Semiconductor nanoparticle, production method thereof, electronic device including the same

Abstract

To provide a manufacturing method capable of manufacturing semiconductor nanoparticles that exhibit improved properties in increased yield; semiconductor nanoparticles manufactured by the method; and an electronic device including the semiconductor nanoparticles.SOLUTION: A method of manufacturing semiconductor nanoparticles includes the steps for: combining a first semiconductor nanocrystal that includes silver, a Group 13 element, and a chalcogen element, a gallium precursor, a sulfur precursor, and a silver compound in a medium including an organic solvent; and heating the medium at a reaction temperature to obtain a crude solution including the semiconductor nanoparticles. The semiconductor nanoparticles include silver, indium, gallium, and sulfur, and their size is greater than or equal to 2 nm and less than or equal to 50 nm.SELECTED DRAWING: Figure 8

Description

[Technical field]

[0001] The present invention relates to semiconductor nanoparticles, a method for producing the same, and an electronic device including the same, and more particularly to semiconductor nanoparticles exhibiting improved physical properties, a method for producing the same, and an electronic device including the same. [Background technology]

[0002] Semiconductor nanoparticles exhibit characteristics that differ from bulk materials in terms of their intrinsic properties and known physical properties (energy band gap, melting point, etc.). For example, the semiconductor nanoparticles are configured to emit light upon energy excitation (eg, irradiation with light or application of a voltage). Such luminescent nanoparticles may find a wide variety of possible applications in a variety of devices (eg, electronic devices).

[0003] However, from an environmental perspective, it would be preferable to develop luminescent nanoparticles that provide improved luminescent properties and that do not contain hazardous heavy metals such as cadmium. Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention has been made in consideration of the above-mentioned problems with conventional semiconductor nanoparticles, and an object of the present invention is to provide a method for producing semiconductor nanoparticles exhibiting improved physical properties with an increased yield. Another object of the present invention is to provide semiconductor nanoparticles or a population thereof produced by the above production method.

[0005] Another object of the present invention is to provide a composition (for example, an ink composition) or a composite containing the semiconductor nanoparticles. Another object of the present invention is to provide a color conversion panel containing the semiconductor nanoparticles. Another object of the present invention is to provide an electronic device (for example, a display device) including the semiconductor nanoparticles or the color conversion panel. [Means for solving the problem]

[0006] The method for producing semiconductor nanoparticles according to the present invention, which has been made to achieve the above-mentioned object, includes the steps of combining a first semiconductor nanocrystal containing silver, a Group 13 element, and a chalcogen element, a gallium precursor, a sulfur precursor, and a silver compound into a medium containing an organic solvent, and heating the medium at a reaction temperature to obtain a crude solution containing the semiconductor nanoparticles, wherein the semiconductor nanoparticles contain silver, indium, gallium, and sulfur and have a size of 2 nm or more and 50 nm or less.

[0007] For example, the size is preferably 10 nm or less. The method may further include adding a non-solvent to the crude solution to precipitate and separate the semiconductor nanoparticles. The crude solution preferably has an optical density, defined by the following mathematical formula 1 at a wavelength of 500 nm, of 1 or more and 10 or less. (Number 1) optical density=log 10 (I O / I T )···Equation 1 (Here, I O is the intensity of incident light supplied to the crude solution, I T is the intensity of transmitted light passing through the crude solution. At a wavelength of 500 nm, said optical density is preferably 1.5 or more and 5 or less. The crude solution preferably has an optical density of 8 or more, for example 10 or more and 100 or less, at a wavelength of 350 nm. It is preferred that the optical density is 12 or more and 50 or less at a wavelength of 350 nm. The crude solution was analyzed by UV-Vis absorption spectroscopy, where the ratio of absorbance at 500 nm to absorbance at 350 nm (A 500 :A 350 ) is preferably 0.01 or more and 0.8 or less.

[0008] The silver compound is preferably added to the medium in a content of 0.1 mol % or more, for example 0.5 mol % or more and 50 mol % or less, for example 25 mol % or less, relative to the gallium precursor. The content of the silver compound is preferably 1 mol % or more and 12 mol % or less. Preferably, the silver compound comprises a silver carboxylate, a silver acetylacetonate, a silver halide, or a combination thereof. In one embodiment, the combining is preferably carried out at a predetermined temperature (eg, a first temperature). The first temperature is preferably 120° C. or higher (eg, 180° C. or higher, or 190° C. or higher, or 200° C. or higher) and lower than the reaction temperature, for example, 280° C. or lower (eg, 250° C. or lower). The reaction temperature is preferably 180° C. or higher, 190° C. or higher and 380° C. or lower, or 280° C. or lower. The predetermined temperature is preferably 210°C or higher and 380°C or lower. The Group 13 element preferably includes indium, gallium, or indium and gallium. The chalcogen element preferably includes sulfur, selenium, or a combination thereof. The first semiconductor nanocrystals preferably contain silver, indium, gallium, and sulfur (Group 11-13-16 compounds containing the same).

[0009] It is preferable that the production method has a production yield of 6% or more, as determined by the following mathematical formula 2. (Number 2) Production yield = A / B × 100 Formula 2 (wherein A is the total weight of silver, Group 13 element, and sulfur in the semiconductor nanoparticles recovered from the crude solution, and B is the total weight of silver, Group 13 element, and sulfur added to the reaction medium for the reaction.) The production yield is preferably 10% or more. The production yield is preferably 100% or less, 90% or less, or 60% or less. The semiconductor nanoparticles preferably have an (absolute) quantum yield of 65% or more.

[0010] The semiconductor nanoparticles preferably have an average size of 5 nm or more and 10 nm or less, with a standard deviation of 20% or less of the average size. Preferably, the standard deviation is 15% or less, or 13% or less. Preferably, said average size is greater than or equal to 5 nm and less than or equal to 8 nm.

[0011] The semiconductor nanoparticles preferably have a charge balance value, calculated by the following Equation 3, of 0.8 or more and 1.3 or less. (Number 3) charge balance value = {[Ag] + 3 × ([In] + [Ga])} / (2 × [S]) Equation 3 (where [Ag], [In], [Ga], and [S] are the molar contents of silver, indium, gallium, and sulfur, respectively, in the semiconductor nanoparticles.) The semiconductor nanoparticles preferably include the first semiconductor nanocrystals and second semiconductor nanocrystals containing silver, gallium, or sulfur. The second semiconductor nanocrystals are preferably disposed on the first semiconductor nanocrystals.

[0012] Preferably, the method further includes the steps of preparing an additional reaction medium containing a zinc precursor and optionally an organic ligand in an organic solvent, and adding and reacting the formed nanoparticles and a chalcogen precursor while heating the additional reaction medium at a reaction temperature to provide a third semiconductor nanocrystal containing a zinc chalcogenide or an outer layer containing the same on a surface of the semiconductor nanoparticle.

[0013] The semiconductor nanoparticles according to the present invention, which have been made to achieve the above object, have the characteristics described herein. Semiconductor nanoparticles according to the present invention can be produced by the methods described herein. The semiconductor nanoparticles include silver (Ag), indium, gallium, and sulfur. It is preferable that the semiconductor nanoparticles according to the present invention have an average size of 5 nm or more and 10 nm or less, a standard deviation of 20% or less and 5% or more of the average size, and that the semiconductor nanoparticles have a charge balance value obtained by the following Equation 3 of 0.95 or more and 1.2 or less. (Number 3) charge balance value = {[Ag] + 3 × ([In] + [Ga])} / (2 × [S]) Equation 3 (where [Ag], [In], [Ga], and [S] are the molar contents of silver, indium, gallium, and sulfur, respectively, in the semiconductor nanoparticles.)

[0014] The semiconductor nanoparticles are configured to emit green light (eg, first light), and the green light preferably has an emission peak wavelength in the range of 520 nm or more and 540 nm or less. The first light preferably has an emission peak wavelength of 500 nm or more and 600 nm or less. The emission peak wavelength of the green light is preferably in the range of 500 nm or more, or 505 nm or more and 580 nm or less, or 550 nm or less. The third semiconductor nanocrystals preferably have a different composition than the first and second semiconductor nanocrystals. In the semiconductor nanoparticles, the third semiconductor nanocrystal is preferably disposed on the second semiconductor nanocrystal. When present, the third semiconductor nanocrystal is preferably the outermost layer of the semiconductor nanoparticle. The first semiconductor nanocrystals are preferably zinc-free. The semiconductor nanoparticles may or may not contain lithium. The semiconductor nanoparticles may or may not include an alkali metal (eg, lithium, sodium, potassium, etc.). The semiconductor nanoparticles preferably have an (absolute) quantum yield of 65% or more. The semiconductor nanoparticles preferably have a quantum yield of 70% or more and 99% or less, and a half-width of 15 nm or more and 70 nm or less. The quantum yield is preferably 70% or more. The quantum yield is preferably 98% or less, or 90% or less. The semiconductor nanoparticles preferably have a half-width of 70 nm or less, 40 nm or less, or 35 nm or less. The half width is preferably 5 nm or more, 10 nm or more, 15 nm or more, or 25 nm or more. Preferably, the charge balance value is greater than or equal to 1 and less than or equal to 1.15.

[0015] In the semiconductor nanoparticles, it is preferred that the molar ratio of gallium to indium (Ga / In) is 1 or more and 10 or less, and the molar ratio of gallium to silver (Ga / Ag) is 1.1 or more and 3 or less. The molar ratio of gallium to indium (Ga / In) is preferably 3.3 or more, 3.5 or more, and 10 or less, 8 or less, 6.5 or less, 5.5 or less, or 4.1 or less. In the semiconductor nanoparticles, the molar ratio of gallium to the sum of indium and gallium [Ga / (In+Ga)] is preferably 0.7 or more, or 0.75 or more and 0.99 or less, or 0.85 or less, or 0.82 or less. The semiconductor nanoparticles preferably have a molar ratio of gallium to silver (Ga / Ag) of 1.1 or more, or 1.35 or more. The semiconductor nanoparticles preferably have a molar ratio of gallium to silver (Ga / Ag) of 3 or less, 2 or less, or 1.58 or less.

[0016] In the semiconductor nanoparticles, it is preferable that the molar ratio of gallium to the sum of gallium, indium, and silver (Ga / (Ga+In+Ag)) is 0.45 or more and 0.65 or less, and the molar ratio of the sum of indium and gallium to silver ((In+Ga) / Ag) is 1.2 or more and 3.5 or less. In the semiconductor nanoparticles, the molar ratio of the sum of indium and gallium to silver ((In+Ga) / Ag) is preferably 1.2 or more, 1.4 or more, or 1.7 or more. In the semiconductor nanoparticles, the molar ratio of the sum of indium and gallium to silver ((In+Ga) / Ag) is preferably 3.7 or less, 3.5 or less, or 2 or less. The semiconductor nanoparticles preferably have a molar ratio of silver to sulfur (Ag / S) of 0.05 or more, 0.2 or more, or 0.32 or more. The semiconductor nanoparticles preferably have a molar ratio of silver to sulfur (Ag / S) of 0.5 or less, 0.41 or less, or 0.35 or less. The semiconductor nanoparticles preferably have a molar ratio of silver to indium (Ag / In) of 1.5 or more, 2 or more, or 2.5 or more. The semiconductor nanoparticles preferably have a molar ratio of silver to indium (Ag / In) of 6 or less, 4.5 or less, or 3 or less.

[0017] The semiconductor nanoparticles include silver, indium, and The molar ratio of silver to the sum of gallium (Ag / (Ag+In+Ga)) is 0.2 or more. and 0.45 or less, silver, indium, and The molar ratio of sulfur to the sum of gallium (S / (Ag+In+Ga)) is 0.8 or more. and It is preferably 1.5 or less. In the semiconductor nanoparticles, the molar ratio of silver to the sum of silver, indium, and gallium (Ag / (Ag+In+Ga)) is preferably 0.2 or more, 0.33 or more, or 0.35 or more. In the semiconductor nanoparticles, the molar ratio of silver to the sum of silver, indium, and gallium (Ag / (Ag+In+Ga)) is preferably 0.45 or less, or 0.41 or less. In the semiconductor nanoparticles, the molar ratio of sulfur to the sum of silver, indium, and gallium (S / (Ag+In+Ga)) is preferably 0.8 or more, 0.9 or more, or 1 or more. In the semiconductor nanoparticles, the molar ratio of sulfur to the sum of silver, indium, and gallium (S / (Ag+In+Ga)) is preferably 1.5 or less, 1.3 or less, 1.13 or less, or 1.08 or less. In the semiconductor nanoparticles, the molar ratio of gallium to sulfur (Ga / S) is preferably 0.4 or more, or 0.44 or more. In the semiconductor nanoparticles, the molar ratio of gallium to sulfur (Ga / S) is preferably 0.6 or less, or 0.51 or less. The green light preferably includes band edge emission.

[0018] One embodiment of the present invention provides a semiconductor nanoparticle or population thereof as described herein. In one embodiment, for example, the plurality of semiconductor nanoparticles comprises first semiconductor nanocrystals comprising silver, indium, gallium, and sulfur, and has an average size of 5 nm or more and 8 nm or less, 7.5 nm or less, with a standard deviation of 20% or less, or 15% or less and 5% or more; the semiconductor nanoparticles are configured to emit a first light (e.g., green light or red light); The semiconductor nanoparticles have a charge balance value, obtained by the following Equation 3, of 0.95 or more and 1.2 or less. (Number 3) charge balance value={[Ag]+3×([In]+[Ga])} / (2×[S]) (where [Ag], [In], [Ga], and [S] are the molar contents of silver, indium, gallium, and sulfur, respectively, in the semiconductor nanoparticles.) Preferably, the semiconductor nanoparticles are arranged to emit green light. Preferably, the semiconducting nanoparticles are arranged to emit red light. The green light preferably has an emission peak wavelength in the range of 520 nm to 540 nm. The red light preferably has an emission peak wavelength in the range of 600 nm or more and 650 nm or less.

[0019] In one embodiment of the present invention, the ink composition preferably comprises the semiconductor nanoparticles described above and a liquid vehicle. The semiconductor nanoparticles or population thereof are preferably dispersed within the liquid vehicle. The liquid vehicle preferably comprises a liquid monomer, an organic solvent, or a combination thereof. The ink composition preferably does not substantially contain a volatile organic solvent. The ink composition preferably further contains metal oxide fine particles.

[0020] In one embodiment of the present invention, the composite preferably comprises a matrix and the semiconductor nanoparticles dispersed in the matrix. The composite preferably further contains metal oxide fine particles. The composite is preferably configured to emit green light. The composite is preferably a patterned film. Preferably, the composite further comprises semiconductor nanoparticles configured to emit a second light different from the green light.

[0021] In one embodiment of the present invention, a display device preferably includes a light source and the composite. The light source is preferably configured to provide incident light to the composite. An embodiment of the present invention preferably provides a color conversion layer (eg, a color conversion structure or a color conversion panel) that includes a color conversion region that includes the semiconductor nanoparticles described above. The color conversion panel or color conversion structure preferably includes a color conversion layer including a color conversion region and a partition wall selectively defining each region of the color conversion layer, the color conversion region including a first region corresponding to a first pixel, and the first region including the semiconductor nanoparticles or the composite. In an embodiment of the present invention, a display panel or display device preferably includes a light source and a color conversion layer (eg, a color conversion structure) disposed on the light source.

[0022] In one embodiment of the present invention, the display panel preferably includes a light emitting panel (or light source), the color conversion panel, and optionally a light transmitting layer disposed between the light emitting panel and the color conversion panel. The light emitting panel (or light source) is preferably configured to provide incident light to the colour conversion panel. Preferably, the incident light comprises blue light and optionally green light. The blue light preferably has a peak wavelength in the range of 440 nm to 460 nm or 450 nm to 455 nm. The light source preferably comprises an organic light emitting diode, a micro LED, a mini LED, an LED including a nanorod, or a combination thereof. In one embodiment of the present invention, an electronic device (or a display device) preferably includes the color conversion panel or the display panel. Effect of the Invention

[0023] According to the method for producing semiconductor nanoparticles according to the present invention, 11-13-16 group semiconductor nanoparticles having improved optical properties (e.g., improved blue light absorptance and narrow half-width, increased luminous efficiency) can be produced with an increased production yield. The light conversion sheet or color conversion panel including the semiconductor nanoparticles of the present invention can utilize various light sources and can be usefully used in liquid crystal displays, QD OLED devices, and QD micro LED displays in which a QD color conversion layer or pixel is applied to a blue micro LED. The semiconductor nanoparticles of the present invention and a color conversion panel including the same can be applied to various devices such as TVs, monitors, mobile devices, VR / AR, and vehicle electrical displays. [Brief description of the drawings]

[0024] [Figure 1a] FIG. 2 is a diagram illustrating a pattern formation process (by photolithography) using an ink composition according to an embodiment of the present invention. [Figure 1b] 1A to 1C are diagrams illustrating a pattern formation process (by an inkjet method) using an ink composition according to an embodiment of the present invention. [Figure 2a] 1 is a cross-sectional view showing a schematic configuration of a color conversion panel according to an embodiment of the present invention. [Figure 2b] FIG. 11 is a cross-sectional view showing a schematic configuration of an electronic device (display device) including a color conversion panel according to another embodiment of the present invention. [Figure 3a] 1 is a perspective view showing an example of a display panel including a color conversion panel according to an embodiment of the present invention. [Figure 3b] FIG. 11 is an exploded perspective view showing a schematic configuration of a display device according to another embodiment of the present invention. [Figure 3c] FIG. 3b is a cross-sectional view of the display panel of FIG. 3a. [Figure 4] FIG. 11 is an exploded perspective view showing a schematic configuration of a display device according to another embodiment of the present invention. [Figure 5a] FIG. 3b is a plan view showing an example of a pixel arrangement of the display panel of FIG. 3a. [Figure 5b] 1 is a cross-sectional view illustrating an example of a light emitting device according to an embodiment of the present invention. [Figure 5c] 1 is a cross-sectional view illustrating an example of a light emitting device according to an embodiment of the present invention. [Figure 5d]1 is a cross-sectional view illustrating an example of a light emitting device according to an embodiment of the present invention. [Figure 5e] 1 is a cross-sectional view illustrating an example of a light emitting device according to an embodiment of the present invention. [Figure 6] 5b is a cross-sectional view taken along line IV-IV in the pixel array of FIG. 5a. FIG. [Figure 7a] 1 is a cross-sectional view showing a schematic configuration of a display device (for example, a liquid crystal display device) according to an embodiment of the present invention. [Figure 7b] 1 is a schematic cross-sectional view of an electronic device (eg, a light-emitting device) according to an embodiment of the present invention. [Figure 8] 1 is a graph showing UV-Vis absorption spectra of a crude solution of Example 1 (100-fold dilution) and a crude solution of Comparative Example 1 (100-fold dilution). [Figure 9] 1 is a graph showing the UV-Vis absorption spectrum of the crude solution (100-fold diluted) of Example 2-4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Next, specific examples of embodiments for carrying out the semiconductor nanoparticles and the method for producing the same according to the present invention, as well as electronic devices including the same, will be described with reference to the drawings.

[0026] The advantages and features of the technology described below, and the methods for achieving them, will become apparent from the following detailed description of the embodiments in conjunction with the accompanying drawings. However, the implementation is not limited to the embodiments disclosed below. Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used with the same meaning as commonly understood by one of ordinary skill in the art. Furthermore, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless expressly and specifically defined. Throughout the specification, when a part is said to "comprise" a certain element, this means that it can further include other elements, but not to the exclusion of other elements, unless specifically stated to the contrary.

[0027] In the drawings, the thickness of layers and regions are exaggerated for clarity. Similar parts are designated by the same reference numbers throughout the specification. When a part such as a layer, film, region, or plate is said to be "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where there is another part in between. Conversely, when one part is said to be "directly above" another part, it means that there is no other part in between. Additionally, the singular forms include the plural forms unless the context specifically dictates otherwise. Thus, a reference to a "semiconductor nanoparticle" may refer to one semiconductor nanoparticle or to a plurality of semiconductor nanoparticles.

[0028] Here, the statement "free of cadmium (or other toxic heavy metals)" may refer to a cadmium (or other heavy metal) concentration of 100 ppm (by weight) or less, 50 ppm or less, 10 ppm or less, 1 ppm or less, 0.1 ppm or less, 0.01 ppm or less, or approximately 0. In one embodiment of the invention, cadmium (or other heavy metals of interest) is substantially absent, or if present, is present in amounts or impurity levels below the detection limit of a given detection means.

[0029] Unless otherwise defined below, "substituted" means that a hydrogen atom in a compound is replaced by an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a heteroalkyl group having 1 to 30 carbon atoms, a heteroalkylaryl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 15 carbon atoms, a cycloalkynyl group having 6 to 30 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, a halogen (-F, -Cl, -Br, or I), a hydroxy group (-OH), a nitro group (-NO 2), cyano group (-CN), amino group (-NRR', where R and R' are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms), azide group (-N 3 ), amidino group (-C(=NH)NH 2 ), hydrazino group (-NHNH 2 ), hydrazono group (=N(NH 2 ), aldehyde group (-C(=O)H), carbamoyl group (-C(O)NH 2 ), thiol group (-SH), ester group (-C(=O)OR, where R is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms), carboxyl group (-COOH) or a salt thereof (-C(=O)OM, where M is an organic or inorganic cation), sulfonic acid group (-SO 3 H) or its salt (-SO 3 M, where M is an organic or inorganic cation), a phosphate group (-PO 3 H 2 ) or its salt (-PO 3 MH or PO 3 M 2 where M is an organic or inorganic cation), and combinations thereof.

[0030] Also, unless otherwise defined below, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S, Si, and P. Furthermore, the term "aliphatic hydrocarbon group" means a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 1 to 30 carbon atoms, or a linear or branched alkynyl group having 1 to 30 carbon atoms, The term "aromatic organic group" means an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms; In this specification, the term "(meth)acrylate" refers to both acrylate and / or methacrylate.

[0031] As used herein, "Group" refers to a Group of the Periodic Table of the Elements. As used herein, nanoparticles or nanostructures refer to structures having at least one region or characteristic dimension that has a dimension on the nanoscale. In one embodiment of the invention, the dimensions of the nanostructures can be less than about 500 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. Such structures may have any shape. The nanoparticles or nanostructures can have any shape, including nanowires, nanorods, nanotubes, multipod-type shapes having two or more pods, nanodots, and the like, without being particularly limited. The nanoparticles or nanostructures can be, for example, substantially crystalline, substantially monocrystalline, polycrystalline, amorphous, or combinations thereof.

[0032] Here, quantum dots refer to nanocrystalline particles (e.g., semiconductor-based) that exhibit quantum confinement or exciton confinement, and are a type of luminescent (e.g., capable of emitting light upon energy excitation) nanoparticles. Herein, the terms quantum dots and semiconductor nanoparticles are not limited in shape unless otherwise specified. As used herein, the term "dispersion" refers to a dispersion in which the dispersed phase is a solid and the continuous medium is either a liquid or contains a solid different from the dispersed phase. A "dispersion" herein can be a colloidal type dispersion in which the dispersed phase has dimensions of 1 nm or more, e.g., 2 nm or more, 3 nm or more, or 4 nm or more, and a few micrometers (μm) or less (e.g., 2 μm or less, or 1 μm or less, 900 nm or less, 800 nm or less, 700 nm or less, 600 nm or less, or 500 nm or less), where the dimensions (size, thickness, etc.) can be values ​​for a single entity or averages for multiple particles. Here, the average can be the "median" or the "mean". In one embodiment, the average may be the "mean." Here, the emission peak wavelength refers to the wavelength at which the light emission spectrum reaches its maximum value.

[0033] Here, quantum efficiency or quantum yield is easily and reproducibly determined using commercially available equipment (e.g., from Hitachi or Hamamatsu, etc.) by referring to, for example, the manual provided by the respective device manufacturer. Quantum efficiency (or quantum yield) is measured in solution or in the solid state (in a complex). In one embodiment, quantum efficiency (or quantum yield) is the ratio of emitted photons to absorbed photons by a nanostructure or a population thereof. In one embodiment, quantum efficiency can be measured in any manner. For example, for fluorescence quantum yield or efficiency, there are two methods: absolute and relative. In this specification, quantum efficiency measured by an absolute method is referred to as absolute quantum efficiency. In the absolute method, the fluorescence of all samples is detected through an integrating sphere to obtain the quantum efficiency. In the relative method, the fluorescence intensity of a standard dye (calibrator) is compared to the fluorescence intensity of an unknown sample to calculate the quantum efficiency of the unknown sample. Standard dyes that can be used based on these PL wavelengths include, but are not limited to, "Coumarin 153", "Coumarin 545", "Rhodamine 101 inner salt", "Anthracene" and "Rhodamine 6G".

[0034] The half-width and emission peak wavelength (eg, photoluminescence (PL) or electroluminescence (EL) wavelength) are measured by an emission (eg, photoluminescence) spectrum obtained by a spectrophotometer, such as, for example, a fluorescence spectrophotometer. Here, the "first absorption peak wavelength" refers to the wavelength of the first main peak that appears in the lowest energy region of the UV-Vis absorption spectrum. The nanoparticles are contained within a variety of electronic devices. The electrical and / or optical properties of the nanoparticles can vary depending on their physical properties (eg, composition, size, and / or shape). In one embodiment, the semiconductor nanoparticles can be semiconductor nanocrystal particles. Semiconductor nanoparticles such as quantum dots have a large surface area per unit volume, exhibit quantum confinement effects, and show physical properties different from those of bulk materials of the same composition. For example, a nanoparticle such as a quantum dot absorbs energy (eg, light) from an excitation source, enters an excited energy state, and emits energy corresponding to its band gap energy.

[0035] Semiconductor nanoparticles are also used in various electronic devices, such as in color conversion panels (eg, light-emitting color filters). For example, in a display device including a quantum dot-based color conversion panel or emissive color filter, instead of the white light emitting backlight unit of a liquid crystal display device, a quantum dot layer of emissive material is placed in front of the device, and blue light (excitation light) provided by a light source is converted into green light or red light by the quantum dot layer. In such a color conversion panel, the color conversion of the excitation light is performed in a relatively forward portion of the device, so that the viewing angle problem of the liquid crystal display can be solved by forward scattering of the light, and the light loss problem of the absorptive color filter can also be eliminated. As used herein, a color conversion panel refers to an electronic device that includes a color conversion layer. As used herein, a color conversion layer may include a structure that includes a color conversion region. In a display device including such a color conversion panel, the physical properties (eg, optical properties and stability) of the luminescent material directly affect the display quality of the device. For example, the luminescent materials contained in the color conversion panel placed in front of the device may be required to have not only high luminous efficiency but also an improved level of absorptivity for the excitation light. When applied to patterned single films such as color filters, a reduction in the excitation light absorptivity can directly cause “blue leakage” in the display device, negatively impacting color reproduction rate (e.g., DCI matching rate), and the use of an absorptive color filter to prevent “blue leakage” can result in an additional reduction in luminous efficiency. The reduced absorptivity of nanoparticles can lead to reduced brightness in devices containing them.

[0036] Many of the semiconductor nanoparticles that can exhibit properties (optical properties and / or stability) that are useful in devices include cadmium-based compounds (eg, cadmium chalcogenides). Cadmium poses serious environmental / health concerns and is one of the regulated elements. Therefore, in-depth research has been carried out into nanocrystals based on III-V compounds for cadmium-free and environmentally friendly nanoparticles. However, there remains a need in the art to provide environmentally friendly nanoparticles that can exhibit increased absorptance, achieve narrower half-widths, and exhibit high levels of luminescence efficiency than non-cadmium semiconductor nanoparticles based on III-V compounds (e.g., indium phosphide).

[0037] Semiconductor nanoparticles according to embodiments of the present invention are cadmium-free. The semiconductor nanoparticles are free of mercury, lead, or a combination thereof. In one embodiment, the semiconductor nanoparticles comprise silver, indium, gallium, and sulfur and can be sized 2 nm or more, or 5 nm or more, and 50 nm or less, 10 nm or less, or 8 nm or less. In one embodiment, the semiconductor nanoparticles include first semiconductor nanocrystals comprising silver, a Group 13 element, and a chalcogen element. The first semiconductor nanocrystal may or may not further comprise zinc. The Group 13 element can include indium, gallium, or a combination thereof. The chalcogen elements may include sulfur and optionally selenium. The first semiconductor nanocrystals can include a quaternary alloy semiconductor material based on Group 11-13-16 compounds including silver (Ag), indium, gallium, and sulfur. The first semiconductor nanocrystal may be silver indium gallium sulfide, e.g., Ag(In x Ga 1-x )S 2 (x is greater than 0 and less than 1). In the first semiconductor nanocrystals, the molar ratio between each component is adjusted so that the final semiconductor nanoparticles exhibit the desired composition and optical properties (eg, emission peak wavelength).

[0038] Semiconductor nanoparticles according to embodiments of the present invention include gallium, sulfur, and optionally silver, and may further include second semiconductor nanocrystals, third semiconductor nanocrystals, or combinations thereof, having a different composition than the first semiconductor nanocrystals. The second semiconductor nanocrystals can 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 selenide sulfide, or combinations thereof. The second semiconductor nanocrystals can include gallium and a chalcogen element (sulfur, selenium, or a combination thereof). The second semiconductor nanocrystals can include a ternary alloy semiconductor material including silver, gallium, and sulfur. In the second semiconductor nanocrystals, the molar ratio between each component is adjusted so that the final semiconductor nanoparticles exhibit the desired composition and optical properties. The third semiconductor nanocrystals can include zinc and sulfur. The third semiconductor nanocrystals can include zinc sulfide.

[0039] The second semiconductor nanocrystals cover at least a portion of the first semiconductor nanocrystals. The second semiconductor nanocrystal has a different band gap energy than the first semiconductor nanocrystal. The bandgap energy of the second semiconductor nanocrystal is greater than the bandgap energy of the first semiconductor nanocrystal. The bandgap energy of the second semiconductor nanocrystal is less than the bandgap energy of the first semiconductor nanocrystal. The band gap energy of the third semiconductor nanocrystal is greater than the band gap energy of the second semiconductor nanocrystal. The band gap energy of the third semiconductor nanocrystal is greater than the band gap energy of the first semiconductor nanocrystal. The layer containing the third semiconductor nanocrystal is the outermost layer of the semiconductor nanoparticle.

[0040] The semiconductor nanoparticles have a core-shell structure having a core and a shell disposed on the core. The core comprises a first semiconductor nanocrystal and the shell comprises a second semiconductor nanocrystal. The shell is a multi-layer shell including a first shell layer disposed on the core, a second shell layer disposed on the first shell layer, and a third shell layer disposed on the second shell layer. The first shell layer includes second semiconductor nanocrystals. The second shell layer includes third semiconductor nanocrystals. The second shell layer or the third shell layer comprises third semiconductor nanocrystals comprising zinc and sulfur (including zinc chalcogenides). In one embodiment, the semiconductor nanoparticles may have a core-multilayer shell structure, such as AgInGaS / AgGaS, AgInGaS / AgGaS / ZnS, etc.

[0041] In the semiconductor nanoparticles, the concentration of indium varies radially. In the semiconductor nanoparticles, the indium content of the inner portion of the particle differs from that of the outer portion of the particle. In one embodiment, the indium content adjacent the surface (eg, the outermost layer or shell) is less than the indium content in the interior portion (or core) of the particle. In one embodiment, the zinc content (concentration) adjacent the surface (eg, the outermost layer) is greater than the zinc content (concentration) in the interior portion (or core) of the particle. In the semiconductor nanoparticles, the concentration of zinc is greater at the outside than at the inside of the particle. The core or the first semiconductor nanocrystal is free of zinc. In the shell, gallium exhibits a radially varying (eg, increasing or decreasing) concentration gradient. The shell has a higher gallium concentration adjacent to the particle surface than adjacent to the core.

[0042] In one embodiment, semiconductor nanoparticles containing silver (Ag) along with a Group 13 element and a chalcogen element can achieve desirable luminescence properties (e.g., increased quantum yield with reduced half-width) while being cadmium-free. The Group 11-13-16 compound-based semiconductor nanoparticles according to one embodiment of the present invention may have their composition (e.g., charge balance values ​​and / or molar ratios between components as described herein) adjusted as described herein to achieve improved optical properties. The present inventors have confirmed that when semiconductor nanoparticles based on Group 11-13-16 compounds are prepared to have desired luminescence properties, the production yield can be significantly reduced. Without wishing to be bound by any particular theory, it is believed that when producing semiconductor nanoparticles based on Group 11-13-16 compounds exhibiting desired luminescent properties by known methods, forming second semiconductor nanocrystals, for example containing gallium and sulfur, on first semiconductor nanocrystals may result in uncontrollable changes in the composition and / or size of the first semiconductor nanocrystals, which may significantly reduce the production yield. The present inventors have surprisingly determined that by utilizing the methods described herein, desired semiconductor nanoparticles can be produced in relatively improved yields.

[0043] Thus, a method of making semiconductor nanoparticles according to an embodiment of the present invention includes obtaining a crude solution that includes semiconductor nanoparticles. The method includes combining, in a medium including an organic solvent, first semiconductor nanocrystals including silver, a Group 13 element, and a chalcogen element, a gallium precursor, a sulfur precursor, and a silver compound. For example, the method includes adding a gallium precursor and a sulfur precursor to a medium (eg, including an organic solvent and optionally an organic ligand). In one embodiment, the method includes adding a first semiconductor nanocrystal to the medium, the first semiconductor nanocrystal including silver, a Group 13 element, and a chalcogen element. In one embodiment, the medium includes first semiconductor nanocrystals, for example, prior to the addition of the gallium precursor and the sulfur precursor. The method includes heating the medium to a predetermined temperature (eg, a first temperature or a second temperature or a reaction temperature). For example, the method further comprises adding a silver compound to the medium. The method may further include adding a non-solvent to the final reaction solution (after heating) to promote precipitation of the (eg, organic ligand-coordinated) semiconductor nanoparticles.

[0044] In one embodiment, obtaining the crude solution includes carrying out a reaction between a gallium precursor and a sulfur precursor in the presence of a first semiconductor nanocrystal comprising silver, a Group 13 element, and a chalcogen element. The medium is the reaction medium for the reaction. The method further comprises adding a silver compound to the reaction medium. The above reaction can be carried out in the presence of a silver compound. Silver compounds can participate in the above reaction. Details regarding the semiconductor nanoparticles and the first semiconductor nanocrystals are as described herein. The method includes pre-treating the medium. In one embodiment, the method can include adding the first semiconductor nanocrystals, the gallium precursor, the sulfur precursor, or all of these to the (reaction) medium that includes an organic solvent (and optionally a sulfur precursor). The reaction medium is pretreated under vacuum conditions at a predetermined temperature prior to addition of the first semiconductor nanocrystal or gallium precursor. The pretreatment temperature is lower than the reaction temperature. The pretreatment temperature can be, for example, 80° C. or more, 100° C. or more, or 120° C. or more and 200° C. or less, or 180° C. or less.

[0045] The method of adding the first semiconductor nanocrystal, the gallium precursor, and the sulfur precursor (eg, the order of addition or the form of addition) is not particularly limited. In one embodiment, a first semiconductor nanocrystal and a gallium precursor can be added to a reaction medium that includes a sulfur precursor. The first semiconductor nanocrystals may be added to the reaction medium dispersed in a suitable organic solvent, but is not limited to this. The gallium precursor may be added to the reaction medium dispersed in a suitable organic solvent, but is not limited thereto. The method of adding the silver compound to the (reaction) medium (eg, the order of addition or the form of addition) is not particularly limited. The silver compound may be added dissolved in a suitable organic solvent (eg, an organic solvent described herein, eg, an amine-based solvent such as oleylamine, or a phosphine-based solvent such as trioctylphosphine). The time point at which the silver compound is added is not particularly limited and can be appropriately selected. The silver compound can be added to the (reaction) medium before or after the addition of the first semiconductor nanocrystal, the gallium precursor, the sulfur precursor, or a combination thereof. In one embodiment, a silver compound may be added to the (reaction) medium after pretreatment.

[0046] The first semiconductor nanocrystal is as described herein. The first semiconductor nanocrystals include silver (Ag), indium, gallium, and sulfur. The method for producing the first semiconductor nanocrystal is not particularly limited and can be appropriately selected. In one embodiment, the first semiconductor nanocrystals can be obtained by reacting required precursors, such as a silver precursor, an indium precursor, a gallium precursor, and a sulfur precursor, depending on the composition, in a solution containing an organic ligand and an organic solvent at a predetermined reaction temperature (e.g., 180°C to 300°C or 200°C to 280°C), and then isolating the reacted precursors. In one embodiment, the first semiconductor nanocrystals produced are separated and washed by selection. The separation and washing can be carried out by methods described herein.

[0047] The predetermined temperature can be 120°C or more, 180°C or more, 190°C or more, 200°C or more, 205°C or more, 210°C or more, 240°C or more, 245°C or more, 250°C or more, 255°C or more, 260°C or more, 265°C or more, 270°C or more, 275°C or more, 280°C or more, 285°C or more, 290°C or more, 295°C or more, 300°C or more, 305°C or more, 310°C or more, 315°C or more, 320°C or more, 330°C or more, 335°C or more, 340°C or more, or 345°C or more. The predetermined temperature may be 380°C or less, 375°C or less, 370°C or less, 365°C or less, 360°C or less, 355°C or less, 350°C or less, 340°C or less, 330°C or less, 320°C or less, 310°C or less, 300°C or less, 290°C or less, 280°C or less, 270°C or less, 260°C or less, or 250°C or less.

[0048] A method according to one embodiment of the invention includes heating a medium (optionally including a sulfur precursor) at a first temperature and adding a first semiconductor nanocrystal, a gallium precursor, a sulfur precursor, or a combination thereof to the medium heated at the first temperature. According to one embodiment the silver compound is added at a first temperature. A method according to one embodiment of the invention includes heating the medium (e.g., a reaction mixture including a first semiconductor nanocrystal, a gallium precursor, a sulfur precursor, and a silver compound) at a second temperature (e.g., a reaction temperature).

[0049] The first temperature may be 120°C or more (e.g., 180°C or more, alternatively, 190°C or more, or 200°C or more) and 280°C or less (e.g., 250°C or less), and the second temperature may be 190°C or more, alternatively, 240°C or more, and 380°C or less, alternatively, 280°C or less. The second temperature is greater than the first temperature. The difference between the first temperature and the second temperature can be 10°C or more, 20°C or more, 30°C or more, 40°C or more, 50°C or more, 60°C or more, 70°C or more, 80°C or more, 90°C or more, or 100°C or more. The difference between the first temperature and the second temperature can be 200°C or less, 190°C or less, 180°C or less, 170°C or less, 160°C or less, 150°C or less, 140°C or less, 130°C or less, 120°C or less, 110°C or less, 100°C or less, 90°C or less, 80°C or less, 70°C or less, 60°C or less, 50°C or less, 40°C or less, 30°C or less, or 20°C or less.

[0050] The first temperature can be 120°C or greater, 190°C or greater, 200°C or greater, 210°C or greater, 220°C or greater, 230°C or greater, 240°C or greater, or 250°C or greater. The first temperature can be 280°C or less, 275°C or less, 270°C or less, 265°C or less, 260°C or less, 255°C or less, 250°C or less, 240°C or less, 230°C or less, 220°C or less, 210°C or less, 200°C or less, 190°C or less, 180°C or less, 170°C or less, 160°C or less, or 150°C or less. The second temperature (or reaction temperature) can be 210°C or more, 220°C or more, 230°C or more, 240°C or more, 245°C or more, 250°C or more, 255°C or more, 260°C or more, 265°C or more, 270°C or more, 275°C or more, 280°C or more, 285°C or more, 290°C or more, 295°C or more, 300°C or more, 305°C or more, 310°C or more, 315°C or more, 320°C or more, 330°C or more, 335°C or more, 340°C or more, or 345°C or more. The second temperature (or reaction temperature) can be 380°C or less, 375°C or less, 370°C or less, 365°C or less, 360°C or less, 355°C or less, 350°C or less, 340°C or less, 330°C or less, 320°C or less, 310°C or less, 300°C or less, 290°C or less, 280°C or less, 270°C or less, 260°C or less, or 250°C or less.

[0051] The reaction time is controlled so that the semiconductor nanoparticles formed in the crude solution can attain a charge balance value as described herein. The reaction time can be 30 minutes or more, 35 minutes or more, 40 minutes or more, 45 minutes or more, 50 minutes or more, 55 minutes or more, 60 minutes or more, 65 minutes or more, 70 minutes or more, 75 minutes or more, or 80 minutes or more. The reaction time can be 3 hours or less, 2 hours or less, or 90 minutes or less. Without wishing to be bound by any particular theory, it is believed that the presence of a silver compound (or the addition of a silver compound) when reacting a gallium precursor and a sulfur precursor in the presence of a first semiconductor nanocrystal can prevent undesired changes to the first semiconductor nanocrystal (e.g., particle-particle bonding or compositional changes), thereby allowing a greater number of semiconductor nanoparticles to be formed in the crude solution.

[0052] The silver compound is added to the reaction medium in a content greater than or equal to 0.1% by mole and greater than or equal to 0.5% by mole with respect to the gallium precursor. The content of the silver compound can be 0.1 mol% or more, 0.5 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, 9 mol% or more, 10 mol% or more, 11 mol% or more, 12 mol% or more, 13 mol% or more, 14 mol% or more, or 15 mol% or more relative to the gallium precursor. The content of the silver compound can be 50 mol% or less, 30 mol% or less, 25 mol% or less, 20 mol% or less, 18 mol% or less, 17 mol% or less, 16 mol% or less, 15 mol% or less, 14 mol% or less, 13 mol% or less, 12 mol% or less, 11 mol% or less, 10 mol% or less, 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, or 2 mol% or less relative to the gallium precursor. The content of the silver compound can be 1 mol % or more and 20 mol % or less, 2 mol % or more and 12 mol % or less, 3 mol % or more and 11 mol % or less, or 4 mol % or more and 10.5 mol % or less. The silver compound may include silver powder, alkylated silver compounds, silver alkoxides, silver carboxylates, silver acetylacetonates, silver nitrates, silver sulfates, silver halides, silver cyanides, silver hydroxides, silver oxides, silver peroxides, silver carbonates, or combinations thereof. The silver compound may include silver nitrate, silver acetate, silver acetylacetonate, silver chloride, silver bromide, silver fluoride, or combinations thereof.

[0053] The above methods are capable of producing semiconductor nanoparticles exhibiting desirable optical properties with increased manufacturing yields. In one embodiment, the crude solution has an optical density, as defined by Equation 1 below, of 1 or more and 10 or less at a wavelength of 500 nm when measured after dilution 100 times with toluene. (Number 1) optical density=log 10 (I O / I T )···Equation 1 (Here, I O is the intensity of incident light supplied to the solution (e.g., crude solution), and I T is the intensity of transmitted light passing through the solution (e.g., the crude solution).

[0054] Optical density is a parameter related to absorbance and is used as a method to quantify the concentration of solutes or semiconductor nanoparticles. According to the Beer-Lambert law, the absorbance is proportional to the concentration and extinction coefficient of the semiconductor nanoparticles in a given sample solution. Optical density is the "optical attenuation" per centimeter of a material as measured using a standard spectrometer, for example with a 1 cm path length. In a solution containing nanoparticles, the molar concentration of the nanoparticles is related to the optical density. The optical density of a nanoparticle-containing solution can be easily and reproducibly measured using a UV-Vis spectrometer (eg, commercially available). For example, to measure the optical density, the resulting crude solution is diluted 100-fold with an organic solvent (e.g., toluene) and the absorbance value (light path length 10 mm) obtained from a UV-Vis spectrometer is multiplied by 100 again to measure.

[0055] The inventors have determined that, when using conventional techniques, the resulting crude solution exhibits a relatively low level of optical density, for example at a wavelength of 500 nm, which indicates that the number of nanoparticles actually produced in the reaction system is low. Surprisingly, the inventors have found that when the methods described herein are used, the resulting crude solutions exhibit significantly increased optical densities, e.g., at least two-fold or even approximately nine-fold or more, compared to conventional techniques. Additionally, the semiconductor nanoparticles contained within the crude solutions produced exhibit improved levels of quantum efficiency (eg, 60% or greater, or 70% or greater) as described herein.

[0056] According to a method of one embodiment of the invention, the crude solution can have an optical density at a wavelength of 500 nm of 1 or more, 1.1 or more, 1.3 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, 2 or more, 2.1 or more, 2.2 or more, 2.3 or more, 2.4 or more, 2.5 or more, 2.6 or more, 2.7 or more, 2.8 or more, 2.9 or more, 3 or more, or 3.5 or more. At a wavelength of 500 nm, the optical density may be 10 or less, 7 or less, 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, or 2.8 or less. The crude solution can have an optical density at a wavelength of 350 nm of 8 or more, 8.5 or more, 9 or more, 9.5 or more, 10 or more, 10.5 or more, 11 or more, 11.5 or more, 12 or more, 12.5 or more, 13 or more, 13.5 or more, 14 or more, 14.5 or more, 15 or more, 15.3 or more, 16 or more, 16.5 or more, 17 or more, 17.5 or more, 18 or more, 18.5 or more, 19 or more, 19.5 or more, 20 or more, 20.5 or more, 21 or more, 23 or more, or 25 or more. At a wavelength of 350 nm, the optical density may be 100 or less, 80 or less, 60 or less, 40 or less, or 35 or less. At a wavelength of 350 nm, the optical density can be 12 or more and 50 or less.

[0057] The crude solution had a UV-Vis absorption spectrum with an absorption ratio of 500 nm to 350 nm of 500 / A 350 ) may be 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, 0.05 or more, 0.06 or more, 0.07 or more, 0.08 or more, 0.09 or more, 0.1 or more, 0.12 or more, 0.13 or more, 0.15 or more, 0.16 or more, 0.17 or more, or 0.18 or more. Absorption ratio A of 500nm / 350nm 500 / A 350 may be 0.8 or less, 0.5 or less, 0.3 or less, or 0.2 or less, 0.15 or less, or 0.14 or less.

[0058] The method according to the embodiment of the present invention has a production yield of 6% or more, as determined by the following Equation 2. (Number 2) Production yield = A / B × 100 Formula 2 (Here, A is the total weight of silver, Group 13 element, and sulfur in the semiconductor nanoparticles recovered from the crude solution, and B is the total weight of silver, Group 13 element, and sulfur added to the reaction medium for the reaction.)

[0059] The production yield can be 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 11% or more, 12% or more, 13% or more, 14% or more, 15% or more, 16% or more, 17% or more, 18% or more, 19% or more, 20% or more, 21% or more, 22% or more, 23% or more, 24% or more, or 25% or more. The manufacturing yield may be 100% or less, 90% or less, 80% or less, 70% or less, or 60% or less.

[0060] The method according to an embodiment of the present invention further includes the steps of preparing an additional reaction medium including a zinc precursor and optionally an organic ligand in an organic solvent, and adding and reacting the formed nanoparticles and a chalcogen precursor while heating the additional reaction medium at a reaction temperature to provide a third semiconductor nanocrystal including a zinc chalcogenide or an outer layer including the same on a surface of the semiconductor nanoparticle. The third semiconductor nanocrystals have a different composition than the first semiconductor nanocrystals and the second semiconductor nanocrystals. In one embodiment, the reaction temperature for zinc chalcogenide formation can be 120° C. or more, 130° C. or more, 150° C. or more, 180° C. or more, 200° C. or more, 205° C. or more, 208° C. or more, and 240° C. or less, 230° C. or less, 225° C. or less, or 215° C. or less. The time for the reaction can be 10 minutes or more, 30 minutes or more, 40 minutes or more, 1 hour or more, 80 minutes or more, or 90 minutes or more, and 5 hours or less, 4 hours or less, 3 hours or less, 2 hours or less, 90 minutes or less, or 70 minutes or less. In methods according to embodiments of the present invention, the manner in which precursors are added to the (eg, heated) reaction medium may include shot addition (eg, syringe addition), drop wise addition, or a combination thereof.

[0061] The type of silver precursor is not particularly limited and can be appropriately selected. The silver precursor may include silver powder, alkylated silver compounds, silver alkoxides, silver carboxylates, silver acetylacetonates, silver nitrates, silver sulfates, silver halides, silver cyanides, silver hydroxides, silver oxides, silver peroxides, silver carbonates, or combinations thereof. The silver precursor may include silver nitrate, silver acetate, silver acetylacetonate, or a combination thereof.

[0062] The type of indium precursor is not particularly limited and can be appropriately selected. The indium precursor can be indium powder, an alkylated indium compound, an indium alkoxide, an indium carboxylate, an indium nitrate, an indium percolate, an indium sulfate, an indium acetylacetonate, an indium halide, an indium cyanide, an indium hydroxide, an indium oxide, an indium peroxide, an indium carbonate, or a combination thereof. Indium precursors may include indium oleate, indium carboxylates such as indium myristate, indium acetate, indium hydroxide, indium chloride, indium bromide, indium iodide, or combinations thereof.

[0063] The type of gallium precursor is not particularly limited and can be appropriately selected. The gallium precursor can be gallium powder, alkylated gallium compounds, gallium alkoxides, gallium carboxylates, gallium nitrates, gallium percolate, gallium sulfates, gallium acetylacetonates, gallium halides, gallium cyanides, gallium hydroxides, gallium oxides, gallium peroxides, gallium carbonates, or combinations 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 combinations thereof.

[0064] The type of sulfur precursor is not particularly limited and can be appropriately selected. The sulfur precursor may be an organic solvent dispersion or reaction product of sulfur (e.g., octadecene sulfide (S-ODE), trioctylphosphine-sulfide (S-TOP), tributylphosphine-sulfide (S-TBP), triphenylphosphine-sulfide (S-TPP), trioctylamine-sulfide (S-TOA)), trimethylsilyl alkyl sulfide, trimethylsilyl sulfide, mercaptopropylsilane, ammonium sulfide, sodium sulfide, C1-30 thiol compounds (e.g., alpha-toluenethiol, octanethiol, dodecanethiol, octadecenethiol, etc.), isothiocyanate compounds (e.g., cyclohexyl isothiocyanate), alkylene trithiocarbonates (e.g., ethylene trithiocarbonate), allyl mercaptans (allyl mercaptans), methyl mercaptans (methyl ... mercaptan), a thiourea compound (for example, a dialkylthiourea having an alkyl group having 1 to 40 carbon atoms, such as dimethylthiourea, diethylthiourea, ethylmethylthiourea, or dipropylthiourea), or a combination thereof. The sulfur precursor may include a thiol compound, an isothiocyanate compound, a thiourea compound, or a combination thereof.

[0065] When present, the selenium precursor may include selenium-trioctylphosphine (Se-TOP), selenium-tributylphosphine (Se-TBP), selenium-triphenylphosphine (Se-TPP), or combinations thereof. The type of zinc precursor is not particularly limited and can be appropriately selected. For example, the zinc precursor may include Zn metal powder, alkylated Zn compounds, Zn alkoxides, Zn carboxylates, Zn nitrates, Zn percolates, Zn sulfates, Zn acetylacetonates, Zn halides, Zn cyanides, Zn hydroxides, Zn oxides, Zn peroxides, or combinations thereof. The zinc precursor can 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, and the like. In one embodiment, during the formation of the second semiconductor nanocrystals, the zinc precursor can include a Zn halide.

[0066] The organic ligands are RCOOH and RNH. 2 , R 2 N.H., R. 3 N, R.S.H., R.H. 2 P.O., R. 2 H.P.O., R. 3 P.O., R.H. 2 P, R 2 H.P., R. 3 P, ROH, RCOOR', RPO(OH) 2 , R.H.P.O.H., R. 2 POOH (wherein R and R' are each independently a substituted or unsubstituted aliphatic hydrocarbon having 1 to 40 carbon atoms (or 3 to 24 carbon atoms) (e.g., an alkyl group, an alkenyl group, an alkynyl group), or a substituted or unsubstituted aromatic hydrocarbon having 6 to 40 carbon atoms (or 6 to 24 carbon atoms) (e.g., an aryl group having 6 to 20 carbon atoms)), or a combination thereof. Organic ligands are attached to the surface of the prepared nanoparticles.

[0067] The organic ligands include methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, benzylthiol; methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, dodecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine, methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, benzoic acid, substituted or unsubstituted methylphosphines (e.g., trimethylphosphine, methyldiphenylphosphine, etc.), substituted or unsubstituted ethylphosphines (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)), and other phosphines; substituted or unsubstituted methylphosphine oxide (e.g., trimethylphosphine oxide, methyldiphenylphosphine oxide, and other); substituted or unsubstituted ethylphosphine oxide (e.g., triethylphosphine oxide, ethyldiphenylphosphine oxide, and other); substituted or unsubstituted propylphosphine oxide, substituted or unsubstituted butylphosphine oxide, substituted or unsubstituted octylphosphine oxide (e.g., trioctylphosphine oxide (TOPO)), and other phosphine oxides; diphenylphosphine, triphenylphosphine compounds, or oxide compounds thereof; phosphonic acids (phosphonic Examples of the phosphinic acid include, but are not limited to, alkyl phosphinic acids having 5 to 20 carbon atoms, such as hexyl phosphinic acid, octyl phosphinic acid, dodecane phosphinic acid, tetradecane phosphinic acid, hexadecane phosphinic acid, and octadecane phosphinic acid, and alkyl phosphonic acids having 5 to 20 carbon atoms. The organic ligands may be used alone or in mixtures of two or more.

[0068] The organic solvent is selected from the group consisting of amine solvents (e.g., C1-50 aliphatic amines), nitrogen-containing heterocyclic compounds such as pyridine, aliphatic hydrocarbons having 6 to 40 carbon atoms (e.g., alkanes, alkenes, alkynes, etc.) such as hexadecane, octadecane, octadecene, and squalane, aromatic hydrocarbons having 6 to 30 carbon atoms such as phenyldodecane, phenyltetradecane, and phenylhexadecane, phosphines substituted with an alkyl group having 6 to 22 carbon atoms such as trioctylphosphine, phosphine oxides substituted with an alkyl group having 6 to 22 carbon atoms such as trioctylphosphine oxide, aromatic ethers having 12 to 22 carbon atoms such as phenyl ether and benzyl ether, and combinations thereof. The amine solvent may be a compound having one or more (e.g., two or three) C1 to C50, C2 to C45, C3 to C40, C4 to C35, C5 to C30, C6 to C25, C7 to C20, C8 to C15, or C6 to C22 aliphatic hydrocarbon groups (alkyl groups, alkenyl groups, or alkynyl groups). In one embodiment, the amine solvent may include a C6-22 primary amine, such as hexadecylamine, oleylamine, a C6-22 secondary amine, such as dioctylamine, a C6-22 tertiary amine, such as trioctylamine, or a combination thereof.

[0069] The content of the organic ligand and each precursor in the reaction medium can be appropriately selected in consideration of the type of solvent, the type of the organic ligand and each precursor, the desired particle size and composition, and the like. The molar ratio between the precursors can be appropriately selected taking into consideration the desired molar ratio in the final nanoparticles, the reactivity between the precursors, and the like. The method of adding each precursor is not particularly limited. Each precursor may be injected in one or more separate injections, or in two or more to ten or less separate injections. The addition of each precursor can be done simultaneously or sequentially. The reaction can be carried out in an inert gas atmosphere or in air or under vacuum, but is not limited thereto.

[0070] After the reaction is complete, the nanoparticles are separated (eg, precipitated) by adding a nonsolvent to the final reaction solution (eg, to which the organic ligands are coordinated). The non-solvent may be a polar solvent that is miscible with the solvent used in the reaction, but is incapable of dispersing the nanocrystals. The non-solvent may be determined by the solvent used in the reaction and may include, for example, acetone, ethanol, butanol, isopropanol, ethanediol, water, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), diethylether, formaldehyde, acetaldehyde, solvents having a solubility parameter similar to the solvents listed above, or combinations thereof.

[0071] Separation may involve centrifugation, sedimentation, chromatography, or distillation. The separated nanocrystals are optionally washed by adding a washing solvent. The washing solvent is not particularly limited, and an organic solvent or a solvent having a solubility parameter similar to that of the ligand is used. Non-solvents or wash solvents include, but are not limited to, alcohols, alkane solvents such as hexane, heptane, octane, etc., aromatic solvents such as chloroform, toluene, benzene, etc., or combinations thereof.

[0072] The produced semiconductor nanoparticles are dispersed in a dispersion solvent. The produced semiconductor nanoparticles form a dispersion in an organic solvent. The organic solvent dispersion does not include water and / or water-miscible organic solvents. The dispersion solvent can be appropriately selected. The dispersion solvent may include the organic solvents described above. The dispersion solvent may include a substituted or unsubstituted aliphatic hydrocarbon having 1 to 40 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 40 carbon atoms, or a combination thereof. The semiconductor nanoparticles are lithium-free. The semiconductor nanoparticles are free of alkali metals (eg, lithium, sodium, potassium, etc.).

[0073] The semiconductor nanoparticles can have a molar ratio of gallium to indium (Ga / In) in the range of 1 or more, 1.5 or more, 2 or more, 2.5 or more, 3 or more, 3.1 or more, 3.3 or more, 3.4 or more, 3.5 or more, 3.6 or more, 3.7 or more, 3.8 or more, 3.9 or more, 4 or more, 4.1 or more, 4.2 or more, 4.3 or more, 4.4 or more, 4.5 or more, 4.6 or more, or 4.7 or more, 10 or less, 9 or less, 8.5 or less, 8 or less, 6 or less, 5.5 or less, 5.3 or less, 5.1 or less, 5 or less, 4.9 or less, 4.7 or less, 4.5 or less, 4.3 or less, 4.2 or less, 4.1 or less, 4 or less, 3.9 or less, 3.8 or less, 3.7 or less, 3.6 or less, or 3.55 or less, or any combination thereof.

[0074] In the semiconductor nanoparticles, the molar ratio of gallium to the sum of indium and gallium [Ga / (In+Ga)] is 0.70 or more, 0.715 or more, 0.72 or more, 0.725 or more, 0.73 or more, 0.735 or more, 0.74 or more, 0.745 or more, 0.75 or more, 0.755 or more, 0.76 or more, 0.765 or more, 0.77 or more, 0.775 or more, 0.78 or more, 0.785 or more, 0.79 or more, 0.795 or more, 0.8 or more, 0.805 or more, 0.81 or more, 0.815 or more, 0.82 or more, or 0.825 or more. or less, 0.99 or less, 0.98 or less, 0.97 or less, 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.87 or less, 0.85 or less, 0.845 or less, 0.84 or less, 0.835 or less, 0.83 or less, 0.825 or less, 0.82 or less, 0.815 or less, 0.81 or less, 0.805 or less, 0.8 or less, 0.795 or less, 0.79 or less, 0.785 or less, 0.78 or less, 0.775 or less, or 0.77 or less, or any combination thereof.

[0075] The semiconductor nanoparticles can have a molar ratio of gallium to silver (Ga / Ag) in the range of 1 or more, 1.1 or more, 1.15 or more, 1.2 or more, 1.22 or more, 1.3 or more, 1.33 or more, 1.34 or more, 1.35 or more, 1.36 or more, 1.4 or more, 1.46 or more, 1.48 or more, 1.5 or more, 1.54 or more, 1.6 or more, or 1.65 or more, 3 or less, 2.9 or less, 2.8 or less, 2.75 or less, 2.5 or less, 2.2 or less, 2 or less, 1.9 or less, 1.8 or less, 1.75 or less, 1.7 or less, 1.65 or less, 1.6 or less, 1.58 or less, 1.55 or less, 1.5 or less, 1.45 or less, 1.4 or less, or 1.35 or less, or any combination thereof.

[0076] The semiconductor nanoparticles can have a molar ratio of gallium to the sum of gallium, indium, and silver (Ga / (Ga+In+Ag)) ranging from 0.45 or more, 0.46 or more, 0.47 or more, 0.48 or more, 0.49 or more, 0.5 or more, 0.51 or more, 0.52 or more, or 0.53 or more, 0.65 or less, 0.6 or less, 0.57 or less, 0.54 or less, 0.53 or less, 0.52 or less, 0.51 or less, 0.5 or less, 0.49 or less, or 0.485 or less, or any combination thereof. The semiconductor nanoparticles can have a molar ratio of the sum of indium and gallium to silver ((In+Ga) / Ag) in the range of 1.2 or more, 1.3 or more, 1.4 or more, 1.45 or more, 1.46 or more, 1.5 or more, 1.63 or more, 1.7 or more, 1.83 or more, 1.9 or more, 1.94 or more, or 2 or more, and 3.7 or less, 3.5 or less, 3 or less, 2.4 or less, 2.37 or less, 2 or less, 1.96 or less, 1.95 or less, or 1.9 or less, or any combination thereof. The semiconductor nanoparticles can have a molar ratio of silver to sulfur (Ag / S) in the range of 0.05 or more, 0.15 or more, 0.2 or more, 0.23 or more, 0.25 or more, 0.28 or more, 0.3 or more, 0.31 or more, 0.32 or more, 0.33 or more, or 0.35 or more, 0.5 or less, 0.45 or less, 0.41 or less, 0.4 or less, 0.36 or less, 0.35 or less, 0.33 or less, or any combination thereof.

[0077] The semiconductor nanoparticles can have a molar ratio of silver to indium (Ag / In) of 1.5 or more, 2 or more, 2.25 or more, 2.3 or more, 2.37 or more, 2.4 or more, 2.5 or more, 2.51 or more, 2.6 or more, 2.65 or more, 2.7 or more, 2.9 or more, 3 or more, or 3.1 or more, 6 or less, 5.5 or less, 5.2 or less, 5 or less, 4.5 or less, 4.4 or less, 4 or less, 3.9 or less, 3.8 or less, 3.7 or less, 3.6 or less, or 3 or less. The semiconductor nanoparticles can have a molar ratio of sulfur to indium (S / In) in the range of 6 or more, 6.5 or more, 7.5 or more, 7.7 or more, 7.8 or more, 8 or more, 8.9 or more, 9 or more, 9.8 or more, or 10 or more, 25 or less, 20 or less, 19 or less, or 18 or less, or any combination thereof.

[0078] The semiconductor nanoparticles can have a molar ratio of silver to the sum of silver, indium, and gallium (Ag / (Ag+In+Ga)) ranging from 0.2 or more, 0.25 or more, 0.3 or more, 0.33 or more, 0.34 or more, 0.35 or more, 0.37 or more, or from 0.4 or more to 0.45 or less, 0.41 or less, 0.4 or less, 0.36 or less, 0.33 or less, 0.32 or less, or 0.28 or less, or any combination thereof. The semiconductor nanoparticles can have a molar ratio of sulfur to the sum of silver, indium, and gallium (S / (Ag+In+Ga)) ranging from 0.8 or more, 0.9 or more, 1 or more, 1.05 or more, 1.12 or more, or 1.3 or more, 1.5 or less, 1.45 or less, 1.35 or less, 1.3 or less, 1.15 or less, 1.13 or less, or 1.08 or less, or any combination thereof. The semiconductor nanoparticles can have a molar ratio of gallium to sulfur (Ga / S) of 0.4 or more, or 0.44 or more, or 0.48 or more, or 0.5 or more, or 0.55 or more. The semiconductor nanoparticles can have a molar ratio of gallium to sulfur (Ga / S) of 0.6 or less, 0.56 or less, or 0.51 or less.

[0079] The semiconductor nanoparticles according to embodiments of the present invention may have a charge balance value, obtained by Equation 3 below, of 0.8 or more, 0.85 or more, 0.9 or more, 0.95 or more, 0.98 or more, 0.99 or more, 1 or more, or 1.1 or more, 1.4 or less, 1.35 or less, 1.3 or less, 1.25 or less, 1.2 or less, 1.18 or less, 1.15 or less, 1.1 or less, 1.05 or less, or 1 or less, or any combination thereof. (Number 3) charge balance value = {[Ag] + 3 × ([In] + [Ga])} / (2 × [S]) Equation 3 (where [Ag], [In], [Ga], and [S] are the molar contents of silver, indium, gallium, and sulfur, respectively, in the semiconductor nanoparticles.)

[0080] The size (or average size) of the first semiconductor nanocrystal can be 0.5 nm or more, 1 nm or more, 1.5 nm or more, 1.7 nm or more, 1.9 nm or more, 2 nm or more, 2.1 nm or more, 2.3 nm or more, 2.5 nm or more, 2.7 nm or more, 2.9 nm or more, 3 nm or more, 3.1 nm or more, 3.3 nm or more, 3.5 nm or more, 3.7 nm or more, 3.9 nm or more, 4 nm or more, or 4.2 nm or more. The size (average size) of the first semiconductor nanocrystals can be 6 nm or less, 5.5 nm or less, 5 nm or less, 4.5 nm or less, 4 nm or less, 3.5 nm or less, 3 nm or less, 2.5 nm or less, 2 nm or less, or 1.5 nm or less. The thickness of the second semiconductor nanocrystals or a layer comprising same can be 0.1 nm or more, or 0.2 nm or more, or 0.3 nm or more. The thickness of the second semiconductor nanocrystals or a layer comprising same can be 3 nm or less, 2.5 nm or less, 2 nm or less, 1.5 nm or less, 1 nm or less, or 0.8 nm or less.

[0081] When present, the third semiconductor nanocrystals or a layer comprising same can have a dimension (eg, thickness) of 0.1 nm or more, 0.3 nm or more, 0.5 nm or more, 0.7 nm or more, or 1 nm or more. The third semiconductor nanocrystals can have a dimension (eg, thickness) of 2 nm or less, 1.5 nm or less, 1 nm or less, or 0.8 nm or less. The thickness of the third semiconductor nanocrystal layer can be in the range of 0.1 nm to 5 nm, 0.2 nm to 4 nm, 0.3 nm to 3.5 nm, 0.4 nm to 3 nm, 0.5 nm to 2.5 nm, 0.6 nm to 2 nm, 0.7 nm to 1.5 nm, 0.8 nm to 1.2 nm, 0.9 nm to 1 nm, or any combination thereof.

[0082] The size (or average particle size, hereafter simply referred to as "size") of the semiconductor nanoparticles according to embodiments of the present invention may be 1 nm or more, 1.5 nm or more, 2 nm or more, 2.5 nm or more, 3 nm or more, 3.5 nm or more, 4 nm or more, 4.5 nm or more, 5 nm or more, 5.5 nm or more, 6 nm or more, 6.5 nm or more, 7 nm or more, 7.5 nm or more, 8 nm or more, 8.5 nm or more, 9 nm or more, 9.5 nm or more, 10 nm or more, or 10.5 nm or more. The size of the semiconductor nanoparticles can be 50 nm or less, 48 ​​nm or less, 46 nm or less, 44 nm or less, 42 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 20 nm or less, 18 nm or less, 16 nm or less, 14 nm or less, 12 nm or less, 11 nm or less, 10 nm or less, 8 nm or less, 7 nm or less, 7.5 nm or less, 6 nm or less, or 4 nm or less.

[0083] As used herein, the size of a semiconductor nanoparticle is the particle diameter. The size of a semiconductor nanoparticle is its equivalent diameter, obtained by a calculation involving converting the two-dimensional area of ​​the particle obtained from an electron microscope image into a circle. The size of the semiconductor nanoparticles can be obtained from images obtained by electron microscopy (eg, transmission electron microscopy) analysis. Such particle sizes can be easily and reproducibly determined from microscope images using a variety of image processing programs (eg, ImageJ or in-house programs that can be written using any coding language). The particle size is a value (eg, nominal particle size) calculated from the composition and emission peak wavelength of the semiconductor nanoparticles.

[0084] Semiconductor nanoparticles according to embodiments of the invention may have an average size of 5 nm or more, or 5.1 nm or more, 5.2 nm or more, and 10 nm or less, 7 nm or less, 6.5 nm or less, 6 nm or less, or 5.4 nm or less. The semiconductor nanoparticles can have a size distribution, expressed as a standard deviation, of 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, or 10% or less of the average size. The standard deviation can be 5% or more, 10% or more, or 12% or more of the average magnitude.

[0085] Semiconductor nanoparticles according to embodiments of the present invention may be configured to emit green light. The emission peak wavelength of the green light may be in the range of 500 nm or more, or 505 nm or more and 580 nm or less, or 550 nm or less. The emission peak wavelength of the semiconductor nanoparticles or green light can be 500 nm or more, 505 nm or more, 510 nm or more, 515 nm or more, 520 nm or more, 525 nm or more, 530 nm or more, 535 nm or more, 540 nm or more, or 545 nm or more, and 580 nm or less, 575 nm or less, 570 nm or less, 565 nm or less, 560 nm or less, 555 nm or less, 550 nm or less, 545 nm or less, 540 nm or less, 535 nm or less, 530 nm or less, 525 nm or less, 520 nm or less, or 515 nm or less.

[0086] Semiconductor nanoparticles according to embodiments of the present invention may be configured to emit red light. The emission peak wavelength of the red light may be in the range of 600 nm or more, 605 nm or more, 610 nm or more, and 660 nm or less, 650 nm or less, 640 nm or less, or 630 nm or less, 623 nm to 632 nm, 625 nm to 630 nm, or 628 nm to 629 nm.

[0087] Semiconductor nanoparticles according to embodiments of the present invention exhibit quantum yields of 50% or greater. The quantum yield can be an absolute quantum yield. The quantum yield can be 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95% or more. The quantum yield can be 100% or less, 99.5% or less, 99% or less, 98% or less, or 97% or less. The semiconductor nanoparticles or green light (or red light) according to embodiments of the present invention may have a half-width of 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, or 30 nm or more. The half width can be 50 nm or less, 45 nm or less, 40 nm or less, 38 nm or less, 36 nm or less, 35 nm or less, 34 nm or less, 33 nm or less, 32 nm or less, 31 nm or less, 30 nm or less, 29 nm or less, 28 nm or less, 27 nm or less, 26 nm or less, 25 nm or less.

[0088] The shape of the produced semiconductor nanoparticles is not particularly limited, and may include, for example, but is not limited to, a sphere, a polyhedron, a pyramid, a multipod, or a cubic shape, a nanotube, a nanowire, a nanofiber, a nanosheet, or a combination thereof. The semiconductor nanoparticles produced contain the aforementioned organic ligands and / or organic solvents on the surface. Organic ligands and / or organic solvents are bound to the surface of semiconductor nanoparticles according to embodiments of the present invention.

[0089] A composite according to an embodiment of the present invention comprises a matrix and semiconductor nanoparticles dispersed in the matrix. The composite further comprises metal oxide particulates. The composite may be configured to emit green light. The composite can be a patterned film. The composite may further include semiconductor nanoparticles configured to emit a second light different from the green light. The composite may be in the form of a sheet. The sheeting may further include semiconducting nanoparticles configured to emit a second light different from the green light (eg, red light).

[0090] The composite according to the embodiment of the present invention has an increased level of blue light absorptance (e.g., improved excitation light absorptance) and improved optical properties (e.g., increased luminous efficiency and narrower half-width) and emits light of a desired wavelength (e.g., a first light such as green light). The composite includes (eg, a predetermined content of) semiconductor nanoparticles or populations thereof and exhibits increased optical absorptivity. The incident light absorptance of composites according to embodiments of the invention can be 70% or more, 73% or more, 75% or more, 77% or more, 80% or more, 83% or more, 85% or more, 87% or more, 90% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more. The incident light absorptance of the composite can be 70%-100%, 80%-98%, 95%-99%, 96%-98%, or a combination thereof. (Number 4) Incident light absorption rate = [(B-B') / B] × 100(%) Formula 4 (where B is the amount of incident light provided to the composite and B' is the amount of incident light transmitted through the composite).

[0091] The composite according to an embodiment of the present invention may have a photoconversion efficiency (CE) calculated by Equation 5 below of 7% or more, 8% or more, 9% or more, 10% or more, 11% or more, 12% or more, 12.5% ​​or more, 12.9% or more, 13% or more, 14.5% or more, 15% or more, 15.5% or more, 16% or more, 16.5% or more, 16.7% or more, or 16.9% or more. (Number 5) Light conversion efficiency (%) = [A / (B-B')] × 100 (%) Formula 5 (where A is the amount of a first light emitted from the composite, B is the amount of incident light provided to the composite, and B' is the amount of incident light transmitted through the composite).

[0092] The inventors have confirmed that luminescent particles comprising semiconductor nanocrystals based on Group 11-13-16 compounds may exhibit significantly reduced physical properties when included in a composite for application in an actual device, even if the desired level of optical properties is achieved. The semiconductor nanoparticles according to the embodiments of the present invention can provide a composite exhibiting improved optical properties by having the compositional and / or structural characteristics described above, and can also exhibit a high optical property retention rate even in the form of a single film.

[0093] Composites according to embodiments of the present invention may be prepared from the ink composition. The ink composition includes a liquid vehicle and semiconducting nanoparticles according to an embodiment (eg, a plurality) of the present invention. Semiconductor nanoparticles according to embodiments of the present invention may be dispersed in a liquid vehicle. The liquid vehicle may include a liquid monomer, an organic solvent, or a combination thereof. The ink composition may further comprise, or may be substantially free of, volatile organic solvents. The ink composition may further include metal oxide nanoparticles (eg, dispersed within the liquid vehicle). The ink composition may further include a dispersant (for dispersing the semiconductor nanoparticles and / or metal oxide nanoparticles). The dispersant may comprise a carboxylic acid group-containing organic compound (monomeric or polymeric). The liquid vehicle does not include (eg, volatile) organic solvents. The ink composition may be a solventless system.

[0094] The liquid monomer may comprise a (photo)polymerizable monomer containing a carbon-carbon double bond. The composition may optionally further comprise an initiator (thermal or photo). The composition is polymerized by light or heat. Details regarding the nanoparticles in the composition (or complex) are as described herein. The content of the semiconductor nanoparticles in the composition (or composite) can be appropriately adjusted taking into consideration the desired end use (e.g., color filter, etc.). In an embodiment of the present invention, the content of semiconductor nanoparticles in the composition (or composite) may be 1 wt % or more, for example, 2 wt % or more, 3 wt % or more, 4 wt % or more, 5 wt % or more, 6 wt % or more, 7 wt % or more, 8 wt % or more, 9 wt % or more, 10 wt % or more, 15 wt % or more, 20 wt % or more, 25 wt % or more, 30 wt % or more, 35 wt % or more, or 40 wt % or more, based on the solid content of the composition or composite (hereinafter, the solid content may be the solid content of the composition or the solid content of the composite). The nanoparticle content can be 70% or less, e.g., 65% or less, 60% or less, 55% or less, or 50% or less, by weight based on the solids content. The weight percentage of a component relative to the total solid content in the composition can represent the content of the component in the composite described below.

[0095] The ink composition according to the embodiment of the present invention may be a nanoparticle-containing photoresist composition applicable in photolithography processes. The ink composition according to the embodiment of the present invention may be a composition that can provide a pattern by a printing method (for example, a droplet ejection method such as inkjet printing). The composition according to one embodiment does not include a conjugated (or conductive) polymer (other than the cull binder described below). A composition according to one embodiment includes a conjugated polymer. Here, the conjugated polymer refers to a polymer having a conjugated double bond in the main chain (for example, polyphenylenevinylene, etc.).

[0096] In the composition according to the embodiment of the present invention, the dispersant ensures the dispersibility of the nanoparticles. In one embodiment, the dispersant is a binder (or binder polymer). The binder may include (eg, in the repeat unit) carboxylic acid groups. The binder may be an insulating polymer. The binder can be a carboxylic acid group-containing compound (monomeric or polymeric). In the composition (or composite) according to the embodiment of the present invention, the content of the dispersant may be, but is not limited to, 0.5% by weight or more, for example, 1% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, or 20% by weight or more, based on the total solid content of the composition (or composite). The dispersant content may be 55% by weight or less, 35% by weight or less, 33% by weight or less, or 30% by weight or less, based on the total solids content of the composition (or composite).

[0097] In the composition (or liquid vehicle) according to an embodiment of the present invention, the liquid monomer or polymerizable (e.g., photopolymerizable) monomer containing a carbon-carbon double bond (hereinafter referred to as monomer) includes a (e.g., photopolymerizable) (meth)acrylic monomer. The monomer may be a precursor for an insulating polymer. The content of the monomer can be 0.5 wt % or more, such as 1 wt % or more, 2 wt % or more, 3 wt % or more, 5 wt % or more, or 10 wt % or more, based on the total weight of the composition. The content of the photopolymerizable monomer can be 30% by weight or less, for example, 28% by weight or less, 25% by weight or less, 23% by weight or less, 20% by weight or less, 18% by weight or less, 17% by weight or less, 16% by weight or less, or 15% by weight or less, based on the total weight of the composition.

[0098] The (photo)initiator contained in the composition according to an embodiment of the invention is for the (photo)polymerization of the aforementioned monomers. An initiator is a compound that can generate radical species under mild conditions (eg, by heat or light) to promote a radical reaction (eg, the radical polymerization of monomers). The initiator may be a thermal initiator or a photoinitiator. The initiator is not particularly limited and can be appropriately selected. In the above composition, the content of the initiator may be appropriately adjusted in consideration of the type and content of the polymerizable monomer used. In one embodiment, the content of the initiator may be, but is not limited to, 0.01 wt % or more, for example, 1 wt % or more, and 10 wt % or less, for example, 9 wt % or less, 8 wt % or less, 7 wt % or less, 6 wt % or less, or 5 wt % or less, based on the total weight of the composition (or the total weight of the solid content).

[0099] The composition (or composite) may further comprise a (multi- or monofunctional) thiol compound having at least one thiol group (e.g., at a terminal end) (or a residue derived therefrom, such as a residue formed by the reaction between a thiol and a carbon-carbon double bond, e.g., a sulfide group), a metal oxide particulate, or a combination thereof. Metal oxide particles are TiO 2 , SiO 2 , BaTiO 3 , B.A. 2 TiO 4 , ZnO, or a combination thereof. The content of metal oxide fine particles in the composition (or composite) may be, based on the total solids content, 1 wt % or more, 2 wt % or more, 3 wt % or more, 5 wt % or more, or 10 wt % or more, and 50 wt % or less, 40 wt % or less, 30 wt % or less, 25 wt % or less, 20 wt % or less, 15 wt % or less, 10 wt % or less, 7 wt % or less, 5 wt % or less, or 3 wt % or less. The diameter of the metal oxide fine particles is not particularly limited and can be appropriately selected. The diameter of the metal oxide particulates can be 100 nm or more, for example 150 nm or more, or 200 nm or more, and 1000 nm or less, or 800 nm or less.

[0100] The multi-thiol compound can be a dithiol compound, a trithiol compound, a tetrathiol compound, or a combination thereof. For example, the thiol compound can be glycol di-3-mercaptopropionate, glycol dimercaptoacetate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 1,6-hexanedithiol, 1,3-propanedithiol, 1,2-ethanedithiol, polyethylene glycol dithiol containing 1 to 10 ethylene glycol repeat units, or a combination thereof. The content of thiol compounds (or residues derived therefrom) can be 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, or 5% by weight or less, based on the total solids content. The content of the thiol compound can be 0.1 wt % or more, for example, 0.5 wt % or more, 1 wt % or more, 5 wt % or more, 10 wt % or more, 15 wt % or more, 18 wt % or more, or 20 wt % or more, based on the total solids content.

[0101] The composition or liquid vehicle may include an organic solvent. Alternatively, the composition or liquid vehicle may be free of organic solvents. If present, the type of solvent that can be used is not particularly limited. The type and amount of the organic solvent are appropriately determined taking into consideration the types and amounts of the main components described above (i.e., semiconductor nanoparticles, dispersant, polymerizable monomer, initiator, and thiol compound, if present) and other additives described below. The composition comprises the solvent in an amount that is the balance of the desired solids (non-volatile) content.

[0102] In one embodiment, examples of the organic solvent include ethylene glycols, glycol ethers, glycol ether acetates, propylene glycols, propylene glycol ethers, propylene glycol ether acetates, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and other amides, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, and other ketones, toluene, xylene, solvent naphtha, and other petroleum products, ethyl acetate, butyl acetate, ethyl lactate, and other esters, diethyl ether, dipropyl ether, dibutyl ether, and other ethers, chloroform, aliphatic hydrocarbons having 1 to 40 carbon atoms (e.g., alkane, alkene, or alkyne), halogen (e.g., chloro)-substituted aliphatic hydrocarbons having 1 to 40 carbon atoms (e.g., dichloroethane, trichloromethane, or the like), aromatic hydrocarbons having 6 to 40 carbon atoms (e.g., toluene, xylene, or the like), like), and halogen (e.g., chloro) substituted aromatic hydrocarbons having 6 to 40 carbon atoms.

[0103] The composition (or composite) may further contain various additives such as a light diffusing agent, a leveling agent, a coupling agent, etc., in addition to the above-mentioned components, if necessary. Components (binder, monomer, solvent, additive, thiol compound, cull binder, etc.) included in the composition according to the embodiment of the present invention can be appropriately selected, and the specific contents thereof can be referred to, for example, the contents described in the specification of US Patent Application Publication US-2017-0052444-A1. The composition according to the embodiment of the present invention can be prepared by mixing the above-mentioned respective components sequentially or simultaneously, and the order is not particularly limited.

[0104] The composition provides a color conversion layer (or composite patterned film) upon (eg, radical) polymerization. The color conversion layer (or composite patterned film) can be fabricated using a photoresist composition. Such a method includes forming a film of the aforementioned composition on a substrate (S1), optionally prebaking the film (S2), exposing selected areas of the film to light (e.g., wavelengths of 400 nm or less) (EXP) (S3), and developing the exposed film with an alkaline developer (DEV) (S4) to obtain a pattern of the quantum dot-polymer composite.

[0105] Referring to FIG. 1a, the composition is applied to a substrate by a suitable method such as spin coating, slit coating, etc. to a desired thickness to form a film. The formed film is optionally subjected to a pre-bake (PRB). The pre-baking conditions such as temperature, time, and atmosphere are known and can be appropriately selected. The formed (or optionally prebaked) film is exposed to light having a predetermined wavelength under a mask having a predetermined pattern. The wavelength and intensity of the light can be selected in consideration of the type and content of the photoinitiator, the type and content of the quantum dots, and the like. The exposed film is treated (eg, by immersion or spraying) with an alkaline developer, which dissolves the unexposed portions of the film to yield the desired pattern. If necessary, the obtained pattern is post-baked (POB) at a temperature of, for example, 150° C. to 230° C. for a predetermined time (for example, 10 minutes or more, or 20 minutes or more) in order to improve the crack resistance and solvent resistance of the pattern.

[0106] When the color conversion layer or the patterned film of the nanoparticle composite has multiple repeating sections (in other words, color conversion regions), multiple compositions containing quantum dots (e.g., red-emitting quantum dots, green quantum dots, or blue quantum dots by choice) having desired luminescent properties (such as light emission peak wavelength) are prepared for the formation of each repeating section, and the above-mentioned patterning process can be repeated a required number of times (e.g., two or more times, or three or more times) for each composition to obtain a nanoparticle-polymer composite having a desired pattern. For example, the nanoparticle-polymer composite can be a repeating pattern of two or more different color blocks (eg, RGB color blocks). Such a nanoparticle-polymer composite pattern can be advantageously used as a light-emitting color filter in a display device. A color conversion layer or a patterned film of the nanoparticle composite is prepared using an ink composition configured to form a pattern by an inkjet method.

[0107] Referring to FIG. 1b, such a method includes the steps of preparing an ink composition, providing a substrate (e.g. patterned with electrodes and optionally pixel regions such as banks or trench-type partitions), and depositing the ink composition onto the substrate (or the pixel regions) to form, for example, a first composite layer or a first quantum dot layer (or a first region). The method may include depositing an ink composition onto the substrate (or the pixel area) to form, for example, a second composite layer or a second quantum dot layer (or a second region). The formation of the first composite layer and the formation of the second composite layer may be carried out simultaneously or sequentially. Deposition of the ink composition is carried out using a suitable liquid crystal ejection device, such as an ink jet or nozzle printing system (eg, having an ink reservoir and one or more printheads). The deposited ink composition undergoes solvent removal and polymerization upon heating to provide a (first or second) composite layer. Such a method can form highly precise nanoparticle-polymer composite films or patterned membranes in a simple manner and in a short time.

[0108] In the composite (eg the first composite) according to an embodiment of the invention, the (polymer) matrix comprises the components mentioned above in relation to the composition. In the composite, the content of the matrix can be 10 wt % or more, 20 wt % or more, 30 wt % or more, 40 wt % or more, 50 wt % or more, or 60 wt % or more, based on the total weight of the composite. The content of the matrix may be 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, or 50% by weight or less, based on the total weight of the composite. The (polymer) matrix may include at least one of a dispersant (e.g., a carboxylic acid group-containing binder polymer), a polymerization product of a polymerizable monomer containing one or more carbon-carbon double bonds (e.g., two or more, three or more, four or more, or five or more), and a polymerization product between a polymerizable monomer and a multi-thiol compound having at least two thiol groups at its terminals (e.g., an insulating polymer). The matrix can include a linear polymer, a crosslinked polymer, or a combination thereof. The (polymer) matrix may be free of conjugated polymers (except for cardo resins). Alternatively, the matrix can include a conjugated polymer.

[0109] The crosslinked polymer may include a thiolene resin, a crosslinked poly(meth)acrylate, a crosslinked polyurethane, a crosslinked epoxy resin, a crosslinked vinyl polymer, a crosslinked silicone resin, or a combination thereof. In one embodiment, the crosslinked polymer may be the polymerization product of the aforementioned polymerizable monomers and optionally multiple thiol compounds. Linear polymers contain repeat units derived from carbon-carbon unsaturated bonds (eg, carbon-carbon double bonds). The repeat unit may include a carboxylic acid group. The linear polymer may comprise ethylene repeat units. The carboxylic acid group-containing repeat unit may include units derived from a monomer containing a carboxylic acid group and a carbon-carbon double bond, units derived from a monomer having a dianhydride moiety, or a combination thereof.

[0110] The (polymer) matrix may comprise a carboxylic acid group-containing compound (eg, a binder, binder polymer, or dispersant) (eg, for dispersing or binding the nanoparticles). The composite (or film or pattern thereof) can, for example, have a thickness of 30 μm or less, e.g., 25 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, 8 μm or less, or 7 μm or less, and a thickness of more than 2 μm, e.g., 3 μm or more, 3.5 μm or more, 4 μm or more, 5 μm or more, 6 μm or more, 7 μm or more, 8 μm or more, 9 μm or more, or 10 μm or more.

[0111] The nanoparticles described above, a composite (pattern) including the same, or a color conversion panel including the same may be included in an electronic device or apparatus. Such electronic devices may include, but are not limited to, 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. The aforementioned quantum dots may also be included in electronic devices. Such electronic devices may include, but are not limited to, mobile terminal devices, monitors, notebook PCs, televisions, electronic displays, cameras, automobiles, and the like. The electronic device may be a mobile terminal device, a monitor, a notebook computer or a television that includes a display device (or light-emitting device) that includes quantum dots. The electronic device may be a camera or a mobile device that includes an image sensor that includes quantum dots. The electronic device may be a camera or an automobile that includes a photodetector that includes quantum dots.

[0112] According to one embodiment of the present invention, there is provided a color conversion layer (eg, color conversion structure or color conversion panel, hereinafter referred to as color conversion panel) that includes color conversion regions that include semiconductor nanoparticles. The color conversion panel includes a color conversion layer including a color conversion region and a partition wall selectively defining each region of the color conversion layer, the color conversion region including a first region corresponding to a first pixel, and the first region including semiconductor nanoparticles or a composite. In one embodiment of the color conversion panel, the composite may be in the form of a patterned film. In other embodiments, the composite may have a sheet form. A color conversion panel according to an embodiment of the present invention includes a color conversion layer having color conversion regions and partition walls selectively defining each region of the color conversion layer. The color transformation area includes a first area corresponding to a first pixel. The first region includes a first composite, the first composite including a matrix and semiconductor nanoparticles dispersed within the matrix, and configured to emit a first light. According to one embodiment, semiconductor nanoparticles or populations thereof are provided. The color conversion layer comprises a composite according to an embodiment of the present invention or a patterned film thereof.

[0113] FIG. 2a is a cross-sectional view showing a schematic configuration of a color conversion panel according to an embodiment of the present invention. Referring to FIG. 2a, the color conversion panel optionally further includes partitions (eg, black matrix (BM), banks, or a combination thereof) that define each area of ​​the color conversion layer (eg, color conversion structures). FIG. 2b is a cross-sectional view showing a schematic configuration of an electronic device (display device) including a color conversion panel and a light source according to another embodiment of the present invention. In an electronic device, a color conversion panel including a color conversion layer or structure is disposed on an "LED on chip" (e.g., a micro LED on chip).

[0114] Referring to FIG. 2b, a circuit (Si Driver IC) for driving a light source is disposed below a light source (eg, a blue LED) configured to emit incident light (eg, blue light). The color conversion layer includes a first composite containing semiconductor nanoparticles that emit a first light (e.g., green light), and a second composite containing semiconductor nanoparticles that emit a second light (red light), or a third composite that emits or transmits a third light (e.g., incident light or blue light). A partition (eg, based on an inorganic material such as silicon or silicon oxide, or based on an organic material) is placed between each composite. The partition may include a trench hole, a via hole, or a combination thereof. A first optical element (eg, an absorptive color filter) is disposed on the light extraction surface of the color conversion layer. An additional optical element, such as a microlens, is further disposed above the first optical element.

[0115] The color conversion region includes a first region configured to emit (eg, upon incident light illumination) the aforementioned first light (or green light). In one embodiment, the first area corresponds to the green pixels. The first region includes a first complex (eg, a luminescent complex). The first light has a peak emission wavelength within a wavelength range described below. The first light will be explained in detail when explaining the contents related to semiconductor nanoparticles. The emission peak wavelength of the green light can be 500 nm or more, 501 nm or more, 504 nm or more, 505 nm or more, or 520 nm or more. The maximum emission peak wavelength of the green light can be 580 nm or less, 560 nm or less, 550 nm or less, 530 nm or less, 525 nm or less, 520 nm or less, 515 nm or less, or 510 nm or less. The color conversion region further includes a (eg, one or more) second region configured to emit (eg, upon irradiation with excitation light) a second light (eg, red light) different from the first light. The second region includes a second composite. The semiconductor nanoparticle composites in the second region include semiconductor nanoparticles (eg, quantum dots) that emit light at a different wavelength (eg, a different color) than the nanoparticle composites in the first region.

[0116] The second light may be red light having an emission peak wavelength in the range of 600 nm to 650 nm (for example, 620 nm to 650 nm). The color conversion panel further includes a third area(s) that emits or passes a third light (eg, blue light) different from the first and second lights. The incident light may include a third light (eg, blue light) and optionally green light. The third light may include blue light having an emission peak wavelength in the range of 380 nm or more (e.g., 440 nm or more, 445 nm or more, 450 nm or more, or 455 nm or more) and 480 nm or less (475 nm or less, 470 nm or less, 465 nm or less, or 460 nm or less). In one embodiment, the color conversion panel or layer includes a plurality of first regions, and the composite is configured in a predetermined pattern to be disposed in each of the first regions of the color conversion panel. The composites (or patterns thereof) can be produced from the (ink) composition by any method, for example photolithography or inkjet methods. Accordingly, embodiments of the present invention relate to compositions that include semiconductor particles, as described in more detail below.

[0117] In one embodiment, the electronic device or display device (eg, a display panel) further comprises a color conversion layer (or color conversion panel) and optionally a light source. The light source is configured to provide incident light to the color conversion layer or panel. In one embodiment, the display panel includes a light-emitting panel (or light source), the aforementioned color conversion panel, and a light-transmitting layer disposed between the light-emitting panel and the color conversion panel. The color conversion panel includes a substrate, and a color conversion layer is disposed on the substrate (see FIG. 3a and FIG. 3c). If present, the light source or light emitting panel is configured to provide incident light to the color conversion panel or layer. The incident light may have an emission peak wavelength in the range of 440 nm or more, such as 450 nm or more, and 580 nm or less, such as 480 nm or less, 470 nm or less, or 460 nm or less.

[0118] In one embodiment, an electronic device (eg, a light-emitting type device) includes a sheet of the nanoparticle composite. Referring to FIG. 3b, the device includes a backlight unit and a liquid crystal panel, where the backlight unit includes a quantum dot-polymer composite sheet (QD sheet). Specifically, the backlight unit has 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 optical films (such as a prism and a double brightness enhance film (DBEF)) are stacked. The liquid crystal panel is disposed on the backlight unit and has a structure including liquid crystal and a color filter between two polarizers (Pol). The quantum dot polymer composite sheet (QD sheet) contains quantum dots that absorb light from a light source and emit red light and quantum dots that emit green light. As the blue light provided by the light source passes through the quantum dot-polymer composite sheet, it is combined with the red and green light emitted from the semiconductor nanoparticles and converted into white light. The white light is separated into blue, green, and red light by color filters in the liquid crystal panel, and is emitted to the outside for each pixel.

[0119] Referring to FIG. 4, the backlight unit (BLU) may be a direct-type BLU without a light guide plate, and may include multiple LEDs (e.g., mini LEDs). The color conversion panel includes a substrate, and a color conversion layer is disposed on the substrate. The color conversion layer or panel comprises a patterned film of nanoparticle composites. The patterned film contains repeating compartments configured to emit desired light. The second region may be a red light emitting section. The first region may be a green light emitting section. The third region may be a section that emits or transmits blue light. Details regarding the first, second and third zones are as above.

[0120] A light emitting panel or light source may be an element that emits incident light (eg, excitation light). The excitation light may include blue light and optionally green light. The light source may include an LED. Alternatively, the light source may include an organic LED (OLED). Alternatively, the light source may include a micro LED. An optical element that blocks (e.g., reflects or absorbs) blue light (and optionally green light), such as a blue light (and optionally green light) blocking layer or a first optical filter as described below, is disposed on the front (light emitting surface) of the first and second regions. When the light source includes a blue light emitting organic light emitting diode and a green light emitting organic light emitting diode, a green light rejection filter is further disposed on the third section through which the blue light passes. The light-emitting panel or light source includes a plurality of light-emitting units corresponding to the first and second regions, respectively, and the light-emitting units include a first electrode and a second electrode facing each other, and an (organic) electroluminescent layer disposed between the first and second electrodes. The electroluminescent layer may comprise an organic light emitting material. For example, each light-emitting unit of the light source can include an electroluminescent device (eg, an organic light-emitting diode) configured to emit light of a predetermined wavelength (eg, blue light, green light, or a combination thereof). The structures and materials of electroluminescent devices and organic light emitting diodes are known and are not particularly limited.

[0121] The display panel and the color conversion panel will be described in more detail below with reference to the drawings. 3a and 3c, a display panel or electronic device 1000 according to an embodiment of the present invention includes a light emitting panel 40 or light source, and a color conversion panel 50. As shown in FIG. The display panel or electronic device may further include, but is not limited to, a light-transmitting layer 60 located between the light-emitting panel 40 and the color conversion panel 50, a bonding material 70 bonding the light-emitting panel 40 and the color conversion panel 50, or a combination thereof. The light transmissive layer may include a passivation layer, a filler material, an encapsulation layer, or a combination thereof. The light-transmitting layer material can be appropriately selected and is not particularly limited. The light transmissive layer material may include inorganic, organic, organic-inorganic hybrid materials, or combinations thereof. The light-emitting panel 40 and the color conversion panel 50 face each other with a light-transmitting layer 60 therebetween, and the color conversion panel 50 is disposed in the direction in which light is emitted from the light-emitting panel 40 . A bonding material 70 is disposed along the edges of the light emitting panel 40 and the color conversion panel 50 and may be, for example, a sealant.

[0122] Referring to FIG. 5a, a display panel 1000 according to an embodiment of the present invention includes a display area 1000D for displaying an image, and a non-display area 1000P located around the display area 1000D and having a bonding material 70 disposed thereon. The display region 1000D includes a plurality of pixels PX arranged along rows (e.g., in the x direction) and / or columns (e.g., in the y direction), and each pixel PX is made up of a plurality of sub-pixels (PX 1 , P.X. 2 , P.X. 3 ). Here, as an example, three sub-pixels (PX 1 , P.X. 2 , P.X. 3 ) forming one pixel, the present invention is not limited to this, and may further include an additional sub-pixel, such as a white sub-pixel, or may further include one or more sub-pixels displaying the same color. The multiple pixels PX are arranged in, for example, a Bayer matrix, a PenTile matrix, and / or a diamond matrix, but are not limited to these.

[0123] Each sub-pixel (PX 1 , P.X. 2 , P.X. 3 ) displays three primary colors or combinations of the three primary colors, for example red, green, blue, or a combination thereof. As an example, the first sub-pixel PX 1 displays red, and the second sub-pixel PX 2 displays green, and the third sub-pixel PX 3 will display the color blue. Although the drawings show an example in which all the sub-pixels have the same size, the present invention is not limited thereto, and at least one of the sub-pixels may be larger or smaller than the other sub-pixels. Although the drawings show an example in which all the sub-pixels have the same shape, the present invention is not limited thereto, and at least one of the sub-pixels may have a shape different from the other sub-pixels.

[0124] In a display panel or electronic device according to an embodiment of the present invention, a light-emitting panel includes a substrate and a (eg, oxide-based) TFT disposed on the substrate. A light emitting device is disposed above the TFT (which may have a tandem structure, for example). The light emitting device includes a light emitting layer (eg, a blue light emitting layer, a green light emitting layer, or a combination thereof) between opposing first and second electrodes. A charge generating layer is disposed between each of the light emitting layers. The first electrode and the second electrode can each be patterned with a plurality of electrode elements to correspond to pixels. The first electrode can be an anode or a cathode. The second electrode can be a cathode or an anode. The light emitting device may include organic LEDs, nanorod LEDs, mini LEDs, micro LEDs, or combinations thereof.

[0125] 5b to 5e are cross-sectional views showing examples of light emitting devices according to embodiments of the present invention. In one embodiment, the mini LED may have a size of, but is not limited to, 100 micrometers (μm) or more, 150 μm or more, 200 μm or more to 1 millimeter or less, 0.5 millimeters or less, 0.15 millimeters or less, or 0.12 millimeters or less. In one embodiment, the micro LEDs may have a size of less than 100 micrometers, 50 micrometers or less, 10 micrometers or less. The size of the micro LEDs may be, but is not limited to, 0.1 μm or more, 0.5 μm or more, 1 μm or more, or 5 μm or more.

[0126] Referring to FIG. 5b, in one embodiment, a light emitting device 180 includes a first electrode 181 and a second electrode 182 facing each other, an emissive layer 183 located between the first electrode 181 and the second electrode 182, and optionally auxiliary layers (184, 185) located between the first electrode 181 and the emissive layer 183 and between the second electrode 182 and the emissive layer 183. The first electrode 181 and the second electrode 182 are disposed to face each other along a thickness direction (e.g., the z direction), and 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 may be a translucent electrode, a semi-transparent electrode, or a reflective electrode, and the second electrode 182 may be a translucent electrode or a semi-transparent electrode.

[0127] The transparent or semi-transparent electrode may be formed of a conductive oxide such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), and fluorine-doped tin oxide (FTO), or a thin single-layer or multi-layer metal film including 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, but not limited to, silver (Ag), copper (Cu), aluminum (Al), gold (Au), titanium (Ti), chromium (Cr), nickel (Ni), alloys thereof, nitrides thereof (e.g., TiN), or combinations thereof.

[0128] Light-emitting layer 18 can emit a first phosphor that emits light having a blue emission spectrum, a second phosphor that emits light having a green emission spectrum, or a combination thereof. The maximum emission wavelength of the blue emission spectrum belongs to a wavelength region of not less than about 400 nm and less than 500 nm, and within the above range, may belong to a wavelength region of about 410 nm to 490 nm, about 420 nm to 480 nm, 430 nm to 470 nm, 440 nm to 465 nm, 445 nm to 460 nm, 450 nm to 458 nm, or a combination thereof. The maximum emission wavelength of the green emission spectrum belongs to a wavelength region of not less than about 500 nm and less than 590 nm, and within the above range, may belong to a wavelength region of about 510 nm to 580 nm, about 515 nm to 570 nm, 520 nm to 560 nm, 525 nm to 555 nm, 530 nm to 550 nm, 535 nm to 545 nm, or a combination thereof.

[0129] As an example, light-emitting layer 183 or the light emitters contained therein can include phosphorescent materials, fluorescent materials, or a combination thereof. As an example, the light emitter may include an organic light emitter, which may be a small molecule compound, a polymeric compound, or a combination thereof. The specific types of phosphorescent and fluorescent substances are not particularly limited, and can be appropriately selected from known materials. Also, by way of example, the light emitter may include an inorganic light emitter, which 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 nitrides, metal oxides, or combinations thereof may include Group III metals, such as aluminum, gallium, indium, thallium, Group IV metals, such as silicon, germanium, tin, or combinations thereof. When the light emitter includes an inorganic light emitter, 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 inorganic luminescent materials are known.

[0130] In one embodiment, the light emitting device 180 further comprises auxiliary layers (184, 185). The auxiliary layers (184, 185) are disposed between the first electrode 181 and the light-emitting layer 183, and between the second electrode 182 and the light-emitting layer 183, respectively. The auxiliary layers (184, 185) may be charge auxiliary layers for adjusting charge injection and / or mobility, respectively. Each of the auxiliary layers (184, 185) may be one or more layers, and may be, for example, 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. At least one of the auxiliary layers (184, 185) may be omitted. The material for each auxiliary layer can be appropriately selected from among materials known for organic electroluminescent devices.

[0131] Each sub-pixel (PX 1 , P.X. 2 , P.X.3 The light emitting devices 180 arranged in the first and second rows may be identical to each other or different. Each sub-pixel (PX 1 , P.X. 2 , P.X. 3 The light emitting devices 180 arranged in the array 180 may emit light with the same or different emission spectra. Each sub-pixel (PX 1 , P.X. 2 , P.X. 3 ) may, for example, emit light in the blue emission spectrum, light in the green emission spectrum, or a combination thereof, respectively. Each sub-pixel (PX 1 , P.X. 2 , P.X. 3) The light emitting devices 180 arranged in the pixel array 140 may be separated by pixel defining membranes (not shown).

[0132] Referring to FIG. 5c, the light emitting device 180 may be a light emitting device having a tandem 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 optionally auxiliary layers (184, 185) located between the first electrode 181 and the first light emitting layer 183a and between the second electrode 182 and the second light emitting layer 183b. The first electrode 181, the second electrode 182, and the auxiliary layers (184, 185) are as described above.

[0133] The first light emitting layer 183a and the second light emitting layer 183b may emit light having the same or different emission spectra. In one embodiment, first light-emitting layer 183a or second light-emitting layer 183b may emit light in the blue emission spectrum or light in the green emission spectrum. The charge generation layer 186 injects charges into the first light-emitting layer 183a and / or the second light-emitting layer 183b, and adjusts the charge balance between the first light-emitting layer 183a and the second light-emitting layer 183b. Charge generation layer 186 may, for example, include n-type and p-type layers, including electron transporting and / or hole transporting materials including, for example, n-type and / or p-type dopants. The charge generating layer 186 may be one layer or two or more layers.

[0134] Referring to FIG. 5d, a light-emitting device (e.g., having a tandem structure) includes a first electrode 181 and a second electrode 182 facing each other, a first light-emitting layer 183a located between the first electrode 181 and the second electrode 182, a second light-emitting layer 183b and a third light-emitting layer 183c, 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 optionally auxiliary layers (184, 185) located between the first electrode 181 and the first light-emitting layer 183a and between the second electrode 182 and the third light-emitting layer 183c. The first electrode 181, the second electrode 182, and the auxiliary layers (184, 185) are as described above.

[0135] 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 emit blue light. In one embodiment, the first light emitting layer 183a and the third light emitting layer 183c emit light in the blue emission spectrum, and the second light emitting layer 183b emits light in the green emission spectrum. In another embodiment, the first light-emitting layer 183a and the third light-emitting layer 183c emit light in a green emission spectrum, and the second light-emitting layer 183b emits light in a blue emission spectrum. The first charge generation layer 186a injects charges into the first light-emitting layer 183a and / or the second light-emitting layer 183b and adjusts the charge balance between the first light-emitting layer 183a and the second light-emitting layer 183b. The second charge generation layer 186a injects charges into the second light emitting layer 183b and / or the third light emitting layer 183c, and adjusts the charge balance between the second light emitting layer 183b and the third light emitting layer 183c. The first and second charge generation layers (186a, 186b) may each be one layer or two or more layers.

[0136] Referring to FIG. 5 e , a light emitting device 180 includes a first electrode 181 , a second electrode 182 , and a light emitting layer 183 including a plurality of nanostructures 187 . One of the first electrode 181 and the second electrode 182 is an anode, and the other is a cathode. The first electrode 181 and the second electrode 182 may be electrodes patterned by the arrangement direction of a plurality of nanostructures 187, and may include, but are not limited to, conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), and fluorine-doped tin oxide (FTO), silver (Ag), copper (Cu), aluminum (Al), gold (Au), titanium (Ti), chromium (Cr), nickel (Ni), alloys thereof, nitrides thereof (e.g., TiN), or combinations thereof.

[0137] The light-emitting layer 183 includes a plurality of nanostructures 187, and each sub-pixel (PX 1 , P.X. 2 , P.X. 3 ) includes a plurality of nanostructures 187. The plurality of nanostructures 187 may be arranged along one direction, but is not limited to this. The nanostructure 187 is a compound semiconductor that emits light of a predetermined wavelength when an electric current is applied, and may be, for example, a linear nanostructure such as a nanorod or a nanoneedle. The diameter or long axis of nanostructure 187 can be, for example, a few to a few hundred nanometers, and the aspect ratio of nanostructure 187 can be in the range of 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, greater than or equal to about 5.0, greater than about 1 and less than or equal to 20, between about 1.5 and 20, between about 2.0 and 20, between about 3.0 and 20, between about 4.0 and 20, between about 4.5 and 20, or between about 5.0 and 20, or any combination thereof.

[0138] Each nanostructure 187 includes a p-type region 187p, an n-type region 187n, and a multiple quantum well region 187i, and emits light from the multiple quantum well region 187i. The nanostructures 187 may include, for example, gallium nitride (GaN), indium gallium nitride (InGaN), aluminum gallium nitride (AlGaN), or combinations thereof, and may have, for example, a core-shell structure. The multiple nanostructures 187 may emit light with the same or different emission spectra. In one embodiment, the first nanostructure 187a emits light with a blue emission spectrum, for example, with a maximum emission wavelength in the wavelength range of about 400 nm to less than 500 nm, about 410 nm to 490 nm, or about 420 nm to 480 nm.

[0139] FIG. 6 is a schematic cross-sectional view of a device (or a display panel) according to an embodiment of the present invention. Referring to FIG. 6, the light source (or light emitting panel) includes an organic light emitting diode (OLED) that emits blue light (and optionally green light). An organic light emitting diode includes two or more pixel electrodes formed on a substrate, a pixel defining film formed between adjacent pixel electrodes, an organic light emitting layer formed on each pixel electrode, and a common electrode layer formed on the organic light emitting layer. Below the organic light emitting diode, a thin film transistor and a substrate are disposed. The pixel regions of the OLED are arranged to correspond to first, second and third regions which will be described later. Although FIG. 6 shows the color conversion panel and the light emitting panel separated from each other, the color conversion panel may be stacked directly above the light emitting panel.

[0140] A laminate structure including a pattern of nanoparticle composites (eg, first areas including red quantum dots and second areas including green quantum dots) and a substrate is disposed over the light source. The blue light emitted from the light source is incident on the first and second regions, which emit red and green light, respectively. The blue light emitted from the light source passes through a third area. An element for blocking excitation light (a first optical filter or an excitation light blocking layer) may be optionally disposed between the nanoparticle composite layer (R, G) and the substrate. If the excitation light includes blue and green light, a green light blocking filter is added to the third section. The first optical filter or excitation light blocking layer is described in more detail below. Such a device can be fabricated by separately fabricating and then combining the color conversion panel described above with LEDs or OLEDs (eg, emitting blue light and optionally green light). Alternatively, the devices can be fabricated by directly patterning the nanoparticle composites on the LED or OLED.

[0141] In the color conversion panel or display device according to the embodiment of the present invention, the substrate may be a substrate including an insulating material. The substrates can be glass, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), various polymers such as polycarbonate, polyacrylate, polysiloxanes (e.g., PDMS), Al, 2 O 3 The materials may include, but are not limited to, inorganic materials such as ZnO, or combinations thereof. The thickness of the substrate is not particularly limited and can be appropriately selected in consideration of the substrate material, etc. The substrate may be flexible. The substrate can be configured to be 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more transmissive to light emitted from the semiconductor nanoparticles.

[0142] A wiring layer including thin film transistors and the like is formed on the substrate. The wiring layer may further include a gate line, a storage voltage line, a gate insulating film, a data line, a source electrode, a drain electrode, a semiconductor layer, a protective film, and the like. The detailed structure of the wiring layer may vary depending on the embodiment. The gate lines and the storage voltage lines are electrically isolated from each other, and the data lines cross the gate lines and the storage voltage lines in an insulated manner. The gate electrode, source electrode, and drain electrode respectively constitute the control terminal, input terminal, and output terminal of the thin film transistor. The drain electrode is electrically connected to a pixel electrode, which will be described later. The pixel electrode functions as an electrode (eg, an anode) of the display device. The pixel electrodes are formed from a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO). The pixel electrodes can also be formed from materials with light-shielding properties, such as gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), and titanium (Ti). The pixel electrode may have a two-layer structure in which the transparent conductive material and the light-shielding material are sequentially laminated.

[0143] A pixel define layer (PDL) is formed between two adjacent pixel electrodes so as to overlap the ends of the pixel electrodes and divide the pixel electrodes into pixel units. The pixel definition layer is an insulating layer that electrically isolates two or more pixel electrodes. The pixel defining layer covers only a portion of the top surface of the pixel electrode, the remaining portion of the pixel electrode not covered by the pixel defining layer forming an opening. An organic light-emitting layer, which will be described later, is formed on the region defined as the opening. The organic light-emitting layer is defined as each pixel area by the pixel electrodes and pixel definition layer described above. That is, a region in which one organic light emitting unit layer is formed and in contact with one pixel electrode separated by a pixel defining layer is defined as one pixel region. In a display device according to an embodiment of the present invention, an organic light emitting layer is defined as a first pixel region, a second pixel region, and a third pixel region, and each pixel region is spaced apart by a pixel defining layer at a predetermined interval.

[0144] The organic light-emitting layer emits a third light which is in the visible light region or in the UV region. The first to third pixel regions of the organic light emitting layer may all emit the third light. In one embodiment, the third light may include light having high energy in the visible light range, for example blue light (and optionally green light). When all pixel regions of the organic light-emitting layer are designed to emit the same light, the pixel regions of the organic light-emitting layer are all made of the same or similar materials or exhibit the same or similar physical properties. Therefore, the degree of difficulty in the process of forming the organic light-emitting layer can be significantly reduced, and such a display device can be easily adapted to a process of enlarging the size / area of ​​the display device. However, the organic light emitting layer according to the embodiment of the present invention is not necessarily limited thereto, and the organic light emitting layer may be configured to emit two or more different lights. The organic light emitting layer includes an organic light emitting unit layer for each pixel region, and each organic light emitting unit layer may further include auxiliary layers (eg, a hole injection layer, a hole transport layer, an electron transport layer, etc.) in addition to the light emitting layer.

[0145] The common electrode functions as the cathode of the display device. The common electrode is formed from a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO). The common electrode is integrally formed on the organic light emitting layer. A planarization or passivation layer (not shown) is formed over the common electrode. The planarization layer includes an insulating material (e.g., transparent) to ensure electrical insulation from the common electrode. In one embodiment, the display device further includes a lower substrate, a polarizer disposed below the lower substrate, and a liquid crystal layer disposed between the laminate and the lower substrate, the laminate being disposed such that the self-emitting layer faces the liquid crystal layer. The display further includes a polarizer between the liquid crystal layer and the light emitting layer. The light source further includes an LED and optionally a light guide plate.

[0146] A display device (eg, a liquid crystal display device) according to a non-limiting embodiment of the present invention will now be described with reference to the drawings. FIG. 7a is a cross-sectional view showing a schematic configuration of a liquid crystal display device according to a non-limiting embodiment. Referring to FIG. 7 a , a display device according to an embodiment of the present invention includes a liquid crystal panel 200 , a polarizer 300 disposed below the liquid crystal panel 200 , and a backlight unit disposed below the polarizer 300 . The liquid crystal panel 200 includes a lower substrate 210, a laminate structure, and a liquid crystal layer 220 interposed between the laminate structure and the lower substrate. The laminate structure includes a transparent substrate 240, a first optical filter layer, and a self-emissive layer 230 that includes a pattern of quantum dot-polymer composite, and a second optical filter layer.

[0147] The bottom substrate 210, also called the array substrate, can be a transparent insulating material substrate. The details regarding the substrate are as described above. A wiring board 211 is provided on the upper surface of the lower substrate 210 . The wiring board 211 includes, but is not limited to, a plurality of gate lines (not shown) and data lines (not shown) that define pixel regions, thin film transistors provided adjacent to the intersections of the gate lines and the data lines, and pixel electrodes for each pixel region. The specific contents of such wiring boards are known and are not particularly limited. A liquid crystal layer 220 is provided on the wiring board 211 . The liquid crystal layer 220 includes alignment films 221 above and below the liquid crystal layer 220 for initial alignment of the liquid crystal material contained therein. Specific details regarding the liquid crystal material and the alignment film (eg, liquid crystal material, alignment film material, method of forming a liquid crystal layer, thickness of the liquid crystal layer, etc.) are known and are not particularly limited.

[0148] A lower polarizer 300 is provided below the lower substrate. The material and structure of the polarizing plate 300 are known and are not particularly limited. Below the polariser 300 a backlight unit (eg emitting blue light) is provided. An upper optical element or an upper polarizer 300 is provided between the liquid crystal layer 220 and the transparent substrate 240, but is not limited thereto. For example, the top polarizer 300 is disposed between the liquid crystal layer 220 and the self-emissive layer 230 . Polarizer 300 can be any polarizer that can be used in a liquid crystal display device. The polarizing plate 300 may be made of triacetyl cellulose (TAC) having a thickness of 200 μm or less, but is not limited thereto. In other embodiments, the top optical element may have a refractive index matching coating with no polarizing function.

[0149] The backlight unit includes a light source 110 . The light source emits blue or white light. The light sources include, but are not limited to, blue LEDs, white LEDs, white OLEDs, or combinations thereof. The backlight unit further includes a light guide plate 120 . In one embodiment, the backlight unit may be of the edge type. For example, the backlight unit may include, but is not limited to, a reflector (not shown), a light guide plate (not shown) provided on the reflector for supplying a surface light source to the liquid crystal panel 200, and / or one or more optical sheets (not shown) positioned on the light guide plate, such as a diffusion plate, a prism sheet, etc. Alternatively, the backlight unit does not need to include a light guide plate. In one embodiment, the backlight unit may be of the direct lighting type. For example, the backlight unit may have a reflector (not shown) and a number of fluorescent lamps arranged at regular intervals on top of the reflector, or may have an LED driving board on which a number of light emitting diodes are arranged, and a diffusion plate and optionally one or more optical sheets thereon. Details of such a backlight unit (for example, details of each component such as a light emitting diode, a fluorescent lamp, a light guide plate, various optical sheets, and a reflector) are known and are not particularly limited.

[0150] The bottom surface of the transparent substrate 240 includes an opening, and is provided with a black matrix 241 for shielding gate lines, data lines, thin film transistors, etc. of the wiring board provided on the lower substrate. For example, the black matrix 241 has a lattice shape. In the opening of the black matrix 241, a self-luminous layer 230 having a nanoparticle-polymer composite pattern is provided, the nanoparticle-polymer composite pattern including a first area R that emits a first light (e.g., red light), a second area G that emits a second light (e.g., green light), and a third area B that emits / transmits, for example, blue light. If desired, the self-luminous layer 230 may further include one or more fourth sections. The fourth section may include quantum dots that emit light of a color different from the light emitted from the first to third sections (eg, cyan, magenta, and yellow).

[0151] The sections forming the pattern in the self-emitting layer 230 are repeated corresponding to the pixel areas formed on the lower substrate. A transparent common electrode 231 is provided on the self-luminous layer 230 . The third area B, which transmits / emits blue light, can be a transparent color filter that does not modify the emission spectrum of the light source. In this case, blue light emitted from the backlight unit is polarized and enters the liquid crystal layer, and is then emitted as is. If desired, the third region may include quantum dots that emit blue light.

[0152] As described above, if desired, the display device or light emitting device according to the embodiments of the present invention may further include an excitation light blocking layer or a first optical filter layer (hereinafter referred to as a first optical filter layer). The first optical filter layer is disposed between the bottom surface of the first region R and the second region G and a substrate (eg, top substrate 240) or on the top surface of a substrate. The first optical filter layer may be a sheet having an opening in the portion corresponding to the pixel area (third region) that displays blue, and may be formed in the portions corresponding to the first and second regions. That is, the first optical filter layer is integrally formed at the remaining positions except for the position overlapping with the third region as shown in Figures 2a, 2b, 6, and 7a, but is not limited thereto. Two or more first optical filter layers are spaced apart from one another and overlap the first and second regions, and optionally the third region, respectively. If the light source includes green light emitting elements, then a green light blocking layer is disposed over the third region.

[0153] The first optical filter layer, for example, blocks light in a certain wavelength range within the visible light range and transmits light in the remaining wavelength range, for example, blocks blue light (or green light) and transmits light other than blue light (or green light). The first optical filter layer transmits, for example, green light, red light, and / or yellow light, which is a mixture of these colors. A first optical filter layer transmits blue light and blocks green light and is disposed over the blue light emitting pixels. The first optical filter layer substantially blocks the excitation light and transmits light in the desired wavelength range. The transmittance of the first optical filter layer for light in the desired wavelength region can be about 70% or more, 80% or more, 90% or more, or even 100%. The first optical filter layer that selectively transmits red light is disposed at a position overlapping the red light emitting section, and the first optical filter layer that selectively transmits green light is disposed at a position overlapping the green light emitting section.

[0154] The first optical filter layer may include at least one of a first filter region that blocks (e.g., absorbs) blue and red light and selectively transmits light in a predetermined range (e.g., about 500 nm or more, about 510 nm or more, or about 515 nm or more and about 550 nm or less, about 545 nm or less, about 540 nm or less, about 535 nm or less, about 530 nm or less, about 525 nm or less, or about 520 nm or less), and a second filter region that blocks (e.g., absorbs) blue and green light and selectively transmits light in a predetermined range (e.g., about 600 nm or more, about 610 nm or more, or about 615 nm or more and about 650 nm or less, about 645 nm or less, about 640 nm or less, about 635 nm or less, about 630 nm or less, about 625 nm or less, or about 620 nm or less). When the light source emits a mixture of blue and green light, the first optical filter further includes a third filter region that selectively transmits blue light and blocks green light. The first filter region is positioned to overlap the green light-emitting section. The second filter region is positioned to overlap the red light emitting section. The third filter region is disposed in a position overlapping with the blue light emitting region. The first filter region, the second filter region, and optionally the third filter region may be optically isolated. Such a first optical filter layer contributes to improving the color purity of the display device.

[0155] The display device according to an embodiment of the present invention further includes a second optical filter layer (e.g., a red / green light or yellow light recycling layer) disposed between the self-emissive layer 230 and the liquid crystal layer 220 (e.g., between the self-emissive layer 230 and the upper polarizer 300) and transmitting at least a portion of the third light (excitation light) and reflecting at least a portion of the first light and / or the second light. The first light is red light, the second light is green light, and the third light is blue light. The second optical filter layer transmits only the third light (B) in the blue light wavelength region having a wavelength region of 500 nm or less, and light in the wavelength region exceeding 500 nm, i.e., green light (G), yellow light, red light (R), etc., cannot pass through the second optical filter layer and is reflected. The reflected green and red lights pass through the first and second areas and are emitted to the outside of the display device 10 . The second optical filter layer or the first optical filter layer is formed as a unitary layer having a relatively flat surface.

[0156] The first optical filter layer comprises a thin polymeric film containing dyes and / or pigments that absorb the wavelengths of light to be blocked. The second optical filter layer and the first optical filter layer each include a single layer having a low refractive index, and may be, for example, a transparent thin film having a refractive index of 1.4 or less, 1.3 or less, or 1.2 or less. The second optical filter layer or the first optical filter layer having a low refractive index can be, for example, a porous silicon oxide, a porous organic, a porous organic / inorganic composite, or a combination thereof. The first optical filter layer or the second optical filter layer includes a plurality of layers having different refractive indices. The two layers having different refractive indices are formed by alternately laminating them. For example, the first and second optical filter layers can be formed by alternately laminating materials having high and low refractive indices.

[0157] Electronic devices according to embodiments of the invention include light emitting devices (eg, electroluminescent devices) that include the nanoparticles described above. FIG. 7b is a schematic cross-sectional view of a light-emitting device (electroluminescent device) according to an embodiment of the present invention. Referring to FIG. 7b, the light-emitting device includes an anode 1 and a cathode 5 facing each other, a quantum dot light-emitting layer 3 located between the anode and the cathode and including a plurality of quantum dots, and a hole auxiliary layer 2 disposed between the anode and the quantum dot light-emitting layer.

[0158] The hole auxiliary layer 2 may further include a hole injecting layer (HIL), a hole transporting layer (HTL), an electron blocking layer (EBL), or a combination thereof. The hole-assisting layer 2 comprises any organic / inorganic material that has hole properties. The quantum dot light-emitting layer 3 further includes an electronic auxiliary layer 4 between the cathode 5 and the quantum dot light-emitting layer 3 . The electron auxiliary layer 4 may further include an electron injecting layer (EIL), an electron transporting layer (ETL), a hole blocking layer (HBL), or a combination thereof. The electronic auxiliary layer 4 comprises any organic / inorganic material that has electronic properties.

[0159] Specific examples of the present invention will now be presented. However, the examples described below are merely intended to specifically illustrate or explain the invention, and should not be construed as limiting the scope of the invention.

[0160] <<Example>> <Analysis method> [1] Photoluminescence analysis (1) Photoluminescence (PL) spectra of the prepared semiconductor nanoparticles and the composites containing the same are obtained using a Hitachi F-7100 spectrophotometer at an excitation wavelength of 450 nm. (2) Absolute quantum efficiency is measured using QE-2100, Otsuka.

[0161] [2] Elemental content analysis and production yield calculation (1) ICP analysis: Inductively coupled plasma atomic emission spectrometry (ICP-AES) is performed using a Shimadzu ICPS-8100. (2) Calculate the production yield using the following formula 2. (Number 2) Production yield = A / B × 100 Formula 2 (Here, A is the total weight of silver, Group 13 element, and sulfur in the semiconductor nanoparticles recovered from the crude solution, and B is the total weight of silver, Group 13 element, and sulfur added to the reaction medium for the reaction.) B was determined from the results of ICP analysis of the first semiconductor nanocrystal and the molar ratio of the precursors used in the synthesis, and A was determined from the results of ICP analysis of the produced semiconductor nanoparticles.

[0162] [3] Optical density measurement and UV-Vis absorption spectroscopy (1) The crude solution is diluted n-fold (e.g., 100-fold) and subjected to UV spectroscopy (preparation of specimens by placing in a cuvette providing a light path length of 10 mm, i.e., 1 centimeter, and the specimens obtained using a Shimadzu UV-2600) to obtain a UV-Visible absorption spectrum. (2) From the obtained UV-Visible absorption spectrum, the UV absorbance at a predetermined wavelength (e.g., 500 nm or 350 nm) is obtained, and the obtained absorbance is again multiplied by n (e.g., 100 times) to obtain the optical density.

[0163] [4] Transmission electron microscope (TEM) analysis Transmission electron microscopy analysis of the fabricated semiconductor nanoparticles is performed using a UT F30 Tecnai electron microscope.

[0164] [Reference Example 1] Silver acetate is dissolved in oleylamine to prepare a 0.06 M silver precursor-containing solution (hereinafter abbreviated as silver precursor). Sulfur is dispersed in oleylamine to prepare a 1 M sulfur precursor-containing solution (hereinafter, abbreviated as sulfur precursor). Indium chloride is dissolved in ethanol to prepare a 1M indium precursor-containing solution (hereinafter, abbreviated as indium precursor). A 100 mL reaction flask is charged with gallium acetylacetonate, octadecene (ODE), and dodecanethiol and heated to 120° C. under vacuum for 10 minutes. The flask is cooled to room temperature, and the gas in the flask is replaced with nitrogen. Then, the silver precursor, sulfur precursor, and indium precursor are added, and the flask temperature is raised to the reaction temperature (210° C.) and reacted for 60 minutes or less. The flask temperature is lowered to 180° C., trioctylphosphine (TOP) is added, and then hexane and ethanol are added to the resulting mixture to promote precipitation, and the precipitate (first semiconductor nanocrystals) is separated by centrifugation. The molar ratio of indium precursor, gallium precursor, and sulfur precursor used was 1:2.3:4.8, and the molar number of silver precursor to indium was within 0.5-1.2.

[0165] Example 1 A solution containing a silver compound is prepared by dissolving silver acetate in oleylamine. Gallium chloride is dissolved in trioctylphosphine to prepare a 1M gallium precursor-containing solution (hereinafter, gallium precursor). Dimethylthiourea (DMTU) (sulfur precursor), oleylamine, and octadecene are placed in a flask and vacuum treated at 120°C for 10 minutes. N 2 After replacing the inside of the reaction flask with , it is heated to 240° C. (first temperature), and then the first semiconductor nanocrystal, the gallium precursor, and the silver compound are added. The reaction is carried out for about 30 minutes, and the reactor is heated to 260°C (second temperature, reaction temperature) and further reacted for about 40 minutes. The temperature of the reaction solution is raised to 180° C., trioctylphosphine is added, and the solution is cooled to room temperature to obtain a crude solution containing semiconductor nanoparticles. The molar ratio of gallium precursor to sulfur precursor used is 1:1.3. The content of the silver compound is 3.5 mol % relative to the gallium precursor. A sample is taken from the crude solution, diluted 100-fold with toluene, and subjected to UV-Vis absorption spectroscopy and optical density measurement. The results are summarized in FIG. 8 and Table 1 below. Hexane and ethanol are added to the resulting crude solution to promote precipitation to obtain semiconductor nanoparticles, which are recovered by centrifugation and redispersed in toluene. The obtained semiconductor nanoparticles were subjected to ICP-AES analysis, and the results are shown in Table 2 below. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis, and the results are shown in Tables 1 and 2.

[0166] Example 2 A crude solution was obtained and semiconductor nanoparticles were separated in the same manner as in Example 1, except that the amount of Ag compound used relative to the gallium precursor was changed as shown in Table 1. A sample is taken from the crude solution and diluted 100 times with toluene, after which UV-Vis absorption spectroscopy and optical density measurement are performed. The results are summarized in Figure 9 and Table 1. Hexane and ethanol are added to the resulting crude solution to promote precipitation to obtain semiconductor nanoparticles, which are recovered by centrifugation and redispersed in toluene. The obtained semiconductor nanoparticles were subjected to ICP-AES analysis, and the results are shown in Table 2. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis, and the results are shown in Table 1.

[0167] Example 3 A crude solution was obtained and semiconductor nanoparticles were separated in the same manner as in Example 1, except that the amount of Ag compound used relative to the gallium precursor was changed as shown in Table 1. A sample is taken from the crude solution and diluted 100 times with toluene, after which UV-Vis absorption spectroscopy and optical density measurement are performed. The results are summarized in Figure 9 and Table 1. Hexane and ethanol are added to the resulting crude solution to promote precipitation to obtain semiconductor nanoparticles, which are recovered by centrifugation and redispersed in toluene. The obtained semiconductor nanoparticles were subjected to ICP-AES analysis, and the results are shown in Table 2. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis and TEM analysis, the results of which are shown in Tables 1 and 2.

[0168] Example 4 A crude solution was obtained and semiconductor nanoparticles were separated in the same manner as in Example 1, except that the amount of Ag compound used relative to the gallium precursor was changed as shown in Table 1 and the reaction scale was increased by 1.3 times. A sample is taken from the crude solution and diluted 100 times with toluene, after which UV-Vis absorption spectroscopy and optical density measurement are performed. The results are summarized in Figure 9 and Table 1. Hexane and ethanol are added to the resulting crude solution to promote precipitation to obtain semiconductor nanoparticles, which are recovered by centrifugation and redispersed in toluene. The obtained semiconductor nanoparticles were subjected to ICP-AES analysis, and the results are shown in Table 2. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis and TEM analysis, the results of which are shown in Tables 1 and 2.

[0169] Comparative Example 1 Gallium chloride is dissolved in toluene to prepare a 5.68 M gallium precursor-containing solution (hereinafter, gallium precursor). Dimethylthiourea (DMTU) and oleylamine are placed in a flask and vacuum treated at 120°C for 10 minutes. N 2 After replacing the inside of the reaction flask with , it is heated to 240° C., and then the first semiconductor nanocrystal, a gallium precursor, is added. The reactor is heated to 280° C. (second temperature) and reacted for about 30 minutes to obtain a contrast liquid containing semiconductor nanoparticles. The molar ratio of gallium precursor to sulfur precursor used is 1:1.3. A sample is taken from the crude solution and diluted 100 times with toluene, after which UV-Vis absorption spectroscopy and optical density measurement are performed. The results are summarized in Figure 8 and Table 1. Hexane and ethanol are added to the resulting crude solution to promote precipitation to obtain semiconductor nanoparticles, which are recovered by centrifugation and redispersed in toluene. The obtained semiconductor nanoparticles were subjected to ICP-AES analysis, and the results are shown in Table 2. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis and TEM analysis, the results of which are shown in Tables 1 and 2.

[0170] Comparative Example 2 A crude solution was obtained in the same manner as in Comparative Example 1, except that the amount of gallium precursor was halved, and semiconductor nanoparticles were separated. A sample is taken from the crude solution and diluted 100 times with toluene, after which UV-Vis absorption spectroscopy and optical density measurement are performed. The results are summarized in Table 1. Hexane and ethanol are added to the resulting crude solution to promote precipitation to obtain semiconductor nanoparticles, which are recovered by centrifugation and redispersed in toluene. The obtained semiconductor nanoparticles were subjected to ICP-AES analysis, and the results are shown in Table 2. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis and TEM analysis, the results of which are shown in Tables 1 and 2.

[0171] [Table 1]

[0172] From the results in Table 1, it can be seen that Comparative Example 1 and Comparative Example 2 have low "optical density" at 500 nm and 350 nm, and also have low manufacturing yields. It can be confirmed that the semiconductor nanoparticles of the examples exhibit high-level optical properties, have high "optical density" at 500 nm and 350 nm, and also have a high production yield.

[0173] [Table 2] From the results in Table 2, it can be seen that the semiconductor nanoparticles of the examples show a significantly more uniform distribution than the nanoparticles of the comparative examples.

[0174] [Table 3]

[0175] The embodiment has been described above in detail. The present invention is not limited to the above-described embodiment and examples, and can be modified and embodied in various ways without departing from the technical scope of the present invention. [Explanation of symbols]

[0176] 40 Light-emitting panel 50 Color Conversion Panel 60 Translucent layer 70 Binding material 110 Light source 120 Light guide plate 180 Light emitting device 181, 182 (first, second) electrodes 183 light-emitting layer 183a, 183b, 183c (first to third light-emitting layers 184, 185 auxiliary layer 186 Charge generation layer 186a, 186b (1st, 2nd) charge generation layer 187 Multiple Nanostructures 187i Multiple quantum well 187n n-type region 187p p-type region 200 LCD Panel 210 Lower Board 211 Wiring board 220 Liquid crystal layer 221 Orientation Film 230 Self-luminous layer 231 Transparent common electrode 240 Transparent Substrate 241 Black Matrix 300 Polarizing Plate 1000 Display Panel 1000D display area 1000P hidden area

Claims

1. 1. A method for producing semiconductor nanoparticles, comprising: The method includes the steps of combining a first semiconductor nanocrystal including silver, a Group 13 element, and a chalcogen element, a gallium precursor, a sulfur precursor, and a silver compound in a medium including an organic solvent; and heating the medium at a reaction temperature to obtain a crude solution containing the semiconductor nanoparticles. The method for producing semiconductor nanoparticles, wherein the semiconductor nanoparticles contain silver, indium, gallium, and sulfur and have a size of 2 nm or more and 50 nm or less.

2. 2. The method for producing semiconductor nanoparticles according to claim 1, wherein the crude solution has an optical density of 1 or more and 10 or less at a wavelength of 500 nm, as defined by the following Equation 1: (Equation 1) Optical density = log １０ (I Ｏ / I Ｔ ) ... Equation 1 (Here, I Ｏ is the intensity of incident light supplied to the crude solution I Ｔ is the intensity of transmitted light passing through the crude solution.

3. 3. The method for producing semiconductor nanoparticles according to claim 2, wherein the optical density of the crude solution is 8 or more and 100 or less at a wavelength of 350 nm.

4. The crude solution was analyzed by UV-Vis absorption spectroscopy, with the ratio of absorbance at 500 nm to absorbance at 350 nm (A ５００ :A ３５０ 2. The method for producing semiconductor nanoparticles according to claim 1, wherein the ratio of the surface area of ​​the semiconductor nanoparticles to the surface area of ​​the semiconductor nanoparticles is 0.01 or more and 0.8 or less.

5. The method of claim 1, wherein the silver compound is added to the medium in an amount of 0.1 mol % or more and 50 mol % or less with respect to the gallium precursor.

6. 2. The method for producing semiconductor nanoparticles according to claim 1, wherein the silver compound comprises a silver carboxylate, a silver acetylacetonate, a silver halide, or a combination thereof.

7. 2. The method for producing semiconductor nanoparticles according to claim 1, wherein the production yield of the method is 6% or more, as determined by the following formula 2. (Equation 2) Production yield = A / B x 100...Equation 2 (wherein A is the total weight of silver, Group 13 elements, and sulfur in the semiconductor nanoparticles recovered from the crude solution, B is the total weight of silver, group 13 element, and sulfur added to the reaction medium for the reaction.

8. 2. The method for producing semiconductor nanoparticles according to claim 1, wherein the semiconductor nanoparticles have a quantum yield of 65% or more.

9. 2. The method for producing semiconductor nanoparticles according to claim 1, wherein the semiconductor nanoparticles have an average size of 5 nm or more and 10 nm or less, and a standard deviation of the average size of 20% or less.

10. 2. The method of claim 1, wherein the semiconductor nanoparticles have a charge balance value obtained by the following Equation 3 of 0.8 or more and 1.3 or less. (Equation 3) Charge balance value = {[Ag] + 3 × ([In] + [Ga])} / (2 × [S]) ... Formula 3 (where [Ag], [In], [Ga], and [S] are the molar contents of silver, indium, gallium, and sulfur, respectively, in the semiconductor nanoparticles.)

11. The method includes the steps of providing an additional reaction medium in an organic solvent, the additional reaction medium including a zinc precursor and optionally an organic ligand; 2. The method of claim 1, further comprising the step of adding and reacting the formed nanoparticles and a chalcogen precursor while heating the additional reaction medium at a reaction temperature to provide a third semiconductor nanocrystal containing zinc chalcogenide or an outer layer containing the same on a surface of the semiconductor nanoparticle.

12. 1. A semiconductor nanoparticle comprising: the semiconductor nanoparticles comprise silver (Ag), indium, gallium, and sulfur; The average size is 5 nm or more and 10 nm or less, and the standard deviation is 20% or less and 5% or more of the average size, The semiconductor nanoparticles are characterized in that a charge balance value obtained by the following Equation 3 is 0.95 or more and 1.2 or less. (Equation 3) Charge balance value = {[Ag] + 3 × ([In] + [Ga])} / (2 × [S]) ... Formula 3 (where [Ag], [In], [Ga], and [S] are the molar contents of silver, indium, gallium, and sulfur, respectively, in the semiconductor nanoparticles.)

13. the semiconductor nanoparticles are configured to emit green light; The semiconductor nanoparticles according to claim 12, wherein the green light has an emission peak wavelength in the range of 520 nm or more and 540 nm or less.

14. The semiconductor nanoparticle of claim 12, wherein the charge balance value is greater than or equal to 1 and less than or equal to 1.

15.

15. The semiconductor nanoparticles have a quantum yield of 70% or more and 99% or less; 13. The semiconductor nanoparticle according to claim 12, characterized in that the half width is 15 nm or more and 70 nm or less.

16. the semiconductor nanoparticles having a molar ratio of gallium to indium of greater than or equal to 1 and less than or equal to 10; 13. The semiconductor nanoparticles according to claim 12, characterized in that the molar ratio of gallium to silver (Ga / Ag) is ≧1.1 and ≦3.

17. The semiconductor nanoparticles, a molar ratio of gallium to the sum of gallium, indium, and silver (Ga / (Ga+In+Ag)) is 0.45 or more and 0.65 or less; 13. The semiconductor nanoparticles according to claim 12, wherein the molar ratio of the sum of indium and gallium to silver ((In+Ga) / Ag) is 1.2 or more and 3.5 or less.

18. The semiconductor nanoparticles, a molar ratio of silver to the sum of silver, indium, and gallium (Ag / (Ag+In+Ga)) is 0.2 or more and 0.45 or less; 13. The semiconductor nanoparticle according to claim 12, wherein the molar ratio of sulfur to the sum of silver, indium, and gallium (S / (Ag+In+Ga)) is 0.8 or more and 1.5 or less.

19. The semiconductor nanoparticles according to claim 12, wherein the molar ratio of gallium to sulfur (Ga / S) in the semiconductor nanoparticles is 0.4 or more and 0.6 or less.

20. An electronic device comprising the semiconductor nanoparticles according to claim 12.

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