Stable aigs films

Abstract

This invention discloses 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 bonded to the nanostructures. In some embodiments, the AIGS nanostructures have a photon conversion efficiency greater than 32% and a peak wavelength emission of 480-545 nm. In some embodiments, the nanostructures have an emission spectrum with an FWHM of 24-38 nm. In some embodiments, the nanostructures have a photon conversion efficiency (PCE) of at least 30% after storage under yellow light and air storage conditions for 24 hours.

Description

Technical Field

[0001] This invention relates to the field of nanotechnology. More specifically, this invention provides a thin, heavy metal-free, stable Ag-In-Ga-S color conversion film that, when excited by a blue light source with a wavelength of approximately 450 nm and after exposure to yellow light and air storage conditions, exhibits a high photon conversion efficiency (PCE) of greater than 30% at a peak emission wavelength of 480-545 nm. Prior Technology

[0002] Effective color conversion is crucial for lighting and display applications. In display applications, blue light sources with a wavelength of approximately 450 nm are most commonly used for backlighting. Most applications require materials free of heavy metals such as Cd and Pb.

[0003] Increased efficiency results in less wasted power and increased emission. Color conversion films are characterized by photon conversion efficiency (PCE), defined as the number of emitted photons divided by the number of source photons. Green, heavy metal-free QD color conversion films for displays typically exhibit poor performance due to their limited absorption in the excited blue light. Blue light absorption is generally inherently limited by the material system in use, leading to the need for much thicker films to absorb sufficient 450 nm light.

[0004] Thin films formed by depositing QD inks are 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. The photon conversion efficiency of these films is limited by a combination of poor absorption and poor light conversion caused by the instability of these processing steps.

[0005] This technology still requires AIGS nanostructures with high-frequency band-edge emission (BE), narrow full width at half maximum (FWHM), high quantum yield (QY), and reduced redshift. It is suitable for preparing films with high photon conversion efficiency (PCE) at peak emission wavelengths between 480 nm and 545 nm using an excitation wavelength of about 450 nm. (Before exposure to yellow light and air storage conditions, greater than 32%) Summary of the Invention

[0006] This invention provides a thin, heavy metal-free, and stable AIGS nanostructure color conversion film that exhibits a high photon conversion efficiency (PCE) of greater than 30% at a peak emission wavelength of 480-545 nm when excited by a blue light source with a wavelength of approximately 450 nm and exposed to air under yellow light conditions. This is achieved by using an AIGS nanostructure 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 treatments, followed by 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 a free-wavelength emission wavelength (FWHM) of 28-38 nm. In other embodiments, the AIGS nanostructure has an FWHM of less than 32 nm. In some embodiments, narrow FWHM is achieved by adding at least one polyamine ligand to an AIGS nanostructure and fabricating a film, wherein all treatments of the nanostructure ink, ink deposition, film treatment, and measurements are performed in an oxygen-free environment.

[0007] Films formed by depositing QD inks are 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. It has been found that photon conversion efficiency is reduced due to poor absorption and poor light conversion caused by the instability of these processing steps.

[0008] This article discloses a membrane comprising an AIGS nanostructure in an ink formulation comprising one or more metal alkoxides, one or more metal alkoxide hydrolysates, one or more metal halides, one or more metal halide hydrolysates, one or more organometallic compounds, or one or more organometallic hydrolysates, or combinations thereof; and at least one ligand, wherein the membrane achieves a PCE greater than (>) 30% after exposure to yellow light and air storage conditions for 24 hours. In some embodiments, a membrane comprising an AIGS nanostructure and at least one ligand is provided, and exhibits a PCE greater than 32% at a peak emission wavelength of 480-545 nm when excited by a blue light source with a wavelength of 450 nm. In some embodiments, a membrane 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 combinations thereof, and at least one ligand exhibits a PCE of 30-39% after exposure to yellow light and air storage conditions. In some embodiments, a membrane 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 combinations thereof, and at least one ligand exhibits a PCE of approximately 30%, approximately 31%, approximately 32%, approximately 33%, approximately 34%, approximately 35%, approximately 36%, approximately 37%, approximately 38%, or approximately 39% after exposure to yellow light conditions.

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

[0010] Such membranes exhibit good (>95%) blue light absorption but moderate emission characteristics. However, when the membranes are treated and / or encapsulated in the absence of oxygen and / or light before being exposed to UV or blue light, the emission characteristics of these membranes are significantly improved.

[0011] A method for preparing an AIGS membrane is provided, comprising: (a) Providing 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 combinations thereof; and at least one ligand; (b) Doping at least one organic resin with the AIGS nanostructure of (a); and (c) Preparing a first film comprising the doped AIGS nanostructure, at least one ligand, and at least one organic resin on a first barrier layer; (d) Curing the film by UV irradiation and / or baking; (e) Encapsulating the first film between the first barrier layer and a second barrier layer; and wherein when excited with a blue light source with a wavelength of about 450 nm and after exposure to yellow light and air storage conditions, the encapsulated film exhibits a photon conversion efficiency (PCE) greater than 30% at a peak emission wavelength of 480-545 nm.

[0012] A method is also provided, which further includes: (f) adding at least one oxygen-reactive material to a mixture of the AIGS nanostructure and the ligand of (a), adding at least one oxygen-reactive material to the dopant of (b), and / or forming a second membrane containing at least one oxygen-reactive material on top of the first membrane prepared in (c); and / or (g) forming a sacrificial barrier layer that temporarily blocks oxygen and / or water on the first membrane prepared in (c), and measuring the PCE of the membrane, and then removing the sacrificial barrier layer.

[0013] A method is also provided, which includes: (a) Encapsulation prior to heat treatment and / or measurement; (b) The use of oxygen-reactive materials as a component in the formulation during heat treatment or light exposure; and / or (c) By temporarily blocking oxygen through the use of a sacrificial barrier layer.

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

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

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

[0017] In some embodiments, the at least one ligand is an amino ligand, a polyamine ligand, a ligand containing a mercapto group, or a ligand containing a silyl group. It was unexpectedly found that using a polyamine ligand produced AIGS-containing films with an FWHM less than 32 nm.

[0018] In some embodiments, the at least one polyamine ligand is a polyamine alkane, a polyamine cycloalkane, a polyamine heterocyclic compound, a polyamine-functionalized polysiloxane, or a polyamine-substituted ethylene glycol. In some embodiments, the polyamine ligand is a C2-20 alkane or C2-20 cycloalkane substituted with two or three amine groups and, where appropriate, contains one or two amine-substituted carbon groups. In some embodiments, the polyamine 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 formula I: in: x is between 1 and 100; y is between 0 and 100; and R2 is a C1-20 alkyl group.

[0020] In some embodiments, x = 19, y = 3, and R² = -CH³.

[0021] In some embodiments, the ligand is a compound of formula II: R3 and R4 are independently C3-6 secondary or tertiary alkyl groups, and R5 is hydrogen or, where appropriate, a substituted C1-6 alkyl group.

[0022] In some embodiments, R3 and R4 are isopropyl, 2-butyl, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, tributyl, 2-methyl-2-pentyl, or 3-methyl-3-pentyl.

[0023] In some embodiments, the substituent present on the C1-6 alkyl group of R5, as appropriate, is nitro, haloalkoxy, aryloxy, arylalkoxy, alkylthio, sulfonylamino, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, ureo, guanidinyl, carbamate, carboxyl, alkoxycarbonyl, carboxylalkyl, or -C(=O)R7, wherein R7 is an alkoxy group that may be further substituted with one or more other alkoxy groups.

[0024] In some embodiments, R 7 has the following formula: Where p is 0-3.

[0025] In some embodiments, R 7 is: .

[0026] In some embodiments, R 7 is: And Equation II is: .

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

[0028] In some embodiments, the at least one ligand is (3-aminopropyl)trimethoxysilane; (3-mercaptopropyl)triethoxysilane; DL-α-lipoic acid; 3,6-dioxa-1,8-octanedithiol; 6-mercapto-1-hexanol; methoxypolyethylene glycolamine (approx. mw 500); poly(ethylene glycol) methyl ether thiol (approx. mw 800); diethyl phenylphosphonite; dibenzyl N,N-diisopropylaminophosphoramidite; di- and tributyl N,N-diisopropylaminophosphoramidite; tris(2-carboxyethyl)phosphonate hydrochloride; poly(ethylene glycol) methyl ether thiol (approx. mw 2000); methoxypolyethylene glycolamine (approx. mw 750); acrylamide; or polyethyleneimine. The mw of the polymer is determined by mass spectrometry.

[0029] In some embodiments, the at least one ligand is a combination of: amino-polyepoxide (about mw 1000) and methoxy polyethylene glycolamine (about mw 500); amino-polyepoxide (about mw 1000) and 6-mercapto-1-hexanol; amino-polyepoxide (about mw 1000) and (3-mercaptopropyl)triethoxysilane; and 6-mercapto-1-hexanol and methoxy polyethylene glycolamine (about mw 500).

[0030] In some embodiments, the one or more metal alkoxides are metal C1-10 alkoxides. In some embodiments, the metal is titanium, zirconium, hafnium, gallium, or barium.

[0031] In some embodiments, the at least one or more metal alkoxides are zirconium tetramethylene (IV), zirconium tetraethanolamine (IV), zirconium tetra-n-propoxide (IV), zirconium tetra-isopropoxide (IV), zirconium tetra-n-butoxide (IV), zirconium tetra-isobutoxide (IV), zirconium tetra-n-pentanol (IV), zirconium tetra-isopentanol (IV), zirconium tetra-n-hexanol (IV), zirconium tetra-isohexanol (IV), zirconium tetra-n-heptanol (IV), zirconium tetra-isoheptanol (IV), zirconium tetra-n-octanol (IV), zirconium tetra-isooctanol (IV), zirconium tetra-n-nonanol (IV), zirconium tetra-isononol (IV), zirconium tetra-n-decanol (IV), or zirconium tetra-isodecanol (IV).

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

[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 combinations thereof are tetra-n-propoxide zirconium (IV), and the membrane further comprises neopentyl tetroxide [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or bis[3-[3-(tert-butyl)-4-hydroxy-5-methylphenyl]propionate]2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diester).

[0034] Also provided is a nanostructure composition comprising: (a) AIGS nanostructures exhibiting a PCE greater than 30% after exposure to yellow light and air storage conditions, and (b) At least one organic resin.

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

[0036] A method for preparing the nanostructured composition described herein is also provided, the method comprising: (a) Providing 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 combinations thereof; and at least one ligand; (b) Incorporating at least one organic resin with the AIGS nanostructure of (a); (c) A first film comprising a doped AIGS nanostructure, at least one ligand and at least one organic resin is prepared on a first barrier layer; (d) The film is cured by UV irradiation and / or baking; and (e) The first film is encapsulated between the first barrier layer and the second barrier layer, wherein when excited with a blue light source with a wavelength of about 450 nm and exposed to yellow light in air, the encapsulated film exhibits a photon conversion efficiency (PCE) greater than 30% at a peak emission wavelength of 480-545 nm.

[0037] In some embodiments, the method is performed before the encapsulated membrane is exposed to air to measure the emission spectrum of the AIGS nanostructure. In some embodiments, the method is performed in an inert atmosphere.

[0038] In some embodiments, the method further includes: (f) adding at least one oxygen-reactive material to 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 combinations thereof, and a mixture of the ligands of (a); (g) adding at least one oxygen-reactive material to the blend of (b); and / or (h) forming a second membrane containing at least one oxygen-reactive material on top of the first membrane prepared in (c); and / or (i) forming a sacrificial barrier layer that temporarily blocks oxygen and / or water on the first membrane prepared in (c), and measuring the PCE of the membrane, and then removing the sacrificial barrier layer.

[0039] In some embodiments, the two barrier layers do not include oxygen and / or water.

[0040] In some embodiments, 92-98% of the transmissions are edge-triggered transmissions. In some embodiments, 93-96% of the transmissions are edge-triggered transmissions.

[0041] A method for preparing a composition is also provided, comprising: (a) Providing 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 combinations thereof; and at least one ligand; and (b) The composition obtained in (a) is blended with at least one second ligand.

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

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

[0044] A device is also provided that includes the membrane described above.

[0045] Also provided is a nanostructured molded article, comprising: (a) First conductive layer; (b) the second conductive layer; and (c) A film comprising an AIGS nanostructure layer between a first conductive layer and a second conductive layer. The nanostructure layer includes AIGS nanostructures with a PCE greater than 30% after exposure to yellow light and air storage conditions.

[0046] Also provided is a nanostructure color converter, which includes Back panel; The display panel, which is mounted on the back panel; and The film comprises an AIGS nanostructure layer containing an AIGS nanostructure with a PCE greater than 30% after exposure to yellow light and air storage conditions, and the nanostructure layer is disposed on the display panel.

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

[0048] Other features and advantages of the invention, as well as the structure and operation of various embodiments of the invention, are described in detail below with reference to the accompanying drawings. It should be noted that the invention is not limited to the specific embodiments described herein. These 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. Simple Explanation of the Diagram

[0049] The accompanying drawings, which are incorporated herein and form part of this specification, illustrate this embodiment and, together with the embodiments, further serve to explain the principles of this embodiment and enable those skilled in the art to perform and use this embodiment.

[0050] Figure 1 shows, from left to right, photographs of the first and third films, which do not contain polyamine ligands and exhibit extended wrinkles. The second and fourth films, which contain polyamine ligands, show no wrinkles.

[0051] Figures 2A to 2C show TEM images of the AIGS nanostructure before ion exchange treatment (Figure 2A), after a single ion exchange treatment (Figure 2B), and after two ion exchange treatments (Figure 2C).

[0052] Figures 3A and 3B are schematic diagrams of unencapsulated (Figure 3A) and encapsulated (Figure 3B) membranes.

[0053] Figure 4 shows the scattering diagram of QY% as a mixture of various ligands.

[0054] Figure 5 shows the scattering diagrams of ligand combinations with improved QY% (good combination) and combinations with reduced QY% (bad combination).

[0055] Figure 6 shows the QY% of various ligand combinations before ligand exchange (NG), after ligand exchange (LE), and 30 min after thermal testing.

[0056] Figure 7 shows the QY% of various ligand combinations under various ligand ratios.

[0057] Figure 8 shows two scattering patterns of PCE in the AIGS membrane after encapsulation, one with normal PCE measurement and the other with PCE measurement.

[0058] Figure 9 shows two scattering patterns of the PCE of AIGS membranes baked at 180°C with the membranes unencapsulated (left) and encapsulated before PCE measurement (right).

[0059] Figure 10 is a line graph showing the EQE% of the film of AIGS ink formulation after auxiliary ligand exchange, compared to the blue light absorption rate.

[0060] Figure 11 is a line graph showing the EQE% of a film containing various auxiliary ligands of AIGS ink formulations over time when stored in the dark.

[0061] Figure 12 is a line graph showing the EQE% of AIGS ink formulations containing various auxiliary ligands over time when exposed to yellow light.

[0062] Figure 13 is a line graph showing the EQE% of the film containing various auxiliary ligands and additives of AIGS ink formulations over time when exposed to yellow light.

[0063] Figure 14 is a line graph showing the EQE% of the film of AIGS ink formulations relative to the blue light absorption rate. These AIGS ink formulations contain auxiliary ligand-1; auxiliary ligand-1 and zirconium propoxide (S2); auxiliary ligand-1, S2 and GaCl3 (S3); and S2 and S3.

[0064] Figure 15 is a bar graph showing the EQE of AIGS membranes after baking under nitrogen and containing auxiliary ligand-1; auxiliary ligand-1 and S2; auxiliary ligand-1, S2 and S3; and S2 and S3.

[0065] Figure 16 is a line graph showing the EQE% over time of cured AIGS films when exposed to yellow light conditions. These cured AIGS films contain auxiliary ligand-1; auxiliary ligand-1 and S2; auxiliary ligand-1, S2 and S3; and S2 and S3.

[0066] Figure 17 is a line graph showing the EQE% of AIGS films containing 1%, 3%, and 6% S3 compared to the blue light absorption rate.

[0067] The features and advantages of the present invention will become more apparent from the embodiments described below in conjunction with the accompanying drawings, in which similar element symbols always identify corresponding elements. In these drawings, the same reference numerals generally indicate identical, functionally similar, and / or structurally similar elements. The first appearance of an element in the drawing is indicated by the leftmost digit in the corresponding element symbol. Unless otherwise indicated, the drawings provided throughout the present invention should not be interpreted as to-scale drawings. Implementation

[0068] definition

[0069] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The definitions below are supplementary to those definitions in this art and pertain to this application, and should not be attributed to any related or unrelated circumstances, such as any jointly owned patents or applications. Although any methods and materials similar to or equivalent to those described herein may be used for testing in the practice of this invention, preferred materials and methods are described herein. Therefore, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be restrictive.

[0070] Unless the context clearly indicates otherwise, as used in this specification and the appended claims, the singular forms "a" and "the" include a plurality of indicators. Thus, for example, references to "nanostructure" include a plurality of such nanostructures and the like.

[0071] As used herein, the term "about" indicates a value of a given quantity that has changed by + / - 10% of that value. For example, "about 100 nm" covers a size range of 90 nm to 110 nm (inclusive).

[0072] A "nanostructure" is a structure having at least one region or feature size less than about 500 nm. In some embodiments, the nanostructure has a size less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm. Typically, the region or feature size is along the smallest axis of the structure. Examples of such structures include nanowires, nanorods, nanotubes, branched nanostructures, nanopile, triangular pyramid, diagonal pyramid, nanocrystal, nanodot, quantum dot, nanoparticle, and the like. The nanostructure can be, for example, substantially crystalline, substantially single-crystal, polycrystalline, amorphous, or a combination thereof. In some embodiments, each of the three dimensions of the nanostructure has a size less than about 500 nm, less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm.

[0073] When used in conjunction with a reference nanostructure, the term "heterogeneous structure" refers to a nanostructure characterized by at least two different and / or distinguishable material types. Typically, one region of the nanostructure contains a first material type, while a second region of the nanostructure contains a second material type. In some embodiments, the nanostructure comprises a core of a first material and an outer shell of at least one second (or third, etc.) material, wherein the different material types are radially distributed around, for example, the long axis of a nanowire, the long axis of a group of branched nanowires, or the center of a nanocrystal. The outer shell may (but does not need to) completely cover the adjacent material considered as the outer shell or the nanostructure considered as a heterostructure; for example, a nanocrystal characterized by a core of one material covering an island-like structure 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 a group of branched nanowires. Different regions within a heterostructure may contain entirely different materials, or different regions may contain a substrate material (e.g., silicon) with different dopants or different concentrations of the same dopant.

[0074] As used herein, the “diameter” of a nanostructure refers to the diameter of a cross-section perpendicular to the nanostructure’s first axis, which has the greatest length difference relative to the second and third axes (which are two axes whose lengths are mostly equal to each other). The first axis is not necessarily the longest axis of the nanostructure; for example, for a disk-shaped nanostructure, the cross-section will be a substantially annular cross-section perpendicular to the disk’s shorter longitudinal axis. When the cross-section is not annular, the diameter is the average of the long and short axes of the cross-section. For elongated or high aspect ratio nanostructures (such as nanowires), the diameter is measured across the entire cross-section perpendicular to the longest axis of the nanowire. For spherical nanostructures, the diameter is measured from one side to the other through the center of the sphere.

[0075] When used in relation to nanostructures, the terms "crystalline" or "substantially crystalline" refer to the fact that nanostructures typically exhibit long-range ordering in one or more dimensions of their structure. Those skilled in the art will understand that the term "long-range ordering" depends on the absolute size of the particular nanostructure, as the ordering of a single crystal cannot extend beyond the crystal boundaries. In this case, "long-range ordering" will mean substantial ordering over at least a majority of the dimensions of the nanostructure. In some cases, nanostructures may carry oxides or other coatings, or may consist of a core and at least one shell. In such cases, it should be understood that the oxide, shell, or other coating may, but does not need to, exhibit such ordering (e.g., it may be amorphous, polycrystalline, or otherwise). In such cases, the phrases "crystalline," "substantially crystalline," "substantially single-crystal," or "single-crystal" refer to the central core of the nanostructure (excluding coatings or shells). As used herein, the terms "crystalline" or "substantially crystalline" are intended to encompass structures containing various defects, stacking flaws, atomic substitutions, and the like, provided that the structure exhibits substantial long-range order (e.g., order exceeding at least about 80% of the length of at least one axis of the nanostructure or its core). Furthermore, it should be understood that interfaces between the core and the exterior of the nanostructure, between the core and an adjacent shell, or between a shell and a second adjacent shell may contain amorphous regions and may even be amorphous. This does not preclude the nanostructure from being crystalline or substantially crystalline as defined herein.

[0076] When used in relation to nanostructures, the term "single crystal" indicates that the nanostructure is substantially crystalline and substantially contains a single crystal. When used in relation to a nanostructure heterostructure comprising a core and one or more shells, "single crystal" indicates that the core is substantially crystalline and substantially contains a single crystal.

[0077] "Nanocrystal" refers to a substantially single-crystal nanostructure. A nanocrystal therefore has at least one region or characteristic size smaller than about 500 nm. In some embodiments, the nanocrystal has a size smaller than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm. The term "nanocrystal" is intended to encompass substantially single-crystal nanostructures that include various defects, stacking defects, atomic substitutions, and the like, as well as substantially single-crystal nanostructures that do not have such defects, defects, or substitutions. In the case of a nanocrystal heterostructure comprising a core and one or more shells, the core of the nanocrystal is typically substantially single-crystal, but the shells need not be single-crystal. In some embodiments, each of the three dimensions of the nanocrystal has a size smaller than about 500 nm, less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm.

[0078] The term "quantum dot" (or "dot") refers to a nanocrystal exhibiting quantum confinement or exciton confinement. Quantum dots can be substantially homogeneous in terms of material properties, or in some embodiments, can be heterogeneous, such as comprising a core and at least one shell. The optical properties of quantum dots can be affected by their particle size, chemical composition, and / or surface composition, and can be determined by suitable optical assays available in this art. The ability to adjust the size of nanocrystals, for example, in the range of about 1 nm to about 15 nm, achieves light emission coverage across the entire spectrum to provide great versatility in color development. []

[0079] The term "oxygen-free ligand" refers to a molecule whose coordination does not contain oxygen atoms that can coordinate with or react with the metal ions used herein.

[0080] "Ligand" is a molecule that can interact (whether weakly or strongly) with one or more surfaces of a nanostructure, for example, through covalent, ionic, van der Waals, or by interacting with other molecules on the surface of the nanostructure. []

[0081] "Photoluminescence quantum yield" (QY) is, for example, the ratio of photons emitted by a nanostructure or group of nanostructures to the photons absorbed. As is known in this art, quantum yield is typically determined by the absolute change in photon count after irradiating a sample inside an integrating sphere or by comparison with a standard sample that is adequately characterized by a known quantum yield value.

[0082] The "peak emission wavelength" (PWL) is the wavelength at which the emission spectrum of a light source reaches its maximum value.

[0083] As used in this article, 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 a Gaussian curve shape. The width of the Gaussian curve is defined as the FWHM and gives an idea of ​​the particle size distribution. A smaller FWHM corresponds to a narrower nanostructure nanocrystal size distribution. FWHM also depends on the maximum emission wavelength.

[0084] Band-edge emission is centered at higher energies (lower wavelengths), with a smaller energy shift from absorption compared to its counterpart, defect emission. Additionally, band-edge emission has a narrower wavelength distribution than defect emission. Both band-edge and defect emission follow a normal (approximately Gaussian) wavelength distribution.

[0085] Optical density (OD) is a commonly used method for quantifying the concentration of solutes or nanoparticles. According to Beer-Lambert's law, the absorption (also known as "extinction") of a particular sample is proportional to the concentration of the solute that absorbs light at a specific wavelength.

[0086] Optical density is the light attenuation per centimeter of material, as measured using a standard spectrometer, and is typically specified as a 1 cm path length. Nanostructured solutions are usually measured by their optical density as a substitute for substance or molar concentration, because it is proportional to concentration and is a more suitable way to represent the amount of light absorption occurring in the nanostructured solution at the wavelength of interest. Compared to a product with an OD of 1, a nanostructured solution with an OD of 100 has 100 times higher concentration (100 times more particles per milliliter).

[0087] 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 loss of light as it passes through a nanostructure solution at a specific wavelength and is calculated using the following formula: OD = log 10*(I OUT / I IN) in: IOUT = the intensity of radiation penetrating and entering the cell; and IIN = the intensity of radiation transmitted through the cell.

[0088] 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 nanostructures present in a sample.

[0089] The "yellow light and air storage conditions" refers to the use of a film covering a white LED light that blocks blue light from shining into the air. The illuminance and color coordinates of the yellow storage conditions were measured to be 140 lux using a Konica-Minolta CL-200A colorimeter, with CIE x = 0.52 and CIE y = 0.45.

[0090] Unless otherwise clearly indicated, the scope listed herein includes the endpoints.

[0091] Various additional terms are defined or otherwise characterized in this document. AIGS nanostructure

[0092] Nanostructures comprising Ag, In, Ga, and S (AIGS) are provided, wherein the nanostructures have 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 emission spectrum of the nanostructure and summing the areas of the peaks that are more energetically closer to the band gap of the nanostructure (which represents band-edge emission) with the areas of all peaks (band-edge + defect emission).

[0093] 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 FWHM emission spectrum of 27-32 nm. In some embodiments, the nanostructure has an FWHM emission spectrum of 29-31 nm.

[0094] In another embodiment, the nanostructure has a QY of about 80% to 99.9%. In another embodiment, the nanostructure has a QY of 85-95%. In another embodiment, the nanostructure has a QY of about 86% to about 94%. In some embodiments, at least 80% of the emission is edge-emission. In other embodiments, at least 90% of the emission is edge-emission. In other embodiments, at least 95% of the emission is edge-emission. In some embodiments, 92-98% of the emission is edge-emission. In some embodiments, 93-96% of the emission is edge-emission.

[0095] AIGS nanostructures offer high blue light absorption. As a predicted value for blue light absorption efficiency, the optical density per mass (OD 450 / mass) at 450 nm is calculated by measuring the optical density of the nanostructure solution in a 1 cm path length photodiode and dividing it by the dry mass (< 200 mTorr) of the same solution per milliliter (mg / mL) after removing all volatiles under vacuum. In one embodiment, the nanostructure provided herein has an OD 450 / mass (mL·mg⁻¹·cm⁻¹) of at least 0.8. In another embodiment, the nanostructure has an OD 450 / mass (mL·mg⁻¹·cm⁻¹) of 0.8–2.5. In yet another embodiment, the nanostructure has an OD 450 / mass (mL·mg⁻¹·cm⁻¹) of 0.87–1.9.

[0096] In one embodiment, the nanostructure has been treated with gallium ions so that indium gallium ion exchange occurs throughout 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 and S ions. In yet another embodiment, the nanostructure has Ag, In, Ga, and S in its core and is treated by ion exchange with silver, gallium, and S ions. In some embodiments, the ion exchange treatment creates a gradient of gallium, silver, and / or sulfur throughout the nanostructure.

[0097] In one embodiment, the average diameter of the nanostructure, as measured by TEM, is less than 10 nm. In another embodiment, the average diameter is about 5 nm. AIGS nanostructures prepared using GaX3 (X = F, Cl, or Br) precursors and oxygen-free ligands

[0098] Reports on AIGS fabrication in the literature have not attempted to exclude oxygen-containing ligands. In gallium-coated AIGS, oxygen-containing ligands are typically used to stabilize the Ga precursor. Gallium(III) acetylacetonate is commonly used as a precursor readily handled in air, while gallium(III) chloride is attributed to its moisture sensitivity and requires careful handling. For example, in Kameyama et al., ACS Appl. Mater. Interfaces 10:42844-42855 (2018), gallium(III) acetylacetonate was used as a precursor for both the core and core / shell structures. Due to gallium's high affinity for oxygen, oxygen-containing ligands and the use of gallium precursors prepared under conditions other than oxygen-free conditions can produce undesirable side reactions, such as gallium oxide, when Ga and S precursors are used to generate nanostructures with significant gallium content. These side reactions can introduce defects in the nanostructure and lead to low quantum yields.

[0099] In some embodiments, oxygen-free GaX3 (X = F, Cl, or Br) is used as a precursor to prepare AIGS nanostructures in the preparation of AIGS cores. In some embodiments, GaX3 (X = F, Cl, or Br) is used as both a precursor and an oxygen-free ligand in the preparation of Ga-enriched AIGS nanostructures. In some embodiments, oxygen-free GaX3 (X = F, Cl, or Br) is used as both a precursor and an oxygen-free ligand in the preparation of AIGS cores. In some embodiments, GaX3 (X = F, Cl, or Br) is used as both a precursor and an oxygen-free ligand in the preparation of AIGS cores and in the ion exchange treatment of the AIGS cores to prepare AIGS nanostructures.

[0100] Nanostructures containing Ag, In, Ga and S are provided, wherein the nanostructures have a peak emission wavelength (PWL) between 480-545 nm, and wherein the nanostructures are prepared using GaX3 (X = F, Cl or Br) precursor and oxygen-free ligands.

[0101] In some embodiments, nanostructures prepared using GaX3 (X = F, Cl, or Br) precursors and anaerobic ligands exhibit FWHM emission spectra of 35 nm or smaller. In some embodiments, nanostructures prepared using GaX3 (X = F, Cl, or Br) precursors and anaerobic ligands exhibit FWHM of 30-38 nm. In some embodiments, nanostructures prepared using GaX3 (X = F, Cl, or Br) precursors and anaerobic ligands have a QY of at least 75%. In some embodiments, nanostructures prepared using GaX3 (X = F, Cl, or Br) precursors and anaerobic ligands have a QY of 75-90%. In some embodiments, nanostructures prepared using GaX3 (X = F, Cl, or Br) precursors and anaerobic ligands have a QY of approximately 80%.

[0102] The AIGS nanostructures prepared in this paper provide high blue light absorption. In some embodiments, the nanostructures have an OD 450 / mass (mL·mg⁻¹·cm⁻¹) of at least 0.8. In some embodiments, the nanostructures have an OD 450 / mass (mL·mg⁻¹·cm⁻¹) of 0.8–2.5. In another embodiment, the nanostructures have an OD 450 / mass (mL·mg⁻¹·cm⁻¹) of 0.87–1.9.

[0103] In some embodiments, the nanostructure is treated with gallium ions to allow indium-gallium ion exchange to occur throughout the AIGS nanostructure. In some embodiments, the nanostructure has a core containing Ag, In, Ga, and S in a gallium gradient between the surface and center of the nanostructure. In some embodiments, the nanostructure is prepared using an AIGS core treated with AGS and a GaX3 (X = F, Cl, or Br) precursor and an oxygen-free ligand within 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 the AIGS nanostructure, followed by ion exchange with gallium through reaction with an oxygen-free Ga salt to form the AIGS nanostructure. Methods for fabricating AIGS nanostructures

[0104] A method for fabricating AIGS nanostructures is provided, comprising: (a) Preparation of a mixture comprising an AIGS core, a sulfur source, and a ligand; (b) The mixture obtained in (a) was added to a mixture of gallium carboxylate and ligands at a temperature of 180-300 °C to obtain an ion-exchange nanostructure with a gallium gradient from the surface to the center of the nanostructure; and (c) Separation of nanostructures.

[0105] In some embodiments, the nanostructure has a pulse wave line (PWL) of 480-545 nm, wherein at least about 60% of the emission is band-edge emission.

[0106] It also provides a method for fabricating AIGS nanostructures, which includes (a) Reacting Ga(acetylacetonate)3, InCl3, and ligands, depending on the situation, in a solvent at a temperature sufficient to obtain the In-Ga reagent, and (b) React the In-Ga reagent with the Ag₂S nanostructure at a temperature sufficient to fabricate the AIGS nanostructure. (c) Reacting AIGS nanostructures with oxygen-free Ga salts in a solvent containing ligands at a temperature sufficient to obtain ion-exchange nanostructures with a gallium gradient from the surface to the center of the nanostructures.

[0107] In some embodiments, the nanostructure has a pulse wave line (PWL) of 480-545 nm, wherein at least about 60% of the emission is band-edge emission.

[0108] In some embodiments, the ligand is an alkylamine. In some embodiments, the alkylamine ligand is oleylamine. In some embodiments, the ligand is used in excess and acts as a solvent, and the listed solvents are 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, a sufficient temperature in (a) is 100°C to 280°C; a sufficient temperature in (b) is 150°C to 260°C; and a sufficient temperature in (c) is 170°C to 280°C. In some embodiments, a sufficient temperature in (a) is about 210°C, a sufficient temperature in (b) is about 210°C, and a sufficient temperature in (c) is about 240°C.

[0109] In some embodiments, at least 80% of the transmissions are edge-triggered. In other embodiments, at least 90% of the transmissions are edge-triggered. In other embodiments, at least 95% of the transmissions are edge-triggered. In some embodiments, 92-98% of the transmissions are edge-triggered. In some embodiments, 93-96% of the transmissions are edge-triggered.

[0110] Examples of ligands are disclosed in U.S. Patents 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 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.

[0111] In some embodiments, the sulfur source in (a) comprises: trioctylphosphine sulfide, elemental sulfur, octyl mercaptan, dodecyl mercaptan, octadecyl mercaptan, tributylphosphine sulfide, cyclohexyl isothiocyanate, α-thiocresol, ethylene trithiocarbonate, allyl mercaptan, bis(trimethylsilyl) sulfide, or combinations thereof. In some embodiments, the sulfur source in (a) is derived from S8.

[0112] In one embodiment, the sulfur source is S8.

[0113] In one embodiment, the temperature in (a) and (b) is approximately 270°C.

[0114] In some embodiments, the mixture in (b) further comprises a solvent. In some embodiments, the solvent is trioctylphosphine, dibenzyl ether, or squalane.

[0115] In some embodiments, gallium carboxylate is C2-24 gallium carboxylate. Examples of C2-24 carboxylates include acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, tridecanoate, tetradecanoate, pentadecanoate, hexadecanoate, octadecanoate (oleate), nonadecanoate, and eicosanoate. In one embodiment, gallium carboxylate is gallium oleate.

[0116] In some embodiments, the ratio of gallium carboxylate to the AIGS core is 0.008-0.2 mmol of gallium carboxylate per milligram of AIGS. In one embodiment, the ratio of gallium carboxylate to the AIGS core is approximately 0.04 mmol of gallium carboxylate per milligram of AIGS.

[0117] In another embodiment, the AIGS nanostructures are separated, for example, by precipitation. In some embodiments, the AIGS nanostructures are precipitated by adding a non-solvent to the AIGS nanostructures. In some embodiments, the non-solvent is a toluene / ethanol mixture. The precipitated nanostructures can be further separated by centrifugation and washing with a non-solvent.

[0118] A method for manufacturing nanostructures is also provided, comprising: (a) The preparation of a mixture comprising an AIGS core and gallium halide in a solvent for a duration sufficient to obtain an ion-exchange nanostructure having a gallium gradient from the surface to the center of the nanostructure; and (b) Separation of nanostructures.

[0119] In some embodiments, the nanostructure has a pulse wave length (PWL) of 480-545 nm, and at least about 60% of the emission is band-edge emission.

[0120] In some embodiments, at least 80% of the transmissions are edge-triggered transmissions. In other embodiments, at least 90% of the transmissions are edge-triggered transmissions. In still other embodiments, at least 95% of the transmissions are edge-triggered transmissions.

[0121] In some embodiments, gallium halide is gallium chloride, gallium bromide, or gallium iodide. In one embodiment, gallium halide is gallium iodide.

[0122] In some embodiments, the solvent comprises trioctylphosphine. In some embodiments, the solvent comprises toluene.

[0123] In some embodiments, the sufficient time in (a) is 0.1-200 hours. In some embodiments, the sufficient time in (a) is about 20 hours.

[0124] In some embodiments, the mixture is kept at 20°C to 100°C. In one embodiment, the mixture is kept at approximately room temperature (20°C to 25°C).

[0125] In some embodiments, the molar ratio of gallium halide to AIGS core is from about 0.1 to about 30.

[0126] In another embodiment, the AIGS nanostructures are separated, for example, by precipitation. In some embodiments, the AIGS nanostructures are precipitated by adding a non-solvent to the AIGS nanostructures. In some embodiments, the non-solvent is a toluene / ethanol mixture. The precipitated nanostructures can be further separated by centrifugation and / or washing with a non-solvent.

[0127] It also provides a method for manufacturing nanostructures, which includes: (a) Preparation of a mixture comprising AIGS nanostructures, a sulfur source, and ligands; (b) The mixture obtained in (a) was added to a mixture of GaX3 (X = F, Cl, or Br) and oxygen-free ligands at a temperature of 180-300 °C to obtain an ion-exchange nanostructure with a gallium gradient from the surface to the center of the nanostructure; and (c) Separation of nanostructures.

[0128] In some embodiments, the nanostructure has a PWL of 480-545 nm.

[0129] In some embodiments, the preparation in (a) is carried out under anaerobic conditions. In some embodiments, the preparation in (a) is carried out in a glove box.

[0130] In some embodiments, the addition in (b) is performed under anaerobic conditions. In some embodiments, the addition in (b) is performed in a glove working chamber.

[0131] In some embodiments, at least 80% of the transmissions are edge-triggered transmissions. In other embodiments, at least 90% of the transmissions are edge-triggered transmissions. In still other embodiments, at least 95% of the transmissions are edge-triggered transmissions.

[0132] 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, the ligand in (a) is an anaerobic ligand. In some embodiments, the ligand in (b) is an anaerobic ligand. In some embodiments, the ligand in (a) and (b) is an alkylamine. In some embodiments, the ligand is an alkylamine selected from the group consisting of: dodecylamine, oleylamine, hexadecylamine, dioctylamine, and octadecylamine. In some embodiments, the ligand in (a) is oleylamine. In some embodiments, the ligand in (b) is oleylamine. In some embodiments, the ligands in (a) and (b) are oleylamines.

[0133] In one embodiment, the sulfur source is S8.

[0134] In one embodiment, the temperature in (a) and (b) is approximately 270°C.

[0135] In some embodiments, the mixture in (b) further comprises a solvent. In some embodiments, the solvent is trioctylphosphine, dibenzyl ether, or squalane.

[0136] In some embodiments, GaX3 is gallium chloride, gallium fluoride, or gallium iodide. In some embodiments, GaX3 is gallium chloride. In some embodiments, GaX3 is gallium(III) chloride.

[0137] In some embodiments, the ratio of GaX3 to AIGS nuclei is 0.008-0.2 mmol GaX3 per milligram of AIGS. In some embodiments, the molar ratio of GaX3 to AIGS nuclei is about 0.1 to about 30. In some embodiments, the ratio of GaX3 to AIGS nuclei is about 0.04 mmol GaX3 per milligram of AIGS.

[0138] In some embodiments, AIGS nanostructures are separated, for example, by precipitation. In some embodiments, AIGS nanostructures are precipitated by adding a non-solvent to the AIGS nanostructure. In some embodiments, the non-solvent is a toluene / ethanol mixture. The precipitated nanostructures can be further separated by centrifugation and / or washing with a non-solvent.

[0139] In some embodiments, the mixture in (a) is kept at 20°C to 100°C. In some embodiments, the mixture in (a) is kept at approximately room temperature (20°C to 25°C).

[0140] In some embodiments, the mixture in (b) is kept at 200°C to 300°C for 0.1 hours to 200 hours. In some embodiments, the mixture in (b) is kept at 200°C to 300°C for about 20 hours. doped AIGS nanostructure

[0141] In some embodiments, the AIGS nanostructure is doped. In some embodiments, the dopant of the nanonucleus comprises a metal, including 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 comprises 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.

[0142] In some embodiments, the core is purified by precipitation from a non-solvent. In some embodiments, the AIGS nanostructure is filtered to remove precipitates from the core solution. Nanostructured Composition

[0143] In some embodiments, the present invention provides a nanostructure composition comprising: (a) at least one AIGS nanostructure group; and (b) At least one organic resin.

[0144] In some embodiments, the nanostructure has a PWL between 480 and 545 nm.

[0145] In some embodiments, at least 80% of the nanostructure emission is edge-emission. In other embodiments, at least 90% of the emission is edge-emission. In other embodiments, at least 95% of the emission is edge-emission. In some embodiments, 92-98% of the emission is edge-emission. In some embodiments, 93-96% of the emission is edge-emission.

[0146] In some embodiments, the nanostructure composition further comprises at least one second nanostructure group. Nanostructures having a pulsed light volume (PWL) between 480-545 nm emit green light. Additional nanostructure groups 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. At least one second nanostructure group may comprise group III-V nanocrystals selected from the following groups: 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 nanostructure group is an InP nanocrystal. organic resin

[0147] In some embodiments, the organic resin is a thermosetting resin or an ultraviolet (UV) curable resin. In some embodiments, the organic resin is cured by a method that facilitates roll-to-roll processing.

[0148] Thermosetting resins require curing, wherein the resin undergoes an irreversible molecular cross-linking process that renders the resin infusible. 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-amide resin, phenolic amine condensation resin, urea-melamine condensation resin, or a combination thereof.

[0149] In some embodiments, the thermosetting resin is an epoxy resin. Epoxy resins are easy to cure without producing volatiles or byproducts from various chemicals. Epoxy resins are also compatible with most substrates and tend to easily wet surfaces. See Boyle, MA et al., "Epoxy Resins", Composites, Vol. 21, ASM Handbook, pp. 78-89 (2001).

[0150] In some embodiments, the organic resin is a polysiloxane thermosetting resin. In some embodiments, the polysiloxane thermosetting resin is OE6630A or OE6630B (Dow Corning Corporation, Auburn, MI).

[0151] In some embodiments, a thermal initiator is used. In some embodiments, the thermal initiator is AIBN [2,2'-azobis(2-methylpropionitrile)] or benzoyl peroxide.

[0152] UV-curable resins are polymers that cure and harden rapidly when exposed to a specific wavelength of light. In some embodiments, UV-curable resins are resins having the following functional groups: free radical polymerizable groups, such as (meth)acryloxy, ethoxy, styrene, or vinyl groups; cationic polymerizable groups, such as epoxy, thioepoxy, ethoxy, or oxo-alkyl 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 polysulfide resins.

[0153] In some embodiments, the UV-curable resin system is selected from the group consisting of: isobornyl acrylate, isobornyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, aminocarbamate, allyloxylated cyclohexyl diacrylate, bis(acryloyloxyethyl)hydroxyisocyanurate, bis(acryloyloxyneopentyl glycol) adipate, bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, and 1,4-butanediol dimethyl acrylate. Ester, 1,3-Butanediol diacrylate, 1,3-Butanediol dimethacrylate, dicyclopentyl diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dinepentylenetetroxide hexaacrylate, dinepentylenetetroxide monohydroxypentacrylate, di(trimethylolpropane)tetraacrylate, ethylene glycol dimethacrylate, glycerol methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentylene glycol dimethacrylate, neopentylene glycol Hydroxypentaenoic acid ester diacrylate, neopentyl tetraacrylate, neopentyl tetraacrylate, dimethicone phosphate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, tetrabromobisphenol A diacrylate, triethylene glycol divinyl ether, triglyceride diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, triacryloxyethyl isocyanurate, triacrylate, diacrylate, propargyl acrylate, ethyl... Alkenyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated trifluoromethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane, monomethacryloxypropyl-terminated polydimethylsiloxane, monovinyl-terminated polydimethylsiloxane, monoallyl monotrimethylsiloxy-terminated polyethylene oxide, and combinations thereof.

[0154] In some embodiments, the UV-curable resin is a mercapto-functional compound that can be crosslinked with isocyanates, epoxy groups, or unsaturated compounds under UV curing conditions. In some embodiments, the polythiol is neopentyltetra(3-mercaptopropionate) (PETMP); trimethylolpropane tri(3-mercaptopropionate) (TMPMP); ethylene glycol di(3-mercaptopropionate) (GDMP); tris(25-(3-mercaptopropoxy)ethyl)isocyanurate (TEMPIC); dinepentyltetra(3-mercaptopropionate) (Di-PETMP); ethoxylated trimethylolpropane tri(3-mercaptopropionate) (ETTMP 1300 and ETTMP 700); polycaprolactone tetra(3-mercaptopropionate) (PCL4MP 1350); neopentyltetramercaptoacetate (PETMA); trimethylolpropane trimercaptoacetate (TMPMA); or ethylene glycol dimercaptoacetate (GDMA). These compounds are sold by Bruno Bock, Marschacht, Germany under the trademark name THIOCURE®.

[0155] 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), trimethylolpropane-3-thioglycolate, trimethylolpropane-3-mercaptopropionate, neopentyltetraethylene glycol tetra(thioglycolate), neopentyltetraethylene glycol tetra(3-mercaptopropionate) (PETMP), and combinations thereof. In some embodiments, the UV-curable resin is PETMP.

[0156] In some embodiments, the UV-curable resin is a thiol-ene formulation comprising polythiol and 1,3,5-triallyl-1,3,5-tris(2,4,6)(1H,3H,5H)-trione (TTT). In some embodiments, the UV-curable resin is a thiol-ene formulation comprising PETMP and TTT.

[0157] In some embodiments, the UV-curable resin further comprises a photoinitiator. The photoinitiator initiates the crosslinking and / or curing reaction of the photosensitive material during exposure to light. In some embodiments, the photoinitiator is based on acetophenone, benzoin, or thioxathenone.

[0158] In some embodiments, the photoinitiator is a vinyl acrylate-based resin. In some embodiments, the photoinitiator is MINS-311RM (Minuta Technology Co., Ltd, Korea).

[0159] In some embodiments, the photoinitiator 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 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-diphenylphosphine oxide) or MBF (methyl benzoate).

[0160] In some embodiments, the weight percentage of at least one organic resin in the nanostructure composition is between about 5% and about 99%, between about 5% and about 95%, between about 5% and about 90%, between about 5% and about 80%, between about 5% and about 70%, between about 5% and about 60%, between about 5% and about 50%, between about 5% and about 40%, between about 5% and about 30%, between about 5% and about 20%, between about 5% and about 10%, between about 10% and about 99%, between about 10% and about 95%, between about 10% and about 90%, between about 10% and about 80%, and about 10%. Between approximately 70% and approximately 10% and approximately 60%, between approximately 10% and approximately 50%, between approximately 10% and approximately 40%, between approximately 10% and approximately 30%, between approximately 10% and approximately 20%, between approximately 20% and approximately 99%, between approximately 20% and approximately 95%, between approximately 20% and approximately 90%, between approximately 20% and approximately 80%, between approximately 20% and approximately 70%, between approximately 20% and approximately 60%, between approximately 20% and approximately 50%, between approximately 20% and approximately 40%, between approximately 20% and approximately 30%, between approximately 30% and approximately 99%, between approximately 30% and approximately 95%, approximately 3 Between 0% and approximately 90%, between approximately 30% and approximately 80%, between approximately 30% and approximately 70%, between approximately 30% and approximately 60%, between approximately 30% and approximately 50%, between approximately 30% and approximately 40%, between approximately 40% and approximately 99%, between approximately 40% and approximately 95%, between approximately 40% and approximately 90%, between approximately 40% and approximately 80%, between approximately 40% and approximately 70%, between approximately 40% and approximately 60%, between approximately 40% and approximately 50%, between approximately 50% and approximately 99%, between approximately 50% and approximately 95%, between approximately 50% and approximately 90%, between approximately 50% and approximately 80%, approximately Between 50% and approximately 70%, between approximately 50% and approximately 60%, between approximately 60% and approximately 99%, between approximately 60% and approximately 95%, between approximately 60% and approximately 90%, between approximately 60% and approximately 80%, between approximately 60% and approximately 70%, between approximately 70% and approximately 99%, between approximately 70% and approximately 95%, between approximately 70% and approximately 90%, between approximately 70% and approximately 80%, between approximately 80% and approximately 99%, between approximately 80% and approximately 95%, between approximately 80% and approximately 90%, between approximately 90% and approximately 99%, between approximately 90% and approximately 95%, or between approximately 95% and approximately 99%. [] Method for preparing AIGS nanostructured compositions []

[0161] This invention provides a method for preparing a nanostructured composition, the method comprising: (a) Provide at least one AIGS nanostructure group; and (b) Blending at least one organic resin with the composition of (a).

[0162] In some embodiments, the nanostructure has a pulsed wave line (PWL) of 480-545 nm, wherein 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.

[0163] This invention also provides a method for preparing a nanostructured composition, the method comprising: (a) Providing at least one AIGS nanostructure group 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; wherein the nanostructure is prepared using a GaX3 (X = F, Cl, or Br) precursor and an oxygen-free ligand; and (b) Blending at least one organic resin with the composition of (a).

[0164] In some embodiments, the nanostructure has a pulse wave length (PWL) of 480-545 nm and at least about 60% of the emission is band-edge emission.

[0165] This invention also provides a method for preparing a nanostructured composition, the method comprising: (a) Providing at least one AIGS nanostructure group, wherein the nanostructure has a band-edge emission (PWL) between 480 and 545 nm, wherein at least about 80% of the emission is band-edge emission, and wherein the nanostructure exhibits 80-99% QY; and (b) Blending at least one organic resin with the composition of (a).

[0166] In some embodiments, between approximately 100 rpm and approximately 10,000 rpm, between approximately 100 rpm and approximately 5,000 rpm, between approximately 100 rpm and approximately 3,000 rpm, between approximately 100 rpm and approximately 1,000 rpm, between approximately 100 rpm and approximately 500 rpm, between approximately 500 rpm and approximately 10,000 rpm, between approximately 500 rpm and approximately 5,000 rpm, between approximately 500 rpm and approximately 3,000 rpm, between approximately 500 rpm and approximately 1,000 rpm, between approximately 1,000 rpm and approximately 10,000 rpm, between approximately 1,000 rpm and approximately 5,000 rpm, between approximately 1,000 rpm and approximately 3,000 rpm, between approximately 3,000 rpm and approximately 10,000 rpm, between approximately 3,000 rpm and approximately 10,000 rpm, between approximately 1,000 rpm and approximately 5,000 rpm, between approximately 1,000 rpm and approximately 3,000 rpm, between approximately 3,000 rpm and approximately 10,000 rpm, between approximately 1 ... At least one nanostructure group is blended with at least one organic resin at a stirring rate between rpm and about 10,000 rpm or between about 5,000 rpm and about 10,000 rpm.

[0167] In some embodiments, at least one nanostructure group is mixed with at least one organic resin 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 The time between approximately 1 hour and approximately 24 hours, between approximately 1 hour and approximately 20 hours, between approximately 1 hour and approximately 15 hours, between approximately 1 hour and approximately 10 hours, between approximately 1 hour and approximately 5 hours, between approximately 5 hours and approximately 24 hours, between approximately 5 hours and approximately 20 hours, between approximately 5 hours and approximately 15 hours, between approximately 5 hours and approximately 10 hours, between approximately 10 hours and approximately 24 hours, between approximately 10 hours and approximately 20 hours, between approximately 10 hours and approximately 15 hours, between approximately 15 hours and approximately 24 hours, between approximately 15 hours and approximately 20 hours, or between approximately 20 hours and approximately 24 hours.

[0168] In some embodiments, at least one group of nanostructures is blended with at least one organic resin at a temperature between about -5°C and about 100°C, between about -5°C and about 75°C, between about -5°C and about 50°C, between about -5°C and about 23°C, between about 23°C and about 100°C, between about 23°C and about 75°C, between about 23°C and about 50°C, between about 50°C and about 100°C, between about 50°C and about 75°C, or between about 75°C and about 100°C. In some embodiments, at least one organic resin is blended with at least one group of nanostructures at a temperature between about 23°C and about 50°C.

[0169] In some embodiments, if more than one organic resin is used, the organic resins are added simultaneously and mixed. In some embodiments, between approximately 100 rpm and approximately 10,000 rpm, between approximately 100 rpm and approximately 5,000 rpm, between approximately 100 rpm and approximately 3,000 rpm, between approximately 100 rpm and approximately 1,000 rpm, between approximately 100 rpm and approximately 500 rpm, between approximately 500 rpm and approximately 10,000 rpm, between approximately 500 rpm and approximately 5,000 rpm, between approximately 500 rpm and approximately 3,000 rpm, between approximately 500 rpm and approximately 1,000 rpm, between approximately 1,000 rpm and approximately 10,000 rpm, between approximately 1,000 rpm and approximately 5,000 rpm, between approximately 1,000 rpm and approximately 3,000 rpm, between approximately 3,000 rpm and approximately 10,000 rpm, between approximately 3,000 rpm and approximately 10,000 rpm, between approximately 1,000 rpm and approximately 5,000 rpm, between approximately 1,000 rpm and approximately 3,000 rpm, between approximately 3,000 rpm and approximately 10,000 rpm, between approximately 1 ... The first organic resin and the second organic resin are mixed at an agitation rate between 10,000 rpm and about 5,000 rpm and about 10,000 rpm.

[0170] In some embodiments, the first organic resin and the second organic resin are mixed 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, and approximately 1 hour. The time between approximately 24 hours, approximately 1 hour and approximately 20 hours, approximately 1 hour and approximately 15 hours, approximately 1 hour and approximately 10 hours, approximately 1 hour and approximately 5 hours, approximately 5 hours and approximately 24 hours, approximately 5 hours and approximately 20 hours, approximately 5 hours and approximately 15 hours, approximately 5 hours and approximately 10 hours, approximately 10 hours and approximately 24 hours, approximately 10 hours and approximately 20 hours, approximately 10 hours and approximately 15 hours, approximately 15 hours and approximately 24 hours, approximately 15 hours and approximately 20 hours, or approximately 20 hours and approximately 24 hours. Characteristics of AIGS nanostructures

[0171] In some embodiments, the AIGS nanostructure exhibits high photoluminescence quantum yield. In some embodiments, the nanostructure is displayed between about 50% and about 99%, about 50% and about 95%, about 50% and about 90%, about 50% and about 85%, about 50% and about 80%, about 50% and about 70%, about 50% and about 60%, about 60% and about 99%, about 60% and about 95%, about 60% and about 90%, about 60% and about 85%, about 60% and about 80%, about 60% and about 70%, about 70% and about 99%, and about 70% and about 95%. The photoluminescence quantum yield is between approximately 70% and approximately 90%, between approximately 70% and approximately 85%, between approximately 70% and approximately 80%, between approximately 80% and approximately 99%, between approximately 80% and approximately 95%, between approximately 80% and approximately 90%, between approximately 80% and approximately 85%, between approximately 85% and approximately 99%, between approximately 80% and approximately 85%, between approximately 85% and approximately 99%, between approximately 85% and approximately 90%, between approximately 90% and approximately 99%, between approximately 90% and approximately 95%, or between approximately 95% and approximately 99%. In some embodiments, the nanostructure exhibits photoluminescence quantum yields between approximately 82% and approximately 96%, between approximately 85% and approximately 96%, and between approximately 93% and approximately 94%.

[0172] The photoluminescence spectrum of nanostructures can cover a wide range of desired portions of the spectrum. In some embodiments, the photoluminescence spectrum of nanostructures has emission maximum values ​​between 300 nm and 750 nm, 300 nm and 650 nm, 300 nm and 550 nm, 300 nm and 450 nm, 450 nm and 750 nm, 450 nm and 650 nm, 450 nm and 550 nm, 450 nm and 750 nm, 450 nm and 650 nm, 450 nm and 550 nm, 550 nm and 750 nm, 550 nm and 650 nm, or 650 nm and 750 nm. In some embodiments, the photoluminescence spectrum of nanostructures has an emission maximum value between 450 nm and 550 nm.

[0173] The size distribution of nanostructures may be relatively narrow. In some embodiments, the photoluminescence spectrum of the nanostructure group may have a full width at half maximum (FWHM) between 10 nm and 60 nm, 10 nm and 40 nm, 10 nm and 30 nm, 10 nm and 20 nm, 20 nm and 60 nm, 20 nm and 40 nm, 20 nm and 30 nm, 25 nm and 60 nm, 25 nm and 40 nm, 25 nm and 30 nm, 30 nm and 60 nm, 30 nm and 40 nm, or 40 nm and 60 nm. In some embodiments, the photoluminescence spectrum of the nanostructure group may have a full WHM between 24 nm and 50 nm, 24 nm and 28 nm, 27 nm and 32 nm, or 29 nm and 38 nm.

[0174] In some embodiments, the nanostructure emits light with a peak emission wavelength (PWL) between about 400 nm and about 650 nm, between about 400 nm and about 600 nm, between about 400 nm and about 550 nm, between about 400 nm and about 500 nm, between about 400 nm and about 450 nm, between about 450 nm and about 650 nm, between about 450 nm and about 600 nm, between about 450 nm and about 550 nm, between about 450 nm and about 500 nm, between about 500 nm and about 650 nm, between about 500 nm and about 600 nm, between about 500 nm and about 550 nm, between about 550 nm and about 650 nm, between about 550 nm and about 600 nm, or between about 600 nm and about 650 nm. In some embodiments, the nanostructure emits light with a PWL between about 500 nm and about 550 nm.

[0175] As a predicted value for blue light absorption efficiency, the optical density per mass at 450 nm (OD 450 / mass) is calculated by measuring the optical density of the nanostructured solution in a photoanalyzer with a path length of 1 cm and dividing it by the dry mass of the same solution per milliliter after all volatiles have been removed under vacuum (< 200 mTorr). In some embodiments, the nanostructure has an optical density (OD 450 / mass) at 450 nm between about 0.28 / mg and about 0.5 / mg, about 0.28 / mg and about 0.4 / mg, about 0.28 / mg and about 0.35 / mg, about 0.28 / mg and about 0.32 / mg, about 0.32 / mg and about 0.5 / mg, about 0.32 / mg and about 0.4 / mg, about 0.32 / mg and about 0.35 / mg, about 0.35 / mg and about 0.5 / mg, about 0.35 / mg and about 0.4 / mg, or about 0.4 / mg and about 0.5 / mg. membrane

[0176] The nanostructures of this invention can be embedded in a polymer matrix using any suitable method. As used herein, the term "embedded" indicates that the nanostructure is encapsulated or covered by a polymer that constitutes the majority of the matrix components. In some embodiments, at least one group of nanostructures is suitably and uniformly distributed throughout the matrix. In some embodiments, at least one group of nanostructures is distributed according to a specific application. In some embodiments, the nanostructures are mixed in a polymer and applied to a substrate surface.

[0177] In some embodiments, the present invention provides a nanostructured film layer comprising: (a) A composition comprising at least one AIGS nanostructure group, 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 bonded to the nanostructure; and (b) At least one organic resin.

[0178] In some embodiments, a portion of the ligands are bonded to the nanostructure. In other embodiments, the surface of the nanostructure is saturated with ligands.

[0179] In some embodiments, the nanostructure has a PWL between 480 nm and 545 nm.

[0180] This invention also provides a method for preparing nanostructured films, comprising: (a) Providing at least one AIGS nanostructure group 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; and (b) Blending at least one organic resin with the composition of (a). In some embodiments, the nanostructure has a PWL between 480 nm and 545 nm.

[0181] In some embodiments, at least 80% of the transmissions are edge-triggered. In other embodiments, at least 90% of the transmissions are edge-triggered. In other embodiments, at least 95% of the transmissions are edge-triggered. In some embodiments, 92-98% of the transmissions are edge-triggered. In some embodiments, 93-96% of the transmissions are edge-triggered. Ligands and Additives

[0182] In some embodiments, the nanostructure composition further comprises an amino ligand having formula I: in: x is between 1 and 100; y is between 0 and 100; and R2 is a C1-20 alkyl group.

[0183] In some embodiments, x is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100. In some embodiments, x is 10 to 50. In some embodiments, x is 10 to 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.

[0184] In some embodiments, R2 is a C1-20 alkyl group. In some embodiments, R2 is a C1-10 alkyl group. In some embodiments, R2 is a C1-5 alkyl group. In some embodiments, R2 is -CH2CH3.

[0185] In some embodiments, the compound of formula I is a commercially available amine-terminated polymer from Huntsman Petrochemical Corporation. In some embodiments, the amine-terminated polymer of formula (VI) has x = 1, y = 9 and R 2 = -CH 3, 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 = -CH 3, 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 = -CH 3, 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 = -CH 3, 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 glycol amine purchased from Creative PEGWorks, such as PEG550-amine and PEG350-amine.

[0186] In some embodiments, the ligand is a sterically hindered phenol having Formula II: R3 and R4 are C3-6 secondary or tertiary alkyl groups, and R5 is hydrogen or, as appropriate, a substituted C1-6 alkyl group. In some embodiments, R3 and R4 are isopropyl, 2-butyl, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, tributyl, 2-methyl-2-pentyl, or 3-methyl-3-pentyl. In some embodiments, R5 is in the 3- or 4-position of Formula II.

[0187] Substituents present, as appropriate, on the C1-6 alkyl group of R5 include nitro, haloalkoxy, aryloxy, arylalkoxy, alkylthio, sulfonamide, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, ureo, guanidinyl, carbamate, carboxyl, alkoxycarbonyl, carboxylalkyl, or -C(=O)R7, wherein R7 is an alkoxy group that may be further substituted with one or more other alkoxy groups. In some embodiments, R7 has the following formula: Where p is 0-3 and the oxygen atom is bonded to the carbonyl group of formula II. In some embodiments, R 7 is: .

[0188] In some embodiments, R 7 is: And Equation II is: , The oxygen atom of R 7 is bonded to the carbonyl group of formula II at the position indicated by *.

[0189] In some embodiments, the compound of formula II is neopentyl tetroxide [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]propionate].

[0190] The ligands of Formula II are bonded to the nanostructure and also act as antioxidants in nanostructure compositions, such as inks and films. In addition, because the ligands are sterically hindered, the free volume on the surface of the nanostructure is reduced, thereby reducing or preventing oxidation by ambient oxygen and improving air stability.

[0191] In some embodiments, the nanostructured film layer is a color conversion layer.

[0192] The nanostructure composition can be deposited by any suitable method known in the art, including but not limited to brush coating, spray coating, solvent spraying, wet coating, adhesive coating, spin coating, tape coating, roller coating, flow coating, inkjet vapor jetting, drop coating, doctor blade coating, fogging deposition, or combinations thereof. In some embodiments, the nanostructure 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 used to form the nanostructure film of the present invention. The nanostructure composition can be directly coated onto the desired layer of a substrate. Alternatively, the nanostructure composition can be formed as a solid layer as an element-independent component and subsequently applied to a substrate. In some embodiments, the nanostructure composition can be deposited on one or more barrier layers. Metal alkoxides

[0193] Metal alkoxides have the general formula M(OR)x, where R is a straight-chain, branched-chain, or cycloalkyl group, typically containing 1 to 10 carbon atoms, and x is the valence number of the metal. In some embodiments, metal alkoxides include metal methoxides, metal ethanoloxides, 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-octanoloxides, metal isooctanoloxides, metal n-nonoxides, metal isononoxides, metal n-decoxides, and metal isodecoxides.

[0194] In some embodiments, the metal of the metal alkoxide includes one or more of the following: lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, argonium, lanthanum, cerium, tungsten, neodymium, samarium, europium, thallium, tektium, dysprosium, holmium, erbium, thionium, 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 metal includes one or more of the following: aluminum, antimony, arsenic, barium, bismuth, boron, cerium, thiocyanate, gallium, germanium, hafnium indium, iron, lanthanum, lithium, magnesium, molybdenum, neodymium, phosphorus, silicon, sodium, strontium, tantalum, thallium, tin, titanium, tungsten, vanadium, yttrium, zinc, and zirconium.

[0195] In some embodiments, the metal alkoxide comprises one or more of Group 4 metals, including titanium, zirconium, and hafnium.

[0196] In some embodiments, the metal alkoxide is at least one zirconium alkoxide, including zirconium tetramethanol (IV), zirconium tetraethanol (IV), zirconium tetra-n-propoxide (IV), zirconium tetra-isopropoxide (IV), zirconium tetra-n-butoxide (IV), zirconium tetra-isobutoxide (IV), zirconium tetra-n-pentoxide (IV), zirconium tetra-isopentoxide (IV), zirconium tetra-n-hexanool (IV), zirconium tetra-isohexanool (IV), zirconium tetra-n-heptanool (IV), zirconium tetra-isoheptanool (IV), zirconium tetra-n-octanol (IV), zirconium tetra-n-nonanool (IV), zirconium tetra-isononanool (IV), zirconium tetra-n-decanol (IV), or zirconium tetra-isodecanol (IV).

[0197] In some embodiments, metal alkoxides can form a sol-gel around the AIGS nanostructure, thus creating an oxygen barrier and providing stabilization for the AIGS nanostructure. See Brinker and Scherer, (1990) Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing. Academic Press.

[0198] In some embodiments, the metal alkoxide is present in the AIGS membrane composition at a concentration of at least 0.005 wt% (50 ppm). In some embodiments, the metal alkoxide is present in the AIGS membrane composition at a concentration of about 0.03 to about 3 wt%. In some embodiments, the metal alkoxide is present in the membrane composition at a concentration 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%. Metal alkoxide hydrolysis products

[0199] Metal alkoxide hydrolysis products have the general formula M(OH)x(OR)y, where R is a straight-chain, branched-chain, or cycloalkyl group, typically containing 1 to 10 carbon atoms, and x + y equals the valence of the metal. Metal alkoxide hydrolysis products include zirconium(IV) monohydric hydroxide triethanolate, zirconium(IV) diethanolate, zirconium(IV) trihydric hydroxide monoethanolate, zirconium(IV) tetrahydric hydroxide (IV), zirconium(IV) monohydric hydroxide triethanolate, zirconium(IV) diethanolate, zirconium(IV) triethanolate, zirconium(IV) monohydric hydroxide tri-n-propanolate, zirconium(IV) di-n-propanolate, zirconium(IV) mono-n-propanolate, zirconium(IV) monoisopropanolate, zirconium(IV) diisopropanolate, zirconium(IV) monoisopropanolate, zirconium(IV) monoisopropanolate, zirconium(IV) tri-n-butanolate, zirconium(IV) di-n-butanolate, zirconium(IV) di-n-butanolate, zirconium(IV) tri ... Zirconium(IV) mono-n-butanol, Zirconium(IV) mono-isobutanol, Zirconium(IV) diisobutanol, Zirconium(IV) tri-isobutanol, Zirconium(IV) tri-n-pentanol, Zirconium(IV) di-n-pentanol, Zirconium(IV) tri-n-pentanol, Zirconium(IV) mono-n-pentanol, Zirconium(IV) triisopentanol, Zirconium(IV) diisopentanol, Zirconium(IV) tri-n-hexanol, Zirconium(IV) di-n-hexanol, Zirconium(IV) tri-n-hexanol, Zirconium(IV) mono-n-hexanol, Zirconium(IV) triisohexanol, Zirconium(IV) di ... Zirconium(IV) monoisohexanol, Zirconium(IV) tri-n-heptyl alcohol, Zirconium(IV) di-n-heptyl alcohol, Zirconium(IV) tri-n-heptyl alcohol, Zirconium(IV) mono-n-heptyl alcohol, Zirconium(IV) diisoheptyl alcohol, Zirconium(IV) tri-n-heptyl alcohol, Zirconium(IV) tri-n-heptyl alcohol, Zirconium(IV) di ... Nononol, Zirconium trioxide (IV) mono-nononol, Zirconium monooxide (IV) tri-isononol, Zirconium dioxide (IV) di-isononol, Zirconium trioxide (IV) mono-isononol, Zirconium monooxide (IV) tri-n-decyl, Zirconium dioxide (IV) di-n-decyl, Zirconium trioxide (IV) mono-n-decyl, Zirconium monooxide (IV) tri-isodecyl, Zirconium dioxide (IV) di-isodecyl, Zirconium trioxide (IV) mono-isodecyl, Titanium monooxide (IV) triethanolol, Titanium dioxide (IV) diethanolol, Titanium trioxide (IV) monoethanolol, Titanium tetraoxide (IV), Titanium monooxide (IV) triethanololTitanium(IV) diethanolate, titanium(IV) triethanolate, titanium(IV) tri-n-propanol, titanium(IV) di-n-propanol, titanium(IV) tri-n-propanol, titanium(IV) tri-n-propanol, titanium(IV) triisopropanol, titanium(IV) diisopropanol, titanium(IV) triisopropanol, titanium(IV) tri-n-butanol, titanium(IV) di-n-butanol, titanium(IV) tri-n-butanol, titanium(IV) isobutanol, titanium(IV) diisobutanol, titanium(IV) triisobutanol, titanium(IV) tri-n-pentanol, titanium(IV) di-n-pentanol, titanium(IV) tri-n-propanol Titanium(IV) mono-n-pentanol, titanium(IV) mono-triisopentanol, titanium(IV) di-diisopentanol, titanium(IV) tri-diisopentanol, titanium(IV) mono-diisopentanol, titanium(IV) tri-n-hexanol, titanium(IV) di-n-hexanol, titanium(IV) mono-n-diisopentanol, titanium(IV) diisopentanol, titanium(IV) tri-n-hexanol, titanium(IV) diisopentanol, titanium(IV) tri-n-hexanol, titanium(IV) di-n-hexanol, titanium(IV) tri-n-hexanol, titanium(IV) diisopentanol, titanium(IV) tri-n-hexanol, titanium(IV) diisopentanol, titanium(IV) monoisopentanol, titanium(IV) mono-n-hexanol, titanium(IV) mono-diisopentanol, titanium(IV) monoisopentanol, titanium(IV) mono-diisopentanol, titanium(IV) mono-diisopentanol, titanium(IV) mono-diisopentanol, titanium(IV) mono-diisopentanol IV) Tri-n-octanol, Titanium dihydroxide (IV) 2-n-octanol, Titanium trihydroxide (IV) mono-n-octanol, Titanium monohydroxide (IV) triisooctanol, Titanium dihydroxide (IV) 2-isooctanol, Titanium trihydroxide (IV) mono-isooctanol, Titanium monohydroxide (IV) tri-n-nonyl alcohol, Titanium dihydroxide (IV) 2-n-nonyl alcohol, Titanium trihydroxide (IV) mono-n-nonyl alcohol, Titanium monohydroxide (IV) tri-isononyl alcohol, Titanium dihydroxide (IV) 2-isononyl alcohol, Titanium trihydroxide (IV) mono-isononyl alcohol, Titanium monohydroxide (IV) tri-n-decanol, Titanium dihydroxide (IV) 2-n-decanol, Titanium trihydroxide (IV) mono-n-decanol, Titanium monohydroxide (IV) tri-isodecanol, Titanium(IV) hydroxide di-isodecyl alcohol, titanium(IV) trioxide mono-isodecyl alcohol, hafnium(IV) triethanolamine monohydric hydroxide, hafnium(IV) diethanolamine dihydric hydroxide, hafnium(IV) monoethanolamine trihydric hydroxide, hafnium(IV) tetrahydric hydroxide, hafnium(IV) triethanolamine monohydric hydroxide, hafnium(IV) diethanolamine dihydric hydroxide, hafnium(IV) monoethanolamine trihydric hydroxide, hafnium(IV) tri-n-propanol monohydric hydroxide, hafnium(IV) di-n-propanol monohydric hydroxide, hafnium(IV) triisopropanol monohydric hydroxide, hafnium(IV) diisopropanol monohydric hydroxide, hafnium(IV) tri-n-butanol monohydric hydroxide, hafnium(IV) di-n-butanol monohydric hydroxide, hafnium(IV) di-n-butanol monohydric hydroxide, hafnium(IV) di-n-butanol monohydric hydroxide,Hafnium trihydride (IV) mono-n-butanol, Hafnium monohydride (IV) isobutanol, Hafnium dihydride (IV) diisobutanol, Hafnium trihydride (IV) monoisobutanol, Hafnium monohydride (IV) tri-n-pentanol, Hafnium dihydride (IV) di-n-pentanol, Hafnium trihydride (IV) mono-n-pentanol, Hafnium monohydride (IV) triisopentanol, Hafnium dihydride (IV) diisopentanol, Hafnium trihydride (IV) monoisopentanol, Hafnium monohydride (IV) monoisopentanol, Hafnium monohydride Hafnium(IV) tri-n-hexanoate, Hafnium(IV) di-n-hexanoate, Hafnium(IV) mono-n-hexanoate, Hafnium(IV) mono-isohexanoate, Hafnium(IV) di-isohexanoate, Hafnium(IV) mono-isohexanoate, Hafnium(IV) tri-n-heptanoate, Hafnium(IV) di-n-heptanoate, Hafnium(IV) mono-n-heptanoate, Hafnium(IV) mono-isoheptanoate, Hafnium(IV) di-heptanoate (IV) Diisoheptyl alcohol, Hafnium trihydride (IV) Monoisoheptyl alcohol, Hafnium monohydride (IV) Tri-n-octanol alcohol, Hafnium dihydride (IV) Di-n-octanol alcohol, Hafnium trihydride (IV) Mono-n-octanol alcohol, Hafnium monohydride (IV) Tri-isooctanol alcohol, Hafnium dihydride (IV) Di-isooctanol alcohol, Hafnium trihydride (IV) Mono-isooctanol alcohol, Hafnium monohydride (IV) Tri-n-nonyl alcohol, Hafnium dihydride (IV) Di-n-nonyl alcohol, Hafnium trihydride Hafnium(IV) mono-n-nonanolate, hafnium(IV) mono-tri-isononanolate, hafnium(IV) di-isononanolate, hafnium(IV) tri-isononanolate, hafnium(IV) tri-n-decanol, hafnium(IV) di-n-decanol, hafnium(IV) mono-n-decanol, hafnium(IV) tri-isodecanolate, hafnium(IV) di-isodecanolate, and hafnium(IV) mono-isononanolate.

[0200] In some embodiments, the metal alkoxide hydrolysis product is present in the AIGS membrane composition at a concentration of at least 0.005 wt% (50 ppm). In some embodiments, the metal oxide hydrolysis product is present in the AIGS membrane composition at a concentration of about 0.03 to about 3 wt%. In some embodiments, the metal oxide hydrolysis product is present in the membrane composition at a concentration 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%. metal halides

[0201] Metal halides have the general formula MX y, where y is the valence number of the metal. Metal halides include zirconium tetrafluoride (IV), zirconium tetrachloride (IV), zirconium tetrabromide (IV), zirconium tetraiodide (IV), titanium tetrafluoride (IV), titanium tetrachloride (IV), titanium tetrabromide (IV), titanium tetraiodide (IV), hafnium tetrafluoride (IV), hafnium tetrachloride (IV), hafnium tetrabromide (IV), hafnium tetraiodide (IV), gallium trifluoride (III), gallium trichloride (III), gallium tribromide (III), and gallium triiodide (III).

[0202] In some embodiments, the metal halide is present in the AIGS membrane composition at a concentration of at least 0.005 wt% (50 ppm). In some embodiments, the metal halide is present in the AIGS membrane composition in an amount of about 0.03 to about 3 wt%. In some embodiments, the metal halide 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 wt%. Metal halide hydrolysis products

[0203] Metal halide hydrolysis products have the general formula MX y(OH) x, where x + y equals the valence of the metal. Metal halide hydrolysis products include zirconium(IV) hydroxide trichloride, zirconium(IV) hydroxide difluoride, zirconium(IV) hydroxide trifluoride, zirconium(IV) hydroxide tetrafluoride, titanium(IV) hydroxide trifluoride, titanium(IV) hydroxide difluoride, titanium(IV) hydroxide trifluoride, titanium(IV) hydroxide tetrafluoride, titanium(IV) hydroxide trifluoride, titanium(IV) hydroxide difluoride, titanium(IV) hydroxide trifluoride, titanium(IV) hydroxide tetrafluoride, hafnium(IV) hydroxide trifluoride, hafnium(IV) hydroxide difluoride, hafnium(IV) hydroxide trifluoride, and hafnium(IV) hydroxide tetrafluoride. Hafnium hydroxide (IV), zirconium hydroxide (IV) trichloride, zirconium hydroxide (IV) dichloride, zirconium hydroxide (IV) monochloride, zirconium hydroxide (IV) tetrachloride, titanium hydroxide (IV) trichloride, titanium hydroxide (IV) dichloride, titanium hydroxide (IV) monochloride, titanium hydroxide (IV) tetrachloride, titanium hydroxide (IV) trichloride, titanium hydroxide (IV) dichloride, titanium hydroxide (IV) monochloride, titanium hydroxide (IV) tetrachloride, hafnium hydroxide (IV) trichloride, hafnium hydroxide (IV) dichloride, hafnium hydroxide (IV) monochloride, titanium hydroxide (IV) tetrachloride Hafnium (IV), Zirconium (IV) monohydric hydroxide tribromide, Zirconium (IV) dibromide dibromide, Zirconium (IV) tribromide tribromide, Zirconium (IV) tetrahydric hydroxide (IV), Titanium (IV) monohydric hydroxide tribromide, Titanium (IV) dibromide dibromide, Titanium (IV) tribromide tribromide, Titanium (IV) tetrahydric hydroxide (IV), Titanium (IV) monohydric hydroxide tribromide, Titanium (IV) dibromide dibromide, Titanium (IV) tribromide tribromide, Titanium (IV) tetrahydric hydroxide (IV), Hafnium (IV) monohydric hydroxide tribromide, Hafnium (IV) dibromide dibromide, Hafnium (IV) tribromide tribromide, Hafnium (IV) tetrahydric hydroxide (I) (V), zirconium(IV) hydroxide triiodide, zirconium(IV) diiodide, zirconium(IV) triiodide, zirconium(IV) tetrahydroxide (IV), titanium(IV) hydroxide triiodide, titanium(IV) diiodide, titanium(IV) triiodide, titanium(IV) tetrahydroxide (IV), titanium(IV) hydroxide triiodide, titanium(IV) diiodide, titanium(IV) tetrahydroxide (IV), titanium(IV) hydroxide triiodide, titanium(IV) triiodide, titanium(IV) tetrahydroxide (IV), hafnium(IV) hydroxide triiodide, hafnium(IV) diiodide, hafnium(IV) triiodide, hafnium(IV) tetrahydroxide (IV) monoiodide and hafnium(IV) tetrahydroxide (IV).

[0204] In some embodiments, the metal halide hydrolysis product is present in the AIGS membrane composition at a concentration of at least 0.005 wt% (50 ppm). In some embodiments, the metal halide hydrolysis product is present in the AIGS membrane composition in an amount of about 0.03 to about 3 wt%. In some embodiments, the metal halide hydrolysis product 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 wt%. Organometallic compounds

[0205] Organometallic compounds contain metal-carbon bonds and may have the formula RxM, where R is a straight-chain, branched-chain, or cycloalkyl group, typically containing 1 to 10 carbon atoms, and x is the valence number of the metal. 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-isooctylzirconium, tetra-n-nonylzirconium, tetra-isononylzirconium, tetra-n-decylzirconium, tetra-isodecylzirconium, tetramethyltitanium, tetraethyltitanium, tetra-n-propyltitanium, tetraisopropyltitanium, tetra-n-butyltitanium, tetraisobutyltitanium, tetra-n-pentyltitanium, tetraisopentyltitanium, tetra- Hexyl titanium, tetraisohexyl titanium, tetra-n-heptyl titanium, tetraisoheptyl titanium, tetra-n-octyl titanium, tetra-isooctyl titanium, tetra-n-nonyl titanium, tetra-isononyl titanium, tetra-n-decyl titanium, tetra-isodecyl titanium, tetramethylhafnium, tetra-n-propylhafnium, tetraisopropylhafnium, tetra-n-butylhafnium, tetraisobutylhafnium, tetra-n-pentylhafnium, tetraisopentylhafnium, tetra-n-hexylhafnium, tetraisohexylhafnium, tetra-n-heptylhafnium, tetraisoheptylhafnium, tetra-n-octylhafnium, tetra-n-nonylhafnium, tetra-isononylhafnium, tetra-n-decylhafnium and tetra-isodecylhafnium.

[0206] In some embodiments, the organometallic compound is present in the AIGS membrane composition at a concentration of at least 0.005 wt% (50 ppm). In some embodiments, the organometallic compound is present in the AIGS membrane composition at a concentration of about 0.03 to about 3 wt%. In some embodiments, the organometallic compound is present in the membrane composition at a concentration 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%. Organometallic hydrolysis compounds

[0207] Organometallic hydrolysis products can have the formula RxM(OH)y, where R is a straight-chain, branched-chain, or cycloalkyl group, typically containing 1 to 10 carbon atoms, and x + y equals the valence of the metal. Organometallic hydrolysis products include trimethyl zirconium monohydric hydroxide, triethyl zirconium monohydric hydroxide, tri-n-propyl zirconium monohydric hydroxide, triisopropyl zirconium monohydric hydroxide, tri-n-butyl zirconium monohydric hydroxide, tri-n-pentyl zirconium monohydric hydroxide, triisopentyl zirconium monohydric hydroxide, tri-n-hexyl zirconium monohydric hydroxide, tri-n-heptyl zirconium monohydric hydroxide, triisoheptyl zirconium monohydric hydroxide, tri-n-octyl zirconium monohydric hydroxide, tri-n-nonyl zirconium monohydric hydroxide, tri-isononyl zirconium monohydric hydroxide, tri-n-decyl zirconium monohydric hydroxide, tri-isodecyl zirconium monohydric hydroxide, trimethyl titanium monohydric hydroxide, triethyl titanium monohydric hydroxide, tri-n-propyl titanium monohydric hydroxide, triisopropyl zirconium monohydric hydroxide, trimethyl titanium monohydric hydroxide, triethyl titanium monohydric hydroxide, tri-n-propyl titanium monohydric hydroxide, tri-isopropyl zirconium monohydric hydroxide, trimethyl titanium monohydric hydroxide, triethyl titanium monohydric hydroxide, tri-n-propyl titanium monohydric hydroxide, tri-ethyl titanium monohydric hydroxide, tri-n-propyl titanium monohydric hydroxide, tri-ethyl titanium monohydric hydroxide, tri-n-propyl titanium monohydric hydroxide, tri-ethyl titanium monohydric hydroxide, tri-n-propane titanium monohydric hydroxide, tri-ethyl titanium monohydric hydroxide, tri-propane titanium monohydric hydroxide, tri-propane titanium monohydric hydroxide, tri-ethyl titanium monohydric hydroxide, tri-propane titanium monohydric hydroxide, tri-propane titanium monohydric hydroxide, tri-ethyl Titanium hydroxide, tri-n-butyl titanium hydroxide, triisobutyl titanium hydroxide, tri-n-pentyl titanium hydroxide, triisopentyl titanium hydroxide, tri-n-hexyl titanium hydroxide, triisohexyl titanium hydroxide, tri-n-heptyl titanium hydroxide, triisoheptyl titanium hydroxide, tri-n-octyl titanium hydroxide, tri-isooctyl titanium hydroxide, tri-n-nonyl titanium hydroxide, tri-isononyl titanium hydroxide, tri-n-decyl titanium hydroxide, tri-isodecyl titanium hydroxide, trimethyl hafnium hydroxide, triethyl hafnium hydroxide, tri-n-propyl hafnium hydroxide, triisopropyl hafnium hydroxide, tri-n-butyl hafnium hydroxide, triisobutyl hafnium hydroxide, tri-n-pentyl hafnium hydroxide, triisopentyl hafnium hydroxide Hafnium hydroxide, tri-n-hexyl hafnium hydroxide, tri-isohexyl hafnium hydroxide, tri-n-heptyl hafnium hydroxide, tri-isoheptyl hafnium hydroxide, tri-n-octyl hafnium hydroxide, tri-isooctyl hafnium hydroxide, tri-n-nonyl hafnium hydroxide, tri-isononyl hafnium hydroxide, tri-n-decyl hafnium hydroxide, tri-isodecyl hafnium hydroxide, dimethyl zirconium dihydrogen hydride, diethyl zirconium dihydrogen hydride, di-n-propyl zirconium dihydrogen hydride, diisopropyl zirconium dihydrogen hydride, di-n-butyl zirconium dihydrogen hydride, diisobutyl zirconium dihydrogen hydride, di-n-pentyl zirconium dihydrogen hydride, diisopentyl zirconium dihydrogen hydride, diisohexyl zirconium dihydrogen hydride, di-n-heptyl zirconium dihydrogen hydride, diisoheptyl zirconium dihydrogen hydride 1. Di-n-octyl zirconium hydroxide, 2-isooctyl zirconium hydroxide, 2-n-nonyl zirconium hydroxide, 2-isononyl zirconium hydroxide, 2-n-decyl zirconium hydroxide, 2-isodecyl zirconium hydroxide, dimethyl titanium hydroxide, diethyl titanium hydroxide, 2-n-propyl titanium hydroxide, diisopropyl titanium hydroxide, 2-n-butyl titanium hydroxide, diisobutyl titanium hydroxide, 2-n-pentyl titanium hydroxide, diisopentyl titanium hydroxide, 2-n-hexyl titanium hydroxide, diisohexyl titanium hydroxide, 2-n-heptyl titanium hydroxide, diisoheptyl titanium hydroxide, 2-n-octyl titanium hydroxide, 2-isooctyl titanium hydroxide, 2-n-nonyl titanium hydroxide, 2-isononyl titanium hydroxideDi-n-decyl titanium dioxide, di-isodecyl titanium dioxide, dimethyl hafnium dioxide, diethyl hafnium dioxide, di-n-propyl hafnium dioxide, diisopropyl hafnium dioxide, di-n-butyl hafnium dioxide, diisobutyl hafnium dioxide, di-n-pentyl hafnium dioxide, diisopentyl hafnium dioxide, di-n-hexyl hafnium dioxide, diisohexyl hafnium dioxide, di-n-heptyl hafnium dioxide, diisoheptyl hafnium dioxide, di-n-octyl hafnium dioxide, di-isooctyl hafnium dioxide, di-n-nonyl hafnium dioxide, di-isononyl hafnium dioxide, di-n-decyl dihydrogen phosphate Hafnium oxide, di-isodecyl hafnium dihydrogen hydride, monomethyl zirconium tetrahydrogen hydride, monoethyl zirconium tetrahydrogen hydride, mono-n-propyl zirconium trihydrogen hydride, mono-isopropyl zirconium trihydrogen hydride, mono-n-butyl zirconium trihydrogen hydride, mono-isobutyl zirconium trihydrogen hydride, mono-n-pentyl zirconium trihydrogen hydride, mono-isopentyl zirconium trihydrogen hydride, mono-n-hexyl zirconium trihydrogen hydride, mono-isohexyl zirconium trihydrogen hydride, mono-n-heptyl zirconium trihydrogen hydride, mono-n-octyl zirconium trihydrogen hydride, mono-n-nonyl zirconium trihydrogen hydride, mono-isononyl zirconium trihydrogen hydride, mono-n-decyl zirconium trihydrogen hydride, mono-isodecyl zirconium trihydrogen hydride Zirconium trioxide, monomethyl titanium trioxide, mono-n-propyl titanium trioxide, monoisopropyl titanium trioxide, mono-n-butyl titanium trioxide, monoisobutyl titanium trioxide, mono-n-pentyl titanium trioxide, monoisopentyl titanium trioxide, mono-n-hexyl titanium trioxide, monoisohexyl titanium trioxide, mono-n-heptyl titanium trioxide, monoisoheptyl titanium trioxide, mono-n-octyl titanium trioxide, mono-isooctyl titanium trioxide, mono-n-nonyl titanium trioxide, mono-isononyl titanium trioxide, mono-n-decyl titanium trioxide, mono-isodecyl titanium trioxide, monomethyl hafnium trioxide, mono... Ethyl hafnium trihydride, mono-n-propyl hafnium trihydride, mono-isopropyl hafnium trihydride, mono-n-butyl hafnium trihydride, mono-isobutyl hafnium trihydride, mono-n-pentyl hafnium trihydride, mono-isopentyl hafnium trihydride, mono-n-hexyl hafnium trihydride, mono-isohexyl hafnium trihydride, mono-n-heptyl hafnium trihydride, mono-n-octyl hafnium trihydride, mono-isooctyl hafnium trihydride, mono-n-nonyl hafnium trihydride, mono-isononyl hafnium trihydride, mono-n-decyl hafnium trihydride, mono-isodecyl hafnium trihydride, zirconium tetrahydride, titanium tetrahydride, and hafnium tetrahydride.

[0208] In some embodiments, the organometallic hydrolysate is present in the AIGS membrane composition at a concentration of at least 0.005 wt% (50 ppm). In some embodiments, the organometallic hydrolysate is present in the AIGS membrane composition at a concentration of about 0.03 to about 3 wt%. In some embodiments, the organometallic hydrolysate is present in the membrane composition at a concentration 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%. Methods for manufacturing hydrolyzed compounds

[0209] The preparation of the hydrolyzed compound can be carried out by contacting the compound with moisture, an acidic solution, or an alkaline solution. In one embodiment, 10 µl of an aqueous solution of 1 N NaOH is added to 4 ml of ethanol containing 1 g of zirconium propoxide. After stirring the reaction mixture at room temperature for 30 min, 10 µl of an aqueous solution of 1 N HCl is added to the neutralization reaction mixture. The resulting viscous liquid is used as the hydrolysis product after removing volatiles by vacuum. Rotary coating

[0210] In some embodiments, spin coating is used to deposit nanostructure compositions onto a substrate. In spin coating, a small amount of material is typically deposited at the center of the substrate, which is supported by a mechanism called a spinner and held in place by vacuum. High-speed rotation is applied to the substrate via the spinner, generating a centripetal force that causes the material to diffuse from the center to the edges of the substrate. Although most of the material will spin dry, a certain amount remains on the substrate, forming a thin film of material on the surface as rotation continues. The final film thickness is determined by the properties of the deposited material and the substrate, in addition to parameters selected for the spin coating method, 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 10–60 seconds. In some embodiments, films are deposited at very low speeds, such as 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. Fog deposition

[0211] In some embodiments, mist deposition is used to deposit nanostructure compositions onto a substrate. Mist deposition occurs at room temperature and atmospheric pressure and allows for precise control of film thickness by varying process conditions. During mist deposition, the liquid source material is atomized into an extremely fine mist and carried into the deposition chamber by nitrogen gas. The mist is then drawn onto the wafer surface by a high voltage potential between an electric field grid and a wafer holder. As 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 solvent and the material to be deposited. It is carried to the atomizer by pressurized nitrogen gas. Price, SC et al., "Formation of Ultra-Thin Quantum Dot Films by Mist Deposition", ESC Transactions 11:89-94 (2007). Spray coating

[0212] In some embodiments, a nanostructure composition is deposited onto a substrate using spray coating. Typical equipment for spray coating includes a nozzle, an atomizer, a precursor solution, and a carrier gas. In the spray deposition process, the precursor solution is atomized into micro-sized droplets by means of a carrier gas or by atomization (e.g., ultrasonic, air impingement, or electrostatic). Droplets ejected from the atomizer pass over the substrate surface, through the nozzle, and are accelerated by a carrier gas that is controlled and regulated as needed. The relative movement between the nozzle and the substrate is designed to completely cover the substrate.

[0213] In some embodiments, the application of the nanostructure composition further comprises a solvent. In some embodiments, the solvent for the application of the nanostructure composition is water, an organic solvent, an inorganic solvent, a halogenated organic solvent, or a mixture thereof. Illustrative solvents include, but are not limited to, water, D₂O, acetone, ethanol, dimethyl ether, ethyl acetate, methyl ethyl ketone, isopropanol, anisole, γ-butyrolactone, dimethylformamide, N-methylpyrrolidone, dimethylacetamide, hexamethylphosphatamide, 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. Inkjet printing

[0214] Solvents suitable for inkjet printing nanostructures are known to those skilled in the art. In some embodiments, the organic solvent is a substituted aromatic or heteroaromatic solvent as described in U.S. Patent Application Publication No. 2018 / 0230321, which is incorporated herein by reference in its entirety.

[0215] In some embodiments, the organic solvent used in nanostructure compositions as inkjet printing formulations is defined by its boiling point, viscosity, and surface tension. The properties of organic solvents suitable for inkjet printing formulations are shown in Table 1. Table 1: Characteristics of Organic Solvents Used in Inkjet Printing Formulations solvent Boiling point (°C) Viscosity (mPa·s) Surface tension (dyne / cm) 1-Methylnaphthalene 240 3.3 38 1-Methoxynaphthalene 270 7.2 43 3-Phenoxytoluene 271 4.8 37 Dibenzyl ether 298 8.7 39 benzyl benzoate 324 10.0 44 Butyl benzoate 249 2.7 34 Hexyl benzoate 272 — — Octylbenzene 265 2.6 31 Cyclohexylbenzene 240 2.0 34 hexadecane 287 3.4 28 4-Methyl anisole 179 — 29

[0216] In some embodiments, the organic solvent has a boiling point between about 150°C and about 350°C at 1 atm. In some embodiments, the organic solvent has a boiling point between about 150°C and about 350°C, between about 150°C and about 300°C, between about 150°C and about 250°C, between about 150°C and about 200°C, between about 200°C and about 350°C, between about 200°C and about 300°C, between about 200°C and about 250°C, between about 250°C and about 350°C, between about 250°C and about 300°C, or between about 300°C and about 350°C at 1 atm.

[0217] In some embodiments, the organic solvent has a viscosity between about 1 mPa·s and about 15 mPa·s. In some embodiments, the organic solvent has a range 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, approximately 2 mPa·s to approximately 4 mPa·s, approximately 4 mPa·s to approximately 15 mPa·s, approximately 4 mPa·s to approximately 10 mPa·s, and approximately 4 mPa·s to approximately 8 mPa·s. Viscosities between approximately 4 mPa·s and approximately 6 mPa·s, between approximately 6 mPa·s and approximately 15 mPa·s, between approximately 6 mPa·s and approximately 10 mPa·s, between approximately 6 mPa·s and approximately 8 mPa·s, between approximately 8 mPa·s and approximately 15 mPa·s, between approximately 8 mPa·s and approximately 10 mPa·s, or between approximately 10 mPa·s and approximately 15 mPa·s.

[0218] In some embodiments, the organic solvent has a surface tension between about 20 dyne / cm and about 50 dyne / cm. In some embodiments, the organic solvent has a viscosity between about 20 dyne / cm and about 50 dyne / cm, between about 20 dyne / cm and about 40 dyne / cm, between about 20 dyne / cm and about 35 dyne / cm, between about 20 dyne / cm and about 30 dyne / cm, between about 20 dyne / cm and about 25 dyne / cm, between about 25 dyne / cm and about 50 dyne / cm, between about 25 dyne / cm and about 40 dyne / cm, between about 25 dyne / cm and about 35 dyne / cm, between about 25 dyne / cm and about 30 dyne / cm, between about 30 dyne / cm and about 50 dyne / cm, between about 30 dyne / cm and about 40 dyne / cm, between about 30 dyne / cm and about 35 dyne / cm, between about 35 dyne / cm and about 50 dyne / cm. Surface tension between dyne / cm, between approximately 35 dyne / cm and approximately 40 dyne / cm, or between approximately 40 dyne / cm and approximately 50 dyne / cm.

[0219] In some embodiments, the organic solvent used in the nanostructure composition is an alkylnaphthalene, an alkoxynaphthalene, an alkylbenzene, an aryl group, an alkyl-substituted benzene, a cycloalkylbenzene, a C9-C20 alkane, a diaryl ether, an alkyl benzoate, an aryl benzoate, or an alkoxy-substituted benzene.

[0220] In some embodiments, the organic solvent used in the nanostructure composition is 1-tetrahydronaphthone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthyl, n-octylbenzene, n-nonylbenzene, 4-methylanisole, n-decylbenzene, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthyl, cyclohexylbenzene, chloronaphthyl, 1,4-dimethylnaphthyl, 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-methylnaphthyl, 1,2,4-trichlorobenzene, diphenyl ether, diphenylmethane, 4-isopropylbiphenyl, benzyl benzoate, 1,2-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthyl, dibenzyl ether, or a combination thereof. In some embodiments, the organic solvent used in the nanostructure composition is 1-methylnaphthalene, n-octylbenzene, 1-methoxynaphthalene, 3-phenoxytoluene, cyclohexylbenzene, 4-methylanisole, n-decylbenzene, or a combination thereof.

[0221] In some embodiments, the organic solvent is an anhydrous organic solvent. In some embodiments, the organic solvent is a substantially anhydrous organic solvent.

[0222] In some embodiments, the organic solvent is a non-volatile monomer or a combination of monomers selected from the list above.

[0223] In some embodiments, the weight percentage of the organic solvent in the nanostructure composition is between about 70% and about 99%. In some embodiments, the weight percentage of the organic solvent in the nanostructure composition is between about 70% and about 99%, between about 70% and about 98%, between about 70% and about 95%, between about 70% and about 90%, between about 70% and about 85%, between about 70% and about 80%, between about 70% and about 75%, between about 75% and about 99%, between about 75% and about 98%, between about 75% and about 95%, between about 75% and about 90%, between about 75% and about 85%, between about 75% and about 80%. Between approximately 80% and approximately 99%, between approximately 80% and approximately 98%, between approximately 80% and approximately 95%, between approximately 80% and approximately 90%, between approximately 80% and approximately 85%, between approximately 85% and approximately 99%, between approximately 85% and approximately 98%, between approximately 85% and approximately 95%, between approximately 85% and approximately 90%, between approximately 90% and approximately 99%, between approximately 90% and approximately 98%, between approximately 90% and approximately 95%, between approximately 95% and approximately 99%, between approximately 95% and approximately 98%, or between approximately 98% and approximately 99%. In some embodiments, the weight percentage of the organic solvent in the nanostructure composition is between approximately 95% and approximately 99%. Film curing

[0224] In some embodiments, the composition is thermosetting to form a nanostructured layer. In some embodiments, the composition is UV-cured. In some embodiments, the nanostructured composition is directly coated onto a barrier layer of the nanostructured film, and an additional barrier layer is subsequently deposited onto the nanostructured layer to produce the nanostructured film. A support substrate may be used under the barrier film to enhance strength, stability, and coating uniformity and to prevent material inconsistencies, air bubble formation, and wrinkles or folds in the barrier layer material or other materials. Furthermore, one or more barrier layers are deposited over the nanostructured layer to seal the material between the top and bottom barrier layers. Suitablely, the barrier layer may be deposited as a laminate and, as appropriate, sealed or further processed, subsequently incorporating the nanostructured film into a specific lighting device. As will be understood by those skilled in the art, the nanostructured composition deposition process may include additional or different components. Such embodiments will allow for in-process tuning of nanostructure emission characteristics, such as brightness and color (e.g., to adjust the white point of the quantum dot film), as well as nanostructured film thickness and other characteristics. Furthermore, these embodiments allow for periodic testing of the nanostructure membrane characteristics during fabrication and any necessary adjustments to achieve precise nanostructure membrane characteristics. Such testing and adjustments can also be performed without altering the mechanical configuration of the processing line, as computer programs can be used to electronically change the corresponding amounts of the mixture used to form the nanostructure membrane.

[0225] It has been found that when the film is treated without exposing the AIGS nanocrystals to blue or UV light, a nanostructure film with high PCE can be obtained, followed by providing an oxygen-free environment for the nanostructure. This oxygen-free environment can be provided by: (a) Encapsulation with an oxygen barrier capsule prior to heat treatment and / or exposure to blue light for PCE measurement; (b) The use of oxygen-reactive materials as a component in heat treatment or light exposure; and / or (c) By temporarily blocking oxygen using a sacrificial barrier layer.

[0226] In some embodiments, improvements to the PCE can be achieved by any method that can form an oxygen barrier on the AIGS layer. In mass production of devices containing such AIGS-CC layers, encapsulation can be performed using a vapor deposition process. In this case, a typical process flow includes inkjet printing of the AIGS layer, followed by UV curing, baking at 180°C to remove volatiles, deposition of an organic planarization layer, and then deposition of an inorganic barrier layer. Techniques for depositing the inorganic layer can include atomic layer deposition (ALD), molecular layer deposition (MLD), chemical vapor deposition (CVD) (with or without plasma enhancement), pulsed vapor deposition (PVD), sputtering, or metal evaporation. Other potential encapsulation methods include solution processing or printing of organic layers, UV or thermally curable adhesives, lamination using barrier films, etc.

[0227] In some embodiments, the membrane is encapsulated in an inert atmosphere. In some embodiments, the membrane is encapsulated in a nitrogen or argon atmosphere.

[0228] Oxygen-reactive materials include any material that is more reactive to oxygen than the AIGS nanostructure. Examples of oxygen-reactive materials include, but are not limited to, phosphites, organometallic precursors, titanium nitride, and tantalum nitride. In some embodiments, the phosphite may be any of the C1-20 trialkylphosphines. In one embodiment, the phosphite is trioctylphosphine. In some embodiments, the phosphite may be a trialkylphosphite, an alkylarylphosphite, or a triarylphosphite. In some embodiments, the organometallic precursor may be trialkylaluminum, trialkylgallium, trialkylindium, dialkylzinc, etc.

[0229] Examples of sacrificial barrier layers include polymer layers that are soluble in and washable in solvents. 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 organic solvents, such as alcohols (e.g., ethanol, methanol), halogenated carbons (e.g., methyl chloride and vinyl chloride), aromatic hydrocarbons (e.g., toluene, xylene), aliphatic hydrocarbons (e.g., hexane, octane, octadecene), tetrahydrofuran, C4-20 ethers (such as diethyl ether), and C2-20 esters (such as ethyl acetate). Characteristics and Examples of Nanostructured Membranes

[0230] In some embodiments, the nanostructure film of the present invention is used to form a display device. As used herein, a display device refers to any system having a light-emitting display. Such devices include, but are not limited to, devices encompassing: liquid crystal displays (LCDs), televisions, computers, mobile phones, smartphones, personal digital assistants (PDAs), gaming devices, e-readers, digital cameras, augmented reality / virtual reality (AR / VR) glass, optical projection systems, head-up displays, and the like.

[0231] In some embodiments, the nanostructure film is part of the nanostructure color conversion layer.

[0232] In some embodiments, the display device includes a nanostructure color converter. In some embodiments, the display device includes a rear plane; a display panel disposed on the rear plane; and a nanostructure layer. In some embodiments, the nanostructure layer is disposed on the display panel. In some embodiments, the nanostructure layer includes a patterned nanostructure layer.

[0233] In some embodiments, the back panel includes a blue LED, LCD, OLED, or micro LED.

[0234] In some embodiments, the nanostructure layer is disposed on a light source element. In some embodiments, the nanostructure layer comprises 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 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 because they allow for rapid drying. Volatile solvents include ethanol, methanol, 1-propanol, 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and tetrahydrofuran. Alternatively, "solvent-free" inks in which the AIGS nanostructures are dispersed in ink monomers can be used for inkjet printing.

[0235] In some embodiments, the nanostructure layer has a thickness between about 1 μm and about 25 μm. In some embodiments, the nanostructure layer has a thickness between about 5 μm and about 25 μm. In some embodiments, the nanostructure layer has a thickness between about 10 μm and about 12 μm.

[0236] In some embodiments, the nanostructured display device exhibits a PCE of at least 32%. In some embodiments, the nanostructured molded article exhibits a PCE of 32-40%. In some embodiments, the nanostructured molded article exhibits a 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%.

[0237] In some embodiments, the optical film comprising the nanostructure layer is substantially cadmium-free. As used herein, the term "substantially cadmium-free" implies that the nanostructure composition contains less than 100 ppm by weight of cadmium. RoHS compliance requires that the cadmium content in the original homogeneous precursor material not exceed 0.01% by weight (100 ppm). The cadmium concentration can be measured by inductively coupled plasma mass spectrometry (ICP-MS) and is at the parts-per-billion (ppb) level. In some embodiments, the "substantially cadmium-free" optical film contains 10 to 90 ppm of cadmium. In other embodiments, the substantially cadmium-free optical film contains less than about 50 ppm, less than about 20 ppm, less than about 10 ppm, or less than about 1 ppm of cadmium. Nanostructured molded products

[0238] In some embodiments, the present invention provides a nanostructured molding article comprising: (a) First barrier layer; (b) the second barrier layer; and (c) A nanostructure layer between the first barrier layer and the second barrier layer, wherein the nanostructure layer comprises a group of nanostructures containing 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; and at least one organic resin.

[0239] In some embodiments, the nanostructure has a PWL between 480 and 545 nm.

[0240] In some embodiments, at least 80% of the emissions are edge-fired. In other embodiments, at least 90% of the emissions are edge-fired. In other embodiments, at least 95% of the emissions are edge-fired. In some embodiments, 92-98% of the emissions are edge-fired. In some embodiments, 93-96% of the emissions are edge-fired. 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 a 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%. barrier layer

[0241] In some embodiments, the nanostructured molded article includes one or more barrier layers disposed on one or both sides of one or both sides of the nanostructured layer. Suitable barrier layers protect the nanostructured layer and the nanostructured molded article from environmental conditions such as high temperatures, oxygen, and humidity. Suitable barrier materials include non-yellowing transparent optical materials that are hydrophobic, chemically and mechanically compatible with the nanostructured molded article, exhibit optical and chemical stability, and are heat-resistant. In some embodiments, one or more barrier layers are refractively matched to the nanostructured molded article. In some embodiments, the substrate materials of the nanostructured molded article and one or more adjacent barrier layers are refractively matched to have similar refractive indices, such that most of the light transmitted through the barrier layers toward the nanostructured molded article is transmitted from the barrier layers to the nanostructured layer. This refractive index matching reduces optical losses at the interface between the barrier and the substrate material.

[0242] The barrier layer is suitably a solid material and may be a cured liquid, gel, or polymer. The barrier layer may comprise flexible or non-flexible materials, depending on the specific application. 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 will be compatible with lamination processing techniques, whereby a nanostructure layer is disposed on at least a first barrier layer, and at least a second barrier layer is disposed on a nanostructure layer on a side opposite to the nanostructure layer to form a nanostructure molded article according to an embodiment of the invention. Suitable barrier materials include any suitable barrier materials 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 oxide, titanium oxide, or aluminum oxide (e.g., SiO₂, Si₂O₃, TiO₂, or Al₂O₃); and suitable combinations thereof. In some embodiments, each barrier layer of the nanostructured molded article comprises at least two layers containing different materials or compositions, such that the multilayer barrier eliminates or reduces pore defects in the barrier layers, thereby providing an effective barrier for oxygen and moisture to penetrate into the nanostructured layer. The nanostructured layer may include any suitable material or combination of materials and any suitable number of barrier layers on any one or both sides of the nanostructured layer. The materials, thickness, and number of barrier layers will be determined based on the specific application and will be appropriately selected to maximize the barrier protection and brightness of the nanostructured layer while minimizing the thickness of the nanostructured molded article. In some embodiments, each barrier layer comprises a laminate, in some embodiments a double-laminated film, wherein the thickness of each barrier layer is sufficient to eliminate wrinkles during roll-to-roll or lamination manufacturing processes. In embodiments where the nanostructure contains heavy metals or other toxic materials, the number or thickness of the barriers may be further determined by statutory toxicity guidelines, which may require more or thicker barrier layers. Additional considerations for the barriers include cost, availability, and mechanical strength.

[0243] In some embodiments, adjacent to each side of the nanostructure layer, the nanostructure film comprises two or more barrier layers, such as two or three layers or two barrier layers on each side of the nanostructure layer. In some embodiments, each barrier layer comprises a thin glass sheet, such as a glass sheet having a thickness of about 100 µm, 100 µm or less, or 50 µm or less.

[0244] The barrier layers of the nanostructured film of the present invention can have any suitable thickness, 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), as will be understood by those skilled in the art. In some embodiments, the barrier layers can 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 some embodiments, the barrier layer comprises an oxide coating, which may comprise materials such as silicon oxide, titanium oxide, and aluminum oxide (e.g., SiO2, Si2O3, TiO2, or Al2O3). The oxide coating can have a thickness of about 10 µm or less, 5 µm or less, 1 µm or less, or 100 nm or less. In some embodiments, the barrier comprises a thinner oxide coating, having a thickness of about 100 nm or less, 10 nm or less, 5 nm or less, or 3 nm or less. The top and / or bottom barrier may consist of a thin oxide coating or may include a thin oxide coating and one or more additional material layers. Display devices with nanostructured color conversion layers

[0245] In some embodiments, the present invention provides a display device comprising: (a) A display panel that emits a first light; (b) A backlight unit configured to provide first light to the display panel; and (c) A color filter comprising at least one pixel region containing a color conversion layer.

[0246] In some embodiments, a color filter includes 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 can be emitted via 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.

[0247] In some embodiments, each pixel region includes a color conversion layer. In some embodiments, the color conversion layer includes a nanostructure configured as described herein to convert incident light into light of a first color. In some embodiments, the color conversion layer includes a nanostructure configured as described herein to convert incident light into blue light.

[0248] 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 nanostructures described herein. In some embodiments, the display device includes two color conversion layers containing the nanostructures described herein. In some embodiments, the display device includes three color conversion layers containing the nanostructures described herein. In some embodiments, the display device includes four color conversion layers containing the nanostructures described herein. In some embodiments, the display device includes at least one red conversion layer, at least one green conversion layer, and at least one blue conversion layer.

[0249] In some embodiments, the color conversion layer has a thickness between about 3 μm and about 10 μm, between about 3 μm and about 8 μm, between about 3 μm and about 6 μm, between about 6 μm and about 10 μm, between about 6 μm and about 8 μm, or between about 8 μm and about 10 μm. In some embodiments, the color conversion layer has a thickness between about 3 μm and about 10 μm.

[0250] The nanostructured color conversion layer can be deposited by any suitable method known in this art, including but not limited to brushing, spraying, solvent spraying, wet coating, adhesive coating, spin coating, tape coating, roller coating, flow coating, inkjet printing, photoresist patterning, drop casting, doctor blade coating, fogging deposition, or combinations 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. Compositions containing AIGS nanostructures and ligands

[0251] In some embodiments, the AIGS nanostructure composition further comprises one or more ligands. Ligands include amino ligands, polyamine ligands, mercapto ligands, phosphine ligands, silane ligands, and polymeric or oligomeric chains, such as polyethylene glycol having amine and silyl groups.

[0252] In some embodiments, the amino ligand has formula I: in: x is between 1 and 100; y is between 0 and 100; and R2 is a C1-20 alkyl group.

[0253] In some embodiments, the polyamine ligand is a polyamine alkane, a polyamine-cycloalkane, a polyamine heterocyclic compound, a polyamine-functionalized polysiloxane, or a polyamine-substituted ethylene glycol. In some embodiments, the polyamine ligand is a C2-20 alkane or a C2-20 cycloalkane that has been substituted with two or three amine groups and, where appropriate, contains one or two amine-substituted carbon groups. In some embodiments, the polyamine 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'-diethylethylenediamine, 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, Tetraethylpentamine, Pentylethylhexamine, 2-(2-amino-ethylamino)ethanol, N,N-bis(hydroxyethyl)ethylenediamine, N-(hydroxyethyl)diethylenetriamine, N-(hydroxyethyl)triethylenetetramine, Piperamide, 1-(2-aminoethyl)piperamide, 4-(2-aminoethyl)phospholine, Polyethylimide, 1,3-Diaminopropane, 1,4-Butanediamine, 1,3-Diaminopentane, 1,5-Diaminopentane, 2,2 -Dimethyl-1,3-propanediamine, hexamethylenediamine, 2-methyl-1,5-diaminopropane, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,4-trimethyl-1,6-hexamethylenediamine, 2,4,4-trimethyl-1,6-hexamethylenediamine, 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'-diethyl-1,3-propanediamine, N,N'-di... Isopropyl-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'-diamine-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-propanediamine, spermine, 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-tetanediamine, 1,3-diamine-hydroxy-propane, 4,4-methylenedipiperidine, 4-(aminomethyl)piperidine, 3-(4-aminobutyl)piperidine, or polyallylamine. In some embodiments, the polyamine ligand is 1,3-cyclohexanebis(methylamine), 2,2-dimethyl-1,3-propanediamine, or tris(2-aminoethyl)amine.

[0254] In some embodiments, the polyamine ligand is a polyamine heterocyclic compound. In some embodiments, the polyamine heterocyclic compound is 2,4-diamine-6-phenyl-1,3,5-tris(II), 6-methyl-1,3,5-tris(II)-2,4-diamine, 2,4-diamine-6-diethylamino-1,3,5-tris(II), 2-N,4-N,6-N-tripropyl-1,3,5-tris(II)-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-di(II)-diaminopyrimidine, 2,4 ... Amines, 1H-imidazol-2,5-diamine, 4-phenyl-N(1)-[(E)-phenylmethylene]-1H-imidazol-1,2-diamine, 2-phenyl-1H-imidazol-4,5-diamine, 1H-imidazol-2,4,5-triamine, 1H-pyrrole-2,5-diamine, 1,2,4,5-tetracycline-3,6-diamine, N,N'-dicyclohexyl-1,2,4,5-tetracycline-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.

[0255] In some embodiments, the polyamine ligand is a polyamine-functionalized polysiloxane. In some embodiments, the polyamine-functionalized polysiloxane is one of the following: .

[0256] In some embodiments, the polyamine ligand is a polyamine-substituted ethylene glycol. In some embodiments, the polyamine-substituted ethylene glycol is 2-[3-amino-4-[2-[2-amino-4-(2-hydroxyethyl)phenoxy]ethoxy]phenyl]ethanol, 1,5-diamine-3-oxapentane, 1,8-diamine-3,6-dioxooctane, bis[5-chloro-1H-indol-2-yl-carbonyl-aminoethyl]ethylene glycol, amino-PEG8-t-Boc-acetylhydrazine, or 2-(2-(2-ethoxyethoxy)ethoxy)ethylamine.

[0257] In some embodiments, the thiol ligand is (3-mercaptopropyl)triethoxysilane, 3,6-dioxa-1,8-octanedithiol; 6-mercapto-1-hexanol; thiosuccinic acid, thiododecanoic acid, thiohexanoic acid, thiopropionic acid, thioacetic acid, cysteine, methionine, and thiol-poly(ethylene glycol).

[0258] 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.

[0259] In some embodiments, the ligands include, but are not limited to, amino-polyepoxides (e.g., about mw 1000); (3-aminopropyl)trimethoxysilane; (3-mercaptopropyl)triethoxysilane; DL-α-lipoic acid; 3,6-dioxa-1,8-octanedithiol; 6-mercapto-1-hexanol; methoxypolyethylene glycolamine (about mw 500); poly(ethylene glycol) methyl ether thiol (about mw 800); diethyl phenylphosphite; N,N-diisopropylaminophosphite dibenzyl ester; N,N-diisopropylaminophosphite di-tributyl ester; tris(2-carboxyethyl)phosphine hydrochloride; poly(ethylene glycol) methyl ether thiol (about mw 2000); methoxypolyethylene glycolamine (about mw 750); acrylamide; and polyethyleneimine.

[0260] Specific combinations of ligands include amino-polyepoxide (approximately mw 1000) and methoxy polyethylene glycolamine (approximately mw 500); amino-polyepoxide (approximately mw 1000) and 6-mercapto-1-hexanol; amino-polyepoxide (approximately mw 1000) and (3-mercaptopropyl)triethoxysilane; and 6-mercapto-1-hexanol and methoxy polyethylene glycolamine (approximately mw 500); which provide excellent dispersibility and thermal stability. See Example 9.

[0261] Compared to films containing AIGS without polyamine ligands, and compared to films with only a single amine ligand, films containing both AIGS nanostructures and polyamine ligands exhibit higher film conversion efficiency (PCE), fewer wrinkles, and less film delamination. Therefore, compositions containing AIGS polyamine ligands are uniquely suitable for use in nanostructured color conversion layers. Scattering medium

[0262] AIGS films may further comprise a scattering medium. Examples of scattering media that may be used include, but are not limited to, metal or metal oxide particles, bubbles, and glass and polymer beads (solid or hollow). In some embodiments, the scattering medium has a spherical shape. In some embodiments, the scattering medium includes, but is not limited to, TiO2, SiO2, BaTiO3, BaSO4, and ZnO particles.

[0263] The following examples are illustrative and non-limiting examples of the products and methods described herein. Various suitable modifications and adaptations to conditions, formulations, and other parameters are commonly encountered in the art and will be readily apparent to those skilled in the art, given that the spirit and scope of this invention are readily apparent. Example Example 1: AIGS Core Synthesis

[0264] Sample ID 1 was prepared using the following typical AIGS core synthesis: 4 mL of oleylamine containing 0.06 M CH₃CO₂Ag, 1 mL of ethanol containing 0.2 M InCl₃, 1 mL of oleylamine containing 0.95 M sulfur, and 0.5 mL of dodecanethiol were injected 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 increased 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, centrifuged, and redispersed in toluene. Samples ID 2 and 3 were also prepared using this method. The optical properties of the AIGS core were measured and summarized in Table 1. The size and morphology of the AIGS core were characterized by transmission electron microscopy (TEM). Table 1 Sample ID QY (%) PWL (nm) FWHM (nm) Through ICP Ag / (Ag+In+Ga) Through ICP, In / (In+Ga) annotation 1 44 519.5 47 0.39 0.44 50 mL flask scale 2 30 514 50 0.37 0.41 Sample ID 1 10× magnification 3 40 518 52 0.38 0.45 Sample ID 1 10× magnification Example 2: AIGS Nanostructures in Ion Exchange Treatment

[0265] Sample ID 4 was prepared using the following typical ion exchange process: 2 mL of octadecene containing 0.3 M gallium oleate solution and 12 mL of oleylamine were introduced into a flask and degassed. The mixture was heated to 270 °C. 1 mL of oleylamine containing 0.95 M sulfur solution and 1 mL of a premixed solution containing the separated AIGS core (15 mg / mL) were injected. 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 ID 4-8 were also prepared using this method. The optical properties of the resulting AIGS nanostructures are summarized in Table 2. Ion exchange with gallium ions resulted in near-complete band-edge emission. An increase in average particle size was observed by TEM. Table 2 Sample ID PWL (nm) FWHM (nm) QY (%) OD 450 / mass (mL .mg -1.cm -1) 4 516 38 61 - 5 517 36 58 0.87 6 520 37 53 1.04 7 514 38 64 0.72 8 514 38 65 1.15 Example 3: Gallium halide and trioctylphosphine ion exchange treatment

[0266] A room-temperature ion exchange reaction with the AIGS nanostructure was achieved by adding trioctylphosphine (0.01–0.25 M) containing GaI₃ solution to the AIGS QD and maintaining it at room temperature for 20 hours. This treatment resulted in a significant enhancement of band-edge emission as summarized in Table 3, while substantially maintaining the peak wavelength (PWL).

[0267] Compositional changes before and after GaI3 addition were monitored using inductively coupled plasma atomic emission spectrometry (ICP-AES) and energy-dispersive X-ray spectroscopy (EDS), as summarized in Table 3. Composite images of In and Ga elemental distributions before and after GaI3 / TOP treatment show a radial distribution from In to Ga, thus indicating a gradient of greater gallium near the surface and less gallium in the nanostructure center resulting from ion exchange treatment. Table 3 ID PWL (nm) FWHM (nm) QY (%) Side weight Through ICP Ag / (Ag+In+Ga) Through ICP, In / (In+Ga) By means of EDS Ag / (Ag+In+Ga) By means of EDS In / (In+Ga) 9 542 38 11 <45% 0.41 0.11 0.45 0.16 10 543 37 twenty four >80% 0.38 0.09 0.44 0.14 Example 4: AIGS ion exchange treatment using an oxygen-free Ga source

[0268] Samples ID 14 and 15 were prepared using the following typical AIGS nanoparticle treatment 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 the addition of 40 mg of AIGS core and then 1.7 mL of oleylamine containing 0.95 M sulfur. After heating to 240 °C, the reaction was maintained for 2 hours and then cooled. The final product was transferred to a glove box, washed with toluene / ethanol, centrifuged, and dispersed in toluene. Samples ID 15 and 16 were also prepared using this method. Samples ID 11-13 were prepared using the method described in Example 2. The optical properties of the treated AIGS materials are shown in Table 4. Table 4 Sample ID PWL (nm) FWHM (nm) QY (%) BE% Gallium source 11 525 43 25 Undetermined Gallium(III) acetylated pyruvate 12 516 34 73 90 Gallium oleate 13 522 35 72 87 Gallium oleate 14 521 35 85 86 Gallium(III) chloride 15 521 35 80 89 Gallium(III) chloride 16 Undetermined Undetermined Undetermined Undetermined Gallium(III) chloride

[0269] As shown in Table 4, the quantum yield of treated AIGS nanostructures can be improved by using gallium(III) chloride instead of gallium(III) acetylacetonate or gallium oleate when using oleylamine as a solvent. The final material obtained by ion exchange with gallium(III) chloride produces similar size and similar band edges to the starting nanostructure for trap emission characteristics. Therefore, the increase in quantum yield (QY) is not simply attributed to an increase in the trap emission component. And unexpectedly, it was found that when gallium(III) iodide was used instead of gallium(III) chloride, the AIGS nanostructures appeared to dissolve in the reaction mixture and no ion exchange occurred.

[0270] High-resolution TEM by energy-dispersive X-ray spectroscopy (EDS) of sample 14 reveals that the nanostructure may contain a slight to lower In gradient from the center to the surface of the AIGS nanostructure. This indicates that the nanostructure was produced under these conditions by a method involving the exchange of Ga from the AIGS structure, with Ag present throughout the structure rather than through the growth of different GS layers. This can also be attributed to the improved quantum yield of the nanostructure with less strain. Example 5: AIGS core derived from thermally injected pre-formed Ag 2S nanostructures mixed with pre-formed In-Ga reagent

[0271] To fabricate Ag₂S nanostructures, 0.5 g AgI and 2 mL oleylamine were added to a 20 mL vial under a N₂ atmosphere and stirred at 58 °C until a clear solution was obtained. In a separate 20 mL vial, 5 mL DDT and 9 mL oleylamine containing 0.95 M sulfur were mixed. The DDT+S-OYA mixture was added to the AgI solution and stirred at 58 °C for 10 min. The obtained Ag₂S nanoparticles were used without washing.

[0272] To prepare the In-Ga reagent mixture, 1.2 g Ga (acetylacetonate)3, 0.35 g InCl3, 2.5 mL oleylamine, and 2.5 mL ODE were placed in a 100 mL flask. The mixture was heated to 210 °C and maintained for 10 min under a N2 atmosphere. An orange and viscous product was obtained.

[0273] To form AIGS nanoparticles, 1.75 g TOPO, 23 mL oleylamine, and 25 mL ODE were added to a 250 mL flask under N2. After degassing under vacuum, the solvent mixture was heated to 210 °C for 40 min. The Ag2S and In-Ga reagent mixture described above was mixed in a 40 mL vial at 58 °C and transferred to a syringe. The Ag-In-Ga mixture was then injected into the solvent mixture at 210 °C and maintained for 3 h. 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 toluene. The final product was precipitated by adding 150 mL of ethanol, centrifuged, and redispersed in toluene. The AIGS nanostructures were then ion-exchanged using the method described in Example 4. The optical properties of materials prepared by this method at a scale of up to 24 × those described above are shown in Table 5. Table 5 [Sample ID] [PWL (nm)] [FWHM (nm)] [BE%] [QY (%)] [OD, 450 , / ] [mass (mL, . mg -1. , cm , -1, ) ] 17 510 34 96 86 - 18 524 38 93 94 1.1 19 520 38 93 88 1.3 20 517 38 94 86 1.3 twenty one 518 38 94 89 1.4 twenty two 528 37 93 93 1.9 Example 7: Improved Photoluminescence Stability of AIGS Nanostructures by Repeated Gallium Ion Exchange 7.1 First Ion Exchange Process

[0274] Oleylamine (OYA, 2.5 L) was degassed under vacuum at 40 °C for 40 min. AIGS nanostructures (25.4 g in toluene) were added, followed by GaCl3 (127 g in trace amounts of toluene) and sulfur dissolved in OYA (0.95 M, 570 mL). The mixture was heated to 240 °C and held for 4 hours after 40 min. After cooling, the mixture was diluted with 1 volume of toluene. After centrifugation to remove some byproducts, the material was washed with 2 volumes of ethanol, collected by centrifugation, and redissolved in toluene. After a second wash, the nanostructures were dissolved in heptane for storage. 7.2 Second Ion Exchange Process

[0275] Oleylamine (OYA, 960 mL) was degassed under vacuum at 40 °C for 20 min. AIGS ion-exchange nanostructures, such as those from Example 7.1 (12 g in heptane), were added to OYA, followed by the addition of GaCl3 (22.5 g in a very small volume of toluene), and then sulfur was dissolved in OYA (0.95 M, 100 mL). The mixture was heated to 240 °C for 40 min and held for 3 h. After cooling, the mixture was diluted with 1 vol toluene, washed (precipitated with 1.6 vol ethanol, centrifuged), and redispersed in toluene or heptane as needed. When performing ligand exchange on the ink formulation, the QD was washed with another ethanol and redispersed in heptane. 7.3 Alternative Secondary Ion Exchange Process

[0276] The oleylamine (15 mL) was degassed under vacuum at 60 °C for 20 min. GaCl3 (360 mg in a very small volume of toluene) was added to OYA, followed by AIGS such as that from Example 7.1 (200 mg in heptane), and then sulfur dissolved in OYA (0.95 M, 1.6 mL). The mixture was heated to 240 °C for 40 min and held for 3 hours. After cooling, the mixture was washed as described in Example 7.1. 7.4 Alternative Secondary Ion Exchange Process

[0277] Perform this instance as described in Instance 7.3, but at a 3x scale. 7.5 Alternative Secondary Ion Exchange Process

[0278] Oleylamine (10 mL) and oleic acid (5 mL) were degassed under vacuum at 90 °C for 20 min. (Ga(NMe3)3)2 (206 mg) and GaCl3 (180 mg in a very small volume of toluene) were added, followed by the addition of AIGS such as that from Example 7.1 (200 mg in heptane). After heating to 130 °C, TMS 2S (0.65 mL containing 50% ODE solution) was added over 20 min, and the mixture was held for 2.5 h. After cooling, the mixture was washed as described in Example 7.1. 7.6 Results

[0279] AIGS nanostructures were subjected to an ion-exchange process, where In was exchanged for Ga. The higher temperature used for this process, compared to core growth (240 °C vs. 210 °C), resulted in maturation and therefore a larger average size than untreated nanostructures. The nanostructures lacked a well-differentiated shell structure, which was observed in cross-sectional TEM elemental mapping. The lack of a high bandgap shell is expected to limit the retention of photoluminescence during film treatment of these materials.

[0280] After the second ion exchange process, the average TEM size did not increase (Figs. 2A to 2C), but TEM elemental mapping confirmed the generation of a more unique gradient in the QD region rich in Ga (higher band gap).

[0281] The elemental composition of single and multiple ion exchange processes is shown in Table 6. Values ​​are averages from 10-20 samples from Examples 7.1 and 7.2. Table 6 [Sample Type] [PWL (nm)] [FWHM (nm)] [Ag / (Ag+In+Ga)] [In / (In+Ga)] [Single ion exchange treatment] 523 34.5 0.39 0.27 [Dual ion exchange treatment] 523 34.1 0.40 0.24

[0282] The characteristics of the ion-exchange AIGS nanostructure are shown in Table 7. The metal ratio is the mole ratio determined by ICP. [] Table 7 [Sample ID] [PWL] [,nm] [FWHM] [,nm] [BE] [,%] [QY] [,%] [Ag / (Ag+In+Ga)] [In / (In+Ga)] Example 7.1 524.2 34.8 90 83 0.41 0.27 Example 7.2 523.6 34.4 90 89 0.40 0.24 Example 7.3 525.1 34.4 90 87 0.42 0.23 Example 7.4 525.9 34.3 90 88 0.42 0.24 Example 7.5 524.4 33.5 90 62 0.28 0.12 Example 7.6 521.0 24.5 92 89 0.41 0.18

[0283] The PCE of the film retained after UV curing and baking at 180°C was significantly improved by a second ion exchange process, as shown in Table 8. This is believed to be due to the process of increasing the Ga concentration in the outer layer of the nanostructure, resulting in a gradient introduced into the higher band gap region through ion exchange. Table 8 [Sample ID] [Blue light absorption rate (%)] [UV] [The following green PCE %] [Green PCE % after baking] [Reserved QY %] Example 7.1 91.5 25.6 9.7 37.9 Example 7.2 91.9 25.8 16.3 63.3 Example 7.3 88.1 23.1 14.7 63.8 Example 7.4 88.5 23.7 14.9 62.8 Example 7.5 95.0 26.4 17.3 64.7 Example 7.6 91.0 31.4 19.7 62.8 Example 8 - Compositions containing AIGS nanostructures and polyamine ligands

[0284] abbreviation ● Polyetheramine - Polyetheramine M-1000 ● HDDA - 1-6-hexanediol diacrylate ● Dimethylamine - 1,3-cyclohexanedimethylamine ● PCE - Photon Conversion Efficiency

[0285] 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 solids. Polyetheramine and HDDA were added to solution 2 for the ligand exchange stage, heated at 80°C for 1 hour, precipitated in heptane, and redispersed in HDDA (solution 3). 83 mg of polyetheramine was added per 100 mg of QD inorganic solids. 0.42 g of HDDA was added per 100 mg of QD inorganic solids. Solution 3 and HDDA were added to an inkjet ink composition containing 10 wt% TiO2 and 90 wt% monomers. The inkjet formulation consists of 10 wt% QD inorganic matter, 4 wt% TiO2, and the remaining 86 wt% is a combination of ligands (bound and unbound), HDDA, monomers, photoinitiators, and other mixed organic matter remaining from the QD solution. This ink formulation is solution 4.

[0286] Add polyamine ligand dimethylamine (50 mg of dimethylamine per 100 mg of QD inorganic solid) to solution 4 and then cast the composition into a film. membrane casting

[0287] Solution 4 was spin-coated onto a 2" × 2" glass substrate. The film was cured using a UV LED curing lamp. The film's power conversion efficiency (PCE) (a measure of brightness) was then tested. The film was then baked on a hot plate set at 180°C for 30 minutes, slightly above the plate temperature. Alternatively, the film was baked on a hot plate set at 180°C for 10 minutes, in direct contact with the hot plate surface.

[0288] Next, the PCE of the film was tested. A 1" × 1" array of blue 448 nm LEDs provided the excitation source for the film. An integrating sphere was placed on top of the film and connected to a fluorometer. See Figures 3A and 3B. The collected spectra were analyzed to obtain the PCE.

[0289] PCE is the ratio of the number of forward-emitted green photons to the number of blue photons generated by the test platform. PCE, LRR, and film morphology are reported in Table 9. Surprisingly, compared to films without ligands, the presence of ligands 1,3-cyclohexanebis(methylamine), tris(2-aminoethyl)amine, and 2,2-dimethyl-1,3-propanediamine resulted in a high PCE retention rate after baking at 180°C, achieving high LRR, and eliminating wrinkles. Table 9 additive PCE after UV curing PCE after baking at 180℃ LRR Membrane morphology No additives 28.4% 14.1% 49.7% folds 1,3-Cyclohexanebis(methylamine) 21.0% 20.4% 96.8% No wrinkles (2-aminoethyl)amine 12.0% 12.1% 100.7% No wrinkles 2,2-Dimethyl-1,3-propanediamine 21.2% 21.1% 99.2% No wrinkles

[0290] Figure 1 illustrates the effect of diamine addition on membrane morphology. From left to right, the membranes in Figure 1 contain: no additive (wrinkled); 2,2-dimethyl-1,3-propanediamine (diamine, no wrinkles); cyclohexanemethylamine (monoamine, wrinkled); and tris(2-aminoethyl)amine (triamine, no wrinkles). From left to right, the first and third membranes, without diamine, exhibit numerous wrinkles. In contrast, the second and fourth membranes do not exhibit wrinkles. Surprisingly, the use of diamine ligands in AIGS membranes resulted in a significant reduction in membrane wrinkles. Example 9 - Testing Additional Ligands in AIGS Nanostructures

[0291] In this experiment, the enhanced QY, high compatibility, and good thermal stability of additional ligands for AIGS nanoparticles were tested. Furthermore, the protective effect of these ligands on the AIGS nanostructure against degradation and oxidation was evaluated. Combinations of ligands that can be formulated into AIGS ink compositions were also tested.

[0292] Ligand exchange with these ligands is carried out in organic solvents such as ethyl acetate, PGMEA, acetone, xylene, 1,2-dichlorobenzene (ODCB), butyl acetate, and diethylene glycol monoethyl ether (DGMEE).

[0293] AIGS nanostructures undergo ligand exchange with ligands containing polymeric or oligomeric chains (such as polyethylene glycol with amines and silyl groups) and soft bases (such as phosphino-, mercapto-, and combinations thereof) for co-passivation.

[0294] Figure 4 depicts the quantum yield values ​​of several individual ligands and AIGS nanostructures that have undergone the single ion exchange treatment described herein. In this figure, [NG]: Natural AIGS; [NG-NL1]: Amino-polyepoxide, approximately 1000 mw; [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]: Methoxylated polyethylene glycol amine 500; [NG-NL8]: Poly(ethylene glycol) methyl ether thiol, Mn 800; [NG-NL9]: Diethyl phenylphosphonite; [NG-NL10]: N,N-Diisopropylaminophosphite dibenzyl ester; [NG-NL11]: N,N-Diisopropylaminophosphite di-tertiary butyl ester; [NG-NL12]: Tris(2-carboxyethyl)phosphonic hydrochloride; [NG-NL13]: Poly(ethylene glycol) methyl ether thiol, Mn 2000; [NG-NL14]: Methoxylated polyethylene glycol amine 750; [NG-NL15]: Acrylamide; and [NG-NL16]: Polyethylene imine.

[0295] As shown in Figure 4, treatment of AIGS nanostructures with (3-mercaptopropyl)triethoxysilane (NL3), 3,6-dioxa-1,8-octanedithiol (NL5), and 6-mercapto-1-hexanol (NL6) yields high QY (73.7%, 72.9%, and 76.1%, respectively). Therefore, this invention provides an AIGS nanostructure composition comprising at least one thiol-substituted ligand that provides the modified QY. It is believed that the thiol-substituted ligand provides high QY by passivating the surface of the AIGS nanostructure and reducing defect emission. Amino-substituted ligands also improve QY.

[0296] In this single ligand test, compared to the natural AIGS nanostructure, the polyethylene glycol amine-substituted ligands (L1, L7, L8, and L13), thiol-substituted ligands (L3, L5, and L6), and silane ligand (L2) exhibited good QY. Furthermore, when dispersed in HDDA, ligands L1, L7, and L8 provided better compatibility with the monomer.

[0297] Figure 5 illustrates the QY% of various 2-ligand combinations that produce improved QY% (good combination) and reduced QY% (bad combination). Surface defects can be reduced by adding thiol ligands. The combination of L6 and L7 produces better stability than other combinations. However, for relatively hydrophilic ink compositions, the preferred ligands are relatively hydrophilic ligands such as methoxy polyethylene glycolamine and poly(ethylene glycol) methyl ether thiol. This thiol also improves QY by passivating surface defects.

[0298] The suitable temperature for ligand exchange is room temperature to 120°C. The total amount of ligands in the composition can be 60% to 150% of the mass of AIGS.

[0299] Table 10 shows the relative changes in QY, PWL, and FWHM before and after ligand exchange with multiple ligands. Table 10 shows that L6 and L7 are the most effective ligand combinations for ink formulations, especially when combined with acrylate monomers. Combinations L2 and L7, L2 and L6, L2 and L3, and L6 and L7 provide excellent dispersibility and thermal stability. See Figure 6. Table 10 QY (%) before LE QY (%) after LE PWL (nm) before LE PWL (nm) after LE FWHM (nm) before LE FWHM (nm) after LE QY change (%) PWL change (nm) FWHM variation (nm) L6,7 55.3 61.5 531.1 531.6 36.3 36.2 +11.2 -0.1 +0.3 L6,2 55.3 57.8 531.1 531.3 36.3 36.3 +4.5 -0.1 0.0 L3,7 55.0 56.6 531.3 531.1 36.2 36.1 +3.0 0.0 +0.1 L5,7 55.0 57.6 531.3 530.8 36.2 36.1 +4.7 +0.1 +0.3 L13,7 55.0 57.5 531.3 531.2 36.2 36.1 +4.6 0.0 +0.2 L2,8 55.0 57.1 531.3 531.9 36.2 36.4 +3.8 -0.1 -0.5 L3,8 55.0 63.8 531.3 530.8 36.2 36.2 +16.0 +0.1 -0.1 L5,8 55.0 63.3 531.3 531.8 36.2 36.6 +15.0 -0.1 -1.0 L2,15 55.3 59.0 531.1 532.1 36.3 36.6 +6.6 -0.2 -0.7 L3,15 55.3 55.5 531.1 532.4 36.3 37.5 +0.4 -0.3 -3.3 L2, 13 55.3 53.6 531.1 532.5 36.3 36.6 -3.1 -0.3 -0.7 L3,13 55.3 62.2 531.1 530.0 36.3 38.5 +12.4 +0.2 -5.6 L2,7 56.6 58.2 530.7 532.0 36.5 36.1 +2.8 -0.3 +0.9 L2,3 54.6 58.7 530.6 531.3 36.2 36.8 +7.5 -0.1 -1.7

[0300] Further studies have shown that ligand combinations provide good thermal stability when heated to 180°C in a glove box for 30 min. Ligand combinations L6 and L7, L2 and L6, and L2 and L3 provide better stability than the single ligand L1. See Figure 6.

[0301] The effect of different ligand ratios on QY was also investigated. The weight ratio of the ligands varied, while the total amount of ligands remained constant. The optimal QY was achieved at a 7:3 ratio of L6 to L7. See Figure 7. Compared to the natural AIGS nanostructure, all combinations with L6 and L7 except for the 9:1 ratio showed enhanced QY. Even though the mixtures exhibited high QY, they were difficult to purify without precipitation. Mixtures of L6 and L2, L3 and L7, and L5 and L7 were good ligand mixtures for AIGS nanostructures. These ligand combinations can be used with various monomers, such as tetrahydrofuran acrylate, tris(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, diethylene glycol ethyl ether aryl, isobornyl acrylate, hydroxypropyl acrylate, 2-(acryloyloxy)ethylhydrosuccinate, and 1,6-hexanediol diacrylate. Example 10 - Improved PCE in AIGS Membranes

[0302] In a glove box filled with N₂, AIGS QD coated with a suitable ligand is mixed into an ink containing one or more monomers, TiO₂ scattering particles, and a photoinitiator. A film is cast by spin-coating this ink, followed by UV curing. The film is then baked on a hot plate at 180°C for 30 minutes to remove any remaining volatile components. All these processes are performed in a glove box filled with N₂ under an inert atmosphere.

[0303] At this stage, the film can be measured in air with its sides facing upwards, placed under 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) to capture the film's emission spectrum. Measurements are repeated using a blank glass substrate (without QD). The blue light absorbance and photon conversion efficiency (PCE) of the QD film are measured using the following formula: Blue light absorption rate = Number of blue photons transmitted through the QD film / Number of incident blue photons PCE = Number of forward-emitted green photons / Number of incident blue photons

[0304] To investigate the effects of air and moisture during measurement, the baked QD film was sealed before being removed from the N2 glove box. This was accomplished by applying a few drops of UV-curable transparent adhesive to the QD layer, then placing a glass cover glass and curing the adhesive by UV irradiation. Measurements were then performed in air using the method described above, using the sealed QD film with glass and adhesive.

[0305] The results demonstrate that encapsulating the QD film in air before measurement is crucial for achieving high photon conversion efficiency (PCE). Table 11 shows the results from a group of films measured with and without encapsulation. For comparison, the PCE values ​​of a typical QDCC film containing InP QDs are also shown. When encapsulated and measured, the film containing the AIGS nanostructure exhibits a higher post-baking PCE value than InP at a much lower QD load. Another improvement in PCE was achieved by irradiating the film with a blue light source (approximately 6 mW / cm²) for 1 hour. Furthermore, the QDCC film prepared with AIGS QDs exhibits a much narrower emission (FWHM approximately 30 nm) compared to the film prepared with InP QDs (FWHM 36 nm). This is a result of the lower FWHM of AIGS QDs in solution (34 nm vs. 39 nm) achieved by using a combination of monoamine and polyamine ligands that enable good dispersibility in ink resins. Table 11 [QD] [type] QD in inks [load] [Pouch Sealed] [Post-sealing treatment] [10 µm] [Blue light absorption rate in the membrane]

[0180] ℃ [PCE after baking] [PWL] [FWHM] AIGS 12.5% Unsealed none >95% 28% 535 30 Glass Encapsulation none >95% 35% 535 30 Glass Encapsulation Exposure to blue light for 1 hour >95% 38% 535 30 InP 30% Unsealed none 85% 32% 540 36

[0306] Figure 9 illustrates the impact of encapsulation and blue light processing on a much wider sample range. Surprisingly, the PCE value achieved through encapsulation was significantly higher (greater than 32%) than that without encapsulation.

[0307] The median FWHM of the film baked at 180°C was 30.5 nm, which further narrowed to 30.1 nm after encapsulation. This narrowing may be a result of the film brightening after encapsulation.

[0308] Although the samples in this study were encapsulated using glass and adhesives, this improvement to PCE can be achieved by any method that can form an oxygen barrier on the QD layer. In mass production of devices containing such QDCC layers, it is possible to use a vapor deposition process for encapsulation. In this case, a typical process flow would include inkjet printing of the QD layer, followed by UV curing, baking at 180°C to remove volatiles, deposition of an organic planarization layer, and then deposition of an inorganic barrier layer. Techniques for depositing the inorganic layer can include atomic layer deposition (ALD), molecular layer deposition (MLD), chemical vapor deposition (CVD) (with or without plasma enhancement), pulsed vapor deposition (PVD), sputtering, or metal evaporation. Other potential encapsulation methods include solution processing or printing of organic layers, UV or thermally curable adhesives, lamination using barrier films, etc. Example 11 Modified AIGS membrane with metal alkoxide

[0309] For application in emerging advanced display technologies such as QD-OLED and QD microLED, films that maintain their optical properties under 24-hour yellow light and air storage conditions are required. It was found that films containing zirconium isopropoxide maintained at least 30% PCE under yellow light and air storage conditions, while films without zirconium isopropoxide showed a decrease in PCE from 35.8% to 14% (item 1 in Table 12).

[0310] The "light and air storage conditions" were determined as follows. The film was manufactured by spin-coating AIGS ink onto a glass substrate, followed by curing with UV light (405 nm) and baking on a hot plate at 180°C for 30 min, all within a glove box filled with nitrogen (N2). The ink contained the following components. Table 12 AIGS QD capped with mercaptohexanol and polyetheramine M1000 18% 1,3-Diaminomethylcyclohexane 5% TiO2 scattering particles 4% Dispersant (Synperonic NP5) 2% Photoinitiator (TPO) 1% Metal alkoxides 0.6% - 2.4% Monomer (HDDA) 67.6% - 69.4%

[0311] The membrane was then moved into the air and stored in a "yellow" room, which was illuminated with a white LED light covered with a blue-blocking filter. Typical illuminance and color coordinates for the yellow room, measured using a Konica-Minolta CL-200A colorimeter, were 140 lux, CIE x = 0.52, and CIE y = 0.45. For reference, typical indoor lighting conditions without blue filtering were illuminance = 620 lux, CIE x = 0.38, and CIE y = 0.38.

[0312] To test the effect of air exposure on PCE, membranes were obtained at periodic time intervals (3 hours, 1 day, 3 days), encapsulated using a second glass slide and a UV-curable transparent adhesive, and measured on a PCE platform. To further test the effect of long-term storage in air, the encapsulated membranes were baked again at 180°C for 30 minutes and measured on a PCE platform. Table 13 entry method PCE, airless PCE, after 1 day of yellow light in the air PCE, baked at 180℃ PCE, Blu-ray after 1 Zirconium propoxide-free 35.8% 14.2% 13.5% 18.3% 2 1.2 wt% Zirconium propoxide N / A 33.8% 32.3% 33.4% 3 1.2wt% Zirconium propoxide hydrolysis products N / A 34.0% 28.0% 33.5% 4 0.6 wt% Zirconium propoxide N / A 32.8% 32.5% 34.9% 5 2.4 wt% Zirconium propoxide N / A 31.8% 31.9% 33.8% 6 0.12wt zirconium propoxide N / A 29.4% 32.1% 33.8% 7 1.2 wt% Zirconium isopropoxide N / A 34.4% 34.9% 36.5% 8 1.5wt% Hafnium Isopropoxide N / A 32.3% 32.8% 31.7% 9 1.2 wt% zirconium propoxide and 0.4 wt% GaCl3 N / A 32.8% 35.8% 38.4%

[0313] As shown in Table 13, the stability of AIGS films was significantly improved by adding zirconium propoxide (IV) or its hydrolysis products to AIGS inks. As shown in Table 13, the PCE of the film remained at 30.1% to 34.4% after 24 hours of yellow light storage, only slightly lower than the 35.8% PCE of the airless film.

[0314] Table 14 shows the film results using inks containing alternative metal alkoxides. Adding gallium isopropoxide or barium isopropoxide produces films with improved air stability similar to those of zirconium propoxide. Table 14. Comparison of different metal alkoxides used to improve membrane properties upon air exposure. Using different batches of quantum dots resulted in lower overall performance. Sample number The metal alkoxides used PCE, after 1 day of yellow light in the air PCE, baked at 180℃ PCE, Blu-ray after Sample 1 1.2% Zirconium propoxide 22.6% 26.1% 27.9% Sample 2 1.2% Gallium Isopropoxide 19.0% 27.0% 28.8% Sample 3 1.2% Barium Isopropoxide 18.4% 23.4% 25.9% Sample 4 1.2% Gallium isopropoxide and Barium isopropoxide 1:1 mixture 22.6% 26.2% 28.0%

[0315] Unbound by any specific theory, it is believed that metal alkoxides form a stable shell around the AIGS nanostructure. In the classic sol-gel process, once tetraethyl orthosilicate (TEOS) is exposed to air moisture, it undergoes natural hydrolysis and condensation reactions. This produces a sol-gel three-dimensional network, and under extreme conditions, SiO2 is formed. Zr(OPr)4 is a typical sol-gel precursor. Once AIGS / Zr ink formulations are exposed to air, a sol-gel process actually occurs. In-situ FTIR visualization of AIGS / Zr(OPr)4 shows that by holding the AIGS / Zr sample on the FTIR window for 5 minutes, the tensile strength of -OH at 3400 cm⁻¹ significantly increases, while AIGS samples without Zr(OPr)4 do not show this change. It is believed that the in-situ formed three-dimensional network acts as an oxygen barrier, and the higher conductivity band formed by ZrO₂(OH)₂ confines excitons, especially electrons. The combination of these two processes effectively prevents the formation of reactive oxygen species (ROS) under light / air conditions, thus significantly improving light / air stability.

[0316] Membrane performance can be further improved by using phenolic additives, including those that act as antioxidants and steric hindrance ligands. Table 15 shows optical data for a group of membranes containing zirconium propoxide and the phenolic additive neopentyl tetroxide [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Table 15. Film results using inks containing metal alkoxides and sterically hindered phenolic ligands Sample ID method PCE, airless PCE after 1 day of air + yellow light Air storage, followed by sealing. Add 180℃ baking Blue light processing 539-074 1.2wt% Zirconium propoxide + 1% Neopentyl tert-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] 33.7% 26.6% 29.2% 32.0% 539-070 37.2% 32.7% 33.0% 36.6% 496-097A 37.2% 25.6% 32.6% 37.1% Example 12 Using a large phenolic auxiliary ligand

[0317] Ligand exchange on the AIGS nanostructure was performed at 80°C for 1 h using 6-mercaptohexanol and polyetheramine M1000. The AIGS nanostructure was then redispersed in the monomer using an auxiliary ligand. The ink formulation contained 12% ligand exchange QD, 10% TiO2 as a scattering medium, and 5% polyetheramine M1000 as a dispersant.

[0318] To select a suitable ligand or auxiliary ligand, several conditions must be met. First, the ligand must protect the surface ligands. Second, the ligand must be compatible with other ink components. Third, the ligand must be air-stabilized by blocking oxygen. Promising candidates that meet these conditions can be found by adding auxiliary ligands to ink formulations to manufacture films.

[0319] Figure 11 illustrates the film performance of ink formulations with different auxiliary ligands. The film with auxiliary ligand-1 exhibits better EQE than the others. This is assumed that the large end group of auxiliary ligand-1 provides steric hindrance and dense surface passivation on the AIGS nanostructure and prevents oxygen permeation and oxidation. Table 16. List of auxiliary ligands used in ink formulations List of auxiliary ligands Comparison 1,3-Bis(aminomethyl)cyclohexane auxiliary ligand 1 Neopentyl tetramethyl [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] auxiliary ligand 2 N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine auxiliary ligand 3 Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-tris(2,4-diyl)-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] Support ligand 4 2,2,6,6-Tetramethyl-4-piperidinium methacrylate Support ligand 5 2-Mercaptobenzimidazole Support ligand 6 N,N'-Di-Secondary Butyl-1,4-Phenylenediamine Support ligand 7 Trihexyl phosphite

[0320] Unlike InP, AIGS nanostructures, which are advantageously bonded to weakly bound L-type ligands, can reduce EQE if reactive free radicals or species that can cause side reactions are present. These side reactions are generated by free radicals from polymerization initiators or reactive free radical species and by oxygen-mediated photo-oxidation. The stability of the membrane was examined under dark conditions. Under dark conditions, auxiliary ligands-1 and 7 exhibited 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 the membrane containing auxiliary ligands-1 and 7 is exposed to air, the membrane does not degrade when not exposed to light.

[0321] Photostability was measured under yellow light to examine changes in film performance. As shown in Figure 12, auxiliary ligand 1 exhibited better stability than the reference ink (control group) under yellow light after 24 h. Furthermore, the phosphorus-based auxiliary ligand 7 exhibited a similar EQE to the reference ink (control group).

[0322] The thermal stability of the membrane was also measured after baking at 180°C. As shown in Table 17, compared with the control group, the large phenol-based auxiliary ligand-1 and phosphorus-based auxiliary ligand-7 exhibited good thermal stability. Table 17. EQE of the membrane after baking at 180°C in a nitrogen atmosphere UV-cured film Film baked at 180℃ (N 2) Blue light absorption rate, % EQE,% PWL,nm FWHM,nm Blue light absorption rate EQE PWL,nm FWHM,nm Changes in EQE, % control group [93.3] [31.38] [535.05] [30.87] [94.5] [15.77] [535.56] [31.1] 50% auxiliary ligand 1 [95.3] [32.68] [535.19] [30.7] [95.9] [19.19] [535.76] [30.85] 59% auxiliary ligand 2 [90.4] [28.6] [533.4] [31.48] [91.7] [16.83] [534.24] [31.37] 59% Support ligand 7 [95.0] [32.34] [534.98] [30.9] [95.9] [24.51] [535.48] [30.8] 76%

[0323] We also modified the manufacturing process of the inks shown in Table 18. When auxiliary ligand-1 was added, the EQE was better than that of the reference ligand 1,3-cyclohexanebis(methylamine). Furthermore, the ink formulations exhibited the highest stable EQE performance when more thiol was added during the ligand exchange with auxiliary ligand-1. See Figure 13, which shows the stability of ink formulations with different ratios of ink and additives over time when exposed to yellow light. Table 18. Changes in the Process [sample] [In ligand exchange] [(] [Compared to QD in ligand exchange] [quality)] [In ink formulations (30%)] [Compared to QD in single-target units] [Inorganic mass] Mercaptohexanol Polyetheramine M 1000 Reference ligand Support ligand-1 1-1 15% 38% 50% Reference ligand 2-1 5% 38% 50% Reference ligand 3-1 15% 38% 50% Reference ligand 4-1 30% 38% 50% Reference ligand 1-9 15% 38% 50% Support ligand-1 2-9 5% 38% 50% Support ligand-1 3-9 15% 38% 50% Support ligand-1 4-9 30% 38% 50% Support ligand-1

[0324] As shown in Figure 14, the additional GaCl3 (S3) treatment of the AIGS nanostructure demonstrates increased EQE performance. Performance is further improved when the inorganic ligand zirconium propoxide (S2) is added along with S3. The addition of multivalent metal-based ligands (such as S2) compensates for excessive sulfur oxidation. Also see Figure 15, which shows that the best performance of the baked film is achieved when the auxiliary ligands-1, S2, and S3 are combined. Figure 16 shows that the film exhibits high lightfastness when exposed to yellow light conditions when the auxiliary ligands-1, S2, and S3 are combined.

[0325] For comparison, Figure 17 is a line graph showing the EQE% of AIGS films containing 1%, 3%, and 6% S3 relative to their blue light absorption rates.

[0326] While various embodiments have been described above, it should be understood that they have been presented by way of example only and are not restrictive. It will be apparent to those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention. Therefore, the breadth and scope should not be limited to any of the exemplary embodiments described above, but should be defined only according to the following claims and their equivalents.

[0327] All publications, patents and patent applications mentioned in this specification indicate the skill level of anyone skilled in the art to which this invention pertains, and are incorporated herein by reference to the same extent that each individual publication, patent or patent application specifically and individually indicates its incorporation by reference.

Claims

1. A membrane comprising: Ag, In, Ga, and S (AIGS) nanostructures; one or more metal alkoxides, one or more metal alkoxide hydrolysis products, or combinations thereof; and at least one ligand, wherein when excited with a blue light source of about 450 nm, the membrane exhibits a photon conversion efficiency (PCE) greater than 32% at a peak emission wavelength of 480-545 nm, and wherein after 24 hours of storage under yellow light and air conditions, the PCE of the membrane is at least 30%.

2. The membrane of claim 1, wherein the at least one ligand has formula II: wherein R3 and R4 are independently C3-6 secondary or tertiary alkyl groups, and R5 is hydrogen or, where appropriate, a substituted C1-6 alkyl group.

3. The membrane of claim 2, wherein the substituents present on the C1-6 alkyl group of R5, as appropriate, are nitro, haloalkoxy, aryloxy, arylalkoxy, alkylthio, sulfonylamino, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, urea, guanidinyl, carbamate, carboxyl, alkoxycarbonyl, carboxylalkyl, or -C(=O)R7, wherein R7 is an alkoxy group that may be further substituted with one or more other alkoxy groups.

4. The membrane as requested in item 3, wherein R7 has the following formula: where p is 0-3.

5. A method for preparing a membrane as claimed in any one of claims 1 to 4, the method comprising: (a) providing an AIGS nanostructure, one or more metal alkoxides, one or more metal alkoxide hydrolysis products or combinations thereof; and at least one ligand; (b) doping at least one organic resin with the AIGS nanostructure of (a); and (c) preparing a first membrane comprising the doped AIGS nanostructure, the at least one ligand and the at least one organic resin on a first barrier layer; (d) curing the membrane; and (e) encapsulating the first membrane between the first barrier layer and a second barrier layer; wherein the encapsulated membrane exhibits a PCE greater than 32% at a peak emission wavelength of 480-545 nm when excited using a blue light source with a wavelength of about 450 nm.

6. The method of claim 5, wherein the method is performed before the encapsulated membrane is exposed to air to a blue LED light source.

7. The method of request item 6, wherein the method is performed in an inert atmosphere.

8. The method of claim 7, wherein the method further comprises: adding at least one oxygen-reactive material to the AIGS nanostructure of (a), one or more metal alkoxides, one or more metal alkoxide hydrolysis products or combinations thereof and a mixture of ligands; adding at least one oxygen-reactive material to the dopant of (b); and / or forming a second membrane comprising at least one oxygen-reactive material on top of the first membrane prepared in (c); and / or forming a sacrificial barrier layer temporarily blocking oxygen and / or water on the first membrane prepared in (c); measuring the PCE of the membrane; and then removing the sacrificial barrier layer.

9. The method of claim 8, wherein the two barrier layers do not include oxygen and / or water.

10. A display device comprising a film as claimed in any one of claims 1 to 4.

11. A nanostructured molded article comprising: (a) a first conductive layer; (b) a second conductive layer; and (c) a film of any one of claims 1 to 4, between the first conductive layer and the second conductive layer.

12. A nanostructure color converter comprising: a backplate; a display panel disposed on the backplate; and a film of any one of claims 1 to 4 disposed on the display panel.

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