Nanoparticles

Abstract

The present invention relates to semiconductor nanoparticles; and processes for synthesizing the nanoparticles.

Description

Technical Field

[0001] Technical Field The present invention relates to nanoparticles; a process for preparing nanoparticles; the use of compositions, formulations and nanoparticles, optical media; and optical devices.

Background Art

[0002] Background Art Luminescent nanoparticles are known in the prior art literature. For example, Turo et al., ACS NANO vol.8, no.10, 10205-10203, 2014 discloses Cu 2 S nanoparticles without a shell layer using dodecanethiol (DDT), and a manufacturing process using DDT at a temperature of 200°C. DDT was used in all synthetic processes. Turo et al., Chem Commun, 2016, 52, 12214-12217 describes CdSe / ZnS using dodecanethiol. Robinson et al., Chem Mater, 2017, 29, 3854-38577 mentions quasi-spherical Cu 2 S nanorods using DDT. Patent Documents No literature

Prior Art Documents

Non-Patent Documents

[0003]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Summary of the Invention

[0004] Summary of the Invention However, the present inventors have newly found that there are still considerable problems that need improvement, as listed below; improvement of particle size distribution, better full width at half maximum (FWHM) value, improved self-absorption value, improvement of absorption amount per 1 mg of nanoparticles, improvement of quantum yield of nanoparticles, well-controlled shell thickness, improved charge injection ability of nanoparticles, higher device efficiency, reduction of trap luminescence of nanoparticles, optimization of surface state of the shell part of nanoparticles, reduction of lattice defects in the shell layer of nanoparticles, reduction / prevention of formation of dangling bonds in the shell layer, better thermal stability, better chemical stability, improved chemical stability in a desired solvent(s), improved thermal stability in a desired solvent(s), improved chemical stability in a desired matrix(es), improved thermal stability in a desired matrix(es), improved dispersibility in a matrix(es), improved dispersibility in a solvent, improved hole injection ability into semiconductor light-emitting nanoparticles, improved external quantum efficiency, optimization of the manufacturing process of nanoparticles, provision of a new manufacturing process for improving the size control of nanoparticles, a new manufacturing process for better kinetic control in shell formation, realizing good control of the shell thickness, and / or a new manufacturing process for reducing lattice defects in the shell layer, providing a more environmentally friendly and safer manufacturing process. The present inventors aimed to solve one or more of the above problems.

[0005] And a novel semiconductor nanoparticle, preferably, it is a semiconductor light-emitting nanoparticle, having a core; an outer layer covering at least a part of the core and containing a metal cation and a divalent anion; and one or more organic moieties directly attached to the anion of the outer layer by a covalent bond Here, the divalent anion is Se 2- , S 2- , Te 2- , O 2- or a combination selected from any of these, preferably, the metal cation is a monovalent, divalent cation, trivalent or tetravalent cation, more preferably, the metal cation is Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ a divalent cation selected from the group consisting of, or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ and Sn 4+ a tetravalent cation selected from the group consisting of is The semiconductor light-emitting nanoparticles have been found to contain, consist essentially of, or consist of these.

[0006] In some embodiments of the present invention, the outer layer is Cu 1+ and In 3+ , Cu 1+ and Ga 3+ , Ag 1+ and Ga 3+ a combination of, or Cu +1 / In +3 / Zn +2 including at least two or three different metal cations such as a combination of.

[0007] In another aspect, the present invention further relates to a process for producing light-emitting nanoparticles, comprising at least the following steps: (a) mixing at least semiconductor nanoparticles, preferably, the semiconductor nanoparticles contain at least a first semiconductor nanomaterial as a core, with another material to obtain a reaction mixture, preferably the other material is a solvent;

[0008] (b) In the reaction mixture, an outer layer is formed on the semiconductor nanoparticles in the reaction mixture by reacting at least an anion source represented by chemical formula (Va) or chemical formula (Vb) with a metal cation precursor. In some embodiments of the present invention, the metal cation precursor can be the same as the cation shell precursor; A-B-X-H (Va) A-B-X-B-A (Vb) wherein A is an organic group; B is a linking unit that links A and X; H is a hydrogen atom; and X is an anchor group containing an anion that can form a monolayer with an added metal cation derived from the added metal cation precursor;

[0009] (c) Cooling the reaction mixture from step (b), wherein the reaction mixture in step (b) is maintained at a temperature in the range of 80 °C to 200 °C, preferably 100 to 200 °C, to form an outer layer in step (b).

[0010] In another aspect, the present invention relates to semiconductor nanoparticles or semiconductor light-emitting nanoparticles that can be obtained or have been obtained from the process of the present invention. In another aspect, the present invention also relates to at least one semiconductor nanoparticle of the present invention, and at least one additional material, preferably the additional material is selected from the group consisting of organic light-emitting materials, inorganic light-emitting materials, charge transport materials, scattering particles, host materials, nano-sized plasmonic particles, photoinitiators, and matrix materials, and relates to a composition comprising, consisting essentially of, or consisting of them.

[0011] In another aspect, the present invention relates to at least one semiconductor nanoparticle of the present invention, or a composition of the present invention, and at least one solvent, preferably the solvent is selected from one or more members of the group consisting of aromatic, halogenated and aliphatic hydrocarbon solvents, ethers, esters, ionic liquids, alcohols and water, more preferably toluene, xylene, tetrahydrofuran, chloroform, dichloromethane and heptane, hexane, purified water, ester acetate, ether acetate, ketone, ether esters such as PGMEA, alcohols such as ethanol, isopropanol, sulfoxide, formamide, nitride, selected from one or more members of the group consisting of ketones, relating to formulations comprising, consisting essentially of, or consisting of these.

[0012] In another aspect, the present invention relates to the use of semiconductor nanoparticles, compositions, or formulations in electronic devices, optical devices, sensing devices or biomedical devices. In another aspect, the present invention further relates to an optical medium comprising at least one luminescent nanoparticle or composition of the present invention. In another aspect, the present invention further relates to an optical device comprising at least said optical medium.

Brief Description of the Drawings

[0013] [Fig. 1] 1H NMR spectra (in toluene d8) of QDs from Example 1 before (a) and after (b) the addition of 3-phenylpropylphosphonic acid (PPPA). [Fig. 2] 1H NMR spectra (in toluene d8) of QDs from Example 1 after treatment with PPPA and washing with ethanol. [Fig. 3] GCMS spectra of QDs from Example 1 after treatment with PPPA and washing. MS spectra of the peak with a retention time of 11.45. [Fig. 4] Figure 4 depicts a general scheme of a multi-step method established to distinguish between ligands bound to the surface and ligands bound to the crystal, using dodecaneselenol (DDSe) as an example (Scheme 1).

[0014] Detailed Description of the Invention -Semiconductor nanoparticles According to the present invention, on one side, the semiconductor nanoparticles, preferably, it is a semiconductor light-emitting nanoparticle, having a core; An outer layer covering at least a part of the core and containing a metal cation and a divalent anion; and An organic moiety, preferably, one or more organic moieties directly attached to the anion of the outer layer by a covalent bond, wherein the divalent anion is Se 2- , S 2- , Te 2- , O 2- or a combination of any of these, preferably, the metal cation is a monovalent, divalent cation, trivalent or tetravalent cation, more preferably, the metal cation is Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ a divalent cation selected from the group consisting of, or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ and Sn 4+ a tetravalent cation selected from the group consisting of, including, consisting essentially of, or consisting of, said semiconductor light-emitting nanoparticles.

[0015] The nanoparticles include at least an outer layer and a core. The nanoparticles may optionally contain one or more other layers (shell layers) between the outer layer and the core. The outer layer covers at least a part of the core. If there is no other layer between the outer layer and the core, the outer layer may be in direct physical contact with the core. The outer layer may cover the core via one or more additional layers disposed between the outer layer and the core. The terms "cover" and "covering" do not necessarily imply that there is necessarily physical contact between the core and the outer layer.

[0016] In some embodiments of the present invention, the outer layer is Cu 1+ and In 3+ , Cu 1+ and Ga 3+ , Ag 1+ and Ga 3+ combinations, or Cu +1 / In +3 / Zn +2 combinations, etc., containing at least two or three different metal cations. According to the present invention, the term "nanosize" means a size between 0.1 nm and 999 nm, preferably between 0.5 nm and 150 nm, more preferably between 1 nm and 50 nm.

[0017] According to the present invention, the term "semiconductor" means a material having an electrical conductivity between that of a conductor (such as copper) and an insulator (such as glass) at room temperature, and preferably, the semiconductor is a material whose electrical conductivity increases with temperature. Therefore, according to the present invention, the term "semiconductor nanoparticle" means a material having an electrical conductivity between that of a conductor (such as copper) and an insulator (such as glass) at room temperature, and preferably, the semiconductor is a material whose electrical conductivity increases with temperature, and the size is between 0.1 nm and 999 nm, preferably between 0.5 nm and 150 nm, more preferably between 1 nm and 50 nm.

[0018] According to the present invention, the term "size" means the average diameter of a circle having an area equivalent to the measured TEM projection of the semiconductor nanosized luminescent particles.

[0019] In a preferred embodiment of the present invention, the semiconductor luminescent nanoparticles of the present invention are quantum size materials. According to the present invention, the term "quantum size" means the size of the first semiconductor nanoparticle itself without ligands or other surface modifications that can exhibit a quantum confinement effect, as described, for example, in ISBN: 978-3-662-44822-9.

[0020] Generally, quantum size materials are said to be able to emit light of adjustable, sharp, and vivid colors due to the "quantum confinement" effect. In some embodiments of the present invention, the size of the overall structure of the quantum size material is from 1 nm to 50 nm.

[0021] In a preferred embodiment of the present invention, the average diameter of the first semiconductor nanoparticle (core) is in the range of 1 to 20 nm, preferably in the range of 1.5 to 12 nm. The average diameter of the semiconductor light-emitting nanoparticle (core) is calculated based on 100 semiconductor light-emitting nanoparticles in the TEM image taken by a Tecnai G2 Spirit Twin T-12 transmission electron microscope. The average diameter of the semiconductor light-emitting nanoparticle is calculated using the Fiji_ImageJ program.

[0022] - Organic moiety In a preferred embodiment of the present invention, the organic moiety has the following chemical formula (I); A - B - * (I) In the formula, A is an organic group; and B is a linking unit; " * " represents the connection point to the outer layer anion, and is represented by.

[0023] More preferably, the organic moiety is represented by the following chemical formula (II), (III) or (IIIa); L - (U) o - (Y) m - (CH 2 ) n - * (II) In the formula, L is an organic group, preferably the organic group is hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), heteroaromatic group, which includes aryl, alkaryl, alkyl or aralkyl, alkylamine, fluoroaryl, fluoroalkaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, which includes fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl; U is O, CH 2 or C=O; Y is O, CH 2 or C=O; n is an integer of 1 or more; m is 0 or an integer of 1 or more, preferably m is 1; o is 0 or an integer of 1 or more, preferably o is 1; 「 * 」 represents a linking point to the outer layer anion, preferably the anion is Se 2- , S 2- , Te 2- and O 2- selected from one or more members of the group consisting of, more preferably, the organic moiety is covalently bonded to the outer layer Se, S, Te or O atom;

[0024] * -(CH 2 ) a -(OCH 2 CH 2 ) p -(V) r -(CH 2 ) q -Z (III) * -(CH 2 ) q -(V) r -(OCH 2 CH 2 ) p -Z (IIIa) wherein, V is O, CH 2 or C=O; Z is a hydrogen atom or an organic group, preferably, Z is a hydrogen atom; a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, a branched unsaturated hydrocarbyl group having 3 to 30 carbon atoms, or an aromatic hydrocarbyl group, for example, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms; -COOH, -SH, or -NH 2 , an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group, which includes a fluoroaryl, a fluoroalkaryl, a fluoroalkyl or a fluoroaralkyl, etc., preferably, Z is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, more preferably, it is a hydrogen atom, a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, even more preferably, it is a hydrogen atom, or a linear alkyl group having 1 to 10 carbon atoms;

[0025] a is an integer of 0 or 1 or more, preferably 0 ≦ a ≦ 25, more preferably 0 ≦ a ≦ 15, even more preferably 1 ≦ a ≦ 10; p is an integer of 0 or 1 or more, preferably 0 ≦ p ≦ 45, more preferably 0 ≦ p ≦ 25, even more preferably 1 ≦ p ≦ 20, still more preferably 4 ≦ p ≦ 16; q is an integer of 0 or 1 or more, preferably 0 ≦ q ≦ 25, more preferably 0 ≦ q ≦ 15, even more preferably 0 ≦ q ≦ 10, still more preferably 1 ≦ q ≦ 5; r is 0 or the integer 1; 「 * 」 represents a connection point to the outer layer anion, preferably, the anion is Se 2- , S 2- , Te 2- and O 2- selected from one or more members of the group consisting of, more preferably, the organic moiety is covalently bonded to the outer layer Se, S, Te or O atom.

[0026] Even more preferably, the organic moiety of the present invention is represented by the following chemical formula (IV): * -(CH 2 ) a -(OCH 2 CH 2 ) p -(O) r -(CH 2 ) q -Z´ (IV) Wherein a is an integer of 0 or 1 or more, preferably 0 ≤ a ≤ 25, more preferably 0 ≤ a ≤ 15, even more preferably 1 ≤ a ≤ 10; p is an integer of 0 or 1 or more, preferably 0 ≤ p ≤ 45, more preferably 0 ≤ p ≤ 25, even more preferably 1 ≤ p ≤ 20, still more preferably 4 ≤ p ≤ 16; q is an integer of 0 or 1 or more, preferably 0 ≤ q ≤ 25, more preferably 0 ≤ q ≤ 15, even more preferably 0 ≤ q ≤ 10, still more preferably, it is 1;

[0027] Z´ is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group, which includes fluoroaryl, fluoroalkaryl, fluoroalkyl, fluoroaralkyl, preferably, Z´ is a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms or a hydrogen atom, more preferably, it is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms or a hydrogen atom, even more preferably, it is a hydrogen atom;

[0028] r is 0 or the integer 1; 「 * 」 represents the connection point to the anion of the outer layer, preferably, it is the connection point to the S atom or Se atom of the outer layer. More preferably, the organic moiety is * -(CH 2 )2 -(OCH 2 CH 2 ) 5≦p≦20 -O-CH 3 and is more preferably linked to the S or Se atom of the outer layer, * -(CH 2 ) 2 -(OCH 2 CH 2 ) 6 -O-CH 3 and / or * -(CH 2 ) 2 -(OCH 2 CH 2 ) 16 -O-CH 3 . In some preferred embodiments, the organic moiety is CH 3 -(CH 2 ) 7<n<18 - * and is linked to the outer S or Se atom.

[0029] In a preferred embodiment of the present invention, the organic moiety selected from formula (I), (II), (III), (III`) or (IV) is covalently bonded to the anion in the outer inorganic lattice and is preferably not removed by ligand exchange. The crystal-binding ligand (covalent ligand) can be characterized as described in Example 7.

[0030] For example, the organic moiety can preferably be described as follows. * -CH 2 -(OCH 2 CH 2 ) 4 -O-CH 3 * -CH 2 -(OCH 2 CH 2 ) 6 -O-CH 3 * -CH 2 -(OCH2 CH 2 ) 8 -O-CH 3 * -(CH 2 ) 2 -(OCH 2 CH 2 ) 2 -O-CH 3 * -(CH 2 ) 2 -(OCH 2 CH 2 ) 6 -O-CH 3 * -(CH 2 ) 2 -(OCH 2 CH 2 ) 8 -O-CH 3 * -(CH 2 ) 2 -(OCH 2 CH 2 ) 6 -CH 3 * -(CH 2 ) 2 -(OCH 2 CH 2 ) 6 -O-(CH 2 ) 2 -SH * -(CH 2 ) 7- CH 3 * -(CH 2 ) 11- CH 3 * -(CH 2 ) 17- CH 3 * -(CH 2 ) 2 -(OCH 2 CH 2 )6 -O-CH 3 * -(CH 2 ) 2 -(OCH 2 CH 2 ) 16 -O-CH 3 * -(CH 2 ) 2 -(OCH 2 CH 2 ) 17 -O-CH 3 「 * 」 represents the connection point to the outer S atom or Se atom; or, * -(CH 2 ) 11- CH 3 「 * 」 represents the connection point to the outer S atom or Se atom.

[0031] In some embodiments, the organic moieties of Formulas (I) and (II) may be organic moieties represented by the following Formulas Ia, Ib, Ic, Id, Ie, IIa, IIb, IIc, IId, IIe, IIf, IIg, IIh, IIi, or IIj;

Chemical formula

[0032] wherein, Y is a bonding unit having two bonding parts, m is 0 or 1, R 6 is a hydrogen atom or R 1 and R 7 is a hydrogen atom or R 1 is. R 1 , and R 5For each occurrence, independently or dependently of one another, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl having 5 to 12 carbon atoms, an alkenyl having 2 to 18 carbon atoms, a cycloalkenyl having 5 to 12 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a radical of a saturated or unsaturated bicyclic or tricyclic hydrocarbon having 7 to 12 carbon atoms, or an aryl having 6 to 10 carbon atoms or the said aryl substituted with an alkyl, or OR x is;

[0033] R x is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl having 5 to 12 carbon atoms, an alkenyl having 2 to 18 carbon atoms, a cycloalkenyl having 5 to 12 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a radical of a saturated or unsaturated bicyclic or tricyclic hydrocarbon having 7 to 12 carbon atoms, or an aryl having 6 to 10 carbon atoms or the said aryl substituted with an alkyl; R 2 is a hydrogen atom or R 3 is;

[0034] R a is an alkyl group having 1 to 36 carbon atoms, preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, docosyl, pentacosyl, heptacosyl, triacontyl, dotriacontyl, tetratriacontyl, hexatriacontyl and their branched isomers; R 3 is a cycloalkyl group having 5 to 12 carbon atoms, phenyl or naphthyl, which is unsubstituted or substituted with an alkyl having 1 to 36 carbon atoms or an aralkyl having 7 to 9 carbon atoms which is unsubstituted or substituted with an alkyl having 1 to 36 carbon atoms.

[0035] R 4is an alkyl group having 1 to 36 carbon atoms, preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, docosyl, pentacosyl, heptacosyl, triacontyl, dotriacontyl, tetratriacontyl, hexatriacontyl and branched isomers thereof; R 6 is a hydrogen atom or R 1 ; R 7 is a hydrogen atom or R 1 ;

[0036] " * " represents a connection point to the outer layer anion, preferably, the anion is selected from one or more members of the group consisting of Se 2- , S 2- , O 2- and Te 2- , more preferably, the organic moiety is bonded to the outer layer Se, S, O or Te atom; n is 0 or an integer;

[0037]

Chemical formula

[0038] In the formula, Z is a bonding unit having two bonding parts, preferably, it is selected from a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxylene group having 1 to 10 carbon atoms, Y is a linking unit; m is 0 or 1; R 6 is a hydrogen atom or R 1 ; R 7 is a hydrogen atom or R 1 ; R 8 is OH, a hydrogen atom, or R 1 ; R 9is OH, a hydrogen atom or R 1 ; R 10 is a hydrogen atom or R 1 ; R 11 is OH, a hydrogen atom or R 1 ; R 12 is a hydrogen atom or R 1 ;

[0039] In some embodiments, the organic moiety represented by Chemical Formula II) is an organic moiety represented by IIa, IIb, IIc, IId, IIe, IIf, IIg, IIh, IIi or IIj.

Chemical formula

[0040]

Chemical formula

[0041]

Chemical formula

[0042] 「 * 」represents a linkage point to the outer layer anion, and preferably, the organic moiety represented by Formula IIa, IIb, IIc, IId, IIe, IIf, IIg, IIh, IIi or IIj is bonded to the outer layer Se, S or Te or O atom; n is 0 or an integer.

[0043] In some embodiments, the organic moiety has a biological function. In some embodiments, the ligand is bifunctional to enable the nanoparticles to bind to specific sites. The organic moiety is thought to prevent aggregation of the nanoparticles or nanosized materials and to enable the organic moiety to disperse the nanoparticles in an organic and / or aqueous medium. Also, the organic moiety is thought to enable increased uptake into cells.

[0044] In some embodiments, the organic moiety is as follows: 1. Chemistry & Biology 18, January 28, 2011, 10-24, 2. J. Am. Chem. Soc., 2007, 129 (45), pp 13987-13996, 3. Materials Today, Volume 20, Issue 7, 2017, Pages 360-376 is similar in structure to that described in. In some embodiments, the organic moiety comprises a protein or protein building block. In some embodiments, the organic moiety comprises a zwitterionic group.

[0045] - core According to the present invention, the semiconductor nanoparticles comprise a core, which core is composed of several semiconductor materials, such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, GaAs, GaP, GaSb, CuS, Cu 2 S, CuSe, Cu 2Se, FeS, FeSe, FeO, FeTe, HgS, HgSe, HgSe, HgTe, InAs, InxGa1-xAs, InP, InP:Zn, InP:ZnS, InP:ZnSe, InP:ZnSSe, InP:Ga, or InP:Ga, InSb InPS, InPZnS, InPSe, InPZn, InPZnSe, InPZnSeS, InPGa, InPGaZn, InP / ZnSe, In / ZnS, InZnP / ZnSe, InP / ZnSeTe, InZnP / ZnSeTe, InGaP / ZnSe, InP / InGaP, InZnP / InGaP, InCdP, InPCdS, InP / ZnSeS, InZnP / ZnSeS, InZnP / ZnS, InZnP / InGaP / ZnSe, InZnP / InGaP / ZnS, InZnP / InGaP / ZnSeS, InPCdSe, InGaP, InGaPZn, PbSe, PbS, InSb, AlAs, AlP, AlSb, CuInS 2 、CuInSe 2 、CuInZnSe, CuInZnS, AgInS 2 、TiO 2 and can be made from any combination thereof.

[0046] In some embodiments of the present invention, the core comprises at least a first element of Group 12 or Group 13 of the periodic table and a second element of Group 15 or Group 16 of the periodic table, preferably, the first element is an element of Group 13 of the periodic table, and the second element is an element of Group 15 of the periodic table, more preferably, the first element is a combination of In and Ga, and the second element is P.

[0047] In a preferred embodiment of the present invention, the first core can further comprise an additional element selected from one or more members of the group consisting of Ga, Zn, S, and Se. In some embodiments, the core is a metal oxide, such as ZnO, FeO, Fe 2 O 3 、ZrO 2 、CuO, SnO Cu 2 O、TiO 2 、WO3、 HfO 2、 In 2 O 3、 MgO, Al 2 O 3 and includes any combination thereof. In some embodiments, the core includes a metal, such as Au, Ag, W, Pd, Pt, Cu, In, Ti, Zn, Pb, Al, Cd, Zn and any combination thereof.

[0048] In a preferred embodiment of the present invention, the first semiconductor nanomaterial is selected from the group consisting of InP, InP:Zn, InP:ZnS, InP:ZnSe, InP:ZnSSe, InP:Ga, or InP:GaZn, InP / ZnSe, InP / ZnS, InP / ZnSeS, InZnP / ZnSe, InZnP / ZnSeS, InZnP / ZnS, InGaP / ZnSe, InP / InGaP, InZnP / InGaP, InZnP / InGaP / ZnSe, InZnP / InGaP / ZnS, InZnP / InGaP / ZnSeS.

[0049] According to the present invention, the type of the first semiconductor nanomaterial of the semiconductor nanoparticles and the shape of the semiconductor light-emitting nanoparticles to be synthesized are not particularly limited. For example, first semiconductor nanosize materials and / or semiconductor light-emitting materials having a spherical shape, an elongated shape, a star shape, a polyhedral shape, a pyramid shape, a multipod shape such as a tetrapod shape, a tetrahedral shape, a platelet shape, a cone shape, and an amorphous shape can be used. In some embodiments of the present invention, the average diameter of the core ranges from 1 to 20 nm, preferably from 1 to 12 nm, more preferably from 1.5 nm to 7 nm.

[0050] - Outer layer According to the present invention, the semiconductor nanoparticles include an outer layer covering at least a part of the core and including at least one metal cation and at least one divalent anion, wherein the divalent anion is Se 2- , S 2- , Te 2- , O 2-Or selected from any combination of these, preferably, the metal cation is a monovalent, divalent cation, trivalent or tetravalent cation, more preferably, the metal cation is Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Fe 2+ , Hg 2+ , Mg 2+ and Pb 2+ selected from the group consisting of divalent cations, or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ and Sn 4+ selected from the group consisting of tetravalent cations,

[0051] In some embodiments, the cation is Cs + , Ag + , Au + , Cu +1 selected from the group consisting of monovalent cations, or Zn 2+ , Fe +2 , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ , Cu +2 selected from the group consisting of divalent cations, or Fe +3 , In +3 , Bi +3 , Ga +3 selected from the group consisting of trivalent cations, or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ and Sn 4+ , Si +4 selected from the group consisting of tetravalent cations.

[0052] In some embodiments of the present invention, the outer layer is Cu 1+ and In3+ , Cu 1+ and Ga 3+ , Ag 1+ and Ga 3+ combinations, or Cu +1 / In +3 / Zn +2 combinations, or Cu +1 / Ga +3 / Zn +2 combinations, or Cu +1 / In +3 / Ga +3 / Zn +2 combinations, or Cu +1 / In +3 / Ga +3 combinations, etc., containing at least two or three different metal cations. In a preferred embodiment, the metal cation is Fe +2 Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ , Cu +2 selected from the group consisting of divalent cations.

[0053] In a preferred embodiment of the present invention, the outer layer has the following chemical formula (VI), QP 1-2h A h (VI) wherein, Q is a divalent anion selected from one or more members of the group consisting of Se 2- , S 2- , Te 2- and O 2- ; P is a divalent metal cation, preferably, P is Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+a divalent cation selected from one or more members of the group consisting of; A is a tetravalent cation, preferably A is Ti 4+ Ge 4+ Si 4+ and Sn 4+ selected from one or more members of the group consisting of; and 0 ≦ h ≦ 0.5, comprising, consisting essentially of, or consisting of the materials represented by.

[0054] For example, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, ZnNiS, ZnNiSe, ZnGeS, ZnGeO, ZnCaS, NiSe, TiGeSeS, ZnTiS, CuInZnS, CuInZnSe, AgInZnS and / or AgInZnSe can be used. According to the present invention, preferably, the outer layer is a single layer. More preferably, it is the last single layer of semiconductor nanoparticles coating the core. Also, when there is one or more shell layers coating the core, the outer layer coats the shell layer.

[0055] - shell layer According to the present invention, in some embodiments, the core can be at least partially embedded in the first shell layer, preferably, the core is completely embedded in one or more shell layers. In a preferred embodiment of the present invention, the shell layer(s) is disposed between the core and the outer layer. In other words, the semiconductor light-emitting nanoparticles of the present invention may optionally include, consist essentially of, or consist of a core, one or more shell layers coating the core, and an outer layer coating the shell layer, in this order.

[0056] - first shell layer In some embodiments of the present invention, as described in the outer layer section, the shell layer contains at least one metal cation, and at least one divalent anion, and / or at least the first element of Group 12 of the periodic table and Se atoms or S atoms, and preferably, the first element is Zn.

[0057] For example, the first shell layer is Cs 2 S, Cs 2 Se, Cs 2 Te, Cs 2 O, Ag 2 S, Ag 2 Se, Ag 2 Te, Ag 2 O, Au 2 S, Au 2 Se, Au 2 Te, Au 2 O, Cu 2 S, Cu 2 Se, Cu 2 Te, Cu 2 O, ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, CaS, CaSe, CaTe, CaO, NiS, NiSe, NiTe, NiO, MgS, MgSe, MgTe, MgO, HgS, HgSe, HgTe, HgO, PbS, PbSe, PbTe, PbO, CuS, CuSe, CuTe, CuO, CoS, CoSe, CoTe, CoO, SrO, SrS, SrSe, CoTe, SrO, FeS, FeSe, FeO, FeTe, In 2 S 3 , In 2 Se 3 , In 2 Te 3 , In 2 O 3 , Ga 2 S 3 , Ga 2 Se 3 , Ga 2 Te 3 , Ga 2 O 3 , Bi 2 S 3 , Bi 2 Se 3 , Bi 2 Te3 , Bi 2 O 3、 , Fe 2 S 3 , Fe 2 Se 3 , Fe 2 Te 3 , Fe 2 O 3 , TiS 2 , TiSe 2 , TiTe 2 , TiO 2 , SiS 2 , SiSe 2 , SiTe 2 , SiO 2 , ZrS 2 , ZrSe 2 , ZrTe 2 , ZrO 2 , HfS 2 , HfSe 2 , HfTe 2 , HfO 2 , SnS 2 , SnSe 2 , SnTe 2 , SnO 2 , GeS 2 , GeSe 2 , GeTe 2 , GeO, CuInZnS, CuInS 2 , CuInZnSe, CuInSe 2、 , AgInZnS, AgInZnSe, CuGaZnS, CuGaZnSe, CuFeS 2 , CuFeSe 2 and is selected from the group consisting of any combination thereof.

[0058] Preferably, it is selected from the group consisting of ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, CaS, CaSe, CaTe, CaO, NiS, NiSe, NiTe, NiO, MgS, MgSe, MgTe, MgO, HgS, HgSe, HgTe, HgO, PbS, PbSe, PbTe, PbO, CuS, CuSe, CuTe, CuO, CoS, CoSe, CoTe, CoO, SrO, SrS, SrSe, CoTe, SrO, FeS, FeSe, FeO, FeTe and any combination thereof. More preferably: ZnS, ZnSe, ZnTe, ZnO or any combination thereof

[0059] In a preferred embodiment of the present invention, the first shell layer has the following formula (VII), ZnSxSe (1-x-z) Te z , -(VII) where 0 ≦ x ≦ 1, 0 ≦ z ≦ 1, and x + z ≦ 1, and preferably, the shell layer is ZnSe, ZnS, ZnS x Se (1-x) , ZnSe (1-x) Te z and more preferably, it is ZnSe or ZnS. It can be represented by.

[0060] In some embodiments of the present invention, the shell layer is an alloy shell layer or a graded shell layer, and preferably, the graded shell layer is ZnSe, ZnS x Se (1-x) or ZnSe (1-z) Te z and more preferably, it is ZnS x Se (1-x) . In some embodiments of the present invention, optionally, the core and the first semiconductor nanoparticles as the first shell layer can be at least partially embedded in the second shell, and preferably, the first semiconductor nanoparticles are completely embedded in the shell layer.

[0061] For example, the second shell layer is Cs 2 S, Cs 2 Se, Cs 2 Te, Cs 2 O, Ag 2 S, Ag 2 Se, Ag 2 Te, Ag 2 O, Au 2 S, Au 2 Se, Au 2 Te, Au 2 O, Cu 2 S, Cu 2 Se, Cu 2 Te, Cu 2 O, ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, CaS, CaSe, CaTe, CaO, NiS, NiSe, NiTe, NiO, MgS, MgSe, MgTe, MgO, HgS, HgSe, HgTe, HgO, PbS, PbSe, PbTe, PbO, CuS, CuSe, CuTe, CuO, CoS, CoSe, CoTe, CoO, SrO, SrS, SrSe, CoTe, SrO, FeS, FeSe, FeO, FeTe, In 2 S 3 , In 2 Se 3 , In 2 Te 3 , In 2 O 3 , Ga 2 S 3 , Ga 2 Se 3 , Ga 2 Te 3 , Ga 2 O 3 , Bi 2 S 3 , Bi 2 Se 3 , Bi 2 Te 3 , Bi 2 O 3 , Fe 2 S 3 , Fe 2 Se 3 , Fe 2 Te 3 , Fe 2 O 3 , TiS2 , TiSe 2 , TiTe 2 , TiO 2 , SiS 2 , SiSe 2 , SiTe 2 , SiO 2 , ZrS 2 , ZrSe 2 , ZrTe 2 , ZrO 2 , HfS 2 , HfSe 2 , HfTe 2 , HfO 2 , SnS 2 , SnSe 2 , SnTe 2 , SnO 2 , GeS 2 , GeSe 2 , GeTe 2 , GeO, CuInZnS, CuInS 2 , CuInZnSe, CuInSe 2、 AgInZnS, AgInZnSe, CuGaZnS, CuGaZnSe, CuFeS 2 , CuFeSe 2 and is selected from the group consisting of any combination thereof.

[0062] Preferably, it is selected from the group consisting of ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, CaS, CaSe, CaTe, CaO, NiS, NiSe, NiTe, NiO, MgS, MgSe, MgTe, MgO, HgS, HgSe, HgTe, HgO, PbS, PbSe, PbTe, PbO, CuS, CuSe, CuTe, CuO, CoS, CoSe, CoTe, CoO, SrO, SrS, SrSe, CoTe, SrO, FeS, FeSe, FeO, FeTe and any combination of these materials. More preferably: ZnS, ZnSe, ZnTe, ZnO or any combination of these materials.

[0063] In some embodiments of the present invention, the second shell layer comprises at least 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, O, or Te.

[0064] In a preferred embodiment of the present invention, the second shell layer has the following formula (VII´) ZnS x Se (1-x-z) Te -(VII´) wherein 0 ≦ x ≦ 1, 0 ≦ z ≦ 1, and x + z ≦ 1, and preferably, the shell layer is ZnSe, ZnS x Se y , ZnSe y Te z or ZnS x Te z , or ZnS, more preferably, ZnSeS or ZnS

[0065] In some embodiments of the present invention, the shell layer is an alloy shell layer or a graded shell layer, preferably, the graded shell layer is ZnS x Se y , ZnSe y Te z or ZnS x Te z and more preferably, it is ZnS x Se y .

[0066] In some embodiments of the present invention, the concentration of Se in the shell layer varies from the side of the high concentration of the first semiconductor nanoparticles in the shell layer to the low concentration on the opposite side of the shell layer, and more preferably, the concentration of S in the shell layer varies from the side of the low concentration of the first semiconductor nanoparticles in the shell layer to the high concentration on the opposite side of the shell layer, and the concentration of Te in the shell layer varies from the side of the high concentration of the first semiconductor nanoparticles in the shell layer to the low concentration and then to the opposite side of the shell layer.

[0067] In some embodiments of the present invention, the composition of the second shell layer can be the same as that of the outer layer. In some embodiments of the present invention, the semiconductor light-emitting nanoparticles can further include, as a multi-shell, one or more additional shell layers on the second shell layer. According to the present invention, the term "multi-shell" means a laminated shell layer composed of three or more shell layers.

[0068] In some embodiments of the present invention, the surface of the semiconductor light-emitting nanoparticles can be overcoated with one or more surface ligands in addition to the organic moieties of the present invention. Although not wishing to be bound by theory, such surface ligands are thought to lead to easier dispersion of the nanosized fluorescent material in a solvent.

[0069] Commonly used surface ligands include phosphines and phosphine oxides such as trioctylphosphine oxide (TOPO), trioctylphosphine (TOP), and tributylphosphine (TBP); phosphonic acids such as dodecylphosphonic acid (DDPA), tridecylphosphonic acid (TDPA); amines such as oleylamine, dodecylamine (DDA), tetradecylamine (TDA), hexadecylamine (I), octadecylamine (ODA), oleylamine (OLA), 1-octadecene (ODE); thiols such as hexadecanethiol, dodecanethiol, hexanethiol, and polyethylene glycol thiol; selenols, the organic moiety of selenols may include a straight-chain or branched alkyl chain that may include a saturated or one or more unsaturated carbon bonds and / or an aromatic ring; mercaptocarboxylic acids such as mercaptopropionic acid and mercaptoundecanoic acid; carboxylic acids such as oleic acid, stearic acid, myristic acid; and any combination thereof. Furthermore, the ligands include Zn-oleate, Zn-acetate, Zn-myristate, Zn-stearate, Zn-laurate, and other Zn-carboxylates, sulfonic acids, halides, carbamates.

[0070] Examples of surface ligands are described, for example, in the published international patent application WO 2012 / 059931A. In some embodiments of the present invention, the nanoparticles have a full width at half maximum (FWHM) of at most 55 nm, preferably in the range of 30 - 55 nm, more preferably 30 - 47 nm, measured at 25 °C using a toluene solution.

[0071] - Determination of full width at half maximum (FWHM) Preferably, the determination of the full width at half maximum (FWHM) is performed in a suitable database preferably containing at least 10, more preferably at least 20, even more preferably at least 50 data points. The determination is preferably carried out using LabVIEW Software (LabVIEW 2017; May 2017) equipped with the following VIs (Virtual Instruments). 1. A peak detector for finding the center wavelength and y - value (count). Preferably, the following parameters are used: width: 10, threshold: the maximum value of the input data divided by 5. 2. Dividing the count value (y - value) at the center wavelength value (see item 1) by 2 gives the y - value of the half - width of the peak. Two points with this y - value of the half - width are found, and the difference between the two wavelength values is taken as the FWHM parameter.

[0072] - Measurement of quantum yield According to the present invention, QY is measured using a Hamamatsu absolute quantum yield spectrometer (model: Quantaurus C11347). Preferably, the nanoparticles emit light having a maximum emission peak wavelength in the range of 350 nm to 3500 nm, preferably 350 nm to 2000 nm, more preferably 400 nm to 800 nm, even more preferably 430 nm to 700 nm.

[0073] - Analysis of nanoparticles, preferably quantum dots (QDs), by GCMS According to the present invention, gas chromatography-mass spectrometry (GCMS) is performed using an Agilent Technologies 7890B GC system equipped with an autosampler and an Agilent DB-5 column, and an MS instrument, an Agilent Technologies 5977B MSD. The analyte was separated using the following injection method: initial temperature 100°C, held at 100°C for 0 minutes; heated to 340°C at a rate of 8°C / minute, held at 340°C for 15 minutes.

[0074] Samples for GCMS are prepared as follows: 3.1 Weigh the starting material. 3.2 Calculate the organic components based on TGA measurements. 3.3 For every 30 mg of organic components, add 10 ml of methanol and 5 ml of concentrated hydrochloric acid (caution! exothermic reaction) to dissolve the nanoparticles, preferably quantum dots (QD). If color still remains, use ultrasonic and Vortex. 3.4 Install a magnetic stirrer and heat the solution at 60°C for 20 minutes (do not heat in a sealed flask! Make sure the stopper is partially open). 3.5 Transfer the solution to a separatory funnel. Add toluene (10 ml for 30 mg of organic material).

[0075] 3.6 Extract the aqueous phase and remove the lower aqueous phase. 3.7 Add 20 ml of distilled water to the funnel and extract the toluene phase again. 3.8 Repeat the extraction of the toluene phase with water at least 3 times, or until the aqueous phase reaches the pH of distilled water (~5). 3.9 Collect the upper phase in a flask containing MgSO4 for at least 30 minutes. Filter the solid MgSO4. 3.10 Transfer the toluene mixture to a GC vial for injection.

[0076] - Process According to the present invention, on one hand, the process for manufacturing semiconductor nanoparticles, preferably semiconductor light-emitting nanoparticles, essentially consists of, consists of, or includes at least the following steps: (a) mixing at least a semiconductor nanomaterial, preferably the semiconductor nanomaterial includes at least a first semiconductor nanoparticle as a core, with another material to obtain a reaction mixture, preferably the other material is a solvent;

[0077] (b) forming an outer layer on the semiconductor nanomaterial in the reaction mixture by reacting at least an anion source represented by chemical formula (Va) or / and chemical formula (Vb) with a metal cation precursor; A-B-X-H (Va) A-B-X-B-A (Vb) wherein, A is an organic group; B is a linking unit connecting A and X; H is a hydrogen atom; and X is an anchor group containing an anion that can form a monolayer with an added metal cation derived from the added metal cation precursor;

[0078] (c) cooling the reaction mixture from step (b), wherein the reaction mixture in step (b) is maintained at a temperature in the range of 80°C to 200°C, preferably in the range of 100 to 200°C, and an outer layer is formed in step (b).

[0079] As the anion source, preferably an organic moiety represented by chemical formula (II´), (III´), (IIIa´) or (IV´), L-(U) o -(Y) m -(CH 2 ) n -X 1 (II´) wherein, L is an organic group, preferably, the organic group is hydrocarbyl (alkyl, aryl, aralkyl, alkylaryl), heteroaromatic group, which includes aryl, alkaryl, alkyl or aralkyl, alkylamine, fluoroaryl, fluoroalkaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, which includes fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl; U is O, CH 2 or C=O; Y is O, CH 2 or C=O; n is an integer of 1 or more; m is 0 or an integer of 1 or more, preferably m is 1; o is 0 or an integer of 1 or more, preferably o is 1; X 1 is Se 2- , S 2- , Te 2- and O 2- is an anchor group containing at least a divalent anion selected from one or more members of the group consisting of, and preferably capable of covalently attaching to the metal cation;

[0080] X 1 -(CH 2 ) a -(OCH 2 CH 2 ) p -(V) r -(CH 2 ) q -Z (III´) X 1 -(CH 2 ) q -(V) r -(OCH 2 CH 2 ) p -Z (IIIa´) In the formula, X 1 is Se 2- , S 2- , Te 2- and O 2-An anchor group comprising at least a divalent anion capable of binding to the metal cation, selected from one or more members of the group consisting of; V is O, CH 2 or C=O;

[0081] Z is a hydrogen atom or an organic group, preferably, Z is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, -COOH, -SH, or -NH 2 , alkylamine, fluoroaryl, fluoroalkaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, which includes fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl, preferably, Z is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, more preferably, it is a hydrogen atom, a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, even more preferably, it is a hydrogen atom, or a linear alkyl group having 1 to 10 carbon atoms;

[0082] a is an integer of 0 or 1 or more, preferably 0 ≦ a ≦ 25, more preferably 0 ≦ a ≦ 15, even more preferably 1 ≦ a ≦ 10; p is an integer of 0 or 1 or more, preferably 0 ≦ p ≦ 45, more preferably 0 ≦ p ≦ 25, even more preferably 1 ≦ p ≦ 20, still more preferably 4 ≦ p ≦ 18; q is an integer of 0 or 1 or more, preferably 0 ≦ q ≦ 25, more preferably 0 ≦ q ≦ 15, even more preferably 0 ≦ q ≦ 10, still more preferably 1 ≦ q ≦ 5; r is 0 or the integer 1;

[0083] HS-(CH 2 ) a -(OCH 2 CH 2 ) p -(O) r -(CH 2 ) q -Z´ (IV´) In the formula, a is an integer of 0 or 1 or more, preferably 0 ≤ a ≤ 25, more preferably 0 ≤ a ≤ 15, and even more preferably 1 ≤ a ≤ 10; p is an integer of 0 or 1 or more, preferably 0 ≤ p ≤ 45, more preferably 0 ≤ p ≤ 25, even more preferably 1 ≤ p ≤ 20, and still more preferably 4 ≤ p ≤ 18; q is an integer of 0 or 1 or more, preferably 0 ≤ q ≤ 25, more preferably 0 ≤ q ≤ 15, even more preferably 0 ≤ q ≤ 10, and still more preferably, it is 1;

[0084] Z´ is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, an alkylamine, a fluoroaryl, a fluoroalkaliyl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group, which includes fluoroaryl, fluoroalkaliyl, fluoroalkyl or fluoroaralkyl. Preferably, Z´ is a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms or a hydrogen atom. More preferably, it is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms or a hydrogen atom. Even more preferably, it is a hydrogen atom; r is 0 or the integer 1.

[0085] For example, preferably the following materials can be used as the anion source. SH-CH 2 -(OCH 2 CH 2 ) 4 -O-CH 3 SH-CH 2 -(OCH 2 CH 2 ) 6 -O-CH 3 SH-CH 2 -(OCH 2 CH 2 ) 8 -O-CH 3 SH-(CH 2 ) 2 -(OCH 2 CH 2 ) 2 -O-CH 3 SH-(CH 2 ) 2 -(OCH 2 CH 2 ) 6 -O-CH 3 SH-(CH 2 ) 2 -(OCH 2 CH 2 ) 8 -O-CH 3 SH-(CH 2 ) 2 -(OCH 2 CH 2 ) 6 -CH 3 SH-(CH 2 ) 2 -(OCH 2 CH 2 ) 6 -O-(CH 2 ) 2 -SH SH-(CH 2 ) 7- CH 3 SeH-(CH 2 ) 7- CH 3 SH-(CH 2 ) 11- CH 3 SeH-(CH 2 ) 11- CH 3 SH-(CH 2 ) 17- CH 3 SeH-(CH 2 ) 17- CH 3 SH-(CH 2 ) 2 -(OCH 2 CH2 ) 6 -O-CH 3 SH-(CH 2 ) 2 -(OCH 2 CH 2 ) 16 -O-CH 3 SH-(CH 2 ) 2 -(OCH 2 CH 2 ) 17 -O-CH 3

[0086] In some embodiments, the organic moieties of the chemical formulas (I) and (II) may be organic moieties represented by the following chemical formulas Ia, Ib, Ic, Id, Ie, IIa, IIb, IIc, IId, IIe, IIf, IIg, IIh, IIi or IIj.

Chemical formula

[0087]

Chemical formula

[0088] Wherein Y is a divalent bond, m is 0 or 1, R6 is a hydrogen atom or R1, and R7 is a hydrogen atom or R1. R 1 , and R 5 are, each time they appear, independently of or dependent on each other, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl having 5 to 12 carbon atoms, an alkenyl having 2 to 18 carbon atoms, a cycloalkenyl having 5 to 12 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a radical of a saturated or unsaturated bicyclic or tricyclic hydrocarbon having 7 to 12 carbon atoms, or an aryl having 6 to 10 carbon atoms, or the aryl substituted with an alkyl, or OR x ;

[0089] R xis a radical of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl having 5 to 12 carbon atoms, an alkenyl having 2 to 18 carbon atoms, a cycloalkenyl having 5 to 12 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a saturated or unsaturated bicyclic or tricyclic hydrocarbon having 7 to 12 carbon atoms, or an aryl having 6 to 10 carbon atoms or the aryl substituted with an alkyl; R 2 is a hydrogen atom or R 3 ;

[0090] R a is an alkyl group having 1 to 36 carbon atoms, preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, docosyl, pentacosyl, heptacosyl, triacontyl, dotriacontyl, tetracontriacontyl, hexatriacontyl and their branched isomers;

[0091] R 3 is a cycloalkyl group having 5 to 12 carbon atoms, phenyl or naphthyl, which is unsubstituted or substituted with an alkyl of 1 to 36 carbon atoms, or an aralkyl having 7 to 9 carbon atoms, which is unsubstituted or substituted with an alkyl having 1 to 36 carbon atoms. R 4 is an alkyl group having 1 to 36 carbon atoms, preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, docosyl, pentacosyl, heptacosyl, triacontyl, dotriacontyl, tetracontriacontyl, hexatriacontyl and their branched isomers;

[0092] X1 is an anchor group selected from Se-H (selenol), S-H (thiol), Te-H (tellurol), or any combination thereof; n is 0 or an integer;

[0093]

Chem.

[0094] In the formula, Z is a divalent bond, preferably selected from a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms and a substituted or unsubstituted alkoxylene group having 1 to 10 carbon atoms; Y is a linking unit; m is 0 or 1; R 6 is a hydrogen atom or R 1 ; R 7 is a hydrogen atom or R 1 ; R 12 is a hydrogen atom or R 1 ; R

[0095] In some embodiments, the organic moiety represented by Chemical Formula II) is an organic moiety represented by IIa´, IIb´, IIc´, IId´, IIe´, IIf´, IIg´, IIh´, IIi´ or IIj´;

Chem.

[0096]

Chem.

[0097]

Chem.

[0098]

Chem.

[0099] X1 is an anchor group selected from Se-H (selenol), S-H (thiol), Te-H (tellurol), O-H (alcohol), or any combination thereof; n is 0 or an integer.

[0100] The temperature range of 80°C to 200°C is considered important for creating a crystalline bond between the organic part and the outer layer. In other words, by maintaining the reaction temperature of step (b) within this temperature range, the anchor groups of chemical formulas (I), (II), (III), and / or (IV) are bonded to the cation to form the outer layer, while the organic part remains covalently attached to the anchor group. In a preferred embodiment of the present invention, in step (a) or step (b), the injection of the anion source is carried out at a temperature in the range of 0°C to 200°C, preferably in the range of 20°C to 180°C.

[0101] To prevent the destruction of the X-B bond, the temperature range of the injection is also considered important. Preferably, step (b) is carried out in the range of 1 minute to 10 hours, preferably 10 minutes to 5 hours, more preferably 20 minutes to 3 hours.

[0102] According to the present invention, preferably, the ratio of the total molar amount of the cation precursor to the total molar amount of the semiconductor nanoparticles in step (b) is in the range of 20:1 to 200000:1, preferably 100:1 to 60000:1, more preferably 110:1 to 58000:1, and even more preferably 120:1 to 5000:1. In a preferred embodiment of the present invention, the ratio of the total molar amount of the chalcogen source to the total molar amount of the semiconductor nanoparticles in step (b) is in the range of 20:1 to 200000:1, preferably 100:1 to 60000:1, more preferably 110:1 to 58000:1, and even more preferably 120:1 to 5000:1.

[0103] In some embodiments of the present invention, the anion source represented by chemical formula (2) can be used alone or in combination with any other chalcogen source as the anion source in step (b) of forming the outer layer. L 1 -U 1 -Y 1 -(CH 2 ) n -Z 1 -Z 2 -(CH 2 ) n -Y 2 -U 2 -L 2 (2) L 1 and L 2 are each independently or dependently on each other an organic group, preferably the organic group is a hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl) group including aryl, alkaryl, alkyl or aralkyl.

[0104] U 1 and U 2 are, each occurrence, independently or dependently on each other, O, -CH 2 - or C=O; Y 1 and Y 2 are, each occurrence, independently or interdependently on each other, O, -CH 2 - or C=O; n is an integer of 1 or more; Z 1 is a divalent anion selected from Se, S, Te, O; Z 2 is a divalent anion selected from Se, S, Te, O.

[0105] In a preferred embodiment of the present invention, the anion source described by formula (2) such as bis-chalcogenide can be used together with a reducing agent in step (b) to form the outer layer, preferably the reducing agent is represented by a secondary phosphine. In a preferred embodiment of the present invention, the ratio of the total amount of the anion source used in step (b) to the total amount of the cation precursor is in the range of 20:1 to 1:20, preferably in the range of 12:1 to 1:12, and even more preferably in the range of 5:1 to 1:5.

[0106] - Chalcogen source According to the present invention, the term "chalcogen" means a chemical element of Group 16 of the periodic table, and preferably, it is sulfur (S), selenium (Se), oxygen (O) and / or tellurium (Te). Therefore, according to the present invention, the term "chalcogen source" means a material containing at least one chemical element of the chemical elements of Group 16 of the periodic table, and preferably, the chemical element of Group 16 is oxygen (O), sulfur (S), selenium (Se), and / or tellurium (Te), and more preferably, it is sulfur (S) or selenium (Se). In a preferred embodiment of the present invention, the chalcogen source is a selenium source, a sulfur source, or a combination of a selenium source and a selenium source. More preferably, it is selected from selenol, diselenide, thiol, disulfide, or a combination thereof.

[0107] Step (a) - Mixing In a preferred embodiment of the present invention, step (a) is carried out under inert conditions such as argon (Ar) or N 2 conditions, more preferably under Ar conditions. In a preferred embodiment of the present invention, the other material used in step (a) is a solvent, more preferably, it is an organic solvent, and even more preferably, it is selected from one or more members of the group consisting of squalene, squalane, heptadecane, octadecane, octadecene, nonadecane, eicosane, henicosane, docosane, tricosane, pentacosane, hexacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, oleylamine, trioctylamine, ketone, ketone ether acetate such as PGMEA, nitrile, ether, ether ester, aromatic solvent such as toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene, mesitylene, etc.

[0108] Preferably, squalene, squalane, heptadecane, octadecane, octadecene, nonadecane, eicosane, henicosane, docosane, tricosane, pentacosane, hexacosane, octacosane, tetracosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, oleylamine, trioctylamine, ketone, ketone ether acetate such as PGMEA, nitrile, ether, aromatic solvent such as toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene, mesitylene, etc.

[0109] More preferably, octadecene, oleylamine, squalane, pentacosane, hexacosane, octacosane, nonacosane, trioctylamine or triacontane, ketone, ketone, ether acetate such as PGMEA, nitrile, ether, ether ester, aromatic solvent such as toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene, mesitylene, etc., even more preferably, octadecene, oleylamine, squalane, pentacosane, trioctylamine or hexacosane, tetracosane, ketone, ketone ether acetate such as PGMEA, ether ester, nitrile, ether, aromatic solvent such as toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene, mesitylene, etc.

[0110] In a preferred embodiment of the present invention, the mixing step is carried out at a temperature in the range of 0 °C to 100 °C, preferably 5 to 60 °C, more preferably 10 to 40 °C. In a preferred embodiment of the present invention, a plurality of first semiconductor nanomaterials can be used in step (a).

[0111] - Semiconductor nanoparticles According to the present invention, the semiconductor nanomaterial comprises, consists essentially of, or consists of at least a first semiconductor nanomaterial, excluding when a ligand attached on the outermost surface of the semiconductor nanoparticles is attached. In some embodiments of the present invention, the semiconductor nanoparticles may optionally include one or more shell layers that cover at least a portion of the first semiconductor nanoparticles, as described in the section "Shell layer" above.

[0112] - First semiconductor nanomaterial According to the present invention, in step (a), several types of first semiconductor nanomaterials can be used as the core, for example, CdS, CdSe, CdTe, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, GaAs, GaP, GaSb, CuS, Cu2 S, CuSe, Cu 2 Se, FeS, FeSe, FeO, FeTe HgS, HgSe, HgSe, HgTe, InAs, InxGa1-xAs, InP, InP:Zn, InP:ZnS, InP:ZnSe, InP:ZnSSe, InP:Ga, or InP:Ga, InSb, InPS, InPZnS, InPSe, InPZn, InPZnSe, InPZnSeS, InPGa, InPGaZn, InP / ZnSe, In / ZnS, InZnP / ZnSe, InP / ZnSeTe, InZnP / ZnSeTe, InGaP / ZnSe, InP / InGaP, InZnP / InGaP, InCdP, InPCdS, InP / ZnSeS, InZnP / ZnSeS, InZnP / ZnS, InZnP / InGaP / ZnSe, InZnP / InGaP / ZnS, InZnP / InGaP / ZnSeS, InPCdSe, InGaP, InGaPZn, InSb, AlAs, AlP, AlSb, Cu 2 S, Cu 2 Se, CuInS2, CuInSe 2 , CuInZnS and any combination thereof.

[0113] In some embodiments, the core is, for example, ZnO, FeO, Fe 2 O 3 , ZrO 2 , CuO, SnO Cu 2 O, TiO 2 , WO 3、 HfO 2、 In 2 O 3、 MgO, Al 2 O 3 and is a metal oxide comprising any combination thereof. In some embodiments, the core comprises a metal, for example, Au, Ag, W, Pd, Pt, Cu, In, Ti, Zn, Pb, Al, Cd, Zn, and any combination thereof.

[0114] In some embodiments of the present invention, the first semiconductor nanomaterial comprises, consists essentially of, or consists of at least a first element of Group 12 or Group 13 of the periodic table and a second element of Group 15 or Group 16 of the periodic table. Preferably, the first element is a Group 13 element of the periodic table and the second element is a Group 15 element of the periodic table. More preferably, the first element is In, Ga, or a combination of In and Ga, and the second element is P, provided that this does not include the case where a ligand is attached to the outermost surface of the first semiconductor nanoparticle.

[0115] In a preferred embodiment of the present invention, the first semiconductor nanomaterial can further include an additional element selected from one or more members of the group consisting of Ga, Zn, S, and Se. In a preferred embodiment of the present invention, the first semiconductor nanomaterial is selected from the group consisting of InP, InP:Zn, InP:ZnS, InP:ZnSe, InP:ZnSSe, InP:Ga, or InP:GaZn, InP / ZnSe, InP / ZnS, InP / ZnSeS, InZnP / ZnSe, InZnP / ZnSeS, InZnP / ZnS, InGaP / ZnSe, InP / InGaP, InZnP / InGaP, InZnP / InGaP / ZnSe, InZnP / InGaP / ZnS, or InZnP / InGaP / ZnSeS.

[0116] In a preferred embodiment, the first semiconductor nanomaterial is alloyed. The type of the first semiconductor nanomaterial of the semiconductor nanoparticles and the shape of the semiconductor light-emitting nanoparticles to be synthesized are not particularly limited. For example, spherical, elongated, star-shaped, polyhedral, pyramid-shaped, multi-pod-shaped such as tetrapod-shaped, tetrahedral, platelet-shaped, cone-shaped, and amorphous first semiconductor nanosize materials and / or semiconductor light-emitting materials can be used. In some embodiments of the present invention, the average diameter of the first semiconductor nanomaterial is in the range of 1 to 20 nm, preferably 1.5 nm to 12 nm.

[0117] Optional step (d) - shell formation According to the present invention, by optionally applying the following step (d), a shell layer can be further formed. Preferably, step (d) is carried out before step (b); (d) Mixing at least a semiconductor nanomaterial and / or a first semiconductor nanoparticle (core), preferably the first semiconductor nanoparticle is obtained in step (h), and at least a first cationic shell precursor and a first anionic shell precursor, optionally in a solvent, to form a shell layer on the first semiconductor material. Preferably, the first anionic shell precursor is injected into the reaction mixture during step (d).

[0118] In a preferred embodiment of the present invention, and preferably, the anionic precursor is a chalcogen source, more preferably, it is selected from one or more members of the group consisting of trioctylphosphine:Se, tributylphosphine:Se, trioctylphosphine:S, tributylphosphine:S, thiol and selenol. Other conditions for shell layer formation are described, for example, in US8679543 B and Chem. Mater. 2015, 27, pp 4893 - 4898. The nanoparticles can be obtained from a public source or can be obtained as described in this application.

[0119] In a preferred embodiment of the present invention, the cationic shell precursor is a salt of a Group 12 element of the periodic table, more preferably, the cationic shell precursor is selected from one or more members of the group consisting of Zn-stearate, Zn-myristate, Zn-oleate, Zn-laurate, Zn-palmitate, Zn-acetylacetonate, Zn-undecylenate, Zn-acetate, Cd-stearate, Cd-myristate, Cd-oleate, Cd-laurate, Cd-palmitate, Cd-acetylacetonate, Cd-undecylenate, Cd-acetate, metal halides represented by chemical formula (XIII), and metal carboxylates represented by chemical formula (XIV).

[0120] MX 3 n (XIII) wherein M is Zn 2+ or Cd 2+ and preferably, M is Zn 2+ and X 3 is a halogen selected from the group consisting of F-, Cl - , Br - and I - and n is 2

[0121] [M(O 2 CR 16 )(O 2 CR 17 )] -(XIV) wherein M is Zn 2+ or Cd 2+ and preferably, M is Zn 2+ ; R 16 is a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, or a branched unsaturated hydrocarbyl group having 3 to 30 carbon atoms, preferably, R 16 is a linear alkyl group having 1 to 30 carbon atoms, or a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, more preferably, R 16is a linear alkyl group having 2 to 25 carbon atoms, or a linear unsaturated hydrocarbyl group having 6 to 25 carbon atoms, and more preferably, R 16 is a linear alkyl group having 2 to 20 carbon atoms, or a linear unsaturated hydrocarbyl group having 10 to 20 carbon atoms, and even more preferably, R 16 is a linear alkyl group having 2 to 20 carbon atoms,

[0122] R 17 is a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, or a branched unsaturated hydrocarbyl group having 4 to 30 carbon atoms, and preferably, R 17 is a linear alkyl group having 1 to 30 carbon atoms, or a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, and more preferably, R 17 is a linear alkyl group having 2 to 25 carbon atoms, or a linear unsaturated hydrocarbyl group having 6 to 25 carbon atoms, and more preferably, R 17 is a linear alkyl group having 2 to 20 carbon atoms, or a linear unsaturated hydrocarbyl group having 10 to 20 carbon atoms, and even more preferably, R 17 is a linear alkyl group having 2 to 20 carbon atoms. In a preferred embodiment, R 16 and R 17 are the same.

[0123] In a preferred embodiment of the present invention, the ratio of the total amount of the chalcogen source to the total amount of the cationic shell precursor used in step (d), preferably, the chalcogen source is a selenium source, a sulfur source, or a combination of a selenium source and a sulfur source, is in the range of 20:1 to 1:20, preferably in the range of 12:1 to 1:12. Step (d) can be applied not only to the synthesis of the first shell layer, but also to the synthesis of the second shell layer and / or the multi-shell layer.

[0124] - Cooling step (e) According to the present invention, cooling the reaction mixture from step (d) is carried out in step (e) after step (d) and before step (b), and preferably, the shell-forming reaction is appropriately stopped. As the cooling method, several methods can be used alone or in combination. For example, removing the heat source, injecting a solvent etc. at room temperature, and / or applying air cooling etc.

[0125] In some embodiments, the cooling rate in step (e) can be in the range of 0.03 °C / s to 50 °C / s, and preferably, it is 0.1 °C / s to 10 °C / s. In a preferred embodiment, the reaction mixture is cooled to a temperature below 200 °C, more preferably, to a temperature in the range of 200 °C to 0 °C.

[0126] Step (f) - Mixing step for producing a second mixture In some embodiments of the present invention, the process further includes step (f), preferably, the process includes step (f) before step (b), more preferably, after step (d) before step (b), even more preferably, the process includes step (f) after step (e) before step (b).

[0127] (f) Mixing the chalcogen source and the cation precursor with the first semiconductor nanoparticles and optionally another material at a temperature in the range of 0 °C to 100 °C, preferably 5 °C to 60 °C, more preferably 10 °C to 40 °C to form a second mixture. In some embodiments, alternatively, pre-mixing the first semiconductor nanoparticles and the cation source to form a pre-mixture, and then injecting the chalcogen source into the pre-mixture can be carried out as step (f'') instead of the said step (f) for producing the second mixture. Also, the same temperature range as described in step (e) can be applied. Preferably, the chalcogen source is injected after the injection of the cation shell precursor.

[0128] In some embodiments of the present invention, to obtain semiconductor nanoparticles, the process may optionally, preferably prior to step (a), include process steps such as those described in, but not limited to, the following steps (g) and (h) in this order.

[0129] (g) Preparing first semiconductor nanoparticles in a first mixture by reacting at least one indium precursor with at least one phosphor precursor or by using clusters obtained by reacting a metal cation precursor with an anion precursor, preferably, the clusters are magic size clusters, the indium precursor is a metal halide represented by the following chemical formula (XV), a metal carboxylate represented by the following chemical formula (XVI), or a combination thereof, and the phosphor precursor is an alkylsilylphosphine such as aminophosphine represented by the following chemical formula (XVII), tris(trimethylsilyl)phosphine, or a combination thereof. InV 1 3 (XV) wherein V 1 is a halogen selected from the group consisting of Cl - , Br - and I - and

[0130] [In(O 2 CR 3 ) 3 -(XVI) wherein R 3 is a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, or a branched unsaturated hydrocarbyl group having 3 to 30 carbon atoms, preferably, R 3 is a linear alkyl group having 1 to 30 carbon atoms or a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, more preferably, R 3is a linear alkyl group having 5 to 25 carbon atoms, or a linear unsaturated hydrocarbyl group having 6 to 25 carbon atoms, and more preferably, R 3 is a linear alkyl group having 10 to 20 carbon atoms, or a linear unsaturated hydrocarbyl group having 10 to 20 carbon atoms, and even more preferably, R 3 is a linear alkyl group having 10 to 20 carbon atoms,

[0131] (R 4 R 5 N) 3 P (XVII) In the formula, R 4 and R 5 are, for each occurrence, independently or dependently, a hydrogen atom or a linear alkyl group having 1 to 25 carbon atoms, or a linear unsaturated hydrocarbyl group having 2 to 25 carbon atoms, preferably a linear alkyl group having 1 to 10 carbon atoms, more preferably a linear alkyl group having 2 to 4 carbon atoms, and even more preferably a linear alkyl group having 2 carbon atoms. Optionally, a zinc salt and / or a zinc carboxylate is added in step (f), and preferably, the zinc salt is represented by the following chemical formulas (XIII) and (XIV´) ZnX 3 n (XIII) In the formula, X 3 is a halogen selected from the group consisting of Cl - , Br - and I - , and n is 2,

[0132] [Zn(O 2 CR 1 )(O 2 CR 2 )] -(XIV´) In the formula, R 1 is a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, or a branched unsaturated hydrocarbyl group having 3 to 30 carbon atoms, preferably, R 1is a linear alkyl group having 1 to 30 carbon atoms, or a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, more preferably, R 1 is a linear alkyl group having 5 to 25 carbon atoms, or a linear unsaturated hydrocarbyl group having 6 to 25 carbon atoms, even more preferably, R 1 is a linear alkyl group having 10 to 20 carbon atoms, or a linear unsaturated hydrocarbyl group having 10 to 20 carbon atoms, still more preferably, R 1 is a linear alkyl group having 10 to 20 carbon atoms,

[0133] R 2 is a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, or a branched unsaturated hydrocarbyl group having 3 to 30 carbon atoms, preferably, R 2 is a linear alkyl group having 1 to 30 carbon atoms, or a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, more preferably, R 2 is a linear alkyl group having 5 to 25 carbon atoms, or a linear unsaturated hydrocarbyl group having 6 to 25 carbon atoms, even more preferably, R 2 is a linear alkyl group having 10 to 20 carbon atoms, or a linear unsaturated hydrocarbyl group having 10 to 20 carbon atoms, still more preferably, R 2 is a linear alkyl group having 10 to 20 carbon atoms. R 1 and R 2 may be the same or different.

[0134] (h) Quenching the formation of the first semiconductor nanoparticles by cooling the first mixture in step (f).

[0135] - The cluster used in step (g) In some embodiments of the present invention, the first semiconductor nanoparticles in step (g) are prepared in the first mixture by using clusters that can be obtained by reacting a metal cation precursor with an anion precursor. In some embodiments of the present invention, the first semiconductor nanoparticles in step (g) are prepared in the first mixture using clusters, the clusters being magic-sized clusters (MSCs) selected from the group consisting of InP, InAs, InSb, GaP, GaAs, and GaSb, preferably an InP magic-sized cluster (MSC InP), and more preferably, it is In 37 P 20 (O 2 CR 4 ) 51 wherein the O 37 P 20 (O 2 CR 4 ) 51 of the In 2 CR 4 is -O 2 CCH 2 phenyl, or a substituted or unsubstituted fatty acid such as hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, dodecanoate, tridecanoate, tetradecanoate, pentadecanoate, hexadecanoate, heptadecanoate, octadecanoate, nonadecanoate, icosanoate or oleate.

[0136] In some embodiments of the present invention, the first semiconductor nanoparticles in step (g) may optionally be prepared in the first mixture using clusters, the clusters being Magic Sized Clusters (MSCs), but not limited thereto. Preferably, the magic-sized cluster (MSC) is based on a nanocrystalline core consisting only of condensed 6-membered rings in which all phosphorus atoms are coordinated to four indium atoms in a pseudo-tetrahedral arrangement, and preferably, the nanocrystalline core has the formula [In 21 P 20 ​3+ , [In 42 P 40 6+ , [In 63 P 60 9+ , [In 84 P 80 12+ , [In 95 P 90 15+ , [In 31 P 30 3+ , [In 41 P 40 3+ , [In 51 P 50 3+ , [In 61 P 60 3+ , [In 71 P 70 3+ , [In 81 P 80 3+ , and / or [In 91 P 90 3+ has.

[0137] In some embodiments of the present invention, the first semiconductor nanoparticles in step (g) are prepared in the first mixture using a cluster, the cluster being a Magic Sized Cluster (MSC), where the magic size cluster (MSC) is an indium-based carboxylate ligand, preferably In(O 2 CR 9 ) 3 including, where the O 2 CR 9 ) 3 of the O 2 CR 9 is -O 2 CCH 2 ​​​​​​​​​​​It is phenyl or a substituted or unsubstituted fatty acid such as hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, dodecanoate, tridecanoate, tetradecanoate, pentadecanoate, hexadecanoate, heptadecanoate, octadecanoate, nonadecanoate, icosanoate or oleate. Such InP magic size clusters (MSCs) as single source precursors (SSPs) are described in D. Gary et al., Chem. Mater., 2015, 27, 1432.

[0138] Step (h) - Quenching step According to the present invention, quenching the formation of the first semiconductor nanoparticles can be done by cooling the reaction mixture. As the cooling method, several methods can be used alone or in combination. Removing the heat source, injecting a solvent such as a solvent at room temperature, and / or applying air cooling, etc.

[0139] In a preferred embodiment of the present invention, the cooling rate in step (h) ranges from 0.01 °C / s to 10 °C / s, preferably it is 0.05 °C / s - 6 °C / s, more preferably 0.05 °C / s - 5 °C / s, and more preferably it is 0.1 °C / s - 1 °C / s, still more preferably 0.2 °C / s - 0.7 °C / s.

[0140] Step (j) - Surface treatment step In some embodiments of the present invention, the process further includes the following step (j) before step (a), preferably before step (a) after step (h), (j) subjecting the first semiconductor nanoparticles to surface treatment with a metal halide represented by the following chemical formula (VIII) or an alkylammonium halide, MX 3 n (VIII) wherein M is Zn 2+ or Cd 2+and preferably, M is Zn 2+ and X 3 is F−, Cl - , Br - and I - is a halogen selected from the group consisting of, and n is 2.

[0141] In some embodiments of the present invention, step (h) is carried out at a temperature in the range of 150° C. to 350° C., preferably in the range of 200° C. to 320° C., more preferably in the range of 250° C. to 300° C., and even more preferably in the range of 250° C. to 280° C. In some embodiments of the present invention, the treatment time of step (j) is in the range of 10 minutes to 10 hours, preferably in the range of 20 minutes to 4 hours, and more preferably in the range of 30 minutes to 3 hours.

[0142] In some embodiments of the present invention, the total molar ratio of the amount of the metal halide to the amount of the first semiconductor nanoparticles in step (j) is in the range of 500 to 50,000, preferably in the range of 1,000 to 20,000, and more preferably in the range of 1,400 to 10,000.

[0143] In some embodiments of the present invention, step (j) is selected from one or more members of the group consisting of squalene, squalane, heptadecane, octadecane, octadecene, nonadecane, eicosane, henicosane, docosane, tricosane, pentacosane, hexacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, oleylamine, trioctylamine, ketone, ketone ether acetate such as PGMEA, nitrile, ether, and aromatic solvents.

[0144] Preferably, squalene, squalane, heptadecane, octadecane, octadecene, nonadecane, icosane, henicosane, docosane, tricosane, pentacosane, hexacosane, octacosane, tetracosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, oleylamine and trioctylamine, more preferably octadecene, trioctylamine, oleylamine, squalane, pentacosane, hexacosane, octacosane, nonacosane, or triacontane, even more preferably, octadecene, trioctylamine, oleylamine, squalane, pentacosane, or hexacosane, tetracosane, ketone, ether acetate, such as PGMEA and the like.

[0145] In a preferred embodiment of the present invention, each of steps (a) to (j) is N 2 or under inert conditions such as under argon (Ar) conditions, preferably under Ar conditions.

[0146] - semiconductor nanoparticles In another aspect of the present invention, the present invention also relates to semiconductor nanoparticles that can be obtained from, or have been obtained from, the process of the present invention. In a preferred embodiment, the semiconductor nanoparticles are luminescent nanoparticles.

[0147] - composition In another aspect, the present invention is also a composition, preferably, but not limited to, at least one nanoparticle of the present invention, preferably, the nanoparticle is the luminescent nanoparticle of the present invention,; and at least one additional material, preferably, the additional material is selected from the group consisting of an organic light-emitting material, an inorganic light-emitting material, a charge transport material, a scattering particle, a host material, a nano-sized plasmon particle, a photoinitiator, and a matrix material, relating to the composition comprising, consisting essentially of, or consisting of these.

[0148] Such a suitable inorganic light-emitting material described above can be a well-known phosphor, including nanosize phosphors and quantum size materials as mentioned in phosphor handbook, 2nd edition (CRC Press, 2006), pp. 155 - pp. 338 (W.M.Yen, S.Shionoya and H.Yamamoto), WO2011 / 147517A, WO2012 / 034625A, and WO2010 / 095140A.

[0149] According to the present invention, as the organic light-emitting material and charge transport material, any known types of materials can be preferably used. For example, well-known organic fluorescent materials, organic host materials, organic dyes, organic electron transport materials, organometallic complexes, and organic hole transport materials, etc.

[0150] Examples of the scattering particles include small particles of inorganic oxides such as SiO 2 、SnO 2 、CuO, CoO, Al 2 O 3 TiO 2 、Fe 2 O 3 、Y 2 O 3 、ZnO, MgO, etc.; organic particles such as polymer polystyrene and polymer PMMA; inorganic hollow oxides such as hollow silica; or any combination thereof; can be preferably used.

[0151] -matrix material According to the present invention, a variety of well-known transparent matrix materials suitable for optical devices can be preferably used. According to the present invention, the term "transparent" means that at least approximately 60% of the incident light is transmitted at the thickness used for the optical medium and at the wavelength or wavelength range used during the operation of the optical medium. Preferably, it is more than 70%, more preferably more than 75%, and most preferably more than 80%.

[0152] In a preferred embodiment of the present invention, as the matrix material, any known type of transparent matrix material described in, for example, WO2016 / 134820A can be used. In some embodiments of the present invention, the transparent matrix material can be a transparent polymer.

[0153] 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. The molecular weight Mw is determined using GPC (= gel permeation chromatography) relative to an internal polystyrene standard.

[0154] 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. Tg is measured based on the change in heat capacity observed by differential scanning calorimetry as described in http: / / pslc.ws / macrog / dsc.htm; Rickey J Seyler, Assignment of the Glass Transition, ASTM publication code number (PCN) 04-012490-50. For example, as the transparent polymer for the transparent matrix material, polyacrylate, poly(meth)acrylate, epoxy, polyurethane, polysiloxane can be preferably used.

[0155] In a preferred embodiment of the present invention, the weight average molecular weight (Mw) of the polymer as the 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. In a preferred embodiment of the present invention, the composition contains a plurality of luminescent nanoparticles and / or a plurality of semiconductor materials.

[0156] - Formulation In another aspect, the present invention relates to a formulation consisting essentially of or consisting of at least one semiconductor nanoparticle, semiconductor light-emitting nanoparticle, or composition of the present invention, and at least one solvent.

[0157] Preferably, the solvent is selected from one or more members of the group consisting of aromatic, halogenated and aliphatic hydrocarbon solvents or alcohols or ethers or ketones or water, and more preferably from one or more members of the group consisting of toluene, xylene, ether, tetrahydrofuran, chloroform, dichloromethane and heptane, pure water, ester acetate, alcohol, sulfoxide, formamide, nitrile, ketone, ether acetate. Preferably, the formulation contains a plurality of light-emitting nanoparticles.

[0158] The amount of the solvent in the formulation can be freely controlled according to the method of coating the composition. For example, when spray-coating the composition, it may contain a solvent in an amount of 90 wt% or more. Further, when performing the slit coating method often employed when coating a large substrate, the solvent content is usually 60 wt% or more, preferably 70 wt% or more.

[0159] - Use In another aspect, the present invention relates to the use of semiconductor light-emitting nanoparticles, or semiconductor nanoparticles, or compositions, or formulations in electronic devices, optical devices, sensing devices or biomedical devices.

[0160] - Optical medium In another aspect, the present invention further relates to an optical medium comprising at least one semiconductor nanoparticle, preferably at least one semiconductor light-emitting nanoparticle of the present invention, or a composition, or a formulation.

[0161] In some aspects of the present invention, the optical medium can be an optical sheet, such as a color filter, a color conversion film, a remote phosphor tape, or another film or filter. According to the present invention, the term "sheet" encompasses structured media such as films and / or layers.

[0162] In some aspects of the present invention, the optical medium includes at least one layer comprising an anode and a cathode, and at least one luminescent nanoparticle or composition of the present invention, preferably, said one organic layer is a light-emitting layer, and more preferably, the medium further includes 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 injection layer.

[0163] According to the present invention, any known types of inorganic and / or organic materials for hole injection layers, hole transport layers, electron blocking layers, light-emitting layers, hole blocking layers, electron injection layers, as described in WO2018 / 024719 A1, US2016 / 233444 A2, US7754841 B, WO2004 / 037887, WO2010 / 097155, can be preferably used.

[0164] In a preferred aspect of the present invention, the optical medium includes a plurality of semiconductor luminescent nanoparticles and / or a plurality of semiconductor nanoparticles. In some aspects, the anode and cathode of the optical medium sandwich an organic layer. In some aspects, said additional layer is also sandwiched by the anode and cathode.

[0165] In some aspects of the present invention, the layer includes at least one semiconductor nanoparticle of the present invention, preferably, it is a semiconductor luminescent nanoparticle, and a host material, preferably, the host material is an organic host material.

[0166] -Optical device In another aspect, the present invention further relates to an optical device including an optical medium. In some embodiments of the present invention, the optical device can be a liquid crystal display device (LCD), an organic light emitting diode (OLED), a backlight unit for an optical display, a light emitting diode device (LED), Micro Electro Mechanical Systems (hereinafter, "MEMS"), an electro-wetting display, or an electrophoretic display, a lighting device, and / or a solar cell.

[0167] Technical Effects The present invention provides one or more of the following effects: Improved particle size distribution, better full width at half maximum (FWHM) value, improved self-absorption value, improved absorption per 1 mg of nanoparticles, improved quantum yield of nanoparticles, well-controlled shell thickness, improved charge injection ability of nanoparticles, higher device efficiency, reduced trap emission of nanoparticles, optimization of the surface state of the shell portion of nanoparticles, reduction of lattice defects in the shell layer of nanoparticles, reduction / prevention of the formation of dangling bonds in the shell layer, better thermal stability, better chemical stability, improved chemical stability in a desired solvent(s), improved thermal stability in a desired solvent(s), improved chemical stability in a desired matrix(es), improved thermal stability in a desired matrix(es), improved dispersibility in a matrix(es), improved dispersibility in a solvent, improved hole injection ability into semiconductor light-emitting nanoparticles, improved external quantum efficiency, optimization of the manufacturing process of nanoparticles, provision of a new manufacturing process for improving the size control of nanoparticles, a new manufacturing process for better kinetic control in shell formation, achieving good control of the shell thickness, and / or a new manufacturing process for reducing lattice defects in the shell layer, providing a more environmentally friendly and safer manufacturing process.

[0168] Core synthesis Examples 1-2 and Examples 1-10 provide the description of the present invention and the detailed description of their manufacture below.

[0169] Example Core Synthesis Example 1: Synthesis of Magic Size Cluster (MSC) Cluster synthesis Weigh 4.65 g (15.9 mmol) of indium acetate and 13.25 g (58.0 mmol) of myristic acid into a 500 mL four-necked flask. The flask is equipped with a reflux condenser, a septum, and a tap between the flask and the condenser. Place it under vacuum at 100 °C for 8 hours and 15 minutes to offgas acetic acid under reduced pressure and leave it overnight at room temperature. The next day, heat the solution to 100 °C again and evacuate it under vacuum for 1 hour and 45 minutes in that state. Vacuum evacuation time of 10 hours at 100 °C, Pressure: 85 mtorr.

[0170] Fill the reaction flask with argon and add 100 mL of dry toluene. Heat the reactants to 110 °C. A mixture of 2.33 mL (2.0 g) of PTMS and 50 mL (43.5 g) of toluene is injected into the flask with indium myristate (In(Ma)) at 110 °C. The formation of MSC was monitored via UV-vis of aliquots taken from the reaction solution at specified times. The peak shape (redshift and sharpness) was gradually improved.

[0171] When the improvement of the peak shape (redshift and sharpness) stopped, a second PTMS solution (1 mL (0.86 g) of PTMS in 10.2 ml (8.77 g) of toluene) was added in 2 mL portions to reach the optimal optical parameters. For example, the following: Add 2 ml of PTMS solution after 13 minutes Add 2 ml of PTMS solution after 19 minutes Add 2 ml of PTMS solution after 32 minutes After 44 minutes, cool the reaction with a fan and store the flask body in an inert atmosphere.

[0172] Results: An InP magic-size cluster with 387 nm excitons is formed. The InP magic-size cluster (MSC) is washed with anhydrous acetonitrile (crude: ratio of acetonitrile 18:13). This process is repeated with a mixture of anhydrous toluene and acetonitrile at ratios of toluene:acetonitrile 1.5:1, 1.4:1, 1.75:1. This product is called the "magic-size cluster (MSC)".

[0173] Core Synthesis Example 2 :Core synthesis: Synthesis of InP nanoparticles with an exciton wavelength of 593 nm A 50 mL, 14 / 20, four-neck round-bottom flask equipped with a reflux condenser is evacuated and 10 mL of distilled squalane is injected. The apparatus is evacuated while stirring (reducing the pressure from 300 mtorr to 200 mTorr over 1 hour) and heated to 375 °C under argon. Inside the glove box, a solution of MSC with a concentration of 3.15×10 -04 M is prepared in distilled squalane. 4 mL (1.26E-06 mol) of this solution is injected into the flask at 375 °C using a 16-gauge needle and a 6 mL syringe. After 4 minutes, the mantle is removed and the flask is cooled to 200 °C by blowing air with a fan. Then the mantle is put back and the flask is heated to 265 °C.

[0174] At this point, more MSC is added using the same solution as the first injection; a 20-gauge needle and a 3 ml syringe are used, and the addition is carried out at a rate of 0.7 ml / min for a predetermined time (compared to the first injection): 15 minutes - 0.6 mL (1.89E-07 mol) 25 minutes - 0.7 mL (2.21E-07 mol) 32 minutes - 0.7 mL Results: InP QDs with 593 nm excitons are formed.

[0175] Comparative Example 1: Synthesis of a ZnSe shell on an InP core, (trioctylphosphine selenide (TOP-Se) as the Se source) In this example, the InP core used is synthesized using the above-described core synthesis (WO 2019 / 224134 A) and has a core exciton CWL of 593 nm. The final core solution is washed with a mixture of anhydrous toluene and ethanol (crude: toluene:ethanol: 1:2:8 ratio). This process is repeated with a crude: toluene:ethanol: 1:2:6 ratio. This solution will be further referred to as the "SSP InP core".

[0176] Core Processing after Synthesis : Inside the glove box (GB), dissolve the SSP InP core (3.5×10 -7 mol) in 0.2 ml of toluene and transfer it to a 50 ml round-bottom flask equipped with 4.8 ml of oleylamine (OLAm) for pumping and 0.085 g of ZnCl2. After pumping briefly at 50 °C to remove toluene, fill the flask with argon and heat it at 250 °C for 30 minutes. Then, cool the solution to 180 °C.

[0177] Shelling Process : At 180 °C, add 2.6 mL of a 0.55 M concentrated solution of Zn(Cl) 2 in OLAm and an amount of the anion shell precursor (0.72 mL of 2 M TOP-Se) to the SSP InP core after core treatment. After 30 minutes, heat the solution to 200 °C. After 30 minutes, heat the solution to 320 °C, inject 3.2 mL of 0.4 M Zn(undecylenate)2, and hold the reaction at 320 °C for 3 hours. After 3 hours at 320 °C, cool the reaction mixture to terminate the reaction. Wash the obtained nanoparticles with a mixture of anhydrous toluene and ethanol (crude: toluene:ethanol: 3:4:8 ratio). Repeat this process. Then, extract the nanoparticles with hexane.

[0178] Comparative Example 2: ZnSeS shell synthesis on InP core (trioctylphosphine selenide (TOP-Se) as Se source, dodecanethiol (DDT) as S source) This comparative example is the same as Comparative Example 1, but 0.9 mmol of TOP-Se is injected at 180 °C; 0.56 mmol of DDT is injected at 320 °C 10 minutes after the injection of Zn(undecylenate)2.

[0179] Example 1: Synthesis of a ZnSe outer layer on InP / ZnSe NPs in ODE using 1-dodecaneselenol (DDSe) as the Se source Synthesis of the Outer Layer : At room temperature, 8.3×10 -8 mol of InP / ZnSe described in Comparative Example 1 is dissolved in 0.2 ml of toluene and transferred to a 50 ml round-bottom flask equipped with 4 ml of 1-octadecene (ODE) for pumping. After pumping at RT for 30 minutes, 1-dodecaneselenol (0.2 mmol) is added and the flask is heated to 150 °C. When the temperature reaches 150 °C, Zn(undecylenate)2 (0.2 mmol) is added and the reaction is maintained at 150 °C for 1.5 hours. After 1.5 hours at 150 °C, the reaction mixture is cooled to terminate the reaction.

[0180] The obtained nanoparticles are washed with a mixture of anhydrous toluene and ethanol (crude: toluene:ethanol: 3:4:8 ratio). This process is repeated. Then, the nanoparticles are extracted with hexane. Table A compares the values of thermal stability, radical resistance stability, and peroxide resistance stability of the described examples and Comparative Example 1.

[0181] Example 2: Synthesis of a ZnS outer layer on InP / ZnSe NPs in ODE using 1-dodecanethiol as the sulfur source This example is the same as Example 1, but 1-dodecanethiol is used as the sulfur precursor.

[0182] Example 3: Synthesis of a ZnSeS outer layer on InP / ZnSe NPs in ODE using 1-dodecaneselenol as the Se source and 1-dodecanethiol as the sulfur This example is the same as Examples 1 and 2, but 1-dodecaneselenene and 1-dodecanethiol are added together in equal molar amounts that keep the amount of Se+S ions the same as before.

[0183] Example 4: Synthesis of ZnSeS Outer Layers on InP / ZnSe NPs in ODE Using 1-Dodecaneselenol as the Se Source and 3-Phenylethanethiol as the Sulfur Source This example differs from Example 3 by utilizing 3-phenylethanethiol as the sulfur source instead of 1-dodecanethiol.

[0184] Example 5: Synthesis of ZnS Outer Layers on InP / ZnSeS NPs in ODE Using 1-Dodecanethiol as the S Source This example is the same as Example 2, except that InP / ZnSeS particles are used. InP / ZnSeS is prepared as described in Comparative Example 2. Table A compares the values of thermal stability, radical resistance stability, and peroxide resistance stability of the described examples and Comparative Example 2.

[0185] Example 6: Synthesis of ZnS Outer Layers on InP / ZnSe NPs in ODE Using Perfluorodecanethiol as the S Source This example is the same as Example 2, except that perfluorodecanethiol is used as the sulfur precursor.

[0186]

Table 1

[0187] Example 7: Experimental Proof of the Surface and Crystal Bonds of the QDs of Example 1 The general scheme (Scheme 1) shown in Figure 4 describes a multi-step method established to characterize the ligands bound to the surface and the ligands bound to the crystal (covalent ligands), using dodecaneselenol (DDSe) as an example. 3-Phenylpropylphosphonic acid (PPPA) is known to have a higher affinity for the QD surface compared to amines, thiols, selenols, and carboxylic acids. The ligand bound to the surface desorbs from the QD surface and is replaced by PPPA. On the other hand, the ligand bound to the crystal is incorporated into the crystal lattice. Thereafter, dissociation from the QD is not possible unless the crystal is destroyed.

[0188] Characterization of QDs from Example 1: Figure 1: QDs from Example 1 before (a) and after (b) the addition of PPPA 1 1H NMR spectrum (in toluene-d8). The addition of PPPA results in the desorption of DDSe from the QD surface. The amount (mmol) of desorbed DDSe (surface-bound) was quantified using duroquinone as an external standard 1 and calculated by 1H NMR to be equal to 0.00135 mmol. That is, only 1.8% mol of the surface-bound DDSe was produced out of the total amount of DDSe introduced into the reaction.

[0189] Figure 2: 1H NMR spectrum (in toluene-d8) of QDs after treatment with PPPA and washing with ethanol. 1 1H NMR spectrum (in toluene-d8). 1 1H NMR shows that the surface-bound DDSe has been completely removed from the QD surface (signals #2 (Se-H) and #3 (CH2-Se) disappear). However, signal #1 (CH3 of DDSe) still exists. This indicates the presence of a second population of DDSe that is not surface-bound. The QDs after all surface-bound DDSe has been removed are analyzed by GCMS. For this purpose, appropriate derivatization is carried out with hydrochloric acid and methanol. This treatment results in the complete decomposition and dissolution of the QDs.

[0190] Figure 3: GCMS spectrum of QDs after treatment and washing with PPPA. MS spectrum of the peak at retention time 11.458. The samples for GCMS were prepared as described in the aspect. GCMS has confirmed the presence of DDSe. This indicates the crystal bond of DDSe. Main conclusion: The QDs from Example 1 contain surface-bound DDSe as well as crystal-bound DDSe.

[0191] Example 8: Synthesis of a ZnS outer layer on InP-based red quantum dots in PGMEA using poly(ethylene glycol) methyl ether thiol Mn800 (mPEG800-SH) as the S source. Weigh 183.5 mg (1 mmol) of Zn(OAc)2 into a 50 mL round-bottom four-neck reaction flask, place it under vacuum for 40 minutes, then under argon, and introduce it into the glove box; add 6 mL of PGMEA and 0.61 mL of InP-based red quantum material (QM). Observation - Red suspension. Place under vacuum at room temperature for 20 minutes. Place under Ar. Add 2 mL of PGMEA.

[0192] Heat to 144 °C (in 8 minutes) (reflux, cool the condenser with a water stream). Inject 1.15 mL of a 0.43 M mPEG-SH solution in PGMEA at 144 °C - t = 0 Maintain at 144 °C for 65 minutes. Inject 1.15 mL of a 0.43 M mPEG-SH solution in PGMEA. Maintain at 144 °C for 70 minutes. End. Total - 2 hours and 15 minutes at 144 °C. Wash the obtained QDs with anhydrous hexane (crude: hexane ratio 1:1). Repeat the process with a mixture of anhydrous PGMEA:hexane 1:1. Then extract the QDs with toluene.

[0193]

Table 2

[0194] Example 9: Synthesis of ZnS Outer Layer on InP-Based Red Quantum Dots in PGMEA Using Poly(Ethylene Glycol) Methyl Ether Thiol Mn800 (mPEG800-SH) as S Source Weigh 1.28 g of zinc acetate (Zn(OAc)2) into a 250 ml round-bottom flask, degas at 200 mTorr for 25 minutes while stirring, place it under an Ar atmosphere, and insert it into a glove box. Add 56 ml of a solution of 2.1 gr of InP-based red quantum material in PGMEA and toluene. Place the mixture on a Schlenk line, put it under argon gas, attach a distillation setup, and distill to remove toluene.

[0195] Heat the flask to reflux and inject 7.7 ml of a 0.4 M mPEG800-SH solution in PGMEA. After 65 minutes, inject 7.7 ml of a 0.4 M mPEG800-SH solution in PGMEA again. After an additional 70 minutes of reflux (total reaction time 2 hours 15 minutes), cool the flask to room temperature. Wash the obtained QDs as follows: Remove the solids by centrifugation, precipitate the QDs with anhydrous hexane (crude: hexane 1:1 ratio), repeat the process with a mixture of anhydrous PGMEA:hexane 1:1, and then repeat twice with anhydrous toluene:hexane 2:3.

[0196] [Table 3] Table C compares the thermal stability values of Example 9 as described with a reference material prepared in the same manner as Example 9 but without Zn(OAc)2.

[0197] Example 10: Synthesis of ZnS Outer Layer on InP-Based Green Quantum Material with Core-Shell Structure in Diisopropylbenzene Using Polyethylene Glycol Methyl Ether Thiol Mn350 (mPEG350-SH) as S Source Weigh 0.215 g of Zn(OAc)₂ into a 50 mL round-bottom flask outside the glove box and introduce the flask into the glove box. Add 8 mL of diisopropylbenzene (DIPB), and then add a toluene solution of 270 mg of InP-based green quantum dots. Place the mixture on a Schlenk line and remove toluene under reduced pressure. Fill the flask with Ar. Heat the flask to 160 °C and inject 1.3 mL of a 0.9 M mPEG(350)-SH solution in diisopropylbenzene. After 90 minutes at 160 °C, cool the reaction to ambient temperature. When cooled below 50 °C, the QDs precipitated. Add toluene (6 mL) to dissolve the quantum dots.

[0198] Wash the obtained QDs as follows: Remove the solids by centrifugation, precipitate the quantum dots with anhydrous heptane ((crude + toluene): heptane in a 1:1 ratio), repeat this process with a mixture of anhydrous PGMEA:heptane 1:2, and then repeat with anhydrous toluene:heptane 1:1.

Claims

1. A semiconductor light-emitting nanoparticle, comprising: a core; an outer layer covering at least a part of the core and containing a metal cation and a divalent anion; and one or more organic moieties directly attached by a covalent bond to the anion of the outer layer, wherein the metal cation is selected from the group consisting of Zn2+ and Hg2+; the divalent anion is selected from Se2−, S2−, Te2−, O2−, or any combination thereof; the organic moiety has the following chemical formula (III) or (III′): wherein ＊ -(CH ２ ) ａ -(OCH ２ CH ２ ) ｐ -(V) ｒ -(CH ２ ) ｑ -Z (III) ＊ -(CH ２ ) ｑ -(V) ｒ -(OCH ２ CH ２ ) ｐ -Z (III´) Z is a hydrogen atom or an organic group; V is O, CH ２ or C=O; a is an integer of 0 or 1 or more; p is an integer of 1 or more; q is an integer of 0 or 1 or more; r is an integer of 0 or 1, and the semiconductor light-emitting nanoparticle is represented by the above formula. " ＊ " represents the connection point to the outer anion,

2. The organic moiety has the following chemical formula (IV): wherein ＊ -(CH ２ ) ａ -(OCH ２ CH ２ ) ｐ -(O) ｒ -(CH ２ ) ｑ -Z´ (IV) a is an integer of 0 or 1 or more; p is an integer of 1 or more; q is an integer of 0 or 1 or more; Z′ is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, or a fluoroaralkyl; r is an integer of 0 or 1.

3. " ＊ " represents the nanoparticle according to claim 1, which represents the connection point to the outer anion. The nanoparticle according to claim 1 or 2, wherein the organic moiety is covalently bonded to the anion of the outer layer of the inorganic lattice.

4. A process for producing a semiconductor light-emitting nanoparticle, comprising at least the following steps: (a) mixing at least the semiconductor light-emitting nanoparticle with another material to obtain a reaction mixture; forming an outer layer on the semiconductor light-emitting nanoparticle in the reaction mixture by reacting at least an anion source represented by the chemical formula (III′), (IIIa′), or (IV′) with a metal cation precursor, wherein the metal cation is selected from the group consisting of Zn2+ and Hg2+; wherein X １ -(CH ２ ) ａ -(OCH ２ CH ２ ) ｐ -(V) ｒ -(CH ２ ) ｑ -Z (III´) X １ -(CH ２ ) ｑ -(V) ｒ -(OCH ２ CH ２ ) ｐ -Z (IIIa'), or HS-(CH ２ ) ａ -(OCH ２ CH ２ ) ｐ -(O) ｒ -(CH ２ ) ｑ -Z´ (IV´) Z is a hydrogen atom or an organic group; X １ is an anchor group containing a divalent anion selected from one or more members of the group consisting of at least Se2−, S2−, Te2−, and O2− that can bind to the metal cation; V is O, CH ２ or C=O; Z′ is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, or a fluoroaralkyl; a is an integer of 0 or 1 or more; p is an integer of 1 or more; q is an integer of 0 or 1 or more; r is an integer of 0 or 1; and (c) cooling the reaction mixture from step (b). Here, the reaction mixture in step (b) is maintained at a temperature in the range of 80°C to 200°C in order to form the outer layer in step (b). Said process, comprising.

5. The process according to claim 4, wherein the anion source is injected at a temperature in the range of 0°C to 200°C in step (a) or step (b).

6. The process according to claim 4 or 5, wherein step (b) is carried out in the range of 1 minute to 10 hours.

7. The process according to any one of claims 4 to 6, wherein the ratio of the total molar amount of the cation precursor to the total molar amount of the semiconductor light-emitting nanoparticles in step (b) is in the range of 20:1 to 200,000:

1.

8. The process according to any one of claims 4 to 7, wherein the anion source is used together with a reducing agent in step (b) to form the outer layer.

9. The process according to any one of claims 4 to 8, wherein the ratio of the total amount of the anion source used in step (b) to the total amount of the cation precursor is in the range of 20:1 to 1:

20.

10. Semiconductor light-emitting nanoparticles obtainable or obtained according to the process of any one of claims 4 to 9.

11. At least one semiconductor light-emitting nanoparticle according to any one of claims 1 to 3 and 10, and at least one additional material comprising a composition.

12. At least one semiconductor light-emitting nanoparticle according to any one of claims 1 to 3 and 10, or the composition according to claim 11, and at least one solvent, comprising a formulation.

13. Use of the semiconductor light-emitting nanoparticles according to any one of claims 1 to 3 and 10, or the composition according to claim 11, or the formulation according to claim 12 in an electronic device, an optical device, a sensing device or a biomedical device.

14. An optical medium comprising the semiconductor light-emitting nanoparticles according to any one of claims 1 to 3 and 10, or the composition according to claim 11, or the formulation according to claim 12.

15. The optical medium according to claim 14, comprising an anode and a cathode, and at least one layer comprising at least one semiconductor light-emitting nanoparticle according to any one of claims 1 to 3 and 10, or the composition according to claim 11.

16. The optical medium according to claim 14 or 15, wherein the layer contains at least one semiconductor light-emitting nanoparticle according to any one of claims 1 to 3 and 10, and a host material. **Claim 17** An optical device comprising the optical medium according to any one of claims 14 to 16.

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