Semiconductor nanoparticles, method for manufacturing the same, and electronic device including the same

Abstract

The present invention relates to a method for manufacturing a semiconductor nanoparticle, a semiconductor nanoparticle manufactured thereby, and an electronic device including the semiconductor nanoparticle. A method of manufacturing semiconductor nanoparticles includes: combining a first semiconductor nanocrystal comprising silver, a Group 13 element, and a chalcogen element with a gallium precursor, a sulfur precursor, and a silver compound in a medium comprising an organic solvent; and heating the medium to a reaction temperature to obtain a crude solution comprising semiconductor nanoparticles. The semiconductor nanoparticles include silver, indium, gallium, and sulfur, and the size of the semiconductor nanoparticles is greater than or equal to about 2 nm and less than or equal to about 50 nm.

Description

[0001] This application claims priority to and the benefits of Korean Patent Application No. 10-2023-0103800 filed in the Korean Intellectual Property Office on August 8, 2023, and all rights arising therefrom, the entire contents of which are incorporated herein by reference. Technical Field

[0002] Disclosed are a semiconductor nanoparticle, a method for manufacturing the semiconductor nanoparticle, and an electronic device including the semiconductor nanoparticle. Background Art

[0003] Semiconductor nanoparticles can show different characteristics or properties from the corresponding bulk materials with substantially the same components. For example, semiconductor nanoparticles can have different physical properties (e.g., band gap energy, luminescent properties, etc.) based on nanostructures. Semiconductor nanoparticles can be constructed to emit light when excited by incident light or applied voltage. It can be found that luminescent nanostructures are applicable to various devices (e.g., display panels or electronic devices including display panels). From an environmental perspective, it is expected and interesting to develop luminescent nanoparticles that do not contain harmful heavy metals (such as cadmium) but provide improved luminescent properties. Summary of the invention

[0004] One aspect relates to a method of producing semiconductor nanoparticles exhibiting improved properties with increased yield.

[0005] One aspect relates to semiconductor nanoparticles and populations of semiconductor nanoparticles produced according to the methods of the embodiments.

[0006] One aspect relates to a method of making semiconductor nanoparticles.

[0007] One aspect relates to a composition (eg, an ink composition) comprising semiconductor nanoparticles. One aspect relates to a color conversion panel comprising semiconductor nanoparticles.

[0008] One aspect provides a method for making semiconductor nanoparticles, the method comprising: combining a first semiconductor nanocrystal comprising silver, a Group 13 element and a chalcogen with a gallium precursor, a sulfur precursor and a silver compound in a medium comprising an organic solvent; and heating the medium to a reaction temperature to obtain a crude solution comprising semiconductor nanoparticles. The semiconductor nanoparticles comprise silver, indium, gallium and sulfur, and the size of the semiconductor nanoparticles is greater than or equal to about 2 nanometers (nm) and less than or equal to about 50 nm (e.g., 10 nm or less).

[0009] The method may further include adding a non-solvent to the crude solution to promote precipitation of the semiconductor nanoparticles, followed by separating and recovering the semiconductor nanoparticles from the mixture.

[0010] The crude solution may have an optical density greater than or equal to about 1 and less than or equal to about 10 at a wavelength of 500 nm, the optical density being defined by Equation 1:

[0011] Equation 1

[0012] Optical density = log 10 (I O / I T )

[0013] I O = the intensity of incident light supplied to the crude solution

[0014] I T = the intensity of light transmitted through the crude solution.

[0015] The optical density of the crude solution at a wavelength of 500 nm may be greater than or equal to 1.5 and less than or equal to 5.

[0016] The optical density of the crude solution at a wavelength of 350 nm may be greater than or equal to about 8 (e.g., greater than or equal to about 10). The optical density of the crude solution at a wavelength of 350 nm may be less than or equal to about 100. For example, the optical density of the crude solution at a wavelength of 350 nm may be greater than or equal to about 12 and less than or equal to about 50.

[0017] In the UV-Vis absorption spectrum of the crude solution, the ratio of the absorbance of the crude solution at 500 nm to the absorbance at 350 nm (A 500 :A 350 ) can be greater than or equal to about 0.01:1 and less than or equal to about 0.8:1.

[0018] The silver compound may be added to the medium in an amount greater than or equal to about 0.1 mol % (eg, greater than or equal to about 0.5 mol %) relative to the gallium precursor.

[0019] The silver compound may be added to the medium in an amount of less than or equal to about 50 mol % (eg, less than or equal to about 25 mol %) relative to the gallium precursor.

[0020] The amount of the silver compound may be greater than or equal to about 1 mol % and less than or equal to about 12 mol %.

[0021] The silver compound may include silver carboxylate, silver acetylacetonate, silver halide, or a combination thereof.

[0022] In an embodiment, the combination may be performed at a predetermined temperature (e.g., a first temperature). The first temperature may be greater than or equal to about 120°C (e.g., greater than or equal to about 180°C, greater than or equal to about 190°C, or greater than or equal to about 200°C) and less than the reaction temperature (e.g., less than or equal to about 280°C (e.g., less than or equal to about 250°C)).

[0023] The reaction temperature may be greater than or equal to about 210°C and less than or equal to about 380°C.

[0024] The Group 13 element may include indium, gallium, or indium and gallium.

[0025] The chalcogen element may include sulfur, selenium, or sulfur and selenium. The first semiconductor nanocrystal may include silver, indium, gallium, and sulfur (a Group 11-13-16 compound containing silver, indium, gallium, and sulfur).

[0026] In the method according to the embodiment, the yield determined by the following equation may be greater than or equal to about 6%:

[0027] Output = A / B × 100%

[0028] A: Total weight of silver, group 13 elements and sulfur in semiconductor nanoparticles recovered from the crude solution

[0029] B: The total weight of silver, Group 13 element, and sulfur added for the reaction (ie, the initial weight of silver, Group 13 element, and sulfur in the respective elemental precursors added to the reaction medium).

[0030] The yield may be greater than or equal to about 10%.The yield may be less than or equal to about 100%, less than or equal to about 90%, or less than or equal to about 60%.

[0031] The semiconductor nanoparticles may be configured to emit a first light (eg, green light).

[0032] The peak emission wavelength of the first light may be greater than or equal to about 500 nm and less than or equal to about 600 nm.

[0033] The peak emission wavelength of the green light may be in a range of greater than or equal to about 500 nm or greater than or equal to about 505 nm and less than or equal to about 580 nm or less than or equal to about 550 nm.

[0034] The (absolute) quantum yield of the semiconductor nanoparticles may be greater than or equal to about 65% or greater than or equal to about 70%. The quantum yield may be less than or equal to about 98% or less than or equal to about 90%.

[0035] The full width at half maximum (FWHM) of the semiconductor nanoparticles can be less than or equal to about 70 nm, less than or equal to about 40 nm, or less than or equal to about 35 nm. The FWHM can be greater than or equal to about 5 nm, greater than or equal to about 10 nm, greater than or equal to about 15 nm, or greater than or equal to about 25 nm. For example, the FWHM of the semiconductor nanoparticles can be from about 15 nm to about 40 nm.

[0036] The size or average size (hereinafter, "size") of the semiconductor nanoparticles may be greater than or equal to about 5 nm and less than or equal to about 10 nm, and the standard deviation of the average size may be less than or equal to about 20%. The standard deviation may be less than or equal to about 15% or less than or equal to about 13%. For example, the size may be greater than or equal to about 5 nm and less than or equal to about 8 nm.

[0037] In an embodiment, the charge balance value of the semiconductor nanoparticles may be greater than or equal to about 0.8 or greater than or equal to about 0.9. The charge balance value of the semiconductor nanoparticles may be less than or equal to about 1.4 or less than or equal to about 1.2, and the charge balance value is determined by the following equation:

[0038] Charge balance value = {[Ag] + 3([In] + [Ga])} / (2[S])

[0039] Wherein, in the equation, [Ag], [In], [Ga] and [S] are the molar amount of silver, the molar amount of indium, the molar amount of gallium and the molar amount of sulfur in the semiconductor nanoparticles, respectively.

[0040] The semiconductor nanoparticles may include a first semiconductor nanocrystal and a second semiconductor nanocrystal, the second semiconductor nanocrystal including silver, gallium, and sulfur. The second semiconductor nanocrystal may be disposed on the first semiconductor nanocrystal.

[0041] The method may also include: preparing an additional medium in an organic solvent, the additional medium comprising a zinc precursor and an optional organic ligand; adding the formed semiconductor nanoparticles and the chalcogen precursor to the additional medium; and heating the additional medium to a reaction temperature to form a third semiconductor nanocrystal comprising zinc chalcogenide or an outer layer comprising zinc chalcogenide on the surface of the semiconductor nanoparticle. The third semiconductor nanocrystal may have a composition different from that of the first semiconductor nanocrystal and the second semiconductor nanocrystal.

[0042] In the semiconductor nanoparticle, the third semiconductor nanocrystal may be disposed on the second semiconductor nanocrystal. If present, the third semiconductor nanocrystal may be the outermost layer of the semiconductor nanoparticle.

[0043] The first semiconductor nanocrystal may not include zinc. The semiconductor nanoparticles may or may not also include lithium. The semiconductor nanoparticles may or may not also include an alkali metal (eg, lithium, sodium, potassium, etc.).

[0044] In the semiconductor nanoparticles, the molar ratio of gallium to indium (Ga:In) can be greater than or equal to about 1:1, greater than or equal to about 3.3:1, or greater than or equal to about 3.5:1 and less than or equal to about 10:1, less than or equal to about 8:1, less than or equal to about 6.5:1, less than or equal to about 5.5:1, or less than or equal to about 4.1:1.

[0045] In the semiconductor nanoparticles, the molar ratio of gallium to the sum of indium and gallium (Ga:(In+Ga)) may be greater than or equal to about 0.7:1, or greater than or equal to about 0.75:1 and less than or equal to about 0.99:1, less than or equal to about 0.85:1, or less than or equal to about 0.82:1.

[0046] In the semiconductor nanoparticles, the molar ratio of gallium to silver (Ga:Ag) may be greater than or equal to about 1.1:1 or greater than or equal to about 1.35:1. In the semiconductor nanoparticles, the molar ratio of gallium to silver (Ga:Ag) may be less than or equal to about 3:1, less than or equal to about 2:1, or less than or equal to about 1.58:1.

[0047] In the semiconductor nanoparticles, the molar ratio of gallium to the sum of gallium, indium and silver (Ga:(Ga+In+Ag)) can be greater than or equal to about 0.45:1, greater than or equal to about 0.50:1, or greater than or equal to about 0.51:1 and less than or equal to about 0.6:1, or less than or equal to about 0.52:1.

[0048] In the semiconductor nanoparticles, the molar ratio of the sum of indium and gallium to silver ((In+Ga):Ag) may be greater than or equal to about 1.2:1, greater than or equal to about 1.4:1, or greater than or equal to about 1.7:1. In the semiconductor nanoparticles, the molar ratio of the sum of indium and gallium to silver ((In+Ga):Ag) may be less than or equal to about 3.7:1, less than or equal to about 3.5:1, or less than or equal to about 2:1.

[0049] In the semiconductor nanoparticles, the molar ratio of silver to sulfur (Ag:S) may be greater than or equal to about 0.05:1, greater than or equal to about 0.2:1, or greater than or equal to about 0.32:1. The molar ratio of silver to sulfur (Ag:S) may be less than or equal to about 0.5:1, less than or equal to about 0.41:1, or less than or equal to about 0.35:1.

[0050] In the semiconductor nanoparticles, the molar ratio of silver to indium (Ag:In) may be greater than or equal to about 1.5:1, greater than or equal to about 2:1, or greater than or equal to about 2.5:1. In the semiconductor nanoparticles, the molar ratio of silver to indium (Ag:In) may be less than or equal to about 6:1, less than or equal to about 4.5:1, or less than or equal to about 3:1.

[0051] In the semiconductor nanoparticles, the molar ratio of silver to the sum of silver, indium and gallium (Ag: (Ag + In + Ga)) may be greater than or equal to about 0.2: 1, greater than or equal to about 0.3: 1, or greater than or equal to about 0.35: 1. In the semiconductor nanoparticles, the molar ratio of silver to the sum of silver, indium and gallium (Ag: (Ag + In + Ga)) may be less than or equal to about 0.45: 1, or less than or equal to about 0.41: 1.

[0052] In the semiconductor nanoparticles, the molar ratio of sulfur to the sum of silver, indium and gallium (S: (Ag + In + Ga)) may be greater than or equal to about 0.8: 1, greater than or equal to about 0.9: 1, or greater than or equal to about 1: 1. In the semiconductor nanoparticles, the molar ratio of sulfur to the sum of silver, indium and gallium (S: (Ag + In + Ga)) may be less than or equal to about 1.5: 1, less than or equal to about 1.3: 1, less than or equal to about 1.13: 1, or less than or equal to about 1.08: 1.

[0053] In the semiconductor nanoparticles, the molar ratio of sulfur to gallium (Ga:S) may be greater than or equal to about 0.4:1, or greater than or equal to about 0.44:1. In the semiconductor nanoparticles, the molar ratio of sulfur to gallium (Ga:S) may be less than or equal to about 0.6:1, or less than or equal to about 0.51:1.

[0054] Green light may include band edge emission.

[0055] Embodiments provide semiconductor nanoparticles or populations of semiconductor nanoparticles as described herein.

[0056] In an embodiment, the semiconductor nanoparticles may include first semiconductor nanocrystals comprising silver, indium, gallium and sulfur, and the average size of the semiconductor nanoparticles may be greater than or equal to about 5 nm and less than or equal to about 8 nm, or less than or equal to about 7.5 nm and the standard deviation of the average size of the semiconductor nanoparticles may be less than or equal to about 20%, or less than or equal to about 15% and greater than or equal to about 5%.

[0057] The semiconductor nanoparticles may be configured to emit a first light (eg, green light or red light), and a charge balance value of the semiconductor nanoparticles may be greater than or equal to about 0.95 and less than or equal to about 1.2:

[0058] Charge balance value = {[Ag] + 3([In] + [Ga])} / (2[S])

[0059] Wherein, in the above equation, [Ag], [In], [Ga] and [S] are the molar amount of silver, the molar amount of indium, the molar amount of gallium and the molar amount of sulfur in the semiconductor nanoparticles, respectively.

[0060] The semiconductor nanoparticles may be configured to emit green light. The semiconductor nanoparticles may be configured to emit red light.

[0061] The peak emission wavelength of green light may be greater than or equal to about 520 nm and less than or equal to about 540 nm. The peak emission wavelength of red light may be greater than or equal to about 600 nm and less than or equal to about 650 nm.

[0062] In an embodiment, the ink composition includes semiconductor nanoparticles and a liquid carrier. The semiconductor nanoparticles or a group of semiconductor nanoparticles can be dispersed in the liquid carrier. The liquid carrier can include a liquid monomer, a (volatile) organic solvent, or a combination thereof. The ink composition can substantially exclude volatile organic solvents. The ink composition can also include fine particles of metal oxides.

[0063] In an embodiment, the composite includes a matrix and semiconductor nanoparticles dispersed in the matrix. The composite may further include metal oxide fine particles. The composite may be configured to emit green light. The composite may be a patterned film. The composite may further include semiconductor nanoparticles configured to emit a second light different from green light.

[0064] Embodiments provide a color conversion layer (eg, a color conversion structure or a color conversion panel) including a color conversion region including the semiconductor nanoparticles described above.

[0065] The color conversion panel or color conversion structure optionally includes a color conversion layer and partition walls, the color conversion layer includes color conversion regions, the partition walls define each region of the color conversion layer, the color conversion regions include a first region corresponding to a first pixel, and the first region includes semiconductor nanoparticles or composites.

[0066] In an embodiment, a display panel or an electronic device includes a light source and a color conversion layer (eg, a color conversion structure) disposed on the light source.

[0067] In an embodiment, the display panel comprises: a light emitting panel (or light source); a color conversion panel; and an optional light transmissive layer located between the light emitting panel and the color conversion panel.

[0068] The light emitting panel (or light source) may be configured to provide incident light to the color conversion panel. The incident light may include blue light and optionally green light. The peak emission wavelength of the blue light may be about 440 nm to about 460 nm or about 450 nm to about 455 nm.

[0069] The light source may include an organic light emitting diode (OLED), a micro-LED, a mini-LED, an LED including nanorods, or a combination thereof.

[0070] In an embodiment, an electronic device (or a display device) includes a color conversion panel or a display panel.

[0071] According to an embodiment, semiconductor nanoparticles based on 11-13-16 group compounds can be manufactured, which have improved optical properties (e.g., improved blue light absorptivity and / or narrow half-maximum full width and / or increased luminous efficiency) and increased yield. On the one hand, a color conversion panel or light conversion sheet containing semiconductor nanoparticles can utilize various light sources and can be effectively used in liquid crystal display devices, QD OLED display devices and / or QD micro LED display devices, wherein the QD color conversion layer or pixel is correspondingly applied to blue LED, blue OLED and / or blue micro LED. Semiconductor nanoparticles and color conversion panels can be applied to various devices such as TV, monitors, mobile devices, VR / AR, car displays, etc., but embodiments are not limited thereto. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] The above and other aspects, features and advantages of certain exemplary embodiments will become more apparent from the following detailed description taken in conjunction with the accompanying drawings.

[0073] Figure 1A is a flow chart illustrating a pattern forming process (photolithography) using the ink composition of one or more embodiments.

[0074] Figure 1B is a flow chart showing a pattern forming process (inkjet method) using the ink composition of one or more embodiments.

[0075] Figure 2A is a schematic cross-sectional view of a color conversion panel according to one or more embodiments.

[0076] Figure 2B is a cross-sectional view of an electronic device (display device) including a color conversion panel according to one or more embodiments.

[0077] Figure 3A is a perspective view illustrating an example of a display panel including a color conversion panel according to one or more embodiments.

[0078] Figure 3Bis an exploded view of a display device according to one or more embodiments.

[0079] Figure 3C yes Figure 3A A cross-sectional view of a display panel.

[0080] Figure 4 is an exploded view of a display device according to one or more embodiments.

[0081] Figure 5A It is shown Figure 3A A plan view of an example of a pixel arrangement of a display panel.

[0082] Figure 5B , Figure 5C , Figure 5D and Figure 5E They are cross-sectional views showing examples of light emitting devices according to one or more embodiments, respectively.

[0083] Figure 6 It was taken along line IV-IV Figure 5A A cross-sectional view of a display panel.

[0084] Fig. 7A is a schematic cross-sectional view of a display device (eg, a liquid crystal display device) according to one or more embodiments.

[0085] Figure 7B is a schematic cross-sectional view of an electronic device (eg, an electroluminescent device) according to one or more embodiments.

[0086] Figure 8 The UV-Vis absorption spectra of a 100-fold dilution of the crude solution of Example 1 and a 100-fold dilution of the crude solution of Comparative Example 1 are shown.

[0087] Fig. 9 The UV-Vis absorption spectra of 100-fold dilutions of the crude solutions of Examples 2, 3, and 4 are shown. DETAILED DESCRIPTION

[0088] The advantages and features of the technology described below and the methods for implementing them will become apparent with reference to the exemplary embodiments described in further detail below in conjunction with the accompanying drawings. However, the embodiments should not be construed as being limited to the exemplary embodiments set forth herein. If not otherwise defined, all terms (including technical terms and scientific terms) as used herein may be defined as commonly understood by those of ordinary skill in the art. Unless clearly defined, the terms defined in the commonly used dictionaries may not be interpreted ideally or exaggeratedly.

[0089] “At least one of” is not to be interpreted as limited to “one” or “an”. “Or” means “and / or”. As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items.

[0090] It will also be understood that when the terms "include" and / or "comprises" or their variations are used in this specification to indicate the presence of stated features, regions, integers, steps, operations, elements and / or components, it does not exclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components and / or groups thereof.

[0091] In addition, unless explicitly described to the contrary, the word “comprise” and variations such as “comprises” or “comprising”, will be understood to imply the inclusion of stated elements but not the exclusion of any other elements.

[0092] In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. Like reference numerals refer to like elements throughout the specification.

[0093] It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements.

[0094] As used herein, the singular forms "a", "an", and "the" are intended to include plural forms including "at least one", unless the context clearly indicates otherwise. For example, the term "semiconductor nanoparticle" may refer to a single semiconductor nanoparticle or may refer to a plurality of semiconductor nanoparticles. "At least one" is not to be construed as limited to "one" or "one". "Or" means "and / or". As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0095] It will be understood that, although the terms "first", "second", "third", etc. may be used herein to describe various elements, components, regions, layers and / or parts, these elements, components, regions, layers and / or parts should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or part from another element, component, region, layer or part. Therefore, without departing from the teachings of the given embodiments, the first element, first component, first region, first layer or first part discussed below may be referred to as the second element, second component, second region, second layer or second part.

[0096] Exemplary embodiments are described herein with reference to schematically illustrated cross-sectional views as idealized embodiments. As such, variations in the shapes of the illustrations due to, for example, manufacturing techniques and / or tolerances are contemplated. Therefore, the embodiments described herein should not be construed as being limited to specific regional shapes as shown herein, but rather include shape deviations, for example, caused by manufacturing. For example, a region shown or described as being flat may typically have rough and / or nonlinear features. In addition, the sharp corners shown may be rounded. Therefore, the regions shown in the figures are schematic in nature, and their shapes are not intended to illustrate the precise shape of the regions, and are not intended to limit the scope of the claims given.

[0097] As used herein, "about" or "almost" is inclusive of the stated value and means within an acceptable range of deviation of the particular value determined by one of ordinary skill in the art taking into account the measurement in question and the errors associated with the measurement of the particular quantity (i.e., the limitations of the measurement system). For example, "about" can mean within one or more standard deviations, or within ±10%, ±5% of the stated value.

[0098] Unless mentioned to the contrary, the numerical ranges described here are inclusive. Unless mentioned to the contrary, the numerical ranges described here include any real number within the endpoints of the stated range and include its endpoints. In this specification, numerical endpoints or upper or lower values ​​(for example, described as "greater than or equal to value", "at least value" or "less than or equal to value", or described as "from" or "to") can be used to form a numerical range for a given feature. In other words, the upper and lower endpoints set forth for various numerical values ​​can be independently combined to provide a range.

[0099] As used herein, the expression "does not include cadmium (or other harmful heavy metals)" may refer to a situation where the concentration of cadmium (or other harmful heavy metals) may be less than or equal to about 100 parts per million by weight (ppmw), less than or equal to about 50 ppmw, less than or equal to about 10 ppmw, less than or equal to about 1 ppmw, less than or equal to about 0.1 ppmw, less than or equal to about 0.01 ppmw, or about zero. In one or more embodiments, a certain amount of cadmium (or other harmful heavy metals) may be substantially absent, or if present, the amount of cadmium (or other harmful heavy metals) may be less than or equal to the detection limit of a given analytical tool or as an impurity level.

[0100] Hereinafter, as used herein, when no definition is otherwise provided, "substituted" means that at least one hydrogen of the compound is substituted with a substituent selected from the group consisting of C1 to C30 alkyl, C2 to C30 alkenyl, C2 to C30 alkynyl, C6 to C30 aryl, C7 to C30 alkylaryl, C7 to C30 arylalkyl, C6 to C30 aryloxy, C6 to C30 arylthio, C1 to C30 alkoxy, C1 to C30 alkylthio, C1 to C30 heterocycloalkyl, C3 to C30 heteroalkylaryl, C2 to C30 alkylheteroaryl, C2 to C30 heteroarylalkyl, C1 to C30 heteroaryloxy, C1 to C30 heteroarylthio, C3 to C30 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C30 cycloalkynyl, C2 to C30 heterocycloalkyl, halogen (—F, —Cl, —Br or —I), hydroxyl (—OH), nitro (—NO 2 ), cyano (-CN), amino or amine (-NRR', wherein R and R' are independently hydrogen or C1 to C6 alkyl), azido (-N 3 ), amidino (-C(=NH)NH 2 ), hydrazino (-NHNH 2 ), hydrazone (=N(NH 2 )), aldehyde group (-C(=O)H), carbamoyl group (-C(O)NH 2 ), thiol group (-SH), ester group (-C(=O)OR, wherein R is C1 to C6 alkyl or C6 to C12 aryl), carboxyl group (-COOH) or its salt (-C(=O)OM, wherein M is an organic cation or an inorganic cation), sulfonic acid group (-SO 3 H) or its salt (-SO 3 M, wherein M is an organic cation or an inorganic cation), a phosphate group (-PO 3 H 2 ) or its salt (-PO 3 MH or -PO 3 M 2 , wherein M is an organic cation or an inorganic cation), or a combination thereof.

[0101] In addition, when no definition is otherwise provided below, “hetero” means a case where 1 to 3 hetero atoms selected from N, O, P, Si, S, Se, Ge, and B are included.

[0102] In addition, as used herein, the term "aliphatic hydrocarbon group" refers to a C1 to C30 straight chain or branched alkyl group, a C2 to C30 straight chain or branched alkenyl group, or a C2 to C30 straight chain or branched alkynyl group, and as used herein, the term "aromatic organic group" refers to a C6 to C30 aryl group or a C2 to C30 heteroaryl group.

[0103] As used herein, the term "(meth)acrylate" refers to acrylate and / or methacrylate.

[0104] As used herein, the term "Group" refers to a Group of the Periodic Table.

[0105] As used herein, the terms "nanoparticle" and "nanostructure" refer to structures having at least one region or characteristic size with nanometer-scale dimensions. In one or more embodiments, the size of a nanoparticle or nanostructure can be less than about 500nm, less than about 300nm, less than about 250nm, less than about 150nm, less than about 100nm, less than about 50nm or less than about 30nm. A nanoparticle or nanostructure can have any shape, such as nanowires, nanorods, nanotubes, multi-armed shapes with two or more arms (pod), nanodots, etc., but embodiments are not limited thereto. A nanoparticle or nanostructure can be, for example, roughly crystalline, roughly monocrystalline, polycrystalline, amorphous or a combination thereof.

[0106] Quantum dots can be, for example, semiconductor-containing nanoparticles that can exhibit quantum confinement effects or exciton confinement effects, and are a type of luminescent nanostructure (e.g., capable of emitting light through energy excitation). Here, unless otherwise specifically defined, the shape of "quantum dots" or nanoparticles is not limited.

[0107] As used herein, the term "dispersion" refers to a dispersion in which the dispersed phase is a solid and the continuous medium includes a liquid or solid different from the dispersed phase. It will be understood that a "dispersion" can be a colloidal dispersion in which the size of the dispersed phase is greater than or equal to about 1 nm (e.g., greater than or equal to about 2 nm, greater than or equal to about 3 nm, or greater than or equal to about 4 nm) and a few micrometers (μm) (e.g., less than or equal to about 2 μm, less than or equal to about 1 μm, less than or equal to about 900 nm, less than or equal to about 800 nm, less than or equal to about 700 nm, less than or equal to about 600 nm, or less than or equal to about 500 nm).

[0108] Here, the dimension (size, diameter or thickness, etc.) can be the value of a single entity or the average value of multiple nanoparticles. As used herein, the term "average value" (e.g., the average size of quantum dots) can be a mean value or a median value. In one or more embodiments, the average value can be an "average" value.

[0109] As used herein, the term "peak emission wavelength" is the wavelength at which a given emission spectrum of light reaches its maximum.

[0110] In one or more embodiments, the quantum efficiency can be easily and reproducibly determined using commercially available equipment (e.g., purchased from Hitachi or Hamamatsu, etc.) and with reference to a manual provided by, for example, a corresponding equipment manufacturer. Quantum efficiency (which can be used interchangeably with the term "quantum yield" (QY)) can be measured in a solution state or a solid state (i.e., in a complex). In one or more embodiments, the quantum efficiency (or quantum yield) is the ratio of photons emitted by a nanostructure or its group to photons absorbed. In one or more embodiments, the quantum efficiency can be measured by any method. For example, there can be two methods for measuring fluorescence quantum yield or efficiency: an absolute method and a relative method. The quantum efficiency measured by the absolute method can be referred to as the absolute quantum efficiency.

[0111] In the absolute method, the quantum efficiency can be obtained by detecting the fluorescence of all samples via an integrating sphere. In the relative method, the quantum efficiency of the unknown sample can be calculated by comparing the fluorescence intensity of the standard dye (standard sample) with the fluorescence intensity of the unknown sample. Coumarin 153, coumarin 545, rhodamine 101 inner salt, anthracene and rhodamine 6G can be used as standard dyes according to their PL wavelengths, but the embodiment is not limited thereto.

[0112] The full width at half maximum (FWHM) and the maximum emission (eg, PL: photoluminescence; or EL: electroluminescence) wavelength can be measured, for example, from a luminescence spectrum (eg, photoluminescence spectrum or electroluminescence spectrum) obtained by a spectrophotometer such as a fluorescence spectrophotometer.

[0113] As used herein, the term "first absorption peak wavelength" refers to a wavelength at which a main peak first appears in the lowest energy region in an ultraviolet-visible (UV-Vis) absorption spectrum.

[0114] Semiconductor nanoparticles can be included in various electronic devices. The electrical properties and / or optical properties of semiconductor nanoparticles can be controlled, for example, by the element composition of semiconductor nanoparticles, the size of semiconductor nanoparticles and / or the shape of semiconductor nanoparticles. In one or more embodiments, semiconductor nanoparticles can be semiconductor nanocrystal particles. Semiconductor nanoparticles such as quantum dots can have a relatively large surface area per unit volume, and therefore can show a quantum confinement effect, thereby showing physical optical properties different from the corresponding bulk material with the same composition. Therefore, semiconductor nanoparticles such as quantum dots can absorb the energy (for example, incident light) supplied from an excitation source to form an excited state, and can emit energy corresponding to its band gap energy when relaxing.

[0115] Semiconductor nanoparticles can also be used in color conversion panels (e.g., photoluminescent color filters). Instead of a white-light-emitting backlight unit used in a liquid crystal display device, in a display device including a quantum dot-based color conversion panel or a light-emitting color filter, a quantum dot layer is used as a light-emitting material and is disposed in a relatively front portion of the display device to convert incident light (e.g., blue light) provided from a light source into light of a different spectrum (e.g., green light or red light). In such a color conversion panel, color conversion of the excitation light can occur in a relatively front portion of the display device, and light can be scattered in all directions, which can solve the viewing angle problem of the liquid crystal display device, and can also solve the light loss problem caused by the use of an absorption-type color filter.

[0116] As used herein, the term "color conversion panel" refers to an electronic device that includes a color conversion layer. As used herein, the term "color conversion layer" also includes structures that include color conversion regions (eg, color conversion structures).

[0117] In a display device including a color conversion panel, the properties of the light-emitting nanostructure (e.g., optical properties, stability, etc.) can have a direct impact on the display quality of the display device. It may be desirable that the light-emitting material included in the color conversion panel disposed in the relatively front portion of the display device exhibits not only a relatively high luminous efficiency, but also a relatively high absorption relative to the incident light. When a patterned film (e.g., a color filter) is used in the display device, the reduced absorption of the incident light may be directly caused by blue light leakage, which may have an adverse effect on the color reproducibility of the display device (e.g., DCI matching rate). The use of an absorption-type color filter to prevent the blue leakage problem may result in an additional reduction in luminous efficiency. This reduced absorption of semiconductor nanoparticles may result in a reduction in brightness in a display device including semiconductor nanoparticles.

[0118] Semiconductor nanoparticles can show properties (for example, optical properties and / or stability) that can be suitable for display devices, but many of them can include cadmium-based compounds (for example, cadmium sulfide). Cadmium causes serious environmental / health problems, and is therefore a banned element in many countries. Therefore, in order to develop cadmium-free, environmentally friendly nanoparticles, nanocrystals based on III-V compounds have been studied in depth. However, compared with the cadmium-free nanoparticles based on III-V compounds (such as indium phosphide), technically still need to develop environmentally friendly nanoparticles that can show higher absorption, narrower half-maximum full width and higher luminous efficiency.

[0119] In an embodiment, the semiconductor nanoparticles may not include cadmium.In one or more embodiments, the semiconductor nanoparticles may not include mercury, lead, or a combination thereof.

[0120] In an embodiment, the semiconductor nanoparticles may include silver, indium, gallium, and sulfur, and may have a size or an average size (referred to herein as "size") greater than or equal to about 2 nm, or greater than or equal to about 5 nm and less than or equal to about 50 nm, less than or equal to about 10 nm, or less than or equal to about 8 nm.

[0121] In an embodiment, the semiconductor nanoparticles may include a first semiconductor nanocrystal, the first semiconductor nanocrystal including silver, a 13-group element, and a chalcogen. The first semiconductor nanocrystal may or may not include zinc. The 13-group element may include indium, gallium, or a combination thereof. The chalcogen may include sulfur and optionally selenium. The first semiconductor nanocrystal may include a quaternary alloy semiconductor material based on a 11-13-16-group compound including silver (Ag), indium, gallium, and sulfur. The first semiconductor nanocrystal may include silver indium gallium sulfide (e.g., Ag (In x Ga 1-x )S 2 (x is greater than 0 and less than 1)). The molar ratio between the components in the first semiconductor nanocrystals can be adjusted so that the final semiconductor nanoparticles can have desired composition and optical properties (eg, maximum emission wavelength).

[0122] The semiconductor nanoparticles may also include second semiconductor nanocrystals, third semiconductor nanocrystals, or both second semiconductor nanocrystals and third semiconductor nanocrystals. The second semiconductor nanocrystals have a composition different from that of the first semiconductor nanocrystals and may include gallium, sulfur, and optionally silver.

[0123] The second semiconductor nanocrystal can include 13-16 family compounds, 11-13-16 family compounds or their combination. The 13-16 family compounds can include gallium sulfide, gallium selenide, indium sulfide, indium selenide, indium gallium sulfide, indium gallium selenide, indium gallium sulfide selenide or their combination. The second semiconductor nanocrystal can include gallium and chalcogen (for example, sulfur, selenium or their combination). The second semiconductor nanocrystal can include a ternary alloy semiconductor material comprising silver, gallium and sulfur. The molar ratio between the components in the second semiconductor nanocrystal can be adjusted so that the final semiconductor nanoparticles can show required composition and optical properties.

[0124] The third semiconductor nanocrystal may include zinc and sulfur. The third semiconductor nanocrystal may include zinc sulfide.

[0125] The second semiconductor nanocrystal may cover at least a portion of the first semiconductor nanocrystal. The band gap energy of the second semiconductor nanocrystal may be different from the band gap energy of the first semiconductor nanocrystal. The band gap energy of the second semiconductor nanocrystal may be greater than the band gap energy of the first semiconductor nanocrystal. The band gap energy of the second semiconductor nanocrystal may be less than the band gap energy of the first semiconductor nanocrystal. The band gap energy of the third semiconductor nanocrystal may be greater than the band gap energy of the second semiconductor nanocrystal. The band gap energy of the third semiconductor nanocrystal may be greater than the band gap energy of the first semiconductor nanocrystal. The layer including the third semiconductor nanocrystal may be the outermost layer of the semiconductor nanoparticle.

[0126] The semiconductor nanoparticle may have a core-shell structure having a core and a shell disposed on the core. The core may include a first semiconductor nanocrystal, and the shell may include a second semiconductor nanocrystal. The shell may be a multilayer shell, and the multilayer shell may include a first shell disposed on the core, a second shell disposed on the first shell, and a third shell disposed on the second shell. The first shell may include a second semiconductor nanocrystal. The second shell may include a third semiconductor nanocrystal. The second shell or the third shell may include a third semiconductor nanocrystal containing zinc and sulfur (a third semiconductor nanocrystal containing zinc chalcogenide).

[0127] In an embodiment, the semiconductor nanoparticles may have a core (multi-layer) shell structure, such as AgInGaS / AgGaS or AgInGaS / AgGaS / ZnS.

[0128] In semiconductor nanoparticles, the concentration of indium can vary or can be different in the radial direction. In semiconductor nanoparticles, the amount of indium in the inner part of the particle can be different from the amount of indium in the outer part of the particle. In an embodiment, the indium content in the portion (e.g., outermost layer or shell) close to the surface or adjacent to the surface can be less than the indium content in the inner part (or core) of the above-mentioned particles. In an example, the zinc content (concentration) in the portion (e.g., outermost layer) close to the surface of the particle or adjacent to the surface of the particle (e.g., outermost layer) can be greater than the zinc content (concentration) in the inner part (or core) of the above-mentioned particles. The core or the first semiconductor nanocrystal may not include zinc.

[0129] In the shell, gallium may exhibit a concentration gradient that varies (eg, increases or decreases) in the radial direction. In the shell, the gallium concentration in a portion near or adjacent to the particle surface may be higher than the gallium concentration in a portion near or adjacent to the core.

[0130] In an embodiment, semiconductor nanoparticles containing a Group 13 element and a chalcogen and silver (Ag) can achieve desired luminescent properties (e.g., increased quantum yield and reduced half-maximum full width) without cadmium. According to an embodiment, semiconductor nanoparticles containing Group 11-13-16 compounds can achieve improved optical properties by adjusting the composition (e.g., the charge balance value and / or molar ratio between the components as described herein).

[0131] Through their research, the inventors first found that although the semiconductor nanoparticles comprising 11-13-16 family compounds can be manufactured to have desired luminescent properties, according to alternative methods, the manufacturing yield of semiconductor nanoparticles remains on a relatively low level. Without wishing to be bound by any theory, if the semiconductor nanoparticles comprising 11-13-16 family compounds and showing desired luminescent properties are manufactured according to known methods, then for example, the process of forming a second semiconductor nanocrystal comprising gallium and sulfur on the first semiconductor nanocrystal may cause the composition and / or size of the first semiconductor nanocrystal to change substantially, which seems difficult to control, and this may cause a significant reduction in yield. The inventors surprisingly found that by using the method described herein, desired semiconductor nanoparticles can be manufactured with a relatively improved yield and / or more consistent nanoparticle size.

[0132] Therefore, the method for manufacturing semiconductor nanoparticles of an embodiment includes: obtaining a crude solution containing semiconductor nanoparticles. The method may include: adding a gallium precursor and a sulfur precursor to a medium (e.g., containing an organic solvent and an optional organic ligand). The method also includes adding a silver compound to the medium. In an embodiment, the method may include adding a first semiconductor nanocrystal containing silver, a Group 13 element, and a chalcogen element to the medium. In an embodiment, before adding the gallium precursor, the sulfur precursor, and / or the silver compound, the medium may already include semiconductor nanocrystal particles. The method may include heating the medium to a temperature (e.g., a predetermined temperature, a first temperature, or a second temperature (i.e., a reaction temperature)). The method may also include (e.g., after heating) adding a non-solvent to the final reaction solution to promote the precipitation of the semiconductor nanoparticles (e.g., semiconductor nanoparticles coordinated with organic ligands) thus formed.

[0133] In an embodiment, obtaining a crude solution may involve: reacting a gallium precursor and a sulfur precursor in the presence of a first semiconductor nanocrystal including silver, a Group 13 element, and a chalcogen and in the presence of a silver compound. The silver compound may participate in the reaction. The medium may be (or serve as) a reaction medium for the reaction. The details of the semiconductor nanoparticles and the first semiconductor nanocrystal are the same as described herein.

[0134] The method may include pre-treating the medium (and optionally the sulfur precursor).

[0135] In an embodiment, the method may include adding the first semiconductor nanocrystal and a gallium precursor, a sulfur precursor, or both to a (reaction) medium comprising an organic solvent.

[0136] Prior to adding the first semiconductor nanocrystal or gallium precursor, the reaction medium may be pretreated at a pretreatment temperature under vacuum. The pretreatment temperature may be lower than the reaction temperature. The pretreatment temperature may be, for example, greater than or equal to about 80° C., greater than or equal to about 100° C., or greater than or equal to about 120° C. and less than or equal to about 200° C., or less than or equal to about 180° C.

[0137] The addition mode (e.g., order of addition or form of addition) of the first semiconductor nanocrystal, gallium precursor or sulfur precursor is not particularly limited. In an embodiment, the first semiconductor nanocrystal and the gallium precursor may be added to a reaction medium containing a sulfur precursor. The first semiconductor nanocrystal may be dispersed in a suitable organic solvent and added to the reaction medium, but is not limited thereto. The gallium precursor may be dispersed in a suitable organic solvent and added to the reaction medium, but is not limited thereto.

[0138] There is no particular restriction on the manner in which the silver compound is added to the (reaction) medium (e.g., order of addition or form of addition). The silver compound can be added in a state dissolved in a suitable organic solvent (e.g., an amine solvent such as oleylamine or a phosphine solvent such as trioctylphosphine). There is no particular restriction on the timing of adding the silver compound and it can be appropriately selected. The silver compound can be added to the (reaction) medium before, at the same time, or after adding the first semiconductor nanocrystal, the gallium precursor, and / or the sulfur precursor. In an embodiment, the silver compound can be added to the (reaction) medium after pretreatment.

[0139] The details of the first semiconductor nanocrystal are the same as described herein. The first semiconductor nanocrystal may include silver (Ag), indium, gallium and sulfur. The method for manufacturing the first semiconductor nanocrystal is not particularly limited and can be appropriately selected. The detailed description of the first semiconductor nanocrystal is as described herein. The first semiconductor nanocrystal may include silver (Ag), indium, gallium and sulfur. The method for manufacturing the first semiconductor nanocrystal is not particularly limited and can be appropriately selected. In an embodiment, the first semiconductor nanocrystal can be obtained by reacting a desired precursor (such as a silver precursor, an indium precursor, a gallium precursor and a sulfur precursor) in a solution including an organic ligand and an organic solvent at a predetermined reaction temperature (e.g., about 180°C to about 300°C or about 200°C to about 280°C) according to the composition and separating it. For separation and recovery, reference can be made to the method to be described herein.

[0140] The predetermined temperature may be greater than or equal to about 120°C, greater than or equal to about 180°C, greater than or equal to about 190°C, greater than or equal to about 200°C, greater than or equal to about 205°C, greater than or equal to about 210°C, greater than or equal to about 240°C, greater than or equal to about 245°C, greater than or equal to about 250°C, greater than or equal to about 255°C, greater than or equal to about 260°C, greater than or equal to about 265°C, greater than or equal to about 270°C, greater than or equal to about 280°C, greater than or equal to about 285°C, greater than or equal to about 290°C, greater than or equal to about 300°C, greater than or equal to about 310°C, greater than or equal to about 320°C, greater than or equal to about 275°C, greater than or equal to about 280°C, greater than or equal to about 285°C, greater than or equal to about 290°C, greater than or equal to about 295°C, greater than or equal to about 300°C, greater than or equal to about 305°C, greater than or equal to about 310°C, greater than or equal to about 315°C, greater than or equal to about 320°C, greater than or equal to about 330°C, greater than or equal to about 335°C, greater than or equal to about 340°C or greater than about 345°C. The predetermined temperature may be less than or equal to about 380°C, less than or equal to about 375°C, less than or equal to about 370°C, less than or equal to about 365°C, less than or equal to about 360°C, less than or equal to about 355°C, less than or equal to about 350°C, less than or equal to about 340°C, less than or equal to about 320°C, less than or equal to about 310°C, less than or equal to about 300°C, less than or equal to about 295°C, less than or equal to about 290°C, less than or equal to about 280°C, less than or equal to about 270°C, less than or equal to about 260°C, or less than or equal to about 250°C.

[0141] The method of the embodiment may include: heating a medium (optionally including a sulfur precursor) to a first temperature, and adding a first semiconductor nanocrystal, a gallium precursor, a sulfur precursor, or a combination thereof to the medium heated to the first temperature. In the method of the embodiment, the addition of the silver compound may also be performed at the first temperature.

[0142] The method of an embodiment may include heating a medium (eg, a reaction mixture including a first semiconductor nanocrystal, a gallium precursor, a sulfur precursor, and a silver compound) to a second temperature (eg, a reaction temperature).

[0143] The first temperature may be greater than or equal to about 120°C (e.g., greater than or equal to about 180°C, greater than or equal to about 190°C, or greater than or equal to about 200°C) and less than or equal to about 280°C (e.g., less than or equal to about 250°C), and the second temperature may be greater than or equal to about 190°C, or greater than or equal to about 240°C and less than or equal to about 380°C, or less than or equal to about 280°C. The second temperature may be higher than the first temperature. The difference between the first temperature and the second temperature may be greater than or equal to about 10°C, greater than or equal to about 20°C, greater than or equal to about 30°C, greater than or equal to about 40°C, greater than or equal to about 50°C, greater than or equal to about 60°C, greater than or equal to about 70°C, greater than or equal to about 80°C, greater than or equal to about 90°C, or greater than or equal to about 100°C. The difference between the first temperature and the second temperature may be less than or equal to about 200°C, less than or equal to about 190°C, less than or equal to about 180°C, less than or equal to about 170°C, less than or equal to about 160°C, less than or equal to about 150°C, less than or equal to about 140°C, less than or equal to about 130°C, less than or equal to about 120°C, less than or equal to about 110°C, less than or equal to about 100°C, less than or equal to about 90°C, less than or equal to about 80°C, less than or equal to about 70°C, less than or equal to about 60°C, less than or equal to about 50°C, less than or equal to about 40°C, less than or equal to about 30°C, or less than or equal to about 20°C.

[0144] The first temperature may be greater than or equal to about 120° C., greater than or equal to about 190° C., greater than or equal to about 200° C., greater than or equal to about 210° C., greater than or equal to about 220° C., greater than or equal to about 230° C., greater than or equal to about 240° C., or greater than or equal to about 250° C. The first temperature may be less than or equal to about 280° C., less than or equal to about 275° C., less than or equal to about 270° C., less than or equal to about 265° C., less than or equal to about 260° C., less than or equal to about 255° C., less than or equal to about 250° C., less than or equal to about 240° C., less than or equal to about 230° C., less than or equal to about 220° C., less than or equal to about 210° C., less than or equal to about 200° C., less than or equal to about 190° C., less than or equal to about 180° C., less than or equal to about 170° C., less than or equal to about 160° C., or less than or equal to about 150° C.

[0145] The second temperature or reaction temperature can be greater than or equal to about 240°C, greater than or equal to about 245°C, greater than or equal to about 250°C, greater than or equal to about 255°C, greater than or equal to about 260°C, greater than or equal to about 265°C, greater than or equal to about 270°C, greater than or equal to about 275°C, greater than or equal to about 280°C, greater than or equal to about 285°C, greater than or equal to about 290°C, greater than or equal to about 295°C, greater than or equal to about 300°C, greater than or equal to about 305°C, greater than or equal to about 310°C, greater than or equal to about 315°C, greater than or equal to about 320°C, greater than or equal to about 330°C, greater than or equal to about 335°C, greater than or equal to about 340°C, or greater than or equal to about 345°C. The second temperature may be less than or equal to about 380°C, less than or equal to about 375°C, less than or equal to about 370°C, less than or equal to about 365°C, less than or equal to about 360°C, less than or equal to about 355°C, less than or equal to about 350°C, less than or equal to about 340°C, less than or equal to about 330°C, less than or equal to about 320°C, less than or equal to about 310°C, less than or equal to about 300°C, less than or equal to about 290°C, less than or equal to about 280°C, less than or equal to about 270°C, less than or equal to about 260°C, or less than or equal to about 250°C.

[0146] The reaction time can be controlled so that the resulting semiconductor nanoparticles included in the crude solution can exhibit the charge balance value described herein. In an embodiment, the reaction time can be greater than or equal to about 30 minutes, greater than or equal to about 35 minutes, greater than or equal to about 40 minutes, greater than or equal to about 45 minutes, greater than or equal to about 50 minutes, greater than or equal to about 55 minutes, greater than or equal to about 60 minutes, greater than or equal to about 65 minutes, greater than or equal to about 70 minutes, greater than or equal to about 75 minutes, or greater than or equal to about 80 minutes. The reaction time can be less than or equal to about 3 hours, less than or equal to about 2 hours, or less than or equal to about 90 minutes.

[0147] Without wishing to be bound by a particular theory, causing the silver compound to be present (e.g., adding the silver compound) in the reaction between the gallium precursor and the sulfur precursor in the presence of the first semiconductor nanocrystals can prevent undesirable changes (e.g., inter-particle bonding or composition changes) in the first semiconductor nanocrystals, thereby allowing for a higher yield of semiconductor nanoparticles in the crude solution.

[0148] The silver compound may be added to the reaction medium in an amount of about 0.1 mol% or more, or about 0.5 mol% or more relative to the gallium precursor. The amount of the silver compound added may be about 0.1 mol% or more, about 0.5 mol% or more, about 1 mol% or more, about 2 mol% or more, about 3 mol% or more, about 4 mol% or more, about 5 mol% or more, about 6 mol% or more, about 7 mol% or more, about 8 mol% or more, about 9 mol% or more, about 10 mol% or more, about 11 mol% or more, about 12 mol% or more, about 13 mol% or more, about 14 mol% or more, or about 15 mol% or more based on the gallium precursor. Based on the gallium precursor, the content of the silver compound may be less than or equal to about 50 mol%, less than or equal to about 30 mol%, less than or equal to about 25 mol%, less than or equal to about 20 mol%, less than or equal to about 18 mol%, less than or equal to about 17 mol%, less than or equal to about 15 mol%, less than or equal to about 14 mol%, less than or equal to about 13 mol%, less than or equal to about 12 mol%, less than or equal to about 11 mol%, less than or equal to about 9 mol%, less than or equal to about 8 mol%, less than or equal to about 6 mol%, less than or equal to about 5 mol%, less than or equal to about 4 mol%, less than or equal to about 3 mol%, or less than or equal to about 2 mol%. For example, the amount of the silver compound may be greater than or equal to about 0.1 mol% and less than or equal to about 25 mol%, greater than or equal to about 1 mol% and less than or equal to about 20 mol%, greater than or equal to about 2 mol% and less than or equal to about 12 mol%, greater than or equal to about 3 mol% and less than or equal to about 11 mol%, or greater than or equal to about 4 mol% and less than or equal to about 10.5 mol%.

[0149] The silver compound may include silver powder, alkylated silver compound, silver alcohol, silver carboxylate, silver acetylacetonate, silver nitrate, silver sulfate, silver halide, silver cyanide, silver hydroxide, silver oxide, silver peroxide, silver carbonate or a combination thereof. The silver compound may include silver nitrate, silver acetate, silver acetylacetonate, silver chloride, silver bromide, silver fluoride or a combination thereof.

[0150] The method can produce semiconductor nanoparticles exhibiting desired optical properties with increased yield. In an embodiment, the optical density defined by the following equation at a wavelength of 500 nm, as measured by diluting the crude solution 100 times with toluene, can be greater than or equal to about 1 and less than or equal to about 10:

[0151] Optical density = log 10 (I O / IT )

[0152] I O = the intensity of the incident light supplied to the solution (eg, to the crude solution)

[0153] I T = the intensity of light transmitted through the solution.

[0154] Optical density is a parameter related to absorbance and can be used to quantify the concentration of solutes or nanoparticles (e.g., in a medium). According to the Beer-Lambert law, absorbance can be proportional to the concentration of solutes (e.g., semiconductor nanoparticles) in a given solution and the extinction coefficient.

[0155] Optical density may be the light attenuation per centimeter of a material as measured using a standard spectrometer (eg, with an optical path length of 1 cm).In a solution including semiconductor nanoparticles, the molar concentration of the semiconductor nanoparticles may be related to the optical density.

[0156] The optical density of a crude solution containing semiconductor nanoparticles can be easily and reproducibly measured using a (e.g., commercially available) UV-Vis spectrometer. For example, to measure the optical density, the crude solution obtained can be diluted 100 times with an organic solvent (e.g., toluene), and can be measured by multiplying the absorbance (optical path length of 10 mm) value obtained by the UV-Vis spectrometer by 100 again.

[0157] In their research, the inventors found that the crude solution obtained according to the method known in the prior art, for example, showed a relatively low level of optical density at a wavelength of 500nm, and this low level of optical density can indicate that the number of semiconductor nanoparticles actually produced in the reaction system is relatively low. The inventors were surprised to find that, compared with the optical density of the existing manufacturing method in the prior art, by the method of the embodiment described herein, the crude solution thus obtained can show a significant increase (for example, 2 times (2X) or more times or about 9 times or more times) optical density. In addition, as described herein, the semiconductor nanoparticles contained in the crude solution obtained can show an improved quantum efficiency level (for example, 60% or higher, or 70% or higher).

[0158] According to the method of the embodiment, the optical density at a wavelength of 500 nm may be greater than or equal to about 1, greater than or equal to about 1.1, greater than or equal to about 1.3, greater than or equal to about 1.4, greater than or equal to about 1.5, greater than or equal to about 1.6, greater than or equal to about 1.7, greater than or equal to about 1.8, greater than or equal to about 1.9, greater than or equal to about 2, greater than or equal to about 2.1, greater than or equal to about 2.2, greater than or equal to about 2.3, greater than or equal to about 2.4, greater than or equal to about 2.5, greater than or equal to about 2.6, greater than or equal to about 2.7, greater than or equal to about 2.8, greater than or equal to about 2.9, greater than or equal to about 3, or greater than or equal to about 3.5. The optical density at a wavelength of 500 nm may be less than or equal to about 10, less than or equal to about 7, less than or equal to about 5, less than or equal to about 4.5, less than or equal to about 4, less than or equal to about 3.5, less than or equal to about 3, or less than or equal to about 2.8.

[0159] In embodiments, the optical density at a wavelength of 350 nm may be greater than or equal to about 8, greater than or equal to about 8.5, greater than or equal to about 9, greater than or equal to about 9.5, greater than or equal to about 10, greater than or equal to about 10.5, greater than or equal to about 11, greater than or equal to about 11.5, greater than or equal to about 12, greater than or equal to about 12.5, greater than or equal to about 13, greater than or equal to about 13.5, greater than or equal to about 14, greater than or equal to about 14.5, greater than or equal to about 15, greater than or equal to about 15.3, greater than or equal to about 16, greater than or equal to about 16.5, greater than or equal to about 17, greater than or equal to about 17.5, greater than or equal to about 18, greater than or equal to about 18.5, greater than or equal to about 19, greater than or equal to about 19.5, greater than or equal to about 20, greater than or equal to about 20.5, greater than or equal to about 21, greater than or equal to about 23, or greater than or equal to about 25. The optical density at a wavelength of 350 nm may be less than or equal to about 100, less than or equal to about 80, less than or equal to about 60, less than or equal to about 40, or less than or equal to about 35. The optical density at a wavelength of 350 nm may be greater than or equal to about 12 and less than or equal to about 50.

[0160] In the UV-Vis absorption spectrum, the ratio of the absorbance of the crude solution at a wavelength of 500 nm to the absorbance at 350 nm (i.e., the absorbance ratio A 500 :A 350) can exhibit an absorbance ratio of greater than or equal to about 0.01:1, greater than or equal to about 0.02:1, greater than or equal to about 0.03:1, greater than or equal to about 0.04:1, greater than or equal to about 0.05:1, greater than or equal to about 0.06:1, greater than or equal to about 0.07:1, greater than or equal to about 0.08:1, greater than or equal to about 0.09:1, greater than or equal to about 0.1:1, greater than or equal to about 0.12:1, greater than or equal to about 0.13:1, greater than or equal to about 0.15:1, greater than or equal to about 0.16:1, greater than or equal to about 0.17:1, or greater than or equal to about 0.18:1. 500 :A 350 It may be less than or equal to about 0.8:1, less than or equal to about 0.5:1, less than or equal to about 0.3:1, less than or equal to about 0.2:1, less than or equal to about 0.15:1, or less than or equal to about 0.14:1.

[0161] In embodiments, the method may exhibit a yield greater than or equal to about 6% as determined by the following equation:

[0162] Yield (%) = A / B × 100

[0163] A: the total weight of silver, Group 13 elements, and sulfur in the semiconductor nanoparticles recovered from the crude solution; and

[0164] B: The total weight of silver, Group 13 elements, and sulfur added (eg, supplied) to the reaction medium for the reaction.

[0165] The yield may be greater than or equal to about 6%, greater than or equal to about 7%, greater than or equal to about 8%, greater than or equal to about 9%, greater than or equal to about 10%, greater than or equal to about 11%, greater than or equal to about 12%, greater than or equal to about 13%, greater than or equal to about 14%, greater than or equal to about 15%, greater than or equal to about 16%, greater than or equal to about 17%, greater than or equal to about 18%, greater than or equal to about 19%, greater than or equal to about 20%, greater than or equal to about 21%, greater than or equal to about 22%, greater than or equal to about 23%, greater than or equal to about 24%, or greater than or equal to about 25%. The yield may be less than or equal to about 100%, less than or equal to about 90%, less than or equal to about 80%, less than or equal to about 70%, or less than or equal to about 60%.

[0166] The method may also include: preparing an additional reaction medium (e.g., a solution) comprising a zinc precursor and an optional organic ligand in an organic solvent; adding the formed semiconductor nanoparticles and the chalcogen precursor to the reaction medium and heating the medium to a temperature to provide a third semiconductor nanocrystal comprising zinc chalcogenide or an outer layer comprising a third semiconductor nanocrystal on, for example, the surface of the semiconductor nanoparticles formed thereby. The third semiconductor nanocrystal may have a composition different from that of the first semiconductor nanocrystal and the second semiconductor nanocrystal.

[0167] In an embodiment, the reaction temperature for forming the third semiconductor nanocrystal (or zinc chalcogenide) may be greater than or equal to about 120° C., greater than or equal to about 130° C., greater than or equal to about 150° C., greater than or equal to about 180° C., greater than or equal to about 200° C., greater than or equal to about 205° C., greater than or equal to about 208° C. and less than or equal to about 240° C., less than or equal to about 230° C., less than or equal to about 225° C., less than or equal to about 215° C. The reaction time for forming the third semiconductor nanocrystal (or zinc chalcogenide) may be greater than or equal to about 10 minutes, greater than or equal to about 30 minutes, greater than or equal to about 40 minutes, greater than or equal to about 1 hour, greater than or equal to about 80 minutes, or greater than or equal to about 90 minutes and less than or equal to about 5 hours, less than or equal to about 4 hours, less than or equal to about 3 hours, less than or equal to about 2 hours, less than or equal to about 90 minutes, or less than or equal to about 70 minutes.

[0168] In the method of the embodiment, the method of adding reagents (precursors, semiconductor nanocrystals, semiconductor nanoparticles, etc.) is not particularly limited, but can be appropriately selected, which may include jet addition (such as syringe addition), dropwise addition or a combination of two different addition methods.

[0169] 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 alcohols, silver carboxylates, silver acetylacetonate, silver nitrate, silver sulfate, silver halide, silver cyanide, silver hydroxide, silver oxide, silver peroxide, silver carbonate, or a combination thereof. The silver precursor may include silver nitrate, silver acetate, silver acetylacetonate, or a combination thereof.

[0170] The type of indium precursor is not particularly limited and can be appropriately selected. The indium precursor can include indium powder, alkylated indium compounds, indium alcohols, indium carboxylates, indium nitrates, indium perchlorates, indium sulfates, indium acetylacetonates, indium halides, indium cyanides, indium hydroxides, indium oxides, indium peroxides, indium carbonates, or combinations thereof. The indium precursor can include indium carboxylates (such as indium oleate and indium myristic acid), indium acetate, indium hydroxides, indium chlorides, indium bromides, indium iodides, or combinations thereof.

[0171] The type of gallium precursor is not particularly limited and can be appropriately selected. The gallium precursor may include gallium powder, alkylated gallium compounds, gallium alcohols, gallium carboxylates, gallium nitrates, gallium perchlorates, 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 acetylacetonates, gallium oleates, gallium palmitates, gallium stearates, gallium myristates, gallium hydroxides, or combinations thereof.

[0172] The type of the sulfur precursor is not particularly limited and may be appropriately selected. The sulfur precursor can be an organic solvent dispersion or a reaction product of sulfur and an organic solvent (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 to C30 thiol compounds (e.g., α-toluene mercaptan, octanethiol, dodecanethiol, octadecene mercaptan, etc.), isothiocyanate compounds (e.g., cyclohexyl isothiocyanate, etc.), alkylene trithiocarbonates (e.g., ethylene trithiocarbonate, etc.), allyl mercaptan, thiourea compounds (e.g., dialkylthioureas having a C1 to C40 alkyl group, such as dimethylthiourea, diethylthiourea, ethylmethylthiourea, dipropylthiourea, etc.), or a combination thereof.

[0173] If present, the selenium precursor may include selenium-trioctylphosphine (Se-TOP), selenium-tributylphosphine (Se-TBP), selenium-triphenylphosphine (Se-TPP), or combinations thereof.

[0174] The type of zinc precursor is not particularly limited and can be appropriately selected. In one or more embodiments, the zinc precursor can include Zn metal powder, alkylated Zn compound, alcohol Zn, carboxylic acid Zn, Zn nitrate, Zn perchlorate, Zn sulfuric acid, Zn acetylacetonate, Zn halogenation, Zn cyanide, Zn hydroxide, Zn oxidation, Zn peroxide or their combination. The zinc precursor can be dimethyl zinc, diethyl zinc, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zinc peroxide, zinc perchlorate, zinc sulfate or their combination. In an embodiment, when forming the third semiconductor nanocrystal comprising zinc and sulfur, the zinc precursor can include Zn halogenation, but is not limited to this.

[0175] Organic ligands can include RCOOH, RNH 2 , R 2 NH, R 3 N, RSH, RH 2 PO, R2 HPO, R 3 PO, RH 2 P.R 2 HP, R 3 P, ROH, RCOOR', RPO(OH) 2 , RHPOOH, R 2 POOH (wherein R and R' are independently substituted or unsubstituted C1 to C40 (or C3 to C24) aliphatic hydrocarbon groups (e.g., alkyl, alkenyl or alkynyl) or substituted or unsubstituted C6 to C40 (or C6 to C24) aromatic hydrocarbon groups (e.g., C6 to C20 aryl)) or a combination thereof. The organic ligand may be bound to the surface of the semiconductor nanoparticle. Examples of organic ligands may include: methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, 1-nonyl mercaptan, decyl mercaptan, dodecanethiol, hexadecyl mercaptan, octadecyl mercaptan, benzyl mercaptan; methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, dodecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine; formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, dodecyl acid, hexadecyl acid, octadecyl acid, oleic acid, benzoic acid; substituted or unsubstituted methyl phosphine (e.g., trimethyl phosphine, methyldiphenyl phosphine, etc.), substituted or unsubstituted ethyl phosphine (e.g., triethyl phosphine, ethyldiphenyl phosphine, etc.), substituted or unsubstituted propyl phosphine, substituted or unsubstituted butyl phosphine, substituted or unsubstituted pentyl phosphine , substituted or unsubstituted octylphosphine (e.g., trioctylphosphine (TOP) etc.); phosphine oxides such as substituted or unsubstituted methylphosphine oxide (e.g., trimethylphosphine oxide, methyldiphenylphosphine oxide etc.), substituted or unsubstituted ethylphosphine oxide (e.g., triethylphosphine oxide, ethyldiphenylphosphine oxide etc.), substituted or unsubstituted propylphosphine oxide, substituted or unsubstituted butylphosphine oxide, substituted or unsubstituted octylphosphine oxide (e.g., trioctylphosphine oxide (TOPO) etc.); diphenylphosphine, triphenylphosphine or their oxide compounds; phosphonic acid, such as C5 to C20 alkylphosphonic acid, C5 to C20 alkylphosphinic acid (such as hexylphosphinic acid, octylphosphinic acid, dodecylphosphinic acid, tetradecylphosphinic acid, hexadecylphosphinic acid, octadecylphosphinic acid etc.); etc., but the embodiment is not limited thereto. The organic ligand may be used alone or as a mixture of two or more.

[0176] The organic solvent may include: amine solvents (e.g., C1 to C50 aliphatic amines); nitrogen-containing heterocyclic compounds, such as pyridine; C6 to C40 aliphatic hydrocarbons (e.g., alkanes, alkenes, alkynes, etc.), such as hexadecane, octadecane, octadecene, squalene, etc.; C6 to C30 aromatic hydrocarbons, such as phenyldodecane, phenyltetradecane, phenylhexadecane, etc.; phosphines substituted with C6 to C22 alkyl groups, such as trioctylphosphine, etc.; phosphine oxides substituted with C6 to C22 alkyl groups, such as trioctylphosphine oxide, etc.; C12 to C22 aromatic ethers, such as phenyl ether, benzyl ether, etc.; or combinations thereof. The amine solvent may be a compound having one or more (e.g., two or three) C1 to C50 aliphatic hydrocarbon groups, C2 to C45 aliphatic hydrocarbon groups, C3 to C40 aliphatic hydrocarbon groups, C4 to C35 aliphatic hydrocarbon groups, C5 to C30 aliphatic hydrocarbon groups, C6 to C25 aliphatic hydrocarbon groups, C7 to C20 aliphatic hydrocarbon groups, C8 to C15 aliphatic hydrocarbon groups, or C6 to C22 aliphatic hydrocarbon groups (e.g., alkyl, alkenyl, or alkynyl). In one or more embodiments, the amine solvent may be: a C6 to C22 primary amine, such as hexadecylamine, oleylamine, etc.; a C6 to C22 secondary amine, such as dioctylamine, etc.; a C6 to C22 tertiary amine, such as trioctylamine, etc.; or a combination thereof.

[0177] In consideration of the type of solvent, the type of organic ligand and each precursor, and the size and composition of the desired semiconductor nanoparticles, the amount of organic ligand and precursor in the reaction medium can be appropriately selected. In consideration of the molar ratio desired in the final semiconductor nanoparticles, the reactivity between the precursors, etc., the molar ratio between the precursors can be changed. For example, when preparing the first semiconductor nanocrystal, the molar ratio of the silver precursor to the indium precursor can be between 0.5:1 and 1.2:1, but is not limited thereto. In an embodiment, the mode of adding each precursor is not particularly limited. In one or more embodiments, all or all amounts of precursors can be added at once. In an embodiment, the total amount of the precursor can be divided into greater than or equal to about 2 aliquots and less than or equal to about 10 aliquots and added. Precursors can be added simultaneously or in a predetermined order. The reaction can be carried out in an inert gas atmosphere, air or vacuum state, but is not limited thereto.

[0178] When a non-solvent is added to the final reaction solution after the reaction is completed (e.g., the organic ligand is coordinated), the nanoparticles or nanocrystals can be separated (e.g., precipitated). The non-solvent can be a polar solvent that is miscible with the solvent used in the reaction but cannot disperse the nanocrystals. The non-solvent can be selected according to the solvent used in the reaction, and can be, for example, acetone, ethanol, butanol, isopropanol, ethylene glycol, water, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), diethyl ether, formaldehyde, acetaldehyde, a solvent with a solubility parameter similar to the aforementioned solvent, or a combination thereof. Separation can be performed by centrifugation, precipitation, chromatography or distillation. The separated nanocrystals can be washed by adding a washing solvent as needed. The washing solvent is not particularly limited, and a solvent with a solubility parameter similar to that of the organic solvent or organic ligand can be used. The non-solvent or washing solvent can be: an alcohol; an alkane solvent such as hexane, heptane, octane, etc.; an aromatic solvent such as toluene, benzene, etc.; a halogenated solvent such as chloroform, etc.; or a combination thereof, but is not limited thereto.

[0179] The semiconductor nanoparticles thus prepared can be dispersed in a dispersing solvent. The semiconductor nanoparticles thus prepared can form an organic solvent dispersion. The organic solvent dispersion may not include water and / or an organic solvent miscible with water. The dispersing solvent can be appropriately selected. The dispersing solvent may include the above-mentioned organic solvent. The dispersing solvent may include substituted or unsubstituted C1 to C40 aliphatic hydrocarbons, substituted or unsubstituted C6 to C40 aromatic hydrocarbons, or a combination thereof.

[0180] In an embodiment, the semiconductor nanoparticles may or may not include lithium. The semiconductor nanoparticles may or may not include alkali metals such as sodium, potassium, and the like.

[0181] In the semiconductor nanoparticles, the molar ratio of gallium to indium (Ga:In) may be greater than or equal to about 1:1, greater than or equal to about 1.5:1, greater than or equal to about 2:1, greater than or equal to about 2.5:1, greater than or equal to about 3:1, greater than or equal to about 3.1:1, greater than or equal to about 3.3:1, greater than or equal to about 3.4:1, greater than or equal to about 3.5:1, greater than or equal to about 3.6:1, greater than or equal to about 3.7:1, greater than or equal to about 3.8:1, greater than or equal to about 3.9:1, greater than or equal to about 4:1, greater than or equal to about 4.1:1, greater than or equal to about 4.2:1, greater than or equal to about 4.3:1, greater than or equal to about 4.4:1, greater than or equal to about 4.5:1, greater than or equal to about 4.6:1, or greater than or equal to about 4.7:1. .7:1; less than or equal to about 10:1, less than or equal to about 9:1, less than or equal to about 8.5:1, less than or equal to about 8:1, less than or equal to about 6.5:1, less than or equal to about 6:1, less than or equal to about 5.5:1, less than or equal to about 5.3:1, less than or equal to about 5.1:1, less than or equal to about 5:1, less than or equal to about 4.9:1, less than or equal to about 4.7:1, less than or equal to about 4.5:1, less than or equal to about 4.3:1, less than or equal to about 4.2:1, less than or equal to about 4.1:1, less than or equal to about 4:1, less than or equal to about 3.9:1, less than or equal to about 3.8:1, less than or equal to about 3.7:1, less than or equal to about 3.6:1, or less than or equal to about 3.55:1; or combinations thereof.

[0182] In the semiconductor nanoparticles, the molar ratio of gallium to the sum of indium and gallium (Ga:(In+Ga)) may be greater than or equal to about 0.70:1, greater than or equal to about 0.715:1, greater than or equal to about 0.72:1, greater than or equal to about 0.725:1, greater than or equal to about 0.73:1, greater than or equal to about 0.735:1, greater than or equal to about 0.74:1, greater than or equal to about 0.745:1, greater than or equal to about 0.75:1, greater than or equal to about 0.755:1, greater than or equal to about 0.76:1, greater than or equal to about 0.775:1, greater than or equal to about 0.78:1, greater than or equal to about 0.79:1, greater than or equal to about 0.80:1, greater than or equal to about 0.81:1, greater than or equal to about 0.82:1, greater than or equal to about 0.83:1, greater than or equal to about 0.84:1, greater than or equal to about 0.85:1, greater than or equal to about 0.86:1, greater than or equal to about 0.875:1, greater than or equal to about 0.88:1, greater than or equal to about 0.89:1, greater than or equal to about 0.90:1, greater than or equal to about 0.91:1, greater than or equal to about 0.92:1, greater than or equal to about 0.93:1, greater than or equal to about 0.94:1, greater than or equal to about 0.95:1, greater than or equal to about 0.96:1, greater than or equal to about greater than or equal to about 0.765:1, greater than or equal to about 0.77:1, greater than or equal to about 0.775:1, greater than or equal to about 0.78:1, greater than or equal to about 0.785:1, greater than or equal to about 0.79:1, greater than or equal to about 0.795:1, greater than or equal to about 0.8:1, greater than or equal to about 0.805:1, greater than or equal to about 0.81:1, greater than or equal to about 0.815:1, greater than or equal to about 0.82:1, or greater than or equal to about 0.825:1; less than or equal to about 0.9 9:1, less than or equal to about 0.98:1, less than or equal to about 0.97:1, less than or equal to about 0.96:1, less than or equal to about 0.95:1, less than or equal to about 0.94:1, less than or equal to about 0.93:1, less than or equal to about 0.92:1, less than or equal to about 0.91:1, less than or equal to about 0.9:1, less than or equal to about 0.87:1, less than or equal to about 0.85:1, less than or equal to about 0.845:1, less than or equal to about 0.84:1, less than or equal to about 0.835: 1, less than or equal to about 0.83:1, less than or equal to about 0.825:1, less than or equal to about 0.82:1, less than or equal to about 0.815:1, less than or equal to about 0.81:1, less than or equal to about 0.805:1, less than or equal to about 0.8:1, less than or equal to about 0.795:1, less than or equal to about 0.79:1, less than or equal to about 0.785:1, less than or equal to about 0.78:1, less than or equal to about 0.775:1, or less than or equal to about 0.77:1; or combinations thereof.

[0183] In the semiconductor nanoparticles, the molar ratio of gallium to silver (Ga:Ag) may be greater than or equal to about 1:1, greater than or equal to about 1.1:1, greater than or equal to about 1.15:1, greater than or equal to about 1.2:1, greater than or equal to about 1.22:1, greater than or equal to about 1.3:1, greater than or equal to about 1.33:1, greater than or equal to about 1.34:1, greater than or equal to about 1.35:1, greater than or equal to about 1.36:1, greater than or equal to about 1.4:1, greater than or equal to about 1.46:1, greater than or equal to about 1.48:1, greater than or equal to about 1.5:1, greater than or equal to about 1.54:1, greater than or equal to about 1.6:1, or greater than or equal to about 1.65:1; less than or equal to about 3:1, less than or equal to about 2.9:1, less than or equal to about 2.8:1, less than or equal to about 2.75:1, less than or equal to about 2.5:1, less than or equal to about 2.2:1, less than or equal to about 2:1, less than or equal to about 1.9:1, less than or equal to about 1.8:1, less than or equal to about 1.75:1, less than or equal to about 1.7:1, less than or equal to about 1.65:1, less than or equal to about 1.6:1, less than or equal to about 1.58:1, less than or equal to about 1.55:1, less than or equal to about 1.5:1, less than or equal to about 1.45:1, less than or equal to about 1.4:1, or less than or equal to about 1.35:1; or combinations thereof.

[0184] In the semiconductor nanoparticles, the molar ratio of gallium to the sum of gallium, indium, and silver (Ga:(Ga+In+Ag)) can be greater than or equal to about 0.45:1, greater than or equal to about 0.46:1, greater than or equal to about 0.47:1, greater than or equal to about 0.48:1, greater than or equal to about 0.49:1, greater than or equal to about 0.5:1, greater than or equal to about 0.51:1, greater than or equal to about 0.52:1, or greater than or equal to about 0.53:1; less than or equal to about 0.65:1, less than or equal to about 0.6:1, less than or equal to about 0.57:1, less than or equal to about 0.54:1, less than or equal to about 0.53:1, less than or equal to about 0.52:1, less than or equal to about 0.51:1, less than or equal to about 0.5:1, less than or equal to about 0.49:1, or less than or equal to about 0.485:1; or combinations thereof.

[0185] In the semiconductor nanoparticles, the molar ratio of the sum of indium and gallium to silver ((In+Ga):Ag) can be greater than or equal to about 1.2:1, greater than or equal to about 1.3:1, greater than or equal to about 1.4:1, greater than or equal to about 1.45:1, greater than or equal to about 1.46:1, greater than or equal to about 1.5:1, greater than or equal to about 1.63:1, greater than or equal to about 1.7:1, greater than or equal to about 1.83:1, greater than or equal to about 1.9:1, greater than or equal to about 1.94:1, or greater than or equal to about 2:1; less than or equal to about 3.7:1, less than or equal to about 3.5:1, less than or equal to about 3:1, less than or equal to about 2.4:1, less than or equal to about 2.37:1, less than or equal to about 2:1, less than or equal to about 1.96:1, less than or equal to about 1.95:1, or less than or equal to about 1.9:1; or combinations thereof.

[0186] In the semiconductor nanoparticles, the molar ratio of silver to sulfur (Ag:S) can be greater than or equal to about 0.05:1, greater than or equal to about 0.15:1, greater than or equal to about 0.2:1, greater than or equal to about 0.23:1, greater than or equal to about 0.25:1, greater than or equal to about 0.28:1, greater than or equal to about 0.3:1, greater than or equal to about 0.31:1, greater than or equal to about 0.32:1, greater than or equal to about 0.33:1, or greater than or equal to about 0.35:1; less than or equal to about 0.5:1, less than or equal to about 0.45:1, less than or equal to about 0.41:1, less than or equal to about 0.4:1, less than or equal to about 0.36:1, less than or equal to about 0.35:1, or less than or equal to about 0.33:1; or combinations thereof.

[0187] In the semiconductor nanoparticles, the molar ratio of silver to indium (Ag:In) may be greater than or equal to about 1.5:1, greater than or equal to about 2:1, greater than or equal to about 2.25:1, greater than or equal to about 2.3:1, greater than or equal to about 2.37:1, greater than or equal to about 2.4:1, greater than or equal to about 2.5:1, greater than or equal to about 2.51:1, greater than or equal to about 2.6:1, greater than or equal to about 2.65:1, greater than or equal to about 2.7:1, greater than or equal to about 2.9:1. 1, greater than or equal to about 3:1, or greater than or equal to about 3.1:1; less than or equal to about 6:1, less than or equal to about 5.5:1, less than or equal to about 5.2:1, less than or equal to about 5:1, less than or equal to about 4.5:1, less than or equal to about 4.4:1, less than or equal to about 4:1, less than or equal to about 3.9:1, less than or equal to about 3.8:1, less than or equal to about 3.7:1, less than or equal to about 3.6:1, or less than or equal to about 3:1; or combinations thereof.

[0188] In the semiconductor nanoparticles, the molar ratio of sulfur to indium (S:In) can be greater than or equal to about 6:1, greater than or equal to about 6.5:1, greater than or equal to about 7.5:1, greater than or equal to about 7.7:1, greater than or equal to about 7.8:1, greater than or equal to about 8:1, greater than or equal to about 8.9:1, greater than or equal to about 9:1, greater than or equal to about 9.8:1, or greater than or equal to about 10:1; less than or equal to about 25:1, less than or equal to about 20:1, less than or equal to about 19:1, or less than or equal to about 18:1; or combinations thereof.

[0189] In the semiconductor nanoparticles, the molar ratio of silver to the sum of silver, indium and gallium (Ag:(Ag+In+Ga)) can be greater than or equal to about 0.2:1, greater than or equal to about 0.25:1, greater than or equal to about 0.3:1, greater than or equal to about 0.33:1, greater than or equal to about 0.34:1, greater than or equal to about 0.35:1, greater than or equal to about 0.37:1, or greater than or equal to about 0.4:1; less than or equal to about 0.45:1, less than or equal to about 0.41:1, less than or equal to about 0.4:1, less than or equal to about 0.36:1, less than or equal to about 0.33:1, less than or equal to about 0.32:1, less than or equal to about 0.28:1; or combinations thereof.

[0190] In the semiconductor nanoparticles, the molar ratio of sulfur to the sum of silver, indium, and gallium (S:(Ag+In+Ga)) can be greater than or equal to about 0.8:1, greater than or equal to about 0.9:1, greater than or equal to about 1:1, greater than or equal to about 1.05:1, greater than or equal to about 1.12:1, or greater than or equal to about 1.3:1; less than or equal to about 1.5:1, less than or equal to about 1.45:1, less than or equal to about 1.35:1, less than or equal to about 1.3:1, less than or equal to about 1.15:1, less than or equal to about 1.13:1, or less than or equal to about 1.08:1; or combinations thereof.

[0191] In the semiconductor nanoparticles, the molar ratio of gallium to sulfur (Ga:S) can be greater than or equal to about 0.4:1, greater than or equal to about 0.44:1, greater than or equal to about 0.48:1, greater than or equal to about 0.5:1, or greater than or equal to about 0.55:1; less than or equal to about 0.6:1, less than or equal to about 0.56:1, or less than or equal to about 0.51:1; or combinations thereof.

[0192] In embodiments, the charge balance value of the semiconductor nanoparticles may be greater than or equal to about 0.8, greater than or equal to about 0.85, greater than or equal to about 0.9, greater than or equal to about 0.91, greater than or equal to about 0.92, greater than or equal to about 0.93, greater than or equal to about 0.95, greater than or equal to about 0.98, greater than or equal to about 0.99, greater than or equal to about 1.02, or greater than or equal to about 1.06; less than or equal to about 1.4, less than or equal to about 1.35, less than or equal to about 1.3, less than or equal to about 1.25, less than or equal to about 1.2, less than or equal to about 1.18, less than or equal to about 1.17, less than or equal to about 1.15, less than or equal to about 1.1, less than or equal to about 1.05, or less than or equal to about 1; or combinations thereof:

[0193] Charge balance value = {[Ag] + 3([In] + [Ga])} / (2[S])

[0194] Wherein, in the above equation, [Ag], [In], [Ga] and [S] are the molar amount of silver, the molar amount of indium, the molar amount of gallium and the molar amount of sulfur in the semiconductor nanoparticles, respectively.

[0195] The size (or average size, hereinafter referred to as "size") of the first semiconductor nanocrystal may be greater than or equal to about 0.5 nm, greater than or equal to about 1 nm, greater than or equal to about 1.5 nm, greater than or equal to about 1.7 nm, greater than or equal to about 1.9 nm, greater than or equal to about 2 nm, greater than or equal to about 2.1 nm, greater than or equal to about 2.3 nm, greater than or equal to about 2.5 nm, greater than or equal to about 2.7 nm, greater than or equal to about 2.9 nm, greater than or equal to about 3 nm, greater than or equal to about 3.1 nm, greater than or equal to about 3.3 nm, greater than or equal to about 3.5 nm, greater than or equal to about 3.7 nm, greater than or equal to about 3.9 nm, greater than or equal to about 4 nm, or greater than or equal to about 4.2 nm. The size of the first semiconductor nanocrystal may be less than or equal to about 6 nm, less than or equal to about 5.5 nm, less than or equal to about 5 nm, less than or equal to about 4.5 nm, less than or equal to about 4 nm, less than or equal to about 3.5 nm, less than or equal to about 3 nm, less than or equal to about 2.5 nm, less than or equal to about 2 nm, or less than or equal to about 1.5 nm.

[0196] The thickness (or average thickness, hereinafter referred to as "thickness") of the second semiconductor nanocrystal or the layer including the second semiconductor nanocrystal may be greater than or equal to about 0.1 nm, greater than or equal to about 0.2 nm, or greater than or equal to about 0.3 nm. The thickness of the second semiconductor nanocrystal or the layer including the second semiconductor nanocrystal may be less than or equal to about 3 nm, less than or equal to about 2.5 nm, less than or equal to about 2 nm, less than or equal to about 1.5 nm, less than or equal to about 1 nm, or less than or equal to about 0.8 nm.

[0197] The thickness of the third semiconductor nanocrystal or the layer including the third semiconductor nanocrystal can be greater than or equal to about 0.1nm, greater than or equal to about 0.3nm, greater than or equal to about 0.5nm, greater than or equal to about 0.7nm, or greater than or equal to about 1nm. The thickness of the third semiconductor nanocrystal or the layer including the third semiconductor nanocrystal can be less than or equal to about 2nm, less than or equal to about 1.5nm, less than or equal to about 1nm, or less than or equal to about 0.8nm. The thickness of the third semiconductor nanocrystal or the layer including the third semiconductor nanocrystal can be about 0.1nm to about 5nm, about 0.2nm to about 4nm, about 0.3nm to about 3.5nm, about 0.4nm to about 3nm, about 0.5nm to about 2.5nm, about 0.6nm to about 2nm, about 0.7nm to about 1.5nm, about 0.8nm to about 1.2nm, about 0.9nm to about 1nm, or a combination thereof.

[0198] The size or average size (hereinafter referred to as "size") of the semiconductor nanoparticles may be greater than or equal to about 1 nm, greater than or equal to about 1.5 nm, greater than or equal to about 2 nm, greater than or equal to about 2.5 nm, greater than or equal to about 3 nm, greater than or equal to about 3.5 nm, greater than or equal to about 4 nm, greater than or equal to about 4.5 nm, greater than or equal to about 5 nm, greater than or equal to about 5.5 nm, greater than or equal to about 6 nm, greater than or equal to about 6.5 nm, greater than or equal to about 7 nm, greater than or equal to about 7.5 nm, greater than or equal to about 8 nm, greater than or equal to about 8.5 nm, greater than or equal to about 9 nm, greater than or equal to about 9.5 nm, greater than or equal to about 10 nm, or greater than or equal to about 10.5 nm. The size of the semiconductor nanoparticles can be less than or equal to about 50 nm, less than or equal to about 48 nm, less than or equal to about 46 nm, less than or equal to about 44 nm, less than or equal to about 42 nm, less than or equal to about 40 nm, less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal to about 25 nm, less than or equal to about 20 nm, less than or equal to about 18 nm, less than or equal to about 16 nm, less than or equal to about 14 nm, less than or equal to about 12 nm, less than or equal to about 11 nm, less than or equal to about 10 nm, less than or equal to about 8 nm, less than or equal to about 7.5 nm, less than or equal to about 6 nm, or less than or equal to about 4 nm.

[0199] As used herein, the size of semiconductor nanoparticles can be particle diameter. The size of semiconductor nanoparticles can be its equivalent diameter, which is obtained by converting the two-dimensional area of ​​the transmission electron microscope image of a given particle into a calculation of a circle. The size of semiconductor nanoparticles can be obtained by analyzing the image obtained by an electron microscope (e.g., transmission electron microscope). Various image processing programs (e.g., internal programs that can be made using image J or coding languages) can be used to repeatably and easily measure this particle size (e.g., particle diameter) by microscopic images. Particle size (e.g., particle diameter) can be a value (e.g., nominal particle size) calculated by the composition and peak emission wavelength of semiconductor nanoparticles.

[0200] The size (or average size) of the semiconductor nanoparticles can be 5 nm or more, 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 exhibit a size distribution represented by 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.

[0201] The semiconductor nanoparticles may be configured to emit green light. The peak emission wavelength of the green light may be greater than or equal to about 500 nm, or greater than or equal to about 505 nm and less than or equal to about 580 nm, or less than or equal to about 550 nm.

[0202] The peak emission wavelength of green light or the peak emission wavelength of the semiconductor nanoparticles may be greater than or equal to about 500 nm, greater than or equal to about 505 nm, greater than or equal to about 510 nm, greater than or equal to about 515 nm, greater than or equal to about 520 nm, greater than or equal to about 525 nm, greater than or equal to about 530 nm, greater than or equal to about 535 nm, greater than or equal to about 540 nm, or greater than or equal to about 545 nm. The peak emission wavelength of green light or the peak emission wavelength of semiconductor nanoparticles can be less than or equal to about 580nm, less than or equal to about 575nm, less than or equal to about 570nm, less than or equal to about 565nm, less than or equal to about 560nm, less than or equal to about 555nm, less than or equal to about 550nm, less than or equal to about 545nm, less than or equal to about 540nm, less than or equal to about 535nm, less than or equal to about 530nm, less than or equal to about 525nm, less than or equal to about 520nm, or less than or equal to about 515nm.

[0203] The semiconductor nanoparticles can be configured to emit red light. The peak emission wavelength of red light or the peak emission wavelength of the semiconductor nanoparticles can be in the range of 600nm to 660nm, 605nm to 650nm, 610nm to 645nm, 615nm to 640nm, 620nm to 635nm, 623nm to 632nm, 625nm to 630nm, 628nm to 629nm, or a combination thereof.

[0204] The semiconductor nanoparticles may exhibit a quantum yield of greater than or equal to about 50%. The quantum yield may be an absolute quantum yield. The quantum yield may be greater than or equal to about 50%, greater than or equal to about 55%, greater than or equal to about 60%, greater than or equal to about 65%, greater than or equal to about 70%, greater than or equal to about 75%, greater than or equal to about 80%, greater than or equal to about 85%, greater than or equal to about 90%, or greater than or equal to about 95%. The quantum yield may be less than or equal to about 100%, less than or equal to about 99.5%, less than or equal to about 99%, less than or equal to about 98%, or less than or equal to about 97%.

[0205] The full width at half maximum (FWHM) of the first light (e.g., green light or red light) or the FWHM of the semiconductor nanoparticles may be greater than or equal to about 5 nm, greater than or equal to about 10 nm, greater than or equal to about 15 nm, greater than or equal to about 20 nm, greater than or equal to about 25 nm, or greater than or equal to about 30 nm. The full width at half maximum can be less than or equal to about 90 nm, less than or equal to about 85 nm, less than or equal to about 80 nm, less than or equal to about 75 nm, less than or equal to about 70 nm, less than or equal to about 65 nm, less than or equal to about 60 nm, less than or equal to about 55 nm, less than or equal to about 50 nm, less than or equal to about 45 nm, less than or equal to about 40 nm, less than or equal to about 38 nm, less than or equal to about 36 nm, less than or equal to about 35 nm, less than or equal to about 34 nm, less than or equal to about 33 nm, less than or equal to about 32 nm, less than or equal to about 31 nm, less than or equal to about 30 nm, less than or equal to about 29 nm, less than or equal to about 28 nm, less than or equal to about 27 nm, less than or equal to about 26 nm, or less than or equal to about 25 nm.

[0206] The shape of the semiconductor nanoparticles thus prepared is not particularly limited, and may include, for example, spheres, polyhedrons, pyramids, multi-arms, cubes, nanotubes, nanowires, nanofibers, nanosheets, or combinations thereof, but is not limited thereto.

[0207] The semiconductor nanoparticles of the embodiments may include an organic ligand and / or an organic solvent on the surface of the semiconductor nanoparticles. The organic ligand and / or the organic solvent may be bound to the surface of the semiconductor nanoparticles of one or more embodiments.

[0208] In one or more embodiments, the composite may include: a matrix; and semiconductor nanoparticles described herein, wherein the semiconductor nanoparticles may be dispersed in the matrix. The composite may also contain metal oxide fine particles. The composite may be configured to emit green light. In an embodiment, the composite may be in the form of a patterned film. The composite may also include semiconductor nanoparticles configured to emit a second light (e.g., red light) different from green light. In an embodiment, the composite may have a sheet form. The sheet may also include semiconductor nanoparticles (e.g., additional semiconductor nanoparticles) configured to emit a second light different from green light.

[0209] The semiconductor nanoparticles described herein or composites comprising the semiconductor nanoparticles can exhibit an increased level of blue light absorptivity (e.g., improved incident light absorptivity) and / or improved optical properties (e.g., increased luminous efficiency and narrower half-maximum full width), and can emit light of a desired wavelength (e.g., first light).

[0210] The composite may include (e.g., in a predetermined amount) a semiconductor nanoparticle of an embodiment or a group of semiconductor nanoparticles of the embodiment and exhibit increased light absorptivity. The composite may have an incident light absorptivity of greater than or equal to about 70%, greater than or equal to about 73%, greater than or equal to about 75%, greater than or equal to about 77%, greater than or equal to about 80%, greater than or equal to about 83%, greater than or equal to about 85%, greater than or equal to about 87%, greater than or equal to about 90%, greater than or equal to about 93%, greater than or equal to about 94%, greater than or equal to about 95%, greater than or equal to about 96%, greater than or equal to about 97%, greater than or equal to about 98%, or greater than or equal to about 99%. The composite may have a blue light absorptivity of about 70% to about 100%, about 80% to about 98%, about 95% to about 99%, about 96% to about 98%, or a combination thereof.

[0211] The incident light absorbance can be calculated according to the following equation:

[0212] Incident light absorption rate = [(B-B') / B] × 100%

[0213] Among them, in the equation,

[0214] B is the amount of incident light provided to the composite, and

[0215] B' is the amount of incident light that passes through the composite.

[0216] The photoconversion efficiency (CE) of the composite may be greater than or equal to about 7%, greater than or equal to about 8%, greater than or equal to about 9%, greater than or equal to about 10%, greater than or equal to about 11%, greater than or equal to about 12%, greater than or equal to about 12.5%, greater than or equal to about 12.9%, greater than or equal to about 13%, greater than or equal to about 14.5%, greater than or equal to about 15%, greater than or equal to about 15.5%, greater than or equal to about 16%, greater than or equal to about 16.5%, greater than or equal to about 16.7%, or greater than or equal to about 16.9%.

[0217] The light conversion efficiency is defined by the following equation:

[0218] Photoconversion efficiency (CE, %) = [A / (B-B')] × 100

[0219] A: the amount of the first light from the composite;

[0220] B: the amount of incident light provided to the composite; and

[0221] B': The amount of incident light that passes through the composite.

[0222] The inventors have also found through their work that luminescent nanoparticles including semiconductor nanoparticles based on 11-13-16 group compounds, even if they exhibit a desired level of optical properties, can also, for example, when they are included in (or present in) a composite matrix (which may be required for the application of nanoparticles in actual working devices) have significantly reduced optical properties. The semiconductor nanoparticles of the embodiments can provide a composite that exhibits improved optical properties by having the above-mentioned composition and / or structural features, thereby exhibiting high optical properties even in the form of a film. The semiconductor nanoparticles of the embodiments can exhibit significantly improved stability (e.g., thermal stability and atmospheric stability).

[0223] In an embodiment, the composite may be prepared from an ink composition. The ink composition may include: a liquid carrier; and a plurality of semiconductor nanoparticles of one or more embodiments described herein. The semiconductor nanoparticles may be dispersed in the liquid carrier.

[0224] The liquid carrier may include a liquid monomer, an organic solvent, or a combination thereof. The ink composition may also include or may not substantially include a volatile organic solvent. The ink composition may also include (e.g., dispersed in the liquid carrier) fine particles of metal oxide (e.g., metal oxide nanoparticles). The ink composition may also include (e.g., dispersed in the liquid carrier) fine particles of metal oxide (e.g., metal oxide nanoparticles). The ink composition may also include (e.g., dispersed in the liquid carrier) fine particles of metal oxide (e.g., metal oxide nanoparticles). The ink composition may also include a dispersant (for dispersing semiconductor nanoparticles and / or metal oxide nanoparticles). The dispersant may include an organic compound (monomer or polymer) containing a carboxylic acid group. The liquid carrier may not include (e.g., volatile) organic solvents. The ink composition may be a solvent-free system.

[0225] The liquid monomer may comprise a (photo)polymerizable monomer comprising a carbon-carbon double bond. The composition may optionally further comprise a (thermal or photo)initiator. Polymerization of the composition may be initiated by light or heat.

[0226] The details of the semiconductor nanoparticles in the composition (or compound) are as described herein. Considering the desired end use (e.g., color filter, etc.), the content or amount of semiconductor nanoparticles in the composition (or compound) can be appropriately adjusted. In one or more embodiments, based on the solid content of the composition or compound (hereinafter, the solid content can be the solid content of the composition or the solid content of the compound), the amount of semiconductor nanoparticles in the composition (or compound) can be greater than or equal to about 1wt%, for example, greater than or equal to about 2wt%, greater than or equal to about 3wt%, greater than or equal to about 4wt%, greater than or equal to about 5wt%, greater than or equal to about 6wt%, greater than or equal to about 7wt%, greater than or equal to about 8wt%, greater than or equal to about 9wt%, greater than or equal to about 10wt%, greater than or equal to about 15wt%, greater than or equal to about 20wt%, greater than or equal to about 25wt%, greater than or equal to about 30wt%, greater than or equal to about 35wt%, or greater than or equal to about 40wt%. Based on the solid content of the composition or composite, the amount of semiconductor nanoparticles can be less than or equal to about 70wt%, for example, less than or equal to about 65wt%, less than or equal to about 60wt%, less than or equal to about 55wt%, or less than or equal to about 50wt%. The weight percentage of a given component relative to the total solid content in the composition can represent the amount of a given component in the composite described herein.

[0227] In one or more embodiments, the ink composition may be a photoresist composition containing semiconductor nanoparticles applicable to photolithography. In one or more embodiments, the ink composition may be a composition containing semiconductor nanoparticles capable of providing a pattern in a printing manner (e.g., a droplet discharge method, such as inkjet printing). The composition according to one or more embodiments may not include a conjugated (or conductive) polymer (except for the cardo adhesive described herein). The composition according to one or more embodiments may include a conjugated polymer. Here, a conjugated polymer refers to a polymer having conjugated double bonds in the main chain (e.g., polyphenylene vinylene, etc.).

[0228] In the composition according to one or more embodiments, the dispersant can ensure the dispersibility of the semiconductor nanoparticles. In one or more embodiments, the dispersant can be a binder (or a binder polymer). The binder can (for example, in a repeating unit) include a carboxylic acid group. The binder can be an insulating polymer. The binder can be a compound (monomer or polymer) containing a carboxylic acid group.

[0229] In the composition (or composite), the content of the dispersant may be greater than or equal to about 0.5 wt %, for example, greater than or equal to about 1 wt %, greater than or equal to about 5 wt %, greater than or equal to about 10 wt %, greater than or equal to about 15 wt %, or greater than or equal to about 20 wt %, based on the total solid content of the composition (or composite). The content of the dispersant may be less than or equal to about 55 wt %, less than or equal to about 35 wt %, less than or equal to about 33 wt %, or less than or equal to about 30 wt %, based on the total solid content of the composition (or composite).

[0230] In the composition (or liquid carrier), the liquid monomer or polymerizable (eg, photopolymerizable) monomer (hereinafter referred to as monomer) containing a carbon-carbon double bond may include (eg, photopolymerizable) (meth)acryloyl-containing monomers. The monomer may be a precursor of an insulating polymer.

[0231] Based on the total weight of the composition, the content of the (photopolymerizable) monomer may be greater than or equal to about 0.5 wt%, for example, greater than or equal to about 1 wt%, greater than or equal to about 2 wt%, greater than or equal to about 3 wt%, greater than or equal to about 5 wt%, or greater than or equal to about 10 wt%. Based on the total weight of the composition, the content of the (photopolymerizable) monomer may be less than or equal to about 30 wt%, for example, less than or equal to about 28 wt%, less than or equal to about 25 wt%, less than or equal to about 23 wt%, less than or equal to about 20 wt%, less than or equal to about 18 wt%, less than or equal to about 17 wt%, less than or equal to about 16 wt%, or less than or equal to about 15 wt%.

[0232] The (photo)initiator included in the composition can be used for the (photo)polymerization of the above-mentioned monomers. An initiator is a compound that accelerates a free radical reaction (e.g., free radical polymerization of a monomer) by generating free radical chemicals under mild conditions (e.g., by heat or light). The initiator can be a thermal initiator or a photoinitiator. The initiator is not particularly limited and can be appropriately selected.

[0233] In the composition, the content of the initiator can be appropriately adjusted in consideration of the type and content of the polymerizable monomer. In one or more embodiments, based on the gross weight (or gross weight of the solid content) of the composition, the content of the initiator can be greater than or equal to about 0.01wt% (e.g., greater than or equal to about 1wt%) and less than or equal to about 10wt% (e.g., less than or equal to about 9wt%, less than or equal to about 8wt%, less than or equal to about 7wt%, less than or equal to about 6wt%, or less than or equal to about 5wt%), but is not limited thereto.

[0234] The composition (or composite) may also include a (poly or mono)thiol compound, metal oxide fine particles, or a combination thereof, wherein the (poly or mono)thiol compound has at least one thiol group at, for example, a terminal (or a portion derived therefrom, such as a portion produced by a reaction between a thiol and a carbon-carbon double bond, such as a thioether group).

[0235] The metal oxide fine particles may include TiO 2 、SiO 2 、BaTiO 3 , Ba 2 TiO 4 , ZnO or a combination thereof. In the composition (or composite), based on the total solid content, the content of the metal oxide fine particles may be greater than or equal to about 1 wt%, greater than or equal to about 2 wt%, greater than or equal to about 3 wt%, greater than or equal to about 5 wt%, or greater than or equal to about 10 wt% and less than or equal to about 50 wt%, less than or equal to about 40 wt%, less than or equal to about 30 wt%, less than or equal to about 25 wt%, less than or equal to about 20 wt%, less than or equal to about 15 wt%, less than or equal to about 10 wt%, less than or equal to about 7 wt%, less than or equal to about 5 wt%, or less than or equal to about 3 wt%.

[0236] The diameter of the metal oxide fine particles is not particularly limited and can be appropriately selected. The diameter of the metal oxide fine particles can be greater than or equal to about 100 nm (e.g., greater than or equal to about 150 nm, or greater than or equal to about 200 nm) and less than or equal to about 1000 nm, or less than or equal to about 800 nm.

[0237] The polythiol compound can be a dithiol compound, a trithiol compound, a tetrathiol compound, or a combination thereof. For example, the thiol compound can be ethylene glycol bis(3-mercaptopropionate), ethylene glycol dimercaptoacetate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), 1,6-hexanedithiol, 1,3-propanedithiol, 1,2-ethanedithiol, polyethylene glycol dithiol containing 1 to 10 ethylene glycol repeating units, or a combination thereof.

[0238] In the composition (or composite), the amount of the thiol compound (or a moiety derived therefrom) may be less than or equal to about 50 wt%, less than or equal to about 40 wt%, less than or equal to about 30 wt%, less than or equal to about 20 wt%, less than or equal to about 10 wt%, less than or equal to about 9 wt%, less than or equal to about 8 wt%, less than or equal to about 7 wt%, less than or equal to about 6 wt%, or less than or equal to about 5 wt%, based on the total solid content. The content of the thiol compound may be greater than or equal to about 0.1 wt%, for example, greater than or equal to about 0.5 wt%, greater than or equal to about 1 wt%, greater than or equal to about 5 wt%, greater than or equal to about 10 wt%, greater than or equal to about 15 wt%, greater than or equal to about 18 wt%, or greater than or equal to about 20 wt%, based on the total solid content.

[0239] The composition or liquid carrier may include an organic solvent. In certain embodiments, the composition or liquid carrier may not include an organic solvent. If present, the type of organic solvent that can be used is not particularly limited. Taking into account the above-mentioned main components (i.e., semiconductor nanoparticles, dispersants, polymerizable monomers, initiators, thiol compounds, etc., if present) and the type and amount of other additives described herein, the type and amount of the organic solvent are appropriately determined. In addition to the (non-volatile) solid of the desired content, the composition may include a residual amount of solvent. In one or more embodiments, examples of organic solvents may be: glycols, such as ethylene glycol, diethylene glycol, polyethylene glycol, etc.; glycol ether solvents, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, etc.; glycol ether acetate solvents, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.; propylene glycol solvents, such as propylene glycol, etc.; propylene glycol ether solvents, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, etc.; propylene glycol ether acetate solvents, such as propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, etc. ; amide solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc.; ketone solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, etc.; petroleum solvents such as toluene, xylene, solvent naphtha, etc.; ester solvents such as ethyl acetate, butyl acetate, ethyl lactate, ethyl 3-ethoxypropionate, etc.; ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, etc.; chloroform, C1 to C40 aliphatic hydrocarbon solvents (e.g., alkanes, olefins or alkynes), halogen (e.g., chlorine) substituted C1 to C40 aliphatic hydrocarbon solvents (e.g., dichloroethane, chloroform, etc.), C6 to C40 aromatic hydrocarbon solvents (e.g., toluene, xylene, etc.), halogen (e.g., chlorine) substituted C6 to C40 aromatic hydrocarbon solvents; or combinations thereof.

[0240] In addition to the above components, the composition (or composite) of one or more embodiments may further include additives such as light diffusers, leveling agents, coupling agents, or combinations thereof. The components (adhesives, monomers, solvents, additives, thiol compounds, cardo adhesives, etc.) included in the composition of one or more embodiments may be appropriately selected, and for specific details thereof, reference may be made to, for example, US-2017-0052444-A1, the entire contents of which are incorporated herein.

[0241] In the preparation of the composition according to the embodiment, each of the above components may be prepared sequentially or mixed simultaneously, and the order thereof is not particularly limited.

[0242] The composition can provide a color conversion layer (or a patterned film of the composite) by (eg, free radical) polymerization. The color conversion layer (or a patterned film of the composite) can be prepared using a photoresist composition. Figure 1A The method may include: forming a film of the above-mentioned composition on a substrate (S1); pre-baking the film as selected (S2); exposing selected areas of the film to light (EXP) (e.g., having a wavelength less than or equal to about 400 nm) (S3); and developing the exposed film with an alkaline developing solution (DEV) to obtain a pattern of the composite (S4).

[0243] Reference Figure 1A , the above composition can be applied to a predetermined thickness on a substrate using an appropriate method (such as spin coating or slit coating) to form a film. The formed film can optionally be subjected to a pre-baking (PRB) step. Pre-baking can be performed by selecting appropriate conditions from known conditions such as temperature, time, atmosphere, etc.

[0244] The formed (or optionally pre-baked) film is exposed to light of a predetermined wavelength under a mask having a predetermined pattern. The wavelength and intensity of the light may be selected taking into account the type and content of the photoinitiator, the type and content of the quantum dots (ie, semiconductor nanoparticles), etc.

[0245] Then, the exposed film can be treated (e.g., dipped or sprayed) with an alkaline developing solution to dissolve the unexposed area and obtain the desired pattern. Optionally, the obtained pattern can be subjected to post-exposure baking (POB) at a temperature of, for example, about 150° C. to about 230° C. for a predetermined time (e.g., greater than or equal to about 10 minutes or greater than or equal to about 20 minutes) to improve the crack resistance and solvent resistance of the pattern (S5).

[0246] When the patterned film of the color conversion layer or the composite has a plurality of repeating parts (i.e., color conversion regions), each repeating part can be formed by preparing a plurality of compositions including quantum dots (e.g., red light-emitting quantum dots, green light-emitting quantum dots, or optional blue light-emitting quantum dots) having desired luminescent properties (photoluminescence peak wavelength, etc.), and repeating the above pattern forming process for each composition as needed for a plurality of times (e.g., 2 or more times or 3 or more times), thereby obtaining a composite having a desired pattern (S6). For example, the composite can have a pattern of at least two repeating color regions (e.g., RGB color parts). The composite pattern can be used as a photoluminescent color filter in a display device.

[0247] The patterned film of the color conversion layer or composite can be manufactured using an ink composition configured to form a pattern in an inkjet manner. Figure 1B, such a method may include: preparing an ink composition according to one or more embodiments; providing a substrate (e.g., having a pixel region patterned with an electrode and an optional bank or trench-type partition wall, etc.); and depositing the ink composition on the substrate (or pixel region) to form, for example, a first composite layer (or first region). The method may include depositing the ink composition on the substrate (or pixel region) to form, for example, a second composite layer (or second region). The formation of the first composite layer and the formation of the second composite layer may be performed simultaneously or sequentially.

[0248] The deposition of the ink composition can be performed using a suitable liquid crystal emitter (e.g., an inkjet or nozzle printing system (having an ink reservoir and at least one print head). The deposited ink composition can provide a (first or second) composite layer (e.g., a first quantum dot layer or a second quantum dot layer) by removing the solvent through heating and performing polymerization. The method can provide a highly accurate composite film or patterned film in a short time by a simple method.

[0249] In the composite of one or more embodiments (e.g., the first composite), the (polymer) matrix may include the components described herein with respect to the composition. In the composite, the amount of the (polymer) matrix may be greater than or equal to about 10 wt%, greater than or equal to about 20 wt%, greater than or equal to about 30 wt%, greater than or equal to about 40 wt%, greater than or equal to about 50 wt%, or greater than or equal to about 60 wt%, based on the total weight of the composite. The amount of the (polymer) matrix may be less than or equal to about 95 wt%, less than or equal to about 90 wt%, less than or equal to about 80 wt%, less than or equal to about 70 wt%, less than or equal to about 60 wt%, or less than or equal to about 50 wt%, based on the total weight of the composite.

[0250] The (polymer) matrix may include at least one of a dispersant (e.g., a binder polymer containing a carboxylic acid group), a polymerization product of a polymerizable monomer containing (at least one, such as at least two, at least three, at least four, or at least five) carbon-carbon double bonds (e.g., an insulating polymer), and a polymerization product of a polymerizable monomer and a polythiol compound having at least two thiol groups at the end. The (polymer) matrix may include a linear polymer, a cross-linked polymer, or a combination thereof. The (polymer) matrix may not include a conjugated polymer (except for cardo resin). The (polymer) matrix may include a conjugated polymer.

[0251] The cross-linked polymer may include a thiol-ene resin, a cross-linked poly(meth)acrylate, a cross-linked polyurethane, a cross-linked epoxy resin, a cross-linked vinyl polymer, a cross-linked silicone resin, or a combination thereof. In one or more embodiments, the cross-linked polymer may be a polymerization product of the above-mentioned polymerizable monomer and an optional polythiol compound.

[0252] The linear polymer may include repeating units derived from carbon-carbon unsaturated bonds (e.g., carbon-carbon double bonds). The repeating units may include carboxylic acid groups. The linear polymer may include ethylene repeating units.

[0253] The repeating unit including a carboxylic acid group may include a unit derived from a monomer including a carboxylic acid group and a carbon-carbon double bond, a unit derived from a monomer having a dianhydride moiety, or a combination thereof.

[0254] The (polymer) matrix may include a compound (eg, a binder, a binder polymer or a dispersant) comprising a carboxylic acid group (eg, for dispersing semiconductor nanoparticles or a binder).

[0255] The thickness of the composite (or its film or pattern) can be, for example, less than or equal to about 25 μm, less than or equal to about 20 μm, less than or equal to about 15 μm, less than or equal to about 10 μm, less than or equal to about 8 μm, or less than or equal to about 7 μm and greater than or equal to about 2 μm (for example, greater than or equal to about 3 μm, greater than or equal to about 3.5 μm, greater than or equal to about 4 μm, greater than or equal to about 5 μm, greater than or equal to about 6 μm, greater than or equal to about 7 μm, greater than or equal to about 8 μm, greater than or equal to about 9 μm, or greater than or equal to about 10 μm).

[0256] The semiconductor nanoparticles, the composite (pattern) containing the semiconductor nanoparticles, or the color conversion panel containing the composite (pattern) may be included in an electronic device. Such an electronic device may include a display device, a light emitting diode (LED), an organic light emitting diode (OLED), a quantum dot LED, a sensor, a solar cell, an image sensor, a photodetector, or a liquid crystal display device, but the embodiment is not limited thereto. The quantum dots may be included in an electronic device. Such an electronic device may include a portable terminal device, a monitor, a notebook PC, a television, an electronic sign, a camera, a car, etc., but the embodiment is not limited thereto. The electronic device may be a portable terminal device, a monitor, a notebook PC, or a television including a display device (or a light emitting device) containing quantum dots. The electronic device may be a camera or a mobile terminal device including an image sensor including quantum dots. The electronic device may be a camera or a vehicle including a photodetector including quantum dots.

[0257] Embodiments provide a color conversion layer (e.g., a color conversion structure or a color conversion panel) including a color conversion region, the color conversion region including semiconductor nanoparticles described herein. The color conversion panel includes a color conversion layer, the color conversion layer including a color conversion region and an optional partition wall 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 the color conversion panel of an embodiment, the composite may be in the form of a patterned film. In another embodiment, the composite may have the form of a sheet.

[0258] The color conversion panel of an embodiment may include a color conversion layer, the color conversion layer including a color conversion region and an optional partition wall defining each region of the color conversion layer. The color conversion region may include a first region corresponding to a first pixel. The first region includes a first composite, the first composite includes a matrix and semiconductor nanoparticles dispersed in the matrix, and is configured to emit a first light. An embodiment provides a semiconductor nanoparticle or a group of semiconductor nanoparticles.

[0259] The color conversion layer (eg, color conversion structure) may include the composite according to one or more embodiments or a patterned film thereof. Figure 2A is a schematic cross-sectional view of a color conversion panel according to one or more embodiments. Figure 2A The color conversion panel may also optionally include partition walls (eg, a black matrix BM, a bank, or a combination thereof) that define each region of the color conversion layer (eg, the color conversion structure). Figure 2B An electronic device (display device) including a color conversion panel and a light source according to another embodiment is shown. In the electronic device of one or more embodiments, the color conversion panel including the color conversion layer or the color conversion structure is disposed on an on-chip LED (e.g., an on-chip micro-LED). Figure 2B , a circuit (Si driver IC) configured to drive a light source can be disposed below a light source (e.g., a blue LED) configured to emit incident light (e.g., blue light). The color conversion layer may include a first composite comprising first semiconductor nanoparticles emitting a first light (e.g., green light) and a second composite comprising second semiconductor nanoparticles emitting a second light (e.g., red light), or may include a third composite that emits a third light (e.g., incident light or blue light) or allows a third light (e.g., incident light or blue light) to pass through. A partition wall PW (e.g., comprising an inorganic material such as silicon or silicon oxide or based on an organic material) may be disposed between the respective composites. The partition wall may include a groove hole, a via hole, or a combination thereof. A first optical element (e.g., an absorptive color filter) may be disposed on a light extraction surface of the color conversion layer. Additional optical elements such as microlenses may be further disposed on the first optical element.

[0260] The color conversion region (e.g., by irradiation with incident light) includes a first region configured to emit the above-mentioned first light (or green light). In one or more embodiments, the first region may correspond to a green pixel. The first region includes a first composite (e.g., a light-emitting composite). The first light may have a peak emission wavelength within a wavelength range described later. The first light will be described in more detail for the semiconductor nanoparticles described herein. The peak emission wavelength of the green light may be greater than or equal to about 500nm, greater than or equal to about 501nm, greater than or equal to about 504nm, greater than or equal to about 505nm, or greater than or equal to about 520nm. The peak emission wavelength of the green light may be less than or equal to about 580nm, less than or equal to about 560nm, less than or equal to about 550nm, less than or equal to about 530nm, less than or equal to about 525nm, less than or equal to about 520nm, less than or equal to about 515nm, or less than or equal to about 510nm.

[0261] The color conversion region may also include (e.g., one or more) second regions configured to emit a second light (e.g., red light) different from the first light (e.g., by irradiation with excitation light). The second region may include a second composite. The second composite in the second region may include semiconductor nanoparticles (e.g., quantum dots) configured to emit light of a different wavelength (e.g., a different color) than the first composite disposed in the first region.

[0262] The second light may be red light having a peak emission wavelength of about 600 nm to about 650 nm (e.g., about 620 nm to about 650 nm). The color conversion panel may further include (one or more) third regions that emit a third light (e.g., blue light) that is different from the first light and the second light or that allow a third light (e.g., blue light) that is different from the first light and the second light to pass through. The incident light may include a third light (e.g., blue light and optionally green light). The third light may include a blue light having a peak emission wavelength greater than or equal to about 380 nm (e.g., greater than or equal to about 440 nm, greater than or equal to about 445 nm, greater than or equal to about 450 nm, or greater than or equal to about 455 nm) and less than or equal to about 480 nm (e.g., less than or equal to about 475 nm, less than or equal to about 470 nm, less than or equal to about 465 nm, or less than or equal to about 460 nm).

[0263] In one or more embodiments, the color conversion panel or color conversion layer may include a plurality of first regions, and the composite may constitute a predetermined pattern to be respectively arranged in the first regions of the color conversion panel. The composite (or its pattern) may be prepared from the (ink) composition by any method (e.g., photolithography or inkjet printing). Therefore, one or more embodiments relate to a composition including semiconductor nanoparticles, which is further described in detail herein.

[0264] In one or more embodiments, the electronic device or display device (eg, display panel) may further include a color conversion layer (or color conversion panel) and an optional light source (see Figure 3A and Figure 3B ). The light source may provide incident light to the color conversion layer or the color conversion panel. In one or more embodiments, the display panel 1000 includes a light emitting panel 40 (or a light source), the color conversion panel 50, and a light transmission layer 70 located between the light emitting panel 40 and the color conversion panel 50. The color conversion panel may include a substrate, and the color conversion layer may be disposed on the substrate.

[0265] When present, the light source or light emitting panel can provide incident light to the color conversion layer or color conversion panel. The peak emission wavelength of the incident light can be greater than or equal to about 440 nm (e.g., greater than or equal to about 450 nm) and less than or equal to about 580 nm (e.g., less than or equal to about 480 nm, less than or equal to about 470 nm, or less than or equal to about 460 nm).

[0266] In one or more embodiments, an electronic device (eg, a photoluminescent device) may also include a sheet of the composite. Figure 3B , the device may include a backlight unit (including a light source) and a liquid crystal panel LC, wherein the backlight unit may include a quantum dot polymer composite sheet (QD sheet). Specifically, the backlight unit may have a structure in which a reflector, a light guide plate (LGP), a light source (blue LED, etc.), a quantum dot polymer composite sheet (QD sheet) and an optical film (prism, dual brightness enhancement film (DBEF), etc.) may be stacked. The liquid crystal panel may be disposed on the backlight unit and have a structure including a thin film transistor (TFT), a liquid crystal (LC) and a color filter between two polarizers (Pol). The quantum dot polymer composite sheet (QD sheet) may include semiconductor nanoparticles (e.g., quantum dots) that emit red and green light after absorbing light from the light source. The blue light provided from the light source may be combined with the red and green light emitted from each semiconductor nanoparticle while passing through the quantum dot polymer composite sheet, and converted into white light. For each pixel, the white light may be divided into blue light, green light and red light by the color filter in the liquid crystal panel, and then emitted to the outside. Reference Figure 4, a backlight unit (BLU) may be a direct-type BLU without a light guide plate, and may include a plurality of LEDs (eg, mini LEDs).

[0267] The color conversion panel may include a substrate, and the color conversion layer may be disposed on the substrate. The color conversion layer or the color conversion panel may include a patterned film of a composite. The patterned film may include a repeating portion configured to emit light of a desired wavelength. The repeating portion may include a second region. The second region may be a red light emitting portion. The repeating portion may include a first region. The first region may be a green light emitting portion. The repeating portion may include a third region. The third region may include a portion that emits or transmits blue light. The details of the first region, the second region, and the third region are as described herein.

[0268] The light emitting panel or light source may be an element that emits incident light (e.g., excitation light). The incident light may include blue light and optionally green light. The light source may include an LED. The light source may include an organic LED (OLED). The light source may include a micro LED. On the front surface (light emitting surface) of the first region and the second region, an optical element (e.g., a blue light (and optionally green light) blocking layer or a first filter) that blocks (e.g., reflects or absorbs) blue light (and optionally green light) as described herein may be provided. In one or more embodiments, the light source may include an organic light emitting diode that emits blue light and an organic light emitting diode that emits green light, and a green light removal filter may be further provided in a third region that transmits blue light.

[0269] The light emitting panel or light source may include a plurality of light emitting units corresponding to the first region and the second region, respectively, and the light emitting unit may include a first electrode and a second electrode facing each other and an (organic) electroluminescent layer disposed between the first electrode and the second electrode. The electroluminescent layer may include an organic light emitting material. For example, each light emitting unit of the light source may include an electroluminescent device (e.g., an organic light emitting diode (OLED)) configured to emit light of a predetermined wavelength (e.g., blue light, green light, or a combination thereof). The structure and material of the electroluminescent device or the organic light emitting diode (OLED) are not particularly limited.

[0270] Hereinafter, a display panel and a color conversion panel will be described in more detail with reference to the accompanying drawings.

[0271] Reference Figure 3A and Figure 3C, the display panel 1000 according to one or more embodiments includes a light emitting panel 40 and a color conversion panel 50. The display panel or electronic device may further include a light transmission layer 60 disposed between the light emitting panel 40 and the color conversion panel 50 and an adhesive material 70 for bonding the light emitting panel 40 and the color conversion panel 50. The light transmission layer may include a passivation layer, a filling material, an encapsulation layer, or a combination thereof (not shown). The material for the light transmission layer may be appropriately selected without particular limitation. The material for the light transmission layer may be an inorganic material, an organic material, an organic / inorganic hybrid material, or a combination thereof.

[0272] The light emitting panel 40 and the color conversion panel 50 each have surfaces facing each other (i.e., the two respective panels face each other) and a light transmission layer (or light transmission panel) 60 is provided between the two panels. The color conversion panel 50 is provided in a direction such that, for example, light emitted from the light emitting panel 40 irradiates the light transmission layer 60. An adhesive material 70 is provided along the edges of the light emitting panel 40 and the color conversion panel 50, and may be, for example, a sealing material.

[0273] Figure 5A is a plan view of one or more embodiments of a pixel arrangement of a display panel. Figure 5A , the display panel 1000 includes a display area 1000D that displays an image and a non-display area 1000P that is located in a peripheral area of ​​the display area 1000D and is provided with an adhesive material.

[0274] The display region 1000D includes a plurality of pixels PX arranged along rows (eg, x direction) and columns (eg, y direction), and each representative pixel PX may include a plurality of sub-pixels PX representing (eg, displaying) colors different from each other. 1 , PX 2 and PX 3 One or more embodiments are shown in which three sub-pixels PX 1 , PX 2 and PX 3 The structure is configured to provide one pixel. One or more embodiments may also include additional sub-pixels such as white sub-pixels, and may also include, for example, at least one sub-pixel that exhibits (e.g., displays) the same color. The plurality of pixels PX may be aligned, for example, in a Bayer matrix, a matrix sold under the trade name PenTile, a diamond matrix, etc., or a combination thereof.

[0275] Sub-pixel PX 1 , PX 2 and PX 3 The first subpixel PX may represent (eg, display) three primary colors or a combination of three primary colors, for example, red, green, blue, or a combination thereof.1 can represent (eg, display) red, and the second sub-pixel PX 2 The green color may be expressed (eg, displayed), and the third sub-pixel PX 3 The blue color may be represented (eg, displayed).

[0276] In the drawings, all sub-pixels are shown as having the same size, but this is not limited thereto, and at least one of the sub-pixels may be larger or smaller than the other sub-pixels. In the drawings, all sub-pixels are shown as having the same shape, but this is not limited thereto, and at least one of the sub-pixels may have a shape different from that of the other sub-pixels.

[0277] In a display panel or electronic device according to one or more embodiments, the light emitting panel may include a substrate and a TFT (eg, a TFT including oxide, etc.) disposed on the substrate. A light emitting device (eg, having a tandem structure, etc.) may be disposed on the TFT.

[0278] The light emitting device may include a light emitting layer (e.g., a blue light emitting layer, a green light emitting layer, or a combination thereof) between a first electrode and a second electrode facing each other. A charge generating layer may be disposed between each light emitting layer. Each of the first electrode and the second electrode may be patterned into a plurality of electrode elements corresponding to a pixel. The first electrode may be an anode or a cathode. The second electrode may be a cathode or an anode.

[0279] The light emitting device may include an organic LED, a nanorod LED, a mini LED, a micro LED, or a combination thereof.

[0280] FIG. 5B to FIG. 5E They are cross-sectional views showing examples of light-emitting devices. In an embodiment, the size of the "micro LED" may be greater than or equal to about 100 microns, greater than or equal to about 150 microns, greater than or equal to about 200 microns and less than or equal to about 1 mm, less than or equal to about 0.5 mm, less than or equal to about 0.15 mm, or less than or equal to about 0.12 mm, but is not limited thereto. In an embodiment, the size of the "micro LED" may be less than or equal to about 100 microns, less than or equal to about 50 microns, or less than or equal to about 10 microns. The size of the micro LED may be greater than or equal to about 0.1 micron, greater than or equal to about 0.5 micron, greater than or equal to about 1 micron, or greater than or equal to about 5 microns, but is not limited thereto.

[0281] Reference Figure 5BThe light emitting device 180 may include: a first electrode 181 and a second electrode 182 facing each other; a light emitting layer 183 located between the first electrode 181 and the second electrode 182; and optional auxiliary layers 184 and 185 located between the first electrode 181 and the light emitting layer 183 and between the second electrode 182 and the light emitting layer 183, respectively.

[0282] The first electrode 181 and the second electrode 182 may be arranged to face each other along the thickness direction (e.g., z direction), and any 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 light-transmitting electrode, a semi-transparent electrode, or a reflective electrode, and the second electrode 182 may be a light-transmitting electrode or a semi-transparent electrode. The light-transmitting electrode or the semi-transparent electrode may be made of, for example, a thin single-layer or multi-layer metal film, the metal film including: a conductive metal oxide (such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), fluorine-doped tin oxide (FTO), etc.); or silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), magnesium-silver (Mg-Ag), magnesium-aluminum (Mg-Al), or a combination thereof. The reflective electrode may include a metal, a metal nitride, or a combination thereof, such as silver (Ag), copper (Cu), aluminum (Al), gold (Au), titanium (Ti), chromium (Cr), nickel (Ni), an alloy thereof, a nitride thereof (e.g., Sn), or a combination thereof, but the embodiment is not limited thereto.

[0283] The light emitting layer 183 may include a first light emitting body that emits light having a blue emission spectrum, a second light emitting body that emits light having a green emission spectrum, or a combination thereof.

[0284] The blue emission spectrum may have a peak emission wavelength in a wavelength region greater than or equal to about 400 nm and less than about 500 nm, and within this range, have a peak emission wavelength in a wavelength region of about 410 nm to about 490 nm, about 420 nm to about 480 nm, about 430 nm to about 470 nm, about 440 nm to about 465 nm, about 445 nm to about 460 nm, or about 450 nm to about 458 nm.

[0285] The green emission spectrum may have a peak emission wavelength in a wavelength region greater than or equal to about 500 nm and less than about 590 nm, and within this range, have a peak emission wavelength in a wavelength region of about 510 nm to about 580 nm, about 515 nm to about 570 nm, about 520 nm to about 560 nm, about 525 nm to about 555 nm, about 530 nm to about 550 nm, or about 535 nm to about 545 nm.

[0286] For example, the light-emitting layer 183 or the light-emitting body included therein may include a phosphorescent material, a fluorescent material, or a combination thereof. For example, the light-emitting body may include an organic light-emitting body, wherein the organic light-emitting body may be a low molecular compound, a polymer compound, or a combination thereof. The specific types of phosphorescent materials and fluorescent materials are not particularly limited, but may be appropriately selected from known materials. For example, the light-emitting body may include an inorganic light-emitting body, and the inorganic light-emitting body may be an inorganic semiconductor, a quantum dot, a perovskite, or a combination thereof. The inorganic semiconductor may include a metal nitride, a metal oxide, or a combination thereof. The metal nitride, the metal oxide, or a combination thereof may include a group III metal (such as aluminum, gallium, indium, thallium, etc.), a group IV metal (such as silicon, germanium, tin, etc.), or a combination thereof. In one or more embodiments, the light-emitting body may include an inorganic light-emitting body, and the light-emitting device 180 may be a quantum dot light-emitting diode, a perovskite light-emitting diode, or a micro light-emitting diode (μLED). The material that can be used as an inorganic light-emitting body may be appropriately selected.

[0287] In one or more embodiments, the light emitting device 180 may further include auxiliary layers 184 and 185. The auxiliary layers 184 and 185 may be disposed between the first electrode 181 and the light emitting layer 183 and / or between the second electrode 182 and the light emitting layer 183, respectively. The auxiliary layers 184 and 185 may be charge auxiliary layers for controlling the injection and / or mobility of charges. The auxiliary layers 184 and 185 may include at least one or two layers, and may include, 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. If desired, at least one of the auxiliary layers 184 and 185 may be omitted. The auxiliary layer may be formed of a material appropriately selected from known materials for organic electroluminescent devices, etc.

[0288] Set in sub-pixel PX 1 , PX 2 and PX 3 The light emitting devices 180 in each of the sub-pixels PX may be the same as or different from each other. 1 , PX 2 and PX 3 The light emitting device 180 in each of the sub-pixels PX may emit light having the same or different emission spectra. 1 , PX 2 and PX 3 The light emitting device 180 in each of the sub-pixels PX may emit, for example, light having a blue emission spectrum, light having a green emission spectrum, or a combination thereof. 1 , PX 2 and PX 3 The light emitting devices 180 in each of the may be separated from each other by a pixel defining layer (not shown).

[0289] Reference Figure 5C The light-emitting device 180 may be a light-emitting device having a series structure, and includes: a first electrode 181 and a second electrode 182, facing each other; a first light-emitting layer 183a and a second light-emitting layer 183b, located between the first electrode 181 and the second electrode 182; a charge generation layer 186, located between the first light-emitting layer 183a and the second light-emitting layer 183b; and optional auxiliary layers 184 and 185, respectively located between the first electrode 181 and the first light-emitting layer 183a and / or between the second electrode 182 and the second light-emitting layer 183b.

[0290] Details of the first electrode 181 , the second electrode 182 , and the auxiliary layers 184 and 185 are as described herein.

[0291] 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 or more embodiments, the first light-emitting layer 183a or the second light-emitting layer 183b may emit light having a blue emission spectrum or light having a green emission spectrum, respectively. The charge generation layer 186 may inject charge into the first light-emitting layer 183a and / or the second light-emitting layer 183b, and may control the charge balance between the first light-emitting layer 183a and the second light-emitting layer 183b. The charge generation layer 186 may include, for example, an n-type layer and a p-type layer, and may include, for example, an electron transport material and / or a hole transport material containing an n-type dopant and / or a p-type dopant. The charge generation layer 186 may include one layer or two or more layers.

[0292] Reference Figure 5D The light-emitting device (having a series structure) may include: a first electrode 181 and a second electrode 182, facing each other; a first light-emitting layer 183a, a second light-emitting layer 183b and a third light-emitting layer 183c, located between the first electrode 181 and the second electrode 182; a first charge generation layer 186a, located between the first light-emitting layer 183a and the second light-emitting layer 183b; a second charge generation layer 186b, located between the second light-emitting layer 183b and the third light-emitting layer 183c; and optional auxiliary layers 184 and 185, respectively located between the first electrode 181 and the first light-emitting layer 183a and / or between the second electrode 182 and the third light-emitting layer 183c.

[0293] Details of the first electrode 181 , the second electrode 182 , and the auxiliary layers 184 and 185 are as described herein.

[0294] The first light-emitting layer 183a, the second light-emitting layer 183b, and the third light-emitting layer 183c may emit light having the same or different emission spectra. The first light-emitting layer 183a, the second light-emitting layer 183b, and the third light-emitting layer 183c may emit blue light. In one or more embodiments, the first light-emitting layer 183a and the third light-emitting layer 183c may emit light of a blue emission spectrum, and the second light-emitting layer 183b may emit light of a green emission spectrum. In another embodiment, the first light-emitting layer 183a and the third light-emitting layer 183c may emit light of a green emission spectrum, and the second light-emitting layer 183b may emit light of a blue emission spectrum.

[0295] The first charge generation layer 186a can inject charges into the first light-emitting layer 183a and / or the second light-emitting layer 183b, and can control the charge balance between the first light-emitting layer 183a and the second light-emitting layer 183b. The second charge generation layer 186b can inject charges into the second light-emitting layer 183b and / or the third light-emitting layer 183c, and can control the charge balance between the second light-emitting layer 183b and the third light-emitting layer 183c. Each of the first charge generation layer 186a and the second charge generation layer 186b can include one layer or two or more layers, respectively.

[0296] Reference Figure 5E In one or more embodiments, the light emitting device 180 includes a light emitting layer 183 , a first electrode 181 , a second electrode 182 , and a plurality of nanostructures 187 arranged in the light emitting layer 183 .

[0297] One of the first electrode 181 and the second electrode 182 may be an anode, and the other may be a cathode. The first electrode 181 and the second electrode 182 may be electrodes patterned according to the arrangement direction of the plurality of nanostructures 187, and may include, for example: a conductive oxide (such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), fluorine-doped tin oxide (FTO), etc.); silver (Ag), copper (Cu), aluminum (Al), gold (Au), titanium (Ti), chromium (Cr), nickel (Ni), their alloys, their nitrides (e.g., TiN); or a combination thereof, but the embodiment is not limited thereto.

[0298] The light emitting layer 183 may include a plurality of nanostructures 187, and the sub-pixel PX 1 , PX 2 and PX 3Each of the nanostructures 187 may include a plurality of nanostructures 187. In one or more embodiments, a plurality of nanostructures 187 may be arranged in one direction, but the embodiment is not limited thereto. The nanostructure 187 may be a semiconductor containing a compound configured to emit light of a predetermined wavelength, for example, by applying an electric current, and may be, for example, a linear nanostructure (such as a nanorod or a nanoneedle). The diameter or long diameter of the nanostructure 187 may be, for example, a few nanometers to several hundred nanometers, and the aspect ratio of the nanostructure 187 may be greater than or equal to about 1, greater than or equal to about 1.5, greater than or equal to about 2.0, greater than or equal to about 3.0, greater than or equal to about 4.0, greater than or equal to about 4.5, or greater than or equal to about 5.0 and less than or equal to about 20, which may be about 1.5 to about 20, about 2.0 to about 20, about 3.0 to about 20, about 4.0 to about 20, about 4.5 to about 20, or about 5.0 to about 20.

[0299] Each nanostructure 187 may include a p-type region 187p, an n-type region 187n, and a plurality of quantum well regions 187i, and may be configured to emit light from the plurality of quantum well regions 187i. The nanostructure 187 may include, for example, gallium nitride (GaN), indium gallium nitride (InGaN), aluminum gallium nitride (AlGaN), or a combination thereof, and may have, for example, a core-shell structure.

[0300] Multiple nanostructures 187 can all emit light having the same or different emission spectra. In one or more embodiments, the nanostructures can emit light having a blue emission spectrum (e.g., light having a blue emission spectrum having a peak emission wavelength in a wavelength range of greater than or equal to about 400 nm to less than 500 nm, about 410 nm to about 490 nm, or about 420 nm to about 480 nm).

[0301] Figure 6 is a schematic cross-sectional view of a device (or display panel) according to one or more embodiments. Figure 6, the light source (or light emitting panel) may include an organic light emitting diode that emits blue light (B) (and optionally green light (G)). The organic light emitting diode (OLED) may include at least two pixel electrodes 90a, 90b, 90c formed on a substrate 100, a pixel defining layer 150a, 150b formed between adjacent pixel electrodes 90a, 90b, 90c, an organic light emitting layer 140a, 140b, 140c formed on each pixel electrode 90a, 90b, 90c, and a common electrode layer 130 formed on the organic light emitting layer 140a, 140b, 140c. A thin film transistor (TFT) and a substrate not shown may be disposed below the organic light emitting diode (OLED). The pixel regions of the OLED may be disposed corresponding to the first region, the second region, and the third region described herein. In one or more embodiments, the color conversion panel and the light emitting panel may be separated, such as Figure 6 In one or more embodiments, the color conversion panel can be stacked directly on the light emitting panel.

[0302] A stacked structure including a light-emitting nanostructure composite pattern 170 (e.g., a first region 11 or R including a light-emitting nanostructure emitting red light, a second region 21 or G including a light-emitting nanostructure emitting green light, and a third region 31 or B including or not including a light-emitting nanostructure (e.g., a light-emitting nanostructure emitting blue light)) and a substrate 240 may be disposed on a light source. Blue light emitted from the light source enters the first region and the second region, and may emit red light and green light, respectively. Blue light emitted from the light source may pass through the third region. If desired, an element configured to block excitation light (a first filter 160 or an excitation light blocking layer) may be disposed between the light-emitting nanostructure composite layers R and G and the substrate. In one or more embodiments, the excitation light includes blue light and green light, and a green light blocking filter (not shown) may be added to the third region. The first filter or the excitation light blocking layer will be described in more detail herein.

[0303] Such a (display) device can be manufactured by separately preparing the above-mentioned stacked structure and (eg, blue-emitting) LED or OLED, and then combining the stacked structure and LED or OLED. The (display) device can be manufactured by directly forming a light-emitting nanostructure composite pattern on an LED or OLED.

[0304] In the color conversion panel or display device, the substrate may be a substrate including an insulating material. The substrate may include: glass; polymers, polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc., polycarbonate, or polyacrylate; polysiloxanes (e.g., PDMS); inorganic materials such as Al 2 O 3, ZnO, etc.; or a combination thereof, but the embodiment is not limited thereto. Considering the substrate material, the thickness of the substrate can be appropriately selected, but is not particularly limited. The substrate can be flexible. For light emitted from the semiconductor nanoparticles, the substrate can have a transmittance greater than or equal to about 50%, greater than or equal to about 60%, greater than or equal to about 70%, greater than or equal to about 80%, or greater than or equal to about 90%.

[0305] A wiring layer including a thin film transistor and the like can be formed on a substrate. The wiring layer can also include a gate line, a sustaining voltage line, a gate insulating film, a data line, a source electrode, a drain electrode, a semiconductor layer, a protective layer, and the like. The detailed structure of the wiring layer can vary according to one or more embodiments. The gate line and the sustaining voltage line can be electrically separated from each other, and the data line can be insulated and crossed with the gate line and the sustaining voltage line. The gate electrode, the source electrode, and the drain electrode can form a control terminal, an input terminal, and an output terminal of the thin film transistor, respectively. The drain electrode can be electrically connected to the pixel electrode to be described herein.

[0306] The pixel electrode may be used as an electrode (e.g., an anode) of a display device. The pixel electrode may be formed of a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO). The pixel electrode may be formed of a material having a light blocking property such as gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), or titanium (Ti). The pixel electrode may have a double-layer structure in which a transparent conductive material and a material having a light blocking property are sequentially stacked.

[0307] Between two adjacent pixel electrodes, a pixel defining layer (PDL) may overlap ends of the pixel electrodes to divide the pixel electrodes into pixel units. The pixel defining layer is an insulating layer that may electrically block at least two pixel electrodes.

[0308] The pixel defining layer may cover a portion of the upper surface of the pixel electrode, and a remaining area of ​​the pixel electrode not covered by the pixel defining layer may provide an opening. The organic light emitting layer to be described herein may be formed in an area defined by the opening.

[0309] The organic light-emitting layer may define each pixel region by the above-mentioned pixel electrode and pixel defining layer. In other words, one pixel region may be defined as a region in which an organic light-emitting unit layer is formed, and the organic light-emitting unit layer is in contact with one pixel electrode divided by the pixel defining layer. In a display device according to one or more embodiments, the organic light-emitting layer may be defined as a first pixel region, a second pixel region, and a third pixel region, and each pixel region may be spaced apart from each other by a pixel defining layer with a predetermined interval.

[0310] In one or more embodiments, the organic light emitting layer may emit a third light belonging to the visible light region or to the ultraviolet (UV) region. Each of the first pixel region to the third pixel region of the organic light emitting layer may emit a third light. In one or more embodiments, the third light may be light having higher energy in the visible light region, and may be, for example, blue light (and optionally green light). In one or more embodiments, all pixel regions of the organic light emitting layer are designed to emit the same light, and each pixel region of the organic light emitting layer may be formed of the same or similar material, or may exhibit the same or similar properties. Therefore, the process of forming the organic light emitting layer may be simplified, and the display device may be easily applied to large-scale / large-area processes (e.g., manufactured by large-scale / large-area processes). However, the organic light emitting layer according to one or more embodiments is not necessarily limited thereto, but the organic light emitting layer may be designed to emit at least two different lights (e.g., at least two different colors of light).

[0311] The organic light emitting layer includes an organic light emitting unit layer in each pixel region, and each organic light emitting unit layer may further include an auxiliary layer (eg, a hole injection layer, a hole transport layer, an electron transport layer, etc.) in addition to the light emitting layer.

[0312] The common electrode may be used as a cathode of a display device. The common electrode may be formed of a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO). The common electrode may be formed on the organic light emitting layer and may be integrated with the organic light emitting layer.

[0313] A planarization layer or a passivation layer (not shown) may be formed on the common electrode. The planarization layer may include an (eg, transparent) insulating material to ensure electrical insulation from the common electrode.

[0314] In one or more embodiments, the display device may further include a lower substrate, a stacked structure disposed below the lower substrate, and a liquid crystal layer disposed between the stacked structure and the lower substrate, and in the stacked structure, the photoluminescent layer (i.e., the light-emitting layer) may be disposed to face the liquid crystal layer. The display device may further include a polarizing plate located between the liquid crystal layer and the light-emitting layer. The light source may further include an LED, and if desired, a light guide plate may further be included.

[0315] In one or more embodiments, a display device (eg, a liquid crystal display device) is illustrated with reference to the accompanying drawings. Fig. 7A 1 is a schematic cross-sectional view showing a liquid crystal display device according to one or more embodiments. Fig. 7A , the display device of one or more embodiments includes a liquid crystal panel 200 , a polarizing plate 300 disposed under the liquid crystal panel 200 , and a backlight unit disposed under the polarizing plate 300 .

[0316] The liquid crystal panel 200 may include a lower substrate 210, a stacked structure, and a liquid crystal layer 220 disposed between the stacked structure and the lower substrate. The stacked structure may include a transparent substrate 240, a first filter layer 310, a photoluminescent layer 230 including a pattern of a composite, and a second filter layer 311.

[0317] The lower substrate 210 (also referred to as an array substrate) may be a transparent insulating material substrate. The substrate may be as described herein. A wiring board 211 may be disposed on the upper surface of the lower substrate 210. The wiring board 211 may include a plurality of gate lines (not shown) and data lines (not shown) defining pixel regions, a thin film transistor disposed adjacent to the intersection region of the gate lines and the data lines, and a pixel electrode for each pixel region, but the embodiment is not limited thereto. The details of such a wiring board are not particularly limited.

[0318] The liquid crystal layer 220 may be disposed on the wiring board 211. The liquid crystal panel 200 may include an alignment layer 221 above and below the liquid crystal layer 220 to initially align the liquid crystal material included therein. Details of the liquid crystal layer and the alignment layer (e.g., liquid crystal material, alignment layer material, method of forming the liquid crystal layer, thickness of the liquid crystal layer, etc.) are not particularly limited.

[0319] The lower polarizing plate 300 may be disposed below the lower substrate. The material and structure of the polarizing plate 300 are not particularly limited. A backlight unit (e.g., emitting blue light) may be disposed below the polarizing plate 300. The upper optical element or polarizing plate 300 may be disposed between the liquid crystal layer 220 and the transparent substrate 240, but is not limited thereto. For example, the upper polarizing plate may be disposed between the liquid crystal layer 220 and the photoluminescent layer 230. The polarizing plate may be any polarizing plate that can be used in a liquid crystal display device. The polarizing plate may be triacetyl cellulose (TAC) and have a thickness of less than or equal to about 200 μm, but is not limited thereto. In another embodiment, the upper optical element may be a coating layer that controls the refractive index without a polarization function.

[0320] The backlight unit includes a light source 110. The light source may emit blue light or white light. The light source may include, but is not limited to, a blue LED, a white LED, a white OLED, or a combination thereof.

[0321] The backlight unit may further include a light guide plate 120. In one or more embodiments, the backlight unit may be edge-type. For example, the backlight unit may include a reflector (not shown), a light guide plate (not shown) disposed on the reflector and providing a planar light source to the liquid crystal panel 200, and / or at least one optical sheet (not shown) on the light guide plate (e.g., a diffuser, a prism sheet, etc.), but the present disclosure is not limited thereto. The backlight unit may not include a light guide plate. In one or more embodiments, the backlight unit may be a direct-type lighting. For example, the backlight unit may have a reflector (not shown) and a plurality of fluorescent lamps arranged at regular intervals on the reflector, or may have an LED operating substrate, on which a plurality of light-emitting diodes, a diffuser on a plurality of light-emitting diodes, and optionally at least one optical sheet. The details of such a backlight unit (e.g., components of light-emitting diodes, fluorescent lamps, light guide plates, various optical sheets, and reflectors) are known without particular limitation.

[0322] The black matrix 241 may be disposed below the transparent substrate 240 and have an opening, and hide the gate lines, data lines, and thin film transistors of the wiring board on the lower substrate. For example, the black matrix 241 may have a grid shape. The photoluminescent layer 230 is disposed in the opening of the black matrix 241 and has a composite pattern including a first region R configured to emit a first light (e.g., red light), a second region G configured to emit a second light (e.g., green light), and a third region B configured to emit / transmit a third light (e.g., blue light). If desired, the photoluminescent layer may further include at least one fourth region. The fourth region may include quantum dots that emit light of a different color (e.g., cyan light, magenta light, and yellow light) than the light emitted from the first region to the third region.

[0323] In the photoluminescent layer 230 , a portion where a pattern is formed may be repeated corresponding to a pixel region formed on a lower substrate. A transparent common electrode 231 may be disposed on the photoluminescent layer 230 .

[0324] The third region B configured to emit / transmit blue light may be a transparent color filter that does not change the emission spectrum of the light source. In this case, the blue light emitted from the backlight unit may enter in a polarized state and may be emitted as is through the polarizing plate and the liquid crystal layer. If desired, the third region may include quantum dots that emit blue light.

[0325] As described herein, if desired, the display device or light-emitting device according to one or more embodiments may further include an excitation light blocking layer or a first filter layer (hereinafter, referred to as the first filter layer). The first filter layer may be disposed between the bottom surface of the first region R and the second region G and a substrate (e.g., the upper substrate 240), or may be disposed on the upper surface of the substrate. The first filter layer may be a sheet having an opening in a portion corresponding to the pixel region (third region) displaying blue, and thus may be formed in a portion corresponding to the first region and the second region. That is, as Figure 2A , Figure 2B , Figure 6 and / or Fig. 7A As shown in , the first filter layer may be integrally formed at a position other than the position overlapping the third region, but is not limited thereto. Two or more first filter layers may be spaced apart from each other at positions overlapping the first region, the second region, and the optional third region. When the light source includes a green light emitting device, a green light blocking layer may be provided in the third region.

[0326] The first filter layer may block light of a predetermined wavelength region, for example, in a visible light region, and may transmit light of other wavelength regions, and for example, the first filter layer may block blue light (or green light), and may transmit light other than blue light (or green light). The first filter layer may transmit, for example, green light, red light, and / or yellow light as a mixture of green light and red light. The first filter layer may transmit blue light and block green light, and may be disposed on a blue light-emitting pixel.

[0327] The first filter layer can substantially block the excitation light and transmit light in the desired wavelength region. The transmittance of the first filter layer to light in the desired wavelength range can be greater than or equal to about 70%, greater than or equal to about 80%, greater than or equal to about 90%, or even about 100%.

[0328] The first filter layer configured to selectively transmit red light may be disposed at a position overlapping the red light emitting portion, and the first filter layer configured to selectively transmit green light may be disposed at a position overlapping the green light emitting portion. The first filter layer may include: a first filter region that blocks (e.g., absorbs) blue light and red light and selectively transmits light in a predetermined range (e.g., greater than or equal to about 500 nm, greater than or equal to about 510 nm, or greater than or equal to about 515 nm and less than or equal to about 550 nm, less than or equal to about 545 nm, less than or equal to about 540 nm, less than or equal to about 535 nm, less than or equal to about 530 nm, less than or equal to about 525 nm, or less than or equal to about 520 nm); and a second ... In one or more embodiments, the light source may emit a mixture of blue light and green light, and the first filter layer may further include a third filter region that selectively transmits blue light and blocks green light.

[0329] The first filter region may be disposed at a position overlapping the green light emitting portion. The second filter region may be disposed at a position overlapping the red light emitting portion. The third filter region may be disposed at a position overlapping the blue light emitting portion.

[0330] The first filter region, the second filter region and the optional third filter region may be optically isolated.Such a first filter layer may help to improve the color purity of the display device.

[0331] The display device may further include a second filter layer (e.g., a recycling layer of red / green or yellow light), the second filter layer being disposed between the photoluminescent layer and the liquid crystal layer (e.g., between the photoluminescent layer and the upper polarizer), 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 may be red light, the second light may be green light, and the third light may be blue light. The second filter layer may transmit only the third light (B) in the blue light wavelength region having a wavelength region less than or equal to about 500 nm, and light having a wavelength region greater than about 500 nm such as green light (G), yellow light, red light (R), etc. may not pass through the second filter layer but be reflected. The reflected green light and red light may pass through the first region and the second region and be emitted to the outside of the display device.

[0332] The second filter layer or the first filter layer may be formed as an integral layer having a relatively flat surface.

[0333] The first filter layer may include a polymer film including a dye and / or a pigment that absorbs light of the wavelength to be blocked. The second filter layer or the first filter layer may include a single layer having a low refractive index, and may be, for example, a transparent film having a refractive index of less than or equal to about 1.4, less than or equal to about 1.3, or less than or equal to about 1.2. The second filter layer or the first filter layer having a low refractive index may include, for example, porous silicon oxide, porous organic material, porous organic-inorganic composite, etc., or a combination thereof.

[0334] The first filter layer or the second filter layer may include a plurality of layers having different refractive indices. The first filter layer or the second filter layer may be formed by laminating two layers having different refractive indices. For example, the first filter layer / the second filter layer may be formed by alternately laminating a material having a high refractive index and a material having a low refractive index.

[0335] In one or more embodiments, an electronic device may include a light emitting device (eg, an electroluminescent device) including the semiconductor nanoparticles described above. Figure 7B is a schematic cross-sectional view of a light emitting device (electroluminescent device) according to one or more embodiments. Figure 7B , the light-emitting device includes: an anode 1 and a cathode 5, facing each other; a quantum dot light-emitting layer 3, arranged between the anode and the cathode and including a plurality of quantum dots; and a hole auxiliary layer 2, located between the anode and the quantum dot light-emitting layer. The hole auxiliary layer may include a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), or a combination thereof. The hole auxiliary layer may include any organic / inorganic material having hole properties. The light-emitting device may also include an electron auxiliary layer 4 located between the cathode and the quantum dot light-emitting layer. The electron auxiliary layer may include an electron injection layer (EIL), an electron transport layer (ETL), a hole blocking layer (HBL), or a combination thereof. The electron auxiliary layer may include any organic / inorganic material having electronic properties.

[0336] Hereinafter, exemplary embodiments will be described in more detail with reference to examples. However, embodiments of the present disclosure are not limited to the examples.

[0337] Example

[0338] Analytical methods

[0339] [1] Photoluminescence analysis

[0340] (1) Photoluminescence (PL) spectra of the produced semiconductor nanoparticles and composites including the semiconductor nanoparticles were obtained at an excitation wavelength of 450 nm using a Hitachi F-7000 spectrometer.

[0341] (2) The absolute quantum yield was measured using QE-2100 (Otsuka).

[0342] [2] Elemental analysis and yield calculation

[0343] (1) Inductively coupled plasma atomic emission spectroscopy (ICP-AES) was performed using a Shimadzu ICPS-8100.

[0344] (2) Calculate the yield by the following method:

[0345] Yield = A / B x 100%

[0346] A: the total weight of silver, Group 13 elements and sulfur in the semiconductor nanoparticles recovered from the crude solution; and

[0347] B: Total weight of silver, Group 13 elements and sulfur added to the reaction medium for the reaction.

[0348] The value B is obtained from the ICP analysis of the first semiconductor nanocrystal and the molar ratio of the element precursors used in the synthesis, and the value A is obtained from the ICP analysis of the prepared semiconductor nanoparticles.

[0349] [3] Optical density measurement and UV-Vis spectroscopy analysis

[0350] (1) A solution for measurement is prepared by diluting a crude solution n times (e.g., 100 times), placing it in a cuvette providing an optical path length of 10 mm (i.e., 1 cm), and performing UV-Vis spectral analysis by using Shimadzu UV-2600, and obtaining a UV-Vis absorption spectrum.

[0351] (2) Read the UV-Vis absorbance at a predetermined wavelength (e.g., 500 nm or 350 nm) from the UV-Vis absorption spectrum, and multiply the obtained absorbance again by n times (e.g., 100 times or the dilution factor of the prepared sample) to obtain the optical density.

[0352] [4] Transmission electron microscopy (TEM) analysis

[0353] Transmission electron microscopy analysis of semiconductor nanoparticles was performed using a UTF30 Tecnai electron microscope.

[0354] Reference Example 1:

[0355] Silver acetate was dissolved in oleylamine to provide a solution containing 0.06 mole (M) of a silver precursor (hereinafter, "silver precursor"). Sulfur was dissolved in oleylamine to provide a solution containing 1M of a sulfur precursor (hereinafter, "sulfur precursor"). Indium chloride was dissolved in ethanol to provide a solution containing 1M of an indium precursor (hereinafter, indium precursor).

[0356] Gallium acetylacetonate, octadecene (ODE) and dodecanethiol are placed in a 100 milliliter (mL) reaction flask and heated at 120°C for 10 minutes under vacuum. The flask is cooled to room temperature and then nitrogen is added to the flask. Silver precursor, sulfur precursor and indium precursor are added to the flask, the flask is heated to a temperature of 210°C, and reacted for 60 minutes. Then, the temperature of the flask is reduced to 180°C, trioctylphosphine (TOP) is added, and the flask is cooled to room temperature. Hexane and ethanol are added to the flask to promote precipitation. The precipitate (i.e., the first semiconductor nanocrystal) is separated by centrifugation.

[0357] The molar ratio of the indium precursor, gallium precursor and sulfur precursor used was 1:2.3:4.8.

[0358] Example 1

[0359] Silver acetate was dissolved in oleylamine to prepare a silver compound solution. Gallium chloride was dissolved in toluene to prepare a 1M gallium precursor solution (hereinafter, gallium precursor).

[0360] Dimethylthiourea (DMTU) and oleylamine as sulfur precursors are placed in a reaction flask and then vacuum treated at 120°C for 10 minutes. Nitrogen is added to the reaction flask, and the flask is heated to 240°C (first temperature). The first semiconductor nanocrystal, gallium precursor and silver compound obtained in Reference Example 1 are added to the flask. The reaction flask is heated to 260°C (second temperature or reaction temperature) and reacted for about 40 minutes. The reaction solution is cooled to 180°C and trioctylphosphine is added to the flask. The reaction mixture is cooled to room temperature to obtain a crude solution containing semiconductor nanoparticles.

[0361] The molar ratio of the gallium precursor to the sulfur precursor used was 1:1.3. The molar percentage of the silver compound to the gallium precursor (ie, the amount of the silver compound based on the gallium precursor) was 3.5 mol%.

[0362] A sample was taken from the crude solution, diluted 100 times with toluene (i.e., crude 0.01x), and subjected to UV-Vis absorption spectroscopy and optical density measurement. The results are summarized in Figure 8 and Table 1.

[0363] Hexane and ethanol were added to the obtained crude product solution to promote precipitation, thereby obtaining semiconductor nanoparticles, which were separated and recovered by centrifugation. The obtained semiconductor nanoparticles were dispersed in toluene.

[0364] The obtained semiconductor nanoparticles were subjected to ICP-AES analysis, and the results are listed in Table 2. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis, and the results are listed in Tables 1 and 2.

[0365] Example 2

[0366] A crude solution and semiconductor nanoparticles were obtained in the same manner as in Example 1, except that the amount of the silver compound relative to the gallium precursor was changed to 2.1 mol % as listed in Table 1.

[0367] A sample was taken from the crude solution, diluted 100 times with toluene, and subjected to UV-Vis absorption spectroscopy and optical density measurement. The results are summarized in Fig. 9 and Table 1.

[0368] Hexane and ethanol were added to the obtained crude solution to promote precipitation of semiconductor nanoparticles, which were then separated and recovered by centrifugation and dispersed in toluene.

[0369] The obtained semiconductor nanoparticles were subjected to ICP-AES analysis, and the results are listed in Table 2. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis, and the results are listed in Tables 1 and 2.

[0370] Example 3

[0371] A crude solution and semiconductor nanoparticles were obtained in the same manner as in Example 1, except that the amount of the silver compound used relative to the gallium precursor was changed to 4.2 mol % as listed in Table 1.

[0372] A sample was taken from the crude solution, diluted 100 times with toluene, and subjected to UV-Vis absorption spectroscopy and optical density measurement. The results are summarized in Fig. 9 and Table 1.

[0373] Hexane and ethanol were added to the obtained crude solution to promote precipitation of semiconductor nanoparticles, which were then separated and recovered by centrifugation and dispersed in toluene.

[0374] 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 Tables 1 and 2.

[0375] Example 4

[0376] A crude solution and semiconductor nanoparticles were obtained in the same manner as in Example 1, except that the amount of the silver compound used relative to the gallium precursor was changed to 10.4 mol % as listed in Table 1.

[0377] A sample was taken from the crude solution, diluted 100 times with toluene, and subjected to UV-Vis absorption spectroscopy and optical density measurement. The results are summarized in Fig. 9 and Table 1.

[0378] Hexane and ethanol were added to the obtained crude solution to promote precipitation of semiconductor nanoparticles, which were then separated and recovered by centrifugation and dispersed in toluene.

[0379] 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 Tables 1 and 2.

[0380] Comparative Example 1

[0381] Gallium chloride was dissolved in toluene to prepare a solution containing 5.68 M of a gallium precursor (hereinafter, referred to as "gallium precursor").

[0382] Dimethylthiourea (DMTU) and oleylamine were added to a reaction flask and vacuum treated at 120°C for 10 minutes. Nitrogen was added to the reaction flask, and the flask was heated to 240°C, and the first semiconductor nanocrystal and gallium precursor were added to the flask. The reaction flask was heated to 280°C and reacted for about 40 minutes. The reaction solution was cooled to 180°C and trioctylphosphine was added to the flask. The reaction mixture was cooled to room temperature to obtain a crude solution containing semiconductor nanoparticles.

[0383] The molar ratio of the gallium precursor to the sulfur precursor used in the preparation of the semiconductor nanoparticles of Reference Example 1 was 1:1.3.

[0384] A sample was taken from the crude solution, diluted 100 times with toluene, and subjected to UV-Vis absorption spectroscopy and optical density measurement. The results are summarized in Figure 8 and Table 1.

[0385] Hexane and ethanol were added to the obtained crude solution to promote precipitation of comparative semiconductor nanoparticles, which were then separated and recovered by centrifugation and dispersed in toluene.

[0386] The obtained semiconductor nanoparticles were subjected to ICP-AES analysis, and the results are listed in Table 2. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis, and the results are listed in Tables 1 and 2.

[0387] Comparative Example 2

[0388] A crude solution and semiconductor nanoparticles were obtained in the same manner as in Comparative Example 1, except that the amount of the gallium precursor used was halved.

[0389] A sample was taken from the crude solution, diluted 100 times with toluene, and subjected to UV-Vis absorption spectrum analysis and optical density measurement. The results are summarized in Table 1.

[0390] Hexane and ethanol were added to the obtained crude solution to promote precipitation of comparative semiconductor nanoparticles, which were then separated and recovered by centrifugation and dispersed in toluene.

[0391] The obtained semiconductor nanoparticles were subjected to ICP-AES analysis, and the results are listed in Table 2. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis, and the results are listed in Tables 1 and 2.

[0392] Table 1

[0393]

[0394] Ag implantation amount: mol% of silver compound relative to gallium

[0395] PWL: Peak emission wavelength

[0396] FWHM: Full Width at Half Maximum

[0397] QY: Quantum Yield

[0398] The results of Table 1 confirm that the crude solutions of Comparative Examples 1 and Comparative Examples 2 have low optical densities at 500 nm and 350 nm, and significantly reduced yields, compared to Examples 1 to 4. In contrast, the semiconductor nanoparticles of Examples 1 to 4 can exhibit high levels of optical properties and high optical densities at 500 nm and 350 nm, as well as high yields.

[0399] Table 2

[0400] Average particle size (nm) Particle size distribution (standard deviation from the mean) Comparative Example 1 7.3 24％ Comparative Example 2 6.56 26％ Example 1 5.23 12％ Example 3 5.18 14％ Example 4 5.92 15％

[0401] The results of Table 2 confirm that the semiconductor nanoparticles of Examples 1 to 4 can exhibit a significantly uniform size distribution compared to the semiconductor nanoparticles of Comparative Examples 1 and 2.

[0402] Table 3

[0403] Ag / In S / In Ga / In Ga / (In+Ga) Ag / (In+Ga+Ag) S / (AIG) Ga / S CBV Comparative Example 1 4.06 10.31 5.46 0.85 0.39 0.98 0.53 1.14 Comparative Example 2 3.05 8.87 3.73 0.79 0.39 1.14 0.42 0.97 Example 1 2.95 8.97 4.03 0.80 0.37 1.12 0.45 1.01 Example 2 2.38 7.00 3.53 0.78 0.34 1.01 0.50 1.14 Example 3 2.66 7.83 3.89 0.80 0.35 1.04 0.50 1.11 Example 4 4.37 10.96 5.41 0.84 0.41 1.02 0.49 1.08

[0404] Ag / (AIG)=Ag / (Ag+In+Ga)

[0405] S / AIG=S / (Ag+In+Ga)

[0406] CBV: Charge balance value = {[Ag] + 3([In] + [Ga])} / (2[S])

[0407] Here, [Ag], [In], [Ga], and [S] are the molar content of silver, the molar content of indium, the molar content of gallium, and the molar content of sulfur in the semiconductor nanoparticles, respectively.

[0408] While the disclosure has been described in conjunction with what are presently considered to be practical embodiments, it is to be understood that the present subject matter is not limited to the disclosed exemplary embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A method for producing semiconductor nanoparticles, the method comprising: combining a first semiconductor nanocrystal with a gallium precursor, a sulfur precursor, and a silver compound in a medium comprising an organic solvent, the first semiconductor nanocrystal comprising silver, a Group 13 element, and a chalcogen; as well as heating the medium to a reaction temperature to obtain a crude solution containing semiconductor nanoparticles, The semiconductor nanoparticles include silver, indium, gallium and sulfur, and the size of the semiconductor nanoparticles is greater than or equal to 2 nm and less than or equal to 50 nm.

2. The method according to claim 1, wherein: The optical density of the crude solution at a wavelength of 500 nm is greater than or equal to 1 and less than or equal to 10, and the optical density is defined by Equation 1: Equation 1 Optical density = log 10 (I O / I T ) I O = the intensity of the incident light supplied to the crude solution, and I T = the intensity of light transmitted through the crude solution.

3. The method according to claim 2, wherein: The optical density of the crude product solution at a wavelength of 350 nm is greater than or equal to 8 and less than or equal to 100.

4. The method according to claim 1, wherein: In the UV-Vis absorption spectrum, the ratio of the absorbance of the crude solution at 500 nm to the absorbance at 350 nm is greater than or equal to 0.01:1 and less than or equal to 0.8:

1.

5. The method according to claim 1, wherein: The silver compound is added to the medium in an amount greater than or equal to 0.1 mol % and less than or equal to 50 mol % relative to the amount of the gallium precursor added to the medium.

6. The method according to claim 1, wherein: The silver compound includes silver carboxylate, silver acetylacetonate, silver halide, or a combination thereof.

7. The method according to claim 1, wherein: Yield greater than or equal to 6%: Yield = A / B × 100% A: the total weight of silver, Group 13 elements, and sulfur in the semiconductor nanoparticles recovered from the crude solution, and B: Total weight of silver, Group 13 elements and sulfur added to the medium.

8. The method according to claim 1, wherein: The quantum yield of the semiconductor nanoparticles is shown to be greater than or equal to 65%.

9. The method according to claim 1, wherein: The semiconductor nanoparticles have an average size greater than or equal to 5 nm and less than or equal to 10 nm and a standard deviation of the average size less than or equal to 20%.

10. The method according to claim 1, wherein: The charge balance value of the semiconductor nanoparticles is shown to be greater than or equal to 0.8 and less than or equal to 1.3: Charge balance value = {[Ag] + 3([In] + [Ga])} / (2[S]) Wherein, [Ag], [In], [Ga] and [S] are the molar amount of silver, the molar amount of indium, the molar amount of gallium and the molar amount of sulfur in the semiconductor nanoparticles, respectively.

11. The method according to claim 1, further comprising: preparing an additional reaction medium in an organic solvent, the additional reaction medium comprising a zinc precursor; Semiconductor nanoparticles and a chalcogen precursor are added to an additional reaction medium and heated to a reaction temperature to form third semiconductor nanocrystals including zinc chalcogenide on the surface of the semiconductor nanoparticles.

12. A semiconductor nanoparticle comprising silver, indium, gallium and sulfur, in, The semiconductor nanoparticles have an average size greater than or equal to 5 nm and less than or equal to 10 nm and a standard deviation of the average size less than or equal to 20% and greater than or equal to 5%, The charge balance value of the semiconductor nanoparticles is greater than or equal to 0.95 and less than or equal to 1.2: Charge balance value = {[Ag] + 3([In] + [Ga])} / (2[S]) Wherein, [Ag], [In], [Ga] and [S] are the molar amount of silver, the molar amount of indium, the molar amount of gallium and the molar amount of sulfur in the semiconductor nanoparticles, respectively.

13. The semiconductor nanoparticle according to claim 12, wherein The semiconductor nanoparticles are configured to emit green light, and The peak emission wavelength of the green light is greater than or equal to 520 nm and less than or equal to 540 nm.

14. The semiconductor nanoparticle according to 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 nanoparticle according to claim 12, wherein: The quantum yield of the semiconductor nanoparticles is greater than or equal to 70% and less than or equal to 99%, and The full width at half maximum of the semiconductor nanoparticles is greater than or equal to 15 nm and less than or equal to 70 nm.

16. The semiconductor nanoparticle according to claim 12, wherein: In semiconductor nanoparticles, The molar ratio of gallium to indium is greater than or equal to 1:1 and less than or equal to 10:1, and The molar ratio of gallium to silver is greater than or equal to 1.1:1 and less than or equal to 3:

1.

17. The semiconductor nanoparticle according to claim 12, wherein: In semiconductor nanoparticles, The molar ratio of gallium to the sum of gallium, indium and silver is greater than or equal to 0.45:1 and less than or equal to 0.65:1, and The molar ratio of the sum of indium and gallium to silver is greater than or equal to 1.2:1 and less than or equal to 3.5:

1.

18. The semiconductor nanoparticle according to claim 12, wherein: In semiconductor nanoparticles, The molar ratio of silver to the sum of silver, indium and gallium is greater than or equal to 0.2:1 and less than or equal to 0.45:1, and The molar ratio of sulfur to the sum of silver, indium and gallium is greater than or equal to 0.8:1 and less than or equal to 1.5:

1.

19. The semiconductor nanoparticle according to claim 12, wherein: In semiconductor nanoparticles, The molar ratio of gallium to sulfur is greater than or equal to 0.4:1 and less than or equal to 0.6:

1.

20. An electronic device comprising the semiconductor nanoparticle according to any one of claims 12 to 19.

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