstract

The present invention provides a quantum dot having a ligand layer on the surface, wherein the ligand layer comprises at least one of a malonic acid derivative, a thiothiol compound, a thiocarboxylic acid compound, and a compound having an ester group and a thiol group. The quantum dot according to the present invention has excellent oxidation stability, and thus can be effectively applied to various uses such as a quantum dot film, a color filter, a quantum dot light-emitting diode, and the like.

Description

Quantum dots with organic ligands and their uses

The present invention relates to a quantum dot with organic ligands and uses thereof, more specifically, to a kind of quantum dots with malonic acid derivatives, thiothiol compounds, thiocarboxylic acid compounds, and compounds containing ester groups and sulfur A quantum dot in which at least one compound of an alcohol group is excellent in oxidative stability as an organic ligand, and its use.

Quantum dots are semiconductor nanocrystals with nanometer size, and have the characteristic that the energy band gap (Eg) varies according to size or shape. Due to the quantum confinement effect, such quantum dots can adjust the emission wavelength only by adjusting the size of the quantum dots, and can show excellent color purity and high photoluminescence (PL) efficiency, so not only In displays, it has also received a lot of attention in the fields of lighting sources, solar cells, semiconductor lasers/optical amplifiers, and biological imaging.

From the viewpoint that quantum dots having excellent optical properties can be mass-produced, quantum dots are mainly produced by wet chemical processes. The wet chemical process is a method of growing particles by adding a precursor substance to an organic solvent. In the case of manufacturing quantum dots by such a wet chemical process, organic ligands are used in order to prevent the aggregation of the quantum dots and to control the particle size of the quantum dots at the nanometer level. As such an organic ligand, oleic acid is generally used [see Korean Registered Patent No. 10-1,447,238].

However, such quantum dots are easily oxidized by oxygen in the air. Therefore, development related to quantum dots excellent in oxidative stability is desired.

An object of the present invention is to provide a quantum dot with excellent oxidation stability.

Another object of the present invention is to provide a quantum dot film including the above quantum dots.

Another object of the present invention is to provide a self-luminous photosensitive resin composition containing the above quantum dots.

Another object of the present invention is to provide a color filter using the self-luminous photosensitive resin composition.

Another object of the present invention is to provide a quantum dot light-emitting diode (Quantum Dot Light-Emitting Diode, QLED) comprising the above quantum dots.

In one aspect, the present invention provides a quantum dot having a ligand layer on a surface, wherein the ligand layer includes at least one of the compounds represented by the following Chemical Formulas 1 to 4.

該等式中，X¹為氫或C₁至C₃之烷基，R¹為C₄至C₂₂之烷基或C₄至C₂₂之烯基，X²及Y¹分別獨立地為氫或C₁至C₃之烷基，R²為C₄至C₂₂之烷基或C₄至C₂₂之烯基， n為0至1之整數，X³為C₁至C₃之伸烷基，R³為C₄至C₂₂之烷基或C₄至C₂₂之烯基，X⁴為C₁至C₅之伸烷基，Y²為C₄至C₂₂之烷基或C₄至C₂₂之烯基。

In this equation, X ¹ is hydrogen or a C ₁ -C ₃ alkyl group, R ¹ is a C ₄ -C ₂₂ alkyl group or a C ₄ -C ₂₂ alkenyl group, and X ² and Y ¹ are each independently hydrogen Or C ₁ to C ₃ alkyl, R ² is C ₄ to C ₂₂ alkyl or C ₄ to C ₂₂ alkenyl, n is an integer from 0 to 1, X ³ is C ₁ to C ₃ alkylene base, R ³ is C ₄ to C ₂₂ alkyl or C ₄ to C ₂₂ alkenyl, X ⁴ is C ₁ to C ₅ alkylene, Y ² is C ₄ to C ₂₂ alkyl or C ₄ to C ₂₂ alkenyl.

In another aspect, the present invention provides a quantum dot film comprising the above quantum dots.

In yet another aspect, the present invention provides a self-luminous photosensitive resin composition comprising the above quantum dots.

In yet another aspect, the present invention provides a color filter using the self-luminous photosensitive resin composition.

In yet another aspect, the present invention provides a quantum dot light-emitting diode comprising the above quantum dots.

The quantum dots formed by the present invention have excellent oxidative stability, and thus can be effectively applied to various applications such as quantum dot films, color filters, quantum dot light-emitting diodes, and the like.

Hereinafter, the present invention will be described in more detail.

An embodiment of the present invention relates to a quantum dot having a ligand layer on the surface, and the ligand layer includes a malonic acid derivative represented by the following chemical formula 1 and a thiol represented by the chemical formula 2 below. At least one of a thiol compound, a thiocarboxylic acid compound represented by Chemical Formula 3, and a compound containing an ester group and a thiol group represented by Chemical Formula 4.

該等式中， X¹為氫或C₁至C₃之烷基，R¹為C₄至C₂₂之烷基或C₄至C₂₂之烯基，X²及Y¹分別獨立地為氫或C₁至C₃之烷基，R²為C₄至C₂₂之烷基或C₄至C₂₂之烯基，n為0至1之整數，X³為C₁至C₃之伸烷基，R³為C₄至C₂₂之烷基或C₄至C₂₂之烯基，X⁴為C₁至C₅之伸烷基，Y²為C₄至C₂₂之烷基或C₄至C₂₂之烯基。

In this equation, X ¹ is hydrogen or a C ₁ -C ₃ alkyl group, R ¹ is a C ₄ -C ₂₂ alkyl group or a C ₄ -C ₂₂ alkenyl group, and X ² and Y ¹ are each independently hydrogen Or C ₁ to C ₃ alkyl, R ² is C ₄ to C ₂₂ alkyl or C ₄ to C ₂₂ alkenyl, n is an integer from 0 to 1, X ³ is C ₁ to C ₃ alkylene base, R ³ is C ₄ to C ₂₂ alkyl or C ₄ to C ₂₂ alkenyl, X ⁴ is C ₁ to C ₅ alkylene, Y ² is C ₄ to C ₂₂ alkyl or C ₄ to C ₂₂ alkenyl.

The C ₁ to C ₃ alkyl groups used in this specification refer to straight-chain or branched hydrocarbons with 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, etc. , but not limited to these.

The C ₄ to C ₂₂ alkyl groups used in this specification refer to straight-chain or branched hydrocarbons with 4 to 22 carbon atoms, such as n-butyl, isobutyl, tertiary butyl, pentyl base, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl , octadecyl, nonadecyl, eicosyl, behenyl, etc., but not limited to these.

The C ₄ to C ₂₂ alkenyl group used in this specification refers to a straight-chain or branched unsaturated hydrocarbon having one or more carbon-carbon double bonds and having 4 to 22 carbon atoms, such as butene. base, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl , hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, docosenyl, etc., but not limited to these.

The C ₁ to C ₃ alkylidene used in this specification refers to a straight-chain or branched divalent hydrocarbon with 1 to 3 carbon atoms, such as methylene, ethylidene, n-propylidene , isopropylidene, etc., but not limited to these.

The C ₁ to C ₅ alkylene groups used in this specification refer to straight-chain or branched divalent hydrocarbons with 1 to 5 carbon atoms, such as methylene, ethylidene, propylidene , butylene, etc., but not limited to these.

In one embodiment of the present invention, the compound represented by Chemical Formula 1 can be the following compound: X ¹ is hydrogen or methyl, R ¹ is C ₁₆ -C ₂₀ alkyl or C ₁₆ -C ₂₀ alkenyl .

In an embodiment of the present invention, the compound represented by Chemical Formula 1 can be the following compound: X ¹ is hydrogen, R ¹ is a C ₁₆ -C ₂₀ alkyl group or a C ₁₆ -C ₂₀ alkenyl group.

In one embodiment of the present invention, the compound represented by Chemical Formula 1 may be a compound represented by any one of the following Chemical Formulas 5 to 7.

In one embodiment of the present invention, the malonic acid derivative represented by Chemical Formula 1 is an organic ligand, and can coordinately bond to the surface of the quantum dots to perform the function of stabilizing the quantum dots.

The malonic acid derivative represented by the chemical formula 1 is a dibasic acid and is a strong acid with a pKa of 3 or less. Therefore, compared with oleic acid whose pKa is 4.25 and is a monobasic acid, the malonic acid derivative and quantum dots The bond strength is excellent.

In addition, when X ¹ is hydrogen, the malonic acid derivative represented by the chemical formula 1 can coexist with an acid functional group and a hydroxyl group due to keto-enol tautomerism. Forms stronger coordination bonds with metal elements that constitute quantum dots.

In one embodiment of the present invention, the compound represented by Chemical Formula 2 can be the following compounds: X ² and Y ¹ are each independently hydrogen, methyl or isopropyl, and R ² is an alkane of C ₁₆ to C ₂₀ or C ₁₆ to C ₂₀ alkenyl, and n is an integer from 0 to 1.

In one embodiment of the present invention, the compound represented by Chemical Formula 2 can be the following compounds: X ² and Y ¹ are hydrogen, R ² is a C ₁₆ -C ₂₀ alkyl group or a C ₁₆ -C ₂₀ alkenyl group , n is an integer from 0 to 1.

In one embodiment of the present invention, the compound represented by Chemical Formula 2 may be a compound represented by any one of the following Chemical Formula 8 to Chemical Formula 12.

In one embodiment of the present invention, the thiothiol compound represented by Chemical Formula 2 is an organic ligand, and can coordinately bond to the surface of the quantum dots to perform the function of stabilizing the quantum dots.

The thiothiol compound represented by the chemical formula 2 is a polar functional group, and has a thiol and a mercapto (thio) group in common, whereby the thiothiol compound and the quantum dot are superior in bonding force compared to oleic acid .

In addition, when X ² and Y ¹ are hydrogen, the thiothiol compound represented by the chemical formula 2 can bond with the quantum dots at a closer distance due to the small steric hindrance, so it can bond with the quantum dots constituting the quantum dots. Metal elements form stronger coordination bonds.

In one embodiment of the present invention, the compound represented by the chemical formula 3 may be a compound represented by any one of the following chemical formulae 13 to 16.

[Chemical formula 15]

該等式中，R³為C₄至C₂₂之烷基或C₄至C₂₂之烯基。

In this equation, R ³ is a C ₄ to C ₂₂ alkyl group or a C ₄ to C ₂₂ alkenyl group.

In an embodiment of the present invention, the compound represented by Chemical Formula 3 may be the following compound: R ³ is a C ₁₀ -C ₁₄ alkyl group or a C ₁₀ -C ₁₄ alkenyl group.

In one embodiment of the present invention, the compound represented by Chemical Formula 3 may be a compound represented by any one of the following Chemical Formulas 17 to 20.

[Chemical formula 19]

In one embodiment of the present invention, the thiocarboxylic acid compound represented by Chemical Formula 3 is an organic ligand, and can coordinately bond to the surface of the quantum dots to perform the function of stabilizing the quantum dots.

The thiocarboxylic acid compound represented by Chemical Formula 3 is a polar functional group, and has a carboxylic acid and a mercapto (sulfur) group in common, whereby the thiocarboxylic acid compound and the quantum dot have excellent bonding strength compared to oleic acid .

In addition, regarding the thiocarboxylic acid compound represented by Chemical Formula 3, the case where X ³ has a straight-chain structure is non-polar compared to the case where X ³ has a branched structure, and therefore, it is favorable for the arrangement of these to be more favorable. good.

In one embodiment of the present invention, the compound represented by Chemical Formula 4 may be the following compound: Y ² is an alkyl group of C ₁₆ to C ₂₀ or an alkenyl group of C ₁₆ to C ₂₀ .

In an embodiment of the present invention, the compound represented by the chemical formula 4 may be a compound represented by any one of the following chemical formulae 21 to 27.

[Chemical formula 21]

In one embodiment of the present invention, the compound represented by Chemical Formula 4 containing an ester group and a thiol group is an organic ligand, and the "=O" of the ester group and the "S" of the thiol group can be doubly Coordinate bonding to the surface of the quantum dots performs the function of stabilizing the quantum dots.

The compound containing an ester group and a thiol group represented by Chemical Formula 4 is a polar functional group, and has a thiol and an ester group in common, whereby, compared with oleic acid, the compound containing an ester group and a thiol group and quantum dots The bond strength is excellent.

In addition, in the case where X ⁴ has a linear structure in the compound containing an ester group and a thiol group represented by Chemical Formula 4, since the steric hindrance is small, it can bond with the quantum dots at a closer distance, so that it can be bonded with the quantum dots at a closer distance. The metal elements that make up the quantum dots form stronger coordination bonds.

At least one of the compounds represented by Chemical Formula 1 to Chemical Formula 4 may cover more than 5% of the surface with respect to the total surface area of the quantum dot.

At this time, the content of at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 4 may be 0.1 mol to 10 mol relative to 1 mol of the quantum dot.

The ligand layer including at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 4 may have a thickness of 0.1 nm to 2 nm, for example, a thickness of 0.5 nm to 1.5 nm.

In one embodiment of the present invention, quantum dots may be referred to as nanometer-sized semiconductor substances. Atoms form molecules, and molecules form small molecular aggregates called clusters to form nanoparticles. When such nanoparticles exhibit semiconducting properties, they are called quantum dots. If the quantum dot receives energy from the outside and becomes a floating state, it releases the energy corresponding to the energy band gap corresponding to the quantum dot itself.

The quantum dot is not particularly limited as long as it is a quantum dot particle that can emit light by light or electric stimulation. For example, it can be selected from the group consisting of: II-VI group semiconductor compounds; III-V group semiconductor compounds; IV-VI group semiconductor compounds; Use alone or in combination of two or more.

Specifically, the H-VI group semiconductor compound may be selected from the group consisting of: CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof Two element compounds of the group; selected from CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, and mixtures thereof tri-element compounds of the group consisting of; and tetra-element compounds selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof, but II-VI The group semiconductor compound is not limited to these.

The III-V semiconductor compound may be selected from the group consisting of: GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof Two element compounds of the group; selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, and mixtures thereof Tri-element compounds; and four elements selected from the group consisting of GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof compounds, but the III-V semiconductor compounds are not limited to these.

The IV-VI semiconductor compound may be at least one selected from the group consisting of: a two-element compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; a three-element compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; and selected from SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof The four-element compound of the composition group, but the group IV-VI semiconductor compound is not limited to these.

Group IV elements or compounds containing them may be selected from the group consisting of: elements selected from the group consisting of Si, Ge, and mixtures thereof; and selected from the group consisting of SiC, SiGe, and mixtures thereof The two-element compound of the group, but the group IV element or the compound containing it is not limited to these.

Quantum dots can have the following structures: a homogeneous single structure; a dual structure such as a core-shell structure, a gradient structure, etc.; or a mixed structure of these. Preferably, the quantum dots may have a core-shell structure including a core and a shell covering the core.

Specifically, in the core-shell dual structure, the substances forming the core and the shell, respectively, may include the aforementioned semiconductor compounds different from each other. For example, the core may comprise InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, HgS, HgSe, HgTe, GaN, GaP, GaAs, InGaN At least one of , InAs, and ZnO, the shell may include ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, InP, InS, GaP, GaN, GaO, InZnP, InGaP, InGaN, InZnSCdSe, PbS, At least one of TiO, SrSe, and HgSe, but not limited to these.

Quantum dots can be synthesized by a wet chemical process.

The so-called wet chemical process is a method in which a precursor substance is added to an organic solvent to grow particles. When the crystal grows, the organic solvent is naturally coordinated on the surface of the quantum dot crystal, and acts as a dispersant to adjust the growth of the crystal. Therefore, compared with the organic metal chemical vapor deposition process or molecular beam epitaxy, etc. The vapor deposition method can control the growth of nanoparticles through an easy and inexpensive process, so it is better to use a wet chemical process to manufacture quantum dots.

In the case of manufacturing quantum dots by a wet chemical process, organic ligands are used in order to prevent aggregation of quantum dots and to control the particle size of quantum dots at the nanometer level. As such an organic ligand, oleic acid is generally used.

In one aspect of the present invention, the oleic acid used in the manufacturing process of the quantum dots is exchanged by a ligand exchange method using at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 4 .

Ligand exchange can be carried out by: adding the organic ligand to be exchanged (i.e. from chemical formula 1 to chemical formula 4) in the dispersion liquid containing the quantum dots with the original organic ligand (i.e. oleic acid). at least one of the compounds represented by the compound), which is stirred at normal temperature to 200° C. for 30 minutes to 3 hours to obtain quantum dots bonded with at least one of the compounds represented by the chemical formulas 1 to 4. If necessary, a process of separating and purifying the quantum dots bound with at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 4 may be further performed.

The quantum dots of one embodiment of the present invention can be produced by the organic ligand exchange method under simple stirring treatment at room temperature as described above, and thus have the advantage of being mass-produced.

In addition, the quantum dot of one embodiment of the present invention can maintain a quantum efficiency of 80% or more relative to the initial quantum efficiency even after 10 days, and can be stored stably for a long time, so that it can be commercialized for various purposes.

<Quantum Dot Film>

An embodiment of the present invention relates to a quantum dot film including the aforementioned quantum dots.

The quantum dot film includes a quantum dot dispersion layer, and the quantum dot dispersion layer includes a polymer resin and the aforementioned quantum dots dispersed in the polymer resin.

As the polymer resin, for example, epoxy resin, epoxy acrylate, lauryl acrylate, norbornene, polyethylene, polystyrene, ethylene-styrene copolymer, bisphenol A and bisphenol A derivatives can be used. Acrylates, Acrylates Containing Perylene Derivatives, Isobornyl Acrylate, Polyphenylalkylsiloxane, Polydiphenylsiloxane, Polydialkylsiloxane, Sisesquioxane, Fluorine Silicone, vinyl-substituted silicone and hydride-substituted silicone, etc. These polymer resins can be used alone or in combination of two or more.

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

The barrier layer may have 0.001 cubic centimeters/square meter. sky. Bar (cm ³ /m ² .day.bar) oxygen transmission rate and 0.001 grams / square meter below. It has a moisture permeability of less than one day (g/m ² ·day), and may contain, for example, polyester, polycarbonate, polyolefin, cyclic olefin polymer, or polyimide.

The thickness of the quantum dot dispersion layer can be from 10 microns to 100 microns, and the thickness of the barrier layer can be from 50 microns to 70 microns.

<Self-luminous photosensitive resin composition>

One embodiment of the present invention relates to a self-luminous photosensitive resin composition comprising the aforementioned quantum dots.

The self-luminous photosensitive resin composition contains quantum dots, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.

The content of the quantum dots in the self-luminous photosensitive resin composition is not particularly limited, for example, it can be 3 to 80% by weight relative to 100% by weight of the total solid content of the self-luminous photosensitive resin composition, for example, it can be 5% to 70% by weight.

The alkali-soluble resin can perform the function of making the non-exposed part of the pattern made of the self-luminous photosensitive resin composition alkali-soluble and removing it, and leaving the exposed area remaining. In addition, when the self-luminous photosensitive resin composition includes an alkali-soluble resin, the following functions can be performed: the quantum dots can be uniformly dispersed in the composition, and the quantum dots can be protected to maintain brightness during the process.

The alkali-soluble resin can be selected and used with an acid value of 50 to 200 (KOH mg/g (KOH mg/g)). The "acid value" is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the polymer, and is related to solubility. If the acid value of the alkali-soluble resin is less than this range, it may be difficult to secure a sufficient development speed, and if the acid value exceeds this range, the following problems may arise: the adhesiveness with the substrate is lowered, and short-circuiting of the pattern is likely to occur. The storage stability of the entire composition decreases and the viscosity increases.

In addition, the weight average molecular weight of the alkali-soluble resin may be 3,000 to 30,000, preferably 5,000 to 20,000, and the molecular weight distribution may be 1.5 to 6.0, preferably 1.8 to 4.0.

The alkali-soluble resin may be a polymer of a carboxyl group-containing unsaturated monomer, or a copolymer of a carboxyl group-containing unsaturated monomer and a monomer having an unsaturated bond that can be copolymerized therewith, and combinations thereof.

As a carboxyl group-containing unsaturated monomer, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated tricarboxylic acid, etc. are mentioned. Specifically, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As an unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc. are mentioned, for example. The unsaturated dicarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated dicarboxylic acid may also be a mono(2-(meth)acryloyloxyalkyl) ester, for example, mono(2-acryloyloxyethyl) succinate, succinic acid mono(2-acryloyloxyethyl) ester, Mono(2-methacryloyloxyethyl) acid, mono(2-acryloyloxyethyl) phthalate, mono(2-methacryloyloxyethyl) phthalate Wait. The unsaturated dicarboxylic acid may also be the mono(meth)acrylate of the dicarboxylate polymer at both ends, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylic acid esters, etc. These carboxyl group-containing monomers may be used alone or in combination of two or more.

In addition, the monomer copolymerizable with the carboxyl group-containing unsaturated monomer may be at least one selected from the group consisting of: aromatic vinyl compounds, unsaturated carboxylate compounds, unsaturated carboxylate aminoalkanes base ester compound, unsaturated glycidyl carboxylate compound, vinyl carboxylate compound, unsaturated ether compound, vinyl cyanide compound, unsaturated imide compound, unsaturated imine compound, aliphatic conjugated diene compound , Macromonomers, bulky monomers, and combinations thereof having a monoacryloyl group or a monomethacryloyl group at the end of the molecular chain.

More specifically, the copolymerizable monomers include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, and o-methoxybenzene Ethylene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidol Aromatic vinyl compounds such as vinyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate , n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, acrylic acid Secondary butyl ester, secondary butyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy acrylate Propyl, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, acrylic acid -3-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate , benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate , 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethyl Glycol Acrylate, Methoxytriethylene Glycol Methacrylate, Methoxy Propylene Glycol Acrylate, Methoxy Propylene Glycol Methacrylate, Methoxy Dipropylene Glycol Acrylate, Methoxy Dipropylene Glycol Methacrylate , isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, Unsaturated carboxylic acid esters such as 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate; acrylic acid- 2-aminoethyl ester, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-amino acrylate Propyl, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, methyl methacrylate 3-aminopropyl acrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate and other unsaturated carboxylic acid aminoalkyl ester compounds; glycidyl acrylate Esters, glycidyl methacrylate and other unsaturated carboxylic acid glycidyl ester compounds; vinyl acetate, vinyl propionate, butyl Vinyl carboxylate compounds such as vinyl acetate and vinyl benzoate; unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile , vinylidene cyanide and other cyanide compounds; acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylate Unsaturated amide compounds such as amide; unsaturated amide compounds such as maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; 1,3-butadiene, isoprene, chloroprene and other aliphatic conjugated diene compounds; and polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly n-Butyl methacrylate, a macromonomer with a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polysiloxane; one with a norbornyl skeleton that reduces the relative permittivity value Monomers, monomers with adamantane skeleton, monomers with rosin skeleton and other bulky monomers, etc.

With respect to 100% by weight of the total solid content of the self-luminous photosensitive resin composition, it can contain 5% by weight to 80% by weight, specifically 10% by weight to 70% by weight, more specifically 15% by weight to 60% by weight of alkali solubility resin.

The photopolymerizable compound is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, difunctional monomers, and other polyfunctional monomers.

The type of monofunctional monomer is not particularly limited, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, Acrylate-2-hydroxyethyl ester, N-vinylpyrrolidone, etc.

The type of the difunctional monomer is not particularly limited, and examples thereof include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.

The types of other polyfunctional monomers are not particularly limited, for example, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated Trimethylolpropane tri(meth)acrylate, neotaerythritol tri(meth)acrylate, neotaerythritol tetra(meth)acrylate, dipivalerythritol tri(meth)acrylate, Dipiveaerythritol Penta(meth)acrylate, Ethoxylated Dipiveaerythritol Hex(meth)acrylate, Propoxylated Dipiveaerythritol Hex(meth)acrylate, Dipivale Tetraol hexa(meth)acrylate etc. Among these, polyfunctional monomers having a bifunctional or more functionalities can be preferably used.

With respect to 100% by weight of the total solid content of the self-luminous photosensitive resin composition, it can contain 5% by weight to 70% by weight, specifically 10% by weight to 60% by weight, more specifically 15% by weight to 50% by weight of photopolymerization sexual compounds.

As long as the photopolymerization initiator can polymerize a photopolymerizable compound, the kind can be used without particular limitation. Especially from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, etc., the photopolymerization initiator preferably uses at least one compound selected from the group consisting of: acetophenone-based compounds, Benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, oxime-based compounds, and thioxanthone-based compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methyl Thiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2 -Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino) -1-(4-Mofolinylphenyl)butan-1-one, etc.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl thioether, 3,3',4,4'-tetrakis(tertiary butylcarbonyl peroxide) benzophenone, 2,4,6-trimethylbenzophenone, etc.

Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis (Trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-sunenyl-1,3,5 -Triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-[2-(5-Methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2 -yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethene base]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5 - Triazine etc.

Specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2 ,3-Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl (Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2,2- Bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or phenyl at 4,4',5,5' position via carbonyl Oxy-substituted biimidazole compounds, etc. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl -1,2'-biimidazole.

Specific examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and as a commercial item, Irgacure OXE 01 manufactured by BASF Corporation , Irgacure OXE 02 is representative.

As the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4 -Propoxythioxanthone, etc.

0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight of light relative to 100% by weight of the total solid content of the self-luminous photosensitive resin composition polymerization initiator.

In order to improve the sensitivity of the self-luminous photosensitive resin composition of the present invention, the photopolymerization initiator may further contain a photopolymerization initiator auxiliary. When a photopolymerization initiation adjuvant is included, there is an advantage that the sensitivity is further increased and the productivity is improved.

For example, the photopolymerization initiation auxiliary can preferably use at least one compound selected from the group consisting of amine compounds, carboxylic acid compounds, and organosulfur compounds having a thiol group, but it is not limited to these.

The self-luminous photosensitive resin composition may further contain a solvent, and the solvent is not particularly limited, and may be an organic solvent commonly used in the technical field to which the present invention pertains.

For example, examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether. Diethylene glycol dialkyl ethers such as ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as esters; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy Alkyl butyl acetate, methoxyamyl acetate and other alkanediol alkyl ether acetates; benzene, toluene, xylene, mesitylene and other aromatic hydrocarbons; methyl ethyl ketone, acetone, Methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone and other ketones; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol and other alcohols; 3- Esters such as ethyl ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone, etc. These solvents may be used alone or in combination of two or more.

The content of the solvent in the self-luminous photosensitive resin composition may be 20 to 90% by weight, preferably 25 to 85% by weight, relative to 100% by weight of the entire self-luminous photosensitive resin composition, More preferably, it contains 30% by weight to 80% by weight.

The self-luminous photosensitive resin composition of the present invention may further contain additives such as adhesion promoters, surfactants, antioxidants, ultraviolet absorbers, and anti-agglomeration agents.

Based on 100% by weight of the entire self-luminous photosensitive resin composition, 0.05% by weight to 10% by weight, specifically 0.1% by weight to 10% by weight, more specifically 0.1% by weight to 5% by weight of additives, but It is not limited to these.

One embodiment of the present invention relates to a color filter produced by using the self-luminous photosensitive resin composition.

The color filter of the present invention comprises a cured product of the self-luminous photosensitive resin composition containing quantum dots of the present invention, and therefore, the quantum dots are excellent in oxidation stability and thus have the advantage of being excellent in light-emitting properties.

The color filter includes a substrate and a pattern layer formed on the upper portion of the substrate.

The substrate may be the color filter itself, or may be a portion where the color filter is located in a display device or the like, and is not particularly limited. The substrate can be glass, silicon (Si), silicon oxide (SiOx) or a polymer substrate, and the polymer substrate can be polyethersulfone (PES) or polycarbonate (PC), etc.

The pattern layer may be a layer comprising the self-luminous photosensitive resin composition of the present invention, or may be a layer produced by coating the self-luminous photosensitive resin composition and exposing, developing, and thermally curing it in a predetermined pattern . The pattern layer may be formed by a method generally known in the technical field to which the present invention pertains.

As mentioned above, the color filter including the substrate and the pattern layer may further include a partition wall or a black matrix formed between the patterns, but is not limited to these.

In addition, a protective film formed on the upper portion of the pattern layer of the color filter may be further included.

The color filter may include at least one selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. Specifically, the color filter may include at least one selected from the group consisting of: a red pattern layer comprising the red quantum dots of the present invention, a green pattern layer comprising the green quantum dots of the present invention, and a pattern layer comprising the present invention The blue pattern layer of the invented blue quantum dot. The red pattern layer, the green pattern layer, and the blue pattern layer can emit red light, green light, and blue light, respectively, when irradiated with light. At this time, the emitted light of the light source is not particularly limited, but it is important for excellent color reproducibility. In one aspect, a light source that emits blue light can be used.

The color filter may include a pattern layer of only two hues among the red pattern layer, the green pattern layer, and the blue pattern layer, but is not limited thereto. Furthermore, in the case where the color filter has a pattern layer of only two hues, the pattern layer may further include a transparent pattern layer that does not contain quantum dots.

In the case where the color filter has a pattern layer of only two hues, the following light sources can be used: the emitted light is a wavelength exhibiting a hue other than the two hues. For example, in the case where the color filter includes a red pattern layer and a green pattern layer, a light source emitting blue light may be used, in which case the red quantum dots emit red light, the green quantum dots emit green light, and the transparent pattern layer The blue color may appear because the blue light from the light source is clearly visible.

An embodiment of the present invention relates to an image display device including the aforementioned color filter.

The color filter of the present invention can be applied not only to ordinary liquid crystal display devices, but also to various image display devices such as electroluminescence display devices, plasma display devices, and electric field emission display devices.

<Quantum Dot Light Emitting Diode>

An embodiment of the present invention relates to a quantum dot light-emitting diode (Quantum Dot Light-Emitting Diode, QLED) comprising the aforementioned quantum dots.

The quantum dot light-emitting diode system is an electroluminescence (Electroluminescence, EL) element in which quantum dots are electrically excited to emit light.

In quantum dot light-emitting diodes, electrons and holes injected from two electrodes form excitons in the quantum dot light-emitting layer, and emit light by luminescent recombination (radiative recombination) of excitons . This is the same as the working principle of OLED (Organic Light-Emitting Diode, OLED), so it can be used in the multilayer device structure directly using the electron/hole injection layer and transport layer of OLED, etc. An organic light-emitting material that uses quantum dots to form a light-emitting layer.

In addition, the quantum dots of one embodiment of the present invention can be applied not only to the aforementioned displays, but also to be used as raw materials for illumination light sources, solar cells, semiconductor lasers/optical amplifiers, biological imaging, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Experimental Examples. Furthermore, it is obvious to those skilled in the art that these Examples, Comparative Examples and Experimental Examples are only for illustrating the present invention, and the scope of the present invention is not limited to them.

Synthesis Example 1: Synthesis of InP core-only quantum dots

0.05839 g of indium acetate, 0.12019 g of oleic acid and 10 ml of 1-octadecene (ODE) were added to a 3-neck flask. After a process of degassing at 110°C, 100 mTorr for 30 minutes while stirring the flask, it was heated at a temperature of 270°C under inert gas until the solution became clear.

As a phosphorus (P) precursor, 0.025054 g of tris(trimethylsilyl)phosphine was prepared, added to 0.5 ml of 1-octadecene and 0.5 ml of tri-n-octylphosphine, stirred, and quickly poured into the In a flask heated at 270°C under inert gas. After performing the reaction for 1 hour, rapid cooling was performed to terminate the reaction. Next, 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, secondary purification was performed using a precipitation and redispersion method. The purified InP core nanoparticles were dispersed in 1-octadecene and stored.

Synthesis Example 2: Synthesis of InP/ZnS Core-Shell Quantum Dots

3.669 g of zinc acetate, 20 ml of oleic acid and 20 ml of 1-octadecene were added to a three-necked flask, and after stirring at 110° C. and 100 mtorr for 30 minutes, the inert The solution was heated at 270°C under gas until the solution became transparent, and then cooled to 60°C to obtain a transparent precursor solution in the form of zinc oleate.

Add 0.6412 g of sulfur and 10 ml of tri-n-octyl phosphine to the three-necked flask, heat at a temperature of 80°C while stirring under an inert gas environment, until the solution becomes transparent, and then cool to room temperature to obtain trioctyl phosphate (Trioctyl phosphate, TOP): S precursor solution in S form.

The InP core nanoparticle solution prepared in Synthesis Example 1 was added to another three-necked flask, the temperature of the flask was adjusted to 300°C, and 0.6 ml of the pre-prepared zinc precursor solution was rapidly injected with a syringe. Next, 0.3 mL of the pre-prepared S precursor solution was injected into the flask at a rate of 2 mL/hour (mL/hr) by means of a syringe pump. After the injection was completed, the reaction was further carried out for 3 hours, and rapid cooling was carried out to terminate the reaction. 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, secondary purification was performed using a precipitation and redispersion method. The purified InP/ZnS core-shell structured nanoparticles were dispersed in 1-octadecene and stored.

Example 1-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 5

To a solution prepared by dispersing 1 g of quantum dots of InP core alone in Synthesis Example 1 with oleic acid bound to the surface in 10 ml of toluene, 0.5 g of a novel ligand of malonic acid derivative represented by Chemical formula 5 was added. grams, mixed for more than 30 minutes. In this process, the novel ligand represented by Chemical Formula 5 replaces oleic acid on the surface of the core-alone quantum dots. Next, 10 ml of ethanol was added to the mixed solution in which the quantum dot-novel ligand binding body and the unreacted ligand were mixed to cause the quantum dot-novel ligand binding body to agglomerate. The agglomerated quantum dot-novel ligand bonds were separated from the oleic acid and unreacted ligands exfoliated from the quantum dots by centrifugation (8000 rpm, 30 minutes). Next, the quantum dot-novel ligand conjugate was dispersed in toluene at a concentration of 0.1 grams per milliliter (g/ml).

Example 1-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 5

To a solution prepared by dispersing 1 g of InP/ZnS quantum dots of Synthesis Example 2 with oleic acid bound on the surface in 10 ml of toluene, 0.5 g of a novel ligand of malonic acid derivative represented by Chemical formula 5 was added. , and mixed for more than 30 minutes. In this process, novel ligands replace oleic acid on the surface of the quantum dots. Next, 10 ml of ethanol was added to the mixed solution in which the quantum dot-novel ligand binding body and the unreacted ligand were mixed to cause the quantum dot-novel ligand binding body to agglomerate. The agglomerated quantum dot-novel ligand bonds were separated from the oleic acid and unreacted ligands exfoliated from the quantum dots by centrifugation (8000 rpm, 30 minutes). Next, the quantum dot-novel ligand conjugate was dispersed in toluene at a concentration of 0.1 g/ml.

Example 2-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 6

It carried out similarly to Example 1-1 except having used the ligand represented by chemical formula 6 instead of the ligand represented by chemical formula 5.

Example 2-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 6

It carried out similarly to Example 1-2 except having used the ligand represented by chemical formula 6 instead of the ligand represented by chemical formula 5.

Example 3-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 7

It carried out similarly to Example 1-1 except having used the ligand represented by chemical formula 7 instead of the ligand represented by chemical formula 5.

Example 3-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 7

It carried out similarly to Example 1-2 except having used the ligand represented by chemical formula 7 instead of the ligand represented by chemical formula 5.

Example 4-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 8

It carried out similarly to Example 1-1 except having used the ligand represented by chemical formula 8 instead of the ligand represented by chemical formula 5.

Example 4-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 8

It carried out similarly to Example 1-2 except having used the ligand represented by chemical formula 8 instead of the ligand represented by chemical formula 5.

Example 5-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 9

It carried out similarly to Example 1-1 except having used the ligand represented by chemical formula 9 instead of the ligand represented by chemical formula 5.

Example 5-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 9

It carried out similarly to Example 1-2 except having used the ligand represented by chemical formula 9 instead of the ligand represented by chemical formula 5.

Example 6-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 12

The same procedure as in Example 1-1 was carried out, except that the ligand represented by the chemical formula 12 was used instead of the ligand represented by the chemical formula 5.

Example 6-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 12

It carried out similarly to Example 1-2 except having used the ligand represented by chemical formula 12 instead of the ligand represented by chemical formula 5.

Example 7-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 17

It carried out similarly to Example 1-1 except having used the ligand represented by chemical formula 17 instead of the ligand represented by chemical formula 5.

Example 7-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 17

It carried out similarly to Example 1-2 except having used the ligand represented by chemical formula 17 instead of the ligand represented by chemical formula 5.

Example 8-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 18

It carried out similarly to Example 1-1 except having used the ligand represented by chemical formula 18 instead of the ligand represented by chemical formula 5.

Example 8-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 18

The same procedure as in Example 1-2 was carried out except that the ligand represented by Chemical Formula 18 was used instead of the ligand represented by Chemical Formula 5.

Example 9-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 19

It carried out similarly to Example 1-1 except having used the ligand represented by chemical formula 19 instead of the ligand represented by chemical formula 5.

Example 9-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 19

It carried out similarly to Example 1-2 except having used the ligand represented by chemical formula 19 instead of the ligand represented by chemical formula 5.

Example 10-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 21

It carried out similarly to Example 1-1 except having used the ligand represented by chemical formula 21 instead of the ligand represented by chemical formula 5.

Example 10-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 21

It carried out similarly to Example 1-2 except having used the ligand represented by chemical formula 21 instead of the ligand represented by chemical formula 5.

Example 11-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 22

The same procedure as in Example 1-1 was carried out except that the ligand represented by Chemical Formula 22 was used instead of the ligand represented by Chemical Formula 5.

Example 11-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 22

It carried out similarly to Example 1-2 except having used the ligand represented by chemical formula 22 instead of the ligand represented by chemical formula 5.

Example 12-1: Manufacture of InP core-only quantum dots having ligands represented by Chemical formula 27

It carried out similarly to Example 1-1 except having used the ligand represented by chemical formula 27 instead of the ligand represented by chemical formula 5.

Example 12-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula 27

It carried out similarly to Example 1-2 except having used the ligand represented by chemical formula 27 instead of the ligand represented by chemical formula 5.

Comparative Example 1-1: Preparation of InP core-only quantum dots without ligand exchange reaction

1 g of the quantum dots of InP core alone of Synthesis Example 1 having oleic acid bound on the surface was dispersed in toluene at a concentration of 0.1 g/ml.

Comparative Example 1-2: Preparation of InP/ZnS core-shell quantum dots without ligand exchange reaction

1 g of InP/ZnS core-shell quantum dots of Synthesis Example 2 with oleic acid bound on the surface were dispersed in toluene at a concentration of 0.1 g/ml.

Comparative Example 2-1: InP core-only quantum dot having a ligand represented by chemical formula a the manufacture of

It carried out similarly to Example 1-1 except having used the ligand represented by the following chemical formula a instead of the ligand represented by chemical formula 5.

Comparative Example 2-2: Production of InP/ZnS Core-Shell Quantum Dots with Ligands Represented by Chemical Formula a

It carried out similarly to Example 1-2 except having used the ligand represented by chemical formula a instead of the ligand represented by chemical formula 5.

Experimental example 1: (1) Maximum absorption wavelength (λmax)

Using an ultraviolet-visible light (UV-Visible) spectrophotometer, the maximum absorption wavelength ( λmax), and the maximum absorption wavelength (λmax) after standing at room temperature for 4 days were measured.

When the surface of the quantum dots is oxidized, the size of the quantum dots decreases, and the maximum light absorption wavelength (λmax) decreases. Therefore, the amount of decrease in the maximum light absorption wavelength (λmax) can be measured to confirm the oxidation stability. That is, the oxidation stability can be confirmed by measuring Δλmax.

The measurement results are shown in Table 1 below.

As shown in Table 1, it was confirmed that the quantum dots of Comparative Example 1-1 and Comparative Example 2-1 had organic coordination of at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 4 of the present invention The quantum dots of Example 1-1 to Example 12-1 were more excellent in oxidation stability.

(2) Quantum efficiency

Using a PL spectrophotometer and an ultraviolet-visible light (UV-Vis) spectrophotometer, the quantum dot dispersions of Examples 1-2 to 12-2 and Comparative Example 1-2 and Comparative Example 2-2 were tested at the initial stage of production. The quantum efficiency (QY%) of , and the quantum efficiency (QY%) after standing at room temperature for 10 days were measured.

When the surface of the quantum dot is oxidized, the quantum efficiency decreases, so the amount of decrease in the quantum efficiency can be measured to confirm the oxidation stability. That is, the oxidation stability can be confirmed by measuring ΔQY%.

As shown in Table 2, it was confirmed that the quantum dots of Comparative Example 1-2 and Comparative Example 2-2 had an organic coordination of at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 4 of the present invention The quantum dots of Examples 1-2 to 12-2 of the bulk were suppressed in the reduction of quantum efficiency. Therefore, it was confirmed that compared with the quantum dots of Comparative Example 1-2 and Comparative Example 2-2, the examples having the organic ligand of at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 4 of the present invention The quantum dots of 1-2 to Example 12-2 were more excellent in oxidation stability.

In particular, it was confirmed that the quantum dots of Example 1-2 to Example 12-2 having an organic ligand of at least one of the compounds represented by Chemical Formula 1 to Chemical Formula 4 of the present invention were relatively stable even after 10 days. The quantum efficiency of the initial quantum efficiency remains above 80%. On the contrary, the quantum efficiency of the quantum dots of Comparative Examples 1-2 with oleic acid ligands is greatly reduced to the level of 35% compared to the initial quantum efficiency. , the quantum dots of Comparative Example 2-2 with thiol group at the end of the ligand also showed a quantum efficiency of 65% compared to the initial quantum efficiency, and the effect of suppressing the reduction of quantum efficiency was poor.

The specific part of the present invention has been described in detail above, but it is obvious to those with ordinary knowledge in the technical field to which the present invention pertains that such specific description is only a preferred implementation example, and the scope of the present invention is not limited by this. Those with ordinary knowledge in the technical field to which the present invention pertains can perform various applications and modifications within the scope of the present invention based on the contents.

Therefore, it can be said that the substantial scope of the present invention is defined by the claims and their equivalents.

Claims (14)

A quantum dot having a ligand layer on the surface, wherein the ligand layer comprises at least one of the compounds represented by the following Chemical Formulas 2 to 4:

In this equation, X ² and Y ¹ are each independently hydrogen or a C ₁ -C ₃ alkyl group, R ² is a C ₄ -C ₂₂ alkyl group or a C ₄ -C ₂₂ alkenyl group, and n is 0 to Integer of 1, X ³ is C ₁ to C ₃ alkylene, R ³ is C ₄ to C ₂₂ alkyl or C ₄ to C ₂₂ alkenyl, X ⁴ is C ₁ to C ₅ alkylene , Y ² is C ₄ to C ₂₂ alkyl or C ₄ to C ₂₂ alkenyl. The quantum dot according to claim 1, wherein in the compound represented by Chemical Formula 2, X ² and Y ¹ are each independently hydrogen, methyl or isopropyl, and R ² is a C ₁₆ to C ₂₀ alkyl group or C ₁₆ to C ₂₀ alkenyl, and n is an integer from 0 to 1. The quantum dot of claim 2, wherein X ² and Y ¹ are hydrogen, R ² is a C ₁₆ -C ₂₀ alkyl group or a C ₁₆ -C ₂₀ alkenyl group, and n is an integer from 0 to 1. The quantum dot according to claim 1, wherein the compound represented by the chemical formula 2 is a compound represented by any one of the following chemical formulas 8 to 12:

[Chemical formula 12]

The quantum dot according to claim 1, wherein the compound represented by Chemical Formula 3 is a compound represented by any one of the following Chemical Formulas 13 to 16:

In this equation, R ³ is a C ₄ to C ₂₂ alkyl group or a C ₄ to C ₂₂ alkenyl group. The quantum dot according to claim 5, wherein R ³ is a C ₁₀ -C ₁₄ alkyl group or a C ₁₀ -C ₁₄ alkenyl group. The quantum dot according to claim 1, wherein the compound represented by Chemical Formula 3 is a compound represented by any one of the following Chemical Formulas 17 to 20:

The quantum dot of claim 1, wherein in the compound represented by Chemical Formula 4, Y ² is a C ₁₆ to C ₂₀ alkyl group or a C ₁₆ to C ₂₀ alkenyl group. The quantum dot according to claim 1, wherein the compound represented by the chemical formula 4 is a compound represented by any one of the following chemical formulas 21 to 27: [chemical formula 21]

[Chemical formula 27]

The quantum dot of claim 1, wherein the quantum dot has a core-shell structure comprising a core and a shell covering the core, the core comprising InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, At least one of CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, HgS, HgSe, HgTe, GaN, GaP, GaAs, InGaN, InAs, and ZnO, the shell includes ZnS, ZnSe, ZnTe, ZnO, CdS , at least one of CdSe, CdTe, CdO, InP, InS, GaP, GaN, GaO, InZnP, InGaP, InGaN, InZnSCdSe, PbS, TiO, SrSe, and HgSe. A quantum dot film comprising the quantum dots according to any one of claim 1 to claim 10. A self-luminous photosensitive resin composition comprising the quantum dots according to any one of claim 1 to claim 10. A color filter is produced using the self-luminous photosensitive resin composition as described in claim 12. A quantum dot light-emitting diode (Quantum Dot Light-Emitting Diode, QLED), comprising the quantum dot according to any one of claim 1 to claim 10.