TW202229159A - Films comprising bright silver based quaternary nanostructures - Google Patents

Abstract

Disclosed are films comprising Ag, In, Ga, and S (AIGS) nanostructures and at least one ligand bound to the nanostructures. In some embodiment, the AIGS nanostructures have a photon conversion efficiency of greater than 32% and a peak wavelength emission of 480-545 nm. In some embodiments, the nanostructures have an emission spectrum with a FWHM of 24-38 nm.

Description

Quaternary Nanostructured Films Containing Bright Silver Substrates

The present invention relates to the field of nanotechnology. More specifically, the present invention provides thin, heavy metal-free, nanostructured color conversion films having peak emission wavelengths of 480-545 nm when excited with a blue light source having a wavelength of about 450 nm. High Photon Conversion Efficiency (PCE) greater than 32%.

Efficient color conversion is important for lighting and display applications. In display applications, a blue light source with a wavelength of about 450 nm is most commonly used as a backlight. Most applications require the material to be free of heavy metals such as Cd and Pb.

Increased efficiency results in less wasted power and increased emissions. Color conversion films are characterized by photon conversion efficiency (PCE), which is defined as the number of photons emitted divided by the number of source photons. Green heavy metal-free QD color conversion films for displays generally have poor performance due to their limited absorption in the blue light that excites them. Blue absorption is often inherently limited by the material system used, resulting in the need for thicker films to absorb sufficient 450 nm light.

Films formed by deposition of QD inks are typically cured by UV radiation. In many cases this was followed by heat treatment at 180°C for up to 1 hour in the presence of air. The photon conversion efficiency of these films is limited by the combination of poor absorption and poor light conversion due to instability through these processing steps.

Ag/In/Ga/S (AIGS) nanostructures with high band-edge emission (BE), narrow full width at half maximum (FWHM), high quantum yield (QY), and reduced red-shift are still needed and available in the industry Films with high (greater than 32%) Photon Conversion Efficiency (PCE) at peak emission wavelengths between 480 nm and 545 nm were prepared using an excitation wavelength of about 450 nm.

The present invention provides thin, heavy metal-free, nanostructured color conversion films that have greater than 32% high photons at a peak emission wavelength of 480-545 nm when excited by a blue light source with a wavelength of about 450 nm Conversion Efficiency (PCE). This is achieved by using Ag/In/Ga/S (AIGS) nanostructures in ink formulations containing one or more ligands, where all handling of the ink, subsequent deposition, prior to exposure to blue or UV light , The treatment and measurement of the membrane are carried out in an oxygen-free environment. In some embodiments, the AIGS nanostructures have a FWHM of 28-38 nm. In other embodiments, the AIGS nanostructures have a FWHM of less than 32 nm. This narrow FWHM is achieved by adding at least one polyamine-based ligand to the AIGS nanostructures and preparing a film layer, where all handling of the nanostructured ink, deposition of the ink, processing of the film, and measurement are performed without oxygen. carried out in the environment.

Films formed by deposition of QD inks are typically cured by UV radiation. In many cases this was followed by heat treatment at 180°C for up to 1 hour in the presence of air. It has been found that poor absorption and poor light conversion reduce photon conversion efficiency due to instability through these processing steps.

Disclosed herein are films comprising AIGS nanostructures in ink formulations comprising at least one ligand that achieve a PCE of greater than (>) 32% after thermal treatment. In some embodiments, films are provided comprising AIGS nanostructures, at least one ligand, and exhibiting greater than 32% PCE at peak emission wavelengths of 480-545 nm when excited with a blue light source having a wavelength of 450 nm. PCE was calculated by integrating the emission spectrum from 484 nm to 700 nm, with the green part defined as 484-588 nm. In some embodiments, the film is a thin (5-15 μm) color conversion film.

The films so prepared have good (>95%) blue light absorption at about 450 nm, but moderate emission properties. However, when processed in the absence of oxygen and/or light and/or encapsulated before exposing the films to UV or blue light, the emission properties of these films are significantly improved.

In some embodiments, the membrane further comprises at least one monomer incorporated into the ligand that coats the AIGS surface. In some embodiments, at least one monosystem acrylate. In some embodiments, the mono-system ethyl acrylate, hexamethylene diacrylate (HDDA), tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy) group) at least one of butane or isobornyl acrylate.

A method of making an AIGS membrane is provided, comprising: (a) providing AIGS nanostructures and at least one ligand coating the nanostructures; (b) mixing at least one organic resin with the AIGS nanostructure of (a); and (c) preparing a first film comprising mixed AIGS nanostructures, at least one nanostructure-coated ligand, and at least one organic resin on the first barrier layer; (d) curing the film by UV irradiation and/or baking; (e) encapsulating the first membrane between the first barrier layer and the second barrier layer; and Among them, the encapsulated films exhibited conversion efficiencies (PCEs) greater than 32% at peak emission wavelengths of 480-545 nm when excited with a blue light source with a wavelength of about 450 nm.

In some embodiments, the AIGS nanostructure further comprises at least one monomer incorporated into at least one ligand that coats the AIGS surface.

Methods further including the following are also provided: (f) adding at least one oxygen-reactive material to the mixture of AIGS nanostructures and ligands of (a), adding at least one oxygen-reactive material to the mixture of (b), and/or preparing in (c) a second film comprising at least one oxygen-reactive material is formed on top of the first film; and/or (g) Forming a sacrificial barrier layer temporarily blocking oxygen and/or water on the first film prepared in (c), measuring the PCE of the film, and then removing the sacrificial barrier layer.

Methods including the following are also provided: (a) encapsulating the film prior to heat treatment and/or measurement; (b) using an oxygen reactive material as part of the formulation during heat treatment or light exposure; and/or (c) Temporarily blocking oxygen through the use of a sacrificial barrier layer.

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

In some embodiments, the nanostructures have a QY of 80-99.9%. In some embodiments, the nanostructures have a QY of 85-95%. In some embodiments, the nanostructures have a QY of about 86-94%. In some embodiments, the nanostructures have an _OD450 /mass (mL.mg ^- 1.cm ^{- 1} ) greater than or equal to 0.8, where OD is optical density. In some embodiments, the nanostructures have an _OD450 /mass (mL.mg ^- 1.cm ^{- 1} ) in the inclusive range of 0.8-2.5. In some embodiments, the nanostructures have an _OD450 /mass (mL.mg-1.cm ^{- 1} ) in the inclusive range of 0.87-1.9 ^. In some embodiments, the average diameter of the nanostructures is less than 10 nm by transmission electron microscopy (TEM). In some embodiments, the average diameter is about 5 nm.

In some embodiments, at least about 80% of the emission tether is edge-emitted. In some embodiments, at least about 90% of the emission tether is edge-emitted. In some embodiments, 92-98% of the emission fringes are edge-emitted. In some embodiments, 93-96% of the emission is fringed edge emission.

In some embodiments, the AIGS nanostructures have a peak emission wavelength (PWL) of about 450 nm.

In some embodiments, the AIGS nanostructure includes a gradient of increasing gallium from the surface of the nanostructure to decreasing gallium in the center of the nanostructure.

In some embodiments, the at least one ligand is an amine-based ligand, a polyamine-based ligand, a thiol-containing ligand, or a silane group-containing ligand. It was unexpectedly found that the use of polyamine-based ligands resulted in AIGS-containing films with FWHM greater than 32 nm.

In some embodiments, at least one polyamine based ligand is a polyaminoalkane, a polyamino-cycloalkane, a polyaminoheterocycle, a polyamine functionalized polysiloxane, or a polyamine substituted ethylene glycol. In some embodiments, the polyamine based ligand systems are _C2-20 alkanes or _C2-20 cycloalkanes substituted with two or three amine groups and optionally containing one or two amine groups in place of carbon groups. In some embodiments, the polyamine-based ligand is 1,3-cyclohexanebis(methylamine), 2,2-dimethyl-1,3-propanediamine, or ps(2-aminoethyl)amine .

其中： x係1至100； y係0至100；且 R ²係C _1-20烷基。 In some embodiments, the ligand is a compound of formula I:

wherein: x is 1 to 100; y is 0 to 100; and R ² is C _1-20 alkyl.

In some embodiments, x=19, y= ³ , and R2= _-CH3 .

In some embodiments, at least one ligand is (3-aminopropyl)trimethoxy-silane); (3-mercaptopropyl)triethoxysilane; DL-alpha-lipoic acid; oxa-1,8-octanedithiol; 6-mercapto-1-hexanol; methoxypolyethylene glycol amine (about m.w. 500); poly(ethylene glycol) methyl ether thiol (about m.w. 800 ); diethyl phenylphosphinate; N,N-diisopropylphosphoramidite dibenzyl ester; N,N-diisopropylphosphoramidite di-tert-butyl ester; (2-carboxyethyl) phosphine hydrochloride; poly(ethylene glycol) methyl ether mercaptan (about m.w. 2000); methoxypolyethylene glycol amine (about m.w. 750); acrylamide; or polyethylene sulfite amine. The M.w. of the polymer was determined by mass spectrometry.

In some embodiments, at least one ligand is a combination of: amino-polyalkylene oxide (about m.w. 1000) and methoxypolyethylene glycol amine (about m.w. 500); amino-polyalkylene oxide (about m.w. 500); m.w. 1000) and 6-mercapto-1-hexanol; amino-polyalkylene oxide (about m.w. 1000) and (3-mercaptopropyl)triethoxysilane; and 6-mercapto-1-hexanol and methyl oxypolyethylene glycol amine (approximately m.w. 500).

In some embodiments, the AIGS nanostructure further comprises at least one monomer incorporated into at least one ligand that coats the AIGS surface.

Also provided are nanostructured compositions comprising: (a) AIGS nanostructures exhibiting greater than 32% PCE, and (b) at least one organic resin.

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

Also provided are methods of making the nanostructured compositions described herein, the methods comprising: (a) providing AIGS nanostructures and at least one ligand coating the nanostructures; (b) mixing at least one organic resin with the nanostructure of (a); (c) preparing a first film comprising mixed AIGS nanostructures, at least one nanostructure-coated ligand, and at least one organic resin on the first barrier layer; (d) curing the film by UV irradiation and/or baking; and (e) encapsulating the first membrane between the first barrier layer and the second barrier layer, Among them, the encapsulated films exhibited conversion efficiencies (PCEs) greater than 32% at peak emission wavelengths of 480-545 nm when excited with a blue light source with a wavelength of about 450 nm.

In some embodiments, the nanostructure of (a) further comprises at least one monomer incorporated into the ligand that coats the AIGS surface. In some embodiments, at least one monosystem acrylate. In some embodiments, the mono-system ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or isobornyl acrylate at least one of esters.

In some embodiments, the method is performed prior to exposing the encapsulated film to air to measure the emission spectrum of the AIGS nanostructure. In some embodiments, the method is carried out under an inert atmosphere.

In some embodiments, the method further comprises: (f) adding at least one oxygen-reactive material to the mixture of AIGS nanostructures and ligands of (a), (g) adding at least one oxygen-reactive material to the mixture of (b), and/or (h) forming a second film comprising at least one oxygen-reactive material on top of the first film prepared in (c); and/or (i) Forming a sacrificial barrier layer temporarily blocking oxygen and/or water on the first film prepared in (c), measuring the PCE of the film, and then removing the sacrificial barrier layer.

In some embodiments, the two barrier layers exclude oxygen and/or water.

In some embodiments, 92-98% of the emission fringes are edge-emitted. In some embodiments, 93-96% of the emission is fringed edge emission.

Also provided are methods of making the compositions comprising (a) providing a composition comprising AIGS nanostructures and at least one ligand coating the surface of the nanostructures; and (b) Mixing the composition obtained in (a) with at least one second ligand.

In some embodiments, the composition of (a) further comprises an organic resin. In some embodiments, the composition of (a) further comprises at least one monomer incorporated into a ligand that coats the AIGS surface. In some embodiments, the method further comprises inkjet printing the composition.

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

Devices comprising the above-described films are also provided.

Nanostructured molded articles are also provided that include: (a) the first conductive layer; (b) the second conductive layer; and (c) a film comprising an AIGS nanostructure layer between the first conductive layer and the second conductive layer, The nanostructure layer comprises AIGS nanostructures with PCE greater than 32%.

Also available are nanostructured color converters that include bottom plate; a display panel arranged on the backplane; and A film comprising an AIGS nanostructure layer, the nanostructure layer comprising AIGS nanostructures with PCE greater than 32%, is arranged on a display panel.

In some embodiments, the nanostructure layer includes a patterned nanostructure layer. In some embodiments, the backplane includes LEDs, LCDs, OLEDs, or micro LEDs.

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

definition

Unless otherwise defined, all technical and scientific terms used herein have the same meanings as commonly understood by those skilled in the art. The following definitions supplement their definitions in the industry and are specific to current application and are not attributable to any related or unrelated circumstances, such as any commonly owned patents or applications. Although any methods and materials similar or equivalent to those described herein can be used in the practice of the present tests, the preferred materials and methods are described herein. Therefore, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

As used in this specification and the appended claims, the singular forms "a (a, an)" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "nanostructures" includes a plurality of such nanostructures and the like.

The term "about" as used herein indicates that a given amount varies by +/- 10% of that value. For example, "about 100 nm" encompasses the size range of 90 nm to 110 nm, inclusive.

A "nanostructure" is a structure having at least one region or feature size less than about 500 nm in size. In some embodiments, the nanostructures have dimensions of 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, nano particles and the like. The nanostructures can be, for example, substantially crystalline, substantially monocrystalline, polymorphic, amorphous, or combinations thereof. In some embodiments, each of the three dimensions of the nanostructure has a dimension of 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 .

When used in reference to nanostructures, the term "heterostructure" refers to nanostructures that are characterized by at least two different and/or distinguishable types of materials. Typically, one region of the nanostructure contains a first material type and a second region of the nanostructure contains a second material type. In certain embodiments, the nanostructure includes a core of a first material and at least one shell of a second (or third, etc.) material, where, for example, different material types surround the long axis of the nanowire, the arms of the branched nanowire The long axis of the nanocrystal or the radial distribution of the center of the nanocrystal. A shell may, but need not, completely cover an adjacent material considered to be a shell or a nanostructure that is considered a heterostructure; for example, a nanocrystalline system heterostructure characterized by a core of one material covered by islands of a second material. In other embodiments, different material types are distributed at different locations within the nanostructure; eg, along the major, long axis of the nanowire or along the long axis of the arms of the branched nanowire. Different regions within the heterostructure may contain entirely different materials, or different regions may contain a base material (eg, silicon) with different dopants or different concentrations of the same dopant.

As used herein, the "diameter" of a nanostructure refers to the diameter of the cross-section orthogonal to the first axis of the nanostructure, where the first axis has the largest difference in length with respect to the second and third axes (the second axis and the two axes whose lengths are closest to each other in the third axis system). 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 short longitudinal axis of the disk. When the cross section is not circular, the diameter is the average of the long and short axes of the cross section. For elongated or high aspect ratio nanostructures, such as nanowires, the diameter is measured across a cross-section perpendicular to the longest axis of the nanowire. For spherical nanostructures, the diameter is measured from one side through the center of the sphere to the other.

The term "crystalline" or "substantially crystalline" when used in reference to nanostructures refers to the fact that nanostructures typically exhibit long-range ordering across one or more dimensions of the structure. It will be understood by those skilled in the art that the term "long-range ordering" will depend on the absolute size of a particular nanostructure, since a single crystal cannot be ordered beyond the boundaries of the crystal. In this context, "long-range order" would mean substantial order across at least most dimensions of the nanostructure. In some cases, the nanostructures may have oxide or other coatings, or may include a core and at least one shell. In such cases, it is understood that the oxide, shell, or other coating may, but need not, exhibit this ordering (eg, it may be amorphous, polycrystalline, or otherwise). In these cases, the phrases "crystalline," "substantially crystalline," "substantially single-crystalline," or "single-crystalline" refer to the central core (excluding the coating or shell) of the nanostructure. The terms "crystalline" or "substantially crystalline" as used herein are intended to also encompass structures comprising various defects, stacking defects, atomic substitutions, and the like, so long as the structure exhibits considerable long-range order (eg, in nanostructures or their ordered within at least about 80% of the length of at least one axis of the core). Furthermore, it should be understood that the interface between the core and the exterior, or between the core and an adjacent shell, or between the shell and a second adjacent shell of the nanostructure may contain amorphous regions, and may even be amorphous. This does not prevent the nanostructures from being crystallized or substantially crystallized as defined herein.

When used in reference to nanostructures, the term "single crystal" indicates that the nanostructures are substantially crystalline and comprise substantially single crystals. When used in reference to a nanostructured heterostructure comprising a core and one or more shells, "single crystal" indicates that the core is substantially crystalline and substantially comprises a single crystal.

A "nanocrystal" is a nanostructure that is essentially a single crystal. Thus, the nanocrystals have at least one region or feature size that is less than about 500 nm in size. In some embodiments, the nanocrystals have dimensions of 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 crystalline nanostructures comprising various defects, stacking defects, atomic substitutions, and the like, as well as substantially single crystalline nanostructures free of such defects, defects or substitutions. In the case of nanocrystal heterostructures comprising a core and one or more shells, the core of the nanocrystal is typically substantially single crystalline, but the shell need not be single crystalline. In some embodiments, each of the three dimensions of the nanocrystal has a size of 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 .

The term "quantum dot" (or "dot") refers to a nanocrystal that exhibits quantum confinement or exciton confinement. Quantum dots may be substantially homogeneous in material properties, or, in certain embodiments, may be heterogeneous, eg, including a core and at least one shell. The optical properties of quantum dots can be affected by their particle size, chemical composition, and/or surface composition, and can be determined by suitable optical tests available in the industry. The ability to tailor the size of nanocrystals, eg, in the range between about 1 nm and about 15 nm, enables photoemission coverage across the spectrum to provide great versatility in color rendering.

The term "oxygen-free ligand" refers to a coordinating molecule that does not contain an oxygen atom capable of coordinating or reacting with a metal ion as used herein.

A "ligand" is one capable of interacting with one or more faces of the nanostructure (whether weak or strong) molecules.

"Photoluminescence quantum yield" (QY) is, for example, the ratio of photons emitted to photons absorbed by a nanostructure or population of nanostructures. As is known in the art, quantum yields are typically determined by the absolute change in photon counts when the sample is irradiated within an integrating sphere, or by comparison methods using well-characterized standard samples with known quantum yield values.

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

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

Compared to the corresponding defect emission, the band-edge emission is centered at higher energy (lower wavelength) and is less offset from the absorption onset energy. Furthermore, band-edge emission has a narrower wavelength distribution than defect emission. Both band-edge emission and defect emission follow a normal (approximately Gaussian) wavelength distribution.

Optical density (OD) is a common 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 directly proportional to the concentration of solutes that absorb light of a particular wavelength.

Optical density is the attenuation of light per centimeter of material as measured using a standard spectrometer, usually specified as a 1 cm path length. Nanostructured solutions are often measured by their optical density instead of mass or molar concentration, as this is proportional to concentration, and this is a more convenient way of expressing nanostructured solutions at the wavelength of interest The amount of light absorption that occurs in . The concentration of the nanostructure solution with an OD of 100 is 100 times that of the product with an OD of 1 (the number of particles per mL is 100 times).

Optical density can be measured at any wavelength of interest, eg, at the wavelength selected to excite fluorescent nanostructures. Optical density is a measure of the intensity of light lost through a nanostructured solution at a specific wavelength and is calculated using the following formula: OD = log ₁₀ *(I _OUT /I _IN ) where: I _OUT = intensity of radiation entering the cell; and I _IN = the intensity of the radiation transmitted through the cell.

The optical density of the nanostructured solution can be measured using a UV-VIS spectrometer. Thus, by using a UV-VIS spectrometer, the optical density can be calculated to determine the amount of nanostructures present in the sample.

The ranges set forth herein are inclusive unless expressly indicated otherwise.

Various additional terms are defined or otherwise characterized herein. AIGS nanostructures

Nanostructures comprising Ag, In, Ga, and S are provided, wherein the nanostructures have a peak emission wavelength (PWL) between 480-545 nm. In some embodiments, at least about 80% of the emission tether is edge-emitted. By fitting the Gaussian peaks (usually 2 or more) of the nanostructure emission spectrum and bringing the energy closer to the peak area of the nanostructure band gap (representing the band-edge emission) and the sum of all peak areas (band-edge) Emission + Defect Emission) are compared and the percentage of band edge emission is calculated.

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

In another embodiment, the nanostructure has a QY of about 80% to 99.9%. In another embodiment, the nanostructure has a QY of 85-95%. In another embodiment, the nanostructure has a QY of about 86% to about 94%. In some embodiments, at least 80% of the emission fringes are edge-emitted. In other embodiments, at least 90% of the firing tethers are edge fired. In other embodiments, at least 95% of the firing tethers are edge fired. In some embodiments, 92-98% of the emission fringes are edge-emitted. In some embodiments, 93-96% of the emission is fringed edge emission.

AIGS nanostructures provide high blue light absorption. As a predicted value for blue light absorption efficiency, the optical density of the nanostructure solution in a 1 cm path length cuvette was measured by dividing by the dryness per mL of the same solution after removing all volatiles under vacuum (< 200 mTorr). Mass (mg/mL), optical density at ₄₅₀ nm by mass (OD450/mass) was calculated. In one embodiment, the nanostructures provided herein have an _OD450 /mass (mL.mg ^- 1.cm ^{- 1} ) of at least 0.8. In another embodiment, the nanostructure has an _OD450 /mass (mL.mg ^- 1.cm ^{- 1} ) of 0.8-2.5. In another embodiment, the nanostructure has an _OD450 /mass (mL.mg-1.cm ^{- 1} ) of 0.87-1.9 ^.

In one embodiment, the nanostructures are treated with gallium ions such that ion exchange of gallium for indium occurs throughout the AIGS nanostructure. In another embodiment, the nanostructure has Ag, In, Ga and S in the core and is processed by ion exchange with gallium ions and S. In another embodiment, the nanostructures have Ag, In, Ga and S in the core and are processed by ion exchange with silver ions, gallium ions and S. In some embodiments, the ion exchange treatment results in a gradient of gallium, silver, and/or sulfur throughout the nanostructure.

In one embodiment, the average diameter of the nanostructures is less than 10 nm as measured by TEM. In another embodiment, the average diameter is about 5 nm. AIGS nanostructures were prepared using GaX ₃ (X = F, Cl or Br) precursors and oxygen-free ligands

Reports in the literature on the preparation of AIGS do not attempt to exclude oxygen-containing ligands. In coatings of AIGS with gallium, oxygen-containing ligands are typically used to stabilize the Ga precursor. Gallium(III) acetylacetonate is often used as a precursor that is easy to air handle, while Ga(III) chloride requires careful handling due to its sensitivity to moisture. For example, in Kameyama et al., ACS Appl. Mater. Interfaces 10: 42844-42855 (2018), gallium(III) acetylacetonate was used as the precursor for the core and core/shell structures. Due to the high affinity of gallium for oxygen, when Ga and S precursors are used to create nanostructures containing significant gallium content, oxygen-containing ligands and the use of gallium precursors not prepared under oxygen-free conditions can produce unwanted side effects Reactions such as gallium oxide. These side reactions can lead to defects in the nanostructure and result in lower quantum yields.

In some embodiments, AIGS nanostructures are prepared using oxygen-free _GaX3 (X = F, Cl or Br) as a precursor in the preparation of AIGS cores. In some embodiments, AIGS nanostructures are prepared using _GaX3 (X = F, Cl, or Br) as a precursor and an oxygen-free ligand in the preparation of Ga-rich AIGS nanostructures. In some embodiments, AIGS nanostructures are prepared using _GaX3 (X = F, Cl or Br) as a precursor and anaerobic ligand in the preparation of AIGS cores. In some embodiments, AIGS nanostructures are prepared using _GaX3 (X=F, Cl or Br) as a precursor and anaerobic ligand in the preparation of AIGS cores and in the ion exchange treatment of AIGS cores.

Nanostructures comprising Ag, In, Ga, and S are provided, wherein the nanostructures have a peak emission wavelength (PWL) between 480-545 nm, and wherein the nanostructures use _GaX3 (X = F, Cl or Br) precursors and anaerobic ligands.

In some embodiments, nanostructures prepared using _GaX3 (X=F, Cl, or Br) precursors and oxygen-free ligands exhibit FWHM emission spectra of 35 nm or less. In some embodiments, nanostructures prepared using _GaX3 (X=F, Cl, or Br) precursors and oxygen-free ligands exhibit FWHMs of 30-38 nm. In some embodiments, nanostructures prepared using _GaX3 (X=F, Cl, or Br) precursors and oxygen-free ligands have a QY of at least 75%. In some embodiments, nanostructures prepared using _GaX3 (X=F, Cl, or Br) precursors and oxygen-free ligands have a QY of 75-90%. In some embodiments, nanostructures prepared using _GaX3 (X=F, Cl, or Br) precursors and oxygen-free ligands have about 80% QY.

The AIGS nanostructures prepared here provide high blue light absorption. In some embodiments, the nanostructures have an _OD450 /mass (mL·mg ^{"1.cm" 1} ) of at least 0.8. In some embodiments, the nanostructures have an _OD450 /mass (mL.mg ^- 1.cm ^{- 1} ) of 0.8-2.5. In another embodiment, the nanostructure has an _OD450 /mass (mL.mg-1.cm ^{- 1} ) of 0.87-1.9 ^.

In some embodiments, the nanostructures are treated with gallium ions such that ion exchange of gallium for indium occurs throughout the AIGS nanostructure. In some embodiments, the nanostructure includes Ag, In, Ga, and S in the core, and there is a gallium gradient between the surface and the center of the nanostructure. In some embodiments, nanostructures are prepared with AGS-treated AIGS cores using _GaX3 (X=F, Cl, or Br) precursors and anaerobic ligands in the cores. In some embodiments, the nanostructures are AIGS nanostructures prepared using _GaX3 (X=F, Cl or Br) precursors and oxygen-free ligands. In some embodiments, AIGS nanostructures are obtained by reacting a preformed In _- Ga reagent with Ag2S nanostructures, followed by ion exchange with gallium by reacting with an oxygen-free Ga salt to form AIGS nanostructures to prepare AIGS nanostructures. Method for preparing AIGS nanostructures

Provided are methods of fabricating AIGS nanostructures comprising: (a) preparing a mixture comprising AIGS core, sulfur source and ligand; (b) Add the mixture obtained in (a) to the mixture of gallium carboxylate and ligand at a temperature of 180-300°C to obtain an ion-exchanged nanostructure with a gallium gradient from the surface to the center of the nanostructure structure; and (c) Isolated nanostructures.

In some embodiments, the nanostructure has a PWL of 480-545 nm with at least about 60% of the emission tethered edge emission.

Also provided are methods of making AIGS nanostructures, comprising: (a) reacting Ga(acetylpyruvate) ₃ , _InCl3 , and a ligand, optionally in a solvent at a temperature sufficient to obtain an In-Ga reagent, and (b) reacting the In-Ga reagent with the Ag ₂ S nanostructures at a temperature sufficient to fabricate the AIGS nanostructures, (c) reacting the AIGS nanostructures with an oxygen-free Ga salt in a solvent containing the ligand at a sufficient temperature The reaction at the temperature resulting in an ion-exchanged nanostructure with a gallium gradient from the surface of the nanostructure to the center.

In some embodiments, the nanostructure has a PWL of 480-545 nm with at least about 60% of the emission tethered edge emission.

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

In some embodiments, at least 80% of the emission fringes are edge-emitted. In other embodiments, at least 90% of the firing tethers are edge fired. In other embodiments, at least 95% of the firing tethers are edge fired. In some embodiments, 92-98% of the emission fringes are edge-emitted. In some embodiments, 93-96% of the emission is fringed edge emission.

Examples of ligands are disclosed in US Patent Nos. 7,572,395; 8,143,703; 8,425,803; 8,563,133; 8,916,064; 9,005,480; middle. In one embodiment, the ligand is an alkylamine. In some embodiments, the ligand system is selected from an alkylamine selected from the group consisting of dodecylamine, oleylamine, cetylamine, dioctylamine, and octadecylamine.

In some embodiments, the sulfur source in (a) comprises trioctylphosphine sulfide, elemental sulfur, octanethiol, dodecanethiol, octadecanethiol, tributylphosphine sulfide, isosulfide Cyclohexyl cyanate, alpha-toluenethiol, ethylene trithiocarbonate, allyl mercaptan, bis(trimethylsilyl)sulfide, trioctylphosphine sulfide, or combinations thereof. In some embodiments, the sulfur source in (a) is from _S8 .

In one embodiment, the sulfur source is from _S8 .

In one embodiment, the temperature in (a) and (b) is about 270°C.

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

In some embodiments, the gallium carboxylate is a _C2-24 gallium carboxylate. Examples of C _2-24 carboxylates include acetate, propionate, butyrate, valerate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, decanoate Triate, myristate, pentadecanoate, hexadecanoate, octadecanoate (oleate), nonadenoate and behenate. In one embodiment, the gallium carboxylate is gallium oleate.

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

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

Also provided are methods of fabricating nanostructures comprising: (a) preparing a mixture comprising AIGS cores and gallium halide in a solvent, and maintaining the mixture for a time sufficient to obtain an ion-exchanged nanostructure with a gallium gradient from the surface of the nanostructure to the center; and (b) Isolated nanostructures.

In some embodiments, the nanostructures have a PWL of 480-545 nm with at least about 60% of the emission tethered edge emission.

In some embodiments, at least 80% of the emission fringes are edge-emitted. In other embodiments, at least 90% of the firing tethers are edge fired. In other embodiments, at least 95% of the firing tethers are edge fired.

In some embodiments, the gallium halide is chloride, bromide or iodide of gallium. In one embodiment, the gallium halide is gallium iodide.

In some embodiments, the solvent comprises trioctylphosphine. In some embodiments, the solvent comprises toluene.

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

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

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

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

Also provided are methods of making nanostructures, comprising: (a) preparing a mixture comprising AIGS nanostructures, a sulfur source and a ligand; (b) subjecting the mixture obtained in (a) at a temperature of 180-300°C 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 (d) separation of the nanostructures structure.

In some embodiments, the nanostructures have a PWL of 480-545 nm.

In some embodiments, the preparation of (a) is carried out under anaerobic conditions. In some embodiments, the preparation in (a) is performed in a glove box.

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

In some embodiments, at least 80% of the emission fringes are edge-emitted. In other embodiments, at least 90% of the firing tethers are edge fired. In other embodiments, at least 95% of the firing tethers are edge fired.

Examples of ligands are disclosed in US Patent Nos. 7,572,395; 8,143,703; 8,425,803; 8,563,133; 8,916,064; 9,005,480; middle. In some embodiments, the ligand in (a) is an oxygen-free ligand. In some embodiments, the ligand in (b) is an oxygen-free ligand. In some embodiments, the ligands in (a) and (b) are alkylamines. In some embodiments, the ligand system is selected from an alkylamine selected from the group consisting of dodecylamine, oleylamine, cetylamine, 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.

In one embodiment, the sulfur source is from _S8 .

In one embodiment, the temperature in (a) and (b) is about 270°C.

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

In some embodiments, GaX ₃ is gallium chloride, gallium fluoride, or gallium iodide. In some embodiments, the GaX ₃ series gallium chloride. In some embodiments, GaX ₃ is Ga(III) chloride.

In some embodiments, the ratio of _GaX3 to AIGS core is 0.008-0.2 mmol _GaX3 /mg AIGS. In some embodiments, the molar ratio of GaX ₃ to AIGS core is from about 0.1 to about 30. In some embodiments, the ratio of _GaX3 to AIGS core is about 0.04 mmol _GaX3 /mg AIGS.

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

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 about room temperature (20°C to 25°C).

In some embodiments, the mixture in (b) is maintained at 200°C to 300°C for 0.1 hour to 200 hours. In some embodiments, the mixture in (b) is maintained at 200°C to 300°C for about 20 hours. Doped AIGS Nanostructures

In some embodiments, AIGS nanostructures are doped. In some embodiments, the dopants of the nanocrystal cores comprise metals, including one or more transition metals. In some embodiments, the dopant is a transition metal selected from the group consisting of: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au and combinations thereof. In some embodiments, the dopant comprises a non-metal. In some embodiments, the dopant is ZnS, ZnSe, ZnTe, CdSe, CdS, CdTe, HgS, HgSe, HgTe, _CuInS2 , _CuInSe2 , AlN, AlP, AlAs, GaN, GaP, or GaAs.

In some embodiments, the core is purified by precipitation from a non-solvent. In some embodiments, the AIGS nanostructures are filtered to remove precipitates from the core solution. Nanostructured composition

In some embodiments, the present invention provides nanostructured compositions comprising: (a) at least one population of AIGS nanostructures; and (b) at least one organic resin.

In some embodiments, the nanostructures have a PWL between 480-545 nm.

In some embodiments, at least 80% of the nanostructures emit tethered edge emission. In other embodiments, at least 90% of the firing tethers are edge fired. In other embodiments, at least 95% of the firing tethers are edge fired. In some embodiments, 92-98% of the emission fringes are edge-emitted. In some embodiments, 93-96% of the emission is fringed edge emission.

In some embodiments, the nanostructure composition further comprises at least one second population of nanostructures. Nanostructures with a PWL between 480-545 nm emit green light. Additional populations of nanostructures emitting in the green, yellow, orange and/or red regions of the spectrum can be added. The nanostructures have PWLs greater than 545 nm. In some embodiments, the nanostructures have a PWL between 550-750 nm. The size of the nanostructure determines the emission wavelength. The at least one second population of nanostructures may comprise III-V nanocrystals selected from the group consisting of BN, BP, BAs, BSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs and InSb. In some embodiments, the cores of the second population of nanostructures are InP nanocrystals. organic resin

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

Thermosetting resins require curing, during which they undergo an irreversible molecular cross-linking process, which makes the resin infusible. In some embodiments, the thermosetting resins are epoxy resins, phenolic resins, vinyl resins, melamine resins, urea resins, unsaturated polyester resins, polyurethane resins, allyl resins, acrylic resins, polyamides Amine resins, polyamide-imide resins, phenolamine polycondensation resins, urea melamine polycondensation resins, or combinations thereof.

In some embodiments, the thermoset resin is an epoxy resin. Epoxies cure easily without volatiles or by-products from various chemicals. Epoxies are also compatible with most substrates and tend to wet surfaces easily. See Boyle, M.A. et al., "Epoxy Resins," Composites, Vol. 21, ASM Handbook, pp. 78-89 (2001).

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

In some embodiments, thermal initiators are used. In some embodiments, the thermal initiator is AIBN [2,2'-azobis(2-methylpropionitrile)] or benzyl peroxide.

UV curable resins are polymers that cure and harden rapidly when exposed to specific wavelengths of light. In some embodiments, the UV curable resins have as functional groups free radical polymerizable groups (eg (meth)acryloyloxy, vinyloxy, styryl or vinyl), cationically polymerizable groups (eg epoxy, thioepoxy, vinyloxy or oxetanyl). In some embodiments, the UV curable resins are polyester resins, polyether resins, (meth)acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resin or polythiol polyene resin.

In some embodiments, the UV curable resin is selected from the group consisting of: isobornyl acrylate, isobornyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, amines carbamate acrylate, allyloxylated cyclohexyl diacrylate, bis(acrylooxyethyl) hydroxy isocyanurate, bis(acrylooxyneopentyl glycol) adipate, bis(acrylooxyneopentyl) adipate Phenol 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, Dipivalerythritol hexaacrylate, Two new Pentaerythritol monohydroxypentaacrylate, di(trimethylolpropane) tetraacrylate, ethylene glycol dimethacrylate, glycerol methacrylate, 1,6-hexanediol diacrylate, 1,6 -Hexanediol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol hydroxypivalate diacrylate, neopentaerythritol triacrylate, neotaerythritol tetraacrylate, phosphoric acid Dimethacrylate, Polyethylene Glycol Diacrylate, Polypropylene Glycol Diacrylate, Tetraethylene Glycol Diacrylate, Tetrabromobisphenol A Diacrylate, Triethylene Glycol Divinyl Ether, Triglycerol Diacrylate Esters, Trimethylolpropane Triacrylate, Tripropylene Glycol Diacrylate, Tris(acryloyloxyethyl)isocyanurate, Phosphate Triacrylate, Phosphate Diacrylate, Propargyl Acrylate, Vinyl End-capped polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated trifluoromethylsiloxane-dimethylsiloxane copolymer, vinyl terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane, monomethyl siloxane Acryloyloxypropyl terminated polydimethylsiloxane, monovinyl terminated polydimethylsiloxane, monoallyl-monotrimethylsiloxy terminated polyethylene oxide and its combinations.

In some embodiments, the UV-curable resins are mercapto-functional compounds that can be cross-linked with isocyanates, epoxy resins, or unsaturated compounds under UV curing conditions. In some embodiments, the polythiol is neotaerythritol tetrakis(3-mercapto-propionate) (PETMP); trimethylol-propane tris(3-mercapto-propionate) (TMPMP); diols bis(3-mercapto-propionate) (GDMP); sam[25-(3-mercapto-propionyloxy)ethyl]isocyanurate (TEMPIC); bis-neopentaerythritol hexa(3 - mercapto-propionate) (Di-PETMP); ethoxylated trimethylolpropane tris(3-mercapto-propionate) (ETTMP 1300 and ETTMP 700); polycaprolactone tetrakis(3-mercapto-propionate) propionate) (PCL4MP 1350); neotaerythritol tetramercaptoacetate (PETMA); trimethylol-propane trimercaptoacetate (TMPMA); or glycol dimercaptoacetate (GDMA). These compounds are sold under the tradename ^THIOCURE® by Bruno Bock, Marschacht, Germany.

In some embodiments, the UV curable resin is a polythiol. In some embodiments, the UV curable resin is a polythiol selected from the group consisting of ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), trimethylol Propane ginseng (mercaptoacetate), trimethylolpropane ginseng (3-mercaptopropionate), neotaerythritol tetrakis (mercaptoacetate), neotaerythritol tetrakis (3-mercaptopropionate) ( PETMP), and combinations thereof. In some embodiments, the UV curable resin is PETMP.

In some embodiments, the UV curable resin system comprises a polythiol and 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-triazine Thiol-ene formulations of ketones (TTT). In some embodiments, the UV curable resin is a thiol-ene formulation comprising PETMP and TTT.

。In some embodiments, the UV curable resin further comprises a photoinitiator. The photoinitiator initiates the crosslinking and/or curing reaction of the photosensitive material during exposure. In some embodiments, the photoinitiator is acetophenone-based, benzoin-based, or oxysulfide-based

.

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

In some embodiments, the photoinitiator is ^IRGACURE 127, IRGACURE 184, ^{IRGACURE 184D} , ^IRGACURE 2022, ^IRGACURE 2100, ^IRGACURE 250, ^IRGACURE 270, IRGACURE ²⁹⁵⁹ , ^IRGACURE 369, ^IRGACURE 369 EG, IRGACURE® 379, IRGACURE® 500, IRGACURE® 651, ^IRGACURE® 754, ^IRGACURE® 784, ^IRGACURE® 819, ^{IRGACURE® 819Dw} , ^IRGACURE® 907, ^IRGACURE® 907 FF, ^{IRGACURE® Oxe01} , ^{IRGACURE® TRURE} ® 1173, IRGACURE® 1173D, IRGACURE® 4265, IRGACURE® BP or IRGACURE® MBF (BASF Corporation, Wyandotte, MI). In some embodiments, the photoinitiator is TPO (2,4,6-trimethylbenzyl-diphenyl-phosphine oxide) or MBF (methyl benzylcarboxylate).

In some embodiments, the weight % of the at least one organic resin in the nanostructure composition is between about 5% and about 99%, about 5% and about 95%, about 5% and about 90%, about 5% and about 5%. About 80%, about 5% and about 70%, about 5% and about 60%, about 5% and about 50%, about 5% and about 40%, about 5% and about 30%, about 5% and about 20% %, about 5% and about 10%, about 10% and about 99%, about 10% and about 95%, about 10% and about 90%, about 10% and about 80%, about 10% and about 70%, About 10% and about 60%, about 10% and about 50%, about 10% and about 40%, about 10% and about 30%, about 10% and about 20%, about 20% and about 99%, about 20% % and about 95%, about 20% and about 90%, about 20% and about 80%, about 20% and about 70%, about 20% and about 60%, about 20% and about 50%, about 20% and about About 40%, about 20% and about 30%, about 30% and about 99%, about 30% and about 95%, about 30% and about 90%, about 30% and about 80%, about 30% and about 70% %, about 30% and about 60%, about 30% and about 50%, about 30% and about 40%, about 40% and about 99%, about 40% and about 95%, about 40% and about 90%, About 40% and about 80%, about 40% and about 70%, about 40% and about 60%, about 40% and about 50%, about 50% and about 99%, about 50% and about 95%, about 50% % and about 90%, about 50% and about 80%, about 50% and about 70%, about 50% and about 60%, about 60% and about 99%, about 60% and about 95%, about 60% and about About 90%, about 60% and about 80%, about 60% and about 70%, about 70% and about 99%, about 70% and about 95%, about 70% and about 90%, about 70% and about 80% %, about 80% and about 99%, about 80% and about 95%, about 80% and about 90%, about 90% and about 99%, about 90% and about 95%, or about 95% and about 99% between.

In some embodiments, the nanostructured composition further comprises at least one monomer incorporated into the ligand coating the AIGS surface. It has been found that AIGS nanostructures containing at least one monomer incorporated into the ligand that coats the AIGS surface have high QY, good compatibility with HDDA (a common monomer used in inkjet printable inks), and good Blue light absorption.

In some embodiments, at least one monosystem acrylate. Examples of acrylate monomers include, but are not limited to, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methyl methacrylate tert-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, tridecyl methacrylate, stearyl methacrylate, methyl methacrylate Decyl methacrylate, dodecyl methacrylate, methoxydiethylene glycol methacrylate, polypropylene glycol monomethacrylate, phenyl methacrylate, oxyethyl benzyl methacrylate ester, tetrahydrofurfuryl methacrylate, tert-butylcyclohexyl methacrylate, behenyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyloxyethyl methacrylate methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isooctyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, lauryl methacrylate , cetyl methacrylate, octadecyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate, ethyl acrylate ester, methyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, 2-carboxyethyl acrylate, acrylic acid, ethylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,4 -Bis(acryloyloxy)butane, isobornyl acrylate, tetrahydrofurfuryl acrylate, cyclic trimethylolpropane formaldehyde acrylate, cyclohexyl methacrylate and 4-tert-butyl acrylate Cyclohexyl ester.

In some embodiments, the mono-system ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or isobornyl acrylate at least one of esters. Methods of making AIGS nanostructure compositions

The present invention provides a method for preparing a nanostructured composition, the method comprising: (a) providing at least one population of AIGS nanostructures; and (b) mixing at least one organic resin with the composition of (a).

In some embodiments, the nanostructures have a PWL between 480-545 nm and an emission tether edge emission of at least about 80%. In some embodiments, at least 80% of the emission fringes are edge-emitted. In other embodiments, at least 90% of the firing tethers are edge fired. In other embodiments, at least 95% of the firing tethers are edge fired. In some embodiments, 92-98% of the emission fringes are edge-emitted. In some embodiments, 93-96% of the emission is fringed edge emission.

The present invention also provides a method of making a nanostructure composition, the method comprising: (a) providing at least one population of AIGS nanostructures, and wherein the nanostructures use a _GaX3 (X = F, Cl or Br) precursor and oxygen-free ligands; and (b) mixing at least one organic resin with the composition of (a).

In some embodiments, the nanostructures have a PWL between 480-545 nm and an emission tethered edge emission of at least about 60%.

The present invention also provides a method of making a nanostructure composition, the method comprising: (a) providing at least one population of AIGS nanostructures, wherein the nanostructures have a PWL between 480-545 nm, wherein at least about 80 % emission tethered edge emission and wherein the nanostructure exhibits 80-99% QY; and (b) mixing at least one organic resin with the composition of (a).

In some embodiments, at least one population of nanostructures and at least one organic resin are mixed at between about 100 rpm and about 10,000 rpm, about 100 rpm and about 5,000 rpm, about 100 rpm and about 3,000 rpm, about 100 rpm and about 100 rpm. about 1,000 rpm, about 100 rpm and about 500 rpm, about 500 rpm and about 10,000 rpm, about 500 rpm and about 5,000 rpm, about 500 rpm and about 3,000 rpm, about 500 rpm and about 1,000 rpm, about 1,000 rpm and about 10,000 Mix at agitation rates between about 1,000 rpm and about 5,000 rpm, about 1,000 rpm and about 3,000 rpm, about 3,000 rpm and about 10,000 rpm, about 3,000 rpm and about 10,000 rpm, or about 5,000 rpm and about 10,000 rpm.

In some embodiments, the at least one population of nanostructures is mixed with the at least one organic resin for between about 10 minutes and about 24 hours, about 10 minutes and about 20 hours, about 10 minutes and about 15 hours, about 10 minutes and about 10 minutes and About 10 hours, about 10 minutes and about 5 hours, about 10 minutes and about 1 hour, about 10 minutes and about 30 minutes, about 30 minutes and about 24 hours, about 30 minutes and about 20 hours, about 30 minutes and about 15 hours, about 30 minutes and about 10 hours, about 30 minutes and about 5 hours, about 30 minutes and about 1 hour, about 1 hour and about 24 hours, about 1 hour and about 20 hours, about 1 hour and about 15 hours, About 1 hour and about 10 hours, about 1 hour and about 5 hours, about 5 hours and about 24 hours, about 5 hours and about 20 hours, about 5 hours and about 15 hours, about 5 hours and about 10 hours, about 10 hours hours and about 24 hours, about 10 hours and about 20 hours, about 10 hours and about 15 hours, about 15 hours and about 24 hours, about 15 hours and about 20 hours, or about 20 hours and about 24 hours .

In some embodiments, at least one population of nanostructures is combined with at least one organic resin at between about -5°C and about 100°C, about -5°C and about 75°C, about -5°C and about 50°C, about -5°C and about 23°C, about 23°C and about 100°C, about 23°C and about 75°C, about 23°C and about 50°C, about 50°C and about 100°C, about 50°C and about 75°C, or about Mix at a temperature between 75°C and about 100°C. In some embodiments, the at least one organic resin and at least one population of nanostructures are mixed at a temperature between about 23°C and about 50°C.

In some embodiments, if more than one organic resin is used, the organic resins are added and mixed together. In some embodiments, the first organic resin and the second organic resin are operated at between about 100 rpm and about 10,000 rpm, about 100 rpm and about 5,000 rpm, about 100 rpm and about 3,000 rpm, about 100 rpm and about 1,000 rpm , about 100 rpm and about 500 rpm, about 500 rpm and about 10,000 rpm, about 500 rpm and about 5,000 rpm, about 500 rpm and about 3,000 rpm, about 500 rpm and about 1,000 rpm, about 1,000 rpm and about 10,000 rpm, about Mix at agitation rates between 1,000 rpm and about 5,000 rpm, about 1,000 rpm and about 3,000 rpm, about 3,000 rpm and about 10,000 rpm, about 3,000 rpm and about 10,000 rpm, or between about 5,000 rpm and about 10,000 rpm.

In some embodiments, the first organic resin and the second organic resin are mixed for between about 10 minutes and about 24 hours, about 10 minutes and about 20 hours, about 10 minutes and about 15 hours, about 10 minutes and about 10 hours , about 10 minutes and about 5 hours, about 10 minutes and about 1 hour, about 10 minutes and about 30 minutes, about 30 minutes and about 24 hours, about 30 minutes and about 20 hours, about 30 minutes and about 15 hours, about 30 minutes and about 10 hours, about 30 minutes and about 5 hours, about 30 minutes and about 1 hour, about 1 hour and about 24 hours, about 1 hour and about 20 hours, about 1 hour and about 15 hours, about 1 hour about 10 hours, about 1 hour and about 5 hours, about 5 hours and about 24 hours, about 5 hours and about 20 hours, about 5 hours and about 15 hours, about 5 hours and about 10 hours, about 10 hours and about 24 hours, about 10 hours and about 20 hours, about 10 hours and about 15 hours, about 15 hours and about 24 hours, about 15 hours and about 20 hours, or the time between about 20 hours and about 24 hours.

In some embodiments, the AIGS nanostructures are combined with at least one monomer incorporated into the ligand that coats the AIGS surface prior to combining with the resin. In some embodiments, a single system acrylate. In some embodiments, the mono-system ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or isobornyl acrylate at least one of esters. Properties of AIGS Nanostructures

In some embodiments, AIGS nanostructures exhibit high photoluminescence quantum yields. In some embodiments, the nanostructure exhibits between about 50% and about 99%, about 50% and about 95%, about 50% and about 90%, about 50% and about 85%, about 50% and about 80% %, about 50% and about 70%, about 50% and about 60%, 60% and about 99%, about 60% and about 95%, about 60% and about 90%, about 60% and about 85%, about 60% and about 80%, about 60% and about 70%, about 70% and about 99%, about 70% and about 95%, about 70% and about 90%, about 70% and about 85%, about 70% with about 80%, about 80% and about 99%, about 80% and about 95%, about 80% and about 90%, about 80% and about 85%, about 85% and about 99%, about 85% and about 95%, about 80% and about 85%, about 85% and about 99%, about 85% and about 90%, about 90% and about 99%, about 90% and about 95%, or about 95% and about 99% % photoluminescence quantum yield. In some embodiments, the nanostructure exhibits between about 82% and about 96%, between about 85% and about 96%, and between about 93% and about 94% photoluminescence quanta Yield.

The photoluminescence spectrum of the nanostructures can cover a broad desired part of the spectrum. In some embodiments, the photoluminescence spectrum of the nanostructure is between 300 nm and 750 nm, 300 nm and 650 nm, 300 nm and 550 nm, 300 nm and 450 nm, 450 nm and 750 nm, 450 nm and 450 nm. Emission maximum at 650 nm, 450 nm and 550 nm, 450 nm and 750 nm, 450 nm and 650 nm, 450 nm and 550 nm, 550 nm and 750 nm, 550 nm and 650 nm, or between 650 nm and 750 nm value. In some embodiments, the photoluminescence spectrum of the nanostructure has an emission maximum between 450 nm and 550 nm.

The size distribution of the nanostructures can be relatively narrow. In some embodiments, the photoluminescence spectrum of the population of nanostructures can have a photoluminescence spectrum between 10 nm and 60 nm, 10 nm and 40 nm, 10 nm and 30 nm, 10 nm and 20 nm, 20 nm and 60 nm, 20 nm and 40 nm, 20 nm and 30 nm, 25 nm and 60 nm, 25 nm and 40 nm, 25 nm and 30 nm, 30 nm and 60 nm, 30 nm and 40 nm, or between 40 nm and 60 nm full width at half maximum. In some embodiments, the photoluminescence spectrum of the population of nanostructures can have a full width at half maximum between 24 nm and 50 nm.

In some embodiments, the nanostructures emit a peak emission wavelength (PWL) between about 400 nm and about 650 nm, about 400 nm and about 600 nm, about 400 nm and about 550 nm, about 400 nm and about 500 nm, About 400 nm and about 450 nm, about 450 nm and about 650 nm, about 450 nm and about 600 nm, about 450 nm and about 550 nm, about 450 nm and about 500 nm, about 500 nm and about 650 nm, about 500 nm Light between about 600 nm and about 600 nm, about 500 nm and about 550 nm, about 550 nm and about 650 nm, about 550 nm and about 600 nm, or about 600 nm and about 650 nm. In some embodiments, the nanostructures emit light with a PWL of between about 500 nm and about 550 nm.

As a predicted value for blue light absorption efficiency, the optical density of the nanostructure solution in a 1 cm path length cuvette was measured by dividing by the dryness per mL of the same solution after removing all volatiles under vacuum (< 200 mTorr). Mass (mg/mL), optical density at ₄₅₀ nm by mass (OD450/mass) was calculated. In some embodiments, the nanostructures have between about 0.28/mg and about 0.5/mg, about 0.28/mg and about 0.4/mg, about 0.28/mg and about 0.35/mg, about 0.28/mg and about 0.32/mg mg, about 0.32/mg and about 0.5/mg, about 0.32/mg and about 0.4/mg, about 0.32/mg and about 0.35/mg, about 0.35/mg and about 0.5/mg, about 0.35/mg and about 0.4/mg mg, or between about 0.4/mg and about 0.5/mg optical density at ₄₅₀ nm by mass (OD450/mass). membrane

The nanostructures of the present invention can be embedded in a polymeric matrix using any suitable method. The term "embedded" as used herein is used to indicate that the nanostructure is surrounded or encased by the polymer that constitutes the bulk of the matrix. In some embodiments, at least one population of nanostructures is suitably uniformly distributed throughout the matrix. In some embodiments, at least one population of nanostructures is distributed according to an application-specific distribution. In some embodiments, the nanostructures are mixed in a polymer and applied to the surface of the substrate.

In some embodiments, the present invention provides nanostructured films comprising: (a) a composition comprising at least one population of AIGS nanostructures and at least one ligand bound to the nanostructure; and (b) at least one organic resin.

In some embodiments, a portion of the ligand is bound to the nanostructure. In other embodiments, the nanostructure surface is saturated with ligands.

In some embodiments, the nanostructures have a PWL between 480 nm and 545 nm.

In some embodiments, the composition comprising at least one population of AIGS nanostructures further comprises at least one monomer incorporated into the ligand coating the AIGS surface. In some embodiments, at least one monosystem acrylate. In some embodiments, the mono-system ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or isobornyl acrylate at least one of esters.

The present invention also provides a method for preparing the nanostructured film, comprising: (a) providing at least one population of AIGS nanostructures; and (b) mixing at least one organic resin with the composition of (a). In some embodiments, the nanostructures have a PWL between 480-545 nm.

In some embodiments, at least 80% of the emission fringes are edge-emitted. In other embodiments, at least 90% of the firing tethers are edge fired. In other embodiments, at least 95% of the firing tethers are edge fired. In some embodiments, 92-98% of the emission fringes are edge-emitted. In some embodiments, 93-96% of the emission is fringed edge emission.

(I) 其中： x係1至100； y係0至100；且 R ²係C _1-20烷基。 In some embodiments, the nanostructure composition further comprises an amine-based ligand of formula I:

(I) wherein: x is 1 to 100; y is 0 to 100; and R ² is C _1-20 alkyl.

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.

In some embodiments, R ² is C _1-20 alkyl. In some embodiments, R ² is C _1-10 alkyl. In some embodiments, R ² is C _1-5 alkyl. In some embodiments, R ² is -CH ₂ CH ₃ .

In some embodiments, the compound of formula I is an amine terminated polymer commercially available from Huntsman Petrochemical Corporation. In some embodiments, the amine terminated polymer of formula (VI) has x=1, y= ⁹ and R2= _-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 R2= _-CH3 and is a 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 R2= _-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 R2= _-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 ligands are polyethylene glycol amines, such as PEG550-amine and PEG350-amine, available from Creative PEGWorks.

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

The nanostructure composition can be deposited by any suitable method known in the art including, but not limited to, painting, spraying, solvent spraying, wet coating, adhesive coating, spin coating, tape coating, roller coating coating, curtain coating, ink jet vapor jetting, drop casting, knife coating, mist deposition, or a combination thereof. In some embodiments, the nanostructure composition is cured after deposition. Suitable curing methods include photocuring (eg, UV curing) and thermal curing. Conventional lamination film processing methods, tape coating methods, and/or roll-to-roll fabrication methods can be used to form the nanostructured films of the present invention. The nanostructured composition can be applied directly to the desired layer of the substrate. Alternatively, the nanostructured composition can be formed as a solid layer as a separate element and subsequently applied to a substrate. In some embodiments, the nanostructured composition can be deposited on one or more barrier layers. spin coating

In some embodiments, spin coating is used to deposit the nanostructure composition onto the substrate. In spin coating, a small amount of material is typically deposited onto the center of a substrate loaded with a machine called a spin coater, which is held in place by a vacuum. High speed rotation is applied to the substrate via a spin coater, which causes centripetal forces to spread the material from the center of the substrate to the edges. Although most of the material is peeled off, a certain amount of material remains on the substrate, forming a thin film of material on the surface as the rotation continues. In addition to the parameters selected for the spin coating process, such as spin coating speed, acceleration, and spin coating time, the final thickness of the film is also determined by the properties of the deposition material and substrate. For typical films, spin coating speeds of 1500 to 6000 rpm are used, and spin coating times are 10-60 seconds. In some embodiments, the films are deposited at very low speeds (eg, less than 1000 rpm). In some embodiments, the film is cast at about 300, about 400, about 500, about 600, about 700, about 800, or about 900 rpm. mist deposition

In some embodiments, the nanostructure composition is deposited onto the substrate using spray deposition. The mist deposition is performed at room temperature and atmospheric pressure, and the film thickness can be precisely controlled by changing the process conditions. During mist deposition, the liquid source material becomes a very fine mist and is carried into the deposition chamber by nitrogen gas. The mist is then attracted to the wafer surface by the high voltage potential between the field screen and the wafer holder. Once the droplets coalesce on the wafer surface, the wafer is removed from the chamber and thermally cured to allow the solvent to evaporate. A mixture of liquid pre-system solvent and material to be deposited. It was brought to the nebulizer by pressurized nitrogen gas. Price, S.C. et al., "Formation of Ultra-Thin Quantum Dot Films by Mist Deposition," ESC Transactions 11:89-94 (2007). spray

In some embodiments, the nanostructure composition is deposited onto the substrate using spray coating. Typical equipment for spraying includes nozzles, atomizers, precursor solutions and carrier gas. In the spray deposition process, the precursor solution is pulverized into micron-sized droplets with the aid of a carrier gas or by atomization (eg, ultrasound, air blast, or electrostatics). The droplets coming out of the atomizer are accelerated by the surface of the substrate through a nozzle with the help of a carrier gas, which is controlled and regulated as required. The relative motion between the nozzle and the substrate is determined by design for full coverage on the substrate.

In some embodiments, the application of the nanostructured composition further comprises a solvent. In some embodiments, the solvent used to apply the nanostructure composition is water, an organic solvent, an inorganic solvent, a halogenated organic solvent, or a mixture thereof. Illustrative solvents include, but are not limited to, water, _D2O , acetone, ethanol, dioxane, ethyl acetate, methyl ethyl ketone, isopropanol, anisole, gamma-butyrolactone, dimethylmethane Amide, N-methylpyrrolidone, dimethylacetamide, hexamethylphosphoramide, toluene, dimethyl sulfoxide, cyclopentanone, tetramethylene sulfoxide, xylene, ε-caprolactone ester, tetrahydrofuran, tetrachloroethylene, chloroform, chlorobenzene, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane or mixtures thereof. inkjet printing

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

In some embodiments, the organic solvent used in the nanostructured composition used as an inkjet printing formulation is defined by its boiling point, viscosity, and surface tension. The properties of organic solvents suitable for ink jet printing formulations are shown in Table 1. Table 1: Properties of organic solvents used in inkjet printing formulations solvent Boiling point (℃) 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-Methylanisole 179 — 29

In some embodiments, the boiling point of the organic solvent at 1 atmosphere is between about 150°C and about 350°C. In some embodiments, the boiling point of the organic solvent at 1 atmosphere is between about 150°C and about 350°C, about 150°C and about 300°C, about 150°C and about 250°C, about 150°C and about 200°C, about 200°C and about 350°C, about 200°C and about 300°C, about 200°C and about 250°C, about 250°C and about 350°C, about 250°C and about 300°C, or between about 300°C and about 350°C.

In some embodiments, the organic solvent has a viscosity ^between about 1 mPa.s and ^about 15 mPa.s. In some embodiments, the organic solvent has ^between about 1 mPa.s and about 15 mPa.s ^, about 1 mPa.s and about 10 mPa.s ^{, about} 1 mPa.s and ^about 8 mPa.s ^, about 1 mPa ^{s with} about 6 mPa.s ^{, about} 1 mPa.s ^with about 4 mPa.s ^, about 1 mPa.s with about 2 mPa.s ^, about 2 mPa.s ^with about 15 mPa.s ^, about 2 mPa.s with about 10 mPa.s ^, about 2 mPa.s ^with about 8 mPa.s ^, about 2 mPa.s ^with about 6 mPa.s ^, about 2 mPa.s ^with about 4 mPa.s ^, about 4 mPa.s ^with about 15 mPa.s ^, about 4 mPa.s and about 10 mPa.s ^{, about} 4 mPa.s and about 8 mPa.s ^{, about} 4 mPa.s and about 6 mPa.s ^{, about} 6 mPa.s and ^about 15 mPa ^{s , about} 6 mPa.s and ^about 10 mPa.s ^{, about} 6 mPa.s and ^about 8 mPa.s ^, about 8 mPa.s and about 15 mPa.s ^, about 8 mPa.s and about 10 mPa.s , or a viscosity ^between about 10 mPa.s and ^about 15 mPa.s.

In some embodiments, the organic solvent has a surface tension between about 20 dynes/cm and about 50 dynes/cm. In some embodiments, the organic solvent has between about 20 dynes/cm and about 50 dynes/cm, about 20 dynes/cm and about 40 dynes/cm, about 20 dynes/cm and about 35 dynes/cm /cm, about 20 dynes/cm and about 30 dynes/cm, about 20 dynes/cm and about 25 dynes/cm, about 25 dynes/cm and about 50 dynes/cm, about 25 dynes/cm cm and about 40 dynes/cm, about 25 dynes/cm and about 35 dynes/cm, about 25 dynes/cm and about 30 dynes/cm, about 30 dynes/cm and about 50 dynes/cm , about 30 dynes/cm and about 40 dynes/cm, about 30 dynes/cm and about 35 dynes/cm, about 35 dynes/cm and about 50 dynes/cm, about 35 dynes/cm and about A surface tension of about 40 dynes/cm, or between about 40 dynes/cm and about 50 dynes/cm.

In some embodiments, the organic solvent used in the nanostructure composition is alkylnaphthalene, alkoxynaphthalene, alkylbenzene, aryl, alkyl substituted benzene, cycloalkylbenzene, _C9 - _C20 alkane , diaryl ether, alkyl benzoate, aryl benzoate or alkoxy substituted benzene.

In some embodiments, the organic solvent used in the nanostructure composition is 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, n-octylbenzene, n-nonyl Benzene, 4-methylanisole, n-decylbenzene, p-diisopropylbenzene, amylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropyl Biphenyl, p-Cumylbenzene, Dipentylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetratoluene, 1,2,3,5 -Tetratoluene, 1,2,4,5-tetratoluene, butylbenzene, dodecylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, diphenyl ether, diphenylmethane, 4-isopropylbiphenyl, benzyl benzoate, 1,2-bi(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-methylnaphthalene Anisole, n-decylbenzene, or a combination thereof.

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

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

In some embodiments, the weight % of the organic solvent in the nanostructure composition is between about 70% and about 99%. In some embodiments, the weight % of the organic solvent in the nanostructure composition is between about 70% and about 99%, about 70% and about 98%, about 70% and about 95%, about 70% and about 90% %, about 70% and about 85%, about 70% and about 80%, about 70% and about 75%, about 75% and about 99%, about 75% and about 98%, about 75% and about 95%, About 75% and about 90%, about 75% and about 85%, about 75% and about 80%, about 80% and about 99%, about 80% and about 98%, about 80% and about 95%, about 80% % and about 90%, about 80% and about 85%, about 85% and about 99%, about 85% and about 98%, about 85% and about 95%, about 85% and about 90%, about 90% and about Between about 99%, about 90% and about 98%, about 90% and about 95%, about 95% and about 99%, about 95% and about 98%, or about 98% and about 99%. In some embodiments, the weight % of the organic solvent in the nanostructure composition is between about 95% and about 99%.

In some embodiments, the composition for inkjet printing further comprises a monomer incorporated into the ligand that coats the AIGS surface. In some embodiments, a single system acrylate. In some embodiments, the mono-system ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or isobornyl acrylate at least one of esters. It has been found that the use of monomers in inkjet compositions provides better compatibility of AIGS nanostructures in inkjet compositions, improves QY, and improves blue light absorption. Film curing

In some embodiments, the composition is thermally cured to form the nanostructured layer. In some embodiments, the compositions are cured using UV light. In some embodiments, the nanostructured composition is directly coated onto the barrier layer of the nanostructured film, and then additional barrier layers are deposited on the nanostructured layer to produce the nanostructured film. A support substrate can be used under the barrier 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. Additionally, one or more barrier layers can be deposited on the nanostructure layer to seal the material between the top and bottom barrier layers. Suitably, the barrier layer can be deposited as a laminate film and optionally sealed or further processed prior to incorporating the nanostructured film into a particular lighting device. As will be understood by those skilled in the art, the nanostructure composition deposition process may include additional or varying components. These embodiments will allow for in-process adjustment of nanostructure emission characteristics such as brightness and color (eg, to adjust quantum film white point), as well as nanostructure film thickness and other characteristics. Furthermore, these embodiments will allow for periodic testing of nanostructured film features during production, as well as any necessary switching to achieve precise nanostructured film features. These tests and adjustments can also be accomplished without changing the mechanical configuration of the production line, as computer programs can be used to electronically vary the individual amounts of the mixtures used in forming the nanostructured films.

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 prior to providing the nanostructures with an oxygen-free environment. An oxygen-free environment can be provided by: (a) Encapsulate the film with an oxygen barrier prior to heat treatment and/or exposure to blue light for PCE measurements; (b) using an oxygen reactive material as part of the formulation during heat treatment or light exposure; and/or (c) Temporarily blocking oxygen through the use of sacrificial barrier layers.

In some embodiments, the improvement of PCE can be achieved by any method capable of forming an oxygen barrier on the AIGS layer. In mass production of devices containing these AIGS-CC layers, encapsulation can be performed using vapor deposition methods. In this case, a typical process flow involves inkjet printing of an AIGS layer, followed by curing with UV radiation, baking at 180° C. to remove volatiles, depositing an organic planarization layer, and then depositing an inorganic barrier layer. Techniques for depositing inorganic layers may 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 evaporates. Other potential encapsulation methods include solution-processed or printed organic layers, UV or thermally cured adhesives, lamination using barrier films, and the like.

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

Oxygen reactive materials include any material that is more reactive with oxygen than AIGS nanostructures. Examples of oxygen-reactive materials include, but are not limited to, phosphines, phosphites, metal-organic precursors, titanium nitride, and tantalum nitride. In some embodiments, the phosphine can be any one of C _1-20 trialkylphosphines. In one embodiment, the phosphine is trioctylphosphine. In some embodiments, the phosphite can be a trialkyl phosphite, an alkylaryl phosphite, or a triaryl phosphite. In some embodiments, the metal-organic precursor may be trialkylaluminum, trialkylgallium, trialkylindium, dialkylzinc, and the like.

Examples of sacrificial barrier layers include polymer layers that can be dissolved and washed away in a solvent. 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, lithium fluoride, and the like. Examples of solvents that can be used to wash off the sacrificial layer include water and organic solvents such as alcohols (eg, ethanol, methanol), halogenated hydrocarbons (eg, methylene chloride and vinyl chloride), aromatic hydrocarbons (eg, toluene, xylene), aliphatics Hydrocarbons (eg, hexane, octane, octadecene), tetrahydrofuran, _C4-20 ethers (eg, diethyl ether), and _C2-20 esters (eg, ethyl acetate). Nanostructured Membrane Features and Examples

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

In some embodiments, the nanostructured film is part of the nanostructured color conversion layer.

In some embodiments, the display device includes a nanostructured color converter. In some embodiments, a display device includes a backplane; a display panel disposed on the backplane; 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.

In some embodiments, the backplane includes blue LEDs, LCDs, OLEDs, or micro LEDs.

In some embodiments, the nanostructure layer is disposed on the light source element. In some embodiments, the nanostructure layer includes a patterned nanostructure layer. The patterned nanostructured layer can be prepared by any method known in the art. In one embodiment, the patterned nanostructured layer is prepared by inkjet printing of nanostructured solutions. Suitable solvents for this 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 in inkjet printing because they allow for fast 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 the ink monomer can be used for inkjet printing.

In some embodiments, AIGS nanostructures are inkjet printed with a composition that also includes at least one monomer incorporated into a ligand that coats the AIGS surface. In some embodiments, at least one monosystem acrylate. In some embodiments, the acrylate is in ethyl acrylate, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or isobornyl acrylate at least one of them. It has been found that AIGS nanostructures treated with at least one monomer during ligand exchange provide better compatibility with HDDA (a common monomer used in inkjet printable inks), improving QY and blue light absorption.

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

In some embodiments, the nanostructured display device exhibits a PCE of at least 32%. In some embodiments, the nanostructured molded articles exhibit a PCE of 32-40%. In some embodiments, the nanostructured molded articles exhibit 33-40%, 34-40%, 35-40%, 36-40%, 37-40%, 38-40%, 39-40%, 33-40% 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% of PCE .

In some embodiments, the optical film including the nanostructured layer is substantially free of cadmium. The term "substantially free of cadmium" as used herein is intended to mean that the nanostructured composition contains less than 100 ppm by weight of cadmium. The RoHS compliance definition requires that no more than 0.01% by weight (100 ppm) of cadmium should be present in the raw homogeneous precursor material. Cadmium concentrations can be measured by inductively coupled plasma mass spectrometry (ICP-MS) analysis and are at the parts per billion (ppb) level. In some embodiments, an optical film that is "substantially free of cadmium" contains 10 to 90 ppm of cadmium. In other embodiments, the optical film that is substantially free of cadmium contains less than about 50 ppm, less than about 20 ppm, less than about 10 ppm, or less than about 1 ppm of cadmium. Nanostructured molded articles

In some embodiments, the present invention provides nanostructured molded articles comprising: (a) the first barrier layer; (b) the second barrier layer; and (c) a nanostructure layer between the first barrier layer and the second barrier layer, wherein the nanostructure layer comprises a nanostructure population comprising AIGS nanostructures; and at least one organic resin.

In some embodiments, the nanostructures have a PWL between 480-545 nm.

In some embodiments, at least 80% of the emission fringes are edge-emitted. In other embodiments, at least 90% of the firing tethers are edge fired. In other embodiments, at least 95% of the firing tethers are edge fired. In some embodiments, 92-98% of the emission fringes are edge-emitted. In some embodiments, 93-96% of the emission is fringed edge emission. In some embodiments, the nanostructured molded articles exhibit a PCE of at least 32%. In some embodiments, the nanostructured molded articles exhibit a PCE of 32-40%. In some embodiments, the nanostructured molded articles exhibit 33-40%, 34-40%, 35-40%, 36-40%, 37-40%, 38-40%, 39-40%, 33-40% 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% of PCE . barrier layer

In some embodiments, the nanostructure molded article includes one or more barrier layers disposed on one or both sides of the nanostructure layer. Suitable barrier layers protect the nanostructured layers and nanostructured molded articles 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 nanostructured moldings, exhibit optical and chemical stability, and are able to withstand high temperatures. In some embodiments, the one or more barrier layers are index-matched to the nanostructured molded article. In some embodiments, the matrix material of the nanostructured molded article and one or more adjacent barrier layers are index matched to have similar refractive indices such that a majority of the light transmitted through the barrier layer to the nanostructured molded article is Transmission from the barrier layer into the nanostructure layer. This index matching reduces optical losses at the interface between the barrier and the matrix material.

The barrier layer is suitably a solid material and can be a solidified liquid, gel or polymer. Depending on the particular application, the barrier layer may comprise a flexible or non-flexible material. The barrier layer is typically a planar layer and, depending on the particular lighting application, can include any suitable shape and surface area configuration. In some embodiments, the one or more barrier layers will be compatible with lamination film processing techniques, wherein the nanostructure layer is disposed on at least a first barrier layer and at least a second barrier layer is disposed opposite the nanostructure layer on the nanostructured layer on one side to form a nanostructured molded article according to one embodiment of the present invention. Suitable barrier materials include any suitable barrier materials known in the art. For example, suitable barrier materials include glass, polymers, and oxides. Suitable barrier layer materials include, but are not limited to, polymers such as polyethylene terephthalate (PET); oxides such as silicon oxide, titanium oxide, or aluminum oxide (eg SiO ₂ , Si ₂ O ₃ , TiO ₂ or Al ₂ O ₃ ); and suitable combinations thereof. In some embodiments, each barrier layer of the nanostructured molded article comprises at least 2 layers comprising different materials or compositions, such that the multilayer barrier layers eliminate or reduce pinhole defect alignment in the barrier layers, thereby providing effective Blocks the penetration of oxygen and moisture into the nanostructured layer. The nanostructured layer may include any suitable material or combination of materials and any suitable number of barrier layers on either or both sides of the nanostructured layer. The material, thickness and quantity of the barrier layer will depend on the particular application and is suitably selected to maximize barrier protection and brightness of the nanostructured layer while minimizing the thickness of the nanostructured molded article. In some embodiments, each barrier layer comprises a laminate film, in some embodiments, a bilayer laminate, wherein the thickness of each barrier layer is sufficiently thick to eliminate wrinkling during roll-to-roll or lamination manufacturing. In embodiments where the nanostructures contain heavy metals or other toxic materials, the number or thickness of the barriers may further depend on legal toxicity guidelines, which may require more or thicker barrier layers. Additional considerations for barriers include cost, availability and mechanical strength.

In some embodiments, the nanostructured film includes two or more barrier layers adjacent to each side of the nanostructured layer, eg, two or three layers on each side of the nanostructured layer or Two barrier layers on each side. In some embodiments, each barrier layer comprises a thin glass plate, such as a glass plate having a thickness of about 100 μm, 100 μm or less, or 50 μm or less.

As will be understood by those skilled in the art, each barrier layer of the nanostructured films of the present invention may have any suitable thickness, which will depend on the specific requirements and characteristics of the lighting device and application, as well as factors such as barrier layer and nanostructured layer. and other individual membrane components. In some embodiments, each barrier layer can have a thickness of 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, or 15 μm or less . In certain embodiments, the barrier layer includes an oxide coating, which may include materials such as silicon oxide, titanium oxide, and aluminum oxide (eg, SiO ₂ , Si ₂ O ₃ , TiO ₂ , or Al ₂ O ₃ ). The oxide coating can have a thickness of about 10 μm or less, 5 μm or less, 1 μm or less, or 100 nm or less. In certain embodiments, the barrier ribs comprise a thin oxide coating having a thickness of about 100 nm or less, 10 nm or less, 5 nm or less, or 3 nm or less. The top and/or bottom barriers may consist of a thin oxide coating, or may comprise a thin oxide coating and one or more additional layers of material. Display device with nanostructured color conversion layer

In some embodiments, the present invention provides a display device comprising: (a) a display panel for emitting the first light; (b) a backlight unit configured to provide the first light to the display panel; and (c) includes at least one color filter including the pixel region of the color conversion layer.

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

In some embodiments, each pixel region includes a color conversion layer. In some embodiments, the color converting layer includes nanostructures described herein that are configured to convert incident light to light of a first color. In some embodiments, the color converting layer includes the nanostructures described herein configured to convert incident light to blue light.

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 a color conversion layer comprising the nanostructures described herein. In some embodiments, the display device includes 2 color conversion layers comprising the nanostructures described herein. In some embodiments, the display device includes 3 color conversion layers comprising the nanostructures described herein. In some embodiments, the display device includes 4 color conversion layers comprising the nanostructures described herein. In some embodiments, the display device includes at least one red conversion layer, at least one green conversion layer, and at least one blue conversion layer.

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

The nanostructured color conversion layer can be deposited by any suitable method known in the art including, but not limited to, painting, spraying, solvent spraying, wet coating, adhesive coating, spin coating, tape coating, Roll coating, curtain coating, ink jet printing, photoresist patterning, drop casting, knife coating, mist deposition, or combinations thereof. In some embodiments, the nanostructured color conversion layer is deposited by photoresist patterning. In some embodiments, the nanostructured color conversion layer is deposited by inkjet printing. Compositions comprising AIGS nanostructures and ligands

In some embodiments, the AIGS nanostructure composition further comprises one or more ligands. Ligands include amine ligands, polyamine ligands, sulfhydryl ligands, phosphine ligands, silane ligands, and polymeric or oligomeric chains such as polyethylene glycols with amine and silane groups.

(I) 其中： x係1至100； y係0至100；且 R ²係C _1-20烷基。 In some embodiments, the amine-ligand is of formula I:

(I) wherein: x is 1 to 100; y is 0 to 100; and R ² is C _1-20 alkyl.

In some embodiments, the polyamine-based ligands are polyaminoalkanes, polyamine-cycloalkanes, polyamine-based heterocycles, polyamine-functionalized polysiloxanes, or polyamine-substituted ethylene glycols. In some embodiments, the polyamine based ligand systems are _C2-20 alkanes or _C2-20 cycloalkanes substituted with two or three amine groups and optionally containing one or two amine groups in place of carbon groups. In some embodiments, the polyamine based ligands are ethylenediamine, 1,2-diaminopropane, 1,2-diamino-2-methylpropane, N-methyl-ethylenediamine, N-ethyl Ethyl-ethylenediamine, N-isopropyl-ethylenediamine, N-cyclohexyl-ethylenediamine, N-cyclohexyl-ethylenediamine, N-octyl-ethylenediamine, N-decyl-ethylenediamine Amine, N-dodecyl-ethylenediamine, N,N-dimethyl-ethylenediamine, N,N-diethyl-ethylenediamine, N,N'-diethyl-ethylenediamine, N,N'-diisopropylethylenediamine, N,N,N'-trimethyl-ethylenediamine, diethylenetriamine, N-isopropyl-diethylenediamine, N- (2-aminoethyl)-1,3-propanediamine, triethylenetetramine, N,N'-bis(3-aminopropyl)ethylenediamine, N,N'-bis(2 -Aminoethyl)-1,3-propanediamine, gins(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, 2-(2-amino-ethyl) Amino) ethanol, N,N-bis(hydroxyethyl)ethylenediamine, N-(hydroxyethyl)diethylenetriamine, N-(hydroxyethyl)triethylenetetramine, hexahydropyridine oxazine, 1-(2-aminoethyl)hexahydropyrazine, 4-(2-aminoethyl)morpholine, polyethyleneimine, 1,3-diaminopropane, 1,4-diamine butane, 1,3-diaminopentane, 1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, hexamethylenediamine, 2-methyl 1,5-diaminopropane, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,4-trimethyl-1,6-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, spermine, 4,4'-methylenebis(cyclohexylamine), 1,2-diamino ring Hexane, 1,4-diaminocyclohexane, 1,3-cyclohexanebis(methylamine), 1,4-cyclohexanebis(methylamine), 1,2-bis(aminoethoxy) base) ethane, 4,9-dioxa-1,12-dodecanediamine, 4,7,10-trioxa-1,13-tridecanediamine, 1,3-diamine -Hydroxy-propane, 4,4-methylenedihexahydro Pyridine, 4-(aminomethyl)hexahydropyridine, 3-(4-aminobutyl)hexahydropyridine or polyallylamine. In some embodiments, the polyamine-based ligand is 1,3-cyclohexanebis(methylamine), 2,2-dimethyl-1,3-propanediamine, or ps(2-aminoethyl)amine .

In some embodiments, the polyamine-based ligands are polyamine-based heterocyclic compounds. In some embodiments, the polyaminoheterocycles are 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-imidazole- 2,5-Diamine, 4-phenyl-N(1)-[(E)-phenylmethylene]-1H-imidazole-1,2-diamine, 2-phenyl-1H-imidazole-4 ,5-diamine, 1H-imidazole-2,4,5-triamine, 1H-pyrrole-2,5-diamine, 1,2,4,5-tetrazine-3,6-diamine, N, N'-dicyclohexyl-1,2,4,5-tetrazine-3,6-diamine, N3-propyl-1H-1,2,4-triazole-3,5-diamine or N, N'-bis(2-methoxybenzyl)-1H-1,2,4-triazole-3,5-diamine.

、

、

、

、

、

或

。 In some embodiments, the polyamine-based ligands are polyamine-functionalized polysiloxanes. In some embodiments, the polyamine functionalized polysiloxane is one of the following:

,

,

,

,

,

or

.

In some embodiments, the polyamine-based ligands are polyamine-substituted ethylene glycols. In some embodiments, the polyamine substituted ethylene glycol is 2-[3-amino-4-[2-[2-amino-4-(2-hydroxyethyl)phenoxy]ethoxy ]Phenyl]ethanol, 1,5-diamino-3-oxopentane, 1,8-diamino-3,6-dioxoctane, bis[5-chloro-1H-indole- 2-yl-carbonyl-aminoethyl]-ethylene glycol, amino-PEG8-t-Boc-hydrazide or 2-(2-(2-ethoxyethoxy)ethoxy)ethanamine.

In some embodiments, the mercapto-ligand system (3-mercaptopropyl)triethoxysilane, 3,6-dioxa-1,8-octanedithiol; 6-mercapto-1-hexanol; mercaptosuccinic acid, mercaptoundecanoic acid, mercaptocaproic acid, mercaptopropionic acid, thioglycolic acid, cysteine, methionine and mercaptopoly(ethylene glycol).

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

In some embodiments, ligands include, but are not limited to, amino-polyalkylene oxides (eg, about m.w. 1000); (3-aminopropyl)trimethoxysilane; (3-mercaptopropyl)triethyl oxysilane; DL-α-lipoic acid; 3,6-dioxa-1,8-octanedithiol; 6-mercapto-1-hexanol; methoxypolyethylene glycol amine (approx. m.w. 500 ); poly(ethylene glycol) methyl ether mercaptan (about m.w. 800); diethyl phenylphosphinate; N,N-diisopropylphosphoramidite dibenzyl ester; Isopropylphosphoramidite di-tert-butyl ester; sine (2-carboxyethyl) phosphine hydrochloride; poly(ethylene glycol) methyl ether mercaptan (about m.w. 2000); methoxypolyethylene glycol Alcohol amines (about m.w. 750); acrylamide; and polyethyleneimine.

Specific combinations of ligands include amino-polyalkylene oxide (about m.w. 1000) and methoxypolyethylene glycol amine (about m.w. 500); amino-polyalkylene oxide (about m.w. 1000) and 6-mercapto- 1-hexanol; amino-polyalkylene oxide (about m.w. 1000) and (3-mercaptopropyl)triethoxysilane; and 6-mercapto-1-hexanol and methoxypolyethylene glycol amine ( about m.w. 500); it provides good dispersibility and thermal stability. See Example 9.

Compared with AIGS-containing films without polyamine-based ligands and compared with monoamine-based ligands, films containing AIGS nanostructures and polyamine-based ligands exhibited higher film photoconversion efficiency (PCE), exhibiting more Less wrinkling and less membrane delamination. Therefore, compositions comprising AIGS-polyamine based ligands are uniquely suitable for use in nanostructured color conversion layers.

The following examples illustrate and do not limit the products and methods described herein. Suitable modifications and adaptations of various conditions, formulations and other parameters commonly encountered in the art and apparent to those skilled in the art from this disclosure are within the spirit and scope of the invention. example Example 1: AIGS Nucleosynthesis

Sample ID 1 was prepared using the following typical synthesis of an 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 Dodecanethiol was 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 minutes, then the temperature was raised to 210°C and held for 100 minutes. After cooling to 180°C, 5 mL of trioctylphosphine was added. The reaction mixture was transferred to the 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. Sample ID 2 and 3 were also prepared using this method. Optical properties of AIGS cores were measured and summarized in Table 2. AIGS nuclear size and morphology were characterized by transmission electron microscopy (TEM). Table 2 Sample ID QY (%) PWL (nm) FWHM (nm) Ag/(Ag+In+Ga) by ICP In/(In+Ga) by ICP Notes 1 44 519.5 47 0.39 0.44 50 mL flask weighing 2 30 514 50 0.37 0.41 10x magnification sample ID 1 3 40 518 52 0.38 0.45 10x magnification sample ID 1 Example 2: AIGS nanostructures subjected to ion exchange treatment

Sample ID 4 was prepared using the following typical ion exchange treatment: 2 mL of a 0.3 M solution of gallium oleate in octadecene and 12 mL of oleylamine were introduced into a flask and degassed. The mixture was heated to 270°C. A total of 1 mL of a premixed solution of 0.95 M sulfur solution in oleylamine and 1 mL of isolated AIGS cores (15 mg/mL) was injected. The reaction was stopped after 30 minutes. The final product was transferred to a glove box, washed with toluene/ethanol, centrifuged, and redispersed in toluene. Sample IDs 4-8 were also prepared using this method. The optical properties of the resulting AIGS nanostructures are summarized in Table 3. Ion exchange with gallium ions results in almost complete band-edge emission. An increase in the average particle size was observed by TEM. table 3 Sample ID PWL (nm) FWHM (nm) QY (%) OD ₄₅₀ /mass (mL.mg ^- 1.cm ^{- 1} ) 4 516 38 61 - 5 517 36 58 0.87 6 520 37 53 1.04 7 514 38 64 0.72 8 514 38 65 1.15 Example 3: Gallium halide and trioctylphosphine ion exchange treatment

Room temperature ion-exchange reactions with AIGS nanostructures were performed by adding a solution of _Gal3 in trioctylphosphine (0.01-0.25 M) to AIGS QDs and maintaining at room temperature for 20 hours. This treatment resulted in a significant enhancement of the band-edge emission outlined in Table 4, while substantially maintaining the peak wavelength (PWL).

Compositional changes before and after _Gal3 addition were monitored by inductively coupled plasma atomic emission spectroscopy (ICP-AE) and energy dispersive X-ray spectroscopy (EDS), as summarized in Table 4. Composite images of In and Ga elemental distributions before and after _GaI3 /TOP treatment show a radial distribution of In to Ga, thereby indicating that ion exchange treatment results in a larger amount of gallium near the surface of the nanostructure and a greater amount of gallium in the center lower gradient. Table 4 ID PWL (nm) FWHM (nm) QY (%) with edge contribution Ag/(Ag+In+Ga) by ICP In/(In+Ga) by ICP Ag/(Ag+In+Ga) by EDS In/(In+Ga) by EDS 9 542 38 11 <45% 0.41 0.11 0.45 0.16 10 543 37 twenty four >80% 0.38 0.09 0.44 0.14 Example 4: AIGS Ion Exchange Treatment Using Oxygen-Free Gallium Source

Sample ID 14 and 15 were prepared using the following typical treatment of AIGS nanoparticles using an oxygen-free Ga source: To 8 mL of degassed oleylamine was added 400 mg GaCl ₃ dissolved in 400 μL toluene followed by 40 mg AIGS core, and then 1.7 mL of 0.95 M sulfur in oleylamine was added. After heating to 240°C, the reaction was held for 2 hours and then cooled. The final product was transferred to a glove box, washed with toluene/ethanol, centrifuged, and dispersed in toluene. Sample IDs 15 and 16 were also prepared using this method. Sample IDs 11-13 were prepared using the method of Example 2. The optical properties of the treated AIGS material are shown in Table 5. table 5 Sample ID PWL (nm) FWHM (nm) QY (%) BE% Gallium source 11 525 43 25 Not determined Acetylpyruvate) 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 Not determined Not determined Not determined Not determined Ga(III) iodide

As shown in Table 5, the quantum of treated AIGS nanostructures can be improved by using Ga(III) chloride instead of Ga(III) acetylpyruvate or gallium oleate when oleylamine is used as solvent Yield. The final material subjected to ion exchange with Ga(III) chloride yielded similar size to the starting nanostructure and similar band-edge-to-trap emission properties. Therefore, the increase in quantum yield (QY) is not only due to the increase in trap emission components. 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.

High-resolution TEM with energy dispersive X-ray spectroscopy (EDS) of sample 14 showed that the nanostructures likely contained a slight gradient of In reduction from the center to the surface of the AIGS nanostructures, indicating that processing under these conditions was caused by Instead of growing a unique GS layer, the In exchanged out of the AIGS structure and was produced by a process of Ga replacement, while Ag was present throughout the structure. This also helps to improve the quantum yield of the nanostructures due to the smaller strain. Example ₅ : AIGS cores from thermal injection of preformed Ag2S nanostructures mixed with preformed In-Ga reagents

To prepare Ag2S nanostructures, under _N2 atmosphere, 0.5 g AgI and ₂ mL oleylamine were added to a 20 mL vial and stirred at 58 °C until a clear solution was obtained. In a separate 20 mL vial, combine 5 mL of DDT and 9 mL of 0.95 M sulfur in oleylamine. The DDT+S-OYA mixture was added to the AgI solution and stirred at 58 °C for 10 min. The obtained Ag ₂ S nanoparticles were used without washing.

To prepare the In-Ga reagent mixture, a 100 mL flask was charged with 1.2 g Ga(acetylpyruvate) ₃ , 0.35 g _InCl3 , 2.5 mL oleylamine, and 2.5 mL ODE. Heat to 210 °C under N atmosphere and hold for ₁₀ min. An orange viscous product was obtained.

To form AIGS nanoparticles, 1.75 g TOPO, 23 mL oleylamine, and 25 mL ODE were added to a 250 mL flask under _N2 . After degassing under vacuum, this solvent mixture was heated to 210 °C in 40 min. In a 40 mL vial, the above Ag2S and In _- Ga reagent mixture was mixed at 58°C and transferred to a syringe. The Ag-In-Ga mixture was then injected into the solvent mixture at 210°C for 3 hr. After cooling to 180°C, 5 mL of trioctylphosphine was added. The reaction mixture was transferred to the 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 ion-exchanged by the method described in Example 4. The optical properties of materials prepared by this method on a scale up to 24 times the above are shown in Table 6. Table 6 Sample ID PWL (nm) FWHM (nm) BE% QY (%) OD ₄₅₀ / mass (mL.mg ^- 1.cm ^{- 1} ) 17 510 34 96 86 - 18 524 38 93 94 1.1 19 520 38 93 88 1.3 20 517 38 94 86 1.3 twenty one 518 38 94 89 1.4 twenty two 528 37 93 93 1.9 Example 7 Repeated gallium ion exchange to improve the photoluminescence stability of AIGS nanostructures 7.1 The first ion exchange process

Oleylamine (OYA, 2.5 L) was degassed at 40 °C for 40 min under vacuum. AIGS nanostructures (25.4 g in toluene) were added followed by _GaCl3 (127 g in minimum toluene) and sulfur dissolved in OYA (0.95 M, 570 mL). The mixture was heated to 240 °C over 40 min and held for 4 h. After cooling, the mixture was diluted with 1 volume of toluene. After centrifugation to remove some by-products, the material was washed with 2 volumes of ethanol, collected by centrifugation, and redissolved in toluene. After the second wash, the nanostructures were dissolved in heptane for storage. 7.2 The second ion exchange process

Oleylamine (OYA, 960 mL) was degassed under vacuum at 40 °C for 20 min. To OYA is added, for example, the AIGS ion-exchanged nanostructures from Example 7.1 (12 g in heptane), followed by _GaCl3 (22.5 g in a minimum volume of toluene), followed by sulfur dissolving OYA in (0.95M, 100 mL). The mixture was heated to 240 °C over 40 min and held for 3 hr. After cooling, the mixture was diluted with 1 volume of toluene, then washed (precipitated with 1.6 volumes of ethanol, centrifuged) and redispersed in toluene or heptane as needed. When ligand exchange was performed on the ink formulation, a further ethanol wash was applied and the QDs were redispersed in heptane. 7.3 Alternative to the second ion exchange process

Oleylamine (15 mL) was degassed under vacuum at 60 °C for 20 min. To OYA was added _GaCl3 (360 mg in a minimum volume of toluene), followed by, eg, AIGS from Example 7.1 (200 mg in heptane), followed by sulfur dissolved in OYA (0.95M, 1.6 mL) ). The mixture was heated to 240 °C over 40 min for 3 hr. After cooling, the mixture was washed as described in Example 7.1. 7.4 Alternative to the second ion exchange process

This example was performed as described in Example 7.3, but on a 3x scale. 7.5 Replacing the second ion exchange process

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 addition of eg AIGS from Example 7.1 (200 mg in heptane). After heating to 130 °C, TMS ₂ S (0.65 mL of a 50% solution in ODE) was added over 20 min and the mixture was held for 2.5 hr. After cooling, the mixture was washed as described in Example 7.1. 7.6 Results

AIGS nanostructures are subjected to an ion exchange process in which In is replaced by Ga. Compared to nuclear growth, the higher temperature used in this process (240°C vs. 210°C) results in maturation and therefore larger average size than untreated nanostructures. Nanostructures do not have well differentiated shell structures. This can be observed in cross-sectional TEM elemental images. The lack of higher bandgap shells is expected to limit the retention of photoluminescence of these materials during film processing.

After the second ion exchange process, the average TEM size did not increase (FIGS. 2A-2C), but the TEM elemental maps revealed that a more pronounced gradient was formed in the QDs towards Ga-rich (higher bandgap) regions.

The elemental compositions of the single and multiple ion exchange processes are shown in Table 7. Values are the average of 10-20 samples of Examples 7.1 and 7.2. Table 7 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

The properties of the ion-exchanged AIGS nanostructures are shown in Table 8. Metal ratios are molar ratios determined by ICP. Table 8 Sample ID PWL , nm FWHM , nm BE , % QY , % Ag/ (Ag+In+Ga) In/ (In+Ga) Example 7.1 524.2 34.8 90 83 0.41 0.27 Example 7.2 523.6 34.4 90 89 0.40 0.24 Example 7.3 525.1 34.4 90 87 0.42 0.23 Example 7.4 525.9 34.3 90 88 0.42 0.24 Example 7.5 524.4 33.5 90 62 0.28 0.12 Example 7.6 521.0 24.5 92 89 0.41 0.18

As shown in Table 9, the membrane PCE remaining after UV curing and 180°C bake was significantly improved by the second ion exchange process. It is believed that this is due to the gradient of the higher bandgap region introduced by ion exchange due to the process of increasing the Ga concentration in the outer layer of the nanostructure. Table 9 Sample ID Blue Absorption (%) Green PCE % after UV Green PCE % after baking Reserved QY % Example 7.1 91.5 25.6 9.7 37.9 Example 7.2 91.9 25.8 16.3 63.3 Example 7.3 88.1 23.1 14.7 63.8 Example 7.4 88.5 23.7 14.9 62.8 Example 7.5 95.0 26.4 17.3 64.7 Example 7.6 91.0 31.4 19.7 62.8 Example 8 - Compositions Comprising AIGS Nanostructures and Polyamine-Based Ligands

abbreviation • Jeffamine - Jeffamine M-1000 • HDDA - 1-6 Hexanediol Diacrylate • Dimethylamine - 1,3 cyclohexane dimethylamine • PCE - Photon Conversion Efficiency

The crude AIGS QD growth solution (solution 1) was purified by washing with ethanol and redispersing in heptane. 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). Add 2 µL of 6-mercapto-1-hexanol 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 with heptane, and redispersed into HDDA (solution 3). Add 83 mg Jeffamine per 100 mg 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 comprising 10 wt% _TiO2 and 90 wt% monomer. The composition of the inkjet formulation was 10 wt% QD inorganics, 4 wt% _TiO2 , and the remaining 86 wt% were ligands (bound and unbound), HDDA, monomers, photoinitiators and various others remaining in the QD solution A combination of organic matter. This ink formulation is Solution 4.

The polyamine based ligand dimethylamine (50 mg dimethylamine/100 mg QD inorganic solids) was added to solution 4, and the composition was then cast into a film. Film casting

Solution 4 was spin coated on a 2'' x 2'' glass substrate. The film was cured with a UV LED curing light. The films were then tested for light conversion efficiency (PCE), a measure of brightness. The film was then baked for 30 minutes on a hot plate set at 180°C, raised slightly above the hot plate. Alternatively, the film was baked on a hot plate set at a temperature of 180°C for 10 minutes, in direct contact with the hot local surface.

The membrane PCE was then tested. A 1'' x 1'' mask array of blue 448 nm LEDs provided the excitation source for the membrane. An integrating sphere was placed on top of the membrane and connected to a fluorometer. See Figures 3A and 3B. The collected spectra were analyzed to obtain PCE.

PCE is the ratio of the number of green photons forward emitted to the number of blue photons generated by the test platform. Although the emission spectrum from 484 nm to 700 nm was used to calculate the PCE, the peak wavelength of green emission is expected to be between 484 nm and 545 nm, and the major part of the emission is below 588 nm. PCE, LRR and membrane morphology are reported in Table 10. Unexpectedly, the presence of the ligands 1,3-cyclohexanebis(methylamine), ps(2-aminoethyl)amine, and 2,2-dimethyl-1,3-propanediamine resulted in Compared with other films, the PCE has high retention, high LRR and no wrinkling after baking at 180°C. Table 10 additive PCE after UV curing PCE after baking at 180℃ LRR Membrane morphology No additives 28.4% 14.1% 49.7% wrinkled 1,3-Cyclohexanebis(methylamine) 21.0% 20.4% 96.8% wrinkle free gins(2-aminoethyl)amine 12.0% 12.1% 100.7% wrinkle free 2,2-Dimethyl-1,3-propanediamine 21.2% 21.1% 99.2% wrinkle free

Figure 1 shows the effect of diamine addition on membrane morphology. The film from left to right in Figure 1 contains: no additive (wrinkle); 2,2-dimethyl-1,3-propanediamine (diamine, no wrinkle); cyclohexanemethylamine (monoamine) , wrinkling); and gins(2-aminoethyl)amine (triamine, no wrinkling). From left to right, the diamine-free first and third films exhibited extensive wrinkling. In contrast, the second and fourth films did not exhibit wrinkling. Unexpectedly, the use of diamine-based ligands in AIGS membranes greatly reduced membrane wrinkling. Example 9 - Testing of Additional Ligands for AIGS Nanostructures

In this experiment, the additional ligands of AIGS nanoparticles were tested for enhanced QY, high compatibility and good thermal stability. In addition, these ligands were assessed to protect AIGS nanostructures from degradation and oxidation. Combinations of ligands that can be formulated into AIGS ink compositions were also tested.

The ligands are formulated in organic solvents such as ethyl acetate, PGMEA, acetone, xylene, 1,2-dichlorobenzene (ODCB), butyl acetate, and diethylene glycol monoethyl ether (DGMEE) body exchange.

AIGS nanostructures perform ligand exchange with ligands containing polymeric or oligomeric chains (eg polyethylene glycol with amine and silane groups) and soft bases for co-passivation (eg phosphino-, Sulfhydryl - and combinations thereof).

Figure 4 depicts quantum yield values for a number of individual ligands and AIGS nanostructures subjected to a single ion exchange treatment as described herein. In this figure, NG : native AIGS; NG-NL1 : amino-polyalkylene oxide, about mw 1000; NG-NL2 : (3-aminopropyl)trimethoxysilane; NG-NL3 : (3-aminopropyl)trimethoxysilane 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 glycol amine 500; NG-NL8 : poly(ethylene glycol) methyl ether thiol Mn 800; NG-NL9 : diethyl phenylphosphinate ; NG-NL10 : N,N-diisopropylphosphoramidite dibenzyl ester; NG-NL11 : N,N-diisopropylphosphoramidite di-tert-butyl ester; NG-NL12 : San (2-carboxyethyl) phosphine hydrochloride; NG-NL13 : poly(ethylene glycol) methyl ether thiol Mn 2000; NG-NL14 : methoxypolyethylene glycol amine 750; NG-NL15 : acrylamide amine; and NG-NL16 : polyethyleneimine.

As can be seen in Figure 4, with (3-mercaptopropyl)triethoxysilane (NL3), 3,6-dioxa-1,8-octanedithiol (NL5) and 6-mercapto-1- Hexanol (NL6) treatment of AIGS nanostructures yielded high QY (73.7%, 72.9% and 76.1%, respectively). Accordingly, the present invention provides AIGS nanostructure compositions comprising at least one thiol-substituted ligand that provide improved QY. It is believed that thiol-substituted ligands provide high QY by passivating the surface of AIGS nanostructures and reducing defect emission. Amino-substituted ligands also improve QY.

In this single ligand assay, the polyethylene glycol amine substituted ligands (L1, L7, L8 and L13), thiol substituted ligands (L3, L5 and L6) and The silane ligand (L2) shows good QY. And when dispersed in HDDA, ligands L1, L7 and L8 have better compatibility with monomers.

Figure 5 is a graph showing the QY % of various 2-ligand combinations resulting in improved QY (good combination) and reduced QY (poor combination). Surface defects can be reduced by adding thiol ligands. The combination of L6 and L7 resulted in better stability than the other combinations. However, for relatively hydrophilic ink compositions, more preferred ligands are relatively hydrophilic ligands, such as methoxypolyethylene glycol amine and poly(ethylene glycol) methyl ether thiol. The thiol also improves QY by passivating surface defects.

Suitable temperatures for ligand exchange range from room temperature to 120°C. The total amount of ligands in the composition may be 60% to 150% of the mass of the AIGS.

Table 11 shows the relative changes in QY, PWL, FWHM before and after ligand exchange with multiple ligands. Table 11 shows the most effective ligand combinations for the L6 and L7 based ink formulations, especially when combined with acrylate monomers. The combination of L2 and L7, L2 and L6, and L2 and L3, L6 and L7 provides good dispersibility and thermal stability. See Figure 6. Table 11 QY before LE (%) QY after LE (%) Before PWL (nm) After PWL (nm) Before FWHM (nm) After FWHM (nm) QY change (%) PWL change (nm) FWHM change (nm) L6, 7 55.3 61.5 531.1 531.6 36.3 36.2 +11.2 -0.1 +0.3 L6, 2 55.3 57.8 531.1 531.3 36.3 36.3 +4.5 -0.1 0.0 L3, 7 55.0 56.6 531.3 531.1 36.2 36.1 +3.0 0.0 +0.1 L5, 7 55.0 57.6 531.3 530.8 36.2 36.1 +4.7 +0.1 +0.3 L13, 7 55.0 57.5 531.3 531.2 36.2 36.1 +4.6 0.0 +0.2 L2, 8 55.0 57.1 531.3 531.9 36.2 36.4 +3.8 -0.1 -0.5 L3, 8 55.0 63.8 531.3 530.8 36.2 36.2 +16.0 +0.1 -0.1 L5, 8 55.0 63.3 531.3 531.8 36.2 36.6 +15.0 -0.1 -1.0 L2, 15 55.3 59.0 531.1 532.1 36.3 36.6 +6.6 -0.2 -0.7 L3, 15 55.3 55.5 531.1 532.4 36.3 37.5 +0.4 -0.3 -3.3 L2, 13 55.3 53.6 531.1 532.5 36.3 36.6 -3.1 -0.3 -0.7 L3, 13 55.3 62.2 531.1 530.0 36.3 38.5 +12.4 +0.2 -5.6 L2, 7 56.6 58.2 530.7 532.0 36.5 36.1 +2.8 -0.3 +0.9 L2, 3 54.6 58.7 530.6 531.3 36.2 36.8 +7.5 -0.1 -1.7

Ligand combinations that provide good thermal stability when heated to 180°C for 30 min in a glove box were further investigated. The ligand combinations L6 and L7, L2 and L6, and L2 and L3 provide better stability than the single ligand L1. See Figure 6.

The effect of different ratios of ligand combinations on QY was also investigated. The weight ratio of ligands is varied, while the total amount of ligands is fixed. Optimum QY is achieved with an L6 to L7 ratio of 7:3. See Figure 7. All combinations with L6 and L7 showed enhanced QY compared to native AIGS nanostructures, except the ratio of 9:1. Although this mixture exhibited a high QY, it was difficult to purify as no precipitation occurred. Mixtures of L6 and L2, L3 and L7, and L5 and L7 are good ligand mixtures for AIGS nanostructures. These ligand combinations can be combined with various monomers such as tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, diethylene glycol ethyl ether acrylic acid ester, isobornyl acrylate, hydroxypropyl acrylate, 2-(acryloyloxy)ethyl hydrosuccinate, and 1,6-hexanediol diacrylate) in combination. Example 10 - Improvement of PCE in AIGS Membrane

In a glove box filled with _N2 , the appropriate ligand-coated AIGS QDs were mixed into an ink containing one or more monomers, _TiO2 scattering particles, and a photoinitiator. The films were cast by spin coating the inks and then cured using UV radiation. The films were then baked on a hot plate at 180°C for 30 minutes to remove residual volatile components. All these processes were carried out in an inert atmosphere - in a glove box filled with _N2 .

Typically at this stage, the film is measured in air by placing the film side up on a blue LED light source. An integrating sphere connected to a spectrophotometer was placed on top of the QD film (see Figures 3A and 3B) and the emission spectrum of the film was captured. Measurements were repeated using blank glass substrates (no QDs). The blue light absorption and photon conversion efficiency (PCE) of the QD films were measured by using the following equations: Blue absorption = number of blue photons transmitted through the QD film / number of incident blue photons PCE = number of green photons (484-588nm) emitted in the forward direction/number of incident blue photons

To investigate the effect of air and moisture during the measurement, encapsulation was performed before the baked QD films were removed from the _N2 glove box. This was done by applying a few drops of UV-curable transparent adhesive on the QD layer, then placing a glass cover slip and curing the adhesive by UV radiation. The QD film thus sealed using glass and adhesive was measured in air using the method described above.

The results show that the encapsulation of QD films prior to measurement in air is critical to achieve high photon conversion efficiency (PCE). Table 12 shows the results measured for a set of membranes both encapsulated and unencapsulated. For comparison, PCE values for typical QDCC films containing InP QDs are also shown. When encapsulated and measured, films comprising AIGS nanostructures had higher post-bake PCE values than InP at much lower QD loadings. Further improvement in PCE was achieved by exposing the film to a blue light source (approximately 6 mW/cm ² ) for a period of 1 hour. Furthermore, QDCC films prepared using AIGS QDs exhibited much narrower emission (FWHM about 30 nm) compared to films prepared using InP QDs (FWHM 36 nm). This is due to the lower FWHM of AIGS QDs in solution (34 nm vs. 39 nm) and the use of mono- and polyamine-based ligands, resulting in good dispersion in ink resins. Table 12 QD type QD loading in ink encapsulation Post-encapsulation treatment Blue absorption in 10µm film PCE after baking at 180 ℃ PWL FWHM AIGS 12.5% no encapsulation none >95% 28% 535 30 glass encapsulation none >95% 35% 535 30 glass encapsulation Irradiate with blue light for 1 hr >95% 38% 535 30 InP 30% no encapsulation none 85% 32% 540 36

Figure 8 shows the effect of encapsulation and blue light treatment over a wider range of samples. Unexpectedly, the PCE values achieved via encapsulation were significantly higher (greater than 32%) than the unencapsulated PCE values.

Figure 9 shows the emission linewidth (FWHM) of the films after the 180°C bake step and subsequent encapsulation. The median FWHM of the films baked at 180°C was 30.5 nm, which was further narrowed to 30.1 nm upon encapsulation. This narrowing may be due to the brightening of the membrane upon encapsulation.

Although the samples in this study were encapsulated using glass and adhesive, this modification of PCE can be achieved by any method that can form an oxygen barrier on the QD layer. In mass production of devices containing these QDCC layers, encapsulation may be performed using a vapor deposition process. In this case, a typical process flow would include inkjet printing of the QD layer, followed by curing with UV radiation, baking at 180°C to remove volatiles, depositing an organic planarization layer, and then depositing an inorganic barrier layer. Techniques for depositing inorganic layers may 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 evaporates. Other potential encapsulation methods include solution-processed or printed organic layers, UV or thermally cured adhesives, lamination using barrier films, and the like. Example 11 - AIGS Ink Comprising Monomers Incorporated into Ligands Coating AIGS Surfaces

It was found that LE of AIGS nanostructures in the presence of monomers resulted in higher solution QY, better compatible inks, and better film performance than ligand exchange (LE) in pure solvent. This is demonstrated through LE and film evaluations using 16 different media.

LE of quantum dots (QDs) such as CdSe and InP can be carried out in organic solvents to replace natural ligands with desired ligands. By dispersing the QDs in monomers, removing the original solvent, and adding other ink components such as scattering media and photoinitiators, the resulting QDs can then be formulated into solvent-free inks.

This procedure can also be used for AIGS nanostructured LEs with high retention of QY. However, this approach generally results in poor dispersibility of the nanostructures in the monomer when the solvent is removed. Good dispersion of AIGS nanostructures in inks and efficient passivation of the nanostructure surfaces by ligands are necessary to maintain film properties under harsh processing conditions (eg, UV irradiation, high temperature baking, etc.). Therefore, AIGS nanostructures using conventional methods for ligand exchange are not suitable for QDCC applications.

Figure 10 shows the results in various organic solvents such as acetone, PGMEA, ethyl acetate, toluene, dichloromethane (DCM), chloroform, dimethylformamide at two temperatures - room temperature (25°C) and 80°C. PLQY of AIGS nanostructures with ligand exchange in (DMF) and ethanol). Jeffamine M1000 was used as the ligand with a mass ratio of 0.8:1 to AIGS nanostructures.

After LE, several solvents such as PGMEA, ethyl acetate, toluene, DCM are very effective for maintaining QY. Notably, LE at room temperature resulted in a higher QY than LE at 80°C. Other solvents tested such as acetone, chloroform, DMF and ethanol resulted in lower QYs.

However, as shown in Table 13 (o = clear dispersion; Δ = cloudy dispersion), ligand-exchanged AIGS nanostructures and HDDA (a common monomer used in inkjet printable inks) were performed in solvent at room temperature ) has poor compatibility. The AIGS nanostructures with ligand exchange at 80°C are more compatible with HDDA, but have lower QY. Therefore, it is difficult to find effective LE conditions that result in high QY and good compatibility with HDDA. Table 13 acetone PGMEA Ethyl acetate Toluene DCM Chloroform DMF Ethanol Comp. w/HDDA O Δ Δ Δ Δ Δ Δ Δ Comp. w/HDDA (80℃ LE) O O O O O - - -

The LE study was repeated using a range of common monomers (shown in Table 14) in place of the organic solvent as the medium. LE was performed by mixing the starting AIGS nanostructures (in heptane) with monomers, then adding Jeffamine M1000 and heating at 80°C. Table 14 Monomer name M1 Diethylene glycol monomethyl ether methacrylate M2 Ethyl acrylate M3 HDDA M4 Tetrahydrofurfuryl Acrylate M5 Tri(propylene glycol) diacrylate M6 1,4-Bis(acryloyloxy)butane M7 Diethylene glycol ethyl ether acrylate M8 Isobornyl Acrylate M9 Diethylene glycol diacrylate M10 2-Methoxyethyl acrylate M11 Tetraethylene glycol diacrylate M13 Diethylene glycol divinyl ether M14 Butyl acrylate M15 2-phenoxyethyl methacrylate M16 1,6-Hexanediol dimethacrylate

Figure 11 shows QY after LE in the presence of monomer. In all 16 cases, QY increased at LE and was also higher than that achieved via LE in organic solvent.

After LE, AIGS nanostructures were isolated and purified by precipitation in heptane, and yields were calculated by recording starting and final QD masses. Unlike LE in solvent, where only small mass changes were observed, the mass of QDs undergoing ligand exchange in the monomer increased by 30-100%, depending on the monomer. Since most of the monomers tested were miscible with heptane and were removed upon precipitation of the QDs, this indicated that a certain amount of monomers was incorporated into the ligands coating the QD surface.

All 16 AIGS samples were dispersed in HDDA and then mixed into an ink containing scattering medium and photoinitiator. Unlike nanostructures that undergo ligand exchange in solvent, all 16 samples tested here show good compatibility in HDDA. Three films were cast from each ink by spin coating at 700, 800 and 900 rpm and then cured with UV radiation.

As shown in Figure 12, some of the monomers M2, M3, M4, M5, M6, and M8 display high-film EQE and can serve as good LE mediators for AIGS QDs.

Figure 13 shows the blue absorption of AIGS nanostructured films spin-coated at 800 RPM. M7, M10, M13, M15 and M16 provide 𣒝 high blue absorption. Example 12 Increasing blue absorption with polyamine ligands

A typical film deposition process involves a hard bake at very high temperatures (usually around 200°C) to completely remove any residual solvent and hair-selective components. This hard bake prevents outgassing during deposition of other layers on top of the QDCC layer. This severe roasting sometimes results in very low EQE. And, either the nanostructures are destroyed by high temperature, or the ligands are separated from the nanostructures, leading to aggregation. Table 15 shows typical AIGS film EQE after UV curing and after 180°C hard bake. Although the EQE was good, above 33% after UV curing, it dropped below 19% after hard bake at 180°C for 30 minutes. The light retention ratio (LRR), which is the ratio of the post-bake EQE to the pre-bake EQE, was very low, below 60%, implying that the post-bake film performance dropped by more than 40%. Table 15 After UV after baking LRR No. 1 film 33.7% 18.4% 54.7% No. 2 film 33.1% 18.3% 55.3%

To overcome such high EQE losses and resulting low LRR during hard bake, two methods were tested to improve LRR.

To keep the AIGS nanostructures uniformly dispersed throughout the film and prevent aggregation, a diamine (1,3-bis(aminomethyl)cyclohexane) was added to the AIGS monomer dispersion prior to ink formulation. Alternatively, other ink components such as scattering media and photoinitiators can be added to the ink formulation after mixing in the AIGS monomer dispersion. As seen in Figure 14, addition of diamine to AIGS monomer dispersion prior to ink formulation increased EQE after UV curing and POB. When the diamine was added in an amount of 5% w/w of AIGS inorganic quality, the EQE after UV curing increased by 3%. Adding more diamine did not further improve the EQE. After POB, the effect of diamines on improving EQE was even higher. The addition of 5% diamine resulted in a 5% improvement in EQE compared to no diamine in the monomer. With the addition of 30% diamine, the EQE increased from 25% to 32%, and the LRR was 92%, similar to what was observed with the InP green QD film. As seen in Figure 15, a side effect of the diamine is an increase in viscosity. However, for monomers such as ethyl acrylate, the ink viscosity drops sharply to levels below 20 cP at room temperature.

As an alternative to increasing EQE, a better AIGS surface passivation with diamines was attempted. As shown in Figure 16, immediately after LE, the QY of the AIGS nanostructures subjected to ligand exchange in the presence of diamines was enhanced by more than 12%. It should be noted that the QY of the AIGS nanostructures was also enhanced after heat treatment at 180°C for 30 minutes (simulating a hard bake) in the presence of the monomer. For LE, the decrease in QY after 30 minutes at 180°C became smaller as the addition of diamine became larger. At 50% w/w diamine in LE, the QY before and after thermal process is almost equal, and when 70% diamine is used for LE, the QY after thermal process becomes higher.

The performance of QDCC films using these AIGS nanostructures is plotted in FIG. 17 . The membrane EQE is better when using diamine for LE compared to no diamine in LE, and the enhancement is even higher with up to 50% more diamine added. The EQE and LE obtained with 70% diamine addition were less than 30% and 50%. It is suspected that the amount of diamine incorporated on the AIGS surface increased when higher amounts of diamine were used for LE, but this decreased the amount of ligand and/or monomer on the AIGS surface. The observed degradation in QD quality after LE with diamines may be due to less ligands and/or monomers on the QD surface. This also occurs when diamines are added to the LE monomer for LE (which results in an increase in ink viscosity).

When both methods were used to improve membrane EQE, as seen in Figure 19, the diamine had the highest effect on membrane EQE when diamine was added in both ligand exchange and monomer dispersion. Viscosity does not necessarily depend on the total amount of diamines in the ink. The samples with the highest diamine content, in which diamines were used in both the LE and the monomer dispersion, had moderate viscosity. This viscosity is lower than when only the same amount of diamine is used in the LE.

EQE enhancement using diamines in LE and/or monomer dispersion was tested using 1,3-bis(aminomethyl)cyclohexane and 5 other additives listed in Table 16. All additives had similar effects on the initial EQE, and A1, A5 and A6 slightly outperformed the other additives when added directly with the monomers. However, after hard bake, A1 and A6 were the 2 best additives in the final film EQE. Furthermore, among the listed amines, good EQEs are obtained without using the same additives in the LE and monomer additions. Even when the same diamine is used in LE and monomer addition, the effect of improving EQE can be different. For example, as shown in Figure 23, A6 is as effective as Al for retaining EQE when used in monomer addition, however, it is not as effective as when Al is used in LE. Table 16 Additive List A1 1,3-Bis(aminomethyl)cyclohexane A2 1,7-Diaminoheptane A3 Cycloheptylamine A4 4,4'-Methylenebis(2-methylcyclohexylamine) A5 Cyclopentylamine A6 2-Methyl-1,5-diaminopentane A7 4-Aminohexahydropyridine

While various embodiments have been described above, it should be understood that these embodiments have been presented by way of example only, and not limitation. It will be apparent to those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. Thus, the breadth and scope should not be limited by any of the exemplary embodiments set forth above, but should be defined only in accordance with the scope of the appended claims and their equivalents.

All publications, patents, and patent applications mentioned in this specification are indicative of the level of skill of those skilled in the art to which this invention pertains, and are incorporated herein by reference to the same extent as if each individual publication, Patents or patent applications are specifically and individually indicated to be incorporated by reference.

The accompanying drawings, which are incorporated herein and form part of this specification, illustrate the present embodiments and together with the description further serve to explain the principles of the present embodiments and to enable those skilled in the relevant art to make and use the present embodiments.

Figure 1 is a photograph of the first and third films from left to right, free of polyamine based ligands and exhibiting extended wrinkling. The second and fourth films containing polyamine based ligands showed no wrinkling.

2A-2C show TEM images of AIGS nanostructures before ion exchange treatment (FIG. 2A), after a single ion exchange treatment (FIG. 2B), and after two ion exchange treatments (FIG. 2C).

3A and 3B are schematic illustrations of unencapsulated (FIG. 3A) and encapsulated (FIG. 3B) membranes.

Figure 4 is a graph showing the QY% scattering exhibited by mixtures of various ligands.

Figure 5 is a scatter plot showing ligand combinations that provide improved QY% (good combinations) and combinations that provide reduced QY% (poor combinations).

Figure 6 is a graph showing the QY% for various ligand combinations before (NG), after ligand exchange (LE) and after 30 min of thermal testing.

Figure 7 is a graph showing the QY% for various ligand combinations at various ligand ratios.

Figure 8 shows two scatter plots of PCE for AIGS films subjected to post normal bake (PoB) measurement (left panel) and encapsulated before PCE measurement (right panel).

Figure 9 shows two scatter plots of PCE for AIGS films baked at 180°C without encapsulation (left panel) and encapsulated (right panel) prior to PCE measurement.

Figure 10 is a bar graph showing the photoluminescence quantum yield (PLQY) of AIGS nanostructures subjected to ligand exchange in various solvents at room temperature and 80°C.

Figure 11 is a bar graph showing the QY of ligand-exchanged AIGS nanostructures in the presence of various monomers.

Figure 12 is a line graph showing the membrane external quantum efficiency (EQE) of AIGS nanostructures subjected to ligand exchange and treated with various monomers and after UV curing.

Figure 13 is a bar graph showing blue light absorption of AIGS nanostructured inks subjected to ligand exchange, treated with various monomers and spin coated at 800 rpm.

Figure 14 is a line graph showing the effect of diamine ((1,3-bis(aminomethyl)cyclohexane) on UV and film EQE after post-baking at 180°C for 30 min (POB).

Figure 15 is a line graph showing the effect of added diamine on viscosity, which is indirectly measured as blue light absorption in films after spin coating at 800 RPM.

Figure 16 is a bar graph showing the effect of ligand exchange (LE) with diamine (DA) on solution QY. The graph shows that after heating at 180°C, the QY drop becomes smaller with increasing amount of diamine.

Figure 17 is a line graph showing the effect of increasing amounts of DA on film PCE after UV curing.

Figure 18 is a line graph showing the effect of increasing the amount of DA in the film on the blue light absorbance of the film.

Figure 19 is a line graph showing the effect of DA added in the monomer dispersion, in the LE, and in both the monomer dispersion and LE on the blue light absorbance of PCE films.

Figure 20 is a line graph showing the effect of DA added in monomer dispersion, in LE, and in both monomer dispersion and LE on film viscosity and blue light absorbance.

Figure 21 is a line graph showing the effect of various additives on the EQE of the initial film.

Figure 22 is a line graph showing the effect of various additives on the EQE of films after POB.

Figure 23 is a line graph showing the effect of having additional additives on film EQE and blue light absorption.

The features and advantages of the present invention will become more apparent from the following detailed description, when taken in conjunction with the accompanying drawings, wherein like reference characters identify corresponding elements throughout. In the drawings, like reference numerals generally indicate identical, functionally similar, and/or structurally similar elements. The drawing in which an element first appears is indicated by the leftmost digit(s) in the corresponding reference number. The drawings provided throughout this disclosure should not be construed as being drawn to scale unless otherwise indicated.

Claims (46)

A film comprising Ag, In, Ga, and S (AIGS) nanostructures, at least one ligand, and exhibiting greater than 32 at a peak emission wavelength of 480-545 nm when excited with a blue light source having a wavelength of about 450 nm % Conversion Efficiency (PCE). The film of claim 1, wherein the nanostructures have an emission spectrum with a full width at half maximum (FWHM) of less than 40 nm. The film of claim 1, wherein the nanostructures have an emission spectrum with a FWHM of 24-38 nm. The film of claim 1, wherein the nanostructures have an emission spectrum with a FWHM of 27-32 nm. The film of claim 1, wherein the nanostructures have an emission spectrum with a FWHM of 29-38 nm. The film of any one of claims 1 to 5, wherein the nanostructures have a quantum yield (QY) of 80-99.9%. The film of claim 6, wherein the nanostructures have a QY of 85-95%. The film of any one of claims 1 to 5, wherein the nanostructures have a QY of about 86-94%. The film of any one of claims 1 to 5, wherein the nanostructures have an OD ₄₅₀ /mass (mL ^. mg ^1. cm ⁻¹ ) greater than or equal to 0.8. The film of claim 9, wherein the nanostructures have an _OD450 /mass (mL.mg ^- 1.cm ^{- 1} ) in the inclusive range of 0.8-2.5. The film of claim 10, wherein the nanostructures have an _OD450 /mass (mL.mg-1.cm ^{- 1} ) in the inclusive range of 0.87-1.9 ^. The film of any one of claims 1 to 5, wherein the nanostructures have an average diameter of less than 10 nm by TEM. The film of claim 12, wherein the average diameter is about 5 nm. The film of any one of claims 1 to 5, wherein at least about 80% of the emission tether is edge-emitted. The film of any one of claims 1 to 5, wherein at least about 90% of the emission tether is edge-emitted. The film of claim 15, wherein 92-98% of the emission tether is edge-emitted. The film of claim 15, wherein 93-96% of the emission tether is edge-emitted. The membrane of any one of claims 1 to 5, wherein the at least one ligand is a polyamine-based ligand. The film of claim 18, wherein the at least one polyamine based ligand is a polyaminoalkane, a polyamino-cycloalkane, a polyamine heterocyclic compound, a polyamine functionalized polysiloxane, or a polyamine substituted ethyl diol. The film of claim 18, wherein the polyamine-based ligand system is C _2-20 alkane or C _2-20 cycloalkane substituted with two or three amine groups and optionally containing one or two amine groups in place of carbon groups . The film of claim 20, wherein the polyamine-based ligands are 1,3-cyclohexanebis(methylamine), 2,2-dimethyl-1,3-propanediamine, gins(2-aminoethylamine) group) amine or 2-methyl-1,5-diaminopentane. The film of any one of claims 1 to 5, wherein the at least one ligand is a compound of formula I:

(I) wherein: x is 1 to 100; y is 0 to 100; and R ² is C _1-20 alkyl. The film of claim 22, wherein x=19, y= ³ , and R2= _-CH3 . The film of any one of claims 1 to 5, wherein the at least one ligand is (3-aminopropyl)trimethoxysilane; (3-mercaptopropyl)triethoxysilane; DL-α-sulfur Octanoic acid; 3,6-dioxa-1,8-octanedithiol; 6-mercapto-1-hexanol; methoxypolyethylene glycol amine (approximately m.w. 500); poly(ethylene glycol) methyl ether mercaptan (approximately m.w. 800); diethyl phenylphosphonite; N,N-diisopropylphosphoramidite dibenzyl ester; N,N-diisopropylphosphoramidite di- tert-butyl ester; sine (2-carboxyethyl) phosphine hydrochloride; poly(ethylene glycol) methyl ether mercaptan (about m.w. 2000); methoxypolyethylene glycol amine (about m.w. 750); propylene amide; or polyethyleneimine. The film of any one of claims 1 to 5, wherein the at least one ligand is a combination of: amine-polyalkylene oxide (about m.w. 1000) and methoxypolyethylene glycol amine (about m.w. 500); Amine-polyalkylene oxide (about m.w. 1000) and 6-mercapto-1-hexanol; amino-polyalkylene oxide (about m.w. 1000) and (3-mercaptopropyl)triethoxysilane; and 6 -Mercapto-1-hexanol and methoxypolyethylene glycol amine (about m.w. 500). The film of any one of claims 1 to 5, further comprising at least one organic resin. The film of claim 26, wherein the at least one organic resin is cured. The film of any one of claims 1 to 5, wherein the film is 5-15 µm thick. The film of any one of claims 1 to 5, further comprising at least one monomer incorporated into the at least one ligand coating the AIGS surface. The film of claim 29, wherein the at least one monomeric acrylate. The film of claim 29, wherein the monosystem ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or acrylic acid At least one of isocamphenyl esters. The film of any one of claims 1 to 5, which exhibits a blue light absorption of greater than 95% at 450 nm. The film of any one of claims 1 to 5, wherein the AIGS nanostructures comprise a gradient of increasing gallium from the surface of the nanostructures to decreasing gallium in the center of the nanostructures. A method of making a film as claimed in any one of claims 26 to 33, the method comprising: (a) providing AIGS nanostructures and at least one ligand coating the surfaces of the AIGS nanostructures; (b) mixing at least one organic resin with the AIGS nanostructures of (a); (c) at the first barrier rib preparing a first film comprising the mixed AIGS nanostructures, the at least one ligand coating the surface, and the at least one organic resin on the layers; (d) curing the film; and (e) curing the first film encapsulated between the first barrier layer and the second barrier layer; and wherein the encapsulated film exhibits greater than 32% at a peak emission wavelength of 480-545 nm when excited with a blue light source having a wavelength of about 450 nm The photon conversion efficiency (PCE). The method of claim 34, wherein the method is performed before the encapsulated film is exposed to a blue LED light source in air. The method of claim 34, wherein the method is carried out under an inert atmosphere. The method of claim 34, wherein the method further comprises: adding at least one oxygen-reactive material to the mixture of AIGS nanostructures and ligands of (a), adding at least one oxygen-reactive material to the mixture of (b), and/or the first oxygen-reactive material prepared in (c) A second film comprising at least one oxygen-reactive material is formed on top of a film, and/or a sacrificial barrier layer temporarily blocking oxygen and/or water is formed on the first film prepared in (c), and the measurement of the The PCE of the film and then the sacrificial barrier layer is removed. The method of claim 34, wherein the two barrier layers exclude oxygen and/or water. The method of any one of claims 34 to 38, wherein the at least one ligand is a polyamine-based ligand. The method of any one of claims 34 to 38, further comprising incorporating at least one monomer into the at least one ligand coating the AIGS surface. A device comprising the membrane of any one of claims 1 to 33. A nanostructured molded article comprising: (a) a first conductive layer; (b) a second conductive layer; and (c) the film of any one of claims 1 to 33 between the first conductive layer and the second conductive layer. A nanostructured color converter comprising: a backplane; a display panel arranged on the backplane; and the film of any one of claims 1 to 33 arranged on the display panel. The nanostructured color converter of claim 43, wherein the film comprises patterned AIGS nanostructures. The nanostructure color converter of claim 43, wherein the film comprises AIGS nanostructures and at least one monomer incorporated into the at least one ligand that coats the AIGS surface. The nanostructured color converter of claim 43, wherein the backplane comprises LEDs, LCDs, OLEDs, or micro LEDs.

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