Surface-modified semiconductor light-emitting nanoparticles and a method for manufacturing the same

Abstract

The present invention relates to a composition comprising nanoparticles and a method for manufacturing the same.

Description

Technology Field

[0001] The present invention relates to a composition comprising semiconductor light-emitting nanoparticles, a formulation, a process for preparing the composition, a use of the composition, a use of a chemical compound, an optical medium, and an optical device. Background Technology

[0002] US 9,701,896 B1 discloses a composition comprising quantum dots of TOPO, TOPO + KDP, or TOPO + Zn oleate and an emission stabilizer.

[0003] US 2010 / 068522 A1 discloses InP quantum dots functionalized with 10-undecylenic acid.

[0004] APL Materials 4, 040702 (2016) mentions the addition of trioctylphosphine oxide to an acrylic polymer composition before curing the composition.

[0005] CN 106590629 A discloses improved stability of perovskite quantum dots by crystallizing carboxybenzene around the quantum material.

[0006] Patent documents

[0007] 1. US 9,701,896 B1

[0008] 2. US 2010 / 068522 A1

[0009] 3. CN 106590629 A

[0010] Non-patent literature

[0011] 4. APL Materials 4, 040702(2016) The problem to be solved

[0012] However, the inventors have newly discovered that there are still one or more significant problems requiring improvement, as listed below:

[0013] Improvement of quantum yield of nanoparticles, prevention or reduction of quantum yield degradation in diluted compositions and / or radiation-rich environments, higher device efficiency, optimization of surface state of nanoparticle shell portions, reduction of lattice defects in the nanoparticle shell layer, reduction / prevention of dangling bond formation in the shell layer, better thermal stability, improved oxidation stability, improved stability against radical substances, improved stability during long-term storage without causing significant QY degradation, improved chemical stability, and a more environmentally friendly and safer manufacturing process.

[0014] The inventors aimed to solve one or more of the problems mentioned above. means of solving the problem

[0015] A novel method for preparing a composition, comprising the following steps and essentially being composed thereof, has been discovered, and the method is:

[0016] a) a step of mixing at least one first organic compound with semiconductor light-emitting nanoparticles comprising a core, preferably together with other materials, to obtain a first mixture, wherein the mixing step comprises, optionally, the nanoparticles comprising at least one shell layer, and

[0017] The above first organic compound is represented by the following chemical formula (I);

[0018] A(B) n C - (I)

[0019] In the formula, A represents the first terminal group; B is the 2-terminal group; C is the second terminal group; and n is 0 or 1.

[0020] In another aspect, the present invention also relates to a composition obtainable or obtained from the process of the present invention.

[0021] In another aspect, the present invention also at least:

[0022] a) a semiconductor light-emitting nanoparticle comprising a core, optionally at least one shell layer,

[0023] b) the first chemical compound, and

[0024] c) Any other compound

[0025] It relates to a composition that includes, is essentially constituted, or is formed of,

[0026] The first organic compound is represented by the following chemical formula (I);

[0027] A(B) n C - (I)

[0028] In the formula, A represents the first terminal group; B is the 2-terminal group; C is the second terminal group; and n is 0 or 1.

[0029] In another aspect, the present invention relates to the use of a first compound represented by formula (I) in a composition comprising at least one semiconductor light-emitting nanoparticle, a method for preparing the composition, or a method for preparing an optical device, and

[0030] A(B) n C - (I)

[0031] In the formula, A represents the first terminal group; B is the 2-terminal group; C is the second terminal group; and n is 0 or 1.

[0032] In another aspect, the present invention also relates to the use of the composition of the present invention in electronic devices, optical devices, or biomedical devices.

[0033] In another aspect, the present invention also relates to an optical medium comprising at least one semiconductor light-emitting nanoparticle and a first chemical compound represented by formula (I), and

[0034] A(B) n C - (I)

[0035] In the formula, A represents the first terminal group; B is the 2-terminal group; C is the second terminal group; and n is 0 or 1.

[0036] In another aspect, the present invention also relates to an optical device comprising at least one optical medium of the present invention. Brief explanation of the drawing

[0037] Figure 1 shows the QY measurement results of Comparative Example 1. Figure 2 shows the QY measurement results of Example 1. Figure 3 shows the QY measurement results of Example 2. Figure 4 shows the QY measurement results of seven different samples of Comparative Example 2. Figure 5 shows the QY measurement results of Operation Example 3. Figure 6 shows the QY measurement results of Example 4. Figure 7 shows the QY measurement results of Operation Example 5. Specific details for implementing the invention

[0038] According to the present invention, a method for preparing a composition comprises the following steps:

[0039] a) a step of mixing at least one first organic compound with a semiconductor light-emitting nanoparticle comprising a core, preferably together with another material, to obtain a first mixture, wherein the nanoparticle optionally comprises at least one shell layer, and the first mixture is a composition, wherein the mixing step is essentially performed or composed, and

[0040] The above first organic compound is represented by the following chemical formula (I);

[0041] A(B) n C - (I)

[0042] In the formula, A represents the first terminal group; B is the 2-terminal group; C is the second terminal group; and n is 0 or 1.

[0043] - First organic compound

[0044] As described above, the first organic compound is represented by the following chemical formula (I), and

[0045] A(B) n C - (I)

[0046] In the formula, A represents the first terminal group; B is the 2-terminal group; C is the second terminal group; and n is 0 or 1.

[0047] One or more of the commercially available chemical compounds represented by the chemical formula (I) mentioned above or the chemical formula (II) mentioned below are preferably selected from, for example, thiols, carboxylic acids, phosphons and / or mercaptoacetates.

[0048] In addition, ligand materials represented by chemical formula (I) or (II) described in, for example, the published international patent application WO 2012 / 059931A may also be used.

[0049] In a preferred embodiment of the present invention, the amount of the first organic compound in the composition is in the range of 0.01 wt.% to 100 wt.% based on the total amount of the inorganic portion of the semiconductor light-emitting nanoparticles in the composition, preferably in the range of 10 wt.% to 50 wt.%, and more preferably in the range of 20 wt.% to 30 wt.%.

[0050] In a preferred embodiment of the present invention, the first organic compound is represented by the following chemical formula (II);

[0051] XR 1 R 2 (R 3 ) n (II)

[0052] In the formula, X is selected from P, O, S, or N;

[0053] If X is O or S, n is 0, and if X is P or N, n is 1;

[0054] R 1 Silver, a hydrogen atom, a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 1 to 15 carbon atoms, a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, a cycloalkane group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, preferably 2 to 25 carbon atoms, an aryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and an aralkyl group having 4 to 40 carbon atoms, preferably 4 to 25 carbon atoms. (These are one or more radicals R in each case a It may also be substituted by, where one or more non-adjacent CH2 groups are R a C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=NR a , SO, SO2, NR a , or CONR a It may be replaced by, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2), or one or more radicals R aSelected from one or more members of the group consisting of aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms that may be substituted by;

[0055] R a In each case, equally or differently, is H, D, or an alkyl group having 1 to 20 carbon atoms, a cyclic alkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 carbon ring atoms, or a heteroaromatic ring system having 5 to 60 carbon atoms, wherein the H atom may be replaced with D, F, Cl, Br, or I; wherein two or more adjacent substituents R a They may also form monocyclic or polycyclic, aliphatic, aromatic, or heteroaromatic ring systems with each other;

[0056] R 2 ... comprises a hydrogen atom, a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 1 to 15 carbon atoms, a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, a cycloalkane group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, preferably 2 to 25 carbon atoms, an aryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and an aralkyl group having 4 to 40 carbon atoms, preferably 4 to 25 carbon atoms. (These are one or more radicals R in each case aIt may also be substituted by, where one or more non-adjacent CH2 groups are R a C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=NR a , SO, SO2, NR a , or CONR a It may be replaced by, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2), or one or more radicals R a Selected from one or more members of the group consisting of aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms that may be substituted by;

[0057] R 3 Silver, a hydrogen atom, a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 1 to 15 carbon atoms, a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, a cycloalkane group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, preferably 2 to 25 carbon atoms, an aryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and an aralkyl group having 4 to 40 carbon atoms, preferably 4 to 25 carbon atoms. (These are one or more radicals R in each case aIt may also be substituted by, where one or more non-adjacent CH2 groups are R a C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=NR a , SO, SO2, NR a , or CONR a It may be replaced by, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2), or one or more radicals R a Selected from one or more members of the group consisting of aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms that may be substituted by;

[0058] Here, R 1 , R 2 , R 3 At least one of them is not a hydrogen atom.

[0059] In a preferred embodiment of the present invention, the first organic compound is selected from the group consisting of thiols, selenols, phosphonic acids, carboxylic acids, amines, and phosphines, preferably, it is a thiol, a carboxylic acid, or a phosphonic acid, such as hexane-1-thiol, a carboxylic acid, 1-dodecanethiol, or hexylphosphonic acid, and more preferably, it is a thiol.

[0060] Preferably, R of formula (II). 2is a substituted or unsubstituted linear alkyl or alkoxyl group having 1 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 5 to 15 carbon atoms; a substituted or unsubstituted branched alkyl or alkoxyl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 5 to 20 carbon atoms; a substituted or unsubstituted cycloalkane group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 5 to 25 carbon atoms; and a substituted or unsubstituted aryl group having 3 to 40 carbon atoms, preferably 5 to 25 carbon atoms.

[0061] More preferably, R 2 is a substituted linear alkyl group having 1 to 40 carbon atoms, an unsubstituted branched alkyl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 5 to 25 carbon atoms, or an alkoxyl group.

[0062] More preferably, R 2 is selected from the table in Table 1 below.

[0063] Table 1

[0064]

[0065] Here, "*" indicates a connection point to another unit.

[0066] As chemical compounds, commercially available mercaptoacetate and / or mercaptopropionate are more suitable as chemical compounds for preventing / reducing the quantum yield of semiconductor light-emitting nanoparticles in a mixture, preferably in a solution, particularly in the presence of a photoinitiator.

[0067] The following chemical compounds available on the market are particularly suitable.

[0068]

[0069] According to the present invention, preferably, step a) is performed with the other material, and the amount of the other material is in the range of 0.01 wt.% to 100 wt.% based on the total amount of the inorganic portion of the semiconductor light-emitting nanoparticles, preferably in the range of 0.1 wt.% to 50 wt.%, and more preferably in the range of 20 wt.% to 30 wt.%.

[0070] In some embodiments of the present invention, step a) is performed with the other material, and the other material is selected from one or more members of the group consisting of photoinitiators, thermal initiators, inorganic materials, organic compounds and solvents.

[0071] In some embodiments of the present invention, the other compound is a solvent selected from inorganic solvents, organic solvents, and mixtures thereof, preferably, ethylene glycol monoalkyl ethers, e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers, e.g., diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; propylene glycol monoalkyl ethers, e.g., propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, and propylene glycol monopropyl ether; ethylene glycol alkyl ether acetates, e.g., methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol alkyl ether acetates, e.g., propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones, e.g., methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols, e.g., ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters, e.g., ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and ethyl lactate; and cyclic asters, e.g., gamma-butyro-lactone; The solvent is selected from one or more members of the group consisting of chlorinated hydrocarbons, such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene, and preferably the solvent is propylene glycol alkyl ether acetate, alkyl acetate, ethylene glycol monoalkyl ether, propylene glycol, and propylene glycol monoalkyl ether;Preferably, the solvent is selected from one or more members of the group consisting of propylene glycol alkyl ether acetate, e.g., propylene glycol monomethyl ether acetate (PGMEA), alkyl acetate, e.g., butyl acetate, ethylene glycol monoalkyl ether, e.g., ethylene glycol monobutyl ether, propylene glycol, or propylene glycol monoalkyl ether, e.g., methoxypropanol, and more preferably, the solvent is selected from propylene glycol alkyl ether acetate.;

[0072] In some embodiments of the present invention, the other compound is selected from photoinitiators, thermal initiators, or mixtures thereof.

[0073] - Semiconductor light-emitting nanoparticles

[0074] According to the present invention, the term "semiconductor" refers to a material having electrical conductivity at room temperature between that of a conductor (e.g., copper) and an insulator (e.g., glass). Preferably, the semiconductor is a material whose electrical conductivity increases with temperature.

[0075] The term "nano" means a size of 0.1 nm to 999 nm, preferably 1 nm to 150 nm, more preferably 3 nm to 50 nm.

[0076] Accordingly, according to the present invention, "semiconductor light-emitting nanoparticles" are considered to mean a light-emitting material having a size of 0.1 nm to 999 nm, preferably 1 nm to 150 nm, more preferably 3 nm to 50 nm, and having electrical conductivity between that of a conductor (e.g., copper) and an insulator (e.g., glass) at room temperature, preferably a semiconductor material whose electrical conductivity increases with temperature, and a size of 0.1 nm to 999 nm, preferably 0.5 nm to 150 nm, more preferably 1 nm to 50 nm.

[0077] According to the present invention, the term "size" refers to the average diameter of the longest axis of a semiconductor nano-sized light-emitting particle.

[0078] The average diameter of semiconductor nano-sized light-emitting particles is calculated based on 100 semiconductor light-emitting nanoparticles in TEM images made with a Tecnai G2 Spirit Twin T-12 transmission electron microscope.

[0079] In a preferred embodiment of the present invention, the semiconductor light-emitting nanoparticles of the present invention are quantum-sized materials. For example, they are quantum dots.

[0080] According to the present invention, the shape of the quantum dots is not particularly limited. For example, spherical, elongated, star, polyhedral, pyramidal, tetrapod, tetrahedral, platelet, conical, and irregularly shaped quantum dots may be used.

[0081] According to the present invention, the term “quantum size” means the size of the semiconductor material itself without ligands or other surface modifiers, which can exhibit quantum confinement effects as described, for example, in ISBN:978-3-662-44822-9.

[0082] In a preferred embodiment of the present invention, the nanoparticles are at least:

[0083] i) The first semiconductor material above;

[0084] ii) at least one shell layer optionally;

[0085] iii) Optionally, a chemical compound as a surface ligand attached to the outermost surface of the nanoparticle, e.g., the outermost surface of the first semiconductor material or the shell layer.

[0086] Includes in this order.

[0087] For example, commercially available quantum dots, such as CdSe / CdS, CdSeS / CdZnS, CdSeS / CdS / ZnS, ZnSe / CdS, CdSe / ZnS, InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InZnP / ZnS, InZnP / ZnSe, InZnP / ZnSe / ZnS, InGaP / ZnS, InGaP / ZnSe, InGaP / ZnSe / ZnS, InZnPS / ZnS, InZnPS ZnSe, InZnPS / ZnSe / ZnS, ZnSe / CdS, ZnSe / ZnS, or any combination thereof, may be used. Preferably, InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InZnP / ZnS, InZnP / ZnSe, InZnP / ZnSe / ZnS, InGaP / ZnS, InGaP / ZnSe, and InGaP / ZnSe / ZnS may be used.

[0088] CdS, CdSe, CdTe, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, GaAs, GaP, GaSb, HgS, HgSe, HgSe, HgTe, InAs, InP, InPS, InPZnS, InPZn, InPZnSe, InCdP, InPCdS, InPCdSe, InGaP, InGaPZn, InSb, AlAs, AlP, AlSb, Cu2S, Cu2Se, CuInS2, CuInSe2, Cu2(ZnSn)S4, Cu2(InGa)S4, TiO2 alloys and any combination thereof can be used as a first semiconductor material (core).

[0089] In a preferred embodiment of the present invention, the first semiconductor material comprises at least one element from Group 13 or Group 12 of the periodic table and one element from Group 16 of the periodic table, preferably the element from Group 13 is selected from In, Ga, Al, and Ti, the element from Group 12 is Zn or Cd, and the element from Group 15 is selected from P, As, and Sb, and more preferably the first semiconductor material is represented by the following chemical formula (III),

[0090] In (1-x-2 / 3y) Ga x Zn y P (III)

[0091] In the formula, 0≤x<1, 0≤y<1, 0≤x+y<1, and preferably, the first semiconductor material is selected from the group consisting of InP, InP:Zn, InP:ZnS, InP:ZnSe, InP:ZnSSe, and InP:Ga.

[0092] According to the present invention, the type of shape of the first semiconductor material of the semiconductor light-emitting nanoparticles and the shape of the semiconductor light-emitting nanoparticles synthesized are not particularly limited.

[0093] For example, a first semiconductor material and / or semiconductor light-emitting nanoparticles of spherical, slender, star, polyhedral, pyramidal, tetrapod, tetrahedral, plate, conical, and irregular shapes can be synthesized.

[0094] In some embodiments of the present invention, the average diameter of the first semiconductor material is in the range of 1.5 nm to 3.5 nm.

[0095] In some embodiments of the present invention, the semiconductor light-emitting nanoparticles comprise or consist of a first element of Group 12 of the periodic table and a second element of Group 16 of the periodic table, preferably the first element is Zn and the second element is S, Se, or Te.

[0096] In a preferred embodiment of the present invention, the shell layer is represented by the following formula (IV).

[0097] ZnS x Se (1-x-z) Te z, - (IV)

[0098] In the formula, 0≤x≤1, 0≤z≤1, and x+z≤1, and preferably the shell layer is ZnSe, ZnS x Se (1-x), ZnSe (1-x) Te z , ZnS, Zn, more preferably, this is ZnSe or ZnS.

[0099] In some embodiments of the present invention, the shell layer is an alloyed shell layer or a graded shell layer, and preferably the graded shell layer is ZnS x Se y , ZnSe y Te z , or ZnS x Te z and, more preferably, this is ZnS x Se y am.

[0100] In some embodiments of the present invention, the semiconductor light-emitting nanoparticle further comprises a second shell layer on the shell layer, preferably the second shell layer comprises or is composed of a third element of Group 12 of the periodic table and a fourth element of Group 16 of the periodic table, more preferably the third element is Zn and the fourth element is S, Se or Te, provided that the fourth element and the second element are not the same.

[0101] In a preferred embodiment of the present invention, the second shell layer is represented by the following chemical formula (IV´), and

[0102] ZnS x Se y Te z, - (IV´)

[0103] In Equation (IV´), 0≤x≤1, 0≤y≤1, 0≤z≤1, and x+y+z=1, and preferably the shell layer is ZnSe, ZnS x Se y , ZnSe y Te z, or ZnS x Te z ..., provided that the shell layer and the second shell layer are not identical.

[0104] In some embodiments of the present invention, the second shell layer may be an alloyed shell layer.

[0105] In some embodiments of the present invention, the semiconductor light-emitting nanoparticles may further include one or more additional shell layers on the second shell layer as multi-shells.

[0106] According to the present invention, the term "multishell" refers to a stacked shell layer composed of three or more shell layers.

[0107] For example, CdS, CdZnS, CdS / ZnS, ZnS, ZnSe, ZnSe / ZnS, or any combination thereof may be used. Preferably, ZnS, ZnSe, or ZnSe / ZnS may be used as the shell layer.

[0108] - Ligand Compound

[0109] In some embodiments of the present invention, the outermost surface of the first semiconductor material or the shell layer of the semiconductor light-emitting nanoparticles may be partially or wholly overcoated with one or more known ligands.

[0110] Commonly used surface ligands include phosphines and phosphine oxides, such as trioctylphosphine oxide (TOPO), trioctylphosphine (TOP), and tributylphosphine (TBP); phosphoric acids, such as dodecylphosphonic acid (DDPA), tridecylphosphonic acid (TDPA), octadecylphosphonic acid (ODPA), and hexylphosphonic acid (HPA); amines, such as oleoleylamine, didecylamine (DDA), tetradecylamine (TDA), hexadecylamine (HDA), and octadecylamine (ODA), oleylamine (OLA), 1-octadecine (ODE); thiols, such as hexadecanethiol and hexanethiol; and mercaptocarboxylic acids, such as mercaptopropionic acid and mercaptoundecanoic acid. Carboxylic acids, such as oleic acid, stearic acid, myristic acid; acetic acid and any combination thereof. Additionally, polyethyleneimine (PEI) may also preferably be used.

[0111] Examples of surface ligands are described, for example, in International Patent Application Publication No. WO 2012 / 059931A.

[0112] In some embodiments of the present invention, an additive selected from one or more members of the group consisting of a solvent, an organic light-emitting material, an inorganic light-emitting material, a charge transport material, a scattering particle, a host material, a nanosized plasmon particle, a photoinitiator, and a matrix material may be added in step a) to obtain a composition.

[0113] In a preferred embodiment, the first mixture is a composition.

[0114] In some embodiments, the additive may be mixed with the semiconductor light-emitting nanoparticles or with the first organic compound to the first mixture obtained in step a) before or after step a) to form a composition.

[0115] Details regarding the additives are described in the "Additives to the Composition" section mentioned below.

[0116] - Composition

[0117] In another aspect, the present invention also relates to a composition obtainable or obtained by the method of the present invention.

[0118] In another aspect, the present invention also at least:

[0119] a) a semiconductor light-emitting nanoparticle comprising a core, optionally at least one shell layer,

[0120] b) the first chemical compound, and

[0121] c) Any other compound

[0122] It relates to a composition that includes, is essentially constituted, or is formed thereof, and

[0123] The above first organic compound is represented by the following chemical formula (I);

[0124] A(B) n C - (I)

[0125] In the formula, A represents the first terminal group; B is the 2-terminal group; C is the second terminal group; and n is 0 or 1.

[0126] More detailed information about the first organic compound is explained in the section "First Organic Compound" above.

[0127] More detailed information regarding semiconductor light-emitting nanoparticles is disclosed in the "Semiconductor Light-emitting Nanoparticles" section above.

[0128] In a preferred embodiment of the present invention, the compound comprises a plurality of semiconductor light-emitting nanoparticles.

[0129] In some embodiments of the present invention, the total amount of the first chemical compound is in the range of 0.1 wt.% to 90 wt.%, preferably 5 wt.% to 70 wt.%, more preferably 20 wt.% to 50 wt.% based on the total amount of the composition.

[0130] In some embodiments of the present invention, the total amount of nanoparticles is in the range of 0.1 wt.% to 100 wt.%, preferably 10 wt.% to 50 wt.%, and more preferably 20 wt.% to 30 wt.% based on the total amount of the composition.

[0131] - Additives to the composition

[0132] In some embodiments of the present invention, the composition may further include an additive selected from one or more members of the group consisting of a solvent, an organic light-emitting material, an inorganic light-emitting material, a charge transport material, scattering particles, a host material, nano-sized plasmon particles, a photoinitiator, and a matrix material.

[0133] For example, the inorganic luminescent material may be selected from one or more members of the group consisting of sulfides, thiogallates, nitrides, oxynitrides, silicates, aluminates, apatites, borates, oxides, phosphates, halophosphates, sulfates, tungstates, tantalates, vanadates, molybdates, niobates, titanates, germanes, halide-based phosphors, and any combination thereof.

[0134] The suitable inorganic luminescent materials described above may be known phosphors, including nano-sized phosphors and quantum-sized materials, as mentioned in the Phosphor Handbook, 2nd Edition (CRC Press, 2006), pp. 155–pp. 338 (WMYen, S. Shionoya and H. Yamamoto), WO2011 / 147517A, WO2012 / 034625A, and WO2010 / 095140A.

[0135] According to the present invention, any type of known material may preferably be used as the organic light-emitting material and charge transport material. Examples include well-known organic fluorescent materials, organic host materials, organic dyes, organic electron transport materials, organic metal complexes, and organic hole transport materials.

[0136] Examples of scattering particles include small particles of inorganic oxides such as SiO2, SnO2, CuO, CoO, Al2O3TiO2, Fe2O3, Y2O3, ZnO, and MgO; organic particles such as polymerized polystyrene and polymerized PMMA; inorganic hollow oxides such as hollow silica or any combination thereof.

[0137] - Matrix material

[0138] According to the present invention, a wide variety of known transparent polymers suitable for optical devices can preferably be used as matrix materials.

[0139] According to the present invention, the term "transparent" means that at least about 60% of incident light is transmitted at the thickness used in the optical medium and at the wavelength or wavelength range used during the operation of the optical medium. Preferably, this exceeds 70%, more preferably exceeds 75%, and most preferably exceeds 80%.

[0140] In a preferred embodiment of the present invention, any type of known transparent polymer described in WO 2016 / 134820A may be used.

[0141] According to the present invention, the term "polymer" means a material having repeating units and a weight average molecular weight (Mw) of 1000 g / mol or more.

[0142] Molecular weight M w It is determined using GPC (= gel permeation chromatography) against an internal polystyrene standard.

[0143] In some embodiments of the present invention, the glass transition temperature (Tg) of the transparent polymer is 70°C or higher and 250°C or lower.

[0144] Tg is measured based on the change in thermal capacity observed in a differential scanning colorimeter, as described in Rickey J Seyler, Glass Transition Designation, ASTM Publication Code Number (PCN) 04-012490-50.

[0145] For example, as a transparent polymer for a transparent matrix material, poly(meth)acrylate, epoxy, polyurethane, and polysiloxane may preferably be used.

[0146] In a preferred embodiment of the present invention, the weight average molecular weight (Mw) of the polymer as a transparent matrix material is in the range of 1,000 to 300,000 g / mol, and more preferably, it is 10,000 to 250,000 g / mol.

[0147] In some embodiments of the present invention, the composition comprises a plurality of semiconductor light-emitting nanoparticles and / or a plurality of semiconductor materials.

[0148] In some embodiments, the total amount of the chemical compound represented by the following formula (I) is in the range of 0.1 wt.% to 90 wt.%, preferably 5 wt.% to 70 wt.%, more preferably 20 wt.% to 50 wt.% based on the total amount of the composition.

[0149] In some embodiments, the total amount of nanoparticles is in the range of 0.1 wt.% to 100 wt.%, preferably 10 wt.% to 50 wt.%, and more preferably 20 wt.% to 30 wt.% based on the total amount of the composition.

[0150] - Uses

[0151] In another aspect, the present invention relates to the use of a first chemical compound represented by formula (I) in a composition comprising at least one semiconductor light-emitting nanoparticle, a method for preparing the composition, or a method for preparing an optical device, and

[0152] A(B) n C - (I)

[0153] In the formula, A represents the first terminal group; B is the 2-terminal group; C is the second terminal group; and n is 0 or 1.

[0154] In another aspect, the present invention relates to the use of the composition of the present invention in electronic devices, optical devices, or biomedical devices.

[0155] - Optical media

[0156] In another aspect, the present invention also relates to an optical device comprising at least one composition of the present invention.

[0157] In another aspect, the present invention also relates to an optical medium comprising at least one semiconductor light-emitting nanoparticle and a first chemical compound represented by formula (I).

[0158] A(B) n C - (I)

[0159] In the formula, A represents the first terminal group; B is the 2-terminal group; C is the second terminal group; and n is 0 or 1.

[0160] In some embodiments of the present invention, the optical medium may be an optical sheet, for example, a color filter, a color conversion film, a remote phosphor tape, or another film or filter.

[0161] According to the present invention, the term "sheet" includes a film and / or a layered structure medium.

[0162] In some embodiments of the present invention, the optical medium comprises an anode and a cathode, and at least one organic layer comprising at least one semiconductor light-emitting nanoparticle or composition of the present invention, preferably said organic layer is a light-emitting layer, and more preferably the medium further comprises one or more additional layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron blocking layer, and an electron injection layer.

[0163] According to the present invention, any type of publicly available inorganic and / or organic material may preferably be used for a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron blocking layer, and an electron injection layer, as described in WO 2018 / 024719 A1, US2016 / 233444 A2, US7754841 B, WO 2004 / 037887 and WO 2010 / 097155.

[0164] In a preferred embodiment of the present invention, the optical medium comprises a composition containing a plurality of semiconductor light-emitting nanoparticles.

[0165] Preferably, the anode and cathode of the optical medium sandwich an organic layer.

[0166] More preferably, the above additional layer is also interposed by the anode and the cathode.

[0167] In some embodiments of the present invention, the organic layer comprises at least one semiconductor light-emitting nanoparticle of the present invention and a host material, and preferably the host material is an organic host material.

[0168] In a preferred embodiment of the present invention, the optical medium comprises a composition containing a plurality of semiconductor light-emitting nanoparticles.

[0169] - Optical device

[0170] In another aspect, the present invention also relates to an optical device comprising at least one optical medium of the present invention.

[0171] In some embodiments of the present invention, the optical device may be a liquid crystal display device (LCD), an organic light-emitting diode (OLED), a backlight unit for an optical display, a light-emitting diode (LED), a microelectromechanical system (hereinafter referred to as "MEMS"), an electrowetting display, or an electrophoretic display, a lighting device, and / or a solar cell.

[0172] Technical effects

[0173] The present invention provides one or more of the following technical effects;

[0174] Improvement of quantum yield of nanoparticles, prevention or reduction of quantum yield degradation in diluted compositions and / or radiation-rich environments, higher device efficiency, optimization of surface state of nanoparticle shell portions, reduction of lattice defects in the nanoparticle shell layer, reduction / prevention of dangling bond formation in the shell layer, better thermal stability, improved oxidation stability, improved stability against radical substances, improved stability during long-term storage without causing significant QY degradation, improved chemical stability, and a more environmentally friendly and safer manufacturing process.

[0175] The following Work Examples 1 to 5 provide a detailed description of the present invention and the manufacture thereof.

[0176] Work example

[0177] Comparative Example 1: Composition of quantum dots in toluene having ligands of dodecanethiol, stearic acid, myristic acid, and palmitic acid

[0178] Red InP-based quantum dots (QDs) having ligands of dodecanethiol, stearic acid, myristic acid, and palmitic acid in toluene are prepared as described in US 7,588,828 B.

[0179] Then, QD is dissolved in dry toluene at a concentration of 0.08 mg / mL and measured for initial quantum yield (hereinafter initial QY) in Hamamatsu Quantaurus.

[0180] Then, 100 mg of QD was dissolved in 2 mL of dry toluene and 3 mg of the photoinitiator Irgacure @ It was mixed with TPO and stirred at room temperature under argon while being exposed to a light source with 365 nm for 60 minutes. Eleven samples were taken. Then, the samples were diluted to 0.08 mg / mL. After that, the quantum yield of the eleven samples was measured using Hamamatsu Quantaurus.

[0181] The initial QY of each sample is set to 100% using the following formula.

[0182] Normalized initial QY (100%) = Initial QY of each sample * α

[0183] Normalized QY is calculated according to the following formula.

[0184] Normalized QY = (QY * α / initial QY) * 100

[0185] Figure 1 shows the measurement results.

[0186] As described in Fig. 1, the average decrease in standardized QY before and after the radical test performed on QDs in toluene without additives is 40% ± 7.5% am.

[0187] Work Example 1: Composition of quantum dots in toluene having an additional chemical compound, hexanethiol, as an additive to the composition

[0188] Red InP-based quantum dots (QDs) having ligands of dodecanethiol, stearic acid, myristic acid, and palmitic acid in toluene are prepared as described in US 7,588,828 B.

[0189] - Ligand exchange

[0190] Three different samples were prepared by dissolving QD in dry toluene containing an additive (hexanethiol) at different concentrations (0.004 M, 0.02 M, 0.1 M). The QD concentration was set to 0.08 mg / mL for all three samples, and the samples were measured against the initial QY in Hamamatsu Quantaurus.

[0191] Then, the initial quantum yield (hereinafter initial QY) is measured in Hamamatsu Quantaurus.

[0192] Then, 100 mg of QD was dissolved in 2 mL of dry toluene and 3 mg of the photoinitiator Irgacure @ The samples were mixed with TPO and stirred at room temperature under argon while being exposed to a light source with 365 nm for 60 minutes. The samples were then taken. The samples were then diluted to 0.08 mg / mL. After that, the quantum yield of the samples was measured using Hamamatsu Quantaurus.

[0193] Figure 2 shows the measurement results.

[0194] Work Example 2: Quantum points in toluene having an additional chemical compound 1-dodecanethiol as an additive to the composition

[0195] The composition of quantum dots in toluene containing the chemical compound 1-dodecanethiol is prepared in the same manner as described in Work Example 1, except that 0.02 M 1-dodecanethiol is used instead of hexanethiol.

[0196] Figure 3 shows the QY measurement results.

[0197] Comparative Example 2: Composition of quantum dots in toluene having ligands of dodecanethiol, stearic acid, myristic acid, and palmitic acid at lower concentrations

[0198] A composition was prepared in the same manner as Comparative Example 1, except that the concentration of the quantum material in the composition was 0.05 mg / mL. Eight different samples were prepared in the same manner as described in Comparative Example 2.

[0199] Figure 4 illustrates the QY measurement results of the seven different samples above.

[0200] Work Example 3: A diluted composition of quantum dots in toluene having an additional chemical compound, hexanethiol, as an additive to the composition

[0201] The composition of quantum dots in toluene containing the chemical compound 1-hexanethiol is prepared in the same manner as described in Work Example 1, except that hexanethiol is used in different amounts to prepare four different samples at different concentrations of hexanethiol (0.004 M, 0.02 M, 0.1 M, and 0.2 M).

[0202] Figure 5 illustrates the measurement results.

[0203] Work Example 4: A diluted composition of quantum dots in toluene having an additional chemical compound, hexane, as an additive to the composition

[0204] The composition of quantum dots in toluene containing the chemical compound hexanoic acid is prepared in the same manner as described in Work Example 1, except that hexanoic acid is used in different amounts to prepare four different samples at different concentrations of hexanoic acid (0.004 M, 0.02 M, 0.1 M, and 0.2 M).

[0205] Figure 6 illustrates the measurement results.

[0206] Work Example 5: A diluted composition of quantum dots in toluene having an additional chemical compound hexylphosphonic acid (HPA) as an additive to the composition

[0207] The composition of quantum dots in toluene containing the chemical compound hexylphosphonic acid (HPA) is prepared in the same manner as described in Work Example 1, except that HPA is used in different amounts to prepare four different samples at different concentrations of HPA (0.004 M and 0.02 M).

[0208] Figure 7 illustrates the measurement results.

Claims

Claim 1 A method for preparing a composition comprising: a) a step of mixing at least a first organic compound with a semiconductor light-emitting nanoparticle having a core, together with other materials to obtain the composition, wherein the semiconductor light-emitting nanoparticle optionally comprises at least one shell layer and is partially or wholly overcoated with one or more types of ligands; wherein the method comprises, after the mixing step a), purification, precipitation, or centrifugation of the semiconductor light-emitting nanoparticle, wherein the first organic compound is a thiol and is represented by the following chemical formula (II); XR 1 R 2 (R 3 ) n In equation (II), X is S; n is 0; and R 1 Silver, a hydrogen atom, a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, or 1 to 25 carbon atoms, or 1 to 15 carbon atoms, a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms, or 3 to 15 carbon atoms, a cycloalkane group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms, or 3 to 15 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, or 2 to 25 carbon atoms, an aryl group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms, and an aralkyl group having 4 to 40 carbon atoms, or 4 to 25 carbon atoms (these are, in each case One or more radicals R a It may also be substituted by, where one or more non-adjacent CH2 groups are R a C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=NR a , SO, SO2, NR a , or CONR a It may be replaced by, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2), or one or more radicals R a Selected from one or more members of the group consisting of aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms that may be substituted by; R a In each case, equally or differently, is H, D, or an alkyl group having 1 to 20 carbon atoms, a cyclic alkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 carbon ring atoms, or a heteroaromatic ring system having 5 to 60 carbon atoms, wherein the H atom may be replaced with D, F, Cl, Br, or I; wherein two or more adjacent substituents R a They may also form monocyclic or polycyclic, aliphatic, aromatic, or heteroaromatic ring systems with each other; R 2 ..., a hydrogen atom; a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, or 1 to 25 carbon atoms, or 1 to 15 carbon atoms; a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms, or 3 to 15 carbon atoms; a cycloalkane group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms, or 3 to 15 carbon atoms; an alkenyl group having 2 to 40 carbon atoms, or 2 to 25 carbon atoms; an aryl group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms; a heteroaryl group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms; and an aralkyl group having 4 to 40 carbon atoms, or 4 to 25 carbon atoms (these are, in each case One or more radicals R a It may also be substituted by, where one or more non-adjacent CH2 groups are R a C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=NR a , SO, SO2, NR a , or CONR a It may be replaced by, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2), or one or more radicals R a Selected from one or more members of the group consisting of aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms that may be substituted by; R 3 Silver, a hydrogen atom, a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, or 1 to 25 carbon atoms, or 1 to 15 carbon atoms, a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms, or 3 to 15 carbon atoms, a cycloalkane group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms, or 3 to 15 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, or 2 to 25 carbon atoms, an aryl group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, or 3 to 25 carbon atoms, and an aralkyl group having 4 to 40 carbon atoms, or 4 to 25 carbon atoms (these are, in each case One or more radicals R a It may also be substituted by, where one or more non-adjacent CH2 groups are R a C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=NR a , SO, SO2, NR a , or CONR a It may be replaced by, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2), or one or more radicals R a Selected from one or more members of the group consisting of aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms that may be substituted by; where R 1 , R 2 , R 3 A method for preparing a composition in which at least one of the atoms is not a hydrogen atom. Claim 2 A method for preparing a composition according to claim 1, wherein the amount of the first organic compound is in the range of 0.01 wt.% to 100 wt.% based on the total amount of the inorganic portion of the semiconductor light-emitting nanoparticles, or is in the range of 10 wt.% to 50 wt.% or 20 wt.% to 30 wt.%. Claim 3 A method for preparing a composition according to claim 1, wherein the first organic compound is hexane-1-thiol or 1-dodecanethiol. Claim 4 A method for preparing a composition according to any one of claims 1 to 3, wherein step a) is performed with the other material, and the amount of the other material is in the range of 0.01 wt.% to 100 wt.% or in the range of 0.1 wt.% to 50 wt.% or in the range of 20 wt.% to 30 wt.% based on the total amount of the inorganic portion of the semiconductor light-emitting nanoparticles. Claim 5 A method for preparing a composition according to any one of claims 1 to 3, wherein step a) is performed together with the other material, and the other material is selected from one or more members of the group consisting of photoinitiators, thermal initiators, inorganic materials, organic compounds, and solvents. Claim 6 In any one of claims 1 to 3, the other material is a solvent selected from inorganic solvents, organic solvents, and mixtures thereof, wherein it is ethylene glycol monoalkyl ether, or ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ether, or diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; propylene glycol monoalkyl ether, or propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, and propylene glycol monopropyl ether; ethylene glycol alkyl ether acetate, or methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol alkyl ether acetate, or propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones, or methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols, or ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters, or ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and ethyl lactate; and cyclic asters, or gamma-butyro-lactone; Chlorinated hydrocarbons, or selected from one or more members of the group consisting of chloroform, dichloromethane, chlorobenzene, and dichlorobenzene, wherein the solvent is propylene glycol alkyl ether acetate, alkyl acetate, ethylene glycol monoalkyl ether, propylene glycol, and propylene glycol monoalkyl ether;A method for preparing a composition, wherein the solvent is selected from one or more members of the group consisting of propylene glycol alkyl ether acetate, or propylene glycol monomethyl ether acetate (PGMEA), alkyl acetate, or butyl acetate, ethylene glycol monoalkyl ether, or ethylene glycol monobutyl ether, propylene glycol or propylene glycol monoalkyl ether, or methoxypropanol, or wherein the solvent is selected from propylene glycol alkyl ether acetate.; Claim 7 A method for preparing a composition according to any one of claims 1 to 3, wherein the other material is selected from a photoinitiator, a thermal initiator, or a mixture thereof. Claim 8 A composition obtainable or obtained by the method according to claim 1. Claim 9 In claim 8, the composition is a composition used in an electronic device, an optical device, or a biomedical device. Claim 10 An optical medium comprising a composition according to at least claim 8. Claim 11 An optical medium according to claim 10, comprising an anode and a cathode, and at least one organic layer comprising said composition, wherein said organic layer is a light-emitting layer, and said medium further comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron blocking layer, and an electron injection layer. Claim 12 In claim 11, the optical medium comprises the organic layer, the composition and the host material, wherein the host material is an organic host material. Claim 13 An optical device comprising at least one optical medium according to claim 10. Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 delete Claim 21 delete Claim 22 delete

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