Stable AIGS film

Abstract

Disclosed is a stable film comprising Ag, In, Ga, and S (AIGS) nanostructures, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof, and at least one ligand bound to the nanostructure. In some embodiments, the AIGS nanostructures have a photon conversion efficiency greater than 32% and a peak emission wavelength between 480 and 545 nm. In some embodiments, the nanostructures have an emission spectrum with a FWHM between 24 and 38 nm. In some embodiments, the nanostructures exhibit a photon conversion efficiency (PCE) of at least 30% after 24 hours under yellow light and air storage conditions.

Description

[Technical Field]

[0001] The present invention relates to the field of nanotechnology. More specifically, the present invention provides a thin, heavy metal-free, and stable Ag-In-Ga-S color conversion film that exhibits a high photon conversion efficiency (PCE) of over 30% at a peak emission wavelength of 480-545 nm when excited using a blue light source having a wavelength of about 450 nm, and after exposure to yellow light and air storage conditions. [Background technology]

[0002] Efficient color conversion is crucial in lighting and display applications. In display applications, blue light sources with a wavelength of approximately 450 nm are most commonly used as backlights, and many applications require materials that do not contain heavy metals such as cadmium and lead.

[0003] Improved efficiency leads to reduced wasted power and increased light emission. Color conversion thin films are characterized by their photon conversion efficiency (PCE), which is defined as the number of photons emitted divided by the number of photons from the light source. Green heavy metal-free QD color conversion thin films used in displays generally suffer from reduced performance because their absorption is limited by the excited blue light. Blue absorption is often inherently limited by the material system used, resulting in the need for much thicker films to absorb sufficient 450 nm light.

[0004] Thin films formed by the deposition of QD inks are typically cured by UV irradiation. In many cases, this is followed by heat treatment at 180°C for up to one hour in the presence of air. Due to instability throughout these processing steps, poor absorption and poor photoconversion combine to reduce the photon conversion efficiency of these films. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] There remains a need in the art for AIGS nanostructures that are useful for creating films with high band-edge emission (BE), narrow full width at half maximum (FWHM), high quantum yield (QY), and reduced red shift, and that have high photon conversion efficiency (PCE) at peak emission wavelengths between 480 and 545 nm (over 32% before exposure to yellow light and air storage conditions) using an excitation wavelength of approximately 450 nm. [Means for solving the problem]

[0006] The present invention provides a thin, heavy metal-free, and stable AIGS nanostructure color-converting film having a high photon conversion efficiency (PCE) of over 30% at a peak emission wavelength of 480-545 nm when excited using a blue light source having a wavelength of approximately 450 nm, and after intermediate exposure to air under yellow light conditions. This is achieved by using AIGS nanostructures in an ink formulation containing one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof, and one or more ligands. In some embodiments, all ink handling, subsequent film deposition, processing, and measurement are performed in an oxygen-free environment before exposure to blue or ultraviolet light. In some embodiments, the AIGS nanostructure has an FWHM of 28-38 nm. In other embodiments, the AIGS nanostructure has an FWHM of less than 32 nm. In some embodiments, a narrow FWHM is achieved by performing all aspects of handling the nanostructured ink, ink deposition, film processing, and measurement in an oxygen-free environment, and by adding at least one type of polyamino ligand to the AIGS nanostructure to create a film layer.

[0007] The thin film formed by the deposition of QD ink is typically cured by UV irradiation. In many cases, this is followed by heat treatment at 180°C for up to 1 hour in the presence of air. Due to instability during these processing steps, a combination of poor absorption and poor photoconversion has been found to reduce the photon conversion efficiency.

[0008] Disclosed herein are films containing AIGS nanostructures in an ink formulation comprising one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof, and at least one ligand, which achieve a PCE greater than 30% (>) after 24 hours of exposure to yellow light and air storage conditions. In some embodiments, films are provided that contain AIGS nanostructures and at least one ligand and exhibit a PCE greater than 32% at a peak emission wavelength of 480–545 nm when excited using a blue light source having a wavelength of about 450 nm. In some embodiments, a film comprising an AIGS nanostructure, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or a combination thereof, and at least one ligand exhibits a PCE of 30-39% after exposure to air, yellow light, and air storage conditions. In some embodiments, films comprising AIGS nanostructures, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof, and at least one ligand exhibit PCE of about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, or about 39% after exposure to yellow light conditions in air.

[0009] In some embodiments, the film is a thin (5-15 μm) color conversion film.

[0010] These films, once prepared, exhibit good (>95%) blue absorption but moderate luminescence properties. However, processing them in the absence of oxygen and / or light, and / or sealing them before exposure to UV or blue light, significantly improves their luminescence properties.

[0011] (a) To provide AIGS nanostructures, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof, and at least one ligand, (b) Mixing at least one type of organic resin with the AIGS nanostructure of (a), (c) Preparing a first film on a first barrier layer comprising a mixed AIGS nanostructure, at least one ligand, and at least one organic resin, (d) Curing the film by UV irradiation and / or firing, (e) Enclosing the first membrane between the first barrier layer and the second barrier layer, A method is provided for preparing an AIGS film, wherein the encapsulated film exhibits a photon conversion efficiency (PCE) of more than 30% at a peak emission wavelength of 480-545 nm when excited using a blue light source having a wavelength of approximately 450 nm, and after exposure to yellow light and air storage conditions.

[0012] Also, (f) Adding at least one oxygen-reactive material in the mixture of AIGS nanostructures and ligands of (a), adding at least one oxygen-reactive material in the admixture of (b), and / or forming a second film containing at least one oxygen-reactive material on the first film prepared in (c), and / or (g)(c) Formation of a sacrificial barrier layer on the first membrane prepared in (g)(c) to temporarily block oxygen and / or water, measurement of the membrane's PCE, and subsequent removal of the sacrificial barrier layer. A method further including this is provided.

[0013] Also, (a) encapsulating the film before heat treatment and / or measurement, (b) using an oxygen-reactive material as part of the formulation during heat treatment or photoexposure, and / or (c) temporarily blocking oxygen by using a sacrificial barrier layer A method is provided that includes.

[0014] In some embodiments, the nanostructure has an emission spectrum with a FWHM of less than 40 nm. In some embodiments, the nanostructure has an emission spectrum with a FWHM of 24 - 38 nm. In some embodiments, the nanostructure has an emission spectrum with a FWHM of 27 - 32 nm. In some embodiments, the nanostructure has an emission spectrum with a FWHM of 29 - 31 nm.

[0015] In some embodiments, the nanostructure has a QY of 80 - 99.9%. In some embodiments, the nanostructure has a QY of 85 - 95%. In some embodiments, the nanostructure has a QY of about 86 - 94%. In some embodiments, the nanostructure has an OD of 0.8 or greater 450 / mass (mL·mg -1 ·cm -1 ). OD is the optical density. In some embodiments, the nanostructure has an OD in the inclusive range of 0.8 - 2.5 450 / mass (mL·mg -1 ·cm -1 ). In some embodiments, the nanostructure has an OD in the inclusive range of 0.87 - 1.9 450 / mass (mL·mg -1 ·cm -1 ). In some embodiments, the average diameter of the nanostructure by transmission electron microscopy (TEM) is less than 10 nm. In some embodiments, the average diameter is about 5 nm.

[0016] In some embodiments, at least about 80% of the emission is band-edge emission. In some embodiments, at least about 90% of the emission is band-edge emission. In some embodiments, 92–98% of the emission is band-edge emission. In some embodiments, 93–96% of the emission is band-edge emission.

[0017] In some embodiments, at least one ligand is an amino ligand, a polyamino ligand, a ligand containing a mercapto group, or a ligand containing a silane group. It was unexpectedly discovered that the use of a polyamino ligand leads to AIGS-containing films having an FWHM of less than 32 nm.

[0018] In some embodiments, at least one polyamino ligand is a polyaminoalkane, polyaminocycloalkane, polyamino heterocyclic compound, polyamino-functionalized silicone, or polyamino-substituted ethylene glycol. In some embodiments, the polyamino ligand is C substituted with two or three amino groups. 2~20 Alkane or C 2~20 These are cycloalkanes that optionally contain one or two amino groups instead of carbon groups. In some embodiments, the polyamino ligand is 1,3-cyclohexanebis(methylamine), 2,2-dimethyl-1,3-propanediamine, or tris(2-aminoethyl)amine.

[0019] In some embodiments, the ligand is a compound of the following formula. [ka] During the ceremony, x is between 1 and 100. y is between 0 and 100, and R 2 is C 1~20 It is alkyl.

[0020] In some embodiments, x=19, y=3, and R 2 = -CH3

[0021] In some embodiments, the ligand is a compound of formula II. [ka] In the formula, R 3 and R 4 Independently, C 3~6 It is a secondary or tertiary alkyl group, R 5 C is a hydrogen atom or optionally substituted C 1~6 It is an alkyl group.

[0022] In some embodiments, R 3 and R 4 These are isopropyl, 2-butyl, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, t-butyl, 2-methyl-2-pentyl, or 3-methyl-3-pentyl.

[0023] In some embodiments, R 5 C 1~6 The optional substituents on the alkyl group are nitro, haloalkoxy, aryloxy, alkyloxy, alkylthio, sulfonamide, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, ureido, guanidino, carbamate, carboxy, alkoxycarbonyl, carboxyalkyl, or C(=O)R 7 (In the formula, R 7 (This is an alkoxy group that may be further substituted by one or more other alkoxy groups.)

[0024] In some embodiments, R 7 The following equation: CH p (CH2-O-) 4-p The formula has the following characteristics (where p is between 0 and 3):

[0025] In some embodiments, R 7 teeth, [ka] That is the case.

[0026] In some embodiments, R 7 teeth, [ka] And equation II is, [ka] That is the case.

[0027] In some embodiments, at least one ligand is pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl)bis[3-[3-(tert-butyl)-4-hydroxy-5-methylphenyl]propanoate].

[0028] In some embodiments, the polymers are (3-aminopropyl)trimethoxysilane; (3-mercaptopropyl)triethoxysilane; DL-α-lipoic acid; 3,6-dioxa-1,8-octanedithiol; 6-mercapto-1-hexanol; methoxypolyethylene glycolamine (mw approximately 500); poly(ethylene glycol)methyl ether thiol (mw approximately 800); diethylphenyl phosphonite; dibenzyl N,N-diisopropyl phosphoramidite; di-tert-butyl N,N-diisopropyl phosphoramidite; tris(2-carboxyethyl)phosphine hydrochloride; poly(ethylene glycol)methyl ether thiol (mw approximately 2000); methoxypolyethylene glycolamine (mw approximately 750); acrylamide; or polyethyleneimine. The mw of the polymer is obtained by mass spectrometry.

[0029] In some embodiments, at least one ligand is an aminopolyalkylene oxide (mW about 1000) and methoxypolyethylene glycolamine (mW about 500); an amino-polyalkylene oxide (mW about 1000) and 6-mercapto-1-hexanol; an aminopolyalkylene oxide (mW about 1000) and (3-mercaptopropyl)triethoxysilane; and a combination of 6-mercapto-1-hexanol and methoxypolyethylene glycolamine (mW about 500).

[0030] In some embodiments, one or more metal alkoxides are metal C 1~10 It is an alkoxide. In some embodiments, the metal is titanium, zirconium, hafnium, gallium, or barium.

[0031] In some embodiments, at least one or more metal alkoxides include zirconium(IV) tetramethoxide, zirconium(IV) tetraethoxide, zirconium(IV) tetra-n-propoxide, zirconium(IV) tetra-isopropoxide, zirconium(IV) tetra-n-butoxide, zirconium(IV) tetra-isobutoxide, zirconium(IV) tetra-n-pentoxide, zirconium(IV) tetra-isopentoxide, and zirconium(IV) tetra These are -n-hexoxide, zirconium(IV) tetra-isohexoxide, zirconium(IV) tetra-n-heptoxide, zirconium(IV) tetra-isoheptoxide, zirconium(IV) tetra-n-octoxide, zirconium(IV) tetra-n-isooctoxide, zirconium(IV) tetra-n-nonoxide, zirconium(IV) tetra-n-isononoxide, zirconium(IV) tetra-n-decyloxide, or zirconium(IV) tetra-n-isodecyloxide.

[0032] In some embodiments, at least one or more metal alkoxides are zirconium(IV) tetra-n-propoxide.

[0033] In some embodiments, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or a combination thereof, is zirconium(IV) tetra-n-propoxide, and the film further comprises pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl)bis[3-[3-(tert-butyl)-4-hydroxy-5-methylphenyl]propanoate].

[0034] Also, (a) AIGS nanostructures that exhibit a PCE of more than 30% after exposure to yellow light and air storage conditions, (b) at least one type of organic resin and Nanostructured compositions containing the above are also provided.

[0035] In some embodiments, at least one organic resin is cured.

[0036] Also, (a) To provide AIGS nanostructures, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof, and at least one ligand, (b) Mixing at least one type of organic resin with the nanostructure of (a), (c) Preparing a first film on a first barrier layer comprising a mixed AIGS nanostructure, at least one ligand, and at least one organic resin, (d) curing the film by UV irradiation and / or firing, (e) Enclosing the first membrane between the first barrier layer and the second barrier layer A method is provided for preparing the nanostructured composition described herein, wherein the encapsulated film exhibits a photon conversion efficiency (PCE) of more than 30% at a peak emission wavelength of 480-545 nm when excited using a blue light source having a wavelength of about 450 nm and after exposure to yellow light in air.

[0037] In some embodiments, this method is carried out before the encapsulated film is exposed to the emission spectrum of the AIGS nanostructure in air. In some embodiments, this method is carried out under an inert atmosphere.

[0038] In some embodiments, this method is (f) Addition of at least one oxygen-reactive material in a mixture of (a) AIGS nanostructures, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof, and ligands. (g) Addition of at least one oxygen-reactive material to the mixture of (b), and / or Formation of a second film containing at least one oxygen-reactive material on the first film prepared in (h)(c), and / or (i) Formation of a sacrificial barrier layer on the first membrane prepared in (c) to temporarily block oxygen and / or water, measurement of the membrane's PCE, and subsequent removal of the sacrificial barrier layer. It also includes.

[0039] In some embodiments, the two barrier layers eliminate oxygen and / or water.

[0040] In some embodiments, 92–98% of the emission is band-edge emission. In some embodiments, 93–96% of the emission is band-edge emission.

[0041] Also, (a) To provide a solvent comprising an AIGS nanostructure, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or a combination thereof, and at least one ligand, (b) Mixing the composition obtained in (a) with at least one second ligand. A method for preparing a composition including the above is also provided.

[0042] In some embodiments, the solvent in (a) comprises an organic resin. In some embodiments, the method includes inkjet printing the composition.

[0043] In some embodiments, the method further comprises preparing a film containing the composition obtained in (b). In some embodiments, the method further comprises curing the film. In some embodiments, the film is cured by heating. In some embodiments, the film is cured by exposure to electromagnetic radiation.

[0044] A device containing the above-mentioned film is also provided.

[0045] Also, (a) A first conductive layer and (b) A second conductive layer, (c) A film including an AIGS nanostructure layer between the first conductive layer and the second conductive layer A nanostructured molded article is also provided, which includes an AIGS nanostructure having a PCE of more than 30% after the nanostructured layer is exposed to yellow light and air storage conditions.

[0046] Also Backplane and A display panel positioned on a backplane, A film containing AIGS nanostructures having a PCE of more than 30% after exposure to yellow light and air storage conditions, and an AIGS nanostructure layer placed on a display panel. A color converter including this is also provided.

[0047] In some embodiments, the nanostructure layer includes a patterned nanostructure layer. In some embodiments, the backplane includes an LED, LCD, OLED, or microLED.

[0048] Further features and advantages of the present invention, as well as the structure and operation of various embodiments of the present invention, will be described in detail below with reference to the accompanying drawings. It should be noted that the present invention is not limited to the specific embodiments described herein. Such embodiments are presented herein for illustrative purposes only. Additional embodiments will be apparent to those skilled in the art based on the teachings contained herein.

[0049] The accompanying drawings incorporated herein and constituting part of this specification illustrate this embodiment and, together with the description herein, illustrate the principles of this embodiment and further assist those skilled in the art in the manufacture and use of this embodiment. [Brief explanation of the drawing]

[0050] [Figure 1] These are photographs of the first and third membranes, which did not contain polyamino ligands and showed elongation wrinkles (from left to right). The second and fourth membranes, which contained polyamino ligands, did not show wrinkles. [Figure 2] These are TEM images showing the AIGS nanostructure before ion exchange treatment (Figure 2A), after one ion exchange treatment (Figure 2B), and after two ion exchange treatments (Figure 2C). [Figure 3]These are schematic diagrams of the unencapsulated (Figure 3A) and encapsulated (Figure 3B) membranes. [Figure 4] This is a scatter plot showing the QY% for various ligand mixtures. [Figure 5] This is a scatter plot showing ligand combinations that provide an improved QY% (good combinations) and combinations that provide a reduced QY% (bad combinations). [Figure 6] This graph shows the QY% for various ligand combinations before ligand exchange (NG), after ligand exchange (LE), and after a 30-minute thermal test. [Figure 7] This graph shows the QY% for various ligand combinations at various ligand ratios. [Figure 8] These are two scatter graphs showing the PCE of AIGS membranes after normal PCE measurement and after PCE measurement following encapsulation. [Figure 9] These are two scatter graphs showing the PCE of AIGS films fired at 180°C, one without mounting before PCE measurement (left graph) and the other with mounting (right graph). [Figure 10] This is a line graph showing the EQE% versus blue light absorbance of the thin film of the AIGS ink formulation after replacement of the auxiliary ligand. [Figure 11] This line graph shows the EQE% over time of thin films of AIGS ink formulations containing various auxiliary ligands when kept in the dark. [Figure 12] This line graph shows the time-dependent EQE% of thin films of AIGS ink formulations containing various auxiliary ligands when exposed to yellow light conditions. [Figure 13] This line graph shows the EQE% over time of thin films of AIGS ink formulations containing various auxiliary ligands and additives when exposed to yellow light conditions. [Figure 14] This is a line graph showing the EQE% versus blue light absorbance of thin films of AIGS ink formulations containing auxiliary ligand-1; auxiliary ligand-1 and zirconium propoxide (S2); auxiliary ligand-1, S2 and GaCl3 (S3); and S2 and S3. [Figure 15]This bar graph shows the EQE of AIGS films containing auxiliary ligand-1, auxiliary ligand-1 and S2, auxiliary ligand-1, S2 and S3, and S2 and S3 after calcination under nitrogen. [Figure 16] This is a line graph showing the time-dependent EQE% of cured AIGS films containing auxiliary ligand-1, auxiliary ligand-1 and S2, auxiliary ligand-1, S2 and S3, and S2 and S3 when exposed to yellow light conditions. [Figure 17] This is a line graph showing the EQE% versus blue light absorbance of AIGS films containing 1% S3, 3% S3, and 6% S3. [Modes for carrying out the invention]

[0051] The features and advantages of the present invention will become more apparent from the detailed description below, when considered in conjunction with the drawings, in which similar reference numerals identify corresponding elements throughout. In the drawings, similar reference numerals generally indicate identical, functionally similar, and / or structurally similar elements. The drawing in which an element first appears is indicated by the leftmost digit of the corresponding reference numeral. Unless otherwise indicated, the drawings provided through this disclosure should not be construed as full-scale drawings.

[0052] definition Unless otherwise defined, all technical and scientific terms used herein have the same meaning as they would be generally understood by an ordinary person skilled in the art to which the present invention relates. The following definitions supplement the definitions in the art and relate to this application and do not belong to any related or unrelated cases, e.g., any patent or application in general ownership. Any methods and materials similar or equivalent to those described herein may be used in carrying out the testing of the present invention, but preferred materials and methods are described herein. Thus, the terms used herein are for the purpose of describing specific embodiments only and are not intended to limit them.

[0053] As used herein and in the appended claims, the singular forms "a," "an," and "the" include multiple references unless the context clearly indicates otherwise. Thus, for example, a reference to "a nanostructure" includes multiple such nanostructures, etc.

[0054] As used herein, the term "approximately" indicates that the value of a given quantity varies by ±10% of that value. For example, "approximately 100 nm" encompasses a size range from 90 nm to 110 nm.

[0055] A "nanostructure" is a structure having at least one region or characteristic dimension having a dimension of less than approximately 500 nm. In some embodiments, the nanostructure has dimensions of less than approximately 200 nm, less than approximately 100 nm, less than approximately 50 nm, less than approximately 20 nm, or less than approximately 10 nm. Typically, the region or characteristic dimension is along the smallest axis of the structure. Examples of such structures include nanowires, nanorods, nanotubes, branched nanostructures, nanotetrapods, tripods, bipods, nanocrystals, nanodots, quantum dots, and nanoparticles. The nanostructure can be, for example, substantially crystalline, substantially monocrystalline, polycrystalline, amorphous, or a combination thereof. In some embodiments, each of the three dimensions of the nanostructure has dimensions of less than approximately 500 nm, less than approximately 200 nm, less than approximately 100 nm, less than approximately 50 nm, less than approximately 20 nm, or less than approximately 10 nm.

[0056] When used in relation to nanostructures, the term “heterostructure” means a nanostructure characterized by at least two different and / or distinguishable material types. Typically, one region of the nanostructure contains a first material type, and a second region of the nanostructure contains a second material type. In certain embodiments, the nanostructure comprises a core of the first material and a shell of at least one of the second (or third, etc.) materials, where the different material types are distributed radially, for example, along the long axis of a nanowire, the long axis of an arm of a branched nanowire, or the center of a nanocrystal. The shell may, but does not have to, completely cover an adjacent material in order to be considered a shell, or in relation to the nanostructure, to be considered a heterostructure. For example, a nanocrystal characterized by a core of one material being covered by small islands of the second material is a heterostructure. In other embodiments, the different material types are distributed at different locations within the nanostructure, for example, along the main (long) axis of a nanowire, or along the long axis of an arm of a branched nanowire. Different regions within the heterostructure may contain entirely different materials, or they may contain different dopants or base materials (e.g., silicon) with different concentrations of the same dopant.

[0057] As used herein, the “diameter” of a nanostructure refers to the diameter of a cross-section perpendicular to a first axis of the nanostructure, where the first axis has the greatest difference in length relative to the second and third axes (the two axes whose lengths are nearly equal to each other). The first axis does not necessarily have to be the longest axis of the nanostructure; for example, in a disk-shaped nanostructure, the cross-section is substantially circular perpendicular to the shortest longitudinal axis of the disk. If the cross-section is not circular, the diameter is the average of the long and short axes of that cross-section. In the case of elongated nanostructures such as nanowires or high aspect ratio nanostructures, the diameter is measured across a cross-section perpendicular to the longest axis of the nanowire. In the case of spherical nanostructures, the diameter is measured from one side to the other passing through the center of the sphere.

[0058] When used in relation to nanostructures, the terms “crystalline” or “substantially crystalline” refer to the fact that the nanostructure typically exhibits long-range order across one or more dimensions of the structure. Since the order of a single crystal cannot extend beyond the crystal boundary, it will be understood by those skilled in the art that the term “long-range order” depends on the absolute size of a particular nanostructure. In this case, “long-range ordering” means substantial ordering across at least the majority of the dimensions of the nanostructure. In some cases, the nanostructure may have an oxide or other coating, or it may consist of a core and at least one type of shell. In such cases, it will be understood that the oxide, shell, or other coating may, but does not have to, exhibit such order (for example, it can be amorphous, polycrystalline, or other). In such cases, the terms “crystalline,” “substantially crystalline,” “substantially monocrystalline,” or “monocrystalline” refer to the central core of the nanostructure (excluding the coating layer or shell). As used herein, the terms “crystalline” or “substantially crystalline” are intended to encompass structures that include various defects, stacking faults, atomic substitutions, etc., insofar as the structure exhibits substantial long-range order (e.g., order over at least about 80% of the length of at least one axis of the nanostructure or its core). In addition, it will be understood that interfaces between the core and the outside of the nanostructure, interfaces between the core and adjacent shells, or interfaces between a shell and a second adjacent shell may include amorphous regions and may be amorphous. This does not prevent the nanostructure from being crystalline or substantially crystalline as defined herein.

[0059] When used in reference to nanostructures, the term "single crystal" indicates that the nanostructure is substantially crystalline and substantially contains a single crystal. When used in reference to nanostructure heterostructures comprising a core and one or more types of shells, "single crystal" indicates that the core is substantially crystalline and substantially contains a single crystal.

[0060] A "nanocrystal" is a nanostructure that is substantially a single crystal. Therefore, a nanocrystal is a structure having at least one region or characteristic dimension having a dimension of less than approximately 500 nm. In some embodiments, nanocrystals have dimensions of less than approximately 200 nm, less than approximately 100 nm, less than approximately 50 nm, less than approximately 20 nm, or less than approximately 10 nm. The term "nanocrystal" is intended to encompass substantially single-crystal nanostructures containing various defects, stacking faults, atomic substitutions, etc., as well as substantially single-crystal nanostructures that do not contain such defects, defects, or substitutions. In the case of a nanocrystalline heterostructure containing a core and one or more types of shells, the core of the nanocrystal is typically substantially a single crystal, but the shells do not necessarily have to be. In some embodiments, each of the three dimensions of the nanocrystal has dimensions of less than approximately 500 nm, less than approximately 200 nm, less than approximately 100 nm, less than approximately 50 nm, less than approximately 20 nm, or less than approximately 10 nm.

[0061] The term "quantum dot" (or "dot") refers to a nanocrystal exhibiting quantum confinement or exciton confinement. Quantum dots can be substantially homogeneous in material properties, or heterogeneous in certain embodiments, and may include, for example, a core and at least one shell. The optical properties of quantum dots may be influenced by their particle size, chemical composition, and / or surface composition, and can be measured by appropriate optical tests available in the art. Since the nanocrystal size can be adjusted, for example, in the range of about 1 nm to about 15 nm, light emission across the entire optical spectrum is possible, providing a wide variety of color rendering.

[0062] The term "oxygen-free ligand" means a coordination molecule that does not contain an oxygen atom and can coordinate to or react with metal ions as used herein.

[0063] A "ligand" is a molecule that can interact (weakly or strongly) with one or more faces of a nanostructure, for example, through covalent bonds, ionic bonds, van der Waals bonds, or other molecular interactions.

[0064] The "photoluminescence quantum yield" (QY) is, for example, the ratio of photons emitted to photons absorbed by a nanostructure or a collection of nanostructures. As is known in the art, the quantum yield is usually determined by the absolute change in the number of photons when a sample is irradiated in an integrating sphere, or by a comparative method using a well-characterized standard sample for which the quantum yield value is known.

[0065] The "peak emission wavelength" (PWL) is the wavelength at which the radiant emission spectrum of a light source reaches its maximum.

[0066] As used herein, the term "full width at half-maximum" (FWHM) is a measure of the size distribution of a nanostructure. The emission spectrum of a nanostructure generally has the shape of a Gaussian curve. The width of the Gaussian curve is defined as FWHM and serves as an indicator of the particle size distribution. A smaller FWHM corresponds to a narrower nanocrystalline size distribution of the nanostructure. FWHM also depends on the maximum emission wavelength.

[0067] Band-edge emission, compared to defect emission, has a smaller offset from the absorption onset energy and is centered at higher energies (lower wavelengths). Furthermore, band-edge emission has a narrower wavelength distribution compared to defect emission. Both band-edge emission and defect emission follow a normal (nearly Gaussian) wavelength distribution.

[0068] Optical density (OD) is a commonly used method for quantifying the concentration of solutes or nanoparticles. According to the Beer-Lambert law, the absorbance (also called "extinction") of a particular sample is proportional to the concentration of the solute that absorbs light of a particular wavelength.

[0069] Optical density is the light attenuation per centimeter of a material, measured using a standard spectrometer, and is usually specified by the optical path length per centimeter. Nanostructured solutions are often measured by optical density rather than mass or molar concentration because it is directly proportional to the concentration and is a more convenient way to represent the amount of light absorption occurring in the nanostructured solution at the desired wavelength. A nanostructured solution with an OD of 100 is 100 times more concentrated (has 100 times more particles per mL) than a product with an OD of 1.

[0070] Optical density can be measured at any wavelength of interest, such as the wavelength selected to excite the fluorescent nanostructure. Optical density is a measure of the intensity lost when light passes through a nanostructure solution at a specific wavelength, and is given by the following equation: OD=log 10 * (I OUT / I IN ) It is calculated using here I OUT = The intensity of radiation incident on the cell, and I IN = This is the intensity of radiation passing through the cell.

[0071] The optical density of nanostructured solutions can be measured using a UV-VIS spectrometer. Therefore, by using a UV-VIS spectrometer, it is possible to calculate the optical density to determine the amount of nanostructure present in the sample.

[0072] "Yellow light and air storage conditions" is intended to mean a film irradiated in air using a white LED light covered with a blue light blocking filter. The illuminance and color coordinates for the yellow storage conditions are measured using a Konica-Minolta CL-200A chromatometer as 140 lux, CIEx=0.52, and CIEy=0.45.

[0073] Unless otherwise specified, the scope described herein is inclusive.

[0074] Various additional terms are defined or otherwise characterized herein.

[0075] AIGS Nanostructure Nanostructures comprising Ag, In, Ga, and S (AIGS) are provided, having a peak emission wavelength (PWL) between 480 and 545 nm. In some embodiments, at least about 80% of the emission is band-edge emission. The percentage of band-edge emission is calculated by fitting the Gaussian peaks (typically two or more) of the nanostructure emission spectrum and comparing the area of ​​the peaks with energy close to the nanostructure band gap (which represents band-edge emission) with the sum of all peak areas (band-edge + defect emission).

[0076] In one embodiment, the nanostructure has an FWHM emission spectrum of less than 40 nm. In another embodiment, the nanostructure has an FWHM of 36-38 nm. In some embodiments, the nanostructure has an emission spectrum of 27-32 nm. In some embodiments, the nanostructure has an emission spectrum with an FWHM of 29-31 nm.

[0077] In another embodiment, the nanostructure has about 80% to 99.9% QY. In another embodiment, the nanostructure has 85% to 95% QY. In another embodiment, the nanostructure has about 86% to about 94% QY. In some embodiments, at least 80% of the emission is band-edge emission. In other embodiments, at least 90% of the emission is band-edge emission. In other embodiments, at least 95% of the emission is band-edge emission. In some embodiments, 92% to 98% of the emission is band-edge emission. In some embodiments, 93% to 96% of the emission is band-edge emission.

[0078] AIGS nanostructures offer high blue light absorption. The predicted value of blue light absorption efficiency is the optical density (OD) at 450 nm per unit mass. 450The OD (dry mass) is calculated by measuring the optical density of the nanostructure solution in a cuvette with a path length of 1 cm and dividing it by the dry mass per mL (mg / mL) of the same solution after removing all volatile substances under vacuum (<200 mTorr). In one embodiment, the nanostructures provided herein have an OD of at least 0.8 450 / mass(mL·mg -1 ·cm -1 ) has. In another embodiment, the nanostructure has an OD of 0.8 to 2.5 450 / mass(mL·mg -1 ·cm -1 ) has. In another embodiment, the nanostructure has an OD of 0.87 to 1.9 450 / mass(mL·mg -1 ·cm -1 ) has.

[0079] In one embodiment, the nanostructure is treated with gallium ions so that ion exchange of gallium to indium occurs through the AIGS nanostructure. In another embodiment, the nanostructure has Ag, In, Ga, and S in its core and is treated by ion exchange with gallium ions and S. In yet another embodiment, the nanostructure has Ag, In, Ga, and S in its core and is treated by ion exchange with silver ions, gallium ions, and S. In some embodiments, the ion exchange treatment leads to a gradient of gallium, silver, and / or sulfur through the nanostructure.

[0080] In one embodiment, the average diameter of the nanostructure is less than 10 nm, as measured by TEM. In another embodiment, the average diameter is approximately 5 nm.

[0081] AIGS nanostructures prepared using GaX3 (X=F, Cl, or Br) precursors and oxygen-free ligands Literature reports on the preparation of AIGS have not attempted to exclude oxygen-containing ligands. In gallium coating of AIGS, oxygen-containing ligands are often used to stabilize the Ga precursor. Generally, gallium(III) acetylacetate is used as a precursor that can be easily handled in air, but Ga(III) chloride is susceptible to moisture and requires careful handling. For example, Kameyama et al., ACS Appl. Matera. Interfaces 10:42844-42855 (2018) used gallium(III) acetylacetate as a precursor for core and core / shell structures. Because gallium has a high affinity for oxygen and oxygen-containing ligands, using gallium precursors that have not been prepared under oxygen-free conditions can lead to undesirable side reactions, such as gallium oxide, when producing nanostructures with a significant gallium content using Ga and S precursors. These side reactions can lead to defects in the nanostructure and low quantum yield.

[0082] In some embodiments, AIGS nanostructures are prepared using oxygen-free GaX3 (X=F, Cl, or Br) as a precursor in the preparation of AIGS cores. In some embodiments, AIGS nanostructures are prepared using GaX3 (X=F, Cl, or Br) and an oxygen-free ligand as a precursor in the preparation of Ga-enriched AIGS nanostructures. In some embodiments, AIGS nanostructures are prepared using GaX3 (X=F, Cl, or Br) and an oxygen-free ligand as a precursor in the preparation of AIGS cores. In some embodiments, AIGS nanostructures are prepared using GaX3 (X=F, Cl, or Br) and an oxygen-free ligand as a precursor in the preparation of AIGS cores and in the ion exchange treatment of AIGS cores.

[0083] The present invention provides nanostructures comprising Ag, In, Ga, and S, having a peak emission wavelength (PWL) between 480 and 545 nm, and prepared using a GaX3 (X=F, Cl, or Br) precursor and an oxygen-free ligand.

[0084] In some embodiments, nanostructures prepared using a GaX3 (X=F, Cl, or Br) precursor and an oxygen-free ligand exhibit an FWHM emission spectrum of 35 nm or less. In some embodiments, nanostructures prepared using a GaX3 (X=F, Cl, or Br) precursor and an oxygen-free ligand exhibit an FWHM of 30–38 nm. In some embodiments, nanostructures prepared using a GaX3 (X=F, Cl, or Br) precursor and an oxygen-free ligand have at least 75% QY. In some embodiments, nanostructures prepared using a GaX3 (X=F, Cl, or Br) precursor and an oxygen-free ligand have 75–90% QY. In some embodiments, nanostructures prepared using a GaX3 (X=F, Cl, or Br) precursor and an oxygen-free ligand have about 80% QY.

[0085] The AIGS nanostructures prepared herein provide high blue light absorption. In some embodiments, the nanostructures have an OD of at least 0.8 450 / mass(mL·mg -1 ·cm -1 ) has. In some embodiments, the nanostructure has an OD of 0.8 to 2.5 450 / mass(mL·mg -1 ·cm -1 ) has. In another embodiment, the nanostructure has an OD of 0.87 to 1.9 450 / mass(mL·mg -1 ·cm -1 ) has.

[0086] In some embodiments, the nanostructure is treated with gallium ions so that ion exchange of gallium to indium occurs through the AIGS nanostructure. In some embodiments, the nanostructure contains Ag, In, Ga, and S in a core with a gallium gradient between the surface and the center of the nanostructure. In some embodiments, the nanostructure is an AIGS core treated with AIGS, prepared using a GaX3 (X=F, Cl, or Br) precursor and an oxygen-free ligand in the core. In some embodiments, the nanostructure is an AIGS nanostructure prepared using a GaX3 (X=F, Cl, or Br) precursor and an oxygen-free ligand. In some embodiments, the AIGS nanostructure is prepared by reacting a pre-formed In-Ga reagent with an Ag2S nanostructure to obtain an AIGS nanostructure, which is then reacted with an oxygen-free Ga salt to exchange ions with gallium, thereby forming the AIGS nanostructure.

[0087] AIGS Nanostructure Manufacturing Method A method for producing AIGS nanostructures, (a) Prepare a mixture containing an AIGS core, a sulfur source, and a ligand, (b) The mixture obtained in (a) is added to a mixture of gallium carboxylate and ligand at a temperature of 180-300°C to obtain an ion-exchange nanostructure having a gallium gradient from the surface to the center of the nanostructure. (c) Isolating nanostructures and A method including this is provided.

[0088] In some embodiments, the nanostructure has a PWL of 480–545 nm, and at least about 60% of the emission is band-edge emission.

[0089] Furthermore, a method for producing AIGS nanostructures, (a) Reacting Ga(acetylacetonate)3, InCl3, and a ligand in a solvent at a temperature sufficient to obtain an In-Ga reagent in an optional manner, (b) Reacting the InGa reagent with the Ag2S nanostructure and the AIGS nanostructure at a temperature sufficient to produce them, (c) Reacting the AIGS nanostructure with an oxygen-free gallium salt in a solvent containing ligands at a temperature sufficient to obtain an ion-exchange nanostructure having a gallium gradient from the surface to the center of the nanostructure. We also provide methods that include this.

[0090] In some embodiments, the nanostructure has a PWL of 480–545 nm, and at least about 60% of the emission is band-edge emission.

[0091] In some embodiments, the ligand is an alkylamine. In some embodiments, the alkylamine ligand is an oleylamine. In some embodiments, the ligand is used in excess and acts as a solvent, and the cited solvent is not present in the reaction. In some embodiments, the solvent is present in the reaction. In some embodiments, the solvent is a high-boiling point solvent. In some embodiments, the solvent is octadecene, squalane, dibenzyl ether, or xylene. In some embodiments, the sufficient temperature in (a) is 100–280°C, in (b) is 150–260°C, and in (c) is 170–280°C. In some embodiments, the sufficient temperature in (a) is about 210°C, in (b) is about 210°C, and in (c) is about 240°C.

[0092] In some embodiments, at least 80% of the emission is band-edge emission. In other embodiments, at least 90% of the emission is band-edge emission. In other embodiments, at least 95% of the emission is band-edge emission. In some embodiments, 92–98% of the emission is band-edge emission. In some embodiments, 93–96% of the emission is band-edge emission.

[0093] Examples of ligands are disclosed in U.S. Patent Nos. 7,572,395, 8,143,703, 8,425,803, 8,563,133, 8,916,064, 9,005,480, 9,139,770, and 9,169,435, as well as U.S. Patent Application Publication No. 2008 / 0118755. In one embodiment, the ligand is an alkylamine. In some embodiments, the ligand is an alkylamine selected from the group consisting of dodecylamine, oleylamine, hexadecylamine, dioctylamine, and octadecylamine.

[0094] In some embodiments, the sulfur source of (a) includes trioctylphosphine sulfide, elemental sulfur, octanthiol, dodecanethiol, octadecanethiol, tributylphosphine sulfide, cyclohexyl isothiocyanate, α-toluenethiol, ethylene trithiocarbonate, allyl mercaptan, bis(trimethylsilyl) sulfide, trioctylphosphine sulfide, or a combination thereof. In some embodiments, the sulfur source of (a) is derived from S8.

[0095] In one embodiment, the sulfur source is derived from S8.

[0096] In one embodiment, the temperatures in (a) and (b) are approximately 270°C.

[0097] In one embodiment, the mixture of (b) further comprises a solvent. In some embodiments, the solvent is trioctylphosphine, dibenzyl ether, or squalane.

[0098] In some embodiments, gallium carboxylate is C 2~24 It is gallium carboxylate. 2~24Examples of carboxylates include acetate, propionate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, tridecanoate, tetradecanoate, pentadecanoate, hexadecanoate, octadecanoate (oleate), nonadecanoate, and eicosanoate. In one embodiment, the gallium carboxylate is gallium oleate.

[0099] In some embodiments, the ratio of gallium carboxylate to AIGS core is 0.008 to 0.2 mmol of gallium carboxylate per 1 mg of AIGS. In one embodiment, the ratio of gallium carboxylate to AIGS core is approximately 0.04 mmol of gallium carboxylate per 1 mg of AIGS.

[0100] In further embodiments, the AIGS nanostructures are isolated, for example, by precipitation. In some embodiments, the AIGS nanostructures are precipitated by adding a non-solvent for AIGS nanostructures. In some embodiments, the non-solvent is a toluene / ethanol mixture. The precipitated nanostructures can be further isolated by centrifugation and washing with the non-solvent for nanostructures.

[0101] Furthermore, a method for manufacturing nanostructures, (a) Prepare a mixture containing the AIGS core and gallium halide in a solvent, and hold the mixture for a sufficient time to obtain an ion-exchanged nanostructure having a gallium gradient from the surface to the center of the nanostructure, (b) Isolating nanostructures and A method including this is provided.

[0102] In some embodiments, the nanostructure has a PWL of 480–545 nm, and at least about 60% of the emission is band-edge emission.

[0103] In some embodiments, at least 80% of the emission is band-edge emission. In other embodiments, at least 90% of the emission is band-edge emission. In still other embodiments, at least 95% of the emission is band-edge emission.

[0104] In some embodiments, the gallium halide is gallium chloride, gallium bromide, or gallium iodide. In one embodiment, the gallium halide is gallium iodide.

[0105] In some embodiments, the solvent comprises trioctylphosphine. In some embodiments, the solvent comprises toluene.

[0106] In some embodiments, a sufficient time in (a) is 0.1 to 200 hours. In some embodiments, a sufficient time in (a) is approximately 20 hours.

[0107] In some embodiments, the mixture is maintained at 20-100°C. In one embodiment, the mixture is maintained at approximately room temperature (20-25°C).

[0108] In some embodiments, the molar ratio of gallium halide to the AIGS core is about 0.1 to about 30.

[0109] In further embodiments, the AIGS nanostructures are isolated, for example, by precipitation. In some embodiments, the AIGS nanostructures are precipitated by adding a non-solvent for AIGS nanostructures. In some embodiments, the non-solvent is a toluene / ethanol mixture. The precipitated nanostructures can be further isolated by centrifugation and / or washing with a non-solvent for nanostructures.

[0110] Furthermore, a method for manufacturing nanostructures, (a) Prepare a mixture containing AIGS nanostructures, a sulfur source, and a ligand, (b) The mixture obtained in (a) is added to a mixture of GaX3 (X=F, Cl, or Br) and an oxygen-free ligand at a temperature of 180-300°C to obtain an ion-exchange nanostructure having a gallium gradient from the surface to the center of the nanostructure. (c) Isolating nanostructures and Methods including this are also provided.

[0111] In some embodiments, the nanostructure has a PWL of 480-545 nm.

[0112] In some embodiments, the preparation of (a) is carried out under oxygen-free conditions. In some embodiments, the preparation of (a) is carried out in a glove box.

[0113] In some embodiments, the addition of (b) is carried out under oxygen-free conditions. In some embodiments, the addition of (b) is carried out in a glove box.

[0114] In some embodiments, at least 80% of the emission is band-edge emission. In other embodiments, at least 90% of the emission is band-edge emission. In still other embodiments, at least 95% of the emission is band-edge emission.

[0115] Examples of ligands are disclosed in U.S. Patent Nos. 7,572,395, 8,143,703, 8,425,803, 8,563,133, 8,916,064, 9,005,480, 9,139,770, and 9,169,435, and U.S. Patent Application Publication No. 2008 / 0118755. In some embodiments, ligand (a) is an oxygen-free ligand. In some embodiments, ligand (b) is an oxygen-free ligand. In some embodiments, ligands (a) and (b) are alkylamines. In some embodiments, the ligand is an alkylamine selected from the group consisting of dodecylamine, oleylamine, hexadecylamine, dioctylamine, and octadecylamine. In some embodiments, ligand (a) is an oleylamine. In some embodiments, ligand (b) is an oleylamine. In some embodiments, ligands (a) and (b) are oleylamines.

[0116] In one embodiment, the sulfur source is derived from S8.

[0117] In one embodiment, the temperatures in (a) and (b) are approximately 270°C.

[0118] In one embodiment, the mixture of (b) further comprises a solvent. In some embodiments, the solvent is trioctylphosphine, dibenzyl ether, or squalane.

[0119] In some embodiments, GaX3 is gallium chloride, gallium fluoride, or gallium iodide. In some embodiments, GaX3 is gallium chloride. In some embodiments, GaX3 is Ga(III) chloride.

[0120] In some embodiments, the ratio of GaX3 to AIGS core is 0.008 to 0.2 mmol of GaX3 per 1 mg of AIGS. In some embodiments, the molar ratio of GaX3 to AIGS core is about 0.1 to about 30. In some embodiments, the ratio of GaX3 to AIGS core is about 0.04 mmol of GaX3 per 1 mg of AIGS.

[0121] In some embodiments, the AIGS nanostructures are isolated, for example, by precipitation. In some embodiments, the AIGS nanostructures are precipitated by the addition of a non-solvent for AIGS nanostructures. In some embodiments, the non-solvent is a toluene / ethanol mixture. The precipitated nanostructures can be further isolated by centrifugation and / or washing with a non-solvent for nanostructures.

[0122] In some embodiments, the mixture of (a) is maintained at 20°C to 100°C. In some embodiments, the mixture of (a) is maintained at approximately room temperature (20°C to 25°C).

[0123] In some embodiments, the mixture of (b) is held at 200°C to 300°C for 0.1 hours to 200 hours. In some embodiments, the mixture of (b) is held at 200°C to 300°C for about 20 hours.

[0124] Doped AIGS nanostructures In some embodiments, the AIGS nanostructure is doped. In some embodiments, the dopant of the nanocrystalline core consists of a metal comprising one or more transition metals. In some embodiments, the dopant is a transition metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and combinations thereof. In some embodiments, the dopant includes a nonmetal. In some embodiments, the dopant is ZnS, ZnSe, ZnTe, CdSe, CdS, CdTe, HgS, HgSe, HgTe, CuInS2, CuInSe2, AlN, AlP, AlAs, GaN, GaP, or GaAs.

[0125] In some embodiments, the core is purified by precipitation from a non-solvent. In some embodiments, the AIGS nanostructure is filtered to remove precipitate from the core solution.

[0126] Nanostructure composition In some embodiments, this disclosure is, (a) At least one type of AIGS nanostructure, (b) at least one type of organic resin and A nanostructured composition containing the following is provided.

[0127] In some embodiments, the nanostructure has a PWL of 480-545 nm.

[0128] In some embodiments, at least 80% of the nanostructure emission is band-edge emission. In other embodiments, at least 90% of the emission is band-edge emission. In other embodiments, at least 95% of the emission is band-edge emission. In some embodiments, 92–98% of the emission is band-edge emission. In some embodiments, 93–96% of the emission is band-edge emission.

[0129] In some embodiments, the nanostructure composition further comprises a second group of at least one type of nanostructure. Nanostructures having a PWL of 480–545 nm emit green light. Further groups of nanostructures emitting in the green, yellow, orange, and / or red regions of the spectrum may be added. These nanostructures have a PWL greater than 545 nm. In some embodiments, the nanostructures have a PWL between 550–750 nm. The size of the nanostructure determines the emission wavelength. The second group of at least one type of nanostructure may include group III-V nanocrystals selected from the group consisting of BN, BP, BAs, BSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb. In some embodiments, the core of the second group of nanostructures is an InP nanocrystal.

[0130] Organic resins In some embodiments, the organic resin is a thermosetting resin or an ultraviolet (UV) curing resin. In some embodiments, the organic resin is cured by a method that facilitates roll-to-roll processing.

[0131] Thermosetting resins require curing through an irreversible molecular crosslinking process that makes the resin injectable. In some embodiments, the thermosetting resin is an epoxy resin, phenolic resin, vinyl resin, melamine resin, urea resin, unsaturated polyester resin, polyurethane resin, allyl resin, acrylic resin, polyamide resin, polyamide-imide resin, phenolamine condensation polymer resin, urea-melamine condensation polymer resin, or a combination thereof.

[0132] In some embodiments, the thermosetting resin is an epoxy resin. Epoxy resins cure readily with a wide range of chemicals without generating volatile substances or by-products. Furthermore, epoxy resins are compatible with most substrates and tend to readily wet surfaces. See Boyle, MA et al, “Epoxy Resins”, Composites, Vol. 21, ASMHandbook, pages 78-89 (2001).

[0133] In some embodiments, the organic resin is a silicone thermosetting resin. In some embodiments, the silicone thermosetting resin is OE6630A or OE6630B (Dow Corning Corporation, Auburn, MI).

[0134] In some embodiments, a thermal initiator is used. In some embodiments, the thermal initiator is AIBN[2,2'-azobis(2-methylpropionitrile)] or benzoyl peroxide.

[0135] UV-curable resins are polymers that harden rapidly when exposed to light of a specific wavelength. In some embodiments, UV-curable resins are resins having radical polymerizable groups as functional groups, such as (meth)acryloyloxy groups, vinyloxy groups, styryl groups, or vinyl groups; or cationic polymerizable groups, such as epoxy groups, thioepoxy groups, vinyloxy groups, or oxetanyl groups. In some embodiments, UV-curable resins are polyester resins, polyether resins, (meth)acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, or polythiol polyene resins.

[0136] In some embodiments, the UV-curable resin is isobornyl acrylate, isobornyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, urethane acrylate, allyl oxycyclohexyl diacrylate, bis(acryloyloxyethyl)hydroxyl isocyanurate, bis(acryloyloxyneopentyl glycol) adipate, bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, dicyclopentanyl diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, di(trimethylolpropane)tetraacrylate, ethylene glycol dimethacrylate, glycerol methacrylate, 1,6-hexanediol diacrylate, 1,6-Hexanediol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol hydroxypivalate diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, phosphate dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, tetrabromobisphenol A diacrylate, triethylene glycol divinyl ether, triglycerol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, tris(acryloxyethyl)iso Selected from the group consisting of cyanurate, triacrylate phosphate, diacrylate phosphate, propargyl acrylate, vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated trifluoromethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polydimethylsiloxane, monomethacryloyloxypropyl-terminated polydimethylsiloxane, monovinyl-terminated polydimethylsiloxane, monoallyl-monotrimethylsiloxy-terminated polyethylene oxide, and combinations thereof.

[0137] In some embodiments, the UV-curable resin is a mercapto-functional compound that can be crosslinked with isocyanates, epoxy, or unsaturated compounds under UV curing conditions. In some embodiments, the polythiol is pentaerythritol tetra(3-mercapto-propionate) (PETMP); trimethylol-propane tri(3-mercapto-propionate) (TMPMP); glycol di(3-mercapto-propionate) (GDMP); tris[25-(3-mercapto-propionyloxy)ethyl]isocyanurate (TEMPIC); di-pentaerythritol hexa(3-mercapto-propionyloxy) These compounds include trimethylolpropane tri(3-mercapto-propionate) (ETTMP1300 and ETTMP700), polycaprolactone tetra(3-mercapto-propionate) (PCL4MP1350), pentaerythritol tetramercaptoacetate (PETMA), trimethylolpropane trimercaptoacetate (TMPMA), or glycol dimercaptoacetate (GDMA). These compounds are sold by Bruno Bock (Marschacht, Germany) under the trade name THIOCURE®.

[0138] In some embodiments, the UV-curable resin is a polythiol. In some embodiments, the UV-curable resin is a polythiol selected from the group consisting of ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropanetris(thioglycolate), trimethylolpropanetris(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), and combinations thereof. In some embodiments, the UV-curable resin is PETMP.

[0139] In some embodiments, the UV-curable resin is a thiol-ene compound comprising polythiol and 1,3,5-trialyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TTT). In some embodiments, the UV-curable resin is a thiol-ene compound comprising PETMP and TTT.

[0140] In some embodiments, the UV-curable resin further comprises a photoinitiator. The photoinitiator initiates the crosslinking and / or curing reaction of the photosensitive material upon exposure to light. In some embodiments, the photoinitiator is acetophenone-based, benzoin-based, or thioxatenon-based.

[0141] In some embodiments, the photopolymerization initiator is a vinyl acrylate-based resin. In some embodiments, the photopolymerization initiator is MINS-311RM (Minuta Technology Co., Ltd, Korea).

[0142] In some embodiments, the photopolymerization initiator is IRGACURE® 127, IRGACURE® 184, IRGACURE® 184D, IRGACURE® 2022, IRGACURE® 2100, IRGACURE® 250, IRGACURE® 270, IRGACURE® 2959, IRGACURE® 369, IRGACURE® 369 EG, IRGACURE® 379, IRGACURE® 500, IRGACURE® 651, IRGACURE® 754, IRGACURE® 784, IRGACURE® 819, IRGACURE® 819Dw, IRGACURE® 907, IRGACURE® 907 These are FF, IRGACURE® Oxe01, IRGACURE® TPO-L, IRGACURE® 1173, IRGACURE® 1173D, IRGACURE® 4265, IRGACURE® BP, or IRGACURE® MBF (BASF Corporation, Wyandotte, MI). In some embodiments, the photoinitiator is TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) or MBF (methylbenzoyl formate).

[0143] In some embodiments, the weight percentage of at least one organic resin in the nanostructured composition is about 5% to about 99%, about 5% to about 95%, about 5% to about 90%, about 5% to about 80%, about 5% to about 70%, about 5% to about 60%, about 5% to about 50%, about 5% to about 40%, about 5% to about 30%, about 5% to about 20%, about 5% to about 10%, about 10% to about 99%, about 10% to about 95%, about 10% to about 90%, Approximately 10% to 80%, approximately 10% to 70%, approximately 10% to 60%, approximately 10% to 50%, approximately 10% to 40%, approximately 10% to 30%, approximately 10% to 20%, approximately 20% to 99%, approximately 20% to 95%, approximately 20% to 90%, approximately 20% to 80%, approximately 20% to 70%, approximately 20% to 60%, approximately 20% to 50%, approximately 20% to 40%, approximately 20% to 30%, approximately 30% to 99%, approximately 30% Approximately 95%, approximately 30% to approximately 90%, approximately 30% to approximately 80%, approximately 30% to approximately 70%, approximately 30% to approximately 60%, approximately 30% to approximately 50%, approximately 30% to approximately 40%, approximately 40% to approximately 99%, approximately 40% to approximately 95%, approximately 40% to approximately 90%, approximately 40% to approximately 80%, approximately 40% to approximately 70%, approximately 40% to approximately 60%, approximately 40% to approximately 50%, approximately 50% to approximately 99%, approximately 50% to approximately 95%, approximately 50% to approximately 90%, approximately 50% to approximately 80%, The percentages are approximately 50% to 70%, 50% to 60%, 60% to 99%, 60% to 95%, 60% to 90%, 60% to 80%, 60% to 70%, 70% to 99%, 70% to 95%, 70% to 90%, 70% to 80%, 80% to 99%, 80% to 95%, 80% to 90%, 90% to 99%, 90% to 95%, or 95% to 99%.

[0144] Method for preparing AIGS nanostructured compositions This disclosure is, (a) To provide at least one type of AIGS nanostructure, (b) Mixing at least one organic resin with the composition of (a) The present invention provides a method for preparing a nanostructured composition containing [a specific element].

[0145] In some embodiments, the nanostructure has a PWL of 480–545 nm, and at least about 80% of the emission is band-edge emission. In some embodiments, at least 80% of the emission is band-edge emission. In other embodiments, at least 90% of the emission is band-edge emission. In other embodiments, at least 95% of the emission is band-edge emission. In some embodiments, 92–98% of the emission is band-edge emission. In some embodiments, 93–96% of the emission is band-edge emission.

[0146] This disclosure is, (a) To provide at least one group of AIGS nanostructures prepared using a GaX3 (X=F, Cl, or Br) precursor and an oxygen-free ligand, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or a combination thereof, (b) Mixing at least one organic resin with the composition of (a) The present invention also provides a method for preparing a nanostructured composition that includes the above.

[0147] In some embodiments, the nanostructure has a PWL of 480–545 nm, and at least about 60% of the emission is band-edge emission.

[0148] This disclosure is, (a) To provide at least one group of AIGS nanostructures having a PWL of 480-545 nm, at least about 80% of the emission being band-edge emission, and the nanostructure exhibiting 80-99% QY, (b) Mixing at least one organic resin with the composition of (a) The present invention also provides a method for preparing a nanostructured composition that includes the above.

[0149] In some embodiments, a group of at least one type of nanostructure is located at approximately 100 rpm to approximately 10,000 rpm, approximately 100 rpm to approximately 5,000 rpm, approximately 100 rpm to approximately 3,000 rpm, approximately 100 rpm to approximately 1,000 rpm, approximately 100 rpm to approximately 500 rpm, approximately 500 rpm to approximately 10,000 rpm, approximately 500 rpm to approximately 5,000 rpm, and approximately 500 rpm to approximately 3,000 rpm. It is mixed with at least one type of organic resin at a stirring speed of rpm, approximately 500 rpm to 1,000 rpm, approximately 1,000 rpm to 10,000 rpm, approximately 1,000 rpm to 5,000 rpm, approximately 1,000 rpm to 3,000 rpm, approximately 3,000 rpm to 10,000 rpm, approximately 3,000 rpm to 10,000 rpm, or approximately 5,000 rpm to 10,000 rpm.

[0150] In some embodiments, a population of at least one type of nanostructure is approximately 10 minutes to approximately 24 hours, approximately 10 minutes to approximately 20 hours, approximately 10 minutes to approximately 15 hours, approximately 10 minutes to approximately 10 hours, approximately 10 minutes to approximately 5 hours, approximately 10 minutes to approximately 1 hour, approximately 10 minutes to approximately 30 minutes, approximately 30 minutes to approximately 24 hours, approximately 30 minutes to approximately 20 hours, approximately 30 minutes to approximately 15 hours, approximately 30 minutes to approximately 10 hours, approximately 30 minutes to approximately 5 hours, approximately 30 minutes to approximately 1 hour, approximately 1 hour to approximately 24 hours, approximately It is mixed with at least one type of organic resin for a period of time of 1 hour to approximately 20 hours, approximately 1 hour to approximately 15 hours, approximately 1 hour to approximately 10 hours, approximately 1 hour to approximately 5 hours, approximately 5 hours to approximately 24 hours, approximately 5 hours to approximately 20 hours, approximately 5 hours to approximately 15 hours, approximately 5 hours to approximately 10 hours, approximately 10 hours to approximately 24 hours, approximately 10 hours to approximately 20 hours, approximately 10 hours to approximately 15 hours, approximately 15 hours to approximately 24 hours, approximately 15 hours to approximately 20 hours, or approximately 20 hours to approximately 24 hours.

[0151] In some embodiments, at least one group of nanostructures is mixed with at least one organic resin at temperatures of about -5°C to about 100°C, about -5°C to about 75°C, about -5°C to about 50°C, about -5°C to about 23°C, about 23°C to about 100°C, about 23°C to about 75°C, about 23°C to about 50°C, about 50°C to about 100°C, about 50°C to about 75°C, or about 75°C to about 100°C. In some embodiments, at least one organic resin is mixed with at least one group of nanostructures at temperatures of about 23°C to about 50°C.

[0152] In some embodiments, when two or more organic resins are used, the organic resins are added together and mixed. In some embodiments, the first organic resin is added at approximately 100 rpm to approximately 10,000 rpm, approximately 100 rpm to approximately 5,000 rpm, approximately 100 rpm to approximately 3,000 rpm, approximately 100 rpm to approximately 1,000 rpm, approximately 100 rpm to approximately 500 rpm, approximately 500 rpm to approximately 10,000 rpm, approximately 500 rpm to approximately 5,000 rpm, and approximately 500 rpm to approximately 3,000 rpm. The first organic resin is mixed with the second organic resin at stirring speeds of approximately 500 rpm to 1,000 rpm, 1,000 rpm to 10,000 rpm, 1,000 rpm to 5,000 rpm, 1,000 rpm to 3,000 rpm, 3,000 rpm to 10,000 rpm, 3,000 rpm to 10,000 rpm, or 5,000 rpm to 10,000 rpm.

[0153] In some embodiments, the first organic resin is used for approximately 10 minutes to approximately 24 hours, approximately 10 minutes to approximately 20 hours, approximately 10 minutes to approximately 15 hours, approximately 10 minutes to approximately 10 hours, approximately 10 minutes to approximately 5 hours, approximately 10 minutes to approximately 1 hour, approximately 10 minutes to approximately 30 minutes, approximately 30 minutes to approximately 24 hours, approximately 30 minutes to approximately 20 hours, approximately 30 minutes to approximately 15 hours, approximately 30 minutes to approximately 10 hours, approximately 30 minutes to approximately 5 hours, approximately 30 minutes to approximately 1 hour, approximately 1 hour to approximately 24 hours, and approximately 1 hour. It is mixed with the second organic resin for a period of time of approximately 20 hours, 1 hour to 15 hours, 1 hour to 10 hours, 1 hour to 5 hours, 5 hours to 24 hours, 5 hours to 20 hours, 5 hours to 15 hours, 5 hours to 10 hours, 10 hours to 24 hours, 10 hours to 20 hours, 10 hours to 15 hours, 15 hours to 24 hours, 15 hours to 20 hours, or 20 hours to 24 hours.

[0154] Characteristics of AIGS Nanostructures In some embodiments, AIGS nanostructures exhibit high photoluminescence quantum yields. In some embodiments, the nanostructures exhibit yields of approximately 50% to 99%, 50% to 95%, 50% to 90%, 50% to 85%, 50% to 80%, 50% to 70%, 50% to 60%, 60% to 99%, 60% to 95%, 60% to 90%, 60% to 85%, 60% to 80%, 60% to 70%, 70% to 99%, and 70% to 95%. The photoluminescence quantum yields are approximately 70% to 90%, 70% to 85%, 70% to 80%, 80% to 99%, 80% to 95%, 80% to 90%, 80% to 85%, 85% to 99%, 85% to 95%, 80% to 85%, 85% to 99%, 85% to 90%, 90% to 99%, 90% to 95%, or 95% to 99%. In some embodiments, the nanostructures exhibit photoluminescence quantum yields of approximately 82% to 96%, 85% to 96%, and 93% to 94%.

[0155] The photoluminescence spectrum of a nanostructure can cover a broad desired portion of the spectrum. In some embodiments, the photoluminescence spectrum of a nanostructure has emission maxima at 300nm-750nm, 300nm-650nm, 300nm-550nm, 300nm-450nm, 450nm-750nm, 450nm-650nm, 450nm-550nm, 450nm-750nm, 450nm-650nm, 450nm-550nm, 550nm-750nm, 550nm-650nm, or 650nm-750nm. In some embodiments, the photoluminescence spectrum of a nanostructure has an emission maxima at 450nm-550nm.

[0156] The size distribution of the nanostructures can be made relatively narrow. In some embodiments, the photoluminescence spectrum of the nanostructure population can have a full width at half maximum in the ranges of 10 nm to 60 nm, 10 nm to 40 nm, 10 nm to 30 nm, 10 nm to 20 nm, 20 nm to 60 nm, 20 nm to 40 nm, 20 nm to 30 nm, 25 nm to 60 nm, 25 nm to 40 nm, 25 nm to 30 nm, 30 nm to 60 nm, 30 nm to 40 nm, or 40 nm to 60 nm. In some embodiments, the photoluminescence spectrum of the nanostructure population can have a full width at half maximum in the ranges of 24 nm to 50 nm, 24 to 28 nm, 27 to 32 nm, or 29 to 38 nm.

[0157] In some embodiments, the nanostructure emits light having a peak emission wavelength (PWL) of approximately 400 nm to 650 nm, approximately 400 nm to 600 nm, approximately 400 nm to 550 nm, approximately 400 nm to 500 nm, approximately 400 nm to 450 nm, approximately 450 nm to 650 nm, approximately 450 nm to 600 nm, approximately 450 nm to 550 nm, approximately 450 nm to 500 nm, approximately 500 nm to 650 nm, approximately 500 nm to 550 nm, approximately 550 nm to 650 nm, or approximately 600 nm to 650 nm. In some embodiments, the nanostructure emits light having a PWL of approximately 500 nm to 550 nm.

[0158] As a predicted value for blue light absorption efficiency, the optical density (OD) at 450 nm per unit mass is used. 450 The optical density (OD) at 450 nm per mass can be calculated by measuring the optical density of a nanostructure solution in a cuvette with a path length of 1 cm and dividing it by the dry mass per mL of the same solution after removing all volatile substances under vacuum (<200 mTorr). In some embodiments, the nanostructure has an optical density (OD) at 450 nm per mass of approximately 0.28 / mg to approximately 0.5 / mg, approximately 0.28 / mg to approximately 0.4 / mg, approximately 0.28 / mg to approximately 0.35 / mg, approximately 0.28 / mg to approximately 0.32 / mg to approximately 0.5 / mg, approximately 0.32 / mg to approximately 0.4 / mg, approximately 0.32 / mg to approximately 0.35 / mg, approximately 0.35 / mg to approximately 0.5 / mg, or approximately 0.4 / mg to approximately 0.5 / mg. 450 It has (mass).

[0159] film The nanostructures of the present invention can be embedded in a polymer matrix using any suitable method. As used herein, the term “embedded” is used to indicate that the nanostructure is surrounded or encased in the polymer that constitutes the majority of the matrix's components. In some embodiments, at least one nanostructure population is appropriately uniformly distributed throughout the matrix. In some embodiments, at least one nanostructure population is distributed according to an application-specific distribution. In some embodiments, the nanostructure is mixed into the polymer and coated onto the surface of the material.

[0160] In some embodiments, this disclosure is, (a) A composition comprising at least one group of AIGS nanostructures, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or a combination thereof, and at least one ligand bonded to the nanostructures, (b) at least one type of organic resin and A nanostructured film layer containing the following is provided.

[0161] In some embodiments, some of the ligands are bonded to the nanostructure. In other embodiments, the surface of the nanostructure is saturated with ligands.

[0162] In some embodiments, the nanostructure has a PWL of 480-545 nm.

[0163] This disclosure is, (a) To provide at least one group of AIGS nanostructures, and one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof, (b) Mixing at least one organic resin with the composition of (a) The present invention also provides a method for preparing a nanostructured film layer, including the above.

[0164] In some embodiments, the nanostructure has a PWL of 480-545 nm.

[0165] In some embodiments, at least 80% of the emission is band-edge emission. In other embodiments, at least 90% of the emission is band-edge emission. In other embodiments, at least 95% of the emission is band-edge emission. In some embodiments, 92–98% of the emission is band-edge emission. In some embodiments, 93–96% of the emission is band-edge emission.

[0166] Ligands and additives In some embodiments, the nanostructured composition further comprises an amino ligand having the following formula I. [ka] During the ceremony, x is between 1 and 100. y is between 0 and 100, and R 2 is C 1~20 The present invention further comprises an amino ligand having an alkyl group.

[0167] In some embodiments, x is 1-100, 1-50, 1-20, 1-10, 1-5, 5-100, 5-50, 5-20, 5-10, 10-100, 10-50, 10-20, 20-100, 20-50, or 50-100. In some embodiments, x is 10-50. In some embodiments, x is 10-20. In some embodiments, x is 1. In some embodiments, x is 19. In some embodiments, x is 6. In some embodiments, x is 10.

[0168] In some embodiments, R 2 C 1~20 It is alkyl. In some embodiments, R 2 C 1~10 It is alkyl. In some embodiments, R 2 C 1~5 It is alkyl. In some embodiments, R 2 It is -CH2CH3.

[0169] In some embodiments, the compound of formula I is an amine-terminated polymer commercially available from Huntsman Petrochemical Corporation. In some embodiments, the amine-terminated polymer of formula (VI) has x=1, y=9, and R 2 It has =-CH3 and is JEFFAMINE M-600 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-600 has a molecular weight of approximately 600. In some embodiments, the amine-terminated polymer of formula (III) has x=19, y=3, and R 2 It has =-CH3 and is JEFFAMINE M-1000 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-1000 has a molecular weight of approximately 1,000. In some embodiments, the amine-terminated polymer of formula (III) has x=6, y=29, and R 2 It has =-CH3 and is JEFFAMINE M-2005 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-2005 has a molecular weight of approximately 2,000. In some embodiments, the amine-terminated polymer of formula (III) has x=31, y=10, and R 2 It has -CH3 and is JEFFAMINE M-2070 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-2070 has a molecular weight of approximately 2,000. In another embodiment, the ligand is a polyethylene glycolamine available from CreativePEGWorks, such as PEG550-amine and PEG350-amine.

[0170] In some embodiments, the ligand is a sterically hindered phenol having the following formula II. [ka] In the formula, R 3 and R4 R is a C3-6 secondary or tertiary alkyl group, 5 R is a hydrogen atom or an optionally substituted C1-6 alkyl group. In some embodiments, R3 and R4 are isopropyl, 2-butyl, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, t-butyl, 2-methyl-2-pentyl, or 3-methyl-3-pentyl. In some embodiments, R 5 It is located in the 3rd or 4th position of equation II.

[0171] R 5 C 1~6 Optional substituents on the alkyl group include nitro, haloalkoxy, aryloxy, alkyloxy, alkylthio, sulfonamide, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, ureido, guanidino, carbamate, carboxy, alkoxycarbonyl, carboxyalkyl, or C(=O)R 7 (In the formula, R 7 Examples include alkoxy groups that may be further substituted by one or more other alkoxy groups.

[0172] In some embodiments, R 7 The following equation: CH p (CH2-O-) 4-p (wherein p is 0 to 3, and the oxygen atom is bonded to the carbonyl group of formula II) is present. In some embodiments, R 7 teeth, [ka] That is the case.

[0173] In some embodiments, R 7 teeth, [ka] And equation II is, [ka] And in the formula, R 7 The oxygen atom is * It is bonded to the carbonyl group of formula II at the position indicated by .

[0174] In some embodiments, the compound of formula II is pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl)bis[3-[3-(tert-butyl)-4-hydroxy-5-methylphenyl]propanoate].

[0175] Ligands having formula II bind to nanostructures and act as antioxidants in nanostructured compositions such as inks and films. In addition, because the ligands are sterically hindered, the free volume of the nanostructure surface is reduced, thereby reducing or preventing oxidation by ambient oxygen and improving air stability.

[0176] In some embodiments, the nanostructured film layer is a color conversion layer.

[0177] The nanostructured composition can be deposited by any suitable method known in the art, but is not limited to painting, spray coating, solvent spray, wet coating, adhesive coating, spin coating, tape coating, roll coating, flow coating, inkjet vapor jetting, drop casting, blade coating, mist deposition, or a combination thereof. In some embodiments, the nanostructured composition is cured after deposition. Suitable curing methods include photocuring, such as UV curing, and thermal curing. Conventional lamination methods, tape coating methods, and / or roll-to-roll manufacturing methods can be employed to form the nanostructured film of the present invention. The nanostructured composition can be directly coated onto a desired layer of a substrate. Alternatively, the nanostructured composition can be formed as a solid layer as an independent element and then applied to the substrate. In some embodiments, the nanostructured composition can be deposited on one or more barrier layers.

[0178] Metal alkoxides Metal alkoxides have the general formula M(OR) x The formula comprises R being a linear, branched, or cyclic alkyl group, typically containing 1 to 10 carbon atoms, and x being the valence of the metal. In some embodiments, metal alkoxides include metal methoxides, metal ethoxides, metal n-propoxides, metal isopropoxides, metal n-butoxides, metal isobutoxides, metal n-pentoxides, metal isopentoxides, metal n-hexoxides, metal isohexoxides, metal n-heptoxides, metal isoheptoxides, metal n-octoxides, metal n-isooctoxides, metal n-nonoxides, metal n-isononoxides, metal n-decyloxides, and metal n-isodecyloxides.

[0179] In some embodiments, the metal of the metal alkoxide can be one or more of the following: lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lutetium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, thulium, erbium, thulium, ytterbium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, nickel, platinum, copper, zinc, cadmium, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, arsenic, antimony, and bismuth. In some embodiments, the metals include one or more of the following: aluminum, antimony, arsenic, barium, bismuth, boron, cerium, gadolinium, gallium, germanium, hafnium, indium, iron, lanthanum, lithium, magnesium, molybdenum, neodymium, phosphorus, silicon, sodium, strontium, tantalum, thallium, tin, titanium, tungsten, vanadium, yttrium, zinc, and zirconium.

[0180] In some embodiments, the metal alkoxide may be one or more Group 4 metals, including titanium, zirconium, and hafnium.

[0181] In some embodiments, the metal alkoxides are zirconium(IV) tetramethoxide, zirconium(IV) tetraethoxide, zirconium(IV) tetra-n-propoxide, zirconium(IV) tetra-isopropoxide, zirconium(IV) tetra-n-butoxide, zirconium(IV) tetra-isobutoxide, zirconium(IV) tetra-n-pentoxide, zirconium(IV) tetra-isopentoxide, zirconium(IV) tetra-n-hexoxide, zirconium(IV) ) is at least one zirconium alkoxide containing tetra-isohexoxide, zirconium(IV) tetra-n-heptoxide, zirconium(IV) tetra-isoheptoxide, zirconium(IV) tetra-n-octoxide, zirconium(IV) tetra-n-isooctoxide, zirconium(IV) tetra-n-nonoxide, zirconium(IV) tetra-n-isononoxide, zirconium(IV) tetra-n-decyloxide, and zirconium(IV) tetra-n-isodecyloxide.

[0182] In some embodiments, metal alkoxides can form a sol-gel around the AIGS nanostructure, thus forming an oxygen barrier and providing stabilization of the AIGS nanostructure. See Brinker and Scherer, (1990) Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing. Academic Press.

[0183] In some embodiments, the metal alkoxide is present in the AIGS film composition at at least 0.005 wt% (50 ppm). In some embodiments, the metal oxide is present in the AIGS film composition in an amount of about 0.03 to about 3 wt%. In some embodiments, the metal oxide is present in the film composition in an amount of about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6, about 2.7, about 2.8, about 2.9 or about 3 wt%.

[0184] Metal alkoxide hydrolysis product The metal alkoxide hydrolysis product has the general formula M(OH) x (OR) y(wherein R is a linear, branched, or cyclic alkyl, typically containing 1 to 10 carbon atoms, and x + y is equal to the valence of the metal). Hydrolysis products of metal alkoxides include zirconium(IV) monohydroxy trimethoxide, zirconium(IV) dihydroxy dimethoxide, zirconium(IV) trihydroxy monomethoxide, zirconium(IV) tetrahydroxy, zirconium(IV) monohydroxy triethoxide, zirconium(IV) dihydroxy diethoxide, zirconium(IV) trihydroxy monoethoxide, zirconium(IV) monohydroxy tri-n-propoxide, and zirconium(IV) di Hydroxydo di-n-propoxide, zirconium(IV) trihydroxydo mono-n-propoxide, zirconium(IV) monohydroxydo triisopropoxide, zirconium(IV) dihydroxydo diisopropoxide, zirconium(IV) trihydroxydo monoisopropoxide, zirconium(IV) monohydroxydo tri-n-butoxide, zirconium(IV) dihydroxydo di-n-butoxide, zirconium(IV) trihydroxydo mono-n-butoxide, zirconium(IV) monohydroxy Dotriisobutoxide, Zirconium(IV) dihydroxydodiisobutoxide, Zirconium(IV) trihydroxydomonoisobutoxide, Zirconium(IV) monohydroxydotri-n-pentoxide, Zirconium(IV) dihydroxydodi-n-pentoxide, Zirconium(IV) trihydroxydomono-n-pentoxide, Zirconium(IV) monohydroxydotriisopentoxide, Zirconium(IV) dihydroxydodiisopentoxide, Zirconium(IV) trihydroxydomonoisopentoxide Zirconium(IV) oxide, zirconium(IV) monohydroxydotri-n-hexoxide, zirconium(IV) dihydroxydodi-n-hexoxide, zirconium(IV) trihydroxydomono-n-hexoxide, zirconium(IV) monohydroxydotriisohexoxide, zirconium(IV) dihydroxydodiisohexoxide, zirconium(IV) trihydroxydomonoisohexoxide, zirconium(IV) monohydroxydotri-n-heptoxide, zirconium(IV) dihydroxydodi-n-heptoxide,Zirconium(IV) trihydroxydomono-n-heptoxide, zirconium(IV) monohydroxydotriisoheptoxide, zirconium(IV) dihydroxydodiisoheptoxide, zirconium(IV) trihydroxydomonoisoheptoxide, zirconium(IV) monohydroxydotri-n-octoxide, zirconium(IV) dihydroxydodi-n-octoxide, zirconium(IV) trihydroxydomono-n-octoxide, zirconium(IV) monohydroxydotri-n-isooctoxide, zirconium(IV) di Hydroxydodi-n-isooctoxide, zirconium(IV) trihydroxydomono-n-isooctoxide, zirconium(IV) monohydroxydotri-n-nonoxide, zirconium(IV) dihydroxydodi-n-nonoxide, zirconium(IV) trihydroxydomono-n-nonoxide, zirconium(IV) monohydroxydotri-n-isononoxide, zirconium(IV) dihydroxydodi-n-isononoxide, zirconium(IV) trihydroxydomono-n-isononoxide, zirconium(IV) monohydroxydotri -n-decyloxide, zirconium(IV) dihydroxydodi-n-decyloxide, zirconium(IV) trihydroxydomono-n-decyloxide, zirconium(IV) monohydroxydotri-n-isodecyloxide, zirconium(IV) dihydroxydodi-n-isodecyloxide, zirconium(IV) trihydroxydomono-n-isodecyloxide, titanium(IV) monohydroxydotrimethoxide, titanium(IV) dihydroxydodimethoxide, titanium(IV) trihydroxydomonomethoxide, titanium(IV) tetrahydroxydo, Tan(IV) monohydroxy triethoxide, Titanium(IV) dihydroxy diethoxide, Titanium(IV) trihydroxy monoethoxide, Titanium(IV) monohydroxy tri-n-propoxide, Titanium(IV) dihydroxy di-n-propoxide, Titanium(IV) trihydroxy mono-n-propoxide, Titanium(IV) monohydroxy triisopropoxide, Titanium(IV) dihydroxy diisopropoxide, Titanium(IV) trihydroxy monoisopropoxide, Titanium(IV) monohydroxy tri-n-butoxide,Titanium(IV) dihydroxydo di-n-butoxide, Titanium(IV) trihydroxydo mono-n-butoxide, Titanium(IV) monohydroxydo triisobutoxide, Titanium(IV) dihydroxydo diisobutoxide, Titanium(IV) trihydroxydo monoisobutoxide, Titanium(IV) monohydroxydo tri-n-pentoxide, Titanium(IV) dihydroxydo di-n-pentoxide, Titanium(IV) trihydroxydo mono-n-pentoxide, Titanium(IV) monohydroxydo triisopentoxide, Titanium(IV) dihydroxydo diisopentoxide Toxide, Titanium(IV) trihydroxy monoisopentoxide, Titanium(IV) monohydroxy tri-n-hexoxide, Titanium(IV) dihydroxy di-n-hexoxide, Titanium(IV) trihydroxy mono-n-hexoxide, Titanium(IV) monohydroxy triisohexoxide, Titanium(IV) dihydroxy diisohexoxide, Titanium(IV) trihydroxy monoisohexoxide, Titanium(IV) monohydroxy tri-n-heptoxide, Titanium(IV) dihydroxy di-n-heptoxide, Titanium(IV) tri Titanium(IV) hydroxydomono-n-heptoxide, titanium(IV) monohydroxydotriisoheptoxide, titanium(IV) dihydroxydodiisoheptoxide, titanium(IV) trihydroxydomono-isoheptoxide, titanium(IV) monohydroxydotri-n-octoxide, titanium(IV) dihydroxydodi-n-octoxide, titanium(IV) trihydroxydomono-n-octoxide, titanium(IV) monohydroxydotri-n-isooctoxide, titanium(IV) dihydroxydodi-n-isooctoxide, titanium(IV) trihydroxydomono- n-isooctoxide, titanium(IV) monohydroxydotri-n-nonoxide, titanium(IV) dihydroxydodi-n-nonoxide, titanium(IV) trihydroxydomono-n-nonoxide, titanium(IV) monohydroxydotri-n-isononoxide, titanium(IV) dihydroxydodi-n-isononoxide, titanium(IV) trihydroxydomono-n-isononoxide, titanium(IV) monohydroxydotri-n-decyloxide, titanium(IV) dihydroxydodi-n-decyloxide, titanium(IV) trihydroxydomono-n-decyloxide,Titanium(IV) monohydroxy tri-n-isodecyloxide, Titanium(IV) dihydroxy di-n-isodecyloxide, Titanium(IV) trihydroxy mono-n-isodecyloxide, Hafnium(IV) monohydroxy trimethoxide, Hafnium(IV) dihydroxy dimethoxide, Hafnium(IV) trihydroxy monomethoxide, Hafnium(IV) tetrahydroxy, Hafnium(IV) monohydroxy triethoxide, Hafnium(IV) dihydroxy diethoxide, Hafnium(IV) trihydroxy monoethoxide Hafnium(IV) monohydroxydotri-n-propoxide, hafnium(IV) dihydroxydodi-n-propoxide, hafnium(IV) trihydroxydomono-n-propoxide, hafnium(IV) monohydroxydotriisopropoxide, hafnium(IV) dihydroxydodiisopropoxide, hafnium(IV) trihydroxydomonoisopropoxide, hafnium(IV) monohydroxydotri-n-butoxide, hafnium(IV) dihydroxydodi-n-butoxide, hafnium(IV) trihydroxydomono-n-butoxide Hafnium(IV) monohydroxy triisobutoxide, hafnium(IV) dihydroxy diisobutoxide, hafnium(IV) trihydroxy monoisobutoxide, hafnium(IV) monohydroxy tri-n-pentoxide, hafnium(IV) dihydroxy di-n-pentoxide, hafnium(IV) trihydroxy mono-n-pentoxide, hafnium(IV) monohydroxy triisopentoxide, hafnium(IV) dihydroxy diisopentoxide, hafnium(IV) trihydroxy monoisopentoxide, hafnium(IV) Hafnium(IV) monohydroxydotri-n-hexoxide, hafnium(IV) dihydroxydodi-n-hexoxide, hafnium(IV) trihydroxydomono-n-hexoxide, hafnium(IV) monohydroxydotriisohexoxide, hafnium(IV) dihydroxydodiisohexoxide, hafnium(IV) trihydroxydomonoisohexoxide, hafnium(IV) monohydroxydotri-n-heptoxide, hafnium(IV) dihydroxydodi-n-heptoxide, hafnium(IV) trihydroxydomono-n-heptoxide,Hafnium(IV) monohydroxydotriisoheptoxide, hafnium(IV) dihydroxydodiisoheptoxide, hafnium(IV) trihydroxydomonoisoheptoxide, hafnium(IV) monohydroxydotri-n-octoxide, hafnium(IV) dihydroxydodi-n-octoxide, hafnium(IV) trihydroxydomono-n-octoxide, hafnium(IV) monohydroxydotri-n-isooctoxide, hafnium(IV) dihydroxydodi-n-isooctoxide, hafnium(IV) trihydroxydomono-n-isooctoxide, hafnium(IV) monohydroxydotri-n-nonoxide, hafnium(IV) dihydroxydodi-n- Examples include nonoxides, hafnium(IV) trihydroxydomono-n-nonoxide, hafnium(IV) monohydroxydotri-n-isononoxide, hafnium(IV) dihydroxydodi-n-isononoxide, hafnium(IV) trihydroxydomono-n-isononoxide, hafnium(IV) monohydroxydotri-n-decyloxide, hafnium(IV) dihydroxydodi-n-decyloxide, hafnium(IV) trihydroxydomono-n-decyloxide, hafnium(IV) monohydroxydotri-n-isodecyloxide, hafnium(IV) dihydroxydodi-n-isodecyloxide, and hafnium(IV) trihydroxydomono-n-isodecyloxide.

[0185] In some embodiments, metal alkoxide hydrolysis products are present in the AIGS film composition in an amount of at least 0.005% by weight (50 ppm). In some embodiments, metal oxide hydrolysis products are present in the AIGS film composition in an amount of about 0.03 to about 3% by weight. In some embodiments, metal oxide hydrolysis products are present in the film composition in an amount of about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6, about 2.7, about 2.8, about 2.9, or about 3% by weight.

[0186] Metal halides Metal halides have the general formula MX y (wherein y is the valence of the metal) Examples of metal halides include zirconium(IV) tetrafluoride, zirconium(IV) tetrachloride, zirconium(IV) tetrabromide, zirconium(IV) tetraiodide, titanium(IV) tetrafluoride, titanium(IV) tetrachloride, titanium(IV) tetrabromide, titanium(IV) tetraiodide, hafnium(IV) tetrafluoride, hafnium(IV) tetrachloride, hafnium(IV) tetrabromide, hafnium(IV) tetraiodide, gallium(III) trifluoride, gallium(III) trichloride, gallium(III) tribromide, and gallium(III) triiodide.

[0187] In some embodiments, metal halides are present in the AIGS film composition at a concentration of at least 0.005% by weight (50 ppm). In some embodiments, metal halides are present in the AIGS film composition in an amount of about 0.03 to about 3% by weight. In some embodiments, metal halides are present in the film composition in an amount of about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6, about 2.7, about 2.8, about 2.9, or about 3% by weight.

[0188] Hydrolysis products of metal halides The hydrolysis products of metal halides are of the general formula MX y (OH) x(wherein x+y is equal to the valence of the metal) The hydrolysis products of the metal halide include zirconium(IV) monohydroxy trichloride, zirconium(IV) dihydroxy difluoride, zirconium(IV) trihydroxy monofluoride, zirconium(IV) tetrahydroxy, titanium(IV) monohydroxy trifluoride, titanium(IV) dihydroxy difluoride, titanium(IV) trihydroxy monofluoride, titanium(IV) tetrahydroxy, titanium(IV) monohydroxy trifluoride, titanium(IV) dihydroxy difluoride, Titanium(IV) trihydroxy monofluoride, Titanium(IV) tetrahydroxy, Hafnium(IV) monohydroxy trifluoride, Hafnium(IV) dihydroxy difluoride, Hafnium(IV) trihydroxy monofluoride, Hafnium(IV) tetrahydroxy, Zirconium(IV) monohydroxy trichloride, Zirconium(IV) dihydroxy dichloride, Zirconium(IV) trihydroxy monochloride, Zirconium(IV) tetrahydroxy, Titanium(IV) monohydroxy trichloride Titanium(IV) dihydroxy dichloride, titanium(IV) trihydroxy monochloride, titanium(IV) tetrahydroxy, titanium(IV) monohydroxy trichloride, titanium(IV) dihydroxy dichloride, titanium(IV) trihydroxy monochloride, titanium(IV) tetrahydroxy, hafnium(IV) monohydroxy trichloride, hafnium(IV) dihydroxy dichloride, hafnium(IV) trihydroxy monochloride, hafnium(IV) tetrahydroxy, zirconium(IV) mo Nohydroxydotribromide, zirconium(IV) dihydroxydodibromide, zirconium(IV) trihydroxydomonobromide, zirconium(IV) tetrahydroxydo, titanium(IV) monohydroxydotribromide, titanium(IV) dihydroxydodibromide, titanium(IV) trihydroxydomonobromide, titanium(IV) tetrahydroxydo, titanium(IV) monohydroxydotribromide, titanium(IV) dihydroxydodibromide, titanium(IV) trihydroxydomonobromide, titanium(IV) tetrahydroxydo,Examples include hafnium(IV) monohydroxy tribromide, hafnium(IV) dihydroxy dibromide, hafnium(IV) trihydroxy monobromide, hafnium(IV) tetrahydroxyd, zirconium(IV) monohydroxy triiodide, zirconium(IV) dihydroxy diiodide, zirconium(IV) trihydroxy monoiodide, zirconium(IV) tetrahydroxyd, titanium(IV) monohydroxy triiodide, titanium(IV) dihydroxy diiodide, titanium(IV) trihydroxy monoiodide, titanium(IV) tetrahydroxyd, titanium(IV) monohydroxy triiodide, titanium(IV) dihydroxy diiodide, titanium(IV) trihydroxy monoiodide, titanium(IV) tetrahydroxyd, hafnium(IV) monohydroxy triiodide, hafnium(IV) dihydroxy diiodide, hafnium(IV) trihydroxy monoiodide, and hafnium(IV) tetrahydroxyd. ,

[0189] In some embodiments, metal halide hydrolysis products are present in the AIGS film composition in an amount of at least 0.005% by weight (50 ppm). In some embodiments, metal oxides are present in the AIGS film composition in an amount of about 0.03 to about 3% by weight. In some embodiments, metal halide hydrolysis products are present in the film composition in an amount of about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6, about 2.7, about 2.8, about 2.9, or about 3% by weight.

[0190] organometallic compounds Organometallic compounds contain metal-carbon bonds, and formula R xM may have a linear, branched, or cyclic alkyl group, typically containing 1 to 10 carbon atoms, and x is the valence of the metal. Examples of organometallic compounds include tetramethylzirconium, tetraethylzirconium, tetra-n-propylzirconium, tetraisopropylzirconium, tetra-n-butylzirconium, tetraisobutylzirconium, tetra-n-pentylzirconium, tetraisopentylzirconium, tetra-n-hexylzirconium, tetraisohexylzirconium, tetra-n-heptylzirconium, tetraisoheptylzirconium, tetra-n-octylzirconium, tetra-n-isooctylzirconium, tetra-n-nonylzirconium, tetra-n-isononylzirconium, tetra-n-decylzirconium, tetramethyltitanium, tetraethyltitanium, tetra-n-propyltitanium, tetraisopropyltitanium, tetra-n-butyltitanium, tetraisobutyltitanium, tetra-n-pentyltitanium, tetraisopentyltitanium, tetra-n-hexyl Lutitan, tetraisohexyl titanium, tetra-n-heptyl titanium, tetraisoheptyl titanium, tetra-n-octyl titanium, tetra-n-isooctyl titanium, tetra-n-nonyl titanium, tetra-n-isononyl titanium, tetra-n-decyl titanium, tetra-n-isodecyl titanium, tetramethylhafnium, tetraethylhafnium, tetra-n-propylhafnium, tetraisopropylhafnium, tetra-n-butylhafnium, tetraisob Examples include tylhafnium, tetra-n-pentylhafnium, tetraisopentylhafnium, tetra-n-hexylhafnium, tetraisohexylhafnium, tetra-n-heptylhafnium, tetraisoheptylhafnium, tetra-n-octylhafnium, tetra-n-isooctylhafnium, tetra-n-nonylhafnium, tetra-n-isononylhafnium, tetra-n-decylhafnium, and tetra-n-isodecylhafnium.

[0191] In some embodiments, the organometallic compound is present in the AIGS film composition at least at 0.005 wt% (50 ppm). In some embodiments, the organometallic compound is present in the AIGS film composition in an amount of about 0.03 to about 3 wt%. In some embodiments, the organometallic compound is present in the film composition in an amount of about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6, about 2.7, about 2.8, about 2.9 or about 3 wt%.

[0192] Organometallic hydrolysis compound The organometallic hydrolysis product has the formula R x M(OH) y(wherein R is a linear, branched, or cyclic alkyl group, typically containing 1 to 10 carbon atoms, and x+y is equal to the valence of the metal) may have the following properties. Organometallic hydrolysis products include trimethylzirconium monohydroxy, triethylzirconium monohydroxy, tri-n-propylzirconium monohydroxy, triisopropylzirconium monohydroxy, tri-n-butylzirconium monohydroxy, triisobutylzirconium monohydroxy, tri-n-pentylzirconium monohydroxy, triisopentylzirconium monohydroxy, tri-n-hexylzirconium monohydroxy, triisohexylzirconium monohydroxy, tri-n-heptylzirconium monohydroxy, triisoheptylzirconium monohydroxy, tri-n-octylzirconium monohydroxy, tri-n-isooctylzirconium monohydroxy, tri-n-nonylzirconium monohydroxy, tri-n-isononylzirconium monohydroxy, tri-n-decylzirconium monohydroxy, trimethyltitanium monohydroxy, triethyltitanium monohydroxy Droxide, tri-n-propyl titanium monohydroxy, triisopropyl titanium monohydroxy, tri-n-butyl titanium monohydroxy, triisobutyl titanium monohydroxy, tri-n-pentyl titanium monohydroxy, triisopentyl titanium monohydroxy, tri-n-hexyl titanium monohydroxy, triisohexyl titanium monohydroxy, tri-n-heptyl titanium monohydroxy, triisoheptyl titanium monohydroxy, tri-n-octyl titanium monohydroxy, tri-n-isooctyl titanium monohydroxy, tri-n-nonyl titanium monohydroxy, tri-n-isononyl titanium monohydroxy, tri-n-decyl titanium monohydroxy, tri-n-isodecyl titanium monohydroxy, trimethylhafnium monohydroxy, triethylhafnium monohydroxy, tri-n-propylhafnium monohydroxy, triisopropylhafnium monohydroxy, tri-n-butylhafnium monohydroxy, triisobutylhafnium monohydroxy,Tri-n-pentylhafnium monohydroxy, triisopentylhafnium monohydroxy, tri-n-hexylhafnium monohydroxy, triisohexylhafnium monohydroxy, tri-n-heptylhafnium monohydroxy, triisoheptylhafnium monohydroxy, tri-n-octylhafnium monohydroxy, tri-n-isooctylhafnium monohydroxy, tri-n-nonylhafnium monohydroxy, tri-n-isononylhafnium monohydroxy, tri-n-decylhafnium monohydroxy Roxide, tri-n-isodecylhafnium monohydroxy, dimethylzirconium dihydroxy, diethylzirconium dihydroxy, di-n-propylzirconium dihydroxy, diisopropylzirconium dihydroxy, di-n-butylzirconium dihydroxy, diisobutylzirconium dihydroxy, di-n-pentylzirconium dihydroxy, diisopentylzirconium dihydroxy, di-n-hexylzirconium dihydroxy, diisohexylzirconium dihydroxy, di-n-heptylzirconium Dioxide, diisoheptylzirconium dihydroxy, di-n-octylzirconium dihydroxy, di-n-isooctylzirconium dihydroxy, di-n-nonylzirconium dihydroxy, di-n-isononylzirconium dihydroxy, di-n-decylzirconium dihydroxy, di-n-isodecylzirconium dihydroxy, dimethyl titanium dihydroxy, diethyl titanium dihydroxy, di-n-propyl titanium dihydroxy, diisopropyl titanium dihydroxy, di-n-butyl titanium dihydroxy Side, diisobutyl titanium dihydroxy, di-n-pentyl titanium dihydroxy, diisopentyl titanium dihydroxy, di-n-hexyl titanium dihydroxy, diisohexyl titanium dihydroxy, di-n-heptyl titanium dihydroxy, diisoheptyl titanium dihydroxy, di-n-octyl titanium dihydroxy, di-n-isooctyl titanium dihydroxy, di-n-nonyl titanium dihydroxy, di-n-isononyl titanium dihydroxy, di-n-decyl titanium dihydroxy, di-n-isodecyl titanium dihydroxy,Dimethylhafnium dihydroxyd, diethylhafnium dihydroxyd, di-n-propylhafnium dihydroxyd, diisopropylhafnium dihydroxyd, di-n-butylhafnium dihydroxyd, diisobutylhafnium dihydroxyd, di-n-pentylhafnium dihydroxyd, diisopentylhafnium dihydroxyd, di-n-hexylhafnium dihydroxyd, diisohexylhafnium dihydroxyd, di-n-heptylhafnium dihydroxyd, diisoheptylhafnium dihydroxyd, di-n-octylhafnium Dihydroxyd, di-n-isooctylhafnium dihydroxyd, di-n-nonylhafnium dihydroxyd, di-n-isononylhafnium dihydroxyd, di-n-decylhafnium dihydroxyd, di-n-isodecylhafnium dihydroxyd, monomethylzirconium trihydroxyd, monoethylzirconium trihydroxyd, mono-n-propylzirconium trihydroxyd, monoisopropylzirconium trihydroxyd, mono-n-butylzirconium trihydroxyd, monoisobutylzirconium trihydroxyd, mono- n-pentylzirconium trihydroxyde, monoisopentylzirconium trihydroxyde, mono-n-hexylzirconium trihydroxyde, monoisohexylzirconium trihydroxyde, mono-n-heptylzirconium trihydroxyde, monoisoheptylzirconium trihydroxyde, mono-n-octylzirconium trihydroxyde, mono-n-isooctylzirconium trihydroxyde, mono-n-nonylzirconium trihydroxyde, mono-n-isononylzirconium trihydroxyde, mono-n-decylzirconium Trihydroxyde, mono-n-isodecylzirconium trihydroxyde, monomethyltitanium trihydroxyde, monoethyltitanium trihydroxyde, mono-n-propyltitanium trihydroxyde, monoisopropyltitanium trihydroxyde, mono-n-butyltitanium trihydroxyde, monoisobutyltitanium trihydroxyde, mono-n-pentyltitanium trihydroxyde, monoisopentyltitanium trihydroxyde, mono-n-hexyltitanium trihydroxyde, monoisohexyltitanium trihydroxyde, mono-n-heptyltitanium trihydroxyde,Monoisoheptyl titanium trihydroxy, mono-n-octyl titanium trihydroxy, mono-n-isooctyl titanium trihydroxy, mono-n-nonyl titanium trihydroxy, mono-n-isononyl titanium trihydroxy, mono-n-decyl titanium trihydroxy, mono-n-isodecyl titanium trihydroxy, monomethyl hafnium trihydroxy, monoethyl hafnium trihydroxy, mono-n-propyl hafnium trihydroxy, monoisopropyl hafnium trihydroxy, mono-n-butyl hafnium trihydroxy, monoisobutyl hafnium trihydroxy, mono-n-pentyl hafnium trihydroxy, mono Examples include sopentylhafnium trihydroxyde, mono-n-hexylhafnium trihydroxyde, monoisohexylhafnium trihydroxyde, mono-n-heptylhafnium trihydroxyde, monoisoheptylhafnium trihydroxyde, mono-n-octylhafnium trihydroxyde, mono-n-isooctylhafnium trihydroxyde, mono-n-nonylhafnium trihydroxyde, mono-n-isononylhafnium trihydroxyde, mono-n-decylhafnium trihydroxyde, mono-n-isodecylhafnium trihydroxyde, zirconium tetrahydroxyde, titanium tetrahydroxyde, and hafnium tetrahydroxyde.

[0193] In some embodiments, the organometallic hydrolysis compound is present in the AIGS membrane composition at a concentration of at least 0.005% by weight (50 ppm). In some embodiments, the organometallic hydrolysis compound is present in the AIGS membrane composition in an amount of about 0.03 to about 3% by weight. In some embodiments, the organometallic hydrolysis compound is present in the membrane composition in an amount of about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6, about 2.7, about 2.8, about 2.9, or about 3% by weight.

[0194] Method for producing hydrolyzed compounds A method for producing hydrolysis compounds can be carried out by contacting the compound with water, an acidic solution, or a basic solution. In one embodiment, 10 μl of 1N NaOH aqueous solution is added to 1 g of zirconium propoxide in 4 ml of ethanol. The reaction mixture is stirred at room temperature for 30 minutes, and then 10 μl of 1N hydrochloric acid aqueous solution is added to neutralize the reaction mixture. The resulting viscous liquid is used as the hydrolysis product after removing volatile matter under vacuum.

[0195] Spin coating In some embodiments, nanostructured compositions are deposited on a substrate using spin coating. In spin coating, typically, a small amount of material is deposited at the center of a substrate loaded into a machine called a spinner, which is held in place by vacuum. When the substrate is rotated at high speed through the spinner, a centripetal force is generated, causing the material to spread from the center to the edges of the substrate. Most of the material is removed by spin, but a certain amount remains on the substrate, and if the rotation continues, a thin film of the material is formed on the surface. The final thickness of the film is determined by the properties of the deposited material and the substrate, in addition to parameters selected for the spin process, such as spin speed, acceleration, and spin time. For typical films, a spin speed of 1500 to 6000 rpm is used with a spin time of 10 to 60 seconds. In some embodiments, films are deposited at very low speeds, e.g., less than 1000 rpm. In some embodiments, films are cast at about 300, about 400, about 500, about 600, about 700, about 800, or about 900 rpm.

[0196] Mist accumulation In some embodiments, the nanostructured composition is deposited onto a substrate using mist deposition. Mist deposition is carried out at room temperature and atmospheric pressure, and the film thickness can be accurately controlled by varying the process conditions. During mist deposition, the liquid source material is transformed into very fine mists and carried into the deposition chamber by nitrogen gas. Thereafter, the mists are attracted to the wafer surface by a high voltage potential between the field screen and the wafer holder. When the droplets coalesce on the wafer surface, the wafer is removed from the chamber and thermally cured to evaporate the solvent. The liquid precursor is a mixture of a solvent and the material to be deposited. This is carried to the nebulizer by pressurized nitrogen gas. Price, S.C., et al., “Formation of Ultra-Thin Quantum Dot Films by Mist Deposition”, ESC Transactions 11:89-94(2007).

[0197] Spray coating In some embodiments, the nanostructured composition is deposited onto a substrate using spray coating. A typical apparatus for spray coating consists of a spray nozzle, a nebulizer, a precursor solution, and a carrier gas. In the spray deposition process, the precursor solution is pulverized into micro-sized droplets by a carrier gas or atomization (e.g., ultrasonic, air blast or electrostatic). The droplets emerging from the nebulizer are accelerated across the substrate surface through the nozzle with the aid of a carrier gas that is controlled and adjusted as needed. The relative movement between the spray nozzle and the substrate is defined by a design for the purpose of complete coverage on the substrate.

[0198] In some embodiments, the application of the nanostructured composition further comprises a solvent. In some embodiments, the solvent for the application of the nanostructured composition is water, an organic solvent, an inorganic solvent, a halogenated organic solvent, or a mixture thereof. Exemplary solvents include, but are not limited to, water, D2O, acetone, ethanol, dioxane, ethyl acetate, methyl ethyl ketone, isopropanol, anisole, γ-butyrolactone, dimethylformamide, N-methylpyrrolidinone, dimethylacetamide, hexamethylphosphoramide, toluene, dimethyl sulfoxide, cyclopentanone, tetramethylene sulfoxide, xylene, ε-caprolactone, tetrahydrofuran, tetrachloroethylene, chloroform, chlorobenzene, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, or a mixture thereof.

[0199] Inkjet printing Solvents suitable for inkjet printing of nanostructures are known to those skilled in the art. In some embodiments, the organic solvent is a substituted aromatic or heteroaromatic solvent described in U.S. Patent Application Publication No. 2018 / 0230321, which is incorporated herein by reference in its entirety.

[0200] In some embodiments, the organic solvent used in the nanostructured composition used as an inkjet printing formulation is defined by its boiling point, viscosity, and surface tension. Table 1 shows the properties of organic solvents suitable for inkjet printing formulations.

[0201]

Table 1

[0202] In some embodiments, the organic solvent has a boiling point of about 150°C to about 350°C at 1 atmosphere. In some embodiments, the organic solvent has a boiling point of about 150°C to about 350°C, about 150°C to about 300°C, about 150°C to about 250°C, about 150°C to about 200°C, about 200°C to about 350°C, about 200°C to about 300°C, about 200°C to about 250°C, about 250°C to about 350°C, about 250°C to about 300°C, or about 300°C to about 350°C at 1 atmosphere.

[0203] In some embodiments, organic solvents have a viscosity of approximately 1 mPa·s to approximately 15 mPa·s. In some embodiments, organic solvents have viscosities of approximately 1 mPa·s to approximately 15 mPa·s, approximately 1 mPa·s to approximately 10 mPa·s, approximately 1 mPa·s to approximately 8 mPa·s, approximately 1 mPa·s to approximately 6 mPa·s, approximately 1 mPa·s to approximately 4 mPa·s, approximately 1 mPa·s to approximately 2 mPa·s, approximately 2 mPa·s to approximately 15 mPa·s, approximately 2 mPa·s to approximately 10 mPa·s, approximately 2 mPa·s to approximately 8 mPa·s, approximately 2 mPa·s to approximately 6 mPa·s, and approximately 2 mPa·s. It has a viscosity of approximately 4 mPa·s, approximately 4 mPa·s to approximately 15 mPa·s, approximately 4 mPa·s to approximately 10 mPa·s, approximately 4 mPa·s to approximately 8 mPa·s, approximately 4 mPa·s to approximately 6 mPa·s, approximately 6 mPa·s to approximately 15 mPa·s, approximately 6 mPa·s to approximately 10 mPa·s, approximately 6 mPa·s to approximately 8 mPa·s, approximately 8 mPa·s to approximately 15 mPa·s, approximately 8 mPa·s to approximately 10 mPa·s, or approximately 10 mPa·s to approximately 15 mPa·s.

[0204] In some embodiments, the organic solvent has a surface tension of about 20 dynes / cm to about 50 dynes / cm. In some embodiments, the organic solvent has a surface tension of about 20 dynes / cm to about 50 dynes / cm, about 20 dynes / cm to about 40 dynes / cm, about 20 dynes / cm to about 35 dynes / cm, about 20 dynes / cm to about 30 dynes / cm, about 20 dynes / cm to about 25 dynes / cm, about 25 dynes / cm to about 50 dynes / cm, about 25 dynes / cm to about 40 dynes / cm, and about 25 dynes / cm. It has a surface tension of approximately 35 dynes / cm to 35 dynes / cm, approximately 25 dynes / cm to 30 dynes / cm, approximately 30 dynes / cm to 50 dynes / cm, approximately 30 dynes / cm to 40 dynes / cm, approximately 30 dynes / cm to 35 dynes / cm, approximately 35 dynes / cm to 50 dynes / cm, approximately 35 dynes / cm to 40 dynes / cm, or approximately 40 dynes / cm to 50 dynes / cm.

[0205] In some embodiments, the organic solvents used in the nanostructured composition are alkylnaphthalene, alkoxynaphthalene, alkylbenzene, aryl, alkylsubstituted benzene, cycloalkylbenzene, C9-C 20 These are alkanes, diaryl ethers, alkylbenzoates, arylbenzoates, or alkoxy-substituted benzenes.

[0206] In some embodiments, the organic solvents used in the nanostructured composition are 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, n-octylbenzene, n-nonylbenzene, 4-methylanisole, n-decylbenzene, p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, dipentylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, diphenyl ether, diphenylmethane, 4-isopropylbiphenyl, benzylbenzoate, 1,2-bi(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, or combinations thereof. In some embodiments, the organic solvents used in the nanostructured composition are 1-methylnaphthalene, n-octylbenzene, 1-methoxynaphthalene, 3-phenoxytoluene, cyclohexylbenzene, 4-methylanisole, n-decylbenzene, or a combination thereof.

[0207] In some embodiments, the organic solvent is an anhydrous organic solvent. In some embodiments, the organic solvent is substantially an anhydrous organic solvent.

[0208] In some embodiments, the organic solvent is a non-volatile monomer or combination of monomers selected from the list presented above.

[0209] In some embodiments, the weight percentage of organic solvent in the nanostructured composition is about 70% to about 99%. The percentages are approximately 80%, 80% to 99%, 80% to 98%, 80% to 95%, 80% to 90%, 80% to 85%, 85% to 99%, 85% to 98%, 85% to 95%, 85% to 90%, 90% to 99%, 90% to 98%, 90% to 95%, 95% to 99%, 95% to 98%, or 98% to 99%. In some applications, the weight percentage of organic solvents in the nanostructured composition is approximately 95% to 99%.

[0210] Film hardening In some embodiments, the composition is thermocured to form a nanostructure layer. In some embodiments, the composition is cured using UV light. In some embodiments, the nanostructure composition is directly coated onto a barrier layer of the nanostructure film, and then an additional barrier layer is deposited on the nanostructure layer to form the nanostructure film. Beneath the barrier film, a support substrate may be employed to enhance strength, stability, and coating uniformity, and to prevent material non-uniformity, bubble formation, wrinkles, or folds of the barrier layer material or other materials. Furthermore, one or more barrier layers may be deposited on the nanostructure layer to seal the material between the upper and lower barrier layers. Optionally, the barrier layers may be deposited as a laminate film, optionally sealed or further processed, and then the nanostructure film may be incorporated into a specific lighting device. The nanostructure composition deposition process may include additional or various components, as will be understood by those skilled in the art. Such embodiments allow for in-line process adjustment of nanostructure luminescence properties such as luminance and color (for example, to adjust the quantum film white point), as well as nanostructure film thickness and other properties. Furthermore, these embodiments allow for periodic testing of the properties of the nanostructured film during manufacturing, and any desired toggling to achieve precise nanostructured film properties. Such testing and adjustment can also be achieved without changing the mechanical configuration of the processing line, as a computer program can be employed to electronically change the amount of each component of the mixture used to form the nanostructured film.

[0211] It has been discovered that if AIGS nanocrystals are treated without exposure to blue or UV light before providing an oxygen-free environment for the nanostructure, a nanostructure film with high PCE can be obtained. An oxygen-free environment can be provided by: (a) The film is sealed with an oxygen barrier before heat treatment and / or exposure to blue light for PCE measurement. (b) Use of oxygen-reactive materials as part of a formulation between heat treatment or light exposure, and / or (c) Temporary blocking of oxygen by using a sacrificial barrier layer.

[0212] In some embodiments, PCE improvement is achievable by any method capable of forming an oxygen barrier on the AIGS layer. In mass production of devices containing these AIGS-CC layers, encapsulation can be performed using a deposition process. A typical process flow in this case involves inkjet printing of the AIGS layer, followed by curing by UV irradiation, firing at 180°C to remove volatiles, deposition of an organic planarization layer, followed by deposition of an inorganic barrier layer. Techniques used for depositing the inorganic layer include atomic layer deposition (ALD), molecular layer deposition (MLD), chemical vapor deposition (CVD) (with or without plasma enhancement), pulsed vapor deposition (PVD), sputtering, and metal deposition. Other potential encapsulation methods include lamination using solution-treated or printed organic layers, UV or thermosetting adhesives, and barrier films.

[0213] In some embodiments, the film is sealed in an inert atmosphere. In some embodiments, the film is sealed in a nitrogen or argon atmosphere.

[0214] Oxygen-reactive materials include any material that is more reactive to oxygen than AIGS nanostructures. Examples of oxygen-reactive materials include, but are not limited to, phosphines, phosphites, organometallic precursors, titanium nitride, and tantalum nitride. In some embodiments, phosphine is C 1~20 It may be any one of the trialkylphosphines. In one embodiment, the phosphine is trioctylphosphine. In some embodiments, the phospite may be a trialkylphosphine, alkylarylphosphine, or triarylphosphine. In some embodiments, the organometallic precursor may be trialkylaluminum, trialkylgallium, trialkylindium, dialkylzinc, etc.

[0215] Examples of sacrificial barrier layers include polymer layers that can be dissolved in a solvent and washed away. Examples of such polymers include, but are not limited to, polyvinyl alcohol, polyvinyl acetate, and polyethylene glycol. Other examples of sacrificial barrier layers include inorganic compounds or salts such as lithium silicate and lithium fluoride. Examples of solvents that can be used to wash away the sacrificial layer include water, and alcohols (e.g., ethanol, methanol), halocarbons (e.g., methylene chloride and ethylene chloride), aromatic hydrocarbons (e.g., toluene, xylene), aliphatic hydrocarbons (e.g., hexane, octane, octadecene), C 4~20 ethers, and organic solvents such as ethyl acetate. 2~20

[0216] Characteristics and Embodiments of the Nanostructured Film In some embodiments, the nanostructured film of the present invention is used to form a display device. As used herein, a display device refers to any system having an illumination display. Such devices include, but are not limited to, liquid crystal displays (LCDs), televisions, computers, mobile phones, smartphones, personal digital assistants (PDAs), gaming devices, electronic reading devices, digital cameras, augmented reality / virtual reality (AR / VR) glasses, light projection systems, head-up displays, and the like.

[0217] In some embodiments, the nanostructured film is part of a nanostructured color conversion layer.

[0218] In some embodiments, the display device includes a nanostructured color converter. In some embodiments, the display device includes a backplane, a display panel disposed on the backplane, and a nanostructured layer. In some embodiments, the nanostructured layer is disposed on the display panel. In some embodiments, the nanostructured layer includes a patterned nanostructured layer.​

[0219] In some embodiments, the backplane includes blue LEDs, LCDs, OLEDs, or microLEDs.

[0220] In some embodiments, the nanostructure layer is arranged on a light source element. In some embodiments, the nanostructure layer includes a patterned nanostructure layer. The patterned nanostructure layer can be prepared by any method known in the art. In one embodiment, the patterned nanostructure layer is prepared by inkjet printing of a solution of nanostructures. Suitable solvents for the solution include, but are not limited to, dipropylene glycol monomethyl ether acetate (DPMA), polyglycidyl methacrylate (PGMA), diethylene glycol monoethyl ether acetate (EDGAC), and propylene glycol methyl ether acetate (PGMEA). Volatile solvents can also be used for inkjet printing to enable rapid drying. Volatile solvents include ethanol, methanol, 1-propanol, 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and tetrahydrofuran. Alternatively, a "solvent-free" ink in which the AIGS nanostructure is dispersed in an ink monomer may be used for inkjet printing.

[0221] In some embodiments, the nanostructured layer has a thickness of about 1 μm to about 25 μm. In some embodiments, the nanostructured layer has a thickness of about 5 μm to about 25 μm. In some embodiments, the nanostructured layer has a thickness of about 10 μm to about 12 μm.

[0222] In some embodiments, the nanostructured display device exhibits at least 32% PCE. In some embodiments, the nanostructured molded article exhibits 32-40% PCE. In some embodiments, the nanostructured molded article exhibits PCE of 33-40%, 34-40%, 35-40%, 36-40%, 37-40%, 38-40%, 39-40%, 33-39%, 34-39%, 35-39%, 36-39%, 37-39%, 38-39%, 33-38%, 34-38%, 35-38%, 36-38%, 37-38%, 33-37%, 34-37%, 35-37%, 36-37%, 33-36%, 34-36%, 35-36%, 33-35%, or 34-35%.

[0223] In some embodiments, optical films containing nanostructured layers are substantially cadmium-free. As used herein, the term “substantially cadmium-free” means that the nanostructured composition contains less than 100 ppm by weight of cadmium. The RoHS-compliant definition requires that there should be no more than 0.01% by weight (100 ppm) of cadmium in the raw, homogeneous precursor material. Cadmium concentration can be measured at the parts per billion (ppb) level by inductively coupled plasma mass spectrometry (ICP-MS) analysis. In some embodiments, “substantially cadmium-free” optical films contain 10 to 90 ppm of cadmium. In other embodiments, substantially cadmium-free optical films contain less than about 50 ppm, less than about 20 ppm, less than about 10 ppm, or less than about 1 ppm of cadmium.

[0224] Nanostructured molded articles In some embodiments, this disclosure is, (a) First barrier layer, (b) A second barrier layer, and (c) Nanostructure layer between the first barrier layer and the second barrier layer The present invention provides a nanostructured molded article comprising an AIGS nanostructure and a group of nanostructures comprising one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof, and at least one organic resin.

[0225] In some embodiments, the nanostructure has a PWL of 480-545 nm.

[0226] In some embodiments, at least 80% of the emission is band-edge emission. In other embodiments, at least 90% of the emission is band-edge emission. In other embodiments, at least 95% of the emission is band-edge emission. In some embodiments, 92–98% of the emission is band-edge emission. In some embodiments, 93–96% of the emission is band-edge emission. In some embodiments, the nanostructured molded article exhibits at least 32% PCE. In some embodiments, the nanostructured molded article exhibits 32–40% PCE. In some embodiments, the nanostructured molded articles exhibit PCE of 33-40%, 34-40%, 35-40%, 36-40%, 37-40%, 38-40%, 39-40%, 33-39%, 34-39%, 35-39%, 36-39%, 37-39%, 38-39%, 33-38%, 34-38%, 35-38%, 36-38%, 37-38%, 33-37%, 34-37%, 35-37%, 36-37%, 33-36%, 34-36%, 35-36%, 33-35%, or 34-35%.

[0227] Barrier layer In some embodiments, the nanostructured article includes one or more barrier layers positioned on either one or both sides of the nanostructure layer. A suitable barrier layer protects the nanostructure layer and the nanostructured article from environmental conditions such as high temperature, oxygen, and moisture. Suitable barrier materials include hydrophobic, chemically and mechanically compatible, photostable and chemically stable, and high-temperature resistant non-yellowing transparent optical materials. In some embodiments, one or more barrier layers are index-matched to the nanostructured article. In some embodiments, the matrix material of the nanostructured article and one or more adjacent barrier layers are index-matched to have similar refractive indices so that most of the light transmitted through the barrier layers toward the nanostructured article is transmitted from the barrier layers to the nanostructure layer. This index-matching reduces light loss at the interface between the barrier layer and the matrix material.

[0228] The barrier layer is preferably a solid material and can be a cured liquid, gel, or polymer. Depending on the specific application, the barrier layer may include a flexible or non-flexible material. The barrier layer is generally a planar layer and may include any suitable shape and surface area configuration depending on the specific lighting application. In some embodiments, one or more barrier layers are adapted to a lamination process, thereby the nanostructure layer is placed on at least a first barrier layer and at least a second barrier layer is placed on the nanostructure layer on the opposite side to the nanostructure layer to form a nanostructured molded article according to one embodiment of the present invention. Suitable barrier materials include any suitable barrier material known in the art. For example, suitable barrier materials include glass, polymers, and oxides. Suitable barrier layer materials include, but are not limited to, polymers such as polyethylene terephthalate (PET); oxides such as silicon dioxide, titanium dioxide, or aluminum oxide (e.g., SiO2, Si2O3, TiO2, or Al2O3); and suitable combinations thereof. In some embodiments, each barrier layer of a nanostructured molded article comprises at least two layers containing different materials or compositions, and the multilayer barrier eliminates or reduces the alignment of pinhole defects in the barrier layer and provides an effective barrier against the penetration of oxygen and moisture into the nanostructure layer. The nanostructure layer may include any suitable material or combination of materials, and any suitable number of barrier layers on either side or both sides of the nanostructure layer. The material, thickness, and number of barrier layers depend on the specific application and are appropriately selected to maximize the barrier protection and brightness of the nanostructure layer while minimizing the thickness of the nanostructured molded article. In some embodiments, each barrier layer includes a laminate film, and in some embodiments, a double laminate film, and the thickness of each barrier layer is sufficient to eliminate wrinkles in a roll-to-roll or lamination manufacturing process. The number or thickness of barriers may further depend on legal toxicity guidelines in embodiments in which the nanostructure contains heavy metals or other toxic substances, and these guidelines may require more or thicker barrier layers. Additional considerations regarding barriers include cost, availability, and mechanical strength.

[0229] In some embodiments, the nanostructured film includes two or more barrier layers adjacent to each side of the nanostructured layer, for example, two or three layers on each side, or two barrier layers on each side of the nanostructured layer. In some embodiments, each barrier layer includes a thin glass sheet, for example, a glass sheet having a thickness of about 100 μm, less than 100 μm, or less than 50 μm.

[0230] Each barrier layer of the nanostructured film of the present invention can have any suitable thickness, which will be understood by those skilled in the art, depending on the specific requirements and characteristics of the lighting device and application, as well as the individual film components such as the barrier layers and nanostructured layers. In some embodiments, each barrier layer may have a thickness of 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, or 15 μm or less. In certain embodiments, the barrier layer includes an oxide coating, which may include materials such as silicon dioxide, titanium dioxide, or aluminum oxide (e.g., SiO2, Si2O3, TiO2, or Al2O3). The oxide coating may have a thickness of about 10 μm or less, 5 μm or less, 1 μm or less, or 100 nm or less. In certain embodiments, the barrier includes a thin oxide coating with a thickness of about 100 nm or less, 10 nm or less, 5 nm or less, or 3 nm or less. The upper and / or lower barrier may consist of an oxide thin film coating, or may include an oxide thin film coating and one or more additional material layers.

[0231] Display device having a nanostructured color conversion layer In some embodiments, the present invention is (a) A display panel that emits a first light, (b) a backlight unit configured to supply a first light to the display panel, and (c) A color filter including at least one pixel region containing a color conversion layer. We provide a display device that includes [this component].

[0232] In some embodiments, the color filter comprises at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 pixel regions. In some embodiments, when blue light is incident on the color filter, red, white, green, and / or blue light may be emitted through the pixel regions, respectively. In some embodiments, the color filter is described in U.S. Patent No. 9,971,076, which is incorporated herein by reference in its entirety.

[0233] In some embodiments, each pixel region includes a color conversion layer. In some embodiments, the color conversion layer includes a nanostructure described herein configured to convert incident light into light of a first color. In some embodiments, the color conversion layer includes a nanostructure described herein configured to convert incident light into blue light.

[0234] In some embodiments, the display device includes 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 color conversion layers. In some embodiments, the display device includes one color conversion layer containing the nanostructure described herein. In some embodiments, the display device includes two color conversion layers containing the nanostructure described herein. In some embodiments, the display device includes three color conversion layers containing the nanostructure described herein. In some embodiments, the display device includes four color conversion layers containing the nanostructure described herein. In some embodiments, the display device includes at least one red color conversion layer, at least one green color conversion layer, and at least one blue color conversion layer.

[0235] In some embodiments, the color conversion layer has a thickness between approximately 3 μm and approximately 10 μm, approximately 3 μm and approximately 8 μm, approximately 3 μm and approximately 6 μm, approximately 6 μm and approximately 10 μm, approximately 6 μm and approximately 8 μm, or approximately 8 μm and approximately 10 μm. In some embodiments, the color conversion layer has a thickness between approximately 3 μm and approximately 10 μm.

[0236] The nanostructured color conversion layer can be deposited by any suitable method known in the art, but is not limited to painting, spray coating, solvent spray, wet coating, adhesive coating, spin coating, tape coating, roll coating, flow coating, inkjet printing, photoresist patterning, drop casting, blade coating, mist deposition, or a combination thereof. In some embodiments, the nanostructured color conversion layer is deposited by photoresist patterning. In some embodiments, the nanostructured color conversion layer is deposited by inkjet printing.

[0237] Composition containing AIGS nanostructures and ligands In some embodiments, the AIGS nanostructure composition further comprises one or more ligands. The ligands include amino ligands, polyamino ligands, mercapto ligands, phosphino ligands, silane ligands, and polymer or oligomer chains such as polyethylene glycol having amine and silane groups.

[0238] In some embodiments, the amino ligand has the following formula I. [ka] During the ceremony, x is between 1 and 100. y is between 0 and 100, and R 2 is C1~ 20 It is alkyl.

[0239] In some embodiments, the polyamino ligand is a polyaminoalkane, polyaminecycloalkane, polyamino heterocyclic compound, polyamino-functionalized silicone, or polyamino-substituted ethylene glycol. In some embodiments, the polyamino ligand is a C2-substituted compound with two or three amino groups. 20 Alkane or C2~ 20The polyamino ligand is a cycloalkane, optionally containing one or two amino groups instead of a carbon group. In some embodiments, the polyamino ligand is ethylenediamine, 1,2-diaminopropane, 1,2-diamino-2-methylpropane, N-methylethylenediamine, N-ethylethylenediamine, N-isopropylethylenediamine, N-cyclohexylethylenediamine, N-cyclohexylethylenediamine, N-octylethylenediamine, N-decylethylenediamine, N-dodecylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N'- Diethyl-ethylenediamine, N,N'-diisopropylethylenediamine, N,N,N'-trimethylethylenediamine, diethylenetriamine, N-isopropyl-diethylenetriamine, N-(2-aminoethyl)-1,3-propanediamine, triethylenetetramine, N,N'-bis(3-aminopropyl)ethylenediamine, N,N'-bis(2-aminoethyl)-1,3-propanediamine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, 2-(2-aminoethyl Mino) Ethanol, N,N-bis(hydroxyethyl)ethylenediamine, N-(hydroxyethyl)diethylenetriamine, N-(hydroxyethyl)triethylenetetramine, piperazine, 1-(2-aminoethyl)piperazine, 4-(2-aminoethyl)morpholine, polyethyleneimine, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diminopemane, 2,2-dimethyl-1,3-propanediamine, hexamethylenediamine, 2-methyl-1,5-diaminopropane, 1,7-di Aminoheptane, 1,8-diaminooctane, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-isopropyl-1,3-propanediamine, N,N-dimethyl-1,3-propanediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3-propanediamine, N,N'-Diisopropyl-1,3-propanediamine, N,N,N'-Trimethyl-1,3-propanediamine, 2-Butyl-2-ethyl-1,5-pentanediamine, N,N'-Dimethyl-1,6-Hexanediamine, 3,3'-Diamino-N-methyl-dipropylamine, N-(3-aminopropyl)-1,3-propanediamine, Spermidine, Bis(hexamethylene)triamine, N,N',N''-Trimethyl-bis(hexamethylene)triamine, 4-Amino-1,8-Octanediamine, N,N'-Bis(3-aminopropyl)-1,3-propiediamine, S The polyamino ligands are permine, 4,4'-methylenebis(cyclohexylamine), 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-cyclohexanebis(methylamine), 1,4-cyclohexanebis(methylamine), 1,2-bis(aminoethoxy)ethane, 4,9-dioxa-1,12-dodecanediamine, 4,7,10-trioxa-1,13-tridecanediamine, 1,3-diamino-hydroxy-propane, 4,4-methylenedipiperidine, 4-(aminomethyl)piperidine, 3-(4-aminobutyl)piperidine, or polyallylamine. In some embodiments, the polyamino ligand is 1,3-cyclohexanebis(methylamine), 2,2-dimethyl-1,3-proparndiamine, or tris(2-aminoethyl)amine.

[0240] In some embodiments, the polyamino ligand is a polyamino heterocyclic compound. In some embodiments, the polyamino heterocyclic compound is 2,4-diamino-6-phenyl-1,3,5-triazine, 6-methyl-1,3,5-triazine-2,4-diamine, 2,4-diamino-6-diethylamino-1,3,5-triazine, 2-N,4-N,6-N-tripropyl-1,3,5-triazine-2,4,6-triamine, 2,4-diaminopyrimidine, 2,4,6-triaminopyrimidine, 2,5-diaminopyridine, 2,4,5,6-tetraaminopyrimidine, pyridine-2,4,5-triamine, 1-(3-aminopropyl)imidazole, 4-phenyl-1H-imidazole-1,2- These are diamines, 1H-imidazole-2,5-diamine, 4-phenyl-N(1)-[(E)-phenylmethylidene]-1H-imidazole-1,2-diamine, 2-phenyl-1H-imidazole-4,5-diamine, 1H-imidazole-2,4,5-triamine, 1H-pyrrole-2,5-diamine, 1,2,4,5-tetrazine-3,6-diamine, N,N'-dicyclohexyl-1,2,4,5-tetrazine-3,6-diamine, N3-propyl-1H-1,2,4-triazole-3,5-diamine, or N,N'-bis(2-methoxybenzyl)-1H-1,2,4-triazole-3,5-diamine.

[0241] In some embodiments, the polyamino ligand is a polyamino-functionalized silicone. In some embodiments, the polyamino-functionalized silicone is [ka] It is one type of.

[0242] In some embodiments, the polyamino ligand is a polyamino-substituted ethylene glycol. In some embodiments, the polyamino-substituted ethylene glycol is 2-[3-amino-4-[2-[2-amino-4-(2-hydroxyethyl)phenoxy]ethoxy]phenyl]ethanol, 1,5-diamino-3-oxapentane, 1,8-diamino-3,6-dioxaoctane, bis[5-chloro-1H-indole-2-YL-carbonyl-aminoethyl]ethylene glycol, amino-PEG8-t-Boc-hydrazide, or 2-(2-(2-ethoxyethoxy)ethoxy)ethaneamine.

[0243] In some embodiments, the mercapto ligands are (3-mercaptopropyl)triethoxysilane, 3,6-dioxa-1,8-octanedithiol; 6-mercapto-1-hexanol; mercaptosuccinic acid, mercaptoundecanoic acid, mercaptohexanoic acid, mercaptopropionic acid, mercaptoacetic acid, cysteine, methionine, and mercaptopoly(ethylene glycol).

[0244] In some embodiments, the silane ligand is an aminoalkyltrialkoxysilane or a thioalkyltrialkoxysilane. In some embodiments, the aminoalkyltrialkoxysilane is 3-aminopropyl)triethoxysilane or 3-mercaptopropyl)triethoxysilane.

[0245] In some embodiments, ligands include, but are not limited to, aminopolyalkylene oxides (e.g., mw approximately 1000); (3-aminopropyl)trimethoxysilane; (3-mercaptopropyl)triethoxysilane; DL-α-lipoic acid; 3,6-dioxa-1,8-octanedithiol; 6-mercapto-1-hexanol; methoxypolyethylene glycolamine (mw approximately 500); poly(ethylene glycol)methyl ether thiol (mw approximately 800); diethylphenylphosphonite; dibenzyl N,N-diisopropyl phosphoramidite; di-tert-butyl N,N-diisopropyl phosphoramidite; tris(2-carboxyethyl)phosphine hydrochloride; poly(ethylene glycol)methyl ether thiol (mw approximately 2000); methoxypolyethylene glycolamine (mw approximately 750); acrylamide; and polyethyleneimine.

[0246] Specific ligand combinations include aminopolyalkylene oxide (mW approximately 1000) and methoxypolyethylene glycolamine (mW approximately 500); amino-polyalkylene oxide (mW approximately 1000) and 6-mercapto-1-hexanol; aminopolyalkylene oxide (mW approximately 1000) and (3-mercaptopropyl)triethoxysilane; and 6-mercapto-1-hexanol and methoxypolyethylene glycolamine (mW approximately 500), which yielded excellent dispersibility and thermal stability. See Example 9.

[0247] Films containing AIGS nanostructures and polyamino ligands exhibit higher film photoconversion efficiency (PCE), less wrinkling, and less film delamination compared to AIGS-containing films without polyamino ligands, and compared to films with monoamino ligands. Thus, compositions containing AIGS-polyamino ligands are particularly suitable for use in nanostructured color conversion layers.

[0248] scattering medium The AIGS film may further contain a scattering medium. Examples of usable scattering mediums, but are not limited to, metal or metal oxide particles, bubbles, and glass beads and polymer beads (solid or hollow). In some embodiments, the scattering medium is spherical. In some embodiments, but are not limited to, TiO2, SiO2, BaTiO3, BaSO4, and ZnO particles.

[0249] The following examples are illustrative of, and not limiting, the products and methods described herein. Appropriate modifications and improvements to various conditions, formulations, and other parameters commonly encountered in the art and obvious to those skilled in the art from the viewpoint of this disclosure are within the spirit and scope of the present invention. [Examples]

[0250] Example 1: AIGS core synthesis Sample ID1 was prepared using the following typical AIGS core synthesis: 4 mL of 0.06 M CH3CO2Ag in oleylamine, 1 mL of 0.2 M InCl3 in ethanol, 1 mL of 0.95 M sulfur in oleylamine, and 0.5 mL of dodecanethiol were poured into a flask containing 5 mL of degassed octadecene, 300 mg of trioctylphosphine oxide, and 170 mg of gallium acetylacetonate. The mixture was heated to 40°C for 5 minutes, then the temperature was raised to 210°C and held for 100 minutes. After cooling to 180°C, 5 mL of trioctylphosphine was added. The reaction mixture was transferred to a glove box and diluted with 5 mL of toluene. The final AIGS product was precipitated by adding 75 mL of ethanol, centrifugation, and redispersion in toluene. Samples ID2 and 3 were also prepared using this method. The optical properties of the AIGS cores were measured and summarized in Table 1. The size and morphology of the AIGS cores were evaluated by transmission electron microscopy (TEM).

[0251] [Table 2]

[0252] Example 2: AIGS nanostructures subjected to ion exchange treatment Sample ID4 was prepared using the following typical ion exchange procedure: 2 mL of 0.3 M gallium oleate solution and 12 mL of oleylamine in octadecene were introduced into a flask and degassed. The mixture was heated to 270°C. A premixed solution of 1 mL of 0.95 M sulfur solution in oleylamine and 1 mL of isolated AIGS core (15 mg / mL) was simultaneously added. The reaction was stopped after 30 minutes. The final product was transferred to a glove box, washed with toluene / ethanol, centrifuged, and redispersed in toluene. Samples ID4-8 were also prepared using this method. The optical properties of the AIGS nanostructures thus prepared are summarized in Table 2. Nearly perfect band-edge emission was obtained by ion exchange with gallium ions. An increase in average particle size was observed by TEM.

[0253] [Table 3]

[0254] Example 3: Ion exchange treatment of gallium halide and trioctylphosphine A GaI3 solution (0.01-0.25 M) in trioctylphosphine was added to AIGS QDs and held at room temperature for 20 hours to induce a room-temperature ion exchange reaction with the AIGS nanostructure. This treatment significantly enhanced the band-edge emission shown in Table 3 while substantially maintaining the peak wavelength (PWL).

[0255] As shown in Table 3, the compositional changes before and after GaI3 addition were monitored using inductively coupled plasma atomic emission spectroscopy (ICP-AES) and energy-dispersive X-ray spectroscopy (EDS). The composite image of the elemental distributions of In and Ga before and after GaI3 / TOP treatment shows a radial distribution from In to Ga, indicating that the ion exchange treatment created a gradient in which the amount of gallium was high near the surface of the nanostructure and low in the center.

[0256] [Table 4]

[0257] Example 4: AIGS ion exchange treatment using an oxygen-free Ga source Samples IDs 14 and 15 were prepared using the following typical treatment of AIGS nanoparticles with an oxygen-free Ga source: 400 mg of GaCl3 dissolved in 400 μL of toluene was added to 8 mL of degassed oleylamine, followed by 40 mg of AIGS core, and then 1.7 mL of 0.95 M sulfur in the oleylamine. After heating to 240 °C, the reaction was held for 2 hours and then cooled. The final product was transferred to a glove box, washed with toluene / ethanol, centrifuged, and redispersed in toluene. Samples IDs 15 and 16 were also prepared using this method. Samples IDs 11-13 were prepared using the method of Example 2. The optical properties of the treated AIGS materials are shown in Table 4.

[0258] [Table 5]

[0259] As shown in Table 4, when using oleylamine as a solvent, the quantum yield of the treated AIGS nanostructure can be improved by using Ga(III) chloride instead of Ga(III) acetylacetonate or gallium oleate. The final material ion-exchanged with Ga(III) chloride exhibited similar size and similar band edge characteristics for trap luminescence to the starting nanostructure. Therefore, the increase in quantum yield (QY) is not simply due to an increase in the trap luminescence component. Furthermore, it was surprisingly found that when Ga(III) iodide was used instead of Ga(III) chloride, the AIGS nanostructure dissolved in the reaction mixture and no ion exchange occurred.

[0260] High-resolution TEM using energy-dispersive X-ray spectroscopy (EDS) on sample 14 suggests that the nanostructure likely contains a slight gradient in In concentration from the AIGS nanostructure center toward the surface, indicating that processing under these conditions results from a process where In is replaced by Ga, but Ag is present throughout the entire structure rather than growing a distinct layer of GS. This may also contribute to an improved quantum yield of the nanostructure due to the lower strain.

[0261] Example 5: AIGS core by hot implantation of preformed Ag2S nanostructures mixed with preformed In-Ga reagent. To produce the Ag2S nanostructure, 0.5 g of AgI and 2 mL of oleylamine were added to a 20 mL vial under an N2 atmosphere and stirred at 58°C until a clear solution was obtained. In another 20 mL vial, 5 mL of DDT and 9 mL of 0.95 M sulfur in the oleylamine were mixed. The DDT+S-OYA mixture was added to the AgI solution and stirred at 58°C for 10 minutes. The resulting Ag2S nanoparticles were used without washing.

[0262] To prepare the In-Ga reagent mixture, 1.2 g of Ga(acetylacetonate)3, 0.35 g of InCl3, 2.5 mL of oleylamine, and 2.5 mL of ODE were placed in a 100 mL flask. The mixture was heated to 210 °C under an N2 atmosphere and held for 10 minutes. An orange, viscous product was obtained.

[0263] To form AIGS nanoparticles, 1.75 g of TOPO, 23 mL of oleylamine, and 25 mL of ODE were added to a 250 mL flask under N2. After degassing under vacuum, this solvent mixture was heated to 210°C over 40 minutes. In a 40 mL vial, Ag2S and the above In-Ga reagent mixture were mixed at 58°C and transferred to a syringe. Next, the Ag-In-Ga mixture was injected into the solvent mixture at 210°C and held for 3 hours. After cooling to 180°C, 5 mL of trioctylphosphine was added. The reaction mixture was transferred to a glove box and diluted with 50 mL of toluene. 150 mL of ethanol was added, and the final product was precipitated by centrifugation and redispersion in toluene. Subsequently, the AIGS nanostructures were ion-exchanged according to the method described in Example 4. The optical properties of the materials produced by this method are shown in Table 5 on a scale up to 24 times the above.

[0264] [Table 6]

[0265] Example 7 Repeated gallium ion exchange improves the photoluminescence stability of AIGS nanostructures. 7.1 First ion exchange process Oleylamine (OYA, 2.5 L) is degassed under vacuum at 40°C for 40 minutes. AIGS nanostructure (25.4 g in toluene) is added, followed by GaCl3 (minimum 127 g in toluene) and sulfur dissolved in OYA (0.95 M, 570 mL). The mixture is heated to 240°C over 40 minutes and held for 4 hours. After cooling, the mixture is diluted with 1 volume of toluene. After removing by-products by centrifugation, the material is washed with 2 volumes of ethanol, recovered by centrifugation, and redissolved in toluene. After the second wash, the nanostructure is dissolved in heptane and stored.

[0266] 7.2 Second Ion Exchange Process Oleylamine (OYA, 960 mL) is degassed under vacuum at 40°C for 20 minutes. AIGS ion exchange nanostructures (12 g in heptane) as in Example 7.1 are added to OYA, followed by GaCl3 (22.5 g in a minimum amount of toluene), and then sulfur dissolved in OYA (0.95 M, 100 mL). The mixture is heated to 240°C over 40 minutes and held for 3 hours. After cooling, the mixture is diluted with 1 volume of toluene, washed (precipitated with 1.6 volume of ethanol and centrifuged), and redispersed in toluene or heptane as needed. If ligand exchange of the ink formulation is required, further ethanol washing is performed and the QDs are redispersed in heptane.

[0267] 7.3 Another second ion exchange process Oleylamine (15 mL) is degassed under vacuum at 60°C for 20 minutes. GaCl3 (360 mg in the minimum amount of toluene) is added to OYA, followed by AIGS (200 mg in heptane) as in Example 7.1, and then sulfur (0.95 M, 1.6 mL) dissolved in OYA. The mixture is heated to 240°C over 40 minutes and held for 3 hours. After cooling, the mixture is washed according to the method described in Example 7.1.

[0268] 7.4 Another second ion exchange process This embodiment was carried out as described in Example 7.3, but on a 3x scale.

[0269] 7.5 Another second ion exchange process Oleylamine (10 mL) and oleic acid (5 mL) are degassed under vacuum at 90°C for 20 minutes. (Ga(NMe3)3)2 (206 mg) and GaCl3 (180 mg in the minimum amount of toluene) are added, followed by AIGS (200 mg in heptane) as in Example 7.1. After heating to 130°C, TMS2S (0.65 mL of a 50% solution in ODE) is added over 20 minutes, and the mixture is held for 2.5 hours. After cooling, the mixture is washed by the method described in Example 7.1.

[0270] 7.6 Results AIGS nanostructures were subjected to an ion exchange process in which In was exchanged for Ga. Due to the higher temperature used in this process compared to core growth (240°C vs. 210°C), maturation progressed, resulting in a larger average size than the untreated nanostructures. These nanostructures exhibited insufficient shell differentiation, which can be observed in cross-sectional TEM elemental mapping. The lack of higher bandgap shells is expected to limit the retention of photoluminescence in these materials during film processing.

[0271] After the second ion exchange process, the average TEM size did not increase (Figures 2A-2C), but TEM elemental mapping showed a more pronounced gradient towards the Ga-rich (higher band gap) region in the QD.

[0272] Table 6 shows the elemental compositions of the single ion exchange process and the multiple ion exchange process. The values ​​are the average values ​​of 10 to 20 samples from Examples 7.1 and 7.2.

[0273] [Table 7]

[0274] Table 7 shows the properties of ion-exchanged AIGS nanostructures. The metallicity ratio is the molar ratio determined by ICP.

[0275] [Table 8]

[0276] The film PCE retained after UV curing and 180°C firing is significantly improved by the second ion exchange process, as shown in Table 8. This is thought to be because the process of increasing the Ga concentration in the outer layer of the nanostructure leads to a gradient to a higher band gap region introduced by ion exchange.

[0277] [Table 9]

[0278] Example 8 - Composition containing AIGS nanostructure and polyamino ligand Abbreviation - Jeffamine - Jeffamine M-1000 - HDDA - 1-6 Hexanediol diacrylate - Bismethylamine - 1,3-cyclohexanebismethylamine - PCE - Photon conversion efficiency

[0279] The crude AIGS QD growth solution was purified by washing with ethanol and redispersing in heptane (Solution 1). 6-mercapto-1-hexanol was added to Solution 1, heated at 50°C for 30 minutes, washed with ethanol, and redispersed in heptane (Solution 2). 2 μL of 6-mercapto-1-hexanol was added per 100 mg of QD inorganic solid. Jeffamine and HDDA were added to Solution 2 for the ligand exchange step, heated at 80°C for 1 hour, precipitated with heptane, and redispersed in HDDA (Solution 3). 83 mg of Jeffamine was added per 100 mg of QD inorganic solid. 0.42 g of HDDA was added per 100 mg of QD inorganic solid. Solution 3 and HDDA were added to an inkjet ink composition containing 10% by weight of TiO2 and 90% by weight of monomer. This inkjet formulation had a composition consisting of 10% by weight of QD inorganic mass, 4% by weight of TiO2, and the remaining 86% by weight of ligands (bonded and unbonded), HDDA, monomers, photopolymerization initiators, and other miscellaneous organic substances remaining from the QD solution. This ink formulation was Solution 4.

[0280] The polyamino ligand bismethylamine (50 mg of bismethylamine per 100 mg of QD inorganic solid) was added to solution 4, and the composition was then cast as a film.

[0281] Membrane casting Solution 4 was spin-coated onto a 2-inch x 2-inch glass substrate. The film was cured with a UV LED curing lamp. The photoconversion efficiency (PCE), a measure of brightness, was then tested. Subsequently, the film was baked for 30 minutes at a height slightly above the hot plate set to 180°C. Alternatively, the film was baked for 10 minutes in direct contact with a hot surface on a hot plate set to 180°C.

[0282] Next, the film PCE was tested. A 1-inch x 1-inch mask array of blue 448nm LEDs provided the excitation light source for the film. An integrating sphere was placed on the film and connected to a fluorometer. See Figures 3A and 3B. The collected spectra were analyzed to determine the PCE.

[0283] PCE is the ratio of the number of green photons in forward emission to the number of blue photons generated by the test platform. PCE, LRR, and film morphology are reported in Table 9. Unexpectedly, the presence of ligands 1,3-cyclohexanebis(methylamine), tris(2-aminoethyl)amine, and 2,2-dimethyl-1,3-propanediamine resulted in higher PCE retention, higher LRR, and no wrinkles after calcination at 180°C compared to films without ligands.

[0284] [Table 10]

[0285] Figure 1 shows the effect of diamine addition on membrane morphology. The membranes in Figure 1, from left to right, contained the following: no diamine (wrinkling); 2,2-dimethyl-1,3-propanediamine (diamine, no wrinkling); cyclohexanemethylamine (monoamine, wrinkling); and tris(2-aminoethyl)amine (triamine, no wrinkling). From left to right, the first and third membranes, which did not contain diamine, showed extensive wrinkling. In contrast, the second and fourth membranes showed no wrinkling. Unexpectedly, the use of diamino ligands in AIGS membranes resulted in a significant reduction in membrane wrinkling.

[0286] Example 9 - Testing of additional ligands for AIGS nanostructures In this experiment, additional ligands for AIGS nanoparticles were tested for improved QY, high compatibility, and good thermal stability. Furthermore, these ligands were evaluated for their ability to protect AIGS nanostructures from degradation and oxidation. Combinations of ligands suitable for incorporation into AIGS ink compositions were also tested.

[0287] Ligand exchange using these ligands was carried out in organic solvents such as ethyl acetate, PGMEA, acetone, xylene, 1,2-dichlorobenzene (ODCB), butyl acetate, and diethylene glycol monoethyl ether (DGMEE).

[0288] AIGS nanostructures were copassivated by ligand exchange with polymer chains or oligomer chains such as polyethylene glycol having amine and silane groups, and ligands containing soft bases such as phosphino groups, mercapto groups, and combinations thereof.

[0289] Figure 4 shows the quantum yield values ​​of various individual ligands and AIGS nanostructures subjected to a single ion-exchange treatment as described herein. In this graph, NG: Native AIGS; NG-NL1: Aminopolyalkylene oxide approx. mw 1000; NG-NL2: (3-aminopropyl)trimethoxysilane; NG-NL3: (3-mercaptopropyl)triethoxysilane; NG-NL4: DL-α-lipoic acid; NG-NL5: 3,6-dioxa-1,8-octanedithiol; NG-NL6: 6-mercapto-1-hexanol; NG-NL7: Methoxypolyethylene glycolamine 500; NG-NL8: Poly(ethylene glycol)methyl etherthiol Mn800; NG-NL9: Diethylphenylphosphonite; NG-NL10: Dibenzyl N,N-diisopropylphosphoramidite; NG-NL11: Di-tert-butyl N,N-diisopropylphosphoramidite; NG-NL12: Tris(2-carboxyethyl)phosphine hydrochloride; NG-NL13: Poly(ethylene glycol)methyl etherthiol Mn2000; NG-NL14: Methoxypolyethylene glycolamine 750; NG-NL15: Acrylamide; and NG-NL16: Polyethyleneimine).

[0290] As can be seen in Figure 4, high QY was obtained when AIGS nanostructures were treated with 3-mercaptopropyl)triethoxysilane (NL3), 3,6-dioxa-1,8-octanedithiol (NL5), and 6-mercapto-1-hexanol (NL6) (73.7%, 72.9%, and 76.1%, respectively). Therefore, the present invention provides an AIGS nanostructure composition comprising at least one mercapto-substituted ligand that provides improved QY. It is thought that the mercapto-substituted ligands provide high QY by passivating the surface of the AIGS nanostructure and reducing defect release. Amino-substituted ligands also improved QY.

[0291] In this single-ligand test, polyethylene glycolamine-substituted ligands (L1, L7, L8, and L13), thiol-substituted ligands (L3, L5, and L6), and silane ligand (L2) showed good QY compared to native AIGS nanostructures. Furthermore, ligands L1, L7, and L8 showed improved compatibility with monomers when dispersed in HDDA.

[0292] Figure 5 is a graph showing the QY% of various 2-ligand combinations that yielded improved QY% (good combinations) and decreased QY% (poor combinations). Surface defects can be reduced by adding thiol ligands. The L6 and L7 combination gave better stability than others. However, in relatively hydrophilic ink compositions, relatively hydrophilic ligands such as methoxypolyethylene glycolamine and poly(ethylene glycol)methyl ether thiol perform well. This thiol also improves QY by passivating surface defects.

[0293] The optimal temperature range for ligand exchange is from room temperature to 120°C. The total amount of ligands in the composition may be 60% to 150% of the mass of AIGS.

[0294] Table 10 shows the relative changes in QY, PWL, and FWHM before and after ligand exchange using multiple ligands. Table 10 indicates that L6 & L7 was the most effective ligand combination for ink formulation, especially when combined with acrylate monomers. Excellent dispersibility and thermal stability were obtained with the combinations of L2 & L7, L2 & L6, and L2 & L3, and L6 and L7. See Figure 6.

[0295] [Table 11]

[0296] Furthermore, we investigated ligand combinations that exhibited good thermal stability when heated to 180°C for 30 minutes in a glove box. Ligand combinations L6&L7, L2&L6, and L2&L3 showed superior stability compared to the single ligand L1. See Figure 6.

[0297] The effect of different ligand combination ratios on QY was also investigated. The total amount of ligands was kept constant while the ligand weight ratio was varied. The best QY was achieved with a ratio of 7:3 for L6 and L7. See Figure 7. The L6 and L7 combinations, except for the 9:1 ratio, showed improved QY compared to the native AIGS nanostructure. While this mixture showed high QY, purification was difficult due to the absence of precipitation. The L6&L2, L3&L7, and L5&L7 mixtures are good ligand mixtures for AIGS nanostructures. These ligand combinations can be used in combination with various monomers such as tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, diethylene glycol ethyl ether arylate, isobronyl acrylate, hydroxypropyl acrylate, 2-(acryloyloxy)ethyl hydrogen succinate, and 1,6-hexanediol diacrylate.

[0298] Example 10 - Improvement of PCE in AIGS films AIGS QDs coated with appropriate ligands were mixed in an ink containing one or more monomers, TiO2 scattering particles, and a photopolymerization initiator within a glove box filled with N2. These inks were spin-coated to cast films, which were then cured by UV irradiation. The films were then baked on a hot plate at 180°C for 30 minutes to remove any remaining volatile components. All of these processes were carried out in an inert atmosphere (inside an N2-filled glove box).

[0299] At this stage, the film can be measured in air by placing it face up on a blue LED light source. An integrating sphere connected to a spectrophotometer is placed on top of the QD film (see Figures 3A and 3B), and the film's emission spectrum is captured. This measurement is repeated with a blank glass substrate (without QD). The blue light absorption and photon conversion efficiency (PCE) of the QD film are measured using the following formula: Blue light absorption = Number of blue photons that passed through the QD film / Number of incident blue photons PCE = Number of green photons emitted in the forward direction / Number of incident blue photons

[0300] To investigate the effects of air and humidity during measurement, the fired QD films were sealed before being removed from the N2 glove box. This was done by applying a few drops of UV-curing transparent adhesive to the QD layer, placing a glass coverslip, and curing the adhesive with UV irradiation. The QD films thus sealed with glass and adhesive were then measured in air using the method described above.

[0301] These results indicate that encapsulating the QD film before measurement in air is crucial for achieving high photon conversion efficiency (PCE). Table 11 shows the results from one set of films measured with and without encapsulation. For comparison, the PCE values ​​of a typical QDCC film containing InP QDs are also shown. When measured with encapsulation, films containing AIGS nanostructures had higher post-bake PCE values ​​than InP at much lower QD loading. Blue light source (approximately 6 mW / cm²) 2 Further improvement in PCE was achieved by irradiating the film by placing it on the surface for 1 hour. Furthermore, the QDCC film created with AIGS QD showed a much narrower emission (FWHM approximately 30 nm) compared to the film created with InP QD (FWHM 36 nm). This is a result of the lower FWHM of AIGS QD in solution (34 nm vs. 39 nm) combined with the use of mono- and poly-amino ligands that enable good dispersion in the ink resin.

[0302] [Table 12]

[0303] Figure 9 shows the effects of mounting and blue light treatment on a wider range of samples. Surprisingly, the PCE values ​​achieved by mounting were significantly higher than those without mounting (higher than 32%).

[0304] The median FWHM of the film fired at 180°C was 30.5 nm, which narrowed further to 30.1 nm after encapsulation. This narrowing may be a result of the film becoming brighter due to encapsulation.

[0305] Although the samples in this study were encapsulated using glass and adhesive, such improvements in PCE can be achieved by any method that can form an oxygen barrier in the QD layer. For mass production of devices containing these QDCC layers, encapsulation can be performed using a deposition process. A typical process flow in this case would include inkjet printing of the QD layer, followed by curing by UV irradiation, firing at 180°C to remove volatiles, deposition of an organic planarization layer, followed by deposition of an inorganic barrier layer. Techniques used for depositing the inorganic layer include atomic layer deposition (ALD), molecular layer deposition (MLD), chemical vapor deposition (CVD) (with or without plasma enhancement), pulsed vapor deposition (PVD), sputtering, and metal deposition. Other potential encapsulation methods include lamination using solution-treated or printed organic layers, UV or thermosetting adhesives, and barrier films.

[0306] Example 11: Improved AIGS film using metal alkoxides To be applied to emerging advanced display technologies such as QD-OLED and QD microLED, a film is needed that can maintain its optical properties under 24-hour yellow light and air storage conditions. Films containing zirconium isopropoxide maintained at least 30% PCE under yellow light and air storage conditions, while films without zirconium propoxide showed a PCE decrease from 35.8% to 14% (Table 12, item 1).

[0307] The "yellow light and air storage conditions" were established as follows. The films were prepared by spin-coating AIGS ink onto a glass substrate, then curing it by irradiation with UV light (405 nm), and baking it on a hot plate at 180°C for 30 minutes, all of which was done in an N2-filled glove box. The ink contained the following components.

[0308] [Table 13]

[0309] The membrane was then moved to the atmosphere and stored in a "yellow" room irradiated with white LED lighting covered with a blue light blocking filter. Typical illuminance and color coordinates in the yellow room, measured with a Konica-Minolta CL-200A colorimeter, were 140 lux, CIEx=0.52, and CIEy=0.45. For reference, typical indoor lighting conditions without blue light filtering are illuminance=620 lux, CIEx=0.38, and CIEy=0.38.

[0310] To test the effects of air exposure on PCE, samples were taken at periodic intervals (3 hours, 1 day, 3 days), encapsulated using a second glass slide and UV-curable clear adhesive, and measured on a PCE platform. To further test the effects of long-term storage in air, the encapsulated samples were again fired at 180°C for 30 minutes and measured on a PCE platform.

[0311] [Table 14]

[0312] As shown in Table 13, the stability of the AIGS film was dramatically improved by adding zirconium(IV) propoxide or its hydrolysate to the AIGS ink. As shown in Table 13, the film's PCE could be maintained at 30.1–34.4% after 24 hours of storage in yellow light, which is only slightly lower than the 35.8% PCE of the air-free film.

[0313] Table 14 shows the results for films using inks containing other metal alkoxides. The addition of gallium or barium isopropoxide results in improved air stability of the films, similar to that achieved with zirconium propoxide.

[0314] [Table 15]

[0315] Without being bound by any particular theory, it is thought that metal alkoxides form a stabilizing shell around the AIGS nanostructure. In the classical sol-gel process, when tetraethyl orthosilicate (TEOS) is exposed to moisture in the air, spontaneous hydrolysis and condensation reactions occur. As a result, a three-dimensional sol-gel network is formed, and under extreme conditions, SiO2 is formed. Zr(OPr)4 is a typical sol-gel precursor. When the AIGS / Zr ink formulation was exposed to air, the sol-gel process actually occurred. In-situ FTIR of AIGS / Zr(OPr)4 was performed by leaving the AIGS / Zr sample on the FTIR window for an extended period of 5 minutes, resulting in a temperature of 3400 cm⁻¹. -1 The intensity of -OH extension in the vicinity increased significantly, whereas no such change was observed in the AIGS sample that did not contain Zr(OPr)4. This suggests that the three-dimensional network formed in situ functions as an oxygen barrier, and ZrO x (OH) y The high conduction band resulting from the formation is thought to confine excitons, particularly electrons. The combination of these two processes effectively prevents the formation of reactive oxygen species (ROS) under light / air conditions, dramatically improving light / air stability.

[0316] The performance of the film can be further improved by including phenolic additives that function as antioxidants and steric hindrance ligands. Table 15 shows optical data from a series of films containing both zirconium propoxide and the phenolic additive pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0317] [Table 16]

[0318] Example 12: Use of bulky phenolic auxiliary ligands Ligand exchange on the AIGS nanostructure was performed using 6-mercaptohexanol and Jeffamine M1000 at 80°C for 1 hour. Subsequently, the AIGS nanostructure was redispersed in a monomer containing auxiliary ligands. The ink formulation contained 12% of the ligand-exchanged QDs, 10% of TiO2 as a scattering medium, and 5% of Jeffamine M1000 as a dispersant.

[0319] To select a suitable ligand or auxiliary ligand, several conditions must be met. First, the ligand must protect the ligand on the surface. Second, the ligand must be compatible with other ink components. Third, the ligand must be air-stable by blocking oxygen. To find promising candidates that meet these conditions, auxiliary ligands were added to ink formulations and films were prepared.

[0320] Figure 11 shows the film performance when different auxiliary ligands are used in the ink formulation. The EQE of the film was better with auxiliary ligand-1 than with the others. This is presumed to be because the bulky terminal groups of auxiliary ligand-1 cause steric hindrance and dense surface passivation on the AIGS nanostructure, which prevents oxygen permeation and oxidation.

[0321] [Table 17]

[0322] Unlike InP, AIGS nanostructures, which can bind well to weakly bonded L-type ligands, may reduce EQE if active radicals or species that can cause side reactions are present. These side reactions are due to radical generation via polymerization initiators or radical active species and photo-oxidation via oxygen. Film stability was confirmed under dark conditions. Under dark conditions, auxiliary ligands-1 and 7 showed very stable EQE compared to the control ink (Figure 11). Auxiliary ligand-2 caused a decrease in EQE and was less stable. Therefore, even when films containing auxiliary ligands-1 and 7 were exposed to air, the films did not degrade without exposure to light.

[0323] To confirm the changes in film performance, photostability was measured under yellow light conditions. As shown in Figure 12, auxiliary ligand-1 showed better stability under yellow light after 24 hours than the reference ink (control group). Furthermore, the phosphorus-based auxiliary ligand 7 showed comparable EQE to the reference ink (control group).

[0324] The thermal stability of the film was also measured after firing the film at 180°C. As shown in Table 17, the bulky phenol-based auxiliary ligand-1 and phosphorus-based auxiliary ligand-7 showed better thermal stability compared to the control group.

[0325] [Table 18]

[0326] Furthermore, the ink manufacturing process was modified as shown in Table 18. When auxiliary ligand-1 was added later, the EQE was better than when the reference ligand 1,3-cyclohexanebis(methylamine) was used. Also, when thiols were further added during ligand exchange with auxiliary ligand-1, the ink formulation showed the most stable EQE performance. See Figure 13, which shows the time-dependent stability of ink formulations with different ink and additive ratios when exposed to yellow light conditions.

[0327] [Table 19]

[0328] As shown in Figure 14, additional GaCl3(S3) treatment of AIGS nanostructures showed improved EQE performance. Further performance improvements were observed when the inorganic ligand zirconium propoxide (S2) was added together with S3. Adding polyvalent metal-based ligands such as S2 can compensate for excessive sulfur oxidation. See also Figure 15, which shows that the best performance is obtained in the calcined film when auxiliary ligand-1, S2, and S3 are combined. Figure 16 shows that when auxiliary ligand-1, S2, and S3 are combined, the film exhibits high lightfastness when exposed to yellow light conditions.

[0329] For comparison, Figure 17 is a line graph showing the EQE% versus blue light absorbance of AIGS films containing 1% S3, 3% S3, and 6% S3.

[0330] While various embodiments have been described above, it should be understood that these are presented as examples only and are not limiting. It will be apparent to those skilled in the art that various modifications in form and detail are possible without departing from the spirit and scope of the invention. Therefore, the breadth and scope should not be limited by any of the exemplary embodiments described above, but should be defined only in accordance with the following claims and their equivalents.

[0331] All publications, patents, and patent applications referenced herein represent the level of skill of those skilled in the art to which the present invention relates, and are incorporated herein by reference to the same extent as when such publications, patents, or patent applications are specifically and individually indicated to be incorporated by reference.

Claims

1. Ag, in, Ga, and S (AIGS) nanostructures, One or more types of metal alkoxides, one or more types of metal alkoxide hydrolysis products, or combinations thereof, Polyamino ligands and A membrane containing, When the film is excited using a blue light source having a wavelength of 450 nm, it exhibits a photon conversion efficiency (PCE) higher than 32% at a peak emission wavelength of 480 to 545 nm, and when the film is excited using a blue light source having a wavelength of 450 nm after 24 hours under yellow light and air storage conditions, it exhibits a photon conversion efficiency (PCE) of at least 30% at a peak emission wavelength of 480 to 545 nm. film.

2. The film according to claim 1, wherein the nanostructure has an emission spectrum having a full width at half maximum (FWHM) of less than 40 nm.

3. The film according to claim 1 or 2, wherein the nanostructure has a quantum yield (QY) of 80 to 99.9%.

4. The aforementioned nanostructure has an OD of 0.8 or higher. ４５０ / mass (mL・mg －１ ・cm －１ A film according to any one of claims 1 to 3, having the following characteristics.

5. The film according to any one of claims 1 to 4, wherein the average diameter of the nanostructure as measured by a transmission electron microscope (TEM) is less than 10 nm.

6. The film according to any one of claims 1 to 5, wherein at least 80% of the emission is band-edge emission.

7. The polyamino ligand comprises the compound of formula I, 【Chemistry 1】 In the formula, x is between 1 and 100, y is between 0 and 100, and R ２ is C １～２０ A film according to any one of claims 1 to 6, wherein the compound is alkyl.

8. Further comprising the ligand of the following formula II, 【Chemistry 2】 In the formula, R ３ and R ４ are, independently, C ３～６ a secondary or tertiary alkyl group, and R ５ is hydrogen or an optionally substituted C １～６ alkyl group. The film according to any one of claims 1 to 6.

9. The one or more of the aforementioned metal alkoxides are metal C １～１０ The film according to any one of claims 1 to 8, wherein the alkoxide is titanium, zirconium, hafnium, gallium, or barium.

10. The aforementioned one or more metal alkoxides, one or more metal alkoxide hydrolysis products, or combinations thereof are zirconium(IV) tetramethoxide, zirconium(IV) tetraethoxide, zirconium(IV) tetra-n-propoxide, zirconium(IV) tetra-isopropoxide, zirconium(IV) tetra-n-butoxide, zirconium(IV) tetra-isobutoxide, zirconium(IV) tetra-n-pentoxide, zirconium(IV) tetra-isopentoxide, zirconium(IV) tetra The film according to any one of claims 1 to 9, wherein the film is -n-hexoxide, zirconium(IV) tetra-isohexoxide, zirconium(IV) tetra-n-heptoxide, zirconium(IV) tetra-isoheptoxide, zirconium(IV) tetra-n-octoxide, zirconium(IV) tetra-n-isooctoxide, zirconium(IV) tetra-n-nonoxide, zirconium(IV) tetra-n-isononoxide, zirconium(IV) tetra-n-decyloxide, or zirconium(IV) tetra-n-isodecyloxide.

11. The film according to any one of claims 1 to 10, wherein the metal alkoxide is zirconium (IV) tetra-n-propoxide.

12. The membrane according to claim 11, wherein the membrane further comprises pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl)bis[3-[3-(tert-butyl)-4-hydroxy-5-methylphenyl]propanoate].

13. The film according to any one of claims 1 to 12, wherein one or more of the aforementioned metal alkoxides, one or more of the metal alkoxide hydrolysis products, or a combination thereof are present in the composition in an amount of 0.03 to 3.3% by weight.

14. (a) To provide an AIGS nanostructure, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, or a combination thereof, and a polyamino ligand. (b) Mixing at least one type of organic resin with the AIGS nanostructure of (a), (c) Preparing a first film on the first barrier layer comprising the mixed AIGS nanostructure, the polyamino ligand, and the at least one organic resin, (d) curing the first film, (e) Enclosing the first film between the first barrier layer and the second barrier layer A method for preparing a film according to any one of claims 1 to 13, wherein the encapsulated film exhibits a PCE of more than 32% at a peak emission wavelength of 480 to 545 nm when excited using a blue light source having a wavelength of 450 nm.

15. The method according to claim 14, wherein the encapsulation of the first film is performed before it is exposed to a blue LED light source in air.

16. The method according to claim 15, which is carried out under an inert atmosphere.

17. The method according to claim 16, further comprising: adding at least one oxygen-reactive material in a mixture of (a) the AIGS nanostructure, one or more metal alkoxides, one or more metal alkoxide hydrolysis products or combinations thereof, and a polyamino ligand; adding at least one oxygen-reactive material in the admixture of (b), and / or forming a second film containing at least one oxygen-reactive material on the first film prepared in (c), and / or forming a sacrificial barrier layer on the first film prepared in (c) to temporarily block oxygen and / or water; and measuring the PCE of the film, followed by removal of the sacrificial barrier layer.

18. The method according to claim 17, wherein the two barrier layers exclude oxygen and / or water.

19. A device comprising the film according to any one of claims 1 to 13.

20. (a) A first conductive layer and (b) A second conductive layer, (c) The film between the first conductive layer and the second conductive layer according to any one of claims 1 to 13 Nanostructured molded articles, including those containing the above.

21. Backplane and A display panel arranged on the backplane, A film according to any one of claims 1 to 13, disposed on the display panel A nanostructured color converter, including...

22. The nanostructured color converter according to claim 21, wherein the film comprises a patterned AIGS nanostructure.

23. The nanostructured color converter according to claim 21, wherein the backplane includes an LED, LCD, OLED, or microLED.

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