Patent Description:
Light emitting nanoparticles are known in the prior art documents.

For example, <NPL> discloses Cu<NUM>S Nanoparticles having no shell layers with dodecanethiol (DDT) and the fabrication process with using DDT at the temperature of <NUM>. DDT was used in the entire synthesis process.

<NPL> describes CdSe/ZnS with dodecanethiol.

<NPL>, mentions experimental procedures of CdSe/ZnS with surface-bound DDT ligands.

<NPL> mentions quasi spherical Cu<NUM>S nanorods with DDT.

However, the inventors newly have found that there is still one or more of considerable problems for which improvement is desired, as listed below; improvement of particle size distribution, better Full Width at Half Maximum (FWHM) value, improved self-absorption value, improvement of absorption per mg of nanoparticle(s), improvement of quantum yield of nanoparticle, well-controlled shell thickness, improved charge injection ability of nanoparticle, higher device efficiency, lowering trap emission of nanoparticle, optimizing a surface condition of shell part of nanoparticle, reducing lattice defects of a shell layer of nanoparticle, reducing / preventing formation of dangling bonds of shell layer, better thermal stability, better chemical stability, improved chemical stability in desired solvent(s), improved thermal stability in desired solvent(s), , improved chemical stability in desired matrix(es), improved thermal stability in desired matrix(es), improved dispersion in matrixes, improved dispersion in solvents, improved hole injection ability into semiconducting light emitting nanoparticle, improved external quantum efficiency, optimizing fabrication process of nanoparticle, providing new fabrication process to improve size control of nanoparticle, providing new fabrication process for better kinetics control in shell formation, new shell formation process to realize well controlled shell thickness and/or reducing lattice defects of a shell layer, environmentally more friendly and safer fabrication process.

The inventors aimed to solve one or more of the above-mentioned problems.

Then it was found a novel semiconducting light emitting nanoparticle as set out in the appended set of claims.

In another aspect, the present invention further relates to a process for fabricating a light emitting nanoparticle as set out in claims <NUM> to <NUM>.

In another aspect, the present invention also relates to composition as set o out in claim <NUM>.

In another aspect, the present invention relates to formulation as set out in claim <NUM>.

In another aspect, the present invention relates to use of the semiconducting nanoparticle, the composition, or the formulation, in an electronic device, optical device, sensing device or a biomedical device.

In another aspect, the present invention further relates to an optical medium comprising at least one light emitting nanoparticle of the present invention, or the composition.

In another aspect, the present invention further relates to an optical device comprising at least said optical medium.

According to the present invention, in one aspect, said semiconducting light emitting nanoparticle, comprising, essentially consisting of, or consisting of, a core;.

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.

The term "cover" and the term "covering" do not necessarily mean that there is always a physical contact between the said core and the outer layer.

In some embodiments of the present invention, said outer layer comprises at least two or three different metal cations such as the combination of Cu<NUM>+ and In<NUM>+, Cu<NUM>+ and Ga<NUM>+, Ag<NUM>+ and Ga<NUM>+ or a combination of Cu+<NUM>/In+<NUM>/Zn+<NUM>.

According to the present invention, the term "nanosized" means the size in between <NUM> and <NUM>, preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>.

According to the present invention, the term "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.

Therefore, according to the present invention, 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 <NUM> and <NUM>, preferably <NUM>,<NUM> to <NUM>, more preferably <NUM> to <NUM>.

According to the present invention, 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.

In a preferred embodiment of the present invention, the semiconducting light emitting nanoparticle of the present invention is a quantum sized material.

According to the present invention, 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:<NUM>-<NUM>-<NUM>-<NUM>-<NUM>.

Generally, it is said that the quantum sized materials can emit tunable, sharp and vivid colored light due to "quantum confinement" effect.

In some embodiments of the invention, the size of the overall structures of the quantum sized material, is from <NUM> to <NUM>.

In a preferred embodiment of the present invention, the average diameter of the first semiconducting nanoparticle (core) is in the range from <NUM> to <NUM>, preferably it is in the range from <NUM> to <NUM>.

The average diameter of the semiconducting light emitting nanoparticles (cores) are calculated based on <NUM> semiconducting light emitting nanoparticles in a TEM image taken by a Tecnai G2 Spirit Twin T-<NUM> Transmission Electron Microscope. The average diameter of the semiconducting light emitting nanoparticles are calculated using Fiji_ImageJ program.

According to the present invention, the organic moiety is represented by following chemical formula,(III) or (IIIa);.

*-(CH<NUM>)a-(OCH<NUM>CH<NUM>)p-(V)r-(CH<NUM>)q-Z     (III).

*-(CH<NUM>)q-(V)r-(OCH<NUM>CH<NUM>)p-Z     (IIIa).

Even more preferably, the organic moiety of the present invention is represented by following chemical formula (IV):.

*-(CH<NUM>)a-(OCH<NUM>CH<NUM>)p-(O)r-(CH<NUM>)q-Z'     (IV).

In some of the preferred embodiments the organic moiety is CH<NUM>-(CH<NUM>)<NUM><n<<NUM>-* and connecting to the S or Se atom in the outer layer.

In a preferred embodiment of the present invention, the organic moiety selected from chemical formula (I), (II), (III), (IIIa) 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 working example <NUM>.

For examples, the organic moiety can be described as follows preferably.

*-CH<NUM>-(OCH<NUM>CH<NUM>)<NUM>-O-CH<NUM>.

*-(CH<NUM>)<NUM>-(OCH<NUM>CH<NUM>)<NUM>-O-CH<NUM>.

*-(CH<NUM>)<NUM>-(OCH<NUM>CH<NUM>)<NUM>-CH<NUM>.

*-(CH<NUM>)<NUM>-(OCH<NUM>CH<NUM>)<NUM>-O-(CH<NUM>)<NUM>-SH.

In some embodiments the organic moiety has a biological function.

In some embodiments the ligand is bifunctional allowing the nanoparticle to bind to a specific site.

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.

It is also believed that the organic moiety allows to increase cellular uptake.

In some embodiments the organic moiety resembles the structures like described in:.

In some embodiments the organic moiety comprises a protein or protein building block.

In some embodiments the organic moiety comprises a zwitterionic group.

According to the present invention, the semiconducting nanoparticle comprises a core, the core can be made from several kinds of semiconducting material, for example, CdS, CdSe, CdTe, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, GaAs, GaP, GaSb, CuS, Cu<NUM>S, CuSe, Cu<NUM>Se, FeS, FeSe, FeO, FeTe, HgS, HgSe, HgSe, HgTe, InAs, InxGa1-xAs, InP, InP:Zn, InP:ZnS, InP:ZnSe, InP:ZnSSe, InP:Ga,or InP:Ga, InSb InPS, InPZnS, InPSe, InPZn, InPZnSe, InPZnSeS, InPGa, InPGaZn, InP/ZnSe, In/ZnS, InZnP/ZnSe, InP/ZnSeTe, InZnP/ZnSeTe, InGaP/ZnSe, InP/InGaP, InZnP/InGaP, InCdP, InPCdS, InP/ZnSeS, InZnP/ZnSeS, InZnP/ZnS, InZnP/InGaP/ZnSe, InZnP/InGaP/ZnS, InZnP/InGaP/ZnSeS, InPCdSe, InGaP, InGaPZn, PbSe, PbS, InSb, AlAs, AlP, AlSb, CuInS<NUM>, CuInSe<NUM>, CuInZnSe, CuInZnS, AgInS<NUM>,TiO<NUM> and a combination of any of these.

In some embodiments of the present invention, the core comprises at least a first element of group <NUM> or group <NUM> elements of the periodic table and a second element of group <NUM> or <NUM> elements of the periodic table, preferably said first element is an element of group <NUM> elements of the periodic table and said second element is an element of group <NUM> elements of the periodic table, more preferably the first element is a combination of In and Ga and the second element is P.

In a preferred embodiment of the present invention, the first core can further comprise additional element selected from one or more member of the group consisting of Ga, Zn, S, and Se.

In some embodiments the core is a metal oxide comprising for example ZnO, FeO, Fe<NUM>O<NUM>, ZrO<NUM>, CuO, SnO Cu<NUM>O, TiO<NUM>, WO<NUM>, HfO<NUM>, In<NUM>O<NUM>, MgO, Al<NUM>O<NUM> and any combination of these.

In some embodiments 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.

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

According to the present invention, a type of shape of the first semiconducting nanomaterial of the semiconducting nanoparticle, and shape of the semiconducting light emitting nanoparticle to be synthesized are not particularly limited.

For examples, spherical shaped, elongated shaped, star shaped, polyhedron shaped, pyramidal shaped, multipod shaped such as tetrapod shaped, tetrahedron shaped, platelet shaped, cone shaped, and irregular shaped first semiconducting nanosized material and - or a semiconducting light emitting material can be used.

In some embodiments of the present invention, the average diameter of the core is in the range from <NUM> to <NUM>, preferably from <NUM> to <NUM>, more preferably from <NUM> to <NUM>.

According to the present invention, the semiconducting.

In some embodiments cation is monovalent cation selected from the group consisting of Cs+, Ag+, Au+, Cu+<NUM> or a divalent cation selected from the group consisting of Zn<NUM>+, Fe+<NUM>, Ni<NUM>+, Co<NUM>+, Ca<NUM>+, Sr<NUM>+, Hg<NUM>+, Mg<NUM>+ and Pb<NUM>+, Cu+<NUM> or a trivalent cation selected from the group Fe+<NUM>, In+<NUM>, Bi+<NUM>, Ga+<NUM> a tetravalent cation selected from the group consisting of Ti<NUM>+, Ge<NUM>+, Si<NUM>+, Zr<NUM>+, Hf<NUM>+, and Sn<NUM>+, Si+<NUM>.

In some embodiments of the present invention, said outer layer comprises at least two or three different metal cations such as the combination of Cu<NUM>+ and In<NUM>+, Cu<NUM>+ and Ga<NUM>+, Ag<NUM>+ and Ga<NUM>+ or a combination of Cu+<NUM>/In+<NUM>/Zn+<NUM> or a combination of Cu+<NUM>/Ga+<NUM>/Zn+<NUM> or a combination of Cu+<NUM>/In+<NUM>/Ga+<NUM>/Zn+<NUM> or a combination of Cu+<NUM>/In+<NUM>/Ga+<NUM>.

In a preferred embodiment, the metal cation is a divalent cation selected from the group consisting of Fe+<NUM> Zn<NUM>+, Ni<NUM>+, Co<NUM>+, Ca<NUM>+, Sr<NUM>+, Hg<NUM>+, Mg<NUM>+ and Pb<NUM>+, Cu+<NUM>.

In a preferred embodiment of the present invention, said outer layer comprising, essentially consisting of, or consisting of a material represented by following chemical formula (VI),.

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

According to the present invention, preferably said outer layer is a monolayer.

More preferably, it is a last monolayer of the semiconducting nanoparticle covering the core. In case there is one or more of shell layers covering the core, then the outer layer is covering the shell layers.

According to the present invention, in some embodiments, the core can be at least partially embedded in the first shell layer, 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. In other words, 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.

In some embodiments of the present invention, 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 <NUM>st element of group <NUM> of the periodic table and a Se atom or a S atom, preferably, the <NUM>st element is Zn.

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

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.

In a preferred embodiment of the present invention, the first shell layer can be represented by following formula (VII),.

wherein <NUM>≤x≤<NUM>, <NUM>≤z≤<NUM>, and x+z≤<NUM>, preferably, the shell layer is ZnSe, ZnS, ZnSxSe(<NUM>-x), ZnSe(<NUM>-x)Tez, more preferably it is ZnSe or ZnS.

In some embodiments of the present invention, said shell layer is an alloyed shell layer or a graded shell layer preferably said graded shell layer is ZnSe, ZnSxSe(<NUM>-x), or ZnSe(<NUM>-z)Tez, more preferably it is ZnSxSe(<NUM>-x),.

In some embodiments of the present invention, optionally, the first semiconducting nanoparticle as a core and a first shell layer can be at least partially embedded in the <NUM>nd shell, preferably said first semiconducting nanoparticle is fully embedded into the shell layer.

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

More preferably: ZnS, ZnSe, ZnTe, ZnO or a combination of any of these materials.

In some embodiments of the present invention, said <NUM>nd shell layer comprises at least a <NUM>st element of group <NUM> of the periodic table and a <NUM>nd element of group <NUM> of the periodic table, preferably, the <NUM>st element is Zn, and the <NUM>nd element is S, Se, O, or Te.

In a preferred embodiment of the present invention, the second shell layer is represented by following formula (VII'),.

wherein <NUM>≤x≤<NUM>, <NUM>≤z≤<NUM>, and x+z≤<NUM>, preferably, the shell layer is ZnSe, ZnSxSey, ZnSeyTez or ZnSxTez, or ZnS, more preferably ZnSeS or ZnS.

In some embodiments of the present invention, 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.

In some embodiments of the present invention, 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.

In some embodiments of the present invention, the composition of the <NUM>nd shell layer can be the same to the composition of the outer shell layer.

In some embodiments of the present invention, the semiconducting light emitting nanoparticle can further comprise one or more additional shell layers onto the <NUM>nd shell layer as a multishell.

According to the present invention, the term "multishell" stands for the stacked shell layers consisting of three or more shell layers.

In some embodiments of the present invention, the surface of the 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.

Without wishing to be bound by theory it is believed that such surface ligands may lead to disperse the nanosized fluorescent material in a solvent more easily.

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), <NUM>-Octadecene (ODE), thiols such as hexadecane thiol, dodecane thiol, hexane thiol and polyethylene glycol thiols; selenols, when organic moiety of selenol may include linear or branched alkyl chain which can be saturated or include one or more unsaturated carbon bonds and/or aromatic rings; mercapto carboxylic acids such as mercapto propionic acid and mercaptoundecanoicacid; carboxylic acids such as oleic acid, stearic acid, myristic acid; acetic acid and a combination of any of these. Furthermore, the ligands can include Zn-oleate, Zn-acetate, Zn-myristate, Zn-Stearate, Zn-laurate and other Zn-carboxylates, sulfonic acids, halides, carbamates.

Examples of surface ligands have been described in, for example, the laid-open international patent application No. <CIT>.

In some embodiments of the present invention, the nanoparticle has a full width half maximum (FWHM) of at most <NUM> measured at <NUM> using a toluene solution, preferably a full width half maximum (FWHM) in the range of <NUM> to <NUM>, more preferably from <NUM> to <NUM>.

Preferably, the determination of the full width half maximum (FWHM) is made with an appropriate data base preferably comprising at least <NUM>, more preferably at least <NUM> and even more preferably at least <NUM> data points. The determination is preferably performed by using LabVIEW Software (LabVIEW <NUM>; May <NUM>) with the following VIs (Virtual Instrument):.

According to the present invention the QY is measured using Hamamatsu absolute quantum yield spectrometer (model: Quantaurus C11347).

Preferably, the nanoparticle emits light having the peak maximum light emission wavelength in the range from <NUM> <NUM>, preferably from <NUM> to <NUM>, more preferably from <NUM> to <NUM>, even more preferably from <NUM> to <NUM>.

According to the present invention the gas chromatography mass spectrometry (GCMS) is performed using Agilent Technologies 7890B GC system equipped with autosampler and Agilent DB-<NUM> column and MS instrument Agilent Technologies 5977B MSD. The analytes were separated using the following injection method: initial temperature <NUM>, hold <NUM> at <NUM>, heat to <NUM> at the rate of <NUM>/min, hold <NUM> at <NUM>. Samples for GCMS are prepared as follows:.

According to the present invention, in one aspect, said process for fabricating a semiconducting nanoparticle, preferably a semiconducting light emitting nanoparticle comprising, essentially consisting of, or consisting of, at least following steps(a) a) mixing at least a semiconducting nanomaterial, preferably said semiconducting nanomaterial comprises at least a <NUM>st semiconducting nanoparticle as a core,.

For examples, following materials can be used as the anion source preferably.

SH-CH<NUM>-(OCH<NUM>CH<NUM>)<NUM>-O-CH<NUM>.

SH -CH<NUM>-(OCH<NUM>CH<NUM>)<NUM>-O-CH<NUM>.

SH -(CH<NUM>)<NUM>-(OCH<NUM>CH<NUM>)<NUM>-O-CH<NUM>.

SH -(CH<NUM>)<NUM>-(OCH<NUM>CH<NUM>)<NUM>-CH<NUM>.

SH -(CH<NUM>)<NUM>-(OCH<NUM>CH<NUM>)<NUM>-O-(CH<NUM>)<NUM>-SH.

SH-(CH<NUM>)<NUM>-(OCH<NUM>CH<NUM>)<NUM>-O-CH<NUM>.

It is believed that the temperature ranges from <NUM> to <NUM> ° C is important to make a crystal binding between the organic moiety and the outer layer. In other words, by keeping the reaction temperature in step (b) within the temperature range, the anchor group of chemical formula (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.

In a preferred embodiment of the present invention, an injection of said anion source is carried out at the temperature in the range from <NUM> to <NUM>, preferably in the range from <NUM> to <NUM> in step (a) or in step (b).

It is believed that the temperature range of the injection is also important to prevent X-B bond breakage.

Preferably, step (b) is carried out in the range from <NUM> minute to <NUM> hours, preferably from <NUM> minutes to <NUM> hours, more preferably <NUM> minutes to <NUM> hours.

According to the present invention, preferably, 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 <NUM>:<NUM> to <NUM>:<NUM>, preferably from <NUM>:<NUM> to <NUM>:<NUM>, more preferably <NUM>:<NUM> to <NUM>:<NUM>, even more preferably <NUM>:<NUM> to <NUM>:<NUM>.

In a preferred embodiment of the present invention, the ratio of the total molar amount of the chalcogen source to the total molar amount of the semiconducting nanoparticle in step (b) is in the range from <NUM>:<NUM> to <NUM>:<NUM>, preferably from <NUM>:<NUM> to <NUM>:<NUM>, more preferably <NUM>:<NUM> to <NUM>:<NUM>, even more preferably <NUM>:<NUM> to <NUM>:<NUM>.

In some embodiments of the present invention, a anion source represented by chemical formula (<NUM>) 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<NUM>-U<NUM>-Y<NUM>-(CH<NUM>)n-Z<NUM>-Z<NUM>-(CH<NUM>)n-Y<NUM>-U<NUM>-L<NUM>     (<NUM>).

In a preferred embodiment of the present invention, the anion source described by the formula (<NUM>), 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.

In a preferred embodiment of the present invention, the 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 <NUM> : <NUM> to <NUM> : <NUM>, preferably in the range from <NUM> : <NUM> to <NUM> : <NUM>, even more preferably <NUM>:<NUM> to <NUM>:<NUM>.

According to the present invention, the term "chalcogen" means a chemical element of the group <NUM> chemical elements of the periodic table, preferably it is sulfur (S), selenium (Se), oxygene (O) and/or tellurium (Te).

Thus, according to the present invention, the term "chalcogen source" means a material containing at least one chemical element of the group <NUM> chemical elements of the periodic table, preferably said chemical element of the group <NUM> chemical elements is oxygen (O), sulfur (S), selenium (Se), and/or tellurium (Te), more preferably it is sulfur (S), or selenium (Se).

In a preferred embodiment of the present invention, 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,.

In a preferred embodiment of the present invention, step (a) is carried out in an inert condition such as under Argon (Ar) or N<NUM> condition, more preferably under Ar condition.

In a preferred embodiment of the present invention, 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 PGMEA, nitriles, ethers, etheric esters, aromatic solvents such as toluene, xylenes, ethylbenzene, diethylbenzes, isopropylbenzene, diisopropylbenzenes, mesitylene, with preferably being of squalene, squalane, heptadecane, octadecane, octadecene, nonadecane, icosane, henicosane, docosane, tricosane, pentacosane, hexacosane, octacosane, tetracosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, oleylamine, , trioctylamines, ketones, ketones ether acetates such as PGMEA, nitriles, ethers, aromatic solvents such as toluene, xylenes, ethylbenzene, diethylbenzes, isopropylbenzene, diisopropylbenzenes, mesitylene, more preferably octadecenes, oleylamine, squalane, pentacosane, hexacosane, octacosane, nonacosane, trioctylamine or triacontane, ketones, ketones, ether acetates such as PGMEA, nitriles, ethers, etheric esters, aromatic solvents such as toluene, xylenes, ethylbenzene, diethylbenzes, isopropylbenzene, diisopropylbenzenes, mesitylene, even more preferably octadecene, oleylamine, squalane, pentacosane, trioctylamine or hexacosane, tetracosane, ketones, ketones ether acetates such as PGMEA, etheric esters, nitriles, ethers, aromatic solvents such as toluene, xylenes, ethylbenzene, diethylbenzes, isopropylbenzene, diisopropylbenzenes, mesitylene.

In a preferred embodiment of the present invention, said mixing step is carried out at the temperature in the range of from <NUM> to <NUM>, preferably from <NUM> to <NUM>, more preferably from <NUM> to <NUM>.

In a preferred embodiment of the present invention, a plurality of first semiconducting nanomaterials can be used in step (a).

According to the present invention, said semiconducting nanomaterial comprises, essentially consists of, or consists of at least a first semiconducting nanomaterial except for any ligand attached onto the outermost surface of the semiconducting nanoparticle if it is attached.

In some embodiments of the present invention, said semiconducting nanoparticle may optionally comprise one or more of shell layers covering at least a part of said first semiconducting nanoparticle as described in the section of "shell layer" above.

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

In some embodiments of the present invention, the first semiconducting nanomaterial comprises, essentially consisting of, or consisting of, at least a first element of group <NUM> or group <NUM> elements of the periodic table and a second element of group <NUM> or <NUM> elements of the periodic table, preferably said first element is an element of group <NUM> elements of the periodic table and said second element is an element of group <NUM> elements of the periodic table, more preferably the first element is In, Ga or a combination of In and Ga, the second element is P, except for ligands attached onto the outermost surface of the first semiconducting nanoparticle if it is attached.

In a preferred embodiment of the present invention, the first semiconducting nanomaterial can further comprise additional element selected from one or more member of the group consisting of Ga, Zn, S, and Se.

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

In a preferable embodiment, the first semiconducting nanomaterial is alloyed.

According to the present invention, a type of shape of the first semiconducting nanomaterial of the semiconducting light emitting nanoparticle, and shape of the semiconducting light emitting nanoparticle to be synthesized are not particularly limited.

For examples, spherical shaped, elongated shaped, star shaped, polyhedron shaped, pyramidal shaped, multipod shaped such as tetrapod shaped, tetrahedron shaped, platelet shaped, cone shaped, and irregular shaped first semiconducting nanoparticle and - or a semiconducting light emitting material can be synthesized.

In some embodiments of the present invention, the average diameter of the first semiconducting nanoparticle is in the range from <NUM> to <NUM>, preferably from <NUM> to <NUM>.

According to the present invention, a shell layer can be further formed optionally by applying following step (d), preferably step (d) is performed before step (b);
(d) mixing at least a semiconducting nanomaterial and/or a first semiconducting nanoparticle (core), preferably said first semiconducting nanoparticle is obtained in the step (h), and at least a first cation shell precursor and a first anion shell precursor, optionally in a solvent, to form a shell layer onto the first semiconducting material,.

Preferably said first anion shell precursor is injected into the reaction mixture during step (d).

In a preferred embodiment of the present invention, and preferably said anion precursor is a chalcogen source, more preferably it is selected from one or more members of the group consisting of Trioctylphosphine : Se, Tributylphosphine : Se, Trioctylphosphine : S, Tributylphosphine : S, thiols and selenols.

Other conditions for formation of a shell layer is described, for example in <CIT> and <NPL>.

Nanoparticles can be obtained from public source or obtained as described in this patent application.

In a preferred embodiment of the present invention, said cation shell precursor is a salt of an element of the group <NUM> 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-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),.

wherein M is Zn<NUM>+, or Cd<NUM>+, preferably M is Zn<NUM>+, X<NUM> is a halogen selected from the group consisting of F-, Cl-, Br- and I-, n is <NUM>,.

[M(O<NUM>CR<NUM>) (O<NUM>CR<NUM>)] -     (XIV).

wherein M is Zn<NUM>+, or Cd<NUM>+, preferably M is Zn<NUM>+,.

In a preferred embodiment, R<NUM> and R<NUM> are the same.

In a preferred embodiment of the present invention, the ratio of the total amount of the chalcogen source, preferably said chalcogen source is a selenium source, sulfur source or a combination of selenium source and a sulphur source, and the total amount of the cation shell precursor used in step (d) is in the range from <NUM> : <NUM> to <NUM> : <NUM>, preferably in the range from <NUM> : <NUM> to <NUM> : <NUM>.

Step (d) can be applied for synthesizing not only a first shell layer but also a second shell layer and/or a multishell layer.

According to the present invention, cooling the reaction mixture from step (d) is carried out in step (e) after step (d) before step (b), preferably to stop shell forming reaction accordingly.

As a 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.

In some embodiment, the cooling rate in step (e) can be in the range from <NUM>/s to <NUM>/s, preferably it is from <NUM>/s to <NUM>/s.

In a preferred embodiment, the reaction mixture is cooled down to the temperature less than <NUM>, more preferably in the rage from <NUM> to <NUM>,.

In some embodiments of the invention, the process further comprises step (f), preferably the process comprises step (f) before step (b), more preferably after step (d) before step (b), even more preferably after step (e) before step (b). (f) mixing said chalcogen source and said cation precursor with the first semiconducting nanoparticle, optionally with another material, to make the second mixture at the temperature in the range of from <NUM> to <NUM>, preferably from <NUM> to <NUM>, more preferably from <NUM> to <NUM>.

In some embodiments, as an option, premixing the first semiconducting nanoparticle and the cation source to make a premixed mixture and then injecting the chalcogen source to the premixed mixture can be done as step (f") instead of said step (f) to make the second mixture. The same temperature range as described in step (e) can be applied.

Preferably, said chalcogen source is injected after injection of said cation shell precursor.

In some embodiments of the invention, to obtain the semiconductor nanoparticles, the process may optionally comprise process steps like described in but not limited to the following steps (g) and (h) in this sequence, preferably before step (a);
(g) preparing a first semiconducting nanoparticle in a first mixture by reacting at least one indium precursor and at least one phosphor precursor or by using a cluster being obtainable by reacting the metal cation precursor and the anion precursor, preferably said cluster is a magic sized cluster, said indium precursor is a metal halide represented by following chemical formula (XV), metal carboxylate represented by following chemical formula (XVI), or a combination of these, and said phosphor precursor is an amino phosphine represented by following chemical formula (XVII), alkyl silyl phosphine such as tris trimethyl silyl phosphine, or a combination of these,.

wherein V<NUM> is a halogen selected from the group consisting of Cl-, Br- and I-,.

wherein R<NUM> is a linear alkyl group having <NUM> to <NUM> carbon atoms, a branched alkyl group having <NUM> to <NUM> carbon atoms, a linear unsaturated hydrocarbyl group having <NUM> to <NUM> carbon atoms, or a branched unsaturated hydrocarbyl group having <NUM> to <NUM> carbon atoms, preferably R<NUM> is a linear alkyl group having <NUM> to <NUM> carbon atoms, or a linear unsaturated hydrocarbyl group having <NUM> to <NUM> carbon atoms, more preferably, R<NUM> is a linear alkyl group having <NUM> to <NUM> carbon atoms, or a linear unsaturated hydrocarbylgroup having <NUM> to <NUM> carbon atoms, even more preferably R<NUM> is a linear alkyl group having <NUM> to <NUM> carbon atoms, or a linear unsaturated hydrocarbylgroup having <NUM> to <NUM> carbon atoms, furthermore preferably R<NUM> is a linear alkyl group having <NUM> to <NUM> carbon atoms,.

wherein R<NUM> and R<NUM> are at each occurrence, independently or dependently, a hydrogen atom or a linear alkyl group having <NUM> to <NUM> carbon atoms or a linear unsaturated hydrocarbylgroup having <NUM> to <NUM> carbon atoms, preferably a linear alkyl group having <NUM> to <NUM> carbon atoms, more preferably a linear alkyl group having <NUM> to <NUM> carbon atoms, even more preferably a linear alkyl group having <NUM> carbon atoms, optionally, a zinc salt and/or a zinc carboxylate is added in step (f), preferably said zinc salt is represented by following chemical formula (XIII), (XIV').

wherein X<NUM> is a halogen selected from the group consisting of Cl-, Br- and I-, n is <NUM>,.

[Zn(O<NUM>CR<NUM>) (O<NUM>CR<NUM>)] -     (XIV').

In some embodiments of the present invention, the first semiconducting nanoparticle in step (g) is prepared in a first mixture by using a cluster being obtainable by reacting the metal cation precursor and the anion precursor.

In some embodiments of the present invention, the first semiconducting nanoparticle in step (g) is prepared in a first mixture by using the cluster, and the cluster is a Magic Sized Cluster(MSC) selected from the group consisting of InP, InAs, InSb, GaP, GaAs, and GaSb, magic sized clusters (MSC), preferably InP magic sized cluster (MSC InP), more preferably, it is In<NUM>P<NUM>(O<NUM>CR<NUM>)<NUM>, wherein said O<NUM>CR<NUM> of said In<NUM>P<NUM>(O<NUM>CR<NUM>)<NUM> is - O<NUM>CCH<NUM>Phenyl, or a substituted or unsubstituted fatty acid such as hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, dodecanoate, tridecanoate, tetradecanoate, pentadecanoate, hexadecanoate, heptadecanoate, octadecanoate, nonadecanoate, icosanoate or oleate.

In some embodiments of the present invention, the first semiconducting nanoparticle in step (g) may optionally be prepared in a first mixture by using the cluster, and the cluster is a Magic Sized Cluster(MSC), but not limited to it.

Preferably, the magic sized cluster (MSC) is based on a nanocrystal core, which consists solely of fused <NUM>-membered rings with all phosphorus atoms coordinated to four indium atoms in a pseudo-tetrahedral arrangement, preferably the nanocrystal core have the formula [In<NUM>P<NUM>]<NUM>+, [In<NUM>P<NUM>]<NUM>+, [In<NUM>P<NUM>]<NUM>+, [In<NUM>P<NUM>]<NUM>+, [In<NUM>P<NUM>]<NUM>+, [IN<NUM>P<NUM>]<NUM>+, [In<NUM>P<NUM>]<NUM>+, [In<NUM>P<NUM>]<NUM>+, [In<NUM>P<NUM>]<NUM>+, [In<NUM>P<NUM>]<NUM>+, [In<NUM>P<NUM>]<NUM>+, and/or [In<NUM>P<NUM>]<NUM>+.

In some embodiments of the present invention, the first semiconducting nanoparticle in step (g) is prepared in a first mixture by using the cluster, and the cluster is a Magic Sized Cluster(MSC), wherein the magic sized cluster (MSC) comprises an Indium based carboxylate ligand, preferably In(O<NUM>CR<NUM>)<NUM>, wherein said O<NUM>CR<NUM> of said In(O<NUM>CR<NUM>)<NUM> is -O<NUM>CCH<NUM>Phenyl, or a substituted or unsubstituted fatty acid such as hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, dodecanoate, tridecanoate, tetradecanoate, pentadecanoate, hexadecanoate, heptadecanoate, octadecanoate, nonadecanoate, icosanoate or oleate. Such InP magic sized clusters (MSCs) as single source precursors (SSP) can be fabricated as described in <NPL>.

According to the present invention, the quenching of the formation of the first semiconducting nanoparticle can be done by cooling the reaction mixture.

In a preferred embodiment of the present invention, the cooling rate in step (h) is in the range from <NUM>/s to <NUM>/s, preferably it is from <NUM>/s to <NUM>/s, more preferably from <NUM>/s to <NUM>/s, more preferably it is from <NUM>/s to <NUM>/s, even more preferably it is from <NUM>/s to <NUM>/s.

In some embodiments of the present invention, the process further comprises following step (j) before step (a), preferably before step (a) after step (h),.

In some embodiments of the present invention, the step (h) is carried out at the temperature in the range from <NUM> to <NUM>, preferably in the range from <NUM> to <NUM>, more preferably in the range from <NUM> to <NUM>, even more preferably from <NUM> to <NUM>.

In some embodiments of the present invention, the treatment time of step (j) is in the range from <NUM> minutes to <NUM> hours, preferably from <NUM> minutes to <NUM> hours, more preferably <NUM> minutes to <NUM> hours.

In some embodiments of the present invention, the total molar ratio between the amount of the metal halide in step (j) and the amount of the first semiconducting nanoparticle is in the range from <NUM> to <NUM>,<NUM>, preferably from <NUM>,<NUM> to <NUM>,<NUM>, more preferably from <NUM> to <NUM>,<NUM>.

In some embodiments of the present invention, step (j) is carried out in a solution comprising at least one solvent 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 PGMEA, nitriles, ethers, aromatic solvents, with preferably being of squalene, squalane, heptadecane, octadecane, octadecene, nonadecane, icosane, henicosane, docosane, tricosane, pentacosane, hexacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, oleylamine, and trioctylamine, more preferably octadecene, trioctylamines, oleylamine, squalane, pentacosane, hexacosane, octacosane, nonacosane, or triacontane, even more preferably octadecene, trioctylamines, oleylamine, squalane, pentacosane, or hexacosane, ketones, ether acetates such as PGMEA.

In a preferred embodiment of the present invention, each step of the steps (a) to (j) is carried out in an inert condition such as under N<NUM> or Argon (Ar) condition, preferably under Ar condition.

In another aspect of the present invention, the invention also relates to a semiconducting nanoparticle obtainable or obtained from the process of the present invention.

In a preferred embodiment the semiconducting nanoparticle is light emitting nanoparticle.

In another aspect, the present invention also relates to composition preferably comprising but not limited to, essentially consisting of, or consisting of, at least one nanoparticle of the present invention, preferably said nanoparticle is a light emitting nanoparticle of the present invention; and at least one additional material, preferably the additional material is selected from the group consisting of organic light emitting materials, inorganic light emitting materials, charge transporting materials, scattering particles, host materials, nanosized plasmonic particles, photo initiators, and matrix materials.

Such suitable inorganic light emitting materials described above can be well known phosphors including nanosized phosphors, quantum sized materials like mentioned in the <NPL>), <CIT>, <CIT>, and <CIT>.

According to the present invention, as said organic light emitting materials, charge transporting materials, any type of publicly known materials can be used preferably. For example, well known organic fluorescent materials, organic host materials, organic dyes, organic electron transporting materials, organic metal complexes, and organic hole transporting materials.

For examples of scattering particles, small particles of inorganic oxides such as SiO<NUM>, SnO<NUM>, CuO, CoO, Al<NUM>O<NUM> TiO<NUM>, Fe<NUM>O<NUM>, Y<NUM>O<NUM>, ZnO, MgO; organic particles such as polymerized polystyrene, polymerized PMMA; inorganic hollow oxides such as hollow silica or a combination of any of these; can be used preferably.

According to the present invention, a wide variety of publicly known transparent matrix materials suitable for optical devices can be used preferably.

According to the present invention, the term "transparent" means at least around <NUM> % of incident light transmits at the thickness used in an optical medium and at a wavelength or a range of wavelength used during operation of an optical medium. Preferably, it is over <NUM> %, more preferably, over <NUM>%, the most preferably, it is over <NUM> %.

In a preferred embodiment of the present invention, as said matrix material, any type of publicly known transparent matrix material, described in for example, <CIT> can be used.

In some embodiments of the present invention, the transparent matrix material can be a transparent polymer.

According to the present invention the term "polymer" means a material having a repeating unit and having the weight average molecular weight (Mw) <NUM>/mol, or more.

The molecular weight Mw is determined by means of GPC (= gel permeation chromatography) against an internal polystyrene standard.

In some embodiments of the present invention, the glass transition temperature (Tg) of the transparent polymer is <NUM> or more and <NUM> or less.

Tg is measured based on changes in the heat capacity observed in Differential scanning colorimetry like described in
http://pslc. ws/macrog/dsc. htm; Rickey J Seyler, Assignment of the Glass Transition, ASTM publication code number (PCN) <NUM>-<NUM>-<NUM>.

For example, as the transparent polymer for the transparent matrix material, polyacrylates, poly(meth)acrylates, epoxys, polyurethanes, polysiloxanes, can be used preferably.

In a preferred embodiment of the present invention, the weight average molecular weight (Mw) of the polymer as the transparent matrix material is in the range from <NUM>,<NUM> to <NUM>,<NUM>/mol, more preferably it is from <NUM>,<NUM> to <NUM>,<NUM>/mol.

In a preferable embodiment of the present invention, the composition comprises a plural of the light emitting nanoparticles and/or a plural of the semiconducting materials.

In another aspect, the present invention relates to formulation comprising, essentially consisting of, or consisting of, at least one semiconducting nanoparticle, semiconducting light emitting nanoparticle or the composition of the present invention,
and at least one solvent.

Preferably the solvent is selected from one or more members of the group consisting of aromatic, halogenated and aliphatic hydrocarbon solvents 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.

Preferably, the formulation contains a plurality of light emitting nanoparticles.

The amount of the solvent in the formulation can be freely controlled according to the method of coating the composition. For example, if the composition is to be spray-coated, it can contain the solvent in an amount of <NUM> wt. Further, if a slit-coating method, which is often adopted in coating a large substrate, is to be carried out, the content of the solvent is normally <NUM> wt. % or more, preferably <NUM> wt.

In another aspect, the present invention relates to use of the semiconducting light emitting nanoparticle, or the semiconducting nanoparticle, or the composition, or the formulation, in an electronic device, optical device, sensing device or in a biomedical device.

In another aspect, the present invention further relates to an optical medium comprising at least one semiconducting nanoparticle, preferably at least one semiconducting light emitting nanoparticle of the present invention, or the composition, or the formulation.

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

According to the present invention, the term "sheet" includes film and / or layer like structured mediums.

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

According to the present invention, any kinds of publicly available inorganic, and/or organic materials for hole injection layers, hole transporting layers, electron blocking layers, light emission layers, hole blocking layers, electron blocking layers, and electron injection layers can be used preferably, like as described in <CIT>, <CIT>, <CIT>, <CIT> and <CIT>.

In a preferable embodiment of the present invention, the optical medium comprises a plural of the semiconducting light emitting nanoparticles and/or a plural of the semiconducting nanoparticles.

In some embodiments the anode and the cathode of the optical medium sandwich the organic layer.

In some embodiments said additional layers are also sandwiched by the anode and the cathode.

In some embodiments of the present invention, the layer comprises at least one semiconducting nanoparticle, preferably it is a semiconducting light emitting nanoparticle, of the present invention, and a host material, preferably the host material is an organic host material.

In another aspect, the invention further relates to an optical device comprising the optical medium.

In some embodiments of the present invention, the optical device can be a liquid crystal display device (LCD), Organic Light Emitting Diode (OLED), backlight unit for an optical display, Light Emitting Diode device (LED), Micro Electro Mechanical Systems (here in after "MEMS"), electro wetting display, or an electrophoretic display, a lighting device, and / or a solar cell.

The present invention provides one or more of following effects; improvement of particle size distribution, better Full Width at Half Maximum (FWHM) value, improved self-absorption value, improvement of absorption per mg of nanoparticle(s), improvement of quantum yield of nanoparticle, well-controlled shell thickness, improved charge injection ability of nanoparticle, higher device efficiency, lowering trap emission of nanoparticle, optimizing a surface condition of shell part of nanoparticle, reducing lattice defects of a shell layer of nanoparticle, reducing / preventing formation of dangling bonds of shell layer, better thermal stability, better chemical stability, improved chemical stability in desired solvent(s), improved thermal stability in desired solvent(s), improved chemical stability in desired matrix(es), improved thermal stability in desired matrix(es), improved dispersion in matrixes, improved dispersion in solvents, improved hole injection ability into semiconducting light emitting nanoparticle, improved external quantum efficiency, optimizing fabrication process of nanoparticle, providing new fabrication process to improve size control of nanoparticle, providing new fabrication process for better kinetics control in shell formation, new shell formation process to realize well controlled shell thickness and/or reducing lattice defects of a shell layer, environmentally more friendly and safer fabrication process.

The core synthesis examples <NUM> to <NUM> and the working examples <NUM> to <NUM> below provide descriptions of the present invention, as well as an in-detail description of their fabrication.

In a <NUM> <NUM>-neck flask, weight <NUM> (<NUM> mmol) of indium acetate and <NUM> (<NUM> mmol) of myristic acid. The flask is equipped with a reflux condenser, septa and a tap between the flask and the condenser.

Put under vacuum at <NUM> for <NUM> <NUM> to off-gas acetic acid under reduced pressure, and overnight at room T.

Day after, the solution heat again to <NUM> and evacuate for <NUM> hour and <NUM> in those conditions.

Total evacuation time at <NUM> for10 hours,.

Fill the reaction flask with argon and add <NUM> of dry toluene. Heat the reaction to <NUM>.

Inject the mixture of <NUM> (<NUM>) of PTMS and <NUM> (<NUM>) of toluene into the flask with indium myristate (In(Ma) at <NUM>.

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).

When the improvement in the peak shape (red-shift and sharpness) is stopped the 2nd PTMS solution (<NUM> (<NUM>) PTMS in <NUM> (<NUM>) Toluene) is added in portions of <NUM> to reach the optimal optical parameters. For example:.

After <NUM> cool the reaction with fan and store the flask itself under inert atmosphere.

InP magic size clusters are formed with exciton at <NUM>.

The InP magic size clusters (MSCs) are cleaned with anhydrous acetonitrile (the ratio of crude:acetonitrile <NUM>:<NUM>). The process is repeated with a mixture of anhydrous toluene and acetonitrile in ratio toluene:acetonitrile <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>. This product is called "magic size clusters (MSCs)".

A <NUM>, <NUM>/<NUM>, four-neck round-bottom flask equipped with a reflux condenser is evacuated, and <NUM> of distilled squalane is injected into it. The apparatus is evacuated with stirring (pressure is lowered from 300mtorr to <NUM> mTorr during 1hour) and heated to <NUM> under argon. In a glove box a solution of MSCs with a concentration of <NUM>. 15x10-<NUM>M is prepared in distilled squalane. <NUM> (<NUM>. 26E-<NUM> moles) of this solution is injected to the flask at <NUM>, using a <NUM>-gauge needle and <NUM> syringe;
after <NUM> minutes the mantle is removed, and the flask is cooled to <NUM> by blowing air with a fan. The mantle is then brought back, and the flask is heated to <NUM>.

At this point more MSCs are added, using the same solution that is initially injected; <NUM>-gauge needle and <NUM> syringe are used, the addition is done at a rate of <NUM>/min at the given times (compared to the initial injection):.

InP QDs are formed with exciton at <NUM>.

In this example InP cores used are synthesized using the core synthesis described above (<CIT>) and have core exciton CWL of <NUM>. The final core solution is cleaned with a mixture of anhydrous toluene and ethanol (ratio crude:toluene:ethanol: <NUM>:<NUM>:<NUM>). The process is repeated with ratio crude:toluene:ethanol: <NUM>:<NUM>:<NUM>. This solution will be called further "SSP InP cores".

Post-synthesis core treatment : In glove box (GB), SSP InP cores (<NUM>. 5X10-<NUM>mol) are dissolved with <NUM> toluene and transferred into <NUM> round bottom flask with <NUM> pumped oleylamine (OLAm) and <NUM> ZnCl2. After short pumping at <NUM> to remove toluene, the flask is filled with argon and heated to <NUM> for <NUM>. The solution is then cooled down to <NUM>.

Shelling process : At <NUM>, <NUM> of a <NUM> concentrated solution of Zn(Cl)<NUM> in OLAm and <NUM> amount (<NUM> of <NUM> TOP-Se) of anion shell precursor are added to SSP InP cores after core treatment. After <NUM>, the solution is heated to <NUM>. After <NUM> the solution is heated to <NUM>, <NUM> of <NUM> Zn(Undecylenate)<NUM> is injected and the reaction kept at <NUM> for <NUM> hrs. After 3hrs at <NUM> the reaction is terminated by cooling down the reaction mixture.

The resulting nanoparticles are is cleaned with a mixture of anhydrous toluene and ethanol (ratio crude:toluene:ethanol: <NUM>:<NUM>:<NUM>). The process is repeated. Then the nanoparticles are extracted with hexane.

The comparative example is similar to comparative example <NUM>, but <NUM> mmol of TOP-Se is injected at <NUM>; and <NUM>. 56mmol of DDT is injected at <NUM>, <NUM> after injection of Zn(Undecylenate)<NUM>.

Outer layer synthesis: At room temperature, <NUM>. 3X10-<NUM>mol of InP/ZnSe, described in comparative example <NUM>, are dissolved with <NUM> toluene and transferred into <NUM> round bottom flask with <NUM> pumped <NUM>-octadecene (ODE). After <NUM> pumping at RT <NUM>-dodecane selenol (<NUM>. 2mmol) is added and the flask is heated to <NUM>. When temperature reached <NUM> Zn(Undecylenate)<NUM> (<NUM>. 2mmol) is added and the reaction kept at <NUM> for <NUM> hrs. After <NUM> hours at <NUM> the reaction is terminated by cooling down the reaction mixture.

Table A compares the values of thermal, anti-radical, anti-peroxide stabilities for the described example and the comparative example <NUM>.

The working example is similar to working example <NUM>, but <NUM>-dodecanethiol is used as sulphur precursor.

The working example is similar to working examples <NUM> and <NUM>, however <NUM>-dodecaneselenol and <NUM>-dodecanethiol are added together at equal molar amounts keeping the amount of Se+S ions same as before.

The working example differs from the working example <NUM> by utilizing <NUM>-phenylethane thiol instead of <NUM>-dodecanethiol as sulphur source.

The working example is similar to working example <NUM>, but InP/ZnSeS particles are used. The InP/ZnSeS prepared as described in comp. Table A compares the values of thermal, anti-radical, anti-peroxide stabilities for the described example and the comparative example <NUM>.

The working example is similar to working example <NUM>, but perfluorodecane thiol is used as sulphur precursor.

Thermal stability test - powder thermal test at <NUM> in air.

Benzoquinone test - <NUM>%wt of p-benzoquinone added to clean NPs in toluene.

Peroxide test - <NUM>%wt of tertbutylperoxybenzoate added to clean NP in toluene.

The general scheme mentioned in <FIG> (scheme1) describes a multi-step method that is established to characterize between surface and crystal bound ligands (covalently bound ligands), exemplified for dodecaneselenol (DOSe).

<NUM>-phenylpropylphosphonic acid (PPPA) 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. On the other hand, crystal-bound ligands are integrated into the crystal lattice. Subsequently, their dissociation from QDs is impossible without destruction of the crystal.

<FIG>: <NUM>H NMR spectra (in toluene d8) of QDs from working example <NUM> 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 <NUM>H NMR using Duroquinone as external standard and is equal to <NUM> mmol. Meaning, Only <NUM>% mol from total amount of DDSe that is inserted to reaction produced surface bound DDSe.

<FIG>: <NUM>H NMR spectrum (in toluene d8) of QDs after treating with PPPA and washing with ethanol.

<NUM>H NMR indicates that surface-bound DDSe is completely removed from the surface of the QDs (signal #<NUM> (Se-H) and signal #<NUM> (CH2-Se) disappeared). however, Signal #<NUM> (CH3 of DDSe) still exist. this is an indication of presence of a second population of DDSe which is not surface bound.

QDs after removing all surface bound DDSe are analyzed in GCMS. For this purpose, proper derivatization with HCl and methanol is performed. This treatment leads to complete decomposition and dissolution of QDs.

<FIG>: GCMS spectrum for QDs after treating with PPPA and washing. MS spectrum of peak at retention time of <NUM>.

The sample for GCMS was prepared as described in embodiments. GCMS confirms presence of DDSe. This indicates crystal binding of DDSe.

Main conclusion: QDs from working example <NUM> contain surface- as well as crystal-bound DDSe.

Weight <NUM> (1mmol) of Zn(OAc)<NUM> in the <NUM>-round bottom <NUM>-neck reaction flask, put under vacuum for 40minutes, put under argon, introduce to the glove box; add <NUM> of PGMEA and <NUM> of InP based red quantum materials (QMs).

The resulting QDs are cleaned with anhydrous hexane (the ratio of crude:hexane <NUM>:<NUM>). The process is repeated with a mixture of anhydrous PGMEA:hexane <NUM>:<NUM>. Then the QDs are extracted with toluene.

Table B compares the values of thermal stability for the described Working example <NUM> and for the used first semiconducting material (InP based red quantum materials).

<NUM> of zinc acetate (Zn(OAc)<NUM>) are weighted into <NUM> round bottom flask and degassed for <NUM> at <NUM> mTorr while stirring. Put under Ar atmosphere. Inserted into the glove box.

<NUM> PGMEA and toluene solution of <NUM> gr of InP based red quantum materials is added. The mixture is mounted on a Schlenk line. Put under Ar. Distillation set-up is mounted and toluene is distilled out.

The flask is heated to reflux and <NUM> of <NUM> mPEG800-SH solution in PGMEA is injected.

After <NUM> another portion of <NUM> of <NUM> mPEG800-SH solution in PGMEA is injected.

The flask is cooled to RT after additional <NUM> at reflux (total reaction time <NUM> and <NUM>).

The resulting QDs are cleaned as follows: solids are removed by centrifugation; QDs are precipitated with anhydrous hexane (the ratio of crude:hexane <NUM>:<NUM>); the process is repeated with a mixture of anhydrous PGMEA:hexane <NUM>:<NUM>, then twice with anhydrous toluene:hexane <NUM>:<NUM>.

Table C compares the values of thermal stability for the described Working example <NUM> with reference material, which is prepared similarly to Working example <NUM>, but without Zn(OAc)<NUM>.

<NUM> of Zn(OAc)<NUM> is weighted outside GB into <NUM> round bottom flask, the flask is introduced to GB. <NUM> of diisopropylbenzene (DIPB) and then toluene solution of <NUM> 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. The flask is heated to <NUM> and <NUM> of <NUM> mPEG(<NUM>)-SH solution in diisopropylbenzene is injected. After <NUM> at <NUM> the reaction cooled to ambient temperature. QDs precipitated upon cooling below 50C. Toluene (<NUM>) is added to dissolve the quantum dots.

Claim 1:
A semiconducting light emitting nanoparticle, comprising a core;
an outer layer covering at least a part of said core, comprising 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,
wherein said divalent anion is selected from Se<NUM>-, S<NUM>-, Te<NUM>- O<NUM>- 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<NUM>+, Ni<NUM>+, Co<NUM>+, Ca<NUM>+, Sr<NUM>+, Hg<NUM>+, Mg<NUM>+ and Pb<NUM>+, or a tetravalent cation selected from the group consisting of Ti<NUM>+, Ge<NUM>+, Si<NUM>+, Zr<NUM>+, Hf<NUM>+, and Sn<NUM>+ wherein the organic moiety is represented by following chemical formula (III) or (III');

        *-(CH<NUM>)a-(OCH<NUM>CH<NUM>)p-(V)r-(CH<NUM>)q-Z     (III)

        *-(CH<NUM>)q-(V)r-(OCH<NUM>CH<NUM>)p-Z     (IIIa)

wherein
V is O, CH<NUM> or C=O;
Z is a hydrogen atom or an organic group, preferably Z is a hydrogen atom, a straight alkyl group having <NUM> to <NUM> carbon atoms, a branched alkyl group having <NUM> to <NUM> carbon atoms, -COOH, -SH, or -NH<NUM>, alkylamine, fluoroaryl, fluoroalkaryl, fluoroalkyl or fluoroaralkyl, preferably Z is a hydrogen atom, a straight alkyl group having <NUM> to <NUM> carbon atoms, a branched alkyl group having <NUM> to <NUM> carbon atoms, more preferably it is a hydrogen atom, a straight alkyl group having <NUM>-<NUM> carbon atoms, a branched alkyl group having <NUM>-<NUM> carbon atoms, even more preferably it is a hydrogen atom, or a straight alkyl group having <NUM>-<NUM> carbon atoms;
a is <NUM> or an integer <NUM> or more, preferably <NUM>≤a≤<NUM>, more preferably <NUM>≤a≤<NUM>, even more preferably <NUM>≤a≤<NUM>;
p is an integer <NUM> or more, preferably <NUM>≤p≤<NUM>, more preferably <NUM>≤p≤<NUM>, even more preferably <NUM>≤p≤<NUM>, furthermore preferably <NUM>≤p≤<NUM>;
q is <NUM> or an integer <NUM> or more, preferably <NUM>≤q≤<NUM>, more preferably <NUM>≤q≤<NUM>, even more preferably <NUM>≤q≤<NUM>, furthermore preferably it is <NUM>≤q≤<NUM>;
r is <NUM> or an integer <NUM>;
"*" represents the connecting point to the anion in the outer layer.