Ink compositions, methods of making same, composites made therefrom, and devices including composites

Abstract

Ink compositions, methods of making the same, composites made therefrom, and devices including the composites are provided. The ink composition includes semiconductor nanoparticles and a polymerizable monomer. The semiconductor nanoparticle includes a Group 11-13-16 compound, the Group 11-13-16 compound including silver, a Group 13 metal including indium and gallium, and a Group 16 element including sulfur, and the ink composition further includes a metal halide and a first organic ligand including a compound or moiety represented by R1-COOA, where R1 is a first organic group, and COOA is a second organic group; and A represents hydrogen or a moiety attached to the surface of the semiconductor nanoparticle.

Description

[0001] This application claims the priority and benefits of, and all rights arising from, Korean Patent Application No. 10-2023-0178939, filed with the Korean Intellectual Property Office on December 11, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0002] Provided are an ink composition, a preparation process of the ink composition, a composite prepared from the ink composition, and an electronic device including the composite. Background Art

[0003] Semiconductor nanoparticles may, for example, exhibit (e.g., show) different aspects compared to corresponding bulk materials having substantially the same composition in terms of physical properties (e.g., band gap, luminescent properties, etc.) inherent to the bulk material. Semiconductor nanoparticles can be configured to emit light when excited by energy (such as incident light or an applied voltage). Such luminescent nanostructures can find applicability in various devices (e.g., display panels or electronic devices). From an environmental perspective, it is desirable to develop luminescent nanoparticles that do not contain harmful heavy metals (such as cadmium) and exhibit improved luminescent properties. Summary of the Invention

[0004] One aspect relates to an ink composition including semiconductor nanoparticles capable of exhibiting improved properties (e.g., optical properties (such as incident light absorption) and / or stability (such as process stability and / or chemical stability)).

[0005] One aspect relates to a semiconductor nanoparticle-polymer composite prepared from the ink composition.

[0006] One aspect relates to a process for preparing an ink composition.

[0007] One aspect relates to a display panel or color conversion panel including the composite.

[0008] One aspect relates to an electronic device (e.g., a display device) including the composite.

[0009] One aspect relates to semiconductor nanoparticles included in the ink composition.

[0010] In one aspect, the ink composition includes a polymerizable monomer and semiconductor nanoparticles, the semiconductor nanoparticles including an 11-13-16 group compound containing silver, a group 13 metal (e.g., indium and gallium), and a group 16 element (sulfur), wherein the ink composition further includes a metal halide (e.g., a first metal halide) and a first organic ligand including a compound represented by R 1 -COOA, wherein R 1is a first organic group, and A represents hydrogen or a moiety attached to the surface of the semiconductor nanoparticle.

[0011] The semiconductor nanoparticle may further include zinc. The semiconductor nanoparticle may further include chlorine.

[0012] The first organic ligand may be attached to the surface of the semiconductor nanoparticle (e.g., via one or two oxygen atoms of R 1 -COO- * attached to the surface of the semiconductor nanoparticle, wherein, * indicates the point of attachment to the surface).

[0013] The first organic ligand attached to the surface of the semiconductor nanoparticle may include a bond bound to the surface, e.g., a coordination bond, an ionic bond, or a covalent bond.

[0014] Group 13 metals may include indium and gallium.

[0015] The surface of the semiconductor nanoparticle may include gallium and zinc.

[0016] The semiconductor nanoparticle or the ink composition may exhibit a charge balance value greater than or equal to about 0.8, greater than or equal to about 1 and less than or equal to about 2.5, less than or equal to about 1.9, less than or equal to about 1.84, less than or equal to about 1.8, or less than or equal to about 1.7 as defined by Equation 1:

[0017] Equation 1

[0018] Charge balance value = {[Ag] + 3([Group 13 metal]) + 2[Zn]} / (2[CHA])

[0019] wherein, in Equation 1,

[0020] [Ag], [Group 13 metal], [Zn], and [CHA] are the number of moles of silver, the number of moles of Group 13 metal, the number of moles of zinc, and the number of moles of chalcogen in the semiconductor nanoparticle, respectively.

[0021] The charge balance value may be greater than or equal to about 1.1. The charge balance value may be less than or equal to about 1.65 or less than or equal to about 1.5.

[0022] Group 13 metals may include indium, gallium, aluminum, or a combination thereof. Group 13 metals may include indium and gallium. Group 16 elements (hereinafter, also referred to as "chalcogens") may include sulfur, selenium, or a combination thereof. The chalcogen may include sulfur and may optionally further include or not include selenium.

[0023] In a semiconductor nanoparticle or ink composition, the molar ratio of zinc to a chalcogen or sulfur (e.g., Zn:S) can be less than or equal to about 1.2:1, less than or equal to about 1:1, less than or equal to about 0.8:1, less than or equal to about 0.3:1, less than or equal to about 0.25:1, or less than or equal to about 0.19:1. In a semiconductor nanoparticle, the molar ratio of zinc to a chalcogen or sulfur can be greater than or equal to about 0.01:1, greater than or equal to about 0.05:1, greater than or equal to about 0.3:1, or greater than or equal to about 0.35:1.

[0024] In a semiconductor nanoparticle or ink composition, the molar ratio of zinc to silver (Zn:Ag) can be greater than or equal to about 0.3:1, greater than or equal to about 0.5:1, or greater than or equal to about 0.7:1 and less than or equal to about 5:1, less than or equal to about 3.5:1, less than or equal to about 2.3:1, less than or equal to about 2:1, or less than or equal to about 1:1.

[0025] In a semiconductor nanoparticle or ink composition, the molar ratio of sulfur to the sum of silver, indium, and gallium [S:(Ag+In+Ga)] can be greater than or equal to 0.5:1, greater than or equal to about 0.7:1, greater than or equal to about 0.77:1, greater than or equal to about 1.1:1, greater than or equal to about 1.3:1, or greater than or equal to about 1.35:1 and less than or equal to about 2:1, less than or equal to about 1.29:1, or less than or equal to about 1.2:1.

[0026] In a semiconductor nanoparticle or ink composition, the molar ratio of the sum of indium and gallium to silver [(In+Ga):Ag] can be greater than or equal to about 1.4:1, greater than or equal to about 1.5:1, greater than or equal to about 1.6:1, or greater than or equal to about 1.7:1 and less than or equal to about 7.0:1, less than or equal to about 3.5:1, or less than or equal to about 2:1.

[0027] In a semiconductor nanoparticle or ink composition, the molar ratio of gallium to the sum of indium and gallium [Ga:(In+Ga)] can be less than or equal to about 0.99:1 or less than or equal to about 0.85:1. The molar ratio of gallium to the sum of indium and gallium [Ga:(In+Ga)] can be greater than or equal to about 0.65:1 or greater than or equal to about 0.7:1.

[0028] In a semiconductor nanoparticle or ink composition, the molar ratio of gallium to sulfur [Ga:S] can be less than or equal to about 0.9:1, less than or equal to about 0.7:1, less than or equal to about 0.5:1, or less than or equal to about 0.41:1. The molar ratio of gallium to sulfur can be greater than or equal to about 0.1:1, greater than or equal to about 0.3:1, greater than or equal to about 0.35:1, or greater than or equal to about 0.4:1.

[0029] Semiconductor nanoparticles can be configured to emit a first light. The semiconductor nanoparticles or the first light can have a full width at half maximum (FWHM) that is greater than or equal to about 5 nm and less than or equal to about 70 nm. For example, the semiconductor nanoparticles can be configured to emit a first light that has an FWHM that is greater than or equal to about 15 nm and less than or equal to about 50 nm, or greater than or equal to about 15 nm and less than or equal to about 40 nm.

[0030] The semiconductor nanoparticles can exhibit a quantum yield that is greater than or equal to about 50%, greater than or equal to about 60%, or greater than or equal to about 70%.

[0031] The first light can be green or red light. Accordingly, the semiconductor nanoparticles or the first light can have a peak emission wavelength that is greater than or equal to about 500 nm to less than or equal to about 650 nm. The peak emission wavelength of the semiconductor nanoparticles or the first light can be greater than or equal to about 505 nm to less than or equal to about 580 nm, greater than or equal to about 515 nm to less than or equal to about 580 nm, greater than or equal to about 520 nm to less than or equal to about 545 nm, greater than or equal to about 525 nm to less than or equal to about 536 nm, or greater than or equal to about 538 nm to less than or equal to about 550 nm. The peak emission wavelength of the semiconductor nanoparticles or the first light can be greater than or equal to about 600 nm to less than or equal to about 650 nm, greater than or equal to about 610 nm to less than or equal to about 645 nm, greater than or equal to about 615 nm to less than or equal to about 639 nm, or greater than or equal to about 620 nm to less than or equal to about 630 nm.

[0032] The semiconductor nanoparticles can exhibit a quantum yield that is greater than or equal to about 60% (e.g., absolute quantum yield, hereinafter “quantum yield”) in an ink composition or a semiconductor nanoparticle-polymer composite. The quantum yield can be greater than or equal to about 62%, greater than or equal to about 65%, or greater than or equal to about 70%. The quantum yield can be from about 80% to about 100%.

[0033] The full width at half maximum (FWHM) can be less than or equal to about 50 nm, less than or equal to about 45 nm, less than or equal to about 40 nm, or less than or equal to about 35 nm. The full width at half maximum can be greater than or equal to about 5 nm, greater than or equal to about 10 nm, greater than or equal to about 15 nm, or greater than or equal to about 25 nm.

[0034] The first organic group can be a substituted or unsubstituted C 1-500 、C 2-300 、C 3-100 、C 4-50 or C 5-10a hydrocarbyl group, and optionally, for example, in the backbone of the hydrocarbyl group, at least one methylene group may be replaced by -CO-, -O-, -COO-, -S-, -SO-, -NHCO- or a combination thereof.

[0035] The first organic group may include a moiety containing a carbon-carbon double bond. The moiety containing a carbon-carbon double bond may include a (meth)acrylate group.

[0036] The first organic ligand may include a C3 to C500 (e.g., C4 to C100, C4 to C50 or C5 to C12) carboxyalkyl (meth)acrylate. The first organic ligand may include a small molecule compound (e.g., a non-polymeric compound) having a molecular weight greater than or equal to about 10 g / mol, greater than or equal to about 50 g / mol, or greater than or equal to about 120 g / mol and less than or equal to about 800 g / mol, less than or equal to about 500 g / mol, less than or equal to about 400 g / mol, less than or equal to about 300 g / mol, or less than or equal to about 250 g / mol.

[0037] The metal halide may include a Group 12 metal, a Group 13 metal, or a combination thereof. The metal halide may include zinc halide, indium halide, gallium halide, or a combination thereof. The metal halide may include metal fluoride, metal chloride, metal bromide, metal iodide, or a combination thereof. The metal halide may include metal chloride. The metal halide may include zinc chloride, indium chloride, gallium chloride, or a combination thereof.

[0038] In the ink composition or semiconductor nanoparticle-polymer composite of the embodiments, based on the total weight of the ink composition, the amount of the semiconductor nanoparticles may be greater than or equal to about 1 wt%, greater than or equal to about 5 wt%, greater than or equal to about 15 wt%, or greater than or equal to about 20 wt%. In the ink composition, based on the total weight of the ink composition, the amount of the semiconductor nanoparticles may be less than or equal to about 99 wt%, less than or equal to about 95 wt%, less than or equal to about 80 wt%, or less than or equal to about 50 wt%.

[0039] In the ink composition or semiconductor nanoparticle-polymer composite of the embodiments, the molar ratio of chlorine to indium (Cl:In) or the molar ratio of halogen to indium may be greater than or equal to about 2:1 (e.g., greater than or equal to about 2.2:1), greater than or equal to about 7:1 and less than or equal to about 10:1 or less than or equal to about 8:1.

[0040] In the ink composition or semiconductor nanoparticle-polymer composite according to the embodiments, the molar ratio of zinc to indium (Zn:In) may be greater than or equal to about 1.8:1, greater than or equal to about 2.2:1, or greater than or equal to about 2.5:1 and less than or equal to about 10:1 or less than or equal to about 7.5:1.

[0041] In the ink composition or semiconductor nanoparticle-polymer composite of the embodiment, the molar ratio of chlorine to gallium (Cl:Ga) or the molar ratio of halogen to gallium may be less than or equal to about 1.08:1, less than or equal to about 1.05:1, or less than or equal to about 1:1 and greater than or equal to about 0.1:1 or greater than or equal to about 0.2:1.

[0042] In the ink composition or semiconductor nanoparticle-polymer composite according to the embodiment, the molar ratio of zinc to gallium (Zn:Ga) may be less than or equal to about 2:1 or less than or equal to about 1.6:1 and greater than or equal to about 0.2:1 or greater than or equal to about 0.5:1.

[0043] In the ink composition, the monomer may include a compound represented by Chemical Formula 1:

[0044] Chemical Formula 1

[0045]

[0046] In Chemical Formula 1, X is a C2 to C30 organic group having a carbon-carbon double bond,

[0047] L is a single bond, a carbon atom, a substituted or unsubstituted C1 to C50 alkylene group, a substituted or unsubstituted C2 to C50 alkenylene group, a substituted or unsubstituted C3 to C50 (e.g., C6 to C30) cycloalkylene group, a substituted or unsubstituted C3 to C50 (e.g., C6 to C30) cycloalkenylene group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a group having at least one alkoxy unit (e.g., (R 1 -O) n4 , where R 1 is a substituted or unsubstituted C1 to C10 alkylene group (such as methylene, ethylene, isopropylidene, butylene), and n4 is greater than or equal to about 1, greater than or equal to about 3, greater than or equal to about 5, or greater than or equal to about 10 and less than or equal to about 500, less than or equal to about 300, less than or equal to about 100, less than or equal to about 50, less than or equal to about 15, or smaller), a sulfonyl group (-S(=O) 2 -), a carbonyl group (-C(=O)-), an ether group (-O-), a thioether group (-S-), a sulfoxide group (-S(=O)-), an ester group (-C(=O)O-), an amide group (-C(=O)NR 2 -)(where R 2 is hydrogen or a C1 to C10 straight-chain or branched-chain alkyl group), an imine group (-NR 2 -)(where R 2 is hydrogen or a C1 to C10 straight-chain or branched-chain alkyl group), or a combination thereof,

[0048] Y is a single bond, a substituted or unsubstituted C1-C50 alkylene group, a substituted or unsubstituted C2-C50 alkenylene group, a sulfonyl group (-S(=O) 2 -), a carbonyl group (-C(=O)-), an ether group (-O-), a thioether group (-S-), a sulfoxide group (-S(=O)-), an ester group (-C(=O)O-), an amide group (-C(=O)NR 2 -)(wherein, R 2 is hydrogen or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms), an imine group (-NR 2 -)(wherein, R 2 is hydrogen or a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms) or a combination thereof,

[0049] n is an integer greater than or equal to 1 (for example, 1, 2, 3 or 4),

[0050] k is an integer greater than or equal to 1 to 8 (for example, 1, 2, 3),

[0051] The sum of n and k can be an integer greater than or equal to about 2 (for example, greater than or equal to about 3 or greater than or equal to about 4 and less than or equal to about 10 or less than or equal to about 5).

[0052] In Chemical Formula 1, n can be determined by the valence of Y, and k can be determined by the valence of L. In Chemical Formula 1, X can include a vinyl group, a (meth)acrylate group or a combination thereof.

[0053] The monomer can include polyethylene glycol methacrylate, polypropylene glycol methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, substituted or unsubstituted alkyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 1,4-butanedial di(meth)acrylate, 1,6-hexanedial di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy acrylate, bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenolic epoxy (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, tris(acryloyloxyethyl) phosphate, propylene glycol di(meth)acrylate, diacryloyloxy alkane or a combination thereof.

[0054] In an embodiment, the monomer may include a photopolymerizable monomer. The monomer may include a substituted or unsubstituted di(meth)acrylate compound, a substituted or unsubstituted tri(meth)acrylate compound, a substituted or unsubstituted tetra(meth)acrylate compound, a substituted or unsubstituted penta(meth)acrylate compound, a substituted or unsubstituted hexa(meth)acrylate compound, or a combination thereof.

[0055] In the ink composition, based on the total weight of the composition, the amount of the monomer may be greater than or equal to about 1 wt% and less than or equal to about 99 wt%, greater than or equal to about 5 wt% and less than or equal to about 80 wt%, or greater than or equal to about 10 wt% and less than or equal to about 60 wt%.

[0056] The ink composition may further include an initiator, metal oxide (nano) particles, or a combination thereof.

[0057] Based on the total weight of the composition, the amount of the initiator may be greater than or equal to about 0.5 wt% and less than or equal to about 10 wt%. Based on the total weight of the composition, the amount of the metal oxide particles may be greater than or equal to about 0.5 wt% and less than or equal to about 30 wt%.

[0058] The ink composition may not include a volatile organic solvent. The ink composition may be a solvent-free ink composition.

[0059] The ink composition may be configured to polymerize into a composite or a pattern in the form of a film having a thickness of less than or equal to about 15 microns, less than or equal to about 10 μm, or 7 μm, for example.

[0060] The ink composition may be configured to form a semiconductor nanoparticle-polymer composite by polymerization, and in the semiconductor nanoparticle-polymer composite, the quantum yield of the semiconductor nanoparticles may be greater than or equal to about 60%, greater than or equal to about 65%, or greater than or equal to about 70%.

[0061] In an embodiment, a method of manufacturing an ink composition includes

[0062] mixing semiconductor nanoparticles with a polymerizable monomer and an optional metal halide (a first metal halide), wherein the step of preparing the semiconductor nanoparticles includes admixing semiconductor nanocrystal particles containing a Group 11-13-16 compound with a first organic ligand and a metal salt compound in an organic solvent, and the metal salt compound includes zinc, indium, gallium, or a combination thereof. The metal salt compound may include a second metal halide (e.g., a metal chloride). The first metal halide may be a metal chloride (e.g., zinc chloride). The second metal halide may be a metal chloride (e.g., indium chloride).

[0063] In an embodiment, a method of manufacturing an ink composition includes mixing semiconductor nanoparticles with a polymerizable monomer. Wherein, the step of preparing the semiconductor nanoparticles includes admixing semiconductor nanocrystal particles containing a Group 11-13-16 compound with a first organic ligand and an indium salt compound in an organic solvent. The indium salt compound may include indium halide (e.g., indium chloride).

[0064] The metal salt compound or (first or second) metal halide may include: zinc halide (such as zinc chloride); indium halide (such as indium chloride); gallium halide (such as gallium chloride); or a combination thereof. The first metal halide may be the same as the second metal halide. The first metal halide may be different from the metal salt compound (e.g., the second metal halide).

[0065] By mixing, the first organic ligand can bind to the surface of the semiconductor nanoparticles. The semiconductor nanoparticles may have (e.g., may include or may be adjacent to) the first organic ligand. During mixing, a ligand exchange reaction may occur on the surface of the semiconductor nanoparticles.

[0066] In an embodiment, the semiconductor nanocrystal particles including a Group 11-13-16 compound may include zinc salt-treated nanocrystal particles, and the zinc salt-treated nanocrystal particles including a Group 11-13-16 compound can be obtained by contacting the semiconductor nanocrystal particles with a zinc salt compound in a first organic solvent at a first temperature (e.g., in the absence of the first organic ligand).

[0067] The method may further include preparing a dispersion in which the zinc salt-treated nanocrystal particles are dispersed in an organic solvent. The method may include adding the first organic ligand and the metal salt compound (described herein) to the dispersion. The zinc salt compound may include a zinc fatty acid ester compound, zinc halide, or a combination thereof.

[0068] The first temperature may be greater than or equal to about 20 °C and less than or equal to about 100 °C, less than or equal to about 80 °C, less than or equal to about 60 °C, or less than or equal to about 50 °C.

[0069] The mixing (admixing) or ligand exchange reaction may be carried out at a temperature of 20 °C or higher and 100 °C or lower, 80 °C or lower, 60 °C or lower, 50 °C or lower, or 40 °C or lower. The mixing (admixing) or ligand exchange reaction may be carried out for 100 minutes or longer and 5 days or shorter.

[0070] The ink composition may be configured to form a complex via polymerization.

[0071] The embodiments relate to semiconductor nanoparticle-polymer composites prepared from an ink composition. In an embodiment, the semiconductor nanoparticle-polymer composite includes: a polymerization product of a polymerizable monomer (e.g., a polymer or a matrix); semiconductor nanoparticles; and a halogen (e.g., chlorine).

[0072] The semiconductor nanoparticles include 11-13-16 group compounds, the 11-13-16 group compounds include silver, a group 13 metal, and a group 16 element, the group 13 metal includes indium and gallium, and the group 16 element includes sulfur.

[0073] In the semiconductor nanoparticle-polymer composite, the molar ratio of the halogen to indium (e.g., the molar ratio of chlorine to indium) can be greater than or equal to about 2:1 (e.g., greater than or equal to about 2.2:1) and less than or equal to about 10:1 or less than or equal to about 8:1.

[0074] In the semiconductor nanoparticle-polymer composite, the molar ratio of zinc to indium (Zn:In) can be greater than or equal to about 1.8:1 or greater than or equal to about 2:1 and less than or equal to about 30:1, less than or equal to about 10:1, less than or equal to about 9:1, less than or equal to about 8:1, less than or equal to about 7:1, or less than or equal to about 6:1.

[0075] In the semiconductor nanoparticle-polymer composite, the molar ratio of chlorine to gallium (Cl:Ga) can be less than or equal to about 1.08:1, less than or equal to about 1.05:1, less than or equal to about 1:1, or less and greater than or equal to about 0.1:1 or greater than or equal to about 0.2:1.

[0076] In the semiconductor nanoparticle-polymer composite, the molar ratio of zinc to gallium (Zn:Ga) can be greater than or equal to about 0.2:1 or greater than or equal to about 0.5:1 and less than or equal to about 2:1 or less than or equal to about 1.6:1.

[0077] In the semiconductor nanoparticle-polymer composite, the molar ratio of zinc to the sum of indium and gallium (Zn:(In+Ga)) can be greater than or equal to about 0.3:1 or greater than or equal to about 2:1 and less than or equal to about 10:1 or less than or equal to about 5:1.

[0078] The halogen can be present in the semiconductor nanoparticle-polymer composite in the form of a metal halide. The semiconductor nanoparticle-polymer composite can also include a compound or a residue represented by R 1 -COO-A (e.g., a first organic ligand). The definitions of R 1 and A are as described herein.

[0079] Details of the semiconductor nanoparticles, metal halides, and first organic ligands in the semiconductor nanoparticle-polymer composite are as described herein.

[0080] In an embodiment, the matrix may include a polymer product of the above monomers. The (polymer) matrix or polymerization product may include a crosslinked polymer. Details of the monomers are as described herein.

[0081] The composite may further include fine metal oxide particles (e.g., nanoparticles). Details of the fine metal oxide particles are as described herein.

[0082] The composite may be provided in the form of a patterned film (e.g., a patterned film including a first region configured to emit a first light and a second region configured to emit a second light). In the patterned film, the first region may include a first composite including semiconductor nanoparticles that emit the first light, and the second region may include a second composite including semiconductor nanoparticles that emit the second light.

[0083] The composite may be a sheet in which semiconductor nanoparticles that emit a first light and semiconductor nanoparticles that emit a second light different from the first light are mixed.

[0084] Based on the total weight of the composite, the amount of semiconductor nanoparticles in the (first or second) composite may be about 1 wt% to about 80 wt%, 5 wt% to about 70 wt%, 15 wt% to about 60 wt%, 20 wt% to about 45 wt%, 25 wt% to about 35 wt%, or a combination thereof.

[0085] The composite may exhibit a blue light absorption rate greater than or equal to about 85%, greater than or equal to about 88%, or greater than or equal to about 90%, where the blue light absorption rate is calculated according to Equation 2:

[0086] Equation 2

[0087] Blue light absorption rate = [(B - B') / B] × 100%

[0088] where, in Equation 2,

[0089] B is the amount of blue light provided to the composite, and

[0090] B' is the amount of blue light passing through the composite.

[0091] The blue light absorption rate of the composite may be measured, for example, in the form of a film having a thickness of about 7 μm.

[0092] The blue light absorption rate can be less than or equal to about 99.5%, less than or equal to about 99%, less than or equal to about 98%, or less than or equal to about 97%. The blue light absorption rate of the composite can be greater than or equal to about 70%, greater than or equal to about 80%, greater than or equal to about 85%, or greater than or equal to about 90%. The blue light absorption rate of the composite can be about 70% to about 100%, about 80% to about 98%, about 95% to about 99%, about 96% to about 98%, or a combination thereof. The composite can have a blue light absorption rate greater than or equal to about 85%.

[0093] The composite or the semiconductor nanoparticles included in the composite can have a luminescence efficiency or quantum efficiency (QE) (e.g., internal QE or external QE) greater than or equal to about 50%, greater than or equal to about 55%, greater than or equal to about 58%, greater than or equal to about 60%, greater than or equal to about 63%, greater than or equal to about 65%, greater than or equal to about 68%, greater than or equal to about 69%, greater than or equal to about 70%, or greater than or equal to about 75%.

[0094] In an embodiment, the semiconductor nanoparticle-polymer composite can exhibit an internal quantum efficiency (IQE) or an external quantum efficiency (EQE) greater than or equal to about 50%, and the IQE and EQE are defined by Equation 3 and Equation 4, respectively:

[0095] Equation 3

[0096] Internal quantum efficiency (%) = [A / (B - B')] × 100

[0097] Equation 4

[0098] External quantum efficiency (%) = [A / B] × 100

[0099] Wherein,

[0100] A: The amount of the first light emitted from the composite

[0101] B: The amount of incident light irradiated

[0102] B': The amount of incident light passing through the composite.

[0103] When exposed to air for 48 hours, the reduction of the internal quantum efficiency of the composite can be greater than or equal to about 50%, greater than or equal to about 55%, or greater than or equal to about 60%.

[0104] On the one hand, a color conversion layer (e.g., a color conversion structure) including a color conversion region is provided, and the color conversion region includes the above semiconductor nanoparticles. In an embodiment, the color conversion panel may include a color conversion layer (e.g., a color conversion structure) including the color conversion region and partition walls defining each region of the color conversion layer optionally. The color conversion region may include a first region corresponding to a first pixel. The first region includes a first composite, and the first composite may include a matrix and semiconductor nanoparticles dispersed in the matrix, wherein the first region is configured to emit first light.

[0105] In an embodiment, a display panel (or a display device) includes a light source and a composite. In an embodiment, the display panel may include a light-emitting panel (or a light source), a color conversion panel, and optionally a light transmission layer (light transport layer) located between the light-emitting panel and the color conversion panel.

[0106] The light-emitting panel (or the light source) may be configured to provide incident light to the color conversion panel (alternatively, the light-emitting panel (or the light source) provides incident light to the color conversion panel). The incident light may include blue light and optionally green light. The blue light may have a peak emission wavelength of about 440 nm to about 460 nm or about 450 nm to about 455 nm.

[0107] The light source may include an organic light-emitting diode (OLED), a micro LED, a mini LED, an LED including nanorods, or a combination thereof.

[0108] In an embodiment, an electronic device (or a display device) includes a color conversion panel or a display panel.

[0109] The electronic device or the display device may include a virtual reality device, an augmented reality device, a portable terminal device, a monitor, a notebook PC, a television, an electronic display board, or an electronic component for an automobile or a vehicle.

[0110] The ink composition according to an embodiment may provide a nanoparticle composite or a pattern thereof exhibiting improved physical properties by an inkjet method. According to an embodiment, the ink composition may exhibit improved process stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0111] The above and other advantages and features of the present disclosure will become more apparent by referring to the exemplary embodiments of the present disclosure described in further detail with reference to the accompanying drawings.

[0112] Figure 1A is a schematic cross-sectional view of a color conversion panel of one or more embodiments.

[0113] Figure 1B is a cross-sectional view of an electronic device (display device) including a color conversion panel according to one or more embodiments.

[0114] Figure 2 is a flowchart showing a pattern formation process (inkjet method) using an ink composition of an embodiment.

[0115] Figure 3A is a perspective view showing an example of a display panel including a color conversion panel according to one or more embodiments.

[0116] Figure 3B is an exploded view of a display device according to one or more embodiments.

[0117] Figure 4A is Figure 3A a cross-sectional view of the display panel.

[0118] Figure 4B is an exploded view of an embodiment of a display device including mini LEDs.

[0119] Figure 5A is showing Figure 3A an example of a pixel arrangement of the display panel.

[0120] Figure 5B , Figure 5C , Figure 5D and Figure 5E is a cross-sectional view showing an example of a light-emitting device according to one or more embodiments.

[0121] Figure 6 is Figure 5A a cross-sectional view of the display panel taken along line IV-IV.

[0122] Figure 7 is a schematic cross-sectional view of a display device (e.g., a liquid crystal display device) according to one or more embodiments.

[0123] Figure 8 Shows the results of transmission electron microscope energy dispersive spectroscopy analysis of the composite prepared in Example 1.

[0124] Figure 9 Shows the results of transmission electron microscope energy dispersive spectroscopy analysis of the composite prepared in Example 6.

[0125] Figure 10 Shows the spectral profile of chlorine in the composite monolayer prepared in Example 1 obtained by transmission electron microscope energy dispersive spectroscopy analysis. Detailed Description

[0126] Advantages and features of the techniques described below and methods of implementing them will become clear by referring to the exemplary embodiments described in further detail below and in conjunction with the accompanying drawings. However, the invention may be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. All terms in the specification (including technical and scientific terms), unless otherwise defined, may be defined as commonly understood by one of ordinary skill in the art.

[0127] Terms defined in commonly used dictionaries, unless clearly defined, may not be idealized or exaggeratedly interpreted. Additionally, unless explicitly described to the contrary, the word "comprising" and variations such as "including" or "containing" will be understood to imply the inclusion of the stated elements but not the exclusion of any other elements. It will also be understood that when the terms "comprising" and / or its variations are used in this specification, it indicates the presence of the stated features, regions, wholes, steps, operations, elements, and / or components, but does not preclude the presence or addition of one or more other features, regions, wholes, steps, operations, elements, components, and / or groups thereof.

[0128] In the drawings, the thickness of layers, films, panels, regions, etc. is exaggerated for clarity. Throughout the specification, the same reference numerals denote the same elements.

[0129] It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, no intervening elements are present.

[0130] It will be understood that although terms such as "first", "second", and "third", etc. may be used herein to describe various elements, components, regions, layers, and / or parts, these elements, components, regions, layers, and / or parts should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or part from another element, component, region, layer, or part. Thus, without departing from the teachings herein, the first "element", first "component", first "region", first "layer", or first "part" discussed below may be named the second element, second component, second region, second layer, or second part.

[0131] The terms used herein are for the purpose of describing particular embodiments only and are not intended to be limiting. As used herein, unless the context clearly dictates otherwise, the singular forms "a", "an", and "the" are intended to include the plural forms including "at least one". For example, the phrase "semiconductor nanoparticles" can refer to a single semiconductor nanoparticle or can refer to a plurality of semiconductor nanoparticles. Thus, a reference to "a" or "an" element in a claim followed by a reference to "the" element includes one or more of the elements. "At least one" is not to be construed as limited to "one" or "a". "Or" means "and / or". As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0132] Exemplary embodiments are described herein with reference to cross-sectional views that are schematic illustrations of idealized embodiments. As such, variations in the illustrated shapes due to, for example, manufacturing techniques and / or tolerances are to be expected. Accordingly, the embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein, but include, for example, shape deviations resulting from manufacturing. For example, regions shown or described as flat will generally have rough and / or non-linear features. Additionally, sharp corners shown may be rounded. Thus, the regions shown in the figures are schematic in nature, and their shapes are not intended to illustrate the exact shape of the regions and are not intended to limit the scope of the claims presented.

[0133] As used herein, "about" or "approximately" includes the stated value and means within an acceptable deviation range of the particular value as determined by one of ordinary skill in the art in view of the measurements discussed and the errors associated with the measurement of a particular quantity (i.e., the limitations of the measurement system). For example, "about" can mean within one or more standard deviations, or within ±10%, ±5% of the stated value. All ranges disclosed herein include the endpoints, and the endpoints can be combined independently of each other (e.g., a range of "up to 25 wt%, or more specifically, 5 wt% to 20 wt%" includes the endpoints and all intermediate values of the range of "5 wt% to 25 wt%", etc.).

[0134] As used herein, the expression "excluding cadmium (or other harmful heavy metals)" may refer to a case where the concentration of cadmium (or other harmful heavy metals) may be less than or equal to about 100 parts per million by weight (100 ppmw), less than or equal to about 50 ppmw, less than or equal to about 10 ppmw, less than or equal to about 1 ppmw, less than or equal to about 0.1 ppmw, less than or equal to about 0.01 ppmw, or zero. In an embodiment, an amount of cadmium (or other harmful heavy metals) may be substantially absent, or if present, the amount of cadmium (or other harmful heavy metals) may be less than or equal to the detection limit or the same as the impurity level of a given analytical tool.

[0135] As used herein, if no definition is otherwise provided, "substituted" means that at least one hydrogen of a compound is replaced by a substituent selected from C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C6-C30 aryl, C7-C30 alkylaryl, C7-C30 arylalkyl, C6-C30 aryloxy, C6-C30 arylthio, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 heteroalkyl, C3-C30 heteroalkylaryl, C2-C30 alkylheteroaryl, C2-C30 heteroarylalkyl, C1-C30 heteroaryloxy, C1-C3 heteroarylthio, C3-C30 cycloalkyl, C3-C15 cycloalkenyl, C6-C30 cycloalkynyl, C2-C30 heterocycloalkyl, halogen (-F, -Cl, -Br or -I), hydroxy (-OH), nitro (-NO 2 )), cyano (-CN), amino or amine group (-NRR', where R and R' are each independently hydrogen or C1-C6 alkyl), azide (-N 3 ), amidino (-C(=NH)NH 2 ), hydrazino (-NHNH 2 ), hydrazone (=N(NH 2 ))), aldehyde (-C(=O)H), carbamoyl (-C(O)NH 2 ), mercapto (-SH), ester group (-C(=O)OR, where R is C1-C6 alkyl or C6-C12 aryl), carboxylic acid group (-COOH) or its salt (-C(=O)OM, where M is an organic cation or an inorganic cation), sulfonic acid group (-SO 3 H) or its salt (-SO 3 M, where M is an organic cation or an inorganic cation), phosphoric acid group (-PO 3 H 2 ) or its salt (-PO 3 MH or -PO 3 M 2, wherein, M is an organic cation or an inorganic cation) or a combination thereof.

[0136] In addition, if no other definition is provided, "hetero" means including the case of 1 to 3 heteroatoms selected from N, O, P, Si, S, Se, Ge, and B.

[0137] In addition, as used herein, the term "aliphatic hydrocarbon group" refers to a C1 to C30 straight-chain or branched-chain alkyl group, a C2 to C30 straight-chain or branched-chain alkenyl group, or a C2 to C30 straight-chain or branched-chain alkynyl group, and the term "aromatic organic group" as used herein refers to a C6 to C30 aryl group or a C2 to C30 heteroaryl group.

[0138] As used herein, the term "(meth)acrylate(salt)" refers to acrylate(salt) and / or methacrylate(salt).

[0139] As used herein, the term "group" refers to the group of the periodic table as defined by the International Union of Pure and Applied Chemistry (IUPAC) nomenclature system from Group 1 to Group 18.

[0140] As used herein, a nanoparticle refers to a nanostructure having at least one region or characteristic dimension with a nanoscale size. In embodiments, the size of the nanoparticle or nanostructure can be less than about 500 nanometers (nm), less than about 300 nm, less than about 250 nm, less than about 150 nm, less than about 100 nm, less than about 50 nm, or less than about 30 nm, and can be greater than about 0.1 nm or about 1 nm. The nanoparticle or nanostructure can have any shape, such as nanowires, nanorods, nanotubes, a multi-arm shape with two or more arms, or nanodots, but the embodiments are not limited thereto. The nanoparticle or nanostructure can be, for example, substantially crystalline, substantially single-crystalline, polycrystalline, amorphous, or a combination thereof.

[0141] Quantum dots can be, for example, semiconductor-containing nanocrystal particles that can exhibit quantum confinement effects or exciton confinement effects, and are a type of luminescent nanostructure (e.g., a luminescent nanostructure capable of emitting light through energy excitation). Herein, unless otherwise defined, the shape of the "quantum dot" or nanoparticle is not limited.

[0142] As used herein, the term "dispersion" refers to a dispersion in which the dispersed phase is a solid and the continuous medium comprises a liquid or a solid different from the dispersed phase. In embodiments, the ink composition may be in the form of a dispersion. Herein, a "dispersion" may be a colloidal dispersion in which the dispersed phase has a size greater than or equal to about 1 nm (e.g., greater than or equal to about 2 nm, greater than or equal to about 3 nm, or greater than or equal to about 4 nm) to several micrometers (μm) or less (e.g., less than or equal to about 2 μm, less than or equal to about 1 μm, less than or equal to about 900 nm, less than or equal to about 800 nm, less than or equal to about 700 nm, less than or equal to about 600 nm, or less than or equal to about 500 nm).

[0143] As used herein, a size (e.g., size (or dimension), diameter, thickness, etc.) may be a value for a single entity or an average for a plurality of particles. As used herein, the term "average value" (e.g., the average size of quantum dots) may be a mean value or a median value. In embodiments, the average value may be a "mean" value.

[0144] As used herein, the term "peak emission wavelength" is the wavelength at which a given emission spectrum of light reaches its maximum.

[0145] In embodiments, commercially available equipment (e.g., from Hitachi or Hamamatsu, etc.) may be used and the quantum efficiency can be easily and reproducibly determined with reference to the operation guides provided by the corresponding equipment manufacturers, for example. The quantum efficiency (which may be used interchangeably with the term "quantum yield" (QY)) can be measured in solution state or in solid state (in a complex). In embodiments, the quantum efficiency (or quantum yield) is the ratio of the photons emitted by a nanostructure (or a population of nanostructures) to the photons absorbed. In embodiments, the quantum efficiency can be measured by any suitable method. For example, there are two methods for measuring the fluorescence quantum yield or efficiency: the absolute method and the relative method. The quantum efficiency measured by the absolute method may be referred to as the absolute quantum efficiency.

[0146] In the absolute method, the quantum yield can be obtained, for example, by detecting the fluorescence of semiconductor nanoparticles through an integrating sphere. In the relative method, the quantum yield of semiconductor nanoparticles can be calculated by comparing the fluorescence intensity of a standard dye (standard sample) with the fluorescence intensity of the semiconductor nanoparticles. Coumarin 153, Coumarin 545, Rhodamine 101 inner salt, Anthracene, and Rhodamine 6G can be used as standard dyes according to their PL wavelengths, but the embodiments are not limited thereto.

[0147] The full width at half maximum and the peak emission wavelength can be measured, for example, by a luminescence spectrum (e.g., a photoluminescence (PL) spectrum or an electroluminescence (EL) spectrum) obtained by a spectrophotometer (such as a fluorescence spectrophotometer, etc.).

[0148] As used herein, the term “first absorption peak wavelength” refers to the wavelength at which the main peak first appears in the lowest energy region in an ultraviolet-visible (UV-Vis) absorption spectrum.

[0149] Semiconductor nanoparticles can be included in various electronic devices. The electrical properties and / or optical properties of semiconductor nanoparticles can be controlled, for example, by their elemental composition, their size, their shape, or a combination thereof. In embodiments, semiconductor nanoparticles can include semiconductor nanocrystals. Semiconductor nanoparticles such as quantum dots can have a relatively large surface area per unit volume and can thus exhibit quantum confinement effects, exhibiting physical properties and optical properties different from those of the corresponding bulk materials having the same composition. Thus, semiconductor nanoparticles such as quantum dots can be supplied with energy from an excitation source (e.g., incident light or voltage) to form an excited state that can emit energy corresponding to its bandgap upon relaxation.

[0150] Semiconductor nanoparticles can also be used in color conversion panels (e.g., photoluminescent color filters, etc.). A display device including a color conversion panel (e.g., a photoluminescent color filter) or a light-emitting type color filter can use a layer including quantum dots as a light-emitting material and include the layer including quantum dots as a light-emitting material in the relatively front part of the device to convert incident light (e.g., blue light) provided from a light source into light of a different spectrum (e.g., green light or red light). In embodiments, a “color conversion panel” is a device (e.g., an electronic device) including a color conversion layer or a color conversion structure.

[0151] In a display device including a color conversion panel, the properties (e.g., optical properties, stability, etc.) of the semiconductor nanoparticles used as a light-emitting material can have a direct impact on the display quality of the device. It is desirable that the light-emitting material included in the color conversion panel provided in the relatively front part of the device not only exhibits a relatively high light-emitting efficiency but also exhibits a relatively high absorption rate with respect to incident light. When a patterned film (e.g., for a color filter) is used in a display device, a relatively low absorption rate with respect to incident light can be a direct cause of blue light leakage, having an adverse effect on the color reproducibility (e.g., DCI matching rate) of the device. In embodiments, the adoption of an absorption type color filter can be considered a measure for preventing such blue light leakage problems. However, without wishing to be bound by any theory, it is believed that a relatively low absorption rate of semiconductor nanoparticles can lead to a reduction in the brightness of a device including semiconductor nanoparticles.

[0152] Some semiconductor nanoparticles may exhibit properties suitable for practical devices (e.g., optical properties and / or stability), but many of them include cadmium-containing compounds (e.g., cadmium chalcogenides). Since cadmium is one of the most restricted elements and may cause serious environmental / health problems, it is desirable to develop cadmium-free and environmentally friendly semiconductor nanoparticles. In this regard, extensive in-depth research has been conducted on nanocrystals including 13-15 group compounds (hereinafter also referred to as III-V group compounds). However, there is still a desire to develop a cadmium-free semiconductor nanoparticle that can exhibit a higher incident light absorption rate and a narrower full width at half maximum.

[0153] A color conversion panel (e.g., a light-emitting color filter) can be manufactured using a composition containing quantum dots via a photolithography process or an inkjet printing process. The photolithography process or the inkjet printing process can reproducibly provide a sophisticated color filter. The photolithography process may require coating, exposure, development, and curing for each (sub) pixel, which may result in an increase in manufacturing time and manufacturing cost. In the inkjet printing process, a liquid ink composition can be ejected through an inkjet head and then deposited in a predetermined position to manufacture a nanoparticle composite in a desired pattern. In the inkjet printing process, pixels each representing a different color (such as red, green, and blue) can be provided simultaneously, which can be desirable in terms of the manufacturing process, time, and cost. Therefore, it is desirable to develop an ink composition capable of manufacturing a composite (e.g., a color conversion panel) that has enhanced process stability and can exhibit improved luminescent properties for the above new composition nanoparticles.

[0154] According to an embodiment, the ink composition can provide a semiconductor nanoparticle-polymer composite (i.e., a composite) or a pattern of a semiconductor nanoparticle-polymer composite that can exhibit improved light conversion efficiency, improved yield, and increased process stability.

[0155] In an embodiment, the ink composition includes semiconductor nanoparticles and monomers (polymerizable monomers). The semiconductor nanoparticles can include or be considered semiconductor nanocrystals. The semiconductor nanoparticles or semiconductor nanocrystals include silver, group 13 metals, and group 16 elements (i.e., chalcogens) (11-13-16 group compounds containing silver, group 13 metals, and group 16 elements (i.e., chalcogens)). The semiconductor nanoparticles may further include zinc. The ink composition or the semiconductor nanoparticles may further include a first organic ligand containing a compound represented by R 1 -COOA (i.e., R 1 -COO-A), where R 1is a first organic group, and A represents hydrogen or a moiety in contact with (or attached to) the surface of the semiconductor nanoparticle (e.g., a point attached to the surface of the semiconductor nanoparticle).

[0156] The ink composition may further include a metal halide (e.g., a first metal halide). The (first) metal halide may include a metal chloride. The (first) metal halide or metal chloride may include zinc, indium, gallium, or a combination thereof.

[0157] In embodiments, the semiconductor nanoparticle may not include cadmium. In embodiments, the semiconductor nanoparticle may not include mercury, lead, or a combination thereof.

[0158] In embodiments, the semiconductor nanoparticle is configured to emit a first light. In embodiments, the semiconductor nanoparticle may emit light of a desired wavelength and may achieve improved optical properties (e.g., a narrow full width at half maximum, an increased quantum yield, and / or a relatively high level of blue light absorption). The semiconductor nanoparticles of the embodiments may, for example, be used as a down-conversion material for a color conversion panel or a color conversion sheet, and may exhibit increased absorption per unit weight of the semiconductor nanoparticles, so that a device (e.g., a panel or a sheet) including the semiconductor nanoparticles can be manufactured at a reduced manufacturing cost and may provide improved light conversion performance.

[0159] In the semiconductor nanoparticle, the group 13 metal may include indium, gallium, aluminum, or a combination thereof. The group 13 metal may include indium and gallium. The group 16 element may include sulfur, selenium, or a combination thereof. The group 16 element may include sulfur. The semiconductor nanoparticle may include, for example, gallium and zinc on the surface of the semiconductor nanoparticle.

[0160] The semiconductor nanoparticle may have a charge balance value defined by Equation 1, which is greater than or equal to about 0.8 to less than or equal to about 2.5 (e.g., less than or equal to about 1.5) (e.g., the charge balance value may be greater than or equal to 0.8, greater than or equal to about 1 and less than or equal to about 2.5, less than or equal to about 1.9, less than or equal to about 1.7 (e.g., less than or equal to about 1.5):

[0161] Equation 1

[0162] Charge balance value = {[Ag] + 3([Group 13 metal]) + 2[Zn]} / (2[CHA])

[0163] wherein, in Equation 1, [Ag], [Group 13 metal], [Zn], and [CHA] are the molar amounts of silver, group 13 metal (e.g., indium, gallium, or a combination thereof), zinc, and chalcogen (e.g., sulfur, selenium, or a combination thereof) in the semiconductor nanoparticle, respectively.

[0164] Group 13 metals may include indium and gallium. The chalcogen may include sulfur. In an embodiment, the charge balance value may be represented by Equation 1A:

[0165] Equation 1A

[0166] Charge balance value = {[Ag] + 3([In] + [Ga]) + 2[Zn]} / (2[S])

[0167] Wherein, in Equation 1A, [Ag], [In], [Ga], [Zn], and [S] are the molar amounts of silver, indium, gallium, zinc, and sulfur in the semiconductor nanoparticles, respectively.

[0168] In an embodiment, the semiconductor nanoparticles may further include or may not include copper.

[0169] In an embodiment, the charge balance value may be less than or equal to about 2.4, less than or equal to about 2.3, less than or equal to about 2.2, less than or equal to about 2.1, less than or equal to about 2, less than or equal to about 1.9, less than or equal to about 1.85, less than or equal to about 1.8, less than or equal to about 1.75, less than or equal to about 1.7, less than or equal to about 1.5, less than or equal to about 1.45, less than or equal to about 1.4, less than or equal to about 1.35, less than or equal to about 1.33, less than or equal to about 1.31, less than or equal to about 1.3, less than or equal to about 1.29, less than or equal to about 1.28, less than or equal to about 1.27, less than or equal to about 1.26, less than or equal to about 1.25, less than or equal to about 1.24, less than or equal to about 1.23, less than or equal to about 1.22, less than or equal to about 1.21, less than or equal to about 1.2, less than or equal to about 1.15, less than or equal to about 1.1, or less than or equal to about 1.05.

[0170] In an embodiment, the charge balance value can be 0.81, greater than or equal to about 0.85, greater than or equal to about 0.9, greater than or equal to about 0.95, greater than or equal to about 0.97, greater than or equal to about 0.99, greater than or equal to about 1, greater than or equal to about 1.01, greater than or equal to about 1.02, greater than or equal to about 1.03, greater than or equal to about 1.04, greater than or equal to about 1.05, greater than or equal to about 1.06, greater than or equal to about 1.07, greater than or equal to about 1.08, greater than or equal to about 1.09, greater than or equal to about 1.1, greater than or equal to about 1.11, greater than or equal to about 1.12, greater than or equal to about 1.13, greater than or equal to about 1.14, greater than or equal to about 1.15, greater than or equal to about 1.16, greater than or equal to about 1.17, greater than or equal to about 1.18, greater than or equal to about 1.19, greater than or equal to about 1.2, greater than or equal to about 1.21, greater than or equal to about 1.22, greater than or equal to about 1.23, greater than or equal to about 1.24, greater than or equal to about 1.25, greater than or equal to about 1.3, greater than or equal to about 1.35, greater than or equal to about 1.4, greater than or equal to about 1.45, greater than or equal to about 1.5, greater than or equal to about 1.55, greater than or equal to about 1.6, greater than or equal to about 1.65, greater than or equal to about 1.7, greater than or equal to about 1.75, greater than or equal to about 1.8 or greater than or equal to about 1.82.

[0171] In the semiconductor nanoparticles of the embodiment, the molar ratio of sulfur to the sum of silver, indium and gallium [S:(Ag+In+Ga)] can be greater than or equal to about 0.65:1, greater than or equal to about 0.68:1, greater than or equal to about 0.7:1, greater than or equal to about 0.75:1, greater than or equal to about 0.77:1, greater than or equal to about 0.8:1, greater than or equal to about 0.82:1, greater than or equal to about 0.85:1, greater than or equal to about 0.9:1, greater than or equal to about 0.95:1, greater than or equal to about 1:1, greater than or equal to about 1.1:1, greater than or equal to about 1.2:1, greater than or equal to about 1.25:1, greater than or equal to about 1.29:1, greater than or equal to about 1.3:1, greater than or equal to about 1.35:1, greater than or equal to about 1.36:1, greater than or equal to about 1.38:1, greater than or equal to about 1.4:1 or greater than or equal to about 1.45:1.

[0172] In the semiconductor nanoparticles of the embodiments, the molar ratio of sulfur to the sum of silver, indium, and gallium [S:(Ag+In+Ga)] can be less than or equal to about 3:1, less than or equal to about 2.5:1, less than or equal to about 2:1, less than or equal to about 1.9:1, less than or equal to about 1.88:1, less than or equal to about 1.6:1, less than or equal to about 1.55:1, less than or equal to about 1.5:1, less than or equal to about 1.45:1, less than or equal to about 1.4:1, less than or equal to about 1.35:1, less than or equal to about 1.33:1, less than or equal to about 1.3:1, less than or equal to about 1.25:1, less than or equal to about 1.2:1, less than or equal to about 1.19:1, less than or equal to about 1.15:1, less than or equal to about 1.09:1, less than or equal to about 1.05:1, or less than or equal to about 1.02:1.

[0173] In the semiconductor nanoparticles of the embodiments, the molar ratio of the sum of indium and gallium to silver [(In+Ga):Ag] can be greater than or equal to about 1.3:1, greater than or equal to about 1.4:1, greater than or equal to about 1.44:1, greater than or equal to about 1.45:1, greater than or equal to about 1.5:1, greater than or equal to about 1.65:1, greater than or equal to about 1.66:1, greater than or equal to about 1.7:1, greater than or equal to about 1.75:1, greater than or equal to about 1.8:1, greater than or equal to about 1.85:1, greater than or equal to about 1.9:1, greater than or equal to about 1.91:1, greater than or equal to about 1.95:1, greater than or equal to about 1.99:1, greater than or equal to about 2:1, greater than or equal to about 2.1:1, greater than or equal to about 2.2:1, greater than or equal to about 2.3:1, or greater than or equal to about 2.35:1. The molar ratio of the sum of indium and gallium to silver [(In+Ga):Ag] can be less than or equal to about 7:1, less than or equal to about 6.5:1, less than or equal to about 6.3:1, less than or equal to about 6:1, less than or equal to about 5.9:1, less than or equal to about 5.7:1, less than or equal to about 5.66:1, less than or equal to about 5.5:1, less than or equal to about 5.3:1, less than or equal to about 5.1:1, less than or equal to about 4.5:1, less than or equal to about 4:1, less than or equal to about 3.5:1, less than or equal to about 3.2:1, less than or equal to about 3:1, less than or equal to about 2.8:1, less than or equal to about 2.6:1, less than or equal to about 2.4:1, less than or equal to about 2:1, less than or equal to about 1.8:1, less than or equal to about 1.75:1, or less than or equal to about 1.7:1.

[0174] In the semiconductor nanoparticles of the embodiments, the molar ratio of gallium to the sum of indium and gallium [Ga:(In+Ga)] can be greater than or equal to about 0.5:1, greater than or equal to about 0.55:1, greater than or equal to about 0.6:1, greater than or equal to about 0.65:1, greater than or equal to about 0.68:1, greater than or equal to about 0.7:1, greater than or equal to about 0.75:1, greater than or equal to about 0.77:1, greater than or equal to about 0.8:1, greater than or equal to about 0.81:1, greater than or equal to about 0.85:1 or greater than or equal to about 0.89:1. The molar ratio of gallium to the sum of indium and gallium [Ga:(In+Ga)] can be less than or equal to about 0.99:1, less than or equal to about 0.98:1, less than or equal to about 0.97:1, less than or equal to about 0.96:1, less than or equal to about 0.95:1, less than or equal to about 0.94:1, less than or equal to about 0.93:1, less than or equal to about 0.92:1, less than or equal to about 0.91:1, less than or equal to about 0.9:1, less than or equal to about 0.89:1, less than or equal to about 0.83:1, less than or equal to about 0.82:1 or less than or equal to about 0.78:1.

[0175] In the semiconductor nanoparticles of the embodiments, the molar ratio of gallium to sulfur (Ga:S) can be greater than or equal to about 0.1:1, greater than or equal to about 0.15:1, greater than or equal to about 0.2:1, greater than or equal to about 0.25:1, greater than or equal to about 0.3:1, greater than or equal to about 0.31:1, greater than or equal to about 0.32:1, greater than or equal to about 0.33:1, greater than or equal to about 0.34:1, greater than or equal to about 0.35:1, greater than or equal to about 0.38:1, greater than or equal to about 0.4:1, greater than or equal to about 0.47:1, greater than or equal to about 0.5:1, greater than or equal to about 0.53:1, greater than or equal to about 0.55:1, greater than or equal to about 0.56:1, greater than or equal to about 0.58:1, greater than or equal to about 0.6:1 or greater than or equal to about 0.62:1. The molar ratio of gallium to sulfur (Ga:S) can be less than or equal to about 1:1, less than or equal to about 0.9:1, less than or equal to about 0.8:1, less than or equal to about 0.6:1, less than or equal to about 0.55:1, less than or equal to about 0.45:1, less than or equal to about 0.42:1, less than or equal to about 0.41:1 or less than or equal to about 0.4:1.

[0176] In the semiconductor nanoparticles of the embodiments, the molar ratio of silver to sulfur (Ag:S) can be greater than or equal to about 0.03:1, greater than or equal to about 0.05:1, greater than or equal to about 0.06:1, greater than or equal to about 0.07:1, greater than or equal to about 0.08:1, greater than or equal to about 0.09:1, greater than or equal to about 0.1:1, greater than or equal to about 0.15:1, greater than or equal to about 0.2:1, greater than or equal to about 0.25:1, greater than or equal to about 0.27:1, greater than or equal to about 0.3:1, greater than or equal to about 0.35:1, greater than or equal to about 0.4:1, greater than or equal to about 0.45:1, or greater than or equal to about 0.47:1. The molar ratio of silver to sulfur (Ag:S) can be less than or equal to about 1:1, less than or equal to about 0.6:1, less than or equal to about 0.5:1, less than or equal to about 0.48:1, less than or equal to about 0.47:1, less than or equal to about 0.4:1, less than or equal to about 0.38:1, less than or equal to about 0.36:1, less than or equal to about 0.35:1, less than or equal to about 0.3:1, less than or equal to about 0.25:1, less than or equal to about 0.24:1, or less than or equal to about 0.23:1.

[0177] In the semiconductor nanoparticles of the embodiments, the molar ratio of indium to sulfur (In:S) can be greater than or equal to about 0.01:1, greater than or equal to about 0.05:1, greater than or equal to about 0.08:1, greater than or equal to about 0.09:1, or greater than or equal to about 0.1:1. The molar ratio of indium to sulfur (In:S) can be less than or equal to about 0.5:1, less than or equal to about 0.4:1, less than or equal to about 0.3:1, less than or equal to about 0.25:1, less than or equal to about 0.15:1, less than or equal to about 0.14:1, less than or equal to about 0.13:1, or less than or equal to about 0.12:1.

[0178] In the semiconductor nanoparticles of the embodiments, the molar ratio of silver to indium (Ag:In) can be greater than or equal to about 1.5:1, greater than or equal to about 1.7:1, greater than or equal to about 1.8:1, greater than or equal to about 1.88:1, greater than or equal to about 1.92:1, greater than or equal to about 2:1, greater than or equal to about 2.5:1, greater than or equal to about 3:1, or greater than or equal to about 3.1:1. The molar ratio of silver to indium (Ag:In) can be less than or equal to about 5.5:1, less than or equal to about 5:1, less than or equal to about 4.83:1, less than or equal to about 4.8:1, less than or equal to about 4.5:1, less than or equal to about 4:1, less than or equal to about 3.5:1, less than or equal to about 3.2:1, less than or equal to about 3:1, less than or equal to about 2.94:1, less than or equal to about 2:1, less than or equal to about 1.88:1, or less than or equal to about 1.8:1.

[0179] In the semiconductor nanoparticles of the embodiments, the molar ratio of zinc to indium (Zn:In) can be greater than or equal to about 0.1:1, greater than or equal to about 0.3:1, greater than or equal to about 0.5:1, greater than or equal to about 0.7:1, greater than or equal to about 0.75:1, greater than or equal to about 0.78:1, greater than or equal to about 0.9:1, greater than or equal to about 1:1, greater than or equal to about 1.2:1, greater than or equal to about 1.4:1, greater than or equal to about 1.5:1, greater than or equal to about 1.54:1, greater than or equal to about 1.6:1, greater than or equal to about 1.8:1, greater than or equal to about 2.2:1, greater than or equal to about 2.5:1, greater than or equal to about 3:1, greater than or equal to about 3.5:1, greater than or equal to about 4:1 or greater than or equal to about 4.5:1. In the semiconductor nanoparticles of the embodiments, the molar ratio of zinc to indium (Zn:In) can be less than or equal to about 10:1, less than or equal to about 9:1, less than or equal to about 8.5:1, less than or equal to about 8:1, less than or equal to about 7.5:1, less than or equal to about 7:1, less than or equal to about 6.97:1, less than or equal to about 6.5:1, less than or equal to about 6:1, less than or equal to about 5.54:1, less than or equal to about 5.5:1, less than or equal to about 5:1, less than or equal to about 4.5:1, less than or equal to about 4:1, less than or equal to about 3.5:1, less than or equal to about 3:1, less than or equal to about 2.5:1, less than or equal to about 2:1, less than or equal to about 1.9:1, less than or equal to about 1.85:1, less than or equal to about 1.7:1, less than or equal to about 1.75:1, or less than or equal to about 1.72:1.

[0180] In an embodiment, the semiconductor nanoparticles may not include lithium. In an embodiment, the semiconductor nanoparticles may not include alkali metals (such as sodium, potassium, etc.).

[0181] In the semiconductor nanoparticles, the amount of indium can have a concentration gradient that varies (decreases) in the radial direction (e.g., from its center to its surface). In the semiconductor nanoparticles of one or more embodiments, the amount of indium (or indium concentration) in a portion of the semiconductor nanoparticles adjacent to (close to) the surface (e.g., the shell or outermost layer) can be less than the amount of indium (or indium concentration) in the interior or core of the semiconductor nanoparticles. In an embodiment, a portion of the semiconductor nanoparticles adjacent to (or close to) the surface (e.g., the shell or outermost layer) may not include indium. In one aspect, the semiconductor nanoparticles can include semiconductor nanocrystals comprising 11-13-16 group compounds, wherein gallium is exposed on the surface of the semiconductor nanocrystals (e.g., on the surface of the semiconductor nanocrystals), zinc is on the surface of the semiconductor nanocrystals, and a first organic ligand is adjacent to or in contact with the surface of the semiconductor nanocrystals (e.g., attached to or bonded to the surface of the semiconductor nanocrystals).

[0182] In an embodiment, the semiconductor nanoparticles may include: a first semiconductor nanocrystal or a core including the first semiconductor nanocrystal; and a second semiconductor nanocrystal or a shell including the second semiconductor nanocrystal (e.g., disposed on or around the first semiconductor nanocrystal). The semiconductor nanoparticles may have a core-shell structure. The first semiconductor nanocrystal may have a composition different from that of the second semiconductor nanocrystal.

[0183] The first semiconductor nanocrystal may include silver, a Group 13 metal (e.g., indium, gallium, or a combination thereof), and a Group 16 element (e.g., sulfur and optionally selenium). The first semiconductor nanocrystal may include a quaternary alloy semiconductor material based on a 11-13-16 group compound including silver, indium, gallium, and sulfur. The semiconductor nanoparticles or the first semiconductor nanocrystal may include indium gallium silver sulfide (hereinafter abbreviated as AIGS). The first semiconductor nanocrystal may include Ag(In x Ga 1-x )S 2 (where x is greater than 0 and less than or equal to 1). The molar ratio between the components in the first semiconductor nanocrystal can be adjusted such that the final semiconductor nanoparticles can have a desired composition and optical properties (e.g., maximum emission wavelength).

[0184] The size (or average size, hereinafter may be simply referred to as "size") of the first semiconductor nanocrystal or core may be greater than or equal to about 0.5 nm, greater than or equal to about 1 nm, greater than or equal to about 1.5 nm, greater than or equal to about 1.7 nm, greater than or equal to about 1.9 nm, greater than or equal to about 2 nm, greater than or equal to about 2.1 nm, greater than or equal to about 2.3 nm, greater than or equal to about 2.5 nm, greater than or equal to about 2.7 nm, greater than or equal to about 2.9 nm, greater than or equal to about 3 nm, greater than or equal to about 3.1 nm, greater than or equal to about 3.3 nm, greater than or equal to about 3.5 nm, greater than or equal to about 3.7 nm, or greater than or equal to about 3.9 nm.

[0185] The size of the first semiconductor nanocrystal or core may be less than or equal to about 5 nm, less than or equal to about 4.5 nm, less than or equal to about 4 nm, less than or equal to about 3.5 nm, less than or equal to about 3 nm, less than or equal to about 2.5 nm, less than or equal to about 2 nm, or less than or equal to about 1.5 nm.

[0186] The shell may include a second semiconductor nanocrystal, the second semiconductor nanocrystal including a Group 13 metal (indium, gallium, or a combination thereof) and a chalcogen (sulfur, selenium, or a combination thereof). The second semiconductor nanocrystal may further include silver. The second semiconductor nanocrystal may include silver, gallium, and sulfur. The second semiconductor nanocrystal may include a ternary alloy semiconductor material comprising silver, gallium, and sulfur (which may be abbreviated herein as AGS). The second semiconductor nanocrystal may have a composition different from that of the first semiconductor nanocrystal. The second semiconductor nanocrystal may include a Group 13-16 compound, a Group 11-13-16 compound, or a combination thereof. The Group 13-16 compound may include gallium sulfide, gallium selenide, indium sulfide, indium selenide, indium gallium sulfide, indium gallium selenide, indium gallium sulfoselenide, or a combination thereof. The shell may further include a third semiconductor nanocrystal, the third semiconductor nanocrystal including zinc, gallium, and sulfur. The third semiconductor nanocrystal may include zinc gallium sulfide (which may be abbreviated herein as ZnGaS). The second semiconductor nanocrystal and the third semiconductor nanocrystal may have a composition different from that of the first semiconductor nanocrystal. The second semiconductor nanocrystal may have a composition different from that of the third semiconductor nanocrystal. The shell (the second semiconductor nanocrystal, the third semiconductor nanocrystal, or a combination thereof) may cover at least a portion of the first semiconductor nanocrystal. The second semiconductor nanocrystal may be disposed between the third semiconductor nanocrystal and the first semiconductor nanocrystal. The bandgap of the second semiconductor nanocrystal may be different from the bandgap of the first semiconductor nanocrystal. The bandgap of the second semiconductor nanocrystal and the bandgap of the third semiconductor nanocrystal may be greater than the bandgap of the first semiconductor nanocrystal. The bandgap of the second semiconductor nanocrystal may be less than the bandgap of the third semiconductor nanocrystal. The molar ratio between the components in the shell or the second semiconductor nanocrystal may be adjusted such that the final semiconductor nanoparticle exhibits a desired composition and optical properties.

[0187] The thickness (or average thickness, hereinafter simply referred to as "thickness") of the second semiconductor nanocrystal, the third semiconductor nanocrystal, or the shell can be greater than or equal to about 0.1 nm, greater than or equal to about 0.3 nm, greater than or equal to about 0.5 nm, greater than or equal to about 0.7 nm, greater than or equal to about 1 nm, greater than or equal to about 1.5 nm, greater than or equal to about 1.7 nm, greater than or equal to about 1.9 nm, greater than or equal to about 2 nm, greater than or equal to about 2.1 nm, greater than or equal to about 2.3 nm, greater than or equal to about 2.5 nm, greater than or equal to about 2.7 nm, greater than or equal to about 2.9 nm, greater than or equal to about 3 nm, greater than or equal to about 3.1 nm, greater than or equal to about 3.3 nm, greater than or equal to about 3.5 nm, greater than or equal to about 3.7 nm, or greater than or equal to about 3.9 nm. The thickness of the second semiconductor nanocrystal, the third semiconductor nanocrystal, or the shell can be less than or equal to about 5 nm, less than or equal to about 4.5 nm, less than or equal to about 4 nm, less than or equal to about 3.5 nm, less than or equal to about 3 nm, less than or equal to about 2.5 nm, less than or equal to about 2 nm, or less than or equal to about 1.5 nm.

[0188] The semiconductor nanoparticle or the shell can also include, for example, a fourth semiconductor nanocrystal containing zinc chalcogenide or an inorganic layer containing zinc chalcogenide as the outermost layer. The zinc chalcogenide can include: zinc; and selenium, sulfur, or a combination thereof. The zinc chalcogenide can include ZnSe, ZnSeS, ZnS, or a combination thereof. In an embodiment, the semiconductor nanoparticle can have a core-multishell structure, and the core-multishell structure includes AgInGaS / GaS / ZnS, AgInGaS / AgGaS / ZnS, AgInGaS / ZnGaS / ZnS, AgInGaS / GaS / ZnGaS / ZnS, AgInGaS / AgGaS / ZnGaS / ZnS, or a combination thereof. It is understood that the foregoing chemical formulas (such as, "AgInGaS", "GaS", and "ZnS") may not necessarily represent a specific stoichiometry, but rather, these chemical formulas are intended to convey the presence of a specific set of substances.

[0189] The thickness of the inorganic layer including zinc chalcogenide can be appropriately selected. The thickness of the inorganic layer or the outermost layer can be less than or equal to about 5 nm, less than or equal to about 4 nm, less than or equal to about 3.5 nm, less than or equal to about 3 nm, less than or equal to about 2.5 nm, less than or equal to about 2 nm, less than or equal to about 1.5 nm, less than or equal to about 1 nm, or less than or equal to about 0.8 nm. The thickness of the inorganic layer or the outermost layer can be greater than or equal to about 0.1 nm, greater than or equal to about 0.3 nm, greater than or equal to about 0.5 nm, or greater than or equal to about 0.7 nm. In an embodiment, the thickness of the inorganic layer or the outermost layer can be about 0.1 nm to about 5 nm, about 0.3 nm to about 4 nm, about 0.5 nm to about 3.5 nm, about 0.7 nm to about 3 nm, about 0.9 nm to about 2.5 nm, about 1 nm to about 2 nm, about 1.5 nm to about 1.7 nm, or a combination thereof.

[0190] In an embodiment, when analyzed by, for example, appropriate analytical means (e.g., X-ray diffraction analysis, electron microscopy analysis such as high-angle annular dark-field (HAADF)-scanning transmission electron microscopy (STEM) analysis, etc.), the semiconductor nanoparticles can be crystalline.

[0191] In an embodiment, the size (or average size, hereinafter simply referred to as "size") of the semiconductor nanoparticles can be greater than or equal to about 1 nm, greater than or equal to about 1.5 nm, greater than or equal to about 2 nm, greater than or equal to about 2.5 nm, greater than or equal to about 3 nm, greater than or equal to about 3.5 nm, greater than or equal to about 4 nm, greater than or equal to about 4.5 nm, greater than or equal to about 5 nm, greater than or equal to about 5.5 nm, greater than or equal to about 6 nm, greater than or equal to about 6.5 nm, greater than or equal to about 7 nm, greater than or equal to about 7.5 nm, greater than or equal to about 8 nm, greater than or equal to about 8.5 nm, greater than or equal to about 9 nm, greater than or equal to about 9.5 nm, greater than or equal to about 10 nm or greater than or equal to about 10.5 nm. The size of the semiconductor nanoparticles can be less than or equal to about 50 nm, less than or equal to about 48 nm, less than or equal to about 46 nm, less than or equal to about 44 nm, less than or equal to about 42 nm, less than or equal to about 40 nm, less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal to about 25 nm, less than or equal to about 20 nm, less than or equal to about 18 nm, less than or equal to about 16 nm, less than or equal to about 14 nm, less than or equal to about 12 nm, less than or equal to about 11 nm, less than or equal to about 10 nm, less than or equal to about 8 nm, less than or equal to about 6 nm or less than or equal to about 4 nm. As used herein, the size of the semiconductor nanoparticles can be the particle diameter (particle size). The size or diameter of the semiconductor nanoparticles can be their equivalent diameter, which is obtained by calculations involving converting the two-dimensional area of a transmission electron microscope image of a given particle into a circle. The size can be a value calculated from the composition and peak emission wavelength of the semiconductor nanoparticles (e.g., the nominal particle size).

[0192] The semiconductor nanoparticles of the embodiment can be configured to emit a first light. The first light can include band-edge emission. The first light can be green light. The first light can be red light.

[0193] In the emission spectrum, the peak emission wavelength of the first light of the semiconductor nanoparticles or the peak emission wavelength of the semiconductor nanoparticles can be greater than or equal to about 500 nm, greater than or equal to about 505 nm, greater than or equal to about 510 nm, greater than or equal to about 515 nm, greater than or equal to about 520 nm, greater than or equal to about 525 nm, greater than or equal to about 530 nm, greater than or equal to about 535 nm, greater than or equal to about 540 nm, greater than or equal to about 545 nm, greater than or equal to about 550 nm, greater than or equal to about 555 nm, greater than or equal to about 560 nm, greater than or equal to about 565 nm, greater than or equal to about 570 nm, greater than or equal to about 575 nm, greater than or equal to about 580 nm, greater than or equal to about 585 nm, greater than or equal to about 590 nm or greater than or equal to about 600 nm.

[0194] The peak emission wavelength of the first light of the semiconductor nanoparticles can be less than or equal to about 650 nm, less than or equal to about 620 nm, less than or equal to about 600 nm, less than or equal to about 595 nm, less than or equal to about 590 nm, less than or equal to about 580 nm, less than or equal to about 575 nm, less than or equal to about 570 nm, less than or equal to about 565 nm, less than or equal to about 560 nm, less than or equal to about 555 nm, less than or equal to about 550 nm, less than or equal to about 545 nm, less than or equal to about 540 nm, less than or equal to about 535 nm, less than or equal to about 530 nm, less than or equal to about 525 nm, less than or equal to about 520 nm, or less than or equal to about 515 nm.

[0195] In the emission spectrum, the full width at half maximum (FWHM) of the peak of the first light of the semiconductor nanoparticles or the FWHM of the peak of the semiconductor nanoparticles can be greater than or equal to about 5 nm, greater than or equal to about 10 nm, greater than or equal to about 15 nm, greater than or equal to about 20 nm, greater than or equal to about 25 nm, or greater than or equal to about 30 nm. The full width at half maximum can be less than or equal to about 70 nm, less than or equal to about 65 nm, less than or equal to about 60 nm, less than or equal to about 55 nm, less than or equal to about 50 nm, less than or equal to about 45 nm, less than or equal to about 40 nm, less than or equal to about 38 nm, less than or equal to about 36 nm, less than or equal to about 35 nm, less than or equal to about 34 nm, less than or equal to about 33 nm, less than or equal to about 32 nm, less than or equal to about 31 nm, less than or equal to about 30 nm, less than or equal to about 29 nm, less than or equal to about 28 nm, less than or equal to about 27 nm, less than or equal to about 26 nm, or less than or equal to about 25 nm.

[0196] The semiconductor nanoparticles can exhibit a quantum yield greater than or equal to about 50%. The quantum yield can be an absolute quantum yield. The quantum yield can be greater than or equal to about 55%, greater than or equal to about 60%, greater than or equal to about 65%, greater than or equal to about 70%, greater than or equal to about 75%, greater than or equal to about 80%, greater than or equal to about 85%, greater than or equal to about 90%, or greater than or equal to about 95%. The quantum yield can be less than or equal to about 100%, less than or equal to about 99.5%, less than or equal to about 99%, less than or equal to about 98%, or less than or equal to about 97%.

[0197] In an embodiment, a method of providing semiconductor nanoparticles or semiconductor nanocrystals may include forming a shell (e.g., a second semiconductor nanocrystal and / or a third semiconductor nanocrystal) and / or an inorganic layer (e.g., a fourth semiconductor nanocrystal) on a first semiconductor nanocrystal. The method may further include ligand exchange on the surface of the semiconductor nanoparticles with a first organic ligand.

[0198] The preparation of the first semiconductor nanocrystal or core may include reacting a composition-dependent desired precursor (such as a silver precursor, an indium precursor, a gallium precursor, and a sulfur precursor) in a solution including an organic ligand and an organic solvent at a predetermined reaction temperature (e.g., about 20 °C to about 300 °C, about 80 °C to about 295 °C, about 120 °C to about 290 °C, or about 200 °C to about 280 °C) and separating it. For separation and recovery, reference may be made to the methods described herein. The method of the embodiment may include: heating a solution in which an indium precursor, a gallium precursor, and a sulfur precursor are dissolved in an organic solvent to a predetermined temperature (e.g., a temperature of about 100 °C to about 150 °C); adding a silver precursor to the heated solution; and reacting at the reaction temperature.

[0199] In an embodiment, the step of shell formation may include: adding a first semiconductor nanocrystal (or a particle including the first semiconductor nanocrystal), a metal precursor, a non-metal precursor, or a combination thereof to a reaction medium; and heating the reaction medium to a reaction temperature. The metal precursor and the non-metal precursor may be determined considering the desired shell composition. The metal precursor may include an indium precursor, a gallium precursor, a zinc precursor, or a combination thereof. The non-metal precursor may include a sulfur precursor.

[0200] In an embodiment, the step of shell formation includes:

[0201] preparing a reaction medium including a first precursor and an optional organic ligand in an organic solvent;

[0202] if necessary, heating the reaction medium to a predetermined temperature;

[0203] adding the first semiconductor nanocrystal and a second precursor to the reaction medium to obtain a reaction mixture; and

[0204] heating the reaction medium to a shell formation temperature and reacting for a first reaction time to form a second semiconductor nanoparticle, a third semiconductor nanoparticle, or a combination thereof. The predetermined temperature may be greater than or equal to about 120 °C and less than or equal to about 280 °C. The shell formation temperature may be greater than or equal to about 180 °C and less than or equal to about 380 °C. The first reaction time may be controlled to obtain a charge balance value as described herein for the semiconductor nanoparticles. The predetermined temperature and the shell formation temperature may be different. The shell formation temperature may be greater than the predetermined temperature. The shell formation temperature may be less than the predetermined temperature.

[0205] In an embodiment, the first shell precursor can be a gallium precursor and the second shell precursor can be a sulfur precursor. In an embodiment, the first shell precursor can include a sulfur precursor and the second precursor can be a gallium precursor, a zinc precursor, or a combination thereof (e.g., a gallium precursor and a zinc precursor).

[0206] In an embodiment, the method can further include the steps of: preparing an additional reaction medium including an organic ligand and a zinc precursor in an organic solvent; heating the additional reaction medium to a reaction temperature; adding the nanoparticles formed as above and a chalcogen precursor to carry out a further reaction and provide an outer layer (or a fourth semiconductor nanocrystal) including zinc chalcogenide on the nanoparticles. The chalcogen precursor can include a sulfur precursor, a selenium precursor, or a combination thereof. Details of the reaction temperature can refer to those described herein for the shell formation temperature.

[0207] In the preparation of the first semiconductor nanocrystal (core) or shell (e.g., the second semiconductor nanocrystal, the third semiconductor nanocrystal, or the fourth semiconductor nanocrystal), the molar ratio between precursors can be controlled to obtain a desired composition of each semiconductor nanocrystal or a desired composition of the semiconductor nanoparticles.

[0208] In an embodiment, the amount of the silver precursor can be greater than or equal to about 0.1 mole, greater than or equal to about 0.3 mole, greater than or equal to about 0.5 mole, greater than or equal to about 0.7 mole, greater than or equal to about 1 mole, greater than or equal to about 1.5 moles, greater than or equal to about 2 moles, or greater than or equal to about 2.5 moles per mole of indium. In an embodiment, the amount of the silver precursor can be less than or equal to about 10 moles, less than or equal to about 8 moles, less than or equal to about 6 moles, less than or equal to about 4 moles, less than or equal to about 2 moles, less than or equal to about 1.2 moles, less than or equal to about 1 mole, or less than or equal to about 0.5 moles per mole of indium.

[0209] In an embodiment, the amount of the gallium precursor can be greater than or equal to about 0.5 mole, greater than or equal to about 1 mole, greater than or equal to about 1.5 moles, greater than or equal to about 2 moles, or greater than or equal to about 2.5 moles per mole of indium. In an embodiment, the amount of the gallium precursor can be less than or equal to about 15 moles, less than or equal to about 12 moles, less than or equal to about 10 moles, less than or equal to about 8 moles, less than or equal to about 5 moles, or less than or equal to about 3 moles per mole of indium.

[0210] In an embodiment, the amount of the sulfur precursor can be greater than or equal to about 0.5 moles, greater than or equal to about 1 mole, greater than or equal to about 1.5 moles, greater than or equal to about 2 moles, greater than or equal to about 2.5 moles, greater than or equal to about 3 moles, greater than or equal to about 3.5 moles, greater than or equal to about 4 moles, or greater than or equal to about 4.5 moles per mole of indium. In an embodiment, the amount of the sulfur precursor can be less than or equal to about 20 moles, less than or equal to about 15 moles, less than or equal to about 10 moles, less than or equal to about 8 moles, less than or equal to about 6 moles, less than or equal to about 4 moles, or less than or equal to about 2 moles per mole of indium.

[0211] In the method of the embodiment, the amount of the zinc precursor per mole of indium can be appropriately selected in consideration of the composition and amount (such as thickness) of the semiconductor nanocrystals to be prepared and the type of the precursor.

[0212] The difference between the predetermined temperature and the shell formation temperature can be greater than or equal to about 10 °C, greater than or equal to about 20 °C, greater than or equal to about 30 °C, greater than or equal to about 40 °C, greater than or equal to about 50 °C, greater than or equal to about 60 °C, greater than or equal to about 70 °C, greater than or equal to about 80 °C, greater than or equal to about 90 °C, or greater than or equal to about 100 °C. The difference between the predetermined temperature and the shell formation temperature can be less than or equal to about 200 °C, less than or equal to about 190 °C, less than or equal to about 180 °C, less than or equal to about 170 °C, less than or equal to about 160 °C, less than or equal to about 150 °C, less than or equal to about 140 °C, less than or equal to about 130 °C, less than or equal to about 120 °C, less than or equal to about 110 °C, less than or equal to about 100 °C, less than or equal to about 90 °C, less than or equal to about 80 °C, less than or equal to about 70 °C, less than or equal to about 60 °C, less than or equal to about 50 °C, less than or equal to about 40 °C, less than or equal to about 30 °C, or less than or equal to about 20 °C.

[0213] The predetermined temperature can be greater than or equal to about 120 °C, greater than or equal to about 200 °C, greater than or equal to about 210 °C, greater than or equal to about 220 °C, greater than or equal to about 230 °C, greater than or equal to about 240 °C, or greater than or equal to about 250 °C. The predetermined temperature can be less than or equal to about 280 °C, less than or equal to about 275 °C, less than or equal to about 270 °C, less than or equal to about 265 °C, less than or equal to about 260 °C, less than or equal to about 255 °C, less than or equal to about 250 °C, less than or equal to about 240 °C, less than or equal to about 230 °C, less than or equal to about 220 °C, less than or equal to about 210 °C, less than or equal to about 200 °C, less than or equal to about 190 °C, less than or equal to about 180 °C, less than or equal to about 170 °C, less than or equal to about 160 °C, or less than or equal to about 150 °C.

[0214] The shell (or outer layer) forming temperature can be greater than or equal to about 240 °C, greater than or equal to about 245 °C, greater than or equal to about 250 °C, greater than or equal to about 255 °C, greater than or equal to about 260 °C, greater than or equal to about 265 °C, greater than or equal to about 270 °C, greater than or equal to about 275 °C, greater than or equal to about 280 °C, greater than or equal to about 285 °C, greater than or equal to about 290 °C, greater than or equal to about 295 °C, greater than or equal to about 300 °C, greater than or equal to about 305 °C, greater than or equal to about 310 °C, greater than or equal to about 315 °C, greater than or equal to about 320 °C, greater than or equal to about 330 °C, greater than or equal to about 335 °C, greater than or equal to about 340 °C or greater than or equal to about 345 °C. The shell (or outer layer) forming temperature can be less than or equal to about 380 °C, less than or equal to about 375 °C, less than or equal to about 370 °C, less than or equal to about 365 °C, less than or equal to about 360 °C, less than or equal to about 355 °C, less than or equal to about 350 °C, less than or equal to about 340 °C, less than or equal to about 330 °C, less than or equal to about 320 °C, less than or equal to about 310 °C, less than or equal to about 300 °C, less than or equal to about 290 °C, less than or equal to about 280 °C, less than or equal to about 270 °C, less than or equal to about 260 °C or less than or equal to about 250 °C.

[0215] In embodiments, the reaction time for shell (or outer layer) formation can be from about 1 minute to about 200 minutes, from about 10 minutes to about 3 hours, from about 20 minutes to about 150 minutes or from about 30 minutes to about 100 minutes. The reaction time for shell (or outer layer) formation can be selected considering the type of precursor, reaction temperature, desired composition of the final particles, etc.

[0216] The type of silver precursor is not particularly limited and can be appropriately selected. The silver precursor can include silver powder, alkylated silver compounds, silver alkoxide, silver carboxylate, silver acetylacetonate, silver nitrate, silver sulfate, silver halide, silver cyanide, silver hydroxide, silver oxide, silver peroxide, silver carbonate or combinations thereof. The silver precursor can include silver nitrate, silver acetate, silver acetylacetonate, silver chloride, silver bromide, silver iodide or combinations thereof.

[0217] The type of indium precursor is not particularly limited and can be appropriately selected. The indium precursor can include indium powder, alkylated indium compounds, indium alkoxide, indium carboxylate, indium nitrate, indium perchlorate, indium sulfate, indium acetylacetonate, indium halide, indium cyanide, indium hydroxide, indium oxide, indium peroxide, indium carbonate, indium acetate or combinations thereof. The indium precursor can include indium carboxylates (such as indium oleate and indium myristate), indium acetate, indium hydroxide, indium chloride, indium bromide, indium iodide or combinations thereof.

[0218] The type of the gallium precursor is not particularly limited and can be appropriately selected. The gallium precursor may include gallium powder, alkylated gallium compounds, gallium alkoxide, gallium carboxylate, gallium nitrate, gallium perchlorate, gallium sulfate, gallium acetylacetonate, gallium halide, gallium cyanide, gallium hydroxide, gallium oxide, gallium peroxide, gallium carbonate, or a combination thereof. The gallium precursor may include gallium chloride, gallium iodide, gallium bromide, gallium acetate, gallium acetylacetonate, gallium oleate, gallium palmitate, gallium stearate, gallium myristate, gallium hydroxide, or a combination thereof.

[0219] The type of the sulfur precursor is not particularly limited and can be appropriately selected. The sulfur precursor may be an organic solvent dispersion or a reaction product of sulfur and an organic solvent, for example, octadecene sulfide (S-ODE), trioctylphosphine sulfide (S-TOP), tributylphosphine sulfide (S-TBP), triphenylphosphine sulfide (S-TPP), trioctylamine sulfide (S-TOA), bis(trimethylsilylalkyl) sulfide, bis(trimethylsilyl) sulfide, mercaptopropylsilane, ammonium sulfide, sodium sulfide, C1 to C30 thiol compounds (such as α-toluenethiol, octanethiol, dodecanethiol, octadecenethiol, etc.), isocyanate compounds (such as cyclohexyl isothiocyanate, etc.), alkylene trithiocarbonate (such as ethylene trithiocarbonate, etc.), allyl mercaptan, thiourea compounds (such as (di)alkylthiourea having C1 to C40 alkyl, such as methylthiourea, dimethylthiourea, ethylthiourea, diethylthiourea, ethylmethylthiourea, dipropylthiourea, etc.; or arylthiourea such as phenylthiourea), or a combination thereof.

[0220] The selenium precursor (if present) may include selenium-trioctylphosphine (Se-TOP), selenium-tributylphosphine (Se-TBP), selenium-triphenylphosphine (Se-TPP), or a combination thereof.

[0221] The type of the zinc precursor is not particularly limited and can be appropriately selected. In the examples, the zinc precursor may include Zn metal powder, alkylated Zn compounds, Zn alcohol, Zn carboxylate, Zn nitrate, Zn perchlorate, Zn sulfate, Zn acetylacetonate, Zn halide, Zn cyanide, Zn hydroxide, Zn oxide, Zn peroxide, or a combination thereof. The zinc precursor may be dimethylzinc, diethylzinc, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zinc peroxide, zinc perchlorate, zinc sulfate, or a combination thereof.

[0222] The organic ligand may include R 3 COOH, R 3 NH 2 、R 3 2 NH, R 33 N, R 3 SH, R 3 H 2 PO, R 3 2 HPO, R 3 3 PO, R 3 H 2 P, R 3 2 HP, R 3 3 P, R 3 OH, R 3 COOR 4 , R 3 PO(OH) 2 , R 3 HPOOH, R 3 2 POOH or their combinations, wherein, R 3 and R 4Each is independently a substituted or unsubstituted C1-C40 (or C3-C24), aliphatic hydrocarbon group (e.g., alkyl, alkenyl or alkynyl) or a substituted or unsubstituted C6-C40 (or C6-C24) aromatic hydrocarbon group (e.g., C6-C20 aryl) or a combination thereof. The organic ligand can bind (e.g., link) to the surface of the semiconductor nanoparticle. In one aspect, the organic ligand can be in contact with or adjacent to the surface of the semiconductor nanoparticle. The organic ligand can be a ligand that binds to the surface of the semiconductor nanoparticle as prepared (i.e., a native ligand). The native ligand can be introduced during the manufacturing process of the semiconductor nanoparticle (such as a quantum dot) and can coordinate with the surface of the semiconductor nanoparticle. Non-limiting examples of the organic ligand can include: methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, benzyl mercaptan; methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, dodecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine; formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, benzoic acid; substituted or unsubstituted methylphosphine (e.g., trimethylphosphine, methyldiphenylphosphine, etc.), substituted or unsubstituted ethylphosphine (e.g., triethylphosphine, ethyldiphenylphosphine, etc.), substituted or unsubstituted propylphosphine, substituted or unsubstituted butylphosphine, substituted or unsubstituted pentylphosphine, substituted or unsubstituted octylphosphine (e.g., trioctylphosphine (TOP)), etc.; phosphine oxides, such as substituted or unsubstituted methylphosphine oxide (e.g., trimethylphosphine oxide, methyldiphenylphosphine oxide, etc.), substituted or unsubstituted ethylphosphine oxide (e.g., triethylphosphine oxide, ethyldiphenylphosphine oxide, etc.), substituted or unsubstituted propylphosphine oxide, substituted or unsubstituted butylphosphine oxide, substituted or unsubstituted octylphosphine oxide (e.g., trioctylphosphine oxide (TOPO)), etc.; diphenylphosphine, triphenylphosphine or their oxide compounds; C5-C20 alkylphosphinic acid or C5-C20 alkylphosphonic acid (such as phosphonic acid, hexylphosphinic acid, octylphosphinic acid, dodecylphosphinic acid, tetradecylphosphinic acid, hexadecylphosphinic acid, octadecylphosphinic acid, etc.), but the examples are not limited thereto. The organic ligand can be used alone or as a mixture of two or more.

[0223] The organic solvent may include: amine solvents (e.g., aliphatic amines, such as C1-C50 aliphatic amines); nitrogen-containing heterocyclic compounds, such as pyridine; C6-C40 aliphatic hydrocarbons (e.g., alkanes, alkenes, alkynes, etc.), such as hexadecane, octadecane, octadecene, or squalene; C6-C30 aromatic hydrocarbons, such as phenyldodecane, phenyltetradecane, phenylhexadecane, etc.; phosphines substituted with C6-C22 alkyl groups, such as trioctylphosphine; phosphine oxides substituted with C6-C22 alkyl groups, such as trioctylphosphine oxide, etc.; C12-C22 aromatic ethers, such as phenyl ether or benzyl ether, etc.; or combinations thereof. The amine solvent may be a compound having one or more (e.g., two or three) C1-C50, C2-C45, C3-C40, C4-C35, C5-C30, C6-C25, C7-C20, C8-C15, or C6-C22 aliphatic hydrocarbon groups (alkyl, alkenyl, or alkynyl). In embodiments, the amine solvent may be a C6-C22 primary amine, such as hexadecylamine and oleylamine; a C6-C22 secondary amine, such as dioctylamine, etc.; a C6-C22 tertiary amine, such as trioctylamine, etc.; or combinations thereof.

[0224] The amounts of the organic ligand and the precursors in the reaction medium can be appropriately selected taking into account the type of the solvent, the type of the organic ligand and each precursor, and the size and composition of the desired particles. The molar ratio between the precursors can be changed taking into account the desired molar ratio in the final semiconductor nanoparticles, the reactivity between the precursors, etc. In embodiments, there is no particular limitation on the manner of adding each precursor. In embodiments, the total amount of the precursors can be added at once. In embodiments, the total amount of the precursors can be divided into greater than or equal to about 2 equal parts and less than or equal to about 10 equal parts and added. The precursors can be added simultaneously or sequentially in a predetermined order. The reaction can be carried out in an inert gas atmosphere, in air, or in a vacuum state, but the embodiments are not limited thereto. In embodiments, after the reaction is completed, a non-solvent can be added to the final reaction solution to promote the separation (e.g., precipitation) of the semiconductor nanoparticles synthesized (e.g., with coordinated organic ligands).

[0225] The non-solvent can be a polar solvent that is miscible with the solvent used in the reaction but cannot disperse semiconductor nanoparticles. The non-solvent can be selected according to the solvent used in the reaction and can be, for example, acetone, ethanol, butanol, isopropanol, ethylene glycol, water, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), diethyl ether, formaldehyde, acetaldehyde, a solvent having a solubility parameter similar to that of the aforementioned solvents, or a combination thereof. Separation can be carried out by centrifugation, precipitation, chromatography, or distillation. The separated semiconductor nanoparticles can be washed by adding them to a washing solvent as needed. The washing solvent is not particularly limited, and a solvent having a solubility parameter similar to that of the organic solvent or ligand can be used. The non-solvent or washing solvent can be: an alcohol; an alkane solvent such as hexane, heptane, octane, etc.; an aromatic solvent such as chloroform, toluene, benzene, etc.; or a combination thereof, but the examples are not limited thereto.

[0226] Prior to the ligand exchange described herein, semiconductor nanoparticles as prepared and, for example, including native ligands (e.g., organic amines such as oleylamine) can be dispersed in a dispersion solvent and can form an organic solvent dispersion. The organic solvent dispersion may not include water and / or an organic solvent miscible with water. The dispersion solvent can be appropriately selected. The dispersion solvent can include the aforementioned organic solvents. The dispersion solvent can include a substituted or unsubstituted C1 to C40 aliphatic hydrocarbon, a substituted or unsubstituted C6 to C40 aromatic hydrocarbon, or a combination thereof.

[0227] The shape of the semiconductor nanoparticles thus prepared is not particularly limited and can include, for example, spherical, polyhedral, pyramidal, multi-armed, cubic, nanotubes, nanowires, nanofibers, nanosheets, or a combination thereof, but the examples are not limited thereto.

[0228] The semiconductor nanoparticles of the examples can include an organic ligand and / or an organic solvent on the surface of the semiconductor nanoparticles. The organic ligand and / or the organic solvent can be bound to the surface of the semiconductor nanoparticles of one or more examples.

[0229] Semiconductor nanoparticles based on group 11-13-16 compounds (such as AIGS-based quantum dots) may suffer significant deterioration of their luminescence properties due to the external environment (e.g., heat, air, light, etc.). The present inventors have found that when included in a composition for forming a complex, semiconductor nanoparticles comprising a group 11-13-16 compound and an amine compound (e.g., oleylamine) as a native ligand may exhibit significant deterioration of their optical properties compared to their optical properties in a solution state. To solve this problem, surface modification of the semiconductor nanoparticles with a metal salt compound has been considered. However, the present inventors have also found that it may still be difficult to form a composition that can exhibit desired properties / conditions (e.g., a dispersed state) with the semiconductor nanoparticles surface-modified with a metal salt compound. In addition, the present inventors have found that the surface-treated group 11-13-16-based semiconductor nanoparticles according to the prior art still suffer significant reduction of their luminescence properties during processes such as heat treatment for forming a complex. Due to this problem, there have been technical limitations in applying AIGS compound-based quantum dots to electronic devices (e.g., display devices). For example, the present inventors have found that in the case of semiconductor nanoparticles comprising a group 11-13-16 compound, when mixed with components (e.g., polymerizable monomers) for forming an ink composition for inkjet, or when fabricated into a complex, their optical properties (e.g., luminescence properties) may be significantly reduced. In display devices including micro-LEDs (e.g., TVs and watches, virtual reality (VR), augmented reality (AR)), etc., increased light conversion (e.g., luminescence efficiency) may be desired. Surprisingly, the present inventors have found that by employing a ligand and a metal halide together with the semiconductor nanoparticles as described herein, the luminescence properties of the semiconductor nanoparticles in a complex, for example, can be significantly improved.

[0230] In an embodiment, the ink composition comprises: semiconductor nanoparticles; a ligand as described herein (e.g., a first organic ligand); and a metal halide (e.g., a first metal halide (such as zinc halide or indium halide)). The (first organic) ligand and / or the metal halide may be bound (e.g., linked) to the surface of the semiconductor nanoparticles (or in contact with or adjacent to the surface of the semiconductor nanoparticles). The semiconductor nanoparticles may include a ligand and / or a metal halide (e.g., on their surface). The ink composition of the embodiment may provide a composite pattern including semiconductor nanoparticles having improved stability (e.g., chemical stability and thermal stability), and the complex prepared therefrom may exhibit desired luminescence properties.

[0231] The first organic ligand may include a compound represented by R 1 -COO-A, wherein R 1is a first organic group, and A represents hydrogen or a moiety attached to or bonded to the surface of the semiconductor nanoparticle (e.g., a point attached to the surface of the semiconductor nanoparticle). The first organic ligand may include at least one compound or at least two compounds. The first organic group may include a substituted or unsubstituted C 1-500 、C 2-300 、C 3-100 、C 4-50 、C 5-40 、C 5-10 、C 6-30 、C 7-15 or C 8-10 hydrocarbon group. In the hydrocarbon group, at least one methylene in the backbone or main chain may be replaced by -CO-, -O-, -COO-, -S-, -SO-, -NHCO- or a combination thereof.

[0232] The first organic ligand may include a carboxylic acid compound represented by R 1 -COOH or a moiety derived therefrom (e.g., a carboxyl group). The first organic group may include a moiety containing a carbon-carbon double bond. The moiety containing a carbon-carbon double bond may include a (meth)acrylate group. The first organic group or the first organic ligand may or may not include a piperidine moiety, an amine moiety (e.g., -NR-, where R is hydrogen or a C1 to C10 hydrocarbon group), an amide moiety or a combination thereof.

[0233] The first organic group or R 1 may include a moiety represented by E1-L-*, where E1 may be hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C2 to C10 alkenyl group, a (meth)acrylate group or a combination thereof, and L may be a direct bond (e.g., a single bond), a substituted or unsubstituted C1 to C50, C3 to C40, C5 to C15, C7 to C14 or C10 to C12 hydrocarbon group (e.g., an alkylene group, an alkenylene group or an alkynylene group), [R 3 -O] n (R 3 is an ethylene group, a propylene group, an isopropylidene group or a combination thereof, n is 1 to 140, 2 to 10, 3 to 7 or 4 to 6), -CO-, -O-, -SO-, -COO-, -S-, -NHCO- or a combination thereof, and * is a moiety connected to an adjacent atom (e.g., a carbonyl carbon). L may be a moiety formed by combining at least two of a substituted or unsubstituted C1 to C50 alkylene group, [R 3 -O] n (R 3 is an ethylene group, a propylene group, an isopropylidene group or a combination thereof, n is 1 to 140, 2 to 10, 3 to 7 or 4 to 6), -CO-, -O-, -SO-, -COO-, -S- and -NHCO-.

[0234] The first organic ligand may include: a carboxylic acid compound represented by Chemical Formula 2-1 or Chemical Formula 2-2; or a group or moiety derived from a carboxylic acid compound (e.g., represented by Chemical Formula 2-3 or Chemical Formula 2-4):

[0235] Chemical Formula 2-1

[0236]

[0237] Chemical Formula 2-2

[0238]

[0239] Chemical Formula 2-3

[0240]

[0241] Chemical Formula 2-4

[0242]

[0243] Wherein, in each of Chemical Formula 2-1, Chemical Formula 2-2, Chemical Formula 2-3, and Chemical Formula 2-4, independently,

[0244] R is the same or different and independently is hydrogen or a C1-C10 alkyl group (e.g., methyl),

[0245] E is hydrogen or a substituted or unsubstituted C1-C10 or C6-C8 (e.g., aliphatic or aromatic) hydrocarbon group (e.g., an alkyl group (such as methyl, alkenyl, or alkynyl)),

[0246] L is a direct bond, a substituted or unsubstituted C1-C50, C3-C40, C5-C15, C7-C14, or C10-C12 hydrocarbon group (e.g., an alkylene group, an alkenylene group, or an alkynylene group), [R 3 -O] n (R 3 is ethylene, propylene, isopropylidene, or a combination thereof, n is 1 to 140, 2 to 10, 3 to 7, or 4 to 6), -CO-, -O-, -SO-, -COO-, -S-, -NHCO-, or a combination thereof (e.g., a moiety formed by combining at least two of the foregoing groups),

[0247] A is a direct bond, a substituted or unsubstituted C1-C50, C3-C40, C5-C15, or C7-C14 hydrocarbon group (e.g., an alkylene group, an alkenylene group, or an alkynylene group), [R 3 -O] n (R 3is ethylene, propylene, isopropylidene, or a combination thereof, n is from 1 to 140, 2 to 10, 3 to 7, or 4 to 6), -CO-, -O-, -SO-, -COO-, -S-, -NHCO-, or a combination thereof (e.g., a moiety formed by combining at least two of the foregoing groups), and

[0248] * is a moiety connected to the semiconductor nanoparticle (e.g., a point attached to the semiconductor nanoparticle).

[0249] In the compound, the COOH group can be converted to COO- (e.g., carboxylate) to enable the ligand to bind to the surface of the semiconductor nanoparticle.

[0250] In the definition of L or A, at least one methylene group in the hydrocarbon group can be replaced by -CO-, -O-, -SO-, -COO-, -S-, -NHCO-, or a combination thereof (e.g., a moiety formed by combining at least two of the foregoing groups).

[0251] The first organic ligand can include a compound represented by any of the following formulas or a moiety derived therefrom (e.g., a carboxylate moiety):

[0252]

[0253]

[0254] wherein, n1 is an integer from 1 to 100, 3 to 80, 5 to 70, 7 to 60, 9 to 50, 10 to 45, or 15 to 35, and n2 is an integer from 1 to 20, 2 to 15, or 3 to 10.

[0255] The first organic ligand can include a small molecule compound (e.g., a non-polymeric compound) having a molecular weight greater than or equal to about 10 g / mol, greater than or equal to about 50 g / mol, or greater than or equal to about 120 g / mol and less than or equal to about 800 g / mol, less than or equal to about 500 g / mol, less than or equal to about 400 g / mol, less than or equal to about 300 g / mol, or less than or equal to about 250 g / mol.

[0256] In an embodiment, the semiconductor nanoparticle can also have a native ligand (such as an amine compound) derived from the organic ligand compound used in the synthesis process (e.g., a primary amine having one aliphatic alkyl group (such as oleylamine)). Examples of the organic ligand compound for the native ligand are the same as those described herein for the organic ligand.

[0257] The present inventors have found that in the case of an ink composition containing semiconductor nanoparticles having only native ligands, it may be difficult to ensure the dispersibility of the semiconductor nanoparticles in the ink composition. Without wishing to be bound by any theory, it is believed that monomers contained in an ink composition for inkjet printing may be incompatible with the native ligands bound to the semiconductor nanoparticles and may therefore not provide the desired dispersibility. In the ink compositions of the examples, semiconductor nanoparticles having a first organic ligand on their surface can be well dispersed in the liquid carrier (e.g., monomer, or solvent if present) of the inkjet composition.

[0258] Surprisingly, the present inventors have found that by including a first organic ligand and a metal halide in the ink composition as described herein, deterioration of the properties (e.g., luminescence efficiency) of the semiconductor nanoparticles that might otherwise occur during the process of forming the complex can be significantly suppressed.

[0259] In an example, the first organic ligand can be attached (e.g., bound) to the surface of the semiconductor nanoparticles, whereby after stirring the semiconductor nanoparticles having the bound first organic ligand in a non-solvent or solvent for a predetermined time (e.g., 30 minutes to 3 hours, 1 hour to 2 hours, or a combination thereof), the first organic ligand does not separate from the semiconductor nanoparticles.

[0260] Without wishing to be bound by any theory, it is believed that by combining with metals (e.g., gallium, zinc, or a combination thereof) present on the surface of the semiconductor nanoparticles, the carboxyl groups of the first organic ligand can passivate the surface of the semiconductor nanoparticles in the form of carboxylates.

[0261] Semiconductor nanoparticles having (e.g., on the surface) a first organic ligand can be obtained according to the methods described herein. The method can involve a ligand exchange reaction.

[0262] In the ink compositions of the examples or in the semiconductor nanoparticle-polymer complexes of the examples, the metal halide can include metal chlorides, metal fluorides, metal bromides, metal iodides, or a combination thereof. The metal halide (e.g., the first metal halide) can include metal chlorides. The metal halide can include zinc halides, indium halides, gallium halides, or a combination thereof. The metal halide can include zinc chloride, zinc bromide, zinc fluoride, zinc iodide, indium chloride, indium bromide, indium fluoride, indium iodide, gallium chloride, gallium bromide, gallium fluoride, gallium iodide, or a combination thereof. In an example, the metal halide can include indium halide (e.g., indium chloride). The metal halide can be distributed (either throughout or relatively uniformly) and present in the ink compositions or complexes described herein. The ink compositions of the examples or the complexes of the examples can include a metal halide present spaced apart from the semiconductor nanoparticles.

[0263] According to an embodiment, a method for preparing an ink composition includes contacting or mixing a monomer with semiconductor nanoparticles (e.g., having or containing a first organic ligand) and optionally a metal halide. The method according to an embodiment may include: dissolving a metal halide in an organic solvent (e.g., a ketone solvent such as acetone, a C1 to C10 alcohol solvent, or a combination thereof) to prepare a metal halide solution; adding the semiconductor nanoparticles and the metal halide solution to the monomer (and mixing with the monomer). The semiconductor nanoparticles may be ligand-exchanged according to the manner described herein and optionally precipitated and washed.

[0264] In the method of the embodiment, preparing semiconductor nanoparticles containing a first organic ligand (e.g., surface-modified with a first organic ligand) may include contacting or mixing (blending) semiconductor nanocrystal particles containing a Group 11-13-16 compound with a first organic ligand and a metal salt compound (e.g., a second metal halide) in an organic solvent. During the contacting or blending, a ligand exchange may occur between the surface of the semiconductor nanocrystal particles and the first organic ligand, and semiconductor nanoparticles surface-treated with the first organic ligand may be obtained.

[0265] The semiconductor nanocrystal particles containing a Group 11-13-16 compound may include (or may be) zinc salt-treated nanocrystal particles. In other words, the semiconductor nanocrystal particles may first be zinc salt-treated and then undergo a ligand exchange reaction. The zinc salt treatment may be carried out by contacting the semiconductor nanocrystal particles (before ligand exchange or semiconductor nanocrystal particles with native ligands) with a zinc salt compound in an organic solvent (e.g., in the absence of a first organic ligand).

[0266] The zinc salt treatment temperature may be 20 °C or higher, 30 °C or higher, 40 °C or higher, 45 °C or higher, or 50 °C or higher. The zinc salt treatment temperature or the ligand exchange reaction temperature may be 150 °C or lower, 100 °C or lower, 80 °C or lower, 60 °C or lower, 55 °C or lower, or 45 °C or lower.

[0267] The method may further include preparing a dispersion in which the zinc salt-treated nanocrystal particles are dispersed in an organic solvent, and the first organic ligand and the metal salt compound may be added to the dispersion for mixing or contacting. In the method of the embodiment, through mixing or contacting, a ligand exchange reaction may occur on the surface of the semiconductor nanocrystal particles. The metal salt compound may include a zinc salt compound. The metal salt compound may include an indium salt compound. The metal salt compound may include an indium salt compound and a zinc salt compound.

[0268] The semiconductor nanocrystal particles may include a first semiconductor nanocrystal and may also include a second semiconductor nanocrystal, a third semiconductor nanocrystal, an inorganic material layer containing a zinc chalcogenide (e.g., a fourth semiconductor nanocrystal), or a combination thereof. Details of the first semiconductor nanocrystal, the second semiconductor nanocrystal, the third semiconductor nanocrystal, the fourth semiconductor nanocrystal, and the inorganic material layer or the outermost layer, as well as details regarding their manufacture, may be incorporated herein by reference.

[0269] The inventors have found that nanocrystal particles having native ligands may not readily participate in ligand exchange reactions involving a first organic ligand. In the methods of the examples, the ligand exchange reaction may involve the use of a metal salt compound. In an example, the ligand exchange reaction may be carried out in the presence of a metal salt compound to obtain semiconductor nanoparticles having a first organic ligand in contact with or adjacent to (e.g., bound to) their surface. In an example, after the nanocrystal particles having native ligands are first treated with a zinc salt, they may undergo a ligand exchange reaction, for example, in the presence of an additional metal salt compound (e.g., zinc halide or indium halide).

[0270] The metal salt compound may include zinc, indium, gallium, or a combination thereof. The metal salt compound may include: a C1 to C50 or C8 to C20 carboxylate compound (e.g., oleate, stearate, myristate, etc.); a halide compound (e.g., chloride, fluoride, bromide, or iodide); or a combination thereof. The metal salt compound may include zinc carboxylate (e.g., zinc oleate, zinc stearate, zinc myristate, etc.), indium carboxylate (e.g., indium oleate, indium stearate, indium myristate, etc.), gallium carboxylate (e.g., gallium oleate, gallium stearate, gallium myristate, etc.), zinc halide (e.g., zinc chloride, zinc bromide, zinc iodide, zinc fluoride, etc.), indium halide (e.g., indium chloride, indium bromide, indium iodide, etc.), gallium halide (e.g., gallium chloride, gallium bromide, gallium iodide, etc.), or a combination thereof. The metal salt compound may include a second metal halide.

[0271] Details of the first organic ligand may be the same as those described herein.

[0272] Taking into account the organic ligand, the native ligand, and the zinc salt compound, an organic solvent may be appropriately selected. The organic solvent may include a C6 to C40 aliphatic hydrocarbon (e.g., alkane, alkene, alkyne) solvent (such as octane, hexane, heptane, etc.); a C6 to C30 aromatic hydrocarbon solvent (such as toluene, xylene, etc.); or a combination thereof.

[0273] The temperature of blending (or ligand exchange) can be greater than or equal to about 20 °C, greater than or equal to about 30 °C, greater than or equal to about 40 °C, greater than or equal to about 45 °C, or greater than or equal to about 50 °C. The temperature of blending (or ligand exchange) can be less than or equal to about 150 °C, less than or equal to about 100 °C, less than or equal to about 80 °C, less than or equal to about 60 °C, less than or equal to about 55 °C, or less than or equal to about 45 °C.

[0274] Blending (e.g., ligand exchange reaction) can be carried out for greater than or equal to about 50 minutes, greater than or equal to about 1 hour, greater than or equal to about 90 minutes, greater than or equal to about 100 minutes, greater than or equal to about 2 hours, or greater than or equal to about 3 hours, and less than or equal to about 5 days, less than or equal to about 3 days, less than or equal to about 2 days, less than or equal to about 1 day, or less than or equal to about 12 hours.

[0275] The amount of the zinc salt compound or metal salt compound can be appropriately selected in consideration of the type of the compound, the type of the ligand compound, the desired degree of exchange, etc.

[0276] In the examples, the amount of the zinc salt compound or metal salt compound (e.g., indium salt compound) used can be greater than or equal to about 10 moles, greater than or equal to about 100 moles, greater than or equal to about 300 moles, greater than or equal to about 500 moles, greater than or equal to about 600 moles, greater than or equal to about 700 moles, greater than or equal to about 1000 moles, greater than or equal to about 1500 moles, greater than or equal to about 2000 moles, greater than or equal to about 2500 moles, greater than or equal to about 3000 moles, greater than or equal to about 3500 moles, greater than or equal to about 4000 moles, greater than or equal to about 4500 moles, greater than or equal to about 5000 moles, greater than or equal to about 5500 moles, greater than or equal to about 6000 moles, greater than or equal to about 6500 moles, greater than or equal to about 7000 moles, greater than or equal to about 15000 moles, or greater than or equal to about 20000 moles per mole of semiconductor nanocrystal particles and less than or equal to about 150000 moles, less than or equal to about 100000 moles, less than or equal to about 50000 moles, less than or equal to about 30000 moles, less than or equal to about 20000 moles, less than or equal to about 10000 moles, less than or equal to about 5000 moles, less than or equal to about 1000 moles, less than or equal to about 500 moles, or less than or equal to about 100 moles.

[0277] The metal salt compound (e.g., the second metal halide) can be used in a range where the amount of the organic ligand compound (e.g., the first organic ligand compound) used per 1 mol is 0.01 mol or more, 0.05 mol or more, 0.1 mol or more, or 0.3 mol or more and 1 mol or less, 0.5 mol or less, or 0.1 mol or less.

[0278] In the method of the examples, based on one mole of semiconductor nanocrystal particles, the amount of the first organic ligand used can be 10 moles or more, 50 moles or more, 100 moles or more, 300 moles or more, 500 moles or more, 600 moles or more, 700 moles or more, 1000 moles or more, 1500 moles or more, 2000 moles or more, 2500 moles or more, 3000 moles or more, 3500 moles or more, 4000 moles or more, 4500 moles or more, 5000 moles or more, 5500 moles or more, 6000 moles or more, 6500 moles or more, 7000 moles or more, 7500 moles or more, 8000 moles or more, 8500 moles or more, 9000 moles or more, 10000 moles or more, 12000 moles or more, 15000 moles or more, 17000 moles or more, 19000 moles or more, or 19500 moles or more and 40000 moles or less, 30000 moles or less, or 20000 moles or less.

[0279] In the examples, compared with the (e.g., synthesized) crude semiconductor nanoparticles, the ligand-exchanged semiconductor nanoparticles can exhibit an increased amount of organic matter. In the examples, the amount of organic matter in the semiconductor nanoparticles can be greater than or equal to about 15 wt%, greater than or equal to about 20 wt%, greater than or equal to about 25 wt%, greater than or equal to about 29 wt%, greater than or equal to about 30 wt%, greater than or equal to about 33 wt%, or greater than or equal to about 35 wt% and less than or equal to about 60 wt%, less than or equal to about 55 wt%, less than or equal to about 45 wt%, or less than or equal to about 40 wt%.

[0280] In embodiments, ligand-exchanged semiconductor nanoparticles may exhibit different dispersibility than before ligand exchange. In embodiments, semiconductor nanoparticles containing a first organic ligand may be dispersed in C1-C10 alcohols (e.g., ethanol, methanol, etc.), C3-C30 ketone solvents (such as acetone), or combinations thereof, and the dispersions thus prepared may exhibit a particle size (hereinafter, DLS particle size) measured by dynamic light scattering analysis as follows: less than or equal to about 1 micron, less than or equal to about 900 nm, less than or equal to about 800 nm, less than or equal to about 700 nm, less than or equal to about 600 nm, less than or equal to about 500 nm, less than or equal to about 400 nm, less than or equal to about 300 nm, less than or equal to about 200 nm, less than or equal to about 100 nm, less than or equal to about 90 nm, less than or equal to about 80 nm, less than or equal to about 70 nm, less than or equal to about 60 nm, or less than or equal to about 50 nm. The DLS particle size may be greater than or equal to about 1 nm, greater than or equal to about 3 nm, greater than or equal to about 5 nm, greater than or equal to about 7 nm, greater than or equal to about 9 nm, greater than or equal to about 10 nm, or greater than or equal to about 20 nm.

[0281] In embodiments, when a C1-C30 or C6-C14 aliphatic hydrocarbon solvent (e.g., an alkane solvent, an alkene solvent, or an alkyne solvent) is added to the dispersion, semiconductor nanoparticles having a first organic ligand may precipitate. Ligand-exchanged semiconductor nanoparticles (e.g., semiconductor nanoparticles having a first organic ligand) may be well dispersed in a liquid carrier for an ink composition (e.g., a monomer described herein).

[0282] In the ink composition (or the semiconductor nanoparticle-polymer composite of the embodiment) or in the semiconductor nanoparticles therein, the molar ratio of zinc to a Group 16 element (e.g., sulfur) (e.g., the Zn to sulfur molar ratio) may be less than or equal to about 0.8:1, less than or equal to about 0.3:1, or less than or equal to about 0.25:1. The molar ratio of zinc to a Group 16 element (e.g., sulfur) (e.g., the Zn to sulfur molar ratio) may be greater than or equal to about 0.01:1, greater than or equal to about 0.05:1, or greater than or equal to about 0.1:1.

[0283] In the ink composition (or semiconductor nanoparticle-polymer composite) or in the semiconductor nanoparticles therein, the molar ratio of zinc to silver (Zn:Ag) can be greater than or equal to about 0.3:1, greater than or equal to about 0.35:1, greater than or equal to about 0.4:1, greater than or equal to about 0.45:1, greater than or equal to about 0.5:1, greater than or equal to about 0.55:1, greater than or equal to about 0.6:1, greater than or equal to about 0.64:1, greater than or equal to about 0.65:1, greater than or equal to about 0.7:1, greater than or equal to about 0.75:1, greater than or equal to about 0.8:1, greater than or equal to about 0.85:1, greater than or equal to about 0.9:1, greater than or equal to about 0.95:1, greater than or equal to about 1:1, greater than or equal to about 1.2:1, greater than or equal to about 1.4:1, greater than or equal to about 1.6:1, greater than or equal to about 1.7:1, greater than or equal to about 1.9:1, greater than or equal to about 2:1, greater than or equal to about 2.5:1, greater than or equal to about 3:1, greater than or equal to about 3.5:1, or greater than or equal to about 4:1. In the ink composition (or semiconductor nanoparticle-polymer composite) or in the semiconductor nanoparticles therein, the molar ratio of zinc to silver (Zn:Ag) can be less than or equal to about 5:1, less than or equal to about 4.7:1, less than or equal to about 4.4:1, less than or equal to about 4.1:1, less than or equal to about 3.9:1, less than or equal to about 3.7:1, less than or equal to about 3.5:1, less than or equal to about 3:1, less than or equal to about 2.7:1, less than or equal to about 2.6:1, less than or equal to about 2.3:1, less than or equal to about 2.25:1, less than or equal to about 1:1, or less than or equal to about 0.9:1.

[0284] In the ink composition (or semiconductor nanoparticle-polymer composite) or in the semiconductor nanoparticles, the molar ratio of zinc to indium (Zn:In) can be the same as described herein. The molar ratio of zinc to indium can be greater than or equal to about 0.7:1, greater than or equal to about 0.9:1, greater than or equal to about 1.1:1, greater than or equal to about 1.3:1, greater than or equal to about 1.5:1, greater than or equal to about 1.7:1, greater than or equal to about 1.9:1, greater than or equal to about 2.1:1, greater than or equal to about 2.3:1, greater than or equal to about 2.5:1, greater than or equal to about 2.7:1, greater than or equal to about 2.9:1, greater than or equal to about 3:1, or greater than or equal to about 4.5:1. The molar ratio of zinc to indium (Zn:In) can be less than or equal to about 10:1, less than or equal to about 8:1, less than or equal to about 6:1, less than or equal to about 5:1, less than or equal to about 4.5:1, less than or equal to about 4:1, less than or equal to about 3.5:1, less than or equal to about 2:1, less than or equal to about 1.7:1, or less than or equal to about 1.6:1.

[0285] In the ink composition (or semiconductor nanoparticle-polymer composite) or in the semiconductor nanoparticles, the molar ratio of zinc to gallium (Zn:Ga) can be greater than or equal to about 0.1:1, greater than or equal to about 0.2:1, greater than or equal to about 0.3:1, greater than or equal to about 0.35:1, greater than or equal to about 0.4:1, greater than or equal to about 0.45:1, greater than or equal to about 0.5:1, greater than or equal to about 0.6:1, or greater than or equal to about 1.65:1. In the ink composition (or semiconductor nanoparticle-polymer composite) or in the semiconductor nanoparticles therein, the molar ratio of zinc to gallium (Zn:Ga) can be less than or equal to about 3:1, less than or equal to about 2.8:1, less than or equal to about 2.5:1, less than or equal to about 2:1, less than or equal to about 1.9:1, less than or equal to about 1.7:1, less than or equal to about 1.5:1, less than or equal to about 1.4:1, less than or equal to about 1.2:1, less than or equal to about 1.1:1, less than or equal to about 0.9:1, less than or equal to about 0.8:1, less than or equal to about 0.7:1, less than or equal to about 0.6:1, or less than or equal to about 0.49:1.

[0286] In the ink composition (or semiconductor nanoparticle-polymer composite) or in the semiconductor nanoparticles, the molar ratio of the number of moles of zinc to the total number of moles of gallium, indium, and silver (Zn:(Ga+In+Ag)) can be greater than or equal to about 0.05:1, greater than or equal to about 0.1:1, greater than or equal to about 0.2:1, greater than or equal to about 0.25:1, greater than or equal to about 0.27:1, greater than or equal to about 0.29:1, greater than or equal to about 0.3:1, greater than or equal to about 0.35:1, greater than or equal to about 0.4:1, greater than or equal to about 0.5:1, greater than or equal to about 0.55:1, greater than or equal to about 0.6:1, greater than or equal to about 0.75:1, or greater than or equal to about 0.8:1. In the ink composition (or semiconductor nanoparticle-polymer composite) or in the semiconductor nanoparticles, the molar ratio of the number of moles of zinc to the total number of moles of gallium, indium, and silver (Zn:(Ga+In+Ag)) can be less than or equal to about 2:1, less than or equal to about 1.7:1, less than or equal to about 1.4:1, less than or equal to about 1.1:1, less than or equal to about 0.9:1, less than or equal to about 0.87:1, less than or equal to about 0.7:1, less than or equal to about 0.5:1, or less than or equal to about 0.45:1.

[0287] In the ink composition (or semiconductor nanoparticle-polymer composite) or in the semiconductor nanoparticles, the molar ratio of zinc to the sum of gallium and indium (Zn:(Ga+In)) can be greater than or equal to about 0.05:1, greater than or equal to about 0.1:1, greater than or equal to about 0.2:1, greater than or equal to about 0.25:1, greater than or equal to about 0.3:1, greater than or equal to about 0.35:1, greater than or equal to about 0.46:1 or greater than or equal to about 1.3:1. In the ink composition (or semiconductor nanoparticle-polymer composite) or in the semiconductor nanoparticles, the molar ratio of zinc to the sum of gallium and indium can be less than or equal to about 10:1, less than or equal to about 2:1, less than or equal to about 1.7:1, less than or equal to about 1.53:1, less than or equal to about 1.45:1, less than or equal to about 1.4:1, less than or equal to about 1.37:1, less than or equal to about 1.33:1, less than or equal to about 1.1:1, less than or equal to about 0.9:1, less than or equal to about 0.7:1, less than or equal to about 0.5:1 or less than or equal to about 0.45:1.

[0288] Taking into account the desired end use (e.g., as a light-emitting color filter), the amount of semiconductor nanoparticles in the ink composition or in the semiconductor nanoparticle-polymer composite can be appropriately adjusted. In embodiments, based on the total weight or total solids content of the composition or composite (hereinafter, "total weight" or "total solids content" can be the total weight or total solids content of the composition or the total weight of the composite), the amount of semiconductor nanoparticles in the ink composition (or in the semiconductor nanoparticle-polymer composite) can be greater than or equal to about 1 wt%, e.g., greater than or equal to about 2 wt%, greater than or equal to about 3 wt%, greater than or equal to about 4 wt%, greater than or equal to about 5 wt%, greater than or equal to about 6 wt%, greater than or equal to about 7 wt%, greater than or equal to about 8 wt%, greater than or equal to about 9 wt%, greater than or equal to about 10 wt%, greater than or equal to about 12 wt%, greater than or equal to about 14 wt%, greater than or equal to about 15 wt%, greater than or equal to about 17 wt%, greater than or equal to about 19 wt%, greater than or equal to about 20 wt%, greater than or equal to about 23 wt%, greater than or equal to about 25 wt%, greater than or equal to about 27 wt%, greater than or equal to about 30 wt%, greater than or equal to about 33 wt%, greater than or equal to about 35 wt%, greater than or equal to about 37 wt% or greater than or equal to about 40 wt%. Based on the total weight or total solids content of the composition or composite, the amount of semiconductor nanoparticles in the ink composition (or composite) can be less than or equal to about 99 wt%, less than or equal to about 95 wt%, less than or equal to about 80 wt%, less than or equal to about 70 wt%, e.g., less than or equal to about 65 wt%, less than or equal to about 60 wt%, less than or equal to about 55 wt%, less than or equal to about 50 wt% or less than or equal to about 45 wt%. The weight percentage of a given component in the composition relative to the total solids content can represent the amount of the given component in the composite or in the solvent-free composition as described herein. The total solids content is the total weight of the solids content. In embodiments, the total weight of the composition or composite can be the total weight of the solids content.

[0289] In the ink composition of the embodiments or in the method thereof, the amount (or usage amount) of the (first) metal halide can be greater than or equal to about 0.1 mole, greater than or equal to about 0.3 mole, greater than or equal to about 0.5 mole, greater than or equal to about 1 mole, greater than or equal to about 5 moles, greater than or equal to about 10 moles, greater than or equal to about 20 moles, greater than or equal to about 30 moles, greater than or equal to about 40 moles, greater than or equal to about 50 moles, greater than or equal to about 60 moles, greater than or equal to about 70 moles, greater than or equal to about 100 moles, greater than or equal to about 150 moles, greater than or equal to about 200 moles per mole of semiconductor nanoparticles. In the ink composition of the embodiments or in the method thereof, the amount (or usage amount) of the (first) metal halide can be 600 moles or less, 500 moles or less, 400 moles or less, 300 moles or less, 260 moles or less, 220 moles or less, 180 moles or less, 160 moles or less, 140 moles or less, 120 moles or less, 100 moles or less, 80 moles or less, 60 moles or less, or 40 moles or less.

[0290] In an embodiment of the ink composition, the polymerizable monomer (e.g., monomer) may include a compound containing one or more carbon-carbon double bonds (e.g., greater than or equal to 2 or greater than or equal to 3 and less than or equal to 10 carbon-carbon double bonds). The monomer can be a precursor for an insulating polymer. The monomer can be polymerized by using light or heat.

[0291] In the ink composition, the monomer may include a compound represented by Chemical Formula 1:

[0292] Chemical Formula 1

[0293]

[0294] In Chemical Formula 1, X is a C2 to C30 organic group having a carbon-carbon double bond,

[0295] L is a single bond, a carbon atom, a substituted or unsubstituted C1 to C50 alkylene group, a substituted or unsubstituted C2 to C50 alkenylene group, a substituted or unsubstituted C3 to C50 (e.g., C6 to C30) cycloalkylene group, a substituted or unsubstituted C3 to C50 (e.g., C6 to C30) cycloalkenylene group, a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C3 to C30 heteroarylene group, a group having at least one oxyalkylene unit (e.g., (R-O) n, wherein R is a substituted or unsubstituted C1-C10 alkylene group (such as methylene, ethylene, isopropylidene, butylene), and n is greater than or equal to about 1, greater than or equal to about 3, greater than or equal to about 5 or greater than or equal to about 10 and less than or equal to about 500, less than or equal to about 300, less than or equal to about 100, less than or equal to about 50, less than or equal to about 15 or less), sulfonyl (-S(=O) 2 -), carbonyl (-C(=O)-), ether (-O-), thioether (-S-), sulfoxide (-S(=O)-), ester (-C(=O)O-), amide (-C(=O)NR-) (wherein R is hydrogen or a straight-chain or branched-chain alkyl group of C1-C10), imine (-NR-) (wherein R is hydrogen or a straight-chain or branched-chain alkyl group of C1-C10), or a combination thereof,

[0296] Y is a single bond, a substituted or unsubstituted C1-C50 alkylene group, a substituted or unsubstituted C2-C50 alkenylene group, sulfonyl (-S(=O) 2 -), carbonyl (-C(=O)-), ether (-O-), thioether (-S-), sulfoxide (-S(=O)-), ester (-C(=O)O-), amide (-C(=O)NR-) (wherein R is hydrogen or a straight-chain or branched-chain alkyl group of C1-C10), imine (-NR-) (wherein R is hydrogen or a straight-chain or branched-chain alkyl group of C1-C10), or a combination thereof,

[0297] n is an integer greater than or equal to 1 (e.g., 1, 2, 3, or 4),

[0298] k is an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8).

[0299] The sum of n and k is an integer of 2 or greater (e.g., 3 or greater, or 4 or greater and 10 or less, or 5 or less).

[0300] In Chemical Formula 1, n can be determined by the valence of Y, and k can be determined by the valence of L.

[0301] In Chemical Formula 1, X may include a vinyl group, a (meth)acrylate group, or a combination thereof.

[0302] The monomer may include polyethylene glycol methacrylate, polypropylene glycol methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, substituted or unsubstituted alkyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy acrylate, bisphenol A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenolic epoxy (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, tris(acryloyloxyethyl) phosphate, propylene glycol di(meth)acrylate, diacryloyloxyalkane, or a combination thereof.

[0303] In an embodiment, the monomer may include a polymerizable monomer (e.g., a photopolymerizable monomer). The monomer may include a substituted or unsubstituted di(meth)acrylate compound, a substituted or unsubstituted tri(meth)acrylate compound, a substituted or unsubstituted tetra(meth)acrylate compound, a substituted or unsubstituted penta(meth)acrylate compound, a substituted or unsubstituted hexa(meth)acrylate compound, or a combination thereof.

[0304] Based on the total weight of the ink composition, the amount of the polymerizable monomer may be greater than or equal to about 0.5 wt%, e.g., greater than or equal to about 1 wt%, greater than or equal to about 2 wt%, greater than or equal to about 3 wt%, greater than or equal to about 5 wt%, greater than or equal to about 10 wt%, greater than or equal to about 20 wt%, greater than or equal to about 30 wt%, or greater than or equal to about 40 wt%. Based on the total weight of the ink composition, the amount of the polymerizable monomer may be less than or equal to about 99 wt%, less than or equal to about 90 wt%, less than or equal to about 80 wt%, less than or equal to about 70 wt%, less than or equal to about 60 wt%, less than or equal to about 50 wt%, less than or equal to about 45 wt%, less than or equal to about 28 wt%, less than or equal to about 25 wt%, less than or equal to about 23 wt%, less than or equal to about 20 wt%, less than or equal to about 18 wt%, less than or equal to about 17 wt%, less than or equal to about 16 wt%, or less than or equal to about 15 wt%.

[0305] The ink composition may further include an initiator, metal oxide (nano or fine) particles, or a combination thereof.

[0306] (Photo)initiators included in the ink composition can be used for (photo)polymerization of the above monomers. An initiator is a compound that accelerates a radical reaction (e.g., radical polymerization of monomers) by generating radical chemicals under mild conditions (e.g., by heat or light). The initiator can be a thermal initiator or a photoinitiator. The initiator is not particularly limited and can be appropriately selected.

[0307] Thermal initiators can include, but are not limited to, azobisisobutyronitrile, benzoyl peroxide, etc. Photoinitiators can include, but are not limited to, triazine compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, oxime ester compounds, aminoketone compounds, phosphine or phosphine oxide compounds, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, biimidazole compounds, or combinations thereof. The initiator can include Igacure 754, hydroxycyclohexyl phenyl ketone (Irgacure 184, CAS 947-19-3), 2,4,6-trimethylbenzoyl diphenylphosphine oxide (Irgacure TPO, CAS 75980-60-8), 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl phenylacetate, or combinations thereof.

[0308] In the ink composition, the amount of the initiator can be appropriately adjusted in consideration of the type and content of the polymerizable monomer. In the examples, based on the total weight of the ink composition (or the total weight of the solid content), the amount of the initiator can be greater than or equal to about 0.01 wt% (e.g., greater than or equal to about 1 wt%) and / or less than or equal to about 10 wt% (e.g., less than or equal to about 9 wt%, less than or equal to about 8 wt%, less than or equal to about 7 wt%, less than or equal to about 6 wt%, or less than or equal to about 5 wt%), but the examples are not limited thereto.

[0309] Metal oxide particles can include TiO 2 、SiO 2 、BaTiO 3 、Ba 2 TiO 4 、ZnO, or combinations thereof. In the ink composition (or composite), based on the total weight of the ink composition (or the total weight of the solid content), the amount of the metal oxide particles can be greater than or equal to about 1 wt%, greater than or equal to about 2 wt%, greater than or equal to about 3 wt%, greater than or equal to about 5 wt%, or greater than or equal to about 10 wt% to less than or equal to about 50 wt%, less than or equal to about 40 wt%, less than or equal to about 30 wt%, less than or equal to about 25 wt%, less than or equal to about 20 wt%, less than or equal to about 15 wt%, less than or equal to about 10 wt%, less than or equal to about 7 wt%, less than or equal to about 5 wt%, or less than or equal to about 3 wt%.

[0310] The diameter of the metal oxide fine particles is not particularly limited and can be appropriately selected. The diameter of the metal oxide fine particles can be greater than or equal to about 100 nm (e.g., greater than or equal to about 150 nm or greater than or equal to about 200 nm) and less than or equal to about 1000 nm or less than or equal to about 800 nm.

[0311] The ink composition according to the embodiments can provide semiconductor nanoparticle-polymer composites (e.g., composites) or patterns thereof via polymerization (e.g., photopolymerization). In an embodiment, a composite including a matrix and the above-described semiconductor nanoparticles (e.g., nanoparticles) dispersed in the matrix is provided. The nanoparticles of the embodiments or composites containing one or more nanoparticles can emit light of a desired wavelength (e.g., a first light) with improved optical properties (e.g., increased luminescence efficiency and narrower full width at half maximum) and an increased level of blue light absorption (e.g., improved incident light absorption). The composite can be in the form of a sheet. The composite can be in the form of a patterned film.

[0312] In one aspect, the semiconductor nanoparticle-polymer composite includes a polymerization product (e.g., a polymer) of a polymerizable monomer and semiconductor nanoparticles. The semiconductor nanoparticle-polymer composite can further include a first organic ligand. The semiconductor nanoparticles can be dispersed in the polymer or polymerization product in a colloidal form. The details of the semiconductor nanoparticles and the first organic ligand are the same as those described herein. The semiconductor nanoparticle-polymer composite can further include a first metal halide and / or a second metal halide. The metal halide can include (or can be) a metal chloride.

[0313] In the semiconductor nanoparticle-polymer composite (or the ink composition for preparing the composite) of the embodiment, the molar ratio of chlorine to indium (Cl:In) (or the molar ratio of halogen to indium) can be greater than or equal to about 1.8:1, greater than or equal to about 1.9:1, greater than or equal to about 2:1, greater than or equal to about 2.1:1, greater than or equal to about 2.16:1, greater than or equal to about 2.2:1, greater than or equal to about 2.3:1, greater than or equal to about 2.4:1, greater than or equal to about 2.5:1, greater than or equal to about 2.6:1, greater than or equal to about 2.7:1, greater than or equal to about 2.8:1, greater than or equal to about 2.9:1, greater than or equal to about 3:1, greater than or equal to about 3.1:1, greater than or equal to about 3.2:1, greater than or equal to about 3.3:1, greater than or equal to about 3.35:1, greater than or equal to about 3.4:1, greater than or equal to about 3.5:1, greater than or equal to about 3.6:1, greater than or equal to about 3.7:1, greater than or equal to about 3.8:1, greater than or equal to about 3.9:1, greater than or equal to about 4:1, greater than or equal to about 4.1:1, greater than or equal to about 4.2:1, greater than or equal to about 4.3:1, greater than or equal to about 4.4:1, greater than or equal to about 4.5:1, greater than or equal to about 4.6:1, greater than or equal to about 4.7:1, greater than or equal to about 4.8:1, greater than or equal to about 4.9:1 or greater than or equal to about 5:1. The molar ratio of chlorine to indium (Cl:In) (or the molar ratio of halogen to indium) can be less than or equal to about 10:1, less than or equal to about 9.5:1, less than or equal to about 9:1, less than or equal to about 8.5:1, less than or equal to about 8:1, less than or equal to about 7.9:1, less than or equal to about 7.7:1, less than or equal to about 7.5:1, less than or equal to about 7.3:1, less than or equal to about 7.1:1, less than or equal to about 7:1, less than or equal to about 6.9:1. Less than or equal to about 6.7:1, less than or equal to about 6.5:1, less than or equal to about 6.3:1, less than or equal to about 6.1:1, less than or equal to about 6:1, less than or equal to about 5.9:1, less than or equal to about 5.7:1, less than or equal to about 5.5:1, less than or equal to about 5.3:1, less than or equal to about 5.1:1, less than or equal to about 5:1, less than or equal to about 4.9:1, less than or equal to about 4.7:1, less than or equal to about 4.5:1, less than or equal to about 4.3:1, less than or equal to about 4.1:1 or less than or equal to about 4:1.

[0314] In the semiconductor nanoparticle-polymer composite (or ink composition for preparing the composite) of the embodiment, the molar ratio of zinc to indium (Zn:In) can be greater than or equal to about 0.7:1, greater than or equal to about 1.1:1, greater than or equal to about 1.4:1, greater than or equal to about 1.54:1, greater than or equal to about 1.8:1, greater than or equal to about 2:1, greater than or equal to about 2.1:1, greater than or equal to about 2.2:1, greater than or equal to about 2.3:1, greater than or equal to about 2.5:1, greater than or equal to about 3:1, greater than or equal to about 3.5:1, greater than or equal to about 4:1, greater than or equal to about 4.5:1, greater than or equal to about 5:1, greater than or equal to about 5.5:1, greater than or equal to about 6:1, greater than or equal to about 6.5:1, greater than or equal to about 6.97:1, greater than or equal to about 7:1, greater than or equal to about 7.5:1 or greater than or equal to about 8:1. The molar ratio of zinc to indium (Zn:In) can be less than or equal to about 30:1, less than or equal to about 25:1, less than or equal to about 20:1, less than or equal to about 15:1, less than or equal to about 10:1, less than or equal to about 9:1, less than or equal to about 8:1, less than or equal to about 7:1, less than or equal to about 6:1, less than or equal to about 5.54:1, less than or equal to about 2.1:1, less than or equal to about 1.9:1, less than or equal to about 1.75:1, less than or equal to about 1.6:1 or less than or equal to about 1.55:1.

[0315] In the semiconductor nanoparticle-polymer composite (or the ink composition for preparing the composite) of the embodiment, the molar ratio of chlorine to gallium (Cl:Ga) (or the molar ratio of halogen to gallium) can be greater than or equal to about 0.1:1, greater than or equal to about 0.3:1, greater than or equal to about 0.5:1, greater than or equal to about 0.6:1, greater than or equal to about 0.65:1, greater than or equal to about 0.7:1, greater than or equal to about 0.75:1, greater than or equal to about 0.8:1, greater than or equal to about 0.85:1, greater than or equal to about 0.9:1, greater than or equal to about 0.95:1, greater than or equal to about 1:1, greater than or equal to about 1.3:1, greater than or equal to about 1.5:1, greater than or equal to about 1.7:1, greater than or equal to about 1.9:1, greater than or equal to about 2:1, greater than or equal to about 2.1:1, greater than or equal to about 2.15:1, greater than or equal to about 2.2:1, greater than or equal to about 2.25:1, greater than or equal to about 2.3:1, greater than or equal to about 2.35:1, greater than or equal to about 2.4:1, greater than or equal to about 2.45:1, or greater than or equal to about 2.5:1. The molar ratio of chlorine to gallium (Cl:Ga) (or the molar ratio of halogen to gallium) can be less than or equal to about 10:1, less than or equal to about 9.5:1, less than or equal to about 9:1, less than or equal to about 8.5:1, less than or equal to about 8:1, less than or equal to about 7.9:1, less than or equal to about 7.7:1, less than or equal to about 7.5:1, less than or equal to about 7.3:1, less than or equal to about 7.1:1, less than or equal to about 7:1, less than or equal to about 6.9:1, less than or equal to about 6.7:1, less than or equal to about 6.5:1, less than or equal to about 6.3:1, less than or equal to about 6.1:1, less than or equal to about 6:1, less than or equal to about 5.9:1, less than or equal to about 5.7:1, less than or equal to about 5.5:1, less than or equal to about 5.3:1, less than or equal to about 5.1:1, less than or equal to about 5:1, less than or equal to about 4.9:1, less than or equal to about 4.7:1, less than or equal to about 4.5:1, less than or equal to about 4.3:1, less than or equal to about 4.1:1, less than or equal to about 4:1, less than or equal to about 3.5:1, less than or equal to about 3:1, less than or equal to about 2.5:1, less than or equal to about 2:1, less than or equal to about 1.5:1, less than or equal to about 1.08:1, less than or equal to about 1.05:1, less than or equal to about 1:1, less than or equal to about 0.9:1, or less than or equal to about 0.85:1.

[0316] In the semiconductor nanoparticle-polymer composite of the embodiment (or the ink composition for preparing the composite), the molar ratio of zinc to gallium (Zn:Ga) can be greater than or equal to about 0.2:1, greater than or equal to about 0.3:1, greater than or equal to about 0.4:1, greater than or equal to about 0.5:1, greater than or equal to about 0.7:1, greater than or equal to about 0.9:1, greater than or equal to about 1:1, greater than or equal to about 1.1:1, greater than or equal to about 1.3:1, greater than or equal to about 1.5:1, greater than or equal to about 1.7:1, greater than or equal to about 1.9:1, greater than or equal to about 2:1, greater than or equal to about 2.1:1, greater than or equal to about 2.3:1, greater than or equal to about 2.5:1, greater than or equal to about 2.7:1, greater than or equal to about 2.9:1, greater than or equal to about 3:1, greater than or equal to about 3.1:1, or greater than or equal to about 3.3:1. The molar ratio of zinc to gallium (Zn:Ga) can be less than or equal to about 10:1, less than or equal to about 9.5:1, less than or equal to about 9:1, less than or equal to about 8.5:1, less than or equal to about 8:1, less than or equal to about 7.5:1, less than or equal to about 7:1, less than or equal to about 6.5:1, less than or equal to about 6:1, less than or equal to about 5.5:1, less than or equal to about 5:1, less than or equal to about 4.5:1, less than or equal to about 4:1, less than or equal to about 3.5:1, less than or equal to about 3:1, less than or equal to about 2.5:1, less than or equal to about 2:1, less than or equal to about 1.5:1, less than or equal to about 1:1, or less than or equal to about 0.9:1.

[0317] In the semiconductor nanoparticle-polymer composite of the embodiment (or the semiconductor nanoparticles therein), the molar ratio of gallium to indium (Ga:In) can be greater than or equal to about 1:1, greater than or equal to about 1.3:1, greater than or equal to about 1.5:1, greater than or equal to about 1.7:1, greater than or equal to about 2:1, greater than or equal to about 2.1:1, greater than or equal to about 2.3:1, greater than or equal to about 2.5:1, greater than or equal to about 2.7:1, greater than or equal to about 2.9:1, greater than or equal to about 3:1, greater than or equal to about 3.1:1, greater than or equal to about 3.3:1, greater than or equal to about 3.5:1, greater than or equal to about 3.7:1, greater than or equal to about 3.9:1, greater than or equal to about 4:1, greater than or equal to about 4.1:1, greater than or equal to about 4.3:1, or greater than or equal to about 4.5:1. The molar ratio of gallium to indium (Ga:In) can be less than or equal to about 10:1, less than or equal to about 9:1, less than or equal to about 8:1, less than or equal to about 7:1, less than or equal to about 6:1, less than or equal to about 5:1, less than or equal to about 4:1, less than or equal to about 3:1, less than or equal to about 2:1, or less than or equal to about 1.2:1.

[0318] (Polymer) matrix may include a polymerization product of polymerizable monomers. The matrix may include linear polymers, crosslinked polymers, or combinations thereof. Crosslinked polymers may include thiol-ene resins, crosslinked poly(meth)acrylates, crosslinked polyurethanes, crosslinked epoxy resins, crosslinked vinyl polymers, crosslinked silicone resins, or combinations thereof. In embodiments, the crosslinked polymer may include a polymerization product of polymerizable monomers and an optional polythiol compound.

[0319] Linear polymers may include repeating units derived from carbon-carbon unsaturated bonds (e.g., carbon-carbon double bonds). The repeating units may include carboxyl groups. Linear polymers may include ethylene repeating units. Repeating units containing carboxyl groups may include units derived from monomers including carboxyl groups and carbon-carbon double bonds, units derived from monomers having dianhydride moieties, or combinations thereof. Linear polymers may be alkali-soluble polymer binders or resins. The ink compositions of the embodiments may not include alkali-soluble polymer binders or resins.

[0320] In a semiconductor nanoparticle-polymer composite (e.g., the first composite) of one or more embodiments, the (polymer) matrix may include the components described herein with respect to the composition. In the composite, based on the total weight of the composite, the amount of the matrix may be greater than or equal to about 10 wt%, greater than or equal to about 20 wt%, greater than or equal to about 30 wt%, greater than or equal to about 40 wt%, greater than or equal to about 50 wt%, or greater than or equal to about 60 wt%. Based on the total weight of the composite, the amount of the matrix may be less than or equal to about 95 wt%, less than or equal to about 90 wt%, less than or equal to about 80 wt%, less than or equal to about 70 wt%, less than or equal to about 60 wt%, or less than or equal to about 50 wt%.

[0321] The semiconductor nanoparticle-polymer composite may have, for example, a predetermined thickness and include a predetermined amount of semiconductor nanoparticles. The ink composition or the composite prepared therefrom may include a film form having a thickness less than or equal to about 10 microns. The semiconductor nanoparticle-polymer composite may be in the form of a film or a pattern, and the thickness of the composite may be, for example, less than or equal to about 30 μm, less than or equal to about 25 μm, less than or equal to about 20 μm, less than or equal to about 15 μm, less than or equal to about 10 μm, less than or equal to about 8 μm, or less than or equal to about 7 μm and greater than about 2 μm (e.g., greater than or equal to about 3 μm, greater than or equal to about 3.5 μm, greater than or equal to about 4 μm, greater than or equal to about 5 μm, greater than or equal to about 6 μm, greater than or equal to about 7 μm, greater than or equal to about 8 μm, greater than or equal to about 9 μm, or greater than or equal to about 10 μm).

[0322] The ink composition or the semiconductor nanoparticle-polymer composite prepared therefrom may exhibit an increased absorption rate of incident light (e.g., blue light). The absorption rate of incident light of the composite may be greater than or equal to about 70%, greater than or equal to about 73%, greater than or equal to about 75%, greater than or equal to about 77%, greater than or equal to about 80%, greater than or equal to about 83%, greater than or equal to about 85%, greater than or equal to about 87%, greater than or equal to about 90%, greater than or equal to about 93%, greater than or equal to about 94%, greater than or equal to about 95%, greater than or equal to about 96%, greater than or equal to about 97%, greater than or equal to about 98% or greater than or equal to about 99%. The absorption rate of blue light of the composite may be about 70% to about 100%, about 80% to about 98%, about 95% to about 99%, about 96% to about 98% or a combination thereof. The absorption rate of incident light can be determined using Equation 2:

[0323] Equation 2

[0324] Absorption rate of incident light = [(B - B') / B] × 100 (%)

[0325] where, in Equation 2,

[0326] B is the amount of incident light provided to the composite, and

[0327] B' is the amount of incident light passing through the composite.

[0328] In embodiments, the semiconductor nanoparticle-polymer composite may exhibit an improved quantum efficiency. In embodiments, the semiconductor nanoparticle-polymer composite may have an internal quantum efficiency (IQE) or an external quantum efficiency (EQE) greater than or equal to about 50%, greater than or equal to about 55%, greater than or equal to about 60%, greater than or equal to about 63%, greater than or equal to about 69% or greater than or equal to about 75%, and the IQE and EQE are defined by Equation 3 and Equation 4 as follows:

[0329] Equation 3

[0330] Internal quantum efficiency (%) = [A / (B - B')] × 100%

[0331] Equation 4

[0332] External quantum efficiency (%) = [A / B] × 100

[0333] A: The amount of the first light emitted from the composite

[0334] B: The amount of incident light irradiated

[0335] B': The amount of incident light passing through the composite.

[0336] The semiconductor nanoparticle-polymer composite can be heat-treated at 180 °C for 30 minutes, and the process retention percentage obtained by Equation 5 can be greater than or equal to about 50%, greater than or equal to about 51%, greater than or equal to about 55%, greater than or equal to about 57%, greater than or equal to about 60%, greater than or equal to about 65%, greater than or equal to about 70%, greater than or equal to about 75%, greater than or equal to about 80%, greater than or equal to about 85%, greater than or equal to about 88% or greater than or equal to about 90%:

[0337] Equation 5

[0338] Process retention percentage (%) = [QE2 / QE1] × 100%.

[0339] QE1: Quantum efficiency of the semiconductor nanoparticle-polymer composite before heat treatment

[0340] QE2: Quantum efficiency of the semiconductor nanoparticle-polymer composite after heat treatment

[0341] In Equation 5, the quantum efficiency can be the internal quantum efficiency or the external quantum efficiency.

[0342] In an embodiment, the semiconductor nanoparticle-polymer composite (herein, also referred to as "composite") can be used in a sheet or a color conversion panel containing light-emitting particles (e.g., a light-emitting color filter). The sheet or the color conversion panel can be disposed on a light source. Accordingly, the embodiment provides a color conversion layer (e.g., a color conversion structure) or a color conversion panel including the same. The color conversion layer or the color conversion structure can include the composite of the embodiment or a patterned film of the composite. The color conversion layer can include a color conversion region.

[0343] The color conversion region can include a first region configured to emit a first light (or green light) (e.g., by irradiating with incident light). In an embodiment, the first region can correspond to a green pixel. The first region includes a first composite (e.g., the light-emitting composite described herein). The first light can have a peak emission wavelength within the wavelength range described herein. The first light can be green light. The peak emission wavelength of the green light can be greater than or equal to about 500 nm, greater than or equal to about 501 nm, greater than or equal to about 504 nm, greater than or equal to about 505 nm or greater than or equal to about 520 nm. The peak emission wavelength of the green light can be less than or equal to about 580 nm, less than or equal to about 560 nm, less than or equal to about 550 nm, less than or equal to about 530 nm, less than or equal to about 525 nm, less than or equal to about 520 nm, less than or equal to about 515 nm or less than or equal to about 510 nm.

[0344] The color conversion region may further include a second region configured to emit (e.g., by irradiating with incident light) a second light (e.g., red light) different from the first light. The second region may include a second composite. The semiconductor nanoparticle composite in the second region may include semiconductor nanoparticles (e.g., quantum dots) configured to emit light having a different wavelength (e.g., different color) from the semiconductor nanoparticle composite disposed in the first region. The second light may be red light having a peak emission wavelength of about 600 nm to about 650 nm (e.g., about 620 nm to about 650 nm).

[0345] The color conversion panel may further include one or more third regions that emit a third light (e.g., blue light) different from the first and second lights or allow a third light (e.g., blue light) different from the first and second lights to pass therethrough. The incident light may include the third light (e.g., blue light and optional green light). The third light may include blue light having a peak emission wavelength greater than or equal to about 380 nm (e.g., greater than or equal to about 440 nm, greater than or equal to about 445 nm, greater than or equal to about 450 nm, or greater than or equal to about 455 nm) to less than or equal to about 480 nm (e.g., less than or equal to about 475 nm, less than or equal to about 470 nm, less than or equal to about 465 nm, or less than or equal to about 460 nm).

[0346] Figure 1A is a schematic cross-sectional view of a color conversion panel according to one or more embodiments. Referring to Figure 1A the color conversion panel may optionally further include partition walls (e.g., black matrix (BM), dams, or combinations thereof) defining each region of the color conversion layer (e.g., color conversion structure). Figure 1B illustrates an electronic device (display device) including a color conversion panel and a light source according to another embodiment. In the electronic device of one or more embodiments, the color conversion panel including the color conversion layer or color conversion structure may be disposed on a chip-on light emitting diode (LED) (e.g., chip-on micro-LED). Referring to Figure 1B, a circuit (Si driver integrated circuit (IC)) configured to drive a light source can be disposed under a light source (e.g., a blue LED) configured to emit incident light (e.g., blue light). The color conversion layer can include a first composite including a plurality of semiconductor nanoparticles emitting a first light (e.g., green light), a second composite including a plurality of semiconductor nanoparticles emitting a second light (e.g., red light), or a third composite emitting a third light (e.g., incident light or blue light) or allowing the third light (e.g., incident light or blue light) to pass therethrough. A partition wall PW (e.g., including an inorganic material such as silicon or silicon oxide, or an organic material-based one) can be disposed between the respective composites. The partition wall can include trench holes, via holes, or a combination thereof. A first optical element (e.g., an absorption-type color filter) can be disposed on a light extraction surface of the color conversion layer. An additional optical element (such as a microlens) can be further disposed on the first optical element.

[0347] In an embodiment, a color conversion layer or a patterned film of a semiconductor nanoparticle-polymer composite can be prepared using an ink composition (e.g., in an inkjet printing manner). Referring to Figure 2 , such a method can include preparing an ink composition according to one or more embodiments, providing a substrate (e.g., having a pixel region patterned with electrodes and optionally a dam or trench-type partition wall, etc.), and depositing the ink composition on the substrate (or pixel region) to form, for example, a first composite layer (or a first region). The method can further include depositing the ink composition on the substrate (or pixel region) to form, for example, a second composite layer (or a second region). The formation of the first composite layer and the formation of the second composite layer can be performed simultaneously or sequentially.

[0348] The deposition of the ink composition can be performed using a suitable liquid crystal ejector (e.g., an inkjet or nozzle printing system having an ink reservoir and at least one print head). The deposited ink composition can be provided with a (first or second) composite layer by removing the solvent through heating and polymerization. The polymerization can include thermal polymerization, photopolymerization, or a combination thereof. In the case of photopolymerization, it can include irradiating the ink composition with light having a predetermined wavelength (e.g., 200 nm or greater and 450 nm or less). This method can provide a highly precise semiconductor nanoparticle-polymer composite film or a patterned film in a short time by a simple method.

[0349] Semiconductor nanoparticles, composites (or patterns of composites) including semiconductor nanoparticles, or color conversion panels including composites (or patterns of composites) may be included in an electronic device. Such an electronic device or electronic equipment may include a display device, a light-emitting diode (LED), an organic light-emitting diode (OLED), a quantum dot LED, a sensor, a solar cell, an imaging sensor, a photodetector, or a liquid crystal display device, but is not limited thereto. The above-mentioned quantum dots may be included in an electronic device or electronic equipment. Such an electronic device or electronic equipment may include, but is not limited to, a portable terminal device, a monitor, a personal computer (PC), a notebook personal computer (PC), a television, an electronic signboard or electronic display board, a camera, an automobile, etc., but the embodiments are not limited thereto. The electronic equipment may be a portable terminal device, a monitor, a notebook PC, or a television including a display device (or light-emitting device) containing quantum dots. The electronic device or electronic equipment may be a camera or a mobile terminal device including an image sensor containing quantum dots. The electronic device or electronic equipment may be a camera or a vehicle including a photodetector containing quantum dots.

[0350] In an embodiment, the electronic device or display device (e.g., a display panel) may further include a color conversion layer (or color conversion panel) and an optional light source. The light source may be configured to provide incident light to the color conversion layer or color conversion panel. In an embodiment, the display panel may include a light-emitting panel (or light source), the above-mentioned color conversion panel, and a light-transmitting layer (light transmission layer) located between the light-emitting panel and the color conversion panel. The color conversion panel includes a substrate, and the color conversion layer may be disposed on the substrate.

[0351] (See Figure 3A and Figure 4A )

[0352] In an embodiment, the light source or light-emitting panel may be configured to provide incident light to the color conversion layer or color conversion panel. The incident light may have a peak emission wavelength greater than or equal to about 440 nm (e.g., greater than or equal to about 450 nm) to less than or equal to about 580 nm (e.g., less than or equal to about 480 nm, less than or equal to about 470 nm, or less than or equal to about 460 nm).

[0353] In an embodiment, the electronic device (e.g., a photoluminescent device) may further include a sheet of a semiconductor nanoparticle-polymer composite. Refer to Figure 3B, the device 400 may include a backlight unit 410 and a liquid crystal panel 420. Among them, the backlight unit 410 may include a quantum dot polymer composite sheet (QD sheet). Specifically, the backlight unit 410 may have a structure in which a reflector, a light guide plate (LGP), a light source (such as a blue LED), a quantum dot polymer composite sheet (QD sheet), and an optical film (prism, dual brightness enhancement film (DBEF, etc.)) are stacked. The liquid crystal panel 420 may be disposed on the backlight unit 410 and have a structure including a thin film transistor (TFT), liquid crystal (LC), and a color filter between two polarizers (Pol). The quantum dot polymer composite sheet (QD sheet) may include semiconductor nanoparticles (such as quantum dots) that emit red and green light after absorbing light from the light source. The blue light provided by the light source may be combined with the red and green light emitted from the semiconductor nanoparticles while passing through the quantum dot polymer composite sheet and converted into white light. The white light is separated into blue, green, and red light by the color filter in the liquid crystal panel and then emitted to the outside for each pixel. Refer to Figure 4B , the backlight unit BLU may be a direct BLU without a light guide plate and may include a plurality of LEDs (such as mini LEDs).

[0354] The color conversion panel may include a substrate, and a color conversion layer may be disposed on the substrate. The color conversion layer or the color conversion panel may include a patterned film of a semiconductor nanoparticle-polymer composite. The patterned film may include repeating segments configured to emit light of a desired wavelength. The repeating segments may include a second region. The second region may be a red light emitting segment. The repeating segments may include a first region. The first region may be a green light emitting segment. The repeating segments may include a third region. The third region may include a segment that emits or transmits blue light. Details of the first region, the second region, and the third region are as described herein.

[0355] The light emitting panel or the light source may be an element that emits incident light (such as excitation light). The incident light may include blue light and optionally green light. The light source may include an LED. The light source may include an organic light emitting diode (OLED). The light source may include a micro LED. On the front surface (light emitting surface) of the first region and the second region, an optical element (such as a blue light (and optionally green light) blocking layer or a first optical filter described herein) for blocking (such as reflecting or absorbing) blue light (and optionally green light) may be provided. In an embodiment, the light source may include an organic light emitting diode that emits blue light and an organic light emitting diode that emits green light, and a green light removal filter may be further disposed on the third region through which the blue light is transmitted.

[0356] The light-emitting panel or light source may include a plurality of light-emitting units corresponding to the first region and the second region, respectively, and the light-emitting unit may include a first electrode and a second electrode facing each other and an (organic) electroluminescent layer located between the first electrode and the second electrode. The electroluminescent layer may include an organic light-emitting material. For example, each light-emitting unit of the light source may include an electroluminescent device (e.g., an organic light-emitting diode (OLED)) configured to emit light of a predetermined wavelength (e.g., blue light, green light, or a combination thereof). The structures and materials of the electroluminescent device and the organic light-emitting diode (OLED) are not particularly limited.

[0357] Hereinafter, the display panel and the color conversion panel will be described in more detail with reference to the accompanying drawings.

[0358] Figure 3A is a perspective view of an embodiment of a display panel constructed as described herein. Figure 4A is Figure 3A a cross-sectional view of the display panel. Referring to Figure 3A and Figure 4A According to an embodiment, the display panel 1000 includes a light-emitting panel 40 and a color conversion panel 50. The display panel or the electronic device may further include a light-transmitting layer 60 disposed between the light-emitting panel 40 and the color conversion panel 50 and an adhesive material 70 that bonds the light-emitting panel 40 and the color conversion panel 50. The light-transmitting layer may include a passivation layer, a filling material, a packaging layer, or a combination thereof (not shown). The material for the light-transmitting layer may be appropriately selected without particular limitation. The material for the light-transmitting layer may be an inorganic material, an organic material, an organic / inorganic hybrid material, or a combination thereof.

[0359] Both the light-emitting panel 40 and the color conversion panel 50 have surfaces facing each other, that is, the two corresponding panels face each other, and the light-transmitting layer (or light-transmitting panel) 60 is disposed between the two panels. The color conversion panel 50 is disposed in a direction such that, for example, light emitted from the light-emitting panel 40 irradiates the light-transmitting layer 60. The adhesive material 70 may be disposed along the edges of the light-emitting panel 40 and the color conversion panel 50 and may be, for example, a sealing material.

[0360] Figure 5A is a plan view of an embodiment of the pixel arrangement of a display panel according to one or more embodiments. Referring to Figure 5A According to an embodiment, the display panel 1000 includes a display area 1000D for displaying an image and a non-display area 1000P located in the peripheral area of the display area 1000D and provided with an adhesive material.

[0361] The display area 1000D includes a plurality of pixels PX arranged along rows (e.g., the x direction) and columns (e.g., the y direction), and each representative pixel PX may include a plurality of sub-pixels PX that express (e.g., display) different colors from each other.1 , PX 2 and PX 3 . Embodiments are illustrated as having three sub-pixels PX therein 1 , PX 2 and PX 3 configured to provide the structure of a pixel. Embodiments may also include additional sub-pixels such as white sub-pixels and may also include at least one sub-pixel expressing (e.g., displaying) the same color. A plurality of pixels PX may be aligned, for example, in a Bayer matrix, a matrix sold under the trade name PenTile, a diamond matrix, etc. or a combination thereof.

[0362] Sub-pixels PX 1 , PX 2 and PX 3 may express (e.g., display) colors of the three primary colors or a combination of the three primary colors, for example, may express (e.g., display) colors of red, green, blue, or a combination thereof. For example, the first sub-pixel PX 1 may express (e.g., display) red, and the second sub-pixel PX 2 may express (e.g., display) green, and the third sub-pixel PX 3 may express (e.g., display) blue.

[0363] In the drawings, all sub-pixels are illustrated as having the same size, but embodiments are not limited thereto, and at least one of the sub-pixels may be larger or smaller than the other sub-pixels. In the drawings, all sub-pixels are illustrated as having the same shape, but are not limited thereto, and at least one of the sub-pixels may have a shape different from that of the other sub-pixels.

[0364] In a display panel or an electronic device according to an embodiment, a light-emitting panel may include a substrate and a TFT (e.g., an oxide-containing TFT) disposed on the substrate. A light-emitting device (e.g., a light-emitting device having a series structure) may be disposed on the TFT.

[0365] In a display panel or an electronic device according to an embodiment, a light-emitting panel may include a substrate and a (e.g., oxide-containing) TFT disposed on the substrate. A (e.g., series-structured) light-emitting device may be disposed on the TFT.

[0366] The light-emitting device may include a light-emitting layer (e.g., a blue light-emitting layer, a green light-emitting layer, or a combination thereof) located between a first electrode and a second electrode facing each other. A charge generation layer may be disposed between each light-emitting layer. Each of the first electrode and the second electrode may be patterned with a plurality of electrode elements to correspond to the pixels. The first electrode may be an anode or a cathode. The second electrode may be a cathode or an anode.

[0367] The light-emitting device may include an organic LED, a nanorod LED, a mini LED, a micro LED, or a combination thereof. In an embodiment, the "mini LED" may have a size greater than or equal to about 100 micrometers, greater than or equal to about 150 micrometers, or greater than or equal to about 200 micrometers and less than or equal to about 1 millimeter, less than or equal to about 0.5 millimeter, less than or equal to about 0.15 millimeter, or less than or equal to about 0.12 millimeter, but is not limited thereto. In an embodiment, the "micro LED" may have a size less than about 100 micrometers, less than or equal to about 50 micrometers, or less than or equal to about 10 micrometers. The size of the micro LED may be greater than or equal to about 0.1 micrometer, greater than or equal to about 0.5 micrometer, greater than or equal to about 1 micrometer, or greater than or equal to about 5 micrometers, but is not limited thereto.

[0368] Figures 5B to 5E They are cross-sectional views showing examples of the light-emitting device, respectively.

[0369] Referring to Figure 5B , the light-emitting device 180 may include: a first electrode 181 and a second electrode 182 facing each other; a light-emitting layer 183 located between the first electrode 181 and the second electrode 182; and optional auxiliary layers 184 and 185 located between the first electrode 181 and the light-emitting layer 183 and between the second electrode 182 and the light-emitting layer 183, respectively.

[0370] The first electrode 181 and the second electrode 182 may be arranged to face each other along the thickness direction (e.g., the z direction), and either the first electrode 181 or the second electrode 182 may be an anode and the other may be a cathode. The first electrode 181 may be a light-transmissive electrode, a semi-transparent electrode, or a reflective electrode, and the second electrode 182 may be a light-transmissive electrode or a semi-transparent electrode. The light-transmissive electrode or the semi-transparent electrode may be made of, for example, a thin single layer or multiple layers of a metal thin film, which includes: a conductive oxide, such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), fluorine-doped tin oxide (FTO), etc.; or silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), magnesium-silver (Mg-Ag), magnesium-aluminum (Mg-Al), or a combination thereof. The reflective electrode may include a metal, a metal nitride, or a combination thereof, such as silver (Ag), copper (Cu), aluminum (Al), gold (Au), titanium (Ti), chromium (Cr), nickel (Ni), their alloys, their nitrides (e.g., TiN), or a combination thereof, but the embodiments are not limited thereto.

[0371] One or more light-emitting layers 183 may include a first light-emitting body that emits light having a blue emission spectrum, a second light-emitting body that emits light having a green emission spectrum, or a combination thereof.

[0372] The blue emission spectrum may have a peak emission wavelength in a wavelength region greater than or equal to about 400 nm to less than about 500 nm (and within this range, in a wavelength region of about 410 nm to about 490 nm, about 420 nm to about 480 nm, about 430 nm to about 470 nm, about 440 nm to about 465 nm, about 445 nm to about 460 nm, or about 450 nm to about 458 nm).

[0373] The green emission spectrum may have a peak emission wavelength in a wavelength region greater than or equal to about 500 nm to less than about 590 nm (and within this range, in a wavelength region of about 510 nm to about 580 nm, about 515 nm to about 570 nm, about 520 nm to about 560 nm, about 525 nm to about 555 nm, about 530 nm to about 550 nm, about 535 nm to about 545 nm, or a combination thereof).

[0374] In an embodiment, the light-emitting layer 183 or the light-emitting body included in the light-emitting layer 183 may include a phosphorescent material, a fluorescent material, or a combination thereof. In an embodiment, the light-emitting body may include an organic light-emitting body, where the organic light-emitting body may be a low-molecular compound, a high-molecular compound, or a combination thereof. The specific types of the phosphorescent material and the fluorescent material are not particularly limited, but may be appropriately selected from known materials. In an embodiment, the light-emitting body may include an inorganic light-emitting body, and the inorganic light-emitting body may be an inorganic semiconductor, a quantum dot, a perovskite, or a combination thereof. The inorganic semiconductor may include a metal nitride, a metal oxide, or a combination thereof. The metal nitride, the metal oxide, or a combination thereof may include group III metals (such as aluminum, gallium, indium, thallium), group IV metals (such as silicon, germanium, tin), or a combination thereof. In an embodiment, the light-emitting body may include an inorganic light-emitting body, and the light-emitting device 180 may be a quantum dot light-emitting diode, a perovskite light-emitting diode, or a micro light-emitting diode (μLED). Materials that can be used as the inorganic light-emitting body may be appropriately selected.

[0375] In an embodiment, the light-emitting device 180 may further include auxiliary layers 184 and 185. The auxiliary layers 184 and 185 may be respectively disposed between the first electrode 181 and the light-emitting layer 183 and / or between the second electrode 182 and the light-emitting layer 183. The auxiliary layers 184 and 185 may be charge auxiliary layers for controlling charge injection and / or mobility. The auxiliary layers 184 and 185 may each include at least one layer or two layers, and for example, may include a hole injection layer, a hole transport layer, an electron blocking layer, an electron injection layer, an electron transport layer, a hole blocking layer, or a combination thereof. If desired, at least one of the auxiliary layers 184 and 185 may be omitted. The auxiliary layers 184 and 185 may be formed of materials appropriately selected from materials known for use in organic electroluminescent devices and the like.

[0376] Provided in sub-pixels PX 1 , PX 2 and PX 3 , the light-emitting devices 180 in each of them may be the same as or different from each other. The sub-pixels PX 1 , PX 2 and PX 3 , the light-emitting devices 180 in each of them may emit light having the same or different emission spectra. The sub-pixels PX 1 , PX 2 and PX 3 , the light-emitting devices 180 in each of them may emit, for example, light having a blue emission spectrum, light having a green emission spectrum, or a combination thereof. The sub-pixels PX 1 , PX 2 and PX 3 , the light-emitting devices 180 in each of them may be separated by a pixel defining layer (not shown).

[0377] Referring to Figure 5C , the light-emitting device 180 may be a light-emitting device having a series structure and includes: a first electrode 181 and a second electrode 182 facing each other; a first light-emitting layer 183a and a second light-emitting layer 183b located between the first electrode 181 and the second electrode 182; a charge generation layer 186 located between the first light-emitting layer 183a and the second light-emitting layer 183b; and optional auxiliary layers 184 and 185 located between the first electrode 181 and the first light-emitting layer 183a and / or between the second electrode 182 and the second light-emitting layer 183b, respectively.

[0378] Details of the first electrode 181, the second electrode 182, and the auxiliary layers 184 and 185 are as described herein.

[0379] The first light-emitting layer 183a and the second light-emitting layer 183b may emit light having the same or different emission spectra. In an embodiment, the first light-emitting layer 183a or the second light-emitting layer 183b may emit light having a blue emission spectrum or a green emission spectrum, respectively. The charge generation layer 186 may inject charges into the first light-emitting layer 183a and / or the second light-emitting layer 183b and may control the charge balance between the first light-emitting layer 183a and the second light-emitting layer 183b. The charge generation layer 186 may include, for example, an n-type layer and a p-type layer, and may include, for example, an electron transport material and / or a hole transport material including an n-type dopant and / or a p-type dopant. The charge generation layer 186 may include one layer or two or more layers.

[0380] Referring to Figure 5D, A light-emitting device (having a series structure) may include: a first electrode 181 and a second electrode 182 facing each other; a first light-emitting layer 183a, a second light-emitting layer 183b, and a third light-emitting layer 183c located between the first electrode 181 and the second electrode 182; a first charge generation layer 186a located between the first light-emitting layer 183a and the second light-emitting layer 183b; a second charge generation layer 186b located between the second light-emitting layer 183b and the third light-emitting layer 183c; and optional auxiliary layers 184 and 185 located between the first electrode 181 and the first light-emitting layer 183a and / or between the second electrode 182 and the third light-emitting layer 183c, respectively.

[0381] Details of the first electrode 181, the second electrode 182, and the auxiliary layers 184 and 185 are as described herein.

[0382] The first light-emitting layer 183a, the second light-emitting layer 183b, and the third light-emitting layer 183c may emit light having the same or different emission spectra. The first light-emitting layer 183a, the second light-emitting layer 183b, and the third light-emitting layer 183c may emit blue light. In an embodiment, the first light-emitting layer 183a and the third light-emitting layer 183c may emit light having a blue emission spectrum, and the second light-emitting layer 183b may emit light having a green emission spectrum. In another embodiment, the first light-emitting layer 183a and the third light-emitting layer 183c may emit light having a green emission spectrum, and the second light-emitting layer 183b may emit light having a blue emission spectrum.

[0383] The first charge generation layer 186a may inject charges into the first light-emitting layer 183a and / or the second light-emitting layer 183b and may control the charge balance between the first light-emitting layer 183a and the second light-emitting layer 183b. The second charge generation layer 186b may inject charges into the second light-emitting layer 183b and / or the third light-emitting layer 183c and may control the charge balance between the second light-emitting layer 183b and the third light-emitting layer 183c. Each of the first charge generation layer 186a and the second charge generation layer 186b may include one layer or two or more layers, respectively.

[0384] Referring to Figure 5E , in an embodiment, the light-emitting device 180 includes a light-emitting layer 183, a first electrode 181, a second electrode 182, and a plurality of nanostructures 187 disposed in the light-emitting layer 183.

[0385] One of the first electrode 181 and the second electrode 182 may be an anode, and the other may be a cathode. The first electrode 181 and the second electrode 182 may be electrodes patterned according to the direction of the arrangement of the plurality of nanostructures 187, and may include, for example: conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), fluorine-doped tin oxide (FTO), etc.; silver (Ag), copper (Cu), aluminum (Al), gold (Au), titanium (Ti), chromium (Cr), nickel (Ni), their alloys, their nitrides (such as TiN); or a combination thereof, but the embodiments are not limited thereto.

[0386] The light-emitting layer 183 may include a plurality of nanostructures 187, and each of the sub-pixels PX 1 , PX 2 and PX 3 may include a plurality of nanostructures 187. In an embodiment, the plurality of nanostructures 187 may be arranged in one direction, but the present disclosure is not limited thereto. The nanostructure 187 may be a compound-containing semiconductor configured to emit light of a predetermined wavelength, for example, by applying a current, and may be, for example, a linear nanostructure (such as a nanorod or a nanoneedle).

[0387] The diameter or major diameter of the nanostructure 187 may be, for example, a few nanometers to several hundred nanometers, and the aspect ratio of the nanostructure 187 may be greater than about 1, greater than or equal to about 1.5, greater than or equal to about 2.0, greater than or equal to about 3.0, greater than or equal to about 4.0, greater than or equal to about 4.5, or greater than or equal to about 5.0 to less than or equal to about 20 (about 1.5 to about 20, about 2.0 to about 20, about 3.0 to about 20, about 4.0 to about 20, about 4.5 to about 20, or about 5.0 to about 20).

[0388] Each of the nanostructures 187 may include a p-type region 187p, an n-type region 187n, and a multi-quantum well region 187i, and may be configured to emit light from the multi-quantum well region 187i. The nanostructure 187 may include, for example, gallium nitride (GaN), indium gallium nitride (InGaN), aluminum gallium nitride (AlGaN), or a combination thereof, and may have, for example, a core-shell structure.

[0389] The plurality of nanostructures 187 may each emit light having the same or different emission spectra. In an embodiment, the nanostructure may emit light having a blue emission spectrum, for example, light having a peak emission wavelength in a wavelength region of greater than or equal to about 400 nm to less than 500 nm, about 410 nm to about 490 nm, or about 420 nm to about 480 nm.

[0390] Figure 6is a schematic cross-sectional view of a device (or display panel) according to an embodiment. Referring to Figure 6 , the light source (or light-emitting panel) may include an organic light-emitting diode that emits blue light (B) (and optionally green light (G)). The organic light-emitting diode (OLED) may include at least two pixel electrodes 90a, 90b, 90c formed on a substrate 100, pixel defining layers 150a, 150b formed between adjacent pixel electrodes 90a, 90b, 90c, organic light-emitting layers 140a, 140b, 140c formed on each pixel electrode 90a, 90b, 90c, and a common electrode layer 130 formed on the organic light-emitting layers 140a, 140b, 140c. Thin film transistors (TFTs) and a substrate (not shown) may be disposed under the organic light-emitting diode (OLED). The pixel regions of the OLED may be set to correspond to the first region, the second region, and the third region as described herein. In an embodiment, the color conversion panel and the light-emitting panel may be separated as shown in Figure 6 . In an embodiment, the color conversion panel may be directly stacked on the light-emitting panel.

[0391] A stacked structure including a light-emitting nanostructure composite pattern 170 (e.g., a first region 11 or R including light-emitting nanostructures that emit red light, a second region 21 or G including light-emitting nanostructures that emit green light, and a third region 31 or B including or not including light-emitting nanostructures (e.g., light-emitting nanostructures that emit blue light)) and a substrate 240 may be disposed on the light source. The blue light emitted from the light source enters the first region and the second region and may emit red light and green light, respectively. The blue light emitted from the light source may pass through the third region. If desired, an element (a first filter 160 or an excitation light blocking layer) configured to block excitation light may be disposed between the light-emitting nanostructure composite layers R and G and the substrate. In an embodiment, the excitation light includes blue light and green light, and a green light blocking filter (not shown) may be added to the third region. The first optical filter or the excitation light blocking layer will be described in more detail herein.

[0392] Such a (display) device may be manufactured by separately manufacturing the above-described stacked structure and an LED or an OLED (e.g., an LED or an OLED that emits blue light) and then combining the stacked structure and the LED or the OLED. The (display) device may be manufactured by directly forming a light-emitting nanostructure composite pattern on the LED or the OLED.

[0393] In the color conversion panel or the display device, the substrate may be a substrate including an insulating material. The substrate may include: glass; polymers such as poly(ethylene terephthalate) (PET), poly(ethylene naphthalate) (PEN), etc., polyesters, polycarbonates, or poly(meth)acrylates; polysiloxanes (e.g., PDMS); inorganic materials such as Al 2 O 3, ZnO, etc.; or combinations thereof, but the embodiments are not limited thereto. Considering the substrate material, the thickness of the substrate can be appropriately selected, but there is no particular limitation. The substrate can be flexible. For the light emitted from the semiconductor nanoparticles, the substrate can have a transmittance of greater than or equal to about 50%, greater than or equal to about 60%, greater than or equal to about 70%, greater than or equal to about 80%, or greater than or equal to about 90%.

[0394] A wiring layer including thin film transistors, etc. can be formed on the substrate. The wiring layer can also include gate lines, sustain voltage lines, gate insulating films, data lines, source electrodes, drain electrodes, semiconductor layers, protective layers, etc. or combinations thereof. The detailed structure of the wiring layer can vary according to one or more embodiments. The gate line and the sustain voltage line can be electrically separated from each other, and the data line is insulated from and crosses the gate line and the sustain voltage line. The gate electrode, source electrode, and drain electrode can form the control terminal, input terminal, and output terminal of the thin film transistor, respectively. The drain electrode can be electrically connected to the pixel electrode to be described later.

[0395] The pixel electrode can be used as an electrode (e.g., anode) of the display device. The pixel electrode can be formed of a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO). The pixel electrode can be formed of a material having light blocking properties such as gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), or titanium (Ti). The pixel electrode can have a two-layer structure in which a transparent conductive material and a material having light blocking properties are sequentially stacked.

[0396] Between two adjacent pixel electrodes, a pixel defining layer (PDL) can be stacked with the terminal end of the pixel electrode to divide the pixel electrode into pixel units. The pixel defining layer is an insulating layer that can resistively block at least two pixel electrodes.

[0397] The pixel defining layer can cover a part of the upper surface of the pixel electrode, and the remaining area of the pixel electrode not covered by the pixel defining layer can provide an opening. The organic light emitting layer to be described here can be formed in the area defined by the opening.

[0398] The organic light emitting layer can define each pixel area through the above-mentioned pixel electrode and pixel defining layer. In other words, a pixel area can be defined as an area in which an organic light emitting unit layer is formed, and the organic light emitting unit layer is in contact with one pixel electrode divided by the pixel defining layer. In the display device according to one or more embodiments, the organic light emitting layer can be defined as a first pixel area, a second pixel area, and a third pixel area, and each pixel area can be separated from each other by the pixel defining layer with a predetermined interval left.

[0399] In an embodiment, the organic light-emitting layer may emit third light belonging to the visible light region or the ultraviolet (UV) region. Each of the first pixel region to the third pixel region of the organic light-emitting layer may emit the third light. In an embodiment, the third light may be light having relatively high energy in the visible light region, and for example, may be blue light (and optionally green light). In an embodiment, all pixel regions of the organic light-emitting layer are designed to emit the same light, and each pixel region of the organic light-emitting layer may be formed of the same or similar material, or may exhibit the same or similar properties. Accordingly, the process of forming the organic light-emitting layer may be simplified, and the display device may be easily applied to a large-scale / large-area process, for example, manufactured by a large-scale / large-area process. However, the organic light-emitting layer according to an embodiment is not limited thereto, but the organic light-emitting layer may be designed to emit at least two different lights, for example, at least two different colors of light.

[0400] The organic light-emitting layer includes an organic light-emitting unit layer in each pixel region, and in addition to the light-emitting layer, each organic light-emitting unit layer may further include auxiliary layers (for example, a hole injection layer, a hole transport layer, an electron transport layer, etc. or a combination thereof).

[0401] The common electrode may serve as a cathode of the display device. The common electrode may be formed of a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO). The common electrode may be formed on the organic light-emitting layer and may be integrated with the organic light-emitting layer.

[0402] A planarization layer or a passivation layer (not shown) may be formed on the common electrode. The planarization layer may include an insulating material (for example, transparent) for ensuring electrical insulation from the common electrode.

[0403] In an embodiment, the display device may further include a lower substrate, a polarizing plate disposed under the lower substrate, and a liquid crystal layer disposed between the stacked structure and the lower substrate, in the stacked structure, a photoluminescent layer (i.e., a light-emitting layer) may be disposed to face the liquid crystal layer. The display device may further include a polarizing plate located between the liquid crystal layer and the light-emitting layer. The light source may further include an LED and a light guide plate (if desired).

[0404] In an embodiment, a display device (for example, a liquid crystal display device) is illustrated with reference to the accompanying drawings. Figure 7 is a schematic cross-sectional view showing a liquid crystal display device according to one or more embodiments. Referring to Figure 7 , the display device of the embodiment includes a liquid crystal panel 200, a polarizing plate 300 disposed under the liquid crystal panel 200, and a backlight unit disposed under the polarizing plate 300.

[0405] The liquid crystal panel 200 may include a lower substrate 210, a stacked structure, and a liquid crystal layer 220 disposed between the stacked structure and the lower substrate. The stacked structure may include a transparent substrate 240, a first optical filter layer 310, a photoluminescent layer 230 including a pattern of semiconductor nanoparticle-polymer composites, and a second optical filter layer 311.

[0406] The lower substrate 210 (also referred to as an array substrate) may be a transparent insulating material substrate. The substrate may be as described herein. A wiring board 211 may be disposed on the upper surface of the lower substrate 210. The wiring board 211 may include a plurality of gate lines (not shown) and data lines (not shown) defining pixel regions, thin film transistors disposed adjacent to the cross regions of the gate lines and the data lines, and pixel electrodes for each pixel region, but the embodiments are not limited thereto. Details of such a wiring board are not particularly limited.

[0407] The liquid crystal layer 220 may be disposed on the wiring board 211. The liquid crystal panel 200 may include alignment layers 221 above and below the liquid crystal layer 220 to initially align the liquid crystal material included in the liquid crystal layer 220. Details of the liquid crystal layer and the alignment layer (such as the liquid crystal material, the alignment layer material, the method of forming the liquid crystal layer, the thickness of the liquid crystal layer, etc.) are not particularly limited.

[0408] A polarizing plate 300 may be disposed below the lower substrate. The material and structure of the polarizing plate 300 are not particularly limited. A backlight unit (such as emitting blue light) may be disposed below the polarizing plate 300. An upper optical element or the polarizing plate 300 may be disposed between the liquid crystal layer 220 and the transparent substrate 240, but the embodiments are not limited thereto. For example, an upper polarizing plate may be disposed between the liquid crystal layer 220 and the photoluminescent layer 230. The polarizing plate may be any suitable polarizer that can be used in a liquid crystal display device. The polarizing plate may be a triacetyl cellulose (TAC) having a thickness less than or equal to about 200 μm, but the embodiments are not limited thereto. In another embodiment, the upper optical element may be a coating that controls the refractive index without a polarizing function.

[0409] The backlight unit includes a light source 110. The light source may emit blue light or white light. The light source may include, but is not limited to, blue LEDs, white LEDs, white OLEDs, or combinations thereof.

[0410] The backlight unit may further include a light guide plate 120. In an embodiment, the backlight unit may be edge-type. For example, the backlight unit may include a reflector (not shown), a light guide plate (not shown) disposed on the reflector and providing a planar light source to the liquid crystal panel 200, and / or at least one optical sheet (not shown) on the light guide plate (e.g., a diffuser, a prism sheet, etc.), but the embodiment is not limited thereto. The backlight unit may not include a light guide plate. In an embodiment, the backlight unit may be a direct-type lighting. For example, the backlight unit may have a reflector (not shown) and a plurality of fluorescent lamps at regular intervals on the reflector, or may have an LED operating substrate on which a plurality of light-emitting diodes, a diffuser on the plurality of light-emitting diodes, and an optional at least one optical sheet. The details of such a backlight unit (e.g., each component of the light-emitting diode, fluorescent lamp, light guide plate, various optical sheets, and reflector) are known and are not particularly limited.

[0411] The black matrix 241 may be disposed below the transparent substrate 240 and have an opening and hide the gate lines, data lines and thin film transistors of the wiring board on the lower substrate. For example, the black matrix 241 may have a lattice shape. The photoluminescent layer 230 may be disposed in the opening of the black matrix 241 and may include a semiconductor nanoparticle-polymer composite pattern including a first region R configured to emit a first light (e.g., red light), a second region G configured to emit a second light (e.g., green light) and a third region B configured to emit / transmit a third light (e.g., blue light). If desired, the photoluminescent layer may further include at least one fourth region. The fourth region may include quantum dots that emit light of a different color (e.g., cyan, magenta and yellow light) than the light emitted from the first region to the third region.

[0412] In the photoluminescent layer 230 , a segment where a pattern is formed may be repeated corresponding to a pixel region formed on the lower substrate. A transparent common electrode 231 may be disposed on the photoluminescent layer 230 .

[0413] The third region B configured to emit / transmit blue light may be a transparent color filter that does not change the emission spectrum of the light source. In this case, the blue light emitted from the backlight unit may enter in a polarized state and may be emitted as is through the polarizer and the liquid crystal layer. If desired, the third region may include quantum dots that emit blue light.

[0414] As described herein, if desired, the display device or the light-emitting device according to an embodiment may further include an excitation light blocking layer or a first optical filter layer (hereinafter, referred to as the first optical filter layer). The first optical filter layer may be disposed between the bottom surfaces of the first region R and the second region G and the substrate (e.g., the upper substrate 240), or may be disposed on the upper surface of the substrate. The first optical filter layer may be a sheet having an opening in a portion corresponding to the pixel region (third region) displaying blue, and thus may be formed in a portion corresponding to the first region and the second region. That is, as Figure 1A , Figure 1B and Figure 6 and / or Figure 7 shown, the first optical filter layer may be integrally formed at a position other than the position overlapping with the third region, but the embodiment is not limited thereto. Two or more first optical filter layers may be separated from each other at positions overlapping with the first region, the second region, and optionally the third region. When the light source includes a green light-emitting device, a green light blocking layer may be disposed on the third region.

[0415] The first optical filter layer may block light in a predetermined wavelength region in the visible light region, for example, and may transmit light in other wavelength regions. For example, it may block blue light (or green light) and may transmit light other than blue light (or green light). The first optical filter layer may transmit, for example, green light, red light, and / or yellow light which is a mixed color of green light and red light. The first optical filter layer may transmit blue light and block green light, and may be disposed on a blue light-emitting pixel.

[0416] The first optical filter layer may substantially block excitation light and transmit light in a desired wavelength region. The transmittance of the first optical filter layer for light in the desired wavelength range may be greater than or equal to about 70%, greater than or equal to about 80%, greater than or equal to about 90%, or about 100%.

[0417] A first optical filter layer configured to selectively transmit red light may be disposed at a position overlapping with the red light-emitting section, and a first optical filter layer configured to selectively transmit green light may be disposed at a position overlapping with the green light-emitting section. The first optical filter layer may include: a first filter region that blocks (e.g., absorbs) blue light and red light and selectively transmits light in a predetermined range (e.g., greater than or equal to about 500 nm, greater than or equal to about 510 nm, or greater than or equal to about 515 nm to less than or equal to about 550 nm, less than or equal to about 545 nm, less than or equal to about 540 nm, less than or equal to about 535 nm, less than or equal to about 530 nm, less than or equal to about 525 nm, or less than or equal to about 520 nm); a second filter region that blocks (e.g., absorbs) blue light and green light and selectively transmits light in a predetermined range (e.g., greater than or equal to about 600 nm, greater than or equal to about 610 nm, or greater than or equal to about 615 nm to less than or equal to about 650 nm, less than or equal to about 645 nm, less than or equal to about 640 nm, less than or equal to about 635 nm, less than or equal to about 630 nm, less than or equal to about 625 nm, or less than or equal to about 620 nm); or the first filter region and the second filter region. In an embodiment, the light source may emit a mixed light of blue and green, and the first optical filter layer may further include a third filter region that selectively transmits blue light and blocks green light.

[0418] The first filter region may be disposed at a position overlapping with the green light-emitting section. The second filter region may be disposed at a position overlapping with the red light-emitting section. The third filter region may be disposed at a position overlapping with the blue light-emitting section.

[0419] The first filter region, the second filter region, and the optional third filter region may be optically isolated. Such a first optical filter layer may contribute to improving the color purity of the display device.

[0420] The display device may further include a second optical filter layer (e.g., a recycling layer for red / green or yellow light), which is disposed between the photoluminescent layer and the liquid crystal layer (e.g., between the photoluminescent layer and the upper polarizer), transmits at least a part of the third light (excitation light), and reflects at least a part of the first light and / or the second light. One of the first light and the second light may be red light, the other may be green light, and the third light may be blue light. The second optical filter layer may transmit only the third light (B) in the blue light wavelength region less than or equal to about 500 nm, and the light (which is green light (G), yellow light, red light (R), etc.) in the wavelength region greater than about 500 nm may not pass through the second optical filter layer and is reflected. The reflected green light and red light may pass through the first region and the second region and be emitted to the outside of the display device.

[0421] The second optical filter layer or the first optical filter layer may be formed as an integral layer having a relatively flat surface.

[0422] The first optical filter layer may include a polymer film containing a dye and / or pigment that absorbs light in the wavelength to be blocked. The second optical filter layer or the first optical filter layer may include a single layer having a low refractive index and may be, for example, a transparent film having a refractive index of less than or equal to about 1.4, less than or equal to about 1.3, or less than or equal to about 1.2. The second optical filter layer or the first optical filter layer having a low refractive index may include, for example, porous silica, porous organic materials, porous organic-inorganic composites, etc. or combinations thereof.

[0423] The first optical filter layer or the second optical filter layer may include a plurality of layers having different refractive indices. The first optical filter layer or the second optical filter layer may be formed by laminating two layers having different refractive indices. For example, the first optical filter layer / second optical filter layer may be formed by alternately laminating a material having a high refractive index and a material having a low refractive index.

[0424] Hereinafter, exemplary embodiments will be described in more detail with reference to examples. However, the embodiments of the present disclosure are not limited to these examples.

[0425] Examples

[0426] Analysis methods

[0427] [1] Photoluminescence analysis

[0428] Photoluminescence (PL) spectra of semiconductor nanoparticles and composites including semiconductor nanoparticles were obtained using a Hitachi F-7000 spectrophotometer. The incident light (or excitation light) had a wavelength of 450 nm.

[0429] [2] Blue light absorption rate, quantum efficiency, and conversion efficiency (CE) of the composite

[0430] The amount (B) of incident light having a wavelength of 450 nm was measured using an integrating sphere or integrating hemisphere of an absolute quantum efficiency-measuring device (e.g., QE-2100, Otsuka Electronics Co., Ltd.). Subsequently, the semiconductor nanoparticle (quantum dot, QD)-polymer composite was placed in the integrating (semi)sphere, and then the incident light was irradiated to measure the amount (A) of the first light from the composite and the amount (B') of the incident light passing through the composite, respectively.

[0431] Using the measured amounts, the incident light absorption rate, conversion efficiency (e.g., internal quantum efficiency), and quantum efficiency (e.g., external quantum efficiency) were calculated according to Equation 2, Equation 3, and Equation 4:

[0432] Equation 2: Incident light absorption rate (%) = [(B - B') / B] × 100%

[0433] Equation 3: Light conversion efficiency (%) = [A / (B - B')] × 100%

[0434] Equation 4: Quantum efficiency (%) = [A / B] × 100%

[0435] Wherein, in Equation 2, Equation 3 and Equation 4,

[0436] A is the amount of the first light emitted from the first complex,

[0437] B is the amount of incident light provided to the first complex, and

[0438] B' is the amount of incident light passing through the first complex.

[0439] [3] Process retention percentage

[0440] The semiconductor nanoparticle-polymer complex obtained by polymerization is heat-treated at 180 °C for 30 minutes, and the process retention percentage is measured according to the following equation:

[0441] Equation 5

[0442] Process retention percentage (%) = [IQE2 / IQE1] × 100%

[0443] In Equation 5, IQE1 is the internal quantum efficiency of the semiconductor nanoparticle-polymer complex after polymerization and before heat treatment, and IQE2 is the internal quantum efficiency of the semiconductor nanoparticle-polymer complex after heat treatment.

[0444] [4] Transmission electron microscopy energy-dispersive X-ray spectroscopy

[0445] Transmission electron microscopy energy-dispersive X-ray spectroscopy of the as-prepared composite film is performed using a UTF30 Tecnai electron microscope.

[0446] Preparation of semiconductor nanocrystal particles

[0447] Reference Example 1: AIGS / AGS

[0448] Silver acetate is dissolved in oleylamine to provide a 0.06 molar (M) solution containing a silver precursor (hereinafter abbreviated as "silver precursor"). Sulfur is dissolved in oleylamine to provide a 1 M solution containing a sulfur precursor (hereinafter abbreviated as "sulfur precursor"). Indium chloride is dissolved in ethanol to provide a 0.2 M solution containing an indium precursor (hereinafter abbreviated as indium precursor).

[0449] Gallium acetylacetonate, octadecene (ODE), and dodecanethiol were placed in a 100 milliliter (mL) reaction flask and heated at 120 °C for 10 minutes under vacuum. After cooling the flask to room temperature and introducing nitrogen gas into the flask, a silver precursor, a sulfur precursor, and an indium precursor were added to the flask. The flask was heated at a reaction temperature of 210 °C and the reaction was carried out for 60 minutes. After reducing the temperature of the flask to 180 °C, trioctylphosphine (TOP) was added to the flask, and then hexane and ethanol were added to the obtained mixture to promote precipitation. The solid first semiconductor nanocrystals were separated from the precipitate by centrifugation, and the solid first semiconductor nanocrystals were dispersed in toluene.

[0450] The molar ratio among the indium precursor, gallium precursor (specifically, gallium acetylacetonate), and sulfur precursor used was 1:2.3:4.8.

[0451] Gallium chloride was dissolved in toluene to prepare a 4.5 M solution containing the gallium precursor (hereinafter abbreviated as "gallium precursor").

[0452] Dimethylthiourea (DMTU), oleylamine, and dodecanethiol were placed in a reaction flask and then vacuum-treated at 120 °C for 10 minutes. After introducing N 2 gas into the reaction flask and heating it at 240 °C (predetermined temperature), the first semiconductor nanocrystals, the gallium precursor, and the silver precursor were added to the flask. Then, the reaction flask was heated to 320 °C (reaction temperature) and the temperature was maintained for about 10 minutes (first reaction time). Then the reaction solution was cooled to 180 °C, and trioctylphosphine was added to the flask. Thereafter, the reaction solution was cooled to room temperature. Hexane and ethanol were added to promote precipitation, and the semiconductor nanoparticles were recovered by centrifugation and the semiconductor nanoparticles were redispersed in toluene.

[0453] The molar ratio among the gallium precursor, silver precursor, and sulfur precursor used was 1:0.5:1.

[0454] Reference Example 2: AIGS / AGS / ZnS

[0455] A 0.5 M solution containing a zinc precursor (hereinafter referred to as the zinc precursor) was prepared by dissolving zinc chloride in trioctylphosphine (TOP).

[0456] Dimethylthiourea (DMTU) was dissolved in a mixed solvent of oleylamine at a concentration of 0.5 M in a reaction flask, and the flask was vacuum-treated at 120 °C for 10 minutes. After introducing N 2After the gas flows into the reaction flask, the flask is heated at 210 °C (predetermined temperature), the AIGS / AGS semiconductor nanoparticles and zinc precursor obtained in Reference Example 1 are added to the flask, and the reaction is carried out for about 40 minutes. The reaction solution is cooled to 180 °C, and trioctylphosphine is added to the flask. Thereafter, the reaction solution is cooled to room temperature. Hexane and ethanol are added thereto to promote the precipitation of the semiconductor nanoparticles, and the semiconductor nanoparticles are recovered by centrifugation and redispersed in toluene.

[0457] The molar ratio of the zinc precursor and sulfur precursor (specifically, dimethylthiourea) used is 1:1.

[0458] Reference Example 3: AIGS / AGS / ZnGaS

[0459] A 0.5 M solution containing a zinc precursor (hereinafter referred to as the zinc precursor) is prepared by dissolving zinc chloride in trioctylphosphine (TOP). Gallium chloride is dissolved in toluene to prepare a 4.5 M solution containing a gallium precursor (hereinafter abbreviated as "gallium precursor").

[0460] Dimethylthiourea (DMTU) is dissolved in a mixed solvent of oleylamine at a concentration of 0.5 M in a reaction flask, and the flask is vacuum-treated at 120 °C for 10 minutes. After 2 The gas flows into the reaction flask, and then after the flask is heated to 210 °C (predetermined temperature), the AIGS / AGS semiconductor nanoparticles, zinc precursor and gallium precursor obtained in Reference Example 1 are added to the flask, and the reaction is carried out for about 40 minutes. Then the reaction solution is cooled to 180 °C, and trioctylphosphine is added to the flask. Thereafter, the reaction solution is cooled to room temperature. Hexane and ethanol are added thereto to promote the precipitation of the semiconductor nanoparticles, and the semiconductor nanoparticles are recovered by centrifugation and redispersed in toluene.

[0461] The molar ratio of the zinc precursor and sulfur precursor (specifically, dimethylthiourea) used is 1:4. The molar ratio of the zinc precursor and gallium precursor used is 1:2.

[0462] Manufacture of ligand-exchanged semiconductor nanoparticles and manufacture of ink compositions and composites therefrom

[0463] Example 1:

[0464] [1] Ligand exchange

[0465] Zinc oleate is added to the toluene dispersion of the semiconductor nanocrystal particles obtained in Reference Example 1 at room temperature, and stirred for 3 hours. Ethanol is added to the resulting dispersion to promote the precipitation of the particles, and the zinc salt-treated semiconductor nanocrystal particles are recovered by centrifugation.

[0466] A first ligand compound solution was prepared by dissolving 2-carboxyethyl acrylate (CAS No.: 24615-84-7, purchased from Sigma Aldrich Co., Ltd.) having the following formula in toluene:

[0467]

[0468] Zinc chloride was dissolved in acetone to provide a second metal halide in solution form. Semiconductor nanocrystal particles treated with a zinc salt were dispersed in toluene to prepare a dispersion. The first ligand compound solution and the second metal halide were mixed with the dispersion and stirred at room temperature for at least about 3 hours to carry out a ligand exchange reaction.

[0469] Then hexane was added to the reaction solution to induce precipitation of the ligand-exchanged particles, and the ligand-exchanged particles were recovered by centrifugation and dried.

[0470] The amount of the first organic ligand used in the ligand exchange was 4000 moles per mole of semiconductor nanocrystals. Based on the number of moles of the organic ligand used, the amount of zinc chloride was 5 mol%.

[0471] [2] Preparation of Ink Composition and Semiconductor Nanoparticle-Polymer Composite

[0472] The ligand-exchanged nanoparticles were dispersed in ethanol to obtain a dispersion. As observed with the naked eye, the dispersion was a transparent dispersion, indicating that the ligand-exchanged nanoparticles could achieve a colloidal dispersion state in ethanol. A washing process was carried out by adding hexane to the dispersion to precipitate the nanoparticles included in the dispersion. The washed nanoparticles were dried to obtain semiconductor nanoparticles in powder form.

[0473] As the first metal halide, zinc chloride was dissolved in acetone to prepare the first metal halide in solution form.

[0474] An ink composition was prepared by adding the washed semiconductor nanoparticles, titanium oxide nanoparticles, the first metal halide (as an acetone solution of zinc chloride), and an initiator to hexanediol diacrylate (monomer). The prepared ink composition was dried under a vacuum state to remove volatile solvent components (e.g., acetone).

[0475] In the ink composition, the amounts of the semiconductor nanoparticles, titanium oxide nanoparticles, and initiator were 38 wt%, 5 wt%, and 1 wt%, respectively. The amount of zinc chloride was 100 moles per mole of semiconductor nanoparticles, and the balance of the composition was the monomer.

[0476] The prepared composition was deposited on a substrate and exposed (exposure dose: 12 joules) for photopolymerization to obtain a film with a thickness of 7 micrometers (μm). The internal quantum efficiency (IQE) of the complex was measured for the prepared film, and the results are summarized in Table 2. The obtained film was heat-treated at a temperature of 180 °C for 30 minutes, and the internal quantum efficiency (IQE) of the heat-treated film was measured in the same manner. The results are summarized in Table 2.

[0477] The prepared composite film was subjected to TED-EDX analysis (transmission electron microscopy energy-dispersive X-ray spectroscopy), and the results are summarized in Table 3 and Figure 8 in.

[0478] The distribution of each element relative to the prepared composite film was measured by TEM-EDX, and some results are shown in Figure 10 in. As a result of measuring the spectral profiles for each element, it was observed that the concentration gradients of carbon and oxygen reached a depth of 500 nm. At the same time, it was confirmed that the distribution of chlorine, like that of zinc, indium, and sulfur, was relatively uniformly distributed in the depth direction.

[0479] Example 2

[0480] [1] Ligand exchange

[0481] The ligand exchange reaction was carried out in the same manner as in Example 1, except that indium chloride (InCl 3 ) was used instead of zinc chloride as the second metal halide.

[0482] [2] Preparation of ink composition and semiconductor nanoparticle-polymer composite

[0483] An ink composition and a composite film were obtained in the same manner as in Example 1, except that the ligand-exchanged semiconductor nanoparticles prepared above were used and the first metal halide was not blended. The internal quantum efficiency (IQE) of the complex was measured for the prepared film, and the results are summarized in Table 2.

[0484] The obtained film was heat-treated at a temperature of 180 °C for 30 minutes, and the internal quantum efficiency (IQE) of the heat-treated film was measured in the same manner. The results are summarized in Table 2.

[0485] Example 3

[0486] [1] Ligand exchange

[0487] The ligand exchange reaction was carried out in the same manner as in Example 1, except that indium chloride was used instead of zinc chloride as the second metal halide.

[0488] [2] Preparation of ink composition and semiconductor nanoparticle-polymer composite

[0489] In addition to using the ligand-exchanged semiconductor nanoparticles prepared above, an ink composition and a composite film were obtained in the same manner as in Example 1. The internal quantum efficiency (IQE) of the composite was measured for the prepared film, and the results are summarized in Table 2.

[0490] The obtained film was heat-treated at a temperature of 180 °C for 30 minutes, and the internal quantum efficiency (IQE) of the heat-treated film was measured in the same manner. The results are summarized in Table 2.

[0491] Example 4

[0492] [1] Ligand exchange

[0493] The ligand exchange reaction was carried out in the same manner as in Example 1, except that indium chloride was used as the second metal halide together with zinc chloride. The amount of zinc chloride was 5 mol% relative to the amount of the first organic ligand, and the amount of indium chloride was 5 mol% relative to the amount of the first organic ligand.

[0494] [2] Preparation of ink composition and semiconductor nanoparticle-polymer composite

[0495] An ink composition and a composite film were obtained in the same manner as in Example 1, except that the ligand-exchanged semiconductor nanoparticles prepared above were used and the first metal halide (zinc chloride) was not added. The internal quantum efficiency (IQE) of the composite was measured for the prepared film, and the results are summarized in Table 2.

[0496] The obtained film was heat-treated at a temperature of 180 °C for 30 minutes, and the internal quantum efficiency (IQE) of the heat-treated film was measured in the same manner. The results are summarized in Table 2.

[0497] Example 5

[0498] [1] Ligand exchange

[0499] The ligand exchange reaction was carried out in the same manner as in Example 1, except that the AIGS / AGS / ZnS semiconductor nanoparticles prepared in Reference Example 2 were used.

[0500] [2] Preparation of ink composition and semiconductor nanoparticle-polymer composite

[0501] An ink composition and a composite film were obtained in the same manner as in Example 1, except that the ligand-exchanged semiconductor nanoparticles prepared above were used. The internal quantum efficiency (IQE) of the composite was measured for the prepared film, and the results are summarized in Table 2.

[0502] The obtained film was heat-treated at a temperature of 180 °C for 30 minutes, and the internal quantum efficiency (IQE) of the heat-treated film was measured in the same manner. The results are summarized in Table 2.

[0503] Example 6

[0504] [1] Ligand exchange

[0505] Except for using the AlGS / AGS / ZnGaS semiconductor nanoparticles prepared in Reference Example 3, the ligand exchange reaction was carried out in the same manner as in Example 1.

[0506] [2] Preparation of ink composition and semiconductor nanoparticle-polymer composite

[0507] Except for using the ligand-exchanged semiconductor nanoparticles prepared above, the ink composition and the composite film were obtained in the same manner as in Example 1. The internal quantum efficiency (IQE) of the composite was measured for the prepared film, and the results are summarized in Table 2.

[0508] The obtained film was heat-treated at a temperature of 180 °C for 30 minutes, and the internal quantum efficiency (IQE) of the heat-treated film was also measured. The results are summarized in Table 2.

[0509] TED-EDX analysis was performed on the prepared composite film, and the results are summarized in Table 3 and Figure 9 in.

[0510] Example 7

[0511] [1] Ligand exchange

[0512] Except for using the AIGS / AGS / ZnGaS semiconductor nanoparticles prepared in Reference Example 3 and using indium chloride instead of zinc chloride as the second metal halide, the ligand exchange reaction was carried out in the same manner as in Example 1.

[0513] [2] Preparation of ink composition and semiconductor nanoparticle-polymer composite

[0514] Except for using the ligand-exchanged semiconductor nanoparticles prepared above, the ink composition and the composite film were obtained in the same manner as in Example 1. The internal quantum efficiency (IQE) of the composite was measured for the prepared film, and the results are summarized in Table 2.

[0515] The obtained film was heat-treated at a temperature of 180 °C for 30 minutes, and the internal quantum efficiency (IQE) of the heat-treated film was also measured. The results are summarized in Table 2.

[0516] Comparative Example 1

[0517] [1] Ligand exchange

[0518] The ligand exchange reaction was carried out in the same manner as in Example 1, except that the semiconductor nanoparticles untreated with zinc salt in Reference Example 1 were used instead of the semiconductor nanoparticles treated with zinc salt, and the second metal halide (i.e., zinc chloride solution) was not used.

[0519] [2] Preparation of Ink Composition and Semiconductor Nanoparticle-Polymer Composite

[0520] The ink composition and the composite film were obtained in the same manner as in Example 1, except that the ligand-exchanged semiconductor nanoparticles prepared above were used and the first metal halide was not used. The internal quantum efficiency (IQE) of the composite was measured for the prepared film, and the results are summarized in Table 2.

[0521] The obtained film was heat-treated at a temperature of 180 °C for 30 minutes, and the internal quantum efficiency (IQE) of the heat-treated film was similarly measured. The results are summarized in Table 2.

[0522] TED-EDX analysis was performed on the prepared composite film, and the results are summarized in Table 3.

[0523] Comparative Example 2

[0524] [1] Ligand Exchange

[0525] Ligand-exchanged semiconductor nanoparticles were prepared in the same manner as in Example 1, except that the first organic ligand was not used (i.e., only zinc chloride was used as the second metal chloride) and ethanol was used for precipitation. The amount of zinc chloride used was controlled to be 5000 to 15000 moles per mole of semiconductor nanoparticles.

[0526] It was confirmed that the ligand-exchanged semiconductor nanoparticles were dispersible in hexane but not in ethanol.

[0527] [2] Preparation of Ink Composition

[0528] An ink composition was prepared in the same manner as in Example 1, except that the ligand-exchanged semiconductor nanoparticles prepared above were used and the first metal halide was not used. It was confirmed that when mixed with the monomer, the semiconductor nanoparticles significantly agglomerated, and thus, an ink capable of forming a thin film was not obtained.

[0529] Comparative Example 3

[0530] [1] Ligand Exchange

[0531] Ligand-exchanged semiconductor nanoparticles were prepared in the same manner as in Example 1, except that the first organic ligand was not used, indium chloride was used instead of zinc chloride as the second metal chloride, and ethanol was used for precipitation. The amount of indium chloride used was controlled to be 5000 to 15000 moles per mole of semiconductor nanoparticles.

[0532] It was confirmed that the ligand-exchanged semiconductor nanoparticles were dispersible in hexane but not in ethanol.

[0533] [2] Preparation of Ink Composition

[0534] An ink composition was prepared in the same manner as in Example 1 except that the ligand-exchanged semiconductor nanoparticles prepared above were used and the first metal halide was not used. It was confirmed that when mixed with the monomer, the semiconductor nanoparticles significantly agglomerated, and thus, an ink capable of forming a thin film was not obtained.

[0535] Table 1

[0536]

[0537]

[0538] Table 2

[0539]

[0540] It was confirmed from Table 2 that the ink composition and the semiconductor nanoparticle-polymer composite of the examples could exhibit significantly improved quantum efficiency and process stability compared to the comparative examples.

[0541] Experimental Example 1

[0542] ICP-AES analysis (inductively coupled plasma atomic emission spectrometry analysis) was performed on the inks prepared in Example 1, Example 6, and Comparative Example 1, and the results are summarized in Table 3.

[0543] Table 3

[0544]

[0545] Charge balance value = {[Ag] + 3([In] + [Ga]) + 2[Zn]} / (2[S])

[0546] Although the present disclosure has been described in connection with what are presently considered to be practical embodiments, it is to be understood that the subject matter is not limited to the disclosed exemplary embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. An ink composition comprising: polymerizable monomers; as well as Semiconductor nanoparticles, wherein the semiconductor nanoparticles include a Group 11-13-16 compound and optionally zinc, the Group 11-13-16 compound includes silver, a Group 13 metal, and a Group 16 element, wherein the Group 13 metal includes indium and gallium, wherein the Group 16 element includes sulfur, Wherein, the ink composition further comprises a metal halide and a first organic ligand, and wherein the first organic ligand comprises a compound or a moiety represented by R1-COO-A, wherein R1 is a first organic group and A represents hydrogen or a moiety connected to the surface of the semiconductor nanoparticle.

2. The ink composition according to claim 1, wherein The first organic ligand includes a compound having a molecular weight greater than or equal to 10 g / mol and less than or equal to 800 g / mol.

3. The ink composition according to claim 1, in, The semiconductor nanoparticles also include zinc.

4. The ink composition according to claim 1, in, The metal halide includes zinc halide, indium halide, gallium halide, or a combination thereof.

5. The ink composition according to claim 1, wherein In the semiconductor nanoparticles, a molar ratio of gallium to indium is greater than or equal to 1:1 and less than or equal to 10:

1.

6. The ink composition according to claim 1, wherein In semiconductor nanoparticles, The molar ratio of zinc to silver is greater than or equal to 0.3:1 and less than or equal to 5:1, or a molar ratio of zinc to gallium greater than or equal to 0.4:1 and less than or equal to 1.5:1, or The molar ratio of zinc to the sum of gallium and indium is greater than or equal to 0.46:1 and less than or equal to 1.33:

1.

7. The ink composition according to claim 1, wherein In the ink composition, The amount of the semiconductor nanoparticles is greater than or equal to 25 wt % and less than or equal to 80 wt % based on the total weight of the ink composition.

8. The ink composition according to claim 1, in, Metal halides include metal chlorides, and Wherein, in the ink composition, a molar ratio of chlorine to indium is greater than or equal to 2:1 and less than or equal to 10:

1.

9. A method for producing the ink composition according to claim 1, the method comprising: Semiconductor nanoparticles and metal halides are admixed with polymerizable monomers.

10. The method according to claim 9, wherein: The steps of preparing semiconductor nanoparticles include: The semiconductor nanocrystal particles including the 11-13-16 group compound are mixed with the metal salt compound and the first organic ligand in an organic solvent. The metal salt compound includes zinc, indium, gallium or a combination thereof.

11. The method according to claim 10, wherein: The metal salt compound includes indium chloride, zinc chloride, or a combination thereof.

12. The method according to claim 10, wherein: Semiconductor nanocrystalline particles comprising Group 11-13-16 compounds include zinc salt treated semiconductor nanoparticles, The zinc salt-treated semiconductor nanoparticles are obtained by contacting semiconductor nanoparticles including a Group 11-13-16 compound with a zinc salt compound in an organic solvent in the absence of a first organic ligand.

13. The method according to claim 9, wherein: The metal halide includes indium halide, zinc halide, gallium halide, or a combination thereof.

14. A semiconductor nanoparticle-polymer composite comprising a polymer and a semiconductor nanoparticle, in, The semiconductor nanoparticles include 11-13-16 group compounds, the 11-13-16 group compounds include silver, 13 group metals and 16 group elements, wherein the 13 group metals include indium and gallium, wherein the 16 group elements include sulfur, wherein the semiconductor nanoparticle-polymer composite further comprises halogen, and Wherein, in the semiconductor nanoparticle-polymer composite, the molar ratio of halogen to indium is greater than or equal to 2:1 and less than or equal to 10:

1.

15. The semiconductor nanoparticle-polymer composite according to claim 14, wherein Semiconductor nanoparticles also include zinc, Wherein, in the semiconductor nanoparticle-polymer composite: The molar ratio of zinc to indium is greater than or equal to 2:1 and less than or equal to 30:1, The molar ratio of zinc to gallium is greater than or equal to 0.5:1 and less than or equal to 10:1, or The molar ratio of gallium to indium is greater than or equal to 2:1 and less than or equal to 10:

1.

16. The semiconductor nanoparticle-polymer composite according to claim 14, wherein In the semiconductor nanoparticle-polymer composite, The molar ratio of halogen to indium is less than or equal to 7:1, and The molar ratio of the halogen to gallium is greater than or equal to 0.1:1 and less than or equal to 1:

1.

17. A color conversion device, comprising: a color conversion layer comprising color conversion regions and optional partition walls defining each color conversion region of the color conversion layer, wherein the color conversion region includes a first region corresponding to the first pixel, and Wherein, the first region comprises the semiconductor nanoparticle-polymer composite according to claim 14 .

18. A display device comprising: light source; as well as The semiconductor nanoparticle-polymer composite according to claim 14, Therein, the light source is configured to provide incident light to the semiconductor nanoparticle-polymer composite.

19. The display device according to claim 17, wherein: The light source includes an organic light emitting diode, a micro light emitting diode, a mini light emitting diode, a light emitting diode including nanorods, or a combination thereof.

20. The display device according to claim 17, wherein: The display device is a portable terminal device, a monitor, a personal computer, a television, an electronic display panel, or an electronic component for a vehicle.

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