Composition

Abstract

The present invention relates to compositions containing light-emitting moieties, such as quantum materials, including quantum dots, and methods for making the compositions.

Description

[Technical Field]

[0001] The present invention relates to compositions comprising light-emitting moieties, methods for making the compositions, formulations, and uses of the compositions to form layers, methods, layers, color conversion devices, and optical devices. [Background technology]

[0002] Luminescent nanoparticles are known in the prior art. For example, Turo et al., ACS NANO vol. 8, no. 10, pp. 10205-10203, 2014, discloses CuS nanoparticles without a shell layer containing dodecanethiol (DDT) and a method for preparing them using DDT at a temperature of 200° C. DDT is used throughout the synthesis process.

[0003] Turo et al., Chem Commun, 2016, 52, 12214-12217, describes CdSe / ZnS with dodecanethiol. Robinson et al., Chem Mater, 2017, 29, 3854-3857, mentions quasi-spherical Cu2S nanorods with DDT.

[0004] Patent documents No references

[0005] Non-patent literature 1.Turo et al.,ACS NANO vol.8,no.10,10205-10203,2014 2.Chem Commun,2016,52,12214-12217 3.Robinson et al.,Chem Mater,2017,29,3854-3857 Summary of the Invention

[0006] However, the present inventors have newly discovered that one or more of the following important problems still exist for which improvement is desired: optimizing the haze value of the cured layer (film), achieving an optimal haze value with an improved EQE value of the cured layer (film), preferably achieving an optimal haze value with an improved EQE value of the cured layer (film) without using scattering particles, improving the thermal stability of the resulting layer (film), improving the thermal stability of the light-emitting moiety in the layer (film), achieving improved dispersibility of the light-emitting moiety in the composition, enabling phase separation between the light-emitting moiety and the matrix material after curing, improving the haze value of the cured film (cured composition), improving the dispersibility of the light-emitting moiety in the resulting layer, and stabilizing the long-term quantum yield (QY) of the light-emitting moiety in the composition when stored for a long period of time with or without external light irradiation. improved long-term external quantum efficiency (EQE) stability of the light-emitting moiety in the composition when stored for a long period with or without external light irradiation; improved long-term quantum yield (QY) stability of the light-emitting moiety in the resulting layer (film) when stored for a long period with or without external light irradiation; improved long-term external quantum efficiency (EQE) stability of the light-emitting moiety in the resulting layer (film) when stored for a long period with or without external light irradiation; improved compatibility between the light-emitting moiety and the matrix material in the composition and / or the resulting layer (film); and / or easier handling of the composition comprising the light-emitting moiety and the matrix material, making the composition suitable for inkjet printing.

[0007] The inventors aimed to solve one or more of the problems set forth above.

[0008] The inventors have surprisingly found that one or more of the above mentioned technical problems can be solved by the features defined in the claims.

[0009] That is, a novel composition, preferably a photocurable composition, has been discovered, which comprises: i) a light-emitting moiety, preferably a semiconductor light-emitting nanoparticle, with an outer layer comprising a metal cation and a divalent anion; and a light-emitting moiety comprising one or more organic moieties covalently bonded directly to the anions of the outer layer; ii) at least one reactive monomer or a mixture of two or more reactive monomers, preferably wherein the monomer has one or more functional groups, more preferably a (meth)acrylate monomer; The divalent anion in the outer layer is Se 2- , S 2- , Te 2- , O 2- or a combination thereof, preferably the metal cations in the outer layer are monovalent, divalent, trivalent or tetravalent cations, more preferably the metal cations are Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ , and Sn 4+ is a tetravalent cation selected from the group consisting of:

[0010] In another aspect, the present invention further relates to a method for preparing the composition of the present invention, said method comprising at least the following steps: (a) mixing at least semiconductor nanoparticles with another material to obtain a reaction mixture, preferably wherein the semiconductor nanoparticles comprise at least a first semiconductor nanomaterial as a core; Preferably, the other material is a solvent; (b) forming an outer layer on the semiconductor nanoparticles in the reaction mixture by reacting at least one anion source represented by Formula (Va) or Formula (Vb) with a metal cation precursor in the reaction mixture, wherein in some embodiments of the present invention, the metal cation precursor can be the same as the cation shell precursor; ABXH (Va) ABXXBA (Vb) [In the formula, A is an organic group; B is a connection unit that connects A and X, H is a hydrogen atom, X is an anchoring group comprising an anion capable of forming a monolayer with an added metal cation derivable from an added metal cation precursor; (c) cooling the reaction mixture from step (b), maintaining the reaction mixture in step (b) 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); (d) mixing the light-emitting moiety resulting from step (c) with at least one reactive monomer or a mixture of two or more reactive monomers to form a composition.

[0011] In another aspect, the present invention relates to compositions obtainable or obtained from the methods of the present invention.

[0012] In another aspect, the present invention relates to a formulation comprising, consisting essentially of, or consisting of at least the 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 selected from one or more members of the group consisting of toluene, xylene, tetrahydrofuran, chloroform, dichloromethane and heptane, hexane, purified water, acetate esters, acetate ethers, ketones, ether esters such as PGMEA, alcohols such as ethanol and isopropanol, sulfoxides, formamides, nitrides, ketones.

[0013] In another aspect, the invention relates to the use of the composition or formulation in an electronic, optical, sensing or biomedical device.

[0014] In another aspect, the present invention relates to a method for forming a layer, the method comprising: S1) providing a composition of the present invention onto a substrate, preferably by inkjet; S2) a step of curing the composition, preferably the curing is photocuring performed by light irradiation, thermal curing, or a combination of photocuring and thermal curing.

[0015] In another aspect, the present invention further relates to a layer obtained or obtainable from the method of the present invention.

[0016] In another aspect, the present invention further relates to a layer, the layer comprising: Xi) a light-emitting moiety, preferably a semiconductor light-emitting nanoparticle, with an outer layer comprising a metal cation and a divalent anion; and a light-emitting moiety comprising one or more organic moieties covalently bonded directly to the anions of the outer layer; Xii) a polymer made from at least one reactive monomer or a mixture of two or more reactive monomers, preferably the monomers have one or more functional groups, more preferably they are (meth)acrylate monomers, The divalent anion in the outer layer is Se2- , S 2- , Te 2- , O 2- or a combination thereof, preferably the metal cations in the outer layer are monovalent, divalent, trivalent or tetravalent cations, more preferably the metal cations are Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ , and Sn 4+ is a tetravalent cation selected from the group consisting of:

[0017] In another aspect, the present invention further relates to a color conversion device (100) comprising at least one first pixel (161) partially or completely filled with a layer of the present invention comprising at least a matrix material (120) containing a light-emitting portion (110), and a bank (150) comprising at least a polymer material, and preferably the color conversion device (100) further comprises a support medium (170).

[0018] In another aspect, the present invention further relates to an optical device (300) comprising at least one functional medium (320, 420, 520) configured to modulate light or configured to emit light, and a color conversion device (100) of the present invention. [Brief explanation of the drawings]

[0019] [Figure 1] A schematic cross-sectional view of one embodiment of a color conversion film (100) is shown. [Figure 2] 1 shows a schematic top view of another embodiment of the color conversion film (100) of the present invention. [Figure 3] 1 shows a schematic cross-sectional view of one embodiment of an optical device (300) of the present invention. [Figure 4] 3 shows a schematic cross-sectional view of another embodiment of an optical device (300) of the present invention. [Figure 5] 3 shows a schematic cross-sectional view of another embodiment of an optical device (300) of the present invention. [Figure 6] 1H NMR spectra (toluene d8) of the QDs of Reference Example 1 (a) before and (b) after the addition of 3-phenylpropylphosphone (PPPA). [Figure 7] 1H NMR spectrum (toluene d8) of the QDs of Reference Example 1 after treatment with PPPA and washing with ethanol. [Figure 8A] 1 shows the GCMS spectrum of the QDs of Reference Example 1 after treatment with PPPA and washing. This is the MS spectrum of the peak at a retention time of 11.45. [Figure 8B] 1 shows the GCMS spectrum of the QDs of Reference Example 1 after treatment with PPPA and washing. This is the MS spectrum of the peak at a retention time of 11.45. [Figure 9] We describe a general scheme of a multistep method established to distinguish surface-bound from crystal-bound ligands, exemplified for dodecane selenol (DDSe) (Scheme 1).

[0020] List of reference numbers for Figure 1 100. Color conversion device 110. Light-emitting part 110R.Light-emitting part (red) 110G. Illuminating part (green) 120.Matrix Materials 130.Light scattering particles (optional) 140. Colorant (optional) 140R. Colorant (red) (optional) 140g. Coloring (green) (optional) 140B. Colorant (blue) (optional) 150. Bank 161. First Pixel 162. Second Pixel 163. The Third Pixel 170.Support medium (substrate) (optional)

[0021] List of reference numbers for Figure 2 200. Color conversion film 210R.pixels (red) 210G pixels (green) 210B.Pixel (Blue) 220. Bank

[0022] List of reference numbers for Figure 3 300. Optical Devices 100. Color conversion device 110. Light-emitting part 110R.Light-emitting part (red) 110G. Illuminating part (green) 120.Matrix Materials 130.Light scattering particles (optional) 140. Colorant (optional) 140R. Colorant (red) (optional) 140g. Coloring (green) (optional) 140B. Colorant (blue) (optional) 150. Bank 320. Optical Modulator 321. Polarizer 322.Electrode 323. Liquid crystal layer 330.Light source 331.LED light source 332.Light guide plate (optional) 333. Light emission from the light source (330)

[0023] List of reference numbers for Figure 4 400. Optical Devices 100. Color conversion device 110. Light-emitting part 110R.Light-emitting part (red) 110G. Illuminating part (green) 120.Matrix Materials 130.Light scattering particles (optional) 140. Colorant (optional) 140R. Colorant (red) (optional) 140g. Coloring (green) (optional) 140B. Colorant (blue) (optional) 150. Bank 420. Optical Modulator 421. Polarizer 422.Electrode 423. Liquid crystal layer 430.Light source 431.LED light source 432.Light guide plate (optional) 440. Color Filter 433. Light radiation from the light source (330)

[0024] List of reference numbers for Figure 5 500. Optical Devices 100. Color conversion device 110. Light-emitting part 110R.Light-emitting part (red) 110G. Illuminating part (green) 120.Matrix Materials 130.Light scattering particles (optional) 140. Colorant (optional) 140R. Colorant (red) (optional) 140g. Coloring (green) (optional) 140B. Colorant (blue) (optional) 150. Bank 520. Light-emitting devices (e.g., OLEDs) 521.TFT 522. Electrode (Anode) 523.Base material 524. Electrode (Cathode) 525. Light-emitting layer (e.g., OLED layer(s)) 526. Light emission from the light-emitting device (520) 530. Optical layer (e.g., polarizer) (optional) 540. Color filter DETAILED DESCRIPTION OF THE INVENTION

[0025] According to the present invention, a composition, preferably a photocurable composition, is provided, i) a light-emitting moiety, preferably a semiconductor light-emitting nanoparticle, with an outer layer comprising a metal cation and a divalent anion; and a light-emitting moiety comprising one or more organic moieties covalently bonded directly to the anions of the outer layer; ii) at least one reactive monomer or a mixture of two or more reactive monomers, preferably wherein the monomer has one or more functional groups, more preferably a (meth)acrylate monomer; The divalent anion in the outer layer is Se 2- , S 2- , Te 2- , O 2- or a combination thereof, preferably the metal cations in the outer layer are monovalent, divalent, trivalent or tetravalent cations, more preferably the metal cations are Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ , and Sn 4+ is a tetravalent cation selected from the group consisting of:

[0026] -Light-emitting part According to the present invention, the light-emitting moiety may be an organic and / or inorganic light-emitting material, preferably an organic dye, an inorganic phosphor, and / or a semiconductor light-emitting nanoparticle such as a quantum dot material. Known organic dyes, inorganic phosphors, and semiconductor light-emitting nanoparticles can be used.

[0027] Such suitable inorganic luminescent materials as mentioned above may be well-known phosphors such as nanosized phosphors, quantum-sized materials, etc., as described in Phosphor Handbook, 2nd edition (CRC Press, 2006), pp. 155-338 (W.M. En, S. Shionoya and H. Yamamoto), WO 2011 / 147517, WO 2012 / 034625, and WO 2010 / 095140.

[0028] As the organic dye, for example, rhodamine, coumarin, pyrromethene, DCM, fluorescein, umbelliferone, and BD Horizon Brilliant™ series can be used.

[0029] Preferably, the light-emitting moiety is an inorganic light-emitting material. More preferably, the light-emitting moiety is a semiconductor light-emitting nanoparticle. The semiconductor light-emitting nanoparticle preferably comprises a core and an outer layer coating at least a portion of the core and comprising a metal cation and a divalent anion; one or more organic moieties directly attached to the outer layer anions, preferably by covalent bonds; The divalent anion is Se 2- , S 2- , Te 2- , O 2- or a combination thereof, preferably the metal cation is a monovalent, divalent, 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+ or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf4+ , and Sn 4+ Alternatively, in some embodiments, the metal cation is a Group 12 or 14 transition metal, preferably Zn 2+ , Hg 2+ or Pb 2+ and is selected from one or more members of the group consisting of:

[0030] A nanoparticle comprises at least an outer layer and a core, and may optionally comprise one or more other layers (shell layers) between the outer layer and the core. The outer layer covers at least a portion of the core. The outer layer may be in direct physical contact with the core when there are no other layers between the outer layer and 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 "envelop" and "enveloping" do not necessarily imply that there is always physical contact between the core and the outer layer. Preferably, the core is completely surrounded by the outer layer and / or one or more shell layers.

[0031] Most preferably, the nanoparticles comprise a core, one or more shell layers, and one outer layer, wherein the outermost shell layer of the one or more shell layers comprises Zn and S atoms.

[0032] In a preferred embodiment of the present invention, the outer layer of the light-emitting moiety is Cu, with a view to improving the covalent bond between the organic moiety and the anions of the outer layer. 1+ and In 3+ , Cu 1+ and Ga 3+ , Ag 1+ and Ga 3+ combination, or Cu +1 / In +3 / Zn +2 The metal cations include at least two or three different metal cations, such as a combination of:

[0033] According to the present invention, the term "nano-sized" means a size of 0.1 nm to 150 nm, preferably 0.5 nm to 100 nm, more preferably 1 nm to 50 nm.

[0034] According to the present invention, the term "semiconductor" means a material that has an electrical conductivity at room temperature that is between that of a conductor (such as copper) and that of an insulator (such as glass); preferably, a semiconductor is a material whose electrical conductivity increases with temperature.

[0035] Therefore, according to the present invention, the term "semiconductor nanoparticles" is taken to mean a material having a conductivity at room temperature that is somewhere between that of a conductor (such as copper) and that of an insulator (such as glass), preferably a semiconductor, whose conductivity increases with temperature, and having a size of 0.1 nm to 999 nm, preferably 0.5 nm to 150 nm, more preferably 1 nm to 50 nm.

[0036] According to the present invention, the term "size" means the average diameter of a circle having an area equal to the measured TEM projection of a semiconductor nano-sized luminescent particle.

[0037] In a preferred embodiment of the present invention, the semiconductor light-emitting nanoparticles of the present invention are quantum-sized materials.

[0038] According to the present invention, the term "quantum size" refers to the size of the first semiconductor nanoparticle itself, without any ligand or other surface modification, which can exhibit quantum confinement effects, as described, for example, in ISBN: 978-3-662-44822-9.

[0039] It is generally believed that quantum-sized materials can emit tunable, sharp, and vivid colored light due to the "quantum confinement" effect.

[0040] In some embodiments of the present invention, the size of the overall structure of the quantum-sized material is between 1 nm and 50 nm.

[0041] In a preferred embodiment of the present invention, the average diameter of the first semiconductor nanoparticles (core) is in the range of 1 to 20 nm, and preferably in the range of 1.5 to 12 nm.

[0042] The average diameter of the semiconductor luminescent nanoparticles (cores) is calculated based on 100 semiconductor luminescent nanoparticles in TEM images taken by a Tecnai G2 Spirit Twin T-12 transmission electron microscope. The average diameter of the semiconductor luminescent nanoparticles is calculated using the Fiji_ImageJ program.

[0043] According to the present invention, the semiconductor luminescent nanoparticles may have a core-shell structure. If the semiconductor luminescent nanoparticles do not have any shell layer, the term "core" refers to the semiconductor luminescent nanoparticle itself.

[0044] In some embodiments of the present invention, the core comprises at least one element from Group 12 or Group 13 of the periodic table and one element from Group 15 or Group 16 of the periodic table.

[0045] In a preferred embodiment of the present invention, the first semiconductor material (hereinafter the "core" of the semiconductor luminescent nanoparticle) comprises at least one element from group 13 of the periodic table and one element from group 15 of the periodic table, preferably the group 13 element is In and the group 15 element is P.

[0046] In a preferred embodiment of the present invention, the first core may further comprise an additional element selected from one or more members of the group consisting of Ga, Zn, S, and Se.

[0047] In some embodiments, the core is a metal oxide including, for example, ZnO, FeO, Fe2O3, ZrO2, CuO, SnO, Cu2O, TiO2, WO3, HfO2, In2O3, MgO, Al2O3, and combinations thereof.

[0048] In some embodiments, the core comprises a metal such as Au, Ag, W, Pd, Pt, Cu, In, Ti, Zn, Pb, Al, Cd, Zn, and combinations thereof.

[0049] In a more preferred embodiment, the core is selected from the group consisting of InP, InPZn, InPZnS, InPZnSe, InPZnSeS, InPZnGa, InPGaS, InPGaSe, InPGaSeS, InPZnGaSeS and InPGa.

[0050] According to the present invention, the type of core shape of the semiconductor light-emitting nanoparticles and the shape of the synthesized semiconductor light-emitting nanoparticles are not particularly limited.

[0051] For example, spherical, elongated, star-shaped, polyhedral, pyramidal, tetrapod-shaped, tetrahedral, platelet-shaped, conical, and irregular core and / or semiconductor light-emitting nanoparticles can be synthesized.

[0052] -Shell layer According to the present invention, in a preferred embodiment, the core is at least partially embedded in the first shell layer, and more preferably, the core is completely embedded in one or more shell layers. In a preferred embodiment of the present invention, the shell layer(s) are disposed between the core and the outer layer. In other words, the semiconductor luminescent nanoparticles of the present invention can optionally comprise, consist essentially of, or consist of a core, one or more shell layers covering the core, and an outer layer covering the shell layers, in this order.

[0053] -First shell layer In some embodiments of the present invention, the shell layer comprises at least one metal cation, at least one divalent anion as described in the outer layer section, and / or at least a first element from group 12 of the periodic table and a Se or S atom, preferably the first element is Zn.

[0054] For example, the first shell layer may be made of Cs2S, Cs2Se, Cs2Te, Cs2O, Ag2S, Ag2Se, Ag2Te, Ag2O, Au2S, Au2Se, Au2Te, Au2O, Cu2S, Cu2Se, Cu2Te, Cu2O, ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, CaS, CaSe, CaTe, CaO, NiS, N iSe, 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, In2S3, In2Se3, In2Te 3, In2O3, Ga2S3, Ga2Se3, Ga2Te3, Ga2O3, Bi2S3, Bi2Se3, Bi2Te3, Bi2O3, Fe2S3, Fe2Se3, Fe2Te3, Fe2O3, TiS2, TiSe2, TiTe2, TiO2, SiS2, SiSe2, SiTe2, SiO2, ZrS2, ZrSe2, ZrTe2, ZrO2, HfS2, HfS e2, HfTe2, HfO2, SnS2, SnSe2, SnTe2, SnO2, GeS2, GeSe2, GeTe2, GeO, CuInZnS, CuInS2, CuInZnSe, CuInSe2, AgInZnS, AgInZnSe, CuGaZnS, CuGaZnSe, CuFeS2, CuFeSe2 and combinations thereof.

[0055] Preferably, this layer 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 combinations of these materials.

[0056] More preferred are ZnS, ZnSe, ZnTe, ZnO, or a combination of these materials.

[0057] In some embodiments of the present invention, at least one (first) shell layer comprises or consists of a first element from group 12 of the periodic table and a second element from group 16 of the periodic table, preferably the first element is Zn and the second element is S, Se, or Te. Preferably, the first shell layer directly on the core comprises or consists of a first element from group 12 of the periodic table and a second element from group 16 of the periodic table, preferably the first element is Zn and the second element is S, Se, or Te.

[0058] In a preferred embodiment of the present invention, at least one shell layer (first shell layer) is represented by the following formula (XI), preferably the shell layer directly covering the core is represented by chemical formula (XI): ZnS x Se y Te z -(XI) [Wherein, 0≦x≦1, 0≦y≦1, 0≦z≦1, and x+y+z=1, preferably 0≦x≦1, 0≦y≦1, z=0, and x+y=1, and preferably the shell layer is ZnSe, ZnS x Se y , ZnS, ZnSe y Te z or ZnS x Te z is].

[0059] 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 ZnS x Se y , ZnSe y Te z , or ZnS x Te z and more preferably ZnS x Se y is.

[0060] In some embodiments of the present invention, the semiconductor luminescent nanoparticles further comprise a second shell layer on the shell layer, preferably the second shell layer comprises or consists of a third element from group 12 of the periodic table and a fourth element from group 16 of the periodic table, more preferably the third element is Zn and the fourth element is S, Se, or Te, provided that the fourth element and the second element are not the same.

[0061] In some embodiments of the present invention, optionally, the first semiconductor nanoparticles as the core and first shell layer may be at least partially embedded in the second shell layer, and preferably, the first semiconductor nanoparticles are completely embedded in the shell layer.

[0062] For example, the second shell layer may be Cs2S, Cs2Se, Cs2Te, Cs2O, Ag2S, Ag2Se, Ag2Te, Ag2O, Au2S, Au2Se, Au2Te, Au2O, Cu2S, Cu2Se, Cu2Te, Cu2O, ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, CaS, CaSe, CaTe, CaO, NiS, N iSe, 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, In2S3, In2Se3, In2Te 3, In2O3, Ga2S3, Ga2Se3, Ga2Te3, Ga2O3, Bi2S3, Bi2Se3, Bi2Te3, Bi2O3, Fe2S3, Fe2Se3, Fe2Te3, Fe2O3, TiS2, TiSe2, TiTe2, TiO2, SiS2, SiSe2, SiTe2, SiO2, ZrS2, ZrSe2, ZrTe2, ZrO2, HfS2, HfS e2, HfTe2, HfO2, SnS2, SnSe2, SnTe2, SnO2, GeS2, GeSe2, GeTe2, GeO, CuInZnS, CuInS2, CuInZnSe, CuInSe2, AgInZnS, AgInZnSe, CuGaZnS, CuGaZnSe, CuFeS2, CuFeSe2 and combinations thereof.

[0063] Preferably, this layer 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 combinations of these materials.

[0064] More preferred are ZnS, ZnSe, ZnTe, ZnO, or a combination of these materials.

[0065] In some embodiments of the present invention, the second shell layer comprises at least a first element from Group 12 of the periodic table and a second element from Group 16 of the periodic table, preferably wherein the first element is Zn and the second element is S, Se, O, or Te.

[0066] In a preferred embodiment of the present invention, the second shell layer is represented by the following formula (XI'): ZnS x Se y Te z -(XI') [Wherein, 0≦x≦1, 0≦y≦1, 0≦z≦1, and x+y+z=1; preferably, the shell layer is ZnSe, ZnS x Se y , ZnSe y Te z or ZnS x Te z , but the shell layer and the second shell layer are not the same].

[0067] In some embodiments of the present invention, the second shell layer may be an alloy shell layer.

[0068] In some embodiments of the present invention, the semiconductor light-emitting nanoparticles can further comprise one or more additional shell layers on the second shell layer as a multishell.

[0069] According to the present invention, the term "multi-shell" refers to a stack of shell layers consisting of three or more shell layers.

[0070] For example, the shell layer may be made of CdS, CdZnS, CdS / ZnS, CdS, ZnS, ZnS / ZnSe, ZnSe / ZnS, or a combination thereof, preferably ZnS, ZnSe, or ZnSe / ZnS.

[0071] For example, examples of semiconductor light-emitting materials having a core / shell structure include CdSe / CdS, CdSeS / CdZnS, CdSeS / CdS / ZnS, ZnSe / CdS, CdSe / ZnS, InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InZnP / ZnS, InZnP / ZnSe, InZnP / ZnSe / ZnS, InGaP / ZnS, InGaP / ZnSe, InGaP / ZnSe, InGaP / ZnSe / ZnS, InZnPS / ZnS, InZnPS / ZnSe, InZnPS / ZnSe / ZnS, ZnSe / CdS, ZnSe / ZnS, and combinations thereof. Preferred are InP / ZnS, InP / ZnSe, InP / ZnSe, InP / ZnSe / ZnS, InZnP / ZnS, InZnP / ZnSe, InZnP / ZnSe / ZnS, InGaP / ZnS, InGaP / ZnSe, and InGaP / ZnSe / ZnS.

[0072] Such semiconductor luminescent nanoparticles are commonly available (e.g., from Sigma Aldrich) and / or can be synthesized by methods described, for example, in U.S. Pat. No. 7,588,828, U.S. Pat. No. 8,679,543, and Chem. Mater. 2015, 27, pp 4893-4898.

[0073] -organic part In a preferred embodiment of the present invention, the organic moiety is represented by the following chemical formula (I): AB- * (I) [In the formula, A is an organic group, preferably the organic group is a hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group (including aryl, alkaryl, alkyl or aralkyl), an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group (including fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl); B is a connection unit, and preferably B is ** -(U) o -(Y) m -(CR IIa R IIb ) n In the formula, ** " represents the connection point to "A", " * " represents the point of attachment to the anion in the outer layer].

[0074] More preferably, the organic moiety is represented by the following chemical formula (II), (III) or (III'): L-(U) o -(Y) m -(CR IIa R IIb ) n - * (II) [In the formula, L is an organic group, preferably the organic group is a hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group (aryl, alkaryl, alkyl or aralkyl), an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl or a fluoroaralkyl); U is O, CH2 or C=O; Y is O, CH2 or C=O; R IIa and R IIbare each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms, and preferably from R IIa and R IIb is a hydrogen atom, n is an integer equal to or greater than 1, m is an integer of 0 or 1 or more, preferably m is 1; o is an integer of 0 or 1 or more, preferably o is 1; " * " represents the point of attachment to the anion in the outer layer], * -(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z (III) * -(CR IIIg R IIIh ) q -(V) r -(OCR IIIa R IIIb CR IIIc R IIId ) p -Z (III') [In the formula, R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and RIIIhare each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms, and preferably from R IIIg and R IIIh is a hydrogen atom, and preferably R IIIe and R IIIf is a hydrogen atom, V is O, CH2 or C=O, 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 -NH2, an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, or a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, or a fluoroaralkyl), preferably Z is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a branched alkyl group having 3 to 25 carbon atoms, more preferably a hydrogen atom, a linear alkyl group having 1 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms, and even more preferably a hydrogen atom, or a linear alkyl group having 1 to 10 carbon atoms; 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 even more preferably 4≦p≦18; q is 0 or an integer of 1 or more, preferably 0≦q≦25, more preferably 0≦q≦15, even more preferably 0≦q≦10, and even more preferably 1≦q≦5; r is 0 or the integer 1; " * " represents the point of attachment to the anion in the outer layer].

[0075] More preferably, the organic moiety is represented by the following formula (IV): * -(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z' (IV) [In the formula, R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and RIIIh are each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms, and preferably from R IIIg and R IIIh is a hydrogen atom, and preferably R IIIe and R IIIf is a hydrogen atom, 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 even more preferably 4≦p≦18; q is 0 or an integer of 1 or more, preferably 0≦q≦25, more preferably 0≦q≦15, even more preferably 0≦q≦10, and still more preferably 1; V is O, CH2 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, a fluoroaralkyl, or a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, or a 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 a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a hydrogen atom, and even more preferably a hydrogen atom; r is 0 or the integer 1; " * " represents a point of attachment to an anion in the outer layer, preferably attached to an S or Se atom in the outer layer.

[0076] In some preferred embodiments, the organic moiety is CH3-(CH2) 7<n<18- * and connects to S or Se atoms in the outer layer.

[0077] In a preferred embodiment of the present invention, organic moieties selected from formula (I), (II), (III), (III') or (IV) are covalently bound to anions in the inorganic lattice of the outer layer and preferably are not removed by ligand exchange.

[0078] The crystal-bound ligands (covalently bound ligands) can be characterized as described in Reference Example 7.

[0079] For example, the organic moiety can preferably be written as follows: * -CH2-(OCH2CH2)4-O-CH3 * -CH2-(OCH2CH2)6-O-CH3 * -CH2-(OCH2CH2)8-O-CH3 *-(CH2)2-(OCH2CH2)2-O-CH3 * -(CH2)2-(OCH2CH2)6-O-CH3 * -(CH2)2-(OCH2CH2)8-O-CH3 * -(CH2)2-(OCH2CH2)6-CH3 * -(CH2)2-(OCH2CH2)6-O-(CH2)2-SH * -(CH2) 7- CH3 * -(CH2) 11- CH3 * -(CH2) 17- CH3 * -(CH2)2-(OCH2CH2)6-O-CH3 * -(CH2)2-(OCH2CH2) 16 -O-CH3 * -(CH2)2-(OCH2CH2) 17 -O-CH3 " * " represents a point of attachment to an S or Se atom in the outer layer; or * -(CH2) 11- CH3 " * " represents a connection point to a Se or S atom in the outer layer. Other thiolated ligand materials such as polypropylene glycol and polypropylene glycol monomethyl ether, the thiolated ligand materials described in U.S. Pat. No. 1,102,651, columns 17-18, formula (I), formula (II), column 25, line 28 to column 26, line 16, and M1000-SH in Example 1 can also be used as a source of organic moieties, and the resulting covalently bonded organic moieties are included in this patent application.

[0080] It is believed that the organic moieties prevent the agglomeration of the nanoparticles or nanosized materials, and that the organic moieties may disperse the nanoparticles in organic and / or aqueous media.

[0081] In particular, it is believed that an organic moiety covalently bonded directly to an anion in the outer layer of the light-emitting moiety can achieve one or more of the technical effects of the present invention when mixed with a reactive monomer or a mixture of two or more reactive monomers of the present invention. Preferably, the reactive monomer or the two or more reactive monomers of the monomer mixture are (meth)acrylate monomer(s). More preferably, they are the specific (meth)acrylate monomers defined in the Reactive Monomers section below. It is believed that such a specific combination of a light-emitting moiety having a covalently bonded organic moiety directly bonded to the outer layer of the light-emitting moiety and a specific (meth)acrylate monomer can surprisingly achieve the following: improve the thermal stability of the resulting layer (film), the thermal stability of the light-emitting moiety in the layer (film), the dispersibility of the light-emitting moiety in the composition, the dispersibility of the light-emitting moiety in the resulting layer, enable phase separation between the light-emitting moiety and the matrix material after curing, improve the haze value of the cured film (cured composition), and increase the long-term quantum yield of the light-emitting moiety in the composition upon long-term storage with or without light irradiation. long-term external quantum efficiency (EQE) stability of the light-emitting moiety in the composition when stored for long periods with or without light irradiation, long-term quantum yield (QY) stability of the light-emitting moiety in the resulting layer (film) when stored for long periods with or without light irradiation, long-term external quantum efficiency (EQE) stability of the light-emitting moiety in the resulting layer (film) when stored for long periods with or without light irradiation, achieve good compatibility between the light-emitting moiety and the matrix material in the composition and / or the resulting layer (film), and / or achieve easy handling of the composition comprising the light-emitting moiety and the matrix material.

[0082] In some embodiments, the organic moiety can include a zwitterionic group.

[0083] -Outer layer In accordance with the present invention, the semiconductor nanoparticles comprise an outer layer covering at least a portion of the core, the outer layer comprising at least one metal cation and at least one divalent anion; The divalent anion is Se 2- , S 2- , Te 2- , O 2- or a combination thereof, preferably the metal cation is a monovalent, divalent, 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+ or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ , and Sn 4+ is a tetravalent cation selected from the group consisting of:

[0084] In some embodiments, the cation is Cs + , Ag + , Au + , Cu +1 a monovalent cation selected from the group consisting of: 2+ , Fe +2 , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ , Cu +2 a divalent cation selected from the group consisting of Fe +3 , In +3 , Bi +3 , Ga +3 a trivalent cation selected from the group consisting of: 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ , and Sn4+ , Si +4 is a tetravalent cation selected from the group consisting of:

[0085] In some embodiments of the present invention, the outer layer comprises at least two or three different metal cations, e.g., Cu 1+ and In 3+ , Cu 1+ and Ga 3+ , Ag 1+ and Ga 3+ Combination of Cu +1 / In +3 / Zn +2 combination, or Cu +1 / Ga +3 / Zn +2 combination, or Cu +1 / In +3 / Ga +3 / Zn +2 combination, or Cu +1 / In +3 / Ga +3 Includes a combination of:

[0086] 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 is a divalent cation selected from the group consisting of:

[0087] In a preferred embodiment of the present invention, the outer layer comprises, consists essentially of, or consists of a material represented by the following formula (VI): QP 1-2h A h (VI) [Wherein Q is Se 2- , S 2- , Te 2- and O 2- and a divalent anion selected from one or more members of the group consisting of: P is a divalent metal cation, preferably Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ and a divalent cation selected from one or more members of the group consisting of: A is a tetravalent cation, preferably Ti 4+ , Ge 4+ , Si 4+ , and Sn 4+ selected from one or more members of the group consisting of 0≦h≦0.5].

[0088] For example, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, ZnNiS, ZnNiSe, ZnGeS, ZnGeO, ZnCaS, NiSe, TiGeSeS, ZnTiS, CuInZnS, CuInZnSe, AgInZnS, and / or AgInZnSe can be used.

[0089] According to the present invention, preferably the outer layer is a single layer. More preferably, this layer is the last monolayer of the semiconductor nanoparticle covering the core. When there is more than one shell layer covering the core, the outer layer covers the shell layer.

[0090] In some embodiments of the present invention, the concentration of Se in the shell layer varies from a high concentration on the first semiconductor nanoparticle side of the shell layer to a low concentration on the opposite side of the shell layer, and more preferably, the concentration of S in the shell layer varies from a low concentration on the first semiconductor nanoparticle side of the shell layer to a high concentration on the opposite side of the shell layer, and the concentration of Te in the shell layer varies from a high concentration on the first semiconductor nanoparticle side of the shell layer to a low concentration on the opposite side of the shell layer.

[0091] In some embodiments of the present invention, the surface of the light-emitting moiety, ie, the semiconductor light-emitting nanoparticle, can be coated with one or more surface ligands in addition to the organic moieties of the present invention.

[0092] Without being bound by theory, it is believed that such surface ligands may allow the nanosized fluorescent material to be more easily dispersed in a solvent.

[0093] 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), and octadecylamine (ODA), oleylamine (OLA), 1-octadecene (ODE); thiols, where the organic portion of the thiol may be saturated or may contain one or more Examples of suitable ligands include octadecanethiol, hexadecanethiol, dodecanethiol, hexanethiol, and polyethylene glycol thiol, which may contain linear or branched alkyl chains that may contain unsaturated carbon bonds and / or aromatic rings; selenol, in which the organic portion of the selenol may be saturated or may contain linear or branched alkyl chains that may contain one or more unsaturated carbon bonds and / or aromatic rings; mercaptocarboxylic acids, such as mercaptopropionic acid and mercaptoundecanoic acid; carboxylic acids, such as oleic acid, stearic acid, myristic acid, isostearic acid, acetic acid, and combinations thereof. Further examples of suitable ligands include Zn-oleate, Zn-acetate, Zn-myristate, Zn-stearate, Zn-laurate, and other Zn-carboxylates, Zn-isostearates, sulfonic acids, halides, and carbamates.

[0094] Examples of surface ligands are described, for example, in WO 2012 / 059931.

[0095] -Quantum yield measurement According to the present invention, the quantum yield (QY) of the quantum dots is measured using a Hamamatsu absolute quantum yield spectrometer (model: Quantaurus C11347).

[0096] Preferably, the nanoparticles emit light having a peak maximum emission wavelength in the range of 350 nm to 3500 nm, preferably 350 nm to 2000 nm, more preferably 400 nm to 800 nm, and even more preferably 430 nm to 700 nm.

[0097] -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 Agilent Technologies 5977B MSD MS instrument. Analytes are separated using the following injection method: initial temperature 100°C, hold at 100°C for 0 minutes, heat to 340°C at a rate of 8°C / min, and hold at 340°C for 15 minutes. Prepare samples for GCMS as follows. 3.1 Weigh out the starting materials. 3.2 Calculate the organic content based on TGA measurements. 3.3 For each 30 mg of organic component, add 10 ml of methanol and 5 ml of concentrated hydrochloric acid (Caution! Exothermic reaction) to dissolve the nanoparticles, preferably quantum dots (QDs). If color still persists, use sonication and vortexing. 3.4 Add a magnetic stirrer and heat the solution to 60°C for 20 minutes (do not heat in a closed flask! Ensure the stopper is partially open). 3.5 Transfer the solution to a separatory funnel and add toluene (10 ml for 30 mg of organic material). 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 three times or until the aqueous phase has the pH of distilled water (approximately 5). 3.9 Collect the upper phase in a flask containing MgSO4 for at least 30 minutes. Filter off the MgSO4 solids. 3.10 Transfer the toluene mixture to a GC vial for injection.

[0098] -reactive monomers Low viscosity is considered to be important for making a low-viscosity composition suitable for inkjet printing.Therefore, (meth)acrylate monomers having viscosity values ​​within the above-mentioned parameter range are particularly suitable for making compositions for inkjet printing.By using these (meth)acrylate monomers in the composition, when mixed with another material such as semiconductor light-emitting nanoparticles at high loading, the composition can still maintain a lower viscosity within a range suitable for inkjet printing.

[0099] a light-emitting portion further comprising an outer layer comprising a reactive monomer or a mixture of two or more reactive monomers, preferably a (meth)acrylate monomer or a mixture of two or more (meth)acrylate monomers of the present invention, and a metal cation and a divalent anion; It is believed that the combination of one or more organic moieties directly attached to the anions of the outer layer by covalent bonds can specifically enhance the optical performance of the light-emitting moieties in the resulting layer (film).

[0100] Furthermore, these combinations may provide the following: thermal stability of the resulting layer (film), thermal stability of the light-emitting moiety in the layer (film), dispersibility of the light-emitting moiety in the composition, improving dispersibility of the light-emitting moiety in the resulting layer, enabling phase separation between the light-emitting moiety and the matrix material after curing, improving the haze value of the cured film (cured composition), long-term quantum yield (QY) stability of the light-emitting moiety in the composition when stored for long periods with or without light irradiation, long-term external quantum efficiency (EQE) stability of the light-emitting moiety in the composition when stored for long periods with or without light irradiation, long-term quantum yield (QY) stability of the light-emitting moiety in the resulting layer (film) when stored for long periods with or without light irradiation, long-term external quantum efficiency (EQE) stability of the light-emitting moiety in the resulting layer (film) when stored for long periods with or without light irradiation, achieving good compatibility between the light-emitting moiety and the matrix material in the composition and / or the resulting layer (film), and / or achieving easy handling of a composition comprising the light-emitting moiety and the matrix material.

[0101] In a preferred embodiment of the present invention, the boiling point (BP) of the reactive monomer is 95°C or higher, preferably in the range of 95°C to 350°C, for large area uniform inkjet printing.

[0102] A high boiling point is also believed to be important in order to produce a composition with a lower vapor pressure, preferably less than 0.001 mmHg, for large area uniform printing, and it is preferred to use reactive monomers, preferably (meth)acrylate monomers, more preferably (meth)acrylate monomers of formula (I), (II) and / or (III), having a viscosity value of 25 cP or less at 25°C and a boiling point of at least 95°C or higher, preferably in the range of 95°C to 350°C, to make the composition suitable for large area uniform ink jet printing, even when mixed with highly loaded other materials, such as highly loaded semiconductor light emitting nanoparticles.

[0103] Here, the term (meth)acrylate is a general term for acrylate and methacrylate. Therefore, according to the present invention, the term "(meth)acrylate monomer" means a methacrylate monomer and / or an acrylate monomer.

[0104] According to the present invention, BP can be estimated by known methods such as those described in Science of Petroleum, Vol. II. p. 1281 (1398).

[0105] According to the present invention, any type of commonly available acrylate and / or methacrylate represented by chemical formula (I) or (II) can be preferably used.

[0106] In particular, for the first aspect, any type of commonly available acrylate and / or methacrylate represented by chemical formula (I), (II) and / or (III) having a viscosity value of 25 cP or less at 25°C can be used.

[0107] Thus, according to the invention, the reactive monomers of the composition are preferably (meth)acrylate monomers selected from mono-, di- and / or tri-(meth)acrylate monomers.

[0108] Preferably, the reactive monomers of the monomer mixture are each independently selected from mono-(meth)acrylate monomers, di-(meth)acrylate monomers and / or tri-(meth)acrylate monomers.

[0109] Preferably, the di-(meth)acrylate monomer is represented by the following formula (I): b ) and the mono-acrylate monomer is represented by the following chemical formula (II b ) and / or the tri-(meth)acrylate monomer is represented by the following chemical formula (III b ) [ka] [In the formula, X 1 is an unsubstituted or substituted ester group, alkyl group or aryl group, in which one or more non-adjacent CH groups of the ester, alkyl or aryl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, and preferably the ester group is represented by the following formula (I bs1 ), [ka] In the formula, R Ib1 is a single bond or an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms; R Ib2 is a single bond, an unsubstituted or substituted straight-chain alkylene chain having 1 to 5 carbon atoms, or an unsubstituted or substituted branched-chain alkylene chain having 3 to 7 carbon atoms, in which one or more non-adjacent CH groups may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and preferably R Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, in which at least one non-adjacent CH group is optionally replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO2; X 2is an unsubstituted or substituted ester group, alkyl group or aryl group, in which one or more non-adjacent CH groups of the ester, alkyl or aryl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, and preferably the ester group is represented by the following formula (I bs2 ), [ka] In the formula, R Ibs1 is a single bond or an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms; R Ibs2 is a single bond, an unsubstituted or substituted straight-chain alkylene chain having 1 to 5 carbon atoms, or an unsubstituted or substituted branched-chain alkylene chain having 3 to 7 carbon atoms, in which one or more non-adjacent CH groups may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and preferably R Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, in which at least one non-adjacent CH group is optionally replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO2; R 1 is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, an aryl group, in which one or more non-adjacent CH groups of the alkyl group or aryl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or X 1is an ester group, preferably the ester group is a carboxylic acid group; R 2 is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, an aryl group, in which one or more non-adjacent CH groups of the alkyl group or aryl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or X 1 is an ester group, preferably the ester group is a carboxylic acid group; Preferably, the symbol X 1 is represented by the formula (I bs1 ) or an ester group of [ka] In the formula, the left side of the formula * " is the terminal group C=CR of formula (I) 1 represents the connection point to the carbon atom of * " is the symbol X in formula (I) 2 Represents the connection point to n is 0 or 1, Preferably, the symbol X 2 is represented by the formula (I bs2 ) or an ester group of [ka] In the formula, the left side of the formula * " represents the connection point to the symbol X1 in formula (I), and " * " is the terminal group C=CR of formula (I) 2 Represents the connection point to m is 0 or 1; Preferably, at least m or n is 1; R 3 is a linear alkylene chain or alkoxylene chain having 1 to 25 carbon atoms, a cycloalkane having 3 to 25 carbon atoms, or an aryl group having 3 to 25 carbon atoms, and preferably R 3is a linear alkylene chain or alkoxylene chain having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms, These are composed of one or more groups R a and one or more non-adjacent CH groups may be substituted by R a C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=Se, C=NR a , P(=O)(R a ), SO, SO2, NR a , OS, or CONR a and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2; R 4 is a linear alkylene chain or alkoxylene chain having 1 to 25 carbon atoms, a cycloalkane having 3 to 25 carbon atoms, or an aryl group having 3 to 25 carbon atoms, and preferably R 4 is a linear alkylene chain or alkoxylene chain having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms, These are composed of one or more groups R a and one or more non-adjacent CH groups may be substituted by R a C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=Se, C=NR a , P(=O)(R a ), SO, SO2, NR a , OS, or CONR a and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2; R aare the same or different in each occurrence and are H, D, or an alkyl group having 1 to 20 carbon atoms, a cyclic alkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 carbon ring atoms, or a heteroaromatic ring system having 5 to 60 carbon atoms, wherein an H atom may be replaced by D, F, Cl, Br, I, and two or more adjacent substituents R a may together form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system. [ka] [In the formula, X 3 is an unsubstituted or substituted ester group, alkyl group, cycloalkyl group, aryl group, or alkoxy group, and X 3 When is an unsubstituted or substituted ester group, the ester group is represented by the following formula (II bs ), [ka] In the formula, R IIb1 is a single bond or an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms; R IIb2 is a substituted or unsubstituted alkyl group, cyclo group, cycloalkyl group, aryl group, or alkoxy group, Preferably, the symbol X 3 is represented by the formula (II bs ) or an ester group of [ka] and In the formula, " * " is the terminal group C=CR of formula (I) 5 Represents the connection point to l is 0 or 1; R 5 is a hydrogen atom, a halogen atom such as Cl, Br or F, a methyl group, an alkyl group, an aryl group, an alkoxy group, an ester group or a carboxylic acid group, R 6is a linear alkylene chain or alkoxylene chain having 1 to 25 carbon atoms, and preferably R 6 is a linear alkylene chain or alkoxylene chain having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms, These are composed of one or more groups R a and one or more non-adjacent CH groups may be substituted by RaC=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=Se, C=NR a , P(=O)(R a ), SO, SO2, NR a , OS, or CONR a and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2; R 7 is a linear alkylene chain or alkoxylene chain having 1 to 25 carbon atoms, and preferably R 7 is a linear alkylene chain or alkoxylene chain having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms, These are composed of one or more groups R a and one or more non-adjacent CH groups may be substituted by R a C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=Se, C=NR a , P(=O)(R a ), SO, SO2, NR a , OS, or CONR a and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2; R aare the same or different in each occurrence and are H, D, or an alkyl group having 1 to 20 carbon atoms, a cyclic alkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 carbon ring atoms, or a heteroaromatic ring system having 5 to 60 carbon atoms, wherein an H atom may be replaced by D, F, Cl, Br, I, and two or more adjacent substituents R a may together form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system.

[0110] [ka] [In the formula, R 9 is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a group of the chemical formula (IV b ) is a (meth)acrylic group represented by [ka] R 10 is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a group of the chemical formula (V b ) is a (meth)acrylic group represented by [ka] R 11 is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a group of the chemical formula (VI b ) is a (meth)acrylic group represented by [ka] In the formula, R 8 , R 8a , R 8b and R 8c are each independently or dependently of one another and at each occurrence are H, CH or CHCH, R 9 , R 10 and R 11 At least one of R is a (meth)acrylic group, preferably R 9 , R10 and R 11 two of which are (meth)acrylic groups and the other is a hydrogen atom or a linear alkyl group containing 1 to 25 carbon atoms, and preferably the electrical conductivity (S / cm) of the (meth)acrylate monomer of formula (III) is 1.0×10 -10 Less than or equal to 5.0 × 10 -11 or less, preferably 5.0 × 10 -11 ~1.0×10 -15 within the range of 5.0×10 -12 ~1.0×10 -15 [In the range of

[0111] More preferably, the reactive monomer is represented by formula (II):

[0112] In a preferred embodiment, the monomer mixture of the composition comprises a (meth)acrylate monomer of formula (II) and another (meth)acrylate monomer selected from a (meth)acrylate monomer of formula (I) and / or a (meth)acrylate monomer of formula (III).

[0113] In a preferred embodiment of the present invention, the (meth)acrylate monomer of formula (II) is present in the composition, and the mixing ratio of the (meth)acrylate monomer of formula (I) to the (meth)acrylate monomer of formula (II) is in the range of 1:99 to 99:1 (formula (I):formula (II)), preferably 5:95 to 50:50, more preferably 10:90 to 40:60, and even more preferably 15:85 to 40:60; preferably, purified (meth)acrylate monomers represented by at least formulas (I) and (II) are used in the composition; more preferably, both the (meth)acrylate monomer of formula (I) and the (meth)acrylate monomer of formula (II) are obtained or can be obtained by a purification method.

[0114] In a preferred embodiment, the boiling point (BP) of the (meth)acrylate monomers of formula (I) and / or formula (II) is 95°C or higher, preferably the boiling point (BP) of both the (meth)acrylate monomers of formula (I) and formula (II) is 100°C or higher, more preferably in the range of 100°C to 350°C, and even more preferably the boiling point (BP) of the (meth)acrylate monomer of formula (I) is in the range of 100 to 300°C, and the boiling point (BP) of the (meth)acrylate monomer of formula (II) is in the range of 150°C to 320°C.

[0115] In a preferred embodiment of the present invention, the viscosity of the composition at room temperature is 35 cP or less, preferably in the range of 1 to 35 cP, more preferably 2 to 30 cP, and even more preferably 2 to 25 cP.

[0116] According to the present invention, the viscosity can be measured at room temperature using a vibration type viscometer VM-10A (SEKONIC). https: / / www.sekonic.co.jp / english / product / viscometer / vm / vm_series.html

[0117] (meth)acrylate monomers of formula (I) as matrix materials Even more preferably, (I bs1 )R Ib1 is a single bond, and (I bs2 )R Ibs1 is a single bond, and (I bs1 )R Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, and R Ibs2 is a single bond, an unsubstituted linear alkylene chain having 1 to 5 carbon atoms, an unsubstituted branched alkylene chain having 3 to 7 carbon atoms, in which one or more non-adjacent CH groups may be replaced by an oxygen atom, or R 3 and R of formula (I) 4 are each independently selected from the following groups:

[0118] [Table 1-1] [Table 1-2]

[0119] Particularly preferably, R 3 and R 4 is, at each occurrence, independently or differently selected from the following groups: [Table 2] [In the formula, “ * " is R 3 In the case of the formula, the connection point to the oxygen atom or the formula X 2 represents the connection point to * " is R 4 In the case of the formula, the connection point to the oxygen atom or the formula X 1 represents the connection point to ].

[0120] Particularly preferably, formula (I) is NDDA (nonanediol diacrylate), HDDMA (hexanediol dimethacrylate), HDDA (hexanediol diacrylate) or DPGDA (DPGDA=di-propylene glycol diacrylate). [ka]

[0121] (meth)acrylate monomers represented by formula (II): It is believed that the (meth)acrylate monomer represented by the following chemical formula (II) exhibits a viscosity value much lower than that of the (meth)acrylate monomer of formula (I). Thus, by using the (meth)acrylate monomer represented by chemical formula (II) in combination with the (meth)acrylate monomer of formula (I), a composition having a much lower viscosity, desirable for smooth inkjet printing, can be achieved, preferably without reducing the external quantum efficiency (EQE) value.

[0122] It is believed that such a combination can achieve a low viscosity composition that contains a large amount of another material, such as a highly loaded semiconductor light-emitting nanoparticle, and is therefore particularly suitable for inkjet printing when the composition contains another material.

[0123] Even more preferably, (II bs )R IIb1 is a single bond, and (II bs )R IIb2 is a substituted or unsubstituted alkyl group, cyclo group, or cycloalkyl group. (II bs )R IIb2 can be selected from the following groups: [Table 3] Or, R in formula (II) 7 is, at each occurrence, independently or differently selected from the following groups, a and preferably R a is not replaced by

[0124] [Table 4] [In the formula, “ * " means that when l is 1, X 3 R 6 When n is 0, X in formula (II) 3 represents the connection point with the oxygen atom.]

[0125] Particularly preferably, formula (II) is lauryl methacrylate (LM, viscosity 6 cP) or lauryl acrylate (LA, viscosity: 4.0 cP) or isobornyl acrylate (IBOA).

[0126] It is believed that the greater the amount of the (meth)acrylate monomer of chemical formula (II) relative to the total amount of the (meth)acrylate monomers of chemical formula (I), the more improved the EQE of the composition. A mixing weight ratio of the (meth)acrylate monomer of chemical formula (II) relative to the total amount of the (meth)acrylate monomers of chemical formula (I) of more than 50% by weight is preferred from the viewpoints of viscosity of the composition and better inkjet properties of the composition.

[0127] Preferably, a (meth)acrylate monomer purified using a silica column is used.

[0128] It is believed that the removal of impurities from the (meth)acrylate monomer by silica column purification leads to an improvement in the QY of the semiconductor light-emitting nanoparticles in the composition.

[0129] - (meth)acrylate monomers of formula (III) The (meth)acrylate monomers of formula (III) are believed to be useful in improving the subsequent robustness of compositions made from the composition after inkjet printing.

[0130] According to the present invention, known (meth)acrylate monomers represented by the following chemical formula (III) can be used to improve the robustness of the layer after inkjet printing and crosslinking.

[0131] Very preferably, trimethylolpropane triacrylate (TMPTA) is used as the (meth)acrylate monomer of formula (III).

[0132] In a preferred embodiment of the present invention, the amount of (meth)acrylate monomer of formula (III) based on the total amount of (meth)acrylate monomers in the composition is in the range of 0.001% by weight to 25% by weight, more preferably in the range of 0.1% by weight to 15% by weight, and even more preferably in the range of 1% by weight to 10% by weight.

[0133] Preferably, these (meth)acrylate monomers are purified using a silica column.

[0134] It is believed that the removal of impurities from the (meth)acrylate monomer by silica column purification leads to an improvement in the QY of the semiconductor light-emitting nanoparticles in the composition.

[0135] -method In one aspect, the present invention also relates to a method for preparing a composition comprising, consisting essentially of, or consisting of at least the following steps: (a) mixing at least a light-emitting portion with another material to obtain a reaction mixture, wherein preferably the light-emitting portion comprises at least a first semiconductor nanomaterial as a core; Preferably, the further material is a solvent, (b) forming an outer layer on the outermost surface of the light-emitting portion 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 the reaction mixture; ABXH (Va) ABXXBA (Vb) [In the formula, A is an organic group; B is the connection unit, H is a hydrogen atom, X is an anchoring group comprising an anion capable of forming a monolayer with an added metal cation derivable from an added metal cation precursor; (c) cooling the reaction mixture from step (b), a step in which 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, so as to form the outer layer in step (b); (d) combining the light-emitting moiety obtained from step (c) with at least one reactive monomer or a mixture of two or more reactive monomers to form a composition.

[0136] The anion source is preferably an organic moiety of formula (II'), (III'), (IIIa'), or (IV'). L-(U) o -(Y) m -(CR IIa R IIb ) n -X 1 (II') [In the formula, L is an organic group, preferably the organic group is a hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group (aryl, alkaryl, alkyl or aralkyl), an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl or a fluoroaralkyl); U is O, CH2 or C=O; Y is O, CH2 or C=O; R IIa and R IIb are each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms, and preferably from R IIa and R IIb is a hydrogen atom, n is an integer equal to or greater than 1, m is an integer of 0 or 1 or more, preferably m is 1; o is an integer of 0 or 1 or more, preferably o is 1; X 1 is Se 2- , S 2- , Te 2- and O 2- an anchor group comprising at least a divalent anion capable of covalently binding to a metal cation, preferably selected from one or more members of the group consisting of: X 1 -(CRIIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z (III') X 1 -(CR IIIg R IIIh ) q -(V) r -(OCR IIIa R IIIb CR IIIc R IIId ) p -Z (IIIa') [In the formula, R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and RIIIh are independently selected at each occurrence from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms, and preferably from R IIIg and R IIIh is a hydrogen atom, and preferably R IIIe and R IIIf is a hydrogen atom, X 1 is Se 2- , S 2- , Te 2- and O 2- is an anchor group comprising at least one divalent anion capable of binding to a metal cation selected from one or more members of the group consisting of: V is O, CH2 or C=O; 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 -NH2, an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, or a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, or a fluoroaralkyl), preferably Z is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a branched alkyl group having 3 to 25 carbon atoms, more preferably a hydrogen atom, a linear alkyl group having 1 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms, and even more preferably a hydrogen atom, or a linear alkyl group having 1 to 10 carbon atoms; 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 even more preferably 4≦p≦18; q is 0 or an integer of 1 or more, preferably 0≦q≦25, more preferably 0≦q≦15, even more preferably 0≦q≦10, and even more preferably 1≦q≦5; r is 0 or the integer 1; HS-(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z' (IV') [In the formula, R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg andRIIIh are each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms, and preferably from R IIIg and R IIIh is a hydrogen atom, and preferably R IIIe and R IIIf is a hydrogen atom, 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 even more preferably 4≦p≦18; q is 0 or an integer of 1 or more, preferably 0≦q≦25, more preferably 0≦q≦15, even more preferably 0≦q≦10, and still more preferably 1; V is O, CH2 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, a fluoroaralkyl, or a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, or a 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 a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a hydrogen atom, and even more preferably a hydrogen atom; r is 0 or the integer 1.

[0137] For example, the following materials can preferably be used as anion sources: SH-CH2-(OCH2CH2)4-O-CH3 SH-CH2-(OCH2CH2)6-O-CH3 SH-CH2-(OCH2CH2)8-O-CH3 SH-(CH2)2-(OCH2CH2)2-O-CH3 SH-(CH2)2-(OCH2CH2)6-O-CH3 SH-(CH2)2-(OCH2CH2)8-O-CH3 SH-(CH2)2-(OCH2CH2)6-CH3 SH-(CH2)2-(OCH2CH2)6-O-(CH2)2-SH SH-(CH2) 7- CH3 SeH-(CH2) 7- CH3 SH-(CH2) 11- CH3 SeH-(CH2) 11- CH3 SH-(CH2) 17- CH3 SeH-(CH2) 17- CH3 SH-(CH2)2-(OCH2CH2)6-O-CH3 SH-(CH2)2-(OCH2CH2) 16 -O-CH3 SH-(CH2)2-(OCH2CH2) 17 -O-CH3

[0138] Other thiolated ligand materials such as polypropylene glycol and polypropylene glycol monomethyl ether, the thiolated ligand materials described in U.S. Pat. No. 1,102,651, columns 17-18, formula (I), formula (II), column 25, line 28 to column 26, line 16, and M1000-SH in Example 1 can also be used as a source of organic moieties, and the resulting covalently bonded organic moieties are included in this patent application.

[0139] The temperature range of 80°C to 200°C is believed to be important for forming a crystalline bond between the organic moiety and the outer layer. In other words, by maintaining the reaction temperature in step (b) within this temperature range, the anchor groups of formula (I), (II), (III) and / or (IV) bond to the cations to form the outer layer, while the organic moieties remain covalently bonded to the anchor groups.

[0140] In a preferred embodiment of the present invention, the injection of the anion source is carried out in step (a) or step (b) at a temperature in the range of 0°C to 200°C, preferably in the range of 20°C to 180°C.

[0141] The temperature range of the implantation is also believed to be important to prevent the destruction of the XB bonds.

[0142] Preferably, step (b) is carried out for a period of 1 minute to 10 hours, preferably 10 minutes to 5 hours, more preferably 20 minutes to 3 hours.

[0143] According to the present invention, the ratio of the total molar amount of cation precursors to the total molar amount of semiconductor nanoparticles in step (b) is preferably in the range of 20:1 to 200,000:1, preferably 100:1 to 60,000:1, more preferably 110:1 to 58,000:1, and even more preferably 120:1 to 5,000:1.

[0144] 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 200,000:1, preferably 100:1 to 60,000:1, more preferably 110:1 to 58,000:1, and even more preferably 120:1 to 5,000:1. Preferably, the ratio of the total mass of the cation precursor to the total mass of the semiconductor nanoparticles in step (b) is in the range of 1:1,000 to 1:1, preferably 1:500 to 1:2, and more preferably 1:400 to 1:2.

[0145] In some embodiments of the present invention, an anion source represented by formula (2), (3), and / or (4), alone or in combination with any other chalcogen source, can be used as the anion source in step (b) to form the outer layer.

[0146] L 1 -(U 1 ) o -(Y 1 ) m -(CR IIa R IIb ) n -Z 1 -Z 2 -(CR IIa R IIb ) n -(Y 2 ) m -(U 2 ) o -L 2 (2) [In the formula, L 1 and L 2 are each independently or dependently an organic group, preferably an organic group is a hydrocarbyl group including aryl, alkaryl, alkyl, or aralkyl (including alkyl, aryl, aralkyl, and alkylaryl); R IIa and R IIb are each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms, and preferably from R IIa and R IIb is a hydrogen atom, n is an integer equal to or greater than 1, m is an integer of 0 or 1 or more, preferably m is 1; o is an integer of 0 or 1 or more, preferably o is 1; U 1 and U 2are, independently or dependently of one another, in each occurrence O, —CH— or C═O, Y 1 and Y 2 are, independently or dependently of one another, in each occurrence O, —CH— or C═O, n is an integer equal to or greater than 1, Z 1 is a divalent anion selected from Se, S, Te, and O; Z 2 is a divalent anion selected from Se, S, Te, and O].

[0147] Z-(CR IIIg R IIIh ) q -(V) r -(OCR IIIa R IIIb CR IIIc R IIId ) p -(CR IIIe R IIIf ) a -Q 1 -Q 2 -(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z (3) Z-(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Q 1 -Q 2 -(CR IIIg R IIIh ) q -(V) r -(OCR IIIa R IIIb CR IIIc R IIId) p -Z (4) [In the formula, R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and RIIIh are independently selected at each occurrence from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms, and preferably from R IIIg and R IIIh is a hydrogen atom, and preferably R IIIe and R IIIf is a hydrogen atom, V is O, CH2 or C=O, 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 -NH2, an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, or a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, or a fluoroaralkyl), preferably Z is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a branched alkyl group having 3 to 25 carbon atoms, more preferably a hydrogen atom, a linear alkyl group having 1 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms, and even more preferably a hydrogen atom, or a linear alkyl group having 1 to 10 carbon atoms; 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 even more preferably 4≦p≦18; q is 0 or an integer of 1 or more, preferably 0≦q≦25, more preferably 0≦q≦15, even more preferably 0≦q≦10, and even more preferably 1≦q≦5; r is 0 or the integer 1; Q 1 and Q 2 are divalent anions independently selected from Se, S, Te, and O.

[0148] For example, mPEG-SS-mPEG can be used. for example, (S, S, Te or O)2-(CH2-(OCH2CH2)4-O-CH3)2 (S, S, Te or O)2-(CH2-(OCH2CH2)6-O-CH3)2 (S, S, Te or O)2-(CH2-(OCH2CH2)8-O-CH3)2 (S, S, Te or O)2-((CH2)2-(OCH2CH2)2-O-CH3)2 (S, S, Te or O)2-((CH2)2-(OCH2CH2)6-O-CH3)2 (S, S, Te or O)2-((CH2)2-(OCH2CH2)8-O-CH3)2 (S, S, Te or O)2-((CH2)2-(OCH2CH2)6-CH3)2 (S, S, Te or O)2-((CH2)2-(OCH2CH2)6-O-(CH2)2-SH)2 (S, S, Te or O)2-((CH2) 7- CH3)2 (S, S, Te or O)2-((CH2) 11- CH3)2 (S, S, Te or O)2-((CH2) 17- CH3)2 (S, S, Te or O)2-((CH2)2-(OCH2CH2)6-O-CH3)2 (S, S, Te or O)2-((CH2)2-(OCH2CH2) 16 -O-CH3)2 (S, S, Te or O)2-((CH2)2-(OCH2CH2)17 -O-CH3)2 or (S, S, Te or O)2-((CH2) 11- CH3)2

[0149] In a preferred embodiment of the present invention, an anion source described by formula (2), (3) or (4), such as a bischalcogenide, can be used in step (b) together with a reducing agent to form the outer layer, preferably the reducing agent is represented by a secondary phosphine.

[0150] In a preferred embodiment of the present invention, the ratio of the molar amount of anion source to the molar amount of cation precursor used in step (b) is in the range of 20:1 to 1:20, preferably in the range of 12:1 to 1:12, more preferably 5:1 to 1:5.

[0151] -Chalcogen source According to the present invention, the term "chalcogen" means a chemical element of group 16 of the periodic table, preferably sulfur (S), selenium (Se), oxygen (O) and / or tellurium (Te).

[0152] Therefore, according to the present invention, the term "chalcogen source" means a material comprising at least one chemical element from group 16 of the periodic table, preferably the chemical element from group 16 is oxygen (O), sulfur (S), selenium (Se), and / or tellurium (Te), more preferably sulfur (S) or selenium (Se).

[0153] 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 selected from a selenol, a diselenide, a thiol, a disulfide, or a combination thereof.

[0154] Step (a)-Mixing In a preferred embodiment of the present invention, step (a) is carried out under inert conditions such as under argon (Ar) or N2 conditions, more preferably under Ar conditions.

[0155] In a preferred embodiment of the present invention, the other material used in step (a) is a solvent, more preferably an organic solvent, and even more preferably squalene, squalane, heptadecane, octadecane, octadecene, nonadecane, icosane, henicosane, docosane, tricosane, pentacosane, hexacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, oleylamine, trioctylamine, ketone, ketone ether acetone ... The solvent may be selected from one or more members of the group consisting of nitrates such as PGMEA, nitriles, ethers, ether esters, aromatic solvents such as toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene, mesitylene, and preferably squalene, squalane, heptadecane, octadecane, octadecene, nonadecane, icosane, henicosane, docosane, tricosane, pentacosane, hexacosane, octacosane, tetracosane, nonacosane, triacontane, hentriacontane, dotriacontane, tetracos ... Lithiacontane, 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, more preferably octadecene, oleylamine, squalane, pentacosane, hexacosane, octacosane, nonacosane, trioctylamine or triacontane, ketone, ketone, ether acetates, such as PGMEA, nitriles, ethers, ether esters, aromatic solvents, such as toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene, mesitylene, more preferably octadecene, oleylamine, squalane, pentacosane, trioctylamine or hexacosane, tetracosane, ketones, ketone ether acetates, such as PGMEA, ether esters, nitriles, ethers, aromatic solvents, such as toluene, xylene, ethylbenzene, diethylbenzene,Isopropyl benzene, diisopropyl benzene, and mesitylene.

[0156] 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.

[0157] The light-emitting moiety, preferably comprising at least a first semiconductor nanomaterial as a core, can be obtained from public sources or as described, for example, in U.S. Pat. No. 8,679,543, WO 2020 / 216813, and Chem. Mater. 2015, 27, pp 4893-4898.

[0158] In a preferred embodiment of the present invention, the cation shell precursor is a salt of an element from Group 12 of the periodic table, and more preferably the cation shell precursor is selected from one or more members of the group consisting of Zn-stearate, Zn-isostearate, 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, a metal halide represented by chemical formula (XIII), a metal carboxylate represented by chemical formula (XIV). MX 3 n (XIII) [Wherein M is Zn 2+ or Cd 2+ and preferably M is Zn 2+ and X 3 is F - , Cl - , Br - and I - and n is 2; [M(O2CR 16 )(O2CR 17 )] -(XIV) [Wherein M is Zn 2+ or Cd2+ and preferably M is Zn 2+ and 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, and 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 16 is a linear alkyl group having 2 to 25 carbon atoms or a linear unsaturated hydrocarbyl group having 6 to 25 carbon atoms, 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 straight chain alkyl group having 2 to 20 carbon atoms, 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, 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, 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, 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 straight chain alkyl group having 2 to 20 carbon atoms].

[0159] In a preferred embodiment, R 16 and R 17 is the same.

[0160] In a preferred embodiment of the present invention, the molar ratio of the total amount of chalcogen source to the total amount of cation shell precursor used in step (b) is in the range of 20:1 to 1:20, preferably in the range of 12:1 to 1:12, and preferably the chalcogen source is a selenium source, a sulfur source, or a combination of a selenium source and a sulfur source.

[0161] -Cooling process (c) According to the present invention, cooling of the reaction mixture from step (b) is carried out in step (c) to stop the formation reaction accordingly.

[0162] Several cooling methods can be used, either alone or in combination: removing the heat source, injecting a solvent, such as a solvent at room temperature, and / or applying air cooling.

[0163] In a preferred embodiment, the reaction mixture is cooled to below 50° C. but above 0° C., preferably to room temperature.

[0164] After cooling, the resulting light-emitting portion can be washed by known methods, preferably by centrifugation. Solids in the reaction mixture from step (c) can be removed by centrifugation. The washed light-emitting portion can then be used in step (d).

[0165] -formulation In another aspect, the present invention provides a method for treating a skin condition comprising administering to a subject a subject a skin condition comprising at least the composition of the present invention and At least one solvent The invention may relate to a formulation comprising, consisting essentially of, or consisting of.

[0166] 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, more preferably selected from one or more members of the group consisting of toluene, xylene, ether, tetrahydrofuran, chloroform, dichloromethane and heptane, purified water, acetate esters, alcohols, sulfoxides, formamides, nitrides, ketones, acetate ethers.

[0167] The amount of solvent in the formulation can be freely controlled according to the method of coating the composition.For example, when the composition is spray coated, the solvent can be contained in an amount of 90% by weight or more.In addition, when the slit coating method, which is often used to coat large substrates, is used, the content of the solvent is usually 60% by weight or more, preferably 70% by weight or more.

[0168] In some embodiments, the formulation may contain only 5% or less by weight of solvent based on the total weight of the composition. Preferably, the composition does not contain any solvent.

[0169] -use In another aspect, the invention also relates to the use of the composition or formulation in an electronic, optical, sensing or biomedical device.

[0170] -How to form layers In another aspect, the present invention provides a method for forming a layer, comprising: S1) providing a composition onto a substrate, preferably by inkjet; S2) a step of curing the composition, preferably the curing is photocuring performed by light irradiation, thermal curing, or a combination of photocuring and thermal curing.

[0171] -layer In another aspect, the present invention also relates to a layer obtained or obtainable from the method of the present invention.

[0172] In another aspect, the present invention also relates to a layer, the layer comprising: Xi) a light-emitting moiety, preferably a semiconductor light-emitting nanoparticle; an outer layer comprising metal cations and divalent anions; and a light-emitting moiety comprising one or more organic moieties covalently bonded directly to the anions of the outer layer; Xii) at least comprising, consisting essentially of, or consisting of a polymer made from at least one reactive monomer or a mixture of two or more reactive monomers, preferably where the monomers have one or more functional groups, more preferably where they are (meth)acrylate monomers; The divalent anion in the outer layer is Se 2- , S 2- , Te 2- , O 2- or a combination thereof, preferably the metal cations in the outer layer are monovalent, divalent, trivalent or tetravalent cations, more preferably the metal cations are Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ , and Sn 4+ is a tetravalent cation selected from the group consisting of:

[0173] -Color conversion device(100) In another aspect, the present invention also relates to a color conversion device (100) comprising, consisting essentially of, or consisting of a first pixel (161) partially or completely filled with a layer according to any one of claims 20 to 22 and 24, the first pixel (161) comprising at least a matrix material (120) containing light-emitting moieties (110), and a bank (150) comprising at least a polymer material, preferably wherein the color conversion device (100) further comprises a support medium (170).

[0174] -First pixel (161) According to the present invention, the first pixel (161) comprises at least a matrix material (120) comprising a light-emitting moiety (110). In a preferred embodiment, the first pixel (161) is a solid layer obtained or obtainable by curing a composition of the present invention comprising at least one acrylate monomer together with at least one light-emitting moiety (110), preferably the curing being photocuring by irradiation with light, thermal curing, or a combination of photocuring and thermal curing.

[0175] In some embodiments of the present invention, the layer thickness of the pixel (161) is in the range of 0.1 to 100 μm, preferably 1 to 50 μm, and more preferably 5 to 25 μm.

[0176] In some embodiments of the present invention, the color conversion device (100) further comprises a second pixel (162), and preferably the device (100) comprises at least a first pixel (161), a second pixel (162) and a third pixel (163), more preferably the first pixel (161) is a red pixel, the second pixel (162) is a green pixel and the third pixel (163) is a blue pixel, and even more preferably the first pixel (161) comprises a red light-emitting portion (110R), the second pixel (162) comprises a green light-emitting portion (110G) and the third pixel (163) does not comprise any light-emitting portion.

[0177] In some embodiments, at least one pixel (160) further comprises at least one light scattering particle (130) in the matrix material (120), and preferably, the pixel (160) comprises a plurality of light scattering particles (130).

[0178] In a preferred embodiment, the first pixel (161) consists of one pixel or two or more sub-pixels configured to emit red light when illuminated by excitation light, and more preferably the sub-pixels comprise the same light-emitting portion (110).

[0179] -Matrix material (120) In a preferred embodiment, the matrix material (120) comprises a (meth)acrylate polymer, preferably a methacrylate polymer, an acrylate polymer or a combination thereof, more preferably an acrylate polymer, further preferably the matrix material (120) is obtained or obtainable from a composition of the present invention comprising at least one acrylate monomer, even more preferably the matrix material (120) is obtained or obtainable from a composition of the present invention comprising at least one diacrylate monomer, particularly preferably the matrix material (120) is obtained or obtainable from a composition of the present invention comprising at least one diacrylate monomer and a monoacrylate monomer, preferably the composition is a photosensitive composition.

[0180] -Bank (150) In some embodiments of the present invention, the height of the bank (150) is in the range of 0.1 to 100 μm, preferably 1 to 50 μm, more preferably 1 to 25 μm, and even more preferably 5 to 20 μm.

[0181] In a preferred embodiment of the present invention, the bank (150) is configured to determine the area of ​​the first pixel (161), and at least a portion of the bank (150) is in direct contact with at least a portion of the first pixel (161), and preferably the second polymer of the bank (150) is in direct contact with at least a portion of the first polymer of the first pixel (161).

[0182] More preferably, the bank (150) is photolithographically patterned and the first pixel (161) is surrounded by the bank (150), and preferably the first pixel (161), the second pixel (162) and the third pixel (163) are all surrounded by the photolithographically patterned bank (150).

[0183] In another aspect, the present invention provides a method for manufacturing the color conversion device (100) of the present invention, comprising at least the following steps: Xi) providing a bank composition on the surface of a support medium; Xii) hardening the bank composition; Xiii) applying photopatterning to the cured composition to produce banks and patterned pixel areas; Xiv) providing, preferably by inkjet, the composition of the present invention to at least one pixel area; Xv) curing the composition, preferably the color conversion device (100) further comprising a support medium (170), preferably in that order.

[0184] In another aspect, the present invention further relates to a color conversion device (100) obtainable or obtained from the method of the present invention.

[0185] In another aspect, the present invention further relates to the use of the color conversion device (100) of the present invention in an optical device (300) comprising at least one functional medium (320, 420, 520) configured to modulate light or configured to emit light.

[0186] Furthermore, in another aspect, the present invention further relates to an optical device (300) comprising, consisting essentially of, or consisting of at least one functional medium (320, 420, 520) configured to modulate light or configured to emit light, and a color conversion device (100) of the present invention.

[0187] In some embodiments of the present invention, the optical device may be a liquid crystal display device (LCD), an organic light emitting diode (OLED), a light emitting diode device (LED), a micro LED, a microelectromechanical system (hereinafter "MEMS"), an electrowetting display, or an electrophoretic display.

[0188] Thus, in preferred embodiments, the functional medium may be an LC layer, an OLED layer, an LED layer, a micro LED layer, a MEMS layer, an electrowetting layer and / or an electrophoretic layer, more preferably the functional medium is an LC layer, a micro LED layer or an OLED layer.

[0189] Preferred Embodiments 1. A composition, preferably a photocurable composition, i) a light-emitting moiety, preferably a semiconductor light-emitting nanoparticle, with an outer layer comprising a metal cation and a divalent anion; and a light-emitting moiety comprising one or more organic moieties covalently bonded directly to the anions of the outer layer; ii) at least one reactive monomer or a mixture of two or more reactive monomers, preferably wherein the monomer has one or more functional groups, more preferably a (meth)acrylate monomer; The divalent anion in the outer layer is Se 2- , S 2- , Te 2- , O 2- or a combination thereof, preferably the metal cations in the outer layer are monovalent, divalent, trivalent or tetravalent cations, more preferably the metal cations are Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ , and Sn 4+ The composition of claim 1, wherein the tetravalent cation is selected from the group consisting of:

[0190] 2. The composition of embodiment 1, wherein the organic moiety is represented by the following chemical formula (I): AB-* (I) [In the formula, A is an organic group, preferably the organic group is a hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group (including aryl, alkaryl, alkyl or aralkyl), an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group (including fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl); B is a connection unit, and preferably B is ** -(U) o -(Y) m -(CR IIa R IIb ) n In the formula, ** " represents the connection point to "A", " * " represents the point of attachment to the anion in the outer layer].

[0191] 3. The composition of embodiment 1 or 2, wherein the organic moiety is represented by the following chemical formula (II), (III), or (III'): L-(U) o -(Y) m -(CR IIa R IIb ) n - * (II) [In the formula, L is an organic group, preferably the organic group is a hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group (aryl, alkaryl, alkyl or aralkyl), an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl or a fluoroaralkyl); U is O, CH2 or C=O; Y is O, CH2 or C=O; R IIa and R IIbare each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms, and preferably from R IIa and R IIb is a hydrogen atom, n is an integer equal to or greater than 1, m is an integer of 0 or 1 or more, preferably m is 1; o is an integer of 0 or 1 or more, preferably o is 1; " * " represents the point of attachment to the anion in the outer layer], * -(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z (III) * -(CR IIIg R IIIh ) q -(V) r -(OCR IIIa R IIIb CR IIIc R IIId ) p -Z (III') [In the formula, R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and RIIIhare each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms, and preferably from R IIIg and R IIIh is a hydrogen atom, and preferably R IIIe and R IIIf is a hydrogen atom, V is O, CH2 or C=O, 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 -NH2, an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, or a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, or a fluoroaralkyl), preferably Z is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a branched alkyl group having 3 to 25 carbon atoms, more preferably a hydrogen atom, a linear alkyl group having 1 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms, and even more preferably a hydrogen atom, or a linear alkyl group having 1 to 10 carbon atoms; 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 even more preferably 4≦p≦18; q is 0 or an integer of 1 or more, preferably 0≦q≦25, more preferably 0≦q≦15, even more preferably 0≦q≦10, and even more preferably 1≦q≦5; r is 0 or the integer 1; " * " represents the point of attachment to the anion in the outer layer].

[0192] 4. The composition of any one of the preceding embodiments, wherein the organic moiety is represented by the following chemical formula (IV): * -(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z' (IV) [In the formula, R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and RIIIh are each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a linear alkyl group having 1 to 5 carbon atoms, and a branched alkyl group having 3 to 5 carbon atoms, and preferably from R IIIg and R IIIh is a hydrogen atom, and preferably R IIIe and R IIIf is a hydrogen atom, 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 even more preferably 4≦p≦18; q is 0 or an integer of 1 or more, preferably 0≦q≦25, more preferably 0≦q≦15, even more preferably 0≦q≦10, and still more preferably 1; V is O, CH2 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, a fluoroaralkyl, or a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, or a 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 a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a hydrogen atom, and even more preferably a hydrogen atom; r is 0 or the integer 1; " * " represents a point of attachment to an anion in the outer layer, preferably attached to an S or Se atom in the outer layer.

[0193] 5. The composition of any one of the preceding embodiments, wherein the organic moieties are covalently bound to anions in the outer layer of the inorganic lattice and preferably have not been removed by ligand exchange.

[0194] 6. The metal cation is a transition metal of Group 12 or 14, preferably Zn 2+ , Hg 2+ or Pb 2+ The composition of any one of the preceding embodiments, wherein the composition is selected from one or more members of the group consisting of:

[0195] 7. The composition of any one of the previous embodiments, wherein the reactive monomer is a (meth)acrylate monomer selected from mono-, di-, and / or tri-(meth)acrylate monomers. Preferably, the two or more reactive monomers of the mixture are each independently selected from mono-(meth)acrylate monomers, di-(meth)acrylate monomers and / or tri-(meth)acrylate monomers.

[0196] 8. The di-(meth)acrylate monomer is represented by the following chemical formula (I b ) and the mono-acrylate monomer is represented by the following chemical formula (II b ) and / or the tri-(meth)acrylate monomer is represented by the following chemical formula (III b 8. The composition of embodiment 7, wherein [ka] [In the formula, X 1 is an unsubstituted or substituted ester group, alkyl group or aryl group, in which one or more non-adjacent CH groups of the ester, alkyl or aryl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, and preferably the ester group is represented by the following formula (I bs1 ), [ka] In the formula, R Ib1 is a single bond or an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms; R Ib2 is a single bond, an unsubstituted or substituted straight-chain alkylene chain having 1 to 5 carbon atoms, or an unsubstituted or substituted branched-chain alkylene chain having 3 to 7 carbon atoms, in which one or more non-adjacent CH groups may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and preferably R Ib2is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, in which at least one of the non-adjacent CH groups may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and even more preferably (I bs1 )R Ib1 is a single bond, and (I bs2 )R Ibs1 is a single bond, and (I bs1 )R Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, and R Ibs2 is a single bond, an unsubstituted linear alkylene chain having 1 to 5 carbon atoms, or an unsubstituted branched alkylene chain having 3 to 7 carbon atoms, in which one or more non-adjacent CH groups are optionally replaced by an oxygen atom; X 2 is an unsubstituted or substituted ester group, alkyl group or aryl group, in which one or more non-adjacent CH groups of the ester, alkyl or aryl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, and preferably the ester group is represented by the following formula (I bs2 ), [ka] In the formula, R Ibs1 is a single bond or an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms; R Ibs2is a single bond, an unsubstituted or substituted straight-chain alkylene chain having 1 to 5 carbon atoms, or an unsubstituted or substituted branched-chain alkylene chain having 3 to 7 carbon atoms, in which one or more non-adjacent CH groups may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2, and preferably R Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, in which at least one non-adjacent CH group is optionally replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO2; R 1 is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, an aryl group, in which one or more non-adjacent CH groups of the alkyl group or aryl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or X 1 is an ester group, preferably the ester group is a carboxylic acid group; R 2 is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, an aryl group, in which one or more non-adjacent CH groups of the alkyl group or aryl group may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or X 1 is an ester group, preferably the ester group is a carboxylic acid group; [ka] [In the formula, X 3is an unsubstituted or substituted ester group, alkyl group, cycloalkyl group, aryl group, or alkoxy group, and X 3 When is an unsubstituted or substituted ester group, the ester group is represented by the following formula (II bs ), [ka] In the formula, R IIb1 is a single bond or an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms; R IIb2 is a substituted or unsubstituted alkyl group, cyclo group, cycloalkyl group, aryl group, or alkoxy group, Even more preferably, (II bs )R IIb1 is a single bond, and (II bs )R IIb2 is a substituted or unsubstituted alkyl group, cyclo group, or cycloalkyl group. (II bs )R IIb2 can be selected from the groups shown in the table on page 44, R 5 is a hydrogen atom, a halogen atom such as Cl, Br or F, a methyl group, an alkyl group, an aryl group, an alkoxy group, an ester group or a carboxylic acid group; [ka] [In the formula, R 9 is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a group of the chemical formula (IV b ) is a (meth)acrylic group represented by [ka] In the formula, R 10 is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a group of the chemical formula (V b ) is a (meth)acrylic group represented by [ka] In the formula, R 11is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a group of the chemical formula (VI b ) is a (meth)acrylic group represented by [ka] In the formula, R 8 , R 8a , R 8b and R 8c are each independently or dependently of one another and at each occurrence are H, CH2CH3 or CH3, R 9 , R 10 and R 11 at least one of which is a (meth)acrylic group].

[0197] 9. A method for producing a composition according to any one of the preceding embodiments, comprising at least the following steps: (a) mixing at least a light-emitting portion with another material to obtain a reaction mixture, wherein preferably the light-emitting portion comprises at least a first semiconductor nanomaterial as a core; Preferably, the further material is a solvent, (b) forming an outer layer on the outermost surface of the light-emitting portion 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 the reaction mixture; ABXH (Va) ABXXBA (Vb) [In the formula, A is an organic group; B is the connection unit, H is a hydrogen atom, X is an anchoring group comprising an anion capable of forming a monolayer with an added metal cation derivable from an added metal cation precursor; (c) cooling the reaction mixture from step (b), a step in which 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, so as to form the outer layer in step (b); (d) combining the light-emitting moiety obtained from step (c) with at least one reactive monomer or a mixture of two or more reactive monomers to form a composition.

[0198] 10. The method of embodiment 9, wherein the injection of the anion source in step (a) or step (b) 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.

[0199] 11. The method according to embodiment 9 or 10, wherein 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.

[0200] 12. The method according to any one of embodiments 9 to 11, wherein 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 200,000:1, preferably 100:1 to 60,000:1, more preferably 110:1 to 58,000:1, and even more preferably 120:1 to 5,000:1; and preferably the ratio of the total mass of the cation precursor to the total mass of the semiconductor nanoparticles in step (b) is 1:1,000 to 1:1, preferably 1:500 to 1: 2, more preferably in the range of 1:400 to 1:2, preferably the ratio of the total mass of the cation precursors to the total mass of the semiconductor nanoparticles in step (b) is in the range of 1:1000 to 1:1, preferably 1:500 to 1:2, more preferably 1:400 to 1:2, and preferably the molar ratio of the total amount of the anion source to the total amount of the cation precursors used in step (b) is in the range of 20:1 to 1:20, preferably in the range of 12:1 to 1:12, even more preferably in the range of 5:1 to 1:5.

[0201] 13. The method of any one of embodiments 9 to 12, wherein an anion source of formula (Vb) is used together with a reducing agent in step (b) to form the outer layer, preferably wherein the reducing agent is represented by a secondary phosphine.

[0202] 14. The method of any one of embodiments 9 to 13, wherein the molar ratio of the total amount of anion sources to the total amount of cation precursors used in step (b) is in the range of 20:1 to 1:20, preferably in the range of 12:1 to 1:12, and more preferably in the range of 5:1 to 1:5.

[0203] 15. A composition obtainable or obtained by the method according to any one of embodiments 9 to 14.

[0204] 16. A formulation comprising at least the composition according to any one of embodiments 1 to 8 and 15 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, acetate esters, acetate ethers, ketones, ether esters, preferably PGMEA, alcohols, preferably ethanol or isopropanol, sulfoxides, formamides, nitrides, ketones, formulations.

[0205] 17. Use of the composition according to any one of embodiments 1 to 8 or 15 or the formulation according to embodiment 16 in an electronic, optical, sensing or biomedical device.

[0206] 18. A method for forming a layer, comprising: S1) providing a composition according to any one of embodiments 1 to 8 or 15 onto a substrate, preferably by inkjet; S2) curing the composition, preferably the curing is photocuring performed by light irradiation, thermal curing, or a combination of photocuring and thermal curing.

[0207] 19. A layer obtained or obtainable by the method according to embodiment 18.

[0208] 20. A layer having at least: Xi) a light-emitting moiety, preferably a semiconductor light-emitting nanoparticle, with an outer layer comprising a metal cation and a divalent anion; and a light-emitting moiety comprising one or more organic moieties covalently bonded directly to the anions of the outer layer; Xii) a polymer made from at least one reactive monomer or a mixture of two or more reactive monomers, preferably the monomers have one or more functional groups, more preferably they are (meth)acrylate monomers, The divalent anion in the outer layer is Se 2- , S 2- , Te 2- , O 2- or a combination thereof, preferably the metal cations in the outer layer are monovalent, divalent, trivalent or tetravalent cations, more preferably the metal cations are Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ or Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ , and Sn 4+ The layer is a tetravalent cation selected from the group consisting of:

[0209] 21. A color conversion device (100) comprising at least one first pixel (161) partially or completely filled with a layer of embodiment 19 or 20 comprising at least a matrix material (120) containing a light-emitting portion (110), and a bank (150) comprising at least a polymer material, and preferably further comprising a support medium (170).

[0210] 22. An optical device (300) comprising at least one functional medium (320, 420, 520) configured to modulate light or configured to emit light, and a color conversion device (100) according to embodiment 21.

[0211] Technical effects The present invention provides one or more of the following advantages. Optimized haze value of the cured layer (film), achieving an optimal haze value with an improved EQE value of the cured layer (film), preferably achieving an optimal haze value with an improved EQE value of the cured layer (film) without using scattering particles, improved thermal stability of the resulting layer (film), improved thermal stability of the light-emitting moiety in the layer (film), achieving improved dispersibility of the light-emitting moiety in the composition, enabling phase separation between the light-emitting moiety and the matrix material after curing, improved haze value of the cured film (cured composition), improved dispersibility of the light-emitting moiety in the resulting layer, stable long-term quantum yield (QY) of the light-emitting moiety in the composition when stored for a long period of time with or without external light irradiation. improved long-term external quantum efficiency (EQE) stability of the light-emitting moiety in the composition when stored for a long period with or without external light irradiation; improved long-term quantum yield (QY) stability of the light-emitting moiety in the resulting layer (film) when stored for a long period with or without external light irradiation; improved long-term external quantum efficiency (EQE) stability of the light-emitting moiety in the resulting layer (film) when stored for a long period with or without external light irradiation; improved compatibility between the light-emitting moiety and the matrix material in the composition and / or the resulting layer (film); and / or easier handling of the composition comprising the light-emitting moiety and the matrix material, making the composition suitable for inkjet printing.

[0212] The following examples provide an explanation of the invention as well as detailed descriptions of their preparation, although the invention need not be limited to the examples. [Example]

[0213] Core synthesis example 1: Synthesis of magic size cluster (MSC) Cluster Synthesis Into a 500 mL four-neck flask, weigh 4.65 g (15.9 mmol) of indium acetate and 13.25 g (58.0 mmol) of myristic acid. Fit the flask with a reflux condenser, a septum, and a stopper between the flask and the condenser. Place under vacuum at 100°C for 8 hours and 15 minutes to degas the acetic acid under reduced pressure, and then place at room temperature overnight. The next day the solution is again heated to 100° C. and evacuated under these conditions for 1 hour 45 minutes. Total pumping time is 10 hours at 100°C. Pressure: 85mTorr.

[0214] Fill the reaction flask with argon and add 100 mL of dry toluene. Heat the reaction 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 a flask containing indium myristate (In(Ma)) at 110 °C. The formation of MSCs was monitored via UV-vis of timed aliquots taken from the reaction solution, and the peak shape (red-shift and sharpness) gradually improved.

[0215] Once the peak shape (red shift and sharpness) stops improving, add 2 mL of the second PTMS solution (1 mL (0.86 g) PTMS in 10.2 mL (8.77 g) toluene) to reach optimal optical parameters, e.g., 2 ml of PTMS solution was added after 13 minutes. 2 ml of PTMS solution was added after 19 minutes. 2 ml of PTMS solution was added after 32 minutes. After 44 minutes, the reaction is cooled with a fan and the flask itself is stored under an inert atmosphere. result: InP magic-size clusters are formed by excitons at 387 nm. The InP magic size clusters (MSCs) were washed with anhydrous acetonitrile (crude:acetonitrile ratio 18:13). This process was repeated using mixtures of anhydrous toluene and acetonitrile with toluene:acetonitrile ratios of 1.5:1, 1.4:1, and 1.75:1. This product was called "magic size clusters (MSCs)."

[0216] 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 poured into it. The apparatus is stirred and evacuated (pressure is increased from 300 mTorr to 200 mTorr over a period of 1 hour) and heated to 375 °C under argon. In a glovebox, 3.15 × 10 -04 A solution of MSC is prepared in distilled squalane with a concentration of M. Using a 16-gauge needle and a 6 mL syringe, 4 mL of this solution (1.26E-06 mol) is injected into a flask at 375°C. After 4 minutes, remove the mantle and allow the flask to cool to 200°C by blowing air through it with a fan. Then replace the mantle and heat the flask to 265°C.

[0217] At this point, more MSCs are added using the same solution as the initial infusion, using a 20 gauge needle and a 3 ml syringe at a rate of 0.7 ml / min for a given time (compared to the initial infusion). 15 min - 0.6 mL (1.89E-07 mol) 25 minutes-0.7mL(2.21E-07mol) 32 minutes - 0.7mL

[0218] result: InP QDs are formed by excitons at 593 nm.

[0219] Shell synthesis example 1: ZnSe shell synthesis on an InP core (trioctylphosphine selenide (TOP-Se) as Se source) In this example, the InP cores used were synthesized using the core synthesis described above (WO 2019 / 224134) and have a core exciton CWL of 593 nm. The final core solution was washed with a mixture of anhydrous toluene and ethanol (crude:toluene:ethanol ratio: 1:2:8). This process was repeated with a crude:toluene:ethanol ratio of 1:2:6. This solution is further referred to as "SSP InP cores."

[0220] Post-synthesis core processing: In a glove box (GB), SSP InP cores (3.5 × 10 -7 (mol) is dissolved in 0.2 ml of toluene and transferred to a 50 ml round-bottom flask containing 4.8 ml of pumped oleylamine (OLAm) and 0.085 g of ZnCl. After a short pump at 50 °C to remove the toluene, the flask is backfilled with argon and heated to 250 °C for 30 min. The solution is then cooled to 180 °C.

[0221] Shell formation process: After core treatment at 180 °C, 2.6 mL of a 0.55 M OLAm concentrated solution containing Zn(Cl)2 and 1 volume of anionic shell precursor (0.72 mL of 2 M TOP-Se) are added to the SSP InP core. After 30 minutes, the solution is heated to 200 °C. After 30 minutes, the solution is heated to 320 °C, 3.2 mL of 0.4 M Zn(undecylenate)2 is injected, and the reaction is maintained at 320 °C for 3 hours. After 3 hours at 320 °C, the reaction is terminated by cooling the reaction mixture.

[0222] The resulting nanoparticles were washed with a mixture of anhydrous toluene and ethanol (ratio of crude:toluene:ethanol:3:4:8). This process was repeated. The nanoparticles were then extracted with hexane.

[0223] Shell synthesis example 2: ZnSeS shell synthesis on an InP core, (trioctylphosphine selenide (TOP-Se) as the Se source and dodecanethiol (DDT) as the S source). The comparative example is similar to comparative example 1, except that 0.9 mmol of TOP-Se is injected at 180° C. and 0.56 mmol of DDT is injected at 320° C. 10 minutes after the injection of Zn(undecylenate) 2 .

[0224] Reference Example 1: Synthesis of a ZnSe outer layer on an ODE containing InP / ZnSe NPs using 1-dodecaneselenol (DDSe) as the Se source.

[0225] Synthesis of outer layer: At room temperature, 8.3 × 10 -8 1 mol of InP / ZnSe is dissolved in 0.2 ml of toluene and transferred to a 50 ml round-bottom flask containing 4 ml of pumped 1-octadecene (ODE). After 30 minutes of pumping at room temperature, 1-dodecaneselenol (0.2 mmol) is added and the flask is heated to 150 °C. Once 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 is terminated by cooling the reaction mixture.

[0226] The resulting nanoparticles were washed with a mixture of anhydrous toluene and ethanol (ratio of crude:toluene:ethanol:3:4:8). This process was repeated. The nanoparticles were then extracted with hexane.

[0227] Table A compares the thermal stability, anti-radical stability, and peroxide stability values ​​for the listed Reference Example and Comparative Example 1.

[0228] Reference Example 2: Synthesis of ZnS outer layer on ODE containing InP / ZnSe NPs using 1-dodecanethiol as S source.

[0229] Reference Example 2 is similar to Reference Example 1, but uses 1-dodecanethiol as the sulfur precursor.

[0230] Reference Example 3: Synthesis of ZnSeS outer layer on ODE containing InP / ZnSe NPs using 1-dodecaneselenol as Se source and 1-dodecanethiol as sulfur.

[0231] Reference Example 3 is similar to Reference Examples 1 and 2, except that 1-dodecaneselenol and 1-dodecanethiol are added together in equimolar amounts, and the amount of Se+S ions is kept the same as before.

[0232] Reference Example 4: Synthesis of ZnSeS outer layer on ODE containing InP / ZnSe NPs using 1-dodecaneselenol as Se source and 3-phenylethanethiol as sulfur source.

[0233] Reference Example 4 differs from Reference Example 3 in that 3-phenylethanethiol is utilized instead of 1-dodecanethiol as the sulfur source.

[0234] Reference Example 5: Synthesis of a ZnS outer layer on an ODE containing InP / ZnSeS NPs using 1-dodecanethiol as the S source.

[0235] Reference Example 5 is similar to Reference Example 2, but uses InP / ZnSeS particles, which are prepared as described in Comparative Example 2. Table A compares the thermal stability, antiradical stability, and peroxide stability values ​​for the listed examples and Comparative Example 2.

[0236] Reference Example 6: Synthesis of ZnS outer layer on ODE containing InP / ZnSe NPs using perfluorodecanethiol as S source.

[0237] Reference Example is similar to Reference Example 2, but uses perfluorodecanethiol as the sulfur precursor.

[0238] [Table 5]

[0239] Thermal Stability Test - Powder thermal test at 150°C in air. Benzoquinone Test - 2.667 wt% p-benzoquinone is added to clean NPs in toluene. Peroxide Test - 50 wt% tert-butyl peroxybenzoate is added to clean NPs in toluene.

[0240] Example 7: Experimental demonstration of surface and crystal binding of DDSe to QDs from Example 1. The general scheme (Scheme 1) depicted in Figure 9 describes a multi-step method established to characterize the relationship between surface-bound and crystal-bound (covalently bound) ligands, exemplified for dodecane selenol (DDSe).

[0241] 3-Phenylpropylphosphonic acid (PPPA) is known to have a stronger affinity for the QD surface compared to amines, thiols, selenols, and carboxylic acids. Surface-bound ligands are desorbed from the QD surface and replaced by PPPA. On the other hand, crystal-bound ligands are incorporated into the crystal lattice. Their dissociation from the QD is then impossible without destroying the crystal. This process can also be used for experimental verification of crystal-bound amine-, thiol-, and other selenol- and carboxylic acid-containing ligands to QDs.

[0242] Characterization of QDs from Reference Example 1 Figure 6: QDs from Reference Example 1 before (a) and after (b) the addition of PPPA. 1 H NMR spectrum (toluene d8).

[0243] The addition of PPPA leads to the desorption of DDSe from the QD surface. The amount (mmol) of desorbed DDSe (surface-bound) was quantitatively determined using duroquinone as an external standard. 1 1 H NMR, equal to 0.00135 mmol, i.e., only 1.8 mol % of the total amount of DDSe inserted in the reaction yielded surface-bound DDSe.

[0244] Figure 7: QDs after treatment with PPPA and washing with ethanol. 1 H NMR spectrum (toluene d8).

[0245] 1 H NMR shows that the surface-bound DDSe has been completely removed from the surface of the QDs (signal #2 (Se-H) and signal #3 (CH2-Se) have disappeared). However, signal #1 (CH3 of DDSe) is still present, indicating the presence of a second population of non-surface-bound DDSe. After removing all surface-bound DDSe, the QDs are analyzed by GCMS. For this purpose, appropriate derivatization with HCl and methanol is performed. This treatment leads to the complete decomposition and dissolution of the QDs.

[0246] Figures 8A and 8B: GCMS spectra of QDs after treatment with PPPA and washing. MS spectrum of the peak at retention time 11.458.

[0247] Samples for GCMS are prepared as described in the embodiments. The presence of DDSe is confirmed by GCMS, which indicates crystalline bonding of DDSe. Main conclusion: The QDs of Reference Example 1 contain surface-bound as well as crystal-bound DDSe.

[0248] Reference Example 8: Synthesis of 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) into a 50 mL round-bottom four-neck reaction flask, place it under vacuum for 40 min, place it under argon, and introduce it into a glove box. Add 6 mL of PGMEA and 0.61 mL of InP-based red quantum dot material (QM). Observation: Red suspension. Place under vacuum at room temperature for 20 minutes. Place it under Ar. Add 2 mL of PGMEA. Heat to 144°C (8 min) (reflux, cool condenser with water stream). At 144 °C, 1.15 mL of a 0.43 M mPEG-SH solution in PGMEA is injected - t = 0. Hold at 144°C for 65 minutes. Inject 1.15 mL of a 0.43 M mPEG-SH solution in PGMEA. Hold at 144°C for 70 minutes. Finish. Cook at 144°C for a total of about 2 hours and 15 minutes. The resulting QDs are washed with anhydrous hexane (crude:hexane ratio 1:1). This process is repeated with a mixture of anhydrous PGMEA:hexane 1:1. The QDs are then extracted with toluene.

[0249] [Table 6]

[0250] Table B compares the thermal stability values ​​for the described Example 8 and the first semiconductor material used (InP-based red quantum material).

[0251] Reference 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 the S source. Weigh 1.28 g of zinc acetate (Zn(OAc)) into a 250 ml round-bottom flask and degas at 200 mTorr for 25 min while stirring. Place under an Ar atmosphere. Insert into the glovebox. Add 56 ml of PGMEA and 2.1 g of the InP-based red quantum material in toluene. Place the mixture in a Schlenk line. Place under Ar. Install a distillation setup and remove the toluene. The flask is heated to reflux and 7.7 ml of a 0.4 M solution of mPEG800-SH in PGMEA is injected. After 65 min, another portion of 7.7 ml of a 0.4 M mPEG800-SH solution in PGMEA is injected. After an additional 70 minutes at reflux, the flask is cooled to room temperature (total reaction time 2 hours 15 minutes). The resulting QDs are washed as follows: the solids are removed by centrifugation; the QDs are precipitated with anhydrous hexane (crude:hexane ratio 1:1); this process is repeated with a mixture of anhydrous PGMEA:hexane 1:1, then twice with a mixture of anhydrous toluene:hexane 2:3.

[0252] [Table 7]

[0253] Table C compares the thermal stability values ​​for the described Example 9 with a reference material prepared similarly to Example 9 but without Zn(OAc)2.

[0254] Reference Example 10: Synthesis of ZnS outer layer on InP-based green quantum dot material with core-shell structure in diisopropylbenzene using poly(ethylene glycol) methyl ether thiol Mn350 (mPEG350-SH) as S source 0.215 g of Zn(OAc)2 is weighed outside the GB into a 50 ml round-bottom flask and the flask is introduced into the GB. 8 ml of diisopropylbenzene (DIPB) is added, followed by 270 mg of a toluene solution of InP-based green quantum dots. The mixture is placed on a Schlenk line and the toluene is removed under reduced pressure. The flask is filled with Ar. The flask is heated to 160 °C and 1.3 ml of a 0.9 M solution of mPEG(350)-SH in diisopropylbenzene is injected. After 90 min at 160 °C, the reaction is cooled to ambient temperature. The QDs precipitate upon cooling below 50 °C. Toluene (6 mL) is added to dissolve the quantum dots.

[0255] The resulting QDs are washed as follows: the solids are removed by centrifugation; the QDs are precipitated with anhydrous heptane (1:1 ratio of (crude + toluene):heptane); this process is repeated with a mixture of anhydrous PGMEA:heptane 1:2, then anhydrous toluene:heptane 1:1.

[0256] Example IBOA = Isobornyl acrylate DPGDA = di-propylene glycol diacrylate LA = Lauryl acrylate HDDA = 1,6-hexanediol diacrylate TMPTA = Trimethylolpropane triacrylate

[0257] Example 1: Passivation and purification of the QD surface is carried out under an inert atmosphere. In a separate vial, 0.242 g of mPEG350-SH and 2 ml of PGMEA are mixed to obtain a mPEG350-SH stock solution. In a reaction flask, 1.09 g of red QDs (InP core, ZnSe / ZnS double shell layer) with oleic acid as a ligand dispersed in heptane, 231 mg of Zn(OAc), and 14 g of propylene glycol methyl ether acetate (PGMEA) were mixed. The heptane was removed under reduced pressure. The resulting mixture was heated to reflux. Half of the mPEG350-SH stock solution is poured into the reaction flask, which is then heated under reflux for 1 hour. The second half of the mPEG350-SH stock solution is poured into the reaction flask and heating at reflux is continued for an additional hour. Cool the reaction to room temperature, transfer to a suitable centrifuge bottle, and centrifuge at 2795G for 5 minutes to remove solids. Transfer the red supernatant to a suitable centrifuge bottle. Add 1 volume of heptane to 1 volume of reaction mixture (e.g., add 15 mL of heptane to 15 mL of reaction mixture). Centrifuge at 2795G for 5 minutes and discard the supernatant. Redisperse the precipitated QDs in 16 mL of toluene. Centrifuge the dispersion at 2795 G for 5 min and discard the residual solids. Transfer the QD dispersion to a brown glass bottle and store under an inert atmosphere.

[0258] Example 2: Passivation and purification of the QD surface is carried out under an inert atmosphere. In a separate vial, 0.364 g of mPEG350-SH and 2 ml of PGMEA are mixed to obtain a mPEG350-SH stock solution. In a reaction flask, 1.09 g of red QDs (InP core, ZnSe / ZnS double shell layer) with oleic acid as a ligand dispersed in heptane, 191 mg of Zn(OAc), and 14 g of propylene glycol methyl ether acetate (PGMEA) were mixed. The heptane was removed under reduced pressure. The resulting mixture was heated to reflux. Half of the mPEG350-SH stock solution is poured into the reaction flask, which is then heated under reflux for 1 hour. The second half of the mPEG350-SH stock solution is poured into the reaction flask and heating at reflux is continued for an additional hour. Cool the reaction to room temperature, transfer to a suitable centrifuge bottle, and centrifuge at 2795G for 5 minutes to remove solids. Transfer the red supernatant to a suitable centrifuge bottle. Add 2.65 volumes of heptane to 1 volume of reaction mixture (e.g., add 47.7 mL of heptane to 18 mL of reaction mixture). Centrifuge at 2795G for 5 minutes and discard the supernatant. Redisperse the precipitated QDs in 6 mL of toluene. Then add 6 mL of heptane. Centrifuge at 2795G for 5 minutes and discard the supernatant. Redisperse the precipitated QDs in 6 mL of toluene. Centrifuge the dispersion at 2795G for 5 minutes and discard the residual solids. Transfer the QD dispersion to a brown glass bottle and store under inert atmosphere.

[0259] Example 3 Passivation and purification of the QD surface is carried out under an inert atmosphere. In a separate vial, 1.216 g of mPEG350-SH and 6 ml of PGMEA are mixed to obtain a mPEG350-SH stock solution. In a reaction flask, 3 g of red QDs (InP core, ZnSe / ZnS double shell layer) with oleic acid as a ligand dispersed in heptane, 558 mg of Zn(OAc)2, and 39 g of propylene glycol methyl ether acetate (PGMEA) were mixed. The heptane was removed under reduced pressure. The resulting mixture was heated to reflux. Half of the mPEG350-SH stock solution is poured into the reaction flask, which is then heated under reflux for 1 hour. The second half of the mPEG350-SH stock solution is poured into the reaction flask and heating at reflux is continued for an additional hour. Cool the reaction to room temperature, transfer to a suitable centrifuge bottle, and centrifuge at 2795G for 5 minutes to remove solids. Transfer the red supernatant to a suitable centrifuge bottle. Add 0.75 volumes of heptane to 1 volume of reaction mixture (e.g., add 30 mL of heptane to 40 mL of reaction mixture). Centrifuge at 2795G for 5 minutes and discard the supernatant. Redisperse the precipitated QDs in 32 mL of toluene. Then add 16 mL of heptane. Centrifuge at 2795G for 5 minutes and discard the supernatant. Redisperse the precipitated QDs in 8 mL of toluene. Centrifuge the dispersion at 2795G for 5 minutes and discard the remaining solids. Transfer the QD dispersion to a brown glass bottle and store under inert atmosphere.

[0260] Example 4: QDs (0.2 g) from Example 1 dispersed in toluene are introduced into a glass vial. Monomers isobornyl acrylate (IBOA) (263.3 mg) and trimethylpropane triacrylate (TMPTA) (29.3 mg) are added. Then, photoinitiator Omnirad 819 (5 mg) and antioxidant IRGANOX 1010 (2.5 mg) are added. The formulation is shaken for 10 minutes, and volatile substances are evaporated in a rotary evaporator under vacuum at 25 °C. Remaining volatiles are removed in a Schlenk line under a vacuum of 60 mTorr.

[0261] Example 5: QDs (0.2 g) from Example 2 dispersed in toluene are introduced into a glass vial. Monomers IBOA (117 mg), polyethylene glycol methacrylate (MW 360) (117 mg), and triethylene glycol dimethacrylate (58.5 mg) are added. Photoinitiator Omnirad 819 (50 mg) and antioxidant IRGANOX 1010 (25 mg) are then added. The formulation is shaken for 10 minutes, and the volatiles are evaporated in a rotary evaporator under vacuum at 25 °C. The remaining volatiles are removed on a Schlenk line under a vacuum of 60 mTorr.

[0262] Example 6: QDs (0.2 g) from Example 3 dispersed in toluene are introduced into a glass vial. Monomers IBOA (147 mg) and triethylene glycol dimethacrylate (147 mg) are added. Then, photoinitiator Omnirad 819 (5 mg) and antioxidant IRGANOX 1010 (2.5 mg) are added. The preparation is shaken for 10 minutes, and the volatiles are evaporated in a rotary evaporator under vacuum at 25 °C. The remaining volatiles are removed in a Schlenk line under a vacuum of 60 mTorr.

[0263] Example 7: QDs (0.2 g) from Example 1 dispersed in toluene are introduced into a glass vial. Monomer IBOA (234 mg), triethylene glycol dimethacrylate (0.058 mg) are added. Then, photoinitiator Omnirad 819 (5 mg) and antioxidant IRGANOX 1010 (2.5 mg) are added. The preparation is shaken for 10 minutes, and the volatiles are evaporated in a rotary evaporator under vacuum at 25 °C. The remaining volatiles are removed in a Schlenk line under a vacuum of 60 mTorr.

[0264] Example 8: QDs (0.2 g) from Example 3 dispersed in toluene are introduced into a glass vial. Monomer polyethylene glycol methacrylate (MW 360) (468 mg) and ethylene glycol dimethacrylate (117 mg) are added. Then, photoinitiator Omnirad 819 (5 mg) and antioxidant IRGANOX 1010 (2.5 mg) are added. The formulation is shaken for 10 minutes, and the volatiles are evaporated in a rotary evaporator under vacuum at 25 °C. The remaining volatiles are removed in a Schlenk line under a vacuum of 60 mTorr.

[0265] Example 9: QDs (0.2 g) from Example 3 dispersed in toluene are introduced into a glass vial together with mPEG-SH (60 mg). Monomers IBOA (472 mg) and TMPTA (53 mg) are added. Then, photoinitiator Omnirad819 (5 mg) and antioxidant IRGANOX1010 (2.5 mg) are added. The formulation is shaken for 10 minutes, and volatiles are evaporated in a rotary evaporator under vacuum at 25 °C. Remaining volatiles are removed on a Schlenk line under a vacuum of 60 mTorr.

[0266] Example 10: QDs (0.2 g) from Example 2 dispersed in toluene are introduced into a glass vial together with mPEG-SH (60 mg). Monomers LA (420 mg) and HDDA (105 mg) are added. Then, photoinitiator Omnirad819 (5 mg) and antioxidant IRGANOX1010 (2.5 mg) are added. The formulation is shaken for 10 minutes, and volatiles are evaporated under vacuum on a rotary evaporator at 25 °C. Remaining volatiles are removed under vacuum at 60 mTorr on a Schlenk line.

[0267] Example 11: QDs (0.4 g) from Example 3 dispersed in toluene are introduced into a glass vial. Monomers IBOA (351 mg) and dipropylene glycol diacrylate (DPGDA) (234 mg) are added. Photoinitiator Omnirad 819 (10 mg) and antioxidant IRGANOX 1010 (5 mg) are then added. The formulation is shaken for 10 minutes, and the volatiles are evaporated in a rotary evaporator under vacuum at 25 °C. The remaining volatiles are removed in a Schlenk line under a vacuum of 60 mTorr.

[0268] Example 12: QDs (0.4 g) from Example 3 dispersed in toluene and mPEG-SH (60 mg) are introduced into a glass vial. The resulting mixture is heated to 40 °C for 80 minutes. Monomers IBOA (315 mg) and dipropylene glycol diacrylate (DPGDA) (210 mg) are added. Then, photoinitiator Omnirad 819 (10 mg) and antioxidant IRGANOX 1010 (5 mg) are added. The formulation is shaken for 10 minutes, and the volatiles are evaporated under vacuum on a rotary evaporator at 25 °C. The remaining volatiles are removed on a Schlenk line under a vacuum of 60 mTorr.

[0269] Example 13: QDs (0.4 g) from Example 3 dispersed in toluene and octadecanethiol (48 mg) are introduced into a glass vial. The suspension is heated to 80 °C for 2 hours. Monomers LA (322 mg) and HAAD (215 mg) are added. Then, photoinitiator Omnirad 819 (10 mg) and antioxidant IRGANOX 1010 (5 mg) are added. The formulation is shaken for 10 minutes and the volatiles are evaporated under vacuum on a rotary evaporator at 25 °C. The remaining volatiles are removed under a vacuum of 60 mTorr on a Schlenk line.

[0270] Example 14: QDs (1.0 g) from Example 3 dispersed in toluene and mPEG350-SH (150 mg) are introduced into a glass vial. The suspension is heated to 40 °C for 2 hours. Monomers IBOA (1.181 g) and TMPTA (131 mg) are added. Then, photoinitiator Omnirad819 (25 mg) and antioxidant IRGANOX1010 (12.5 mg) are added. The formulation is shaken for 10 minutes and the volatiles are evaporated under vacuum on a rotary evaporator at 25 °C. The remaining volatiles are removed on a Schlenk line under a vacuum of 60 mTorr.

[0271] Comparative Example 1: (Comparison with Example 4) The solvent-based ink is formed with native QDs. 0.2 g of red QDs (InP core, ZnSe / ZnS double shell layer) with oleic acid as a ligand dispersed in heptane are introduced into a glass vial. Monomers IBOA (263.3 mg) and TMPTA (29.3 mg) are added. Then, photoinitiator Omnirad819 (50 mg) and antioxidant 1010 (25 mg) are added. The preparation is shaken for 10 min, and the volatiles are evaporated under vacuum on a rotary evaporator at 25 °C. The remaining volatiles are removed under a vacuum of 60 mTorr on a Schlenk line.

[0272] Comparative Example 2: (Comparison with Example 4) A solvent-based ink is formed using native QDs and the additive mPEG-SH. 0.2 g of red QDs (InP core, ZnSe / ZnS double shell layer) with oleic acid as a ligand dispersed in heptane and 51.9 mg of mPEG-SH (MW 350) are introduced into a glass vial. Monomers IBOA (263.3 mg) and TMPTA (29.3 mg) are added. Then, photoinitiator Omnirad 819 (50 mg) and antioxidant 1010 (25 mg) are added. The preparation is shaken for 10 min, and the volatiles are evaporated under vacuum on a rotary evaporator at 25 °C. The remaining volatiles are removed under a vacuum of 60 mTorr on a Schlenk line.

[0273] Comparative Example 3: (Comparison with Examples 11 and 12) A solvent-based ink is formed using native QDs and the additive mPEG-SH. 0.16 g of red QDs (InP core, ZnSe / ZnS double shell layer) with oleic acid as a ligand dispersed in heptane and 40 mg of mPEG-SH (MW 350) are introduced into a glass vial. Monomers IBOA (116 mg) and DPGDA (78 mg) are added. Then, photoinitiator Omnirad819 (40 mg) and antioxidant IRGANOX1010 (20 mg) are added. The preparation is shaken for 10 min, and the volatiles are evaporated under vacuum on a rotary evaporator at 25 °C. The remaining volatiles are removed under a vacuum of 60 mTorr on a Schlenk line.

[0274] Film Formation: A film is formed by filling a glass sandwich cell (gap approximately 10 μm) with the ink described in the previous example. The film is then exposed to UV light (300 mW / cm). 2 The cell is then opened, resulting in an open film deposited on one of the cell glasses. The released membrane is heated (thermal annealed) at 180° C. for 30 minutes under an inert atmosphere. After thermal annealing, the film is stored in a humidity-controlled chamber at 25° C. and 45% relative humidity (RH). QY and EQE are measured 1 hour after thermal annealing and after 3 or 5 days of storage, as shown in Tables 1 to 4 below. EQE = photons [emission] / photons [excitation light measured without a sample] According to the present invention, EQE is measured at room temperature by the following EQE measurement process, which is based on using an integrating sphere equipped with a 450 nm excitation light source and a spectrometer (CompassX, BWTEK) coupled via an optical fiber, which consists of a first measurement using air as a reference to detect incident photons of the excitation light, and a second measurement in which a sample or test cell is placed in front of the integrating sphere between the opening of the integrating sphere and the exit of the optical fiber, thereby detecting incident photons from the excitation light source transmitted through the sample and photons emitted from the sample or test cell, and in both measurements, photons exiting the integrating sphere are counted by the spectrometer, and the calculation of EQE and BL is performed using the following equations, where the number of excitation light and emission photons is calculated by integration over the following wavelength range: EQE = photons [emission] / photons [excitation light measured without a sample] BL = photons [excitation light measured with a sample placed] / photons [excitation light measured without a sample placed] Emission when green light emitting part is used: 490nm~600nm Emission when red light emitting part is used: 580nm~780nm Excitation light: 390nm to 490nm

[0275] [Table 8] [Table 9] [Table 10] [Table 11]

[0276] Example 15 A red QD ink containing red QDs (with InP core and ZnSe / ZnS double shell layers) with two different types of ligands made from mPEG-(SH) and oleic acid was prepared by mixing the materials listed in Table 5 below.

[0277] [Table 12]

[0278] Example 16 The QD film obtained by Example 15 is stored under an atmosphere of 25°C and 45% RH. The EQE of the QD film is monitored for up to 5 days.

[0279] result The red QD ink of Example 15 shows excellent dispersibility. Example 16 yields a QD film with a thickness of 10 μm. The EQE remains above 97% after 5 days under ambient conditions.

Claims

1. a composition, preferably a photocurable composition; i) a light-emitting moiety, preferably a semiconductor light-emitting nanoparticle, with an outer layer comprising a metal cation and a divalent anion; and a light-emitting moiety comprising one or more organic moieties covalently bonded directly to the anions of the outer layer; ii) at least one reactive monomer or a mixture of two or more reactive monomers, preferably said monomer having one or more functional groups, more preferably a (meth)acrylate monomer; The divalent anion of the outer layer is Se ２－ , S ２－ , Te ２－ , O ２－ or a combination thereof, preferably the metal cations of the outer layer are monovalent, divalent, trivalent or tetravalent cations, more preferably the metal cations are selected from Zn ２＋ , Ni ２＋ , Co ２＋ , Ca ２＋ , Sr ２＋ , Hg ２＋ , Mg ２＋ and Pb ２＋ or Ti ４＋ , Ge ４＋ , Si ４＋ , Zr ４＋ , Hf ４＋ , and Sn ４＋ The composition of claim 1, wherein the tetravalent cation is selected from the group consisting of:

2. 10. The composition of claim 1, wherein the organic moiety is represented by the following chemical formula (I): A-B- ＊ (I) [In the formula, A is an organic group, preferably the organic group is a hydrocarbyl (including alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group (including aryl, alkaryl, alkyl or aralkyl), an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group (including fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl); B is a connection unit, preferably B is ＊＊ - (U) ｏ -(Y) ｍ - (CR ＩＩａ R ＩＩｂ ) ｎ In the formula, ＊＊ " represents the connection point to "A", " ＊ " represents a point of attachment to the anion in the outer layer.

3. 3. The composition of claim 1, wherein the organic moiety is represented by the following chemical formula (II), (III), or (III'): L-(U) ｏ -(Y) ｍ -(CR ＩＩａ R ＩＩｂ ) ｎ - ＊ (II) [In the formula, L is an organic group, preferably the organic group is a hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group (aryl, alkaryl, alkyl or aralkyl), an alkylamine, a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl or a fluoroaralkyl); U is O, CH ２ or C=O, Y is O, CH ２ or C=O, R ＩＩａ and R ＩＩｂ are each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a straight chain alkyl group having 1 to 5 carbon atoms, a branched chain alkyl group having 3 to 5 carbon atoms, and preferably from R ＩＩａ and R ＩＩｂ is a hydrogen atom, n is an integer of 1 or more, m is an integer of 0 or 1 or more, preferably m is 1; o is an integer of 0 or 1 or more, preferably o is 1; " ＊ " represents a point of attachment to the anion in the outer layer; ＊ -(CR ＩＩＩｅ R ＩＩＩｆ ) ａ -(OCR ＩＩＩａ R ＩＩＩｂ CR ＩＩＩｃ R ＩＩＩｄ ) ｐ -(V) ｒ -(CR ＩＩＩｇ R ＩＩＩｈ ) ｑ -Z (III) ＊ -(CR ＩＩＩｇ R ＩＩＩｈ ) ｑ -(V) ｒ -(OCR ＩＩＩａ R ＩＩＩｂ CR ＩＩＩｃ R ＩＩＩｄ ) ｐ -Z (III’) [In the formula, R ＩＩＩａ , R ＩＩＩｂ , R ＩＩＩｃ , R ＩＩＩｄ , R ＩＩＩｅ , R ＩＩＩｆ , R ＩＩＩｇ and ＲＩＩＩｈ are each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a straight chain alkyl group having 1 to 5 carbon atoms, a branched chain alkyl group having 3 to 5 carbon atoms, and preferably from R ＩＩＩｇ and R ＩＩＩｈ is a hydrogen atom, and preferably, R ＩＩＩｅ and R ＩＩＩｆ is a hydrogen atom, and V is O, CH ２ or C=O, Z is a hydrogen atom or an organic group, and 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 (including fluoroaryl, fluoroalkaryl, fluoroalkyl, or fluoroaralkyl), and Z is preferably a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a branched alkyl group having 3 to 25 carbon atoms, more preferably a hydrogen atom, a linear alkyl group having 1 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms, and even more preferably a hydrogen atom, or a linear alkyl group having 1 to 10 carbon atoms; a is 0 or an integer of 1 or more, preferably 0≦a≦25, more preferably 0≦a≦15, and even more preferably 1≦a≦10; p is 0 or an integer of 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 0 or an integer of 1 or more, preferably 0≦q≦25, more preferably 0≦q≦15, even more preferably 0≦q≦10, and still more preferably 1≦q≦5; r is 0 or the integer 1; " ＊ " represents a point of attachment to the anion in the outer layer.

4. The composition of any one of claims 1 to 3, wherein the organic moiety is represented by the following chemical formula (IV): ＊ -(CR ＩＩＩｅ R ＩＩＩｆ ) ａ -(OCR ＩＩＩａ R ＩＩＩｂ CR ＩＩＩｃ R ＩＩＩｄ ) ｐ -(V) ｒ -(CR ＩＩＩｇ R ＩＩＩｈ ) ｑ -Z’ (IV) [In the formula, R ＩＩＩａ , R ＩＩＩｂ , R ＩＩＩｃ , R ＩＩＩｄ , R ＩＩＩｅ , R ＩＩＩｆ , R ＩＩＩｇ and ＲＩＩＩｈ are each independently selected at each occurrence from a hydrogen atom, a hydroxy group, a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 10 carbon atoms, preferably from a hydrogen atom, a hydroxy group, a straight chain alkyl group having 1 to 5 carbon atoms, a branched chain alkyl group having 3 to 5 carbon atoms, and preferably from R ＩＩＩｇ and R ＩＩＩｈ is a hydrogen atom, and preferably, R ＩＩＩｅ and R ＩＩＩｆ is a hydrogen atom, a is 0 or an integer of 1 or more, preferably 0≦a≦25, more preferably 0≦a≦15, and even more preferably 1≦a≦10; p is 0 or an integer of 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 0 or an integer of 1 or more, preferably 0≦q≦25, more preferably 0≦q≦15, even more preferably 0≦q≦10, and still more preferably 1; 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, a fluoroaralkyl, a heteroaromatic group (including a fluoroaryl, a fluoroalkaryl, a fluoroalkyl, or a 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 a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a hydrogen atom, and even more preferably a hydrogen atom; r is 0 or the integer 1; " ＊ " represents a point of connection to the anion in the outer layer, preferably connected to a S or Se atom in the outer layer.

5. 5. The composition of any one of claims 1 to 4, wherein the organic moieties are covalently bound to the anions in the outer layer of the inorganic lattice and preferably are not removed by ligand exchange.

6. The metal cation is a transition metal of Group 12 or 14, preferably Zn ２＋ , Hg ２＋ or Pb ２＋ The composition of any one of claims 1 to 5, selected from one or more members of the group consisting of:

7. the reactive monomer is a (meth)acrylate monomer selected from a mono-(meth)acrylate monomer, a di-(meth)acrylate monomer, and / or a tri-(meth)acrylate monomer; 7. The composition of any one of claims 1 to 6, wherein the two or more reactive monomers of the mixture are each independently selected from mono-(meth)acrylate monomers, di-(meth)acrylate monomers and / or tri-(meth)acrylate monomers.

8. The di-(meth)acrylate monomer is represented by the following chemical formula (I): ｂ ) and the mono-acrylate monomer is represented by the following chemical formula (II ｂ ) and / or the tri-(meth)acrylate monomer is represented by the following chemical formula (III ｂ The composition according to claim 7, wherein 【Chemical 1】 [In the formula, X １ is an unsubstituted or substituted ester group, alkyl group, or aryl group, and one or more non-adjacent CH ２ The group is an oxygen atom, C=O, C=S, C=Se, C=NH, SiH ２ , SO, SO ２ , OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ and preferably the ester group is of the following formula (I ｂｓ１ ) and 【Chemistry 2】 In the formula, R Ｉｂ１ is a single bond, an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms, R Ｉｂ２ is a single bond, an unsubstituted or substituted straight-chain alkylene chain having 1 to 5 carbon atoms, or an unsubstituted or substituted branched-chain alkylene chain having 3 to 7 carbon atoms, and ２ The group is an oxygen atom, C=O, C=S, C=Se, C=NH, SiH ２ , SO, SO ２ , OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ and preferably R Ｉｂ２ is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, ２ At least one of the groups is an oxygen atom, C═O, C═S, C═Se, C═NH, SiH ２ , SO, SO ２ , OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ may be replaced by X ２ is an unsubstituted or substituted ester group, alkyl group, or aryl group, and one or more non-adjacent CH ２ The group is an oxygen atom, C=O, C=S, C=Se, C=NH, SiH ２ , SO, SO ２ , OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ and preferably the ester group is of the following formula (I ｂｓ２ ) and 【Chemistry 3】 In the formula, R Ｉｂｓ１ is a single bond, an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms, R Ｉｂｓ２ is a single bond, an unsubstituted or substituted straight-chain alkylene chain having 1 to 5 carbon atoms, or an unsubstituted or substituted branched-chain alkylene chain having 3 to 7 carbon atoms, and ２ The group is an oxygen atom, C=O, C=S, C=Se, C=NH, SiH ２ , SO, SO ２ , OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ and preferably R Ｉｂ２ is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, ２ At least one of the groups is an oxygen atom, C═O, C═S, C═Se, C═NH, SiH ２ , SO, SO ２ , OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ may be replaced by R １ is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, an aryl group, and one or more non-adjacent CH ２ The group is an oxygen atom, C=O, C=S, C=Se, C=NH, SiH ２ , SO, SO ２ , OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ or X １ is an ester group, preferably the ester group is a carboxylic acid group; R ２ is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, an aryl group, and one or more non-adjacent CH ２ The group is an oxygen atom, C=O, C=S, C=Se, C=NH, SiH ２ , SO, SO ２ , OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ or X １ is an ester group, and preferably, the ester group is a carboxylic acid group; 【Chemistry 4】 [In the formula, X ３ is an unsubstituted or substituted ester group, alkyl group, cycloalkyl group, aryl group, or alkoxy group, and X ３ is an unsubstituted or substituted ester group, the ester group is represented by the following formula (II ｂｓ ) and 【Chemistry 5】 In the formula, R ＩＩｂ１ is a single bond, an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms, R ＩＩｂ２ is a substituted or unsubstituted alkyl group, cyclo group, cycloalkyl group, aryl group, or alkoxy group, R ５ is a hydrogen atom, a halogen atom such as Cl, Br or F, a methyl group, an alkyl group, an aryl group, an alkoxy group, an ester group or a carboxylic acid group; 【Chemistry 6】 [In the formula, R ９ is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a group of the formula (IV ｂ ) is a (meth)acrylic group represented by 【Chemistry 7】 In the formula, R １０ is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a group of the formula (V ｂ ) is a (meth)acrylic group represented by 【Chemistry 8】 In the formula, R １１ is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, or a group of the formula (VI ｂ ) is a (meth)acrylic group represented by 【Chemistry 9】 In the formula, R ８ , R ８ａ , R ８ｂ and R ８ｃ are each independently or dependently of one another, and at each occurrence, ２ CH ３ or CH ３ and R ９ , R １０ and R １１ At least one of the groups is a (meth)acrylic group.

9. A method for producing a composition according to any one of claims 1 to 8, comprising at least the following steps: (a) mixing at least a light emitting portion with another material to obtain a reaction mixture, preferably wherein the light emitting portion comprises at least a first semiconductor nanomaterial as a core; Preferably, said other material is a solvent, (b) forming an outer layer on the outermost surface of the light-emitting portion 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 the reaction mixture; A-B-X-H (Va) A-B-X-X-B-A (Vb) [In the formula, A is an organic group; B is a connection unit, H is a hydrogen atom, X is an anchoring group comprising an anion capable of forming a monolayer with added metal cations derivable from added metal cation precursors; (c) cooling the reaction mixture from step (b), maintaining the reaction mixture in step (b) at a temperature in the range of 80°C to 200°C, preferably 100 to 200°C, to form the outer layer in step (b); (d) combining the light-emitting moiety obtained from step (c) with at least one reactive monomer or a mixture of two or more reactive monomers to form a composition.

10. The method of claim 9, wherein the ratio of the total molar amount of the cation precursors to the total molar amount of the semiconductor nanoparticles in step (b) is in the range of 20:1 to 200,000:1, preferably 100:1 to 60,000:1, more preferably 110:1 to 58,000:1, and even more preferably 120:1 to 5,000:1; and preferably the ratio of the total mass of the cation precursors to the total mass of the semiconductor nanoparticles in step (b) is in the range of 1:1,000 to 1:1, preferably 1:500 to 1:2, and more preferably 1:400 to 1:

2.

11. A formulation comprising at least the composition according to any one of claims 1 to 8 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, acetate esters, acetate ethers, ketones, ether esters, preferably PGMEA, alcohols, preferably ethanol or isopropanol, sulfoxides, formamides, nitrides, ketones.

12. 1. A method for forming a layer, comprising: S1) providing a composition according to any one of claims 1 to 8 onto a substrate, preferably by inkjet; S2) a step of curing the composition, preferably the curing is photocuring performed by light irradiation, thermal curing, or a combination of photocuring and thermal curing.

13. a layer, the layer including at least Xi) a light-emitting moiety, preferably a semiconductor light-emitting nanoparticle, with an outer layer comprising a metal cation and a divalent anion; and a light-emitting moiety comprising one or more organic moieties covalently bonded directly to the anions of the outer layer; Xii) a polymer made from at least one reactive monomer or a mixture of two or more reactive monomers, preferably said monomers having one or more functional groups, more preferably (meth)acrylate monomers; The divalent anion of the outer layer is Se ２－ , S ２－ , Te ２－ , O ２－ or a combination thereof, preferably the metal cations of the outer layer are monovalent, divalent, trivalent or tetravalent cations, more preferably the metal cations are selected from Zn ２＋ , Ni ２＋ , Co ２＋ , Ca ２＋ , Sr ２＋ , Hg ２＋ , Mg ２＋ and Pb ２＋ or Ti ４＋ , Ge ４＋ , Si ４＋ , Zr ４＋ , Hf ４＋ , and Sn ４＋ The layer is a tetravalent cation selected from the group consisting of:

14. 14. A color conversion device (100) comprising at least one first pixel (161) partially or completely filled with the layer of claim 13, comprising at least a matrix material (120) containing a light-emitting portion (110), and a bank (150) comprising at least a polymer material, and preferably further comprising a support medium (170).

15. 15. An optical device (300) comprising at least one functional medium (320, 420, 520) configured to modulate light or configured to emit light, and a color conversion device (100) according to claim 14.

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