Semiconductor nanoparticles, method of manufacturing semiconductor nanoparticles, and ink composition, semiconductor nanoparticle composite, display device, and electronic device including semiconductor nanoparticles

Abstract

Provided are a semiconductor nanoparticle, a method for manufacturing the semiconductor nanoparticle, an ink composition including the semiconductor nanoparticle, a semiconductor nanoparticle composite including the semiconductor nanoparticle, a display device including the semiconductor nanoparticle, and an electronic device including the semiconductor nanoparticle. In the semiconductor nanoparticles, a molar ratio of gallium to indium (Ga: In) is greater than or equal to 20: 1 and less than or equal to 40: 1, and the semiconductor nanoparticles have a quantum yield of greater than or equal to 70% and less than or equal to 100%.

Description

[0001] This application claims priority and all benefits arising therefrom to Korean Patent Application No. 10-2024-0109023, filed on August 14, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0002] Semiconductor nanoparticles, methods for manufacturing semiconductor nanoparticles, ink compositions including semiconductor nanoparticles, semiconductor nanoparticle composites, display devices including semiconductor nanoparticles, and electronic devices including semiconductor nanoparticles are disclosed. Background Technology

[0003] Semiconductor nanoparticles can exhibit different aspects, properties, or characteristics compared to their bulk counterparts with essentially the same composition. For example, semiconductor nanoparticles can possess different physical properties (e.g., band gap energy, luminescence properties, etc.) based on their nanostructure. Semiconductor nanoparticles can be configured to emit light upon excitation by incident light or applied voltage. Luminescent nanostructures can find applicability in a variety of devices (e.g., display panels or electronic devices including display panels). From an environmental perspective, it is of interest and expectation to develop luminescent nanoparticles that do not contain harmful heavy metals (such as cadmium) while still achieving comparability or improvement in one or more luminescent or optical properties. Summary of the Invention

[0004] On the one hand, it relates to a semiconductor nanoparticle or a group of such semiconductor nanoparticles, which exhibit physical properties having acceptable conversion yield, quantum yield or efficiency.

[0005] One aspect relates to a method for manufacturing semiconductor nanoparticles or groups of semiconductor nanoparticles.

[0006] One aspect relates to a composition (e.g., an ink composition) comprising semiconductor nanoparticles or groups of semiconductor nanoparticles.

[0007] One aspect relates to a semiconductor nanoparticle composite, which comprises semiconductor nanoparticles or a group of semiconductor nanoparticles.

[0008] One aspect relates to a color conversion panel or display device, the display device comprising semiconductor nanoparticles or a group of semiconductor nanoparticles.

[0009] One aspect relates to an electronic device that includes semiconductor nanoparticles or groups of semiconductor nanoparticles (e.g., semiconductor nanoparticles or groups of semiconductor nanoparticles are included in the color conversion panel of an electronic device or display device).

[0010] One aspect provides a semiconductor nanoparticle comprising silver, indium, gallium, and sulfur. In the semiconductor nanoparticle, the molar ratio of gallium to indium (Ga:In) is greater than or equal to about 20:1 and less than or equal to about 40:1, and the semiconductor nanoparticle has a quantum yield greater than or equal to about 70% and less than or equal to about 100%.

[0011] The semiconductor nanoparticles may include group 11-13-16 compounds comprising silver, indium, gallium, and sulfur. The semiconductor nanoparticles may include a first semiconductor nanocrystal comprising silver, indium, gallium, and sulfur, and a second semiconductor nanocrystal comprising silver, gallium, and sulfur.

[0012] In the semiconductor nanoparticles, the molar ratio of gallium to indium (Ga:In) can be greater than or equal to about 20.1:1, greater than or equal to about 20.5:1, greater than or equal to about 21:1, or greater than or equal to about 22.5:1. In the semiconductor nanoparticles, the molar ratio of gallium to indium (Ga:In) can be greater than or equal to about 23:1. In the semiconductor nanoparticles, the molar ratio of gallium to indium (Ga:In) can be less than or equal to about 40:1, less than or equal to about 37:1, less than or equal to about 35:1, or less than or equal to about 28:1. In the semiconductor nanoparticles, the molar ratio of gallium to indium (Ga:In) can be within any combination thereof.

[0013] In the semiconductor nanoparticles, the molar ratio of silver to indium (Ag:In) can be greater than or equal to about 5:1, greater than or equal to about 7:1, greater than or equal to about 9:1, greater than or equal to about 10:1, greater than or equal to about 11:1, or greater than or equal to about 13:1. In the semiconductor nanoparticles, the molar ratio Ag:In can be less than or equal to about 30:1, less than or equal to about 25:1, less than or equal to about 20:1, less than or equal to about 18:1, less than or equal to about 16:1, or less than or equal to about 15.7:1. In the semiconductor nanoparticles, the molar ratio of silver to indium (Ag:In) can be within any combination thereof.

[0014] In the semiconductor nanoparticles, the molar ratio of sulfur to indium (S:In) can be greater than or equal to about 31:1, greater than or equal to about 33:1, or greater than or equal to about 37:1. In the semiconductor nanoparticles, the molar ratio S:In can be less than or equal to about 45:1, less than or equal to about 42:1, less than or equal to about 41:1, less than or equal to about 38:1, or less than or equal to about 32:1. The molar ratio of sulfur to indium (S:In) can be within any combination thereof.

[0015] In the semiconductor nanoparticles, the molar ratio of indium to sulfur (In:S) may be less than or equal to about 0.045:1, or less than or equal to about 0.04:1. In the semiconductor nanoparticles, the molar ratio In:S may be greater than or equal to about 0.01:1, greater than or equal to about 0.02:1, greater than or equal to about 0.025:1, or greater than or equal to about 0.03:1. The molar ratio of indium to sulfur (In:S) may be within any combination thereof.

[0016] 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 0.5:1, or greater than or equal to about 0.7:1. In the semiconductor nanoparticles, the molar ratio Ga:S can be less than or equal to about 0.8:1, less than or equal to about 0.77:1, or less than or equal to about 0.75:1. The molar ratio of gallium to sulfur (Ga:S) can be within any combination thereof.

[0017] In the semiconductor nanoparticles, the molar ratio of gallium to silver (Ga:Ag) can be greater than or equal to about 1.2:1, greater than or equal to about 1.4:1, greater than or equal to about 1.6:1, or greater than or equal to about 2:1. In the semiconductor nanoparticles, the molar ratio Ga:Ag can be less than or equal to about 2.3:1, less than or equal to about 2.2:1, or less than or equal to about 1.7:1. The molar ratio of gallium to silver (Ga:Ag) can be within any combination thereof.

[0018] In the semiconductor nanoparticles, the molar ratio of gallium to indium and the sum of gallium, Ga:(In+Ga), can be greater than about 0.95:1, greater than or equal to about 0.952:1, greater than or equal to about 0.957:1, or greater than or equal to about 0.958:1. In the semiconductor nanoparticles, the molar ratio Ga:(In+Ga) can be less than or equal to about 0.99:1, less than or equal to about 0.98:1, or less than or equal to about 0.965:1. The molar ratio of gallium to indium and the sum of gallium, Ga:(In+Ga), can be within any combination thereof.

[0019] In the semiconductor nanoparticles, the molar ratio of indium to the sum of indium and gallium, In:(In+Ga), can be greater than or equal to about 0.011:1, greater than or equal to about 0.02:1, greater than or equal to about 0.024:1, or greater than or equal to about 0.028:1. In the semiconductor nanoparticles, the molar ratio In:(In+Ga) can be less than about 0.05:1, less than or equal to about 0.049:1, less than or equal to about 0.048:1, or less than or equal to about 0.043:1. The molar ratio In:(In+Ga) can be within any combination thereof.

[0020] In the semiconductor nanoparticles, the molar ratio of indium and gallium to silver (In+Ga):Ag can be greater than or equal to about 1.3:1, greater than or equal to about 1.4:1, or greater than or equal to about 1.5:1. In the semiconductor nanoparticles, the molar ratio (In+Ga):Ag can be less than or equal to about 2.5:1, less than or equal to about 2.3:1, less than or equal to about 2.2:1, less than or equal to about 1.7:1, less than or equal to about 1.65:1, or less than or equal to about 1.6:1. The molar ratio (In+Ga):Ag can be within any combination thereof.

[0021] In the semiconductor nanoparticles, the molar ratio of indium and gallium to sulfur (In+Ga):S can be greater than or equal to about 0.4:1, greater than or equal to about 0.55:1, greater than or equal to about 0.58:1, or greater than or equal to about 0.75:1. In the semiconductor nanoparticles, the molar ratio (In+Ga):S can be less than or equal to about 0.9:1, less than or equal to about 0.84:1, less than or equal to about 0.8:1, less than or equal to about 0.65:1, or less than or equal to about 0.6:1. The molar ratio (In+Ga):S can be within any combination thereof.

[0022] 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 0.31:1, greater than or equal to about 0.32:1, greater than or equal to about 0.38:1, or greater than or equal to about 0.39:1 and less than or equal to about 0.45:1, or less than or equal to about 0.42:1. The molar ratio (Ag:(Ag+In+Ga)) can be within any combination thereof.

[0023] 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 0.85:1, greater than or equal to about 0.95:1, or greater than or equal to about 1:1. In the semiconductor nanoparticles, the molar ratio S:(Ag+In+Ga) can be less than or equal to about 1.12:1, or less than or equal to about 1.1:1, less than or equal to about 1.09:1, or less than or equal to about 1.08:1. The molar ratio S:(Ag+In+Ga) can be within any combination thereof.

[0024] The semiconductor nanoparticles may have a charge balance value defined by Equation 1A, wherein the charge balance value is greater than or equal to about 0.95, or greater than or equal to about 1.3. The semiconductor nanoparticles may have a charge balance value defined by Equation 1A, wherein the charge balance value is less than or equal to about 1.44, less than or equal to about 1.35, less than or equal to about 1.1, or less than or equal to about 1.08, or may be within any combination thereof.

[0025] Equation 1A

[0026] Charge balance value = {[Ag] + 3([In] + [Ga])} / 2[S]

[0027] In Equation 1A, [Ag], [In], [Ga], and [S] represent the molar amounts of silver, indium, gallium, and sulfur in the semiconductor nanoparticles, respectively.

[0028] The semiconductor nanoparticles may include group 11-13-16 compounds comprising silver, indium, gallium, and sulfur. The semiconductor nanoparticles may include first semiconductor nanocrystals comprising silver, indium, gallium, and sulfur, and second semiconductor nanocrystals comprising silver, gallium, and sulfur.

[0029] The semiconductor nanoparticles may also include zinc. The semiconductor nanoparticles may include semiconductor nanocrystals (e.g., third or fourth semiconductor nanocrystals) containing zinc, sulfur, and optionally gallium.

[0030] The semiconductor nanoparticles may or may not include sodium. The semiconductor nanoparticles may or may not include lithium.

[0031] The semiconductor nanoparticles may have a quantum yield greater than or equal to about 71%, or greater than or equal to about 75%. The quantum yield may be less than or equal to about 99%. The (absolute) quantum yield of the semiconductor nanoparticles may be greater than or equal to about 71%, greater than or equal to about 73%, greater than or equal to about 75%, or greater than or equal to about 80%. The (absolute) quantum yield of the semiconductor nanoparticles may be greater than or equal to about 71% to about 99%, greater than or equal to about 72% to about 98%, or greater than or equal to about 73% to about 97%.

[0032] The semiconductor nanoparticles can be configured to emit a first light. The first light can be green light. The first light can be red light.

[0033] The peak emission wavelength of the first light or the semiconductor nanoparticle may be greater than or equal to about 480 nanometers (nm) and less than or equal to about 660 nm.

[0034] The peak emission wavelength of the first light or the semiconductor nanoparticle may be greater than or equal to about 500 nm, or greater than or equal to about 515 nm and less than or equal to about 580 nm, or less than or equal to about 560 nm, or less than or equal to about 550 nm, or may be within any combination thereof.

[0035] The peak emission wavelength of the first light or the semiconductor nanoparticle may be greater than or equal to about 600 nm, or greater than or equal to about 605 nm and less than or equal to about 660 nm, or less than or equal to about 650 nm, or may be within any combination thereof.

[0036] The full width at half maximum (FWHM) of the first light or the semiconductor nanoparticle may be greater than or equal to about 5 nm, or greater than or equal to about 10 nm and less than or equal to about 50 nm, or less than or equal to about 45 nm, or may be within any combination thereof.

[0037] The semiconductor nanoparticles may have a trap emission percentage of less than or equal to about 20%, less than or equal to about 19%, less than or equal to about 18%, or less than or equal to about 17%, calculated by the following equation 1B:

[0038] Equation 1B

[0039] Trapped emission percentage = [Trap emission area of ​​the emission spectrum / Total area of ​​the emission spectrum] × 100%

[0040] In the above equation, the trap emission area refers to the area of ​​the trap emission region (i.e., the region of the emission spectrum at a wavelength greater than or equal to the peak emission wavelength plus 50 nanometers; in other words, the region of the emission spectrum in a wavelength range at least 50 nm longer than the given peak emission wavelength).

[0041] The semiconductor nanoparticles may have a size greater than or equal to about 7 nm, greater than or equal to about 7.5 nm, or greater than or equal to about 8 nm and less than or equal to about 30 nm, less than or equal to about 17 nm, less than or equal to about 15 nm, or less than or equal to about 12 nm (or may be within any combination thereof).

[0042] In one embodiment, a method for manufacturing semiconductor nanoparticles may include:

[0043] In a first medium including an organic solvent, a first semiconductor nanocrystal comprising silver, a group 13 element and a chalcogenide element is combined (or contacted) with a first sulfur precursor, a first gallium precursor and an optional silver compound (e.g., a first silver compound).

[0044] The first medium is heated to a first reaction temperature to form intermediate particles;

[0045] Separate the formed intermediate particles (e.g., separate the formed intermediate particles from the first medium).

[0046] In a second medium comprising a second organic solvent, the separated intermediate particles, the second sulfur precursor, the second gallium precursor, and an optional silver compound (e.g., a second silver compound) are combined (or contacted); and

[0047] The second medium is heated to a second reaction temperature to form semiconductor nanoparticles.

[0048] The semiconductor nanoparticles comprise silver, indium, gallium, and sulfur, and in which the molar ratio of gallium to indium is greater than or equal to about 20:1 and less than or equal to about 40:1. The semiconductor nanoparticles may have (e.g., exhibit) a quantum yield of greater than or equal to about 70%, greater than or equal to about 75% and less than or equal to about 100%, or less than or equal to about 99%. Details of the semiconductor nanoparticles are the same as those described herein.

[0049] The separated intermediate particles can be washed with a washing solvent before being added to the second medium.

[0050] Washing solvents may include polar organic solvents or combinations thereof (e.g., mixtures thereof).

[0051] Washing solvents or polar organic solvents may include C1 to C10 alcohols, C3 to C30 ketone solvents, nitrile solvents, or combinations thereof.

[0052] Washing solvents or polar organic solvents may include C1 to C10 alcohols.

[0053] The first gallium precursor may include gallium bromide and optionally gallium chloride (or gallium iodide).

[0054] The second gallium precursor may include gallium bromide and optionally gallium chloride (or gallium iodide).

[0055] In an embodiment, the first gallium precursor or the second gallium precursor includes both gallium bromide and gallium chloride (or gallium iodide), and the amount of gallium chloride (or gallium iodide) relative to 1 mole of gallium bromide may be greater than or equal to about 0.001 mol, greater than or equal to about 0.01 mol, greater than or equal to about 0.1 mol, greater than or equal to about 0.3 mol, greater than or equal to about 0.5 mol, or greater than or equal to about 0.7 mol and less than or equal to about 5 mol, less than or equal to about 3 mol, less than or equal to about 2 mol, less than or equal to about 1.5 mol, less than or equal to about 1 mol, less than or equal to about 0.8 mol, less than or equal to about 0.4 mol, or less than or equal to about 0.2 mol.

[0056] In embodiments, the silver compound in the first or second medium (e.g., the first silver compound in the first medium or the second silver compound in the second medium) may be greater than or equal to about 0.01 mol%, greater than or equal to about 0.1 mol%, greater than or equal to about 0.5 mol%, greater than or equal to about 1 mol%, or greater than or equal to about 3 mol% relative to the amount of the (first or second) gallium precursor (present in an amount greater than or equal to about 0.01 mol%, greater than or equal to about 0.1 mol%, greater than or equal to about 0.5 mol%, greater than or equal to about 1 mol%, or greater than or equal to about 3 mol%). The silver compound in the first or second medium (e.g., the first silver compound in the first medium or the second silver compound in the second medium) may be less than or equal to about 50 mol% (e.g., less than or equal to about 25 mol%, less than or equal to about 10 mol%, or less than or equal to about 6 mol%) relative to the amount of the (first or second) gallium precursor (in an amount of less than or equal to about 50 mol% (e.g., less than or equal to about 25 mol%, less than or equal to about 10 mol%, or less than or equal to about 6 mol%)).

[0057] Silver compounds (e.g., a first silver compound in a first medium or a second silver compound in a second medium) may include silver carboxylates, silver acetylacetonates, silver halides, or combinations thereof.

[0058] The first reaction temperature may be greater than or equal to about 200°C, or greater than or equal to about 260°C and less than or equal to about 380°C.

[0059] The second reaction temperature can be greater than or equal to about 200°C, or greater than or equal to about 260°C and less than or equal to about 380°C.

[0060] The temperature of the first reaction may be the same as or different from the temperature of the second reaction.

[0061] The first reaction temperature may be higher than the second reaction temperature. The first reaction temperature may be lower than the second reaction temperature. The temperature difference between the first and second reaction temperatures may be greater than or equal to about 10°C and less than or equal to about 50°C.

[0062] In an embodiment, an ink composition may include the aforementioned semiconductor nanoparticles and a liquid carrier. The semiconductor nanoparticles may be dispersed within the liquid carrier. The liquid carrier may include polymerizable (or liquid) monomers, organic solvents, or combinations thereof. The ink composition may be substantially free of volatile organic solvents. The ink composition may also include metal oxide nanoparticles.

[0063] In one aspect, a semiconductor nanoparticle composite may include a matrix and semiconductor nanoparticles, wherein the semiconductor nanoparticles are dispersed in the matrix. The semiconductor nanoparticle composite may be a patterned film. The semiconductor nanoparticle composite may be a sheet in which a first semiconductor nanoparticle emitting a first light and a second semiconductor nanoparticle emitting a second light are mixed, wherein the first light and the second light may be different.

[0064] In the embodiments, the semiconductor nanoparticle composite may exhibit an internal quantum efficiency (IQE) or external quantum efficiency (EQE) greater than or equal to about 50%, and the IQE and EQE are defined by Equations 2 and 3, respectively:

[0065] Equation 2

[0066] Internal quantum efficiency (IQE, %) = [A / (B-B')] × 100

[0067] Equation 3

[0068] External quantum efficiency (EQE, %) = [A / B] × 100

[0069] in:

[0070] A: The amount of first light emitted from the semiconductor nanoparticles or the semiconductor nanoparticle composite.

[0071] B: The amount of incident light provided to irradiate the semiconductor nanoparticle composite.

[0072] B': The amount of incident light that passes through the semiconductor nanoparticle composite.

[0073] The internal quantum efficiency (or external quantum efficiency) of the semiconductor nanoparticle composite may be in the range of about 36% to about 100%, about 37% to about 98%, about 39% to about 96%, about 41% to about 92%, about 43% to about 90%, or in any combination thereof.

[0074] The semiconductor nanoparticle composite can be heat-treated at 180°C for 30 minutes, and the process retention percentage obtained by Equation 4 can be greater than or equal to about 75%, or greater than or equal to about 80%.

[0075] Equation 4

[0076] Process retention percentage (%) = [QE2 / QE1] × 100.

[0077] in

[0078] QE1: The quantum efficiency of the semiconductor nanoparticle composite prior to heat treatment.

[0079] QE2: The quantum efficiency of the semiconductor nanoparticle composite after heat treatment.

[0080] Quantum efficiency can be either IQE or EQE.

[0081] The process retention percentage may be greater than or equal to about 77% to about 130%, greater than or equal to about 81% to about 100%, or any combination thereof.

[0082] One aspect provides a color conversion layer or color conversion structure (hereinafter, "color conversion layer"), said color conversion layer or color conversion structure including a color conversion region comprising the aforementioned semiconductor nanoparticles. In an embodiment, a color conversion panel may include a color conversion layer comprising a color conversion region and optionally partition walls 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, and the first composite may include a matrix and semiconductor nanoparticles dispersed in the matrix, wherein the first region is configured to emit first light.

[0083] One aspect provides a display device comprising semiconductor nanoparticles. In one embodiment, a display panel (or display device) may include a light source and a semiconductor nanoparticle composite. In another embodiment, a display panel may include a light-emitting panel (or light source) and a color conversion panel, and optionally a light-transmitting layer located between the light-emitting panel and the color conversion panel.

[0084] The light-emitting panel (or light source) can be configured to provide incident light to the color conversion panel (or the light-emitting panel (or light source) provides incident light to the color conversion panel). The incident light may include blue light and optionally green light. The blue light may have a peak emission wavelength of about 440 nm to about 460 nm or about 450 nm to about 455 nm.

[0085] The light source may include organic light-emitting diodes (OLEDs), micro LEDs, mini LEDs, LEDs containing nanorods, or combinations thereof.

[0086] In an embodiment, the electronic device (or display device) may include a color conversion panel or a display panel.

[0087] Electronic devices or display devices may include virtual reality devices, augmented reality devices, portable terminal devices, monitors, notebook personal computers (PCs), televisions, electronic display panels, or electronic components for automobiles or vehicles.

[0088] The semiconductor nanoparticles of the embodiments may exhibit improved optical properties (e.g., high quantum yield and narrow full width at half maximum). The semiconductor nanoparticles of the embodiments, or polymer composites comprising semiconductor nanoparticles, may exhibit suppressed trap emission. The semiconductor nanoparticles of the embodiments, or polymer composites comprising semiconductor nanoparticles, may exhibit improved process stability (e.g., thermal stability and / or chemical stability). Attached Figure Description

[0089] The above and other aspects, features and advantages of some exemplary embodiments will become clearer from the following detailed description taken in conjunction with the accompanying drawings.

[0090] Figure 1 It is a model emission spectrum showing the photoluminescence (PL) intensity (e.g., normalized photoluminescence (PL) intensity) versus wavelength (nanometer, nm), including the concept of trap emission percentage.

[0091] Figure 2A This is a flowchart illustrating the patterning process (photolithography) of the ink composition used in the embodiment.

[0092] Figure 2B This is a flowchart illustrating a patterning process (inkjet printing) of the ink composition used in an embodiment.

[0093] Figure 3A This is a schematic cross-sectional view of the color conversion panel according to an embodiment.

[0094] Figure 3B This is a cross-sectional view of an electronic device (or display device) including a color conversion panel according to an embodiment.

[0095] Figure 4A This is a perspective view showing a display panel including a color conversion panel according to an embodiment.

[0096] Figure 4B This is an exploded view of a display device according to an embodiment.

[0097] Figure 4C yes Figure 4A A cross-sectional view of the display panel.

[0098] Figure 4D This is an exploded view of the display panel according to an embodiment.

[0099] Figure 5A It is shown Figure 4A A plan view of the pixel arrangement of the display panel.

[0100] Figure 5B , Figure 5C , Figure 5D and Figure 5EThese are cross-sectional views showing the light-emitting device according to an embodiment.

[0101] Figure 6 yes Figure 5A A sectional view of the display panel taken along line IV-IV.

[0102] Figure 7A This is a schematic cross-sectional view of a display device (e.g., a liquid crystal display device) according to an embodiment.

[0103] Figure 7B This is a schematic cross-sectional view of an electronic device (e.g., a light-emitting device) according to an embodiment.

[0104] Figure 8A This is a graph showing the normalized photoluminescence (PL) intensity versus wavelength (nanometers, nm) of the photoluminescence spectra of the semiconductor nanoparticles prepared in Examples 1 to 5 and Comparative Examples 1 to 4.

[0105] Figure 8B yes Figure 8A A magnified view of the trap emission portion in the photoluminescence spectrum. Detailed Implementation

[0106] The advantages and features of the technologies described below, as well as methods for implementing them, will become clear from the exemplary embodiments described in further detail below in conjunction with the accompanying drawings. However, the embodiments should not be construed as limiting oneself to the exemplary embodiments set forth herein. Unless otherwise defined, all terms used herein (including technical and scientific terms) are as commonly understood by one of ordinary skill in the art. Terms defined in general dictionaries should not be interpreted ideally or exaggeratedly unless clearly defined.

[0107] Furthermore, unless explicitly stated otherwise, the word “including” and its variations such as “contains” or “comprising” will be understood to imply inclusion of the stated element but not exclusion of any other element.

[0108] In the accompanying drawings, the thickness of layers, films, panels, areas, etc., is exaggerated for clarity. Throughout the specification, the same reference numerals denote the same elements.

[0109] What will be understood is that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it may be directly on the other element, or there may be intermediate elements present. Conversely, when an element is referred to as being "directly on" another element, there are no intermediate elements present.

[0110] As used herein, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” are intended to include the plural forms containing “at least one.” For example, the term “semiconductor nanoparticle” may refer to a single semiconductor nanoparticle or multiple semiconductor nanoparticles. “At least one” should not be construed as limited to “a” 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.

[0111] It will be understood that while the terms “first,” “second,” “third,” etc., may be used herein to describe various elements, components, regions, layers, and / or portions, these elements, components, regions, layers, and / or portions should not be limited by these terms. These terms are used only to distinguish one element, component, region, layer, or portion from another element, component, region, layer, or portion. Therefore, without departing from the teachings of the present embodiments, the terms “first element,” “first component,” “first region,” “first layer,” or “first portion” discussed below may be designated as a second element, second component, second region, second layer, or second portion.

[0112] Exemplary embodiments are described herein with reference to cross-sectional views, which are schematic illustrations of idealized embodiments. Thus, variations in the shape of the illustrations will be anticipated due to factors such as manufacturing techniques and / or tolerances. Therefore, the embodiments described herein should not be construed as limited to the specific shapes of the areas shown herein, but will include shape deviations, for example, due to manufacturing processes. For example, areas shown or described as flat may generally have rough and / or non-linear characteristics. Furthermore, sharp corners (acute angles) shown may be rounded (rounded). Therefore, the areas shown in the figures are schematic in nature, and their shapes are not intended to show the precise shapes of the areas, nor are they intended to limit the scope of the present claims.

[0113] As used, “about” or “approximately” includes the stated value and means within an acceptable range of deviation from the particular value, as determined by a person skilled 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” may mean within one or more standard deviations, or within ±10%, ±5%, or ±3% of the stated value.

[0114] As used herein, the expression "excluding cadmium (or other hazardous heavy metals)" may mean that the concentration of cadmium (or other hazardous heavy metals) is less than or equal to about 100 parts per million by weight (100 ppmw), less than or equal to about 50 ppmw, less than or equal to about 10 ppmw, less than or equal to about 1 ppmw, less than or equal to about 0.1 ppmw, less than or equal to about 0.01 ppmw, or about zero. In one or more embodiments, the amount of cadmium (or other hazardous heavy metals) may be substantially absent, or if present, the amount of cadmium (or other hazardous heavy metals) may be less than or equal to the detection limit of a given analytical tool or the same as an impurity level.

[0115] In the following text, as used herein, unless otherwise defined, “substituted” means that at least one hydrogen atom of a compound is replaced by a substituent selected from 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, and C1 to C30 alkyl Thioyl, C1 to C30 heteroalkyl, 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 (-NO2), cyanide The following groups are used: α-CN, α-amino or amine (-NRR', where R and R' are each independently hydrogen or C1 to C6 alkyl), α-azido (-N3), α-amidinyl (-C(=NH)NH2), hydrazine (-NHNH2), hydrazone (=N(NH2)), aldehyde (-C(=O)H), carbamoyl (-C(O)NH2), thiol (-SH), ester (-C(=O)OR, where R is C1 to C6 alkyl or C6 to C12 aryl), carboxylic acid (-COOH) or a salt thereof (-C(=O)OM, where M is an organic or inorganic cation), sulfonic acid (-SO3H) or a salt thereof (-SO3M, where M is an organic or inorganic cation), phosphate (-PO3H2) or a salt thereof (-PO3MH or -PO3M2, where M is an organic or inorganic cation), or combinations thereof. The specific number or range of carbon atoms in the group excludes any substituents.

[0116] In addition, unless otherwise defined below, “heterogeneous” means the presence of one to three heteroatoms (such as N, O, P, Si, S, Se, Ge, or B).

[0117] Furthermore, as used herein, the term "aliphatic hydrocarbon group" refers to a C1 to C30 straight-chain or branched alkyl, a C1 to C30 straight-chain or branched alkenyl, or a C1 to C30 straight-chain or branched alkynyl, and as used herein, the term "aromatic organic group" refers to a C6 to C30 aryl or a C2 to C30 heteroaryl.

[0118] As used herein, the term "(meth)acrylate (salt)" refers to acrylate (salt) and / or methacrylate (salt).

[0119] As used herein, the term "family" refers to a group of elements in the periodic table.

[0120] As used herein, the terms "nanoparticle" and "nanostructure" refer to a structure having at least one region or characteristic size at the nanoscale. In one or more embodiments, the size of the nanoparticle or nanostructure may be less than about 500 nm, less than about 300 nm, less than about 250 nm, less than about 150 nm, less than about 100 nm, less than about 50 nm, or less than about 30 nm. The nanoparticle or nanostructure may have any shape, such as nanowires, nanorods, nanotubes, multi-arm shapes with two or more arms, nanodots, etc., but the embodiments are not limited thereto. The nanoparticle or nanostructure may be, for example, substantially crystalline, substantially single-crystal, polycrystalline, amorphous, or a combination thereof.

[0121] Quantum dots can be, for example, semiconductor nanocrystal particles that exhibit quantum confinement or exciton confinement effects, and are a type of luminescent nanostructure (e.g., a luminescent nanostructure capable of emitting light upon energy excitation). Here, unless otherwise explicitly defined, the shape of a “quantum dot” or nanoparticle is not limited.

[0122] As used herein, the term "dispersion" refers to a dispersion in which the dispersed phase is a solid and the continuous medium comprises a liquid or solid state different from the dispersed phase. It will be understood that a "dispersion" can be a colloidal dispersion in which the dispersed phase has a size greater than or equal to about 1 nm (e.g., greater than or equal to about 2 nm, greater than or equal to about 3 nm, or greater than or equal to about 4 nm) and less than or equal to 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).

[0123] Here, size (size, diameter, or thickness, etc.) can be a value for a single entity or an average value for multiple nanoparticles. As used herein, the term "average value" (e.g., the average size of a quantum dot) can be the mean or the median. In one or more embodiments, the average value can be the "mean" average.

[0124] As used herein, the term “maximum emission wavelength (or peak emission wavelength)” is the wavelength at which a given emission spectrum of light reaches its maximum (maximum value).

[0125] In one or more embodiments, the quantum efficiency can be easily and reproducibly determined using commercially available equipment (e.g., from Hitachi or Hamamatsu, etc.) and with reference to operating instructions provided by, for example, the respective equipment manufacturer. The quantum efficiency (which can be used interchangeably with the term "quantum yield" (QY)) can be measured in solution or in the solid state (i.e., in a composite). In one or more embodiments, the quantum efficiency (or quantum yield) is the ratio of photons emitted to photons absorbed by a nanostructure or a population of nanostructures. In one or more embodiments, the quantum efficiency can be measured by any method. For example, there are two methods for measuring fluorescence quantum yield or efficiency: absolute methods and relative methods. The quantum efficiency measured by the absolute method can be referred to as the absolute quantum efficiency.

[0126] In the absolute method, 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 a 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 photoluminescence (PL) wavelengths, but the examples are not limited thereto.

[0127] Full width at half maximum (FWHM) and peak emission wavelength (e.g., photoluminescence (PL) or electroluminescence (EL)) can be measured, for example, from the emission spectrum (e.g., photoluminescence spectrum or electroluminescence spectrum) obtained by a spectrophotometer (such as a fluorescence spectrophotometer, etc.).

[0128] As used herein, the term "first absorption peak wavelength" refers to the wavelength at which the main peak first appears in the lowest energy region of the ultraviolet-visible (UV-Vis) absorption spectrum.

[0129] Semiconductor nanoparticles can be used in various electronic devices, for example, in color conversion panels (or emitting color filters). Liquid crystal display devices may include a white emitting backlight unit and an absorptive color filter, and the backlight unit may include a quantum dot sheet. In display devices including quantum dot-based color conversion panels or emitting color filters, a quantum dot layer, as the emitting material, is disposed at the front of the device, and blue light (excitation light) provided by a light source is converted into green or red light through the quantum dot layer. In the color conversion panel, the color conversion of incident light can occur at the relatively front of the device, and a wide viewing angle can be achieved through omnidirectional scattering of light. Emitting color filters can reduce light loss. The color conversion panel can be an electronic device including a color conversion layer or a color conversion structure.

[0130] In display devices including color conversion panels, the properties of the light-emitting nanostructures (e.g., optical properties, stability, etc.) can have a direct impact on the display quality of the device. It is expected that the light-emitting material included in the color conversion panel, located at the relatively front of the device, will exhibit not only relatively high luminous efficiency but also relatively high absorptivity relative to incident light. When patterned films (e.g., color filters) are used in display devices, reduced absorptivity to incident light can be a direct cause of blue light leakage, which has an adverse effect on the device's color reproducibility (e.g., DCI matching rate). The use of absorptive color filters to prevent blue light leakage can lead to an additional reduction in luminous efficiency. Such reduced absorptivity of semiconductor nanoparticles can result in reduced brightness in devices including semiconductor nanoparticles.

[0131] Semiconductor nanoparticles can exhibit properties suitable for device applications (e.g., optical properties and / or stability), but many of them may include cadmium-containing compounds (e.g., cadmium chalcogenides). Cadmium causes serious environmental / health problems and is therefore one of the restricted elements in many countries. Consequently, extensive research has been conducted on cadmium-free, environmentally friendly nanoparticles based on group III-V compounds to develop such nanoparticles. However, cadmium-free nanoparticles including group III-V compounds (e.g., indium phosphide) encounter technical limitations in incident light absorptivity and full width at half maximum (FWHM). Therefore, there remains a technical need to develop such environmentally friendly nanoparticles that are compatible with group III-V compounds. Compared to cadmium-free nanoparticles of Group V compounds (such as indium phosphide), these nanoparticles exhibit higher absorption rates, narrower full width at half maximum (FWHM), and higher luminescence efficiency.

[0132] Display devices comprising a color conversion layer containing semiconductor nanoparticles as color conversion materials may or may not include a light source (e.g., a blue light-emitting diode, such as a blue LED or blue OLED) that provides incident light of a relatively short wavelength. The incident light (e.g., blue light) may have a higher energy (e.g., less than or equal to about 2.75 electron volts (eV)) compared to the color-converted light (e.g., red or green light). It is desirable to provide a color conversion layer that maintains light conversion efficiency and color purity even under repeated irradiation of the incident light to the color conversion layer. The fabrication of the color conversion layer may include the formation of a composite containing semiconductor nanoparticles (e.g., a polymer composite or a pattern thereof), which may involve a high-temperature process. The inventors have confirmed that when AIGS-based semiconductor nanoparticles (e.g., semiconductor nanoparticles containing silver indium gallium sulfide) are exposed to such a high-temperature process, a significant decrease in light conversion efficiency, particularly a significant increase in trap emission (i.e., long-wavelength emission), can be observed compared to before exposure. When using AIGS-based semiconductor nanoparticles as a color conversion layer, it may be necessary to ensure the stability of the AIGS semiconductor nanoparticles (e.g., process durability in terms of emission properties and trap emission).

[0133] The semiconductor nanoparticles of the embodiments can achieve desired emission properties (e.g., increased quantum yield and reduced full width at half maximum) without including cadmium, and can exhibit enhanced stability.

[0134] In embodiments, the semiconductor nanoparticles may be cadmium-free. The semiconductor nanoparticles may be mercury-free, lead-free, or combinations thereof. In embodiments, the semiconductor nanoparticles may comprise silver, indium, gallium, and sulfur (including group 11-13-16 compounds of silver, indium, gallium, and sulfur). The semiconductor nanoparticles may have dimensions greater than or equal to about 2 nm, greater than or equal to about 5 nm, or greater than or equal to about 8 nm and less than or equal to about 50 nm, less than or equal to about 30 nm, less than or equal to about 12 nm, or less than or equal to about 10 nm. As described herein, embodiments of semiconductor nanoparticles based on group 11-13-16 compounds can achieve improved optical properties and stability by adjusting their composition (e.g., the molar ratios or charge balance values ​​between elements as described herein).

[0135] The semiconductor nanoparticles of the embodiments comprise Ag, In, Ga, and S, or group 11-13-16 compounds containing Ag, In, Ga, and S, and exhibit increased levels of absorptivity compared to, for example, indium phosphide-based semiconductor nanoparticles. The semiconductor nanoparticles of the embodiments exhibit enhanced stability and thus maintain or achieve desired levels of optical properties (e.g., light conversion efficiency) even after processes (e.g., post-bake processes) at relatively high temperatures required for composite formation. The semiconductor nanoparticles of the embodiments can be prepared by methods described herein (e.g., involving the formation and separation of intermediate particles), and thus emit light of desired wavelengths with relatively improved efficiency even when the ratio of gallium to indium is relatively high. The semiconductor nanoparticles of the embodiments can be prepared by methods described herein and may have the composition described herein. The semiconductor nanoparticles of the embodiments maintain desired luminescence efficiency even after film formation processes involving relatively high-temperature baking processes, while exhibiting improved levels of optical properties (e.g., high quantum yield and narrow full width at half maximum), and suppress trapped emission to desired levels.

[0136] Without wishing to be bound by any theory, in the method of the embodiments, when a semiconductor nanocrystal layer with a high gallium content is formed, the generation of byproducts (e.g., gallium oxide) that could further negatively affect the properties of the semiconductor nanoparticles can be suppressed, which is believed to help ensure improved optical properties and stability of the semiconductor nanoparticles.

[0137] Therefore, in the semiconductor nanoparticles of the embodiments, the molar ratio of gallium (Ga) to indium (In) (Ga:In) can be greater than or equal to about 20:1, greater than or equal to about 20:1, or greater than or equal to about 23:1. In the semiconductor nanoparticles of the embodiments, the molar ratio of Ga to In (Ga:In) can be greater than or equal to about 20.1:1, greater than or equal to about 20.2:1, greater than or equal to about 20.3:1, greater than or equal to about 20.4:1, greater than or equal to about 20.5:1, greater than or equal to about 20.6:1, greater than or equal to about 20.7:1, greater than or equal to about 20.8:1, greater than or equal to about 20.9:1, greater than or equal to about 21:1, greater than or equal to about 21.1:1, greater than or equal to about 21.3:1, greater than... Or equal to approximately 21.5:1, greater than or equal to approximately 21.7:1, greater than or equal to approximately 21.9:1, greater than or equal to approximately 22:1, greater than or equal to approximately 22.1:1, greater than or equal to approximately 22.3:1, greater than or equal to approximately 22.5:1, greater than or equal to approximately 22.7:1, greater than or equal to approximately 22.9:1, greater than or equal to approximately 23:1, greater than or equal to approximately 23.1:1, greater than or equal to approximately 23.3:1, greater than or equal to approximately 23.5:1, greater than or equal to approximately 23.7:1, or greater than or equal to approximately 23. 9:1; less than or equal to approximately 40:1, less than or equal to approximately 38:1, less than or equal to approximately 36:1, less than or equal to approximately 35:1, less than or equal to approximately 34:1, less than or equal to approximately 33:1, less than or equal to approximately 32:1, less than or equal to approximately 31:1, less than or equal to approximately 30:1, less than or equal to approximately 29:1, less than or equal to approximately 28:1, less than or equal to approximately 27:1, less than or equal to approximately 26:1, less than or equal to approximately 25:1, less than or equal to approximately 24:1, less than or equal to approximately 23.8:1, less than or equal to Approximately 23.6:1, less than or equal to approximately 23.4:1, less than or equal to approximately 23:1, less than or equal to approximately 22.8:1, less than or equal to approximately 22.6:1, less than or equal to approximately 22.4:1, less than or equal to approximately 22.2:1, less than or equal to approximately 21.8:1, less than or equal to approximately 21.6:1, less than or equal to approximately 21.4:1, less than or equal to approximately 21.2:1, less than or equal to approximately 21:1, less than or equal to approximately 20.8:1, or less than or equal to approximately 20.6:1; or a range of combinations thereof.

[0138] In the semiconductor nanoparticles of the embodiments, the molar ratio of silver (Ag) to indium (In) (Ag:In) may be greater than or equal to about 4.9:1, greater than or equal to about 5:1, greater than or equal to about 5.1:1, greater than or equal to about 5.2:1, greater than or equal to about 5.5:1, greater than or equal to about 5.7:1, greater than or equal to about 5.9:1, greater than or equal to about 6:1, greater than or equal to about 6.5:1, greater than or equal to about 7:1, greater than or equal to about 7.5:1, greater than or equal to about 8:1, greater than or equal to about 8.5:1, greater than or equal to about 9:1, greater than or equal to about 9.5:1, greater than or equal to about 10:1, or greater than or equal to about 10.4: 1. Greater than or equal to approximately 11:1, greater than or equal to approximately 11.5:1, greater than or equal to approximately 11.8:1, greater than or equal to approximately 12:1, greater than or equal to approximately 12.5:1, greater than or equal to approximately 13:1, greater than or equal to approximately 13.2:1, greater than or equal to approximately 13.5:1, greater than or equal to approximately 13.7:1, greater than or equal to approximately 13.9:1, greater than or equal to approximately 14:1, greater than or equal to approximately 14.5:1, greater than or equal to approximately 15:1, greater than or equal to approximately 15.1:1, greater than or equal to approximately 15.2:1, greater than or equal to approximately 15.3:1, greater than or equal to approximately 16:1, greater than or equal to approximately 16.5:1, greater than or equal to approximately 17:1, greater than or equal to about 17.5:1, greater than or equal to about 18:1, greater than or equal to about 18.5:1, greater than or equal to about 19:1, greater than or equal to about 19.5:1, or greater than or equal to about 20:1; less than or equal to about 30:1, less than or equal to about 29.5:1, less than or equal to about 29:1, less than or equal to about 28:1, less than or equal to about 27:1, less than or equal to about 26:1, less than or equal to about 25:1, less than or equal to about 24:1, less than or equal to about 23:1, less than or equal to about 22:1, less than or equal to about 21:1, less than or equal to about 20:1, less than or equal to about 19.4:1, less than or Equal to approximately 18.2:1, less than or equal to approximately 17.3:1, less than or equal to approximately 16.2:1, less than or equal to approximately 15.6:1, less than or equal to approximately 15.4:1, less than or equal to approximately 14.8:1, less than or equal to approximately 14.4:1, less than or equal to approximately 13.8:1, less than or equal to approximately 13.2:1, less than or equal to approximately 13:1, less than or equal to approximately 12.4:1, less than or equal to approximately 12.2:1, less than or equal to approximately 11.9:1, less than or equal to approximately 11.6:1, less than or equal to approximately 11.4:1, less than or equal to approximately 10.5:1, or less than or equal to approximately 10.3:1; or a range of combinations thereof.

[0139] In semiconductor nanoparticles, the molar ratio of sulfur to indium (S:In) can be greater than or equal to approximately 20:1, greater than or equal to approximately 25:1, greater than or equal to approximately 27:1, greater than or equal to approximately 29:1, greater than or equal to approximately 30:1, greater than or equal to approximately 30.5:1, greater than or equal to approximately 31:1, greater than or equal to approximately 33:1, greater than or equal to approximately 35:1, greater than or equal to approximately 36:1, greater than or equal to approximately 36.5:1, greater than or equal to approximately 37:1, greater than or equal to approximately 37.3:1, greater than or equal to approximately 37.5:1, and greater than... Or equal to approximately 38:1, or greater than or equal to approximately 39:1; less than or equal to approximately 48:1, less than or equal to approximately 45:1, less than or equal to approximately 42:1, less than or equal to approximately 41:1, less than or equal to approximately 40:1, less than or equal to approximately 39:1, less than or equal to approximately 38.5:1, less than or equal to approximately 37.7:1, less than or equal to approximately 36.3:1, less than or equal to approximately 35.2:1, less than or equal to approximately 34:1, less than or equal to approximately 32:1, or less than or equal to approximately 31.5:1; or a range of combinations thereof.

[0140] In semiconductor nanoparticles, the molar ratio of indium to sulfur (In:S) can be greater than or equal to about 0.01:1, greater than or equal to about 0.015:1, greater than or equal to about 0.02:1, greater than or equal to about 0.025:1, or greater than or equal to about 0.03:1; less than or equal to about 0.1:1, less than or equal to about 0.07:1, less than or equal to about 0.05:1, or less than or equal to about 0.04:1; or a range of combinations thereof.

[0141] In semiconductor nanoparticles, the molar ratio of gallium to sulfur (Ga:S) can be greater than or equal to approximately 0.45:1, greater than or equal to approximately 0.48:1, greater than or equal to approximately 0.49:1, greater than or equal to approximately 0.51:1, greater than or equal to approximately 0.52:1, greater than or equal to approximately 0.53:1, greater than or equal to approximately 0.54:1, greater than or equal to approximately 0.55:1, greater than or equal to approximately 0.56:1, or greater than or equal to approximately 0.5. 7:1, greater than or equal to approximately 0.58:1, greater than or equal to approximately 0.59:1, greater than or equal to approximately 0.6:1, greater than or equal to approximately 0.63:1, greater than or equal to approximately 0.65:1, greater than or equal to approximately 0.67:1, greater than or equal to approximately 0.69:1, greater than or equal to approximately 0.7:1, greater than or equal to approximately 0.72:1, greater than or equal to approximately 0.74:1, greater than or equal to approximately 0.76:1, or greater than or equal to Equal to approximately 0.78:1; less than or equal to approximately 1:1, less than or equal to approximately 0.95:1, less than or equal to approximately 0.9:1, less than or equal to approximately 0.85:1, less than or equal to approximately 0.8:1, less than or equal to approximately 0.79:1, less than or equal to approximately 0.78:1, less than or equal to approximately 0.77:1, less than or equal to approximately 0.75:1, less than or equal to approximately 0.73:1, less than or equal to approximately 0.71:1, less than or equal to... The range is equal to approximately 0.7:1, less than or equal to approximately 0.69:1, less than or equal to approximately 0.68:1, less than or equal to approximately 0.65:1, less than or equal to approximately 0.64:1, less than or equal to approximately 0.61:1, less than or equal to approximately 0.6:1, less than or equal to approximately 0.56:1, less than or equal to approximately 0.54:1, less than or equal to approximately 0.52:1, or less than or equal to approximately 0.5:1; or a range of combinations thereof.

[0142] In semiconductor nanoparticles, the molar ratio of silver (Ag) to sulfur (S) (Ag:S) can be greater than or equal to about 0.33:1, greater than or equal to about 0.35:1, greater than or equal to about 0.355:1, greater than or equal to about 0.37:1, greater than or equal to about 0.375:1, greater than or equal to about 0.39:1, greater than or equal to about 0.4:1, or greater than or equal to about 0.41:1; less than or equal to about 0.5:1, less than or equal to about 0.45:1, less than or equal to about 0.44:1, less than or equal to about 0.43:1, less than or equal to about 0.42:1, less than or equal to about 0.41:1, less than or equal to about 0.4:1, less than or equal to about 0.39:1, less than or equal to about 0.38:1, less than or equal to about 0.36:1, or less than or equal to about 0.34:1; or a range of combinations thereof.

[0143] In semiconductor nanoparticles, the molar ratio of gallium (Ga) to silver (Ag) (Ga:Ag) can be greater than or equal to approximately 1:1, greater than or equal to approximately 1.1:1, greater than or equal to approximately 1.15:1, greater than or equal to approximately 1.2:1, greater than or equal to approximately 1.25:1, greater than or equal to approximately 1.3:1, greater than or equal to approximately 1.35:1, greater than or equal to approximately 1.38:1, greater than or equal to approximately 1.4:1, and greater than or equal to approximately 1.45. :1, greater than or equal to about 1.5:1, greater than or equal to about 1.55:1, greater than or equal to about 1.6:1, greater than or equal to about 1.65:1, greater than or equal to about 1.7:1, greater than or equal to about 1.75:1, greater than or equal to about 1.8:1, greater than or equal to about 1.85:1, greater than or equal to about 1.9:1, greater than or equal to about 1.95:1, greater than or equal to about 2:1, or greater than or equal to about 2.05:1; smaller The ratios are approximately 3:1, 2.9:1, 2.8:1, 2.7:1, 2.6:1, 2.5:1, 2.4:1, 2.3:1, 2.2:1, 2.1:1, 2:1, 1.9:1, 1.8:1, and less than 3:1. Or equal to approximately 1.75:1, less than or equal to approximately 1.7:1, less than or equal to approximately 1.65:1, less than or equal to approximately 1.6:1, less than or equal to approximately 1.58:1, less than or equal to approximately 1.56:1, less than or equal to approximately 1.52:1, less than or equal to approximately 1.48:1, less than or equal to approximately 1.46:1, less than or equal to approximately 1.44:1, or less than or equal to approximately 1.42:1; or a range of combinations thereof.

[0144] In semiconductor nanoparticles, the molar ratio of gallium (Ga) to the sum of indium (In) and gallium (Ga:(In+Ga)) can be greater than approximately 0.95:1, greater than or equal to approximately 0.951:1, greater than or equal to approximately 0.952:1, greater than or equal to approximately 0.953:1, greater than or equal to approximately 0.954:1, greater than or equal to approximately 0.955:1, greater than or equal to approximately 0.956:1, greater than or equal to approximately 0.957: 1. Greater than or equal to about 0.958:1, greater than or equal to about 0.959:1, or greater than or equal to about 0.96:1; less than or equal to about 0.99:1, less than or equal to about 0.985:1, less than or equal to about 0.98:1, less than or equal to about 0.975:1, less than or equal to about 0.97:1, less than or equal to about 0.965:1, or less than or equal to about 0.962:1; or a range of combinations thereof.

[0145] In semiconductor nanoparticles, the molar ratio of indium to the sum of indium and gallium (In:(In+Ga)) can be less than about 0.05:1, less than or equal to about 0.049:1, less than or equal to about 0.048:1, less than or equal to about 0.047:1, less than or equal to about 0.046:1, less than or equal to about 0.045:1, less than or equal to about 0.04:1, less than or equal to about 0.035:1, or less than or equal to about 0.03:1; greater than or equal to about 0.01:1, or greater than or equal to about 0.011. :1, greater than or equal to about 0.015:1, greater than or equal to about 0.02:1, greater than or equal to about 0.023:1, greater than or equal to about 0.024:1, greater than or equal to about 0.025:1, greater than or equal to about 0.027:1, greater than or equal to about 0.028:1, greater than or equal to about 0.029:1, greater than or equal to about 0.03:1, greater than or equal to about 0.035:1, greater than or equal to about 0.04:1, or greater than or equal to about 0.041:1; or a range of combinations thereof.

[0146] In semiconductor nanoparticles, the molar ratio of indium and gallium to silver ((In+Ga):Ag) can be greater than or equal to approximately 1.2:1, greater than or equal to approximately 1.3:1, greater than or equal to approximately 1.4:1, greater than or equal to approximately 1.41:1, greater than or equal to approximately 1.43:1, greater than or equal to approximately 1.45:1, greater than or equal to approximately 1.46:1, greater than or equal to approximately 1.47:1, greater than or equal to approximately 1.48:1, greater than or equal to approximately 1.5:1, greater than or equal to approximately 1.53:1, greater than or equal to approximately 1.54:1, greater than or equal to approximately 1.57:1, greater than or equal to approximately 1.58:1, greater than or equal to approximately 1.59:1, greater than or equal to approximately 1.6:1, greater than or equal to approximately 1.63:1, greater than or equal to approximately 1.65:1, greater than or equal to approximately 1.68. :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, greater than or equal to about 2:1, greater than or equal to about 2.1:1, greater than or equal to about 2.15:1, or greater than or equal to about 2.19:1; 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 2.3:1, less than or equal to about 2.25:1, less than or equal to about 2.2:1, less than or equal to about 2:1, less than or equal to about 1.96:1, less than or equal to about 1.95:1, less than or equal to about 1.9:1, less than or equal to about 1.7:1, or less than or equal to about 1.62:1; or a range of combinations thereof.

[0147] In semiconductor nanoparticles, the molar ratio of indium and gallium to sulfur ((In+Ga):S) can be greater than or equal to approximately 0.3:1, greater than or equal to approximately 0.4:1, greater than or equal to approximately 0.45:1, greater than or equal to approximately 0.5:1, greater than or equal to approximately 0.52:1, greater than or equal to approximately 0.53:1, greater than or equal to approximately 0.54:1, greater than or equal to approximately 0.55:1, greater than or equal to approximately 0.56:1, greater than or equal to approximately 0.57:1, greater than or equal to approximately 0.58:1, greater than or equal to approximately 0.59:1, greater than or equal to approximately 0.6:1, greater than or equal to approximately 0.62:1, greater than or equal to approximately 0.64:1, greater than or equal to approximately 0.68:1, or greater than or equal to approximately 0.7:1. The range of values ​​is greater than or equal to approximately 0.72:1, greater than or equal to approximately 0.75:1, greater than or equal to approximately 0.77:1, greater than or equal to approximately 0.78:1, greater than or equal to approximately 0.79:1, or greater than or equal to approximately 0.81:1; less than or equal to approximately 0.9:1, less than or equal to approximately 0.88:1, less than or equal to approximately 0.86:1, less than or equal to approximately 0.84:1, less than or equal to approximately 0.82:1, less than or equal to approximately 0.78:1, less than or equal to approximately 0.73:1, less than or equal to approximately 0.71:1, less than or equal to approximately 0.69:1, less than or equal to approximately 0.67:1, less than or equal to approximately 0.66:1, or less than or equal to approximately 0.65:1; or a range of combinations thereof.

[0148] In semiconductor nanoparticles, the molar ratio of silver (Ag) to the sum of silver (Ag), indium (In), and gallium (Ga) (Ag:(Ag+In+Ga)) can be greater than or equal to approximately 0.31:1, greater than or equal to approximately 0.33:1, greater than or equal to approximately 0.34:1, greater than or equal to approximately 0.35:1, greater than or equal to approximately 0.37:1, greater than or equal to approximately 0.38:1, greater than or equal to approximately 0.39:1, greater than or equal to approximately 0.4:1, greater than or equal to... Approximately 0.41:1, greater than or equal to approximately 0.43:1, or greater than or equal to approximately 0.44:1; less than or equal to approximately 0.55:1, less than or equal to approximately 0.5:1, less than or equal to approximately 0.45:1, less than or equal to approximately 0.42:1, less than or equal to approximately 0.4:1, less than or equal to approximately 0.36:1, less than or equal to approximately 0.33:1, less than or equal to approximately 0.32:1, or less than or equal to approximately 0.28:1; or a range of combinations thereof.

[0149] In semiconductor nanoparticles, the molar ratio of gallium (Ga) to the sum of gallium (Ga), indium (In), and silver (Ag) (Ga:(Ga+In+Ag)) can be greater than or equal to approximately 0.45:1, greater than or equal to approximately 0.46:1, greater than or equal to approximately 0.47:1, greater than or equal to approximately 0.48:1, greater than or equal to approximately 0.49:1, greater than or equal to approximately 0.5:1, greater than or equal to approximately 0.51:1, greater than or equal to approximately 0.52:1, greater than or equal to approximately 0.53:1, greater than or equal to approximately 0.55:1, greater than or equal to approximately 0.56:1, greater than or equal to approximately 0.57:1, greater than or equal to approximately 0.58:1, greater than or equal to approximately 0.59:1, greater than or equal to approximately 0.595:1, greater than or equal to approximately 0.6:1, greater than or equal to approximately 0.61:1, greater than or equal to approximately 0.63:1. Greater than or equal to about 0.64:1, or greater than or equal to about 0.65:1; less than or equal to about 0.85:1, less than or equal to about 0.8:1, less than or equal to about 0.77:1, less than or equal to about 0.74:1, less than or equal to about 0.73:1, less than or equal to about 0.72:1, less than or equal to about 0.71:1, less than or equal to about 0.69:1, less than or equal to about 0.67:1, less than or equal to about 0.658:1, less than or equal to about 0.64:1, less than or equal to about 0.62:1, less than or equal to about 0.61:1, less than or equal to about 0.59:1, less than or equal to about 0.56:1, less than or equal to about 0.54:1, less than or equal to about 0.53:1, less than or equal to about 0.49:1, or less than or equal to about 0.485:1; or a range of combinations thereof.

[0150] In semiconductor nanoparticles, the molar ratio of sulfur (S) to the sum of silver (Ag), indium (In), and gallium (Ga) (S:(Ag+In+Ga)) can be greater than or equal to approximately 0.85:1, greater than or equal to approximately 0.87:1, greater than or equal to approximately 0.88:1, greater than or equal to approximately 0.89:1, greater than or equal to approximately 0.9:1, greater than or equal to approximately 0.92:1, greater than or equal to approximately 0.95:1, greater than or equal to approximately 1:1, greater than or equal to approximately 1.02:1, greater than or equal to approximately 1.03:1, greater than or equal to approximately 1.04:1, greater than or equal to approximately 1.05:1, greater than or equal to approximately 1.06:1, greater than or equal to approximately... 1.07:1, greater than or equal to about 1.08:1, greater than or equal to about 1.09:1, greater than or equal to about 1.1:1, or greater than or equal to about 1.2:1; 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 1.15:1, less than or equal to about 1.13:1, less than or equal to about 1.12:1, less than or equal to about 1.11:1, less than or equal to about 1.1:1, less than or equal to about 1.09:1, less than or equal to about 1.08:1, less than or equal to about 0.9:1, or less than or equal to about 0.89:1; or a range of combinations thereof.

[0151] Semiconductor nanoparticles may have a charge balance value obtained by the following equation A1, which is greater than or equal to about 0.95, greater than or equal to about 0.98, greater than or equal to about 1, or greater than or equal to about 1.01; less than or equal to about 1.45, less than or equal to about 1.4, less than or equal to about 1.35, less than or equal to about 1.3, less than or equal to about 1.25, less than or equal to about 1.2, less than or equal to about 1.15, less than or equal to about 1.1, less than or equal to about 1.09, less than or equal to about 1.08, less than or equal to about 1.07, less than or equal to about 1.06, or less than or equal to about 1.05; or a range of combinations thereof.

[0152] Equation A1

[0153] Charge balance value = {[Ag] + 3([In] + [Ga])} / 2[S]

[0154] Wherein, [Ag], [In], [Ga], and [S] represent the molar contents of silver, indium, gallium, and sulfur in the semiconductor nanoparticles, respectively.

[0155] Semiconductor nanoparticles may also include halogens (e.g., chlorine, bromine, or combinations thereof).

[0156] In semiconductor nanoparticles, the content of halogens (e.g., chlorine, bromine, or combinations thereof) can be based on indium from 0.4 mol% to less than or equal to about 3200 mol% (i.e., for every 1 mole of indium, 0.004 mol to less than or equal to about 32 mol of halogens (chlorine, bromine, or combinations thereof)).

[0157] In semiconductor nanoparticles, based on indium (e.g., per mole of indium), the content of halogens (e.g., chlorine, bromine, or combinations thereof) may be greater than or equal to about 0.01 mol% (e.g., greater than or equal to about 0.0001 mol), greater than or equal to about 0.03 mol%, greater than or equal to about 0.05 mol%, greater than or equal to about 0.08 mol%, greater than or equal to about 0.1 mol%, greater than or equal to about 0.15 mol%, greater than or equal to about 0.25 mol%, greater than or equal to about 0.3 mol%, greater than or equal to about 0.35 mol%, greater than or equal to about 0. 4 mol%, greater than or equal to about 0.45 mol%, greater than or equal to about 0.5 mol%, greater than or equal to about 0.6 mol%, greater than or equal to about 0.7 mol%, greater than or equal to about 0.8 mol%, greater than or equal to about 0.9 mol%, greater than or equal to about 1 mol%, greater than or equal to about 1.5 mol%, greater than or equal to about 2 mol%, greater than or equal to about 2.5 mol%, greater than or equal to about 3 mol%, greater than or equal to about 3.5 mol%, greater than or equal to about 4 mol%, greater than or equal to about 4.5 mol%, greater than or equal to about 5 mol%. Greater than or equal to about 5.5 mol%, greater than or equal to about 6 mol%, greater than or equal to about 6.5 mol%, greater than or equal to about 7 mol%, greater than or equal to about 7.5 mol%, greater than or equal to about 8 mol%, greater than or equal to about 8.5 mol%, greater than or equal to about 9 mol%, greater than or equal to about 10 mol%, greater than or equal to about 13 mol%, greater than or equal to about 15 mol%, greater than or equal to about 17 mol%, greater than or equal to about 20 mol%, greater than or equal to about 25 mol%, greater than or equal to about 30 mol%, greater than or equal to about 35 mol% %, greater than or equal to about 40 mol%, greater than or equal to about 45 mol%, greater than or equal to about 50 mol%, greater than or equal to about 60 mol%, greater than or equal to about 70 mol%, greater than or equal to about 80 mol%, greater than or equal to about 90 mol%, greater than or equal to about 100 mol%, greater than or equal to about 150 mol%, greater than or equal to about 200 mol%, greater than or equal to about 250 mol%, greater than or equal to about 300 mol%, greater than or equal to about 350 mol%, greater than or equal to about 400 mol%, or greater than or equal to about 450 mol%.

[0158] Based on indium (e.g., per 1 mole of indium), the amount of halogen (e.g., chlorine, bromine, or combinations thereof) may be less than or equal to about 3200 mol% (e.g., less than or equal to about 32 mol, Br:In≈32), less than or equal to about 3000 mol%, less than or equal to about 2500 mol%, less than or equal to about 2000 mol%, less than or equal to about 1500 mol%, less than or equal to about 1000 mol%, less than or equal to about 900 mol%, less than or equal to about 800 mol%, less than or equal to about 700 mol%, less than or equal to about 600 mol%, less than or equal to about 500 mol%, less than or equal to about 380 mol%, less than or equal to about 230 mol%. %, less than or equal to about 120 mol%, less than or equal to about 110 mol%, less than or equal to about 100 mol%, less than or equal to about 85 mol%, less than or equal to about 75 mol%, less than or equal to about 65 mol%, less than or equal to about 55 mol%, less than or equal to about 44 mol%, less than or equal to about 42 mol%, less than or equal to about 37 mol%, less than or equal to about 23 mol%, less than or equal to about 19 mol%, less than or equal to about 14 mol%, less than or equal to about 7.2 mol%, less than or equal to about 6.8 mol%, less than or equal to about 4.3 mol%, less than or equal to about 3.9 mol%, or less than or equal to about 2.3 mol%.

[0159] In semiconductor nanoparticles, the concentration of indium can vary in the radial direction. The indium content in the inner portion of the nanoparticle can differ from the indium content in the outer portion. In embodiments, the indium content in the portion adjacent to the surface (e.g., the outermost layer or outermost shell) can be lower than the indium content in the inner portion of the particle (e.g., the core).

[0160] In embodiments, the zinc content (zinc concentration) in the portion adjacent to the surface (e.g., the outermost layer) may be greater than the zinc content (zinc concentration) in the inner portion of the particle (e.g., the core). In semiconductor nanoparticles, the zinc concentration may be greater in the outer region of the particle than in the inner region. The core or the first semiconductor nanocrystal may not contain zinc. In the shell, gallium may exhibit a radial concentration gradient (e.g., a radial concentration gradient that increases or decreases in the radial direction (e.g., towards the surface of the particle). In the shell, the gallium concentration in the portion of the particle adjacent to the surface may be greater than the gallium concentration in the portion adjacent to the core.

[0161] Semiconductor nanoparticles may have a core-shell structure comprising 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 a multilayer shell may include a first shell layer disposed on the core, a second shell layer disposed on the first shell layer, and a third shell layer disposed on the second shell layer. The first shell layer may include the second semiconductor nanocrystal. The second or third shell layer may include additional semiconductor nanocrystals comprising zinc, sulfur, and optionally gallium (e.g., zinc chalcogenide or zinc gallium chalcogenide), and may include a third semiconductor nanocrystal and / or a fourth semiconductor nanocrystal.

[0162] In embodiments, the semiconductor nanoparticles or first semiconductor nanocrystals may include silver, group 13 elements, and chalcogenides (or group 11-13-16 compounds comprising silver, group 13 elements, and chalcogenides). The first semiconductor nanocrystals may or may not further include zinc. Group 13 elements may include indium, gallium, or combinations thereof. Chalcogenides may include sulfur and optionally selenium. The first semiconductor nanocrystals may include silver, group 13 metals (e.g., indium, gallium, or combinations thereof), and group 16 elements (e.g., sulfur and optionally selenium). The first semiconductor nanocrystals may include quaternary alloy semiconductor materials based on group 11-13-16 compounds comprising silver, indium, gallium, and sulfur. The semiconductor nanoparticles or first semiconductor nanocrystals may include silver indium gallium sulfide (hereinafter abbreviated as AIGS). The first semiconductor nanocrystals may include Ag(In) x Ga 1-x S2 (x is greater than 0 and less than or equal to 1). The molar ratio between the components in the first semiconductor nanocrystal can be adjusted so that the final semiconductor nanoparticles can have the desired composition and optical properties (e.g., maximum emission wavelength).

[0163] In the first semiconductor nanocrystal, the molar ratio of Ga to the sum of In and Ga (Ga:(In+Ga)) can be greater than about 0, or greater than or equal to about 0.1:1, greater than or equal to about 0.2:1, greater than or equal to about 0.3:1, greater than or equal to about 0.4:1, or greater than or equal to about 0.45:1. In the first semiconductor nanocrystal, the molar ratio of Ga to the sum of In and Ga (Ga:(In+Ga)) can be less than or equal to about 0.55:1, less than or equal to about 0.5:1, less than or equal to about 0.49:1, less than or equal to about 0.45:1, less than or equal to about 0.42:1, less than or equal to about 0.33:1, or less than or equal to about 0.25:1.

[0164] The semiconductor nanoparticles may also include a second semiconductor nanocrystal, additional semiconductor nanocrystals (e.g., a third and / or fourth semiconductor nanocrystal), or combinations thereof, wherein the second semiconductor nanocrystal comprises gallium, sulfur, and optionally silver and has a composition different from that of the first semiconductor nanocrystal. The second semiconductor nanocrystal may include group 13-16 compounds, group 11-13-16 compounds, or combinations thereof. Group 13-16 compounds may include gallium sulfide, gallium selenide, indium sulfide, indium selenide, indium gallium sulfide, indium gallium selenide, indium gallium selenide, or combinations thereof. The second semiconductor nanocrystal may include gallium and chalcogenides (sulfur and optionally selenium). The second semiconductor nanocrystal may include a ternary alloy semiconductor material comprising silver, gallium, and sulfur. The molar ratios between the components in the second semiconductor nanocrystal can be adjusted to achieve the desired composition and optical properties of the final semiconductor nanoparticles.

[0165] Additional semiconductor nanocrystals may include zinc, sulfur, and optionally gallium. In one embodiment, a third semiconductor nanocrystal may include zinc, gallium, and sulfur. A fourth semiconductor nanocrystal may include zinc and sulfur. The third semiconductor nanocrystal may include zinc gallium sulfide. The fourth semiconductor nanocrystal may include zinc sulfide.

[0166] A second semiconductor nanocrystal may cover at least a portion of the first semiconductor nanocrystal. The band gap energy of the second semiconductor nanocrystal may differ from that of the first semiconductor nanocrystal. The band gap energy of the second semiconductor nanocrystal may be greater than that of the first semiconductor nanocrystal. The band gap energy of the second semiconductor nanocrystal may be less than that of the first semiconductor nanocrystal. The band gap energy of an additional semiconductor nanocrystal (e.g., a third or fourth semiconductor nanocrystal) may be greater than that of the second semiconductor nanocrystal. The layer comprising the third or fourth semiconductor nanocrystal may be the outermost layer of the semiconductor nanoparticles.

[0167] In the embodiments, the semiconductor nanoparticles may have a core / multilayer shell structure (such as AgInGaS / AgGaS, AgInGaS / AgGaS / GaS, AgInGaS / AgGaS / ZnGaS, AgInGaS / AgGaS / ZnS or AgInGaS / AgGaS / ZnGaS / ZnS).

[0168] The size (or average 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 (average 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; or may be a range of combinations thereof.

[0169] The thickness of the second semiconductor nanocrystal or the layer comprising 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 comprising the second semiconductor nanocrystal may be less than or equal to about 4 nm, less than or equal to about 3.5 nm, less than or equal to about 3 nm, less than or equal to about 2.5 nm, less than or equal to about 2 nm, less than or equal to about 1.5 nm, less than or equal to about 1 nm, or less than or equal to about 0.8 nm; or may be a range of combinations thereof.

[0170] When present, the size (e.g., thickness) of the third semiconductor nanocrystal or the layer comprising the third semiconductor nanocrystal may be greater than or equal to about 0.1 nm, greater than or equal to about 0.3 nm, greater than or equal to about 0.5 nm, greater than or equal to about 0.7 nm, or greater than or equal to about 1 nm. The size (e.g., thickness) of the third semiconductor nanocrystal or the layer comprising the third semiconductor nanocrystal may be less than or equal to about 2 nm, less than or equal to about 1.5 nm, less than or equal to about 1 nm, or less than or equal to about 0.8 nm. The thickness of the third semiconductor nanocrystal layer may be in the range of 0.1 nm to 5 nm, 0.2 nm to 4 nm, 0.3 nm to 3.5 nm, 0.4 nm to 3 nm, 0.5 nm to 2.5 nm, 0.6 nm to 2 nm, 0.7 nm to 1.5 nm, 0.8 nm to 1.2 nm, 0.9 nm to 1 nm, or combinations thereof.

[0171] In the embodiments, the size or average particle size of the semiconductor nanoparticles (hereinafter referred to as the "size") 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 may 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 nm, less than or equal to about 6 nm, or less than or equal to about 4 nm; or may be a range of combinations thereof.

[0172] In an embodiment, the size of the semiconductor nanoparticles can be the particle diameter. The size of the semiconductor nanoparticles can be obtained from images identified by analysis using an electron microscope (e.g., a transmission electron microscope). The size (e.g., diameter) of the semiconductor nanoparticles can be an equivalent diameter obtained through calculations involving converting a two-dimensional region of the particle obtained from the electron microscope image into a circle. Such particle sizes can be reproducibly and easily obtained from microscope images using various image processing programs (e.g., ImageJ or internal programs created using a coding language). The particle size can also be a value calculated from the composition and peak emission wavelength of the semiconductor nanoparticles (e.g., the nominal particle size).

[0173] Semiconductor nanoparticles may have an average size greater than or equal to about 5 nm, greater than or equal to about 5.1 nm, or greater than or equal to about 5.2 nm and less than or equal to about 10 nm, less than or equal to about 7 nm, less than or equal to about 6.5 nm, less than or equal to about 6 nm, or less than or equal to about 5.4 nm.

[0174] Semiconductor nanoparticles may have a size distribution expressed as a standard deviation, which is less than or equal to about 20%, less than or equal to about 19%, less than or equal to about 18%, less than or equal to about 17%, less than or equal to about 16%, less than or equal to about 15%, less than or equal to about 14%, less than or equal to about 13%, less than or equal to about 12%, less than or equal to about 11%, or less than or equal to about 10% of the average size. The standard deviation may be greater than or equal to about 5%, greater than or equal to about 10%, or greater than or equal to about 12%.

[0175] The semiconductor nanoparticles described in this embodiment can be manufactured using the method described herein.

[0176] In color conversion layer-based display technologies, research has been conducted on using environmentally friendly InP-based quantum dots as luminescent materials. InP-based quantum dots can include an inorganic coating (e.g., ZnSe or ZnS) as a shell on an indium phosphide semiconductor nanocrystal serving as the emission center. However, the inventors have found that the relatively large volume ratio occupied by the inorganic coating (i.e., the shell) in the quantum dots limits the achievement of desired levels of incident light (e.g., blue light) absorption.

[0177] Semiconductor nanocrystals based on 11-13-16 compound semiconductors (e.g., including silver, indium, gallium, and sulfur) can provide increased incident light absorption, and much research is being conducted in this field. To apply semiconductor nanoparticles as color conversion materials in color conversion layers, the semiconductor nanoparticles can undergo a film-forming process. This film-forming process may involve contacting the semiconductor nanoparticles with a monomer and, for example, high-temperature treatment at 180°C or higher. The inventors have discovered that during such film-forming processes, semiconductor nanoparticles can experience a significant reduction in optical properties (e.g., emission efficiency). To prevent this significant reduction, semiconductor nanoparticles can be formed by reacting sulfur and gallium (and optionally a silver compound) in the presence of semiconductor nanocrystals based on 11-13-16 compounds. Compared to semiconductor nanocrystals based on 11-13-16 compounds, semiconductor nanoparticles formed by such a reaction exhibit a significantly increased gallium to indium molar ratio, and particle stability also increases with the increase of the gallium to indium molar ratio. However, the inventors have also discovered that as the molar ratio of gallium to indium increases (e.g., when the molar ratio of gallium to indium increases to 20:1 or greater), the emission efficiency of the resulting semiconductor nanoparticles can decrease significantly (e.g., substantially). Without wishing to be bound by any theory, it is believed that byproducts including gallium formed during the reaction can negatively impact the emission properties of the final semiconductor nanoparticles.

[0178] A method for manufacturing semiconductor nanoparticles according to an embodiment may include: contacting a sulfur precursor, a gallium precursor, and optionally a silver compound in the presence of a semiconductor nanocrystal based on a group 11-13-16 compound (hereinafter referred to as a first contact or a first reaction) to increase the size of the semiconductor nanoparticles and form intermediate particles; separating the formed intermediate particles, and optionally washing the separated intermediate particles; and contacting the sulfur precursor, gallium precursor, and optionally a silver compound in the presence of the intermediate particles (e.g., as optionally washed) (i.e., a second contact or a second reaction). The semiconductor nanoparticles thus prepared may (e.g., in a crude solution) exhibit the properties described herein, such as simultaneously possessing enhanced stability and efficiency.

[0179] Therefore, in the embodiments, the method for manufacturing semiconductor nanoparticles may include:

[0180] In a first medium comprising a first organic solvent, a first semiconductor nanocrystal comprising silver, a group 13 element and a chalcogenide element is mixed (or contacted) with a first sulfur precursor, a first gallium precursor and an optional first silver compound.

[0181] The first medium is heated to a first reaction temperature (e.g., for a first reaction time) to form intermediate particles;

[0182] Separate the intermediate particles thus formed (e.g., separate the formed intermediate particles from the first medium);

[0183] In a second medium comprising a second organic solvent, the separated intermediate particles are mixed (or contacted) with a second sulfur precursor, a second gallium precursor, and optionally a second silver compound; and

[0184] The second medium is heated to a second reaction temperature (e.g., for a second reaction time) to form semiconductor nanoparticles.

[0185] The separated intermediate particles can be washed with solvent before being added to the second medium.

[0186] In the methods of the embodiments, mixing or contacting may include adding an organic ligand, a first semiconductor nanocrystal (or intermediate particle), and a first (or second) gallium precursor to a first (or second) medium (e.g., this can be done by adding the organic ligand, the first semiconductor nanocrystal (or intermediate particle), and the first (or second) gallium precursor to the first (or second) medium). In the methods of the embodiments, mixing or contacting may include adding a first (or second) silver compound to the first (or second) medium (e.g., this can be done by adding the first (or second) silver compound to the first (or second) medium). Both the first and second media may also independently include an organic ligand. For example, the first (or second) medium may include a first (or second) organic solvent, a first (or second) sulfur precursor, and optionally a first (or second) organic ligand.

[0187] The methods of the embodiments will be described in more detail below.

[0188] Preparation of the first semiconductor nanocrystal

[0189] Details of the first semiconductor nanocrystal are described herein. The first semiconductor nanocrystal may include silver (Ag), indium, gallium, and sulfur. There are no particular limitations on the method used to manufacture the first semiconductor nanocrystal, and it may be suitably selected. In embodiments, the first semiconductor nanocrystal is obtained by contacting (or reacting) a desired precursor (such as a silver precursor, indium precursor, gallium precursor, and sulfur precursor) depending on its composition in a solution comprising organic ligands and an organic solvent at a predetermined nucleation reaction temperature (e.g., 180°C to 300°C, or 200°C to 280°C) for a predetermined time, followed by separation.

[0190] In an embodiment, the manufactured first semiconductor nanocrystal can be separated and optionally washed. Separation and washing can be performed by the method described herein.

[0191] In embodiments, the nucleation reaction 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 220°C, greater than or equal to about 230°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, or 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 nucleation reaction temperature can be less than or equal to about 380°C, less than or equal to about 375°C, less than or equal to about 370°C, less than or equal to about 365°C, less than or equal to about 360°C, less than or equal to about 355°C, less than or equal to about 350°C, less than or equal to about 340°C, less than or equal to about 330°C, less than or equal to about 320°C, less than or equal to about 310°C, less than or equal to about 300°C, less than or equal to about 290°C, less than or equal to about 280°C, less than or equal to about 270°C, less than or equal to about 260°C, or less than or equal to about 250°C.

[0192] The nucleation reaction time is not particularly limited and can be appropriately selected taking into account the desired size of the first semiconductor nanocrystal, the peak emission wavelength of the first semiconductor nanocrystal or the final semiconductor nanoparticle, the reactivity of the precursor, and the reaction temperature. The nucleation reaction time can be greater than or equal to about 1 minute, greater than or equal to about 3 minutes, greater than or equal to about 5 minutes, greater than or equal to about 10 minutes, greater than or equal to about 20 minutes, or greater than or equal to about 30 minutes. The nucleation reaction time can be from about 1 minute to about 2 hours, from about 5 minutes to about 90 minutes, from about 10 minutes to about 70 minutes, or a combination thereof.

[0193] In embodiments, the nucleation reaction 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 220°C, greater than or equal to about 230°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, or 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 nucleation reaction temperature can be less than or equal to about 380°C, less than or equal to about 375°C, less than or equal to about 370°C, less than or equal to about 365°C, less than or equal to about 360°C, less than or equal to about 355°C, less than or equal to about 350°C, less than or equal to about 340°C, less than or equal to about 330°C, less than or equal to about 320°C, less than or equal to about 310°C, less than or equal to about 300°C, less than or equal to about 290°C, less than or equal to about 280°C, less than or equal to about 270°C, less than or equal to about 260°C, or less than or equal to about 250°C.

[0194] The nucleation reaction time is not particularly limited and can be appropriately selected taking into account the desired size of the first semiconductor nanocrystal, the peak emission wavelength of the first semiconductor nanocrystal or the final semiconductor nanoparticle, the reactivity of the precursor, and the reaction temperature. The nucleation reaction time can be greater than or equal to about 1 minute, greater than or equal to about 3 minutes, greater than or equal to about 5 minutes, greater than or equal to about 10 minutes, greater than or equal to about 20 minutes, or greater than or equal to about 30 minutes. The nucleation reaction time can be from about 1 minute to about 2 hours, from about 5 minutes to about 90 minutes, from about 10 minutes to about 70 minutes, or a combination thereof.

[0195] Formation of intermediate particles

[0196] In a first medium comprising a first organic solvent, a first semiconductor nanocrystal is mixed (or contacted) with a first sulfur precursor, a first gallium precursor, and optionally a first silver compound, and the first medium is heated to a first reaction temperature (e.g., for a first reaction time) to form intermediate particles. During heating, the first medium may further comprise the first sulfur precursor, the first gallium precursor, and optionally the first silver compound.

[0197] In the method, the first medium may be pretreated (e.g., pretreated under vacuum). The first medium (e.g., a first medium including a first sulfur precursor) may be pretreated under vacuum prior to the addition of the first semiconductor nanocrystal or the first gallium precursor. The pretreatment temperature may be below the first reaction temperature. The pretreatment temperature may, for example, be greater than or equal to about 20°C, greater than or equal to about 25°C, 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.

[0198] In embodiments, the method may include adding a first semiconductor nanocrystal along with a first gallium precursor, a first sulfur precursor, or both, to a first (reaction) medium comprising a first organic solvent (and optionally the first sulfur precursor). The method may also include adding a first silver compound to the first medium. There are no particular limitations on the manner in which the first semiconductor nanocrystal, the first gallium precursor, and the first sulfur precursor are added (e.g., the order or form of addition). The first semiconductor nanocrystal may be added to the reaction medium in a state dispersed in a suitable organic solvent, but is not limited thereto.

[0199] A first medium (e.g., obtained after mixing) is heated to a first reaction temperature for a first reaction time to form intermediate particles. The formation of the intermediate particles may include performing a reaction (first reaction) between a sulfur precursor and a gallium precursor (and optionally a silver compound) in the presence of a first semiconductor nanocrystal comprising a group 13 element and a chalcogenide. Where it is not desired to be bound by any theory, a second semiconductor nanocrystal comprising gallium sulfide or silver gallium sulfide may be formed on the first semiconductor nanocrystal via a reaction, and the molar ratio of gallium to indium in the particles may be increased. The first medium may be a reaction medium used for the first reaction.

[0200] Embodiments of the method may include heating a first medium (including a first organic solvent and optionally a first sulfur precursor) to a first injection temperature under vacuum or in an inert atmosphere, and adding a first semiconductor nanocrystal, a first gallium precursor, a first sulfur precursor, or a combination thereof to the medium heated to the first injection temperature. Embodiments of the method may include heating a reaction mixture comprising the first semiconductor nanocrystal, the first gallium precursor, the first sulfur precursor, and a first silver compound to a first reaction temperature.

[0201] The first injection 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 injection 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.

[0202] The first reaction temperature may be higher than the first injection temperature. The difference between the first reaction temperature and the first injection temperature may be greater than or equal to about 5°C, greater than or equal to about 10°C, greater than or equal to about 15°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 and less than or equal to about 200°C, less than or equal to about 190°C, or 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.

[0203] The initial reaction temperature may be: 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, 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 33°C. The temperature ranges are: 0°C, greater than or equal to approximately 335°C, greater than or equal to approximately 340°C, or greater than or equal to approximately 345°C; less than or equal to approximately 380°C, less than or equal to approximately 375°C, less than or equal to approximately 370°C, less than or equal to approximately 365°C, less than or equal to approximately 360°C, less than or equal to approximately 355°C, less than or equal to approximately 350°C, less than or equal to approximately 340°C, less than or equal to approximately 330°C, less than or equal to approximately 320°C, less than or equal to approximately 310°C, less than or equal to approximately 300°C, less than or equal to approximately 290°C, less than or equal to approximately 280°C, less than or equal to approximately 270°C, less than or equal to approximately 260°C, or less than or equal to approximately 250°C; or combinations thereof. The first reaction temperature can be adjusted within the above temperature ranges.

[0204] The first reaction time can be appropriately controlled taking into account the precursor, reaction temperature, and peak emission wavelength of the intermediate particles or the final semiconductor nanoparticles. In embodiments, the first 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, greater than or equal to about 80 minutes, greater than or equal to about 90 minutes, greater than or equal to about 2 hours, greater than or equal to about 150 minutes, greater than or equal to about 3 hours, greater than or equal to about 190 minutes, greater than or equal to about 200 minutes, greater than or equal to about 210 minutes, greater than or equal to about 220 minutes, greater than or equal to about 230 minutes, greater than or equal to about 4 hours, greater than or equal to about 250 minutes, greater than or equal to about 260 minutes, greater than or equal to about 270 minutes, or greater than or equal to about 280 minutes. The initial reaction time may be less than or equal to about 10 hours, less than or equal to about 6 hours, less than or equal to about 5 hours, less than or equal to about 4 hours, or less than or equal to about 3 hours. In an embodiment, the reaction time may be greater than or equal to about 1 hour and less than or equal to about 5 hours, or greater than or equal to about 2 hours and less than or equal to about 4 hours, or greater than or equal to about 3 hours and less than or equal to about 3 hours and 30 minutes.

[0205] The first gallium precursor may include gallium bromide and optionally gallium chloride (or gallium iodide).

[0206] The first gallium precursor or gallium halide may include gallium bromide and gallium chloride. In the first gallium precursor, the amount of gallium chloride per mole of gallium bromide may be greater than or equal to about 0 mol, greater than or equal to about 0.005 mol, greater than or equal to about 0.01 mol, greater than or equal to about 0.05 mol, greater than or equal to about 0.1 mol, or greater than or equal to about 0.15 mol. In the first gallium precursor, the amount of gallium chloride per mole of gallium bromide may be less than or equal to about 0.2 mol.

[0207] Without wishing to be bound by any theory, in the embodiments it is believed that the use of gallium bromide as a gallium precursor (and optionally, the addition of a silver compound as described below) can help control the composition of the final semiconductor nanoparticles as described herein (e.g., using GaBr3 can suppress the trap ratio by removing excess Ag from the surface), and the resulting final nanoparticles can exhibit enhanced stability and a reduced trap ratio compared to semiconductor nanoparticles prepared by conventional techniques.

[0208] The first gallium precursor may be dispersed in a suitable organic solvent (e.g., an aromatic solvent (such as toluene, octadecene), or an aliphatic or aromatic phosphine compound (such as TOP), or an aliphatic or aromatic phosphine oxide compound (such as TOPO)) and added to the first reaction medium, but is not limited thereto.

[0209] The first silver compound may be added to the reaction medium in an amount greater than or equal to about 0.01 mol% (i.e., greater than or equal to about 0.0001 mol), greater than or equal to about 0.1 mol% (i.e., greater than or equal to about 0.001 mol), greater than or equal to about 0.5 mol%, greater than or equal to about 0.7 mol%, greater than or equal to about 0.9 mol%, greater than or equal to about 1 mol%, or greater than or equal to about 3 mol% relative to the first gallium precursor (e.g., per 1 mole of the first gallium precursor). The amount of the first silver compound relative to the first gallium precursor may be greater than or equal to about 0.015 mol%, greater than or equal to about 0.1 mol%, greater than or equal to about 0.3 mol%, greater than or equal to about 0.5 mol%, greater than or equal to about 0.6 mol%, greater than or equal to about 0.7 mol%, greater than or equal to about 0.8 mol%, greater than or equal to about 0.9 mol%, greater than or equal to about 1 mol%, greater than or equal to about 1.5 mol%, greater than or equal to about 2 mol%, greater than or equal to about 2.5 mol%, greater than or equal to about 3 mol%, greater than or equal to about 3.5 mol%, greater than or equal to about 4 mol%. Greater than or equal to about 4.5 mol%, greater than or equal to about 5 mol%, greater than or equal to about 5.5 mol%, greater than or equal to about 6 mol%, greater than or equal to about 6.5 mol%, greater than or equal to about 7 mol%, greater than or equal to about 7.5 mol%, greater than or equal to about 8 mol%, greater than or equal to about 8.5 mol%, greater than or equal to about 9 mol%, greater than or equal to about 9.5 mol%, greater than or equal to about 10 mol%, greater than or equal to about 11 mol%, greater than or equal to about 12 mol%, greater than or equal to about 13 mol%, greater than or equal to about 14 mol%, or greater than or equal to about 15 mol%. The amount of the first silver compound relative to the first gallium precursor 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 16 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 10 mol%, less than or equal to about 9 mol%, less than or equal to about 8 mol%, less than or equal to about 7 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%, or less than or equal to about 3 mol%. The amount of the first silver compound relative to the first gallium precursor may be greater than or equal to about 1 mol%, or greater than or equal to about 4.2 mol% and less than or equal to about 12 mol%, or less than or equal to about 8 mol%.

[0210] The first silver compound may include silver powder, alkylated silver compounds, silver alkoxides, silver carboxylates, silver acetylacetonates, silver nitrates, silver sulfates, silver halides, silver cyanides, silver hydroxides, silver oxides, silver peroxides, silver carbonates, or combinations thereof. The first silver compound may also include silver nitrate, silver acetate, silver acetylacetonate, silver chloride, silver bromide, silver fluoride, or combinations thereof.

[0211] There are no particular limitations on the manner (e.g., the order or form of addition) by which the first silver compound is added to the first (reaction) medium. The first silver compound can be added in a dissolved state to a suitable organic solvent (e.g., organic solvents described herein, such as solvents including amines (e.g., oleylamine) or solvents including phosphine (e.g., trioctylphosphine)). There are also no particular limitations on the timing of the addition of the first silver compound, and it can be appropriately selected. The first silver compound can be added to the first (reaction) medium before or after the addition of the first semiconductor nanocrystal, the first gallium precursor, the first sulfur precursor, or combinations thereof. In an embodiment, the first silver compound can be added to the first (reaction) medium after pretreatment.

[0212] In an embodiment, when the first gallium precursor and the first sulfur precursor react in the presence of the first semiconductor nanocrystal, the addition of the first silver compound can prevent undesirable changes to the first semiconductor nanocrystal (e.g., particle aggregation or changes in composition).

[0213] During the intermediate particle synthesis process, the amount of the first gallium precursor relative to the first sulfur precursor can be appropriately adjusted taking into account the composition of the final semiconductor nanoparticles, the type of precursor, the reaction temperature, etc.

[0214] According to the method of the embodiment, the amount of the first gallium precursor relative to the first sulfur precursor (i.e., per 1 mole of the first sulfur precursor) may be greater than or equal to about 0.5 moles, greater than or equal to about 0.55 moles, greater than or equal to about 0.6 moles, greater than or equal to about 0.65 moles, greater than or equal to about 0.7 moles, greater than or equal to about 0.71 moles, greater than or equal to about 0.75 moles, greater than or equal to about 0.77 moles, greater than or equal to about 0.8 moles, greater than or equal to about 0.85 moles, greater than or equal to about 0.9 moles, greater than or equal to about 0.95 moles, greater than or equal to about 0.1 moles, greater than or equal to about 1.05 moles, greater than or equal to about 1.1 moles, greater than or equal to about 1.12 moles, greater than or equal to about 1.15 moles, greater than or equal to about 1.2 moles, greater than or equal to about 1.25 moles, or greater than or equal to... The amount may be approximately 1.3 moles, greater than or equal to approximately 1.35 moles, greater than or equal to approximately 1.4 moles, or greater than or equal to approximately 1.45 moles, and may be less than or equal to approximately 10 moles, less than or equal to approximately 9.5 moles, less than or equal to approximately 9 moles, less than or equal to approximately 8.5 moles, less than or equal to approximately 8 moles, less than or equal to approximately 7.5 moles, less than or equal to approximately 7 moles, less than or equal to approximately 6.5 moles, less than or equal to approximately 6 moles, less than or equal to approximately 5.5 moles, less than or equal to approximately 5 moles, less than or equal to approximately 4.5 moles, less than or equal to approximately 4 moles, less than or equal to approximately 3.5 moles, less than or equal to approximately 3 moles, less than or equal to approximately 2.5 moles, less than or equal to approximately 2 moles, less than or equal to approximately 1.5 moles, less than or equal to approximately 1.3 moles, less than or equal to approximately 1 mole, or less than or equal to approximately 0.98 moles.

[0215] Separation and optional washing of intermediate particles and subsequent reactions

[0216] The formed intermediate particles can be separated from the first medium. (After the first reaction) A poor solvent can be added to the first reaction medium to promote the precipitation of the intermediate particles (e.g., intermediate particles coordinated with organic ligands). The separated intermediate particles can be washed with a washing solvent before being added to the second medium. Details regarding the poor solvent, precipitation, and washing are provided below. Surprisingly, the inventors have discovered that when semiconductor nanoparticles are prepared from intermediate particles that have undergone such separation and optional washing via the subsequent reactions described below, the semiconductor nanoparticles can have the composition described herein and can even exhibit improved process stability and desired optical properties (e.g., emission wavelength, increased quantum efficiency, suppressed trap emission, such as significantly reduced full width at half maximum) during composite formation.

[0217] The separated intermediate particles can be mixed (or contacted) with a second sulfur precursor, a second gallium precursor and an optional second silver compound in a second medium including a second organic solvent, and the second medium can be heated to a second reaction temperature (e.g., for a second reaction time) to form semiconductor nanoparticles.

[0218] In this method, the second medium may be pretreated. The second medium (e.g., a second medium comprising a second sulfur precursor) may be pretreated under vacuum before the addition of the separated intermediate particles or the second gallium precursor. The pretreatment temperature may be referenced to the temperature used for the first medium (e.g., the pretreatment temperature).

[0219] The intermediate particles, along with the second gallium precursor, the second sulfur precursor, or both, can be added to a second (reaction) medium comprising a second organic solvent (and optionally the second sulfur precursor). A second silver compound can be added to the second medium. There are no particular limitations on the manner (e.g., the order or form of addition) of the separated intermediate particles, the second gallium precursor, and the second sulfur precursor. The separated intermediate particles can be dispersed in a suitable organic solvent and added to the second reaction medium, but are not limited thereto.

[0220] The resulting second medium can be heated to a second reaction temperature for a second reaction time to form semiconductor nanoparticles. By heating, the reaction between the second sulfur precursor and the second gallium precursor (and optionally a second silver compound) (the second reaction) can proceed in the presence of intermediate particles. Without wishing to be bound by any theory, the resulting final semiconductor nanoparticles obtained through this reaction can have the composition described herein (e.g., molar ratio of gallium to indium), and can even exhibit improved process stability and desired optical properties (e.g., emission wavelength, increased quantum efficiency, suppressed trap emission, such as a significantly reduced full width at half maximum). The second medium can be used as the reaction medium for the second reaction.

[0221] According to the method of the embodiments, a second medium (optionally including a second sulfur precursor) may be heated to a second injection temperature under vacuum or in an inert atmosphere, and intermediate particles, a second gallium precursor, a second sulfur precursor, or a combination thereof may be added to the medium heated to the second injection temperature. According to the method of the embodiments, a reaction mixture including intermediate particles, a second gallium precursor, a second sulfur precursor, and optionally a second silver compound may be heated to a second reaction temperature.

[0222] The second injection temperature and the second reaction temperature can be referred to the description of the first injection temperature and the first reaction temperature.

[0223] The second gallium precursor may include gallium bromide, gallium chloride, gallium iodide, or combinations thereof. The second gallium precursor may include gallium bromide and optionally gallium chloride (or gallium iodide). The second gallium precursor may be the same as or different from the first gallium precursor. In embodiments, the second gallium precursor may or may not include gallium bromide. In embodiments, the second gallium precursor may or may not include gallium chloride. In embodiments, the second gallium precursor may or may not include gallium iodide.

[0224] The amount of gallium chloride per mole of gallium bromide in the second gallium precursor can be referenced in the description of the first gallium precursor.

[0225] The second gallium precursor can be dispersed in a suitable organic solvent (e.g., octadecene, or an aliphatic or aromatic phosphine compound (such as TOP), or an aliphatic or aromatic phosphine oxide compound (such as TOPO)) and added to the second reaction medium, but is not limited thereto. Details regarding the second silver compound can be found in the description of the first silver compound. In embodiments, the addition of the second silver compound prevents undesirable changes to the intermediate particles (e.g., aggregation or compositional changes) when the second gallium precursor reacts with the second sulfur precursor in the presence of intermediate particles. According to the method of the embodiments, a greater number of semiconductor nanoparticles can be formed in the solution.

[0226] The amount of the second gallium precursor relative to the second sulfur precursor can be appropriately adjusted taking into account the composition of the final semiconductor nanoparticles, the type of precursor, the reaction temperature, etc. According to the method of the embodiment, the amount of the second gallium precursor relative to the second sulfur precursor (i.e., per 1 mole of the second sulfur precursor) can be greater than or equal to about 0.5 moles, greater than or equal to about 0.55 moles, greater than or equal to about 0.6 moles, greater than or equal to about 0.65 moles, greater than or equal to about 0.7 moles, greater than or equal to about 0.75 moles, greater than or equal to about 0.8 moles, greater than or equal to about 0.85 moles, greater than or equal to about 0.9 moles, greater than or equal to about 0.95 moles, greater than or equal to about 1 mole, greater than or equal to about 1.05 moles, greater than or equal to about 1.1 moles, greater than or equal to about 1.12 moles, greater than or equal to about 1.15 moles, greater than or equal to about 1.2 moles, greater than or equal to about 1.25 moles, greater than or equal to about 1.3 moles, etc. Greater than or equal to about 1.35 moles, greater than or equal to about 1.4 moles, or greater than or equal to about 1.45 moles, and less than or equal to about 10 moles, less than or equal to about 9.5 moles, less than or equal to about 9 moles, less than or equal to about 8.5 moles, less than or equal to about 8 moles, less than or equal to about 7.5 moles, less than or equal to about 7 moles, less than or equal to about 6.5 moles, less than or equal to about 6 moles, less than or equal to about 5.5 moles, less than or equal to about 5 moles, less than or equal to about 4.5 moles, less than or equal to about 4 moles, less than or equal to about 3.5 moles, less than or equal to about 3 moles, less than or equal to about 2.5 moles, less than or equal to about 2 moles, less than or equal to about 1.5 moles, less than or equal to about 1 mole, or less than or equal to about 0.98 moles.

[0227] The amount of the second gallium precursor relative to the first gallium precursor (e.g., the molar ratio of the second gallium precursor to the first gallium precursor) can be suitably selected. In the method of the embodiments, the molar ratio of the second gallium precursor to the first gallium precursor can be greater than or equal to about 0.1:1, greater than or equal to about 0.15:1, greater than or equal to about 0.3:1, greater than or equal to about 0.35:1, greater than or equal to about 0.5:1, greater than or equal to about 0.55:1, greater than or equal to about 0.6:1, greater than or equal to about 0.65:1, greater than or equal to about 0.7:1, greater than or equal to about 0.75:1, greater than or equal to about 0.8:1, greater than or equal to about 0.85:1, greater than or equal to about 0.9:1, or greater than or equal to about 0.95:1. The molar ratio of the second gallium precursor to the first gallium precursor may be in the range of about 0.4:1 to about 4:1, about 0.58:1 to about 3:1, about 0.63:1 to about 2:1, about 0.79:1 to about 1.8:1, about 0.9:1 to about 1.3:1, about 1:1 to about 1.2:1, or combinations thereof.

[0228] For every 1 mole of indium precursor (the indium precursor added in the synthesis of the first semiconductor nanocrystal (or core)), the total amount of the first gallium precursor and the second gallium precursor can be greater than or equal to about 100 moles, greater than or equal to about 150 moles, greater than or equal to about 200 moles, greater than or equal to about 250 moles, greater than or equal to about 300 moles, greater than or equal to about 310 moles, greater than or equal to about 350 moles, greater than or equal to about 400 moles, greater than or equal to about 450 moles, or greater than or equal to about 500 moles. Greater than or equal to about 550 moles, greater than or equal to about 600 moles, greater than or equal to about 650 moles, greater than or equal to about 700 moles, greater than or equal to about 750 moles, greater than or equal to about 800 moles, greater than or equal to about 850 moles, greater than or equal to about 900 moles, greater than or equal to about 950 moles, greater than or equal to about 1000 moles, greater than or equal to about 1050 moles, greater than or equal to about 1100 moles, greater than or equal to about 1150 moles, or greater than or equal to about 1200 moles.

[0229] For every 1 mole of indium precursor (the indium precursor added in the synthesis of the first semiconductor nanocrystal (or core)), the total amount of the first gallium precursor and the second gallium precursor may be less than or equal to about 5000 moles, less than or equal to about 3000 moles, less than or equal to about 2000 moles, less than or equal to about 1800 moles, less than or equal to about 1500 moles, less than or equal to about 1080 moles, or less than or equal to about 1000 moles.

[0230] Formation of an additional semiconductor nanocrystal layer (e.g., an additional semiconductor nanocrystal layer including a third semiconductor nanocrystal or a fourth semiconductor nanocrystal).

[0231] In embodiments, the method may further include: preparing an additional reaction medium comprising an organic solvent and an organic ligand; heating the additional reaction medium; and contacting (reacting) a zinc precursor, a gallium precursor, and a sulfur precursor in the additional reaction medium in the presence of a first semiconductor nanocrystal comprising indium, gallium, silver, and sulfur, or particles comprising the first semiconductor nanocrystal (e.g., semiconductor nanoparticles) to form a third semiconductor nanocrystal. The third semiconductor nanocrystal may comprise zinc gallium sulfide (ZnGaS). Details regarding the third semiconductor nanocrystal are as described herein.

[0232] The method may further include: preparing an additional reaction medium comprising an organic ligand in an organic solvent; heating the additional reaction medium; and contacting (e.g., reacting) a zinc precursor and a chalcogenide precursor (e.g., a sulfur precursor) in the presence of the formed semiconductor nanoparticles (e.g., contacting (e.g., reacting) at a reaction temperature) to provide a fourth semiconductor nanocrystal comprising a zinc chalcogenide or an outer layer comprising a fourth semiconductor nanocrystal on the surface of the semiconductor nanoparticles. The fourth semiconductor nanocrystal is as described herein.

[0233] In embodiments, the reaction temperature for forming the third or fourth semiconductor nanocrystal 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, or 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, or less than or equal to about 215°C. The reaction time for forming the third or fourth semiconductor nanocrystal 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, 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.

[0234] In the methods of the embodiments, the precursor may be added to (e.g., heated) the reaction medium by injection (e.g., injection using a syringe), dropwise addition, or a combination thereof.

[0235] There are no particular limitations on the type of silver precursor (e.g., a silver precursor for nucleation) and it may be selected appropriately. Silver precursors or silver compounds may include silver powder, alkylated silver compounds, silver alkoxides, silver carboxylates, silver acetylacetonates, silver nitrates, silver sulfates, silver halides, silver cyanides, silver hydroxides, silver oxides, silver peroxides, silver carbonates, or combinations thereof. Silver precursors may include silver nitrate, silver acetate, silver acetylacetonate, or combinations thereof.

[0236] There are no particular limitations on the type of indium precursor (e.g., indium precursor for nucleation), and it can be appropriately selected. Indium precursors may include indium powder, indium alkylates, indium alkoxides, 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. Indium precursors may include indium oleate, indium myristate (i.e., indium carboxylate), indium acetate, indium hydroxide, indium chloride, indium bromide, indium iodide, or combinations thereof.

[0237] There are no particular restrictions on the type of sulfur precursor (e.g., a first or second sulfur precursor, hereinafter referred to as sulfur precursor). It may be selected as appropriate. Sulfur precursors may include dispersions or reaction products of sulfur in organic solvents (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 thiols (e.g., α-toluenethiol, octylthiol, dodecanethiol, octadecenethiol), isothiocyanate compounds (e.g., cyclohexyl isothiocyanate), alkyltrithiocarbonates (e.g., ethyltrithiocarbonate), allyl thiols, thiourea compounds (e.g., dialkylthioureas having C1 to C40 alkyl groups (such as dimethylthiourea, diethylthiourea, ethylmethylthiourea, dipropylthiourea)) or combinations thereof. Sulfur precursors may include thiols, isothiocyanates, thioureas, or combinations thereof.

[0238] When present, selenium precursors may include selenium-trioctylphosphine (Se-TOP), selenium-tributylphosphine (Se-TBP), selenium-triphenylphosphine (Se-TPP), or combinations thereof.

[0239] There are no particular limitations on the type of zinc precursor, and it can be appropriately selected. For example, zinc precursors may include zinc metal powder, alkyl zinc compounds, zinc alkoxides, zinc carboxylates, zinc nitrates, zinc perchlorates, zinc sulfates, zinc acetylacetonates, zinc halides, zinc cyanides, zinc hydroxides, zinc oxides, zinc peroxides, or combinations thereof. Zinc precursors may include 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 combinations thereof. In embodiments, zinc precursors may include zinc halides in the formation of the second semiconductor nanocrystal.

[0240] There are no particular limitations on the type of gallium precursor (e.g., a gallium precursor used in the preparation of a first semiconductor nanocrystal or an additional semiconductor nanocrystal) and it may be selected suitably. Gallium precursors may include gallium powder, alkyl gallium compounds, gallium alkoxides, 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. Gallium precursors may also include gallium chloride, gallium iodide, gallium bromide, gallium acetate, gallium acetylacetonate, gallium oleate, gallium palmitate, gallium stearate, gallium myristate, gallium hydroxide, or combinations thereof.

[0241] The first or second organic ligand (hereinafter referred to as the organic ligand) may include RCOOH, RNH2, R2NH, R3N, RSH, RH2PO, R2HPO, R3PO, RH2P, R2HP, R3P, ROH, RCOOR', RPO(OH)2, RHPOOH, R2POOH, or combinations thereof, wherein R and R' are each independently a substituted or unsubstituted C1 to C40 (or C3 to C24) aliphatic hydrocarbon group (e.g., alkyl, alkenyl, or alkynyl), a substituted or unsubstituted C6 to C40 (or C6 to C24) aromatic hydrocarbon group (e.g., C6 to C20 aryl), or combinations thereof. The organic ligand may bind to the surface of the formed nanoparticles. Organic ligands may include: methanethiol, ethanethiol, propanethiol, butanethiol, pentathiol, hexanethiol, heptathiol, octylthiol, nonanethiol, decanethiol, dodecylthiol, hexadecylthiol, octadecylthiol, benzylthiol; methylamine, ethylamine, propylamine, butylamine, pentaamine, hexaneamine, octylamine, dodecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine; formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, benzoic acid; substituted or unsubstituted methylphosphine (e.g., trimethylphosphine, methyldiphenylphosphine), substituted or unsubstituted ethylphosphine (e.g., triethylphosphine, ethyldiphenylphosphine). Substituted or unsubstituted propylphosphine, butylphosphine, pentylphosphine, octylphosphine (e.g., trioctylphosphine (TOP)); substituted or unsubstituted methylphosphine oxide (e.g., trimethylphosphine oxide, methyldiphenylphosphine oxide), ethylphosphine oxide (e.g., triethylphosphine oxide, ethyldiphenylphosphine oxide), propylphosphine oxide, butylphosphine oxide, octylphosphine oxide (e.g., trioctylphosphine oxide (TOPO)); diphenylphosphine, triphenylphosphine compounds or oxides thereof; phosphonic acids, hexylphosphine, octylphosphine, dodecylphosphine, tetradecylphosphine, hexadecylphosphine, octadecylphosphine, C5 to C20 alkylphosphines; or combinations thereof. Organic ligands may be used alone or as a mixture of two or more.

[0242] The first or second organic solvent (hereinafter referred to as "organic solvent") may be an amine solvent (e.g., C1 to C50 aliphatic amines), a nitrogen-containing heterocyclic compound (such as pyridine); a C6 to C40 aliphatic hydrocarbon (e.g., alkanes, alkenes, or alkynes) (such as hexadecane, octadecane, octadecene, or squalane), a C6 to C30 aromatic hydrocarbon (such as phenyldodecane, phenyltetradecane, or phenylhexadecane), a phosphine substituted with a C6 to C22 alkyl group (such as trioctylphosphine), a phosphine oxide substituted with a C6 to C22 alkyl group (such as trioctylphosphine oxide), a C12 to C22 aromatic ether (such as phenyl ether or benzyl ether), or a combination thereof. The amine solvent can be a compound having one or more (e.g., two or three) aliphatic hydrocarbon groups (alkyl, alkenyl, or alkynyl). In embodiments, the amine solvent may include C6 to C22 primary amines (such as hexadecylamine or oleylamine), C6 to C22 secondary amines (such as dioctylamine), C6 to C22 tertiary amines (such as trioctylamine), or combinations thereof.

[0243] The amounts of organic ligands and each precursor in the reaction medium can be appropriately selected taking into account the type of solvent, the type of organic ligands and each precursor, and the desired size and composition of the particles. The molar ratio between the individual precursors can be appropriately selected based on the desired molar ratio in the final nanoparticles and the reactivity between the individual precursors. There are no particular limitations on the method of adding each precursor. Each precursor can be injected in batches once or multiple times (e.g., two or more times, and up to ten times). Each precursor can be added simultaneously or sequentially. The reaction can be carried out in an inert gas atmosphere, in air, or under vacuum, but is not limited to these methods.

[0244] In embodiments, the amounts of the first gallium precursor (for the formation of intermediate particles) and the second gallium precursor (for the second reaction), as well as the ratio between the first and second gallium precursors, may be appropriately selected taking into account the type of precursors and the composition of the final semiconductor nanoparticles. In embodiments, the molar ratio of the first to the second gallium precursor may be within the range of 1:about 0.1 to 1:about 10, 1:about 0.3 to 1:about 3, 1:about 0.4 to 1:about 2.5, 1:about 0.5 to 1:about 2, 1:about 0.6 to 1:about 1.8, 1:about 0.65 to 1:about 1.3, 1:about 0.7 to 1:about 1.2, 1:about 0.8 to 1:about 1.1, or combinations thereof, but is not limited thereto. In the method of the embodiment, the molar ratio of the second gallium precursor to the first gallium precursor (second gallium precursor / first gallium precursor) may be greater than or equal to about 0.1:1, greater than or equal to about 0.15:1, greater than or equal to about 0.2:1, greater than or equal to about 0.25:1, greater than or equal to about 0.3:1, greater than or equal to about 0.35:1, greater than or equal to about 0.4:1, greater than or equal to about 0.45:1, greater than or equal to about 0.5:1, greater than or equal to about 0.55:1, greater than or equal to about 0.6:1, greater than or equal to about 0.64:1, greater than or equal to about 0.7:1, greater than or equal to... The ratios are approximately 0.76:1, greater than or equal to approximately 0.8:1, greater than or equal to approximately 0.81:1, greater than or equal to approximately 0.9:1, greater than or equal to approximately 0.91:1, greater than or equal to approximately 0.94:1, greater than or equal to approximately 1:1, greater than or equal to approximately 1.07:1, greater than or equal to approximately 1.1:1, greater than or equal to approximately 1.15:1, greater than or equal to approximately 1.2:1, greater than or equal to approximately 1.25:1, greater than or equal to approximately 1.3:1, greater than or equal to approximately 1.35:1, greater than or equal to approximately 1.4:1, greater than or equal to approximately 1.46:1, or greater than or equal to approximately 1.5:1. In the method of the embodiment, the molar ratio of the second gallium precursor to the first gallium precursor (second gallium precursor: first gallium precursor) may be less than or equal to about 10:1, less than or equal to about 3:1, less than or equal to about 2.5:1, less than or equal to about 2:1, less than or equal to about 1.8:1, less than or equal to about 1.5:1, less than or equal to about 1.3:1, or less than or equal to about 1.2:1.

[0245] When a non-solvent is added to the final reaction solution after the reaction is complete, nanoparticles (e.g., those coordinated with organic ligands) can be separated (e.g., precipitated). The non-solvent can be a polar solvent miscible with the solvent used in the reaction but unable to disperse the nanocrystals. The non-solvent can be selected depending on 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, solvents having a solubility parameter similar to the aforementioned solvents, or combinations thereof. Separation can be performed by centrifugation, precipitation, chromatography, or distillation. If necessary, the separated nanocrystals can be washed by adding them to a washing solvent. There are no particular limitations on the washing solvent, and solvents having a solubility parameter similar to that of the organic solvent or ligand can be used. The non-solvent or washing solvent may 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.

[0246] The semiconductor nanoparticles thus prepared can be dispersed in a dispersion 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 dispersion solvent may be suitably selected. The dispersion solvent may include the aforementioned organic solvents. The dispersion solvent may include substituted or unsubstituted C1 to C40 aliphatic hydrocarbons, substituted or unsubstituted C6 to C40 aromatic hydrocarbons, or combinations thereof.

[0247] In an embodiment, the semiconductor nanoparticles may be configured to emit green light. The peak emission wavelength of the green light or the semiconductor nanoparticles 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. Specifically, the peak emission wavelength of the green light or 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 514 nm, greater than or equal to about 515 nm, greater than or equal to about 517 nm, greater than or equal to about 519 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. m; and less than or equal to about 580 nm, less than or equal to about 575 nm, less than or equal to about 570 nm, less than or equal to about 565 nm, less than or equal to about 560 nm, less than or equal to about 555 nm, less than or equal to about 550 nm, less than or equal to about 545 nm, less than or equal to about 540 nm, less than or equal to about 535 nm, less than or equal to about 530 nm, less than or equal to about 525 nm, less than or equal to about 520 nm, or less than or equal to about 515 nm.

[0248] In an embodiment, the semiconductor nanoparticles may be configured to emit red light. The peak emission wavelength of the red light or the semiconductor nanoparticles may be greater than or equal to about 600 nm, greater than or equal to about 605 nm, greater than or equal to about 610 nm and less than or equal to about 650 nm, less than or equal to about 640 nm, or less than or equal to about 630 nm.

[0249] In this embodiment, the semiconductor nanoparticles may exhibit a quantum yield greater than or equal to about 70% (e.g., absolute quantum yield). The quantum yield may be an absolute quantum yield. The quantum yield (e.g., absolute quantum yield) may be greater than or equal to about 70%, greater than or equal to about 71%, greater than or equal to about 72%, greater than or equal to about 73%, greater than or equal to about 74%, greater than or equal to about 75%, greater than or equal to about 76%, greater than or equal to about 77%, greater than or equal to about 78%, greater than or equal to about 79%, greater than or equal to about 80%, greater than or equal to about 81%, greater than or equal to about 82%, greater than or equal to about 83%, greater than or equal to about 84%, greater than or equal to about 85%, greater than or equal to about 86%, greater than or equal to about 87%, greater than or equal to about 88%, greater than or equal to about 89%, greater than or equal to about 90%, greater than or equal to about 91%, greater than or equal to about 92%, greater than or equal to about 93%, greater than or equal to about 94%, or greater than or equal to about 95%, and 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%.

[0250] Semiconductor nanoparticles or green light may have a full width at half maximum (FWHM) 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 and 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.

[0251] In embodiments, the first light (e.g., green or red light) may include band-edge emission. In embodiments, the light emitted from the semiconductor nanoparticles may also include defect site emission or trap emission. Compared to trap emission, band-edge emission can be centered at a higher energy (lower wavelength) and has a smaller offset relative to the absorption initiation energy. Band-edge emission may have a narrower wavelength distribution than trap emission. Band-edge emission may have a normal wavelength distribution (e.g., a Gaussian wavelength distribution).

[0252] In the photoluminescence spectrum of semiconductor nanoparticles or composites comprising semiconductor nanoparticles, the percentage of the area or peak area of ​​the trap emission (e.g., the area of ​​the emission peak portion above "peak emission wavelength + 50 nm") relative to the total peak area (A) may be less than or equal to about 25%, less than or equal to about 24%, less than or equal to about 23%, less than or equal to about 22%, less than or equal to about 21%, less than or equal to about 20%, less than or equal to about 15%, less than or equal to about 12%, less than or equal to about 10%, less than or equal to about 9%, less than or equal to about 8%, less than or equal to about 7%, less than or equal to about 6%, less than or equal to about 5%, less than or equal to about 4%, less than or equal to about 3%, or less than or equal to about 2%.

[0253] Equation 5

[0254] Trap launch percentage (%) = [Trap / A] × 100

[0255] In Equation 5, Trap is the area of ​​the trap emission, and A is the total area of ​​the emission peak. (See Equation 5) Figure 1 )

[0256] The inventors have discovered limitations in suppressing and eliminating trapped emission in semiconductor nanoparticles based on silver-based group 13-16 compounds. Providing a zinc chalcogenide layer can increase the stability of the semiconductor nanoparticles; however, the inventors have also discovered that the formation of the zinc chalcogenide layer can increase the trapped emission of the final particles. The semiconductor nanoparticles of the embodiments can, for example, exhibit photoluminescence spectra in which trapped emission is substantially suppressed or eliminated by having the structure and composition described herein.

[0257] The shape of the semiconductor nanoparticles manufactured is not particularly limited and may include, for example, spherical, polyhedral, pyramidal, multi-legged, cubic, nanotube, nanowire, nanofiber, nanosheet or combination thereof, but is not limited thereto.

[0258] The fabricated semiconductor nanoparticles may include organic ligands and / or organic solvents on their surface. Organic ligands and / or organic solvents may be incorporated into the surface of the semiconductor nanoparticles of the embodiments. The organic ligands and organic solvents are as described herein.

[0259] In embodiments, the semiconductor nanoparticle composite may include a matrix and semiconductor nanoparticles as described herein, wherein the semiconductor nanoparticles may be dispersed in the matrix. The semiconductor nanoparticle composite (hereinafter, may be referred to as the "composite") may also include fine particles of metal oxide. The composite or semiconductor nanoparticles may be configured to emit a first light (e.g., green or red light). In embodiments, the composite may be in the form of a patterned film. The composite may also include semiconductor nanoparticles configured to emit a second light different from the first light. In embodiments, the composite may be in the form of a sheet. The sheet may also include semiconductor nanoparticles (e.g., additional semiconductor nanoparticles) configured to emit a second light different from the first light.

[0260] The semiconductor nanoparticles described herein, or composites comprising semiconductor nanoparticles, may exhibit increased levels of blue light absorption (e.g., improved incident light absorption) and / or improved optical properties (e.g., increased luminous efficiency and narrower full width at half maximum), and may emit light of a desired wavelength (e.g., a first light).

[0261] The composite may include semiconductor nanoparticles or groups of semiconductor nanoparticles (e.g., including semiconductor nanoparticles or groups of semiconductor nanoparticles in a predetermined amount) and exhibits increased light absorption. The incident light absorption (e.g., blue light absorption) of the composite may be greater than or equal to about 70%, greater than or equal to about 73%, greater than or equal to about 75%, greater than or equal to about 77%, greater than or equal to about 80%, greater than or equal to about 83%, greater than or equal to about 85%, greater than or equal to about 87%, greater than or equal to about 90%, greater than or equal to about 93%, greater than or equal to about 94%, greater than or equal to about 95%, greater than or equal to about 96%, greater than or equal to about 97%, greater than or equal to about 98%, or greater than or equal to about 99%. The incident light absorption (e.g., blue light absorption) of the composite may be about 70% to about 100%, about 80% to about 98%, about 95% to about 99%, about 96% to about 98%, or combinations thereof.

[0262] The incident light absorptivity of the complex can be calculated according to Equation 6:

[0263] Equation 6

[0264] Incident light absorptivity = [(B-B') / B] × 100%

[0265] In equation 6,

[0266] B is the amount of incident light provided to the complex, and

[0267] B' is the amount of incident light that passes through the complex.

[0268] The light conversion efficiency (CE) of the composite (e.g., external quantum efficiency or internal quantum efficiency) 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%, or greater than or equal to about 75%.

[0269] Equation 2

[0270] Internal quantum efficiency (%) = [A / (B-B')] × 100

[0271] Equation 3

[0272] External quantum efficiency (%) = [A / B] × 100

[0273] in:

[0274] A: The amount of the first light emitted from the complex

[0275] B: The amount of incident light irradiated

[0276] B': The amount of incident light passing through the complex.

[0277] According to the inventors' findings, in the case of luminescent particles (e.g., semiconductor nanoparticles) comprising semiconductor nanocrystals based on group 11-13-16 compounds, a significant reduction in properties can be observed when the luminescent particles are incorporated into a composite for practical device applications, even when the desired level of optical properties is achieved. The semiconductor nanoparticles of the embodiments can provide composites exhibiting improved optical properties by having the above-described compositional and / or structural characteristics, and can exhibit high retention of optical properties even in thin film form. The semiconductor nanoparticles of the embodiments can exhibit significantly improved stability (e.g., thermal stability and environmental stability).

[0278] Therefore, the composite including the semiconductor nanoparticles of the embodiments may have a process retention rate (i.e., process retention percentage) as defined by Equation 4, which is 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 100%.

[0279] Equation 4

[0280] Process retention rate (%) = [QE2 / QE1] × 100

[0281] In the above equation, QE1 is the internal or external quantum efficiency of the semiconductor nanoparticle-polymer composite after polymerization and before heat treatment, and QE2 is the internal or external quantum efficiency of the semiconductor nanoparticle-polymer composite after heat treatment.

[0282] The process retention rate (process retention percentage) may be in the range of about 10% to about 150%, about 20% to about 130%, about 25% to about 100%, about 30% to about 99%, about 68% to about 95%, about 70% to about 85%, or a combination thereof.

[0283] In the embodiments, the composite may be prepared from an ink composition. The ink composition may include a liquid carrier and a plurality of semiconductor nanoparticles as described in the embodiments. The semiconductor nanoparticles may be dispersed in the liquid carrier.

[0284] The liquid carrier may include liquid monomers, organic solvents, or combinations thereof. The ink composition may also include metal oxide nanoparticles (e.g., metal oxide nanoparticles dispersed in the liquid carrier). The ink composition may also include a dispersant (a dispersant for dispersing the 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 include or may substantially exclude (e.g., volatile) organic solvents. The ink composition may be a solvent-free system.

[0285] The liquid monomer may include a (photo)polymerizable monomer containing a carbon-carbon double bond. The composition may optionally further include a (thermal or photo) initiator. Polymerization of the composition may be initiated by light or heat.

[0286] Details of the nanoparticles(s) in the composition (or composite) are as described herein. The amount of semiconductor nanoparticles in the composition (or composite) may be appropriately adjusted with regard to the desired end use (e.g., color filters, etc.). In embodiments, based on the solids content of the composition or composite (hereinafter, solids content may refer to the solids content of the composition or the solids content of the composite), the amount of semiconductor nanoparticles in the composition (or composite) may be greater than or equal to about 1 wt% (e.g., greater than or equal to about 2 wt%, greater than or equal to about 3 wt%, greater than or equal to about 4 wt%, greater than or equal to about 5 wt%, greater than or equal to about 6 wt%, greater than or equal to about 7 wt%, greater than or equal to about 8 wt%, greater than or equal to about 9 wt%, greater than or equal to about 10 wt%, greater than or equal to about 15 wt%, greater than or equal to about 20 wt%, greater than or equal to about 25 wt%, greater than or equal to about 30 wt%, greater than or equal to about 35 wt%, or greater than or equal to about 40 wt%). Based on the solids content of the composition or composite, the amount of semiconductor nanoparticles may be less than or equal to about 70 wt% (e.g., less than or equal to about 65 wt%, less than or equal to about 60 wt%, less than or equal to about 55 wt%, or less than or equal to about 50 wt%). The weight percentage of a given component relative to the total solids content in the composition can represent the amount of the given component in the composite described herein.

[0287] In embodiments, the ink composition may be a photoresist composition comprising semiconductor nanoparticles suitable for photolithography. In embodiments, the ink composition may be a composition comprising semiconductor nanoparticles capable of providing patterns by printing methods (e.g., droplet emission methods, such as inkjet printing). The compositions according to embodiments may not include conjugated (or conductive) polymers (other than the cardo adhesive described herein). The compositions according to embodiments may include conjugated polymers. Here, a conjugated polymer refers to a polymer having conjugated double bonds in its main chain (e.g., polyphenylene ethylene, etc.).

[0288] In the compositions according to the embodiments, the dispersant ensures the dispersibility of nanoparticles (e.g., semiconductor nanoparticles). In the embodiments, the dispersant may be a binder (or binder polymer). The binder may include carboxylic acid groups (e.g., including carboxylic acid groups in repeating units). The binder may be an insulating polymer. The binder may be a compound (monomer or polymer) including carboxylic acid groups.

[0289] In the composition (or complex), the amount of dispersant may be greater than or equal to about 0.5 wt% (e.g., greater than or equal to about 1 wt%, greater than or equal to about 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 solids content of the composition (or complex). The amount of 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 solids content of the composition (or complex).

[0290] In the composition (or liquid carrier), liquid monomers comprising carbon-carbon double bonds or polymerizable (e.g., photopolymerizable) monomers (hereinafter referred to as monomers) may include (e.g., photopolymerizable) monomers containing (meth)acryloyl groups. The monomers may be precursors for insulating polymers.

[0291] Based on the total weight or total solids content of the composition, the amount of (photopolymerizable) monomer may be greater than or equal to about 0.5 wt% (e.g., greater than or equal to about 1 wt%, greater than or equal to about 2 wt%, greater than or equal to about 3 wt%, greater than or equal to about 5 wt%, or greater than or equal to about 10 wt%). Based on the total weight or total solids content of the composition, the amount of (photopolymerizable) monomer may be less than or equal to about 30 wt% (e.g., 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%).

[0292] The (photo)initiator included in the composition can be used for the (photo)polymerization of the aforementioned monomers. An initiator is a compound that promotes a free radical reaction (e.g., free radical polymerization of monomers) by generating free radical chemicals under mild conditions (e.g., via heat or light). The initiator can be a thermal initiator or a photoinitiator. There are no particular limitations on the initiator, and it can be selected appropriately.

[0293] In the composition, the amount of initiator may be appropriately adjusted taking into account the type and amount of polymerizable monomers. In the examples, based on the total weight (or total solids content) of the composition, the amount of initiator may be greater than or equal to about 0.01 wt% (e.g., greater than or equal to about 1 wt%) and less than or equal to about 10 wt% (e.g., less than or equal to about 9 wt%, less than or equal to about 8 wt%, less than or equal to about 7 wt%, less than or equal to about 6 wt%, or less than or equal to about 5 wt%), but is not limited thereto.

[0294] The composition (or complex) may also include (polyfunctional or monofunctional) thiol compounds (or portions derived therefrom, such as portions generated by a reaction between a thiol and a carbon-carbon double bond, for example, sulfide groups), metal oxide particles, or combinations thereof having at least one thiol group at the end.

[0295] Metal oxide particles (e.g., metal oxide nanoparticles) may include TiO2, SiO2, BaTiO3, Ba2TiO4, ZnO, or combinations thereof. In the composition (or composite), based on the total solids content, the amount of metal oxide 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%.

[0296] There is no particular limitation on the diameter of the metal oxide particles, and they can be appropriately selected. The diameter of the metal oxide 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.

[0297] Polythiol compounds can be dithiols, trithiols, tetrathiols, or combinations thereof. For example, thiols can be ethylene glycol bis(3-mercaptopropionate), ethylene glycol dimercaptoacetate, trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), 1,6-hexanedithiol, 1,3-propanedithiol, 1,2-ethylenedithiol, polyethylene glycol dithiols comprising one to ten ethylene glycol repeating units, or combinations thereof.

[0298] Based on the total solids content, the amount of thiols (or derivatives thereof) 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 solids content, the amount of thiols (or derivatives thereof) may be greater than or equal to about 0.1 wt% (e.g., 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%).

[0299] The composition or liquid carrier may include an organic solvent. In the examples, the composition or liquid carrier may not include an organic solvent. If present, there are no particular limitations on the type of organic solvent that may be used. The type and amount of the organic solvent are appropriately determined taking into account the aforementioned main components (i.e., nanoparticles, dispersants, polymerizable monomers, initiators, thiols, etc., if present) and the type and amount of other additives described herein. The composition may include the balance of solvent in addition to the desired amount of (non-volatile) solids. In the embodiments, examples of organic solvents may be: ethylene 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 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, alkenes, 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.

[0300] In addition to the foregoing components, the compositions (or complexes) of the embodiments may also include additives (such as light diffusing agents, leveling agents, coupling agents, or combinations thereof). Components (adhesives, monomers, solvents, additives, thiols, cardo adhesives, etc.) included in the compositions of the embodiments may be suitably selected, and for specific details, for example, reference may be made to US-2017-0052444-A1 (which is entirely incorporated herein by reference).

[0301] In the preparation of the composition according to the embodiments, each of the above components may be manufactured sequentially or mixed simultaneously, and there is no particular limitation on their order.

[0302] The composition can provide a color conversion layer (or a patterned film of the composite) through polymerization (e.g., free radical polymerization). The color conversion layer (or the patterned film of the composite) can be manufactured using a photoresist composition. See reference. Figure 2A The method may include: forming a film of the aforementioned composition on a substrate (S1); pre-baking the film according to selection (S2); exposing selected areas of the film to light (e.g., light having a wavelength less than or equal to about 400 nm) (S3); and developing the exposed film with an alkaline developing solution to obtain a pattern of the quantum dot-polymer composite (S4).

[0303] Reference Figure 2A The aforementioned composition can be applied to a substrate to a predetermined thickness using appropriate methods (such as spin coating or slot coating) to form a film. The formed film may optionally undergo a pre-baking (PRB) step. Pre-baking can be performed by selecting appropriate conditions from known temperature, time, atmosphere, etc.

[0304] The formed (or optionally pre-baked) film can be exposed to light of a predetermined wavelength (EXP) under a mask with a predetermined pattern. The wavelength and intensity of the light can be selected taking into account factors such as the type and amount of photoinitiator, the type and amount of quantum dots, etc.

[0305] The exposed film can then be treated (e.g., dipped or sprayed) with an alkaline developing solution to dissolve the unexposed areas and obtain the desired pattern (DEV). The obtained pattern can (optionally) be post-exposure baked (POB) at a temperature of 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).

[0306] When the color conversion layer or patterned film of the nanoparticle composite has multiple repeating portions (i.e., color conversion regions), each repeating portion can be formed by preparing multiple compositions including quantum dots with desired luminescent properties (such as photoluminescence peak wavelength, etc.) (e.g., quantum dots emitting red light, quantum dots emitting green light, or optionally quantum dots emitting blue light) and repeating the aforementioned patterning process multiple times (e.g., two or more times, or three or more times) as needed for each composition, thereby obtaining a nanoparticle-polymer composite with a desired pattern (S6). For example, the nanoparticle-polymer composite may have a pattern with at least two repeating color portions (e.g., RGB color portions). This nanoparticle-polymer composite pattern can be used as a photoluminescent color filter in a display device.

[0307] The color conversion layer or patterned film of the semiconductor nanoparticle composite can be manufactured using an ink composition configured to form patterns by inkjet printing. (See reference) Figure 2BSuch a method may include preparing an ink composition according to embodiments, providing a substrate (e.g., a substrate having pixel regions patterned by electrodes and optionally dikes or trench-type partitions, etc.), and depositing the ink composition on the substrate (or pixel regions) to form, for example, a first composite layer (or a first region). The method may also include depositing the ink composition on the substrate (or pixel regions) to form, for example, a second composite layer (or a second region). The first composite layer and the second composite layer may be a first quantum dot layer and a second quantum dot layer, respectively. The formation of the first composite layer and the formation of the second composite layer may be performed simultaneously or sequentially.

[0308] The deposition of the ink composition can be performed using a suitable liquid crystal emitter (e.g., an inkjet or nozzle printing system with an ink reservoir and at least one printhead). The deposited ink composition can be used to provide a (first or second) composite layer via solvent removal and polymerization under heating. This method can provide high-precision nanoparticle-polymer composite films or patterned films in a short time using a simple approach.

[0309] In the nanoparticle-polymer composites (e.g., the first composite) of the embodiments, the (polymer) matrix may include the components described herein with respect to the composition. In the composite, based on the total weight of the composite, the amount of 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 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%.

[0310] The (polymer) matrix may include dispersants (e.g., adhesive polymers comprising carboxylic acid groups), polymeric products containing (at least one, e.g., at least two, at least three, at least four, or at least five) carbon-carbon double bonds (e.g., insulating polymers), polymeric products of polymeric monomers and (e.g., at the end) polythiol compounds having at least two thiol groups, or combinations thereof. The matrix may include linear polymers, crosslinked polymers, or combinations thereof. The (polymer) matrix may not include conjugated polymers (conjugated polymers other than cardo resins). The matrix may include conjugated polymers.

[0311] Crosslinked polymers may include thiol-olefin resins, crosslinked poly(meth)acrylates, crosslinked polyurethanes, crosslinked epoxy resins, crosslinked vinyl polymers, crosslinked silicone resins, or combinations thereof. In embodiments, the crosslinked polymer may be a polymer of the aforementioned polymerizable monomers and optionally polythiol compounds.

[0312] Linear polymers may include repeating units derived from carbon-carbon unsaturated bonds (e.g., carbon-carbon double bonds). Repeating units may include carboxylic acid groups. Linear polymers may include ethylene repeating units.

[0313] Repeating units containing carboxylic acid groups may include units derived from monomers containing carboxylic acid groups and carbon-carbon double bonds, units derived from monomers having dianhydride moieties, or combinations thereof.

[0314] The (polymer) matrix may include compounds containing carboxylic acid groups (e.g., adhesives, binder polymers, or dispersants) (e.g., for dispersing or binding nanoparticles).

[0315] The first composite (or its film or pattern) may have a thickness of, for example, less than or equal to about 30 micrometers (μm), less than or equal to about 25 μm, less than or equal to about 20 μm, less than or equal to about 15 μm, less than or equal to about 10 μm, less than or equal to about 8 μm, or less than or equal to about 7 μm to greater than about 2 μm (e.g., greater than or equal to about 3 μm, greater than or equal to about 3.5 μm, greater than or equal to about 4 μm, greater than or equal to about 5 μm, greater than or equal to about 6 μm, greater than or equal to about 7 μm, greater than or equal to about 8 μm, greater than or equal to about 9 μm, or greater than or equal to about 10 μm).

[0316] One or more semiconductor nanoparticles, composites comprising one or more semiconductor nanoparticles (or patterns thereof), or color conversion panels comprising them may be included in electronic devices. Such electronic devices may include display devices, light-emitting diodes (LEDs), organic light-emitting diodes (OLEDs), quantum dot LEDs, sensors, solar cells, imaging sensors, photodetectors, or liquid crystal display devices, but embodiments are not limited thereto. The aforementioned quantum dots (or semiconductor nanoparticles) in the embodiments may be included in electronic devices. Such electronic devices may include (but are not limited to) virtual reality devices, augmented reality devices, portable terminal devices, monitors, laptop personal computers (PCs), televisions, electronic signal boards, electronic display boards, cameras, vehicles (e.g., automobiles), etc., but embodiments are not limited thereto. Electronic devices may be portable terminal devices, monitors, laptop personal computers, or televisions that include display devices (or light-emitting devices) containing quantum dots. Electronic devices may be cameras or mobile terminal devices that include image sensors containing quantum dots. Electronic devices may be cameras or vehicles that include photodetectors containing quantum dots.

[0317] Embodiments provide a color conversion layer (e.g., a color conversion structure or a color conversion panel) including color conversion regions comprising semiconductor nanoparticles described herein. The color conversion panel may include a color conversion layer comprising color conversion regions and optionally separators defining each region of the color conversion layer. The color conversion regions may include a first region corresponding to a first pixel, and the first region may include semiconductor nanoparticles or semiconductor nanoparticle composites. In the color conversion panel of the embodiments, the semiconductor nanoparticle composite may be in the form of a patterned film. In another embodiment, the semiconductor nanoparticle composite may be in the form of a sheet.

[0318] The first region may include a first composite, and the first composite may include a matrix and semiconductor nanoparticles dispersed in the matrix and may be configured to emit first light. Embodiments provide semiconductor nanoparticles or groups of semiconductor nanoparticles.

[0319] The color conversion layer (e.g., color conversion structure) may include a semiconductor nanoparticle composite or a patterned film of a semiconductor nanoparticle composite according to embodiments. Figure 3A This is a schematic cross-sectional view of a color conversion panel according to an embodiment. (Refer to...) Figure 3A The color conversion panel may optionally further include partition walls (e.g., black matrix (BM), dike, or a combination thereof) that define each region of the color conversion layer (e.g., color conversion structure). Figure 3B An electronic device (or display device) including a color conversion panel and a light source according to another embodiment is shown. In the electronic device of the embodiment, the color conversion panel, including a color conversion layer or color conversion structure, may be disposed on an on-chip LED (e.g., an on-chip micro-LED). See also... Figure 3B A circuit configured to drive a light source (e.g., a Si driver integrated circuit (IC)) may 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 containing semiconductor nanoparticles emitting a first light (e.g., green light) and a second composite containing semiconductor nanoparticles emitting a second light (e.g., red light) or a third composite emitting a third light (e.g., incident light or blue light) or allowing the third light (e.g., incident light or blue light) to pass through. Partition walls (PWs) (e.g., partition walls comprising inorganic materials (such as silicon or silicon oxide) or based on organic materials) may be disposed between the respective composites. Partition walls may include trench holes, via holes, or combinations thereof. A first optical element (e.g., an absorptive color filter) may be disposed on the light extraction surface of the color conversion layer. Additional optical elements (e.g., microlenses) may be further disposed on the first optical element.

[0320] The color conversion region may include a first region configured to emit (e.g., by illumination with incident light) the first light (or green light) described above. In an embodiment, the first region may correspond to a green pixel. The first region may include a first composite material (e.g., a luminescent composite material). The first light may have a peak emission wavelength within the wavelength range described later. The first light will be described in more detail with respect to the semiconductor nanoparticles described herein. The peak emission wavelength of the green light may be greater than or equal to about 500 nm, greater than or equal to about 501 nm, greater than or equal to about 504 nm, greater than or equal to about 505 nm, or greater than or equal to about 520 nm. The peak emission wavelength of the green light may be less than or equal to about 580 nm, less than or equal to about 560 nm, less than or equal to about 550 nm, less than or equal to about 530 nm, less than or equal to about 525 nm, less than or equal to about 520 nm, less than or equal to about 515 nm, or less than or equal to about 510 nm.

[0321] The color conversion region may also include (e.g., one or more) second regions configured to emit (e.g., by irradiation with excitation light) a second light (e.g., red light) different from the first light. The second region may include a second composite. The semiconductor nanoparticle composite in the second region may include semiconductor nanoparticles (e.g., quantum dots) configured to emit light of a different wavelength (e.g., a different color) than the semiconductor nanoparticle composite disposed in the first region.

[0322] 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 also include one or more third regions that emit or pass through a third light (e.g., blue light) that is different from the first and second light. The incident light may include the third light (e.g., blue light and optional green light). The third light may include blue light with a peak emission wavelength greater than or equal to about 380 nm (e.g., greater than or equal to about 440 nm, greater than or equal to about 445 nm, greater than or equal to about 450 nm, or greater than or equal to about 455 nm) to less than or equal to about 480 nm (e.g., less than or equal to about 475 nm, less than or equal to about 470 nm, less than or equal to about 465 nm, or less than or equal to about 460 nm).

[0323] In embodiments, the color conversion panel or color conversion layer may include a plurality of first regions, and the semiconductor nanoparticle composite may form a predetermined pattern to be disposed in the first regions of the color conversion panel. The semiconductor nanoparticle composite (or the pattern of the semiconductor nanoparticle composite) may be prepared from the (ink) composition by any method (e.g., photolithography or inkjet printing). Therefore, embodiments may relate to compositions comprising semiconductor nanoparticles as described in further detail herein.

[0324] In embodiments, the electronic device or display device (e.g., a display panel) may further include a color conversion layer (or color conversion panel) and an optional light source. The light source can provide incident light to the color conversion layer or color conversion panel. In embodiments, the display panel may include a light-emitting panel (or light source), the aforementioned color conversion panel, and a light-transmitting layer located between the aforementioned light-emitting panel and the aforementioned color conversion panel. The color conversion panel may include a substrate, and the color conversion layer may be disposed on the substrate.

[0325] When present, a light source or emitting panel can provide incident light to a color conversion layer or color conversion panel. The incident light may have a peak emission wavelength greater than or equal to about 440 nm (e.g., greater than or equal to about 450 nm) 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).

[0326] In embodiments, the electronic device (e.g., a photoluminescent device) may also include a sheet of nanoparticle composite. See also... Figure 4B The device 400 may include a backlight unit 410 and a liquid crystal panel 420, wherein optionally, the backlight unit 410 may include a quantum dot-polymer composite sheet (QD sheet). For example, the backlight unit 410 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 optical films (prisms, dual brightness enhancement films (DBEF, etc.) can be stacked. The liquid crystal panel 420 may be disposed on the backlight unit 410 and has a structure in which thin-film transistors (TFTs), liquid crystals (LCs), and color filters are included in two polarizers (Pols). 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. Blue light provided from the light source may be combined with red and green light emitted from the individual semiconductor nanoparticles while passing through the quantum dot-polymer composite sheet and converted into white light. This white light may be separated into blue, green, and red light by a color filter in the liquid crystal panel and then emitted to the outside for each pixel. Figure 4D The backlight unit (BLU) can be a direct-type BLU without a light guide plate and may include multiple LEDs (e.g., mini LEDs), and a light conversion sheet or QD sheet may be disposed on the BLU.

[0327] A color conversion panel may include a substrate, and a color conversion layer may be disposed on the substrate. The color conversion layer or color conversion panel may include a patterned film of a nanoparticle composite. The patterned film may include repeating segments configured to emit light of a desired wavelength. The repeating segments may include a second region. The second region may be a segment emitting red light. The repeating segments may include a first region. The first region may be a segment emitting green light. The repeating segments may include a third region. The third region may include a segment emitting or transmitting blue light. Details of the first, second, and third regions are described herein.

[0328] The light-emitting panel or light source can 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 surfaces (light-emitting surfaces) of the first and second regions, optical elements (e.g., a blue light (and optionally green light) blocking layer or a first filter, which will be described herein, may be disposed for blocking (e.g., reflecting or absorbing) blue light (and optionally green light). In an embodiment, the light source may include an organic light-emitting diode that emits blue light and an organic light-emitting diode that emits green light, and a green light removal filter may be further disposed on a third region through which blue light is transmitted.

[0329] 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 units may include a first electrode and a second electrode facing each other, and an (organic) electroluminescent layer located between the first electrode and the second electrode. The electroluminescent layer may include organic light-emitting materials. 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). There are no particular limitations on the structure and materials of the electroluminescent device and the organic light-emitting diode (OLED).

[0330] The display panel and color conversion panel will be described in further detail below with reference to the accompanying drawings.

[0331] Reference Figure 4A and Figure 4C The display panel 1000 according to an embodiment may include a light-emitting panel 40 and a color conversion panel 50. The display panel or electronic device may also include a light-transmitting 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-transmitting layer may include a passivation layer, a filler material, an encapsulation layer, or a combination thereof (not shown). The material used for the light-transmitting layer may be suitably selected without particular limitation. The material used for the light-transmitting layer may be an inorganic material, an organic material, an organic / inorganic hybrid material, or a combination thereof.

[0332] Both the light-emitting panel 40 and the color-converting panel 50 can have surfaces facing each other, i.e., the two corresponding panels can face each other, and a light-transmitting layer (or light-transmitting panel) 60 is disposed between the two panels. The color-converting panel 50 can be disposed in a direction such that light emitted from, for example, the light-emitting panel 40 can illuminate the light-transmitting layer 60. An adhesive material 70 can be disposed along the edges of the light-emitting panel 40 and the color-converting panel 50, and can be, for example, a sealing material.

[0333] Figure 5A This is a plan view of an embodiment of the pixel arrangement of a display panel. (Refer to...) Figure 5A The display panel 1000 may include a display area 1000D for displaying images and a non-display area 1000P located in the peripheral area of ​​the display area 1000D and provided with adhesive material.

[0334] Display area 1000D may include a plurality of pixels PX arranged along rows (e.g., the x-direction) and columns (e.g., the y-direction), and each representative pixel PX may include a plurality of sub-pixels PX1, PX2, and PX3 that express (e.g., display) different colors from each other. An embodiment may be idealized to have a structure in which three sub-pixels PX1, PX2, and PX3 are configured to provide a pixel. Embodiments may also include additional sub-pixels such as white sub-pixels, and may also include sub-pixels that express (e.g., display) the same color (e.g., at least one). 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, or a combination thereof.

[0335] Subpixels PX1, PX2, and PX3 can express (e.g., display) the colors of the three primary colors or combinations thereof, such as red, green, blue, or combinations thereof. For example, the first subpixel PX1 can express (e.g., display) red, the second subpixel PX2 can express (e.g., display) green, and the third subpixel PX3 can express (e.g., display) blue.

[0336] In the accompanying drawings, all subpixels are idealized to have the same size, but this is not a limitation, and at least one subpixel may be larger or smaller than the others. In the accompanying drawings, all subpixels are idealized to have the same shape, but this is not a limitation, and at least one subpixel may have a different shape than the others.

[0337] In a display panel or electronic device according to an embodiment, the light-emitting panel may include a substrate and TFTs (e.g., oxide-containing TFTs) disposed on the substrate. Light-emitting devices (e.g., light-emitting devices having a cascade structure, etc.) may be disposed on the TFTs.

[0338] The light-emitting device may include a light-emitting layer (e.g., a blue light-emitting layer, a green light-emitting layer, or a combination thereof) located between a first electrode and a second electrode facing each other. Charge-generating layers may be disposed between the various light-emitting layers. Each of the first and second electrodes may be patterned as a plurality of electrode elements to correspond to pixels. The first electrode may be an anode or a cathode. The second electrode may be a cathode or an anode.

[0339] Light-emitting devices may include organic LEDs, nanorod LEDs, mini LEDs, micro LEDs, or combinations thereof.

[0340] Figures 5B to 5E These are cross-sectional views illustrating the light-emitting devices of the embodiments. In the embodiments, the "mini LED" may have dimensions greater than or equal to about 100 micrometers, greater than or equal to about 150 micrometers, or greater than or equal to about 200 micrometers and less than or equal to about 1 millimeter, less than or equal to about 0.5 millimeters, less than or equal to about 0.15 millimeters, or less than or equal to about 0.12 millimeters, but is not limited thereto. In the embodiments, the "micro LED" may have dimensions less than about 100 micrometers, less than or equal to about 50 micrometers, or less than or equal to about 10 micrometers. The dimensions of the micro LED may be greater than or equal to about 0.1 micrometers, greater than or equal to about 0.5 micrometers, greater than or equal to about 1 micrometer, or greater than or equal to about 5 micrometers, but is not limited thereto.

[0341] Reference Figure 5B The light-emitting device 180 may include: a first electrode 181 and a second electrode 182 facing each other; a light-emitting layer 183 located between the first electrode 181 and the second electrode 182; and optionally, 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.

[0342] The first electrode 181 and the second electrode 182 may be configured to face each other along the thickness direction (e.g., the z-direction), and either the first electrode 181 or the second electrode 182 may be an anode, and the other may be a cathode. The first electrode 181 may be a light-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, for example, be made of a thin monolayer or multiple layers of a metal thin film, including: conductive metal oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), fluorine-doped tin oxide (FTO), etc.; or silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), magnesium-silver (Mg-Ag), magnesium-aluminum (Mg-Al), or combinations thereof. The reflective electrode may include metal, metal nitride, or combinations thereof (e.g., silver (Ag), copper (Cu), aluminum (Al), gold (Au), titanium (Ti), chromium (Cr), nickel (Ni), alloys thereof, nitrides thereof (e.g., TiN), or combinations thereof), but the embodiments are not limited thereto.

[0343] One or more light-emitting layers 183 may include a first light emitter that emits light with a blue emission spectrum, a second light emitter that emits light with a green emission spectrum, or a combination thereof.

[0344] The blue emission spectrum may have a peak emission wavelength in the wavelength region greater than or equal to about 400 nm to less than about 500 nm (and within this range, in the wavelength regions 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).

[0345] Green emission spectra may have peak emission wavelengths in the wavelength region greater than or equal to about 500 nm to less than about 590 nm (and within this range, in the wavelength regions 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).

[0346] For example, the light-emitting layer 183 or the light-emitting body included in the light-emitting layer 183 may include phosphorescent materials, fluorescent materials, or combinations 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-weight compound, a high-molecular-weight compound, or a combination thereof. There are no particular limitations on the specific types of phosphorescent and fluorescent materials, but they may be suitably 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, quantum dot, perovskite, or a combination thereof. Inorganic semiconductors may include metal nitrides, metal oxides, or combinations thereof. Metal nitrides, metal oxides, or combinations thereof may include group III metals (such as aluminum, gallium, indium, thallium, etc.), group IV metals (such as silicon, germanium, tin), or combinations thereof. In 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-LED. Materials available as inorganic light-emitting bodies may be suitably selected.

[0347] In an embodiment, the light-emitting device 180 may further include auxiliary layers 184 and 185. Auxiliary layers 184 and 185 may be disposed between the first electrode 181 and the light-emitting layer 183, and between the second electrode 182 and the light-emitting layer 183, respectively. Auxiliary layers 184 and 185 may be charge-assisted layers for controlling charge injection and / or mobility. Auxiliary layers 184 and 185 may include at least one or two layers, and for example, may include a hole injection layer, a hole transport layer, an electron blocking layer, an electron injection layer, an electron transport layer, a hole blocking layer, or a combination thereof. At least one of auxiliary layers 184 and 185 may be omitted if desired. The auxiliary layers may be formed of a material suitably selected from materials known for use in organic electroluminescent devices, etc.

[0348] The light-emitting devices 180 disposed in each of sub-pixels PX1, PX2, and PX3 may be the same or different from each other. The light-emitting devices 180 in each of sub-pixels PX1, PX2, and PX3 may emit light with the same or different emission spectra. The light-emitting devices 180 in each of sub-pixels PX1, PX2, and PX3 may emit light, for example, light with a blue emission spectrum, light with a green emission spectrum, or a combination thereof. The light-emitting devices 180 in each of sub-pixels PX1, PX2, and PX3 may be separated by a pixel-defining layer (not shown).

[0349] Reference Figure 5CThe light-emitting device 180 may be a light-emitting device with a cascaded structure and may include: 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-generating layer 186 located between the first light-emitting layer 183a and the second light-emitting layer 183b; and optionally, auxiliary layers 184 and / or 185 located between the first electrode 181 and the first light-emitting layer 183a and / or between the second electrode 182 and the second light-emitting layer 183b, respectively.

[0350] Details of the first electrode 181, the second electrode 182, and the auxiliary layers 184 and 185 are described herein.

[0351] The first light-emitting layer 183a and the second light-emitting layer 183b can emit light with the same or different emission spectra. In an embodiment, the first light-emitting layer 183a or the second light-emitting layer 183b can emit light with a blue emission spectrum or light with a green emission spectrum, respectively. The charge-generating layer 186 can inject charge 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 charge-generating 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 n-type dopants and / or p-type dopants. The charge-generating layer 186 may include one layer or two or more layers.

[0352] Reference Figure 5D The light-emitting device (with a cascaded 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-generating layer 186a located between the first light-emitting layer 183a and the second light-emitting layer 183b; a second charge-generating layer 186b located between the second light-emitting layer 183b and the third light-emitting layer 183c; and optionally, auxiliary layers 184 and / or 185 located between the first electrode 181 and the first light-emitting layer 183a and / or between the second electrode 182 and the third light-emitting layer 183c, respectively.

[0353] Details of the first electrode 181, the second electrode 182, and the auxiliary layers 184 and 185 are described herein.

[0354] The first light-emitting layer 183a, the second light-emitting layer 183b, and the third light-emitting layer 183c can emit light with 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 can emit blue light. In one embodiment, the first light-emitting layer 183a and the third light-emitting layer 183c can emit light with a blue emission spectrum, and the second light-emitting layer 183b can emit light with a green emission spectrum. In another embodiment, the first light-emitting layer 183a and the third light-emitting layer 183c can emit light with a green emission spectrum, and the second light-emitting layer 183b can emit light with a blue emission spectrum.

[0355] The first charge generating layer 186a can inject charge 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 generating layer 186b can inject charge 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 generating layer 186a and the second charge generating layer 186b may each include one layer or two or more layers.

[0356] Reference Figure 5E In an embodiment, the light-emitting device 180 may include a light-emitting layer 183, a first electrode 181, a second electrode 182, and a plurality of nanostructures 187 disposed in the light-emitting layer 183.

[0357] One of the first electrode 181 and the second electrode 182 can be an anode, and the other can be a cathode. The first electrode 181 and the second electrode 182 can be electrodes patterned according to the orientation of the arrangement of a plurality of nanostructures 187, and can include, for example: conductive oxides, such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), fluorine-doped tin oxide (FTO), etc.; or silver (Ag), copper (Cu), aluminum (Al), gold (Au), titanium (Ti), chromium (Cr), nickel (Ni), their alloys, their nitrides (e.g., TiN); or combinations thereof, but the embodiments are not limited thereto.

[0358] The light-emitting layer 183 may include a plurality of nanostructures 187, and each of the sub-pixels PX1, PX2, and PX3 may include a plurality of nanostructures 187. In one embodiment, the plurality of nanostructures 187 may be arranged in one direction, but the embodiment is not limited thereto. The nanostructures 187 may be compound-containing semiconductors configured to emit light of a predetermined wavelength, for example, by the application of an electric current, and may be, for example, linear nanostructures (such as nanorods or nanoneedles). The diameter or major axis of the nanostructure 187 can be, for example, a few nanometers to several hundred nanometers, and the aspect ratio (or length-to-width ratio) of the nanostructure 187 can be greater than about 1, greater than or equal to about 1.5, greater than or equal to about 2.0, greater than or equal to about 3.0, greater than or equal to about 4.0, greater than or equal to about 4.5, or greater than or equal to about 5.0 to less than or equal to about 20 (e.g., greater than about 1 to about 20, greater than or equal to about 1.5 to about 20, greater than or equal to about 2.0 to about 20, greater than or equal to about 3.0 to about 20, greater than or equal to about 4.0 to about 20, greater than or equal to about 4.5 to about 20, or greater than or equal to about 5.0 to about 20).

[0359] Each of the nanostructures 187 may include a p-type region 187p, an n-type region 187n, and a multiple quantum well region 187i, and may be configured to emit light from the multiple quantum well region 187i. The nanostructures 187 may include, for example, gallium nitride (GaN), indium gallium nitride (InGaN), aluminum gallium nitride (AlGaN), or combinations thereof, and may have, for example, a core-shell structure.

[0360] Each of the multiple nanostructures 187 can emit light having the same or different emission spectra. In an embodiment, the nanostructures can emit light with a blue emission spectrum, for example, light having a blue emission spectrum with a peak emission wavelength in the wavelength region of about 400 nm to less than 500 nm, about 410 nm to about 490 nm, or about 420 nm to about 480 nm.

[0361] Figure 6 This is a schematic cross-sectional view of the device (or display panel) according to an embodiment. (Refer to...) Figure 6The light source (or light-emitting panel) may include an organic light-emitting diode (OLED) that emits blue light (B) (and optionally green light (G)). The OLED may include at least two pixel electrodes 90a, 90b, 90c formed on a substrate 100, pixel defining layers 150a, 150b formed between adjacent pixel electrodes 90a, 90b, 90c, organic light-emitting layers 140a, 140b, 140c formed on each pixel electrode 90a, 90b, 90c, and a common electrode layer 130 formed on the organic light-emitting layers 140a, 140b, 140c. Thin-film transistors (TFTs) and a substrate may be disposed below the OLED, which are not shown. The pixel regions of the OLED may be configured to correspond to the first, second, and third regions described herein. In embodiments, the color conversion panel and the light-emitting panel may be as follows: Figure 6 The separation is shown in the figure. In an embodiment, the color conversion panel can be directly stacked on the light-emitting panel.

[0362] A stacked structure comprising a semiconductor nanoparticle composite pattern 170 (e.g., a first region 11 or R comprising semiconductor nanoparticles emitting red light, a second region 21 or G comprising semiconductor nanoparticles emitting green light, and a third region 31 or B comprising or excluding semiconductor nanoparticles (e.g., semiconductor nanoparticles emitting blue light)) and a substrate 240 may be disposed on a light source. Blue light emitted from the light source may enter the first and second regions and may emit red 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 semiconductor nanoparticle composite layers R and G and the substrate. In an embodiment, the excitation light may include blue and green light, and a green light blocking filter (not shown) may be added to the third region. The first optical filter or excitation light blocking layer will be described in more detail here.

[0363] Such a display device can be manufactured by separately fabricating the aforementioned stacked structure and (e.g., a blue light-emitting LED or OLED), and then combining the stacked structure and the LED or OLED. The display device can also be manufactured by directly forming a semiconductor nanoparticle composite pattern on the LED or OLED.

[0364] In color conversion panels or display devices, the substrate can be a substrate comprising an insulating material. The substrate may include: glass; polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyesters, polycarbonates, or polyacrylates; polysiloxanes (e.g., polydimethylsiloxane (PDMS); inorganic materials such as Al₂O₃, ZnO, etc.; or combinations thereof, but the embodiments are not limited thereto. The thickness of the substrate may be suitably selected taking into account the substrate material, but is not particularly limited thereto. The substrate may be flexible. For light emitted from semiconductor nanoparticles, the substrate may 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%.

[0365] A wiring layer, including thin-film transistors, can be formed on the substrate. The wiring layer may also include gate lines, sustaining voltage lines, a gate insulating film, data lines, source electrodes, drain electrodes, a semiconductor layer, a protective layer, etc. The detailed structure of the wiring layer may vary depending on the embodiment. The gate lines and sustaining voltage lines may be electrically isolated from each other, and the data lines may be insulated and intersect with the gate lines and sustaining voltage lines. The gate electrode, source electrode, and drain electrode may respectively form the control terminal, input terminal, and output terminal of the thin-film transistor. The drain electrode may be electrically connected to the pixel electrode, which will be described herein.

[0366] Pixel electrodes can be used as electrodes (e.g., anodes) in display devices. Pixel electrodes can be formed from transparent conductive materials such as indium tin oxide (ITO) or indium zinc oxide (IZO). Pixel electrodes can also be formed from materials with light-blocking properties such as gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), or titanium (Ti). Pixel electrodes can have a two-layer structure in which transparent conductive materials and light-blocking materials are sequentially stacked.

[0367] Between two adjacent pixel electrodes, a pixel defining layer (PDL) may be stacked on the end of the pixel electrode to divide the pixel electrode into pixel units. The pixel defining layer is an insulating layer that provides resistive isolation between at least two pixel electrodes.

[0368] A pixel defining layer may cover a portion of the upper surface of the pixel electrode, and the remaining area of ​​the pixel electrode not covered by the pixel defining layer may provide an opening. An organic light-emitting layer, which will be described herein, may be formed on the area defined by the opening.

[0369] The organic light-emitting layer can define each pixel region by the aforementioned pixel electrode and pixel defining layer. In other words, a pixel region can be defined as a region in which an organic light-emitting unit layer is formed, which is in contact with a pixel electrode defined by the pixel defining layer. In the display device according to the embodiment, the organic light-emitting layer can be defined as a first pixel region, a second pixel region, and a third pixel region, and each pixel region can be spaced apart from each other by the pixel defining layer with a predetermined interval.

[0370] In embodiments, the organic light-emitting layer may emit a third light belonging to either the visible light region or the ultraviolet (UV) light region. Each of the first to third pixel regions of the organic light-emitting layer may emit the third light. In embodiments, the third light may be light with higher energy in the visible light region, and may be, for example, blue light (and optionally green light). In embodiments, all pixel regions of the organic light-emitting layer may be designed to emit the same light, and each pixel region of the organic light-emitting layer may be formed of the same or similar materials, or may exhibit the same or similar properties. Therefore, the process for forming the organic light-emitting layer can be simplified, and the display device can 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 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).

[0371] The organic light-emitting layer may include an organic light-emitting unit layer in each pixel region, and in addition to the light-emitting layer, each organic light-emitting unit layer may also include auxiliary layers (e.g., hole injection layer, hole transport layer, electron transport layer, etc.).

[0372] The common electrode can be used as the cathode of a display device. The common electrode can be formed from a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO). The common electrode can be formed on and integrated with the organic light-emitting layer.

[0373] A planarization layer or passivation layer (not shown) may be formed on the common electrode. The planarization layer may include an insulating material (e.g., transparent) to ensure electrical insulation from the common electrode.

[0374] In an embodiment, the display device may further include a lower substrate, a polarizing plate disposed below the lower substrate, and a liquid crystal layer disposed between the laminated structure and the lower substrate, wherein in the laminated structure, a photoluminescent layer (i.e., an emissive layer) may be configured to face the liquid crystal layer. The display device may also include a polarizing plate located between the liquid crystal layer and the emissive layer. The light source may further include an LED and a light guide plate (if desired).

[0375] In the embodiments, a display device (e.g., a liquid crystal display device) is shown with reference to the accompanying drawings. Figure 7AThis is a schematic cross-sectional view illustrating a liquid crystal display device according to an embodiment. (Refer to...) Figure 7A The display device in the embodiment may include a liquid crystal panel 200, a polarizing plate 300 disposed below the liquid crystal panel 200, and a backlight unit disposed below the polarizing plate 300.

[0376] The liquid crystal panel 200 may include a lower substrate 210, a stacked structure, and a liquid crystal layer 220 disposed between the stacked structure and the lower substrate. The stacked structure may include a transparent substrate 240, a first optical filter layer 310, a photoluminescent layer 230 containing a pattern of semiconductor nanoparticle-polymer composite, and a second optical filter layer 311.

[0377] The lower substrate 210 (also referred to as the array substrate) may be a transparent insulating material substrate. The substrate may be as described herein. A wiring board 211 may be disposed on the upper surface of the lower substrate 210. The wiring board 211 may include a plurality of gate lines (not shown) and data lines (not shown) defining pixel regions, thin-film transistors positioned adjacent to the intersection regions of the gate lines and data lines, and pixel electrodes for each pixel region, but embodiments are not limited thereto. The details of such a wiring board are not particularly limited.

[0378] The liquid crystal layer 220 may be disposed on the wiring board 211. The liquid crystal panel 200 may include alignment layers 221 above and below the liquid crystal layer 220, the alignment layers 221 being used to initially align the liquid crystal material included in the liquid crystal layer 220. The 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.

[0379] The polarizer 300 may be disposed below the lower substrate. The material and structure of the polarizer 300 are not particularly limited. For example, a backlight unit (e.g., emitting blue light) may be disposed below the polarizer 300. The upper optical element or polarizer 300 may be disposed between the liquid crystal layer 220 and the transparent substrate 240, but is not limited thereto. For example, the upper polarizer may be disposed between the liquid crystal layer 220 and the photoluminescent layer 230. The polarizer can be any polarizer that can be used in a liquid crystal display device. The polarizer may be triacetyl cellulose (TAC) with 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 that controls the refractive index but does not have a polarization function.

[0380] The backlight unit may include 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.

[0381] The backlight unit may also include a light guide plate 120. In embodiments, the backlight unit may be edge-mounted. 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) (e.g., a diffuser, prism sheet, etc.) on the light guide plate, but this disclosure is not limited thereto. The backlight unit may not include a light guide plate. In embodiments, the backlight unit may be direct-illuminated. For example, the backlight unit may have a reflector (not shown) and a plurality of fluorescent lamps located at regular intervals on the reflector, or it may have an LED operating substrate on which a plurality of light-emitting diodes may be disposed, a diffuser on the plurality of light-emitting diodes, and optionally at least one optical sheet. Details of such backlight units (e.g., each component of the light-emitting diodes, fluorescent lamps, light guide plate, various optical sheets, and reflector) are known and are not particularly limited.

[0382] The black matrix 241 may be disposed beneath the transparent substrate 240 and may have openings to conceal gate lines, data lines, and thin-film transistors of the wiring board on the underlying substrate. For example, the black matrix 241 may have a lattice shape. The photoluminescent layer 230 may be disposed within the openings of the black matrix 241 and has a nanoparticle-polymer composite pattern comprising 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 a fourth region. The fourth region may include quantum dots that emit light of a different color (e.g., cyan, magenta, and yellow light) than the light emitted from the first to the third regions.

[0383] In the photoluminescent layer 230, the patterned segments can be repeated corresponding to the pixel regions formed on the lower substrate. A transparent common electrode 231 can be disposed on the photoluminescent layer 230.

[0384] The third region (B) configured to emit / transmit blue light can be a transparent color filter that does not alter the emission spectrum of the light source. In this case, blue light emitted from the backlight unit can enter in a polarized state and can pass through the polarizer and liquid crystal layer as is. If desired, the third region may include quantum dots that emit blue light.

[0385] As described herein, if desired, the display device or light-emitting device according to the embodiments may further include an excitation light blocking layer or a first optical filter layer (hereinafter referred to as the first optical filter layer). The first optical filter layer may be disposed between the bottom surface of the first region (R) and the second region (G) and the substrate (e.g., upper substrate 240) or on the upper surface of the substrate. The first optical filter layer may be a sheet having an opening in the portion corresponding to the pixel region (third region) displaying blue, and thus may be formed in the portion corresponding to the first region and the second region. In other words, the first optical filter layer may be integrally formed on the substrate. Figure 3A , Figure 3B , Figure 6 and / or Figure 7A The locations shown are excluding, but not limited to, those overlapping with the third region. Two or more first optical filter layers may be spaced apart from each other at locations overlapping with the first region, the second region, and optionally the third region. When the light source includes a green light-emitting device, a green light-blocking layer may be disposed on the third region.

[0386] The first optical filter layer can block light in a predetermined wavelength region, for example, within the visible light region, and can transmit light in other wavelength regions. For example, it can block blue light (or green light) and can transmit light other than blue light (or green light). The first optical filter layer can transmit, for example, green light, red light, and / or yellow light as a mixture of green and red light. The first optical filter layer can transmit blue light and block green light, and can be disposed on a blue emitting pixel.

[0387] The first optical filter layer can substantially block the excitation light and transmit light in the desired wavelength range. The transmittance of the first optical filter layer for 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%.

[0388] A first optical filter layer configured to selectively transmit red light may be disposed at a position superimposed on the red emitting segment, and a first optical filter layer configured to selectively transmit green light may be disposed at a position superimposed on the green emitting segment. The first optical filter layer may include: a first filter region that blocks (e.g., absorbs) blue and red light and selectively transmits light within a predetermined range (e.g., greater than or equal to about 500 nm, greater than or equal to about 510 nm, or greater than or equal to about 515 nm to less than or equal to about 550 nm, less than or equal to about 545 nm, less than or equal to about 540 nm, less than or equal to about 535 nm, less than or equal to about 530 nm, less than or equal to about 525 nm, or less than or equal to about 520 nm); a second filter region; and a second filter region. The filter region includes a second filter region that blocks (e.g., absorbs) blue and green light and selectively transmits light within a predetermined range (e.g., greater than or equal to about 600 nm, greater than or equal to about 610 nm, or greater than or equal to about 615 nm to less than or equal to about 650 nm, less than or equal to about 645 nm, less than or equal to about 640 nm, less than or equal to about 635 nm, less than or equal to about 630 nm, less than or equal to about 625 nm, or less than or equal to about 620 nm); or a first filter region and a second filter region. In an embodiment, the light source may emit a mixture of blue and green light, and the first optical filter layer may further include a third filter region that selectively transmits blue light and blocks green light.

[0389] The first filter area can be positioned overlapping the green light-emitting section. The second filter area can be positioned overlapping the red light-emitting section. The third filter area can be positioned overlapping the blue light-emitting section.

[0390] The first filter area, the second filter area, and the optional third filter area can be optically isolated. Such a first optical filter layer can help improve the color purity of the display device.

[0391] The display device may further include a second optical filter layer (e.g., a red / green or yellow light recycling layer) 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 optical 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 in the wavelength region greater than about 500 nm (which is green light (G), yellow light, red light (R), etc.) may not pass through the second optical filter layer and be reflected. The reflected green and red light may pass through the first and second regions to be emitted to the outside of the display device.

[0392] The second optical filter layer or the first optical filter layer can be formed as an integrated layer with a relatively flat surface.

[0393] The first optical filter layer may include a polymer film containing dyes and / or pigments that absorb light in wavelengths to be blocked. The second optical filter layer or the first optical filter layer may include a single layer having a low refractive index, and may be, for example, a transparent film having a refractive index less than or equal to about 1.4:1, less than or equal to about 1.3, or less than or equal to about 1.2. The second optical filter layer or the first optical filter layer having a low refractive index may include, for example, porous silica, porous organic materials, porous organic-inorganic composites, or combinations thereof.

[0394] The first or second optical filter layer may comprise multiple layers with different refractive indices. The first or second optical filter layer can be formed by stacking two layers with different refractive indices. For example, the first / second optical filter layer can be formed by alternately stacking a material with a high refractive index and a material with a low refractive index.

[0395] In an embodiment, the electronic device may include a light-emitting device (e.g., an electroluminescent device) comprising the aforementioned nanoparticles. Figure 7B This is a schematic cross-sectional view of a light-emitting device (electroluminescent device) according to an embodiment. (Refer to...) Figure 7BThe light-emitting device may include: an anode 1 and a cathode 5 facing each other; a quantum dot light-emitting layer 3 comprising multiple quantum dots disposed between the anode and the cathode; and a hole auxiliary layer 2 located between the anode and the quantum dot light-emitting layer. The hole auxiliary layer may also 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 quantum dot 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.

[0396] In the following description, exemplary embodiments are further described in detail with reference to examples. However, embodiments of this disclosure are not limited to these examples.

[0397] Example

[0398] Analytical methods

[0399] [1] Photoluminescence analysis

[0400] Photoluminescence (PL) spectra of the fabricated nanoparticles and composites including the nanoparticles were obtained using a Hitachi F-7000 spectrophotometer at an excitation wavelength of 450 nm.

[0401] [2] Blue light absorption rate, quantum efficiency, and light conversion efficiency (CE) of the composite.

[0402] The amount (B) of incident light at a wavelength of 450 nm was measured using an integrating sphere or integrating hemisphere of an absolute quantum efficiency measuring device (e.g., QE-2100, Otsuka Electronics Co., Ltd.). Subsequently, a semiconductor nanoparticle (quantum dot, QD)-polymer composite was placed in the integrating (hemispheric) sphere and then incident light was irradiated to measure the amount (A) of first light from the composite and the amount (B') of incident light passing through the composite, respectively.

[0403] Using the measured quantities, calculate the incident light absorptivity, light conversion efficiency (e.g., internal quantum efficiency), and quantum efficiency (e.g., external quantum efficiency) according to Equations 2 to 4:

[0404] Equation 2: Internal quantum efficiency (%) = [A / (B-B')] × 100%

[0405] Equation 3: External quantum efficiency (%) = [A / B] × 100%

[0406] Equation 6: Incident light absorptivity (%) = [(B-B') / B] × 100%

[0407] Among them, in equations 2, 3 and 6,

[0408] A is the amount of the first light emitted from the first complex.

[0409] B is the amount of incident light provided to the first complex, and

[0410] B' is the amount of incident light that passes through the first complex.

[0411] [3] Process retention percentage (i.e., process retention percentage)

[0412] The semiconductor nanoparticle-polymer composite obtained by polymerization was heat-treated at 180 °C for 30 minutes, and the process retention percentage was measured according to the following equation (Equation 4):

[0413] Equation 4

[0414] Process retention percentage (%) = [IQE2 / IQE1] × 100%

[0415] In Equation 4, IQE1 is the internal quantum efficiency of the semiconductor nanoparticle-polymer composite after polymerization and before heat treatment, and IQE2 is the internal quantum efficiency of the semiconductor nanoparticle-polymer composite after heat treatment.

[0416] [4] ICP-AES analysis

[0417] Inductively coupled plasma atomic emission spectrometry (ICP-AES) analysis was performed using a Shimadzu ICPS-8100.

[0418] Example 1:

[0419] [1] Formation of the first semiconductor nanocrystal (or core)

[0420] Sulfur was dissolved in oleylamine to prepare a 1 volume molar (M) solution of sulfur precursor (hereinafter abbreviated as "sulfur precursor"). Octadectoene (ODE), oleylamine, silver acetate, indium acetate, and gallium acetylacetonate were added to a 100 mL reaction flask and the mixture was evacuated at room temperature for 10 min. Nitrogen gas was introduced into the reaction flask, and the sulfur precursor and dodecanethiol were added. The flask was heated to a reaction temperature of 210 °C and the reaction was carried out for 60 min. After the temperature of the flask was lowered to 180 °C, trioctylphosphine (TOP) was added to the flask. The mixture was then cooled to room temperature, and ethanol (a non-solvent) was added to promote precipitation. The obtained first semiconductor nanocrystals (or cores) were separated and recovered by centrifugation and redispersed in toluene.

[0421] The molar ratio of the silver precursor, indium precursor, gallium precursor and sulfur precursor used is 0.8:1:1.1:4.

[0422] [2] Formation, separation and washing of intermediate particles

[0423] Gallium bromide was dissolved in trioctylphosphine to prepare a 1 volume molar (M) gallium precursor solution (hereinafter referred to as the first gallium precursor). A dispersion of the silver compound was prepared by dispersing a silver compound (silver acetate, 0.06 M) in oleylamine.

[0424] In a flask, dimethylthiourea (DMTU), oleylamine, and octadecene, serving as the first sulfur precursor, were added, and the mixture was vacuum-treated at 120°C for 10 minutes. After replacing the atmosphere inside the reaction flask with N2, the mixture was heated to 240°C (first injection temperature), followed by the addition of a dispersion of the first gallium precursor, the first semiconductor nanocrystals, and the silver compound. The reaction mixture was then heated to 260°C (first reaction temperature) and reacted for 180 minutes (first reaction time). The reaction solution was cooled to 180°C, and trioctylphosphine was added. The mixture was then cooled to room temperature. An antisolvent (ethanol) was added to the room-temperature reaction mixture to promote the precipitation of the resulting intermediate particles. The obtained intermediate particles were recovered by centrifugation and redispersed in toluene. Precipitation and separation (centrifugation) were repeated using ethanol as a washing solvent.

[0425] A silver compound is used at approximately 4 mol% relative to the gallium precursor. The molar ratio of the first gallium precursor to the first sulfur precursor is 0.72:1 (gallium precursor: sulfur precursor).

[0426] [3] Formation of semiconductor nanoparticles

[0427] Gallium bromide and gallium chloride were both dissolved in trioctylphosphine to prepare a 1 M solution (hereinafter referred to as the second gallium precursor). A dispersion of the silver compound was prepared by dispersing a silver compound (silver acetate, 0.06 M) in oleylamine.

[0428] In a flask, dimethylthiourea (DMTU), oleylamine, and octadecene, serving as the second sulfur precursor, were added, and the mixture was vacuum-treated at 120 °C for 10 minutes. After replacing the atmosphere inside the reaction flask with N2, the mixture was heated to 240 °C (second injection temperature), followed by the addition of the second gallium precursor, intermediate particles, and a dispersion of the silver compound. The reaction mixture was then heated to 260 °C (second reaction temperature) and reacted for 200 minutes. The reaction solution was cooled to 180 °C, and trioctylphosphine was added. The mixture was then cooled to room temperature. An antisolvent (ethanol) was added to the room-temperature reaction mixture to promote the precipitation of the resulting semiconductor nanoparticles. The obtained semiconductor nanoparticles were recovered by centrifugation and redispersed in toluene.

[0429] A silver compound is used at approximately 5 mol% relative to the second gallium precursor. In the second gallium precursor, the content of gallium chloride is approximately 0.3 mol per 1 mol of gallium bromide.

[0430] The molar ratio of the second gallium precursor to the second sulfur precursor used is 0.75:1 (second gallium precursor: second sulfur precursor). For every 1 mole of the first gallium precursor, the amount of the second gallium precursor is approximately 0.81 moles. For every 1 mole of the indium precursor (for indium precursors added in nucleation synthesis), the total amount of gallium precursors used in subsequent processes is approximately 388 moles.

[0431] ICP-AES and photoluminescence analyses were performed on the fabricated semiconductor nanoparticles. The results are summarized in Table 1 (molar ratios and charge balance values ​​between elements), Table 2 (photoluminescence properties), and... Figure 8A and Figure 8B middle.

[0432] Example 2:

[0433] Semiconductor nanoparticles were prepared in the same manner as in Example 1, except that the molar ratio of the first gallium precursor to the first sulfur precursor was changed to 0.77:1; the content of the silver compound used in the synthesis of intermediate particles was adjusted to about 2.8 mol% relative to the gallium precursor; the amount of the second gallium precursor was about 0.94 mol% per mol of the first gallium precursor; and the total amount of gallium precursor used in subsequent processes was about 317 mol% per mol of indium precursor (for indium precursor added in nucleation synthesis).

[0434] The fabricated semiconductor nanoparticles were analyzed using ICP-AES and photoluminescence analysis. The results are summarized in Table 1 (molar ratios and charge balance values ​​between elements), Table 2 (photoluminescence properties), and... Figure 8A and Figure 8B middle.

[0435] Example 3:

[0436] Semiconductor nanoparticles were prepared in the same manner as in Example 1, except that the molar ratio of the first gallium precursor to the first sulfur precursor used in the intermediate particle synthesis was changed to 0.77:1; the molar ratio of the second gallium precursor to the second sulfur precursor was changed to 1.125:1; the content of the silver compound used in the intermediate particle synthesis was adjusted to approximately 5.5 mol% relative to the gallium precursor; the amount of the second gallium precursor per 1 mol of the first gallium precursor was approximately 1.46 mol; and the total amount of gallium precursor used in subsequent processes per 1 mol of indium precursor (for indium precursor added in nucleation synthesis) was approximately 553 mol.

[0437] The fabricated semiconductor nanoparticles were analyzed by ICP-AES and photoluminescence analysis. The results are summarized in Tables 1 and 2. Figure 8A and Figure 8B middle.

[0438] Example 4:

[0439] Semiconductor nanoparticles were prepared in the same manner as in Example 1, except that: in the intermediate particle synthesis, the molar ratio of the first gallium precursor to the first sulfur precursor was changed to 0.71:1; the content of the silver compound used in the intermediate particle synthesis was adjusted to approximately 5.7 mol% relative to the gallium precursor; the amount of the second gallium precursor was approximately 0.76 mol% per mol of the first gallium precursor; and the total amount of gallium precursor used in subsequent processes was approximately 589 mol% per mol of indium precursor (for indium precursor added in nucleation synthesis).

[0440] The fabricated semiconductor nanoparticles were analyzed by ICP-AES and photoluminescence analysis. The results are summarized in Tables 1 and 2. Figure 8A and Figure 8B middle.

[0441] Example 5:

[0442] Semiconductor nanoparticles were prepared in the same manner as in Example 1, except that: in the intermediate particle synthesis, the molar ratio of the first gallium precursor to the first sulfur precursor was changed to about 0.9:1; the content of the silver compound used in the intermediate particle synthesis was adjusted to about 3.5 mol% relative to the gallium precursor; the amount of the second gallium precursor was about 0.91 mol per mol of the first gallium precursor; and the total amount of gallium precursor used in subsequent processes was about 415 mol per mol of indium precursor (for indium precursor added in nucleation synthesis).

[0443] The fabricated semiconductor nanoparticles were analyzed by ICP-AES and photoluminescence analysis. The results are summarized in Tables 1 and 2. Figure 8A and Figure 8B middle.

[0444] Comparison Example 1:

[0445] [1] The core was obtained in the same manner as in Example 1, except that the molar ratio of silver precursor, indium precursor, gallium precursor and sulfur precursor was adjusted to 0.8:0.9:1.25:4.

[0446] [2] Gallium bromide was dissolved in trioctylphosphine to prepare a 1 M gallium precursor solution (hereinafter referred to as the gallium precursor). A dispersion of the silver compound was prepared by dispersing the silver compound (silver acetate, 0.06 M) in oleylamine.

[0447] In a flask, dimethylthiourea (DMTU), oleylamine, and octadecene, serving as sulfur precursors, were added, and the mixture was vacuum-treated at 120°C for 10 minutes. After replacing the atmosphere inside the reaction flask with N2, the mixture was heated to 240°C (first injection temperature), followed by the addition of a gallium precursor, a first semiconductor nanocrystal, and a dispersion of a silver compound. The reaction mixture was then heated to 260°C (first reaction temperature) and reacted for 180 minutes (first reaction time). The temperature of the reaction solution was lowered to 180°C, and trioctylphosphine was added. The mixture was then cooled to room temperature. An antisolvent (ethanol) was added to the room-temperature reaction solution to promote the precipitation of the formed semiconductor nanoparticles. The semiconductor nanoparticles were recovered by centrifugation and redispersed in toluene.

[0448] The molar ratio of gallium precursor to sulfur precursor is 1.125:1 (gallium precursor:sulfur precursor). A silver compound is used at approximately 9.2 mol% relative to the gallium precursor. For every 1 mole of indium precursor (referring to indium precursor added in nucleation synthesis), the total amount of gallium precursor used in subsequent processes is approximately 715 moles.

[0449] ICP-AES and photoluminescence analyses were performed on the fabricated semiconductor nanoparticles. The results are summarized in Table 1 (molar ratios and charge balance values ​​between elements), Table 2 (photoluminescence properties), and... Figure 8A and Figure 8B middle.

[0450] Comparison Example 2:

[0451] Semiconductor nanoparticles were prepared in the same manner as in Comparative Example 1, except that the total amount of gallium precursor used in subsequent processes was increased to 931 moles per 1 mole of indium precursor (for indium precursor added in nucleation).

[0452] The fabricated semiconductor nanoparticles were analyzed using ICP-AES and photoluminescence analysis. The results are summarized in Table 1 (molar ratios and charge balance values ​​between elements), Table 2 (photoluminescence properties), and... Figure 8A and Figure 8B middle.

[0453] Comparison Example 3:

[0454] Semiconductor nanoparticles were prepared in the same manner as in Comparative Example 1, except that a silver compound was used in an amount of about 14 mol% relative to the gallium precursor.

[0455] The fabricated semiconductor nanoparticles were analyzed using ICP-AES and photoluminescence analysis. The results are summarized in Table 1 (molar ratios and charge balance values ​​between elements), Table 2 (photoluminescence properties), and... Figure 8A and Figure 8B middle.

[0456] Compare Example 4:

[0457] Semiconductor nanoparticles were prepared in the same manner as in Comparative Example 1, except that the molar ratio of gallium precursor to sulfur precursor used was 0.9:1; a silver compound was used in an amount of about 4.6 mol% relative to the gallium precursor; and the total amount of gallium precursor used in subsequent processes was increased to 1429 moles per 1 mole of indium precursor (for indium precursor added in nucleosynthesis).

[0458] The fabricated semiconductor nanoparticles were analyzed using ICP-AES and photoluminescence analysis. The results are summarized in Table 1 (molar ratios and charge balance values ​​between elements), Table 2 (photoluminescence properties), and... Figure 8A and Figure 8B middle.

[0459] Table 1

[0460] CBV: Charge balance value

[0461] Table 2

[0462] PWL: Peak Emission Wavelength

[0463] FWHM: Full Width at Half Peak

[0464] The results in Tables 1 and 2 confirm that the semiconductor nanoparticles of the examples exhibit improved luminescence properties (high quantum yield and narrow full width at half maximum) while having a Ga / In molar ratio greater than or equal to 20:1. Figure 8A and Figure 8B The results confirmed that, compared with the semiconductor nanoparticles of the comparative example, the semiconductor nanoparticles of the embodiment exhibited a significant reduction in traps.

[0465] Experimental Example 1

[0466] Semiconductor nanoparticles prepared in Examples 1, 2, 4, and 5, and each of Comparative Examples 1 to 4, were mixed with a solution of a binder (a quaternary copolymer of methacrylic acid, benzyl methacrylate, hydroxyethyl methacrylate, and styrene, having an acid value of 130 mg potassium hydroxide per gram (KOH / g) and a molecular weight of 8000 g per mole) (at a concentration of 30 wt%) in propylene glycol monomethyl ether acetate (PGMEA) to obtain a semiconductor nanoparticle-binder dispersion.

[0467] A hexaacrylate having the following structure as a photopolymerizable monomer, an oxime-ester compound as an initiator, TiO2 nanoparticles as fine metal oxide particles, and PGMEA are added to each of the semiconductor nanoparticle-binder dispersion and mixed together to provide a composition.

[0468]

[0469]

[0470] The compositions thus prepared each comprise 20 wt% semiconductor nanoparticles based on the total solid weight of the composition.

[0471] Each of the components was spin-coated onto a glass substrate at 600 rpm for 5 seconds to obtain a film. The resulting film was then pre-baked (PRB) at 100°C. The pre-baked film was irradiated with light (at a wavelength of 395 nm and an intensity of 4 J) to obtain a nanoparticle-polymer composite film (with a thickness of approximately 7 μm).

[0472] It has been confirmed that all composites, including the example semiconductor nanoparticles, exhibit an incident light absorption rate of over 90%.

[0473] The light conversion efficiency (internal quantum efficiency) of each of the semiconductor nanoparticle composites, including example and comparative examples, was measured, and the results are summarized in Table 3 below.

[0474] The light conversion efficiency (internal quantum efficiency) of the composites of semiconductor nanoparticles, including example and comparative examples, was measured, and the internal quantum efficiency after POB, the percentage of trapped emission after PRB, and the percentage of trapped emission after POB were calculated, and a portion of the results are listed in Table 3.

[0475] Table 3

[0476] Relative internal quantum efficiency (%) after POB: [Internal quantum efficiency of the given complex after POB / Internal quantum efficiency of the complex in Comparison Example 1 after POB] × 100%

[0477] The composite including the semiconductor nanoparticles of Example 2 has a relative internal quantum efficiency of 141.18% after POB, and the trap emission percentage of the composite after POB is 17.3%.

[0478] The results from Table 3, etc., confirm that the semiconductor nanoparticles of the embodiments can exhibit improved luminescence efficiency in the composite and even maintain a relatively suppressed percentage of trapped emission after heat treatment (i.e., exhibit improved stability).

[0479] The process retention percentage (or process retention rate) was measured for the composites including semiconductor nanoparticles of Examples 1, 4 and 5, respectively, and the results are listed in Table 4.

[0480] Table 4

[0481] The results in Table 4 confirm that the composite including the semiconductor nanoparticles of the examples can exhibit increased process retention.

[0482] Experimental Example 2

[0483] Semiconductor nanoparticles, hexanediol diacrylate (monomer, CAS No. 13048-33-4, supplier: Sigma-Aldrich), TiO2 fine particles, and an initiator prepared in each of Examples 1, 3, 4, and 5 were mixed together to provide a composition. Based on the total weight of the composition, the semiconductor nanoparticles, titanium dioxide fine particles, and photoinitiator in the composition were 20 wt%, 5 wt%, and 1 wt%, respectively, with the balance being monomer. The prepared composition was deposited on a substrate and exposed to light (4 joules exposure dose, 395 nm wavelength) to perform photopolymerization, thereby obtaining a film with a thickness of 7 μm. The prepared film underwent post-baking at 100 °C for 30 minutes.

[0484] The internal quantum efficiency, trap emission percentage after exposure, and trap emission percentage after exposure of the prepared composites were calculated respectively, and a portion of the results are shown in Table 5 below.

[0485] Table 5

[0486] The results in Table 5 confirm that the semiconductor nanoparticles of the embodiments exhibit relatively high levels of internal quantum efficiency and process retention, and maintain a relatively low trap emission percentage of the composite after exposure or after POB.

[0487] While this disclosure has been described in conjunction with what is now considered a practical embodiment, it will be understood that the subject matter is not limited to the disclosed exemplary embodiments. Rather, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A semiconductor nanoparticle comprising silver, indium, gallium, and sulfur. in, In the semiconductor nanoparticles, the molar ratio of gallium to indium is greater than or equal to 20:1 and less than or equal to 40:1, and The semiconductor nanoparticles have a quantum yield of 70% or higher.

2. The semiconductor nanoparticles according to claim 1, in, The molar ratio of gallium to indium is greater than or equal to 23:1 and less than or equal to 37:

1.

3. The semiconductor nanoparticles according to claim 1, in, In the semiconductor nanoparticles, the molar ratio of silver to indium is greater than or equal to 10:1 and less than or equal to 16:1; and / or The molar ratio of the sum of indium and gallium to sulfur is greater than or equal to 0.3:1 and less than or equal to 0.66:

1.

4. The semiconductor nanoparticles according to claim 1, in, In the semiconductor nanoparticles, the molar ratio of indium to the sum of indium and gallium is greater than or equal to 0.024:1 and less than 0.05:

1.

5. The semiconductor nanoparticles according to claim 1, in, In the semiconductor nanoparticles, The molar ratio of indium to sulfur is greater than or equal to 0.01:1 and less than or equal to 0.045:1, or The molar ratio of gallium to sulfur is greater than or equal to 0.45:1 and less than or equal to 0.78:

1.

6. The semiconductor nanoparticles according to claim 1, in, In the semiconductor nanoparticles, The molar ratio of the sum of indium and gallium to silver is greater than or equal to 1.3:1 and less than or equal to 2.2:

1.

7. The semiconductor nanoparticles according to claim 1, in, The semiconductor nanoparticles include: a first semiconductor nanocrystal comprising silver, indium, gallium, and sulfur; and a second semiconductor nanocrystal comprising silver, gallium, and sulfur.

8. The semiconductor nanoparticles according to claim 1, in, The semiconductor nanoparticles have a quantum yield of greater than or equal to 75% and less than or equal to 99%.

9. The semiconductor nanoparticles according to claim 1, in, The semiconductor nanoparticles are configured to emit a first light. The first light has a peak emission wavelength greater than or equal to 500 nanometers and less than or equal to 560 nanometers, and The full width at half maximum (FWHM) of the emission spectrum of the first light is greater than or equal to 5 nanometers and less than or equal to 50 nanometers.

10. The semiconductor nanoparticles according to claim 1, in, The semiconductor nanoparticles have a trap emission percentage of less than or equal to 20%, calculated by the following equation: Trapped emission percentage = [trapped emission area of ​​the emission spectrum of the semiconductor nanoparticle / total area of ​​the emission spectrum] × 100%. The trap emission area is the area of ​​the emission spectrum at a wavelength greater than or equal to the peak emission wavelength plus 50 nanometers.

11. A method for preparing semiconductor nanoparticles, in, Semiconductor nanoparticles include silver, indium, gallium, and sulfur, and in the semiconductor nanoparticles, the molar ratio of gallium to indium is greater than or equal to 20:1 and less than or equal to 40:

1. The method includes: In a first medium comprising a first organic solvent, a first semiconductor nanocrystal comprising silver, group 13 elements and chalcogens is combined with a first sulfur precursor, a first gallium precursor and an optional first silver compound. The first medium is heated to a first reaction temperature to form intermediate particles; Separate the intermediate particles formed; In a second medium comprising a second organic solvent, the separated intermediate particles, the second sulfur precursor, the second gallium precursor, and an optional second silver compound are combined; and The second medium is heated to a second reaction temperature to form semiconductor nanoparticles.

12. The method according to claim 11, in, The first gallium precursor includes gallium bromide and gallium chloride, and The second gallium precursor includes gallium bromide, gallium chloride, or a combination thereof.

13. The method of claim 11, further comprising: After the step of separating the intermediate particles, the intermediate particles are washed with a washing solvent, and The washing solvent includes C1 to C10 alcohols.

14. The method according to claim 11, in, The first silver compound in the first medium is present in an amount greater than or equal to 0.1 mole percent and less than or equal to 50 mole percent relative to the first gallium precursor, and / or The second silver compound in the second medium exists in an amount greater than or equal to 0.1 mole percent and less than or equal to 50 mole percent relative to the second gallium precursor.

15. An ink composition comprising: Semiconductor nanoparticles according to any one of claims 1 to 10; And liquid carriers, The liquid carrier includes polymerizable monomers, organic solvents, or combinations thereof.

16. A semiconductor nanoparticle composite, comprising: The semiconductor nanoparticles according to any one of claims 1 to 10 are dispersed in a matrix.

17. The semiconductor nanoparticle composite according to claim 16, in, The semiconductor nanoparticle composite has a trap emission percentage of less than or equal to 20%, calculated by the following equation: Trapped emission percentage = [trapped emission area of ​​the emission spectrum of the semiconductor nanoparticle composite / total area of ​​the emission spectrum] × 100%. The trap emission area is the area of ​​the emission spectrum at a wavelength greater than or equal to the peak emission wavelength plus 50 nanometers.

18. A display device, comprising: Semiconductor nanoparticles according to any one of claims 1 to 10.

19. An electronic device comprising: Semiconductor nanoparticles according to any one of claims 1 to 10.

20. The electronic device according to claim 19, in, The electronic device includes virtual reality devices, augmented reality devices, portable terminal devices, monitors, laptop computers, televisions, electronic display panels, or electronic components for vehicles.

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