Semiconductor nanoparticles, method of manufacturing the same, and composite, color conversion structure and electronic device

Abstract

Provided are a semiconductor nanoparticle, a method of manufacturing the same, and a composite, a color conversion structure, and an electronic device including the same. The semiconductor nanoparticles include silver, indium, gallium, and sulfur, in which the semiconductor nanoparticles are configured to emit green light, and in which the semiconductor nanoparticles have a relative molar value of zinc of greater than or equal to about 0.25 and less than or equal to about 0.9 as defined by Equation 1: Relative molar value of zinc of Equation 1 = [Zn] / ([Ag] + [In] + [Ga] + [Zn]), in Equation 1, in Equation 1, in Equation 1, in Equation 2, in Equation 3, in Equation 4, in Equation 5, in Equation 6, in Equation 6, in Equation 6, in Equation 7, in Equation 6, in Equation 7, in Equation 6, in Equation 7, in [Ag], [In], [Ga], and [Zn] are molar amounts of silver, indium, gallium, and zinc in the semiconductor nanoparticles, respectively, and wherein the molar ratio of gallium to indium is greater than about 2.5: 1 and less than about 5.6: 1.

Description

[0001] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0103799 filed in the Korean Intellectual Property Office on August 8, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0002] Disclosed are semiconductor nanoparticles, methods of making semiconductor nanoparticles, and electronic devices including semiconductor nanoparticles. Background Art

[0003] Semiconductor nanoparticles may exhibit different aspects, characteristics or properties from corresponding bulk materials having substantially the same composition. For example, semiconductor nanoparticles may have different physical properties (e.g., band gap energy, luminescent properties, etc.) based on nanostructures. Semiconductor nanoparticles may be configured to emit light when excited by incident light or an applied voltage. Luminescent nanostructures may be applicable to various devices (e.g., display panels or electronic devices including display panels). From an environmental perspective, it is desirable to develop luminescent nanoparticles that do not contain harmful heavy metals such as cadmium, and also to achieve improvements in one or more luminescent or optical properties. Summary of the invention

[0004] One aspect relates to a color conversion panel including semiconductor nanoparticles capable of emitting light and exhibiting improved optical properties (eg, relatively high excitation light absorbance or narrow half-maximum full width) and improved stability (eg, process stability and / or chemical stability).

[0005] One aspect relates to a population of semiconductor nanoparticles.

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

[0007] One aspect relates to a color conversion panel including semiconductor nanoparticles.

[0008] One aspect relates to compositions (eg, ink compositions) including semiconductor nanoparticles.

[0009] One aspect relates to an electronic device (eg, a display device) including semiconductor nanoparticles or a color conversion panel.

[0010] In one aspect, the semiconductor nanoparticles include silver, indium, gallium, and sulfur, wherein the semiconductor nanoparticles are configured to emit green light.

[0011] The semiconductor nanoparticles have a relative molar value of zinc of greater than or equal to about 0.25 to less than or equal to about 0.9 as defined by Equation 1:

[0012] Equation 1

[0013] Relative molar value of zinc = [Zn] / ([Ag]+[In]+[Ga]+[Zn])

[0014] Where, in equation 1,

[0015] [Ag], [In], [Ga], and [Zn] are the molar amounts of silver, indium, gallium, and zinc in the semiconductor nanoparticles, respectively, and

[0016] The molar ratio of gallium to indium (Ga:In) is greater than about 2.5:1 and less than about 5.6:1, or less than or equal to about 5:1.

[0017] In an embodiment, the semiconductor nanoparticles may have a charge balance value greater than or equal to about 0.8, greater than or equal to about 0.9, greater than or equal to about 0.93 and less than or equal to about 1.4, less than or equal to about 1.35, or less than or equal to about 1.1, as represented by the following Equation 2:

[0018] Equation 2

[0019] Charge balance value = {[Ag] + 3([In] + [Ga]) + 2[Zn]} / 2[S]

[0020] Wherein, in Equation 2, [Ag], [In], [Ga], [Zn], and [S] are the molar amounts of silver, indium, gallium, zinc, and sulfur in the semiconductor nanoparticles, respectively.

[0021] In the semiconductor nanoparticles, the relative molar value of zinc may be greater than or equal to about 0.28, greater than or equal to about 0.35, and less than or equal to about 0.48, less than or equal to about 0.43, less than or equal to about 0.33, or less than or equal to about 0.31.

[0022] In the semiconductor nanoparticles, the relative molar value of zinc may be greater than about 0.48, or greater than or equal to about 0.6, and less than or equal to about 0.75, or less than or equal to about 0.67.

[0023] In the semiconductor nanoparticles, the molar ratio of gallium to indium (Ga:In) may be greater than or equal to about 2.9:1, or greater than or equal to about 3.5:1. In the semiconductor nanoparticles, the molar ratio of gallium to indium (Ga:In) may be less than or equal to about 5:1, less than or equal to about 4.5:1, less than or equal to about 4:1, or less than or equal to about 3.9:1.

[0024] In the semiconductor nanoparticles, a molar ratio of gallium to the sum of indium and gallium (Ga:(In+Ga)) may be greater than about 0.72:1, or greater than or equal to about 0.73:1, and less than or equal to about 0.84:1, or less than or equal to about 0.8:1.

[0025] In the semiconductor nanoparticles, a molar ratio of zinc to indium (Zn:In) may be greater than or equal to about 2.7:1, and less than or equal to about 10.5:1 or less than or equal to about 5.9:1.

[0026] In the semiconductor nanoparticles, a molar ratio of sulfur to indium (S:In) may be greater than or equal to about 7.5:1, or greater than or equal to about 9:1, and less than or equal to about 17:1, or less than or equal to about 12:1.

[0027] In the semiconductor nanoparticles, a molar ratio of silver to indium (Ag:In) may be greater than or equal to about 1.1:1 or greater than or equal to about 2.1:1, and less than or equal to about 5:1 or less than or equal to about 3.1:1.

[0028] In the semiconductor nanoparticles, a molar ratio of gallium to silver (Ga:Ag) may be greater than or equal to about 1.1:1 or greater than or equal to about 1.4:1, and less than or equal to about 3:1 or less than or equal to about 2.8:1.

[0029] In the semiconductor nanoparticles, a molar ratio of gallium to the sum of gallium, indium and silver (Ga:(Ga+In+Ag)) may be greater than or equal to about 0.45:1 or greater than or equal to about 0.48:1, and less than or equal to about 0.7:1 or less than or equal to about 0.6:1.

[0030] In the semiconductor nanoparticles, a molar ratio of zinc to sulfur (Zn:S) may be greater than or equal to about 0.1: 1. In the semiconductor nanoparticles, a molar ratio of zinc to sulfur (Zn:S) may be less than or equal to about 0.8:1.

[0031] In the semiconductor nanoparticles, a molar ratio of the sum of indium and gallium to sulfur ((In+Ga):S) may be greater than or equal to about 0.1:1 or greater than or equal to about 0.25:1. A molar ratio of the sum of indium and gallium to sulfur ((In+Ga):S) may be less than or equal to about 0.8:1 or less than or equal to about 0.5:1.

[0032] In the semiconductor nanoparticles, a molar ratio of silver to sulfur (Ag:S) may be greater than or equal to about 0.1: 1. A molar ratio of silver to sulfur (Ag:S) may be less than or equal to about 0.5:1 or less than or equal to about 0.33:1.

[0033] In the semiconductor nanoparticles, a molar ratio of silver to the sum of silver, indium, and gallium (Ag: (Ag + In + Ga)) may be greater than or equal to about 0.2: 1 or greater than or equal to about 0.3: 1. In the semiconductor nanoparticles, a molar ratio of silver to the sum of silver, indium, and gallium (Ag: (Ag + In + Ga)) may be less than or equal to about 0.5: 1 or less than or equal to about 0.4: 1.

[0034] In the semiconductor nanoparticles, a molar ratio of sulfur to the sum of silver, indium, and gallium (S: (Ag + In + Ga)) may be greater than or equal to about 1: 1. In the semiconductor nanoparticles, a molar ratio of sulfur to the sum of silver, indium, and gallium (S: (Ag + In + Ga)) may be less than or equal to about 2.5: 1.

[0035] In the semiconductor nanoparticles, a molar ratio of sulfur to the sum of silver, indium, gallium, and zinc (S:(Ag+In+Ga+Zn)) may be greater than or equal to about 0.8 and less than or equal to about 1.3:1.

[0036] In the semiconductor nanoparticles, a molar ratio of the sum of indium and gallium to silver ((In+Ga):Ag) may be greater than or equal to about 1.4:1 and less than or equal to about 3.7:1.

[0037] The semiconductor nanoparticles may include a first particle including silver, indium, gallium, and sulfur, and a semiconductor nanocrystal layer disposed on the first particle and including zinc and sulfur.

[0038] The first particles may include first semiconductor nanocrystals and optionally second semiconductor nanocrystals. The first semiconductor nanocrystals may include silver, indium, gallium, and sulfur.

[0039] The first semiconductor nanocrystals or first particles may not include zinc.

[0040] In the semiconductor nanoparticle, the second semiconductor nanocrystal may be disposed on the first semiconductor nanocrystal or may surround at least a portion of the first semiconductor nanocrystal. The second semiconductor nanocrystal may include gallium, sulfur and optionally silver. The semiconductor nanocrystal layer may include a third semiconductor nanocrystal containing zinc and sulfur. The second semiconductor nanocrystal may have a composition different from the first semiconductor nanocrystal and the third semiconductor nanocrystal. The third semiconductor nanocrystal may include zinc sulfide. The third semiconductor nanocrystal may have a composition different from the first semiconductor nanocrystal. The semiconductor nanocrystal layer or the third semiconductor nanocrystal may provide the outermost layer of the semiconductor nanoparticle.

[0041] In the semiconductor nanoparticle, the second semiconductor nanocrystal may be disposed between the first semiconductor nanocrystal and the semiconductor nanocrystal layer.

[0042] In a semiconductor nanoparticle, the amount (or concentration) of indium in a portion adjacent to the surface of the particle may be less than the amount (or concentration) of indium in a central portion (e.g., core) of the particle. In a nanoparticle, the amount (or concentration) of zinc in a portion adjacent to or close to the surface of the particle may be greater than the amount (or concentration) of zinc in a central portion (e.g., core) of the particle. In a nanoparticle, the concentration of zinc may be greater at the outer portion than inside the particle near the core.

[0043] The thickness of the semiconductor nanocrystal layer may be greater than or equal to about 0.1 nm, or greater than or equal to about 0.5 nm. The thickness of the semiconductor nanocrystal layer may be less than or equal to about 5 nm, less than or equal to about 3 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.

[0044] The green light may include band edge emission.

[0045] The green light may have a peak emission wavelength 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.

[0046] The semiconductor nanoparticles may have an (absolute) quantum yield of greater than or equal to about 65% or greater than or equal to about 70%. The quantum yield may be less than or equal to about 98% or less than or equal to about 85%.

[0047] The semiconductor nanoparticles may have a half-maximum full width of less than or equal to about 40 nm or less than or equal to about 35 nm. The half-maximum full width may be greater than or equal to about 5 nm, greater than or equal to about 10 nm, greater than or equal to about 15 nm, or greater than or equal to about 25 nm.

[0048] The semiconductor nanoparticles may have a trap emission percentage of less than or equal to about 25%, 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% obtained by the following Equation 3:

[0049] Equation 3

[0050] Trap emission percentage (%)=[trap emission area in emission spectrum / total area of ​​emission spectrum]×100.

[0051] In Equation 3, the well emission area refers to the peak area having (eg, corresponding to) a wavelength greater than the peak emission wavelength plus 50 nm.

[0052] The method of manufacturing semiconductor nanoparticles of an embodiment includes: reacting a zinc precursor with a sulfur precursor in the presence of a first particle containing indium, gallium, silver and sulfur to form a semiconductor nanocrystal layer containing zinc and sulfur on the first particle. The reaction includes adding the first particle and the zinc precursor to a reaction medium containing a sulfur precursor and a first organic solvent, and reacting at a temperature greater than about 180° C. and less than about 240° C.

[0053] The sulfur precursor may include a thiol compound, an isothiocyanate compound, a thiourea compound, or a combination thereof.

[0054] The zinc precursor may include a zinc halide.

[0055] The reaction temperature may be greater than or equal to about 205°C and less than or equal to about 220°C.

[0056] The reaction time may be greater than or equal to about 10 minutes and less than or equal to about 5 hours.

[0057] The reaction time may be greater than or equal to about 30 minutes or longer and less than or equal to about 2 hours.

[0058] The first organic solvent may include a C5-C40 aliphatic (eg, alkane, alkene, or alkyne) hydrocarbon solvent, a C6-C40 aromatic hydrocarbon solvent, a C5-C40 amine solvent (eg, an aliphatic amine solvent), or a combination thereof.

[0059] The first organic solvent may include a mixture of two or more organic solvents.

[0060] The mixture of organic solvents may be a mixture of a first solvent including a C5-C40 aliphatic hydrocarbon solvent and a second solvent including a C5-C40 amine solvent. In the mixture of organic solvents, the mixing ratio between the first solvent and the second solvent may be about 1:0.01 to 1:10, about 1:0.03 to 1:9, about 1:0.05 to 1:8, about 1:0.07 to 1:7, about 1:0.1 to 1:6, about 1:0.2 to 1:5, about 1:0.5 to 1:2, about 1:0.8 to 1:1.3 or a combination thereof. In an embodiment, the amount of the first solvent in the mixture of organic solvents may be greater than the amount of the second solvent.

[0061] In an embodiment, the first particle can be prepared by the following method, the method comprising:

[0062] obtaining a first semiconductor nanocrystal comprising silver, indium, gallium, and sulfur;

[0063] preparing a reaction medium including the first precursor in a second organic solvent;

[0064] heating the reaction medium to a first temperature;

[0065] adding a first semiconductor nanocrystal and a second precursor to a reaction medium, wherein one of the first precursor and the second precursor is a gallium precursor and the other is a sulfur precursor; and

[0066] heating the reaction medium to a second temperature and reacting for a first reaction time to form first particles (eg, including first semiconductor nanocrystals and second semiconductor nanocrystals),

[0067] The first temperature is greater than or equal to about 120°C and less than or equal to about 280°C, and the second temperature is greater than or equal to about 190°C and less than or equal to about 380°C.

[0068] The reaction medium may further comprise an organic ligand.

[0069] In an embodiment, the first reaction time may be controlled so that the first particles may have a charge balance value greater than or equal to about 0.8 or greater than or equal to about 0.9, and less than or equal to about 1.3 or less than or equal to about 1.1, as defined by Equation 4:

[0070] Equation 4

[0071] Charge balance value = {[Ag] + 3([In] + [Ga])} / 2[S]

[0072] Where, in equation 4,

[0073] [Ag], [In], [Ga], and [S] are the molar amounts of silver, indium, gallium, and sulfur in the first particles, respectively.

[0074] The first temperature and the second temperature may be different. The second temperature may be greater than the first temperature.

[0075] The gallium precursor may include a gallium halide, gallium acetylacetonate, or a combination thereof. The second organic solvent may be the same as the first organic solvent. The second organic solvent may be different from the first organic solvent. The second organic solvent may include a substituted or unsubstituted C5-C40 aliphatic hydrocarbon solvent, a substituted or unsubstituted C6-C40 aromatic hydrocarbon solvent, a C5-C40 amine solvent (e.g., an aliphatic amine solvent), or a combination thereof. The organic ligand may include a thiol compound.

[0076] The second temperature may be greater than or equal to about 250° C., greater than or equal to about 260° C., or greater than or equal to about 290° C. to less than or equal to about 330° C. The first reaction time may be greater than or equal to about 10 minutes to less than about 50 minutes. The second temperature may be less than about 290° C. (e.g., greater than or equal to about 200° C. to less than or equal to about 250° C.), and the first reaction time may be greater than or equal to about 30 minutes, and for example, less than or equal to about 90 minutes, less than or equal to about 70 minutes, or less than or equal to about 60 minutes.

[0077] In an embodiment, the ink composition comprises semiconductor nanoparticles and a liquid carrier. The semiconductor nanoparticles or a population thereof may be dispersed in the liquid carrier. The liquid carrier may include a liquid monomer, a (volatile) organic solvent, or a combination thereof. The ink composition may not include a volatile organic solvent in large amounts. The ink composition may also include metal oxide particles.

[0078] In an embodiment, a composite includes a matrix and semiconductor nanoparticles dispersed in the matrix. The composite may further include metal oxide particles. The composite may be configured to emit green light. The composite may be a patterned film. The composite may further include semiconductor nanoparticles configured to emit a second light different from green light.

[0079] In an embodiment, when the composite is kept in air at room temperature (eg, 25° C.) for 48 hours, the relative luminous efficiency defined by the following equation may exceed 50%, or be 60% or higher:

[0080] Relative luminous efficiency (%) = [luminous efficiency of the complex after 48 hours / initial luminous efficiency of the complex] × 100

[0081] Embodiments provide a color-converting layer (eg, a color-converting structure or a color-converting panel) that includes a color-converting region that includes semiconductor nanoparticles as described herein.

[0082] The color conversion panel includes a color conversion layer including color conversion regions and optionally partition walls defining each region of the color conversion layer, the color conversion regions including a first region corresponding to a first pixel, and the first region including semiconductor nanoparticles or composites.

[0083] In an embodiment, a display panel or an electronic device includes a light source and a color conversion layer (eg, a color conversion structure) disposed on the light source.

[0084] In an embodiment, the display panel comprises a light emitting panel (or light source), a color conversion panel and optionally a light transmissive layer between the light emitting panel and the color conversion panel.

[0085] The light emitting panel (or light source) may be configured to provide incident light to the color conversion panel. The incident light may include blue light, and optionally green light. The blue light may have a peak emission wavelength of about 440 nm to about 460 nm or about 450 nm to about 455 nm.

[0086] The light source may include an organic light emitting diode (OLED), a micro-LED, a mini-LED, an LED including nanorods, or a combination thereof.

[0087] In an embodiment, an electronic device (or a display device) includes a color conversion panel or a display panel.

[0088] In an embodiment, the semiconductor nanoparticles include silver, indium, gallium, and sulfur, wherein the semiconductor nanoparticles are configured to emit green light,

[0089] Wherein, the semiconductor nanoparticles have a relative molar value of zinc greater than or equal to about 0.25 and less than or equal to about 0.9 as defined in Equation 1:

[0090] Equation 1

[0091] Relative molar value of zinc = [Zn] / ([Ag]+[In]+[Ga]+[Zn])

[0092] Wherein, in equation 1, [Ag], [In], [Ga] and [Zn] are the molar amounts of silver, indium, gallium and zinc in the semiconductor nanoparticles, respectively,

[0093] wherein the molar ratio of gallium to indium in the semiconductor nanoparticles is greater than about 2.5:1 and less than about 5.6:1,

[0094] Wherein, the semiconductor nanoparticles have a charge balance value greater than or equal to about 0.93 and less than or equal to about 1.17 as defined in Equation 2:

[0095] Equation 2

[0096] Charge balance value = {[Ag] + 3([In] + [Ga]) + 2[Zn]} / 2[S]

[0097] Wherein, in Equation 2, [Ag], [In], [Ga], [Zn] and [S] are the molar amounts of silver, indium, gallium, zinc and sulfur in the semiconductor nanoparticles, respectively, and

[0098] Wherein the semiconductor nanoparticles exhibit a trap emission percentage less than or equal to about 25% as defined by the formula:

[0099] Trap emission percentage (%) = [trap emission area in emission spectrum / total area of ​​emission spectrum] × 100

[0100] The well emission area is the peak area corresponding to a wavelength greater than the emission peak wavelength plus 50 nm.

[0101] According to one aspect, the semiconductor nanoparticles may exhibit improved optical properties, for example, improved blue light absorbance, relatively narrow half-maximum full width, relatively high luminous efficiency, and / or suppressed trap emission and / or may exhibit stability, for example, chemical and / or thermal stability, which helps to improve device stability. According to one aspect, the color conversion panel may utilize various light sources and may be usefully used in a liquid crystal display device, a QD OLED display device, and / or a QD micro LED display device in which a quantum dot (QD) color conversion layer or pixel is applied to a blue LED, a blue OLED, and / or a blue micro LED, respectively. The semiconductor nanoparticles and the color conversion panel may be applied to various devices such as TVs, monitors, mobile devices, VR / AR, automotive displays, etc., but the embodiments are not limited thereto. BRIEF DESCRIPTION OF THE DRAWINGS

[0102] The above aspects and other aspects, features and advantages of certain exemplary embodiments will become more apparent from the following detailed description taken in conjunction with the accompanying drawings.

[0103] Figure 1 is a schematic view showing the concept of well emission percentage.

[0104] Figure 2A is a flow chart showing a pattern forming process (photolithography) using the ink composition of one or more embodiments.

[0105] Figure 2B is a flow chart showing a pattern forming process (inkjet method) using the ink composition of one or more embodiments.

[0106] Figure 3A is a schematic cross-sectional view of a color conversion panel according to one or more embodiments.

[0107] Figure 3B is a cross-sectional view of an electronic device (display device) including a color conversion panel according to one or more embodiments.

[0108] Figure 4A is a perspective view illustrating an example of a display panel including a color conversion panel according to one or more embodiments.

[0109] Figure 4B is an exploded view of a display device according to one or more embodiments.

[0110] Figure 4C yes Figure 4A A cross-sectional view of a display panel.

[0111] Figure 4D is an exploded view of a display device according to one or more embodiments.

[0112] Figure 5A It is shown Figure 4A A plan view of an example of a pixel arrangement of a display panel.

[0113] Figure 5B , Figure 5C , Figure 5D and Figure 5E Each is a cross-sectional view showing an example of a light emitting device according to one or more embodiments.

[0114] Figure 6 It is taken along line IV-IV Figure 5A A cross-sectional view of a display panel.

[0115] Fig. 7A is a schematic cross-sectional view of a display device (eg, a liquid crystal display device) according to one or more embodiments.

[0116] Figure 7B is a schematic cross-sectional view of an electronic device (eg, an electroluminescent device) according to one or more embodiments.

[0117] Fig. 8A and Figure 8B The mapping results of transmission electron microscope energy dispersive spectroscopy (TEM-EDX) of the semiconductor nanoparticles of Example 1 are shown. DETAILED DESCRIPTION

[0118] The advantages and features of the technology described below and the methods for implementing them will become apparent with reference to the exemplary embodiments described in further detail below in conjunction with the accompanying drawings. However, the embodiments should not be construed as being limited to the exemplary embodiments set forth herein. In the accompanying drawings, the thickness of layers, films, panels, regions, etc., is exaggerated for clarity. Throughout the specification, the same reference numerals represent the same elements.

[0119] It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements.

[0120] As used herein, the singular forms "a", "an", and "the" are intended to include plural forms including "at least one", unless the context clearly indicates otherwise. For example, the term "semiconductor nanoparticle" may refer to a single semiconductor nanoparticle or may refer to a plurality of semiconductor nanoparticles. "At least one" should not be interpreted as limited to "one" or "an". "Or" means "and / or". As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0121] It will be understood that, although the terms first, second, third, etc. can be used to describe various elements, components, regions, layers and / or parts in this article, these elements, components, regions, layers and / or parts should not be limited by these terms. These terms are only used to distinguish an element, component, region, layer or part from another element, component, region, layer or part. Therefore, without departing from the teaching of the present embodiment, the first element, component, region, layer or part discussed below can be referred to as the second element, component, region, layer or part.

[0122] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present disclosure belongs. It will also be understood that terms such as those defined in common dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the present disclosure and the relevant art, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0123] Exemplary embodiments are described herein with reference to schematic cross-sectional illustrations that are schematic illustrations of idealized embodiments. Therefore, variations in the shapes of the illustrations due to, for example, manufacturing techniques and / or tolerances are expected. Therefore, the embodiments described herein should not be interpreted as being limited to the specific shapes of the regions as shown herein, but rather include shape deviations, for example, caused by manufacturing. For example, a region shown or described as flat may typically have rough and / or nonlinear features. In addition, the sharp angles shown may be rounded. Therefore, the regions shown in the figures are schematic in nature, their shapes are not intended to illustrate the precise shape of the regions, and are not intended to limit the scope of the claims.

[0124] Unless mentioned to the contrary, the numerical ranges recorded here are open. Unless mentioned to the contrary, the numerical ranges recorded here include any real number within the endpoints of the range, and include its endpoints. In this specification, numerical endpoints (e.g., recorded as "greater than or equal to a value", "at least a value" or "less than or equal to a value" or recorded as "from" or "to") can be used to form the numerical range of a given feature. In other words, the upper and lower endpoints set for various numerical values ​​can be independently combined to provide a range.

[0125] As used herein, "about" or "approximately" is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, taking into account the measurement in question and the errors associated with the measurement of the particular quantity (i.e., the limitations of the measurement system). For example, "about" can mean within one or more standard deviations, or within ±10%, 5% of the stated value.

[0126] As used herein, the expression "does not include cadmium (or other harmful heavy metals)" may refer to a situation where the concentration of cadmium (or other harmful heavy metals) may be less than or equal to about 100 parts per million by weight (ppmw), less than or equal to about 50 ppmw, less than or equal to about 10 ppmw, less than or equal to about 1 ppmw, less than or equal to about 0.1 ppmw, less than or equal to about 0.01 ppmw, or about zero. In one or more embodiments, the amount of cadmium (or other harmful heavy metals) may be substantially absent, or if present, the amount of cadmium (or other harmful heavy metals) may be less than or equal to the detection limit, or as an impurity level for a given analytical tool.

[0127] Hereinafter, when no definition is provided otherwise, "substituted" means that at least one hydrogen of the compound is substituted by a substituent selected from the group consisting of C1-C30 alkyl, C2-C30 alkenyl, C2-C30 alkynyl, C6-C30 aryl, C7-C30 alkylaryl, C7-C30 aralkyl, C6-C30 aryloxy, C6-C30 arylthio, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 heteroalkyl, C3-C30 heteroalkylaryl, C2-C30 heteroarylalkyl, C1-C30 heteroaryloxy, C1-C30 heteroarylthio, C3-C30 cycloalkyl, C3-C15 cycloalkenyl, C6-C30 cycloalkynyl, C2-C30 heterocycloalkyl, halogen (-F, -Cl, -Br or -I), hydroxyl (-OH), nitro (-NO), 2 ), cyano (-CN), amino or amine (-NRR' wherein R and R' are each independently hydrogen or C1-C6 alkyl); azido (-N 3 ), amidino (-C(=NH)NH 2 ), hydrazino (-NHNH 2 ), hydrazine (=N(NH 2 )), aldehyde group (-C(=O)H), carbamoyl group (-C(O)NH 2 ), thiol group (-SH), ester group (-C(=O)OR, wherein R is C1-C6 alkyl or C6-C12 aryl), carboxyl group (-COOH) or its salt (-C(=O)OM, wherein M is an organic or inorganic cation), sulfonic acid group (-SO 3 H) or its salt (-SO 3 M, where M is an organic or inorganic cation), a phosphate group (-PO 3 H 2 ) or its salt (-PO 3 MH or -PO 3 M 2 , wherein M is an organic or inorganic cation), or a combination thereof.

[0128] In addition, when no definition is otherwise provided herein, “hetero” means a case where 1 to 3 heteroatoms selected from N, O, P, Si, S, Se, Ge and B are included.

[0129] In addition, the term "aliphatic hydrocarbon group" used herein refers to a C1-C30 straight chain or branched alkyl group, a C1-C30 straight chain or branched alkenyl group, or a C1-C30 straight chain or branched alkynyl group, and the term "aromatic organic group" used herein refers to a C6-C30 aryl group or a C2-C30 heteroaryl group.

[0130] As used herein, the term "(meth)acrylate" refers to acrylate and / or methacrylate.

[0131] As used herein, the term "Group" refers to a Group of the Periodic Table of Elements.

[0132] As used herein, the terms "nanoparticle" and "nanostructure" refer to a structure having at least one region or characteristic size of nanometer-scale size. In one or more embodiments, the size of the nanoparticle or nanostructure may be less than about 500nm, less than about 300nm, less than about 250nm, less than about 150nm, less than about 100nm, less than about 50nm or less than about 30nm. The nanoparticle or nanostructure may have any shape, such as nanowires, nanorods, nanotubes, multi-pod shapes with two or more pods, nanodots, etc., but embodiments are not limited thereto. The nanoparticle or nanostructure may be, for example, substantially crystalline, substantially monocrystalline, polycrystalline, amorphous, or a combination thereof.

[0133] Quantum dot can be, for example, can show the nanocrystalline particle of semiconductor containing quantum confinement or exciton confinement effect, and is a kind of (for example, can be by energy excitation luminescence) luminescent nanostructure.Herein, unless otherwise clearly defined, otherwise " quantum dot " or nanoparticle's shape is not limited.

[0134] As used herein, the term "dispersion" refers to a dispersion in which the dispersed phase is a solid, and the continuous medium includes a liquid or a solid different from the dispersed phase. It should be understood that the "dispersion" can be a colloidal dispersion in which the dispersed phase has a size greater than or equal to about 1 nm, for example, 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 has a size of a few microns (μm) or less, for example, 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.

[0135] In this article, the size (size, diameter or thickness, etc.) can be a value for a single entity or an average of multiple nanoparticles. As used herein, the term "average" (e.g., the average size of quantum dots) can be an average or a median. In one or more embodiments, the average can be a "mean" average.

[0136] As used herein, the term "peak emission wavelength" is the wavelength at which a given emission spectrum of light reaches its maximum.

[0137] 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 a manual provided by, for example, the corresponding equipment manufacturer. Quantum efficiency (which can be used interchangeably with the term "quantum yield" (QY)) can be measured in a solution state or in a solid state (i.e., in a complex). In one or more embodiments, the quantum efficiency (or quantum yield) is the ratio of photons emitted by a nanostructure or a population thereof to photons absorbed. In one or more embodiments, the quantum efficiency can be measured by any method. For example, there can be two methods for measuring fluorescence quantum yield or efficiency: an absolute method and a relative method. The quantum efficiency measured by the absolute method can be referred to as the absolute quantum efficiency.

[0138] In the absolute method, the quantum efficiency can be obtained by detecting the fluorescence of all samples by an integrating sphere. In the relative method, the quantum efficiency of the unknown sample can be calculated by comparing the fluorescence intensity of the standard dye (standard sample) with the fluorescence intensity of the unknown sample. Coumarin 153, coumarin 545, rhodamine 101 inner salt, anthracene and rhodamine 6G can be used as standard dyes according to their PL wavelengths, but the embodiment is not limited thereto.

[0139] The full width at half maximum (FWHM) and the maximum emission (eg, PL: photoluminescence or EL: electroluminescence) wavelength may be measured, for example, from a luminescence spectrum (eg, photoluminescence spectrum or electroluminescence spectrum) obtained by a spectrophotometer such as a fluorescence spectrophotometer.

[0140] As used herein, the term "first absorption peak wavelength" refers to a wavelength at which a main peak first appears in the lowest energy region of an ultraviolet-visible (UV-Vis) absorption spectrum.

[0141] Semiconductor nanoparticles may be included in various electronic devices. For example, the electrical and / or optical properties of semiconductor nanoparticles can be controlled by the element composition of semiconductor nanoparticles, the size of semiconductor nanoparticles and / or the shape of semiconductor nanoparticles. In one or more embodiments, semiconductor nanoparticles may be semiconductor nanocrystalline particles. Semiconductor nanoparticles such as quantum dots may have a relatively large surface area per unit volume, and therefore may exhibit a quantum confinement effect, exhibiting physical optical properties different from corresponding bulk materials with the same composition. Therefore, semiconductor nanoparticles such as quantum dots may absorb energy (e.g., incident light) supplied from an excitation source to form an excited state, which can emit energy corresponding to its energy band gap when relaxed.

[0142] Semiconductor nanoparticles can also be used in color conversion panels (e.g., photoluminescent color filters). Instead of a backlight unit emitting white light used in a liquid crystal display device, in a display device including a color conversion panel based on quantum dots or a light-emitting color filter, a quantum dot layer is used as a light-emitting material and is disposed at a relatively front portion of the device to convert incident light (e.g., blue light) provided from a light source into light of a different spectrum (e.g., green light or red light). In such a color conversion panel, color conversion of the excitation light can occur in a relatively front portion of the device, and light can be scattered in all directions, which can solve the viewing angle problem of the liquid crystal display and can also solve the light loss problem caused by the use of an absorption-type color filter.

[0143] As used herein, the term "color conversion panel" refers to an electronic device that includes a color conversion layer. As used herein, the term "color conversion layer" also includes structures having color conversion regions (eg, color conversion structures).

[0144] In a display device including a color conversion panel, the properties of the light-emitting nanostructure (e.g., optical properties, stability, etc.) may have a direct impact on the display quality of the device. It may be expected that the light-emitting material included in the color conversion panel disposed in the relatively front portion of the device exhibits not only a relatively high luminous efficiency, but also a relatively high light absorbance for incident light. When a patterned film (e.g., a color filter) is used in a display device, a reduction in the absorbance of incident light may be a direct cause of blue light leakage, which has an adverse effect on the color reproducibility of the device (e.g., a DCI matching rate). Using an absorptive color filter to prevent the blue light leakage problem may result in an additional reduction in luminous efficiency. This reduced absorbance of semiconductor nanoparticles may result in a reduction in brightness in a device including the semiconductor nanoparticles.

[0145] Semiconductor nanoparticles can show properties (e.g., optical properties and / or stability) that can be applicable to devices, but many of them may include cadmium-based compounds (e.g., cadmium sulfide compounds). Cadmium causes serious environmental / health problems and is therefore one of the restricted elements in many countries. Therefore, in order to develop cadmium-free, environmentally friendly nanoparticles, nanocrystals based on III-V compounds have been studied in depth. However, compared with cadmium-free nanoparticles based on III-V compounds such as indium phosphide, there is still a technical demand to develop environmentally friendly nanoparticles that can show higher absorbance, narrower full width at half maximum and higher luminous efficiency.

[0146] In an embodiment, the semiconductor nanoparticles may not include cadmium. In one or more embodiments, the semiconductor nanoparticles may not include mercury, lead, or a combination thereof. It should be understood that undesirable heavy metals include cadmium, mercury, and / or lead.

[0147] In an embodiment, the semiconductor nanoparticles include silver, indium, gallium, zinc, and sulfur, and the semiconductor nanoparticles are configured to emit a first light (eg, green light or red light). The first light may be green light. The first light may be red light.

[0148] The semiconductor nanoparticles may have a relative molar value of zinc greater than or equal to about 0.25 and less than or equal to about 0.9, as defined by Equation 1:

[0149] Equation 1

[0150] Relative molar value of zinc = [Zn] / ([Ag]+[In]+[Ga]+[Zn])

[0151] Where, in equation 1,

[0152] [Ag], [In], [Ga], and [Zn] are the molar amounts of silver, indium, gallium, and zinc in the semiconductor nanoparticles, respectively, and

[0153] In the semiconductor nanoparticles, a molar ratio of gallium to indium (Ga:In) may be greater than about 2.5:1 and less than about 5.6:1 or less than or equal to about 5:1.

[0154] Due to the structure / composition described herein, the semiconductor nanoparticles can emit light of a desired wavelength and can achieve improved optical properties (e.g., a relatively narrow half-maximum full width, an increased quantum yield, and / or a relatively high level of blue light absorbance). The semiconductor nanoparticles of the embodiments can exhibit increased stability (chemical stability and / or thermal stability), and the composites including them can exhibit relatively high levels of luminescence properties compared to their initial values, even when the composites are exposed to air for a period of time (e.g., about 48 hours or 72 hours). The semiconductor nanoparticles of the embodiments can be used, for example, as down-conversion materials for color conversion panels or color conversion sheets, and can exhibit increased absorbance per given weight of semiconductor nanoparticles, so that devices including them (e.g., panels or sheets) can be manufactured at reduced production costs and can provide improved light conversion performance. In embodiments, the semiconductor nanoparticles can exhibit reduced or suppressed emission (e.g., trap emission) in an unwanted wavelength range.

[0155] The inventors have found that in the case of semiconductor nanoparticles containing Group 13 metals and chalcogen elements and silver (Ag), it may be difficult to achieve the desired luminescent properties (e.g., reduced full width at half maximum and increased quantum yield). In addition, the inventors have found that by adjusting the composition of semiconductor nanoparticles including Group 11-13-16 compounds (e.g., charge balance values ​​and / or molar ratios between elemental components described below), improvements in the optical properties of the nanoparticles can be achieved. Unfortunately, however, when semiconductor nanoparticles are included in a composite, the improved optical properties observed with the nanoparticles generally do not extend to the composite. In other words, forming the composite can have a negative impact on previous optical improvements. When such semiconductor nanoparticles are applied to a color conversion layer including pixels configured to emit different colors (e.g., red pixels or green pixels), a relatively high dose of blue light can be incident on a relatively narrow area of ​​the color conversion layer, which may cause photobleaching of the semiconductor nanoparticles or cause degradation of the polymer component of the composite. In order to apply semiconductor nanoparticles in practical devices, a composite comprising semiconductor nanoparticles dispersed in a matrix (e.g., a polymer) may be prepared, including mixing the semiconductor nanoparticles with an organic material such as a polymer, followed by a thermal / photocuring process. The inventors have found that, for example, when the composite is exposed to air for a period of time, the semiconductor nanoparticles may show a decrease in efficiency in the process of making such a composite, thereby indicating that the quantum efficiency of the composite is significantly reduced.

[0156] The semiconductor nanoparticles of one embodiment may be manufactured according to the methods described herein, and by exhibiting the structure and / or characteristics as described herein, increased stability of the semiconductor nanoparticles may be achieved, and the semiconductor nanoparticles of the embodiments may contribute to increased device reliability.

[0157] In the semiconductor nanoparticles, the relative molar value of zinc may be greater than or equal to about 0.25, greater than or equal to about 0.255, greater than or equal to about 0.26, greater than or equal to about 0.265, greater than or equal to about 0.27, greater than or equal to about 0.275, greater than or equal to about 0.28, greater than or equal to about 0.285, greater than or equal to about 0.29, greater than or equal to about 0.295, greater than or equal to about 0.3, greater than or equal to about 0.31, greater than or equal to about 0.32, greater than or equal to about 0.33, greater than or equal to about 0.34, greater than or equal to about 0.35, greater than or equal to about 0.46, greater than or equal to about 0.37, greater than or equal to about 0.38, or greater than or equal to about 0.39. In the semiconductor nanoparticles, the relative molar value of zinc can be less than or equal to about 0.9, less than or equal to about 0.85, less than or equal to about 0.8, less than or equal to about 0.75, less than or equal to about 0.7, less than or equal to about 0.65, less than or equal to about 0.6, less than or equal to about 0.55, less than or equal to about 0.5, less than or equal to about 0.49, less than or equal to about 0.485, less than or equal to about 0.48, less than or equal to about 0.475, less than or equal to about 0.47, less than or equal to about 0.465, less than or equal to about 0.46, less than or equal to about 0.455, less than or equal to about 0.45, less than or equal to about 0.445, less than or equal to about 0.44, less than or equal to about 0.435, less than or equal to about 0.43, less than or equal to about 0.425, less than or equal to about 0 .42, less than or equal to about 0.415, less than or equal to about 0.41, less than or equal to about 0.405, less than or equal to about 0.4, less than or equal to about 0.395, less than or equal to about 0.39, less than or equal to about 0.385, less than or equal to about 0.38, less than or equal to about 0.375, less than or equal to about 0.37, less than or equal to about 0.365, less than or equal to about 0.36, less than or equal to about 0.355, less than or equal to about 0.35, less than or equal to about 0.345, less than or equal to about 0.34, less than or equal to about 0.335, less than or equal to about 0.33, less than or equal to about 0.325, less than or equal to about 0.32, less than or equal to about 0.315, less than or equal to about 0.31, less than or equal to about 0.305, or less than or equal to about 0.3

[0158] In the semiconductor nanoparticles, the molar ratio of gallium to indium (Ga:In) may be greater than or equal to 2.5:1, greater than or equal to about 2.55:1, greater than or equal to about 2.6:1, greater than or equal to about 2.65:1, greater than or equal to about 2.7:1, greater than or equal to about 2.75:1, greater than or equal to about 2.8:1, greater than or equal to about 2.85:1, greater than or equal to about 2.9:1, greater than or equal to about 2.95:1, greater than or equal to about 3:1, greater than or equal to about 3.05:1, greater than or equal to about 3.1:1, greater than or equal to about 3.15:1, greater than or equal to about 3.2:1, greater than or equal to about 3.25:1, greater than or equal to about 3.3:1, greater than or equal to about 3.35:1, greater than or equal to about 3.4:1, greater than or equal to about 3.45:1, or greater than or equal to about 3.5:1. In the semiconductor nanoparticles, the molar ratio of gallium to indium (Ga:In) may be less than or equal to about 5.55:1, less than or equal to about 5.5:1, less than or equal to about 5.3:1, less than or equal to about 5.1:1, less than or equal to about 5:1, less than or equal to about 4.9:1, less than or equal to about 4.7:1, less than or equal to about 4.5:1, less than or equal to about 4.3:1, less than or equal to about 4.2:1, less than or equal to about 4.1:1, less than or equal to about 4:1, less than or equal to about 3.9:1, less than or equal to about 3.8:1, less than or equal to about 3.7:1, less than or equal to about 3.6:1, or less than or equal to about 3.55:1.

[0159] In the semiconductor nanoparticles, the molar ratio of gallium to the sum of indium and gallium (Ga:(In+Ga)) may be greater than or equal to about 0.71:1, greater than or equal to about 0.715:1, greater than or equal to about 0.72:1, greater than or equal to about 0.725:1, greater than or equal to about 0.73:1, greater than or equal to about 0.735:1, greater than or equal to about 0.74:1, greater than or equal to about 0.745:1, greater than or equal to about 0.75:1, greater than or equal to about 0.755:1, greater than or equal to about 0.76:1, greater than or equal to about 0.765:1, greater than or equal to about 0.77:1, greater than or equal to about 0.775:1, greater than or equal to about 0.78:1, greater than or equal to about 0.785:1, greater than or equal to about 0.79:1, or greater than or equal to about 0.795:1. In the semiconductor nanoparticles, the molar ratio of gallium to the sum of indium and gallium (Ga:(In+Ga)) may be less than or equal to about 0.845:1, less than or equal to about 0.84:1, less than or equal to about 0.835:1, less than or equal to about 0.83:1, less than or equal to about 0.825:1, less than or equal to about 0.82:1, less than or equal to about 0.815:1, less than or equal to about 0.81:1, less than or equal to about 0.805:1, less than or equal to about 0.8:1, less than or equal to about 0.795:1, less than or equal to about 0.79:1, less than or equal to about 0.785:1, less than or equal to about 0.78:1, less than or equal to about 0.775:1, or less than or equal to about 0.77:1.

[0160] In the semiconductor nanoparticles, the molar ratio of zinc to indium (Zn:In) may be greater than or equal to about 2.5:1, greater than or equal to about 2.55:1, greater than or equal to about 2.6:1, greater than or equal to about 2.65:1, greater than or equal to about 2.7:1, greater than or equal to about 2.75:1, greater than or equal to about 2.8:1, greater than or equal to about 2.85:1, greater than or equal to about 2.9:1, greater than or equal to about 2.95:1, greater than or equal to about 3:1, greater than or equal to about 3.05:1, greater than or equal to about 3.1:1, greater than or equal to about 3.2:1, greater than or equal to about 3.3:1, greater than or equal to about 3.4:1, greater than or equal to about 3.5:1, greater than or equal to about 3.6:1, greater than or equal to about 3.7:1, greater than or equal to about 3.8:1, greater than or equal to about 3.9:1, or greater than or equal to about 4:1. In the semiconductor nanoparticles, the molar ratio of zinc to indium (Zn:In) may be less than or equal to about 15:1, less than or equal to about 13:1, less than or equal to about 11:1, less than or equal to about 10.5:1, less than or equal to about 10:1, less than or equal to about 9.5:1, less than or equal to about 9:1, less than or equal to about 8.5:1, less than or equal to about 8:1, less than or equal to about 7.5:1, less than or equal to about 7:1, less than or equal to about 6.5:1, less than or equal to about 6:1, less than or equal to about 5.5:1, or less than or equal to about 5:1.

[0161] In the semiconductor nanoparticles, the molar ratio of sulfur to indium (S:In) may be greater than or equal to about 7.5:1, greater than or equal to about 7.6:1, greater than or equal to about 7.8:1, greater than or equal to about 8:1, greater than or equal to about 8.5:1, 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, greater than or equal to about 10.5:1, or greater than or equal to about 11:1. In the semiconductor nanoparticles, the molar ratio of sulfur to indium (S:In) may be less than or equal to about 17:1, less than or equal to about 16.7:1, less than or equal to about 16:1, less than or equal to about 15.5:1, less than or equal to about 15:1, less than or equal to about 14.5:1, less than or equal to about 14:1, less than or equal to about 13.5:1, less than or equal to about 13:1, less than or equal to about 12.5:1, less than or equal to about 12:1, less than or equal to about 11.5:1, less than or equal to about 11.2:1, less than or equal to about 10.5:1, or less than or equal to about 9.8:1.

[0162] In the semiconductor nanoparticles, the molar ratio of silver to indium (Ag:In) may be greater than or equal to about 1.1:1, greater than or equal to about 1.3:1, greater than or equal to about 1.4:1, greater than or equal to about 1.5:1, greater than or equal to about 1.6:1, greater than or equal to about 1.7:1, greater than or equal to about 1.8:1, greater than or equal to about 1.9:1, greater than or equal to about 2:1, greater than or equal to about 2.1:1, greater than or equal to about 2.2:1, greater than or equal to about 2.3:1, greater than or equal to about 2.4:1, or greater than or equal to about 2.5:1. In the semiconductor nanoparticles, the molar ratio of silver to indium (Ag:In) may be less than or equal to about 5:1, less than or equal to about 4.5:1, less than or equal to about 4:1, less than or equal to about 3.5:1, less than or equal to about 3.3:1, less than or equal to about 3.1:1, less than or equal to about 3:1, less than or equal to about 2.9:1, less than or equal to about 2.8:1, less than or equal to about 2.7:1, or less than or equal to about 2.6:1.

[0163] In the semiconductor nanoparticles, the molar ratio of gallium to silver (Ga:Ag) may be greater than or equal to about 1:1, greater than or equal to about 1.1:1, greater than or equal to about 1.15:1, greater than or equal to about 1.18:1, greater than or equal to about 1.2:1, greater than or equal to about 1.25:1, greater than or equal to about 1.3:1, greater than or equal to about 1.33:1, greater than or equal to about 1.37:1, greater than or equal to about 1.4:1, greater than or equal to about 1.43:1, greater than or equal to about 1.45:1 , greater than or equal to about 1.5:1, greater than or equal to about 1.55:1, 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, greater than or equal to about 2.1:1, greater than or equal to about 2.3:1, or greater than or equal to about 2.5:1. In the semiconductor nanoparticles, the molar ratio of gallium to silver (Ga:Ag) may be less than or equal to about 3:1, less than or equal to about 2.8:1, less than or equal to about 2.75:1, less than or equal to about 2.5:1, less than or equal to about 2.2:1, less than or equal to about 2:1, less than or equal to about 1.9:1, less than or equal to about 1.8:1, less than or equal to about 1.75:1, less than or equal to about 1.7:1, less than or equal to about 1.65:1, less than or equal to about 1.6:1, less than or equal to about 1.55:1, less than or equal to about 1.5:1, less than or equal to about 1.45:1, less than or equal to about 1.4:1, or less than or equal to about 1.35:1.

[0164] In the semiconductor nanoparticles, the molar ratio of zinc to gallium (Zn:Ga) may be 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 0.78:1, greater than or equal to about 0.8:1, greater than or equal to about 0.82:1, greater than or equal to about 0.85:1, greater than or equal to about 0.9:1, greater than or equal to about 0.95:1, greater than or equal to about 1:1, greater than or equal to about 1.2:1, greater than or equal to about 1.4:1, or greater than or equal to about 1.45:1. In the semiconductor nanoparticles, the molar ratio of zinc to gallium (Zn:Ga) may be less than or equal to about 3.5:1, less than or equal to about 3.3:1, less than or equal to about 2.7:1, less than or equal to about 2.6:1, less than or equal to about 2:1, less than or equal to about 1.6:1, less than or equal to about 1.55:1, less than or equal to about 1.45:1, less than or equal to about 1.3:1, less than or equal to about 1.2:1, less than or equal to about 1.1:1, less than or equal to about 1:1, or less than or equal to about 0.94:1.

[0165] In the semiconductor nanoparticles, the molar ratio of gallium to the sum of gallium, indium, and silver (Ga:(Ga+In+Ag)) may be greater than or equal to about 0.3:1, greater than or equal to about 0.35:1, greater than or equal to about 0.4:1, greater than or equal to about 0.45:1, greater than or equal to about 0.46:1, greater than or equal to about 0.47:1, greater than or equal to about 0.48:1, greater than or equal to about 0.49:1, greater than or equal to about 0.5:1, greater than or equal to about 0.51:1, greater than or equal to about 0.52:1, greater than or equal to about 0.53:1, greater than or equal to about 0.54:1, greater than or equal to about 0.55:1, or greater than or equal to about 0.56:1. In the semiconductor nanoparticles, the molar ratio of gallium to the sum of gallium, indium, and silver (Ga:(Ga+In+Ag)) may be less than or equal to about 0.8:1, less than or equal to about 0.7:1, less than or equal to about 0.6:1, less than or equal to about 0.57:1, less than or equal to about 0.54:1, less than or equal to about 0.53:1, less than or equal to about 0.52:1, less than or equal to about 0.51:1, less than or equal to about 0.5:1, less than or equal to about 0.49:1, or less than or equal to about 0.485:1.

[0166] In the semiconductor nanoparticles, the molar ratio of the sum of indium and gallium to sulfur ((In+Ga):S) 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 0.26:1, greater than or equal to about 0.28:1, greater than or equal to about 0.29:1, greater than or equal to about 0.3:1, greater than or equal to about 0.33:1, greater than or equal to about 0.35:1, greater than or equal to about 0.4:1, greater than or equal to about 0.41:1, greater than or equal to about 0.43:1, greater than or equal to about 0.45:1, greater than or equal to about 0.47:1, or greater than or equal to about 0.5:1. In the semiconductor nanoparticles, the molar ratio of the sum of indium and gallium to sulfur ((In+Ga):S) may be less than or equal to about 0.8:1, less than or equal to about 0.6:1, less than or equal to about 0.55:1, less than or equal to about 0.52:1, less than or equal to about 0.51:1, less than or equal to about 0.5:1, less than or equal to about 0.48:1, or less than or equal to about 0.46:1.

[0167] In the semiconductor nanoparticles, the molar ratio of silver to sulfur (Ag:S) may be greater than or equal to about 0.05:1, greater than or equal to about 0.07:1, greater than or equal to about 0.1:1, greater than or equal to about 0.12:1, greater than or equal to about 0.15:1, greater than or equal to about 0.18:1, greater than or equal to about 0.25:1, or greater than or equal to about 0.3: 1. In the semiconductor nanoparticles, the molar ratio of silver to sulfur (Ag:S) may be less than or equal to about 0.5:1, less than or equal to about 0.35:1, less than or equal to about 0.33:1, less than or equal to about 0.28:1, less than or equal to about 0.26:1, or less than or equal to about 0.26:1.

[0168] In the semiconductor nanoparticles, the molar ratio of zinc to sulfur (Zn:S) 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 0.21:1, greater than or equal to about 0.24:1, greater than or equal to about 0.245:1, greater than or equal to about 0.25:1, greater than or equal to about 0.28:1, greater than or equal to about 0.3:1, or greater than or equal to about 0.35:1. In the semiconductor nanoparticles, the molar ratio of zinc to sulfur (Zn:S) may be less than or equal to about 0.8:1, less than or equal to about 0.75:1, less than or equal to about 0.72:1, less than or equal to about 0.7:1, less than or equal to about 0.67:1, less than or equal to about 0.65:1, less than or equal to about 0.6:1, less than or equal to about 0.55:1, less than or equal to about 0.5:1, less than or equal to about 0.49:1, less than or equal to about 0.48:1, less than or equal to about 0.42:1, or less than or equal to about 0.36:1.

[0169] In the semiconductor nanoparticles, the molar ratio of gallium to sulfur (Ga:S) may be greater than or equal to about 0.2:1, greater than or equal to about 0.21:1, greater than or equal to about 0.22:1, greater than or equal to about 0.23:1, greater than or equal to about 0.24:1, greater than or equal to about 0.28:1, greater than or equal to about 0.3:1, greater than or equal to about 0.32:1, greater than or equal to about 0.33:1, greater than or equal to about 0.35:1, greater than or equal to about 0.38:1, greater than or equal to about 0.4:1, greater than or equal to about 0.45:1, or greater than or equal to about 0.5:1. In the semiconductor nanoparticles, the molar ratio of gallium to sulfur (Ga:S) may be less than or equal to about 0.6:1, less than or equal to about 0.55:1, less than or equal to about 0.5:1, less than or equal to about 0.46:1, less than or equal to about 0.43:1, less than or equal to about 0.38:1, or less than or equal to about 0.32:1.

[0170] In the semiconductor nanoparticles, the molar ratio of indium to sulfur (In:S) may be greater than or equal to about 0.05:1, greater than or equal to about 0.06:1, greater than or equal to about 0.08:1, greater than or equal to about 0.09:1, greater than or equal to about 0.1:1, greater than or equal to about 0.11:1, greater than or equal to about 0.12:1, greater than or equal to about 0.13:1, greater than or equal to about 0.14:1, greater than or equal to about 0.15:1. In the semiconductor nanoparticles, the molar ratio of indium to sulfur (In:S) may be less than or equal to about 0.3:1, less than or equal to about 0.25:1, less than or equal to about 0.18:1, less than or equal to about 0.16:1, less than or equal to about 0.11:1, less than or equal to about 0.07:1, or less than or equal to about 0.03:1.

[0171] In the semiconductor nanoparticles, the molar ratio of silver to the sum of silver, indium, and gallium (Ag:(Ag+In+Ga)) may be greater than or equal to about 0.1:1, greater than or equal to about 0.15:1, greater than or equal to about 0.2:1, greater than or equal to about 0.23:1, greater than or equal to about 0.27:1, greater than or equal to about 0.28:1, greater than or equal to about 0.29:1, greater than or equal to about 0.3:1, greater than or equal to about 0.32:1, greater than or equal to about 0.35:1, greater than or equal to about 0.37:1, or greater than or equal to about 0.39:1. In the semiconductor nanoparticles, the molar ratio of silver to the sum of silver, indium, and gallium (Ag:(Ag+In+Ga)) may be less than or equal to about 0.5:1, 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 0.37:1, less than or equal to about 0.36:1, less than or equal to about 0.33:1, less than or equal to about 0.32:1, or less than or equal to about 0.28:1.

[0172] In the semiconductor nanoparticles, the molar ratio of sulfur to the sum of silver, indium, and gallium (S:(Ag+In+Ga)) may be greater than or equal to about 1:1, greater than or equal to about 1.1:1, greater than or equal to about 1.15:1, greater than or equal to about 1.2:1, greater than or equal to about 1.25:1, greater than or equal to about 1.3:1, greater than or equal to about 1.35:1, greater than or equal to about 1.4:1, greater than or equal to about 1.45:1, greater than or equal to about 1.47:1, 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, or greater than or equal to about 1.7:1. In the semiconductor nanoparticles, the molar ratio of sulfur to the sum of silver, indium, and gallium (S:(Ag+In+Ga)) may be less than or equal to about 2.8:1, less than or equal to about 2.75:1, less than or equal to about 2.7:1, less than or equal to about 2.6:1, less than or equal to about 2.5:1, less than or equal to about 2.3:1, less than or equal to about 2.1:1, less than or equal to about 2:1, less than or equal to about 1.9:1, less than or equal to about 1.7:1, less than or equal to about 1.55:1, less than or equal to about 1.5:1, less than or equal to about 1.45:1, less than or equal to about 1.35:1, less than or equal to about 1.2:1, or less than or equal to about 1.15:1.

[0173] In the semiconductor nanoparticles, the molar ratio of sulfur to the sum of silver, indium, gallium and zinc (S:(Ag+In+Ga+Zn)) may be greater than or equal to about 0.75:1, greater than or equal to about 0.8:1, greater than or equal to about 0.82:1, greater than or equal to about 0.84:1, greater than or equal to about 0.86:1, greater than or equal to about 0.9:1, greater than or equal to about 0.95:1, greater than or equal to about 1:1, greater than or equal to about 1.1:1, or greater than or equal to about 1.15:1. In the semiconductor nanoparticles, the molar ratio of sulfur to the sum of silver, indium, gallium and zinc (S:(Ag+In+Ga+Zn)) may be less than or equal to about 1.4:1, less than or equal to about 1.35:1, less than or equal to about 1.3:1, less than or equal to about 1.27:1, less than or equal to about 1.26:1, less than or equal to about 1.25:1, less than or equal to about 1.24:1, less than or equal to about 1.21:1, less than or equal to about 1.2:1, less than or equal to about 1.15:1, or less than or equal to about 1.1:1.

[0174] In the semiconductor nanoparticles, the molar ratio of the sum of indium and gallium to silver ((In+Ga):Ag) may be greater than or equal to about 1.3:1, greater than or equal to about 1.4:1, greater than or equal to about 1.5:1, greater than or equal to about 1.55:1, greater than or equal to about 1.6:1, greater than or equal to about 1.63:1, greater than or equal to about 1.7:1, greater than or equal to about 1.8:1, or greater than or equal to about 2: 1. In the semiconductor nanoparticles, the molar ratio of the sum of indium and gallium to silver ((In+Ga):Ag) may be less than or equal to about 3.7:1, less than or equal to about 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 2:1, or less than or equal to about 1.9:1.

[0175] In an embodiment, the semiconductor nanoparticles may have a charge balance value represented by Equation 2 that is greater than or equal to about 0.8, greater than or equal to about 0.85, greater than or equal to about 0.9, greater than or equal to about 0.91, greater than or equal to about 0.92, greater than or equal to about 0.93, greater than or equal to about 0.95, greater than or equal to about 0.98, greater than or equal to about 0.99, greater than or equal to about 1.02, or greater than or equal to about 1.06. The semiconductor nanoparticles may have a charge balance value represented by Equation 2 that is less than or equal to about 1.4, less than or equal to about 1.35, less than or equal to about 1.3, less than or equal to about 1.25, less than or equal to about 1.2, less than or equal to about 1.18, less than or equal to about 1.17, less than or equal to about 1.15, less than or equal to about 1.1, less than or equal to about 1.05, or less than or equal to about 1:

[0176] Equation 2

[0177] Charge balance value = {[Ag] + 3([In] + [Ga]) + 2[Zn]} / 2[S]

[0178] Wherein, in Equation 2, [Ag], [In], [Ga], [Zn], and [S] are the molar amounts of silver, indium, gallium, zinc, and sulfur in the semiconductor nanoparticles, respectively.

[0179] The semiconductor nanoparticles may include first particles including silver, indium, gallium and sulfur, and a semiconductor nanocrystal layer disposed on the first particles and including zinc and sulfur. The first particles (e.g., particles including first semiconductor nanocrystals and second semiconductor nanocrystals) may have a charge balance value of 0.8 to 1.3, 0.9 to 1.2, 1 to 1.1, or any combination of the listed low and high values.

[0180] The first particle may include a first semiconductor nanocrystal (or a core including the first semiconductor nanocrystal) and optionally include a second semiconductor nanocrystal (or a shell including the second semiconductor nanocrystal). In the semiconductor nanoparticle, the second semiconductor nanocrystal may be disposed on the first semiconductor nanocrystal or may surround or cover at least a portion of the first semiconductor nanocrystal.

[0181] The first semiconductor nanocrystal may include silver, indium, gallium and sulfur. The first semiconductor nanocrystal or the first particle may not include zinc. The second semiconductor nanocrystal may include gallium, sulfur and optionally silver. The second semiconductor nanocrystal may have a composition different from the first semiconductor nanocrystal and the third semiconductor nanocrystal. The third semiconductor nanocrystal may include zinc sulfide. The third semiconductor nanocrystal may have a composition different from the first semiconductor nanocrystal.

[0182] In semiconductor nanoparticles, the concentration of indium may vary or may be different in the radial direction. In semiconductor nanoparticles, the indium content of the inner portion (e.g., core) of the particle may be different from the indium content of the outer portion (e.g., shell) of the particle. In an embodiment, the indium content in the portion close to the surface (e.g., outermost layer or shell) may be less than the indium content in the inner portion (or core) of the particle. In an example, the zinc content (concentration) in the portion close to the surface (e.g., outermost layer) of the particle may be greater than the zinc content (concentration) in the inner portion (or core) of the particle.

[0183] The core or the first semiconductor nanocrystal may not include zinc. In the nanoparticle, the zinc content in the portion close to the surface of the particle may be greater than the zinc content in the center (e.g., core) of the particle. In the nanoparticle, the zinc concentration outside the particle may be greater than the zinc concentration inside the particle.

[0184] The first semiconductor nanocrystal may include silver, a Group 13 metal (e.g., indium, gallium, or a combination thereof), and a chalcogen element (e.g., sulfur and optionally selenium). The first semiconductor nanocrystal may include a quaternary alloy semiconductor material based on a Group 11-13-16 compound including silver (Ag), indium, gallium, and sulfur. The first semiconductor nanocrystal may include silver indium gallium sulfide, e.g., Ag (In x Ga 1-x )S 2 (x is greater than 0 and less than 1). The molar ratios between the components in the first semiconductor nanocrystals may be adjusted so that the final semiconductor nanoparticles may have desired compositions and optical properties (eg, maximum emission wavelength).

[0185] The second semiconductor nanocrystal may include a Group 13 metal (indium, gallium, or a combination thereof) and a chalcogenide (sulfur and optionally selenium). The second semiconductor nanocrystal may also include silver (Ag). The second semiconductor nanocrystal may include silver, gallium, and sulfur. The second semiconductor nanocrystal may include a ternary alloy semiconductor material comprising silver, gallium, and sulfur. The second semiconductor nanocrystal may have a composition different from that of the first semiconductor nanocrystal. The second semiconductor nanocrystal may include a Group 13-16 compound, a Group 11-13-16 compound, or a combination thereof. The Group 13-16 compound may include gallium sulfide, gallium selenide, indium sulfide, indium selenide, indium gallium sulfide, indium gallium selenide, indium gallium sulfide selenide, or a combination thereof.

[0186] The energy band gap of the second semiconductor nanocrystal may be different from the energy band gap of the first semiconductor nanocrystal. The energy band gap of the second semiconductor nanocrystal may be greater than the energy band gap of the first semiconductor nanocrystal. The energy band gap of the second semiconductor nanocrystal may be less than the energy band gap of the first semiconductor nanocrystal. The molar ratio between each element component in the second semiconductor nanocrystal may be adjusted so that the final semiconductor nanoparticles show desired composition and optical properties.

[0187] The semiconductor nanocrystal layer may include a third semiconductor nanocrystal including zinc (e.g., including zinc sulfide) and sulfur. The semiconductor nanocrystal layer may surround the first particle. In the semiconductor nanoparticle, the second semiconductor nanocrystal may be disposed between the first semiconductor nanocrystal and the semiconductor nanocrystal layer. The semiconductor nanocrystal layer may be the outermost layer of the semiconductor nanoparticle.

[0188] The size (or average size, hereinafter referred to as "size") of the first semiconductor nanocrystal may be greater than or equal to about 0.5 nm, greater than or equal to about 1 nm, greater than or equal to about 1.5 nm, greater than or equal to about 1.7 nm, greater than or equal to about 1.9 nm, greater than or equal to about 2 nm, greater than or equal to about 2.1 nm, greater than or equal to about 2.3 nm, greater than or equal to about 2.5 nm, greater than or equal to about 2.7 nm, greater than or equal to about 2.9 nm, greater than or equal to about 3 nm, greater than or equal to about 3.1 nm, greater than or equal to about 3.3 nm, greater than or equal to about 3.5 nm, greater than or equal to about 3.7 nm, or greater than or equal to about 3.9 nm. The size of the first semiconductor nanocrystal may be less than or equal to about 5 nm, less than or equal to about 4.5 nm, less than or equal to about 4 nm, less than or equal to about 3.5 nm, less than or equal to about 3 nm, less than or equal to about 2.5 nm, less than or equal to about 2 nm, or less than or equal to about 1.5 nm.

[0189] The thickness (or average thickness, hereinafter referred to as "thickness") of the second 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 0.9 nm. The thickness of the second semiconductor nanocrystal may be 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.

[0190] The thickness of the semiconductor nanocrystal layer can be greater than or equal to about 0.1nm, greater than or equal to about 0.3nm, greater than or equal to about 0.4nm or greater to 0.5nm, greater than or equal to about 0.8nm, greater than or equal to about 1.1nm, greater than or equal to about 1.3nm, or greater than or equal to about 1.6nm. The thickness of the semiconductor nanocrystal layer can be less than or equal to about 3nm, less than or equal to about 1.5nm, less than or equal to about 1nm, or less than or equal to about 0.8nm or less. The thickness of the semiconductor nanocrystal layer can be about 0.1nm to 5nm, about 0.3nm to 4nm, about 0.5nm to 3.5nm, about 0.7nm to 3nm, about 0.9nm to 2.5nm, about 1nm to 2nm, about 1.5nm to 1.7nm or a combination thereof.

[0191] In an embodiment, the semiconductor nanoparticles may or may not include lithium. The semiconductor nanoparticles may or may not include an alkali metal, such as sodium, potassium, or the like.

[0192] The size (or average size, hereinafter referred to as "size") of the semiconductor nanoparticles may be greater than or equal to about 1 nm, greater than or equal to about 1.5 nm, greater than or equal to about 2 nm, greater than or equal to about 2.5 nm, greater than or equal to about 3 nm, greater than or equal to about 3.5 nm, greater than or equal to about 4 nm, greater than or equal to about 4.5 nm, greater than or equal to about 5 nm, greater than or equal to about 5.5 nm, greater than or equal to about 6 nm, greater than or equal to about 6.5 nm, greater than or equal to about 7 nm, greater than or equal to about 7.5 nm, greater than or equal to about 8 nm, greater than or equal to about 8.5 nm, greater than or equal to about 9 nm, greater than or equal to about 9.5 nm, greater than or equal to about 10 nm, or greater than or equal to about 10.5 nm. The size of the semiconductor nanoparticles 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 6 nm, or less than or equal to about 4 nm.

[0193] As used herein, the size of a semiconductor nanoparticle can be a particle diameter. The size of a semiconductor nanoparticle can be its equivalent diameter, obtained by a calculation involving converting the two-dimensional area of ​​a transmission electron microscope image of a given particle into a circle. Particle size (particle size, also translated particle size, particle diameter) can be a value (e.g., nominal particle size) calculated from the composition and peak emission wavelength of the semiconductor nanoparticle.

[0194] The peak emission wavelength of green light or the peak emission wavelength of the semiconductor nanoparticles may be greater than or equal to about 500 nm, greater than or equal to about 505 nm, greater than or equal to about 510 nm, greater than or equal to about 515 nm, greater than or equal to about 520 nm, greater than or equal to about 525 nm, greater than or equal to about 530 nm, greater than or equal to about 535 nm, greater than or equal to about 540 nm, or greater than or equal to about 545 nm. The peak emission wavelength of green light or the peak emission wavelength of the semiconductor nanoparticles may be less than or equal to about 580 nm, less than or equal to about 575 nm, less than or equal to about 570 nm, less than or equal to about 565 nm, less than or equal to about 560 nm, less than or equal to about 555 nm, less than or equal to about 550 nm, less than or equal to about 545 nm, less than or equal to about 540 nm, less than or equal to about 535 nm, less than or equal to about 530 nm, less than or equal to about 525 nm, less than or equal to about 520 nm, or less than or equal to about 515 nm.

[0195] The peak emission wavelength of red light or the peak emission wavelength of semiconductor nanoparticles may be in the range of 600nm to 660nm, 605nm to 650nm, 610nm to 645nm, 615nm to 640nm, 620nm to 635nm, 623nm to 632nm, 625nm to 630nm, 628nm to 629nm, or a combination thereof.

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

[0197] The full width at half maximum (FWHM) of the first light (e.g., green light or red light) or the FWHM of the semiconductor nanoparticles may be greater than or equal to about 5 nm, greater than or equal to about 10 nm, greater than or equal to about 15 nm, greater than or equal to about 20 nm, greater than or equal to about 25 nm, or greater than or equal to about 30 nm. The full width at half maximum may be less than or equal to about 90 nm, less than or equal to about 85 nm, less than or equal to about 80 nm, less than or equal to about 75 nm, less than or equal to about 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.

[0198] In an embodiment, the semiconductor nanocrystal layer can contribute to improving the stability of semiconductor nanoparticles. The first particle based on the 11th-13th-16th family compound can show relatively improved luminous efficiency and narrow half-peak full width. However, the inventor has found that, in the process of, for example, making a composite, the luminescent properties of the first particle may be reduced quickly, and even in the form of a composite, when it is exposed to an external environment (for example, O in the atmosphere), the luminescent properties of the first particle may be reduced rapidly. 2 or moisture), it is difficult to avoid further reduction of luminescent properties. The semiconductor nanoparticles according to the embodiments may show improved process retention rate in terms of, for example, luminous efficiency during the composite manufacturing process, and the manufactured composite may show improved stability to the external environment.

[0199] The inventors have found that the formation of a zinc sulfide-based semiconductor nanocrystal layer on a first particle comprising a Group 11-13-16 compound may not be able to avoid adverse effects on the luminescent properties of the first particle. The inventors have found that when a semiconductor nanocrystal layer is formed by the reaction of zinc and a chalcogen element according to the prior art, the ratio of trap light emission (i.e., the emission peak area exceeding the maximum emission peak wavelength + 50nm) in the emission peak of the final particle is significantly increased. Without wishing to be bound by any theory, it is believed that it may be difficult to form zinc sulfide-based semiconductor nanocrystals, or that zinc ions may be replaced with gallium in the first particle or may diffuse into the first particle, resulting in an increase in trap light emission in the final semiconductor nanoparticles. The semiconductor nanoparticles of the embodiments can be manufactured, for example, according to the method described herein, and exhibit increased stability and significantly suppressed trap light emission.

[0200] In an embodiment, the first light (green light or red light) may include band-edge emission. In an embodiment, the light emitted by the semiconductor nanoparticles may also include defect site emission or trap emission. Compared with trap emission, band-edge emission may be centered at a higher energy (lower wavelength) with a smaller offset relative to the absorption start energy. Band-edge emission may have a narrower wavelength distribution than trap emission. Band-edge emission may have a normal (e.g., Gaussian) wavelength distribution.

[0201] In the photoluminescence spectrum of the semiconductor nanoparticles, the percentage of the trap light emission area (Trap) (e.g., the emission peak area exceeding the emission peak wavelength +50nm) relative to the total emission 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 5%, less than or equal to about 4%, less than or equal to about 2%, or less:

[0202] Trap emission percentage (%) = [Trap / A] × 100

[0203] In the above equation, Trap is the area of ​​the trapped light emission

[0204] A is the total area of ​​the emission spectrum, see Figure 1

[0205] The inventors have found that there are limitations to suppressing and removing trap light emission in Group 13-16 compound-based semiconductor nanoparticles containing silver. Providing a zinc chalcogenide layer can increase the stability of the semiconductor nanoparticles, but it can also increase the trap light emission of the final particles. By having the structure / composition described herein, the semiconductor nanoparticles of the embodiments can exhibit a luminescence spectrum that substantially suppresses or removes trap light emission.

[0206] In an embodiment, a method of making semiconductor nanoparticles includes: reacting a zinc precursor with a sulfur precursor in the presence of a first particle including indium, gallium, silver and sulfur to form a semiconductor nanocrystal layer including zinc and sulfur on the first particle. The reaction includes adding the first particle and the zinc precursor to a reaction medium including a sulfur precursor and a first organic solvent. The reaction is performed at a temperature greater than 180° C. and less than about 240° C.

[0207] The details of the semiconductor nanoparticles and the first particles are the same as described herein.

[0208] Prior to adding the first particles and / or the zinc precursor, the reaction medium can be heated to a predetermined temperature under vacuum, for example, to a temperature greater than or equal to about 80°C, greater than or equal to about 100°C, greater than or equal to about 120°C, greater than or equal to about 200°C, and less than or equal to about 180°C, less than or equal to about 150°C, or less than or equal to about 130°C.

[0209] The reaction temperature may be greater than or equal to about 203° C., greater than or equal to about 205° C., greater than or equal to about 208° C. or higher and less than or equal to about 225° C., less than or equal to about 215° C. or lower. The reaction time may be 10 minutes or more, 30 minutes or more, 40 minutes or more, 1 hour or more, 80 minutes or more, or 90 minutes or more, and 5 hours or less, 4 hours or less, 3 hours or less, 2 hours or less, 90 minutes or less, or 70 minutes or less.

[0210] The first organic solvent may include substituted or unsubstituted C5-C40 aliphatic hydrocarbon (e.g., alkane, olefin, alkyne) solvent, substituted or unsubstituted C6-C40 aromatic hydrocarbon solvent, C5-C40 amine solvent (e.g., aliphatic amine solvent), phosphine solvent or combination thereof having substituted or unsubstituted C5-C50 aliphatic or aromatic groups. C5-C40 (or C10-C20 or C12-C18) aliphatic hydrocarbon solvent may include octane, heptane, hexane, octadecene or a combination thereof. C6-C40 aromatic hydrocarbon solvent may include toluene, benzene, etc. C5-C40 (or C10-C20 or C12-C18) amine solvent may include aliphatic amine solvent (such as trioctylamine or oleylamine), or aromatic amine solvent (such as triphenylamine). Amine solvent may include primary amine (such as hexylamine, decylamine or stearamide). The first organic solvent may not include phosphine solvents (which have 1, 2, or 3 aliphatic or aromatic groups), such as trioctylphosphine.

[0211] The first organic solvent may include a mixture of two or more organic solvents.

[0212] The mixture of organic solvents may be a mixture of a first solvent including a C5-C40 aliphatic hydrocarbon solvent and a second solvent including a C5-C40 amine solvent.

[0213] In the mixture of organic solvents, the mixing ratio between the first organic solvent and the second organic solvent may be about 1:0.01 to 1:10, 1:0.02 to 1:95, 1:0.03 to 1:9, 1:0.04 to 1:8.5, 1:0.05 to 1:8, 1:0.06 to 1:7.5, 1:0.07 to 1:7, 1:0.1 to 1:6, 1:0.15 to 1:5.5, 1:0.2 to 1:5, 1:0.25 to 1: 4.5, 1:0.25 to 1:4, 1:0.3 to 1:3, 1:0.4 to 1:2.5, 1:0.5 to 1:2, 1:0.7 to 1:1.5, 1:0.75 to 1:1.3, 1:0.78 to 1:1.28, 1:0.8 to 1:1.25, 1:0.85 to 1:0.99, 1:0.88 to 1:0.96, 1:0.9 to 1:0.95, 1:0.93 to 1:0.94 or a combination thereof. In an embodiment, the content of the first solvent in the organic solvent mixture may be greater than the content of the second solvent.

[0214] Unexpectedly, the present inventors have discovered that semiconductor nanoparticles prepared by a process involving the use of such a mixed solvent may exhibit further improved stability (eg, relative luminescence efficiency when stored in air, as described below) when present in the form of a complex.

[0215] Methods of adding first particles and / or zinc precursors to a (eg, heated) reaction medium to form a semiconductor nanocrystal layer (eg, including zinc chalcogenide) may include injection addition (eg, syringe addition), dropwise addition, or a combination thereof.

[0216] Unexpectedly, the inventors have found that if a semiconductor nanocrystal layer comprising zinc and sulfur is formed on a first particle based on Groups 11-13-16 by the methods described herein, the final particle can achieve stability with improved luminescent properties (e.g., narrow full width at half maximum, improved quantum yield (QY), and / or suppressed trap light emission). Without wishing to be bound by any particular theory, it is believed that in the methods described herein, a semiconductor nanocrystal layer comprising zinc sulfide can be formed without significantly changing the composition of the first particle (e.g., the gallium content is reduced). In addition, the inventors have found that a semiconductor nanocrystal layer comprising zinc-sulfur formed in this manner can also contribute to the improvement of thermal stability and atmospheric stability of the final semiconductor nanoparticles.

[0217] In an embodiment, the preparation of the first particle may involve a method comprising: preparing a reaction medium containing a first precursor in a second organic solvent; heating the reaction medium to a first temperature; and adding a first semiconductor nanocrystal and a second precursor to the reaction medium to obtain a reaction mixture, one of the first precursor and the second precursor being a gallium precursor and the other being a sulfur precursor. The reaction medium is heated to a second temperature and the reaction is carried out for a first reaction time to form the first particle.

[0218] The first temperature may be greater than or equal to about 120° C. or more (e.g., greater than or equal to about 180° C., greater than or equal to about 190° C., or greater than or equal to about 200° C.), and the first temperature may be 280° C. or less (e.g., 250° C. or less), and the second temperature may be greater than or equal to about 190° C., greater than or equal to about 240° C. or more and less than or equal to about 380° C., or less than or equal to about 280° C. or less. The first reaction time may be controlled so that the first particles can obtain the charge balance value described herein.

[0219] The second organic solvent may include a substituted or unsubstituted C5-C40 aliphatic hydrocarbon solvent (e.g., octadecene), a substituted or unsubstituted C6-C40 aromatic hydrocarbon solvent (toluene, etc.), a C5-C40 amine solvent (e.g., an aliphatic amine solvent such as trioctylamine, oleylamine, etc.), or a combination thereof. The second organic solvent may include a mixture of two or more organic solvents (e.g., a mixture of an aliphatic hydrocarbon solvent and an aliphatic amine solvent). The second organic solvent may be the same as the first organic solvent. The second organic solvent may be different from the first organic solvent.

[0220] The details of the first semiconductor nanocrystal, the second semiconductor nanocrystal, and the charge balance value are the same as described herein. The first temperature and the second temperature may be different. The second temperature may be higher than the first temperature.

[0221] In one or more embodiments, the first precursor may be a sulfur precursor, and the second precursor may be a gallium precursor. According to the method of one or more embodiments, oxidation of the gallium precursor may be effectively suppressed.

[0222] In an embodiment, the prepared first particles may be separated and optionally washed. The separation and washing may be performed in the manner described herein.

[0223] The detailed description of the first semiconductor nanocrystal is the same as described herein. The first semiconductor nanocrystal may include silver (Ag), indium, gallium and sulfur. The method for manufacturing the first semiconductor nanocrystal is not specifically limited and can be appropriately selected. In one or more embodiments, the first semiconductor nanocrystal can be obtained by reacting the desired precursor (such as a silver precursor, an indium precursor, a gallium precursor and a sulfur precursor) in a solution including an organic ligand and an organic solvent at a predetermined reaction temperature (e.g., about 180°C to about 300°C or about 200°C to about 280°C) according to the composition and separating it. For separation and recovery, reference can be made to the method described herein.

[0224] The second temperature may be higher than the first temperature. The difference between the first temperature and the second temperature may be greater than or equal to about 10°C, greater than or equal to about 20°C, greater than or equal to about 30°C, greater than or equal to about 40°C, greater than or equal to about 50°C, greater than or equal to about 60°C, greater than or equal to about 70°C, greater than or equal to about 80°C, greater than or equal to about 90°C, or greater than or equal to about 100°C. The difference between the first temperature and the second temperature may be less than or equal to about 200°C, less than or equal to about 190°C, less than or equal to about 180°C, less than or equal to about 170°C, less than or equal to about 160°C, less than or equal to about 150°C, less than or equal to about 140°C, less than or equal to about 130°C, less than or equal to about 120°C, less than or equal to about 110°C, less than or equal to about 100°C, less than or equal to about 90°C, less than or equal to about 80°C, less than or equal to about 70°C, less than or equal to about 60°C, less than or equal to about 50°C, less than or equal to about 40°C, less than or equal to about 30°C, or less than or equal to about 20°C.

[0225] The first temperature may be greater than or equal to about 120° C., greater than or equal to about 190° C., greater than or equal to about 200° C., greater than or equal to about 210° C., greater than or equal to about 220° C., greater than or equal to about 230° C., greater than or equal to about 240° C., or greater than or equal to about 250° C. The first temperature may be less than or equal to about 280° C., less than or equal to about 275° C., less than or equal to about 270° C., less than or equal to about 265° C., less than or equal to about 260° C., less than or equal to about 255° C., less than or equal to about 250° C., less than or equal to about 240° C., less than or equal to about 230° C., less than or equal to about 220° C., less than or equal to about 210° C., less than or equal to about 200° C., less than or equal to about 190° C., less than or equal to about 180° C., less than or equal to about 170° C., less than or equal to about 160° C., or less than or equal to about 150° C.

[0226] The second temperature may be greater than or equal to about 240°C, greater than or equal to about 245°C, greater than or equal to about 250°C, greater than or equal to about 255°C, greater than or equal to about 260°C, greater than or equal to about 265°C, greater than or equal to about 270°C, greater than or equal to about 275°C, greater than or equal to about 280°C, greater than or equal to about 285°C, greater than or equal to about 290°C, greater than or equal to about 295°C, greater than or equal to about 300°C, greater than or equal to about 305°C, greater than or equal to about 310°C, greater than or equal to about 315°C, greater than or equal to about 320°C, greater than or equal to about 330°C, greater than or equal to about 335°C, greater than or equal to about 340°C, or greater than or equal to about 345°C. The second temperature may be less than or equal to about 380°C, less than or equal to about 375°C, less than or equal to about 370°C, less than or equal to about 365°C, less than or equal to about 360°C, less than or equal to about 355°C, less than or equal to about 350°C, less than or equal to about 340°C, less than or equal to about 330°C, less than or equal to about 320°C, less than or equal to about 310°C, less than or equal to about 300°C, less than or equal to about 290°C, less than or equal to about 280°C, less than or equal to about 270°C, less than or equal to about 260°C, or less than or equal to about 250°C.

[0227] The first reaction time can be controlled to obtain a charge balance value for the first particles. The inventors have found that by controlling the first temperature and the second temperature in the aforementioned reaction and the first reaction time, the generation of side reaction products (e.g., gallium oxide) can be effectively suppressed during the formation of semiconductor nanoparticles, and the first particles can thereby have the charge balance value described herein (optionally, and the molar ratio between each component described herein), which can help achieve the properties of the semiconductor nanoparticles as described herein.

[0228] In one or more embodiments, the first reaction time may be from about 10 minutes to about 3 hours, from about 20 minutes to about 150 minutes, from about 30 minutes to about 100 minutes, or a combination thereof. The first reaction time may be selected taking into account the type of precursor, the reaction temperature, the desired composition of the final particles, etc. In one or more embodiments, the second reaction temperature may be in a relatively high temperature range (e.g., greater than or equal to about 280°C, about 285°C to about 340°C, or about 290°C to about 330°C), and the first reaction time may be greater than or equal to about 10 minutes, greater than or equal to about 15 minutes, greater than or equal to about 20 minutes, or greater than or equal to about 25 minutes to less than or equal to about 2 hours, less than or equal to about 90 minutes, less than or equal to about 80 minutes, less than or equal to about 70 minutes, less than or equal to about 60 minutes, less than or equal to about 50 minutes, less than or equal to about 45 minutes, less than or equal to about 40 minutes, or less than or equal to about 35 minutes. In one or more embodiments, the second reaction temperature may be within a relatively low temperature range (e.g., less than about 290° C.), and the first reaction time may be greater than or equal to about 30 minutes, greater than or equal to about 35 minutes, greater than or equal to about 40 minutes, greater than or equal to about 45 minutes, greater than or equal to about 50 minutes, greater than or equal to about 55 minutes, greater than or equal to about 60 minutes, greater than or equal to about 65 minutes, greater than or equal to about 70 minutes, greater than or equal to about 75 minutes, or greater than or equal to about 80 minutes.

[0229] The type of silver precursor is not particularly limited and can be appropriately selected. The silver precursor may include silver powder, alkylated silver compounds, silver alkoxides, silver carboxylates, silver acetylacetonate, silver nitrate, silver sulfate, silver halide, silver cyanide, silver hydroxide, silver oxide, silver peroxide, silver carbonate, or a combination thereof. The silver precursor may include silver nitrate, silver acetate, silver acetylacetonate, or a combination thereof.

[0230] The type of indium precursor is not particularly limited and can be appropriately selected. The indium precursor may include indium powder, alkylated indium compounds, 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. The indium precursor may include indium carboxylates (such as indium oleate, indium myristic acid, and indium acetate), indium hydroxides, indium chlorides, indium bromides, indium iodides, or combinations thereof.

[0231] The type of gallium precursor is not particularly limited and can be appropriately selected. The gallium precursor may include gallium powder, alkylated gallium compounds, gallium 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. The gallium precursor may include gallium chloride, gallium iodide, gallium bromide, gallium acetate, gallium acetylacetonates, gallium oleates, gallium palmitates, gallium stearates, gallium myristates, gallium hydroxides, or combinations thereof.

[0232] The type of the sulfur precursor is not particularly limited and may be appropriately selected. The sulfur precursor may be an organic solvent dispersion or a reaction product of sulfur and an organic solvent (e.g., octadecene sulfide (S-ODE), trioctylphosphine-sulfide (S-TOP), tributylphosphine-sulfide (S-TBP), triphenylphosphine-sulfide (S-TPP), trioctylamine-sulfide (S-TOA)), trimethylsilylalkylsulfide, trimethylsilylsulfide, mercaptopropylsilane, ammonium sulfide, sodium sulfide, C1-30 thiol compounds (e.g., α-toluenethiol, octanethiol, dodecanethiol, octadecenethiol, etc.), isothiocyanate compounds (e.g., cyclohexyl isothiocyanate, etc.), alkylene trithiocarbonates (e.g., ethylene trithiocarbonate, etc.), allyl mercaptan, thiourea compounds (e.g., dialkylthioureas having a C1-C40 alkyl group such as dimethylthiourea, diethylthiourea, ethylmethylthiourea, dipropylthiourea, etc.), thioacetamide compounds, or combinations thereof.

[0233] If present, the selenium precursor may include selenium-trioctylphosphine (Se-TOP), selenium-tributylphosphine (Se-TBP), selenium-triphenylphosphine (Se-TPP), or combinations thereof.

[0234] The type of zinc precursor is not specifically limited and can be appropriately selected. In one or more embodiments, the zinc precursor may include zinc metal powder, alkylated 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. The zinc precursor may be dimethyl zinc, diethyl zinc, zinc acetate, zinc acetylacetonates, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanides, zinc nitrates, zinc oxides, zinc peroxides, zinc perchlorates, zinc sulfates, or combinations thereof. In an embodiment, when a semiconductor nanocrystal layer comprising zinc and sulfur is formed, the zinc precursor may include zinc halides, but is not limited thereto.

[0235] Organic ligands may include RCOOH, RNH 2 , R 2 NH, R 3 N, RSH, RH 2 PO, R 2 HPO, R 3 PO, RH 2 P.R 2 HP, R 3 P, ROH, RCOOR', RPO(OH) 2 , RHPOOH, R 2POOH (wherein, R and R' are each independently a substituted or unsubstituted C1-C40 (or C3-C24) aliphatic hydrocarbon group (e.g., alkyl, alkenyl or alkynyl) or a substituted or unsubstituted C6-C40 (or C6-C24) aromatic hydrocarbon group (e.g., C6-C20 aryl)) or a combination thereof. The organic ligand may be bound to the surface of the semiconductor nanoparticle. Examples of organic ligands may include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, 1-nonyl mercaptan, decyl mercaptan, dodecanethiol, hexadecyl mercaptan, octadecyl mercaptan, benzyl mercaptan; methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, dodecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine; formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, benzoic acid; substituted or unsubstituted methyl phosphine (e.g., trimethyl phosphine, methyl diphenyl phosphine, etc.), substituted or unsubstituted ethyl phosphine (e.g., triethyl phosphine, ethyl diphenyl phosphine, etc.), substituted or unsubstituted propyl phosphine, substituted or unsubstituted butyl phosphine, substituted or unsubstituted pentyl phosphine, phosphine, substituted or unsubstituted octyl phosphine (e.g., trioctyl phosphine (TOP) etc.); phosphine oxide (such as substituted or unsubstituted methyl phosphine oxide (e.g., trimethyl phosphine oxide, methyl diphenyl phosphine oxide etc.)), substituted or unsubstituted ethyl phosphine oxide (e.g., triethyl phosphine oxide, ethyl diphenyl phosphine oxide etc.), substituted or unsubstituted propyl phosphine oxide, substituted or unsubstituted butyl phosphine oxide, substituted or unsubstituted octyl phosphine oxide (e.g., trioctyl phosphine oxide (TOPO) etc.); diphenyl phosphine, triphenyl phosphine compound or its oxide; phosphonic acid; C5-C20 alkyl phosphonic acid; C5-C20 alkyl phosphinic acid (such as hexyl phosphinic acid, octyl phosphinic acid, dodecane phosphinic acid, tetradecane phosphinic acid, hexadecane phosphinic acid, octadecane phosphinic acid etc.), but the embodiment is not limited thereto. The organic ligand can be used alone or as a mixture of two or more.

[0236] The first organic solvent or the second organic solvent, or the organic solvent, may include an amine solvent (e.g., a C1-50 aliphatic amine), a nitrogen-containing heterocyclic compound such as pyridine; a C6-C40 aliphatic hydrocarbon (e.g., alkane, alkene, alkyne, etc.) such as hexadecane, octadecane, octadecene, squalene, etc.; a C6-C30 aromatic hydrocarbon such as phenyldodecane, phenyltetradecane, phenylhexadecane, etc.; a phosphine substituted with a C6-C22 alkyl group such as trioctylphosphine; a phosphine oxide substituted with a C6-C22 alkyl group such as trioctylphosphine oxide; a C12-C22 aromatic ether such as phenyl ether or benzyl ether; or a combination thereof. The amine solvent may be a compound having one or more (e.g., two or three) C1-50, C2-45, C3-40, C4-35, C5-30, C6-25, C7-20, C8-15 or C6-22 aliphatic hydrocarbon groups (e.g., alkyl, alkenyl or alkynyl). In one or more embodiments, the amine solvent can be a C6-22 primary amine (such as hexadecylamine, oleylamine, etc.); a C6-22 secondary amine (such as dioctylamine, etc.); a C6-22 tertiary amine (such as trioctylamine, etc.); or a combination thereof.

[0237] In consideration of the type of solvent, the type of organic ligand and each precursor, and the size and composition of the desired nanoparticles, the amount of organic ligand and precursor in the reaction medium can be appropriately selected. In consideration of the desired molar ratio in the final nanoparticles, the reactivity between the precursors, etc., the molar ratio between the precursors can be changed. In one or more embodiments, the mode of adding each precursor is not specifically limited. In one or more embodiments, all or all amounts of precursors can be added at once. In one or more embodiments, the total amount of the precursor can be divided and added to greater than or equal to about 2 aliquots and less than or equal to about 10 aliquots. The precursors can be added simultaneously or sequentially in a predetermined order. The reaction can be carried out in an inert gas atmosphere, in air, or in a vacuum, but is not limited thereto.

[0238] When the non-solvent is added to the final reaction solution after the reaction is completed, the nanoparticles (e.g., the organic ligands are coordinated) can be separated (e.g., precipitated). The non-solvent can be a polar solvent that is miscible with the solvent used in the reaction but cannot disperse the nanocrystals. The non-solvent can be selected according to the solvent used in the reaction, and can be, for example, acetone, ethanol, butanol, isopropanol, ethylene glycol, water, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), ether, formaldehyde, acetaldehyde, a solvent with a solubility parameter similar to the aforementioned solvent, or a combination thereof. The above separation can be performed by centrifugation, precipitation, chromatography or distillation. The separated nanocrystals can be washed by adding to a washing solvent as needed. The washing solvent is not specifically limited, and a solvent with a solubility parameter similar to that of the organic solvent or organic ligand can be used. The non-solvent or washing solvent can be ethanol; 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.

[0239] The semiconductor nanoparticles thus prepared can be dispersed in a dispersing solvent. The semiconductor nanoparticles thus prepared can form an organic solvent dispersion. The organic solvent dispersion may not include water and / or an organic solvent miscible with water. The dispersing solvent may be appropriately selected. The dispersing solvent may include the aforementioned organic solvent. The dispersing solvent may include substituted or unsubstituted C1-C40 aliphatic hydrocarbons, substituted or unsubstituted C6-C40 aromatic hydrocarbons, or a combination thereof.

[0240] The shape of the semiconductor nanoparticles thus prepared is not particularly limited, and may include, for example, spheres, polyhedrons, pyramids, multi-legged (or multi-pod) shapes, cubes, nanotubes, nanowires, nanofibers, nanosheets, or combinations thereof, but is not limited thereto.

[0241] The semiconductor nanoparticles of the embodiments may include an organic ligand and / or an organic solvent on the surface of the semiconductor nanoparticle. The organic ligand and / or the organic solvent may be bound to the surface of the semiconductor nanoparticles of one or more embodiments.

[0242] In one or more embodiments, a composite may include a matrix and semiconductor nanoparticles as described herein, wherein the semiconductor nanoparticles may be dispersed in the matrix. The composite may also include metal oxide particles. The composite may be configured to emit green light. In an embodiment, the composite may be in the form of a patterned film. The composite may also include semiconductor nanoparticles configured to emit a second light different from green light. In an embodiment, the composite may have a sheet form. The sheet may also include semiconductor nanoparticles configured to emit a second light different from green light (e.g., additional semiconductor nanoparticles).

[0243] The semiconductor nanoparticles described herein or composites comprising the semiconductor nanoparticles may exhibit an increased level of blue light absorbance (e.g., improved incident light absorbance) and / or improved optical properties (e.g., increased luminous efficiency and a narrower half-maximum full width), and may emit light of a desired wavelength (e.g., a first light).

[0244] In the color conversion panel of one or more embodiments, the first composite may exhibit an increased level of blue light absorbance (e.g., improved excitation light absorbance) and improved optical properties (e.g., increased luminous efficiency and narrowed half-maximum full width) and may emit light of a desired wavelength (e.g., first light). In the color conversion panel of one or more embodiments, the composite may be in the form of a patterned film. In other embodiments, the composite may be in the form of a sheet.

[0245] The composite may include semiconductor nanoparticles or a population thereof (e.g., in a predetermined amount) and exhibit increased light absorbance. The composite may have an incident light absorbance of greater than or equal to about 70%, greater than or equal to about 73%, greater than or equal to about 75%, greater than or equal to about 77%, greater than or equal to about 80%, greater than or equal to about 83%, greater than or equal to about 85%, greater than or equal to about 87%, greater than or equal to about 90%, greater than or equal to about 93%, greater than or equal to about 94%, greater than or equal to about 95%, greater than or equal to about 96%, greater than or equal to about 97%, greater than or equal to about 98%, or greater than or equal to about 99%. The composite may have a blue light absorbance of about 70% to about 100%, about 80% to about 98%, about 95% to about 99%, about 96% to about 98%, or a combination thereof.

[0246] The incident light absorbance can be calculated according to Equation 5:

[0247] Equation 5

[0248] Incident light absorbance = [(B-B') / B] × 100%

[0249] Where, in equation 5,

[0250] B is the amount of incident light provided to the first composite, and

[0251] B' is the amount of incident light that passes through the composite.

[0252] The photoconversion efficiency (CE) of the composite may be greater than or equal to about 7%, greater than or equal to about 8%, greater than or equal to about 9%, greater than or equal to about 10%, greater than or equal to about 11%, greater than or equal to about 12%, greater than or equal to about 12.5%, greater than or equal to about 12.9%, greater than or equal to about 13%, greater than or equal to about 14.5%, greater than or equal to about 15%, greater than or equal to about 15.5%, greater than or equal to about 16%, greater than or equal to about 16.5%, greater than or equal to about 16.7%, or greater than or equal to about 16.9%.

[0253] The light conversion efficiency is defined by the following equation:

[0254] Photoconversion efficiency (CE, %) = [A / (B-B')] × 100 (%)

[0255] A: The amount of light from the first light of the composite

[0256] B: The amount of incident light provided to the composite

[0257] B': The amount of incident light that passes through the composite.

[0258] The inventors have found that luminescent particles including semiconductor nanocrystals based on Group 11-13-16 compounds, even if the desired level of optical properties is achieved, will exhibit significantly reduced properties when included in a composite used in an actual device. The semiconductor nanoparticles of the embodiments can provide a composite that exhibits improved optical properties due to the above-mentioned components and / or structural features, even in the form of a film, and exhibit high optical properties. The semiconductor nanoparticles of the embodiments can exhibit significantly improved stability (e.g., thermal stability and atmospheric stability).

[0259] Composites containing semiconductor nanoparticles of embodiments may exhibit a process retention rate of greater than or equal to about 30%, greater than or equal to about 45%, greater than or equal to about 60%, greater than or equal to about 65%, or greater than or equal to about 70%, wherein the process retention rate is defined by the following equation:

[0260] Process retention rate = {composite film state light conversion rate / quantum yield of semiconductor nanoparticles in solution} × 2 × 100%

[0261] The process retention rate may be about 30%-99%, 68%-95%, 70%-85%, or any combination of lower and higher values ​​thereof.

[0262] Composites including semiconductor nanoparticles of embodiments may exhibit a thermal stability defined by the following equation of greater than or equal to about 60%, greater than or equal to about 65%, or greater than or equal to about 70%:

[0263] Thermal stability (%) = [light conversion efficiency of the composite after POB process / light conversion efficiency of the composite after PRB process] × 100

[0264] In embodiments, when the nanoparticles are kept in air (e.g., at room temperature or 25° C.) for 48 hours, the composite may exhibit a relative luminous efficiency (or stability) of 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 68%, or greater than or equal to about 70% or more:

[0265] Relative luminous efficiency (%)=[quantum efficiency of the light emitting film after 48 hours / initial luminous efficiency of the light emitting film]×100.

[0266] In an embodiment, the composite may be prepared from an ink composition. The ink composition may include a liquid carrier; and a plurality of semiconductor nanoparticles of one or more embodiments. The semiconductor nanoparticles may be dispersed in the liquid carrier.

[0267] The liquid carrier may include a liquid monomer, an organic solvent, or a combination thereof. The ink composition may also include, for example, metal oxide nanoparticles dispersed in the liquid carrier. The ink composition may also include 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 not include an (e.g., volatile) organic solvent. The ink composition may be a solvent-free system.

[0268] The liquid monomer may comprise a (photo)polymerizable monomer containing a carbon-carbon double bond. Optionally, the composite may further comprise a (thermal or photo)initiator. The polymerisation of the composite may be initiated by light or heat.

[0269] The details of the nanoparticles in the composition (or composite) are as described herein. The content or amount of the semiconductor nanoparticles in the composition (or composite) can be appropriately adjusted in view of the desired end use (e.g., color filter, etc.). In one or more embodiments, based on the solid content of the composition or composite (hereinafter, the solid content may be the solid content of the composition or the solid content of the composite), the amount of semiconductor nanoparticles in the composition (or composite) may be greater than or equal to about 1wt%, for example, greater than or equal to about 2wt%, greater than or equal to about 3wt%, greater than or equal to about 4wt%, greater than or equal to about 5wt%, greater than or equal to about 6wt%, greater than or equal to about 7wt%, greater than or equal to about 8wt%, greater than or equal to about 9wt%, greater than or equal to about 10wt%, greater than or equal to about 15wt%, greater than or equal to about 20wt%, greater than or equal to about 25wt%, greater than or equal to about 30wt%, greater than or equal to about 35wt%, or greater than or equal to about 40wt%. Based on the solid content of the composition or composite, the amount of semiconductor nanoparticles may be less than or equal to about 70 wt %, for example, 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 solid content in the composition may represent the amount of a given component in the composition described herein.

[0270] In one or more embodiments, the ink composition may be a photoresist composition containing semiconductor nanoparticles applicable in a photolithography method. In one or more embodiments, the ink composition may be a composition containing semiconductor nanoparticles that can provide a pattern in a printing manner (e.g., a droplet discharge method, such as inkjet printing). The composition according to one or more embodiments may not include a conjugated (or conductive) polymer (except for the cardo binder to be described herein). The composition according to one or more embodiments may include a conjugated polymer. In this article, a conjugated polymer refers to a polymer having conjugated double bonds in the main chain (e.g., polyphenylenevinylene, etc.).

[0271] In the composition according to one or more embodiments, the dispersant can ensure the dispersibility of the nanoparticles. In one or more embodiments, the dispersant can be a binder (or a binder polymer). The binder can (e.g., in repeating units) include a carboxylic acid group. The binder can be an insulating polymer. The binder can be a compound (monomer or polymer) containing a carboxylic acid group.

[0272] In the composition (or composite), the content of the dispersant may be greater than or equal to about 0.5 wt %, for example, greater than or equal to about 1 wt %, greater than or equal to about 5 wt %, greater than or equal to about 10 wt %, greater than or equal to about 15 wt %, or greater than or equal to about 20 wt % based on the total solid content of the composition (or composite). Based on the total solid content, the content of the dispersant may be less than or equal to about 55 wt %, less than or equal to about 35 wt %, less than or equal to about 33 wt %, or less than or equal to about 30 wt %.

[0273] In the composition (or liquid carrier), a liquid monomer or a polymerizable monomer (e.g., a photopolymerizable monomer) including a carbon-carbon double bond is hereinafter referred to as a monomer. The monomer may include a (meth)acryloyl-containing monomer (e.g., a photopolymerizable (meth)acryloyl-containing monomer). The monomer may be a precursor of an insulating polymer.

[0274] Based on the total weight of the composition, the content of the (photopolymerizable) monomer may be greater than or equal to about 0.5 wt%, for example, greater than or equal to about 1 wt%, greater than or equal to about 2 wt%, greater than or equal to about 3 wt%, greater than or equal to about 5 wt%, or greater than or equal to about 10 wt%. Based on the total weight of the composition, the content of the (photopolymerizable) monomer may be less than or equal to about 30 wt%, for example, less than or equal to about 28 wt%, less than or equal to about 25 wt%, less than or equal to about 23 wt%, less than or equal to about 20 wt%, less than or equal to about 18 wt%, less than or equal to about 17 wt%, less than or equal to about 16 wt%, or less than or equal to about 15 wt%.

[0275] The (photo) initiator included in the composition can be used for the (photo) polymerization of the aforementioned monomers. The initiator is a compound that accelerates a free radical reaction (e.g., free radical polymerization of a monomer) by generating free radical chemicals under mild conditions (e.g., by heat or light). The initiator can be a thermal initiator or a photoinitiator. The initiator is not specifically limited and can be appropriately selected.

[0276] In the composition, the content of the initiator may be appropriately adjusted in consideration of the type and content of the polymerizable monomer. In one or more embodiments, based on the total weight of the composition (or the total weight of the solid content), the content of the initiator may be greater than or equal to about 0.01wt%, such as greater than or equal to about 1wt%, and less than or equal to about 10wt%, such as less than or equal to about 9wt%, less than or equal to about 8wt%, less than or equal to about 7wt%, less than or equal to about 6wt%, or less than or equal to about 5wt%, but is not limited thereto.

[0277] The composition (or composite) may also include a (multifunctional or monofunctional) thiol compound, metal oxide particles, or a combination thereof, wherein the thiol compound has at least one thiol group (or a moiety derived therefrom, such as a moiety resulting from a reaction between a thiol and a carbon-carbon double bond, e.g., a thioether group) at a terminal end.

[0278] The metal oxide particles may include TiO 2 、SiO 2 、BaTiO 3 , Ba 2 TiO 4 , ZnO, or a combination thereof. In the composition (or composite), based on the total solid content, the content of the metal oxide 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%.

[0279] The diameter of the metal oxide particles is not particularly limited and can be appropriately selected. The diameter of the metal oxide particles may be greater than or equal to about 100 nm, for example 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.

[0280] The polythiol compound can be a dithiol compound, a trithiol compound, a tetrathiol compound, or a combination thereof. For example, the thiol compound can be ethylene glycol bis(3-mercaptopropionate), ethylene glycol dimercaptoacetate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), 1,6-hexanedithiol, 1,3-propanedithiol, 1,2-ethanedithiol, polyethylene glycol dithiol comprising 1 to 10 ethylene glycol repeating units, or a combination thereof.

[0281] Based on the total solid content, the content of the thiol compound (or a portion derived therefrom) may be less than or equal to about 50 wt%, less than or equal to about 40 wt%, less than or equal to about 30 wt%, less than or equal to about 20 wt%, less than or equal to about 10 wt%, less than or equal to about 9 wt%, less than or equal to about 8 wt%, less than or equal to about 7 wt%, less than or equal to about 6 wt%, or less than or equal to about 5 wt%. Based on the total solid content, the content of the thiol compound may be greater than or equal to about 0.1 wt%, for example, greater than or equal to about 0.5 wt%, greater than or equal to about 1 wt%, greater than or equal to about 5 wt%, greater than or equal to about 10 wt%, greater than or equal to about 15 wt%, greater than or equal to about 18 wt%, or greater than or equal to about 20 wt%.

[0282] The composition or liquid carrier may include an organic solvent. In certain embodiments, the composition or liquid carrier may not include an organic solvent. If present, the type of organic solvent that can be used is not specifically limited. Taking into account the aforementioned main components (i.e., nanoparticles, dispersants, polymerizable monomers, initiators, thiol compounds, etc., if present) and the types and amounts of other additives to be described herein, the type and amount of the organic solvent are appropriately determined. In addition to the desired content of (non-volatile) solids, the composition may include a residual amount of solvent. In one or more embodiments, examples of organic solvents may be glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, and the like; 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, and the like; glycol ether acetate solvents such as ethylene glycol acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like; propylene glycol solvents such as propylene glycol, and the like; 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, and the like; propylene glycol ether acetate solvents such as propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and the like; amides 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 ethyl ether, dipropyl ether, dibutyl ether, etc.; chloroform, C1-C40 aliphatic hydrocarbon solvents (e.g., alkanes, olefins or alkynes), halogen (e.g., chlorine) substituted C1-C40 aliphatic hydrocarbon solvents (e.g., dichloroethane, chloroform, etc.), C6-C40 aromatic hydrocarbon solvents (e.g., toluene, xylene, etc.), halogen (e.g., chlorine) substituted C6-C40 aromatic hydrocarbon solvents; or combinations thereof.

[0283] In addition to the aforementioned components, the composition (or composite) of one or more embodiments may further include additives, such as light diffusers, leveling agents, coupling agents, or combinations thereof. The components (adhesives, monomers, solvents, additives, thiol compounds, cardo adhesives, etc.) included in the composition of one or more embodiments may be appropriately selected, and for specific details thereof, reference may be made to, for example, US-2017-0052444-A1, the entire contents of which are incorporated herein.

[0284] In the preparation of the composition according to one embodiment, each of the aforementioned components may be mixed sequentially or simultaneously for preparation, and the order thereof is not particularly limited.

[0285] The composition can provide a color conversion layer (or a patterned film of the composite) by (eg, free radical) polymerization. The color conversion layer (or a patterned film of the composite) can be prepared using a photoresist composition. Figure 2A , the method may include: forming a film of the aforementioned composition on a substrate (S1); pre-baking the film as selected (S2); exposing selected areas of the film to light (e.g., having a wavelength of less than or equal to about 400 nm) (S3); and developing the exposed film with an alkaline developer to obtain a pattern of quantum dot-polymer composites (S4).

[0286] Reference Figure 2A , the aforementioned composition can be applied to a substrate to a predetermined thickness using an appropriate method (such as spin coating or slit coating) to form a film. The formed film can optionally be subjected to a pre-baking (PRB) step. Pre-baking can be performed by selecting appropriate conditions from known conditions such as temperature, time, atmosphere, etc.

[0287] The formed (or optionally pre-baked) film is exposed to light having a predetermined wavelength under a mask having a predetermined pattern (EXP). The wavelength and intensity of the light may be selected taking into account the type and content of the photoinitiator, the type and content of the quantum dots, etc.

[0288] The exposed film may then be treated (e.g., dipped or sprayed) with an alkaline developing solution to dissolve the unexposed areas and obtain a desired pattern (DEV). Alternatively, the obtained pattern may be post-exposure baked (POB) (S5), for example, 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 crack resistance and solvent resistance of the pattern.

[0289] When the patterned film or color conversion layer of the nanoparticle composite has multiple repeating segments (i.e., color conversion regions), each repeating segment can be formed by preparing multiple compositions including quantum dots (e.g., red light-emitting quantum dots, green light-emitting quantum dots, or optional blue light-emitting quantum dots) having desired luminescent properties (photoluminescence peak wavelength, etc.), and repeating the aforementioned pattern forming process multiple times (e.g., 2 times or more, or 3 times or more) as needed for each composition, and finally obtaining a nanoparticle-polymer composite (S6) having a desired pattern. For example, the nanoparticle-polymer composite may have a pattern of at least two repeating color segments (e.g., RGB color segments). Such a nanoparticle-polymer composite pattern can be used as a photoluminescent color filter in a display device.

[0290] Patterned films or color conversion layers of nanoparticle composites can be made using ink compositions configured to form patterns using an inkjet method. Figure 2B , the method may include: preparing an ink composition according to one or more embodiments; providing a substrate (e.g., having a pixel region patterned by an electrode and an optional bank or trench-type partition wall, etc.); and depositing the ink composition on the substrate (or pixel region) to form, for example, a first composite layer (or first region). The method may include depositing the ink composition on the substrate (or pixel region) to form, for example, a second composite layer (or second region). The 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.

[0291] The deposition of the ink composition can be performed using a suitable liquid crystal ejector (e.g., an inkjet or nozzle printing system (having an ink reservoir and at least one print head). The deposited ink composition can be provided by solvent removal and polymerization via heating to provide a (first or second) composite layer. The method can provide a highly precise nanoparticle-polymer composite film or patterned film in a short time by a simple method.

[0292] In the nanoparticle-polymer composite (e.g., first composite) of one or more embodiments, the (polymer) matrix may include the components described herein for the composition. In the composite, the amount of the matrix may be greater than or equal to about 10wt%, greater than or equal to about 20wt%, greater than or equal to about 30wt%, greater than or equal to about 40wt%, greater than or equal to about 50wt%, or greater than or equal to about 60wt%, based on the total weight of the composite. The amount of the matrix may be less than or equal to about 95wt%, less than or equal to about 90wt%, less than or equal to about 80wt%, less than or equal to about 70wt%, less than or equal to about 60wt%, or less than or equal to about 50wt%, based on the total weight of the composite.

[0293] The (polymer) matrix may include at least one of the following: a dispersant (e.g., a binder polymer containing a carboxylic acid group), a polymerization product of a polymerizable monomer including (at least one, such as at least two, at least three, at least four, or at least five) carbon-carbon double bonds (e.g., an insulating polymer), and a polymerization product of the polymerizable monomer and a polythiol compound having at least two thiol groups at the end. The matrix may include a linear polymer, a cross-linked polymer, or a combination thereof. The (polymer) matrix may not include a conjugated polymer (except for cardo resin). The matrix may include a conjugated polymer.

[0294] The cross-linked polymer may include: thiol-ene resin, cross-linked poly (meth) acrylate, cross-linked polyurethane, cross-linked epoxy resin, cross-linked vinyl polymer, cross-linked silicone resin, or a combination thereof. In one or more embodiments, the cross-linked polymer may be a polymerization product of the aforementioned polymerizable monomer and an optional polythiol compound.

[0295] The linear polymer may include: a repeating unit derived from a carbon-carbon unsaturated bond (eg, a carbon-carbon double bond). The repeating unit may include a carboxylic acid group. The linear polymer may include an ethylene repeating unit.

[0296] The repeating unit containing a carboxylic acid group may include a unit derived from a monomer containing a carboxylic acid group and a carbon-carbon double bond, a unit derived from a monomer having a dianhydride moiety, or a combination thereof.

[0297] The (polymer) matrix may include: a compound (eg, a binder, a binder polymer, or a dispersant) containing carboxylic acid groups (eg, for dispersing nanoparticles or binders).

[0298] The first composite (or a film or pattern thereof) may have a thickness of, for example, less than or equal to about 25 μm, less than or equal to about 20 μm, less than or equal to about 15 μm, less than or equal to about 10 μm, less than or equal to about 8 μm, or less than or equal to about 7 μm 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).

[0299] The aforementioned nanoparticles, a composite (or a pattern thereof) including the aforementioned nanoparticles, or a color conversion panel including them may be included in an electronic device. Such an electronic device may include a display device, a light emitting diode (LED), an organic light emitting diode (OLED), a quantum dot LED, a sensor, a solar cell, an image sensor, a photodetector, or a liquid crystal display device, but the embodiment is not limited thereto. The aforementioned quantum dots may be included in an electronic device. Such an electronic device may include, but is not limited to, a portable terminal device, a monitor, a notebook PC, a television, an electronic sign, a camera, a car, etc., but the embodiment is not limited thereto. The electronic device may be a portable terminal device, a monitor, a notebook PC, or a television including a display device (or a light emitting device) containing quantum dots. The electronic device may be a camera or a mobile terminal including an image sensor containing quantum dots. The electronic device may be a camera or a vehicle including a photodetector containing quantum dots.

[0300] Embodiments provide a color conversion layer (e.g., a color conversion structure or a color conversion panel) comprising a color conversion region, the color conversion region comprising semiconductor nanoparticles as described herein. The color conversion panel comprises a color conversion layer, the color conversion layer comprising a color conversion region and optionally comprising a partition wall defining each region of the color conversion layer, the color conversion region comprising a first region corresponding to a first pixel, the first region comprising semiconductor nanoparticles or a composite. In the color conversion panel of one embodiment, the composite may be in the form of a patterned film. In another embodiment, the composite may have a sheet form.

[0301] The first region includes a first composite, the first composite includes a matrix and semiconductor nanoparticles dispersed in the matrix, and the first composite is configured to emit a first light. An embodiment provides the semiconductor nanoparticles or a group thereof.

[0302] The color conversion layer (eg, color conversion structure) may include a composite according to one or more embodiments or a patterned film thereof. Figure 3A is a schematic cross-sectional view of a color conversion panel according to one or more embodiments. Figure 3A The color conversion panel may optionally further include a partition wall (eg, a black matrix BM, a bank, or a combination thereof) defining each region of the color conversion layer (eg, the color conversion structure). Figure 3B An electronic device (display device) including a color conversion panel and a light source according to another embodiment is shown. In the electronic device of one or more embodiments, the color conversion panel including the color conversion layer or the color conversion structure is provided on an on-chip LED (eg, an on-chip micro LED). Figure 3B, a circuit configured to drive a light source (e.g., a Si driver 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 and a second composite or a third composite, the first composite including semiconductor nanoparticles emitting a first light (e.g., green light), the second composite including semiconductor nanoparticles emitting a second light (e.g., red light), and the third composite emitting or transmitting a third light (e.g., emitting blue light or transmitting incident light). A partition wall PW (e.g., a partition wall including an inorganic material such as silicon or silicon oxide, or a partition wall based on an organic material) may be disposed between the corresponding composites. The partition wall may include a groove hole, a through hole, or a combination thereof. A first optical element (e.g., an absorptive color filter) may be disposed on a light extraction surface of the color conversion layer. Additional optical elements such as microlenses may also be disposed on the first optical element.

[0303] The color conversion region includes a first region configured to emit (e.g., by irradiating with incident light) the aforementioned first light (or green light). In one or more embodiments, the first region may correspond to a green pixel. The first region includes a first composite (e.g., a light-emitting composite). The first light may have a peak emission wavelength within a wavelength range described later. The first light will be described in more detail 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.

[0304] The color conversion region may further include (e.g., one or more) second regions configured to emit (e.g., by irradiating 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.

[0305] The second light may be red light having a peak emission wavelength of about 600 nm to about 650 nm (e.g., about 620 nm to about 650 nm). The color conversion panel may further include (one or more) third regions that emit or transmit a third light (e.g., blue light) that is different from the first light and the second light. The incident light may include the third light (e.g., blue light and optionally green light). The third light may include blue light having a peak emission wavelength greater than or equal to about 380 nm (e.g., greater than or equal to about 440 nm, greater than or equal to about 445 nm, greater than or equal to about 450 nm, or greater than or equal to about 455 nm) and less than or equal to about 480 nm (e.g., less than or equal to about 475 nm, less than or equal to about 470 nm, less than or equal to about 465 nm, or less than or equal to about 460 nm).

[0306] In one or more embodiments, the color conversion panel or color conversion layer may include a plurality of first regions, and the composite may form a predetermined pattern to be respectively arranged in the first regions of the color conversion panel. The composite (or its pattern) may be prepared by any method, for example, by photolithography or by inkjet printing, from an (ink) composition. Therefore, one or more embodiments relate to a composition including semiconductor nanoparticles, which is further described in detail herein.

[0307] In one or more embodiments, the electronic device or display device (e.g., a display panel) may further include a color conversion layer (or a color conversion panel) and may optionally further include a light source. The light source may provide incident light to the color conversion layer or the color conversion panel. In one or more embodiments, the display panel includes a light emitting panel (or a light source), the aforementioned color conversion panel, and a light-transmitting layer between the aforementioned light emitting panel and the aforementioned color conversion panel. The color conversion panel includes a substrate, and the color conversion layer may be disposed on the substrate.

[0308] When a light source or a light emitting panel is present, the light source or the light emitting panel may provide incident light to the color conversion layer or the 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).

[0309] In one or more embodiments, an electronic device (eg, a photoluminescent device) may further include a sheet of the nanoparticle composite. Figure 4B, the device 400 may include a backlight unit 410 and a liquid crystal panel 420, optionally, wherein 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 an optical film (prism, double brightness enhancement film DBEF, etc.) can be stacked. The liquid crystal panel 420 may be disposed on the backlight unit 410 and have a structure in which a thin film transistor TFT, a liquid crystal LC and a color filter are included between two polarizers Pol. The quantum dot polymer composite sheet (QD sheet) may include semiconductor nanoparticles (e.g., quantum dots) that emit red and green light after absorbing light from a light source. The blue light provided from the light source may be combined with the red and green light emitted from the corresponding semiconductor nanoparticles while passing through the quantum dot polymer composite sheet and converted into white light. The white light may be separated into blue light, green light and red light by the color filter in the liquid crystal panel and then emitted to the outside of each pixel. Referring to Figure 4D , a backlight unit (BLU) may be a direct type BLU without a light guide plate and may include a plurality of LEDs (eg, mini LEDs), and a photoelectric conversion sheet or a QD sheet may be disposed on the BLU.

[0310] The color conversion panel may include a substrate, and the color conversion layer may be disposed on the substrate. The color conversion layer or the color conversion panel may include a patterned film of a nanoparticle composite. The patterned film may include a repeating segment configured to emit light of a desired wavelength. The repeating segment may include a second region. The second region may be a segment that emits red light. The repeating segment may include a first region. The first region may be a segment that emits green light. The repeating segment may include a third region. The third region may include a segment that emits or transmits blue light. Details of the first region, the second region, and the third region are as described herein.

[0311] The light emitting panel or light source may be an element that emits incident light (e.g., excitation light). The incident light may include blue light, and may optionally include green light. The light source may include an LED. The light source may include an organic LED (OLED). The light source may include a micro-LED. On the front surface (light emitting surface) of the first region and the second region, an optical element for blocking (e.g., reflecting or absorbing) blue light (and optionally green light) may be provided, such as a blue light (and optionally green light) blocking layer or a first filter to be described herein. In one or more embodiments, the light source may include an organic light emitting diode that emits blue light and an organic light emitting diode that emits green light, and a filter that removes green light may also be provided on a third region that transmits blue light.

[0312] The light-emitting panel or light source may include a plurality of light-emitting units, the plurality of light-emitting units corresponding to the first region and the second region, respectively, and the plurality of 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 an organic light-emitting material. For example, each light-emitting unit of the light source may include an electroluminescent device (e.g., an organic light-emitting diode (OLED)) configured to emit light of a predetermined wavelength (e.g., blue light, green light, or a combination thereof). The structure and material of the electroluminescent device and the organic light-emitting diode (OLED) are not specifically limited.

[0313] Hereinafter, a display panel and a color conversion panel will be described in more detail with reference to the accompanying drawings.

[0314] Reference Figure 4A and Figure 4C , the display panel 1000 according to one or more embodiments may include a light emitting panel 40 and a color conversion panel 50. The display panel or the electronic device may further include a light-transmitting layer 60 disposed between the light-emitting panel 40 and the color conversion panel 50, and an adhesive material 70 for bonding the light-emitting panel 40 and the color conversion panel 50. The light-transmitting layer may include a passivation layer, a filling material, an encapsulation layer, or a combination thereof (not shown). The material for the light-transmitting layer may be appropriately selected without specific limitation. The material for the light-transmitting layer may be an inorganic material, an organic material, an organic / inorganic hybrid material, or a combination thereof.

[0315] The light emitting panel 40 and the color conversion panel 50 each have surfaces facing each other, that is, the two respective panels face each other, and a light-transmitting layer (or light-transmitting panel) 60 is disposed between the two panels. The color conversion panel 50 is disposed, for example, in a direction in which light emitted from the light emitting panel 40 is irradiated to the light-transmitting layer 60. The adhesive material 70 is disposed along the edges of the light emitting panel 40 and the color conversion panel 50, and may be, for example, a sealing material.

[0316] Figure 5A is a plan view of one or more embodiments of a pixel arrangement of a display panel. Figure 5A , the display panel 1000 includes a display area 1000D displaying an image and a non-display area 1000P which is provided in a peripheral area of ​​the display area 1000D and provided with an adhesive material.

[0317] The display region 1000D includes a plurality of pixels PX arranged along rows (eg, x direction) and columns (eg, y direction), and each representative pixel PX may include a plurality of sub-pixels PX representing (eg, displaying) colors different from each other. 1 , PX 2 and PX 3 . With three sub-pixels PX 1 , PX2 and PX 3 The structure of one pixel is configured to illustrate one or more embodiments. One or more embodiments may also include additional sub-pixels (such as white sub-pixels) and may also include (e.g., at least one) sub-pixel that exhibits (e.g., displays) the same color. The plurality of pixels PX may be arranged, for example, in a Bayer matrix, a matrix sold under the trade name PenTile, a diamond matrix, etc., or a combination thereof.

[0318] Sub-pixel PX 1 , PX 2 and PX 3 The color of the three primary colors or the combination of the three primary colors may be represented (eg, displayed), for example, the color of red, green, blue or the combination thereof may be represented (eg, displayed). 1 The second sub-pixel PX may represent (eg, display) red. 2 The third sub-pixel PX may represent (eg, display) green. 3 The color blue may be represented (eg, displayed).

[0319] In the drawings, all sub-pixels are illustrated as having the same size, but these are not limited thereto, and at least one of the sub-pixels may be larger or smaller than the other sub-pixels. In the drawings, all sub-pixels are illustrated as having the same shape, but they are not limited thereto, and at least one of the sub-pixels may have a shape different from the other sub-pixels.

[0320] In a display panel or an electronic device according to one or more embodiments, the light emitting panel may include a substrate and a TFT (eg, a TFT including an oxide, etc.) disposed on the substrate. A light emitting device (eg, having a tandem structure, etc.) may be disposed on the TFT.

[0321] The light emitting device may include a light emitting layer (e.g., a blue light emitting layer, a green light emitting layer, or a combination thereof) between a first electrode and a second electrode facing each other. A charge generating layer may be disposed between each light emitting layer. Each of the first electrode and the second electrode may be patterned to correspond to a pixel using a plurality of electrode elements. The first electrode may be an anode or a cathode. The second electrode may be a cathode or an anode.

[0322] The light emitting device may include an organic LED, a nanorod LED, a mini LED, a micro LED, or a combination thereof.

[0323] FIG. 5B to FIG. 5Eare cross-sectional views showing examples of light emitting devices, respectively. In an embodiment, a "mini LED" may have a size of greater than or equal to about 100 microns, greater than or equal to about 150 microns, greater than or equal to about 200 microns and less than or equal to about 1 mm, less than or equal to about 0.5 mm, less than or equal to about 0.15 mm, or less than or equal to about 0.12 mm, but is not limited thereto. In an embodiment, a "mini LED" may have a size of less than about 100 microns, less than or equal to about 50 microns, or less than or equal to about 10 microns. The size of a micro LED may be greater than or equal to about 0.1 micron, greater than or equal to about 0.5 micron, greater than or equal to about 1 micron, or greater than or equal to about 5 microns, but is not limited thereto.

[0324] 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 optional auxiliary layers 184 and 185 located between the first electrode 181 and the light emitting layer 183 and between the second electrode 182 and the light emitting layer 183, respectively.

[0325] The first electrode 181 and the second electrode 182 may be arranged to face each other in the thickness direction (e.g., z direction), and one of the first electrode 181 and the second electrode 182 may be an anode and the other may be a cathode. The first electrode 181 may be a light-transmitting electrode, a semi-transparent electrode, or a reflective electrode, and the second electrode 182 may be a light-transmitting electrode or a semi-transparent electrode. The light-transmitting electrode or the semi-transparent electrode may be made of, for example, a thin single-layer or multi-layer metal film, the metal film including a conductive metal oxide (such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), fluorine-doped tin oxide (FTO), etc.); or silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), magnesium-silver (Mg-Ag), magnesium-aluminum (Mg-Al) or a combination thereof. The reflective electrode may include a metal, a metal nitride, or a combination thereof, such as silver (Ag), copper (Cu), aluminum (Al), gold (Au), titanium (Ti), chromium (Cr), nickel (Ni), an alloy thereof, a nitride thereof (e.g., Sn), or a combination thereof, but the embodiment is not limited thereto.

[0326] The light emitting layer 183 may include a first light emitting body that emits light having a blue emission spectrum, a second light emitting body that emits light having a green emission spectrum, or a combination thereof.

[0327] The blue emission spectrum may have a peak emission wavelength within a wavelength range of greater than or equal to about 400 nm to less than about 500 nm, and within this range, have a peak emission wavelength within a wavelength range 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.

[0328] The green emission spectrum may have a peak emission wavelength within a wavelength range of greater than or equal to about 500 nm to less than about 590 nm, and within this range, have a peak emission wavelength within a wavelength range 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.

[0329] For example, the light-emitting layer 183 or the light-emitting body included therein may include a phosphorescent material, a fluorescent material, or a combination thereof. For example, the light-emitting body may include an organic light-emitting body, wherein the organic light-emitting body may be a low molecular compound, a polymer compound, or a combination thereof. The specific types of phosphorescent materials and fluorescent materials are not particularly limited, but may be appropriately selected from known materials. For example, the light-emitting body may include an inorganic light-emitting body, and the inorganic light-emitting body may be an inorganic semiconductor, a quantum dot, a perovskite, or a combination thereof. The inorganic semiconductor may include a metal nitride, a metal oxide, or a combination thereof. The metal nitride, the metal oxide, or a combination thereof may include a group III metal (such as aluminum, gallium, indium, thallium, etc.), a group IV metal (such as silicon, germanium, tin, etc.), or a combination thereof. In one or more embodiments, the light-emitting body may include an inorganic light-emitting body, and the light-emitting device 180 may be a quantum dot light-emitting diode, a perovskite light-emitting diode, or a micro light-emitting diode (μLED). The material that can be used as an inorganic light-emitting body may be appropriately selected.

[0330] In one or more embodiments, the light emitting device 180 may further include auxiliary layers 184 and 185. The auxiliary layers 184 and 185 may be disposed between the first electrode 181 and the light emitting layer 183 and between the second electrode 182 and the light emitting layer 183, respectively. The auxiliary layers 184 and 185 may be charge auxiliary layers for controlling the injection and / or mobility of charges. The auxiliary layers 184 and 185 may include at least one or two layers, for example, a hole injection layer, a hole transport layer, an electron blocking layer, an electron injection layer, an electron transport layer, a hole blocking layer, or a combination thereof. If desired, at least one of the auxiliary layers 184 and 185 may be omitted. The auxiliary layer may be formed of a material appropriately selected from materials known for use in organic electroluminescent devices, and the like.

[0331] Set in sub-pixel PX 1 , PX 2and PX 3 The light emitting devices 180 in each of the sub-pixels PX may be the same as or different from each other. 1 , PX 2 and PX 3 The light emitting device 180 in each of the sub-pixels PX may emit light having the same or different emission spectra. 1 , PX 2 and PX 3 The light emitting device 180 in each of the sub-pixels PX may emit, for example, light having a blue light emission spectrum, light having a green light emission spectrum, or a combination thereof. 1 , PX 2 and PX 3 The light emitting devices 180 in each of the may be separated from each other by a pixel defining layer (not shown).

[0332] Reference Figure 5C The light-emitting device 180 may be a light-emitting device having a tandem structure, and includes a first electrode 181 and a second electrode 182 facing each other, a first light-emitting layer 183a and a second light-emitting layer 183b located between the first electrode 181 and the second electrode 182, and a charge generation layer 186 located between the first light-emitting layer 183a and the second light-emitting layer 183b, and may optionally include auxiliary layers 184 and 185 located between the first electrode 181 and the first light-emitting layer 183a and between the second electrode 182 and the second light-emitting layer 183b, respectively.

[0333] Details of the first electrode 181 , the second electrode 182 , and the auxiliary layers 184 and 185 are as described herein.

[0334] The first light-emitting layer 183a and the second light-emitting layer 183b may emit light having the same or different emission spectra. In one or more embodiments, the first light-emitting layer 183a or the second light-emitting layer 183b may emit light having a blue emission spectrum or light having a green emission spectrum, respectively. The charge generation layer 186 may inject charge into the first light-emitting layer 183a and / or the second light-emitting layer 183b, and may control the charge balance between the first light-emitting layer 183a and the second light-emitting layer 183b. The charge generation layer 186 may include, for example, an n-type layer and a p-type layer, and may include, for example, an electron transport material and / or a hole transport material including an n-type dopant and / or a p-type dopant. The charge generation layer 186 may include one or more layers.

[0335] Reference Figure 5D, a light-emitting device (having a tandem structure) may include a first electrode 181 and a second electrode 182 facing each other; a first light-emitting layer 183a, a second light-emitting layer 183b and a third light-emitting layer 183c located between the first electrode 181 and the second electrode 182; a first charge generation layer 186a located between the first light-emitting layer 183a and the second light-emitting layer 183b; a second charge generation layer 186b located between the second light-emitting layer 183b and the third light-emitting layer 183c; and optionally include auxiliary layers 184 and 185 located between the first electrode 181 and the first light-emitting layer 183a and between the second electrode 182 and the third light-emitting layer 183c, respectively.

[0336] Details of the first electrode 181 , the second electrode 182 , and the auxiliary layers 184 and 185 are as described herein.

[0337] The first light-emitting layer 183a, the second light-emitting layer 183b, and the third light-emitting layer 183c may emit light having the same or different emission spectra. The first light-emitting layer 183a, the second light-emitting layer 183b, and the third light-emitting layer 183c may emit blue light. In one or more embodiments, the first light-emitting layer 183a and the third light-emitting layer 183c may emit light of a blue emission spectrum, and the second light-emitting layer 183b may emit light of a green emission spectrum. In another embodiment, the first light-emitting layer 183a and the third light-emitting layer 183c may emit light of a green emission spectrum, and the second light-emitting layer 183b may emit light of a blue emission spectrum.

[0338] The first charge generation layer 186a can inject charges into the first light-emitting layer 183a and / or the second light-emitting layer 183b, and can control the charge balance between the first light-emitting layer 183a and the second light-emitting layer 183b. The second charge generation layer 186b can inject charges into the second light-emitting layer 183b and / or the third light-emitting layer 183c, and can control the charge balance between the second light-emitting layer 183b and the third light-emitting layer 183c. Each of the first charge generation layer 186a and the second charge generation layer 186b can include one layer or two or more layers.

[0339] Reference Figure 5E In one or more embodiments, the light emitting device 180 includes a light emitting layer 183 , a first electrode 181 , a second electrode 182 , and a plurality of nanostructures 187 arranged in the light emitting layer 183 .

[0340] One of the first electrode 181 and the second electrode 182 may be an anode, and the other may be a cathode. The first electrode 181 and the second electrode 182 may be electrodes patterned according to the arrangement direction of the plurality of nanostructures 187, and may include, for example, a conductive oxide such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), tin oxide (SnO), aluminum tin oxide (AlTO), fluorine-doped tin oxide (FTO), etc.; or silver (Ag), copper (Cu), aluminum (Al), gold (Au), titanium (Ti), chromium (Cr), nickel (Ni), alloys thereof, nitrides thereof (e.g., tin); or a combination thereof, but the embodiment is not limited thereto.

[0341] The light emitting layer 183 may include a plurality of nanostructures 187, and the sub-pixel PX 1 , PX 2 and PX 3 Each of the nanostructures 187 may include a plurality of nanostructures 187. In one or more embodiments, a plurality of nanostructures 187 may be arranged in one direction, but the embodiment is not limited thereto. The nanostructure 187 may be a compound-containing semiconductor configured to emit light of a predetermined wavelength, for example, by applying an electric current, and may be, for example, a linear nanostructure, such as a nanorod or a nanoneedle. The diameter or long diameter of the nanostructure 187 may be, for example, a few nanometers to a few hundred nanometers, and the aspect ratio of the nanostructure 187 may be greater than about 1, greater than or equal to about 1.5, greater than or equal to about 2.0, greater than or equal to about 3.0, greater than or equal to about 4.0, greater than or equal to about 4.5, greater than or equal to about 5.0, greater than about 1 to less than or equal to about 20, about 1.5 to about 20, about 2.0 to about 20, about 3.0 to about 20, about 4.0 to about 20, about 4.5 to about 20, or about 5.0 to about 20.

[0342] Each nanostructure 187 may include a p-type region 187p, an n-type region 187n, and a multi-quantum well region 187i, and may be configured to emit light from the multi-quantum well region 187i. The nanostructure 187 may include, for example, gallium nitride (GaN), indium gallium nitride (InGaN), aluminum gallium nitride (AlGaN), or a combination thereof, and may have, for example, a core-shell structure.

[0343] The plurality of nanostructures 187 may each emit light having the same or different emission spectra. In one or more embodiments, the nanostructures may emit light of a blue emission spectrum, for example, light of a blue emission spectrum having a peak emission wavelength in a wavelength range of greater than or equal to about 400 nm to less than 500 nm, about 410 nm to about 490 nm, or about 420 nm to about 480 nm.

[0344] Figure 6is a schematic cross-sectional view of a device (or display panel) according to one or more embodiments. Figure 6 , the light source (or light emitting panel) may include an organic light emitting diode that emits blue light (B) (and optionally green light (G)). The organic light emitting diode (OLED) may include: at least two pixel electrodes 90a, 90b and 90c formed on a substrate 100, pixel defining layers 150a and 150b formed between adjacent pixel electrodes 90a, 90b and 90c, organic light emitting layers 140a, 140b and 140c formed on each pixel electrode 90a, 90b and 90c, and a common electrode layer 130 formed on the organic light emitting layers 140a, 140b and 140c. A thin film transistor (TFT) and a substrate not shown may be disposed under the organic light emitting diode (OLED). The pixel area of ​​the OLED may be disposed corresponding to the first area, the second area, and the third area described herein. In one or more embodiments, as Figure 6 As shown in , the color conversion panel and the light emitting panel can be separated. In one or more embodiments, the color conversion panel can be directly stacked on the light emitting panel.

[0345] A stacked structure may be disposed on a light source, the stacked structure including a light-emitting nanostructure composite pattern 170 and a substrate 240, the light-emitting nanostructure composite pattern 170 may be, for example: a first region 11 or R including a light-emitting nanostructure emitting red light, a second region 21 or G including a light-emitting nanostructure emitting green light, and a third region 31 or B including or not including a light-emitting nanostructure (e.g., a light-emitting nanostructure emitting blue light). The blue light emitted from the light source enters the first region and the second region, and may emit red light and green light, respectively. The blue light emitted from the light source may pass through the third region. If desired, an element configured to block excitation light (a first filter 160 or an excitation light blocking layer) may be disposed between the light-emitting nanostructure composite layers R and G and the substrate. In one or more embodiments, the excitation light includes blue light and green light, and a green light blocking filter (not shown) may be added to the third region. The first filter or the excitation light blocking layer will be described in more detail herein.

[0346] Such a (display) device can be produced by separately producing the aforementioned stacked structure and (for example, emitting blue light) LED or OLED, and then combining the stacked structure and LED or OLED. The (display) device can be manufactured by directly forming a light-emitting nanostructure composite pattern on an LED or OLED.

[0347] In the color conversion panel or display device, the substrate may be a substrate including an insulating material. The substrate may include glass; polymers such as polyesters, polycarbonates, or polyacrylates such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.; polysiloxanes (e.g., PDMS, etc.); inorganic materials such as Al 2 O 3 , ZnO, etc.; or a combination thereof, but the embodiment is not limited thereto. The thickness of the substrate may be appropriately selected in consideration of the substrate material, but is not particularly limited. The substrate may be flexible. For light emitted from the 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%.

[0348] A wiring layer including a thin film transistor and the like may be formed on a substrate. The wiring layer may also include a gate line, a sustaining voltage line, a gate insulating film, a data line, a source electrode, a drain electrode, a semiconductor layer, a protective layer, and the like. The detailed structure of the wiring layer may vary according to one or more embodiments. The gate line and the sustaining voltage line may be electrically separated from each other, and the data line may be insulated from and cross the gate line and the sustaining voltage line. The gate electrode, the source electrode, and the drain electrode may form a control terminal, an input terminal, and an output terminal of the thin film transistor, respectively. The drain electrode may be electrically connected to a pixel electrode to be described herein.

[0349] The pixel electrode may be used as an electrode (e.g., an anode) of a display device. The pixel electrode may be formed of a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO). The pixel electrode may be formed of a light-shielding material such as gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), or titanium (Ti). The pixel electrode may have a double-layer structure in which a transparent conductive material and a light-shielding material are stacked in sequence.

[0350] Between two adjacent pixel electrodes, a pixel defining layer (PDL) may overlap an end portion of the pixel electrode to divide the pixel electrode into pixel units. The pixel defining layer is an insulating layer that may electrically block at least two pixel electrodes.

[0351] The 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. The organic light emitting layer to be described herein may be formed on the area defined by the opening.

[0352] The organic light-emitting layer may be defined by the aforementioned pixel electrode and pixel defining layer for each pixel region. In other words, one pixel region may be defined as a region in which one organic light-emitting unit layer is formed, and the organic light-emitting unit layer is in contact with one pixel electrode divided by the pixel defining layer. In the display device according to one or more embodiments, the organic light-emitting layer may be defined as a first pixel region, a second pixel region, and a third pixel region, and each pixel region may be spaced apart from each other by a predetermined distance by the pixel defining layer.

[0353] In one or more embodiments, the organic light-emitting layer may emit a third light, and the third light belongs to the visible light region or to the ultraviolet (UV) region. Each of the first pixel region to the third pixel region of the organic light-emitting layer may emit a third light. In one or more embodiments, the third light may be light with higher energy in the visible light region, for example, blue light (and optionally green light). In one or more 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 of forming the organic light-emitting layer can be simplified, and the display device can be easily applied to a large-scale / large-area process (for example, manufactured by the process). However, the organic light-emitting layer according to one or more embodiments is not necessarily limited thereto, but the organic light-emitting layer may be designed to emit at least two different lights, for example, at least two different colors of light.

[0354] The organic light emitting layer includes an organic light emitting unit layer in each pixel region, and each organic light emitting unit layer may further include an auxiliary layer (eg, a hole injection layer, a hole transport layer, an electron transport layer, etc.) in addition to the light emitting layer.

[0355] The common electrode may be used as a cathode of the display device. The common electrode may be formed of a transparent conductive material such as indium tin oxide (ITO) or indium zinc oxide (IZO). The common electrode may be formed on the organic light emitting layer and may be integrated therewith.

[0356] A planarization layer or a passivation layer (not shown) may be formed on the common electrode. The planarization layer may include an (eg, transparent) insulating material to ensure electrical insulation from the common electrode.

[0357] In one or more embodiments, 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 stacked structure and the lower substrate, and in the stacked structure, the photoluminescent layer (i.e., the light-emitting layer) may be disposed to face the liquid crystal layer. The display device may further include a polarizing plate located between the liquid crystal layer and the light-emitting layer. The light source may further include an LED and, if necessary, a light guide plate.

[0358] In one or more embodiments, a display device (eg, a liquid crystal display device) is illustrated with reference to the accompanying drawings. Fig. 7A is a schematic cross-sectional view showing a liquid crystal display device according to one or more embodiments. Fig. 7A , the display device of one or more embodiments includes a liquid crystal panel 200 , a polarizing plate 300 disposed under the liquid crystal panel 200 , and a backlight unit disposed under the polarizing plate 300 .

[0359] The liquid crystal panel 200 may include a lower substrate 210, a stacked structure, and a liquid crystal layer 220 disposed between the stacked structure and the lower substrate. The stacked structure may include a transparent substrate 240, a first filter layer 310, a photoluminescent layer 230 including a pattern of a semiconductor nanoparticle polymer composite, and a second optical filter layer 311.

[0360] The lower substrate 210, also referred to as an array substrate, may be a transparent insulating material substrate. The substrate may be as described herein. A wiring board 211 may be disposed on the upper surface of the lower substrate 210. The wiring board 211 may include a plurality of gate wirings (not shown) and data wirings (not shown) defining a pixel region, a thin film transistor disposed adjacent to the intersection region of the gate wiring and the data wiring, and a pixel electrode for each pixel region, but the embodiment is not limited thereto. The details of such a wiring board are not specifically limited.

[0361] The liquid crystal layer 220 may be disposed on the wiring board 211. The liquid crystal panel 200 may include an alignment layer 221 above and below the liquid crystal layer 220 to initially align the liquid crystal material included therein. Details of the liquid crystal layer and the alignment layer (e.g., liquid crystal material, alignment layer material, method of forming the liquid crystal layer, thickness of the liquid crystal layer, etc.) are not particularly limited.

[0362] The lower polarizing plate 300 may be disposed below the lower substrate. The material and structure of the polarizing plate 300 are not specifically limited. A backlight unit (e.g., emitting blue light) may be disposed below the polarizing plate 300. The upper optical element or the upper polarizing plate 300 may be disposed between the liquid crystal layer 220 and the transparent substrate 240, but is not limited thereto. For example, the upper polarizing plate may be disposed between the liquid crystal layer 220 and the photoluminescent layer 230. The polarizing plate may be any polarizer that can be used for a liquid crystal display device. The polarizing plate may be triacetyl cellulose (TAC) having 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 without a polarization function.

[0363] The backlight unit includes a light source 110. The light source may emit blue light or white light. The light source may include, but is not limited to, a blue LED, a white LED, a white OLED, or a combination thereof.

[0364] The backlight unit may further include a light guide plate 120. In one or more embodiments, the backlight unit may be edge-type. For example, the backlight unit may include a reflector (not shown), a light guide plate (not shown) disposed on the reflector and providing a planar light source to the liquid crystal panel 200, and / or at least one optical sheet (not shown) on the light guide plate, such as a diffuser, a prism sheet, etc., but the present disclosure is not limited thereto. The backlight unit may not include a light guide plate. In one or more embodiments, the backlight unit may be directly illuminated. For example, the backlight unit may have a reflector (not shown) and a plurality of fluorescent lamps arranged at regular intervals on the reflector, or may have an LED operating substrate, on which a plurality of light emitting diodes, a diffuser plate thereon, and optionally at least one optical sheet may be provided. The details of such a backlight unit (e.g., each component of a light emitting diode, a fluorescent lamp, a light guide plate, various optical sheets, and a reflector, etc.) are well known and are not specifically limited.

[0365] The black matrix 241 may be disposed below the transparent substrate 240 and have an opening, and hide the gate lines, data lines, and thin film transistors of the wiring board on the lower substrate. For example, the black matrix 241 may have a grid shape. The photoluminescent layer 230 is disposed in the opening of the black matrix 241 and has a nanoparticle-polymer composite pattern, which includes: 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 necessary, the photoluminescent layer may further include at least one fourth region. The fourth region may include quantum dots that emit light of a different color (e.g., cyan light, magenta light, and yellow light) than the light emitted from the first region to the third region.

[0366] In the photoluminescent layer 230 , a segment forming a pattern may be repeated corresponding to a pixel region formed on the lower substrate. A transparent common electrode 231 may be disposed on the photoluminescent layer 230 .

[0367] The third region B configured to emit / transmit blue light may be a transparent color filter that does not change the emission spectrum of the light source. In this case, the blue light emitted from the backlight unit may enter in a polarized state and may be emitted directly through the polarizing plate and the liquid crystal layer as is. If desired, the third region may include quantum dots that emit blue light.

[0368] As described herein, if necessary, the display device or light-emitting device according to one or more embodiments may further include an excitation light blocking layer or a first filter layer (hereinafter referred to as the first filter layer). The first filter layer may be disposed between the bottom surface of the first region R and the second region G and a substrate (e.g., an upper substrate 240), or disposed on the upper surface of the substrate. The first filter layer may be a sheet having an opening in a portion corresponding to a pixel region (third region) displaying blue, and thus may be formed in a portion corresponding to the first region and the second region. That is, as Figure 1 , Figure 6 and / or Fig. 7A As shown in , the first filter layer may be integrally formed at a position other than the position overlapping the third region, but is not limited thereto. Two or more first filter layers may be spaced apart from each other at positions overlapping the first region and the second region and optionally the third region. When the light source includes a green light emitting device, the green light blocking layer may be disposed on the third region.

[0369] The first filter layer may block light in a predetermined wavelength region, for example, in a visible light region, and may transmit light in other wavelength regions, for example, the first filter layer may block blue light (or green light) and may transmit light other than blue light (or green light). The first filter layer may transmit, for example, green light, red light, and / or yellow light as a mixed color thereof. The first filter layer may transmit blue light and block green light, and may be disposed on a blue light emitting pixel.

[0370] The first filter layer can substantially block the excitation light and transmit light in the desired wavelength region. The transmittance of the first filter layer to light in the desired wavelength range can be greater than or equal to about 70%, greater than or equal to about 80%, greater than or equal to about 90%, or even about 100%.

[0371] A first filter layer configured to selectively transmit red light may be disposed at a position overlapping the red light emission segment, and a first filter layer configured to selectively transmit green light may be disposed at a position overlapping the green light emission segment. The first filter layer may include: a first filter region, a second filter region, or a first filter region and a second filter region, wherein the first filter region blocks (e.g., absorbs) blue light and red light and selectively transmits 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 551 nm, less than or equal to about 560 nm, less than or equal to about 570 nm, less than or equal to about 580 nm, less than or equal to about 590 nm, less than or equal to about 591 nm, less than or equal to about 592 nm, less than or equal to about 593 nm, less than or equal to about 597 nm, less than or equal to about 598 nm, less than or equal to about 599 nm, less than or equal to about 600 nm, less than or equal to about 610 nm, less than or equal to about 611 nm, less than or equal to about 613 nm, less than or equal to about 614 nm, less than or equal to about 615 nm, less than or equal to about 620 nm, less than or equal to about 630 nm, less than or equal to about 640 nm, less than or equal to about 650 nm, less than or equal to about 661 nm, less than or equal to about 671 nm, less than or equal to about 680 nm, less than or equal to about 691 nm, less than or In one or more embodiments, the light source may emit a mixture of blue and green light, and the first filter layer may further include a third filter region that selectively transmits blue light and blocks green light.

[0372] The first filter region may be disposed at a position overlapping the green light emission segment. The second filter region may be disposed at a position overlapping the red light emission segment. The third filter region may be disposed at a position overlapping the blue light emission segment.

[0373] The first filter region, the second filter region and optionally the third filter region may be optically isolated.Such a first filter layer may help to improve the color purity of the display device.

[0374] The display device may further include a second filter layer (e.g., a recycling layer of red / green light or yellow light), which is disposed between the photoluminescent layer and the liquid crystal layer (e.g., between the photoluminescent layer and the upper polarizing plate), transmits at least a portion of the third light (excitation light), and reflects at least a portion of the first light and / or the second light. The first light may be red light, the second light may be green light, and the third light may be blue light. The second filter layer may transmit only the third light (B) in the blue light wavelength range having a wavelength range less than or equal to about 500 nm, and the light in the wavelength range greater than about 500 nm such as green light (G), yellow light, red light (R), etc. may not pass through the second filter layer and be reflected. The reflected green light and red light may pass through the first region and the second region to be emitted to the outside of the display device.

[0375] The second filter layer or the first filter layer may be formed as an integral layer having a relatively flat surface.

[0376] The first filter layer may include a polymer film including a dye and / or a pigment that absorbs light of a wavelength to be blocked. The second filter layer or the first filter layer may include a single layer having a low refractive index, and may be, for example, a transparent film having a refractive index of less than or equal to about 1.4:1, less than or equal to about 1.3, or less than or equal to about 1.2. The second filter layer or the first filter layer having a low refractive index may include, for example, porous silicon oxide, porous organic material, porous organic-inorganic composite, etc., or a combination thereof.

[0377] The first filter layer or the second filter layer may include a plurality of layers having different refractive indices. The first filter layer or the second filter layer may be formed by laminating two layers having different refractive indices. For example, the first filter layer and the second filter layer may be formed by alternately laminating a material having a high refractive index and a material having a low refractive index.

[0378] In one or more embodiments, an electronic device may include a light emitting device (eg, an electroluminescent device) including the nanoparticles described above. Figure 7B is a schematic cross-sectional view of a light emitting device (electroluminescent device) according to one or more embodiments. Figure 7B , the light-emitting device includes an anode 1 and a cathode 5 facing each other; a quantum dot light-emitting layer 3 disposed between the anode and the cathode and including a plurality of quantum dots; and a hole auxiliary layer 2 located between the anode and the quantum dot light-emitting layer. The hole auxiliary layer may 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.

[0379] Hereinafter, exemplary embodiments will be explained in more detail with reference to examples. However, embodiments of the present disclosure are not limited to these examples.

[0380] Example

[0381] Analytical methods

[0382] [1] Photoluminescence analysis

[0383] Photoluminescence (PL) spectra of the produced nanoparticles and composites including the nanoparticles were obtained using a Hitachi F-7000 spectrophotometer at an excitation wavelength of 450 nm.

[0384] [2]ICP analysis

[0385] Inductively coupled plasma atomic emission spectrometry (ICP-AES) was performed using a Shimadzu ICPS-8100.

[0386] [3] Blue light absorbance and photoconversion efficiency (CE) of the complex

[0387] The amount of incident light (B) having a wavelength of 450 nm is measured by using an integrating hemisphere of an absolute quantum efficiency measurement device (e.g., QE-2100, Otsuka Electronics Co., Ltd.) Subsequently, a QD-polymer composite, which may be referred to as a first composite, is placed in the integrating hemisphere, and incident light is irradiated to measure the amount of first light from the composite (A) and the amount of incident light transmitted through the composite (B'), respectively.

[0388] Using the measured amounts, incident light absorbance and light conversion efficiency were calculated according to the following equations.

[0389] Incident light absorbance (%) = [(B-B') / B] × 100%

[0390] Photoconversion efficiency (%) = [A / (B-B')] × 100%

[0391] Among them, in the equation,

[0392] A is the amount of first light emitted from the first composite,

[0393] B is the amount of incident light provided to the first composite, and

[0394] B' is the amount of incident light transmitted through the first composite

[0395] [4] Transmission electron microscopy (TEM) analysis and TEM-EDX (energy dispersive spectroscopy) analysis

[0396] Transmission electron microscopy analysis and EELS analysis of the produced nanoparticles were performed using a UT F30 Tecnai electron microscope.

[0397] Reference Example 1:

[0398] Silver acetate was dissolved in oleylamine to provide a solution containing 0.06 mole (M) of a silver precursor (hereinafter, silver precursor). Sulfur was dissolved in oleylamine to provide a 1 M solution containing a sulfur precursor (hereinafter, sulfur precursor). Indium chloride was dissolved in ethanol to provide a 1 M solution containing an indium precursor (hereinafter, indium precursor).

[0399] Gallium acetylacetonate, octadecene (ODE) and dodecanethiol are placed in a 100 milliliter (mL) reaction flask and heated at 120°C for 10 minutes under vacuum. After the flask is cooled to room temperature, nitrogen is added to the flask, and a silver precursor, a sulfur precursor and an indium precursor are added to the flask. The flask is heated at a reaction temperature of 210°C, and the reaction is carried out for 60 minutes. After the temperature of the flask is reduced to 180°C, trioctylphosphine (TOP) is added to the flask, and hexane and ethanol are subsequently added to the obtained mixture to promote precipitation. Precipitate (that is, the first semiconductor nanocrystal) is separated by centrifugation.

[0400] The molar ratios of the added indium precursor, gallium acetylacetonate and sulfur precursor were 1:2.3:4.8, respectively.

[0401] Gallium chloride was dissolved in toluene to provide a 4.5 M solution of a gallium-containing precursor (hereinafter, gallium precursor).

[0402] Dimethylthiourea (DMTU) and oleylamine are placed in a reaction flask and then vacuum treated at 120°C for 10 minutes. Nitrogen is added to the reaction flask and the flask is heated to 240°C. The first semiconductor nanocrystals obtained above, a gallium precursor and a silver compound (e.g., silver acetate) are added to the flask. Then, the reaction flask is heated to 280°C (second temperature) for about 40 minutes. The reaction solution is cooled to 180°C and trioctylphosphine is added to the solution, and the solution is cooled to room temperature. Hexane and ethanol are added to promote the precipitation of the first particles, and the first particles are separated and recovered by centrifugation. Then, the separated solid is dispersed in toluene.

[0403] The molar ratio of the gallium precursor to the sulfur precursor was 1:1.3. The amount of the silver compound was 3.5 mol% (molar percentage) compared to the gallium precursor.

[0404] The obtained semiconductor nanoparticles were subjected to ICP-AES analysis. The results are shown in Table 1. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis. The results are shown in Table 2.

[0405] Example 1

[0406] Zinc chloride was dissolved in trioctylphosphine (TOP) to provide a 0.5 M solution containing a zinc precursor (hereinafter, "zinc precursor").

[0407] Dimethylthiourea (DMTU) was dissolved in a mixed solvent of oleylamine and octadecene in a 100 mL flask at a concentration of 0.5 M, and the flask was vacuum treated at 120 ° C for 10 minutes. Nitrogen was added to the flask and the flask was heated to 210 ° C. A zinc precursor and the first particles prepared in Reference Example 1 were added to the flask and reacted for 40 minutes. The reaction solution was cooled to 180 ° C, and trioctylphosphine was added, and the reaction flask was cooled to room temperature. Hexane and ethanol were added thereto to promote the precipitation of semiconductor nanoparticles. The semiconductor nanoparticles were separated and recovered by centrifugation, and then the semiconductor nanoparticles were dispersed in toluene.

[0408] The molar ratio of the zinc precursor to the sulfur precursor used was 1:1.

[0409] The obtained semiconductor nanoparticles were subjected to ICP-AES analysis. The results are shown in Table 1. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis. The results are shown in Table 2.

[0410] The obtained nanoparticles were subjected to TEM-EDS mapping analysis and the results are shown in Fig. 8A and Figure 8B In. From Fig. 8A and Figure 8B TEM-EDS micrographs of the obtained particles confirmed that the obtained particles included silver, indium, gallium and zinc, that the indium was inside the particles and that the content of zinc near the surface of the particles was higher than that inside the particles.

[0411] Example 2

[0412] Semiconductor nanoparticles were prepared in the same manner as in Example 1, except that the amount of the zinc precursor was increased by 2 times (2X, double).

[0413] The obtained semiconductor nanoparticles were subjected to ICP-AES analysis. The results are shown in Table 1. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis. The results are shown in Table 2.

[0414] Example 3

[0415] Semiconductor nanoparticles were prepared in the same manner as in Example 1, except that the amount of the zinc precursor was increased by 3.5 times.

[0416] The obtained semiconductor nanoparticles were subjected to ICP-AES analysis. The results are shown in Table 1. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis. The results are shown in Table 2.

[0417] Comparative Example 1

[0418] Semiconductor nanoparticles were prepared in the same manner as in Example 2, except that the reaction temperature was 150°C.

[0419] The obtained semiconductor nanoparticles were subjected to ICP-AES analysis. The results are shown in Table 1. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis. The results are shown in Table 2.

[0420] Comparative Example 2

[0421] Semiconductor nanoparticles were prepared in the same manner as in Example 2, except that the reaction temperature was 180°C.

[0422] The obtained semiconductor nanoparticles were subjected to ICP-AES analysis. The results are shown in Table 1. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis. The results are shown in Table 2.

[0423] Comparative Example 3

[0424] Semiconductor nanoparticles were prepared in the same manner as in Example 2, except that the reaction temperature was 240°C.

[0425] The obtained semiconductor nanoparticles were subjected to ICP-AES analysis. The results are shown in Table 1. The obtained semiconductor nanoparticles were subjected to photoluminescence analysis. The results are shown in Table 2.

[0426] Experimental Example 1: Preparation of the composite and evaluation of its luminescent properties

[0427] The toluene solution of each of the prepared semiconductor nanoparticles in Examples 1, 2 and 3, Reference Example 1, Comparative Examples 1, 2 and 3 was mixed with a binder (a tetrapolymer of methacrylic acid, benzyl methacrylate, hydroxyethyl methacrylate and styrene, with an acid value of 130 mg KOH / g and a molecular weight of 8000 g / mol) solution (in PGMEA (propylene glycolmethyl ether acetate) at a concentration of 30 wt %) to obtain a semiconductor nanoparticle-binder dispersion.

[0428] To each semiconductor nanoparticle-binder dispersion, hexaacrylate having the following structure as a photopolymerizable monomer, ethylene glycol bis(3-mercaptopropionate) (hereinafter, 2T), an oxime-ester compound as an initiator, TiO 2 , and PGMEA, and are mixed together to provide a composition.

[0429]

[0430]

[0431] The prepared composition included 20 wt % of semiconductor nanoparticles based on the total solid weight of the composition.

[0432] Each composition was spin-coated on a glass substrate at 600 rpm for 5 seconds to obtain a film. The film thus obtained was pre-baked at 100° C. (PRB). The pre-baked film was irradiated with light (at a wavelength of 365 nm and an intensity of 4 J) and heated at 180° C. for 30 minutes (POB) to obtain a nanoparticle-polymer composite film (having a thickness of about 7 μm).

[0433] For each of the patterned films thus obtained, the light conversion efficiency (CE), absorbance, and process retention rate of the composite were measured, and the results are shown in Table 3.

[0434] Table 1

[0435] S:In Ag:In Ga:In Zn:In Relative molar value of Zn CBV Ga:Ag Example 1 11.1 2.67 3.78 3.33 0.31 1.07 1.42 Example 2 14.3 2.28 3.71 5.14 0.43 0.94 1.63 Example 3 14.3 1.14 3.14 10.3 0.66 1.19 2.75 Comparative Example 1 5.56 2.22 2.89 1.17 0.16 1.46 1.3 Comparative Example 2 8.33 2 2.83 3.58 0.38 1.24 1.42 Comparative Example 3 11.6 2.6 3.4 3.6 0.16 0.99 1.3 Reference Example 1 7.69 3.23 4.31 0 0 1.25 1.3

[0436] Relative molar value of Zn = Zn / (Ag+In+Ga+Zn)

[0437] CBV (charge balance value) = {[Ag] + 3([In] + [Ga]) + 2[Zn]} / 2[S]

[0438] where [Ag], [In], [Ga], [Zn], and [S] are the molar amounts of silver, indium, gallium, zinc, and sulfur in the nanoparticles, respectively.

[0439] Table 2

[0440] PWL(nm) FWHM(nm) Example 1 522 34 Example 2 532 33 Example 3 525 35 Comparative Example 1 528 33 Comparative Example 2 528 32 Comparative Example 3 527 34 Reference Example 1 519 37

[0441] PWL: Peak emission wavelength

[0442] FWHM: Full Width at Half Maximum

[0443] Table 3

[0444]

[0445] Thermal stability of the composite (%) = [photoconversion efficiency (CE) of the composite after POB process / CE of the composite after PRB process] × 100

[0446] It is confirmed from the results of Table 2 and Table 3 that the nanoparticles according to the examples may exhibit improved light emitting characteristics and stability compared to the comparative examples.

[0447] Experimental Example 2: Evaluation of the stability of the membrane in air

[0448] In the same manner as in Experimental Example 1, composites of semiconductor nanoparticles of Example 1, Example 2, Example 3 and Reference Example 1 were prepared, respectively, and the prepared films were placed in air at room temperature for 48 hours, and the initial luminous efficiency of the composite and the luminous efficiency after 48 hours were measured to measure the stability (relative luminous efficiency) for 48 hours. The measurement results are summarized in Table 4.

[0449] Table 4

[0450] Semiconductor nanoparticles in composites 48 hours stability Example 1 67％ Example 2 75％ Example 3 78％ Reference Example 1 50％

[0451] From the results of Table 4, it is confirmed that the semiconductor nanoparticles of Examples 1, 2, and 3 may exhibit significantly improved stability compared to the semiconductor nanoparticles of Reference Example 1 that does not include a ZnS semiconductor nanocrystal layer.

[0452] Experimental Example 3: Comparison of Emission Efficiency Excluding Trap Emission

[0453] For the composites containing the semiconductor nanoparticles of Example 1 and Comparative Example 3, respectively, the tail emission percentage in the wavelength range greater than the emission peak wavelength + 50 nm was measured. As a result, it was confirmed that the tail emission percentage of the composite containing the semiconductor nanoparticles of Comparative Example 3 was 1.3 times the tail emission percentage of the composite containing the semiconductor nanoparticles of Example 1. The above results show that the tail emission occupies a considerable part in the light conversion efficiency (CE, 19%) of the composite containing the semiconductor nanoparticles of Comparative Example 3.

[0454] While the present disclosure has been described in conjunction with what are presently considered to be practical embodiments, it should be understood that the present 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, wherein: The semiconductor nanoparticles are configured to emit green light, Wherein, the semiconductor nanoparticles have a relative molar value of zinc greater than or equal to 0.25 and less than or equal to 0.9 as defined in Equation 1: Equation 1 Relative molar value of zinc = [Zn] / ([Ag]+[In]+[Ga]+[Zn]) Wherein, in Equation 1, [Ag], [In], [Ga] and [Zn] are the molar amounts of silver, indium, gallium and zinc in the semiconductor nanoparticles, respectively, and Wherein, the molar ratio of gallium to indium is greater than 2.5:1 and less than 5.6:

1.

2. The semiconductor nanoparticle according to claim 1, wherein The semiconductor nanoparticles have a charge balance value greater than or equal to 0.91 and less than or equal to 1.2 as defined by Equation 2: Equation 2 Charge balance value = {[Ag] + 3([In] + [Ga]) + 2[Zn]} / 2[S] Wherein, in Equation 2, [Ag], [In], [Ga], [Zn] and [S] are the molar amounts of silver, indium, gallium, zinc and sulfur in the semiconductor nanoparticles, respectively.

3. The semiconductor nanoparticle according to claim 2, wherein The charge balance value is greater than or equal to 0.93 and less than or equal to 1.

17.

4. The semiconductor nanoparticle according to claim 1, wherein In the semiconductor nanoparticles, The relative molar value of zinc is greater than or equal to 0.28 and less than or equal to 0.66, and The molar ratio of gallium to indium is greater than or equal to 2.9:1 and less than or equal to 4.5:

1.

5. The semiconductor nanoparticle according to claim 1, wherein In the semiconductor nanoparticles, The molar ratio of zinc to indium is greater than or equal to 2.7:1 and less than or equal to 10.5:1, and The molar ratio of gallium to silver is greater than or equal to 1.1:1 and less than or equal to 3:

1.

6. The semiconductor nanoparticle according to claim 1, wherein In the semiconductor nanoparticles, The molar ratio of gallium to the sum of gallium, indium and silver is greater than or equal to 0.45:1 and less than or equal to 0.7:1, The molar ratio of zinc to sulfur is greater than or equal to 0.1:1 and less than or equal to 0.8:1, or The molar ratio of the sum of indium and gallium to sulfur is greater than or equal to 0.1:1 and less than or equal to 0.8:

1.

7. The semiconductor nanoparticle according to claim 1, wherein In the semiconductor nanoparticles, The molar ratio of silver to the sum of silver, indium and gallium is greater than or equal to 0.2:1 and less than or equal to 0.5:1, or The molar ratio of sulfur to the sum of silver, indium and gallium is greater than or equal to 1:1 and less than or equal to 2.5:

1.

8. The semiconductor nanoparticle according to claim 1, wherein The semiconductor nanoparticles include a first particle including silver, indium, gallium, and sulfur, and a semiconductor nanocrystal layer disposed on the first particle and including zinc and sulfur.

9. The semiconductor nanoparticle according to claim 1, wherein The peak emission wavelength of green light is greater than or equal to 500 nm and less than or equal to 580 nm, and The semiconductor nanoparticles have a quantum yield greater than or equal to 70% and less than or equal to 99%.

10. The semiconductor nanoparticle according to claim 1, wherein The semiconductor nanoparticles have a full width at half maximum of less than or equal to 40 nm.

11. The semiconductor nanoparticle according to claim 1, wherein The semiconductor nanoparticles exhibit a trap emission percentage of less than or equal to about 25% as defined by the formula: Trap emission percentage (%) = [trap emission area in emission spectrum / total area of ​​emission spectrum] × 100 The well emission area is the peak area corresponding to a wavelength greater than the peak emission wavelength plus 50 nm.

12. A method for producing the semiconductor nanoparticles according to claim 1, the method comprising: reacting a zinc precursor with a sulfur precursor in the presence of a first particle comprising indium, gallium, silver, and sulfur to form a semiconductor nanocrystal layer comprising zinc and sulfur on the first particle, The reaction includes adding the first particles and the zinc precursor to a reaction medium including a sulfur precursor and a first organic solvent, and the reaction temperature is greater than 180°C and less than 240°C.

13. The method according to claim 12, wherein: The sulfur precursor includes a thiol compound, an isothiocyanate compound, a thiourea compound, a thioacetamide compound, or a combination thereof, and Zinc precursors include zinc halides.

14. The method according to claim 12, wherein: The reaction temperature is greater than or equal to 205°C and less than or equal to 215°C, and The reaction time is greater than or equal to 30 minutes and less than or equal to 2 hours.

15. The method according to claim 12, wherein: The first organic solvent includes a mixture of a C5 to C40 aliphatic hydrocarbon solvent and a C5 to C40 amine solvent.

16. A composite comprising a matrix and the semiconductor nanoparticles according to claim 1 dispersed in the matrix.

17. The composite according to claim 16, wherein The composite exhibits a relative luminous efficiency greater than or equal to 60%, and the relative luminous efficiency is defined by the following equation: Relative luminous efficiency (%)=[luminous efficiency of the composite after 48 hours / initial luminous efficiency of the composite]×100.

18. A color conversion structure comprising: a color conversion layer comprising a color conversion region and optionally comprising partition walls defining the color conversion region, The color conversion region includes a first region corresponding to a first pixel, and the first region includes the semiconductor nanoparticles according to claim 1 .

19. An electronic device comprising the semiconductor nanoparticle according to claim 1.

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