Composition

Abstract

The present invention relates to a composition comprising a luminescent moiety, such as a quantum material, including quantum dots; and a method for manufacturing the composition.

Description

Field of the Invention

[0001] The present invention relates to a composition containing a luminescent portion; a method for producing the composition; a formulation; use of the composition, a method for forming a layer; a layer; a color conversion device; and an optical device. Background Art

[0002] Luminescent nanoparticles are known in the prior art. For example, Turo et al., ACS NANO, Vol. 8, No. 10, 10205-10203, 2014 disclose Cu without a shell layer using dodecanethiol (DDT). 2 S nanoparticles and the method of manufacturing them at a temperature of 200°C using DDT. DDT was used throughout the synthesis method.

[0003] Turo et al., Chem Commun, 2016, 52, 12214-12217 describe CdSe / ZnS with dodecanethiol.

[0004] Robinson et al., Chem Mater, 2017, 29, 3854-3857 mentioned quasi-spherical Cu with DDT 2 S nanorods.

[0005] Patent Literature

[0006] No literature

[0007] Non-patent literature

[0008] 1. Turo et al., ACS NANO, Vol. 8, No. 10, 10205-10203, 2014

[0009] 2.Chem Commun,2016,52,12214-12217

[0010] 3. Robinson et al., Chem Mater, 2017, 29, 3854-3857 SUMMARY OF THE INVENTION

[0012] However, the present inventors have newly discovered that there are still one or more considerable problems that need to be improved, as listed below: achieving an optimized haze value of a cured layer (film), an optimal haze value and an improved EQE value of a cured layer (film) (preferably, obtaining an optimal haze value and an improved EQE value of a cured layer (film) without using scattering particles), an improved thermal stability of the obtained layer (film), an improved thermal stability of the luminescent portion in the layer (film), an improved dispersibility of the luminescent portion in the composition, enabling the luminescent portion and the matrix material to phase separate after curing to achieve an improved haze value of a cured film (cured composition), an improved dispersibility of the luminescent portion in the obtained layer, and a longer storage period with or without external light irradiation in the composition. Improved long-term quantum yield (QY) stability of the light-emitting part, improved long-term external quantum efficiency (EQE) stability of the light-emitting part in the composition during longer-term storage with or without external light irradiation, improved long-term quantum yield (QY) stability of the light-emitting part in the obtained layer (film) during longer-term storage with or without external light irradiation, improved long-term external quantum efficiency (EQE) stability of the light-emitting part in the obtained layer (film) during longer-term storage with or without external light irradiation, improved good compatibility of the light-emitting part in the composition and / or the obtained layer (film) with the matrix material, and / or easy processing of the composition containing the light-emitting part and the matrix material, making the composition suitable for inkjet printing.

[0013] The present inventors aim to solve one or more of the above mentioned problems.

[0014] The inventors have surprisingly found that one or more of the technical problems described above can be solved by the features defined in the claims.

[0015] That is, a novel composition, preferably a photocurable composition, is found comprising at least, consisting essentially of, or consisting of;

[0016] i) a luminescent moiety, preferably a semiconductor luminescent nanoparticle comprising an outer layer containing a metal cation and a divalent anion; and

[0017] one or more types of organic moieties covalently attached directly to the anions of the outer shell,

[0018] ii) at least one reactive monomer or a mixture of two or more reactive monomers, preferably the monomer has one or more functional groups, more preferably it is a (meth)acrylate monomer;

[0019] The divalent anion of the outer layer is selected from Se 2- , S 2- 、Te 2- , O 2-Or any combination thereof, preferably, the metal cation in the outer layer is a monovalent, divalent, trivalent or tetravalent cation, more preferably, the metal cation is selected from Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ The divalent cations of the group consisting of or selected from Ti 4+ ,Ge 4+ 、Si 4 + 、Zr 4+ , Hf 4+ Sn 4+ The group consisting of tetravalent cations.

[0020] In another aspect, the present invention further relates to a method for preparing the composition of the present invention, comprising, consisting essentially of or consisting of at least the following steps,

[0021] (a) mixing at least semiconductor nanoparticles, preferably, the semiconductor nanoparticles comprising at least a first semiconductor nanomaterial as a core, with another material to obtain a reaction mixture, preferably, the other material is a solvent;

[0022] (b) forming an outer layer onto the semiconductor nanoparticles in the reaction mixture by reacting a source of anions represented by at least formula (Va) or formula (Vb) with a metal cation precursor in the reaction mixture, wherein in some embodiments of the invention, the metal cation precursor may be the same as the cationic shell precursor;

[0023] ABXH(Va)

[0024] ABXXBA(Vb)

[0025] Wherein A is an organic group;

[0026] B is a connecting unit connecting A and X;

[0027] H is a hydrogen atom; and

[0028] X is an anchoring group comprising an anion capable of forming a monolayer with an added metal cation that may be derived from an added metal cation precursor;

[0029] (c) cooling the reaction mixture from step (b),

[0030] wherein the reaction mixture in step (b) is maintained at a temperature in the range of 80° C. to 200° C., preferably 100 to 200° C. to form the outer layer in step (b),

[0031] (d) mixing the light-emitting portion obtained from step (c) with at least one reactive monomer or a mixture of two or more reactive monomers to form a composition.

[0032] In another aspect, the invention relates to a composition obtainable or obtained by the method of the invention.

[0033] In another aspect, the present invention relates to a formulation comprising, consisting essentially of, or consisting of at least a composition of the present invention

[0034] 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, pure water, ester acetate, ether acetate, ketone, ether ester (such as PGMEA), alcohol (such as ethanol, isopropanol, etc.), sulfoxide, formamide, nitride, ketone.

[0035] In another aspect, the invention relates to use of a composition or formulation in an electronic device, an optical device, a sensing device or a biomedical device.

[0036] In another aspect, the present invention relates to a method for forming a layer, comprising:

[0037] S1) providing the composition of the invention onto a substrate, preferably by inkjet;

[0038] S2) curing the composition, preferably, the curing is photocuring performed by light irradiation, thermal curing, or a combination of photocuring and thermal curing.

[0039] In another aspect, the present invention further relates to a layer obtained or obtainable by the process of the present invention.

[0040] In another aspect, the present invention further relates to a layer comprising at least, consisting essentially of, or consisting of;

[0041] Xi) a luminescent moiety, preferably a semiconductor luminescent nanoparticle comprising an outer layer containing a metal cation and a divalent anion; and

[0042] one or more types of organic moieties covalently attached directly to the anions of the outer shell,

[0043] Xii) a polymer made from at least one reactive monomer or a mixture of two or more reactive monomers, preferably the monomer has one or more functional groups, more preferably it is a (meth)acrylate monomer;

[0044] The divalent anion of the outer layer is selected from Se 2- , S 2- 、Te 2- , O 2- Or any combination thereof, preferably, the metal cation in the outer layer is a monovalent, divalent, trivalent or tetravalent cation, more preferably, the metal cation is selected from Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ The divalent cations of the group consisting of or selected from Ti 4+ ,Ge 4+ 、Si 4 + 、Zr 4+ , Hf 4+ Sn 4+ The group consisting of tetravalent cations.

[0045] In another aspect, the present invention further relates to a color conversion device (100), comprising at least a first pixel (161), the first pixel being partially or completely filled with a layer of at least a matrix material (120) containing a light-emitting portion (110) according to the present invention; and a bank (150) containing at least a polymer material. Preferably, the color conversion device (100) further comprises a supporting medium (170).

[0046] In another aspect, the present invention further relates to an optical device (300) containing at least one functional medium (320, 420, 520) configured to modulate light or configured to emit light, and the color conversion device (100) of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 : A cross-sectional view showing a schematic diagram of one embodiment of a color conversion film (100).

[0048] Figure 2 : A top view showing a schematic diagram of another embodiment of the color conversion film (100) of the present invention.

[0049] Figure 3: A cross-sectional view showing a schematic diagram of one embodiment of an optical device (300) of the present invention.

[0050] Figure 4 : A cross-sectional view showing a schematic diagram of another embodiment of the optical device (300) of the present invention.

[0051] Figure 5 : A cross-sectional view showing a schematic diagram of another embodiment of the optical device (300) of the present invention.

[0052] Figure 6 : QDs from Reference Example 1 before (a) and after (b) addition of 3-phenylpropylphosphonic acid (PPPA) 1 H NMR spectrum (in toluene d8).

[0053] Figure 7 : QDs from Reference Example 1 after treatment with PPPA and washing with ethanol 1 H NMR spectrum (in toluene d8).

[0054] Fig. 8A , 8B : GCMS spectrum of QDs from Reference Example 1 after treatment with PPPA and washing. MS spectrum of the peak at retention time of 11.45.

[0055] Fig. 9 : A general scheme describing the multi-step method established to distinguish surface- and crystal-bound ligands, using dodecylselenol (DDSe) as an example (Scheme 1).

[0056] Figure 1 List of reference symbols

[0057] 100. Color conversion device

[0058] 110. Luminous part

[0059] 110R. Luminous part (red)

[0060] 110G. Luminous part (green)

[0061] 120. Matrix material

[0062] 130. Light scattering particles (optional)

[0063] 140. Colorant (optional)

[0064] 140R. Colorant (red) (optional)

[0065] 140g. Colorant (green) (optional)

[0066] 140B. Colorant (blue) (optional)

[0067] 150. Library

[0068] 161. Pixel 1

[0069] 162. Pixel 2

[0070] 163. Pixel 3

[0071] 170. Support medium (substrate) (optional)

[0072] Figure 2 List of reference symbols in

[0073] 200. Color conversion film

[0074] 210R.Pixel (red)

[0075] 210G.Pixel (green)

[0076] 210B.Pixel (blue)

[0077] 220. Library

[0078] Figure 3 List of reference symbols in

[0079] 300.Optical Devices

[0080] 100. Color conversion device

[0081] 110. Luminous part

[0082] 110R. Luminous part (red)

[0083] 110G. Luminous part (green)

[0084] 120. Matrix material

[0085] 130. Light scattering particles (optional)

[0086] 140. Colorant (optional)

[0087] 140R. Colorant (red) (optional)

[0088] 140g. Colorant (green) (optional)

[0089] 140B. Colorant (blue) (optional)

[0090] 150. Library

[0091] 320.Light modulator

[0092] 321. Polarizer

[0093] 322. Electrode

[0094] 323. Liquid crystal layer

[0095] 330. Light Source

[0096] 331.LED light source

[0097] 332. Light guide plate (optional)

[0098] 333. Light emission from light source (330)

[0099] Figure 4 List of reference symbols in

[0100] 400.Optical Devices

[0101] 100. Color conversion device

[0102] 110. Luminous part

[0103] 110R. Luminous part (red)

[0104] 110G. Luminous part (green)

[0105] 120. Matrix material

[0106] 130. Light scattering particles (optional)

[0107] 140. Colorant (optional)

[0108] 140R. Colorant (red) (optional)

[0109] 140g. Colorant (green) (optional)

[0110] 140B. Colorant (blue) (optional)

[0111] 150. Library

[0112] 420.Light Modulator

[0113] 421. Polarizer

[0114] 422. Electrode

[0115] 423. Liquid crystal layer

[0116] 430. Light Source

[0117] 431.LED light source

[0118] 432. Light guide plate (optional)

[0119] 440. Color Filter

[0120] 433. Light emission from light source (330)

[0121] Figure 5 List of reference symbols in

[0122] 500. Optical Devices

[0123] 100. Color conversion device

[0124] 110. Luminous part

[0125] 110R. Luminous part (red)

[0126] 110G. Luminous part (green)

[0127] 120. Matrix material

[0128] 130. Light scattering particles (optional)

[0129] 140. Colorant (optional)

[0130] 140R. Colorant (red) (optional)

[0131] 140g. Colorant (green) (optional)

[0132] 140B. Colorant (blue) (optional)

[0133] 150. Library

[0134] 520. Light-emitting devices (e.g. OLED)

[0135] 521.TFT

[0136] 522. Electrode (anode)

[0137] 523.Substrate

[0138] 524. Electrode (cathode)

[0139] 525. Light-emitting layer (e.g. OLED layer(s))

[0140] 526. Light emission from the light emitting device (520)

[0141] 530. Optical layer (such as polarizer) (optional)

[0142] 540. Color Filter DETAILED DESCRIPTION OF THE INVENTION

[0144] According to the present invention, a composition, preferably a photocurable composition, comprises at least;

[0145] i) a luminescent moiety, preferably a semiconductor luminescent nanoparticle comprising an outer layer containing a metal cation and a divalent anion; and

[0146] one or more types of organic moieties covalently attached directly to the anions of the outer shell,

[0147] ii) at least one reactive monomer or a mixture of two or more reactive monomers, preferably the monomer has one or more functional groups, more preferably it is a (meth)acrylate monomer;

[0148] The divalent anion of the outer layer is selected from Se 2- , S 2- 、Te 2- , O 2- Or any combination thereof, preferably, the metal cation in the outer layer is a monovalent, divalent, trivalent or tetravalent cation, more preferably, the metal cation is selected from Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ The divalent cations of the group consisting of or selected from Ti 4+ ,Ge 4+ 、Si 4 + 、Zr 4+ , Hf 4+ Sn 4+ The group consisting of tetravalent cations.

[0149] - Luminous part

[0150] According to the present invention, the luminescent part can be an organic and / or inorganic luminescent material, preferably, it is an organic dye, an inorganic phosphor and / or a semiconductor luminescent nanoparticle, such as a quantum material. As the organic dye, inorganic phosphor, semiconductor luminescent nanoparticle, those publicly known can be used.

[0151] Such suitable inorganic light-emitting materials described above may be well-known phosphors, including nano-sized phosphors, quantum-sized materials, as mentioned in Phosphor Handbook, 2nd Edition (CRC Press, 2006), pages 155-338 (WM Yen, S. Shionoya and H. Yamamoto), WO2011 / 147517A, WO2012 / 034625A and WO2010 / 095140A.

[0152] As the organic dye, for example, rhodamine, coumarin, pyrromethene, DCM, fluorescein, umbelliferone, BD Horizon BrilliantTM series.

[0153] Preferably, the luminescent moiety is an inorganic luminescent material. More preferably, it is a semiconductor luminescent nanoparticle. The semiconductor luminescent nanoparticle is preferably a semiconductor luminescent nanoparticle comprising, consisting essentially of, or consisting of: a core;

[0154] an outer layer covering at least a portion of the core, comprising a metal cation and a divalent anion; and

[0155] an organic moiety, preferably one or more types of organic moieties directly attached to the anion of the outer shell via a covalent bond,

[0156] Wherein the divalent anion is selected from Se 2- , S 2- 、Te 2- , O 2- or any combination thereof, preferably, the metal cation is a monovalent, divalent, trivalent or tetravalent cation, more preferably, the metal cation is selected from Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ The divalent cations of the group consisting of or selected from Ti 4+ ,Ge 4+ 、Si 4+ 、Zr 4+ , Hf 4+ Sn 4+ Or in some embodiments, the metal cation is a transition metal of Group 12 or Group 14, preferably, it is selected from Zn 2+ , Hg 2+ or Pb 2+ One or more members of a group.

[0157] The nanoparticle comprises at least an outer layer and a core. The nanoparticle may optionally contain one or more further layers (shell layers) between the outer layer and the core.

[0158] The outer layer covers at least a portion of the core. If no other layers are present between the outer layer and the core, the outer layer may have direct physical contact with the core.

[0159] The outer layer may cover the core via one or more of the additional layers placed between the outer layer and the core.

[0160] The term "cover" and the term "covering" do not necessarily mean that there is always a physical contact between the core and the outer layer. Preferably, the core is completely covered by the outer layer and / or one or more shell layers.

[0161] Most preferably, the nanoparticle comprises a core, one or more shells and an outer layer, wherein the outermost layer of the one or more shells comprises Zn and S atoms.

[0162] In a preferred embodiment of the present invention, from the viewpoint of producing improved covalent bonds between the organic part and the anions of the outer layer, the outer layer of the luminescent part comprises at least two or three different metal cations, such as Cu 1+ and 3+ , Cu 1+ and Ga 3+ 、Ag 1+ and Ga 3+ Combination or Cu +1 / In +3 / Zn +2 combination.

[0163] According to the present invention, the term "nano-sized" means a size between 0.1 nm and 150 nm, preferably 0.5 nm to 100 nm, more preferably 1 nm to 50 nm.

[0164] According to the present invention, the term "semiconductor" means a material having a conductivity at room temperature that is between the conductivity of a conductor (such as copper) and the conductivity of an insulator (such as glass), preferably a semiconductor, a material whose conductivity increases with temperature.

[0165] Therefore, according to the present invention, the term "semiconductor nanoparticles" means a material having an electrical conductivity at room temperature that is between the conductivity of a conductor (such as copper) and the conductivity of an insulator (such as glass), preferably a semiconductor whose conductivity increases with temperature and whose size is between 0.1nm and 999nm, preferably 0.5nm to 150nm, and more preferably 1nm to 50nm.

[0166] According to the present invention, the term "size" means the average diameter of a circle whose area is equivalent to the measured TEM projection of the semiconductor nano-sized luminescent particles.

[0167] In a preferred embodiment of the present invention, the semiconductor light-emitting nanoparticles of the present invention are quantum-sized materials.

[0168] According to the present invention, the term "quantum sized" means the size of the first semiconductor nanoparticle itself without ligands or another surface modification, which may show quantum confinement effects as described in, for example, ISBN: 978-3-662-44822-9.

[0169] Generally speaking, it is said that due to the "quantum confinement" effect, the quantum-sized material can emit tunable, sharp and vivid colored light.

[0170] In some embodiments of the present invention, the overall structure of the quantum-sized material has a size of 1 nm to 50 nm.

[0171] In a preferred embodiment of the present invention, the average diameter of the first semiconductor nanoparticles (cores) is in the range of 1 to 20 nm, preferably, it is in the range of 1.5 to 12 nm.

[0172] The average diameter of the semiconductor luminescent nanoparticles (cores) was calculated based on 100 semiconductor luminescent nanoparticles in a TEM image taken by a Tecnai G2 Spirit Twin T-12 transmission electron microscope. The average diameter of the semiconductor luminescent nanoparticles was calculated using the Fiji_ImageJ program.

[0173] According to the present invention, the semiconductor luminescent nanoparticle may have a core-shell structure. If the semiconductor luminescent nanoparticle does not have any shell layer, the term "core" refers to the semiconductor luminescent nanoparticle itself.

[0174] In some embodiments of the invention, the core comprises at least one element of Group 12 or Group 13 of the Periodic Table and one element of Group 15 or 16 of the Periodic Table.

[0175] In a preferred embodiment of the present invention, the first semiconductor material (hereinafter referred to as the "core" of the semiconductor luminescent nanoparticle) comprises at least one element of Group 13 of the periodic table and one element of Group 15 of the periodic table. Preferably, the element of Group 13 is In, and the element of Group 15 is P.

[0176] 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.

[0177] In some embodiments, the core is a material comprising, for example, ZnO, FeO, Fe 2 O 3 、ZrO 2 , CuO, SnO, Cu 2 O、TiO 2 , WO 3 , HfO2 、In 2 O 3 、MgO、Al 2 O 3 and metal oxides of any combination thereof.

[0178] In some embodiments, the core comprises a metal such as Au, Ag, W, Pd, Pt, Cu, In, Ti, Zn, Pb, Al, Cd, Zn, and any combination of these.

[0179] 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.

[0180] According to the present invention, the shape type of the core of the semiconductor light-emitting nanoparticle and the shape of the semiconductor light-emitting nanoparticle to be synthesized are not particularly limited.

[0181] For example, spherical, elongated, star-shaped, polyhedral, pyramidal, tetrapod-shaped, tetrahedral, plate-shaped, cone-shaped, and irregularly shaped cores and - or semiconductor luminescent nanoparticles can be synthesized.

[0182] -Shell

[0183] According to the present invention, in a preferred embodiment, the core is slightly embedded in the first shell, more preferably, the core is completely embedded in one or more shells. In a preferred embodiment of the present invention, the shell (one or more) is placed between the core and the outer layer. In other words, the semiconductor luminescent nanoparticles of the present invention may optionally comprise, consist essentially of, or consist of a core, one or more shells covering the core, and an outer layer covering the shell in this order.

[0184] -First Shell

[0185] In some embodiments of the present invention, the shell comprises at least one metal cation and at least one divalent anion as described in the outer layer portion and / or at least the first element of Group 12 of the periodic table and a Se atom or a S atom, preferably, the first element is Zn.

[0186] For example, the first shell is selected from Cs 2 S、Cs 2 Se, Cs 2 Te, Cs 2 O、Ag 2 S, Ag 2 Se, Ag 2Te、No 2 Oh、Me 2 S、I 2 Or、I 2 You、I 2 O、Cu 2 S、Cu 2 If、With 2 You、Cu 2 O、ZnS、ZnSe、ZnTe、ZnO、CdS、CdSe、CdTe、CdO、CaS、CaSe、CaTe 、CaO、NiS、NiC、NiTe、NiO、MgS、MgSe、MgTe、MgO、HgS、HgSe、Hg Te、HgO、PbS、PbSe、PbTe、PbO、CuS、CuSe、CuTe、CuO、CoS、CoSe 、CoTe、CoO、SrO、SrS、SrSe、CoTe、SrO、FeS、FeSe、FeO、FeTe、In 2 S 3 ,My 2 This 3 ,My 2 Tea 3 ,My 2 Oh 3 、No 2 S 3 、No 2 This 3 、No 2 Tea 3 、No 2 Oh 3 、Wind 2 S 3 、Wind 2 This 3 、Wind 2 Tea 3 、Wind 2 Oh 3 、Faith 2 S 3 、Faith 2 This 3 、Faith 2 Tea 3 、Faith 2 Oh 3 、TiS 2 、Tell yourself 2 、Tea 2 、TiO 2 、Yes 2 、Yes 2 、Yes 2 、SiO 2 、ZrS2 、ZrSe 2 、ZrTe 2 、ZrO 2 , HfS 2 , HfSe 2 、HfTe 2 , HfO 2 、SnS 2 SnSe 2 SnTe 2 SnO 2 ,GeS 2 ,GeSe 2 , Gete 2 、GeO、CuInZnS、CuInS 2 、CuInZnSe、CuInSe 2 ,AgInZnS,AgInZnSe,CuGaZnS,CuGaZnSe,CuFeS 2 ,CuFeSe 2 and groups consisting of any combination of these.

[0187] Preferably, it is selected from the group consisting of ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, CaS, CaSe, CaTe, CaO, NiS, NiSe, NiTe, NiO, MgS, MgSe, MgTe, MgO, HgS, HgSe, HgTe, HgO, PbS, PbSe, PbTe, PbO, CuS, CuSe, CuTe, CuO, CoS, CoSe, CoTe, CoO, SrO, SrS, SrSe, CoTe, SrO, FeS, FeSe, FeO, FeTe and any combination of these materials.

[0188] More preferred are: ZnS, ZnSe, ZnTe, ZnO or any combination of these materials.

[0189] In some embodiments of the present invention, at least one (first) shell comprises or consists of a first element of group 12 of the periodic table and a second element of group 16 of the periodic table, preferably, the first element is Zn, and the second element is S, Se or Te; preferably, the first shell directly covering the core comprises or consists of a first element of group 12 of the periodic table and a second element of group 16 of the periodic table, preferably, the first element is Zn, and the second element is S, Se or Te.

[0190] 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);

[0191] ZnS x Se y Te z -(XI)

[0192] 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, preferably, the shell layer is ZnSe, ZnS x Se y 、ZnS、ZnSe y Te z or ZnS x Te z .

[0193] In some embodiments of the present invention, the shell layer is an alloyed shell layer or a graded shell layer. Preferably, the graded shell layer is ZnS x Se y 、ZnSe y Te z or ZnS x Te z , more preferably, it is ZnS x Se y .

[0194] In some embodiments of the present invention, the semiconductor luminescent nanoparticle further comprises a second shell layer on the shell layer. Preferably, the second shell layer comprises or consists of a third element of group 12 of the periodic table and a fourth element of group 16 of the periodic table. More preferably, the third element is Zn, and the fourth element is S, Se or Te, with the restriction that the fourth element and the second element are not the same.

[0195] In some embodiments of the present invention, optionally, the first semiconductor nanoparticle and the first shell layer as the core may be at least partially embedded in the second shell. Preferably, the first semiconductor nanoparticle is completely embedded in the shell layer.

[0196] For example, the second shell is selected from the group consisting of: Cs 2 S、Cs 2 Se, Cs 2 Te, Cs 2 O、Ag 2 S, Ag 2 Se, Ag 2 Te、Ag 2 O. Au 2 S.Au 2 Se, Au 2 Te, Au 2 O, Cu 2S、Cu 2 If、With 2 You、Cu 2 O、ZnS、ZnSe、ZnTe、ZnO、CdS、CdSe、CdTe、CdO、CaS、CaSe、CaTe 、CaO、NiS、NiC、NiTe、NiO、MgS、MgSe、MgTe、MgO、HgS、HgSe、Hg Te、HgO、PbS、PbSe、PbTe、PbO、CuS、CuSe、CuTe、CuO、CoS、CoSe 、CoTe、CoO、SrO、SrS、SrSe、CoTe、SrO、FeS、FeSe、FeO、FeTe、In 2 S 3 ,My 2 This 3 ,My 2 Tea 3 ,My 2 Oh 3 、No 2 S 3 、No 2 This 3 、No 2 Tea 3 、No 2 Oh 3 、Wind 2 S 3 、Wind 2 This 3 、Wind 2 Tea 3 、Wind 2 Oh 3 、Faith 2 S 3 、Faith 2 This 3 、Faith 2 Tea 3 、Faith 2 Oh 3 、TiS 2 、Tell yourself 2 、Tea 2 、TiO 2 、Yes 2 、Yes 2 、Yes 2 、SiO 2 、ZrS 2 、ZrSe 2 、ZrTe 2 、ZrO 2 、HfS 2 、HfSe 2 、HfTe2 , HfO 2 、SnS 2 SnSe 2 SnTe 2 SnO 2 ,GeS 2 ,GeSe 2 , Gete 2 、GeO、CuInZnS、CuInS 2 、CuInZnSe、CuInSe 2 ,AgInZnS,AgInZnSe,CuGaZnS,CuGaZnSe,CuFeS 2 ,CuFeSe 2 and any combination of these.

[0197] Preferably, it is selected from the group consisting of ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, CaS, CaSe, CaTe, CaO, NiS, NiSe, NiTe, NiO, MgS, MgSe, MgTe, MgO, HgS, HgSe, HgTe, HgO, PbS, PbSe, PbTe, PbO, CuS, CuSe, CuTe, CuO, CoS, CoSe, CoTe, CoO, SrO, SrS, SrSe, CoTe, SrO, FeS, FeSe, FeO, FeTe and combinations of any of these materials.

[0198] More preferred are: ZnS, ZnSe, ZnTe, ZnO or any combination of these materials.

[0199] In some embodiments of the present invention, the second shell comprises at least a first element of group 12 of the periodic table and a second element of group 16 of the periodic table, preferably, the first element is Zn, and the second element is S, Se, O or Te.

[0200] In a preferred embodiment of the present invention, the second shell is represented by the following formula (XI'): ZnS x Se y Te z -(XI′)

[0201] Where 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, with the restriction that the first shell and the second shell are different.

[0202] In some embodiments of the present invention, the second shell layer may be an alloyed shell layer.

[0203] In some embodiments of the present invention, the semiconductor luminescent nanoparticle may further comprise one or more additional shell layers on the second shell layer as a multi-shell.

[0204] According to the invention, the term "multi-shell" stands for stacked shells consisting of three or more shells.

[0205] For example, as the shell layer, CdS, CdZnS, CdS / ZnS, CdS, ZnS, ZnS / ZnSe, ZnSe / ZnS or any combination thereof can be used, preferably ZnS, ZnSe or ZnSe / ZnS.

[0206] For example, as a semiconductor light-emitting material with a core / shell structure, CdSe / CdS, CdSeS / CdZnS, CdSeS / CdS / ZnS, ZnSe / CdS, CdSe / ZnS, InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InZnP / ZnS, InZnP / ZnSe, InZnP / ZnSe, InZnP / ZnSe / ZnS, InGaP / ZnS, InGaP / ZnSe, InGaP / ZnSe / ZnS, InZnPS / ZnS, InZnPS / ZnSe, InZnPS / ZnSe / ZnS, ZnSe / CdS, ZnSe / ZnS or any combination of these can be used. Preferred are InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InZnP / ZnS, InZnP / ZnSe, InZnP / ZnSe / ZnS, InGaP / ZnS, InGaP / ZnSe, and InGaP / ZnSe / ZnS.

[0207] Such semiconductor luminescent nanoparticles are publicly available (eg, from Sigma Aldrich) and / or can be synthesized using methods described in, for example, US 7,588,828 B, US 8,679,543 B, and Chem. Mater. 2015, 27, pp. 4893-4898.

[0208] -Organic part

[0209] In a preferred embodiment of the present invention, the organic moiety is represented by the following chemical formula (I);

[0210] AB-*(I)

[0211] in

[0212] A is an organic group, preferably, the organic group is a hydrocarbon group (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group, including an aryl, an alkaryl, an alkyl or an aralkyl, an alkylamine, a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group, including a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl or a fluoroaralkyl;

[0213] B is a connecting unit, preferably, B is **-(U) o -(Y) m -(CR IIa R IIb ) n , where “**” indicates the point of connection to “A”; and

[0214] "*" indicates the point of attachment to the anion in the outer layer.

[0215] More preferably, the organic moiety is represented by the following chemical formula (II), (III) or (III′);

[0216] L-(U) o -(Y) m -(CR IIa R IIb ) n -*(II)

[0217] in

[0218] L is an organic group, preferably, the organic group is a hydrocarbon group (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group, including an aryl, an alkaryl, an alkyl or an aralkyl, an alkylamine, a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group, including a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl or a fluoroaralkyl;

[0219] U is O, CH 2 Or C=O;

[0220] Y is O, CH 2 Or C=O;

[0221] R IIa and R IIb Each occurrence is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIa and R IIb is a hydrogen atom;

[0222] n is an integer of 1 or greater;

[0223] m is 0 or an integer of 1 or greater, preferably, m is 1;

[0224] o is 0 or an integer of 1 or greater, preferably, o is 1;

[0225] "*" indicates the point of attachment to the anion in the outer layer;

[0226] *-(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z(III)

[0227] *-(CR IIIg R IIIh ) q -(V) r -(OCR IIIa R IIIb CR IIIc R IIId ) p -Z(III′)

[0228] in

[0229] R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and R IIIh Each occurrence is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIIg and R IIIh is a hydrogen atom, preferably, R IIIe and R IIIf is a hydrogen atom; V is O, CH 2 Or C=O;

[0230] Z is a hydrogen atom or an organic group. Preferably, Z is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, -COOH, -SH or -NH 2, alkylamine, fluoroaryl, fluoroalkylaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, including fluoroaryl, fluoroalkylaryl, fluoroalkyl or fluoroaralkyl, preferably, Z is a hydrogen atom, a straight chain alkyl group having 1 to 25 carbon atoms, a branched chain alkyl group having 3 to 25 carbon atoms, more preferably, it is a hydrogen atom, a straight chain alkyl group having 1 to 15 carbon atoms, a branched chain alkyl group having 3 to 15 carbon atoms, even more preferably, it is a hydrogen atom or a straight chain alkyl group having 1 to 10 carbon atoms;

[0231] a is 0 or an integer of 1 or greater, preferably 0≤a≤25, more preferably 0≤a≤15, even more preferably 1≤a≤10;

[0232] 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 further preferably 4≤p≤18;

[0233] 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 further, preferably, it is 1≤q≤5;

[0234] r is 0 or integer 1;

[0235] "*" indicates the point of attachment to the anion in the outer layer.

[0236] Even more preferably, the organic moiety is represented by the following chemical formula (IV):

[0237] *-(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z′(IV)

[0238] in

[0239] R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and R IIIhEach occurrence is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIIg and R IIIh is a hydrogen atom, preferably, R IIIe and R IIIf is a hydrogen atom;

[0240] a is 0 or an integer of 1 or greater, preferably 0≤a≤25, more preferably 0≤a≤15, even more preferably 1≤a≤10;

[0241] 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 further preferably 4≤p≤18;

[0242] 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 more preferably, it is 1;

[0243] V is O, CH 2 Or C=O;

[0244] Z′ is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, a branched-chain alkyl group having 3 to 25 carbon atoms, an alkylamine, a fluoroaryl group, a fluoroalkylaryl group, a fluoroalkyl group, a fluoroaralkyl group, a heteroaromatic group, including a fluoroaryl group, a fluoroalkylaryl group, a fluoroalkyl group or a fluoroaralkyl group, preferably, Z′ is a straight-chain alkyl group having 1 to 25 carbon atoms, a branched-chain alkyl group having 3 to 25 carbon atoms or a hydrogen atom, more preferably, it is a straight-chain alkyl group having 1 to 15 carbon atoms, a branched-chain alkyl group having 3 to 15 carbon atoms or a hydrogen atom, even more preferably, it is a hydrogen atom;

[0245] r is 0 or integer 1;

[0246] "*" indicates the point of connection to the anion in the outer shell, preferably, it is connected via a S or Se atom in the outer shell.

[0247] In some preferred embodiments, the organic moiety is CH 3 -(CH 2 ) 7＜n＜18 -* and connected to the S or Se atom in the outer shell.

[0248] In a preferred embodiment of the present invention, the organic moiety selected from chemical formula (I), (II), (III), (III') or (IV) is covalently bound to anions in the inorganic lattice of the outer layer, preferably, it is not removed by ligand exchange.

[0249] Crystal-bound ligands (covalently bound ligands) can be characterized as described in Reference Example 7.

[0250] For example, the organic part may preferably be described as follows.

[0251] *-CH 2 -(OCH 2 CH 2 ) 4 -O-CH 3

[0252] *-CH 2 -(OCH 2 CH 2 ) 6 -O-CH 3

[0253] *-CH 2 -(OCH 2 CH 2 ) 8 -O-CH 3

[0254] *-(CH 2 ) 2 -(OCH 2 CH 2 ) 2 -O-CH 3

[0255] *-(CH 2 ) 2 -(OCH 2 CH 2 ) 6 -O-CH 3

[0256] *-(CH 2 ) 2 -(OCH 2 CH 2 ) 8 -O-CH 3

[0257] *-(CH 2 ) 2 -(OCH 2 CH 2 ) 6 -CH 3

[0258] *-(CH 2 ) 2 -(OCH 2 CH 2 )6 -O-(CH 2 ) 2 -SH

[0259] *-(CH 2 ) 7- CH 3

[0260] *-(CH 2 ) 11- CH 3

[0261] *-(CH 2 ) 17- CH 3

[0262] *-(CH 2 ) 2 -(OCH 2 CH 2 ) 6 -O-CH 3

[0263] *-(CH 2 ) 2 -(OCH 2 CH 2 ) 16 -O-CH 3

[0264] *-(CH 2 ) 2 -(OCH 2 CH 2 ) 17 -O-CH 3

[0265] "*" indicates the point of attachment to an S atom or a Se atom in the outer shell; or

[0266] *-(CH 2 ) 11- CH 3

[0267] “*” indicates the connection point to the Se atom or S atom in the outer layer.

[0268] Other thiolated ligand materials (such as polypropylene glycol and polypropylene glycol monomethyl ether, thiolated ligand materials described in US11021651B2, formula (I) in columns 17 to 18, column 25, line 28 to column 26, line 16, formula (II), M1000-SH in Example 1) can also be used as a source of organic moieties and the resulting covalently bound organic moieties are included in this patent application.

[0269] It is believed that the organic moiety prevents aggregation of the nanoparticles or nano-sized materials and that the organic moiety allows the nanoparticles to be dispersed in an organic medium and / or an aqueous medium.

[0270] In particular, it is believed that the organic part of the anion directly attached to the outer layer of the light-emitting part via a covalent bond can achieve one or more of the technical effects of the present invention when it is mixed with the reactive monomer of the present invention or a mixture of two or more reactive monomers. Preferably, the reactive monomer or two or more reactive monomers of the monomer mixture are (meth) acrylate monomers. More preferably, it is a specific (meth) acrylate monomer as defined in the following reactive monomer section. It is believed that this specific combination of the covalently bound organic part directly attached to the light-emitting part and the light-emitting part on the outer layer of the specific (meth) acrylate monomer can surprisingly improve the thermal stability of the obtained layer (film), the thermal stability of the light-emitting part in the layer (film), the dispersibility of the light-emitting part in the composition, the dispersion of the light-emitting part in the obtained layer that enables the light-emitting part and the matrix material to phase separate after curing to achieve the improved haze value of the cured film (cured composition), and the long-term quantum yield (QY) stability of the light-emitting part in the composition in longer storage with or without light irradiation. , long-term external quantum efficiency (EQE) stability of the light-emitting part in the composition during longer-term storage with or without light irradiation, long-term quantum yield (QY) stability of the light-emitting part in the obtained layer (film) during longer-term storage with or without light irradiation, long-term external quantum efficiency (EQE) stability of the light-emitting part in the obtained layer (film) during longer-term storage with or without light irradiation, good compatibility of the light-emitting part in the composition and / or the obtained layer (film) with the matrix material, and / or easy processing of the composition containing the light-emitting part and the matrix material.

[0271] In some embodiments, the organic moiety may comprise a zwitterionic group.

[0272] -Outer layer

[0273] According to the invention, the semiconductor nanoparticle comprises an outer layer covering at least a portion of the core, which comprises at least one metal cation and at least one divalent anion,

[0274] Wherein the divalent anion is selected from Se 2- , S 2- 、Te 2- , O 2- or any combination thereof, preferably, the metal cation is a monovalent, divalent, trivalent or tetravalent cation, more preferably, the metal cation is selected from Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr2+ , Fe 2+ , Hg 2+ Mg 2+ and Pb 2+ The divalent cations of the group consisting of or selected from Ti 4+ ,Ge 4+ 、Si 4+ 、Zr 4+ , Hf 4+ Sn 4+ The group consisting of tetravalent cations,

[0275] In some embodiments, the cation is selected from Cs + 、Ag + 、Au + , Cu +1 The monovalent cations of the group consisting of or selected from Zn 2+ , Fe +2 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ , Cu +2 The divalent cations of the group consisting of or selected from the group Fe +3 、In +3 、Bi +3 , Ga +3 trivalent cations selected from Ti 4+ ,Ge 4+ 、Si 4+ 、Zr 4+ , Hf 4+ Sn 4+ 、Si +4 The group consisting of tetravalent cations.

[0276] In some embodiments of the invention, the outer layer comprises at least two or three different metal cations, such as Cu 1+ and 3+ , Cu 1+ and Ga 3+ Combination of Ag 1+ and Ga 3+ Combination or 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 combination.

[0277] In a preferred embodiment, the metal cation is selected from Fe +2 、Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ , Cu +2 Composed of a group of divalent cations.

[0278] In a preferred embodiment of the present invention, the outer layer comprises, consists essentially of, or consists of a material represented by the following chemical formula (VI),

[0279] QP 1-2h A h (VI)

[0280] Where Q is selected from Se 2- , S 2- 、Te 2- and O 2- a divalent anion of one or more members of the group consisting of;

[0281] P is a divalent metal cation, preferably, P is selected from Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ a divalent cation of one or more members of the group consisting of;

[0282] A is a tetravalent cation, preferably, A is selected from Ti 4+ ,Ge 4+ 、Si 4+ Sn 4+ one or more members of a group consisting of; and

[0283] 0≤h≤0.5.

[0284] For example, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, ZnNiS, ZnNiSe, ZnGeS, ZnGeO, ZnCaS, NiSe, TiGeSeS, ZnTiS, CuInZnS, CuInZnSe, AgInZnS and / or AgInZnSe may be used.

[0285] According to the present invention, preferably, the outer layer is a single layer.

[0286] More preferably, it is the last monolayer of the semiconductor nanoparticle covering the core. If there are one or more shell layers covering the core, the outer layer covers the shell layer.

[0287] 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, 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 higher 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 lower concentration on the opposite side of the shell layer.

[0288] In some embodiments of the present invention, the surface of the luminescent moiety (ie, semiconductor luminescent nanoparticle) may be over coated with one or more surface ligands in addition to the organic moiety of the present invention.

[0289] Without wishing to be bound by theory, it is believed that such surface ligands may cause the nano-sized fluorescent material to be more easily dispersed in the solvent.

[0290] 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, when the organic part of the thiol may contain a straight chain or branched When the organic part of selenol can include a linear or branched alkyl chain, it can be saturated or include one or more unsaturated carbon bonds and / or aromatic rings, such as octadecyl mercaptan, hexadecyl mercaptan, dodecanethiol, hexanethiol and polyethylene glycol mercaptan; selenol, when the organic part of selenol can include a linear or branched alkyl chain, it can be saturated or include 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 any combination of these. In addition, the ligand can include Zn oleate, Zn acetate, Zn myristic acid, Zn stearate, Zn laurate and other carboxylic acids, Zn isostearate, sulfonic acid, halide, carbamate.

[0291] Examples of surface ligands have been described, for example, in Published International Patent Application No. WO2012 / 059931A.

[0292] -Quantum yield measurement

[0293] 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).

[0294] Preferably, the nanoparticles emit light having a peak maximum light emission wavelength in the range of 350 nm to 3500 nm, preferably 350 nm to 2000 nm, more preferably 400 nm to 800 nm, even more preferably 430 nm to 700 nm.

[0295] - Analysis of nanoparticles (preferably quantum dots (QD)) by GCMS

[0296] According to the present invention, gas chromatography mass spectrometry (GCMS) was performed using an Agilent Technologies 7890B GC system equipped with an autosampler and an Agilent DB-5 column and an MS instrument Agilent Technologies 5977B MSD. The analytes were separated using the following injection method: initial temperature 100°C, maintained at 100°C for 0 minutes; heated to 340°C at a rate of 8°C / min, and maintained at 340°C for 15 minutes.

[0297] Samples for GCMS were prepared as follows:

[0298] 3.1 Weigh the starting materials.

[0299] 3.2 Calculate the organic matter content based on TGA measurements.

[0300] 3.3 For every 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 (QD)). If color still exists, use ultrasonic treatment and vortex (Vortex).

[0301] 3.4 Place a magnetic stirrer and heat the solution at 60°C for 20 minutes (do not heat in a closed flask! Make sure the stopper is partially open)

[0302] 3.5 Transfer the solution to a separatory funnel and add toluene (10 ml for 30 mg of organic material).

[0303] 3.6 Extract the aqueous phase and remove the lower aqueous phase.

[0304] 3.7 Add 20 ml of distilled water to the funnel and extract the toluene phase again.

[0305] 3.8 Repeat the extraction of the toluene phase with water at least 3 times or until the aqueous phase has the pH of distilled water (about 5).

[0306] 3.9 Collect the upper phase into a flask containing MgSO4 for at least 30 minutes. Filter the MgSO4 solid.

[0307] 3.10 Transfer the toluene mixture to a GC vial for injection.

[0308] -Reactive monomers

[0309] It is believed that lower viscosity is important for preparing low viscosity compositions suitable for inkjet printing. Therefore, (meth)acrylate monomers having viscosity values ​​within the parameter ranges mentioned above are particularly suitable for preparing compositions for inkjet printing. By using these (meth)acrylate monomers in the composition, when it is mixed with another material (such as semiconductor light-emitting nanoparticles with high loading), the composition can still maintain a lower viscosity within a range suitable for inkjet printing.

[0310] Furthermore, it is believed that 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 light-emitting portion comprising an outer layer containing a metal cation and a divalent anion, and

[0311] The combination of one or more types of organic moieties directly attached to the anions of the outer layer via covalent bonds; can particularly improve the optical properties of the light-emitting part in the obtained layer (film).

[0312] It is also believed that the combination may also lead to improved thermal stability of the obtained layer (film), thermal stability of the light-emitting part in the layer (film), dispersibility of the light-emitting part in the composition, dispersion of the light-emitting part in the obtained layer so that the light-emitting part and the matrix material can be phase-separated after curing to achieve improved haze value of the cured film (cured composition), long-term quantum yield (QY) stability of the light-emitting part in the composition in longer-term storage with or without light irradiation, long-term external quantum efficiency (EQE) stability of the light-emitting part in the composition in longer-term storage with or without light irradiation, long-term quantum yield (QY) stability of the light-emitting part in the obtained layer (film) in longer-term storage with or without light irradiation, long-term external quantum efficiency (EQE) stability of the light-emitting part in the obtained layer (film) in longer-term storage with or without light irradiation, good compatibility of the light-emitting part in the composition and / or the obtained layer (film) with the matrix material, and / or easy handling of the composition containing the light-emitting part and the matrix material.

[0313] In a preferred embodiment of the present invention, the boiling point (BP) of the reactive monomer is 95°C or higher, preferably, it is in the range of 95°C to 350°C for large-area uniform inkjet printing.

[0314] It is believed that this high boiling point is also important for preparing compositions with lower vapor pressures, preferably less than 0.001 mmHg, for large-area uniform printing. 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, it is in the range of 95°C to 350°C) to prepare compositions suitable for large-area uniform inkjet printing, even if they are mixed with a high load of another material (such as a high load of semiconductor light-emitting nanoparticles).

[0315] 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 methacrylate monomer and / or acrylate monomer.

[0316] According to the present invention, the BP can be estimated by a known method such as described in Science of Petroleum, Vol. II, p. 1281 (1398).

[0317] According to the present invention, any type of publicly available acrylate and / or methacrylate represented by the chemical formula (I) or (II) can be preferably used.

[0318] Particularly for the first viscosity, any type of publicly available acrylate and / or methacrylate represented by the chemical formula (I), (II) and / or (III) having a viscosity value of 25 cP or less at 25° C. may be used.

[0319] Therefore, according to the present invention, the reactive monomer of the composition is preferably a (meth)acrylate monomer selected from mono-(meth)acrylate monomers, di-(meth)acrylate monomers and / or tri-(meth)acrylate monomers.

[0320] 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.

[0321] Preferably, the di-(meth)acrylate monomer is represented by the following chemical formula (I b ) represents, 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 )express;

[0322]

[0323] in

[0324] X 1 is an unsubstituted or substituted ester group, alkyl group or aryl group, wherein one or more non-adjacent CH 2 The radical can be 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 Preferably, the ester group is composed of the following formula (I bs1 )express;

[0325]

[0326] Where R Ib1 is a single bond, an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms;

[0327] R Ib2 is a single bond, an unsubstituted or substituted straight chain alkylene chain having 1 to 5 carbon atoms, an unsubstituted or substituted branched chain alkylene chain having 3 to 7 carbon atoms, wherein one or more non-adjacent CH 2 The radical can be 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 Alternative; preferably, R Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, wherein non-adjacent CH 2 At least one of the groups may be substituted by 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 Replacement;

[0328] X 2 is an unsubstituted or substituted ester group, alkyl group or aryl group, wherein one or more non-adjacent CH 2The radical can be 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 Preferably, the ester group is composed of the following formula (I bs2 )express;

[0329]

[0330] Where R Ibs1 is a single bond, an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms;

[0331] R Ibs2 is a single bond, an unsubstituted or substituted straight chain alkylene chain having 1 to 5 carbon atoms, an unsubstituted or substituted branched chain alkylene chain having 3 to 7 carbon atoms, wherein one or more non-adjacent CH 2 The radical can be 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 Alternative; preferably, R Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, wherein non-adjacent CH 2 At least one of the groups may be substituted by 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 Replacement;

[0332] R 1 is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, or an aryl group, wherein one or more non-adjacent CH 2 The radical can be 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 Replace; or X 1 is an ester group; preferably, the ester group is a carboxylic acid group;

[0333] R 2is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, or an aryl group, wherein one or more non-adjacent CH 2 The radical can be 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 Replace; or X 1 is an ester group; preferably, the ester group is a carboxylic acid group;

[0334] Preferably, the symbol X 1 Formula (I bs1 ) or The "*" on the left side of the formula represents the terminal group C=CR of formula (I). 1 The connection point of the carbon atom and the "*" on the right side represent the symbol X of formula (I) 2 The connection point;

[0335] n is 0 or 1;

[0336] Preferably, the symbol X 2 Formula (I bs2 ) or The "*" on the left side of the formula represents the connection point with the symbol X1 of formula (I) and the "*" on the right side represents the terminal group C=CR of formula (I) 2 The connection point;

[0337] m is 0 or 1;

[0338] Preferably, at least m or n is 1;

[0339] R 3 is a linear alkylene chain or alkyleneoxy 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. Preferably, R 3 is a linear alkylene chain or alkyleneoxy chain having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms,

[0340] It can be substituted by one or more groups R a Substitution, where one or more non-adjacent CH 2 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=NRa ,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 NO 2 Replacement;

[0341] R 4 is a linear alkylene chain or alkyleneoxy 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. Preferably, R 4 is a linear alkylene chain or alkyleneoxy chain having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms,

[0342] It can be substituted by one or more groups R a Substitution, where one or more non-adjacent CH 2 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 NO 2 Replacement;

[0343] R a is, identically or differently on each occurrence, H, D or an alkyl radical having 1 to 20 carbon atoms, a cyclic alkyl radical or alkoxy radical 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, whereby an H atom may be replaced by D, F, Cl, Br, I; here two or more adjacent substituents R a They may also form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system with each other;

[0344]

[0345] X 3 is an unsubstituted or substituted ester group, an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, if X 3 is an unsubstituted or substituted ester group, the ester group is represented by the following formula (II bs )express;

[0346]

[0347] Where R IIb1 is a single bond, an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms;

[0348] R IIb2 is a substituted or unsubstituted alkyl group, a cyclic group, a cycloalkyl group, an aryl group or an alkoxy group.

[0349] Preferably, the symbol X 3 Formula (II bs ) or

[0350] The "*" on the left side of the above formula represents the terminal group C=CR of formula (I) 5 The connection point;

[0351] l is 0 or 1;

[0352] R 5 is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, an aryl group, an alkoxy group, an ester group or a carboxylic acid group;

[0353] R 6 is a linear alkylene chain or alkyleneoxy chain having 1 to 25 carbon atoms, preferably, R 6 is a linear alkylene chain or alkyleneoxy chain having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms, which may be substituted by one or more radicals R a Substitution, where one or more non-adjacent CH 2 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 NO 2 Replacement;

[0354] R 7 is a linear alkylene chain or alkyleneoxy chain having 1 to 25 carbon atoms, preferably, R 7is a linear alkylene chain or alkyleneoxy chain having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms, which may be substituted by one or more radicals R a Substitution, where one or more non-adjacent CH 2 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 NO 2 Replacement;

[0355] R a is, identically or differently on each occurrence, H, D or an alkyl radical having 1 to 20 carbon atoms, a cyclic alkyl radical or alkoxy radical 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, whereby an H atom may be replaced by D, F, Cl, Br, I; here two or more adjacent substituents R a They may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.

[0356]

[0357] Where R 9 is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, or a radical of the formula (IV b ) represented by (meth)acryloyl

[0358]

[0359] R 10 is a hydrogen atom, a straight chain alkyl group having 1 to 25 carbon atoms, or a radical of the formula (V b ) represented by (meth)acryloyl

[0360]

[0361] R 11 is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, or a radical of the formula (VI b ) represented by (meth)acryloyl

[0362]

[0363] Where R 8 , R 8a , R 8b and R 8c Each occurrence is, independently or mutually, H, CH 3 or CH 2 CH 3 ;

[0364] Where R 9 , R 10 and R 11 At least one of them is a (meth)acryloyl group, preferably, R 9 , R 10 and R 11 Wherein two are (meth)acryloyl groups and the other is a hydrogen atom or a linear alkyl group having 1 to 25 carbon atoms, preferably, the electrical conductivity (S / cm) of the (meth)acrylate monomer of formula (III) is 1.0*10 -10 or lower, preferably, it is 5.0*10 -11 or lower, more preferably, it is 5.0*10 -11 Up to 1.0*10 -15 In the range of 5.0*10 -12 Up to 1.0*10 -15 within the range.

[0365] More preferably, the reactive monomer is represented by formula (II).

[0366] 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).

[0367] In a preferred embodiment of the present invention, the (meth)acrylate monomer of formula (II) is 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, even more preferably, it is 15:85 to 40:60. Preferably, purified (meth)acrylate monomers represented by at least formula (I) and (II) are used in the composition. More preferably, the (meth)acrylate monomer of formula (I) and the (meth)acrylate monomer of formula (II) are both obtained or obtainable by a purification method.

[0368] In a preferred embodiment, the boiling point (BP) of the (meth)acrylate monomer of formula (I) and / or formula (II) is 95°C or higher, preferably, the (meth)acrylate monomer of formula (I) and formula (II) is 100°C or higher, more preferably, it is in the range of 100°C to 350°C, even more preferably, the boiling point (BP) of the (meth)acrylate monomer of formula (I) is in the range of 100°C 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.

[0369] 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, even more preferably 2 to 25 cP.

[0370] According to the present invention, the viscosity can be measured at room temperature by a vibration type viscometer VM-10A (SEKONIC).

[0371] https: / / www.sekonic.co.jp / english / product / viscometer / vm / vm_series.html

[0372] - (meth)acrylate monomer represented by chemical formula (I) as a matrix material

[0373] In addition, preferably, (I bs1 ) Ib1 is a single bond, (I bs2 ) Ibs1 is a single bond, (I bs1 ) Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, R Ibs2 is a single bond, an unsubstituted straight alkylene chain having 1 to 5 carbon atoms, an unsubstituted branched alkylene chain having 3 to 7 carbon atoms, wherein one or more non-adjacent CH 2 The group may be replaced by an oxygen atom; or the R 3 and R of formula (I) 4 Each is independently selected from the following groups.

[0374]

[0375]

[0376] Particularly preferably, the R 3 and R 4 is independently or differently selected at each occurrence from the following groups.

[0377]

[0378] Where "*" indicates the point of attachment to the oxygen atom of the formula or in R 3 In the case of X 2 and wherein "*" represents the point of attachment to the oxygen atom of the formula or at R 4 In the case of X 1 connection point.

[0379] Particularly preferably, the formula (I) is NDDA (nonanediol diacrylate), HDDMA (hexanediol dimethacrylate), HDDA (hexanediol diacrylate) or DPGDA (DPGDA=dipropylene glycol diacrylate).

[0380]

[0381] - (Meth)acrylate monomer represented by chemical formula (II)

[0382] It is believed that the (meth)acrylate monomer represented by the following chemical formula (II) shows a much lower viscosity value than the viscosity of the (meth)acrylate monomer of formula (I). Therefore, by using the (meth)acrylate monomer represented by the chemical formula (II) in combination with the (meth)acrylate monomer of the chemical formula (I), a composition having a much lower viscosity required for smooth inkjet printing can be achieved, preferably without reducing the external quantum efficiency (EQE) value.

[0383] It is believed that this combination can achieve a low viscosity composition comprising a high content of another material (such as a high loading of semiconductor light-emitting nanoparticles). Therefore, when the composition comprises another material, it is particularly suitable for inkjet printing.

[0384] Furthermore, preferably, (II bs ) IIb1 is a single bond, (II bs ) IIb2 is a substituted or unsubstituted alkyl, cyclyl or cycloalkyl group; (II bs ) IIb2 It can be selected from the following groups.

[0385]

[0386]

[0387] or the R of formula (II) 7 is independently or differently selected at each occurrence from the following groups, wherein the group may be a substituted, preferably, without Ra replace.

[0388] <![CDATA[*-(CH 2 ) 6 -CH 3 ]]> <![CDATA[*-(CH 2 ) 7 -CH 3 ]]> <![CDATA[*-(CH 2 ) 8 -CH 3 ]]> <![CDATA[*-(CH 2 ) 9 -CH 3 ]]> <![CDATA[*-(CH 2 ) 10 -CH 3 ]]> <![CDATA[*-(CH 2 ) 11 -CH 3 ]]> <![CDATA[*-(CH 2 ) 12 -CH 3 ]]> <![CDATA[*-(CH 2 ) 4 -OH]]> <![CDATA[*-(CH 2 ) 2 -OH]]> <![CDATA[*-(CH 2 ) 6 -OH]]> <![CDATA[*-(CH 2 ) 3 -OH]]> <![CDATA[*-(CH 2 ) 5 -OH]]>

[0389] The "*" indicates the same as X 3 R 6 The connection point of (if l is 1), and it represents the connection point with X of formula (II) 3 The point of attachment of the oxygen atom of (if n is 0).

[0390] Particularly preferably, the formula (II) is lauryl methacrylate (LM, viscosity 6 cP) or lauryl acrylate (LA, viscosity 4.0 cP) or isobornyl acrylate (IBOA).

[0391] It is believed that a higher amount of the (meth)acrylate monomer of formula (II) than the total amount of the (meth)acrylate monomer of formula (I) leads to improved EQE of the composition, and from the viewpoint of the viscosity of the composition, a mixing weight ratio of the (meth)acrylate monomer of formula (II) to the total amount of the (meth)acrylate monomer of formula (I) greater than 50 wt % is preferred, and the inkjet performance of the composition is better.

[0392] Preferably, a (meth)acrylate monomer purified by using a silica gel column is used.

[0393] It is believed that the removal of impurities from the (meth)acrylate monomer by silica gel column purification results in improved QY of the semiconductor light emitting nanoparticles in the composition.

[0394] - (Meth)acrylate monomer of formula (III)

[0395] It is believed that the (meth)acrylate monomer of formula (III) can be used to improve the curability of the layer made from the composition after inkjet printing.

[0396] According to the present invention, the publicly known (meth)acrylate monomer represented by the following chemical formula (III) can be used to improve the curability of the layer after inkjet printing and crosslinking.

[0397] Very preferably, trimethylolpropane triacrylate (TMPTA) is used as the (meth)acrylate monomer of the formula (III).

[0398] In a preferred embodiment of the present invention, the amount of the (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 wt % to 25 wt %, more preferably in the range of 0.1 wt % to 15 wt %, even more preferably 1 wt % to 10 wt %.

[0399] Preferably, a (meth)acrylate monomer purified by using a silica gel column is used herein.

[0400] It is believed that the removal of impurities from the (meth)acrylate monomer by silica gel column purification results in improved QY of the semiconductor light emitting nanoparticles in the composition.

[0401] -method

[0402] 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;

[0403] (a) at least a light-emitting portion, preferably, the light-emitting portion comprises at least a first semiconductor nanomaterial as a core,

[0404] mixing with another material to obtain a reaction mixture, preferably, the other material is a solvent;

[0405] (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 formula (Va) or formula (Vb) with a metal cation precursor in the reaction mixture;

[0406] ABXH (Va)

[0407] ABXXBA (Vb)

[0408] in

[0409] A is an organic group;

[0410] B is the connection unit;

[0411] H is a hydrogen atom; and

[0412] X is an anchoring group comprising an anion capable of forming a monolayer with an added metal cation that may be derived from an added metal cation precursor;

[0413] (c) cooling the reaction mixture from step (b),

[0414] wherein the reaction mixture in step (b) is maintained at a temperature in the range of 80° C. to 200° C., preferably 100 to 200° C. to form the outer layer in step (b),

[0415] (d) mixing the light-emitting portion obtained from step (c) with at least one reactive monomer or a mixture of two or more reactive monomers to form a composition.

[0416] As anion source, preference is given to organic moieties of the formula (II′), (III′), (IIIa′) or (IV′),

[0417] L-(U) o -(Y) m -(CR IIa R IIb ) n -X 1 (II′)

[0418] in

[0419] L is an organic group, preferably, the organic group is a hydrocarbon group (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group, including an aryl, an alkaryl, an alkyl or an aralkyl, an alkylamine, a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group, including a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl or a fluoroaralkyl;

[0420] U is O, CH 2 Or C=O;

[0421] Y is O, CH 2 Or C=O;

[0422] R IIa and R IIb Each occurrence is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIa and R IIb is a hydrogen atom;

[0423] n is an integer of 1 or greater;

[0424] m is 0 or an integer of 1 or greater, preferably, m is 1;

[0425] o is 0 or an integer of 1 or greater, preferably, o is 1;

[0426] X 1 is an anchoring group, which comprises at least a divalent anion capable of being preferably covalently bonded to the metal cation, which is selected from Se 2- , S 2- 、Te 2- and O 2- One or more members of a group,

[0427] X 1 -(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId )p -(V) r -(CR IIIg R IIIh ) q -Z(III′)

[0428] X 1 -(CR IIIg R IIIh ) q -(V) r -(OCR IIIa R IIIb CR IIIc R IIId ) p -Z(IIIa′)

[0429] in

[0430] R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and R IIIh is independently selected at each occurrence from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIIg and R IIIh is a hydrogen atom, preferably, R IIIe and R IIIf is a hydrogen atom;

[0431] X 1 is an anchoring group, which at least comprises a divalent anion capable of connecting to the metal cation, which is selected from Se 2- , S 2- 、Te 2- and O 2- One or more members of a group,

[0432] V is O, CH 2 Or C=O;

[0433] Z is a hydrogen atom or an organic group. Preferably, Z is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, -COOH, -SH or -NH 2, alkylamine, fluoroaryl, fluoroalkylaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, including fluoroaryl, fluoroalkylaryl, fluoroalkyl or fluoroaralkyl, preferably, Z is a hydrogen atom, a straight chain alkyl group having 1 to 25 carbon atoms, a branched chain alkyl group having 3 to 25 carbon atoms, more preferably, it is a hydrogen atom, a straight chain alkyl group having 1 to 15 carbon atoms, a branched chain alkyl group having 3 to 15 carbon atoms, even more preferably, it is a hydrogen atom or a straight chain alkyl group having 1 to 10 carbon atoms;

[0434] a is 0 or an integer of 1 or greater, preferably 0≤a≤25, more preferably 0≤a≤15, even more preferably 1≤a≤10;

[0435] 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 further preferably 4≤p≤18;

[0436] 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 further, preferably, it is 1≤q≤5;

[0437] r is 0 or integer 1;

[0438] HS-(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z′(IV′)

[0439] in

[0440] R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and R IIIh Each occurrence is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIIg and R IIIh is a hydrogen atom, preferably, R IIIe and R IIIf is a hydrogen atom;

[0441] a is 0 or an integer of 1 or greater, preferably 0≤a≤25, more preferably 0≤a≤15, even more preferably 1≤a≤10;

[0442] 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 further preferably 4≤p≤18;

[0443] 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 more preferably, it is 1;

[0444] V is O, CH 2 Or C=O;

[0445] Z′ is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, a branched-chain alkyl group having 3 to 25 carbon atoms, an alkylamine, a fluoroaryl group, a fluoroalkylaryl group, a fluoroalkyl group, a fluoroaralkyl group, a heteroaromatic group, including a fluoroaryl group, a fluoroalkylaryl group, a fluoroalkyl group or a fluoroaralkyl group, preferably, Z′ is a straight-chain alkyl group having 1 to 25 carbon atoms, a branched-chain alkyl group having 3 to 25 carbon atoms or a hydrogen atom, more preferably, it is a straight-chain alkyl group having 1 to 15 carbon atoms, a branched-chain alkyl group having 3 to 15 carbon atoms or a hydrogen atom, even more preferably, it is a hydrogen atom;

[0446] r is 0 or integer 1.

[0447] For example, preferably, the following materials can be used as the anion source.

[0448] SH-CH 2 -(OCH 2 CH 2 ) 4 -O-CH 3

[0449] SH-CH 2 -(OCH 2 CH 2 ) 6 -O-CH 3

[0450] SH-CH 2 -(OCH 2 CH 2 ) 8 -O-CH 3

[0451] SH-(CH 2 ) 2 -(OCH 2 CH 2 )2 -AND 3

[0452] SH-(CH 2 ) 2 -(AND 2 CH 2 ) 6 -AND 3

[0453] SH-(CH 2 ) 2 -(AND 2 CH 2 ) 8 -AND 3

[0454] SH-(CH 2 ) 2 -(AND 2 CH 2 ) 6 -CH 3

[0455] SH-(CH 2 ) 2 -(AND 2 CH 2 ) 6 -AND 2 ) 2 -SH

[0456] SH-(CH 2 ) 7- CH 3

[0457] SeH-(CH 2 ) 7- CH 3

[0458] SH-(CH 2 ) 11- CH 3

[0459] SeH-(CH 2 ) 11- CH 3

[0460] SH-(CH 2 ) 17- CH 3

[0461] SeH-(CH 2 ) 17- CH 3

[0462] SH-(CH 2 ) 2 -(OCH 2 CH 2 ) 6 -O-CH 3

[0463] SH-(CH 2 ) 2 -(OCH 2 CH 2 ) 16 -O-CH 3

[0464] SH-(CH 2 ) 2 -(OCH 2 CH 2 ) 17 -O-CH 3

[0465] Other thiolated ligand materials (such as polypropylene glycol and polypropylene glycol monomethyl ether, thiolated ligand materials described in US11021651B2, formula (I) in columns 17 to 18, column 25, line 28 to column 26, line 16, formula (II), M1000-SH in Example 1) can also be used as a source of organic moieties and the resulting covalently bound organic moieties are included in this patent application.

[0466] It is believed that the temperature range of 80° C. to 200° C. is important for the crystalline bonding between the organic moiety and the outer layer. In other words, by maintaining the reaction temperature in step (b) within this temperature range, the anchoring group of formula (I), (II), (III) and / or (IV) is attached to the cation to form the outer layer, while the organic moiety remains attached to the anchoring group via a covalent bond.

[0467] In a preferred embodiment of the present invention, the injection of the anion source is carried out in step (a) or in step (b) at a temperature in the range of 0°C to 200°C, preferably in the range of 20°C to 180°C.

[0468] It is believed that the temperature range of this injection is also important to prevent XB bond cleavage.

[0469] Preferably, step (b) is carried out in the range of 1 minute to 10 hours, preferably 10 minutes to 5 hours, more preferably 20 minutes to 3 hours.

[0470] According to the present invention, preferably, the ratio of the total molar amount of the cationic precursor in step (b) to the total molar amount of the semiconductor nanoparticles is in the range of 20:1 to 200000:1, preferably 100:1 to 60000:1, more preferably 110:1 to 58000:1, even more preferably 120:1 to 5000:1.

[0471] In a preferred embodiment of the present invention, the ratio of the total molar amount of the chalcogen source in step (b) to the total molar amount of the semiconductor nanoparticles is in the range of 20: 1 to 200000: 1, preferably 100: 1 to 60000: 1, more preferably 110: 1 to 58000: 1, even more preferably 120: 1 to 5000: 1. Preferably, the ratio of the total mass of the cationic precursor in step (b) to the total mass of the semiconductor nanoparticles is in the range of 1: 1000 to 1: 1, preferably 1: 500 to 1: 2, more preferably 1: 400 to 1: 2.

[0472] In some embodiments of the present invention, an anion source represented by formula (2), (3) and / or (4) may be used alone or in combination with any other chalcogen source as an anion source in step (b) to form an outer layer.

[0473] 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)

[0474] L 1 and L 2 Each is independently or mutually an organic group, preferably, the organic group is a hydrocarbon group (alkyl, aryl, aralkyl and alkylaryl), including aryl, alkaryl, alkyl or aralkyl;

[0475] R IIa and R IIbEach occurrence is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIa and R IIb is a hydrogen atom;

[0476] n is an integer of 1 or greater;

[0477] m is 0 or an integer of 1 or greater, preferably, m is 1;

[0478] o is 0 or an integer of 1 or greater, preferably, o is 1;

[0479] U 1 and U 2 at each occurrence, independently or dependently, O, -CH2- or C=O;

[0480] Y 1 and Y 2 at each occurrence, independently or dependently, O, -CH2- or C=O;

[0481] n is an integer of 1 or greater;

[0482] Z 1 is a divalent anion selected from Se, S, Te, and O;

[0483] Z 2 It is a divalent anion selected from Se, S, Te, and O.

[0484] 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)

[0485] 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)

[0486] in

[0487] R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and R IIIh is independently selected at each occurrence from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIIg and R IIIh is a hydrogen atom, preferably, R IIIe and R IIIf is a hydrogen atom; V is O, CH 2 Or C=O;

[0488] Z is a hydrogen atom or an organic group. Preferably, Z is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, -COOH, -SH or -NH 2 , alkylamine, fluoroaryl, fluoroalkylaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, including fluoroaryl, fluoroalkylaryl, fluoroalkyl or fluoroaralkyl, preferably, Z is a hydrogen atom, a straight chain alkyl group having 1 to 25 carbon atoms, a branched chain alkyl group having 3 to 25 carbon atoms, more preferably, it is a hydrogen atom, a straight chain alkyl group having 1 to 15 carbon atoms, a branched chain alkyl group having 3 to 15 carbon atoms, even more preferably, it is a hydrogen atom or a straight chain alkyl group having 1 to 10 carbon atoms;

[0489] a is 0 or an integer of 1 or greater, preferably 0≤a≤25, more preferably 0≤a≤15, even more preferably 1≤a≤10;

[0490] 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 further preferably 4≤p≤18;

[0491] 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 further, preferably, it is 1≤q≤5;

[0492] r is 0 or integer 1;

[0493] Q 1 and Q2 are independently a divalent anion selected from Se, S, Te, O;

[0494] For example, mPEG-SS-mPEG can be used.

[0495] For example,

[0496] (S, S, Te or O) 2 -(CH 2 -(OCH 2 CH 2 ) 4 -O-CH 3 ) 2

[0497] (S, S, Te or O) 2 -(CH 2 -(OCH 2 CH 2 ) 6 -O-CH 3 ) 2

[0498] (S, S, Te or O) 2 -(CH 2 -(OCH 2 CH 2 ) 8 -O-CH 3 ) 2

[0499] (S, S, Te or O) 2 -((CH 2 ) 2 -(OCH 2 CH 2 ) 2 -O-CH 3 ) 2

[0500] (S, S, Te or O) 2 -((CH 2 ) 2 -(OCH 2 CH 2 ) 6 -O-CH 3 ) 2

[0501] (S, S, Te or O) 2 -((CH 2 ) 2 -(OCH 2 CH 2 ) 8 -O-CH 3 ) 2

[0502] (S, S, Te or O) 2 -((CH 2 ) 2 -(OCH 2 CH 2 ) 6 -CH 3 ) 2

[0503] (S, S, Te or O) 2 -((CH 2 ) 2 -(OCH 2 CH 2 ) 6 -O-(CH 2 ) 2 -SH) 2

[0504] (S, S, Te or O) 2 -((CH 2 ) 7- CH 3 ) 2

[0505] (S, S, Te or O) 2 -((CH 2 ) 11- CH 3 ) 2

[0506] (S, S, Te or O) 2 -((CH 2 ) 17- CH 3 ) 2

[0507] (S, S, Te or O) 2 -((CH 2 ) 2 -(OCH 2 CH 2 ) 6 -O-CH 3 ) 2

[0508] (S, S, Te or O) 2 -((CH 2 ) 2 -(OCH 2 CH 2 ) 16 -O-CH 3 ) 2

[0509] (S, S, Te or O) 2 -((CH 2 ) 2 -(OCH 2 CH 2 ) 17 -O-CH 3 ) 2

[0510] or

[0511] (S, S, Te or O) 2 -((CH 2 ) 11- CH 3 ) 2 .

[0512] In a preferred embodiment of the present invention, an anion source described by formula (2), (3) or (4), such as a bis-chalcogenide, may 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.

[0513] In a preferred embodiment of the present invention, the ratio of the molar amount of the anion source to the molar amount of the 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, even more preferably in the range of 5:1 to 1:5.

[0514] - Chalcogen source

[0515] According to the present invention, the term "chalcogen element" refers to a chemical element of Group 16 of the periodic table, preferably, sulfur (S), selenium (Se), oxygen (O) and / or tellurium (Te).

[0516] Therefore, according to the present invention, the term "chalcogen source" means a material containing at least one chemical element of the 16th group of the periodic table, preferably, the chemical element of the 16th group of the periodic table is oxygen (O), sulfur (S), selenium (Se) and / or tellurium (Te), more preferably, it is sulfur (S) or selenium (Se).

[0517] 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 sulfur source. More preferably, it is selected from selenol, diselenide, thiol, disulfide or a combination of these.

[0518] Step (a) - Mixing

[0519] In a preferred embodiment of the present invention, step (a) is carried out under inert conditions, such as under argon (Ar) or N 2 conditions, more preferably under Ar conditions.

[0520] In a preferred embodiment of the present invention, the further material used in step (a) is a solvent, more preferably, it is an organic solvent, even more preferably, it is selected from one or more members of the group consisting of: squalene, squalane, heptadecane, octadecane, octadecane, octadecene, nonadecane, eicosane, heneicosane, docosane, tricosane, pentacosane, hexacosane, octacosane, nonacosane, triacontan, heneicosane, dotriacontan, tricosane, tetratriacontan, pentatriacontan, hexatriacontan, oleylamine, trioctylamine, ketones, ketone ether acetates such as PGMEA, nitriles, ethers, ether esters, aromatic solvents such as toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene, mesitylene, among which squalene, squalane, heptadecane, octadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, pentacosane, hexacosane, octacosane, nonacosane, triacontan, heneicosane, dotriacontan, tricosane, tetratriacontan, pentatriacontan, hexatriacontan, oleylamine, trioctylamine, ketones, ketone ether acetates such as PGMEA, nitriles, ethers, ether esters, aromatic solvents such as toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene, mesitylene are preferred. octadecane, tetracosane, nonacosane, triacontan, hetacontan, dotriacontan, tricriacontan, tetratriacontan, pentacontan, hexatriacontan, 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 triacontan, ketone , ketone ether acetates such as PGMEA, nitriles, ethers, ether esters, aromatic solvents such as toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene, mesitylene, even 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, isopropylbenzene, diisopropylbenzene, mesitylene.

[0521] In a preferred embodiment of the present invention, the mixing step is carried out at a temperature ranging from 0 to 100°C, preferably from 5 to 60°C, more preferably from 10 to 40°C.

[0522] The light-emitting portion, preferably, the light-emitting portion comprises at least the first semiconductor nanomaterial as a core, which can be obtained from a public source or as described in, for example, US8679543 ​​B2, WO 2020 / 216813A and Chem.Mater.2015, 27, pp. 4893-4898.

[0523] In a preferred embodiment of the present invention, the cationic shell precursor is a salt of an element of Group 12 of the periodic table, more preferably, the cationic shell precursor is one or more members selected from the group consisting of Zn stearate, Zn isostearate, Zn myristic acid, Zn oleate, Zn laurate, Zn palmitic acid, Zn acetylacetonate, Zn undecylenate, Zn acetate, Cd stearate, Cd myristic acid, Cd oleate, Cd laurate, Cd palmitic acid, Cd acetylacetonate, Cd undecylenate, Cd acetate, a metal halogen represented by formula (XIII) and a metal carboxylate represented by formula (XIV),

[0524] MX 3 n(XIII)

[0525] Where M is Zn 2+ or Cd 2+ , preferably, M is Zn 2+ , X 3 is a halogen selected from the group consisting of F-, Cl-, Br- and I-, n is 2,

[0526] [M(O 2 CR 16 )(O 2 CR 17 )]-(XIV)

[0527] Where M is Zn 2+ or Cd 2+ , preferably, M is Zn 2+ ;

[0528] R 16 is a straight-chain alkyl group having 1 to 30 carbon atoms, a branched-chain alkyl group having 3 to 30 carbon atoms, a straight-chain unsaturated hydrocarbon group having 2 to 30 carbon atoms, or a branched-chain unsaturated hydrocarbon group having 3 to 30 carbon atoms. 16 is a linear alkyl group having 1 to 30 carbon atoms or a linear unsaturated hydrocarbon group having 2 to 30 carbon atoms, more preferably, R 16is a straight-chain alkyl group having 2 to 25 carbon atoms or a straight-chain unsaturated hydrocarbon group having 6 to 25 carbon atoms, and even more preferably, R 16 is a linear alkyl group having 2 to 20 carbon atoms or a linear unsaturated hydrocarbon group having 10 to 20 carbon atoms. In addition, preferably, R 16 is a straight-chain alkyl group having 2 to 20 carbon atoms,

[0529] R 17 is a straight-chain alkyl group having 1 to 30 carbon atoms, a branched-chain alkyl group having 3 to 30 carbon atoms, a straight-chain unsaturated hydrocarbon group having 2 to 30 carbon atoms, or a branched-chain unsaturated hydrocarbon group having 43 to 30 carbon atoms. 17 is a linear alkyl group having 1 to 30 carbon atoms or a linear unsaturated hydrocarbon group having 2 to 30 carbon atoms, more preferably, R 17 is a straight-chain alkyl group having 2 to 25 carbon atoms or a straight-chain unsaturated hydrocarbon group having 6 to 25 carbon atoms, and even more preferably, R 17 is a linear alkyl group having 2 to 20 carbon atoms or a linear unsaturated hydrocarbon group having 10 to 20 carbon atoms. In addition, preferably, R 17 is a straight-chain alkyl group having 2 to 20 carbon atoms.

[0530] In a preferred embodiment, R 16 and R 17 for the same.

[0531] In a preferred embodiment of the present invention, the molar ratio of the total amount of the chalcogen source (preferably, the chalcogen source is a selenium source, a sulfur source or a combination of a selenium source and a sulfur source) to the total amount of the cationic 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.

[0532] - Cooling step (c)

[0533] According to the invention, cooling of the reaction mixture from step (b) is carried out in step (c) in order to stop the formation reaction accordingly.

[0534] As a cooling method, several methods may be used alone or in combination, such as removing a heat source, injecting a solvent (such as a solvent at room temperature), and / or applying air cooling.

[0535] In a preferred embodiment, the reaction mixture is cooled down to 50°C or below and above 0°C, preferably, to room temperature.

[0536] After cooling, the resulting luminescent moiety can be cleaned by known methods and preferably centrifuged. The solids in the reaction mixture from step (c) can be removed by centrifugation. The cleaned luminescent moiety can then be used in step (d).

[0537] - Formulations

[0538] In another aspect, the present invention may be directed to a formulation comprising at least, consisting essentially of, or consisting of: a composition of the present invention;

[0539] and at least one solvent.

[0540] 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, pure water, ester acetates, alcohols, sulfoxides, formamides, nitrides, ketones, ether acetates.

[0541] The amount of solvent in the formulation can be freely controlled depending on the method of coating the composition. For example, if the composition is to be sprayed, it may contain 90% by weight or more of solvent. In addition, if a slot coating method is to be performed, which is often used in coating large substrates, the content of solvent is usually 60% by weight or more, preferably 70% by weight or more.

[0542] In some embodiments, the formulation may contain only 5 wt% or less solvent, based on the total amount of the composition. Preferably, the composition does not contain any solvent.

[0543] -use

[0544] In another aspect, the present invention also relates to use of a composition or formulation in an electronic device, an optical device, a sensing device or a biomedical device.

[0545] - Method for forming layers

[0546] In another aspect, the present invention also relates to a method for forming a layer, comprising:

[0547] S1) providing the composition on a substrate, preferably by inkjet;

[0548] S2) curing the composition, preferably, the curing is photocuring by light irradiation, thermal curing or a combination of photocuring and thermal curing.

[0549] -layer

[0550] In another aspect, the present invention also relates to a layer obtained or obtainable by the process of the present invention.

[0551] In another aspect, the present invention also relates to a layer comprising at least, consisting essentially of, or consisting of;

[0552] Xi) a luminescent moiety, preferably a semiconductor luminescent nanoparticle comprising an outer layer containing a metal cation and a divalent anion; and

[0553] one or more types of organic moieties covalently attached directly to the anions of the outer shell,

[0554] Xii) a polymer made from at least one reactive monomer or a mixture of two or more reactive monomers, preferably the monomer has one or more functional groups, more preferably it is a (meth)acrylate monomer;

[0555] The divalent anion of the outer layer is selected from Se 2- , S 2- 、Te 2- , O 2- Or any combination thereof, preferably, the metal cation in the outer layer is a monovalent, divalent, trivalent or tetravalent cation, more preferably, the metal cation is selected from Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ The divalent cations of the group consisting of or selected from Ti 4+ ,Ge 4+ 、Si 4 + 、Zr 4+ , Hf 4+ Sn 4+ The group consisting of tetravalent cations.

[0556] -Color conversion device (100)

[0557] In another aspect, the present invention also relates to a color conversion device (100), comprising at least, essentially consisting of or consisting of: a first pixel (161), which is partially or completely filled with a layer comprising a matrix material (120) containing at least a light-emitting part (110) as claimed in any one of claims 20 to 22 and 24; and a reservoir (150) comprising at least a polymer material, preferably, the color conversion device (100) further comprising a supporting medium (170).

[0558] -1st pixel (161)

[0559] According to the present invention, the first pixel (161) comprises a matrix material (120) containing at least a light-emitting portion (110). In a preferred embodiment, the first pixel (161) is a solid layer obtained or obtainable by curing a composition containing at least one acrylate monomer and at least one light-emitting portion (110) of the present invention, preferably, the curing is photocuring by light irradiation, thermal curing, or a combination of photocuring and thermal curing.

[0560] 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, it is 1 to 50 μm, more preferably 5 to 25 μm.

[0561] In some embodiments of the present invention, the color conversion device (100) further contains a second pixel (162). Preferably, the device (100) contains at least the first pixel (161), the second pixel (162) and the 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. Even more preferably, the first pixel (161) contains a red light emitting portion (110R), the second color pixel (162) contains a green light emitting portion (110G) and the third pixel (163) does not contain any light emitting portion.

[0562] In some embodiments, at least one pixel (160) further comprises at least one light scattering particle (130) in the matrix material (120), preferably, the pixel (160) contains a plurality of light scattering particles (130).

[0563] In a preferred embodiment, the first pixel (161) is composed of one pixel or two or more sub-pixels, which are configured to emit red when illuminated by excitation light, and more preferably, the sub-pixels contain the same light-emitting portion (110).

[0564] - Matrix material (120)

[0565] In a preferred embodiment, the matrix material (120) contains a (meth)acrylate polymer, preferably, it is a methacrylate polymer, an acrylate polymer or a combination thereof, more preferably, it is an acrylate polymer, even more preferably, the matrix material (120) is obtained or obtainable from a composition containing at least one acrylate monomer of the present invention, still more preferably, the matrix material (120) is obtained or obtainable from a composition containing at least one diacrylate monomer of the present invention, particularly preferably, the matrix material (120) is obtained or obtainable from a composition containing at least one diacrylate monomer and a monoacrylate monomer of the present invention, preferably, the composition is a photosensitive composition.

[0566] - Library (150)

[0567] In some embodiments of the present invention, the height of the reservoir (150) is in the range of 0.1 to 100 μm, preferably, it is 1 to 50 μm, more preferably, it is 1 to 25 μm, and further preferably, it is 5 to 20 μm.

[0568] In a preferred embodiment of the present invention, the library (150) is configured to determine the area of ​​the first pixel (161) and at least a portion of the library (150) is in direct contact with at least a portion of the first pixel (161), preferably, the second polymer of the library (150) is in direct contact with at least a portion of the first polymer of the first pixel (161).

[0569] More preferably, the library (150) is photolithographically patterned and the first pixel (161) is surrounded by the library (150). Preferably, the first pixel (161), the second pixel (162) and the third pixel (163) are all surrounded by the library (150) that is photolithographically patterned.

[0570] In another aspect, the present invention also relates to a method for manufacturing a color conversion device (100) according to the present invention, comprising at least the following steps, preferably in this order:

[0571] Xi) Providing the library composition onto the surface of the support medium

[0572] Xii) solidifying the library composition,

[0573] Xiii) applying photopatterning to the cured composition to produce a reservoir and patterned pixel regions,

[0574] Xiv) applying the composition of the invention to at least one pixel area, preferably by inkjetting,

[0575] xv) curing the composition. Preferably, the color conversion device (100) further comprises a supporting medium (170).

[0576] In another aspect, the present invention further relates to a color conversion device (100) obtainable or obtained by the method of the present invention.

[0577] In another aspect, the present invention further relates to a use of the color conversion device (100) of the present invention in an optical device (300) containing at least one functional medium (320, 420, 520) configured to modulate light or configured to emit light.

[0578] In addition, in another aspect, the present invention further relates to an optical device (300), which contains at least, consists essentially of, or consists of: a functional medium (320, 420, 520) configured to modulate light or configured to emit light, and the color conversion device (100) of the present invention.

[0579] 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 micro-electromechanical system (hereinafter referred to as "MEMS"), an electrowetting display, or an electrophoretic display.

[0580] Therefore, in a preferred embodiment, the functional medium can be an LC layer, an OLED layer, an LED layer, a microLED layer, a MEMS layer, an electrowetting layer and / or an electrophoretic layer. More preferably, it is an LC layer, a microLED layer or an OLED layer.

[0581] Preferred Implementation

[0582] 1. A composition, preferably a photocurable composition, comprising at least;

[0583] i) a luminescent moiety, preferably a semiconductor luminescent nanoparticle comprising an outer layer containing a metal cation and a divalent anion; and

[0584] one or more types of organic moieties covalently attached directly to the anions of the outer shell,

[0585] ii) at least one reactive monomer or a mixture of two or more reactive monomers, preferably the monomer has one or more functional groups, more preferably it is a (meth)acrylate monomer;

[0586] The divalent anion of the outer layer is selected from Se 2- , S 2- 、Te 2- , O 2- Or any combination thereof, preferably, the metal cation in the outer layer is a monovalent, divalent, trivalent or tetravalent cation, more preferably, the metal cation is selected from Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ The divalent cations of the group consisting of or selected from Ti 4+ ,Ge 4+ 、Si 4 + 、Zr4+ , Hf 4+ Sn 4+ The group consisting of tetravalent cations.

[0587] 2. The composition of embodiment 1, wherein the organic portion is represented by the following chemical formula (I);

[0588] AB-*(I)

[0589] in

[0590] A is an organic group, preferably, the organic group is a hydrocarbon group (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group, including an aryl, an alkaryl, an alkyl or an aralkyl, an alkylamine, a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group, including a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl or a fluoroaralkyl;

[0591] B is a connecting unit, preferably, B is **-(U) o -(Y) m -(CR IIa R IIb ) n , where “**” indicates the point of connection to “A”; and

[0592] "*" indicates the point of attachment to the anion in the outer layer.

[0593] 3. The composition of embodiment 1 or 2, wherein the organic part is represented by the following chemical formula (II), (III) or (III′);

[0594] L-(U) o -(Y) m -(CR IIa R IIb ) n -*(II)

[0595] in

[0596] L is an organic group, preferably, the organic group is a hydrocarbon group (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group, including an aryl, an alkaryl, an alkyl or an aralkyl, an alkylamine, a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group, including a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl or a fluoroaralkyl;

[0597] U is O, CH 2 Or C=O;

[0598] Y is O, CH 2 Or C=O;

[0599] R IIa and R IIbEach occurrence is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIa and R IIb is a hydrogen atom;

[0600] n is an integer of 1 or greater;

[0601] m is 0 or an integer of 1 or greater, preferably, m is 1;

[0602] o is 0 or an integer of 1 or greater, preferably, o is 1;

[0603] "*" indicates the point of attachment to the anion in the outer layer;

[0604] *-(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z(III)

[0605] *-(CR IIIg R IIIh ) q -(V) r -(OCR IIIa R IIIb CR IIIc R IIId ) p -Z(III′)

[0606] in

[0607] R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and R IIIh Each of the occurrences is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIIg and R IIIhis a hydrogen atom, preferably, R IIIe and R IIIf is a hydrogen atom; V is O, CH 2 Or C=O;

[0608] Z is a hydrogen atom or an organic group. Preferably, Z is a hydrogen atom, a linear alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, -COOH, -SH or -NH 2 , alkylamine, fluoroaryl, fluoroalkylaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, including fluoroaryl, fluoroalkylaryl, fluoroalkyl or fluoroaralkyl, preferably, Z is a hydrogen atom, a straight chain alkyl group having 1 to 25 carbon atoms, a branched chain alkyl group having 3 to 25 carbon atoms, more preferably, it is a hydrogen atom, a straight chain alkyl group having 1 to 15 carbon atoms, a branched chain alkyl group having 3 to 15 carbon atoms, even more preferably, it is a hydrogen atom or a straight chain alkyl group having 1 to 10 carbon atoms;

[0609] a is 0 or an integer of 1 or greater, preferably 0≤a≤25, more preferably 0≤a≤15, even more preferably 1≤a≤10;

[0610] 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 further preferably 4≤p≤18;

[0611] 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 further, preferably, it is 1≤q≤5;

[0612] r is 0 or integer 1;

[0613] "*" indicates the point of attachment to the anion in the outer layer.

[0614] 4. A composition according to any one of the preceding embodiments, wherein the organic portion is represented by the following chemical formula (IV):

[0615] *-(CR IIIe R IIIf ) a -(OCR IIIa R IIIb CR IIIc R IIId ) p -(V) r -(CR IIIg R IIIh ) q -Z′(IV)

[0616] in

[0617] R IIIa, R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and R IIIh Each occurrence is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIIg and R IIIh is a hydrogen atom, preferably, R IIIe and R IIIf is a hydrogen atom;

[0618] a is 0 or an integer of 1 or greater, preferably 0≤a≤25, more preferably 0≤a≤15, even more preferably 1≤a≤10;

[0619] 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 further preferably 4≤p≤18;

[0620] 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 more preferably, it is 1;

[0621] V is O, CH 2 Or C=O;

[0622] Z′ is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, a branched-chain alkyl group having 3 to 25 carbon atoms, an alkylamine, a fluoroaryl group, a fluoroalkylaryl group, a fluoroalkyl group, a fluoroaralkyl group, a heteroaromatic group, including a fluoroaryl group, a fluoroalkylaryl group, a fluoroalkyl group or a fluoroaralkyl group, preferably, Z′ is a straight-chain alkyl group having 1 to 25 carbon atoms, a branched-chain alkyl group having 3 to 25 carbon atoms or a hydrogen atom, more preferably, it is a straight-chain alkyl group having 1 to 15 carbon atoms, a branched-chain alkyl group having 3 to 15 carbon atoms or a hydrogen atom, even more preferably, it is a hydrogen atom;

[0623] r is 0 or integer 1;

[0624] "*" indicates the point of connection to the anion in the outer shell, preferably, it is connected to the S or Se atom in the outer shell.

[0625] 5. The composition of any of the preceding embodiments, wherein the organic moiety is covalently bound to anions in the outer layer of the inorganic lattice, preferably, which are not removed by ligand exchange.

[0626] 6. A composition according to any one of the preceding embodiments, wherein the metal cation is a transition metal of Group 12 or Group 14, preferably, selected from Zn 2+ , Hg 2+ or Pb 2+ One or more members of a group.

[0627] 7. The composition of any of the preceding embodiments, wherein the reactive monomer is a (meth)acrylate monomer selected from mono-(meth)acrylate monomers, di-(meth)acrylate monomers and / or tri-(meth)acrylate monomers.

[0628] 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.

[0629] 8. The composition of embodiment 7, wherein the di-(meth)acrylate monomer is represented by the following chemical formula (I b ) represents, 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 )express;

[0630]

[0631] in

[0632] X 1 is an unsubstituted or substituted ester group, alkyl group or aryl group, wherein one or more non-adjacent CH 2 The radical can be 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 Preferably, the ester group is composed of the following formula (I bs1 )express;

[0633]

[0634] Where R Ib1 is a single bond, an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms;

[0635] R Ib2 is a single bond, an unsubstituted or substituted straight chain alkylene chain having 1 to 5 carbon atoms, an unsubstituted or substituted branched chain alkylene chain having 3 to 7 carbon atoms, wherein one or more non-adjacent CH 2The radical can be 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 Alternative; preferably, R Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, wherein non-adjacent CH 2 At least one of the groups may be substituted by 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 Replacement; In addition, preferably, (I bs1 ) Ib1 is a single bond, (I bs2 ) Ibs1 is a single bond, (I bs1 ) Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, R Ibs2 is a single bond, an unsubstituted straight alkylene chain having 1 to 5 carbon atoms, an unsubstituted branched alkylene chain having 3 to 7 carbon atoms, wherein one or more non-adjacent CH 2 The radical may be replaced by an oxygen atom;

[0636] X 2 is an unsubstituted or substituted ester group, alkyl group or aryl group, wherein one or more non-adjacent CH 2 The radical can be 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 Preferably, the ester group is composed of the following formula (I bs2 )express;

[0637]

[0638] Where R Ibs1 is a single bond, an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms;

[0639] R Ibs2 is a single bond, an unsubstituted or substituted straight chain alkylene chain having 1 to 5 carbon atoms, an unsubstituted or substituted branched chain alkylene chain having 3 to 7 carbon atoms, wherein one or more non-adjacent CH 2The radical can be 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 Alternative; preferably, R Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, wherein non-adjacent CH 2 At least one of the groups may be substituted by 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 Replacement;

[0640] R 1 is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, or an aryl group, wherein one or more non-adjacent CH 2 The radical can be 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 Replace; or X 1 is an ester group; preferably, the ester group is a carboxylic acid group;

[0641] R 2 is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, or an aryl group, wherein one or more non-adjacent CH 2 The radical can be 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 Replace; or X 1 is an ester group; preferably, the ester group is a carboxylic acid group;

[0642]

[0643] X 3 is an unsubstituted or substituted ester group, an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, if X 3 is an unsubstituted or substituted ester group, the ester group is represented by the following formula (II bs )express;

[0644]

[0645] Where R IIb1 is a single bond, an unsubstituted or substituted alkylene chain having 1 to 5 carbon atoms;

[0646] R IIb2 is a substituted or unsubstituted alkyl group, a cyclic group, a cycloalkyl group, an aryl group or an alkoxy group.

[0647] Furthermore, preferably, (II bs ) IIb1 is a single bond, (II bs ) IIb2 is a substituted or unsubstituted alkyl, cyclyl or cycloalkyl group; (II bs ) IIb2 The group may be selected from the group shown in the table on page 44.

[0648] R 5 is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, an aryl group, an alkoxy group, an ester group or a carboxylic acid group;

[0649]

[0650] Where R 9 is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, or a radical of the formula (IV b ) represented by (meth)acryloyl

[0651]

[0652] R 10 is a hydrogen atom, a straight chain alkyl group having 1 to 25 carbon atoms, or a radical of the formula (V b ) represented by (meth)acryloyl

[0653]

[0654] R 11 is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, or a radical of the formula (VI b ) represented by (meth)acryloyl

[0655]

[0656] Where R 8 , R 8a , R 8b and R 8c Each occurrence is, independently or mutually, H, CH 2 CH 3 or CH 3 ;

[0657] Where R9 , R 10 and R 11 At least one of them is a (meth)acryloyl group.

[0658] 9. A method for producing a composition according to any one of the preceding embodiments, comprising at least the following steps,

[0659] (a) at least a light-emitting portion, preferably, the light-emitting portion comprises at least a first semiconductor nanomaterial as a core,

[0660] mixing with another material to obtain a reaction mixture, preferably, the other material is a solvent;

[0661] (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 formula (Va) or formula (Vb) with a metal cation precursor in the reaction mixture;

[0662] ABXH(Va)

[0663] ABXXBA(Vb)

[0664] in

[0665] A is an organic group;

[0666] B is the connection unit;

[0667] H is a hydrogen atom; and

[0668] X is an anchoring group comprising an anion capable of forming a monolayer with an added metal cation that may be derived from an added metal cation precursor;

[0669] (c) cooling the reaction mixture from step (b),

[0670] wherein the reaction mixture in step (b) is maintained at a temperature in the range of 80° C. to 200° C., preferably 100 to 200° C. to form the outer layer in step (b),

[0671] (d) mixing the light-emitting portion obtained from step (c) with at least one reactive monomer or a mixture of two or more reactive monomers to form a composition.

[0672] 10. The method according to embodiment 9, wherein the injection of the anion source is carried out in step (a) or in step (b) at a temperature in the range of 0°C to 200°C, preferably in the range of 20°C to 180°C.

[0673] 11. The method of embodiment 9 or 10, wherein step (b) is performed in the range of 1 minute to 10 hours, preferably 10 minutes to 5 hours, more preferably 20 minutes to 3 hours.

[0674] 12. The method according to any one of embodiments 9 to 11, wherein the ratio of the total molar amount of the cationic precursor to the total molar amount of the semiconductor nanoparticles in step (b) is in the range of 20:1 to 200000:1, preferably 100:1 to 60000:1, more preferably 110:1 to 58000:1, even more preferably 120:1 to 5000:1. Preferably, the ratio of the total mass of the cationic precursor 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. Preferably, the ratio of the total mass of the cationic precursor 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. Preferably, the molar ratio of the total amount of the anion source to the total amount of the 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, even more preferably in the range of 5:1 to 1:5.

[0675] 13. The process according to any one of embodiments 9 to 12, wherein the anion source of formula (Vb) is used together with a reducing agent in step (b) to form the outer layer, preferably the reducing agent is represented by a secondary phosphine.

[0676] 14. A method as described in any one of embodiments 9 to 13, wherein the molar ratio of the total amount of the anion source to the total amount of the cationic 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, even more preferably in the range of 5:1 to 1:5.

[0677] 15. A composition obtainable or obtained by the method according to any one of embodiments 9 to 14.

[0678] 16. A formulation comprising at least the composition according to any one of embodiments 1 to 8 and 15,

[0679] 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, pure water, ester acetate, ether acetate, ketone, ether ester, preferably, it is PGMEA, alcohol (preferably ethanol or isopropanol), sulfoxide, formamide, nitride, ketone.

[0680] 17. Use of a composition according to any one of embodiments 1 to 8 or 15 or a formulation according to embodiment 16 in an electronic device, an optical device, a sensing device or a biomedical device.

[0681] 18. A method for forming a layer, comprising:

[0682] S1) providing a composition according to any one of embodiments 1 to 8 or 15 onto a substrate, preferably by inkjet;

[0683] S2) curing the composition, preferably, the curing is photocuring by light irradiation, thermal curing or a combination of photocuring and thermal curing.

[0684] 19. A layer obtained or obtainable by the method according to embodiment 18.

[0685] 20. A layer comprising at least;

[0686] Xi) a luminescent moiety, preferably a semiconductor luminescent nanoparticle comprising an outer layer containing a metal cation and a divalent anion; and

[0687] one or more types of organic moieties covalently attached directly to the anions of the outer shell,

[0688] Xii) a polymer made from at least one reactive monomer or a mixture of two or more reactive monomers, preferably the monomer has one or more functional groups, more preferably it is a (meth)acrylate monomer;

[0689] The outer divalent anion is selected from Se 2- , S 2- 、Te 2- , O 2- Or any combination thereof, preferably, the metal cation in the outer layer is a monovalent, divalent, trivalent or tetravalent cation, more preferably, the metal cation is selected from Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ The divalent cations of the group consisting of or selected from Ti 4+ ,Ge 4+ 、Si 4 + 、Zr 4+ , Hf 4+ Sn 4+ The group consisting of tetravalent cations.

[0690] 21. A color conversion device (100), comprising at least a first pixel (161), the first pixel being partially or completely filled with a layer comprising at least a matrix material (120) containing a light-emitting portion (110) as in embodiment 19 or 20; and a reservoir (150) comprising at least a polymer material, preferably, the color conversion device (100) further comprising a supporting medium (170).

[0691] 22. An optical device (300) comprising at least one functional medium (320, 420, 520) configured to modulate light or configured to emit light, and the color conversion device (100) according to embodiment 21.

[0692] Technical Effects

[0693] The present invention provides one or more of the following effects:

[0694] The invention relates to a method for achieving an optimized haze value of a cured layer (film), an optimal haze value and an improved EQE value of a cured layer (film), preferably an optimal haze value and an improved EQE value of a cured layer (film) without using scattering particles, an improved thermal stability of the obtained layer (film), an improved thermal stability of the luminescent portion in the layer (film), an improved dispersibility of the luminescent portion in the composition, enabling the luminescent portion and the matrix material to phase separate after curing to achieve an improved haze value of the cured film (cured composition), an improved dispersibility of the luminescent portion in the obtained layer, and an improved long-term quantum yield (QY) stability of the luminescent portion in the composition during longer-term storage with or without external light irradiation. qualitative, improved long-term external quantum efficiency (EQE) stability of the light-emitting part in the composition during longer-term storage with or without external light irradiation, improved long-term quantum yield (QY) stability of the light-emitting part in the obtained layer (film) during longer-term storage with or without external light irradiation, improved long-term external quantum efficiency (EQE) stability of the light-emitting part in the obtained layer (film) during longer-term storage with or without external light irradiation, improved good compatibility of the light-emitting part in the composition and / or the obtained layer (film) with the matrix material, and / or easy processing of the composition containing the light-emitting part and the matrix material, making the composition suitable for inkjet printing.

[0695] The following examples provide a description of the invention and detailed descriptions of its manufacture. However, the invention is not necessarily limited to the working examples. Example

[0696] Nucleosynthesis Example 1: Synthesis of Magic Sized Clusters (MSC)

[0697] Cluster synthesis

[0698] In a 500 mL 4-necked flask, 4.65 g (15.9 mmol) of indium acetate and 13.25 g (58.0 mmol) of myristic acid were weighed in. The flask was equipped with a reflux condenser, a septum, and a tap between the flask and the condenser.

[0699] The acetic acid was degassed under reduced pressure by placing under vacuum at 100°C for 8 hours and 15 minutes and at room temperature overnight.

[0700] The next day, the solution was heated to 100°C again and evacuated under those conditions for 1 hour and 45 minutes.

[0701] The total vacuum time at 100°C is 10 hours.

[0702] At pressure: 85mTorr.

[0703] The reaction flask was filled with argon and 100 mL of anhydrous toluene was added. The reaction was heated to 110 °C.

[0704] A mixture of 2.33 mL (2.0 g) PTMS and 50 mL (43.5 g) toluene was injected into the flask with indium myristic acid (In(Ma)) at 110°C.

[0705] The formation of MSCs was monitored via UV-vis of timed aliquots taken from the reaction solution. The peak shape (red shift and sharpness) improved gradually.

[0706] When the improvement of the peak shape (red shift and sharpness) ceased, the second PTMS solution (1 ml (0.86 g)) containing PTMS in 10.2 ml (8.77 g) toluene) was added in 2 ml portions to achieve the best optical parameters. For example:

[0707] After 13 minutes, add 2 ml of PTMS solution

[0708] After 19 minutes, 2 ml of PTMS solution was added

[0709] After 32 minutes, 2 ml of PTMS solution was added

[0710] After 44 minutes, the reaction was cooled with a fan and the flask itself was stored under an inert atmosphere.

[0711] result:

[0712] InP magic-sized clusters are formed with excitons at 387 nm.

[0713] The InP magic size clusters (MSC) were cleaned with anhydrous acetonitrile (crude:acetonitrile ratio 18:13). The process was repeated with a mixture of anhydrous toluene and acetonitrile at toluene:acetonitrile ratios of 1.5:1, 1.4:1, and 1.75:1. This product is called "magic size clusters (MSC)".

[0714] Nucleosynthesis Example 2: Nucleosynthesis:

[0715] Synthesis of InP nanoparticles with an exciton wavelength of 593 nm

[0716] A 50 mL, 14 / 20, four-necked round bottom flask equipped with a reflux condenser was evacuated and 10 mL of distilled squalane was injected into it. The apparatus was evacuated with stirring (pressure was loaded from 300 mtorr to 200 mTorr during 1 hour) and heated to 375° C. under argon. In a glove box, a 3.15×10 -04 M MSC solution. At 375°C, 4 mL (1.26E-06 moles) of the solution was injected into the flask using a 16-gauge needle and a 6 mL syringe;

[0717] After 4 minutes, the mantle was removed and the flask was cooled to 200° C. by blowing air with a fan. The mantle was then brought back and the flask was heated to 265° C.

[0718] At this point, more MSCs were added using the same solution that was initially injected; using a 20 gauge needle and a 3 ml syringe, the addition was done at a rate of 0.7 ml / min at a given time (compared to the initial injection):

[0719] 15th minute - 0.6mL (1.89E-07mol)

[0720] 25 minutes - 0.7 mL (2.21E-07 mol)

[0721] 32nd minute - 0.7mL

[0722] result:

[0723] InP QDs were formed with excitons at 593 nm.

[0724] Shell Synthesis Example 1: ZnSe Shell Synthesis on InP Core (Trioctylphosphine Selenide (TOP-Se) as Se Source)

[0725] In this example, the InP cores used were synthesized using the core synthesis described above (WO 2019 / 224134A) and had a core exciton CWL of 593 nm. The final core solution was cleaned with a mixture of anhydrous toluene and ethanol (ratio of crude: toluene: ethanol: 1:2:8). The process was repeated with a ratio of crude: toluene: ethanol: 1:2:6. This solution will be further referred to as "SSPInP core".

[0726] Post-synthesis core treatment: In a glove box (GB), SSPInP cores (3.5×10 -7 mol) was dissolved with 0.2 ml toluene and transferred to a 50 ml round bottom flask with 4.8 ml pumped oleylamine (OLAm) and 0.085 g ZnCl. After briefly pumping at 50°C to remove toluene, the flask was filled with argon and heated to 250°C for 30 minutes. The solution was then cooled down to 180°C.

[0727] Shelling process: After core treatment, 2.6 mL of 0.55 M concentrated Zn(Cl) 2 OLAm solution and 1 amount (0.72 mL 2M TOP-Se) of anion shell precursor were added to the SSPInP core. After 30 minutes, the solution was heated to 200°C. After 30 minutes, the solution was heated to 320°C, 3.2 mL 0.4M Zn(undecenoate)2 was injected and the reaction was kept at 320°C for 3 hours. After 3 hours, at 320°C, the reaction was terminated by cooling the reaction mixture down.

[0728] The obtained nanoparticles were cleaned with a mixture of anhydrous toluene and ethanol (ratio of crude material: toluene: ethanol: 3:4:8). The process was repeated. Then, the nanoparticles were extracted with hexane.

[0729] Shell Synthesis Example 2: Synthesis of ZnSeS Shell on InP Core (Trioctylphosphine Selenide (TOP-Se) as Se Source, Dodecanethiol (DDT) as S Source)

[0730] This comparative example is similar to comparative example 1, but 0.9 mmol TOP-Se is injected at 180°C; and 0.56 mmol DDT is injected at 320°C 10 minutes after the injection of Zn(undecenoate)2.

[0731] Reference Example 1: Synthesis of ZnSe outer layer on InP / ZnSe NP in ODE using 1-dodecyl selenol (DDSe) as Se source

[0732] Outer layer synthesis: At room temperature, the 8.3X10 -8mol InP / ZnSe was dissolved with 0.2 ml toluene and transferred to a 50 ml round bottom flask with 4 ml pumped 1-octadecene (ODE). After 30 minutes of pumping at RT, 1-dodecane selenol (0.2 mmol) was added and the flask was heated to 150°C. When the temperature reached 150°C, Zn(undecylenate)2 (0.2 mmol) was added and the reaction was maintained at 150°C for 1.5 hours. After 1.5 hours at 150°C, the reaction was terminated by cooling the reaction mixture.

[0733] The obtained nanoparticles were cleaned with a mixture of anhydrous toluene and ethanol (ratio of crude material: toluene: ethanol: 3:4:8). The process was repeated. Then, the nanoparticles were extracted with hexane.

[0734] Table A compares the thermal, free radical, and peroxide stability values ​​of the reference example and comparative example 1.

[0735] Reference Example 2: Synthesis of ZnS outer layer on InP / ZnSe NPs in ODE using 1-dodecanethiol as S source

[0736] This Reference Example 2 is similar to Reference Example 1, but 1-dodecanethiol is used as the sulfur precursor.

[0737] Reference Example 3: Synthesis of ZnSeS outer layer on InP / ZnSe NP in ODE using 1-dodecane selenol as Se source and 1-dodecanethiol as sulfur

[0738] This Reference Example 3 is similar to Reference Examples 1 and 2, however, 1-dodecaneselenol and 1-dodecanethiol are added together in equimolar amounts while keeping the amount of Se+S ions the same as before.

[0739] Reference Example 4: Synthesis of ZnSeS outer layer on InP / ZnSe NP in ODE using 1-dodecaneselenol as Se source and 3-phenylethanethiol as sulfur source

[0740] This Reference Example 4 differs from Reference Example 3 in that 3-phenylethanethiol is used as the sulfur source instead of 1-dodecanethiol.

[0741] Reference Example 5: Synthesis of ZnS outer layer on InP / ZnSeS NPs in ODE using 1-dodecanethiol as S source

[0742] This reference example 5 is similar to reference example 2, but uses InP / ZnSeS particles. The InP / ZnSeS was prepared as described in comparative example 2.

[0743] Table A compares the thermal, free radical, and peroxide stability values ​​of the Example and Comparative Example 2.

[0744] Reference Example 6: Synthesis of ZnS outer layer on InP / ZnSe NPs in ODE using perfluorodecanethiol as S source

[0745] This Reference Example is similar to Reference Example 2, but perfluorodecanethiol is used as the sulfur precursor.

[0746] Table A:

[0747]

[0748] Thermal stability test - powder thermal test in air at 150°C

[0749] Benzoquinone test – Addition of 2.667 wt% p-benzoquinone to clean NPs in toluene

[0750] Peroxide testing – Addition of 50 wt% tert-butyl perbenzoate to clean NPs in toluene

[0751] Reference Example 7: Experimental demonstration of the surface and crystal binding of DDSe QDs in Reference Example 1

[0752] Mentioned in Fig. 9 The general scheme in (Scheme 1) describes a multi-step approach to establish characterization between a surface and a crystal-bound ligand (covalently bound ligand), using dodecylselenol (DDSe) as an example.

[0753] 3-phenylpropylphosphonic acid (PPPA) is known for its stronger affinity to QD surface compared with amine, thiol, selenol and carboxylic acid. Surface-bound ligands are desorbed from the QD surface and replaced by PPPA. On the other hand, crystal-bound ligands are integrated into the lattice. Subsequently, it is impossible to dissociate from QD without destroying the crystal. This process can also be used to experimentally prove that crystals bind to amine-containing ligands, thiol-containing ligands (such as mPEG thiol), other selenol-containing ligands and carboxylic acid-containing ligands of QD.

[0754] Characterization of QDs of Reference Example 1:

[0755] Figure 6 : Before (a) and after (b) adding PPPA, QDs of Reference Example 1 1 H NMR spectrum (in toluene d8)

[0756] The addition of PPPA resulted in the desorption of DDSe from the QD surface.

[0757] By quantitative 1The amount of isolated DDSe (surface bound) was calculated in mmol using tetramethyl-p-benzoquinone as an external standard by H NMR and was equal to 0.00135 mmol, meaning that only 1.8 mol% of the total amount of DDSe inserted into the reaction resulted in surface bound DDSe.

[0758] Figure 7 : After treatment with PPPA and washing with ethanol, the 1 H NMR spectrum (in toluene d8).

[0759] 1 H NMR indicated that the surface-bound DDSe was completely removed from the surface of the QD (signal #2 (Se-H) and signal #3 (CH2-Se) disappeared). However, signal #1 (CH3 of DDSe) still existed. This indicated the presence of a second non-surface-bound DDSe population.

[0760] The QDs were analyzed in GCMS after removal of all surface-bound DDSe. For this purpose, appropriate derivatization with HCl and methanol was performed. This treatment resulted in complete decomposition and dissolution of the QDs.

[0761] Fig. 8A , 8B : GCMS spectrum of QDs after treatment with PPPA and washing. MS spectrum of the peak at retention time of 11.458.

[0762] The sample for GCMS was prepared as described in the embodiment. GCMS confirmed the presence of DDSe. This indicates crystalline incorporation of DDSe.

[0763] Main conclusion: The QDs of Reference Example 1 contain surface-bound DDSe as well as crystal-bound DDSe.

[0764] Reference Example 8: Synthesis of ZnS outer layer on InP-based red quantum dots in PGMEA using poly(ethylene glycol) methyl ether thiol Mn 800 (mPEG800-SH) as S source

[0765] 183.5 mg (1 mmol) Zn(OAc) 2 was weighed into a 50 mL round-bottom 4-necked reaction flask, placed under vacuum for 40 minutes, placed under argon, and introduced into a glove box; 6 mL PGMEA and 0.61 mL of InP-based red quantum material (QM) were added.

[0766] Observation - Red suspension.

[0767] Place under vacuum at room temperature for 20 minutes.

[0768] Place under Ar.

[0769] Add 2 mL PGMEA.

[0770] Heat (in 8 minutes) to 144°C (reflux, condenser cooled with water flow).

[0771] At 144°C, 1.15 mL of 0.43 M mPEG-SH solution in PGMEA was injected - t = 0

[0772] The mixture was allowed to stand at 144°C for 65 minutes.

[0773] 1.15 mL of a 0.43 M mPEG-SH solution in PGMEA was injected.

[0774] Stand at 144°C for 70 minutes. End. Total - 2 hours 15 minutes at 144°C.

[0775] The resulting QDs were cleaned with anhydrous hexane (crude: hexane ratio 1: 1). The process was repeated with a mixture of anhydrous PGMEA: hexane 1: 1. The QDs were then extracted with toluene.

[0776] Table B:

[0777]

[0778] Table B compares the values ​​of thermal stability of the reference example 8 and the first semiconductor material used (the red quantum material based on InP).

[0779] Reference Example 9: Synthesis of ZnS outer layer on InP-based red quantum dots in PGMEA using poly(ethylene glycol) methyl ether thiol Mn 800 (mPEG800-SH) as S source

[0780] 1.28 g of zinc acetate (Zn(OAc)2) was weighed into a 250 ml round bottom flask and degassed at 200 mTorr for 25 minutes while stirring. Placed under Ar atmosphere. Inserted into the glove box.

[0781] Add 56 ml of PGMEA and 2.1 gr of a toluene solution of an InP-based red quantum material. Install the mixture on a Schlenk line. Place under Ar. Install a distillation apparatus and distill off toluene.

[0782] The flask was heated to reflux and 7.7 ml of a 0.4 M solution of mPEG800-SH in PGMEA was injected.

[0783] After 65 minutes, another 7.7 ml of a 0.4 M solution of mPEG800-SH in PGMEA was injected.

[0784] After a further 70 minutes at reflux the flask was cooled to RT (total reaction time 2 h 15 min).

[0785] The resulting QDs were cleaned as follows: solids were removed by centrifugation; QDs were precipitated with anhydrous hexane (ratio of crude:hexane 1:1); the process was repeated with a mixture of anhydrous PGMEA:hexane 1:1 and then twice with anhydrous toluene:hexane 2:3.

[0786] Table C:

[0787]

[0788] Table C compares the values ​​of thermal stability of Working Example 9 with a reference material prepared similarly to Working Example 9 but without Zn(OAc)2.

[0789] Reference Example 10: Synthesis of ZnS outer layer on InP-based green quantum material with core-shell structure in diisopropylbenzene using poly(ethylene glycol) methyl ether thiol Mn 350 (mPEG350-SH) as S source,

[0790] 0.215 g Zn(OAc)2 was weighed outside the GB into a 50 ml round bottom flask, which was introduced into the GB. 8 ml diisopropylbenzene (DIPB) was added and then 270 mg of a toluene solution of InP-based green quantum dots was added. The mixture was mounted on a Schlenk line and toluene was removed under reduced pressure. The flask was filled with Ar. The flask was heated to 160 °C and 1.3 ml of a 0.9 M mPEG(350)-SH solution in diisopropylbenzene was injected. After 90 minutes at 160 °C, the reaction was cooled to ambient temperature. After cooling below 50 °C, QDs precipitated. Toluene (6 mL) was added to dissolve the quantum dots.

[0791] The resulting QDs were cleaned by removing solids by centrifugation; precipitating the QDs with anhydrous heptane ((crude material + toluene): heptane ratio 1:1), repeating the process with a mixture of anhydrous PGMEA: heptane 1:2, and then anhydrous toluene: heptane 1:1.

[0792] Working Example

[0793] IBOA = Isobornyl Acrylate

[0794] DPGDA = dipropylene glycol diacrylate

[0795] LA = Lauryl acrylate

[0796] HDDA = 1,6-hexanediol diacrylate

[0797] TMPTA = trimethylolpropane triacrylate

[0798] Working Example 1:

[0799] QD surface passivation and purification were performed under an inert atmosphere.

[0800] In a separate vial, 0.242 g of mPEG350-SH and 2 ml of PGMEA were mixed to obtain a mPEG350-SH stock solution.

[0801] In a reaction flask, 1.09 g of red QDs (with InP core, ZnSe / ZnS double shell) with oleic acid as ligand dispersed in heptane, 31 mg of Zn(OAc)2, 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.

[0802] Half the amount of the mPEG350-SH stock solution was injected into the reaction flask, and the reaction flask was continued to be heated to reflux for 1 hour.

[0803] The second half of the mPEG350-SH stock solution was injected into the reaction flask, and the reaction flask continued to be heated to reflux for another hour.

[0804] The reaction was cooled to room temperature, transferred to a suitable centrifuge bottle and centrifuged at 2795G for 5 minutes to remove any solids. The red supernatant was transferred to a suitable centrifuge bottle. For each volume of reaction mixture, one volume of heptane was added (e.g., for 15 mL reaction mixture, 15 mL of heptane was added). Centrifuged at 2795G for 5 minutes and the supernatant was drained.

[0805] The precipitated QDs were redispersed in 16 mL of toluene. The dispersion was centrifuged at 2795 G for 5 minutes to discard the residual solids.

[0806] The QD dispersion was transferred to a brown glass bottle and stored under an inert atmosphere.

[0807] Working Example 2:

[0808] QD surface passivation and purification were performed under an inert atmosphere.

[0809] In a separate vial, 0.364 g of mPEG350-SH and 2 ml of PGMEA were mixed to obtain a mPEG350-SH stock solution.

[0810] In a reaction flask, 1.09 g of red QDs (with InP core, ZnSe / ZnS double shell) with oleic acid as ligand dispersed in heptane, 191 mg of Zn(OAc)2, 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.

[0811] Half the amount of the mPEG350-SH stock solution was injected into the reaction flask, and the reaction flask was continued to be heated to reflux for 1 hour.

[0812] The second half of the mPEG350-SH stock solution was injected into the reaction flask, and the reaction flask continued to be heated to reflux for another hour.

[0813] The reaction is cooled to room temperature, transferred to a suitable centrifuge bottle and centrifuged at 2795G for 5 minutes to remove any solids. The red supernatant is transferred to a suitable centrifuge bottle. For each volume of reaction mixture, 2.65 volumes of heptane are added (e.g., for 18mL reaction mixture, 47.7mL of heptane is added). Centrifuged at 2795G for 5 minutes, the supernatant is discharged. The precipitated QDs are dispersed again in 6mL toluene. Then 6mL of heptane is added. Centrifuged at 2795G for 5 minutes, the supernatant is discharged. The precipitated QDs are dispersed again in 6mL toluene. The dispersion is centrifuged at 2795G for 5 minutes to discard residual solids. The QD dispersion is transferred to a brown glass bottle and stored under an inert atmosphere.

[0814] Working Example 3:

[0815] QD surface passivation and purification were performed under an inert atmosphere.

[0816] In a separate vial, 1.216 g of mPEG350-SH and 6 ml of PGMEA were mixed to obtain a mPEG350-SH stock solution.

[0817] In a reaction flask, 3 g of red QDs (with InP core, ZnSe / ZnS double shell) with oleic acid as 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.

[0818] Half the amount of the mPEG350-SH stock solution was injected into the reaction flask, and the reaction flask was continued to be heated to reflux for 1 hour.

[0819] The second half of the mPEG350-SH stock solution was injected into the reaction flask, and the reaction flask continued to be heated to reflux for another hour.

[0820] The reaction is cooled to room temperature, transferred to a suitable centrifuge bottle and centrifuged at 2795G for 5 minutes to remove any solids. The red supernatant is transferred to a suitable centrifuge bottle. For each volume of reaction mixture, 0.75 volume of heptane is added (e.g., for a 40mL reaction mixture, 30mL of heptane is added). Centrifuged at 2795G for 5 minutes, the supernatant is discharged. The precipitated QDs are dispersed again in 32mL toluene. Then 16mL of heptane is added. Centrifuged at 2795G for 5 minutes, the supernatant is discharged. The precipitated QDs are dispersed again in 8mL toluene. The dispersion is centrifuged at 2795G for 5 minutes to discard residual solids. The QD dispersion is transferred to a brown glass bottle and stored under an inert atmosphere.

[0821] Working Example 4:

[0822] QDs from working example 1 (0.2 g) dispersed in toluene were introduced into a glass vial. Monomers isobornyl acrylate (IBOA) (263.3 mg) and trimethylolpropane triacrylate (TMPTA) (29.3 mg) were added. Then, photoinitiator Omnirad 819 (5 mg) and antioxidant IRGANOX 1010 (2.5 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated under vacuum at 25 ° C on a rotary evaporator. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0823] Working Example 5:

[0824] QDs from working example 2 (0.2 g) dispersed in toluene were introduced into a glass vial. Monomer IBOA (117 mg), poly(ethylene glycol methacrylate) (MW 360) (117 mg) and triethylene glycol dimethacrylate (58.5 mg) were added. Then, photoinitiator Omnirad 819 (50 mg) and antioxidant IRGANOX 1010 (25 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated on a rotary evaporator under vacuum at 25 ° C. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0825] Working Example 6:

[0826] QDs from working example 3 (0.2 g) dispersed in toluene were introduced into a glass vial. Monomer IBOA (147 mg), triethylene glycol dimethacrylate (147 mg) were added. Then, photoinitiator Omnirad 819 (5 mg) and antioxidant IRGANOX 1010 (2.5 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated on a rotary evaporator under vacuum at 25 °C. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0827] Working Example 7:

[0828] QDs from working example 1 (0.2 g) dispersed in toluene were introduced into a glass vial. Monomer IBOA (234 mg), triethylene glycol dimethacrylate (0.058 mg) were added. Then, photoinitiator Omnirad 819 (5 mg) and antioxidant IRGANOX 1010 (2.5 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated on a rotary evaporator under vacuum at 25 °C. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0829] Working Example 8:

[0830] QDs from working example 3 (0.2 g) dispersed in toluene were introduced into a glass vial. Monomers poly(ethylene glycol methacrylate) (MW 360) (468 mg), ethylene glycol dimethacrylate (117 mg) were added. Then, photoinitiator Omnirad 819 (5 mg) and antioxidant IRGANOX 1010 (2.5 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated on a rotary evaporator under vacuum at 25 ° C. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0831] Working Example 9:

[0832] QDs from working example 3 (0.2 g) dispersed in toluene were introduced into a glass vial together with mPEG-SH (60 mg). Monomer IBOA (472 mg) and TMPTA (53 mg) were added. Then, photoinitiator Omnirad 819 (5 mg) and antioxidant IRGANOX 1010 (2.5 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated under vacuum at 25 °C on a rotary evaporator. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0833] Working Example 10:

[0834] QDs from working example 2 (0.2 g) dispersed in toluene were introduced into a glass vial together with mPEG-SH (60 mg). Monomers LA (420 mg) and HDDA (105 mg) were added. Then, photoinitiator Omnirad 819 (5 mg) and antioxidant IRGANOX 1010 (2.5 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated on a rotary evaporator under vacuum at 25 ° C. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0835] Working Example 11:

[0836] QDs from working example 3 (0.4 g) dispersed in toluene were introduced into a glass vial. Monomers IBOA (351 mg) and dipropylene glycol diacrylate (DPGDA) (234 mg) were added. Then, photoinitiator Omnirad 819 (10 mg) and antioxidant IRGANOX 1010 (5 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated on a rotary evaporator under vacuum at 25 ° C. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0837] Working Example 12:

[0838] QDs from working example 3 (0.4 g) dispersed in toluene and mPEG-SH (60 mg) were introduced into a glass vial. The resulting mixture was heated to 40 ° C for 80 minutes. Monomers IBOA (315 mg) and dipropylene glycol diacrylate (DPGDA) (210 mg) were added. Then, photoinitiator Omnirad819 (10 mg) and antioxidant IRGANOX 1010 (5 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated under vacuum at 25 ° C on a rotary evaporator. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0839] Working Example 13:

[0840] QDs from working example 3 (0.4 g) dispersed in toluene and octadecyl mercaptan (48 mg) were introduced into a glass vial. The suspension was heated to 80 ° C for 2 hours. Monomers LA (322 mg) and HAAD (215 mg) were added. Then, photoinitiator Omnirad819 (10 mg) and antioxidant IRGANOX 1010 (5 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated on a rotary evaporator under vacuum at 25 ° C. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0841] Working Example 14:

[0842] QDs from working example 3 (1.0 g) dispersed in toluene and mPEG350-SH (150 mg) were introduced into a glass vial. The suspension was heated to 40 °C for 2 hours. Monomer IBOA (1.181 g) and TMPTA (131 mg) were added. Then, photoinitiator Omnirad819 (25 mg) and antioxidant IRGANOX 1010 (12.5 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated on a rotary evaporator under vacuum at 25 °C. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0843] Comparative Example 1: (Compared with Working Example 4)

[0844] Formation of solvent-based inks with natural QDs.

[0845] 0.2 g of red QDs (with InP core, ZnSe / ZnS double shell) with oleic acid as ligand dispersed in heptane were introduced into a glass vial. Monomer IBOA (263.3 mg) and TMPTA (29.3 mg) were added. Then, photoinitiator Omnirad819 (50 mg) and antioxidant 1010 (25 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated on a rotary evaporator under vacuum at 25 ° C. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0846] Comparative Example 2: (Compared with Working Example 4)

[0847] The solvent-based ink was formed with natural QDs and the additive mPEG-SH.

[0848] 0.2 g of red QDs (with InP core, ZnSe / ZnS double shell) with oleic acid as ligand dispersed in heptane and 51.9 mg of mPEG-SH (MW350) were introduced into a glass vial. Monomers IBOA (263.3 mg) and TMPTA (29.3 mg) were added. Then, photoinitiator Omnirad819 (50 mg) and antioxidant 1010 (25 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated on a rotary evaporator under vacuum at 25 ° C. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0849] Comparative Example 3: (Compared with Working Examples 11 and 12)

[0850] The solvent-based ink was formed with natural QDs and the additive mPEG-SH.

[0851] 0.16 g of red QDs (with InP core, ZnSe / ZnS double shell) with oleic acid as ligand dispersed in heptane and 40 mg of mPEG-SH (MW350) were introduced into a glass vial. Monomers IBOA (116 mg) and DPGDA (78 mg) were added. Then, photoinitiator Omnirad819 (40 mg) and antioxidant IRGANOX 1010 (20 mg) were added. The formulation was shaken for 10 minutes and the volatiles were evaporated on a rotary evaporator under vacuum at 25 ° C. The remaining volatiles were removed on a Schlenk line under a vacuum of 60 mTorr.

[0852] Film formation:

[0853] The film was formed by filling the glass sandwich unit (gap about 10 um) with the ink described in the previous example. The film was formed by UV light (300 mW / cm 2 , 10 seconds) to cure the film. The cell is then opened, resulting in an open film deposited in one cell glass.

[0854] The opened film was heated (thermal annealed) at 180° C. for 30 minutes under an inert atmosphere. After thermal annealing, the film was stored in a humidity controlled chamber at 25° C. and 45% relative humidity (RH).

[0855] QY and EQE were measured after thermal annealing for 1 hour and after storage for 3 or 5 days as indicated in Tables 1 to 4 below.

[0856] EQE = photons [emitted light] / photons [excitation light measured without sample];

[0857] According to the present invention, the EQE is measured at room temperature by the following EQE measurement process, which is based on the use of an integrating sphere and a spectrometer (Compass X, BWTEK) equipped with a 450 nm excitation light source coupled in via an optical fiber, and 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 a test cell is placed in front of the integrating sphere between the opening of the integrating sphere and the outlet of the optical fiber to detect photons incident from the excitation light source, transmitted through the sample, and photons emitted from the sample or the test cell, and for both cases, the photons leaving the integrating sphere are counted by the spectrometer and the EQE and BL calculations are performed by the following equations and the number of photons of the excitation light and the emitted light is calculated by integration in the following wavelength ranges;

[0858] EQE = photons [emitted light] / photons [excitation light measured without sample];

[0859] BL = photons [-excitation light measured when the sample is placed] / photons [excitation light measured when no sample is placed];

[0860] If the green light emitting part is used, the emitted light is: 490nm to 600nm,

[0861] If the red light emitting part is used, the emitted light is: 580nm to 780nm

[0862] Excitation light: 390nm to 490nm.

[0863] Table 1

[0864]

[0865] Table 2

[0866]

[0867]

[0868] Table 3

[0869]

[0870] Table 4

[0871]

[0872] Working Example 15:

[0873] Red QD ink containing red QDs (with InP core, ZnSe / ZnS double shell) having two different types of ligands made of mPEG-(SH) and oleic acid was prepared by mixing the materials mentioned in Table 5 below.

[0874] Table 5

[0875]

[0876] Working Example 16:

[0877] The QD film obtained by Working Example 15 was stored in an atmosphere of 25° C., 45% RH. The EQE of the QD film was monitored up to 5 days.

[0878] result

[0879] The red QD ink of Working Example 15 showed excellent dispersibility.

[0880] A QD film with a film thickness of 10 um was obtained through Working Example 16.

[0881] Under atmospheric conditions, the EQE remained over 97% after 5 days.

Claims

1. A composition, preferably a photocurable composition, comprising at least: i) a luminescent moiety, preferably a semiconductor luminescent nanoparticle comprising an outer layer containing a metal cation and a divalent anion; and one or more types of organic moieties directly attached to said anion of said outer layer via covalent bonds, ii) at least one reactive monomer or a mixture of two or more reactive monomers, preferably, the monomer has one or more functional groups, more preferably, it is a (meth)acrylate monomer; The divalent anion in the outer layer is selected from Se 2- , S 2- 、Te 2- , O 2- or any combination thereof, preferably, the metal cation in the outer layer is a monovalent, divalent, trivalent or tetravalent cation, more preferably, the metal cation is selected from Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ A divalent cation selected from the group consisting of Ti 4+ ,Ge 4+ 、Si 4+ 、Zr 4+ , Hf 4+ Sn 4+ The group consisting of tetravalent cations.

2. The composition according to claim 1, wherein the organic part is represented by the following chemical formula (I); AB-*(I) in A is an organic group, preferably, the organic group is a hydrocarbon group (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group, including an aryl, an alkaryl, an alkyl or an aralkyl, an alkylamine, a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group, including a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl or a fluoroaralkyl; B is a connecting unit, preferably, B is **-(U) o -(Y) m -(CR IIa R IIb ) n , where "**" indicates the point of attachment to "A"; and "*" indicates the point of connection to the anion in the outer layer.

3. The composition according to claim 1 or 2, wherein the organic part is represented by the following chemical formula (II), (III) or (III'); READ) o -(Y) m -(CR IIa R IIb ) n -*(II) in L is an organic group, preferably, the organic group is a hydrocarbon group (alkyl, aryl, aralkyl and alkylaryl), a heteroaromatic group, including an aryl, an alkaryl, an alkyl or an aralkyl, an alkylamine, a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl, a fluoroaralkyl, a heteroaromatic group, including a fluoroaryl, a fluoroalkylaryl, a fluoroalkyl or a fluoroaralkyl; U is O, CH2 or C=O; Y is O, CH2 or C=O; R IIa and R IIb Each occurrence is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIa and R IIb is a hydrogen atom; n is an integer of 1 or greater; m is 0 or an integer of 1 or greater, preferably, m is 1; o is 0 or an integer of 1 or greater, preferably, o is 1; "*" indicates the point of connection 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 R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and R IIIh Each of the occurrences is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIIg and R IIIh is a hydrogen atom, 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 straight-chain alkyl group having 1 to 25 carbon atoms, a branched-chain alkyl group having 3 to 25 carbon atoms, -COOH, -SH or -NH2, an alkylamine, a fluoroaryl group, a fluoroalkylaryl group, a fluoroalkyl group, a fluoroaralkyl group, a heteroaromatic group, including a fluoroaryl group, a fluoroalkylaryl group, a fluoroalkyl group or a fluoroaralkyl group, preferably, Z is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, a branched-chain alkyl group having 3 to 25 carbon atoms, more preferably, it is a hydrogen atom, a straight-chain alkyl group having 1 to 15 carbon atoms, a branched-chain alkyl group having 3 to 15 carbon atoms, even more preferably, it is a hydrogen atom or a straight-chain alkyl group having 1 to 10 carbon atoms; a is 0 or an integer of 1 or greater, preferably 0≤a≤25, more preferably 0≤a≤15, 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 further 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 further, preferably, it is 1≤q≤5; r is 0 or integer 1; "*" indicates the point of connection to the anion in the outer layer.

4. A composition according to any one of the preceding claims, 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 R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and R IIIh Each occurrence is independently selected from hydrogen, hydroxy, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms; preferably hydrogen, hydroxy, straight-chain alkyl having 1 to 5 carbon atoms, branched-chain alkyl having 3 to 5 carbon atoms; preferably, R IIIg and R IIIh is a hydrogen atom, preferably, R IIIe and R IIIf is a hydrogen atom; a is 0 or an integer of 1 or greater, preferably 0≤a≤25, more preferably 0≤a≤15, 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 further 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 more preferably, it is 1; V is O, CH2 or C=O; Z′ is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, a branched-chain alkyl group having 3 to 25 carbon atoms, an alkylamine, a fluoroaryl group, a fluoroalkylaryl group, a fluoroalkyl group, a fluoroaralkyl group, a heteroaromatic group, including a fluoroaryl group, a fluoroalkylaryl group, a fluoroalkyl group or a fluoroaralkyl group, preferably, Z′ is a straight-chain alkyl group having 1 to 25 carbon atoms, a branched-chain alkyl group having 3 to 25 carbon atoms or a hydrogen atom, more preferably, it is a straight-chain alkyl group having 1 to 15 carbon atoms, a branched-chain alkyl group having 3 to 15 carbon atoms or a hydrogen atom, even more preferably, it is a hydrogen atom; r is 0 or integer 1; "*" indicates the point of connection to the anion in the outer shell, preferably, it is connected via a S or Se atom in the outer shell.

5. A composition according to any preceding claim, wherein the organic moiety is covalently bound to the anion in the outer layer of the inorganic lattice, preferably without being removed by ligand exchange.

6. A composition according to any one of the preceding claims, wherein the metal cation is a transition metal of Group 12 or Group 14, preferably selected from Zn 2+ , Hg 2+ or Pb 2+ One or more members of a group.

7. The composition according to any one of the preceding claims, wherein the reactive monomer is a (meth)acrylate monomer selected from mono-(meth)acrylate monomers, di-(meth)acrylate monomers 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.

8. The composition according to claim 7, wherein the di-(meth)acrylate monomer is represented by the following chemical formula (I b ) represents, 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 )express; in X 1 is an unsubstituted or substituted ester group, alkyl group or aryl group, wherein one or more non-adjacent CH2 groups of the ester group, 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 wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; preferably, the ester group is of the following formula (I bs1 )express; Where 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 alkylene chain having 1 to 5 carbon atoms, an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by oxygen atoms, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; preferably, R Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, wherein at least one of the non-adjacent CH2 groups may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; X 2 is an unsubstituted or substituted ester group, alkyl group or aryl group, wherein one or more non-adjacent CH2 groups of the ester group, 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 wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; preferably, the ester group is of the following formula (I bs2 )express; Where 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 alkylene chain having 1 to 5 carbon atoms, an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, wherein one or more non-adjacent CH2 groups may be replaced by oxygen atoms, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH and wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; preferably, R Ib2 is an unsubstituted or substituted branched alkylene chain having 3 to 7 carbon atoms, wherein at least one of the non-adjacent CH2 groups may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS or CONH and wherein one or more H atoms may be 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, wherein one or more non-adjacent CH2 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 wherein 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, wherein one or more non-adjacent CH2 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 wherein 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; X 3 is an unsubstituted or substituted ester group, an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, if X 3 is an unsubstituted or substituted ester group, the ester group is represented by the following formula (II bs )express; Where 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, cyclyl, cycloalkyl, aryl or alkoxy group, R 5 is a hydrogen atom, a halogen atom of Cl, Br or F, a methyl group, an alkyl group, an aryl group, an alkoxy group, an ester group or a carboxylic acid group; Where R 9 is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, or a radical of the formula (IV b ) represented by (meth)acryloyl R 10 is a hydrogen atom, a straight chain alkyl group having 1 to 25 carbon atoms, or a radical of the formula (V b ) represented by (meth)acryloyl R 11 is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, or a radical of the formula (VI b ) represented by (meth)acryloyl Where R 8 , R 8a , R 8b and R 8c Each at each occurrence, independently or dependently, is H, CH2CH3 or CH3; Where R 9 , R 10 and R 11 At least one of them is a (meth)acryloyl group.

9. A process for producing a composition according to any one of the preceding claims, comprising at least the following steps, (a) mixing at least a light-emitting part with another material to obtain a reaction mixture, preferably, the light-emitting part comprises at least a first semiconductor nanomaterial as a core, and preferably, the 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; ABXH(Va) ABXXBA(Vb) in A is an organic group; B is the connection unit; H is a hydrogen atom; and X is an anchoring group comprising an anion capable of forming a monolayer with an added metal cation that may be derived from an added metal cation precursor; (c) cooling the reaction mixture from step (b), wherein the reaction mixture in step (b) is maintained at a temperature in the range of 80°C to 200°C, preferably 100°C to 200°C to form the outer layer in step (b), (d) mixing the light-emitting portion 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 according to claim 9, wherein the ratio of the total molar amount of the cationic precursors to the total molar amount of the semiconductor nanoparticles in step (b) is in the range of 20:1 to 200000:1, preferably 100:1 to 60000:1, more preferably 110:1 to 58000:1, even more preferably 120:1 to 5000:1, and preferably, the ratio of the total mass of the cationic 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.

11. A formulation comprising at least a 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 selected from one or more members of the group consisting of toluene, xylene, tetrahydrofuran, chloroform, dichloromethane and heptane, hexane, pure water, ester acetate, ether acetate, ketone, ether ester, preferably, it is PGMEA, alcohol, preferably ethanol or isopropanol, sulfoxide, formamide, nitride, ketone.

12. 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 inkjetting; S2) 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 comprising at least: Xi) a luminescent moiety, preferably a semiconductor luminescent nanoparticle comprising an outer layer containing a metal cation and a divalent anion; and one or more types of organic moieties directly attached to said anion of said outer layer via covalent bonds, Xii) a polymer made from at least one reactive monomer or a mixture of two or more reactive monomers, preferably the monomer has one or more functional groups, more preferably it is a (meth)acrylate monomer; The divalent anion in the outer layer is selected from Se 2- , S 2- 、Te 2- , O 2- or any combination thereof, preferably, the metal cation in the outer layer is a monovalent, divalent, trivalent or tetravalent cation, more preferably, the metal cation is selected from Zn 2+ 、Ni 2+ 、Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ Mg 2+ and Pb 2+ A divalent cation selected from the group consisting of Ti 4+ ,Ge 4+ 、Si 4+ 、Zr 4+ , Hf 4+ Sn 4+ The group consisting of tetravalent cations.

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

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

Images