Surface modified semiconducting light emitting nanoparticles and process for preparing the same

Abstract

To provide a composition comprising a nanoparticle and a process for preparing thereof.SOLUTION: A process for preparing a composition comprises mixing a first organic compound with a semiconducting light-emitting nanoparticle comprising a core comprising at least one element of Group 13 of the Periodic Table, wherein the nanoparticle is a quantum sized material, and optionally comprises at least one shell layer, and is partially or totally covered with two or more ligands, wherein the first organic compounds are represented by the following formula (I) XR1R2- (I) (wherein X is S, R1 is hydrogen atom, R2 is a linear alkyl group having 1 to 40 carbon atoms or a branched alkyl group having 3 to 40 carbon atoms), and the ligands that partially or totally cover the semiconducting light-emitting nanoparticles are exchanged with ligands. The process does not comprise purification, centrifugation and vacuum drying of the semiconducting light-emitting material after the mixing step.SELECTED DRAWING: None

Description

[Technical field]

[0001] FIELD OF THE PRESENT APPLICATION The present invention relates to compositions comprising semiconducting luminescent nanoparticles, processes for preparing the compositions, uses of the compositions, uses of the chemical compounds, optical media, and optical devices. [Background technology]

[0002] Background technology In US 9,701,896 B1 compositions are disclosed that include quantum dots and the radiation stabilizers TOPO, TOPO+KDP, or TOPO+Zn oleate. In US 2010 / 068522 A1, InP quantum dots functionalized with 10-undecylenic acid are disclosed. APL Materials 4, 040702 (2016) describes the addition of trioctylphosphine oxide to an acrylic polymer composition prior to curing of the composition. CN 106590629 A discloses that the stability of perovskite quantum dots is improved by crystallizing carboxybenzene around the quantum material. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] 1. US 9,701,896 B1 [Patent Document 2] 2.US 2010 / 068522 A1 [Patent Document 3] 3.CN 106590629A [Non-patent literature]

[0004] [Non-Patent Document 1] 4.APL Materials 4, 040702 (2016)

[0005] SUMMARY OF THE PRESENT APPLICATION However, the present inventors have newly discovered that there are still one or more significant problems for which improvement is desired, as listed below:

[0006] Improved quantum yield of nanoparticles, preventing or reducing the decrease in quantum yield in dilute compositions and / or radical-rich environments, higher device efficiency, optimizing the surface state of the shell portion of the nanoparticles, reducing lattice defects in the shell layer of the nanoparticles, reducing / preventing the formation of dangling bonds in the shell layer, better thermal stability, improved oxidative stability, improved stability against radical substances, improved stability during long-term storage without significant decrease in QY, better chemical stability, more environmentally friendly, and safer fabrication process.

[0007] The present inventors set out to solve one or more of the problems set forth above. Then, the following steps: a) mixing at least a first organic compound with semiconducting, luminescent nanoparticles comprising a core, the nanoparticles optionally comprising at least one shell layer, preferably with another material to obtain a first mixture; wherein the first organic compound has the following chemical formula (I): A(B) n C - (I) wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1; We have discovered a novel process for the preparation of a composition comprising, consisting essentially of, or consisting of:

[0008] In another aspect, the present invention also relates to a composition obtainable or obtained by the process of the present invention.

[0009] In another aspect, the present invention further comprises at least a) a semiconducting, luminescent nanoparticle comprising a core and, optionally, at least one shell layer; b) a first chemical compound, and c) optionally another compound wherein the first organic compound has the following chemical formula (I): A(B) n C - (I) wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1; The present invention relates to a composition comprising, consisting essentially of, or consisting of:

[0010] In another aspect, the present invention also provides a compound of formula I: A(B) n C - (I) wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1, in a composition comprising at least one semiconducting, luminescent nanoparticle, or for making a composition, or for a process for making an optical device. In another aspect, the present invention also relates to the use of the compositions of the present invention in electronic devices, optical devices or in biomedical devices.

[0011] In another aspect, the present invention further comprises at least one semiconducting, luminescent nanoparticle and a compound represented by formula I): A(B) n C - (I) wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1. In another aspect, the present invention further relates to an optical device comprising at least one optical medium of the present invention. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 shows the results of the QY measurement of Comparative Example 1. [Diagram 2] FIG. 2 shows the results of the QY measurement of Example 1. [Diagram 3] FIG. 3 shows the results of the QY measurement of Example 2. [Figure 4] FIG. 4 shows the results of QY measurements of seven different samples of Comparative Example 2. [Diagram 5] FIG. 5 shows the results of the QY measurement of Example 3. [Figure 6] FIG. 6 shows the results of the QY measurement of Example 4. [Figure 7] FIG. 7 shows the results of the QY measurement of Example 5.

[0013] Detailed Description of the Invention According to the present invention, the process for preparing the composition comprises the following steps: a) mixing at least a first organic compound with semiconducting, luminescent nanoparticles comprising a core, the nanoparticles optionally comprising at least one shell layer, preferably with another material to obtain a first mixture, preferably said first mixture being a composition; wherein the first organic compound has the following chemical formula (I): A(B) n C - (I) wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1; Comprising, consisting essentially of, or consisting of.

[0014] -First organic compound As described above, the first organic compound has the following chemical formula (I): A(B) n C - (I) wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1.

[0015] The one or more publicly available chemical compounds represented by formula (I) above or formula (II) below are preferably selected from, for example, thiols, carboxylic acids, phosphonic acids, and / or mercaptoacetates. And, ligand materials represented by chemical formula (I) or (II), for example as described in International Patent Application Publication No. WO 2012 / 059931A, may also be used.

[0016] In a preferred embodiment of the present invention, the amount of the first organic compound in the composition ranges from 0.01 wt.% to 100 wt.%, preferably it ranges from 10 wt.% to 50 wt.%, more preferably it ranges from 20 wt.% to 30 wt.%, based on the total amount of the inorganic portion of the semiconducting luminescent nanoparticles in the composition.

[0017] In a preferred embodiment of the present invention, the first organic compound has the following chemical formula (II): XR 1 R 2 (R 3 ) n (II) (In the formula, X is selected from P, O, S, or N; n is 0 when X is O or S, and n is 1 when X is P or N;

[0018] R 1 is selected from one or more elements from the group consisting of a hydrogen atom, a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 1 to 15 carbon atoms, a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, a cycloalkane group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, preferably 2 to 25 carbon atoms, an aryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and an aralkyl group having 4 to 40 carbon atoms, preferably 4 to 25 carbon atoms, in each case one or more radicals R a wherein one or more non-adjacent CH groups are replaced by Ra C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=NR a , SO, SO2, NR a , or CONR a and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or one or more radicals R a an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms,

[0019] R a is, identically or differently at each occurrence, H, D, or an alkyl group having 1 to 20 carbon atoms, a cyclic alkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 carbon ring atoms, or a heteroaromatic ring system having 5 to 60 carbon atoms, in which an H atom may be replaced by D, F, Cl, Br, I, and in which two or more adjacent substituents R a may together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system,

[0020] R 2is selected from one or more elements from the group consisting of a hydrogen atom, a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 1 to 15 carbon atoms, a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, a cycloalkane group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, preferably 2 to 25 carbon atoms, an aryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and an aralkyl group having 4 to 40 carbon atoms, preferably 4 to 25 carbon atoms, in each case one or more radicals R a wherein one or more non-adjacent CH groups are replaced by R a C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=NR a , SO, SO2, NR a , or CONR a and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or one or more radicals R a an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms,

[0021] R 3is selected from one or more elements from the group consisting of a hydrogen atom, a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 1 to 15 carbon atoms, a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, a cycloalkane group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, preferably 2 to 25 carbon atoms, an aryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and an aralkyl group having 4 to 40 carbon atoms, preferably 4 to 25 carbon atoms, in each case one or more radicals R a wherein one or more non-adjacent CH groups are replaced by R a C=CR a , C≡C, Si(R a )2, Ge(R a )2, Sn(R a )2, C=O, C=S, C=NR a , SO, SO2, NR a , or CONR a and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or one or more radicals R a an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, Here, R 1 , R 2 , R 3 At least one of is not a hydrogen atom.

[0022] In a preferred embodiment of the invention, the first organic compound is selected from the group consisting of thiols, selenols, phosphonic acids, carboxylic acids, amines, and phosphines, preferably it is a thiol, a carboxylic acid, or a phosphonic acid, such as hexane-1-thiol, carboxylic acid, 1-dodecanethiol, or hexylphosphonic acid, and even more preferably it is a thiol.

[0023] Preferably, R of formula II) 2 is a substituted or unsubstituted linear alkyl or alkoxy group having 1 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and more preferably 5 to 15 carbon atoms; a substituted or unsubstituted branched alkyl or alkoxy group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and more preferably 5 to 20 carbon atoms; a substituted or unsubstituted cycloalkane group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and more preferably 5 to 25 carbon atoms; or a substituted or unsubstituted aryl group having 3 to 40 carbon atoms, preferably 5 to 25 carbon atoms.

[0024] More preferably, R 2 is a substituted linear alkyl group having 1 to 40 carbon atoms, an unsubstituted branched alkyl group or an alkoxy group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and more preferably 5 to 25 carbon atoms. More preferably, R 2 is selected from the group in Table 1 below.

[0025] Table 1 [Table 1]

[0026] Here and " * " represents a connection point to another unit. As chemical compounds, publicly available mercaptoacetates and / or mercaptopropionates are furthermore also suitable as chemical compounds for preventing / reducing the decrease in quantum yield of semiconductor light-emitting nanoparticles in mixtures, preferably in solution, in particular in the presence of a photoinitiator. The following publicly available chemical compounds are particularly suitable:

[0027] [ka]

[0028] According to the present invention, preferably step a) is carried out with said further material and the amount of the further material is in the range of 0.01 wt.% to 100 wt.%, preferably it is in the range of 0.1 wt.% to 50 wt.%, more preferably it is in the range of 20 wt.% to 30 wt.%, based on the total amount of the inorganic part of the semiconducting luminescent nanoparticles.

[0029] In some embodiments of the invention, step a) is performed with the other material, and the other material is selected from one or more members of the group consisting of a photoinitiator, a thermal initiator, an inorganic material, an organic compound, and a solvent.

[0030] In some embodiments of the invention, the other compound is a solvent selected from inorganic solvents, organic solvents, and mixtures thereof, preferably it is an ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; a diethylene glycol dialkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; a propylene glycol monoalkyl ether such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, and propylene glycol monopropyl ether. ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and ethyl lactate; and cyclic esters such as gamma-butyro-lactone;The solvent is selected from one or more members of the group consisting of chlorinated hydrocarbons such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene, preferably the solvent is propylene glycol alkyl ether acetate, alkyl acetate, ethylene glycol monoalkyl ether, propylene glycol, and propylene glycol monoalkyl ether, preferably the solvent is selected from one or more members of the group consisting of propylene glycol alkyl ether acetate such as propylene glycol monomethyl ether acetate (PGMEA), alkyl acetate such as butyl acetate, ethylene glycol monoalkyl ether such as ethylene glycol monobutyl ether, propylene glycol, or propylene glycol monoalkyl ether such as methoxypropanol, more preferably the solvent is selected from propylene glycol alkyl ether acetate;

[0031] In some embodiments of the invention, the additional compound is selected from a photoinitiator, a thermal initiator, or a mixture thereof.

[0032] -Semiconductive luminescent nanoparticles According to the present invention, the term "semiconductor" means a material that has an electrical conductivity at room temperature between that of a conductor (such as copper) and that of an insulator (such as glass). Preferably, a semiconductor is a material whose electrical conductivity increases with temperature.

[0033] The term "nano" refers to a size between 0.1 nm and 999 nm, preferably between 1 nm and 150 nm, more preferably between 3 nm and 50 nm. Thus, in accordance with the present invention, "semiconducting luminescent nanoparticles" is taken to mean luminescent materials having a size between 0.1 and 999 nm, preferably 1 nm to 150 nm, more preferably 3 nm to 50 nm, having an electrical conductivity at room temperature between that of a conductor (such as copper) and that of an insulator (such as glass), preferably a semiconductor is a material whose electrical conductivity increases with temperature, and having a size between 0.1 and 999 nm, preferably 0.5 nm to 150 nm, more preferably 1 nm to 50 nm.

[0034] According to the present invention, the term "size" refers to the average diameter of the longest axis of the semiconducting nano-sized luminescent particles. The average diameter of the semiconducting nano-sized luminescent particles is calculated based on 100 semiconducting luminescent nanoparticles in the TEM images made by a Tecnai G2 Spirit Twin T-12 Transmission Electron Microscope.

[0035] In a preferred embodiment of the present invention, the semiconducting, luminescent nanoparticles of the present invention are quantum-sized materials, such as quantum dots. According to the present invention, the shape of the quantum dots is not particularly limited. For example, spherical, elongated, star-shaped, polyhedral, pyramidal, tetrapod-shaped, tetrahedral, platelet-shaped, cone-shaped, and irregularly shaped quantum dots may be used.

[0036] According to the present invention, the term "quantum size" refers to the size of the semiconducting material itself, without any ligands or other surface modifications, and may represent quantum confinement effects, for example as described in ISBN: 978-3-662-44822-9.

[0037] In a preferred embodiment of the present invention, the nanoparticles comprise at least i) a first semiconducting material; ii) optionally, at least one shell layer; iii) optionally, chemical compounds as surface ligands attached to the outermost surface of the nanoparticle, such as the outermost surface or shell layer of the first semiconducting material; in that order.

[0038] For example, publicly available quantum dots such as CdSe / CdS, CdSeS / CdZnS, CdSeS / CdS / ZnS, ZnSe / CdS, CdSe / ZnS, InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InZnP / ZnS, InZnP / ZnSe, InZnP / ZnSe / ZnS, InGaP / ZnS, InGaP / ZnSe, InGaP / ZnSe / ZnS, InZnPS / ZnS, InZnPS ZnSe, InZnPS / ZnSe / ZnS, ZnSe / CdS, ZnSe / ZnS, or any combination thereof may be used. Preferably, InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InZnP / ZnS, InZnP / ZnSe, InZnP / ZnSe / ZnS, InGaP / ZnS, InGaP / ZnSe, InGaP / ZnSe / ZnS may be used.

[0039] CdS, CdSe, CdTe, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, GaAs, GaP, GaSb, HgS, HgSe, HgSe, HgTe, InAs, InP, InPS, InPZnS, InPZn, InPZnSe, InCdP, InPCdS, InPCdSe, InGaP, InGaPZn, InSb, AlAs, AlP, AlSb, Cu2S, Cu2Se, CuInS2, CuInSe2, Cu2(ZnSn)S4, Cu2(InGa)S4, TiO2 alloy, and any combination thereof may be used as the first semiconducting material (core).

[0040] In a preferred embodiment of the present invention, the first semiconducting material comprises at least one of group 13 or group 12 elements of the periodic table and one of group 16 elements of the periodic table, preferably the group 13 element is selected from In, Ga, Al, Ti, the group 12 element is Zn or Cd, and the group 15 element is selected from P, As, Sb, more preferably the first semiconducting material has the following chemical formula (III): In (1-x-2 / 3y) Ga x Zinc y P (III) (wherein 0≦x<1, 0≦y<1, 0≦x+y<1, and preferably the first semiconducting material is selected from the group consisting of InP, InP:Zn, InP:ZnS, InP:ZnSe, InP:ZnSSe, and InP:Ga).

[0041] In accordance with the present invention, the type of shape of the first semiconducting material of the semiconducting luminescent nanoparticles and the shape of the synthesized semiconducting luminescent nanoparticles are not specifically limited. For example, spherical, elongated, star-shaped, polyhedral, pyramidal, tetrapod-shaped, tetrahedral, platelet-shaped, cone-shaped, and irregularly shaped first semiconducting material and / or semiconducting luminescent nanoparticles may be synthesized.

[0042] In some embodiments of the present invention, the average diameter of the first semiconducting material ranges from 1.5 nm to 3.5 nm.

[0043] In some embodiments of the invention, the semiconducting luminescent nanoparticles comprise at least one shell layer and comprise or consist of a first element from group 12 of the periodic table and a second element from group 16 of the periodic table, preferably the first element is Zn and the second element is S, Se, or Te.

[0044] In a preferred embodiment of the present invention, the shell layer is represented by the following formula (IV): ZnS x Se (1-x-z) Te z、 - (IV) (wherein 0≦x≦1, 0≦z≦1, and x+z≦1. Preferably, the shell layer is ZnSe, ZnS x Se (1-x)、 ZnSe (1-x) Te z , ZnS, Zn, and more preferably it is ZnSe or ZnS).

[0045] In some embodiments of the present invention, the shell layer is an alloy shell layer or a grade shell layer, and preferably the grade shell layer is ZnS x Se y , ZnSe y Te z , or ZnS x Te z and more preferably it is ZnS x Se y It is.

[0046] In some embodiments of the present invention, the semiconducting luminescent nanoparticles further comprise a second shell layer on the shell layer, preferably the second shell layer comprises or consists of a third element in group 12 of the periodic table and a fourth element in group 16 of the periodic table, more preferably the third element is Zn and the fourth element is S, Se, or Te, provided that the fourth element and the second element are not the same.

[0047] In a preferred embodiment of the present invention, the second shell layer is represented by the following formula (IV'): ZnS x Se y Te z、 -(IV´) In formula (IV'), 0≦x≦1, 0≦y≦1, 0≦z≦1, and x+y+z=1. Preferably, the shell layer is ZnSe, ZnS x Se y , ZnSe y Te z、 or ZnS x Te z where the shell layer and the second shell layer are not the same.

[0048] In some embodiments of the present invention, the second shell layer may be an alloy shell layer. In some embodiments of the present invention, the semiconducting luminescent nanoparticles may further comprise one or more additional shell layers on the second shell layer as a multishell. In accordance with the present invention, the term "multishell" refers to a stack of shell layers consisting of three or more shell layers.

[0049] For example, CdS, CdZnS, CdS / ZnS, ZnS, ZnSe, ZnSe / ZnS or any combination thereof may be used. Preferably, ZnS, ZnSe, or ZnSe / ZnS may be used as the shell layer.

[0050] -Ligand Compound In some embodiments of the present invention, the outermost surface of the first semiconducting material or the shell layer of the semiconducting luminescent nanoparticles may be partially or entirely covered with one or more known ligands.

[0051] Commonly used surface ligands include phosphines and phosphine oxides such as trioctylphosphine oxide (TOPO), trioctylphosphine (TOP), and tributylphosphine (TBP), phosphonic acids such as dodecylphosphonic acid (DDPA), tridecylphosphonic acid (TDPA), octadecylphosphonic acid (ODPA), and hexylphosphonic acid (HPA), amines such as oleylamine, dedecylamine (DDA), tetradecylamine (TDA), hexadecylamine (HDA), and octadecylamine (ODA), oleylamine (OLA), thiols such as 1-octadecene (ODE), hexadecanethiol, and hexanethiol, mercaptocarboxylic acids such as mercaptopropionic acid and mercaptoundecanoic acid, oleic acid, stearic acid, myristic acid; carboxylic acids such as acetic acid, and any combination thereof. And also. Polyethylenimine (PEI) may also be preferably used.

[0052] Examples of surface ligands are described, for example, in International Patent Application Publication No. WO 2012 / 059931A. In some embodiments of the present invention, an additive selected from one or more members of the group consisting of a solvent, an organic light-emitting material, an inorganic light-emitting material, a charge transport material, a scattering particle, a host material, a nano-sized plasmonic particle, a photoinitiator, and a matrix material may be added in step a) to obtain the composition.

[0053] In a preferred embodiment, the first mixture is a composition. In some embodiments, the additive may be mixed with the semiconducting luminescent nanoparticles or with the first organic compound into the first mixture obtained in step a) before or after step a) to form a composition. Details of the additives are described below in the "Additives for the Composition" section.

[0054] -composition In another aspect, the present invention also relates to a composition obtainable or obtained by the process of the present invention. In another aspect, the present invention further comprises at least a) a semiconducting, luminescent nanoparticle comprising a core and, optionally, at least one shell layer; b) a first chemical compound, and c) optionally another compound wherein the first organic compound has the following chemical formula (I): A(B) n C - (I) wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1; The present invention relates to a composition comprising, consisting essentially of, or consisting of.

[0055] Further details of the first organic compound are described above in the "First Organic Compound" section. Further details of semiconducting luminescent nanoparticles are disclosed above in the "Semiconducting Luminescent Nanoparticles" section. In a preferred embodiment of the present invention, the compound includes a plurality of semiconducting luminescent nanoparticles.

[0056] In some embodiments of the present invention, the total amount of the first chemical compound ranges from 0.1 wt.% to 90 wt.%, preferably from 5 wt.% to 70 wt.%, and more preferably from 20 wt.% to 50 wt.%, based on the total amount of the composition. In some embodiments of the invention, the total amount of nanoparticles ranges from 0.1 wt.% to 100 wt.%, preferably from 10 wt.% to 50 wt.%, more preferably from 20 wt.% to 30 wt.%, based on the total amount of the composition.

[0057] Additives for the composition In some embodiments of the present invention, the composition may further contain an additive selected from one or more members of the group consisting of a solvent, an organic light-emitting material, an inorganic light-emitting material, a charge transport material, a scattering particle, a host material, a nano-sized plasmonic particle, a photoinitiator, and a matrix material.

[0058] For example, the inorganic luminescent material may be selected from one or more members of the group consisting of sulfides, thiogallates, nitrides, oxynitrides, silicates, aluminates, apatites, borates, oxides, phosphates, halophosphates, sulfates, tungstates, tantalates, vanadates, molybdates, niobates, titanates, germinates, halide-based phosphors, and any combination thereof.

[0059] Such suitable inorganic light-emitting materials as mentioned above may be well-known phosphors, including quantum-sized materials, nano-sized phosphors, such as those described in phosphor handbook, 2nd edition (CRC Press, 2006), pp. 155 - pp. 338 (W.M.En, S.Shionoya and H.Yamamoto), WO2011 / 147517A, WO2012 / 034625A, and WO2010 / 095140A.

[0060] According to the present invention, any type of known material can be preferably used as the organic light-emitting material, charge transport material, such as well-known organic fluorescent materials, organic host materials, organic dyes, organic electron transport materials, organic metal complexes, and organic hole transport materials.

[0061] As examples of scattering particles, small particles of inorganic oxides such as SiO2, SnO2, CuO, CoO, Al2O3TiO2, Fe2O3, Y2O3, ZnO, MgO, organic particles such as polymerized polystyrene, polymerized PMMA, inorganic hollow oxides such as hollow silica, or any combination of these may be preferably used.

[0062] -Matrix material In accordance with the present invention, a wide variety of known clear polymers suitable for optical devices may be preferably used as the matrix material. In accordance with the present invention, the term "clear" means that at least approximately 60% of the incident light is transmitted at the thickness used in the optical medium and at the wavelength or range of wavelengths used during operation of the optical medium. Preferably, it is greater than 70%, more preferably greater than 75%, and most preferably greater than 80%.

[0063] In a preferred embodiment of the present invention, any type of known transparent polymer may be used, for example as described in WO2016 / 134820A. According to the present invention, the term "polymer" means a material having repeating units and having a weight average molecular weight (Mw) of 1000 g / mol or more. Molecular weight M w is determined using GPC (=gel permeation chromatography) against the internal standard polystyrene.

[0064] In some embodiments of the present invention, the glass transition temperature (Tg) of the clear polymer is 70°C or more and 250°C or less. Tg is http: / / pslc.ws / macrog / dsc.htm ; based on the change in heat capacity observed by differential scanning calorimetry, such as that described in Rickey J Seyler, Assignment of the Glass Transition, ASTM publication code number (PCN) 04-012490-50.

[0065] For example, poly(meth)acrylate, epoxy, polyurethane, polysiloxane may be preferably used as the transparent polymer for the transparent matrix material. In a preferred embodiment of the present invention, as a transparent matrix material, the weight average molecular weight (Mw) of the polymer ranges from 1,000 to 300,000 g / mol, more preferably it ranges from 10,000 to 250,000 g / mol.

[0066] In some embodiments of the present invention, the composition comprises a plurality of semiconducting luminescent nanoparticles and / or a plurality of semiconducting materials. In some embodiments, the total amount of chemical compounds represented by the following chemical formula (I) ranges from 0.1 wt.% to 90 wt.%, preferably from 5 wt.% to 70 wt.%, and more preferably from 20 wt.% to 50 wt.%, based on the total amount of the composition.

[0067] In some embodiments, the total amount of nanoparticles ranges from 0.1 wt.% to 100 wt.%, preferably from 10 wt.% to 50 wt.%, and more preferably from 20 wt.% to 30 wt.%, based on the total amount of the composition.

[0068] -use In another aspect, the present invention provides a compound of formula I: A(B) n C - (I) wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1, in a composition comprising at least one semiconducting luminescent nanoparticle, or for making a composition, or for a process for making an optical device. In another aspect, the invention relates to the use of a composition according to the invention in an electronic device, an optical device or in a biomedical device.

[0069] -Optical media In another aspect, the present invention further relates to an optical medium comprising at least the composition of the present invention. In another aspect, the present invention also provides a method for producing a semiconductor device comprising the steps of: A(B) n C - (I) The present invention also relates to an optical medium comprising a first chemical compound represented by the formula: wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1.

[0070] In some embodiments of the present invention, the optical medium may be an optical sheet, such as a color filter, a color conversion film, a remote phosphorescent tape, or another film or filter.

[0071] In accordance with the present invention, the term "sheet" encompasses films and / or layers of structured media, etc. In some embodiments of the invention, the optical medium comprises an anode and a cathode and at least one organic layer comprising a composition of the invention, preferably the one organic layer is a light-emitting layer, and more preferably the medium further comprises one or more additional layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron blocking layer, and an electron injection layer.

[0072] According to the present invention, for the hole injection layer, hole transport layer, electron blocking layer, light emitting layer, hole blocking layer, electron blocking layer, and electron injection layer, any kind of publicly available inorganic and / or organic materials may preferably be used, such as those described in WO 2018 / 024719 A1, US2016 / 233444 A2, US7754841 B, WO 2004 / 037887 and WO 2010 / 097155.

[0073] In a preferred embodiment of the present invention, the optical medium comprises a compound that includes a plurality of semiconducting, luminescent nanoparticles. Preferably, the anode and cathode of the optical medium sandwich the organic layers. More preferably, said additional layer is also sandwiched by the anode and cathode.

[0074] In some embodiments of the present invention, the organic layer comprises at least one semiconducting luminescent nanoparticle of the present invention and a host material, preferably the host material is an organic host material. In a preferred embodiment of the present invention, the optical medium comprises a composition containing a plurality of semiconducting, luminescent nanoparticles.

[0075] -Optical devices In another aspect, the present invention further relates to an optical device comprising at least one optical medium of the present invention. In some embodiments of the present invention, the optical device may be a liquid crystal display device (LCD), an organic light emitting diode (OLED), a backlight unit for an optical display, a light emitting diode device (LED), a microelectromechanical system (hereinafter "MEMS"), an electrowetting display, or an electrophoretic display, a lighting device, and / or a solar cell.

[0076] Technical effects The present invention provides one or more of the following technical advantages: Improved quantum yield of nanoparticles, preventing or reducing the decrease in quantum yield in dilute compositions and / or radical-rich environments, higher device efficiency, optimizing the surface state of the shell portion of the nanoparticles, reducing lattice defects in the shell layer of the nanoparticles, reducing / preventing the formation of dangling bonds in the shell layer, better thermal stability, improved oxidative stability, improved stability against radical substances, improved stability during long-term storage without significant decrease in QY, better chemical stability, more environmentally friendly, and safer fabrication process. The following Examples 1-5 provide an illustration of the present invention, as well as detailed descriptions of their preparation.

[0077] Working Example Comparative Example 1: Composition of quantum dots with dodecanethiol, stearic acid, myristic acid, and palmitic acid ligands in toluene Red InP 2 -based quantum dots (QDs) with dodecanethiol, stearic acid, myristic acid, and palmitic acid ligands in toluene are prepared as described in US Pat. No. 7,588,828 B. The QDs are then dissolved in dry toluene at a concentration of 0.08 mg / mL and the initial quantum yield (hereafter initial QY) is measured on a Hamamatsu Quantaurus.

[0078] Then, 100 mg of QDs were dissolved in 2 mL of dry toluene and 3 mg of the photoinitiator Irgacure were added. @ Mix with TPO and stir at room temperature under argon while exposing to a light source with 365 nm for 60 min. Take 11 samples. Then dilute the samples to 0.08 mg / mL. And then measure the quantum yield of 11 samples by Hamamatsu Quantaurus.

[0079] The initial QY of each sample is set to 100% by using the following formula: Normalized initial QY (100%) = initial QY of each sample * α The normalized QY is calculated based on the following formula: Normalized QY = (QY * α / Initial QY) * 100 The measurement results are shown in Figure 1. As depicted in FIG. 1, the average decrease in normalized QY before and after the radical test performed on QDs in toluene without additives is 40%±7.5%.

[0080] Example 1: A composition of quantum dots in toluene having the additional chemical compound hexanethiol as an additive to the composition. Red InP 2 -based quantum dots (QDs) with dodecanethiol, stearic acid, myristic acid, and palmitic acid ligands in toluene are prepared as described in US Pat. No. 7,588,828 B.

[0081] -Ligand exchange The QDs are dissolved in dry toluene containing various concentrations (0.004 M, 0.02 M, 0.1 M) of an additive (hexanethiol) to create three different samples. The QD concentration in all three samples is set to 0.08 mg / mL, and the samples are measured on a Hamamatsu Quantaurus for initial QY. It is then measured in a Hamamatsu Quantaurus for initial quantum yield (hereinafter initial QY).

[0082] Then, 100 mg of QDs were dissolved in 2 mL of dry toluene and 3 mg of the photoinitiator Irgacure were added. @ Mix with TPO and stir at room temperature under argon while exposing to a light source with 365 nm for 60 min. Take a sample. Then dilute the sample to 0.08 mg / mL. And then measure the quantum yield of the sample by Hamamatsu Quantaurus. The measurement results are shown in Figure 2.

[0083] Example 2: Quantum dots in toluene with the additional chemical compound 1-dodecanethiol as an additive to the composition A composition of quantum dots and chemical compound 1-dodecanethiol in toluene is prepared in the same manner as described in Example 1, except that 0.02 M of 1-dodecanethiol is used instead of hexanethiol. FIG. 3 shows the results of the QY measurements.

[0084] Comparative Example 2 : Composition of quantum dots in toluene with lower concentrations of dodecanethiol, stearic acid, myristic acid, and palmitic acid ligands. Prepare the composition in the same manner as described in Comparative Example 1, except that the concentration of quantum material in the composition is 0.05mg / mL. Prepare 8 different samples in the same manner as described in Comparative Example 2. FIG. 4 shows the results of the QY measurements of the seven different samples mentioned above.

[0085] Example 3 : A diluted composition of quantum dots in toluene with the additional chemical compound hexanethiol as an additive to the composition. A composition of quantum dots and chemical compound 1-hexanethiol in toluene is prepared in the same manner as described in Example 1, except that different amounts of hexanethiol are used to create four different samples with different concentrations of hexanethiol (0.004M, 0.02M, 0.1M, and 0.2M). FIG. 5 shows the measurement results.

[0086] Example 4: A diluted composition of quantum dots in toluene having the additional chemical compound hexanoic acid as an additive to the composition. A composition of quantum dots and chemical compound hexanoic acid in toluene is prepared in the same manner as described in Example 1, except that different amounts of hexanoic acid are used to create four different samples with different concentrations of hexanoic acid (0.004M, 0.02M, 0.1M, and 0.2M). FIG. 6 shows the measurement results.

[0087] Example 5: A diluted composition of quantum dots in toluene with the additional chemical compound hexylphosphonic acid (HPA) as an additive to the composition. A composition of quantum dots in toluene containing the chemical compound hexylphosphonic acid (HPA) is prepared in the same manner as described in Example 1, except that different amounts of HPA are used to create four different samples with different concentrations of HPA (0.004M and 0.02M). FIG. 7 shows the measurement results.

Claims

1. The following steps: a) mixing at least a first organic compound with semiconducting, luminescent nanoparticles comprising a core, optionally comprising at least one shell layer, preferably with another material to obtain a first mixture; wherein the first organic compound has the following chemical formula (I): A(B) ｎ C - (I) wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1; 23. A process for the preparation of a composition comprising:

2. 2. The process according to claim 1, wherein the amount of the first organic compound ranges from 0.01 wt.% to 100 wt.%, preferably it ranges from 10 wt.% to 50 wt.%, more preferably it ranges from 20 wt.% to 30 wt.%, based on the total amount of the inorganic part of the semiconducting luminescent nanoparticles.

3. The first organic compound has the following chemical formula (I): XR １ R ２ (R ３ ) ｎ (In the formula, X is selected from P, O, S, or N; n is 0 when X is O or S, and n is 1 when X is P or N; R １ is selected from one or more elements from the group consisting of a hydrogen atom, a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 1 to 15 carbon atoms, a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, a cycloalkane group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, preferably 2 to 25 carbon atoms, an aryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and an aralkyl group having 4 to 40 carbon atoms, preferably 4 to 25 carbon atoms, and in each case one or more radicals R ａ wherein one or more non-adjacent CH ２ The group is R ａ C=CR ａ , C≡C, Si(R ａ ) ２ , Ge(R ａ ) ２ , Sn(R ａ ) ２ , C=O, C=S, C=NR ａ , SO, SO2, NR ａ , or CONR ａ and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ２ or one or more radicals R ａ by an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by R ａ is, identically or differently at each occurrence, H, D, or an alkyl group having 1 to 20 carbon atoms, a cyclic alkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 carbon ring atoms, or a heteroaromatic ring system having 5 to 60 carbon atoms, in which an H atom may be replaced by D, F, Cl, Br, I, and in which two or more adjacent substituents R ａ may together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system, R ２ is selected from one or more elements from the group consisting of a hydrogen atom, a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 1 to 15 carbon atoms, a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, a cycloalkane group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, preferably 2 to 25 carbon atoms, an aryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and an aralkyl group having 4 to 40 carbon atoms, preferably 4 to 25 carbon atoms, and in each case one or more radicals R ａ wherein one or more non-adjacent CH ２ The group is R ａ C=CR ａ , C≡C, Si(R ａ ) ２ , Ge(R ａ ) ２ , Sn(R ａ ) ２ , C=O, C=S, C=NR ａ , SO, SO2, NR ａ , or CONR ａ and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ２ or one or more radicals R ａ by an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by R ３ is selected from one or more elements from the group consisting of a hydrogen atom, a linear alkyl or alkoxyl group having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 1 to 15 carbon atoms, a branched alkyl or alkoxyl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, a cycloalkane group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, more preferably 3 to 15 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, preferably 2 to 25 carbon atoms, an aryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, preferably 3 to 25 carbon atoms, and an aralkyl group having 4 to 40 carbon atoms, preferably 4 to 25 carbon atoms, and in each case one or more radicals R ａ wherein one or more non-adjacent CH ２ The group is R ａ C=CR ａ , C≡C, Si(R ａ ) ２ , Ge(R ａ ) ２ , Sn(R ａ ) ２ , C=O, C=S, C=NR ａ , SO, SO2, NR ａ , or CONR ａ and one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ２ or one or more radicals R ａ by an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by Here, R １ , R ２ , R ３ wherein at least one of is not a hydrogen atom.

4. 4. The process according to any one of claims 1 to 3, wherein the first organic compound is selected from the group consisting of thiols, selenols, phosphonic acids, carboxylic acids, amines, and phosphines, preferably it is a thiol, a carboxylic acid, or a phosphonic acid, even more preferably it is hexane-1-thiol, a carboxylic acid, 1-dodecanethiol, or a hexylphosphonic acid.

5. The process according to any one of claims 1 to 4, wherein step a) is carried out with said another material and the amount of the another material ranges from 0.01 wt.% to 100 wt.%, preferably it ranges from 0.1 wt.% to 50 wt.%, more preferably it ranges from 20 wt.% to 30 wt.%, based on the total amount of inorganic part of the semiconducting luminescent nanoparticles.

6. 6. The process of any one of claims 1 to 5, wherein step a) is performed with said another material, and said another material is selected from one or more members of the group consisting of a photoinitiator, a thermal initiator, an inorganic material, an organic compound, and a solvent.

7. The further compound is a solvent selected from inorganic solvents, organic solvents, and mixtures thereof, preferably it is ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, and propylene glycol monopropyl ether; methyl cellosol. propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and ethyl lactate; and cyclic esters such as gamma-butyro-lactone;The process according to any one of claims 1 to 6, wherein the solvent is selected from one or more members of the group consisting of chlorinated hydrocarbons such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene, preferably the solvent is selected from one or more members of the group consisting of propylene glycol alkyl ether acetates, alkyl acetates, ethylene glycol monoalkyl ethers, propylene glycol, and propylene glycol monoalkyl ethers, preferably the solvent is selected from one or more members of the group consisting of propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), alkyl acetates such as butyl acetate, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, propylene glycol, or propylene glycol monoalkyl ethers such as methoxypropanol, more preferably the solvent is selected from propylene glycol alkyl ether acetates;

8. The process according to any one of claims 1 to 7, wherein the further compound is selected from a photoinitiator, a thermal initiator or a mixture thereof.

9. A composition obtainable or obtained by the process according to any one of claims 1 to 8.

10. at least, a) a semiconducting, luminescent nanoparticle comprising a core and, optionally, at least one shell layer; b) a first chemical compound, and c) optionally another compound wherein the first organic compound has the following chemical formula (I): A(B) ｎ C - (I) wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1; A composition comprising:

11. 11. The composition according to claim 9 or 10, wherein the total amount of the first chemical compound ranges from 0.1 wt.% to 90 wt.%, preferably from 5 wt.% to 70 wt.%, more preferably from 20 wt.% to 50 wt.%, based on the total amount of the composition.

12. The composition according to any one of claims 9 to 11, wherein the total amount of nanoparticles ranges from 0.1 wt.% to 100 wt.%, preferably from 10 wt.% to 50 wt.%, more preferably from 20 wt.% to 30 wt.%, based on the total amount of the composition.

13. Chemical formula I) A(B) ｎ C - (I) 2. Use of a first chemical compound of the formula: wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1 in a composition comprising at least one semiconducting luminescent nanoparticle, or for making a composition, or for a process for making an optical device.

14. Use of a composition according to any one of claims 9 to 12 in an electronic device, an optical device or in a biomedical device.

15. An optical medium comprising at least the composition according to any one of claims 9 to 12.

16. at least one semiconducting luminescent nanoparticle, and a compound of formula I): A(B) ｎ C - (I) 1. An optical medium comprising a first chemical compound represented by the formula: wherein A represents a first end group, B is a divalent bond, C is a second end group, and n is 0 or 1.

17. 17. An optical medium according to claim 15 or 16, comprising an anode and a cathode and at least one organic layer comprising the composition according to any one of claims 9 to 12, preferably said one organic layer being an emissive layer, more preferably the medium further comprising one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron blocking layer and an electron injection layer.

18. Optical medium according to any one of claims 15 to 17, wherein the organic layer comprises a composition according to any one of claims 9 to 12 and a host material, preferably the host material is an organic host material.

19. An optical device comprising at least one optical medium according to any one of claims 15 to 18.

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