WO2024028426A1 - Composition - Google Patents

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Publication number
WO2024028426A1
WO2024028426A1 PCT/EP2023/071515 EP2023071515W WO2024028426A1 WO 2024028426 A1 WO2024028426 A1 WO 2024028426A1 EP 2023071515 W EP2023071515 W EP 2023071515W WO 2024028426 A1 WO2024028426 A1 WO 2024028426A1
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Prior art keywords
group
carbon atoms
alkyl group
substituted
hydrogen atom
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PCT/EP2023/071515
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English (en)
Inventor
Elizaveta KOSSOY
Suzanna AZOUBEL
Gil BERNSTEIN TOKER
Hiromoto Sato
Tadashi Kishimoto
Tomohisa Goto
Teruaki Suzuki
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Merck Patent Gmbh
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Publication of WO2024028426A1 publication Critical patent/WO2024028426A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium

Definitions

  • the present invention relates to a composition containing a light emitting moiety; a process for fabricating the composition; formulation; use of a composition, method for forming a layer; a layer; a color conversion device; and an optical device.
  • Turo et al., ACS NANO vol.8, no.10, 10205-10203, 2014 discloses CU2S Nanoparticles having no shell layers with dodecanethiol (DDT) and the fabrication process with using DDT at the temperature of 200°C. DDT is used in the entire synthesis process.
  • DDT dodecanethiol
  • the inventors aimed to solve one or more of the above-mentioned problems.
  • a novel composition preferably it is being of a photocurable composition, comprising at least, mainly consisting of, or consisting of; i) a light emitting moiety, preferably it is a semiconducting light emitting nanoparticle, comprising an outer layer containing a metal cation and a divalent anion; and one or more types of organic moieties directly attached to the anion of the outer layer by covalent bond, ii) at least one reactive monomer or a mixture of two or more reactive monomers, preferably said monomer having one or more of functional groups, more preferably it is a (meth)acrylate monomer; wherein said divalent anion of the outer layer is selected from Se 2- , S 2- , Te 2- O 2 ' or a combination of any of these, preferably said metal cation of the outer layer is a monovalent, divalent, trivalent or
  • the present invention further relates to a process for preparing the composition of the present invention comprising, mainly consisting of, or consisting of, at least following steps,
  • A is an organic group
  • B is a connecting unit connecting A and X;
  • H is a hydrogen atom
  • X is an anchor group comprising an anion, capable to form a monolayer with the added metal cation derivable from the added metal cation precursor;
  • step (c) cooling the reaction mixture from step (b), wherein the reaction mixture in step (b) is kept at a temperature in the range from 80°C to 200 °C, preferably 100 to 200 °C to form the outer layer in step (b) ,
  • step (d) mixing a light emitting moiety obtained from step (c) with at least one reactive monomer or a mixture of two or more reactive monomers to from a composition.
  • the present invention relates to a composition obtainable or obtained from the process of the present invention.
  • the present invention relates to formulation comprising, essentially consisting of, or consisting of, at least a composition of the present invention, and at least one solvent, preferably the solvent is selected from one or more members of the group consisting of aromatic, halogenated and aliphatic hydrocarbon solvents, ethers, esters, ionic liquids, alcohols and water, more preferably selected from one or more members of the group consisting of toluene, xylene, tetrahydrofuran, chloroform, dichloromethane and heptane, hexane, purified water, ester acetates, ether acetates, ketones, etheric esters such as PGMEA , alcohols such as ethanol, isopropanol etc., sulfoxides, formamides, nitrides, ketones.
  • the present invention relates to use of the composition, or the formulation, in an electronic device, optical device, sensing device or a biomedical device.
  • the present invention relates to a method for forming a layer comprising:
  • composition of the present invention onto a substrate, preferably by ink-jetting;
  • curing the composition preferably said curing is a photo curing performed by photo irradiation, thermal curing or a combination of a photo curing and a thermal curing.
  • the present invention further relates to a layer obtained or obtainable from the method of the present invention.
  • the present invention further relates to a layer containing at least, mainly consisting of or consisting of; Xi) a light emitting moiety, preferably it is a semiconducting light emitting nanoparticle, comprising an outer layer containing a metal cation and a divalent anion; and one or more types of organic moieties directly attached to the anion of the outer layer by covalent bond,
  • the present invention further relates to a color conversion device (100) comprising at least a 1 st pixel (161 ) partly or fully filled with the layer of the present invention comprising at least a matrix material (120) containing a light emitting moiety (110), and a bank (150) comprising at least a polymer material, preferably the color conversion device (100) further contains a supporting medium (170).
  • the present invention further relates to an optical device (300) containing at least one functional medium (320, 420, 520) configured to modulate a light or configured to emit light, and the color conversion device (100) of the present invention.
  • Fig. 1 shows a cross sectional view of a schematic of one embodiment of a color conversion film (100).
  • Fig.2 shows a top view of a schematic of another embodiment of a color conversion film (100) of the invention.
  • Fig. 3 shows a cross sectional view of a schematic of one embodiment of an optical device (300) of the invention.
  • Fig. 4 shows a cross sectional view of a schematic of another embodiment of an optical device (300) of the invention.
  • Fig. 5 shows a cross sectional view of a schematic of another embodiment of an optical device (300) of the invention.
  • Fig. 8A,8B GCMS spectrum for QDs from reference example 1 after treating with PPPA and washing. MS spectrum of peak at retention time of 11.45.
  • Fig.9 describes the general scheme of a multi-step method that is established to differentiate between surface and crystal bound ligands, exemplified for dodecaneselenol (DDSe) (scheme1 ).
  • DDSe dodecaneselenol
  • a supporting medium (a substrate) (optional)
  • a light emitting device e.g., OLED
  • light emitting layer e.g., OLED layer(s)
  • an optical layer e.g., polarizer (optional)
  • a composition preferably it is being of a photocurable composition, comprises at least; i) a light emitting moiety, preferably it is a semiconducting light emitting nanoparticle, comprising an outer layer containing a metal cation and a divalent anion; and one or more types of organic moieties directly attached to the anion of the outer layer by covalent bond, ii) at least one reactive monomer or a mixture of two or more reactive monomers, preferably said monomer having one or more of functional groups, more preferably it is a (meth)acrylate monomer; wherein said divalent anion of the outer layer is selected from Se 2- , S 2- , Te 2- O 2 ' or a combination of any of these, preferably said metal cation of the outer layer is a monovalent, divalent, trivalent or tetravalent cation, more preferably said metal cation is a divalent cation selected from the group consisting of Zn 2+ , Ni 2+ ,
  • said light emitting moiety may be an organic and/or inorganic light emitting material, preferably it is an organic dye, inorganic phosphor and/or a semiconducting light emitting nanoparticle such as a quantum material.
  • an organic dye, inorganic phosphor, a semiconducting light emitting nanoparticle a publicly known one can be used.
  • Such suitable inorganic light emitting materials described above can be well known phosphors including nanosized phosphors, quantum sized materials like mentioned in the phosphor handbook, 2 nd edition (CRC Press, 2006), pp. 155 - pp. 338 (W.M.Yen, S.Shionoya and H. Yamamoto), WO201 1/147517A, WO2012/034625A, and WO2010/095140A.
  • organic dyes For examples rhodamine, coumarin, pyrromethene, DCM, Fluorescein, umbelliferone, BD Horizon BrilliantTM series can be used.
  • said light emitting moiety is an inorganic light emitting material. More preferably it is a semiconducting light emitting nanoparticle.
  • Said semiconducting light emitting nanoparticle is preferably a semiconducting light emitting nanoparticle, comprising, essentially consisting of, or consisting of, a core; an outer layer covering at least a part of said core, comprising a metal cation and a divalent anion; and an organic moiety, preferably one or more types of organic moieties directly attached to the anion of the outer layer by covalent bond, wherein said divalent anion is selected from Se 2- , S 2- , Te 2- O 2- or a combination of any of these, preferably said metal cation is a monovalent, divalent cation, trivalent or tetravalent cation, more preferably said metal cation is a divalent cation selected from the group consisting of Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+
  • the nanoparticle comprises at least an outer layer and a core.
  • Said nanoparticle may optionally contain one or more of other layers (shell layers) between the outer layer and the core.
  • the outer layer covers at least a part of said core.
  • the outer layer may have a direct physical contact with said core if there is no other layers between the outer layer and the core.
  • the outer layer may cover the core via one or more of additional layers placed between the outer layer and the core.
  • cover and the term “covering” do not necessarily mean that there is always a physical contact between the said core and the outer layer.
  • the core is fully covered by an outer layer and/or one or more of shell layers.
  • said nanoparticle comprises a core, one or more of shell layers and one outer layer, wherein the outermost shell layer of said one or more of shell layers comprises Zn and S atom.
  • said outer layer of the light emitting moiety comprises at least two or three different metal cations such as the combination of Cu 1 + and ln 3+ , Cu 1 + and Ga 3+ , Ag 1 + and Ga 3+ or a combination of Cu +1 /ln +3 /Zn +2 from the view point of making an improved covalent bond between the organic moieties and the anions of the outer layer
  • the term “nanosized” means the size in between 0.1 nm and 150 nm, preferably 0.5nm to 100 nm, more preferably 1 nm to 50 nm.
  • semiconductor means a material having electrical conductivity to a degree between that of a conductor (such as copper) and that of an insulator (such as glass) at room temperature, preferably, a semiconductor is a material whose electrical conductivity increases with the temperature.
  • the term “semiconductor nanoparticle” is taken to mean that a material having electrical conductivity to a degree between that of a conductor (such as copper) and that of an insulator (such as glass) at room temperature, preferably, a semiconductor is a material whose electrical conductivity increases with the temperature and the size is in between 0.1 nm and 999 nm, preferably 0,5 nm to 150 nm, more preferably 1 nm to 50 nm.
  • the term “size” means the average diameter of the circle with the area equivalent to the measured TEM projection of the semiconducting nanosized light emitting particles.
  • the semiconducting light emitting nanoparticle of the present invention is a quantum sized material.
  • the term “quantum sized” means the size of the first semiconducting nanoparticle itself without ligands or another surface modification, which can show the quantum confinement effect, like described in, for example, ISBN:978-3-662-44822-9.
  • the quantum sized materials can emit tunable, sharp and vivid colored light due to “quantum confinement” effect.
  • the size of the overall structures of the quantum sized material is from 1 nm to 50 nm.
  • the average diameter of the first semiconducting nanoparticle (core) is in the range from 1 to 20 nm, preferably it is in the range from 1 .5 to 12nm.
  • the average diameter of the semiconducting light emitting nanoparticles are calculated based on 100 semiconducting light emitting nanoparticles in a TEM image taken by a Tecnai G2 Spirit Twin T-12 Transmission Electron Microscope.
  • the average diameter of the semiconducting light emitting nanoparticles are calculated using FijiJmageJ program.
  • said semiconducting light emitting nanoparticle may have a core-shell structure.
  • the term “core” means semiconducting light emitting nanoparticle itself.
  • the core comprises at least one element of group 12 or group 13 elements of the periodic table and one element of group 15 or 16 elements of the periodic table.
  • the 1 st semiconducting material (hereafter “core” of the semiconducting light emitting nanoparticle”) comprises at least one element of the group 13 of the periodic table, and one element of the group 15 of the periodic table, preferably the element of the group 13 is In, and the element of the group 15 is P.
  • the first core can further comprise additional element selected from one or more member of the group consisting of Ga, Zn, S, and Se.
  • the core is a metal oxide comprising for example ZnO, FeO, Fe2O3, ZrO2, CuO, SnO CU2O, TiO2, WO3, HfO2, ln2Os, MgO, AI2O3 and any combination of these.
  • the core comprises a metal, for example Au, Ag, W, Pd, Pt, Cu, In, Ti, Zn, Pb, Al, Cd, Zn and a combination of any of these.
  • a metal for example Au, Ag, W, Pd, Pt, Cu, In, Ti, Zn, Pb, Al, Cd, Zn and a combination of any of these.
  • the core is selected from the group consisting of InP, InPZn, InPZnS, InPZnSe, InPZnSeS, InPZnGa, InPGaS, InPGaSe, InPGaSeS, InPZnGaSeS and InPGa.
  • a type of shape of the core of the semiconducting light emitting nanoparticle, and shape of the semiconducting light emitting nanoparticle to be synthesized are not particularly limited.
  • spherical shaped, elongated shaped, star shaped, polyhedron shaped, pyramidal shaped, tetrapod shaped, tetrahedron shaped, platelet shaped, cone shaped, and irregular shaped core and – or a semiconducting light emitting nanoparticle can be synthesized.
  • -Shell layer According to the present invention, in a preferable embodiment, the core is at least partially embedded in the first shell layer, more preferably said core is fully embedded into one or more shell layers. In a preferred embodiment of the present invention, said shell layer(s) are placed in between the core and the outer layer.
  • the semiconducting light emitting nanoparticle of the present invention optionally may comprise, essentially consisting of, or consisting of a core, one or more shell layers covering said core, an outer layer covering said shell layers in this sequence.
  • said shell layer comprises at least one metal cation and at least one divalent anion as described in the section of outer layer and/or at least a 1 st element of group 12 of the periodic table and a Se atom or a S atom, preferably, the 1 st element is Zn.
  • said first shell layer is selected from the group consisting of Cs2S, Cs2Se, Cs2Te, Cs2O, Ag2S, Ag 2Se, Ag2Te, Ag2O, Au2S, Au2Se, Au2Te, Au2O, , Cu2S, Cu2Se, Cu2Te, Cu2O, 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, CoT
  • At least one (first) the shell layer comprises or a
  • said shell layer is an alloyed shell layer or a graded shell layer, preferably said graded shell layer is ZnSxSey, ZnSeyTez, or ZnSxTez, more preferably it is ZnSxSey.
  • the semiconducting light emitting nanoparticle further comprises 2 nd shell layer onto said shell layer, preferably the 2 nd shell layer comprises or a consisting of a 3 rd element of group 12 of the periodic table and a 4 th element of group 16 of the periodic table, more preferably the 3 rd element is Zn, and the 4 th element is S, Se, or Te with the proviso that the 4 th element and the 2 nd element are not same.
  • the first semiconducting nanoparticle as a core and a first shell layer can be at least partially embedded in the 2 nd shell, preferably said first semiconducting nanoparticle is fully embedded into the shell layer.
  • said second shell layer is selected from the group consisting of Cs2S, Cs2Se, Cs2Te, Cs2O, Ag2S, Ag 2Se, Ag2Te, Ag2O, Au2S, Au2Se, Au2Te, Au2O, , Cu2S, Cu2Se, Cu2Te, Cu2O, 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, CoT
  • 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 a combination of any of these materials More preferably: ZnS, ZnSe, ZnTe, ZnO or a combination of any of these materials.
  • said 2 nd shell layer comprises at least a 1 st element of group 12 of the periodic table and a 2 nd element of group 16 of the periodic table, preferably, the 1 st element is Zn, and the 2 nd element is S, Se, O, or Te.
  • said 2 nd shell layer can be an alloyed shell layer.
  • the semiconducting light emitting nanoparticle can further comprise one or more additional shell layers onto the 2 nd shell layer as a multishell.
  • multishell stands for the stacked shell layers consisting of three or more shell layers.
  • CdS, CdZnS, CdS/ZnS, CdS, ZnS, ZnS/ZnSe, ZnSe/ZnS or combination of any of these can be used as a shell layer.
  • CdS, CdZnS, CdS/ZnS, CdS, ZnS, ZnS/ZnSe, ZnSe/ZnS or combination of any of these can be used.
  • ZnS, ZnSe or ZnSe/ZnS Preferably, ZnS, ZnSe or ZnSe/ZnS.
  • Such semiconducting light emitting nanoparticles are publicly available (for example from Sigma Aldrich) and / or can be synthesized with the method described for example in US 7,588,828 B, US 8,679,543 B and Chem. Mater.2015, 27, pp 4893-4898.
  • the organic moiety is represented by following chemical formula (I); A-B-* (I) wherein A is an organic group, preferably said organic group is hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), heteroaromatic group, including aryl, alkaryl, alkyl or aralkyl, alkylamine, fluoroaryl, fluoroalkaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, including fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl; B is a connecting unit, preferably B is **-(U)o-(Y)m-(CR IIa R IIb )n, wherein “**” represents the connecting point to “A;” and represents the connecting point to the anion in the outer layer.
  • A is an organic group, preferably said organic group is hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), heteroaromatic
  • the organic moiety is represented by 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) wherein R IIIa , R IIIb , R IIIc , R IIId , R IIIe , R IIIf , R IIIg and R IIIh are, each independently each other, at each occurrence, selected from hydrogen atom, a hydroxy group, a straight alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms; preferably a hydrogen atom, a hydroxy group, a straight alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms; preferably R IIIg and R IIIh are hydrogen atom, preferably R IIIe and R IIIf are hydrogen atom; a is 0 or an integer 1
  • the organic moiety is CH 3 - (CH 2 ) 7 ⁇ n ⁇ 18-* and connecting to the S or Se atom in the outer layer.
  • the organic moiety selected from chemical formula (I), (II), (III), (III ⁇ ) or (IV) is covalently bound to the anion in an inorganic lattice of the outer layer, preferably it is not removed by a ligand exchange.
  • Crystal bound ligands (covalently bound ligands) can be characterized as described in reference example 7.
  • the organic moiety can be described as follows preferably.
  • thiolated ligand materials like polypropyleneglycol and polypropyleneglycol monomethyl ether, thiolated ligand materials described in US 11021651 B2, formula (I), formula (II) of column 17-18, line 28 of column 25 to line 16 of column26, M1000-SH of Example 1 can also be used as a source of organic moiety and the resulting covalently bonded organic moiety is included in this patent application. It is believed that the organic moiety prevents aggregation of nanoparticles or nanosized material, the organic moiety allows to disperse the nanoparticles in the organic medium and/or in aqueous medium.
  • the organic moiety directly attached to the anion of the outer layer of the light emitting moiety by covalent bond can realize one or more of the technical effects of the present invention when it is mixed with the reactive monomer or a mixture of two or more reactive monomers of the present invention.
  • said reactive monomer or two or more reactive monomers of the monomer mixture is a (meth)acrylate monomer(s). More preferably it is a specific (meth)acrylate monomer as defined in the section of reactive monomer below.
  • the semiconducting nanoparticle comprises an outer layer covering at least a part of said core, comprising at least one metal cation and at least one divalent anion, wherein said divalent anion is selected from Se 2- , S 2- , Te 2- O 2- or a combination of any of these, preferably said metal cation is a monovalent, divalent cation, trivalent or tetravalent cation, more preferably said metal cation is a divalent cation selected from the group consisting of Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Fe 2+ , Hg 2+ , Mg 2+ and Pb 2+ , or a tetravalent cation selected from the group consisting of Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ , and Sn 4+ ,
  • cation is monovalent cation selected from the group consisting of Cs + , Ag + , Au + , Cu +1 or a divalent cation selected from the group consisting of Zn 2+ , Fe +2 , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ , Cu +2 or a trivalent cation selected from the group Fe +3 , ln +3 , Bi +3 , Ga +3 a tetravalent cation selected from the group consisting of Ti 4+ , Ge 4+ , Si 4+ , Zr 4+ , Hf 4+ , and Sn 4+ , Si +4 .
  • said outer layer comprises at least two or three different metal cations such as the combination of Cu 1 + and ln 3+ , Cu 1 + and Ga 3+ , Ag 1 + and Ga 3+ or a combination of Cu +1 /ln +3 /Zn +2 or a combination of Cu +1 /Ga +3 /Zn +2 or a combination of Cu +1 /ln +3 /Ga +3 /Zn +2 or a combination of Cu +1 /ln +3 /Ga +3 /Zn +2 or a combination of Cu +1 /ln +3 /Ga +3 /Zn +2 or a combination of Cu +1 /ln +3 /Ga +3 .
  • the metal cation is a divalent cation selected from the group consisting of Fe +2 Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ , Cu +2 .
  • said outer layer comprising, essentially consisting of, or consisting of a material represented by following chemical formula (VI),
  • Q is a divalent anion selected from one or more members of the group consisting of Se 2 S 2- , Te 2- and O 2- ;
  • P is a divalent metal cation, preferably P is a divalent cation selected from one or more member of the group consisting of Zn 2+ , Ni 2+ , Co 2+ , Ca 2+ , Sr 2+ , Hg 2+ , Mg 2+ and Pb 2+ ;
  • A is a tetravalent cation, preferably A is selected from one or more members of the group consisting of Ti 4+ , Ge 4+ , Si 4+ , and Sn 4+ ; and 0 ⁇ h ⁇ 0.5.
  • ZnS, ZnSe, ZnSeS, ZnTe, ZnO, ZnNiS, ZnNiSe, ZnGeS, ZnGeO, ZnCaS, NiSe, TiGeSeS, ZnTiS, CulnZnS, CulnZnSe, AglnZnS, and/or AglnZnSe can be used.
  • said outer layer is a monolayer.
  • the outer layer is covering the shell layers.
  • the concentration of Se in the shell layer varies from a high concentration of the first semiconducting nanoparticle side in the shell layer to a low concentration of the opposite side in the shell layer, more preferably, the concentration of S in the shell layer varies from a low concentration of first semiconducting nanoparticle side of the shell layer to a higher concentration to the opposite side of the shell layer, the concentration of Te in the shell layer varies from a high concentration of first semiconducting nanoparticle side of the shell layer to a lower concentration to the opposite side of the shell layer.
  • the surface of the light emitting moiety namely a semiconducting light emitting nanoparticle can be over coated with one or more kinds of surface ligands in addition to the organic moiety of the present invention.
  • the surface ligands in common use 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, Dodecyl amine (DDA), Tetradecyl amine (TDA), Hexadecyl amine (I), and Octadecyl amine (ODA), Oleylamine (OLA), 1- Octadecene (ODE); thiols, when organic moiety of thiol may include linear or branched alkyl chain which can be saturated or include one or more unsaturated carbon bonds and/or aromatic rings, such as octadecane thiol, hexadecane thiol, dodecane thio
  • the ligands can include Zn-oleate, Zn-acetate, Zn-myristate, Zn-Stearate, Zn-laurate and other Zn-carboxylates, Zn-isostearate, sulfonic acids, halides, carbamates.
  • Examples of surface ligands have been described in, for example, the laid- open international patent application No. WO 2012/059931 A.
  • Quantum Yield of the quantum dots is measured using Hamamatsu absolute quantum yield spectrometer (model: Quantaurus C11347).
  • the nanoparticle emits light having the peak maximum light emission wavelength in the range from 350nm 3500nm, preferably from 350nm to 2000nm, more preferably from 400nm to 800nm, even more preferably from 430nm to 700nm.
  • GCMS gas chromatography mass spectrometry
  • Agilent Technologies 7890B GC system equipped with autosampler and Agilent DB-5 column and MS instrument Agilent Technologies 5977B MSD.
  • the analytes are separated using the following injection method: initial temperature 100°C, hold 0 min at 100°C; heat to 340°C at the rate of 8°C/min, hold 15 min at 340°C.
  • a (meth)acrylate monomer having the viscosity value within the above-mentioned parameter ranges are especially suitable to make a composition for inkjet printing.
  • a combination of the 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 the light emitting moiety comprising an outer layer containing a metal cation and a divalent anion, and one or more types of organic moieties directly attached to the anion of the outer layer by covalent bond; may specifically improve optical performance of the light emitting moiety in an obtained layer (film).
  • said combination may also lead improve thermal stability of an obtained layer (film), thermal stability of a light emitting moiety in a layer (film), dispersibility of a light emitting moiety in a composition, dispersibility of a light emitting moiety in an obtained layer enabling a phase separation of light emitting moiety and matrix material after curing realizing an improved haze value of the cured film (cured composition), long term Quantum Yield (QY) stability of a light emitting moiety in the composition in a longer term storage with or without light irradiation, long term External Quantum Efficiency (EQE) stability of a light emitting moiety in the composition in a longer term storage with or without light irradiation,, long term Quantum Yield (QY) stability of a light emitting moiety in the obtained layer (film) in a longer term storage with or without light irradiation, long term External Quantum Efficiency (EQE) stability of a light emitting moiety in the obtained layer (film) in a longer term storage with or without light
  • the boiling point (B.P.) of said reactive monomer is 95°C or more, preferably it is in the range from 95°C to 350°C, for large area uniform inkjet printing.
  • said high boiling point is also important to make a composition having a lower vapor pressure preferably less than 0.001 mmHg for large area uniform printing
  • a reactive monomer preferably a (meth)acrylate monomer, more preferably a (meth)acrylate monomer of formula (I), (II) and/or (III) having the viscosity value of 25 cP or less at 25°C and the boiling point at least 95°C or more, preferably it is in the range from 95°C to 350°C, to make a composition suitable for large area uniform inkjet printing even if it is mixed with high loading of another materials such as high loading of semiconducting light emitting nanoparticles.
  • (meth)acrylate“ is a general term for an acrylate and a methacrylate. Therefore, according to the present invention, the term “(meth)acrylate monomer” means a methacrylate monomer and/or an acrylate monomer.
  • said B.P can be estimate by the known method such as like described in Science of Petroleum, Vol. II. p.1281 (1398).
  • any types of publicly available acrylates and /or methacrylates represented by chemical formula (I) or (II) can be used preferably.
  • any types of publicly available acrylates and I or methacrylates having the viscosity value of 25 cP or less at 25°C represented by chemical formula (I), (II) and/or (III) can be used.
  • the reactive monomer of the composition is preferably a (meth)acrylate monomer selected from a mono- (meth)acrylate monomer, a di-(meth)acrylate monomer and/or a tri- (meth)acrylate monomer.
  • said reactive monomers of the monomer mixture is each independently selected from a mono-(meth)acrylate monomer, a di- (meth)acrylate monomer and/or a tri-(meth)acrylate monomer.
  • said di-(meth)acrylate monomer is represented by following chemical formula (l b )
  • said mono-acrylate monomer is represented by following chemical formula (ll b )
  • said tri-(meth)acrylate monomer is represented by following chemical formula (IIP);
  • R a is at each occurrence, identically or differently, H, D or an alkyl group having 1 to 20 carbon atoms, cyclic alkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 carbon ring atoms, or a hetero aromatic ring system having 5 to 60 carbon atoms, wherein H atoms may be replaced by D, F, Cl, Br, I; two or more adjacent substituents R a here may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another;
  • X 3 is a non-substituted or substituted ester group, alkyl group, cyclo-alkyl group, aryl group or an alkoxy group, in case of X 3 is a non-substituted or substituted ester group, said ester group is represented by following formula (ll bs ); wherein R llb1 is a single bond, a non-substituted
  • R llb2 is a substituted or non-substituted alkyl group, cyclo group, cyclo-alkyl group, aryl group or an alkoxy group.
  • I is 0 or 1 ;
  • R 5 is a hydrogen atom, halogen atom of Cl, Br, or F, methyl group, alkyl group, aryl group, alkoxy group, ester group, or a carboxylic acid group;
  • R a is at each occurrence, identically or differently, H, D or an alkyl group having 1 to 20 carbon atoms, cyclic alkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 carbon ring atoms, or a hetero aromatic ring system having 5 to 60 carbon atoms, wherein H atoms may be replaced by D, F, Cl, Br, I; two or more adjacent substituents R a here may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.
  • R 9 is hydrogen atom, a straight alkyl group having 1 to 25 carbon atoms or a (meth)acryl group represented by chemical formula (IV b )
  • R 10 is hydrogen atom, a straight alkyl group having 1 to 25 carbon atoms or a (meth)acryl group represented by chemical formula (V b )
  • R 11 is hydrogen atom, a straight alkyl group having 1 to 25 carbon atoms or a (meth)acryl group represented by chemical formula (Vl b ) wherein R 8 , R 8a , R 8b and R 8c are, each independently or dependently of each other at each occurrence, H, CH 3 or CH 2 CH 3 ; wherein at least one of R 9 , R 10 and R 11 is a (meth)acryl group, preferably two of R 9 , R 10 and R 11 are a (meth)acryl group and other one is a hydrogen atom or a straight alkyl group having 1 to 25 carbon atoms, preferably the electric conductivity (S/cm) of the (meth)acrylate monomer of formula (III) is 1.0*10 -10 or less, preferably it is 5.0*10 -11 or less, more preferably it is in the range from 5.0*10 -11 to 1 .0*10 -15 , even more preferably it is in the range from 5.0*10 -12 to 1
  • the monomer mixture of the composition comprises a(meth)acrylate monomer of chemical formula (II) and another (meth)acrylate monomer selected from the (meth)acrylate monomer of chemical formula (I) and/or a (meth)acrylate monomer of chemical formula (III).
  • the (meth)acrylate monomer of chemical formula (II) is in the composition and the mixing ratio of the (meth)acrylate monomer of chemical formula (I) to the (meth)acrylate monomer of chemical formula (II) is in the range from 1 :99 to 99:1 (formula
  • (I) formula (II)), preferably from 5:95 to 50:50, more preferably from 10:90 to 40:60, even more preferably it is from 15:85 to 40:60, preferably at least a purified (meth)acrylate monomer represented by chemical formula (I), (II) is used in the composition, more preferably the (meth)acrylate monomer of chemical formula (I) and the (meth)acrylate monomer of chemical formula
  • the boiling point (B.P.) of said (meth)acrylate monomer of chemical formula (I) and/or chemical formula (II) is 95°C or more, preferably the (meth)acrylate monomers of chemical formula (I) and chemical formula (II) are both 100°C or more, more preferably it is in the range from 100°C to 350°C, even more preferably the boiling point (B.P.) of the (meth)acrylate monomers of chemical formula (I) is in the range from 100°C to 300°C and the boiling point (B.P.) of the (meth)acrylate monomers of chemical formula (II) is in the range from 150°C to 320°C..
  • the viscosity of the composition is 35 cP or less at room temperature, preferably in the range from 1 to 35 cP, more preferably from 2 to 30 cP, even more preferably from 2 to 25 cP.
  • said viscosity can be measured by vibration type viscometer VM-10A (SEKONIC) at room temperature. https://www.sekonic.co.jp/english/product/viscometer/vm/vm_series.html
  • R lb1 of (l bs1 ) is a single bond
  • R lbs1 of (l bs2 ) is a single bond
  • R lb2 of (l bs1 ) is a non-substituted or substituted branched alkylene chain having carbon atoms 3 to 7
  • said R 3 and R 4 of formula (I) are, at each occurrence, independently or differently, selected from the following groups. wherein represents the connecting point to oxygen atom of the formula or the connecting point to X 2 of the formula in case of R 3 , and wherein represents the connecting point to oxygen atom of the formula or the connecting point to X 1 of the formula in case of R 4 .
  • said combination can realize a low viscosity composition comprising high amount of another materials, such as high loading of semiconducting light emitting nanoparticles.
  • another material such as high loading of semiconducting light emitting nanoparticles.
  • R llb1 of (ll bs ) is a single bond
  • R llb2 of (ll bs ) is a substituted or non-substituted alkyl group, cyclo group, cyclo-alkyl group
  • R llb2 of (ll bs ) can be selected from the following groups. or said R 7 of formula (II) is, at each occurrence, independently or differently, selected from the following groups, wherein the groups can be substituted with R a , preferably they are unsubstituted by R a .
  • R 7 of formula (II) is, at each occurrence, independently or differently, selected from the following groups, wherein the groups can be substituted with R a , preferably they are unsubstituted by R a .
  • said formula (II) is Lauryl methacrylate (LM, viscosity 6 cP) or Lauryl acrylate (LA, viscosity: 4.0cP) or isobornyl acrylate (IBOA).
  • LM Lauryl methacrylate
  • LA Lauryl acrylate
  • IBOA isobornyl acrylate
  • (meth)acrylate monomers purified by using silica column are used. It is believed that an impurity removal from the (meth)acrylate monomers by the silica column purification leads improved QY of the semiconducting light emitting nanoparticle in the composition.
  • (meth)acrylate monomer of chemical formula (III) is useful to improve its solidity of a later made from the composition after inkjet printing.
  • a publicly known a (meth)acrylate monomer represented by following chemical formula (III) can be used to improve solidity of a layer after inkjet printing and cross linking.
  • TMPTA Trimethylolpropane Triacrylate
  • the amount of the (meth)acrylate monomer of chemical formula (III) based on the total amount of (meth)acrylate monomers in the composition is in the range from 0.001 wt.% to 25wt.%, more preferably in the range from 0.1wt.% to 15wt.%, even more preferably from 1wt.% to 10wt.%.
  • the present invention also relates to a process for preparing the composition comprising, essentially consisting of, or consisting of, at least following steps;
  • A is an organic group
  • B is a connecting unit
  • H is a hydrogen atom
  • X is an anchor group comprising an anion, capable to form a monolayer with the added metal cation derivable from the added metal cation precursor;
  • step (c) cooling the reaction mixture from step (b), wherein the reaction mixture in step (b) is kept at a temperature in the range from 80 °C to 200 °C, preferably from 100 to 200 °C to form the outer layer in step (b), (d) mixing a light emitting moiety obtained from step (c) with at least one reactive monomer or a mixture of two or more reactive monomers to from a composition.
  • L is an organic group, preferably said organic group is hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), heteroaromatic group, including aryl, alkaryl, alkyl or aralkyl, alkylamine, fluoroaryl, fluoroalkaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, including fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl;
  • R IIa and R IIb are, each independently each other, at each occurrence, selected from hydrogen atom, a hydroxy group, a straight
  • the temperature ranges from 80 °C to 200 ° C is important to make a crystal binding between the organic moiety and the outer layer.
  • the anchor group of chemical formula (I), (II), (III) and / or (IV) is being attached to a cation to form the outer layer, while the organic moiety is kept attached to the anchor group by covalent bond
  • an injection of said anion source is carried out at the temperature in the range from 0°C to 200°C, preferably in the range from 20°C to 180 °C in step (a) or in step (b).
  • step (b) is carried out in the range from 1 minute to 10 hours, preferably from 10 minutes to 5 hours, more preferably 20 minutes to 3 hours.
  • the ratio of the total molar amount of the cation precursor to the total molar amount of the semiconducting nanoparticle in step (b) is in the range from 20:1 to 200000:1 , preferably from 100:1 to 60000:1 , more preferably 110:1 to 58000:1 , even more preferably 120:1 to 5000:1.
  • the ratio of the total molar amount of the chalcogen source to the total molar amount of the semiconducting nanoparticle in step (b) is in the range from 20:1 to 200000:1 , preferably from 100:1 to 60000:1 , more preferably 110:1 to 58000:1 , even more preferably 120:1 to 5000:1.
  • the ratio of the total mass amount of the cation precursor to the total mass amount of the semiconducting nanoparticle in step (b) is in the range from 1 :1000 to 1 :1 , preferably from 1 :500 to 1 :2, more preferably 1 :400 to 1 :2.
  • an anion source represented by chemical formula (2), (3) and/or (4) can be used singly or in combination with any other chalcogen source as the anion source in step (b) to form the outer layer.
  • L 1 and L 2 are each independently or dependently of each other, an organic group, preferably said organic group is a hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl) group, including aryl, alkary I, alkyl or aralkyl;
  • R lla and R llb are, each independently each other, at each occurrence, selected from hydrogen atom, a hydroxy group, a straight alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms; preferably a hydrogen atom, a hydroxy group, a straight alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms; preferably R lla and R llb are hydrogen atom; n is an integer 1 or more; m is 0 or an integer 1 or more, preferably m is 1 ; o is 0 or an integer 1 or more, preferably o is 1 ;
  • Z 1 is a divalent anion selected from Se, S, Te, 0;
  • Z 2 is a divalent anion selected from Se, S, Te, 0.
  • R llla , R lllb , R lllc , R llld , R llle , R lllf , R lllg and R lllh are, independently of each other, at each occurrence, selected from hydrogen atom, a hydroxy group, a straight alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms; preferably a hydrogen atom, a hydroxy group, a straight alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms; preferably R ll
  • g and R lllh are hydrogen atom, preferably R llle and R lllf are hydrogen atom; V is 0, CH 2 or C O;
  • Z is a hydrogen atom or an organic group, preferably Z is a hydrogen atom, a straight alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, -COOH, -SH, or -NH2, alkylamine, fluoroaryl, fluoroalkaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, including fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl, preferably Z is a hydrogen atom, a straight alkyl group having 1 to 25 carbon atoms, a branched alkyl group having 3 to 25 carbon atoms, more preferably it is a hydrogen atom, a straight alkyl group having 1-15 carbon atoms, a branched alkyl group having 3-15 carbon atoms, even more preferably it is a hydrogen atom, or a straight alkyl group having 1 -10 carbon atoms; a
  • Q 1 and Q2 are, independently of each other, a divalent anion selected from Se, S, Te, O;
  • mPEG-S-S-mPEG can be used.
  • the anion source described by the formula (2), (3) or (4), such as bis-chalcogenides can be used in step (b) together with a reducing agent to form the outer layer, preferably said reducing agent is represented by secondary phosphines.
  • the ratio of the molar amount of the anion source and the molar amount of the cation precursor used in step (b) is in the range from 20 : 1 to 1 : 20, preferably in the range from 12 : 1 to 1 : 12, even more preferably 5:1 to 1 :5.
  • chalcogen means a chemical element of the group 16 chemical elements of the periodic table, preferably it is sulfur (S), selenium (Se), oxygen (0) and/or tellurium (Te)
  • the term “chalcogen source” means a material containing at least one chemical element of the group 16 chemical elements of the periodic table, preferably said chemical element of the group 16 chemical elements is oxygen (O), sulfur (S), selenium (Se), and/or tellurium (Te), more preferably it is sulfur (S), or selenium (Se).
  • said chalcogen source is a selenium source, sulfur source or a combination of selenium source and a selenium source. More preferably, it is selected from selenols, diselenides, thiols, disulphides or a combination of these,
  • step (a) is carried out in an inert condition such as under Argon (Ar) or N2 condition, more preferably under Ar condition.
  • said another 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 squalenes, squalanes, heptadecanes, octadecanes, octadecenes, nonadecanes, icosanes, henicosanes, docosanes, tricosanes, pentacosanes, hexacosanes, octacosanes, nonacosanes, triacontanes, hentriacontanes, dotriacontanes, tritriacontanes, tetratriacontanes, pentatriacontanes, hexatriacontanes, oleylamines, , trioctylamines, ketones, ketones ether acetates such as PG
  • said mixing step is carried out at the temperature in the range of from 0°C to 100°C, preferably from 5 to 60°C, more preferably from 10 to 40°C.
  • Light emitting moieties preferably a light emitting moiety comprises at least a 1 st semiconducting nanomaterial as a core, can be obtained from public source or obtained as described for example in US8679543 B2, WO 2020/216813 A and Chem. Mater. 2015, 27, pp 4893-4898.
  • said cation shell precursor is a salt of an element of the group 12 of the periodic table, more preferably said cation shell precursor is selected from one or more members of the group consisting of Zn-stearate, Zn-isostearate, Zn- myristate, Zn-oleate, Zn-laurate, Zn-palmitate, Zn-acetylacetonate, Zn- undecylenate, Zn-Acetate, Cd-stearate, Cd-myristate, Cd-oleate, Cd- laurate, Cd-palmitate, Cd-acetylacetonate, Cd-undecylenate, Cd-acetate, a metal halogen represented by chemical formula (XIII) and a metal carboxylate represented by chemical formula (XIV),
  • MX 3 n (XIII) wherein 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, [M(O 2 CR 16 ) (O2CR 17 )] - (XIV) wherein M is Zn 2+ , or Cd 2+ , preferably M is Zn 2+ ;
  • R 16 is a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, or a branched unsaturated hydrocarbyl group having 3 to 30 carbon atoms, preferably R 16 is a linear alkyl group having 1 to 30 carbon atoms, or a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, more preferably, R 16 is a linear alkyl group having 2 to 25 carbon atoms, or a linear unsaturated hydrocarbyl group having 6 to 25 carbon atoms, even more preferably R 16 is a linear alkyl group having 2 to 20 carbon atoms, or a linear unsaturated hydrocarbyl group having 10 to 20 carbon atoms, furthermore preferably R 16 is a linear alkyl group having 2 to 20 carbon atoms,
  • R 17 is a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, or a branched unsaturated hydrocarbyl group having 43 to 30 carbon atoms, preferably R 17 is a linear alkyl group having 1 to 30 carbon atoms, or a linear unsaturated hydrocarbyl group having 2 to 30 carbon atoms, more preferably R 17 is a linear alkyl group having 2 to 25 carbon atoms, or a linear unsaturated hydrocarbyl group having 6 to 25 carbon atoms, even more preferably R 17 is a linear alkyl group having 2 to 20 carbon atoms, or a linear unsaturated hydrocarbyl group having 10 to 20 carbon atoms, furthermore preferably R 17 is a linear alkyl group having 2 to 20 carbon atoms.
  • R 16 and R 17 are the same.
  • step (b) is carried out in step (c) to stop forming reaction accordingly.
  • cooling method several methods can be used singly or in combination. Such as removing a heat source, injecting a solvent such as a solvent at a room temperature, and/or applying air cooling.
  • the reaction mixture is cooled down to 50°C or less and above 0°C. preferably to a room temperature.
  • the resulted light emitting moiety can be cleaned by a known method and preferably centrifuged. Solids in the reaction mixture from step
  • step (c) can be removed by centrifugation. Then cleaned light emitting moiety can be used in step (d).
  • the present invention may relate to formulation comprising, essentially consisting of, or consisting of, at least the composition of the present invention; and at least one solvent.
  • 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 ketons or water, more preferably selected from one or more members of the group consisting of toluene, xylene, ethers, tetrahydrofuran, chloroform, dichloromethane and heptane, purified water, ester acetates, alcohols, sulfoxides, formamides, nitrides, ketones, ether acetates.
  • the amount of the solvent in the formulation can be freely controlled according to the method of coating the composition.
  • the composition if the composition is to be spray-coated, it can contain the solvent in an amount of 90 wt. % or more.
  • the content of the solvent is normally 60 wt. % or more, preferably 70 wt. % or more.
  • the formulation may only contain 5wt% or less solvent based on the total amount of the composition.
  • the composition does not contain any solvent.
  • the present invention also relates to use of the composition or the formulation in an electronic device, optical device, sensing device or in a biomedical device.
  • the present invention also relates to a method for forming a layer comprising:
  • curing the composition preferably said curing is a photo curing performed by photo irradiation, thermal curing or a combination of a photo curing and a thermal curing.
  • the present invention also relates to a layer obtained or obtainable from the method of the present invention. In another aspect, the present invention also relates to a layer containing at least, essentially consisting of or consisting of;
  • a light emitting moiety preferably it is a semiconducting light emitting nanoparticle, comprising an outer layer containing a metal cation and a divalent anion; and one or more types of organic moieties directly attached to the anion of the outer layer by covalent bond,
  • the present invention also relates to a color conversion device (100) comprising at least, essentially consisting of or consisting of; a 1 st pixel (161 ) partly or fully filled with the layer of any one of claims 20 to 22 and 24 comprising at least a matrix material (120) containing a light emitting moiety (110), and a bank (150) comprising at least a polymer material, preferably the color conversion device (100) further contains a supporting medium (170).
  • a color conversion device (100) comprising at least, essentially consisting of or consisting of; a 1 st pixel (161 ) partly or fully filled with the layer of any one of claims 20 to 22 and 24 comprising at least a matrix material (120) containing a light emitting moiety (110), and a bank (150) comprising at least a polymer material, preferably the color conversion device (100) further contains a supporting medium (170).
  • said 1 st pixel (161 ) comprises at least a matrix material (120) containing a light emitting moiety (110).
  • the1 st pixel (161 ) is a solid layer obtained or obtainable by curing the composition of the present invention containing at least one acrylate monomer together with at least one light emitting moiety (110), preferably said curing is a photo curing by photo irradiation, thermal curing or a combination of a photo curing and a thermal curing.
  • the layer thickness of the pixel (161 ) is in the range from 0.1 to 100pm, preferably it is from 1 to 50pm, more preferably from 5 to 25pm.
  • the color conversion device (100) further contains a 2 nd pixel (162), preferably the device (100) contains at least said 1 st pixel (161 ), 2 nd pixel (162) and a 3 rd pixel (163), more preferably said 1 st pixel (161 ) is a red color pixel, the 2 nd pixel (162) is a green color pixel and the 3 rd pixel (163) is a blue color pixel, even more preferably the 1 st pixel (161 ) contains a red light emitting moiety (11 OR), the 2 nd color pixel (162) contains a green light emitting moiety (110G) and the 3 rd pixel (163) does not contain any light emitting moiety.
  • the 1 st pixel (161 ) contains a red light emitting moiety (11 OR)
  • the 2 nd color pixel (162) contains a green light emitting moiety (110G)
  • the 3 rd pixel (163) does not contain any light emitting moiety
  • At least one pixel (160) additionally 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).
  • said 1 st pixel (161 ) consists of one pixel or two or more sub-pixels configured to emit red-color when irradiated by an excitation light, more preferably said sub-pixels contains the same light emitting moiety (110).
  • the matrix material (120) contains a (meth)acrylate polymer, preferably it is a methacrylate polymer, an acrylate polymer or a combination of thereof, more preferably it is an acrylate polymer, even more preferably said matrix material (120) is obtained or obtainable from the composition of the present invention containing at least one acrylate monomer, further more preferably said matrix material (120) is obtained or obtainable from the composition of the present invention containing at least one di-acrylate monomer, particularly preferably said matrix material (120) is obtained or obtainable from the composition of the present invention containing at least one di-acrylate monomer and a mono- acrylate monomer, preferably said composition is a photosensitive composition.
  • a (meth)acrylate polymer preferably it is a methacrylate polymer, an acrylate polymer or a combination of thereof, more preferably it is an acrylate polymer, even more preferably said matrix material (120) is obtained or obtainable from the composition of the present invention containing at least one
  • the height of the bank (150) is in the range from 0.1 to 100pm, preferably it is from 1 to 50pm, more preferably from 1 to 25pm, furthermore preferably from 5 to 20pm.
  • the bank (150) is configured to determine the area of said 1 st pixel (161 ) and at least a part of the bank (150) is directly contacting to at least a part of the 1 st pixel (161 ), preferably said 2 nd polymer of the bank (150) is directly contacting to at least a part of the 1 st polymer of the 1 st pixel (161 ).
  • said bank (150) is photolithographically patterned and said 1 st pixel (161 ) is surrounded by the bank (150), preferably said 1 st pixel (161 ), the 2 nd pixel (162) and the 3 rd pixel (163) are all surrounded by the photolithographically patterned bank (150).
  • the present invention also relates to a method for fabricating a color conversion device (100) of the present invention, containing at least the following steps, preferably in this sequence;
  • composition of the present invention Providing the composition of the present invention to at least one pixel region, preferably by ink-jetting,
  • composition preferably said color conversion device (100) further contains a supporting medium (170).
  • the present invention further relates to a color conversion device (100) obtainable or obtained from the method of the present invention.
  • the present invention further relates to 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 a light or configured to emit light.
  • the present invention further relates to an optical device (300) containing at least, essentially consisting of or consisting of; one functional medium (320, 420, 520) configured to modulate a light or configured to emit light, and the color conversion device (100) of the present invention.
  • said optical device can be a liquid crystal display device (LCD), Organic Light Emitting Diode (OLED), Light Emitting Diode device (LED), Micro LED, Micro Electro Mechanical Systems (here in after “MEMS”), electro wetting display, or an electrophoretic display.
  • LCD liquid crystal display device
  • OLED Organic Light Emitting Diode
  • LED Light Emitting Diode device
  • MEMS Micro Electro Mechanical Systems
  • electro wetting display or an electrophoretic display.
  • said functional medium can be a LC layer, OLED layer, LED layer, micro LED layer, MEMS layer, electro wetting layer and/or an electrophoretic layer. More preferably it is a LC layer, micro LED layer or an OLED layer.
  • LC layer LC layer, micro LED layer or an OLED layer.
  • a composition preferably it is being of a photocurable composition, comprising at least; i) a light emitting moiety, preferably it is a semiconducting light emitting nanoparticle, comprising an outer layer containing a metal cation and a divalent anion; and one or more types of organic moieties directly attached to the anion of the outer layer by covalent bond, ii) at least one reactive monomer or a mixture of two or more reactive monomers, preferably said monomer having one or more of functional groups, more preferably it is a (meth)acrylate monomer; wherein said divalent anion of the outer layer is selected from Se 2- , S 2- , Te 2- O 2 ' or a combination of any of these, preferably said metal cation of the outer layer is a monovalent, divalent, trivalent or tetravalent cation, more preferably said metal cation is a divalent cation selected from the group consisting of Zn 2+ , Ni 2+ , Co 2+ ,
  • composition of embodiment 1 wherein the organic moiety is represented by following chemical formula (I);
  • A is an organic group, preferably said organic group is hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), heteroaromatic group, including aryl, alkaryl, alkyl or aralkyl, alkylamine, fluoroaryl, fluoroalkaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, including fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl;
  • B is a connecting unit, preferably B is **-(U)o-(Y)m-(CR lla R llb )n, wherein “**” represents the connecting point to “A;” and represents the connecting point to the anion in the outer layer.
  • composition of embodiment 1 or 2, wherein the organic moiety is represented by following chemical formula (II), (III) or (III');
  • L is an organic group, preferably said organic group is hydrocarbyl (alkyl, aryl, aralkyl and alkylaryl), heteroaromatic group, including aryl, alkaryl, alkyl or aralkyl, alkylamine, fluoroaryl, fluoroalkaryl, fluoroalkyl, fluoroaralkyl, heteroaromatic group, including fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl;
  • R lla and R llb are, each independently each other, at each occurrence, selected from hydrogen atom, a hydroxy group, a straight alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms; preferably a hydrogen atom, a hydroxy group, a straight alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms; preferably R lla and R llb are hydrogen atom; n is an integer 1 or more; m is 0 or an integer 1 or more, preferably m is 1 ; o is 0 or an integer 1 or more, preferably o is 1 ; represents the connecting point to the anion in the outer layer;
  • metal cation is a transition metal of group 12 or group 14, preferably it is selected from one or more members of the group consisting of Zn 2+ , Hg 2+ or Pb 2+ .
  • said two or more reactive monomers of the mixture is each independently selected from a mono-(meth)acrylate monomer, a di- (meth)acrylate monomer and/or a tri-(meth)acrylate monomer.
  • said di-(meth)acrylate monomer is represented by following chemical formula (l b )
  • said mono-acrylate monomer is represented by following chemical formula (ll b )
  • said tri- (meth)acrylate monomer is represented by following chemical formula (lll b );
  • X 3 is a non-substituted or substituted ester group, alkyl group, cyclo-alkyl group, aryl group or an alkoxy group, in case of X 3 is a non-substituted or substituted ester group, said ester group is represented by following formula (ll bs ); wherein R llb1 is a single bond, a non-substituted or substituted alkylene chain having carbon atoms 1 to 5;
  • R llb2 is a substituted or non-substituted alkyl group, cyclo group, cyclo-alkyl group, aryl group or an alkoxy group.
  • R llb1 of (ll bs ) is a single bond
  • R llb2 of (ll bs ) is a substituted or non-substituted alkyl group, cyclo group, cyclo-alkyl group
  • R llb2 of (ll bs ) can be selected from the groups indicated on table of page 44.
  • R 5 is a hydrogen atom, halogen atom of Cl, Br, or F, methyl group, alkyl group, aryl group, alkoxy group, ester group, or a carboxylic acid group; wherein R 9 is hydrogen atom, a straight alkyl group having 1 to 25 carbon atoms or a (meth)acryl group represented by chemical formula (IV b )
  • R 10 is hydrogen atom, a straight alkyl group having 1 to 25 carbon atoms or a (meth)acryl group represented by chemical formula (V b )
  • R 11 is hydrogen atom, a straight alkyl group having 1 to 25 carbon atoms or a (meth)acryl group represented by chemical formula (Vl b ) wherein R 8 , R 8a , R 8b and R 8c are, each independently or dependently of each other at each occurrence, H, CH 2 CH 3 or CH 3 ; wherein at least one of R 9 , R 10 and R 11 is a (meth)acryl group.
  • a method for fabricating the composition of any one of preceding embodiments comprising at least following steps, (a) mixing at least a light emitting moiety, preferably said light emitting moiety comprises at least a 1 st semiconducting nanomaterial as a core, with another material to get a reaction mixture, preferably said another material is a solvent;
  • A is an organic group
  • B is a connecting unit
  • H is a hydrogen atom
  • X is an anchor group comprising an anion, capable to form a monolayer with the added metal cation derivable from the added metal cation precursor;
  • step (c) cooling the reaction mixture from step (b), wherein the reaction mixture in step (b) is kept at a temperature in the range from 80 °C to 200 °C, preferably from 100 to 200 °C to form the outer layer in step (b),
  • step (d) mixing a light emitting moiety obtained from step (c) with at least one reactive monomer or a mixture of two or more reactive monomers to from a composition.
  • a light emitting moiety obtained from step (c) with at least one reactive monomer or a mixture of two or more reactive monomers to from a composition.
  • an injection of said anion source is carried out at the temperature in the range from 0°C to 200°C, preferably in the range from 20°C to 180 °C in step (a) or in step (b).
  • step (b) is carried out in the range from 1 minute to 10 hours, preferably from 10 minutes to 5 hours, more preferably 20 minutes to 3 hours.
  • the ratio of the total molar amount of the cation precursor to the total molar amount of the semiconducting nanoparticle in step (b) is in the range from 20:1 to 200000:1 , preferably from 100:1 to 60000:1 , more preferably 110:1 to 58000:1 , even more preferably 120:1 to 5000:1.
  • the ratio of the total mass amount of the cation precursor to the total mass amount of the semiconducting nanoparticle in step (b) is in the range from 1 :1000 to 1 :1 , preferably from 1 :500 to 1 :2, more preferably 1 :400 to 1 :2.
  • the ratio of the total mass amount of the cation precursor to the total mass amount of the semiconducting nanoparticle in step (b) is in the range from 1 :1000 to 1 :1 , preferably from 1 :500 to 1 :2, more preferably 1 :400 to 1 :2.
  • the molar ratio of the total amount of the anion source and the total amount of the cation precursor used in step (b) is in the range from 20 : 1 to 1 : 20, preferably in the range from 12 : 1 to 1 : 12, even more preferably 5:1 to 1 : 5.
  • step (b) The process according to any one of embodiments 9 to 13, wherein the molar ratio of the total amount of the anion source and the total amount of the cation precursor used in step (b) is in the range from 20 : 1 to 1 : 20, preferably in the range from 12 : 1 to 1 : 12, even more preferably 5:1 to 1 :5.
  • composition obtainable or obtained from the process according to any one of embodiments 9 to 14.
  • Formulation comprising at least a composition of any one of embodiments 1 to 8 and 15, and at least one solvent, preferably the solvent is selected from one or more members of the group consisting of aromatic, halogenated and aliphatic hydrocarbon solvents, ethers, esters, ionic liquids, alcohols and water, more preferably selected from one or more members of the group consisting of toluene, xylene, tetrahydrofuran, chloroform, dichloromethane and heptane, hexane, purified water, ester acetates, ether acetates, ketones, etheric esters, preferably it is PGMEA, alcohols, preferably ethanol or isopropanol, sulfoxides, formamides, nitrides, ketones.
  • 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
  • compositions of any one of embodiments 1 to 8 or 15 or the formulation according to embodiment 16 in an electronic device, optical device, sensing device or in a biomedical device.
  • Method for forming a layer comprising:
  • curing the composition preferably said curing is a photo curing performed by photo irradiation, thermal curing or a combination of a photo curing and a thermal curing.
  • a color conversion device (100) comprising at least a 1 st pixel (161 ) partly or fully filled with the layer of embodiment 19 or 20 comprising at least a matrix material (120) containing a light emitting moiety (110), and a bank (150) comprising at least a polymer material, preferably the color conversion device (100) further contains a supporting medium (170).
  • the present invention provides one or more of following effects; realizing an optimized haze value of the cured layer (film), optimal haze value with improved EQE value of the cured layer (film), preferably obtaining optimal haze value with improved EQE value of the cured layer (film) without using scatting particle, improved thermal stability of an obtained layer (film), improved thermal stability of a light emitting moiety in a layer (film), improved dispersibility of a light emitting moiety in a composition, enabling a phase separation of light emitting moiety and matrix material after curing realizing an improved haze value of the cured film (cured composition), improved dispersibility of a light emitting moiety in an obtained layer, improved long term Quantum Yield (QY) stability of a light emitting moiety in the composition in a longer term storage with our without external light irradiation, improved long term External Quantum Efficiency (EQE) stability of a light emitting moiety in the composition in a longer term storage with our without external light irradiation,
  • MSCs The formation of MSCs was monitored via UV-vis of timed aliquots taken from the reaction solution. There was a gradual improvement in the peak shape (red shift and sharpness).
  • InP magic size clusters are formed with exciton at 387nm.
  • the InP magic size clusters (MSCs) are cleaned with anhydrous acetonitrile (the ratio of crude: acetonitrile 18:13).
  • the process is repeated with a mixture of anhydrous toluene and acetonitrile in ratio toluene: acetonitrile 1 .5: 1 , 1 .4: 1 , 1 .75:1 .
  • This product is called “magic size clusters (MSCs)”.
  • InP QDs are formed with exciton at 593nm.
  • Shell synthesis example 1 ZnSe shell synthesis on InP cores, (trioctyl phosphine selenide (TOP-Se) as Se source)
  • InP cores used are synthesized using the core synthesis described above (WO 2019/224134 A) and have core exciton CWL of 593 nm.
  • the final core solution is cleaned with a mixture of anhydrous toluene and ethanol (ratio crude:toluene:ethanol: 1 :2:8).
  • the process is repeated with ratio crude:toluene:ethanol: 1 :2:6. This solution will be called further “SSP InP cores”.
  • Post-synthesis core treatment In glove box (GB), SSP InP cores (3.5X10- 7 mol) are dissolved with 0.2ml toluene and transferred into 50ml round bottom flask with 4.8ml pumped oleylamine (OLAm) and 0.085g ZnCI2.
  • the flask After short pumping at 50°C to remove toluene, the flask is filled with argon and heated to 250°C for 30min. The solution is then cooled down to 180°C.
  • Shelling process At 180°C, 2.6mL of a 0.55M concentrated solution of Zn(CI) 2 in OLAm and 1 amount (0.72mL of 2M TOP-Se) of anion shell precursor are added to SSP InP cores after core treatment. After 30m in, the solution is heated to 200°C. After 30m in the solution is heated to 320°C, 3.2m L of 0.4M Zn(Undecylenate) 2 is injected and the reaction kept at 320°C for 3 hrs. After 3hrs at 320°C the reaction is terminated by cooling down the reaction mixture.
  • the resulting nanoparticles are cleaned with a mixture of anhydrous toluene and ethanol (ratio crude:toluene:ethanol: 3:4:8). The process is repeated. Then the nanoparticles are extracted with hexane.
  • Shell synthesis example 2 ZnSeS shell synthesis on InP cores, (trioctyl phosphine selenide (TOP-Se) as Se source, dodecanethiol (DDT) as S source)
  • TOP-Se trioctyl phosphine selenide
  • DDT dodecanethiol
  • the comparative example is similar to comparative example 1 , but 0.9 mmol of TOP-Se is injected at 180°C; and 0.56mmol of DDT is injected at 320°C, 10 min after injection of Zn(Undecylenate) 2 .
  • the resulting nanoparticles are cleaned with a mixture of anhydrous toluene and ethanol (ratio crude:toluene:ethanol: 3:4:8). The process is repeated. Then the nanoparticles are extracted with hexane.
  • Table A compares the values of thermal, anti-radical, anti-peroxide stabilities for the described reference example and the comparative example 1 .
  • the reference example 2 is similar to reference example 1 , but 1 - dodecanethiol is used as sulphur precursor.
  • the reference example 3 is similar to reference examples 1 and 2, however 1-dodecaneselenol and 1 -dodecanethiol are added together at equal molar amounts keeping the amount of Se+S ions same as before.
  • Reference Example 4 ZnSeS outer layer synthesis on InP/ZnSe NPs in ODE, with 1-dodecaneselenol as Se source and 3-phenylethane thiol as sulphur source
  • the reference example 4 differs from the reference example 3 by utilizing 3-phenylethane thiol instead of 1 -dodecanethiol as sulphur source.
  • Reference Example 5 ZnS outer layer synthesis on InP/ZnSeS NPs in ODE, with 1 -dodecanethiol as S source
  • the reference example 5 is similar to reference example 2, but InP/ZnSeS particles are used.
  • the InP/ZnSeS prepared as described in comp. ex. 2.
  • Table A compares the values of thermal, anti-radical, anti-peroxide stabilities for the described example and the comparative example 2.
  • the reference example is similar to reference example 2, but perfluorodecane thiol is used as sulphur precursor.
  • Reference Example 7 experimental proof of surface and crystal binding of DDSe of QDs from reference example 1
  • 3-phenylpropylphosphonic acid is known for its stronger affinity to QDs surface compared to amines, thiols, selenols and carboxylic acids.
  • Surface-bound ligands are desorbed from QDs surface and replaced by PPPA.
  • crystal-bound ligands are integrated into the crystal lattice. Subsequently, their dissociation from QDs is impossible without destruction of the crystal.
  • This process can also be used for experimental proof of crystal binding amine containing ligands, thiol containing ligands (e.g., mPEG thiols), other selenol containing ligands and carboxylic acid containing ligands of QDs.
  • Figure 6 1 H NMR spectra (in toluene d8) of QDs from reference example 1 before (a) and after (b) addition of PPPA Addition of PPPA leads to desorption of DDSe from QDs surface.
  • Amount (in mmol) of detached DDSe (surface-bound) is calculated by quantitative 1 H NMR using Duroquinone as external standard and is equal to 0.00135 mmol. Meaning, Only 1.8% mol from total amount of DDSe that is inserted to reaction produced surface bound DDSe.
  • Figure 7 1 H NMR spectrum (in toluene d8) of QDs after treating with PPPA and washing with ethanol
  • QDs after removing all surface bound DDSe are analyzed in GCMS. For this purpose, proper derivatization with HCI and methanol is performed. This treatment leads to complete decomposition and dissolution of QDs.
  • Figure 8A, 8B GCMS spectrum for QDs after treating with PPPA and washing. MS spectrum of peak at retention time of 11 .458.
  • the sample for GCMS is prepared as described in embodiments. GCMS confirms presence of DDSe. This indicates crystal binding of DDSe.
  • QDs from reference example 1 contain surface- as well as crystal-bound DDSe.
  • Reference Example 8 ZnS outer layer synthesis on InP based red quantum dots in PGMEA, with poly(ethylene glycol) methyl ether thiol Mn 800 (mPEG800-SH) as S source
  • the resulting QDs are cleaned with anhydrous hexane (the ratio of crude: hexane 1 :1 ). The process is repeated with a mixture of anhydrous PGMEA: hexane 1 :1. Then the QDs are extracted with toluene.
  • Table B compares the values of thermal stability for the described reference example 8 and for the used first semiconducting material (InP based red quantum materials).
  • Reference example 9 ZnS outer layer synthesis on InP based red quantum dots in PGMEA, with poly(ethylene glycol) methyl ether thiol Mn 800 (mPEG800-SH) as S source 1 ,28g of zinc acetate (Zn(0Ac) 2 ) are weighted into 250ml round bottom flask and degassed for 25 min at 200 mTorr while stirring. Put under Ar atmosphere. Inserted into the glove box.
  • mPEG800-SH poly(ethylene glycol) methyl ether thiol Mn 800
  • the flask is heated to reflux and 7.7ml of 0.4M mPEG800-SH solution in PGMEA is injected.
  • the flask is cooled to RT after additional 70m in at reflux (total reaction time 2h and 15min).
  • the resulting QDs are cleaned as follows: solids are removed by centrifugation; QDs are precipitated with anhydrous hexane (the ratio of crude:hexane 1 :1 ); the process is repeated with a mixture of anhydrous PGMEA:hexane 1 :1 , then twice with anhydrous toluene:hexane 2:3.
  • Table C compares the values of thermal stability for the described Working example 9 with reference material, which is prepared similarly to Working example 9, but without Zn(OAc) 2 .
  • Reference example 10 ZnS outer layer synthesis on InP based green quantum material having core-shell structure in diisoptopylbenzene, with poly(ethylene glycol) methyl ether thiol Mn 350 (mPEG350-SH) as S source 0.215g of Zn(OAc)2 is weighted outside GB into 50ml round bottom flask, the flask is introduced to GB.8ml of diisopropylbenzene (DIPB) and then toluene solution of 270mg of InP based green quantum dots are added. The mixture is mounted on a Schlenk line and the toluene is removed under reduced pressure. The flask is filled with Ar.
  • DIPB diisopropylbenzene
  • the flask is heated to 160 ⁇ C and 1.3ml of 0.9M mPEG(350)-SH solution in diisopropylbenzene is injected. After 90min at 160 ⁇ C the reaction cooled to ambient temperature. QDs precipitated upon cooling below 50C. Toluene (6mL) is added to dissolve the quantum dots. The resulting QDs are cleaned as follows: solids are removed by centrifugation; QDs are precipitated with anhydrous heptane (the ratio of (crude+toluene):heptane 1:1), the process is repeated with a mixture of anhydrous PGMEA:heptane 1:2, then with anhydrous toluene:heptane 1:1.
  • the reaction is cooled to room temperature, transferred into appropriate centrifuge bottle and centrifuged at 2795G for 5 minutes to remove any solids.
  • the red supernatant is transferred to an appropriate centrifuge bottle.
  • For every volume of the reaction mixture one volume of heptane is added (e.g., for 15mL of the reaction mixture 15mL of heptane is added). Centrifuged at 2795G for 5 minutes, the supernatant is discharged.
  • the precipitated QDs are redispersed in 16 mL of toluene.
  • the dispersion is centrifugated at 2795G for 5 minutes to discard residual solids.
  • the QD dispersion is transferred to a brown glass bottle and stored under inert atmosphere.
  • the precipitated QDs are redispersed in 6 mL of toluene. Then 6mL of heptane is added. Centrifuged at 2795G for 5 minutes, the supernatant is discharged. The precipitated QDs are redispersed in 6 mL of toluene. The dispersion is centrifugated at 2795G for 5 minutes to discard residual solids. The QD dispersion is transferred to a brown glass bottle and stored under inert atmosphere.
  • Working Example 3 QD surface passivation and purification is performed under inert atmosphere. In a separate vial, 1.216 g of mPEG350-SH and 6 ml of PGMEA is mixed to give mPEG350-SH stock solution.
  • red QD having InP core, ZnSe/ZnS double shell layers
  • oleic acid as ligand dispersed in heptane
  • 558 mg of Zn(OAc)2 and 39 g of propylene glycol methyl ether acetate (PGMEA) are mixed.
  • Heptane is removed under reduced pressure.
  • the resulting mixture is headed to reflux.
  • Half of the amount of the mPEG350-SH stock solution is injected to the reaction flask, which continued to be heated to reflux for 1 h.
  • the second half of the mPEG350-SH stock solution is injected into the reaction flask, which continued to be heated to reflux for another 1 h.
  • the reaction is cooled to room temperature, transferred into appropriate centrifuge bottle and centrifuged at 2795G for 5 minutes to remove any solids.
  • the red supernatant is transferred to an appropriate centrifuge bottle.
  • For every volume of the reaction mixture 0.75 volumes of heptane is added (e.g., for 40mL of the reaction mixture 30mL of heptane is added). Centrifuged at 2795G for 5 minutes, the supernatant is discharged.
  • the precipitated QDs are redispersed in 32 mL of toluene. Then 16mL of heptane is added. Centrifuged at 2795G for 5 minutes, the supernatant is discharged.
  • the precipitated QDs are redispersed in 8 mL of toluene.
  • the dispersion is centrifugated at 2795G for 5 minutes to discard residual solids.
  • the QD dispersion is transferred to a brown glass bottle and stored under inert atmosphere.
  • QDs from working Example 2 (0.2 g) dispersed in toluene are introduced in a glass vial.
  • the monomers IBOA (117 mg), polyethylene glycol methacrylate (MW 360) (117 mg) and triethylene glycol dimethacrylate (58.5 mg) are added.
  • the photoinitiator Omnirad819 50 mg
  • the antioxidant IRGANOX 1010 25 mg
  • the formulation is shook for 10 minutes and volatiles are evaporated on rotary evaporator under vacuum at 25°C. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line.
  • QDs from Working Example 3 (0.2 g) dispersed in toluene are introduced in a glass vial.
  • the monomers polyethylene glycol methacrylate (MW 360) (468 mg), ethylene glycol dimethacrylate (117 mg) are added.
  • the photoinitiator Omnirad819 (5 mg) and the antioxidant IRGANOX 1010 (2.5 mg) are added.
  • the formulation is shook for 10 minutes and volatiles are evaporated on rotary evaporator under vacuum at 25°C. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line.
  • QDs from Working Example 2 (0.2 g) dispersed in toluene are introduced with mPEG-SH (60 mg) in a glass vial.
  • the monomers LA (420 mg) and HDDA (105 mg) are added.
  • the photoinitiator Omnirad819 (5 mg) and the antioxidant IRGANOX 1010 (2.5 mg) are added.
  • the formulation is shook for 10 minutes and volatiles are evaporated on rotary evaporator under vacuum at 25°C. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line.
  • a solvent borne ink is formed with native QDs.
  • red QDs having InP core, ZnSe/ZnS double shell layers
  • oleic acid as ligand dispersed in heptane
  • the monomers IBOA 263.3 mg
  • TMPTA 29.3 mg
  • the photoinitiator Omnirad819 50 mg
  • the antioxidant1010 25 mg
  • the formulation is shook for 10 minutes and volatiles are evaporated on rotary evaporator under vacuum at 25°C. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line.
  • a solvent borne ink is formed with native QDs and the additive mPEG-SH.
  • 0.2 g red QDs having InP core, ZnSe/ZnS double shell layers
  • oleic acid as ligand dispersed in heptane
  • 51 ,9mg of mPEG-SH MW 350
  • the monomers IBOA 263.3 mg
  • TMPTA 29.3 mg
  • the photoinitiator Omnirad819 50 mg
  • the antioxidant1010 25 mg
  • the formulation is shook for 10 minutes and volatiles are evaporated on rotary evaporator under vacuum at 25°C. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line.
  • a solvent borne ink is formed with native QDs and the additive mPEG-SH.
  • 0.16 g red QDs (having InP core, ZnSe/ZnS double shell layers) with oleic acid as ligand dispersed in heptane, and 40 mg of mPEG-SH (MW 350) are introduced in a glass vial.
  • the monomers IBOA (116 mg), and DPGDA (78 mg) are added.
  • the photoinitiator Omnirad819 (40 mg) and the antioxidant IRGANOX 1010 (20 mg) are added.
  • the formulation is shook for 10 minutes and volatiles are evaporated on rotary evaporator under vacuum at 25°C. Remaining volatiles are removed under vacuum of 60 mTorr on a Schlenk line
  • Films are formed by filling glass sandwiches cells (gap around 10 urn) with inks described in the previous examples.
  • the films are cured by UV light (300 mW/cm 2 for 10 seconds).
  • the cells are then opened, resulting in an open films deposited in one of the cell glass.
  • the open films are heated (thermal annealing) at 180°C for 30 minutes under inert atmosphere. After the thermal annealing, the films are stored in a humidity controlled chamber under 25°C and relative humidity (RH) of 45%.
  • RH relative humidity
  • the QY and EQE are measured 1 h after the thermal annealing and after 3 or 5 days of storage, as indicated in the tables 1 to 4 below.
  • said EQE is measured by the following EQE measurement process at room temperature which is based on using an integrating sphere, equipped with a 450nm excitation light source coupled in via an optical fiber, and a spectrometer (Compass X, BWTEK), and which consists of a first measurement using air as the reference to detect the incident photons of the excitation light and a second measurement with the sample or test cell placed in front of the integrating sphere in between the opening of the integrating sphere and the exit of the optical fiber to detect the photons incident from the excitation light source transmitted through the sample and the photos emitted from the sample or test cell, whereas for both cases photons exiting the integrating sphere are counted by the spectrometer and EQE and BL calculation is done with the following equations and the number of photons of the excitation light and emission light is calculated by integration over the following wavelength ranges;
  • Red QD ink containing Red QDs (having InP core, ZnSe/ZnS double shell layers) having two different types of ligands made from mPEG-(SH) and oleic acid, is prepared by mixing the materials mentioned below in table 5.
  • QD films obtained by working example 15 is stored under atmosphere at 25°C, 45%RH. EQE of QD films is monitored until 5days.
  • the red QD inks of working example 15 shows excellent dispersibility.

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Abstract

La présente invention concerne une composition contenant une fraction électroluminescente telle que des matériaux quantiques, notamment des points quantiques ; et un procédé de fabrication de la composition.
PCT/EP2023/071515 2022-08-05 2023-08-03 Composition WO2024028426A1 (fr)

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