Stable AIGS membrane

Abstract

A stabilizing film is disclosed, 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 said nanostructure. In some embodiments, the AIGS nanostructures have a photon conversion efficiency greater than 32% and a peak emission wavelength of 480-545 nm. In some embodiments, the nanostructures have an emission spectrum with an FWHM of 24-38 nm. In some embodiments, after storage for 24 hours under yellow light and air storage conditions, the nanostructures have a photon conversion efficiency (PCE) of at least 30%.

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 exhibits a high photon conversion efficiency (PCE) of greater than 30% at a peak emission wavelength of 480-545 nm when excited with a blue light source at a wavelength of approximately 450 nm and after exposure to yellow light and air storage conditions. Background Technology

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

[0003] The increased efficiency results in lower power consumption 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 used in displays typically exhibit poor performance due to their limited absorption of the blue light that excites them. Blue light absorption is often inherently limited by the material system used, leading to the need for thicker films to absorb sufficient 450nm light.

[0004] Thin films formed by depositing QD ink are typically cured by UV irradiation. In many cases, this is followed by thermal processing at 180°C for up to 1 hour in the presence of air. Due to the instability of these processing steps, the photon conversion efficiency of these films is limited by a combination of poor absorption and poor light conversion.

[0005] There remains a need in the field for AIGS nanostructures that possess high band-edge emission (BE), narrow full width at half maximum (FWHM), high quantum yield (QY), and reduced redshift, and that can be used to prepare films with high (greater than 32% before exposure to yellow light and air storage conditions) photon conversion efficiency (PCE) at peak emission wavelengths of 480 to 545 nm using an excitation wavelength of about 450 nm. Summary of the Invention

[0006] This invention provides a thin, heavy metal-free, stable AIGS nanostructure color conversion film that exhibits a high photon conversion efficiency (PCE) 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 moderately exposed to air under yellow light conditions. This is achieved by using AIGS nanostructures in ink formulations containing: 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 one or more ligand formulations. In some embodiments, all ink processing is performed in an oxygen-free environment prior to exposure to blue or ultraviolet light, followed by film deposition, processing, and measurement. In some embodiments, the AIGS nanostructures have a free wave size (FWHM) of 28-38 nm. In other embodiments, the AIGS nanostructures have an FWHM of less than 32 nm. In some embodiments, narrow FWHM is achieved by adding at least one polyamino-ligand to the AIGS nanostructure and preparing a film layer, wherein all processing of the nanostructure ink, ink deposition, film processing and measurement are carried out in an oxygen-free environment.

[0007] Thin films formed by depositing QD ink are typically cured by UV irradiation. In many cases, this is followed by thermal processing at 180°C for up to 1 hour in the presence of air. It has been found that photon conversion efficiency is reduced by poor absorption and poor light conversion due to the instability of these processing steps.

[0008] This document discloses films comprising AIGS nanostructures in ink formulations, including 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 film achieves a PCE greater than (>) 30% after exposure to yellow light and air storage conditions for 24 hours. In some embodiments, a film comprising AIGS nanostructures 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 using a blue light source with a wavelength of 450 nm. In some embodiments, a film comprising AIGS nanostructures, 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. In some embodiments, the membrane comprises, upon exposure to yellow light and air storage conditions in air, exhibiting about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, or about 39% of PCE:AIGS nanostructures, 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.

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

[0010] These prepared films exhibit good (>95%) blue light absorption but moderate emission properties. However, the emission properties of these films are significantly improved when processed in the absence of oxygen and / or light and / or when encapsulated before exposing the films to UV or blue light.

[0011] A method for preparing an AIGS membrane is provided, the method comprising:

[0012] (a) Provides an AIGS nanostructure, 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;

[0013] (b) blending (admixing) at least one organic resin with the AIGS nanostructure of (a); and

[0014] (c) A first film is prepared on a first barrier layer, the first film comprising a blend of AIGS nanostructures, the at least one ligand, and the at least one organic resin;

[0015] (d) Curing the film by UV irradiation and / or baking;

[0016] (e) Encapsulating the first film between the first barrier layer and the second barrier layer; and

[0017] When excited by a blue light source with a wavelength of approximately 450 nm, and after exposure to yellow light and air storage conditions, the encapsulated film exhibits a conversion efficiency (PCE) greater than 30% at peak emission wavelengths of 480-545 nm.

[0018] A method is also provided, which further includes:

[0019] (f) adding at least one oxygen-reactive material to the mixture of AIGS nanostructures and ligands in (a), adding at least one oxygen-reactive material to the blend in (b), and / or forming a second film comprising at least one oxygen-reactive material on top of the first film prepared in (c); and / or

[0020] (g) A sacrificial barrier layer temporarily blocking oxygen and / or water is formed on the first membrane prepared in (c), and the PCE of the membrane is measured, and then the sacrificial barrier layer is removed.

[0021] A method is also provided, which includes:

[0022] (a) Encapsulating the film prior to heat treatment and / or measurement;

[0023] (b) Using oxygen-reactive materials as part of the formulation during thermal processing or light exposure; and / or

[0024] (c) Temporarily block oxygen by using a sacrificial barrier layer.

[0025] In some embodiments, the nanostructure has an emission spectrum with an FWHM of less than 40 nm. In some embodiments, the nanostructure has an emission spectrum with an FWHM of 24-38 nm. In some embodiments, the nanostructure has an emission spectrum with an FWHM of 27-32 nm. In some embodiments, the nanostructure has an emission spectrum with an FWHM of 29-31 nm.

[0026] In some embodiments, the nanostructure has a QY of 80-99.9%. In some embodiments, the nanostructure has a QY of 85-95%. In some embodiments, the nanostructure has a QY of about 86-94%. In some embodiments, the nanostructure has an OD greater than or equal to 0.8. 450 / mass (mL.mg) -1 ·cm -1 ), where OD is optical density. In some embodiments, the nanostructure has an OD in the inclusive range of 0.8-2.5. 450 / mass (mL·mg) -1 ·cm -1 In some embodiments, the nanostructure has an OD in the range of 0.87-1.9. 450 / mass (mL·mg) -1 ·cm -1 In some embodiments, the average diameter of the nanostructure is less than 10 nm using transmission electron microscopy (TEM). In other embodiments, the average diameter is about 5 nm.

[0027] In some embodiments, at least about 80% of the transmissions are edge-triggered transmissions. In some embodiments, at least about 90% of the transmissions are edge-triggered transmissions. In some embodiments, 92-98% of the transmissions are edge-triggered transmissions. In some embodiments, 93-96% of the transmissions are edge-triggered transmissions.

[0028] In some embodiments, the at least one ligand is an amino ligand, a polyamino ligand, a ligand containing a thiol group, or a ligand containing a silane group. Surprisingly, the use of polyamino ligands has resulted in AIGS-containing films with an FWHM of less than 32 nm.

[0029] In some embodiments, the at least one polyamino-ligand is a polyamino alkane, a polyamino-cycloalkane, a polyamino heterocyclic compound, a polyamino-functionalized silicone, or a polyamino-substituted ethylene glycol. In some embodiments, the polyamino-ligand is a C14-hydroxyl group substituted with two or three amino groups and optionally contains one or two amino groups that substitute for the carbon group. 2-20 Alkanes or C 2-20 Cycloalkanes. In some embodiments, the polyamino-ligand is 1,3-cyclohexanebis(methylamine), 2,2-dimethyl-1,3-propanediamine, or tris(2-aminoethyl)amine.

[0030] In some embodiments, the ligand is a compound of formula I:

[0031]

[0032] in:

[0033] x is between 1 and 100;

[0034] y is between 0 and 100; and

[0035] R 2 C 1-20 alkyl.

[0036] In some implementations, x = 19, y = 3, and R 2 =-CH3.

[0037] In some embodiments, the ligand is a compound of formula II:

[0038]

[0039] Where R 3 and R 4 Independently for C 3-6 Secondary or tertiary alkyl groups, and R 5 C is hydrogen or optionally substituted 1-6 alkyl.

[0040] In some implementations, R 3 and R 4 It is isopropyl, 2-butyl, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, tert-butyl, 2-methyl-2-pentyl, or 3-methyl-3-pentyl.

[0041] In some implementations, R 5 C 1-6 Optional substituents on the alkyl group are nitro, haloalkoxy, aryloxy, arylalkoxy, alkylthio, sulfonylamino, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, ureyl, guanidinyl, carbamate, carboxyl, alkoxycarbonyl, carboxylalkyl, or -C(=O)R 7 , where R 7 It is an alkoxy group that can be further substituted by one or more other alkoxy groups.

[0042] In some implementations, R 7 It has the following formula:

[0043] CH P (CH2-O-) 4-P ,

[0044] Where p is 0-3.

[0045] In some implementations, R 7 for:

[0046]

[0047]

[0048] In some implementations, R 7 for:

[0049]

[0050] And Equation II is:

[0051]

[0052] In some embodiments, the at least one ligand is pentaerythritol tetra[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].

[0053] 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); diethylphenylphosphonite; dibenzyl N,N-diisopropylphosphonamide; di-tert-butyl N,N-diisopropylphosphonamide; tris(2-carboxyethyl)phosphine 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.

[0054] In some embodiments, the at least one ligand is a combination of: amino-polyepoxide (about mw1000) and methoxy polyethylene glycolamine (about mw500); amino-polyepoxide (about mw1000) and 6-mercapto-1-hexanol; amino-polyepoxide (about mw1000) and (3-mercaptopropyl)triethoxysilane; and 6-mercapto-1-hexanol and methoxy polyethylene glycolamine (about mw500).

[0055] In some embodiments, the one or more metal alkoxides are metal C. 1-10 Alkoxide. In some embodiments, the metal is titanium, zirconium, hafnium, gallium, or barium.

[0056] In some embodiments, the at least one or more metal alkoxides are zirconium tetramethylene (IV), zirconium tetraethanolamine (IV), zirconium tetra-n-propoxide (IV), zirconium tetraisopropoxide (IV), zirconium tetra-n-butoxide (IV), zirconium tetraisobutoxide (IV), zirconium tetra-n-pentoxide (IV), zirconium tetraisopentoxide (IV), zirconium tetra-n-hexanool (IV), zirconium tetraisohexanool (IV), zirconium tetra-n-heptanol (IV), zirconium tetraisoheptanol (IV), zirconium tetra-n-octanol (IV), zirconium tetra-n-isooctanol (IV), zirconium tetra-n-nonoxide (IV), zirconium tetra-n-isononoxide (IV), zirconium tetra-n-decanool (IV), or zirconium tetra-n-isodecanool (IV).

[0057] In some embodiments, the at least one or more metal alkoxides are tetra-n-propoxide zirconium(IV).

[0058] In some embodiments, the 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, are tetra-n-propoxide zirconium (IV), and the membrane further comprises pentaerythritol tetra[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].

[0059] A nanostructure composition is also provided, comprising:

[0060] (a) AIGS nanostructures exhibiting a PCE greater than 30% after exposure to yellow light and air storage conditions, and

[0061] (b) At least one organic resin.

[0062] In some embodiments, the at least one organic resin is cured.

[0063] A method for preparing the nanostructure composition described herein is also provided, the method comprising:

[0064] (a) Provides an AIGS nanostructure, 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;

[0065] (b) Blend at least one organic resin with the nanostructure of (a);

[0066] (c) A first film is prepared on a first barrier layer, the first film comprising a blend of AIGS nanostructures, the at least one ligand, and the at least one organic resin;

[0067] (d) Curing the film by UV irradiation and / or baking; and

[0068] (e) The first film is encapsulated between the first barrier layer and the second barrier layer.

[0069] When excited by a blue light source with a wavelength of approximately 450 nm and exposed to yellow light in air, the encapsulated film exhibits a conversion efficiency (PCE) greater than 30% at peak emission wavelengths of 480-545 nm.

[0070] In some embodiments, the method is performed before exposing the encapsulated film to air to measure the emission spectrum of the AIGS nanostructure. In some embodiments, the method is performed under an inert atmosphere.

[0071] In some embodiments, the method further includes:

[0072] (f) Adding at least one oxygen-reactive material to: (a) an AIGS nanostructure, 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 a mixture of ligands.

[0073] (g) To the blend of (b), add at least one oxygen-reactive material, and / or

[0074] (h) Forming a second membrane comprising at least one oxygen-reactive material on top of the first membrane prepared in (c); and / or

[0075] (i) A sacrificial barrier layer temporarily blocking oxygen and / or water is formed on the first membrane prepared in (c), and the PCE of the membrane is measured, and then the sacrificial barrier layer is removed.

[0076] In some implementations, the two barrier layers exclude oxygen and / or water.

[0077] In some implementations, 92-98% of the launches are edge-fired. In some implementations, 93-96% of the launches are edge-fired.

[0078] A method for preparing the composition is also provided, the method comprising:

[0079] (a) Provides a solvent comprising: an AIGS nanostructure, 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; and

[0080] (b) Blend the composition obtained in (a) with at least one second ligand.

[0081] In some embodiments, the solvent in (a) comprises an organic resin. In some embodiments, the method further comprises inkjet printing the composition.

[0082] In some embodiments, the method further includes preparing a membrane comprising the composition obtained in (b). In some embodiments, the method further includes curing the membrane. In some embodiments, the membrane is cured by heating. In some embodiments, the membrane is cured by exposure to electromagnetic radiation.

[0083] An apparatus comprising the aforementioned membrane is also provided.

[0084] Nanostructured molded articles are also provided, which include:

[0085] (a) First conductive layer;

[0086] (b) the second conductive layer; and

[0087] (c) A film containing an AIGS nanostructure layer between the first conductive layer and the second conductive layer.

[0088] The nanostructure layer comprises AIGS nanostructures with a PCE greater than 30% after exposure to yellow light and air storage conditions.

[0089] A nanostructure color converter is also provided, which includes:

[0090] Back plane;

[0091] A display panel disposed on the back panel; and

[0092] The film comprises an AIGS nanostructure layer, the AIGS nanostructure layer comprising AIGS nanostructures having a PCE greater than 30% after exposure to yellow light and air storage conditions, the nanostructure layer being disposed on a display panel.

[0093] In some embodiments, the nanostructure layer comprises a patterned nanostructure layer. In some embodiments, the backplane comprises an LED, LCD, OLED, or microLED.

[0094] Further 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. Note that the invention is not limited to the specific embodiments described herein. Such embodiments are presented herein for illustrative purposes only. Further embodiments will become apparent to those skilled in the art based on the teachings contained herein. Attached Figure Description

[0095] The accompanying drawings, which are incorporated herein and form part of the specification, illustrate embodiments of the invention and, together with the specification, further serve to explain the principles of the embodiments of the invention and enable those skilled in the art to make and use the embodiments of the invention.

[0096] Figure 1 The images, from left to right, show the first and third membranes without polyamino ligands and exhibiting extended wrinkling. The second and fourth membranes, containing polyamino ligands, do not show wrinkling.

[0097] Figure 2A-2C This shows the results before ion exchange treatment ( Figure 2A After a single ion exchange treatment ( Figure 2B ) and after two ion exchange treatments ( Figure 2C TEM image of AIGS nanostructures.

[0098] Figure 3A and 3B It is unpackaged. Figure 3A ) and packaged ( Figure 3B (A schematic diagram of the membrane.)

[0099] Figure 4 It is a scatter plot showing the QY% of a mixture of multiple ligands.

[0100] Figure 5 It is a scatter plot showing ligand combinations that provide improved QY% (good combinations) and combinations that provide decreased QY% (bad combinations).

[0101] Figure 6 It is a graph showing the QY% of various ligand combinations before ligand exchange (NG), after ligand exchange (LE), and 30 minutes after thermal testing.

[0102] Figure 7 It is a graph showing the QY% of various ligand combinations at various ligand ratios.

[0103] Figure 8These are two scatter plots showing the PCE of the AIGS film after normal PCE measurement and after PCE measurement following encapsulation.

[0104] Figure 9 These are two scatter plots showing the PCE of AIGS films baked at 180°C before PCE measurement (left image) and after encapsulation (right image).

[0105] Figure 10 This is a line graph showing the EQE% of the AIGS ink formulation film relative to blue light absorbance after auxiliary ligand exchange.

[0106] Figure 11 It is a line graph showing the EQE% of a thin film containing multiple auxiliary ligands containing AIGS ink formulations over time when kept in the dark.

[0107] Figure 12 It is a line graph showing the EQE% of AIGS ink formulations containing multiple auxiliary ligands over time when exposed to yellow light.

[0108] Figure 13 It is a line graph showing the EQE% of a thin film containing various auxiliary ligands and additives over time when exposed to yellow light.

[0109] Figure 14 It is a line graph showing the EQE% of the film containing auxiliary ligand-1; auxiliary ligand-1 and zirconium propoxide (S2); auxiliary ligand-1, S2 and GaCl3 (S3); and S2 and S3 of the AIGS ink formulation, relative to the blue light absorbance.

[0110] Figure 15 It is a bar graph showing the EQE of AIGS membranes containing auxiliary ligand-1; auxiliary ligand-1 and S2; auxiliary ligand-1, S2 and S3; and S2 and S3 after baking under nitrogen.

[0111] Figure 16 It is a line graph showing the EQE% of cured AIGS films containing auxiliary ligand-1; auxiliary ligand-1 and S2; auxiliary ligand-1, S2 and S3; and S2 and S3 over time when exposed to yellow light.

[0112] Figure 17 This is a line graph showing the EQE% of AIGS films containing 1%, 3%, and 6% S3 relative to blue light absorbance.

[0113] The features and advantages of the invention will become more apparent from the specific embodiments set forth below when viewed in conjunction with the accompanying drawings, wherein similar reference numerals identify corresponding elements throughout. In the drawings, similar 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 numeral of the corresponding reference numeral. Unless otherwise specified, the drawings provided throughout this disclosure should not be construed as being drawn to scale. Detailed Implementation

[0114] definition

[0115] 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 following definitions supplement those in the art and are specific to the present application, and do not fall under any related or unrelated case, such as any co-owned patent or application. While any methods and materials similar to or equivalent to those described herein may be used in the practice of testing the invention, preferred materials and methods are described herein. Therefore, the terminology used herein is for descriptive purposes only and is not intended to be limiting.

[0116] As used in this specification and the appended claims, the singular forms “a,” “an,” and “described” include a plurality of indicators unless the context clearly specifies otherwise. Thus, for example, a reference to “a nanostructure” includes a plurality of such nanostructures, etc.

[0117] As used herein, the term “about” indicates that the value of a given quantity varies within + / - 10% of that value. For example, “about 100 nm” covers a size range from 90 nm to 110 nm (inclusive).

[0118] 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 will be along the smallest axis of the structure. Examples of such structures include nanowires, nanorods, nanotubes, branched nanostructures, nanotetrapods, tripods, bipods, nanocrystals, nanodots, quantum dots, nanoparticles, etc. Nanostructures can be, for example, substantially crystalline, substantially single-crystal, polycrystalline, amorphous, or combinations 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.

[0119] When used with respect to nanostructures, the term "heterogeneous structure" refers to a nanostructure characterized by at least two different and / or distinguishable material types. Typically, one region of a 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 at least one shell of a second (or third, etc.) material, wherein, for example, the different material types are radially distributed around the long axis of a nanowire, the long axis of an arm of a branched nanowire, or the center of a nanocrystal. The shell may, but does not need to, completely cover the adjacent material to be considered a shell or, for the nanostructure, a heterostructure; for example, a nanocrystal characterized by a core of one material covered by islands of a second material is a heterostructure. In other embodiments, the different material types are distributed at different locations within the nanostructure; for example, along the main (long) axis of a nanowire or along the long axis of an arm of a branched nanowire. Different regions within a heterostructure may contain entirely different materials, or different regions may contain a matrix material (e.g., silicon) with different dopants or different concentrations of the same dopant.

[0120] As used herein, the “diameter” of a nanostructure refers to the diameter of a cross-section orthogonal to the nanostructure’s first axis, which has the largest length difference relative to the second and third axes (the second and third axes being the two axes whose lengths are closest 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 would be a substantially circular cross-section orthogonal to the disk’s shorter longitudinal axis. In cases where the cross-section is not circular, the diameter is the average of the principal and secondary axes of that cross-section. For elongated or high aspect ratio nanostructures, such as nanowires, the diameter is measured on a cross-section orthogonal to the nanowire’s longest axis. For spherical nanostructures, the diameter is measured from one side to the other through the center of the sphere.

[0121] When used in relation to nanostructures, the term "crystalline" or "substantially crystalline" refers to the fact that a nanostructure typically exhibits long-range order in one or more dimensions of the structure. Those skilled in the art will understand that the term "long-range order" will depend on the absolute size of the specific nanostructure, as the order of a single crystal cannot extend beyond the crystal boundaries. In this case, "long-range order" will mean substantial order in at least most of the dimensions of the nanostructure. In some cases, the nanostructure may have oxides or other coatings, or may consist of a core and at least one shell. In this case, it will be understood that the oxide, one or more shells, or other coatings may, but do not need to, exhibit such order (e.g., it may be amorphous, polycrystalline, or otherwise). In this case, the phrases "crystalline," "substantially crystalline," "substantially single-crystal," or "single-crystal" refer to the central core of the nanostructure (excluding the coating or shell). As used herein, the term "crystalline" or "substantially crystalline" is also intended to cover structures containing various defects, stacking faults, atomic substitutions, etc., provided that the structure exhibits substantial long-range order (e.g., at least about 80% order along the length of at least one axis of the nanostructure or its core). Furthermore, it will be understood that the interfaces between the core and the outer shell of a nanostructure, or 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.

[0122] 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 containing a core and one or more shells, "single crystal" indicates that the core is substantially crystalline and substantially contains a single crystal.

[0123] A "nanocrystal" is a substantially single-crystal nanostructure. Therefore, a nanocrystal has at least one region or characteristic dimension with a size less than about 500 nm. In some embodiments, the nanocrystal 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. The term "nanocrystal" is intended to encompass substantially single-crystal nanostructures that include various defects, stacking faults, atomic substitutions, etc., as well as substantially single-crystal nanostructures that do not have such defects, stacking faults, 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 one or more shells need not be. In some embodiments, each of the three dimensions of the nanocrystal 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.

[0124] The term "quantum dot" (or "dot") refers to a nanocrystal exhibiting quantum confinement or exciton confinement. Quantum dots can be substantially homogeneous in material properties, or in some embodiments, heterogeneous, for example, comprising a core and at least one shell. The optical properties of quantum dots can be influenced by their particle size, chemical composition, and / or surface composition, and can be determined by suitable optical tests available in the art. The ability to tune the size of nanocrystals (e.g., in the range of about 1 nm to about 15 nm) enables light emission to cover the entire spectrum, providing great versatility in terms of color rendering.

[0125] The term "oxygen-free ligand" refers to a coordination molecule that does not contain oxygen atoms and is capable of coordinating or reacting with metal ions used in this article.

[0126] A "ligand" is a molecule that can interact (whether weakly or strongly) with one or more faces of a nanostructure, for example, through covalent, ionic, van der Waals, or other molecular interactions with the surface of the nanostructure.

[0127] "Photoluminescence quantum yield" (QY) is, for example, the ratio of photons emitted by a nanostructure or group of nanostructures to the number of photons absorbed. As is known in the art, quantum yield is typically determined by the absolute change in the photon count of a sample within an integral sphere under illumination, or by comparison with well-characterized standard samples having known quantum yield values.

[0128] The "peak emission wavelength" (PWL) is the wavelength at which the emission spectrum of a light source reaches its maximum value in a radiation measurement.

[0129] As used herein, the term "full width at half maximum" (FWHM) is a measure of the size distribution of a nanostructure. The emission spectrum of a nanostructure generally has the shape of a Gaussian curve. The width of the Gaussian curve is defined as the FWHM and gives the concept of the particle size distribution. A smaller FWHM corresponds to a narrower nanocrystal size distribution in the nanostructure. FWHM also depends on the maximum emission wavelength.

[0130] Compared to corresponding defect emission, band-edge emission is centered at a higher energy (lower wavelength) and has a smaller offset from the absorption initiation energy. Additionally, band-edge emission has a narrower wavelength distribution compared to defect emission. Both band-edge and defect emission follow a normal (approximately Gaussian) wavelength distribution.

[0131] Optical density (OD) is a commonly used method for quantifying the concentration of solutes or nanoparticles. According to Beer-Lambert's law, the absorbance (also known as "extinction") of a particular sample is proportional to the concentration of the solute that absorbs light at a particular wavelength.

[0132] Optical density is the light attenuation per centimeter of material, as measured using a standard spectrometer, typically specified in 1 cm path lengths. Nanostructured solutions are often measured by their optical density instead of mass or molar concentration because it is proportional to concentration and is a more convenient way to express the amount of light absorption occurring in the nanostructured solution at the wavelength of interest. A nanostructured solution with an OD of 100 is 100 times more concentrated (100 times more particles per mL) than a product with an OD of 1.

[0133] Optical density can be measured at any wavelength of interest, such as the wavelength chosen to excite the fluorescent nanostructure. Optical density is a measure of the intensity of light lost when it passes through a nanostructure solution at a specific wavelength, and is calculated using the following formula:

[0134] OD = log 10 *(I OUT / I IN )

[0135] in:

[0136] I OUT = The intensity of radiation transmitted into the pool; and

[0137] I IN = The intensity of radiation transmitted through the pool.

[0138] The optical density of nanostructured solutions can be measured using a UV-VIS spectrometer. Therefore, by using a UV-VIS spectrometer, the optical density can be calculated to determine the amount of nanostructures present in the sample.

[0139] The “yellow light and air storage conditions” refers to illuminating the film in air using a white LED light covered with a blue light blocking filter, where the illuminance and color coordinates of the yellow light storage conditions were measured by a Konica-Minolta CL-200A colorimeter as 140 lux, CIE x = 0.52, and CIE y = 0.45.

[0140] Unless otherwise expressly stated, the scope listed in this document is inclusive.

[0141] This document defines or otherwise characterizes a variety of other terms.

[0142] AIGS nanostructures

[0143] 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 nanostructure emission spectrum and comparing the area of ​​the peak whose energy is closer to the band gap of the nanostructure (which represents band-edge emission) with the sum of the areas of all peaks (band-edge + defect emission).

[0144] 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.

[0145] 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 yet another embodiment, the nanostructure has a QY of about 86% to about 94%. In some embodiments, at least 80% of the emission is band-edge emission. In other embodiments, at least 90% of the emission is band-edge emission. In other embodiments, at least 95% of the emission is band-edge emission. In some embodiments, 92-98% of the emission is band-edge emission. In some embodiments, 93-96% of the emission is band-edge emission.

[0146] AIGS nanostructures provide high blue light absorption. As a predicted value for blue light absorption efficiency, the optical density per unit mass (OD) at 450 nm was calculated by measuring the optical density of the nanostructure solution in a cuvette with a 1 cm path length and dividing it by the dry mass per mL (mg / mL) of the same solution after all volatiles were removed under vacuum (<200 mTorr). 450 / mass). In one embodiment, the nanostructures provided herein have an OD of at least 0.8. 450 / mass (mL·mg) -1 ·cm -1 In another embodiment, the nanostructure has an OD of 0.8-2.5. 450 / mass (mL·mg) -1 ·cm -1 In another embodiment, the nanostructure has an OD of 0.87-1.9. 450 / mass (mL·mg) -1 ·cm -1 ).

[0147] In one embodiment, the nanostructure has been treated with gallium ions, causing gallium-indium ion exchange 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 results in a gradient of gallium, silver, and / or sulfur throughout the nanostructure.

[0148] In one embodiment, the average diameter of the nanostructure is less than 10 nm, as measured by TEM. In another embodiment, the average diameter is about 5 nm.

[0149] AIGS nanostructures prepared using GaX3 (X = F, Cl, or Br) precursors and oxygen-free ligands

[0150] Reports on AIGS preparation in the literature have not attempted to exclude oxygen-containing ligands. Oxygen-containing ligands are frequently used to stabilize Ga precursors when coating AIGS with gallium. Gallium acetylacetonate (Ga(III)) is conventionally used as a precursor readily handled in air, while gallium chloride (Ga(III)) requires careful handling due to its humidity sensitivity. For example, in Kameyama et al., ACS Appl. Mater. Interfaces 10: 42844-42855 (2018), gallium acetylacetonate (Ga(III)) was used as a precursor for both core and core / shell structures. Because gallium has a high affinity for oxygen, oxygen-containing ligands, as well as the use of gallium precursors not prepared under oxygen-free conditions, can produce undesirable side reactions, such as gallium oxide, when using Ga and S precursors to generate nanostructures with significant gallium content. These side reactions can lead to defects in the nanostructures and result in lower quantum yields.

[0151] 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) and oxygen-free ligands are used as precursors to prepare AIGS nanostructures in the preparation of Ga-rich AIGS nanostructures. In some embodiments, GaX3 (X = F, Cl, or Br) and oxygen-free ligands are used as precursors to prepare AIGS nanostructures in the preparation of AIGS cores and in the ion-exchange treatment of AIGS cores.

[0152] Nanostructures comprising Ag, In, Ga and S are provided, wherein the nanostructures have a peak emission wavelength (PWL) between 480 and 545 nm, and wherein the nanostructures are prepared using GaX3 (X = F, Cl, or Br) precursors and oxygen-free ligands.

[0153] In some embodiments, nanostructures prepared using GaX3 (X = F, Cl, or Br) precursors and anaerobic ligands exhibit FWHM emission spectra of 35 nm or less. 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 at least 75% QY. In some embodiments, nanostructures prepared using GaX3 (X = F, Cl, or Br) precursors and anaerobic ligands have 75-90% QY. In some embodiments, nanostructures prepared using GaX3 (X = F, Cl, or Br) precursors and anaerobic ligands have approximately 80% QY.

[0154] The AIGS nanostructures prepared in this paper provide high blue light absorption. In some embodiments, the nanostructures have an OD of at least 0.8. 450 / mass (mL·mg) -1 ·cm -1 In some embodiments, the nanostructure has an OD of 0.8-2.5. 450 / mass (mL·mg) -1 ·cm -1 In another embodiment, the nanostructure has an OD of 0.87-1.9. 450 / mass (mL·mg) -1 ·cm -1 ).

[0155] In some embodiments, the nanostructure is treated with gallium ions, causing gallium-indium ion exchange throughout the AIGS nanostructure. In some embodiments, the nanostructure contains Ag, In, Ga, and S in its core and exhibits a gallium gradient between the surface and center of the nanostructure. In some embodiments, the nanostructure is an AIGS core treated with AGS, prepared using a GaX3 (X = F, Cl, or Br) precursor and an oxygen-free ligand. 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 gallium ion exchange via reaction with an oxygen-free Ga salt to form the AIGS nanostructure.

[0156] Methods for preparing AIGS nanostructures

[0157] A method for preparing AIGS nanostructures is provided, the method comprising:

[0158] (a) Preparation of a mixture comprising an AIGS core, a sulfur source, and ligands;

[0159] (b) At a temperature of 180–300 °C, the mixture obtained in (a) is added to a mixture of gallium carboxylate and ligands to obtain an ion-exchanged nanostructure with a gallium gradient from the surface to the center of the nanostructure; and

[0160] (c) Separate the nanostructure.

[0161] In some embodiments, the nanostructure has a pulse wave line (PWL) between 480 and 545 nm, wherein at least about 60% of the emission is band-edge emission.

[0162] A method for preparing AIGS nanostructures is also provided, the method comprising:

[0163] (a) Optionally, Ga(acetylacetone)3, InCl3, and the ligand are reacted in a solvent at a temperature sufficient to obtain the In-Ga reagent, and

[0164] (b) React the In-Ga reagent with the Ag2S nanostructure at a temperature sufficient to prepare the AIGS nanostructure.

[0165] (c) In a solvent containing ligands, AIGS nanostructures are reacted with oxygen-free Ga salts at a temperature sufficient to obtain nanostructures with ion exchange having a gallium gradient from the surface to the center of the nanostructures.

[0166] In some embodiments, the nanostructure has a pulse wave line (PWL) between 480 and 545 nm, wherein at least about 60% of the emission is band-edge emission.

[0167] 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 solvent is not present in the reaction. In some embodiments, the solvent is present in the reaction. In some embodiments, the solvent is a high-boiling-point solvent. In some embodiments, the solvent is octadecene, squalane, dibenzyl ether, or xylene. In some embodiments, a sufficient temperature in (a) is 100 to 280°C; a sufficient temperature in (b) is 150 to 260°C; and a sufficient temperature in (c) is 170 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.

[0168] 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 other embodiments, at least 95% of the transmissions are edge-triggered transmissions. In some embodiments, 92-98% of the transmissions are edge-triggered transmissions. In some embodiments, 93-96% of the transmissions are edge-triggered transmissions.

[0169] 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 one embodiment, the ligand is an alkylamine. In some embodiments, the ligand is an alkylamine selected from dodecylamine, oleylamine, hexadecylamine, dioctylamine, and octadecylamine.

[0170] In some embodiments, the sulfur source in (a) comprises trioctylphosphine sulfide, elemental sulfur, octyl mercaptan, dodecanethiol, octadecyl mercaptan, tributylphosphine sulfide, cyclohexyl isothiocyanate, α-toluene mercaptan, ethylene trithiocarbonate, allyl mercaptan, bis(trimethylsilyl) sulfide, trioctylphosphine sulfide, or combinations thereof. In some embodiments, the sulfur source in (a) is derived from S8.

[0171] In one implementation, the sulfur source is derived from S8.

[0172] In one embodiment, the temperature in (a) and (b) is approximately 270°C.

[0173] In some embodiments, the mixture in (b) further comprises a solvent. In some embodiments, the solvent is trioctylphosphine, dibenzyl ether, or squalane.

[0174] In some embodiments, gallium carboxylate is C 2-24 Gallium carboxylate. C 2-24 Examples of carboxylates include acetates, propionates, butates, valerates, hexanoates, heptates, octanoates, nonanoates, decanoates, undecanoates, tridecanoates, tetradecanoates, pentadecanoates, hexadecanoates, octadecanoates (oleates), nonadecanates, and eicosanoates. In one embodiment, gallium carboxylate is gallium oleate.

[0175] In some embodiments, the gallium carboxylate to AIGS core ratio is 0.008-0.2 mmol gallium carboxylate / mg AIGS. In one embodiment, the gallium carboxylate to AIGS core ratio is 0.04 mmol gallium carboxylate / mg AIGS.

[0176] In another embodiment, AIGS nanostructures are separated, for example, by precipitation. In some embodiments, the AIGS nanostructures are precipitated by adding a non-solvent specific 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 specific to the nanostructures.

[0177] A method for preparing nanostructures is also provided, which includes:

[0178] (a) Preparing a mixture comprising an AIGS core and gallium halide in a solvent, and holding the mixture for a sufficient time to obtain nanostructures with ion-exchange having a gallium gradient from the surface to the center of the nanostructure; and

[0179] (b) Separate the nanostructure.

[0180] In some embodiments, the nanostructure has a pulse wave volume (PWL) between 480 and 545 nm, and at least about 60% of the emission is band-edge emission.

[0181] 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.

[0182] In some embodiments, gallium halide is gallium chloride, gallium bromide, or gallium iodide. In one embodiment, gallium halide is gallium iodide.

[0183] In some embodiments, the solvent comprises trioctylphosphine. In some embodiments, the solvent comprises toluene.

[0184] 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.

[0185] In some embodiments, the mixture is maintained at 20 to 100°C. In one embodiment, the mixture is maintained at approximately room temperature (20 to 25°C).

[0186] In some implementations, the molar ratio of gallium halide to AIGS cores is from about 0.1 to about 30.

[0187] In another embodiment, AIGS nanostructures are separated, for example, by precipitation. In some embodiments, the AIGS nanostructures are precipitated by adding a non-solvent specific 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 specific to the nanostructures.

[0188] A method for preparing nanostructures is also provided, which includes:

[0189] (a) Preparation of a mixture comprising AIGS nanostructures, a sulfur source, and ligands;

[0190] (b) At a temperature of 180–300 °C, the mixture obtained in (a) was added to a mixture of GaX3 (X = F, Cl, or Br) and oxygen-free ligands to obtain ion-exchanged nanostructures with a gallium gradient from the surface to the center of the nanostructures; and

[0191] (c) Separate the nanostructure.

[0192] In some implementations, the nanostructure has a PWL between 480-545 nm.

[0193] 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.

[0194] In some embodiments, the addition in (b) is performed under anaerobic conditions. In some embodiments, the addition in (b) is performed in a glove box.

[0195] 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.

[0196] 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 ligands in (a) and (b) are alkylamines. In some embodiments, the ligand is an alkylamine selected from 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 oleylamine.

[0197] In one implementation, the sulfur source is derived from S8.

[0198] In one embodiment, the temperature in (a) and (b) is approximately 270°C.

[0199] In some embodiments, the mixture in (b) further comprises a solvent. In some embodiments, the solvent is trioctylphosphine, dibenzyl ether, or squalane.

[0200] In some embodiments, GaX3 is gallium chloride, gallium fluoride, or gallium iodide. In some embodiments, GaX3 is gallium chloride. In some embodiments, GaX3 is Ga(III) chloride.

[0201] In some embodiments, the GaX3 to AIGS nucleus ratio is 0.008-0.2 mmol GaX3 / mg AIGS. In some embodiments, the GaX3 to AIGS nucleus molar ratio is about 0.1 to about 30. In some embodiments, the GaX3 to AIGS nucleus ratio is 0.04 mmol GaX3 / mg AIGS.

[0202] In some embodiments, AIGS nanostructures are separated, for example, by precipitation. In some embodiments, AIGS nanostructures are precipitated by adding a non-solvent specific to 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 specific to the nanostructures.

[0203] In some embodiments, the mixture in (a) is maintained at 20°C to 100°C. In some embodiments, the mixture in (a) is maintained at approximately room temperature (20°C to 25°C).

[0204] In some embodiments, the mixture in (b) is maintained at 200°C to 300°C for 0.1 hours to 200 hours. In some embodiments, the mixture in (b) is maintained at 200°C to 300°C for about 20 hours.

[0205] Doped AIGS nanostructures

[0206] In some embodiments, the AIGS nanostructure is doped. In some embodiments, the dopant of the nanocrystal core comprises a metal, including one or more transition metals. In some embodiments, the dopant is selected from the transition metals: 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.

[0207] In some embodiments, the nucleus is purified by precipitation from a non-solvent. In some embodiments, the AIGS nanostructures are filtered to remove precipitates from the nucleus solution.

[0208] Nanostructure Composition

[0209] In some embodiments, this disclosure provides a nanostructure composition comprising:

[0210] (a) at least one group of AIGS nanostructures; and

[0211] (b) At least one organic resin.

[0212] In some implementations, the nanostructure has a PWL between 480-545 nm.

[0213] In some embodiments, at least 80% of the nanostructure emission is band-edge emission. In other embodiments, at least 90% of the emission is band-edge emission. In other embodiments, at least 95% of the emission is band-edge emission. In some embodiments, 92-98% of the emission is band-edge emission. In some embodiments, 93-96% of the emission is band-edge emission.

[0214] In some embodiments, the nanostructure composition further comprises at least one second nanostructure group. Nanostructures having a pulsed light wavelength (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 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.

[0215] organic resin

[0216] In some embodiments, the organic resin is a thermosetting resin or a UV-curable resin. In some embodiments, the organic resin is cured using a method that promotes roll-to-roll processing.

[0217] Thermosetting resins require curing, during which they undergo an irreversible molecular cross-linking process, making the resin infusible (refractory). In some embodiments, the thermosetting resin is an epoxy resin, phenolic resin, vinyl resin, melamine resin, urea resin, unsaturated polyester resin, polyurethane resin, allyl resin, acrylic resin, polyamide resin, polyamide-imide resin, phenolic amine condensation resin, urea melamine condensation resin, or a combination thereof.

[0218] In some embodiments, the thermosetting resin is an epoxy resin. Epoxy resins are easy to cure and do not produce volatiles or byproducts through a wide range of chemicals. Epoxy resins are also compatible with most substrates and tend to wet surfaces easily. See Boyle, MA et al., "Epoxy Resins," Composites, Vol. 21, ASM Handbook, pp. 78-89 (2001).

[0219] In some embodiments, the organic resin is a silicone thermosetting resin. In some embodiments, the silicone thermosetting resin is OE6630A or OE6630B (Dow Corning Corporation, Auburn, MI).

[0220] In some embodiments, a thermal initiator is used. In some embodiments, the thermal initiator is AIBN [2,2′-azobis(2-methylpropionitrile)] or benzoyl peroxide.

[0221] 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)acryloyloxy, ethyleneoxy, styrene, or vinyl groups; cationic polymerizable groups, such as epoxy, thioepoxy, ethyleneoxy, or oxetanyl. In some embodiments, UV-curable resins are polyester resins, polyether resins, (meth)acrylic resins, epoxy resins, polyurethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, or polythiol polyene resins.

[0222] In some embodiments, the UV-curable resin is selected from isobornyl acrylate, isobornyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, polyurethane acrylate, allyloxylated cyclohexyl diacrylate, bis(acryloyloxyethyl)hydroxyisocyanurate, bis(acryloyloxyneopentyl)adipate, bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol diacrylate, 1, 3-Butanediol dimethacrylate, dicyclopentyl diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentacrylate, di(trimethylolpropane)tetraacrylate, ethylene glycol dimethacrylate, glycerol methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol hydroxypentanoic acid diacrylate diacrylate), pentaerythritol triacrylate, pentaerythritol 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, tri(acryloyloxyethyl) isocyanurate, triacrylate phosphate, diacrylate phosphate, propargyl acrylate, vinyl End-capped polydimethylsiloxanes, vinyl-end-capped diphenylsiloxane-dimethylsiloxane copolymers, vinyl-end-capped polyphenylmethylsiloxanes, vinyl-end-capped trifluoromethylsiloxane-dimethylsiloxane copolymers, vinyl-end-capped diethylsiloxane-dimethylsiloxane copolymers, vinylmethylsiloxanes, monomethacryloyloxypropyl-end-capped polydimethylsiloxanes, monovinyl-end-capped polydimethylsiloxanes, monoallyl-monotrimethylsiloxy-end-capped polyethylene oxides, and combinations thereof.

[0223] In some embodiments, the UV-curable resin is a mercapto-functional compound that can be crosslinked with isocyanate, epoxy resin, or unsaturated compound under UV curing conditions. In some embodiments, the polythiol is pentaerythritol tetra(3-mercaptopropionate) (PETMP); trimethylolpropane tri(3-mercaptopropionate) (TMPMP); diol di(3-mercaptopropionate) (GDMP); tris[25-(3-mercaptopropionyloxy)ethyl]isocyanurate (TEMPIC); di-pentaerythritol hexa(3-mercaptopropionate) (Di-PETMP); ethoxylated trimethylolpropane tri(3-mercaptopropionate) (ETTMP 1300 and ETTMP 700); polycaprolactone tetra(3-mercaptopropionate) (PCL4MP 1350); pentaerythritol tetramercaptoacetate (PETMA); trimethylolpropane trimercaptoacetate (TMPMA); or ethylene glycol dimercaptoacetate (GDMA). These compounds are marketed by Bruno Bock (Marschacht, Germany) under the trade name... sell.

[0224] In some embodiments, the UV-curable resin is a polythiol. In some embodiments, the UV-curable resin is a polythiol selected from ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tri(thioglycolate), trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra(thioglycolate), pentaerythritol tetra(3-mercaptopropionate) (PETMP), and combinations thereof. In some embodiments, the UV-curable resin is PETMP.

[0225] In some embodiments, the UV-curable resin is a thiol-olefin formulation comprising polythiol and 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TTT). In some embodiments, the UV-curable resin is a thiol-olefin formulation comprising PETMP and TTT.

[0226] In some embodiments, the UV-curable resin further comprises a photoinitiator. The photoinitiator initiates a 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.

[0227] In some embodiments, the photoinitiator is a vinyl acrylate-based resin. In some embodiments, the photoinitiator is MINS-311RM (Minuta Technology Co., Ltd, Korea).

[0228] In some implementations, the photoinitiator is 127. 184. 184D 2022 2100 250 270. 2959 369、 369EG 379、 500 651, 754 784、 819、 819Dw 907 907FF Oxe01、 TPO-L, 1173, 1173D, 4265、 BP, or MBF (BASF Corporation, Wyandotte, MI). In some embodiments, the photoinitiator is TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) or MBF (methyl benzoylformate).

[0229] In some embodiments, the weight percentage of the at least one organic resin in the nanostructure composition is about 5% to about 99%, about 5% to about 95%, about 5% to about 90%, about 5% to about 80%, about 5% to about 70%, about 5% to about 60%, about 5% to about 50%, about 5% to about 40%, about 5% to about 30%, about 5% to about 20%, about 5% to about 10%, about 10% to about 99%, about 10% to about 95%, about 10% to about 90%, about 10% to about 8%. 0%, about 10% to about 70%, about 10% to about 60%, about 10% to about 50%, about 10% to about 40%, about 10% to about 30%, about 10% to about 20%, about 20% to about 99%, about 20% to about 95%, about 20% to about 90%, about 20% to about 80%, about 20% to about 70%, about 20% to about 60%, about 20% to about 50%, about 20% to about 40%, about 20% to about 30%, about 30% to about 99%, about 30% to about 95% %, about 30% to about 90%, about 30% to about 80%, about 30% to about 70%, about 30% to about 60%, about 30% to about 50%, about 30% to about 40%, about 40% to about 99%, about 40% to about 95%, about 40% to about 90%, about 40% to about 80%, about 40% to about 70%, about 40% to about 60%, about 40% to about 50%, about 50% to about 99%, about 50% to about 95%, about 50% to about 90%, about 50% to about 80% Approximately 50% to approximately 70%, approximately 50% to approximately 60%, approximately 60% to approximately 99%, approximately 60% to approximately 95%, approximately 60% to approximately 90%, approximately 60% to approximately 80%, approximately 60% to approximately 70%, approximately 70% to approximately 99%, approximately 70% to approximately 95%, approximately 70% to approximately 90%, approximately 70% to approximately 80%, approximately 80% to approximately 99%, approximately 80% to approximately 95%, approximately 90% to approximately 99%, or approximately 95% to approximately 99%.

[0230] Method for preparing AIGS nanostructure compositions

[0231] This disclosure provides a method for preparing nanostructure compositions, the method comprising:

[0232] (a) providing at least one group of AIGS nanostructures; and

[0233] (b) Blend at least one organic resin with the composition of (a).

[0234] In some embodiments, the nanostructure has a pulsed wave volume (PWL) between 480-545 nm, and at least about 80% of the emission is band-edge emission. In some embodiments, at least 80% of the emission is band-edge emission. In other embodiments, at least 90% of the emission is band-edge emission. In other embodiments, at least 95% of the emission is band-edge emission. In some embodiments, 92-98% of the emission is band-edge emission. In some embodiments, 93-96% of the emission is band-edge emission.

[0235] This disclosure also provides a method for preparing nanostructure compositions, the method comprising:

[0236] (a) Providing at least one group of AIGS nanostructures, and one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof; and wherein the nanostructures are prepared using a GaX3 (X = F, Cl, or Br) precursor and an oxygen-free ligand; and

[0237] (b) Blend at least one organic resin with the composition of (a).

[0238] In some embodiments, the nanostructure has a pulse wave length (PWL) between 480 and 545 nm, and at least about 60% of the emission is band-edge emission.

[0239] This disclosure also provides a method for preparing nanostructure compositions, the method comprising:

[0240] (a) Providing at least one group of AIGS nanostructures, wherein the nanostructures have 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 nanostructures exhibit 80-99% QY; and

[0241] (b) Blend at least one organic resin with the composition of (a).

[0242] In some embodiments, the at least one group of nanostructures is blended with at least one organic resin at the following stirring rates: about 100 rpm to about 10,000 rpm, about 100 rpm to about 5,000 rpm, about 100 rpm to about 3,000 rpm, about 100 rpm to about 1,000 rpm, about 100 rpm to about 500 rpm, about 500 rpm to about 10,000 rpm, about 500 rpm to about 5,000 rpm, about 500 rpm to about 3,000 rpm, about 500 rpm to about 1,000 rpm, about 1,000 rpm to about 10,000 rpm, about 1,000 rpm to about 5,000 rpm, about 1,000 rpm to about 3,000 rpm, about 3,000 rpm to about 10,000 rpm, or about 5,000 rpm to about 10,000 rpm.

[0243] In some embodiments, the at least one group of nanostructures is mixed with at least one organic resin for the following durations: about 10 minutes to about 24 hours, about 10 minutes to about 20 hours, about 10 minutes to about 15 hours, about 10 minutes to about 10 hours, about 10 minutes to about 5 hours, about 10 minutes to about 1 hour, about 10 minutes to about 30 minutes, about 30 minutes to about 24 hours, about 30 minutes to about 20 hours, about 30 minutes to about 15 hours, about 30 minutes to about 10 hours, about 30 minutes to about 5 hours, about 30 minutes to about 1 hour, about 1 hour to about 24 hours, about 1 hour to about 20 hours, about 1 hour to about 15 hours, about 1 hour to about 10 hours, about 1 hour to about 5 hours, about 5 hours to about 24 hours, about 5 hours to about 20 hours, about 5 hours to about 15 hours, about 5 hours to about 10 hours, about 10 hours to about 24 hours, about 10 hours to about 20 hours, about 10 hours to about 15 hours, about 15 hours to about 24 hours, about 15 hours to about 20 hours, or about 20 hours to about 24 hours.

[0244] In some embodiments, the at least one group of nanostructures is blended with at least one organic resin at temperatures ranging from about -5°C to about 100°C, from about -5°C to about 75°C, from about -5°C to about 50°C, from about -5°C to about 23°C, from about 23°C to about 100°C, from about 23°C to about 75°C, from about 23°C to about 50°C, from about 50°C to about 100°C, from about 50°C to about 75°C, or from about 75°C to about 100°C. In some embodiments, at least one organic resin is blended with the at least one group of nanostructures at a temperature between about 23°C and about 50°C.

[0245] In some embodiments, if more than one organic resin is used, the organic resins are added together and blended. In some embodiments, the first organic resin and the second organic resin are mixed at the following stirring rates: about 100 rpm to about 10,000 rpm, about 100 rpm to about 5,000 rpm, about 100 rpm to about 3,000 rpm, about 100 rpm to about 1,000 rpm, about 100 rpm to about 500 rpm, about 500 rpm to about 10,000 rpm, about 500 rpm to about 5,000 rpm, about 500 rpm to about 3,000 rpm, about 500 rpm to about 1,000 rpm, about 1,000 rpm to about 10,000 rpm, about 1,000 rpm to about 5,000 rpm, about 1,000 rpm to about 3,000 rpm, about 3,000 rpm to about 10,000 rpm, or about 5,000 rpm to about 10,000 rpm.

[0246] In some embodiments, the first organic resin and the second organic resin are mixed for the following durations: about 10 minutes to about 24 hours, about 10 minutes to about 20 hours, about 10 minutes to about 15 hours, about 10 minutes to about 10 hours, about 10 minutes to about 5 hours, about 10 minutes to about 1 hour, about 10 minutes to about 30 minutes, about 30 minutes to about 24 hours, about 30 minutes to about 20 hours, about 30 minutes to about 15 hours, about 30 minutes to about 10 hours, about 30 minutes to about 5 hours, about 30 minutes. From about 1 hour, from about 1 hour to about 24 hours, from about 1 hour to about 20 hours, from about 1 hour to about 15 hours, from about 1 hour to about 10 hours, from about 1 hour to about 5 hours, from about 5 hours to about 24 hours, from about 5 hours to about 20 hours, from about 5 hours to about 15 hours, from about 5 hours to about 10 hours, from about 10 hours to about 24 hours, from about 10 hours to about 20 hours, from about 10 hours to about 15 hours, from about 15 hours to about 24 hours, from about 15 hours to about 20 hours, or from about 20 hours to about 24 hours.

[0247] Properties of AIGS Nanostructures

[0248] In some embodiments, the AIGS nanostructures exhibit high photoluminescence quantum yields. In some embodiments, the nanostructures exhibit photoluminescence quantum yields as follows: about 50% to about 99%, about 50% to about 95%, about 50% to about 90%, about 50% to about 85%, about 50% to about 80%, about 50% to about 70%, about 50% to about 60%, 60% to about 99%, about 60% to about 95%, about 60% to about 90%, about 60% to about 85%, about 60% to about 80%, about 60% to about 70%, about 70% to about 99%, about 70% to about 95%, about 70% to about 90%, about 70% to about 85%, about 70% to about 80%, about 80% to about 99%, about 80% to about 95%, about 80% to about 90%, about 80% to about 85%, about 85% to about 99%, about 85% to about 95%, about 80% to about 85%, about 85% to about 99%, about 85% to about 90%, about 90% to about 99%, or about 95% to about 99%. In some embodiments, the nanostructures exhibit photoluminescence quantum yields of about 82% to about 96%, about 85% to about 96%, and about 93% to about 94%.

[0249] The photoluminescence spectrum of the nanostructure can cover a broad desired portion of the spectrum. In some embodiments, the photoluminescence spectrum of the nanostructure has emission maximum values ​​of 300 nm to 750 nm, 300 nm to 650 nm, 300 nm to 550 nm, 300 nm to 450 nm, 450 nm to 750 nm, 450 nm to 650 nm, 450 nm to 550 nm, 450 nm to 750 nm, 450 nm to 650 nm, 450 nm to 550 nm, 550 nm to 750 nm, 550 nm to 650 nm, or 650 nm to 750 nm. In some embodiments, the photoluminescence spectrum of the nanostructure has an emission maximum value of 450 nm to 550 nm.

[0250] The size distribution of the nanostructures can be relatively narrow. In some embodiments, the photoluminescence spectrum of the nanostructure group can have the following full width at half maximum (FWHM): 10 nm to 60 nm, 10 nm to 40 nm, 10 nm to 30 nm, 10 nm to 20 nm, 20 nm to 60 nm, 20 nm to 40 nm, 20 nm to 30 nm, 25 nm to 60 nm, 25 nm to 40 nm, 25 nm to 30 nm, 30 nm to 60 nm, 30 nm to 40 nm, or 40 nm to 60 nm. In some embodiments, the photoluminescence spectrum of the nanostructure group can have a FWHM of 24 nm to 50 nm, 24-28 nm, 27-32 nm, or 29-38 nm.

[0251] In some embodiments, the nanostructure emits light with a peak emission wavelength (PWL) of approximately 400 nm to approximately 650 nm, approximately 400 nm to approximately 600 nm, approximately 400 nm to approximately 550 nm, approximately 400 nm to approximately 500 nm, approximately 400 nm to approximately 450 nm, approximately 450 nm to approximately 650 nm, approximately 450 nm to approximately 600 nm, approximately 450 nm to approximately 550 nm, approximately 450 nm to approximately 500 nm, approximately 500 nm to approximately 650 nm, approximately 500 nm to approximately 600 nm, approximately 500 nm to approximately 550 nm, approximately 550 nm to approximately 650 nm, approximately 550 nm to approximately 600 nm, or approximately 600 nm to approximately 650 nm. In some embodiments, the nanostructure emits light with a PWL of approximately 500 nm to approximately 550 nm.

[0252] As a predictor of blue light absorption efficiency, the optical density per unit mass (OD) at 450 nm can be calculated by measuring the optical density of the nanostructured solution in a cuvette with a path length of 1 cm and dividing it by the dry mass per mL of the same solution after all volatiles have been removed under vacuum (<200 mTorr). 450 / mass). In some embodiments, the nanostructure has the following optical density (OD) per unit mass at 450 nm. 450 / weight): about 0.28 / mg to about 0.5 / mg, about 0.28 / mg to about 0.4 / mg, about 0.28 / mg to about 0.35 / mg, about 0.28 / mg to about 0.32 / mg, about 0.32 / mg to about 0.5 / mg, about 0.32 / mg to about 0.4 / mg, about 0.32 / mg to about 0.35 / mg, about 0.35 / mg to about 0.5 / mg, about 0.35 / mg to about 0.4 / mg, or about 0.4 / mg to about 0.5 / mg.

[0253] membrane

[0254] The nanostructures of the present invention can be embedded in a polymer matrix using any suitable method. As used herein, the term "embedded" indicates that the group of nanostructures is enclosed or encased by the polymer constituting the majority of the matrix component. In some embodiments, the at least one group of nanostructures is suitably uniformly distributed throughout the matrix. In some embodiments, the at least one group of nanostructures is distributed according to the specific application. In some embodiments, the nanostructures are mixed in a polymer and applied to the surface of a substrate.

[0255] In some embodiments, this disclosure provides a nanostructured film layer comprising:

[0256] (a) A composition comprising at least one group of AIGS nanostructures, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof; and at least one ligand bonded to the nanostructure; and

[0257] (b) At least one organic resin.

[0258] In some embodiments, a portion of the ligand is bonded to the nanostructure. In other embodiments, the surface of the nanostructure is saturated with the ligand.

[0259] In some embodiments, the nanostructure has a PWL between 480 and 545 nm.

[0260] This disclosure also provides a method for preparing nanostructured films, the method comprising:

[0261] (a) Providing at least one group of AIGS nanostructures, and one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, one or more metal halide hydrolysis products, one or more organometallic compounds, or one or more organometallic hydrolysis products, or combinations thereof; and

[0262] (b) Blend at least one organic resin with the composition of (a).

[0263] In some implementations, the nanostructure has a PWL between 480-545 nm.

[0264] 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 other embodiments, at least 95% of the transmissions are edge-triggered transmissions. In some embodiments, 92-98% of the transmissions are edge-triggered transmissions. In some embodiments, 93-96% of the transmissions are edge-triggered transmissions.

[0265] Ligands and additives

[0266] In some embodiments, the nanostructure composition further comprises an amino ligand having Formula I:

[0267]

[0268] in:

[0269] x is between 1 and 100;

[0270] y is between 0 and 100; and

[0271] R2 C 1-20 alkyl.

[0272] 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.

[0273] In some implementations, R 2 C 1-20 Alkyl group. In some embodiments, R 2 C 1-10 Alkyl group. In some embodiments, R 2 C 1-5 Alkyl group. In some embodiments, R 2 It is -CH2CH3.

[0274] In some embodiments, the compound of formula I is a commercially available amine-terminated polymer (obtained from Huntsman Petrochemical Corporation). In some embodiments, the amine-terminated polymer of formula (VI) has x = 1, y = 9, and R 2 =-CH3, and is JEFFAMINE M-600 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-600 has a molecular weight of about 600. In some embodiments, the amine-terminated polymer of formula (III) has x=19, y=3, and R 2 =-CH3, and is JEFFAMINE M-1000 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-1000 has a molecular weight of about 1,000. In some embodiments, the amine-terminated polymer of formula (III) has x=6, y=29, and R 2 =-CH3, and is JEFFAMINE M-2005 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-2005 has a molecular weight of about 2,000. In some embodiments, the amine-terminated polymer of formula (III) has x = 31, y = 10, and R 2=-CH3, and is JEFFAMINE M-2070 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-2070 has a molecular weight of about 2,000. In another embodiment, the ligand is a polyethylene glycol amine (obtained from CreativePEGWorks), such as PEG550-amine and PEG350-amine.

[0275] In some embodiments, the ligand is a sterically hindered phenol having Formula II:

[0276]

[0277] Where R 3 and R 4 R3 is a C3-6 secondary or tertiary alkyl group, and R5 is hydrogen or an optionally substituted C1-6 alkyl group. In some embodiments, R3 and R4 are isopropyl, 2-butyl, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, tert-butyl, 2-methyl-2-pentyl, or 3-methyl-3-pentyl. In some embodiments, R... 5 It is in position 3 or 4 of formula II.

[0278] R 5 C 1-6 Optional substituents on the alkyl group include nitro, haloalkoxy, aryloxy, arylalkoxy, alkylthio, sulfonylamino, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, ureyl, guanidinyl, carbamate, carboxyl, alkoxycarbonyl, carboxylalkyl, or -C(=O)R 7 , where R 7 It is an alkoxy group that can be further substituted with one or more other alkoxy groups. In some embodiments, R 7 It has the following formula:

[0279] CH P (CH2-O-) 4-P

[0280] Where p is 0-3, and the oxygen atom is bonded to the carbonyl group of formula II. In some embodiments, R 7 for:

[0281]

[0282] In some implementations, R 7 for:

[0283]

[0284] And Equation II is:

[0285]

[0286] Where R 7 The oxygen atom is bonded to the carbonyl group of formula II at the position indicated by *.

[0287] In some embodiments, the compound of formula II is pentaerythritol tetra[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].

[0288] Ligands of Formula II bond to nanostructures and also act as antioxidants in nanostructure compositions such as inks and films. Furthermore, due to the steric hindrance of the ligands, the free volume on the surface of the nanostructures is reduced, thereby reducing or preventing oxidation by ambient oxygen and improving air stability.

[0289] In some implementations, the nanostructure film is a color conversion layer.

[0290] The nanostructure composition can be deposited by any suitable method known in the art, including but not limited to coating, spraying, solvent spraying, wet coating, adhesive coating, spin coating, tape coating, roll coating, flow coating, ink vapor jetting, drop casting, doctor blade coating, fog 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 processes, 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 a desired layer of a substrate. Alternatively, the nanostructure composition can be formed as a solid layer as an independent element and subsequently applied to a substrate. In some embodiments, the nanostructure composition can be deposited onto one or more barrier layers.

[0291] Metal alkoxides

[0292] Metal alkoxides have the general formula M(OR). x Where R is a straight-chain, branched, or cyclic alkyl group typically containing 1 to 10 carbon atoms, and x is the valence of the metal. In some embodiments, the metal alkoxide includes metal methanol, metal ethanol, metal-n-propanol, metal isopropanol, metal-n-butanol, metal isobutanol, metal-n-pentanol, metal isopentanol, metal-n-hexanol, metal isohexanol, metal-n-heptanol, metal isoheptanol, metal-n-octanol, metal-n-isooctanol, metal-n-nonanol, metal-n-isonononol, metal-n-decanool, and metal-n-isodecanool.

[0293] In some embodiments, the metal alkoxide comprises one or more of the following: lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lutetium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, 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, gadolinium, gallium, germanium, hafnium, indium, iron, lanthanum, lithium, magnesium, molybdenum, neodymium, phosphorus, silicon, sodium, strontium, tantalum, thallium, tin, titanium, tungsten, vanadium, yttrium, zinc, and zirconium.

[0294] In some embodiments, the metal alkoxide comprises one or more Group 4 metals, including titanium, zirconium, and hafnium.

[0295] In some embodiments, the metal alkoxide is at least one zirconium alkoxide, including zirconium tetramethylene (IV), zirconium tetraethanolamine (IV), zirconium tetra-n-propoxide (IV), zirconium tetraisopropoxide (IV), zirconium tetra-n-butoxide (IV), zirconium tetraisobutoxide (IV), zirconium tetra-n-pentoxide (IV), zirconium tetraisopentoxide (IV), zirconium tetra-n-hexanool (IV), zirconium tetraisohexanool (IV), zirconium tetra-n-heptanol (IV), zirconium tetraisoheptanol (IV), zirconium tetra-n-octanol (IV), zirconium tetra-n-isooctanol (IV), zirconium tetra-n-nonoxide (IV), zirconium tetra-n-isononoxide (IV), zirconium tetra-n-decanool (IV), and zirconium tetra-n-isodecanool (IV).

[0296] In some embodiments, metal alkoxides can form a sol-gel around the AIGS nanostructure, thereby 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.

[0297] In some embodiments, the metal alkoxide is present in the AIGS membrane composition at a concentration of at least 0.005% by weight (50 ppm). In some embodiments, the metal oxide is present in the AIGS membrane composition in an amount of about 0.03% to about 3% by weight. In some embodiments, the metal oxide is present in the membrane composition in amounts 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 2.6%, about 2.7%, about 2.8%, about 2.9%, or about 3% by weight.

[0298] Metal alkoxide hydrolysis products

[0299] The hydrolysis products of metal alkoxides have the general formula M(OH). x (OR) yIn this system, R is typically a straight-chain, branched, or cyclic alkyl group containing 1 to 10 carbon atoms, and x + y equals the valence of the metal. Metal alkoxide hydrolysis products include zirconium trioxide(IV) monohydroxide, zirconium dioxide(IV) dihydroxide, zirconium trioxide(IV) trihydroxide, zirconium tetrahydroxide(IV) monohydroxide, zirconium triethanoloxide(IV) dihydroxide, zirconium triethanoloxide(IV) tri-n-propoxide(IV) monohydroxide, zirconium dioxide(IV) dihydroxide, zirconium trioxide(IV) tri-n-propoxide(IV) trihydroxide, zirconium triisopropoxide(IV) monohydroxide, zirconium diisopropoxide(IV) dihydroxide, zirconium triisopropoxide(IV) trihydroxide, zirconium trioxide(IV) monohydroxide, zirconium trioxide(IV) monohydroxide, zirconium trioxide(IV) dihydroxide, zirconium dioxide(IV) dihydroxide, zirconium trioxide(IV) tri-n-butoxide(IV) monohydroxide, zirconium dioxide(IV) dihydroxide, zirconium trioxide(IV) tri-n-butoxide(IV) monohydroxide, zirconium tri ... Zirconium triisobutylate (IV), Zirconium diisobutylate (IV), Zirconium triisobutylate (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium dioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium dioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV), Zirconium trioxide (IV) Zirconium di-n-heptanol dihydroxy (IV), Zirconium mono-n-heptanol trihydroxy (IV), Zirconium triisoheptanol monohydroxy (IV), Zirconium di-isoheptanol dihydroxy (IV), Zirconium monoisoheptanol trihydroxy (IV), Zirconium tri-n-octanol monohydroxy (IV), Zirconium di-n-octanol dihydroxy (IV), Zirconium tri-n-octanol trihydroxy (IV), Zirconium tri-n-isooctanol monohydroxy (IV), Zirconium tri-n-isooctanol dihydroxy (IV), Zirconium tri-n-isooctanol trihydroxy (IV), Zirconium tri-n-nonyl alcohol monohydroxy (IV), Zirconium di-n-nonyl alcohol dihydroxy (IV), Zirconium tri-n-nonyl alcohol monohydroxy (IV), Zirconium tri-n-isononyl alcohol monohydroxy (IV) Zirconium di-n-isononyl alcohol (IV), Zirconium tri-n-isononyl alcohol (IV), Zirconium tri-n-decyl alcohol (IV), Zirconium di-n-decyl alcohol (IV), Zirconium tri-n-decyl alcohol (IV), Zirconium tri-n-isodecyl alcohol (IV), Zirconium tri-n-isodecyl alcohol (IV), Zirconium di-n-isodecyl alcohol (IV), Zirconium tri-n-isodecyl alcohol (IV), Titanium trioxide (IV), Titanium dioxide (IV), Titanium trioxide (IV), Titanium tetraoxide (IV), Titanium triethanolamine (IV), Titanium dioxide (IV), Titanium triethanolamine (IV), Titanium triethanolamine (IV), Titanium trioxide (IV), Titanium trioxide (IV), Titanium trioxide (IV), Titanium tri-n-propoxide (IV)Titanium di-n-propoxide dihydrogen phosphate (IV), titanium mono-n-propoxide trihydrogen phosphate (IV), titanium mono-isopropoxide trihydrogen phosphate (IV), titanium di-isopropoxide dihydrogen phosphate (IV), titanium mono-isopropoxide trihydrogen phosphate (IV), titanium mono-n-butanol trihydrogen phosphate (IV), titanium di-n-butanol dihydrogen phosphate (IV), titanium mono-n-butanol trihydrogen phosphate (IV), titanium mono-isobutanol trihydrogen phosphate (IV), titanium di-isobutanol dihydrogen phosphate (IV), titanium mono-isobutanol trihydrogen phosphate (IV), titanium mono-n-pentanol trihydrogen phosphate (IV), titanium mono-isopentanol trihydrogen phosphate (IV), titanium mono-isopentanol trihydrogen phosphate (IV), titanium di-isopentanol dihydrogen phosphate (IV), titanium mono-isopentanol trihydrogen phosphate (I) V), titanium tri-n-hexanol monohydric hydroxide (IV), titanium di-n-hexanol dihydric hydroxide (IV), titanium tri-n-hexanol trihydric hydroxide (IV), titanium triisohexanol monohydric hydroxide (IV), titanium diisohexanol dihydric hydroxide (IV), titanium triisohexanol trihydric hydroxide (IV), titanium triisohexanol monohydric hydroxide (IV), titanium di-n-hexanol dihydric hydroxide (IV), titanium triisohexanol trihydric hydroxide (IV), titanium triisohexanol mono ... Titanium di-n-isooctanol hydroxide (IV), titanium tri-n-isooctanol hydroxide (IV), titanium tri-n-nonyl alcohol hydroxide (IV), titanium di-n-nonyl alcohol hydroxide (IV), titanium tri-n-nonyl alcohol hydroxide (IV), titanium tri-n-isononyl alcohol hydroxide (IV), titanium di-n-isononyl alcohol hydroxide (IV), titanium tri-n-isononyl alcohol hydroxide (IV), titanium tri-n-isononyl alcohol hydroxide (IV), titanium tri-n-decyl alcohol hydroxide (IV), titanium di-n-decyl alcohol hydroxide (IV), titanium tri-n-isodecanol hydroxide (IV), titanium tri-n-isodecanol hydroxide (IV), titanium tri-n-isodecanol hydroxide (IV), titanium di-n-isodecanol hydroxide (IV), titanium trimethylol(IV), hafnium(IV) hydroxide (IV), titanium di-n-isodecanol hydroxide (IV), titanium tri-n-isodecanol hydroxide (IV), titanium trimethylol(IV), titanium trioxide (IV), titanium di-n-isodecanol hydroxide (IV) Hafnium methanol (IV), hafnium trihydride (IV), hafnium tetrahydride (IV), hafnium monohydric triethanolol (IV), hafnium dihydric diethanolol (IV), hafnium trihydride (IV), hafnium monohydric tri-n-propanol (IV), hafnium dihydric di-n-propanol (IV), hafnium trihydride (IV), hafnium monoisopropanol (IV), hafnium dihydric diisopropanol (IV), hafnium trihydride (IV), hafnium monoisopropanol (IV), hafnium monohydric tri-n-butanol (IV), hafnium dihydric di-n-butanol (IV), hafnium trihydride (IV), hafnium monoisobutanol (IV), hafnium dihydric diisobutanol (IV), hafnium trihydride (IV)Hafnium tri-n-pentanol monohydric hydroxide (IV), Hafnium di-n-pentanol dihydric hydroxide (IV), Hafnium tri-n-pentanol monohydric hydroxide (IV), Hafnium tri-isopentanol monohydric hydroxide (IV), Hafnium di-isopentanol dihydric hydroxide (IV), Hafnium tri-isopentanol monohydric hydroxide (IV), Hafnium tri-n-hexanol monohydric hydroxide (IV), Hafnium di-n-hexanol dihydric hydroxide (IV), Hafnium tri-n-hexanol monohydric hydroxide (IV), Hafnium tri-n-hexanol monohydric hydroxide (IV), Hafnium tri-n-hexanol monohydric hydroxide (IV), Hafnium tri-n-hexanol monohydric hydroxide Hafnium triisohexanol (IV), Hafnium diisohexanol dihydroxyl (IV), Hafnium monoisohexanol trihydroxyl (IV), Hafnium tri-n-heptanol monohydroxyl (IV), Hafnium diisoheptanol dihydroxyl (IV), Hafnium mono-n-heptanol trihydroxyl (IV), Hafnium monoisoheptanol monohydroxyl (IV), Hafnium diisoheptanol dihydroxyl (IV), Hafnium monoisoheptanol trihydroxyl (IV), Hafnium mono-n-octanol monohydroxyl (IV) Hafnium dihydrogen bis(n-octanol) (IV), Hafnium trihydrogen mono(n-octanol) (IV), Hafnium mono(n-isooctanol) (IV), Hafnium dihydrogen bis(n-isooctanol) (IV), Hafnium trihydrogen mono(n-isooctanol) (IV), Hafnium mono(n-nonanol) (IV), Hafnium dihydrogen bis(n-nonanol) (IV), Hafnium trihydrogen mono(n-nonanol) (IV), Hafnium mono(n-isooctanol) (IV), Hafnium mono(n-isooctanol) (IV) Hafnium nonyl alcohol (IV), hafnium di-n-isononyl alcohol (IV) dihydroxyl, hafnium tri-n-isononyl alcohol (IV) trihydroxyl, hafnium tri-n-decyl alcohol (IV) dihydroxyl, hafnium tri-n-decyl alcohol (IV) trihydroxyl, hafnium tri-n-isodecyl alcohol (IV) trihydroxyl, hafnium di-n-isodecyl alcohol (IV) dihydroxyl, and hafnium tri-n-isodecyl alcohol (IV) trihydroxyl.

[0300] In some embodiments, the metal alkoxide hydrolysis product is present in the AIGS membrane composition at a concentration of at least 0.005% by weight (50 ppm). In some embodiments, the metal oxide hydrolysis product is present in the AIGS membrane composition at an amount of about 0.03% to about 3% by weight. In some embodiments, the metal oxide hydrolysis product is present in the membrane composition in amounts 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 2.6, about 2.7, about 2.8, about 2.9, or about 3% by weight.

[0301] metal halides

[0302] Metal halides have the general formula MX y, where y is the valence 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).

[0303] In some embodiments, the metal halide is present in the AIGS membrane composition at a concentration of at least 0.005% by weight (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% by weight. In some embodiments, the metal halide is present in the membrane composition in amounts 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 2.6, about 2.7, about 2.8, about 2.9, or about 3% by weight.

[0304] Metal halide hydrolysis products

[0305] Metal halide hydrolysis products have the general formula MX y (OH) xWhere x + y equals the valence of the metal. Hydrolysis products of metal halides include zirconium trichloride monohydric hydroxide (IV), zirconium difluoride dihydric hydroxide (IV), zirconium monofluoride trihydric hydroxide (IV), zirconium tetrahydric hydroxide (IV), titanium trifluoride monohydric hydroxide (IV), titanium difluoride dihydric hydroxide (IV), titanium monofluoride trihydric hydroxide (IV), titanium tetrahydric hydroxide (IV), titanium trifluoride monohydric hydroxide (IV), titanium difluoride dihydric hydroxide (IV), titanium monofluoride trihydric hydroxide (IV), titanium tetrahydric hydroxide (IV), hafnium trifluoride monohydric hydroxide (IV), hafnium difluoride dihydric hydroxide (IV), hafnium monofluoride trihydric hydroxide (IV), and tetrahydrogen... Hafnium oxide (IV), zirconium trichloride monohydric hydroxide (IV), zirconium dichloride dihydric hydroxide (IV), zirconium trichloride monohydric hydroxide (IV), zirconium tetrahydric hydroxide (IV), titanium trichloride monohydric hydroxide (IV), titanium dichloride dihydric hydroxide (IV), titanium trichloride monohydric hydroxide (IV), titanium tetrahydric hydroxide (IV), titanium trichloride monohydric hydroxide (IV), titanium dichloride dihydric hydroxide (IV), titanium trichloride monohydric hydroxide (IV), titanium tetrahydric hydroxide (IV), hafnium trichloride monohydric hydroxide (IV), hafnium dichloride dihydric hydroxide (IV), hafnium trichloride monohydric hydroxide (IV), hafnium tetrahydric hydroxide (IV), Zirconium tribromide monohydric hydroxide (IV), Zirconium dibromide dihydric hydroxide (IV), Zirconium tribromide monohydric hydroxide (IV), Zirconium tetrahydric hydroxide (IV), Titanium tribromide monohydric hydroxide (IV), Titanium dibromide dihydric hydroxide (IV), Titanium tribromide monohydric hydroxide (IV), Titanium tetrahydric hydroxide (IV), Titanium tribromide monohydric hydroxide (IV), Titanium dibromide dihydric hydroxide (IV), Titanium tribromide monohydric hydroxide (IV), Hafnium tribromide monohydric hydroxide (IV), Hafnium dibromide dihydric hydroxide (IV), Hafnium tribromide monohydric hydroxide (IV), Hafnium tetrahydric hydroxide (IV) Zirconium triiodide monohydric hydroxide (IV), zirconium diiodide dihydric hydroxide (IV), zirconium triiodide monohydric hydroxide (IV), zirconium tetrahydric hydroxide (IV), titanium triiodide monohydric hydroxide (IV), titanium diiodide dihydric hydroxide (IV), titanium triiodide monohydric hydroxide (IV), titanium tetrahydric hydroxide (IV), titanium triiodide monohydric hydroxide (IV), titanium diiodide dihydric hydroxide (IV), titanium triiodide monohydric hydroxide (IV), titanium tetrahydric hydroxide (IV), hafnium triiodide monohydric hydroxide (IV), hafnium diiodide dihydric hydroxide (IV), hafnium triiodide monohydric hydroxide (IV), and hafnium tetrahydric hydroxide (IV).

[0306] In some embodiments, the metal halide hydrolysis product is present in the AIGS membrane composition at a concentration of at least 0.005% by weight (50 ppm). In some embodiments, the metal oxide is present in the AIGS membrane composition at a concentration of about 0.03% to about 3% by weight. In some embodiments, the metal halide hydrolysis product is present in the membrane composition in amounts 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 2.6, about 2.7, about 2.8, about 2.9, or about 3% by weight.

[0307] Organometallic compounds

[0308] Organometallic compounds contain metal-carbon bonds and can have the formula R x M, where R is typically a straight-chain, branched, or cyclic alkyl group containing 1 to 10 carbon atoms, and x is the valence 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-n-isooctylzirconium, tetra-n-nonylzirconium, tetra-n-isononylzirconium, tetra-n-decylzirconium, tetra-n-isodecylzirconium, tetramethyltitanium, tetraethyltitanium, tetra-n-propyltitanium, tetraisopropyltitanium, tetra-n-butyltitanium, tetraisobutyltitanium, tetra-n-pentyltitanium, tetraisopentyltitanium, tetra-n-hexyltitanium, tetraiso... Hexyl titanium, tetra-n-heptyl titanium, tetra-isoheptyl titanium, tetra-n-octyl titanium, tetra-n-isooctyl titanium, tetra-n-nonyl titanium, tetra-n-isononyl titanium, tetra-n-decyl titanium, tetra-n-isodecyl titanium, tetramethyl hafnium, tetraethyl hafnium, tetra-n-propyl hafnium, tetraisopropyl hafnium, tetra-n-butyl hafnium, tetraisobutyl hafnium, tetra-n-pentyl hafnium, tetraisopentyl hafnium, tetra-n-hexyl hafnium, tetraisohexyl hafnium, tetra-n-heptyl hafnium, tetraisoheptyl hafnium, tetra-n-octyl hafnium, tetra-n-isooctyl hafnium, tetra-n-nonyl hafnium, tetra-n-isononyl hafnium, tetra-n-decyl hafnium, and tetra-n-isodecyl hafnium.

[0309] In some embodiments, the organometallic compound is present in the AIGS membrane composition at a concentration of at least 0.005% by weight (50 ppm). In some embodiments, the organometallic compound is present in the AIGS membrane composition in an amount of about 0.03 to about 3% by weight. In some embodiments, the organometallic compound is present in the membrane composition in amounts 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 2.6, about 2.7, about 2.8, about 2.9, or about 3% by weight.

[0310] Organometallic hydrolysis compounds

[0311] Organometallic hydrolysis products may have R x M(OH) yIn this system, R is typically a straight-chain, branched, or cyclic alkyl group containing 1 to 10 carbon atoms, and x + y equals the valence of the metal. Organometallic hydrolysis products include trimethylzirconium monohydroxide, triethylzirconium monohydroxide, tri-n-propylzirconium monohydroxide, triisopropylzirconium monohydroxide, tri-n-butylzirconium monohydroxide, triisobutylzirconium monohydroxide, tri-n-pentylzirconium monohydroxide, triisopentylzirconium monohydroxide, tri-n-hexylzirconium monohydroxide, triisohexylzirconium monohydroxide, -n-n-heptylzirconium monohydroxide, triisoheptylzirconium monohydroxide, tri-n-octylzirconium monohydroxide, tri-n-isooctylzirconium monohydroxide, tri-n-nonylzirconium monohydroxide, tri-n-isononylzirconium monohydroxide, tri-n-decylzirconium monohydroxide, tri-n-isodecylzirconium monohydroxide, trimethyltitanium monohydroxide, triethyltitanium monohydroxide, and tri-n-... -Propyltitanium, Triisopropyltitanium Monohydric Hydroxide, Tri-n-Butyltitanium Monohydric Hydroxide, Tri-n-Pentyltitanium Monohydric Hydroxide, Tri-Isopentyltitanium Monohydric Hydroxide, Tri-n-Hexyltitanium Monohydric Hydroxide, Tri-n-Heptyltitanium Monohydric Hydroxide, Tri-Isoheptyltitanium Monohydric Hydroxide, Tri-n-Octyltitanium Monohydric Hydroxide, Tri-n-Isooctyltitanium Monohydric Hydroxide, Tri-n-Nonyltitanium Monohydric Hydroxide, Tri-n-Isononyltitanium Monohydric Hydroxide, Tri-n-Decyltitanium Monohydric Hydroxide, Tri-n-Isodecyltitanium Monohydric Hydroxide, Trimethylhafnium Monohydric Hydroxide, Triethylhafnium Monohydric Hydroxide, Tri-n-Propylhafnium Monohydric Hydroxide, Triisopropylhafnium Monohydric Hydroxide, Tri-n-Butylhafnium Monohydric Hydroxide, Triisobutylhafnium Monohydric Hydroxide Tri-n-pentyl hafnium hydroxide, Tri-isopentyl hafnium hydroxide, Tri-n-hexyl hafnium hydroxide, Tri-n-hexyl hafnium hydroxide, Tri-n-heptyl hafnium hydroxide, Tri-isoheptyl hafnium hydroxide, Tri-n-octyl hafnium hydroxide, Tri-n-isooctyl hafnium hydroxide, Tri-n-nonyl hafnium hydroxide, Tri-n-isononyl hafnium hydroxide, Tri-n-decyl hafnium hydroxide, Tri-n-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, Di-n-hexyl hafnium hydroxide Zirconium, diisohexylzirconium dihydroxy, di-n-heptylzirconium dihydroxy, diisoheptylzirconium dihydroxy, di-n-octylzirconium dihydroxy, di-n-isooctylzirconium dihydroxy, di-n-nonylzirconium dihydroxy, di-n-isononylzirconium dihydroxy, di-n-decylzirconium dihydroxy, di-n-isodecylzirconium dihydroxy, dimethyltitanium dihydroxy, diethyltitanium dihydroxy, di-n-propyltitanium dihydroxy, diisopropyltitanium dihydroxy, di-n-butyltitanium dihydroxy, diisobutyltitanium dihydroxy, di-n-pentyltitanium dihydroxy, diisopentyltitanium dihydroxy, di-n-hexyltitanium dihydroxy, diisohexyltitanium dihydroxy, di-n-heptyltitanium dihydroxy, diisoheptyltitanium dihydroxyDi-n-octyl titanium dihydrogen phosphate, Di-n-isooctyl titanium dihydrogen phosphate, Di-n-nonyl titanium dihydrogen phosphate, Di-n-isononyl titanium dihydrogen phosphate, Di-n-decyl titanium dihydrogen phosphate, Di-n-isodecyl titanium dihydrogen phosphate, Dimethyl hafnium dihydrogen phosphate, Diethyl hafnium dihydrogen phosphate, Di-n-propyl hafnium dihydrogen phosphate, Diisopropyl hafnium dihydrogen phosphate, Di-n-butyl hafnium dihydrogen phosphate, Diisobutyl hafnium dihydrogen phosphate, Di-n-pentyl hafnium dihydrogen phosphate, Diisopentyl hafnium dihydrogen phosphate, Di-n-hexyl hafnium dihydrogen phosphate, Di-n-heptyl hafnium dihydrogen phosphate, Di-n-octyl hafnium dihydrogen phosphate, Di-n-isooctyl hafnium dihydrogen phosphate Hafnium, di-n-nonylhafnium dihydrogen , di-n-isononylhafnium dihydrogen , di-n-decylhafnium dihydrogen , di-n-isodecylhafnium dihydrogen , monomethylzirconium trihydrogen , monoethylzirconium trihydrogen , mono-n-propylzirconium trihydrogen , monoisopropylzirconium trihydrogen , mono-n-butylzirconium trihydrogen , monoisobutylzirconium trihydrogen , mono-n-pentylzirconium trihydrogen , monoisopentylzirconium trihydrogen , mono-n-hexylzirconium trihydrogen , mono-n-heptylzirconium trihydrogen , monoisoheptylzirconium trihydrogen , mono-n-octylzirconium trihydrogen , mono-n-nonylzirconium trihydrogen , mono-n-isononylzirconium trihydrogen , mono-n-isononylzirconium trihydrogen , Zirconium trioxide, mono-n-decyl zirconium trioxide, mono-n-isodecyl zirconium trioxide, monomethyl titanium trioxide, monoethyl 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-n-isooctyl titanium trioxide, mono-n-nonyl titanium trioxide, mono-n-isononyl titanium trioxide, mono-n-decyl titanium trioxide, mono-n-iso Decyl titanium, monomethyl hafnium trihydride, monoethyl hafnium trihydride, mono-n-propyl hafnium trihydride, monoisopropyl hafnium trihydride, mono-n-butyl hafnium trihydride, monoisobutyl hafnium trihydride, mono-n-pentyl hafnium trihydride, monoisopentyl hafnium trihydride, mono-n-hexyl hafnium trihydride, mono-n-heptyl hafnium trihydride, mono-n-isoheptyl hafnium trihydride, mono-n-octyl hafnium trihydride, mono-n-nonyl hafnium trihydride, mono-n-isononyl hafnium trihydride, mono-n-decyl hafnium trihydride, mono-n-isodecyl hafnium trihydride, zirconium tetrahydroxide, titanium tetrahydroxide, and hafnium tetrahydroxide.

[0312] In some embodiments, the organometallic hydrolysate is present in the AIGS membrane composition at a concentration of at least 0.005% by weight (50 ppm). In some embodiments, the organometallic hydrolysate is present in the AIGS membrane composition in an amount of about 0.03 to about 3% by weight. In some embodiments, the organometallic hydrolysate is present in the membrane composition in amounts 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 2.6, about 2.7, about 2.8, about 2.9, or about 3% by weight.

[0313] Methods for preparing hydrolyzed compounds

[0314] The hydrolyzed compound can be prepared by contacting it with water, an acidic solution, or an alkaline solution. In one embodiment, 10 μl of 1N NaOH aqueous solution is added to 4 ml of ethanol containing 1 g of zirconium propoxide. After stirring the reaction mixture at room temperature for 30 minutes, 10 μl of 1N HCl aqueous solution is added to neutralize the reaction mixture. After removing the volatiles by vacuum, the resulting viscous liquid is used as the hydrolysis product.

[0315] Spin coating

[0316] 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 a substrate mounted on a machine called a spin coater, which is held in place by a vacuum. The spin coater applies high-speed rotation to the substrate, causing a centripetal force that propels the material from the center to the edges of the substrate. Although most of the material is ejected, a certain amount remains on the substrate, forming a thin film on the surface as rotation continues. The final thickness of the film is determined by the properties of the deposited material and the substrate, as well as parameters selected for the spin coating process, such as spin coating speed, acceleration, and spin coating time. For typical films, spin coating speeds of 1500 to 6000 rpm are used, with spin coating times of 10–60 seconds. In some embodiments, the film is deposited at extremely low speeds (e.g., less than 1000 rpm). In some embodiments, the film is cast at approximately 300, 400, 500, 600, 700, 800, or 900 rpm.

[0317] Mist deposition

[0318] In some embodiments, mist deposition is used to deposit nanostructure compositions onto a substrate. Mist deposition is performed at room temperature and atmospheric pressure, allowing for precise control of film thickness by varying process conditions. During mist deposition, the liquid source material is atomized into a very fine mist and carried to the deposition chamber by nitrogen gas. The mist is then drawn onto the wafer surface by a high voltage potential between a field screen and a wafer holder. Once droplets have condensed on the wafer surface, the wafer is removed from the chamber and thermally cured to allow solvent evaporation. The liquid precursor is a mixture of solvent and 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).

[0319] Spraying

[0320] In some embodiments, spraying is used to deposit nanostructure compositions onto a substrate. Typical equipment for spraying includes a nozzle, an atomizer, a precursor solution, and a carrier gas. In a spray deposition process, the precursor solution is atomized into micron-sized droplets by means of a carrier gas or by atomization (e.g., ultrasonic, airflow impingement, or electrostatic). Droplets exiting the atomizer are accelerated from the substrate surface through the nozzle with the aid of a carrier gas, which can be controlled and adjusted as needed. The relative movement between the nozzle and the substrate is defined by design to completely cover the substrate.

[0321] In some embodiments, the application of the nanostructure composition further includes a solvent. In some embodiments, the solvent used for applying the nanostructure composition is water, an organic solvent, an inorganic solvent, a halogenated organic solvent, or a mixture thereof. Exemplary solvents include, but are not limited to, water, D2O, acetone, ethanol, dioxane, ethyl acetate, methyl ethyl ketone, isopropanol, anisole, γ-butyrolactone, dimethylformamide, N-methylpyrroledione, dimethylacetamide, hexamethylphosphoramide, toluene, dimethyl sulfoxide, cyclopentanone, tetramethylene sulfoxide, xylene, ε-caprolactone, tetrahydrofuran, tetrachloroethylene, chloroform, chlorobenzene, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, or a mixture thereof.

[0322] Inkjet printing

[0323] Solvents suitable for inkjet printing of nanostructures are known to those skilled in the art. In some embodiments, the organic solvent is a substituted aromatic or heteroaromatic solvent as described in U.S. Patent Application Publication No. 2018 / 0230321, which is incorporated herein by reference in its entirety.

[0324] In some embodiments, the organic solvents used in the nanostructure compositions for inkjet printing formulations are defined by their boiling point, viscosity, and surface tension. The properties of organic solvents suitable for inkjet printing formulations are shown in Table 1.

[0325] Table 1: Properties of organic solvents used in inkjet printing formulations

[0326] solvent Boiling point (°C) Viscosity (mPa·s) Surface tension (dynes / 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

[0327] In some embodiments, the organic solvent has a boiling point of about 150°C to about 350°C at 1 atmosphere. In some embodiments, the organic solvent has a boiling point of about 150°C to about 350°C, about 150°C to about 300°C, about 150°C to about 250°C, about 150°C to about 200°C, about 200°C to about 350°C, about 200°C to about 300°C, about 200°C to about 250°C, about 250°C to about 350°C, about 250°C to about 300°C, or about 300°C to about 350°C at 1 atmosphere.

[0328] In some embodiments, the organic solvent has a viscosity of about 1 mPa·s to about 15 mPa·s. In some embodiments, the organic solvent has the following viscosities: about 1 mPa·s to about 15 mPa·s, about 1 mPa·s to about 10 mPa·s, about 1 mPa·s to about 8 mPa·s, about 1 mPa·s to about 6 mPa·s, about 1 mPa·s to about 4 mPa·s, about 1 mPa·s to about 2 mPa·s, about 2 mPa·s to about 15 mPa·s, about 2 mPa·s to about 10 mPa·s, about 2 mPa·s to about 8 mPa·s, about 2 mPa·s to about 6 mPa·s. About 2 mPa·s to about 4 mPa·s, about 4 mPa·s to about 15 mPa·s, about 4 mPa·s to about 10 mPa·s, about 4 mPa·s to about 8 mPa·s, about 4 mPa·s to about 6 mPa·s, about 6 mPa·s to about 15 mPa·s, about 6 mPa·s to about 10 mPa·s, about 6 mPa·s to about 8 mPa·s, about 8 mPa·s to about 15 mPa·s, about 8 mPa·s to about 10 mPa·s, or about 10 mPa·s to about 15 mPa·s.

[0329] In some embodiments, the organic solvent has a surface tension of about 20 dynes / cm to about 50 dynes / cm. In some embodiments, the organic solvent has a surface tension of about 20 dynes / cm to about 50 dynes / cm, about 20 dynes / cm to about 40 dynes / cm, about 20 dynes / cm to about 35 dynes / cm, about 20 dynes / cm to about 30 dynes / cm, about 20 dynes / cm to about 25 dynes / cm, about 25 dynes / cm to about 50 dynes / cm, about 25 dynes / cm to about 40 dynes / cm, about 25 dynes / cm to about 35 dynes / cm, about 25 dynes / cm to about 30 dynes / cm, about 30 dynes / cm to about 50 dynes / cm, about 30 dynes / cm to about 40 dynes / cm, about 30 dynes / cm to about 35 dynes / cm, about 35 dynes / cm to about 50 dynes / cm, about 35 dynes / cm to about 40 dynes / cm, or about 40 dynes / cm to about 50 dynes / cm.

[0330] In some embodiments, the organic solvent used in the nanostructure composition is alkylnaphthalene, alkoxynaphthalene, alkylbenzene, aryl, alkyl-substituted benzene, cycloalkylbenzene, C9-C 20 Alkanes, diaryl ethers, alkyl benzoates, aryl benzoates, or alkoxy-substituted benzenes.

[0331] In some embodiments, the organic solvent used in the nanostructure composition is 1-naphthobenzene, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, n-octylbenzene, n-nonylbenzene, 4-methylanisole, n-decylbenzene, p-diisopropylbenzene, pentylbenzene, naphthobenzene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, dipentylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, diphenyl ether, diphenylmethane, 4-isopropylbiphenyl, benzyl benzoate, 1,2-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, or combinations 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.

[0332] In some embodiments, the organic solvent is an anhydrous organic solvent. In some embodiments, the organic solvent is substantially anhydrous organic solvent.

[0333] In some embodiments, the organic solvent is a combination of non-volatile monomers or monomers selected from the list presented above.

[0334] In some embodiments, the weight percentage of the organic solvent in the nanostructure composition is from about 70% to about 99%. In some embodiments, the weight percentage of the organic solvent in the nanostructure composition is from about 70% to about 99%, from about 70% to about 98%, from about 70% to about 95%, from about 70% to about 90%, from about 70% to about 85%, from about 70% to about 80%, from about 70% to about 75%, from about 75% to about 99%, from about 75% to about 98%, from about 75% to about 95%, from about 75% to about 90%, from about 75% to about 85%, from about 75% to about 99%. 80%, about 80% to about 99%, about 80% to about 98%, about 80% to about 95%, about 80% to about 90%, about 80% to about 85%, about 85% to about 99%, about 85% to about 98%, about 85% to about 95%, about 85% to about 90%, about 90% to about 99%, about 90% to about 98%, about 90% to about 95%, about 95% to about 99%, about 95% to about 98%, or about 98% to about 99%. In some embodiments, the weight percentage of the organic solvent in the nanostructure composition is about 95% to about 99%.

[0335] Film curing

[0336] In some embodiments, the nanostructure composition is thermally cured to form a nanostructure layer. In some embodiments, a UV-curable composition is used. In some embodiments, the nanostructure composition is directly coated onto a barrier layer of a nanostructure film, followed by the deposition of an additional barrier layer on the nanostructure layer to create the nanostructure film. To increase strength, stability, and coating uniformity, and to prevent material inconsistencies, bubble formation, and wrinkling or folding of the barrier layer material or other materials, a support substrate may be used beneath the barrier film. Additionally, one or more barrier layers may be deposited on the nanostructure layer to seal the material between the top and bottom barrier layers. Suitably, the barrier layer may be deposited as a laminate and optionally sealed or further processed before the nanostructure film is incorporated into a specific lighting device. Those skilled in the art will understand that the nanostructure composition deposition process may include additional or different components. Such embodiments will allow for in-line process tuning of nanostructure emission characteristics such as brightness and color (e.g., adjusting the quantum dot white point) as well as nanostructure film thickness and other characteristics. Furthermore, these implementations will allow for periodic testing of nanostructured membrane characteristics during production, as well as any desired toggling to achieve precise nanostructured membrane characteristics. Such testing and adjustments can also be performed without altering the mechanical configuration of the processing line, as computer programs can electronically change the respective amounts of the mixtures used to form the nanostructured membranes.

[0337] It has been found that nanostructured films with high PCE can be obtained when the films are processed without exposing the AIGS nanocrystals to blue or UV light before providing an oxygen-free environment for the nanostructures. The oxygen-free environment can be provided by:

[0338] (a) Encapsulate the film with an oxygen barrier layer before thermal processing and / or exposure to blue light for PCE measurements;

[0339] (b) Using oxygen-reactive materials as part of the formulation during thermal processing or light exposure; and / or

[0340] (c) Temporarily block oxygen by using a sacrificial barrier layer.

[0341] In some implementations, improvements in PCE can be achieved through any method that allows an oxygen barrier layer to be formed on the AIGS layer. In the mass production of devices containing these AIGS-CC layers, vapor deposition processes can be used for encapsulation. A typical process flow in this case involves inkjet printing the AIGS layer, followed by UV curing, baking at 180°C to remove volatiles, depositing an organic planarization layer, and then depositing 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 thermosetting adhesives, and the use of barrier film lamination.

[0342] In some embodiments, the membrane is encapsulated in an inert atmosphere. In some embodiments, the membrane is encapsulated in a nitrogen and argon atmosphere.

[0343] Oxygen-reactive materials include any material that is more reactive to oxygen than AIGS nanostructures. Examples of oxygen-reactive materials include, but are not limited to, phosphine, phosphites, organometallic precursors, titanium nitride, and tantalum nitride. In some embodiments, phosphine may be C 1-20 Any of the trialkylphosphines. In one embodiment, the phosphine 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.

[0344] Examples of sacrificial barrier layers include polymer layers that are soluble in and washable away 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 hydrocarbons (e.g., dichloromethane and dichloroethane), aromatic hydrocarbons (e.g., toluene, xylene), aliphatic hydrocarbons (e.g., hexane, octane, octadecene), tetrahydrofuran, and C64. 4-20 Ethers such as diethyl ether, and C 2-20 Esters, such as ethyl acetate.

[0345] Characteristics and implementation methods of nanostructured membranes

[0346] 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 an illuminated 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) glasses, light projection systems, head-up displays, and the like.

[0347] In some implementations, the nanostructure film is part of the nanostructure color conversion layer.

[0348] In some embodiments, the display device includes a nanostructure color converter. In some embodiments, the display device includes a back panel; a display panel disposed on the back panel; 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.

[0349] In some implementations, the backplane includes blue LEDs, LCDs, OLEDs, or microLEDs.

[0350] 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 of a nanostructure solution. 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.

[0351] In some embodiments, the nanostructure layer has a thickness of about 1 μm to about 25 μm. In some embodiments, the nanostructure layer has a thickness of about 5 μm to about 25 μm. In some embodiments, the nanostructure layer has a thickness of about 10 μm to about 12 μm.

[0352] 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%.

[0353] In some embodiments, the optical film comprising the nanostructure layer is substantially cadmium-free. As used herein, the term "substantially cadmium-free" means that the nanostructure composition contains less than 100 ppm of cadmium by weight. RoHS compliance definition requires that the cadmium in the homogeneous precursor raw materials should not exceed 0.01% (100 ppm) by weight. Cadmium concentration can be measured by inductively coupled plasma mass spectrometry (ICP-MS) analysis 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.

[0354] Nanostructured molded products

[0355] In some embodiments, this disclosure provides a nanostructure molded article comprising:

[0356] (a) First barrier layer;

[0357] (b) the second barrier layer; and

[0358] (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.

[0359] In some implementations, the nanostructure has a PWL of 480-545 nm.

[0360] 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. 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 PCEs 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%.

[0361] Barrier layer

[0362] In some embodiments, the nanostructured molded article includes one or more barrier layers disposed on 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 temperature, oxygen, and moisture. 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 can withstand high temperatures. In some embodiments, the one or more barrier layers have a refractive index matched to the nanostructured molded article. In some embodiments, the matrix material of the nanostructured molded article has a refractive index matched to the one or more adjacent barrier layers 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 matrix material.

[0363] 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, the 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 the nanostructure layer on the opposite side of the nanostructure layer to form a nanostructure molded article according to one 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 oxides, titanium oxides, or aluminum oxides (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 multilayered barrier layers eliminate or reduce pinhole defect alignment in the barrier layers, thereby providing an effective barrier against oxygen and moisture penetration into the nanostructured layer. The nanostructured layer may comprise any suitable material or combination of materials on either side or both sides of the nanostructured layer, and any suitable number of barrier layers. The material, thickness, and number of barrier layers will depend 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 laminated film; in some embodiments, a double-laminated film, wherein each barrier layer is thick enough to eliminate wrinkling in 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 barrier layers may further depend on legal toxicity guidelines, which may require more or thicker barrier layers. Other considerations for the barrier layers include cost, availability, and mechanical strength.

[0364] In some embodiments, the nanostructured film comprises two or more barrier layers adjacent to each side of the nanostructured layer, for example, two or three layers on each side or two barrier layers on each side of the nanostructured layer. In some embodiments, each barrier layer comprises a thin glass sheet, for example, a glass sheet with a thickness of about 100 μm, 100 μm or less, or 50 μm or less.

[0365] Each barrier layer of the nanostructured membrane 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 membrane components such as the barrier layer and the nanostructured layer, as will be understood by those skilled in the art. In some embodiments, each barrier layer may have a thickness of 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, or 15 μm or less. In 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 may 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 layer comprises a thin oxide coating with a thickness of about 100 nm or less, 10 nm or less, 5 nm or less, or 3 nm or less. The top and / or bottom barrier layers may consist of a thin oxide coating, or may contain a thin oxide coating and one or more additional material layers.

[0366] Display devices with nanostructured color conversion layers

[0367] In some embodiments, the present invention provides a display device comprising:

[0368] (a) A display panel for emitting a first light;

[0369] (b) a backlight unit configured to provide a first light to the display panel; and

[0370] (c) A color filter comprising at least one pixel region containing a color conversion layer.

[0371] In some embodiments, the color filter comprises at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 pixel regions. In some embodiments, when blue light is incident on the color filter, red, white, green, and / or blue light can be emitted through the pixel regions respectively. In some embodiments, the color filter is described in U.S. Patent No. 9,971,076, the entire contents of which are incorporated herein by reference.

[0372] In some embodiments, each pixel region includes a color conversion layer. In some embodiments, the color conversion layer includes a nanostructure described herein configured to convert incident light into light of a first color. In some embodiments, the color conversion layer includes a nanostructure described herein configured to convert incident light into blue light.

[0373] 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 a nanostructure described herein. In some embodiments, the display device includes two color conversion layers containing nanostructures described herein. In some embodiments, the display device includes three color conversion layers containing nanostructures described herein. In some embodiments, the display device includes four color conversion layers containing 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.

[0374] In some embodiments, the color conversion layer has a thickness of about 3 μm to about 10 μm, about 3 μm to about 8 μm, about 3 μm to about 6 μm, about 6 μm to about 10 μm, about 6 μm to about 8 μm, or about 8 μm to about 10 μm. In some embodiments, the color conversion layer has a thickness of about 3 μm to about 10 μm.

[0375] The nanostructure color conversion layer can be deposited by any suitable method known in the art, including but not limited to coating, spraying, solvent spraying, wet coating, binder coating, spin coating, strip coating, roll coating, flow coating, inkjet printing, photoresist patterning, drop casting, blade coating, fog deposition, or combinations thereof. In some embodiments, the nanostructure color conversion layer is deposited by photoresist patterning. In some embodiments, the nanostructure color conversion layer is deposited by inkjet printing.

[0376] Compositions containing AIGS nanostructures and ligands

[0377] In some embodiments, the AIGS nanostructure composition further comprises one or more ligands. Ligands include amino-ligands, polyamino-ligands, thiol-ligands, phospho-ligands, silane-ligands, and polymer or oligomer chains, such as polyethylene glycol having amine and silane groups.

[0378] In some embodiments, the amino-ligand has formula I:

[0379]

[0380] in:

[0381] x is between 1 and 100;

[0382] y is between 0 and 100; and

[0383] R 2 C 1-20 alkyl.

[0384] In some embodiments, the polyamino-ligand is a polyamino alkane, a polyamine-cycloalkane, a polyamino heterocyclic compound, a polyamino-functionalized silicone, or a polyamino-substituted ethylene glycol. In some embodiments, the polyamino-ligand is a C14-hydroxyl group substituted with two or three amino groups and optionally contains one or two amino groups that replace the carbon group. 2-20 Alkanes or C 2-20Cycloalkanes. In some embodiments, the polyamino-ligands are 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-isopropyldiethylenetriamine, N-(2-aminoethyl)-1,3-propanediamine, triethylenetetramine, and N,N′-bis(3-aminopropyl) Ethylenediamine, N,N′-bis(2-aminoethyl)-1,3-propanediamine, tris(2-aminoethyl)amine, tetraethylpentaneamine, pentaethylhexane, 2-(2-amino-ethylamino)ethanol, N,N-bis(hydroxyethyl)ethylenediamine, N-(hydroxyethyl)diethylenetriamine, N-(hydroxyethyl)triethylenetetramine, piperazine, 1-(2-aminoethyl)piperazine, 4-(2-aminoethyl)morpholine, polyethyleneimine, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane (1,5-diminopemane), 2,2-dimethyl-1,3-propanediamine, hexamethylenediamine, 2-methyl-1,5-diaminopropane, 1,7-diamino Heptane, 1,8-diaminooctane, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-isopropyl-1,3-propanediamine, N,N-dimethyl-1,3-propanediamine, N,N′-dimethyl-1,3-propanediamine, N,N′-diethyl-1,3-propanediamine, N,N′-diisopropyl-1,3-propanediamine, N,N,N′-trimethyl-1,3-propanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, N,N′-dimethyl-1,6-hexanediamine, 3, 3′-Diamino-N-methyl-dipropylamine, N-(3-aminopropyl)-1,3-propanediamine, spermidine, bis(hexamethylene)triamine, N,N′,N″-trimethyl-bis(hexamethylene)triamine, 4-amino-1,8-octanediamine, N,N′-bis(3-aminopropyl)-1,3-propanediamine (propiediamine), 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-tridecanediamine, 1,3-Diamino-hydroxy-propane, 4,4-methylenedipiperidine, 4-(aminomethyl)piperidine, 3-(4-aminobutyl)piperidine, or polyacrylamine. In some embodiments, the polyamino-ligand is 1,3-cyclohexanebis(methylamine), 2,2-dimethyl-1,3-propanediamine, or tris(2-aminoethyl)amine.

[0385] In some embodiments, the polyamino-ligand is a polyamino heterocyclic compound. In some embodiments, the polyamino heterocyclic compound is 2,4-diamino-6-phenyl-1,3,5-triazine, 6-methyl-1,3,5-triazine-2,4-diamine, 2,4-diamino-6-diethylamino-1,3,5-triazine, 2-N,4-N,6-N-tripropyl-1,3,5-triazine-2,4,6-triamine, 2,4-diaminopyrimidine, 2,4,6-triaminopyrimidine, 2,5-diaminopyridine, 2,4,5,6-tetraaminopyrimidine, pyridine-2,4,5-triamine, 1-(3-aminopropyl)imidazole, 4-phenyl-1H-imidazole-1,2 -Diamine, 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-tetraazine-3,6-diamine, N,N′-dicyclohexyl-1,2,4,5-tetraazine-3,6-diamine, N3-propyl-1H-1,2,4-triazol-3,5-diamine, or N,N′-bis(2-methoxybenzyl)-1H-1,2,4-triazol-3,5-diamine.

[0386] In some embodiments, the polyamino-ligand is a polyamino-functionalized silicone. In some embodiments, the polyamino-functionalized silicone is one of the following:

[0387]

[0388]

[0389] In some embodiments, the polyamino-ligand is a polyamino-substituted ethylene glycol. In some embodiments, the polyamino-substituted ethylene glycol is 2-[3-amino-4-[2-[2-amino-4-(2-hydroxyethyl)phenoxy]ethoxy]phenyl]ethanol, 1,5-diamino-3-oxapentane, 1,8-diamino-3,6-dioxaoctane, bis[5-chloro-1H-indole-2-YL-carbonyl-aminoethyl]ethylene glycol, amino-PEG8-t-Boc-hydrazide, or 2-(2-(2-ethoxyethoxy)ethoxy)ethylamine.

[0390] In some embodiments, the thiol-ligand is (3-mercaptopropyl)triethoxysilane, 3,6-dioxa-1,8-octanedithiol; 6-mercapto-1-hexanol; thiosuccinic acid, mercaptoundecanoic acid, mercaptohexanoic acid, mercaptopropionic acid, mercaptoacetic acid, cysteine, methionine, and thiol poly(ethylene glycol).

[0391] 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.

[0392] In some embodiments, the ligands include, but are not limited to, amino-polyepoxides (e.g., about mw1000); (3-aminopropyl)trimethoxysilane; (3-mercaptopropyl)triethoxysilane; DL-α-lipoic acid; 3,6-dioxa-1,8-octanedithiol; 6-mercapto-1-hexanol; methoxypolyethylene glycolamine (about mw500); poly(ethylene glycol) methyl ether thiol (about mw800); diethylphenylphosphonite; dibenzyl N,N-diisopropylphosphonamide; di-tert-butyl N,N-diisopropylphosphonamide; tris(2-carboxyethyl)phosphine hydrochloride; poly(ethylene glycol) methyl ether thiol (about mw2000); methoxypolyethylene glycolamine (about mw750); acrylamide; and polyethyleneimine.

[0393] Specific combinations of ligands include amino-polyepoxide (approximately MW1000) and methoxy polyethylene glycolamine (approximately MW500); amino-polyepoxide (approximately MW1000) and 6-mercapto-1-hexanol; amino-polyepoxide (approximately MW1000) and (3-mercaptopropyl)triethoxysilane; and 6-mercapto-1-hexanol and methoxy polyethylene glycolamine (approximately MW500); which provide excellent dispersibility and thermal stability. See Example 9.

[0394] Compared to AIGS-containing films without multi-amino ligands and compared to films with single amino ligands, films containing AIGS nanostructures and multi-amino ligands exhibit higher film photon conversion efficiency (PCE), less wrinkling, and less film delamination. Therefore, compositions containing AIGS-multi-amino ligands are uniquely suitable for use in nanostructured color conversion layers.

[0395] Scattering medium

[0396] AIGS films may further comprise a scattering medium. Examples of usable scattering media 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.

[0397] The following embodiments are exemplary and non-limiting examples of the products and methods described herein. Appropriate modifications and adjustments to various conditions, formulations, and other parameters that are commonly encountered in the art and are clear to those skilled in the art in light of this disclosure are within the spirit and scope of the invention.

[0398] Example

[0399] Example 1: AIGS nucleosynthesis

[0400] Sample ID 1 was prepared using a typical synthesis of the following AIGS core: 4 mL of 0.06 M CH3CO2Ag in oleylamine, 1 mL of 0.2 M InCl3 in ethanol, 1 mL of 0.95 M sulfur in oleylamine, and 0.5 mL of dodecanethiol were 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 and held for 5 min, then the temperature was increased to 210 °C and held for 100 min. 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 cores were measured and are summarized in Table 1. The size and morphology of the AIGS cores were characterized by transmission electron microscopy (TEM).

[0401] Table 1

[0402]

[0403] Example 2: AIGS nanostructures treated with ion exchange

[0404] Sample ID 4 was prepared using the following typical ion exchange process: 2 mL of a 0.3 M gallium oleate solution in octadecene and 12 mL of oleylamine were introduced into a flask and degassed. The mixture was heated to 270 °C. 1 mL of a 0.95 M sulfur solution in oleylamine and 1 mL of a premixed solution of isolated AIGS cores (15 mg / mL) were co-injected. The reaction was stopped after 30 min. The final product was transferred to a glove box, washed with toluene / ethanol, centrifuged, and redispersed in toluene. Samples IDs 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 almost complete band-edge emission. An increase in average particle size was observed by TEM.

[0405] Table 2

[0406]

[0407] Example 3: Gallium halide and trioctylphosphine ion exchange treatment

[0408] A room-temperature ion exchange reaction with AIGS nanostructures was performed by adding a solution of GaI3 in trioctylphosphine (0.01–0.25 M) to AIGS QDs and holding it at room temperature for 20 hours. This treatment resulted in significantly enhanced band-edge emission, as summarized in Table 3, while essentially maintaining the peak wavelength (PWL).

[0409] Compositional changes before and after GaI3 addition were monitored using inductively coupled plasma atomic emission spectroscopy (ICP-AES) and energy-dispersive X-ray spectroscopy (EDS), as summarized in Table 3. Composite images of In and Ga elemental distributions before and after GaI3 / TOP treatment show the radial distribution of In and Ga, indicating that ion exchange treatment resulted in a gradient with a higher gallium content near the surface and a lower gallium content at the center of the nanostructure.

[0410] Table 3

[0411]

[0412] Example 4: AIGS ion exchange treatment using an oxygen-free Ga source

[0413] Samples ID 14 and 15 were prepared using an oxygen-free Ga source with the following typical treatment of AIGS nanoparticles: 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 0.95 M sulfur in oleylamine. The reaction was maintained at 240 °C for 2 hours after heating, 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 of Example 2. The optical properties of the treated AIGS materials are shown in Table 4.

[0414] Table 4

[0415] Sample ID PWL(nm) FWHM(nm) QY(%) BE% Gallium source 11 525 43 25 Undetermined Acetylacetone (Ga(III)) 12 516 34 73 90 Gallium oleate 13 522 35 72 87 Gallium oleate 14 521 35 85 86 Ga(III) chloride 15 521 35 80 89 Ga(III) chloride 16 Undetermined Undetermined Undetermined Undetermined Ga(III) iodide

[0416] As shown in Table 4, when using oleylamine as a solvent, the quantum yield of the treated AIGS nanostructures can be improved by using Ga(III) chloride instead of Ga(III) acetylacetone or gallium oleate. The final material subjected to ion exchange using Ga(III) chloride exhibits similar size and similar band-edge-trap emission properties to the starting nanostructures. Therefore, the increase in quantum yield (QY) is not simply due to an increase in the trap emission component. And unexpectedly, it was found that when Ga(III) iodide was used instead of Ga(III) chloride, the AIGS nanostructures appeared to dissolve in the reaction mixture and no ion exchange occurred.

[0417] High-resolution TEM and energy-dispersive X-ray spectroscopy (EDS) of sample 14 revealed that the nanostructure may contain a slight gradient of decreasing In from the center to the surface of the AIGS nanostructure. This indicates that the treatment under these conditions resulted from a process in which In was exchanged from the AIGS structure and replaced by Ga, while Ag remained throughout the structure rather than growing a distinct GS layer. This may also contribute to the improved quantum yield of the nanostructure due to the smaller strain.

[0418] Example 5: Thermally injected AIGS core from a pre-formed Ag2S nanostructure mixed with a pre-formed In-Ga reagent

[0419] To prepare Ag₂S nanostructures, 0.5 g of AgI and 2 mL of 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 of DDT and 9 mL of 0.95 M sulfur in oleylamine were mixed. The DDT+S-OYA mixture was added to the AgI solution and stirred at 58 °C for 10 minutes. The obtained Ag₂S nanoparticles were ready for use without washing.

[0420] To prepare the In-Ga reagent mixture, 1.2 g Ga(acetylacetone)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 under a nitrogen atmosphere (atm) and maintained for 10 minutes. An orange, viscous product was obtained.

[0421] To form AIGS nanoparticles, 1.75 g of TOPO, 23 mL of oleylamine, and 25 mL of ODE were added to a 250 mL flask under N2. After degassing under vacuum, the solvent mixture was heated to 210 °C over 40 minutes. The Ag2S and In-Ga reagent mixture was mixed at 58 °C in a 40 mL vial and transferred to a syringe. The Ag-In-Ga mixture was then injected into the solvent mixture at 210 °C and held for 3 hours. After cooling to 180 °C, 5 mL of trioctylphosphine was added. The reaction mixture was transferred to a glove box and diluted with 50 mL of toluene. The final product was precipitated by adding 150 mL of ethanol, centrifuged, and redispersed in toluene. The AIGS nanostructures were then subjected to ion exchange as described in Example 4. The optical properties of the materials prepared by this method at a scale up to 24x are shown in Table 5.

[0422] Table 5

[0423]

[0424] Example 7: Repeated gallium ion exchange improves the photoluminescence stability of AIGS nanostructures

[0425] 7.1 First Ion Exchange Process

[0426] 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 minimal toluene) and sulfur dissolved in OYA (0.95 M, 570 mL). The mixture was heated to 240 °C over 40 min and maintained for 4 h. 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.

[0427] 7.2 Second Ion Exchange Process

[0428] Oleylamine (OYA, 960 mL) was degassed under vacuum at 40 °C for 20 min. AIGS ion-exchange nanostructures (12 g in heptane) as described in Example 7.1 were added to OYA, followed by GaCl3 (22.5 g in a minimum volume of toluene), and then sulfur dissolved in OYA (0.95 M, 100 mL). The mixture was heated to 240 °C over 40 min and held for 3 h. After cooling, the mixture was diluted with 1 volume of toluene, washed (precipitated with 1.6 volumes of ethanol, centrifuged), and redispersed in toluene or heptane as needed. When performing ligand exchange on the ink formulation, further ethanol washing was applied, and the QD was redispersed in heptane.

[0429] 7.3 Alternative Second Ion Exchange Process

[0430] The oleylamine (15 mL) was degassed under vacuum at 60 °C for 20 minutes. GaCl3 (360 mg in a minimum volume of toluene) was added to OYA, followed by AIGS (200 mg in heptane) as described in Example 7.1, and then sulfur dissolved in OYA (0.95 M, 1.6 mL). The mixture was heated to 240 °C over 40 minutes and maintained for 3 hours. After cooling, the mixture was washed as described in Example 7.1.

[0431] 7.4 Alternative Second Ion Exchange Process

[0432] This implementation is performed, for example, as described in Example 7.3, but on a scale of 3x.

[0433] 7.5 Substituted Second Ion Exchange Process

[0434] 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 minimum volume of toluene) were added, followed by AIGS (200 mg in heptane) as described in Example 7.1. After heating to 130 °C, TMS2S (0.65 mL of 50% ODE solution) was added over 20 min, and the mixture was maintained for 2.5 h. After cooling, the mixture was washed as described in Example 7.1.

[0435] 7.6 Results

[0436] AIGS nanostructures underwent an ion-exchange process in which In was replaced by Ga. This process, conducted at a higher temperature (240 °C vs. 210 °C) compared to nucleus growth, resulted in ripening, leading to a larger average size than untreated nanostructures. The nanostructures lack a well-distinguished shell structure, which can be observed in cross-sectional TEM elemental mapping. This lack of a higher bandgap shell is expected to limit photoluminescence retention in these materials during film processing.

[0437] After the second ion exchange process, the average TEM size did not increase. Figure 2A-2C However, TEM element mapping proves that a more pronounced gradient has developed in the Ga-rich (higher bandgap) region of QD.

[0438] The elemental composition of single and multiple ion exchange processes is shown in Table 6. The values ​​are averages from 10-20 samples from Examples 7.1 and 7.2.

[0439] Table 6

[0440] Sample type PWL(nm) FWHM(nm) Ag / (Ag+In+Ga) In / (In+Ga) Single ion exchange treatment 523 34.5 0.39 0.27 Double ion exchange treatment 523 34.1 0.40 0.24

[0441] The properties of the ion-exchanged AIGS nanostructures are shown in Table 7. The metal ratios are molar ratios determined by ICP.

[0442] Table 7

[0443]

[0444] The PCE of the membrane 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 introduction of a gradient in the higher bandgap region via ion exchange, resulting from the process of increasing the Ga concentration in the outer layer of the nanostructure.

[0445] Table 8

[0446]

[0447] Example 8 – Compositions comprising AIGS nanostructures and polyamino-ligands

[0448] abbreviation

[0449] ·Jeffamine——Jeffamine M-1000

[0450] HDDA—1-6-hexanediol diacrylate

[0451] • Dimethylamine — 1,3-cyclohexanedimethylamine

[0452] PCE – Photon Conversion Efficiency

[0453] 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. Jeffamine 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 Jeffamine 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 (bonded and unbonded), HDDA, monomers, photoinitiators, and other miscellaneous organic compounds remaining in the QD solution. This ink formulation is solution 4.

[0454] Add the polyamino ligand dimethylamine (50 mg dimethylamine per 100 mg QD inorganic solid) to solution 4, and then cast the composition into a film.

[0455] film casting

[0456] Solution 4 was spin-coated onto a 2” x 2” glass substrate. The film was cured using a UV LED curing lamp. The film photon conversion efficiency (PCE) (a measure of brightness) was then tested. The film was then baked for 30 minutes at a temperature slightly above the heating plate set to 180°C. Alternatively, the film was baked for 10 minutes with the heating plate in direct contact with the heating plate surface set to 180°C.

[0457] Then, the film's PCE was tested. A 1” x 1” blue 448nm LED mask array provided the excitation source for the film. A monolithic sphere was placed on top of the film and connected to a fluorometer. See [link to related documentation] Figure 3A and 3B The collected spectra are analyzed to obtain PCE.

[0458] PCE is the ratio of the number of forward-emission 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 with films without ligands, the presence of ligands 1,3-cyclohexanebis(methylamine), tris(2-aminoethyl)amine, and 2,2-dimethyl-1,3-propanediamine resulted in high PCE retention, high LRR, and no wrinkling after baking at 180 °C.

[0459] Table 9

[0460]

[0461]

[0462] Figure 1 The effect of diamine addition on membrane morphology was shown. Figure 1 The membranes in the image, from left to right, contain: no additive (wrinkled); 2,2-dimethyl-1,3-propanediamine (diamine, no wrinkling); cyclohexanemethylamine (monoamine, wrinkled); and tris(2-aminoethyl)amine (triamine, no wrinkling). From left to right, the first and third membranes, which do not contain diamines, exhibit significant wrinkling. In contrast, the second and fourth membranes do not exhibit wrinkling. Surprisingly, the use of diamino ligands in AIGS membranes resulted in a substantial reduction in membrane wrinkling.

[0463] Example 9 – Testing of Additional Ligands for AIGS Nanostructures

[0464] In this experiment, additional ligands for AIGS nanoparticles were tested to enhance QY, improve biocompatibility, and improve thermal stability. Furthermore, the protective effects of these ligands on AIGS nanostructures against degradation and oxidation were evaluated. Combinations of ligands that can be formulated into AIGS ink compositions were also tested.

[0465] Ligand exchange with these ligands is performed in organic solvents such as ethyl acetate, PGMEA, acetone, xylene, 1,2-dichlorobenzene (ODCB), butyl acetate, and diethylene glycol monoethyl ether (DGMEE).

[0466] AIGS nanostructures exchange ligands with ligands containing polymer or oligomer chains, such as polyethylene glycol with amine and silane groups, and soft bases for co-passivation, such as phosphino-, mercapto-, and combinations thereof.

[0467] Figure 4Quantum yield values ​​for numerous individual ligands and AIGS nanostructures subjected to single-ion exchange treatments as described in this paper are depicted. In this figure, NG: original AIGS; NG-NL1: amino-polyepoxyalkylene (approx. mw1000); NG-NL2: (3-aminopropyl)trimethoxysilane; NG-NL3: (3-mercaptopropyl)triethoxysilane; NG-NL4: DL-α-lipoic acid; NG-NL5: 3,6-dioxa-1,8-octanedithiol; NG-NL6: 6-mercapto-1-hexanol; NG-NL7: methoxypolyethylene glycolamine 500; NG-NL8: poly(ethylene glycol) methyl ether thiol Mn 800; NG-NL9: diethyl phenylphosphonite; NG-NL10: dibenzyl N,N-diisopropylphosphonamide; NG-NL11: di-tert-butyl N,N-diisopropylphosphonamide; NG-NL12: tris(2-carboxyethyl)phosphonic acid hydrochloride; NG-NL13: poly(ethylene glycol) methyl ether thiol Mn 2000; NG-NL14: methoxy polyethylene glycolamine 750; NG-NL15: acrylamide; and NG-NL16: polyethyleneimine).

[0468] like Figure 4 As observed, treatment of AIGS nanostructures with 3-mercaptopropyltriethoxysilane (NL3), 3,6-dioxa-1,8-octanedithiol (NL5), and 6-mercapto-1-hexanol (NL6) resulted in high QY (73.7%, 72.9%, and 76.1%, respectively). Therefore, the present invention provides AIGS nanostructure compositions comprising at least one thiol-substituted ligand that provides improved QY. It is believed that thiol-substituted ligands provide high QY by passivating the surface of the AIGS nanostructures and reducing defect emission. Amino-substituted ligands also improve QY.

[0469] In this single-ligand test, the polyethylene glycolamine-substituted ligands (L1, L7, L8, and L13), the thiol-substituted ligands (L3, L5, and L6), and the silane ligand (L2) exhibited good QY compared to the original AIGS nanostructure. Furthermore, ligands L1, L7, and L8 provided better compatibility with the monomer when dispersed in HDDA.

[0470] Figure 5 This graph shows the QY% for various 2-ligand combinations, indicating improved QY% (good combinations) and decreased QY% (bad combinations). Surface defects can be reduced by adding thiol ligands. The combination of L6 and L7 provides better stability than other combinations. However, for relatively hydrophilic ink compositions, better 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.

[0471] The suitable temperature for ligand exchange is from room temperature to 120°C. The total amount of ligands in the composition can be 60% to 150% of the mass of AIGS.

[0472] Table 10 shows the relative changes in QY, PWL, and FWHM before and after ligand exchange with various ligands. Table 10 shows that L6 & L7 are the most effective ligand combinations for ink formulations, especially when combined with acrylate monomers. Combinations of L2 & L7, L2 & L6, and L2 & L3, L6, and L7 provide excellent dispersibility and thermal stability. See also Figure 6 .

[0473] Table 10

[0474]

[0475]

[0476] Further investigation was conducted on ligand combinations that provided good thermal stability when heated to 180°C and maintained in a glove box for 30 minutes. The ligand combinations L6&L7, L2&L6, and L2&L3 provided better stability than the single ligand L1. See [link to relevant documentation] Figure 6 .

[0477] The effect of different ligand ratios on QY was also investigated. The weight ratio of the ligands was varied while the total amount of ligands remained constant. Optimal QY was achieved at a 7:3 L6 to L7 ratio. (See also...) Figure 7 Except for the 9:1 ratio, all combinations with L6 and L7 showed enhanced QY compared to the original AIGS nanostructures. Despite the high QY, this mixture was difficult to purify due to the lack of precipitation. Mixtures of L6 & L2, L3 & L7, and L5 & L7 are good ligand mixtures for AIGS nanostructures. These ligand combinations can be used with a variety of monomers, such as tetrahydrofurfuryl acrylate, tris(propylene glycol)diacrylate, 1,4-bis(acryloyloxy)butane, arylated diethylene glycol ethyl ether, isobornyl acrylate, hydroxypropyl acrylate, 2-(acryloyloxy)ethyl hydrogen succinate, and 1,6-hexanediol diacrylate.

[0478] Example 10 – PCE Improvement of AIGS Membrane

[0479] In a N2-filled glove box, AIGS QD coated with appropriate ligands is mixed into an ink containing one or more monomers, TiO2 scattering particles, and a photoinitiator. The ink is then spin-coated to create a film, which is subsequently cured using UV irradiation. The film is then baked on a heated plate at 180°C for 30 minutes to remove any residual volatile components. All of these processes are carried out in an inert atmosphere—a N2-filled glove box.

[0480] At this stage, the membrane can be measured in air by placing it over a blue LED light source (with the membrane side facing upwards). A monolithic sphere connected to the spectrophotometer is placed on top of the QD membrane (see [link to spectrophotometer]). Figure 3A and 3B The emission spectrum of the film was captured. This measurement was repeated using a blank glass substrate (without QD). The blue light absorption and photon conversion efficiency (PCE) of the QD film were measured using the following formula:

[0481] Blue light absorption = # of blue photons transmitted through the QD film / # of incident blue photons

[0482] PCE = forward-emitted green photon # / incident blue photon #

[0483] To investigate the effects of air and moisture during measurement, the baked QD film was encapsulated before being removed from the N2 glove box. This was done by applying a few drops of UV-curable transparent adhesive to the QD layer, placing a glass cover glass, and curing the adhesive by UV irradiation. Using this method, the QD film thus encapsulated with glass and adhesive was measured in air.

[0484] The results show that encapsulating the QD film before measurement in air is crucial for achieving high photon conversion efficiency (PCE). Table 11 shows the results for 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 AIGS nanostructures exhibits a higher post-baking PCE value than InP with a much lower QD loading. This was achieved by placing the film under a blue light source (~6 mW / cm²). 2 Further improvements in PCE were achieved by irradiating the film for 1 hour. Furthermore, the QDCC film made with AIGS QD exhibited a narrower emission (FWHM ~30nm) compared to the film made with InP QD (FWHM 36nm). This is due to the lower FWHM of AIGS QD in solution (34nm vs 39nm), coupled with the use of mono- and poly-amino ligands that allow for good dispersion in the ink resin.

[0485] Table 11

[0486]

[0487] Figure 9 The effects of encapsulation and blue light treatment on a wider range of samples were shown. Surprisingly, the PCE value achieved through encapsulation was significantly higher (greater than 32%) than that of unencapsulated samples.

[0488] 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 during encapsulation.

[0489] Although the samples in this study were encapsulated using glass and adhesives, this improvement in PCE can be achieved by any method that can form an oxygen barrier layer on the QD layer. In the mass production of devices containing these QDCC layers, vapor deposition processes may be used for encapsulation. A typical process flow in this case would involve inkjet printing the QD layer, followed by UV curing, baking at 180°C to remove volatiles, depositing an organic planarization layer, and then depositing 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 thermosetting adhesives, and the use of barrier film lamination.

[0490] Example 11: Improving AIGS Films with Metal Alkoxides

[0491] For applications of emerging advanced display technologies, such as QD-OLED and QD microLED, films need to maintain their optical properties under 24-hour yellow light and air storage conditions. 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% (entry 1 in Table 12).

[0492] The “light and air storage conditions” were established as follows. The film was manufactured by spin-coating AIGS ink onto a glass substrate, followed by curing by irradiation with UV light (405 nm) and baking on a hot plate at 180°C for 30 minutes. All processes were carried out in a glove box filled with N2. The ink contained the following components.

[0493] Table 12

[0494] AIGS QD capped with mercaptohexanol and Jeffamine M1000 18％ 1,3-Diaminomethylcyclohexane 5％ <![CDATA[TiO2 scattering particles]]> 4％ Dispersant (Synperonic NP5) 2％ Photoinitiator (TPO) 1％ Metal alkoxides 0.6％-2.4％ Monomer (HDDA) 67.6％-69.4％

[0495] The membrane was then exposed to air and stored in a "yellow light" chamber illuminated with a white LED lamp covered with a blue light blocking filter. Typical illuminance and color coordinates for the yellow light chamber, as measured by a Konica-Minolta CL-200A colorimeter, were 140 lux, CIE x = 0.52, and CIE y = 0.45. For reference, typical chamber illumination without blue filtering was illuminance = 620 lux, CIE x = 0.38, and CIE y = 0.38.

[0496] To test the effect of air exposure on PCE, films were acquired at periodic 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 film was baked again at 180°C for 30 minutes and measured on a PCE platform.

[0497]

[0498] 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, after 24 hours of yellow light storage, the film PCE remained at 30.1% to 34.4%, only slightly lower than the 35.8% PCE of the airless film.

[0499] Table 14 shows the results for films using inks containing alternative metal alkoxides. The addition of gallium isopropoxide or barium isopropoxide resulted in a similar improvement in air stability as with zirconium propoxide films.

[0500] Table 14. Comparison of the effects of different metal alkoxides on improving membrane properties under air exposure. The use of different batches of quantum dots resulted in lower overall performance.

[0501]

[0502] Unbound by any particular theory, it is believed that metal alkoxides form a stabilizing shell around the AIGS nanostructures. In the classic sol-gel process, once tetraethyl orthosilicate (TEOS) is exposed to air moisture, spontaneous hydrolysis and condensation reactions occur. This leads to a three-dimensional sol-gel network, and under extreme conditions, SiO2 is formed. Zr(OPr)4 is a typical sol-gel precursor. Once the AIGS / Zr ink formulation is exposed to air, the sol-gel process actually occurs. In-situ FTIR of AIGS / Zr(OPr)4 shows that by holding the AIGS / Zr sample in an FTIR window for more than 5 minutes at 3400 cm⁻¹, the sol-gel process can be achieved. -1The tensile strength of the nearby -OH groups increased significantly, while AIGS samples without Zr(OPr)4 did not show such a change. It is believed that the in-situ formed three-dimensional network acts as an oxygen barrier, and ZrO2... x (OH) y The resulting higher conductivity band restricts 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.

[0503] Membrane performance can be further improved by including phenolic additives, which act as antioxidants and steric hindrance ligands. Table 15 shows optical data from a group of membranes containing zirconium propoxide and the phenolic additive pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0504] Table 15. Membrane results using inks containing metal alkoxides and sterically hindered phenolic ligands

[0505]

[0506] Example 12 uses a bulky phenolic auxiliary ligand.

[0507] Ligand exchange on the AIGS nanostructures was performed using 6-mercaptohexanol and Jeffamine M1000 at 80°C for 1 hour. The AIGS nanostructures were then redispersed in monomers with auxiliary ligands. The ink formulation contained 12% ligand-exchanged QD, 10% TiO2 as a dispersion medium, and 5% Jeffamine M1000 as a dispersant.

[0508] To select suitable ligands or auxiliary ligands, several conditions must be met. First, the ligand must protect the ligands on the surface. Second, the ligand must be compatible with other ink components. Third, the ligand must be stable in air by blocking oxygen. Films are prepared by adding auxiliary ligands to ink formulations to identify promising candidates that meet these conditions.

[0509] Figure 11 The membrane properties of ink formulations with different auxiliary ligands were demonstrated. The membrane with auxiliary ligand-1 showed better EQE than those with other ligands. It is hypothesized 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.

[0510] Table 16. List of auxiliary ligands used in ink formulations

[0511]

[0512] Unlike InP, AIGS nanostructures can preferentially bond with weakly bonded L-type ligands, which can reduce EQE if reactive free radicals or active substances are present that may cause side reactions. These side reactions are caused by free radical generation and oxygen-mediated photo-oxidation via polymerization initiators or reactive free radicals. The stability of the film was examined under dark conditions. Under dark conditions, auxiliary ligands -1 and -7 showed considerably stable EQE compared to the control group. Figure 11 The auxiliary ligand-2 causes a decrease in EQE and makes the membrane less stable. Therefore, even when the membrane containing auxiliary ligands-1 and-7 is exposed to air, it does not degrade without exposure to light.

[0513] Photostability was measured under yellow light to examine changes in film properties. For example... Figure 12 The results showed that, after 24 hours, auxiliary ligand-1 exhibited better stability under yellow light than the reference ink (control group). Furthermore, phosphorus-based auxiliary ligand-7 showed comparable EQE compared to the reference ink (control group).

[0514] The thermal stability of the film was also measured after baking at 180 °C. As shown in Table 17, the large phenolic auxiliary ligand-1 and phosphoric auxiliary ligand-7 showed good thermal stability compared with the control group.

[0515] Table 17. EQE of the membrane after baking at 180°C in a nitrogen atmosphere

[0516]

[0517] We also improved the ink preparation process, as shown in Table 18. When auxiliary ligand-1 was added afterward, the EQE was superior to that of the reference ligand 1,3-cyclohexanebis(methylamine). Furthermore, the ink formulation exhibited the highest stability EQE performance when more thiols were added during ligand exchange with auxiliary ligand-1. See also Figure 13 It shows the stability of ink formulations with different ratios of ink and additives over time when exposed to yellow light conditions.

[0518] Table 18. Changes in the process

[0519]

[0520]

[0521] like Figure 14 As shown, further GaCl3 (S3) treatment of AIGS nanostructures exhibits improved EQE performance. Performance is further improved when the inorganic ligand zirconium propoxide (S2) is added together with S3. The addition of multivalent metal-based ligands (such as S2) can compensate for excessive sulfur oxidation. See also Figure 15The results showed that the best performance in the baked film was achieved when the auxiliary ligands -1, S2 and S3 were combined. Figure 16 The results show that when the auxiliary ligands -1, S2 and S3 are combined, the membrane exhibits high light resistance when exposed to yellow light.

[0522] For comparison, Figure 17 This is a line graph showing the EQE% vs. blue light absorbance of AIGS films containing 1%, 3%, and 6% S3.

[0523] Although various embodiments have been described above, it should be understood that they are presented by way of example only and not as a limitation. It will be apparent to those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention. Therefore, the breadth and scope should not be limited by any of the exemplary embodiments described above, but should be defined solely by the following claims and their equivalents.

[0524] All publications, patents, and patent applications mentioned in this specification indicate the level of expertise of a person skilled in the art to which this invention pertains, and are incorporated herein by reference to the extent that each individual publication, patent, or patent application is specifically and individually indicated to be incorporated by reference.

Claims

1. A membrane, which comprises: AIGS nanostructures composed of Ag, In, Ga, and S; One or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, or combinations thereof, wherein the one or more metal alkoxides are metal C. 1-10 An alkoxide, wherein the metal is titanium, zirconium, hafnium, gallium, or barium; and At least one ligand, When excited by a blue light source with a wavelength of 450 nm, the film exhibits a photon conversion efficiency (PCE) greater than 32% at a peak emission wavelength of 480-545 nm, and After 24 hours of storage under yellow light and air conditions, the PCE of the membrane is at least 30%.

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

3. The membrane according to any one of claims 1-2, wherein the nanostructure has a quantum yield QY of 80-99.9%.

4. The membrane according to any one of claims 1-2, wherein the nanostructure has an OD greater than or equal to 0.

8. 450 / mass, in mL . mg -1. cm -1 .

5. The membrane according to any one of claims 1-2, wherein, When tested by transmission electron microscopy (TEM), the average diameter of the nanostructure was less than 10 nm.

6. The membrane according to any one of claims 1-2, wherein at least 80% of the emission is edge emission.

7. The membrane according to any one of claims 1-2, wherein the at least one ligand is a polyamino ligand.

8. The membrane according to claim 7, wherein the at least one polyamino ligand is a polyamino alkane, a polyamino-cycloalkane, a polyamino heterocyclic compound, a polyamino-functionalized silicone, or a polyamino-substituted ethylene glycol.

9. The membrane according to claim 7, wherein the polyamino ligand is a C14 group substituted with two or three amino groups and optionally contains one or two amino groups replacing the carbon group. 2-20 Alkanes or C 2-20 Cycloalkanes.

10. The membrane according to any one of claims 1-2, wherein the at least one ligand is a compound of formula I: in: x is between 1 and 100; y is between 0 and 100; and R 2 C 1-20 alkyl.

11. The membrane according to any one of claims 1-2, wherein the at least one ligand has formula II: Where R 3 and R 4 Independently for C 3-6 Secondary or tertiary alkyl groups, and R 5 C is hydrogen or optionally substituted 1-6 alkyl.

12. The membrane of claim 11, further comprising gallium halide.

13. The membrane according to any one of claims 1-2, wherein the one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, or combinations thereof are present in the composition in an amount of 0.03 to 3% by weight.

14. A method for preparing a membrane according to any one of claims 1-13, the method comprising: (a) Providing AIGS nanostructures, one or more metal alkoxides, one or more metal alkoxide hydrolysis products, one or more metal halides, or combinations thereof, wherein the one or more metal alkoxides are metal C. 1-10 An alkoxide, wherein the metal is titanium, zirconium, hafnium, gallium, or barium; and at least one ligand; (b) Blend at least one organic resin with the AIGS nanostructure of (a); as well as (c) A first film is prepared on a first barrier layer, the first film comprising a blend of AIGS nanostructures, the at least one ligand, and the at least one organic resin; (d) Curing the membrane; (e) Encapsulating the first film between the first barrier layer and the second barrier layer; and When excited by a blue light source with a wavelength of 450 nm, the encapsulated film exhibits a PCE greater than 32% at a peak emission wavelength of 480-545 nm.

15. The method of claim 14, wherein the method is performed before exposing the encapsulated film to a blue LED light source in air.

16. The method of claim 15, wherein the method is performed under an inert atmosphere.

17. The method of claim 16, wherein the method further comprises: In (a) an AIGS nanostructure, one or more metal alkoxides, one or more metal alkoxide hydrolysates, one or more metal halides, or combinations thereof, and a mixture of ligands, at least one oxygen-reactive material is added; in (b) a blend, at least one oxygen-reactive material is added; and / or a second membrane comprising at least one oxygen-reactive material is formed on top of the first membrane prepared in (c); and / or a sacrificial barrier layer temporarily blocking oxygen and / or water is formed on the first membrane prepared in (c), and the PCE of the membrane is measured, and then the sacrificial barrier layer is removed.

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

19. An apparatus comprising a membrane according to any one of claims 1-13 or a membrane prepared by the method according to any one of claims 14-18.

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