JP2023554669A - Films containing bright silver-based quaternary nanostructures - Google Patents

Abstract

A film is disclosed that includes Ag, In, Ga, and S (AIGS) nanostructures and at least one ligand attached to the nanostructures. In some embodiments, the AIGS nanostructures have photon conversion efficiency greater than 32% and peak wavelength emission between 480 and 545 nm. In some embodiments, the nanostructures have an emission spectrum with a FWHM of 24-38 nm. [Selection diagram] None

Description

The present invention relates to the field of nanotechnology. More specifically, the present invention provides a thin film with a high photon conversion efficiency (PCE) of greater than 32% at a peak emission wavelength of 480-545 nm when excited using a blue light source with a wavelength of about 450 nm. The present invention provides a nanostructure color conversion film that is free of heavy metals.

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

Improved efficiency means less power is wasted and more light is emitted. Color conversion thin films are characterized by photon conversion efficiency (PCE), defined as the number of emitted photons divided by the number of source photons. Green heavy metal-free QD color conversion films used in displays usually have poor performance due to limited absorption in the excited blue light. Blue absorption is often inherently limited by the material system used, with the result that thicker films are required to fully absorb 450 nm light.

Thin films formed by QD ink deposition are typically cured by UV radiation. This is often followed by thermal processing at 180° C. for up to 1 hour in the presence of air. The photon conversion efficiency of these films is limited by a combination of poor absorption and poor light conversion due to instability throughout these processing steps.

Peak emission wavelength between 480 and 545 nm, with high band edge emission (BE), narrow full width at half maximum (FWHM), high quantum yield (QY), and reduced red shift, using an excitation wavelength of approximately 450 nm. There remains a need in the art for Ag/In/Ga/S (AIGS) nanostructures that are useful for preparing films with high (greater than 32%) photon conversion efficiency (PCE).

The present invention provides a thin heavy metal-free nanostructure with a high photon conversion efficiency (PCE) of over 32% at a peak emission wavelength of 480-545 nm when excited using a blue light source with a wavelength of about 450 nm. Provide conversion film. It uses Ag/In/Ga/S (AIGS) nanostructures in ink formulations containing one or more ligands, and all ink handling, film deposition, processing, and measurement can be performed using blue light. Alternatively, this can be accomplished in an oxygen-free environment prior to exposure to ultraviolet light. 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 polyamino ligand to the AIGS nanostructures to create a film layer, and all handling of the nanostructure ink, ink deposition, film processing and measurements are performed in an oxygen-free environment. It will be held in

Thin films formed by QD ink deposition are typically cured by UV radiation. This is often followed by thermal processing at 180° C. for up to 1 hour in the presence of air. It has been discovered that photon conversion efficiency is reduced by insufficient absorption and insufficient light conversion due to instabilities due to these processing steps.

Disclosed herein are films that include AIGS nanostructures in an ink formulation that includes at least one ligand that achieves a PCE greater than (>) 32% after thermal processing. Some embodiments include an AIGS nanostructure and at least one ligand and have a PCE of greater than 32% at a peak emission wavelength of 480-545 nm when excited using a blue light source having a wavelength of 450 nm. A film showing this is provided. PCE is calculated by integrating the emission spectrum from 484 nm to 700 nm, with the green portion defined as 484 to 588 nm. In some embodiments, the film is a thin (5-15 μm) color conversion film.

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

In some embodiments, the film further comprises at least one monomer incorporated into the ligand coating the AIGS surface. In some embodiments, at least one monomer is an acrylate. In some embodiments, the monomer is ethyl acrylate, hexamethylene diacrylate (HDDA), tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane or isobornyl acrylate. At least one of them.

A method of preparing an AIGS film is provided,
(a) providing an AIGS nanostructure and at least one ligand coating the nanostructure;
(b) mixing at least one organic resin with the AIGS nanostructures of (a);
(c) preparing a first film comprising mixed AIGS nanostructures, at least one ligand coating the nanostructures, 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 film between the first barrier layer and the second barrier layer;
The encapsulated film exhibits a conversion efficiency (PCE) of greater than 32% with a peak emission wavelength of 480-545 nm when excited using 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 coating the AIGS surface.

Also,
(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 adding at least one oxygen-reactive material to the mixture of AIGS nanostructures and ligands of (a); (c) forming a second film comprising a reactive material over the first film prepared in (g) a sacrificial barrier layer temporarily blocking oxygen and/or water; A method is also provided that further comprises forming the sacrificial barrier layer on the first film prepared in c), measuring the PCE of the film, and then removing the sacrificial barrier layer.

Also,
(a) encapsulating the film prior to thermal processing and/or measurement;
(b) use of an oxygen-reactive material as part of the formulation during thermal processing or exposure, and/or (c) temporary blocking of oxygen by using a sacrificial barrier layer is also provided. .

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 nanostructures have 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 OD ₄₅₀ /mass (mL ^. mg ^−1. cm ⁻¹ ) of 0.8 or greater, where OD is optical density. In some embodiments, the nanostructures have an OD ₄₅₀ /mass (mL ^. mg ^−1. cm ⁻¹ ) ranging from 0.8 to 2.5, inclusive. In some embodiments, the nanostructures have an OD ₄₅₀ /mass (mL ^. mg ^−1. cm ⁻¹ ) ranging from 0.87 to 1.9, inclusive. In some embodiments, the nanostructures have an average diameter of 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 is band edge emission. In some embodiments, at least about 90% of the emission is band edge emission. In some embodiments, 92-98% of the emission is band edge emission. In some embodiments, 93-96% of the emission is band edge emission.

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 from increased gallium from the surface of the nanostructure to decreased gallium at the center of the nanostructure.

In some embodiments, at least one ligand is an amino ligand, a polyamino ligand, a ligand containing a mercapto group, or a ligand containing a silane group. It has been unexpectedly discovered that the use of polyamino ligands results in AIGS-containing films with FWHM greater than 32 nm.

In some embodiments, the at least one polyamino ligand is a polyaminoalkane, polyaminocycloalkane, polyaminoheterocycle, polyamino-functionalized silicone, or polyamino-substituted ethylene glycol. In some embodiments, the polyamino ligand is a C 2-20 alkane or a C _2-20 alkane substituted with two or three amino groups and optionally containing one or two amino groups in place of _carbon groups. It is a cycloalkane. In some embodiments, the polyamino-ligand is 1,3-cyclohexanebis(methylamine), 2,2-dimethyl-1,3-propanediamine, or tris(2-aminoethyl)amine.

式中、
ｘは、１～１００であり、
ｙは、０～１００であり、
Ｒ^２は、Ｃ_１－２０アルキルである。 In some embodiments, the ligand is a compound of Formula I;

During the ceremony,
x is 1 to 100,
y is 0 to 100,
R ² is C _1-20 alkyl.

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

In some embodiments, the at least one ligand is (3-aminopropyl)trimethoxysilane), (3-mercaptopropyl)triethoxysilane, DL-α-lipoic acid, 3,6-dioxa-1,8 -Octane dithiol, 6-mercapto-1-hexanol, methoxypolyethylene glycolamine (about m.w. 500), poly(ethylene glycol) methyl ether thiol (about m.w. 800), diethylphenylphosphonite, dibenzyl N, N-diisopropylphosphoramidite, di-tert-butyl N,N-diisopropylphosphoramidite, tris(2-carboxyethyl)phosphine hydrochloride, poly(ethylene glycol) methyl ether thiol (approx. m.w. 2000), methoxy Polyethylene glycolamine (about m.w. 750), acrylamide, or polyethyleneimine. polymer m. w. is determined by mass spectrometry.

In some embodiments, the at least one ligand is an amino-polyalkylene oxide (about m.w. 1000) and a methoxypolyethylene glycolamine (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 glycolamine ( It is a combination of approximately m.w.500).

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

Also,
Nanostructure compositions are provided that include (a) AIGS nanostructures exhibiting a PCE of greater than 32%, and (b) at least one organic resin.

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

Also provided is a method of preparing the nanostructure compositions described herein, the method comprising:
(a) providing an AIGS nanostructure and at least one ligand coating the nanostructure;
(b) mixing at least one organic resin with the nanostructures of (a);
(c) preparing a first film comprising mixed AIGS nanostructures, at least one ligand coating the nanostructures, 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 film between the first barrier layer and the second barrier layer;
The encapsulated film exhibits a conversion efficiency (PCE) of greater than 32% with a peak emission wavelength of 480-545 nm when excited using 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 coating the AIGS surface. In some embodiments, at least one monomer is an acrylate. In some embodiments, the monomer is at least one of ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or isobornyl acrylate. It is.

In some embodiments, the method is performed before the encapsulated film is exposed to air for measurement of the emission spectra of the AIGS nanostructures. In some embodiments, the method is performed under an inert atmosphere.

In some embodiments, the method includes:
(f) adding at least one oxygen-reactive material into the mixture of AIGS nanostructures and the ligand of (a);
(g) adding at least one oxygen-reactive material into the mixture of (b); and/or (h) adding at least one oxygen-reactive material onto the first film prepared in (c). forming a second film comprising (i) a sacrificial barrier layer temporarily blocking oxygen and/or water on the first film prepared in (c); 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 is band edge emission. In some embodiments, 93-96% of the emission is band edge emission.

There is also a method of preparing the composition, comprising:
(a) providing an AIGS nanostructure and at least one ligand coating the nanostructure surface;
(b) mixing the composition obtained in (a) with at least one second ligand.

In some embodiments, the composition in (a) further includes an organic resin. In some embodiments, the composition in (a) further comprises at least one monomer incorporated into the ligand coating the AIGS surface. In some embodiments, the method further includes 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 includes curing the film. In some embodiments, the film is cured by heating. In some embodiments, the film is cured by exposure to electromagnetic radiation.

Also provided are devices comprising the above film.

Also,
(a) a first conductive layer;
(b) a second conductive layer;
(c) a film comprising an AIGS nanostructure layer between the first conductive layer and the second conductive layer;
The nanostructure layer includes AIGS nanostructures with a PCE greater than 32%.

Also,
backplane and
A display panel placed on the backplane,
Provided is a film comprising an AIGS nanostructure layer comprising AIGS nanostructures having a PCE of greater than 32%, the nanostructure layer being disposed 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 microLEDs.

Further features and advantages of the invention, as well as the construction and operation of various embodiments of the invention, are described in detail below with reference to the accompanying drawings. Note that the invention is not limited to the particular embodiments described herein. Such embodiments are presented herein for illustrative purposes only. Additional embodiments will be apparent to one of ordinary skill in the art based on the teachings contained herein.

The accompanying drawings, which are incorporated in and form a part of this specification, illustrate the embodiments and, together with the specification, explain the principles of the embodiments and explain the principles of the embodiments and that will be understood by one or more persons skilled in the art to demonstrate the embodiments. It further functions to enable the creation and use of forms.

From left to right, the first and third films, pictured and containing no polyamino ligand, exhibited stretch wrinkles. The second and fourth films containing polyamino ligands showed no wrinkles. A to C are TEM images showing AIGS nanostructures before ion exchange treatment (A), after one ion exchange treatment (B), and after two ion exchange treatments (C). FIG. 2 is a schematic diagram of an unencapsulated film (A) and an encapsulated film (B). FIG. 2 is a schematic diagram of an unencapsulated film (A) and an encapsulated film (B). Figure 2 is a scatter plot showing the QY% exhibited by various mixtures of ligands. FIG. 2 is a scatter plot showing combinations of ligands that provide improved QY% (good combinations) and combinations that provide reduced QY% (poor combinations). Figure 2 is a graph showing the QY% of various ligand combinations before (NG), after (LE), and after a 30 minute thermal test. Figure 3 is a graph showing QY% of various ligand combinations at various ligand ratios. Two scatter plots showing the PCE of AIGS films using conventional post-bake (PoB) measurements (left graph) and encapsulation before PCE measurements (right graph). Two scatter plots showing the PCE of AIGS films baked at 180° C. without encapsulation (left graph) and with encapsulation (right graph) before PCE measurements. 1 is a bar graph showing the photoluminescence quantum yield (PLQY) of AIGS nanostructures ligand-exchanged in various solvents at room temperature and 80° C. Figure 2 is a bar graph showing the QY of ligand-exchanged AIGS nanostructures in the presence of various monomers. Figure 3 is a line graph showing the film external quantum efficiency (EQE) of AIGS nanostructures after being ligand exchanged, treated with various monomers, and UV cured. Figure 2 is a bar graph showing the blue light absorption of AIGS nanostructured inks that have been ligand exchanged, treated with various monomers, and spin-coated at 800 rpm. Figure 2 is a line graph showing the effect of diamine ((1,3-bis(aminomethyl)cyclohexane) on film EQE after UV and post-bake (POB) at 180°C for 30 minutes. Figure 2 is a line graph showing the effect of added diamine on viscosity, measured indirectly as blue light absorption in the film after spin coating at 800 RPM. Figure 2 is a bar graph showing the effect of ligand exchange (LE) with diamine (DA) on solution QY. The graph shows that the QY reduction after heating at 180° C. decreased with increasing amount of diamine. Figure 2 is a line graph showing the effect of increasing amounts of DA on film PCE after UV curing. 2 is a line graph showing the effect on film blue light absorption of increasing the amount of DA in the film. Figure 3 is a line graph showing the effect of added DA on PCE film blue light absorption in the monomer dispersion, in the LE, and in both the monomer dispersion and the LE. Figure 2 is a line graph showing the effect of added DA on film viscosity and blue light absorption in the monomer dispersion, in the LE, and in both the monomer dispersion and the LE. 1 is a line graph showing the effect of various additives on initial film EQE. 1 is a line graph showing the effect of various additives on film EQE after POB. 2 is a line graph showing the effect of film EQE and blue light absorption with additional additives.

The features and advantages of the invention will become more apparent from the detailed description set forth below when considered in conjunction with the drawings, in which like reference characters identify corresponding elements throughout. In the drawings, like reference numbers generally indicate identical, functionally similar, and/or structurally similar elements. The drawing in which an element first appears is indicated by the left-most digit(s) in the corresponding reference number. Unless otherwise indicated, the drawings provided throughout this disclosure are not to be construed as drawings to scale.

Definitions Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The following definitions supplement those in the art and are directed to this application and are not to be attributed to any related or unrelated instances, such as any jointly owned patents or applications. Although any methods and materials similar or equivalent to those described herein can be used in the testing practice of the present invention, the preferred materials and methods are described herein. Accordingly, 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," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a "nanostructure" includes a plurality of such nanostructures, and the like.

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

A "nanostructure" is a structure that has at least one region or characteristic dimension that is less than about 500 nm. 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 area or characteristic dimension is along the smallest axis of the structure. Examples of such structures include nanowires, nanorods, nanotubes, branched nanostructures, nanotetrapods, tripods, bipods, nanocrystals, nanodots, quantum dots, nanoparticles, and the like. Nanostructures can be, for example, substantially crystalline, substantially monocrystalline, polycrystalline, 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.

The term "heterostructure" when used in reference to nanostructures refers to nanostructures characterized by at least two different and/or distinguishable material types. Typically, one region of the nanostructure includes a first material type and a second region of the nanostructure includes a second material type. In certain embodiments, the nanostructure comprises a core of a first material and at least one shell of a second (or third, etc.) material, where the different material types are different, e.g. It is distributed radially around the long axis of the arms of the nanowire, or the center of the nanocrystal. The shell can, but need not, completely cover the adjacent material to be considered a shell, or for a nanostructure to be considered a heterostructure, e.g. covered with islets of a second material. Nanocrystals characterized by a core of one material are heterostructures. In other embodiments, different material types are distributed at different locations within the nanostructure, for example, along the major (long) axis of the nanowire or along the long axis of the arms of a branched nanowire. Different regions within the heterostructure can include completely different materials, or different regions can include base materials (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 nanostructure in a cross section perpendicular to the first axis, which is relative to the second and third axes. (the second and third axes are two axes whose lengths are approximately equal to each other). The first axis is not necessarily the longest axis of the nanostructure; for example, for a disk-shaped nanostructure, the cross section is a substantially circular cross section perpendicular to the short longitudinal axis of the disk. If the cross-section is not circular, the diameter is the average of the major and minor 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 to the other through the center of the sphere.

The term "crystalline" or "substantially crystalline" when used in reference to nanostructures refers to the fact that the nanostructures typically exhibit long-range ordering over one or more dimensions of the structure. It will be understood by those skilled in the art that the term "long-range ordering" depends on the absolute size of the particular nanostructure, since single-crystal ordering cannot extend beyond the boundaries of the crystal. In this case, "long-range ordering" means substantial order over at least a majority of the dimensions of the nanostructure. In some examples, a nanostructure can have an oxide or other coating, or can consist of a core and at least one shell. In such cases, the oxide, shell(s), or other coating may exhibit such ordering, but need not (e.g., it may be amorphous, polycrystalline, or otherwise). That will be understood. In such cases, the phrases "crystalline," "substantially crystalline," "substantially monocrystalline," or "monocrystalline" refer to the central core (excluding any coating layer or shell) of the nanostructure. As used herein, the term "crystalline" or "substantially crystalline" means that the structure has substantial long-range ordering (e.g., at least the length of at least one axis of the nanostructure or its core). It is also intended to include structures containing various defects, stacking faults, atomic substitutions, etc., as long as they exhibit order (order over about 80%). In addition, the interface between the core and the outside of the nanostructure, or between the core and an adjacent shell, or between a shell and a second adjacent shell, may contain amorphous regions, It will be understood that it may even be a quality. This does not preclude the nanostructure from being crystalline or substantially crystalline as defined herein.

The term "single crystal" when used in reference to a nanostructure indicates that the nanostructure is substantially crystalline and includes substantially a single crystal. When used in reference to a nanostructured heterostructure that includes a core and one or more shells, "single crystal" indicates that the core is substantially crystalline and includes substantially a single crystal.

A "nanocrystal" is a nanostructure that is substantially single crystal. Thus, a nanocrystal has at least one region or characteristic dimension having a dimension of less than about 500 nm. 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" encompasses substantially single-crystalline nanostructures that contain various defects, stacking faults, atomic substitutions, etc., as well as substantially single-crystalline nanostructures that do not contain such defects, imperfections, or substitutions. It is intended that For nanocrystalline heterostructures that include a core and one or more shells, the core of the nanocrystal is typically substantially single crystal, but the shell(s) need not be. In some embodiments, each of the three dimensions of the nanocrystal 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.

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

The term "anoxygen-free ligand" as used herein refers to a coordination molecule that does not contain an oxygen atom that can coordinate or react with a metal ion.

A "ligand" may interact (weakly or strongly) with one or more faces of a nanostructure, e.g., through covalent, ionic, van der Waals, or other molecular interactions with the surface of the nanostructure. It is a molecule.

“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 yield is typically measured by the absolute change in the number of photons upon illumination of a sample within an integrating sphere, or by a well-characterized method with a known quantum yield value. Determined by comparative method using standard samples.

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

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

Band edge emission is centered at higher energy (lower wavelength) and has a smaller offset from the absorption onset energy compared to the corresponding defect emission. In addition, 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 commonly used method to quantify the concentration of solutes or nanoparticles. According to Beer-Lambert's law, the absorbance (also known as "absorbance") of a particular sample is proportional to the concentration of solute that absorbs a particular wavelength of light.

Optical density is the optical attenuation per centimeter of material, usually measured using a standard spectrometer specified at a path length of 1 cm. Nanostructure solutions are often measured by their optical density instead of mass or molar concentration, which is directly proportional to the concentration and the amount of optical absorption that occurs within the nanostructure solution at the wavelength of interest. This is because it is a more convenient way to represent . A nanostructure solution with an OD of 100 is 100 times more concentrated (has 100 times more particles per mL) than a product with an OD of 1.

Optical density can be measured at any wavelength of interest, such as the wavelength chosen to excite fluorescent nanostructures. Optical density is a measure of the intensity lost when light passes through a nanostructure solution at a particular wavelength,
OD= _log10 *( _IOUT / _IIN )
is calculated using the formula, where:
I _OUT = intensity of radiation entering the cell;
I _IN =Intensity of radiation transmitted through the cell.

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

Unless explicitly stated otherwise, ranges described herein are inclusive.

Various additional terms are defined or characterized herein.

AIGS Nanostructures Nanostructures are provided that include Ag, In, Ga, and S and have a peak emission wavelength (PWL) of 480-545 nm. In some embodiments, at least about 80% of the emission is band edge emission. The fraction of band-edge emission is calculated by fitting the Gaussian peaks (usually two or more) of the nanostructure emission spectrum and subtracting the area of the peak whose energy is closer to the nanostructure band gap (representing the band-edge emission) out of the total peak area. Calculated by comparing to the sum (band edge + defect emission).

In one embodiment, the nanostructures have a FWHM emission spectrum of less than 40 nm. In another embodiment, the nanostructures have a FWHM of 36-38 nm. In some embodiments, the nanostructures have 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 nanostructures have a QY of about 80% to 99.9%. In another embodiment, the nanostructure has a QY of 85-95%. In another embodiment, the nanostructure has a QY of about 86% to about 94%. In some embodiments, at least 80% of the emission is band edge emission. In other embodiments, at least 90% of the emission is band edge emission. In other embodiments, at least 95% of the emission is band edge emission. In some embodiments, 92-98% of the emission is band edge emission. In some embodiments, 93-96% of the emission is band edge emission.

AIGS nanostructures provide high blue light absorption. As a prediction of blue light absorption efficiency, we measured the optical density at 450 nm per mass (OD ₄₅₀ /mass) of the nanostructure solution in a 1 cm path length cuvette and Calculated by dividing by the dry mass per mL of the same solution after removal of volatiles (mg/mL). In one embodiment, the nanostructures provided herein have an OD ₄₅₀ /mass (mL ^. mg ^−1. cm ⁻¹ ) of at least 0.8. In another embodiment, the nanostructures have an OD ₄₅₀ /mass ( ^{mL.mg −1.cm −1} ) of 0.8 to 2.5. In another embodiment, the nanostructures have an OD ₄₅₀ /mass (mL ^. mg ^−1. cm ⁻¹ ) of 0.87 to 1.9.

In one embodiment, the nanostructures are treated with gallium ions such that ion exchange of gallium with indium occurs throughout the AIGS nanostructures. In another embodiment, the nanostructure has Ag, In, Ga, and S in the core and is treated by ion exchange with gallium ions and S. In another embodiment, the nanostructure has Ag, In, Ga, and S in the core and is treated by ion exchange with silver ions, gallium ions, and S. In some embodiments, the ion exchange treatment provides gradients of gallium, silver, and/or sulfur across 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 Prepared Using GaX ₃ (X=F, Cl, or Br) Precursors and Anoxic Ligands Reports of AIGS preparation in the literature have not attempted to exclude oxygen-containing ligands. In coating AIGS with gallium, oxygen-containing ligands are often used to stabilize the Ga precursor. Generally, gallium(III) acetylacetonate is used as a precursor that is easily air-processed, whereas Ga(III) chloride requires careful handling due to moisture sensitivity. For example, Kameyama et al. , ACS Appl. Mater. Gallium(III) acetylacetonate was used as a precursor for the core and core/shell structures as described in Interfaces 10:42844-42855 (2018). Because gallium has a high affinity for oxygen, oxygen-containing ligands that use gallium precursors that were not prepared under anoxic conditions can be used with Ga and S precursors to achieve significant gallium content. When producing nanostructures containing gallium oxide, undesirable side reactions such as gallium oxide can occur. These side reactions can lead to defects within the nanostructures, resulting in low quantum yields.

In some embodiments, AIGS nanostructures are prepared using oxygen-free GaX ₃ (X=F, Cl, or Br) as a precursor in the preparation of AIGS cores. In some embodiments, AIGS nanostructures are prepared using GaX ₃ (X=F, Cl, or Br) as a precursor and an oxygen-free ligand in the preparation of Ga-enriched AIGS nanostructures. In some embodiments, AIGS nanostructures are prepared using GaX ₃ (X=F, Cl, or Br) and an oxygen-free ligand as a precursor in the preparation of the AIGS core. In some embodiments, AIGS nanostructures are prepared using _GaX (X=F, Cl, or Br) as a precursor and oxygen-free ligands in the preparation of the AIGS core and in the ion exchange treatment of the AIGS core. Ru.

Nanostructures containing Ag, In, Ga, and S with peak emission wavelengths (PWL) of 480-545 nm using _GaX (X=F, Cl, or Br) precursors and oxygen-free ligands Nanostructures are provided.

In some embodiments, nanostructures prepared using GaX ₃ (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 GaX ₃ (X=F, Cl, or Br) precursors and oxygen-free ligands exhibit a FWHM of 30-38 nm. In some embodiments, nanostructures prepared using a GaX ₃ (X=F, Cl, or Br) precursor and an oxygen-free ligand have a QY of at least 75%. In some embodiments, nanostructures prepared using GaX ₃ (X=F, Cl, or Br) precursors and oxygen-free ligands have a QY of 75-90%. In some embodiments, nanostructures prepared using GaX ₃ (X=F, Cl, or Br) precursors and oxygen-free ligands have a QY of about 80%.

The AIGS nanostructures prepared herein provide high blue light absorption. In some embodiments, the nanostructures have an OD ₄₅₀ /mass (mL·mg ^{−1.cm −1} ) of at least 0.8. In some embodiments, the nanostructures have an OD ₄₅₀ /mass ( ^{mL.mg −1.cm −1} ) of 0.8 to 2.5. In another embodiment, the nanostructures have an OD ₄₅₀ /mass (mL ^. mg ^−1. cm ⁻¹ ) of 0.87 to 1.9.

In some embodiments, the nanostructures are treated with gallium ions such that ion exchange of gallium with indium occurs throughout the AIGS nanostructures. In some embodiments, the nanostructure includes Ag, In, Ga, and S in the core and has a gallium gradient between the surface and the center of the nanostructure. In some embodiments, the nanostructure is an AGS-treated AIGS core prepared using a GaX ₃ (X=F, Cl, or Br) precursor and an oxygen-free ligand in the core. In some embodiments, the nanostructure is an AIGS nanostructure prepared using a GaX ₃ (X=F, Cl, or Br) precursor and an oxygen-free ligand. In some embodiments, AIGS nanostructures are prepared by reacting preformed In-Ga reagents with _Ag2S nanostructures to obtain AIGS nanostructures, and then reacting with oxygen-free Ga salts to form gallium and ions. prepared by exchanging to form AIGS nanostructures.

METHODS OF MAKING AIGS NANOSTRUCTURES United States Patent Application 20100000001 A method of making AIGS nanostructures is provided, comprising:
(a) preparing a mixture comprising an AIGS core, a sulfur source, and a ligand;
(b) The mixture obtained in (a) was added to the mixture of gallium carboxylate and the ligand at a temperature of 180-300°C to form an ion-exchanged mixture with a gradient of gallium from the surface to the center of the nanostructure. Obtaining nanostructures;
(c) isolating the nanostructure.

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

Also provided is a method of making AIGS nanostructures,
(a) reacting Ga(acetylacetonate) ₃ , InCl ₃ , and the ligand, optionally in a solvent, at a temperature sufficient to obtain an In-Ga reagent;
(b) reacting an In-Ga reagent with the Ag ₂ S nanostructures at a temperature sufficient to create AIGS nanostructures;
(c) Reacting the AIGS nanostructures with an oxygen-free Ga salt in a solvent containing the ligand at a temperature sufficient to obtain an ion-exchanged nanostructure with a gradient of gallium from the surface to the center of the nanostructure. Including.

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

In some embodiments, the ligand is an alkylamine. In some embodiments, the alkylamine ligand is oleylamine. In some embodiments, the ligand is used in excess and acts as a solvent, and the listed solvents are not present during the reaction. In some embodiments, a solvent is present during the reaction. In some embodiments, the solvent is a high boiling point solvent. In some embodiments, the solvent is octadecene, squalane, dibenzyl ether or xylene. In some embodiments, the sufficient temperature for (a) is 100-280°C, the sufficient temperature for (b) is 150-260°C, and the sufficient temperature for (c) is 170-280°C. be. In some embodiments, the sufficient temperature for (a) is about 210<0>C, the sufficient temperature for (b) is about 210<0>C, and the sufficient temperature for (c) is about 240<0>C.

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

Examples of ligands include U.S. Pat. No. 7,572,395, U.S. Pat. No. 8,143,703, U.S. Pat. , No. 9,005,480, No. 9,139,770, and No. 9,169,435, and US Patent Application Publication No. 2008/0118755. In one embodiment, the ligand is an alkylamine. In some embodiments, the ligand is an alkylamine selected from the group consisting of dodecylamine, oleylamine, hexadecylamine, dioctylamine, and octadecylamine.

In some embodiments, the sulfur source in (a) is trioctylphosphine sulfide, elemental sulfur, octanethiol, dodecanethiol, octadecanethiol, tributylphosphine sulfide, cyclohexylisothiocyanate, alpha-toluenethiol, ethylene trithiol carbonate, allyl mercaptan, bis(trimethylsilyl) sulfide, trioctylphosphine sulfide, or combinations thereof. In some embodiments, the sulfur source in (a) is derived from _S8 .

In one embodiment, the sulfur source is derived from _S8 .

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

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

In some embodiments, the gallium carboxylate is gallium C _2-24 carboxylate. Examples of C _2-24 carboxylates include acetate, propionate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, decanoate, undecanoate, tridecanoate, tetradecanoate, pentadecanoate, hexadecanoate, octadecanoate. Noate (oleate), nonadecanoate, and icosanoate. In one embodiment, the gallium carboxylate is gallium oleate.

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

In further embodiments, AIGS nanostructures are isolated, eg, by precipitation. In some embodiments, the AIGS nanostructures are precipitated by the addition of 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 for the nanostructures.

Also provided is a method of making nanostructures,
(a) preparing a mixture comprising an AIGS core and a gallium halide in a solvent and holding the mixture for a sufficient time to obtain an ion-exchange nanostructure with a gradient of gallium from the surface to the center of the nanostructure; ,
(b) isolating the nanostructure.

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

In some embodiments, at least 80% of the emission is band edge emission. In other embodiments, at least 90% of the emission is band edge emission. In other embodiments, at least 95% of the emission is band edge emission.

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

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

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

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

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

In further embodiments, AIGS nanostructures are isolated, eg, by precipitation. In some embodiments, the AIGS nanostructures are precipitated by the addition of 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 the nanostructures with a non-solvent.

Also provided is a method of making nanostructures,
(a) preparing a mixture comprising an AIGS nanostructure, a sulfur source, and a ligand;
(b) The mixture obtained in (a) is added to the mixture of GaX ₃ (X=F, Cl, or Br) and an oxygen-free ligand at a temperature of 180-300° C. from the surface to the center of the nanostructure. obtaining an ion-exchanged nanostructure with a gallium gradient of
(d) isolating the nanostructure.

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

In some embodiments, the preparation in (a) is under anoxic conditions. In some embodiments, the preparation in (a) is in a glove box.

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

In some embodiments, at least 80% of the emission is band edge emission. In other embodiments, at least 90% of the emission is band edge emission. In other embodiments, at least 95% of the emission is band edge emission.

Examples of ligands include U.S. Pat. No. 7,572,395, U.S. Pat. No. 8,143,703, U.S. Pat. , No. 9,005,480, No. 9,139,770, and No. 9,169,435, and US Patent Application Publication No. 2008/0118755. In some embodiments, the ligand in (a) is an anoxic ligand. In some embodiments, the ligand in (b) is an anoxic ligand. In some embodiments, the ligand in (a) and (b) is an alkylamine. In some embodiments, the ligand is an alkylamine selected from the group consisting of dodecylamine, oleylamine, hexadecylamine, dioctylamine, and octadecylamine. In some embodiments, the ligand in (a) is oleylamine. In some embodiments, the ligand in (b) is oleylamine. In some embodiments, the ligand in (a) and (b) is oleylamine.

In one embodiment, the sulfur source is derived from _S8 .

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

In some embodiments, the mixture of (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, GaX ₃ is gallium chloride. In some embodiments, GaX ₃ is Ga(III) chloride.

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

In some embodiments, AIGS nanostructures are isolated, for example, by precipitation. In some embodiments, the AIGS nanostructures are precipitated by the addition of 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 the nanostructures with a non-solvent.

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

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

Doped AIGS Nanostructures In some embodiments, the AIGS nanostructures are doped. In some embodiments, the dopant of the nanocrystalline core includes a metal, including one or more transition metals. In some embodiments, the dopants include Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, The transition metal is selected from the group consisting of Pt, Cu, Ag, Au, and combinations thereof. In some embodiments, the dopant includes 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 Compositions In some embodiments, the present disclosure provides
(a) at least one population of AIGS nanostructures;
(b) at least one organic resin.

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

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

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

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.

Thermoset resins require curing to undergo an irreversible molecular crosslinking process that renders the resin infusible. In some embodiments, the thermosetting resin includes an epoxy resin, a phenolic resin, a vinyl resin, a melamine resin, a urea resin, an unsaturated polyester resin, a polyurethane resin, an allyl resin, an acrylic resin, Preferably, the resin is a polyamide resin, a polyamide-imide resin, a phenolamine condensation resin, a urea-melamine condensation resin, or a combination thereof.

In some embodiments, the thermoset resin is an epoxy resin. Epoxy resins are easily cured by a wide range of chemicals without producing volatiles or by-products. Epoxy resins are also compatible with most substrates and tend to wet surfaces easily. Boyle, M. A. , et al. , “Epoxy Resins,” Composites, Vol. 21, ASM Handbook, pages 78-89 (2001).

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

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

UV-curable resins are polymers that harden and solidify rapidly when exposed to specific wavelengths of light. In some embodiments, the UV curable resin includes, as a functional group, a radically polymerizable group such as a (meth)acrylyloxy group, a vinyloxy group, a styryl group, or a vinyl group, an epoxy group, a thioepoxy group, a vinyloxy group, Alternatively, it is a resin having a cationically polymerizable group such as an oxetanyl group. In some embodiments, the UV-curable resin is a polyester-based resin, a polyester-based resin, a (meth)acrylic resin, an epoxy resin, a urethane-based resin, an alkyd-based resin, a spiroacetal-based resin, a polybutadiene-based resin, or a polythiol. It is a polyene resin.

In some embodiments, the UV-curable resin is isobornyl acrylate, isobornyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, urethane acrylate, allyl oxide cyclohexyl diacrylate, bis(acryloxyethyl) hydroxyl isocyanurate. , bis(acryloxyneopentyl glycol) adipate, bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol diacrylate, 1, 3-Butylene glycol dimethacrylate, dicyclopentanyl diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, di(trimethylolpropane)tetraacrylate, ethylene glycol dimethacrylate , glycerol methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol hydroxypivalate diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, phosphoric acid Dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, tetrabromobisphenol A diacrylate, triethylene glycol divinyl ether, triglycerol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, Tris (acryloxyethyl) isocyanurate, phosphoric acid triacrylate, phosphoric acid diacrylate, acrylic acid propargyl ester, vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated trifluoromethyl The group consisting of siloxane-dimethylsiloxane copolymers, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymers, vinylmethylsiloxanes, monomethacryloyloxypropyl-terminated polydimethylsiloxanes, monovinyl-terminated polydimethylsiloxanes, monoallyl-monotrimethylsiloxy-terminated polyethylene oxides, and combinations thereof. selected from.

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

In some embodiments, the UV curable resin is a polythiol. In some embodiments, the UV-curable resins include ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris(3-mercaptopropionate), -mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptopropionate) (PETMP), and combinations thereof. In some embodiments, the UV curable resin is PETMP.

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

In some embodiments, the UV curable resin further includes a photoinitiator. The photoinitiator initiates crosslinking and/or curing reactions of the photosensitive material during exposure. In some embodiments, the photoinitiator is acetophenone-based, benzoin-based, or thioxatenon-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® Trademark) 250, IRGACURE (registered trademark) 270, IRGACURE (registered trademark) 2959, IRGACURE (registered trademark) 369, IRGACURE (registered trademark) 369EG, IRGACURE (registered trademark) 379, IRGACURE (registered trademark) 500, IRGACURE (registered trademark) ) 651, IRGACURE (registered trademark) 754, IRGACURE (registered trademark) 784, IRGACURE (registered trademark) 819, IRGACURE (registered trademark) 819Dw, IRGACURE (registered trademark) 907, IRGACURE (registered trademark) 907FF, IRGACURE (registered trademark) Oxe01, IRGACURE® TPO-L, IRGACURE® 1173, IRGACURE® 1173D, IRGACURE® 4265, IRGACURE® BP, or IRGACURE® MBF (BASF Corporation n, Wyandotte, MI). In some embodiments, the photoinitiator is TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) or MBF (methylbenzoyl formate).

In some embodiments, the weight percent of at least one organic resin in the nanostructured composition is about 5% to about 99%, about 5% to about 95%, about 5% to about 90%, about 5% ～about 80%, about 5% to about 70%, about 5% to about 60%, about 5% to about 50%, about 5% to about 40%, about 5% to about 30%, about 5% to about 20%, about 5% to about 10%, about 10% to about 99%, about 10% to about 95%, about 10% to about 90%, about 10% to about 80%, about 10% to about 70% , about 10% to about 60%, about 10% to about 50%, about 10% to about 40%, about 10% to about 30%, about 10% to about 20%, about 20% to about 99%, about 20% to about 95%, about 20% to about 90%, about 20% to about 80%, about 20% to about 70%, about 20% to about 60%, about 20% to about 50%, about 20% ~40%, about 20% to about 30%, about 30% to about 99%, about 30% to about 95%, about 30% to about 90%, about 30% to about 80%, about 30% to about 70%, about 30% to about 60%, about 30% to about 50%, about 30% to about 40%, about 40% to about 99%, about 40% to about 95%, about 40% to about 90% , about 40% to about 80%, about 40% to about 70%, about 40% to about 60%, about 40% to about 50%, about 50% to about 99%, about 50% to about 95%, about 50% to about 90%, about 50% to about 80%, about 50% to about 70%, about 50% to about 60%, about 60% to about 99%, about 60% to about 95%, about 60% ～about 90%, about 60% to about 80%, about 60% to about 70%, about 70% to about 99%, about 70% to about 95%, about 70% to about 90%, about 70% to about 80%, about 80% to about 99%, about 80% to about 95%, about 80% to about 90%, about 90% to about 99%, about 90% to about 95%, or about 95% to about 99 %.

In some embodiments, the nanostructure composition further comprises at least one monomer incorporated into the ligand coating the AIGS surface. AIGS nanostructures containing at least one monomer incorporated into the ligand coating the AIGS surface exhibit high QY, good compatibility with HDDA, a common monomer used in inkjet printable inks, and It has been discovered that it has strong blue light absorption.

In some embodiments, at least one monomer is an acrylate. Examples of acrylate monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, tridecyl methacrylate, stearyl methacrylate, decyl Methacrylate, dodecyl methacrylate, methoxydiethylene glycol methacrylate, polypropylene glycol monomethacrylate, phenyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, tert-butylcyclohexyl methacrylate, behenyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyloxyethyl methacrylate, 2- Ethylhexyl methacrylate, octyl methacrylate, isooctyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate, ethyl acrylate, methyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, 2-carboxyethyl acrylate, acrylic acid, ethylene glycol diacrylate, 1,3-propanediol diacrylate, 1,4-bis(acryloyloxy)butane, isobornyl acrylate, Examples include, but are not limited to, tetrahydrofurfuryl acrylate, cyclic trimethylolpropane formal acrylate, cyclohexyl methacrylate, and 4-tert-butylcyclohexyl acrylate.

In some embodiments, the monomer is at least one of ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or isobornyl acrylate. It is.

Methods of Preparing AIGS Nanostructure Compositions The present disclosure provides methods of preparing nanostructure compositions, the methods comprising:
(a) providing at least one population of AIGS nanostructures;
(b) mixing at least one organic resin with the composition of (a).

In some embodiments, the nanostructures have a PWL of 480-545 nm and at least about 80% of the emission is band edge emission. In some embodiments, at least 80% of the emission is band edge emission. In other embodiments, at least 90% of the emission is band edge emission. In other embodiments, at least 95% of the emission is band edge emission. In some embodiments, 92-98% of the emission is band edge emission. In some embodiments, 93-96% of the emission is band edge emission.

The present disclosure also provides a method of preparing a nanostructured composition, the method comprising:
(a) providing at least one population of AIGS nanostructures, wherein the nanostructures are prepared using a GaX ₃ (X=F, Cl, or Br) precursor and an oxygen-free ligand; to do and
(b) mixing at least one organic resin with the composition of (a).

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

The present disclosure also provides a method of preparing a nanostructured composition, the method comprising:
(a) providing at least one population of AIGS nanostructures, wherein the nanostructures have a PWL of 480-545 nm, at least about 80% of the emission is band edge emission, and the nanostructures have a PWL of 80-99 nm; indicating or providing a QY of %;
(b) mixing at least one organic resin with the composition of (a).

In some embodiments, the population of at least one nanostructure is at about 100 rpm to about 10,000 rpm, about 100 rpm to about 5,000 rpm, about 100 rpm to about 3,000 rpm, about 100 rpm to about 1,000 rpm, about 100 rpm ～about 500 rpm, about 500 rpm to about 10,000 rpm, about 500 rpm to about 5,000 rpm, about 500 rpm to about 3,000 rpm, about 500 rpm to about 1,000 rpm, about 1,000 rpm to about 10,000 rpm, about 1,000 rpm At a stirring speed of ~ about 5,000 rpm, about 1,000 rpm to about 3,000 rpm, about 3,000 rpm to about 10,000 rpm, about 3,000 rpm to about 10,000 rpm, or about 5,000 rpm to about 10,000 rpm , mixed with at least one organic resin.

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

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

In some embodiments, when two or more organic resins are used, the organic resins are added and mixed together. In some embodiments, the first organic resin is heated at about 100 rpm to about 10,000 rpm, about 100 rpm to about 5,000 rpm, about 100 rpm to about 3,000 rpm, about 100 rpm to about 1,000 rpm, about 100 rpm to about 500 rpm, about 500 rpm to about 10,000 rpm, about 500 rpm to about 5,000 rpm, about 500 rpm to about 3,000 rpm, about 500 rpm to about 1,000 rpm, about 1,000 rpm to about 10,000 rpm, about 1,000 rpm to about at a stirring speed of 5,000 rpm, about 1,000 rpm to about 3,000 rpm, about 3,000 rpm to about 10,000 rpm, about 3,000 rpm to about 10,000 rpm, or about 5,000 rpm to about 10,000 rpm. 2 organic resin.

In some embodiments, the first organic resin is applied for about 10 minutes to about 24 hours, about 10 minutes to about 20 hours, about 10 minutes to about 15 hours, about 10 minutes to about 10 hours, about 10 minutes to about Approximately 5 hours, approximately 10 minutes to approximately 1 hour, approximately 10 minutes to approximately 30 minutes, approximately 30 minutes to approximately 24 hours, approximately 30 minutes to approximately 20 hours, approximately 30 minutes to approximately 15 hours, approximately 30 minutes to approximately 10 Time, about 30 minutes to about 5 hours, about 30 minutes to about 1 hour, about 1 hour to about 24 hours, about 1 hour to about 20 hours, about 1 hour to about 15 hours, about 1 hour to about 10 hours, About 1 hour to about 5 hours, about 5 hours to about 24 hours, about 5 hours to about 20 hours, about 5 hours to about 15 hours, about 5 hours to about 10 hours, about 10 hours to about 24 hours, about 10 hours The mixture is mixed with the second organic resin for a period of time to about 20 hours, about 10 hours to about 15 hours, about 15 hours to about 24 hours, about 15 hours to about 20 hours, or about 20 hours to about 24 hours.

In some embodiments, the AIGS nanostructures are combined with at least one monomer incorporated into the ligand that coats the AIGS surface before being combined with the resin. In some embodiments, the monomer is an acrylate. In some embodiments, the monomer is at least one of ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or isobornyl acrylate. It is.

Properties of AIGS Nanostructures In some embodiments, AIGS nanostructures exhibit high photoluminescence quantum yield. In some embodiments, the nanostructures are about 50% to about 99%, about 50% to about 95%, about 50% to about 90%, about 50% to about 85%, about 50% to about 80% , about 50% to about 70%, about 50% to about 60%, 60% to about 99%, about 60% to about 95%, about 60% to about 90%, about 60% to about 85%, about 60 % to about 80%, about 60% to about 70%, about 70% to about 99%, about 70% to about 95%, about 70% to about 90%, about 70% to about 85%, about 70% to about about 80%, about 80% to about 99%, about 80% to about 95%, about 80% to about 90%, about 80% to about 85%, about 85% to about 99%, about 85% to about 95 %, about 80% to about 85%, about 85% to about 99%, about 85% to about 90%, about 90% to about 99%, about 90% to about 95%, or about 95% to about 99% shows the photoluminescence quantum yield of In some embodiments, the nanostructures exhibit photoluminescence quantum yields of about 82% to about 96%, about 85% to about 96%, and about 93% to about 94%.

The photoluminescence spectrum of nanostructures can cover a wide desired portion of the spectrum. In some embodiments, the photoluminescence spectrum of the nanostructure is from 300 nm to 750 nm, 300 nm to 650 nm, 300 nm to 550 nm, 300 nm to 450 nm, 450 nm to 750 nm, 450 nm to 650 nm, 450 nm to 550 nm, 450 nm to 750 nm, 450 nm to It has an emission maximum of 650 nm, 450 nm to 550 nm, 550 nm to 750 nm, 550 nm to 650 nm, or 650 nm to 750 nm. In some embodiments, the photoluminescence spectrum of the nanostructure has an emission maximum 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 is from 10 nm to 60 nm, from 10 nm to 40 nm, from 10 nm to 30 nm, from 10 nm to 20 nm, from 20 nm to 60 nm, from 20 nm to 40 nm, from 20 nm to 30 nm, from 25 nm to 60 nm, It can have a full width at half maximum of 25 nm to 40 nm, 25 nm to 30 nm, 30 nm to 60 nm, 30 nm to 40 nm, or 40 nm to 60 nm. In some embodiments, the photoluminescence spectrum of the population of nanostructures can have a full width at half maximum from 24 nm to 50 nm.

In some embodiments, the nanostructures are about 400 nm to about 650 nm, about 400 nm to about 600 nm, about 400 nm to about 550 nm, about 400 nm to about 500 nm, about 400 nm to about 450 nm, about 450 nm to about 650 nm, about 450 nm to about about 600 nm, about 450 nm to about 550 nm, about 450 nm to about 500 nm, about 500 nm to about 650 nm, about 500 nm to about 600 nm, about 500 nm to about 550 nm, about 550 nm to about 650 nm, about 550 nm to about 600 nm, or about 600 nm to about It emits light with a peak emission wavelength (PWL) of 650 nm. In some embodiments, the nanostructures emit light with a PWL of about 500 nm to about 550 nm.

As a predictor of blue light absorption efficiency, the optical density at 450 nm per mass reference (OD ₄₅₀ /mass) was determined by measuring the optical density of the nanostructure solution in a 1 cm path length cuvette and all under vacuum (<200 mTorr). can be calculated by dividing by the dry mass per mL of the same solution after removing volatiles. In some embodiments, the nanostructures are about 0.28/mg to about 0.5/mg, about 0.28/mg to about 0.4/mg, about 0.28/mg to about 0.35 /mg, about 0.28/mg to about 0.32/mg, about 0.32/mg to about 0.5/mg, about 0.32/mg to about 0.4/mg, about 0.32/mg mg to about 0.35/mg, about 0.35/mg to about 0.5/mg, about 0.35/mg to about 0.4/mg, or about 0.4/mg to about 0.5/mg It has an optical density at 450 nm (OD ₄₅₀ /mass) per mg mass basis.

Films The nanostructures of the present invention can be embedded in a polymer matrix using any suitable method. As used herein, the term "embedded" is used to indicate that the nanostructures are surrounded or encapsulated by the polymer that makes up the majority of the components of the matrix. In some embodiments, the at least one population of nanostructures is preferably 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 into a polymer and applied to the surface of a substrate.

In some embodiments, the present disclosure provides:
(a) a composition comprising at least one population of AIGS nanostructures and at least one ligand bound to the nanostructures;
(b) providing a nanostructured film layer comprising at least one organic resin;

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

In some embodiments, the nanostructures have a PWL of 480-545 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 monomer is an acrylate. In some embodiments, the monomer is at least one of ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or isobornyl acrylate. It is.

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

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

式中、
ｘは、１～１００であり、
ｙは、０～１００であり、
Ｒ^２は、Ｃ_１－２０アルキルである。 In some embodiments, the nanostructure composition further comprises an amino ligand having Formula I;

During the ceremony,
x is 1 to 100,
y is 0 to 100,
R ² is C _1-20 alkyl.

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

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 R ² =-CH ₃ and is JEFFAMINE M-600 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-600 has a molecular weight of approximately 600. In some embodiments, the amine-terminated polymer of formula (III) has x=19, y=3, and R ² =-CH ₃ and is JEFFAMINE M-1000 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-1000 has a molecular weight of approximately 1,000. In some embodiments, the amine-terminated polymer of formula (III) has x=6, y=29, and R ² =-CH ₃ and is JEFFAMINE M-2005 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-2005 has a molecular weight of approximately 2,000. In some embodiments, the amine-terminated polymer of formula (III) has x=31, y=10, and R ² =-CH ₃ and is JEFFAMINE M-2070 (Huntsman Petrochemical Corporation, Texas). JEFFAMINE M-2070 has a molecular weight of approximately 2,000. In another embodiment, the ligand is a polyethylene glycolamine available from Creative PEG Works, such as PEG550-amine and PEG350-amine.

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

Nanostructured compositions can be applied, but are not limited to, painting, spray coating, solvent atomization, wet coating, adhesive coating, spin coating, tape coating, roll coating, flow coating, inkjet vapor jetting, drop casting, blade coating, mist deposition. , or combinations thereof, by any suitable method known in the art. In some embodiments, the nanostructure composition is cured after being deposited. Suitable curing methods include photocuring, such as UV curing, and heat curing. Conventional laminated film processing methods, tape coating methods, and/or roll-to-roll fabrication methods can be employed in forming the nanostructured films of the present invention. The nanostructure composition can be coated directly onto the desired layer of the substrate. Alternatively, the nanostructured composition can be formed into a solid layer as a separate element and then applied to the substrate. In some embodiments, nanostructure compositions may be deposited on one or more barrier layers.

Spin Coating In some embodiments, the nanostructure composition is deposited onto a substrate using spin coating. In spin coating, a small amount of material is deposited onto the center of a substrate that is loaded into a machine called a spinner, which is usually held in place by a vacuum. High speed rotation is applied to the substrate via a spinner that creates a centripetal force that spreads the material from the center of the substrate to the edges. Although most of the material is shaken off, some amount remains on the substrate and forms a thin film of material on the surface as rotation continues. The final thickness of the film is determined by the parameters chosen for the spinning process, such as spin speed, acceleration, and spin time, as well as the nature of the material and substrate being deposited. For typical films, spin speeds of 1500-6000 rpm are used with spin times of 10-60 seconds. In some embodiments, the film is 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 a substrate using mist deposition. Mist deposition is performed at room temperature and atmospheric pressure, and film thickness can be precisely controlled by changing process conditions. During mist deposition, liquid source material is turned into a very fine mist and carried into the deposition chamber by nitrogen gas. The mist is then drawn to the wafer surface by the high voltage potential between the field screen and the wafer holder. Once the droplets have coalesced on the wafer surface, the wafer is removed from the chamber and thermally cured to evaporate the solvent. A liquid precursor is a mixture of a solvent and the material to be deposited. It is conveyed to the atomizer 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 Coating In some embodiments, the nanostructure composition is deposited onto a substrate using spray coating. Typical equipment for spray coating includes a spray nozzle, an atomizer, a precursor solution, and a carrier gas. In a spray deposition process, a precursor solution is broken into micro-sized droplets using a carrier gas or by atomization (eg, ultrasound, air blast, or electrostatic). The droplets emerging from the atomizer are accelerated by the substrate surface through the nozzle with the aid of a carrier gas that is controlled and regulated as desired. The relative movement between the spray nozzle and the substrate is dictated by the design for complete coverage on the substrate.

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

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

In some embodiments, the organic solvent used in a nanostructured composition used as an inkjet printing formulation is defined by its boiling point, viscosity, and surface tension. Properties of organic solvents suitable for inkjet printing formulations are shown in Table 1.

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

In some embodiments, the organic solvent has a pressure of about 1 mPa ^. s~about 15mPa ^. It has a viscosity of s. In some embodiments, the organic solvent has a pressure of about 1 mPa ^. s~about 15mPa ^. s, approximately 1 mPa ^. s~about 10mPa ^. s, approximately 1 mPa ^. s~about 8mPa ^. s, approximately 1 mPa ^. s~about 6mPa ^. s, approximately 1 mPa ^. s~about 4mPa ^. s, approximately 1 mPa ^. s~about 2mPa ^. s, approximately 2mPa ^. s~about 15mPa ^. s, approximately 2mPa ^. s~about 10mPa ^. s, approximately 2mPa ^. s~about 8mPa ^. s, approximately 2mPa ^. s~about 6mPa ^. s, approximately 2mPa ^. s~about 4mPa ^. s, about 4 mPa ^. s~about 15mPa ^. s, about 4 mPa ^. s~about 10mPa ^. s, about 4 mPa ^. s~about 8mPa ^. s, about 4 mPa ^. s~about 6mPa ^. s, about 6 mPa ^. s. ～About 15mPa ^. s, about 6 mPa ^. s~about 10mPa ^. s, about 6 mPa ^. s~about 8mPa ^. s, about 8 mPa ^. s~about 15mPa ^. s, about 8 mPa ^. s~about 10mPa ^. s, or about 10 mPa ^. s~about 15mPa ^. It has a viscosity of s.

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

In some embodiments, the organic solvent used in the nanostructure composition is an alkylnaphthalene, an alkoxynaphthalene, an alkylbenzene, an aryl, an alkyl-substituted benzene, a cycloalkylbenzene, a _C9 - _C20 alkane, a diaryl ether, an 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-nonylbenzene, 4-methylanisole, n-decylbenzene, p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, dipentylbenzene, o-diethylbenzene, m-diethylbenzene, p- Diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, 1-methylnaphthalene, 1 , 2,4-trichlorobenzene, diphenyl ether, diphenylmethane, 4-isopropylbiphenyl, benzyl benzoate, 1,2-bi(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, or a combination thereof. . In some embodiments, the organic solvent used in the nanostructure composition includes 1-methylnaphthalene, n-octylbenzene, 1-methoxynaphthalene, 3-phenoxytoluene, cyclohexylbenzene, 4-methylanisole, n-decyl benzene, 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 combination of monomers selected from the list provided above.

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

In some embodiments, the inkjet printing composition further comprises monomers incorporated into the ligand coating the AIGS surface. In some embodiments, the monomer is an acrylate. In some embodiments, the monomer is ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(incorporated into the ligand coating the AIGS surface lyloyloxy) butane, or at least one of nyl acrylates. 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 a nanostructured layer. In some embodiments, the composition is cured using UV light. In some embodiments, the nanostructured composition is coated directly onto the barrier layer of the nanostructured film, and an additional barrier layer is subsequently deposited onto the nanostructured layer to produce the nanostructured film. A support substrate is placed beneath the barrier film to add strength, stability, and coating uniformity, as well as to prevent material mismatches, bubble formation, and wrinkling or folding of the barrier layer material or other materials. It can be used for. Additionally, one or more barrier layers may be deposited over the nanostructure layer to seal the material between the top and bottom barrier layers. Preferably, the barrier layer is deposited as a laminated film and optionally encapsulated or further processed, after which the nanostructured film can be incorporated into a particular lighting device. The nanostructure composition deposition process can include additional or various components, as will be understood by those skilled in the art. Such embodiments would allow in-line process tuning of nanostructure emission properties such as brightness and color (eg, to tune quantum film white point), as well as nanostructure film thickness and other properties. Additionally, these embodiments will allow periodic testing of nanostructured film properties during production, as well as any necessary switching to achieve precise nanostructured film properties. Such testing and adjustment can be done without changing the mechanical configuration of the processing line, since the amount of each of the mixtures used in forming the nanostructured film can be electronically varied using a computer program. It can also be achieved.

Nanostructured films with high PCE can be obtained when the films are processed without exposing the AIGS nanocrystals to blue or UV light before providing an oxygen-free environment for the nanostructures. It's been found. The anoxic environment is
(a) encapsulating the film with an oxygen barrier prior to thermal processing and/or exposure to blue light for PCE measurements;
(b) the use of oxygen-reactive materials as part of the formulation during thermal processing or exposure; and/or (c) temporary blockage of oxygen by the use of sacrificial barrier layers.

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

In some embodiments, the film is encapsulated in an inert atmosphere. In some embodiments, the film 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, organometallic 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 organometallic precursor can be trialkylaluminum, trialkyllallium, trialkylindium, dialkylzinc, and the like.

Examples of sacrificial barrier layers include polymeric layers that can be dissolved in a solvent and washed away. Examples of such polymers include, but are not limited to, polyvinyl alcohol, polyvinyl acetate, and polyethylene glycol. Other examples of sacrificial barrier layers include inorganic compounds or salts such as lithium silicate, lithium fluoride, and the like. Examples of solvents that can be used to wash away the sacrificial layer include water, as well as alcohols (e.g., ethanol, methanol), halocarbons (e.g., methylene chloride and ethylene chloride), aromatic hydrocarbons (e.g., toluene, xylene), aliphatic hydrocarbons (eg, hexane, octane, octadecene), C _4-20 ethers such as tetrahydrofuran, diethyl ether, and C _2-20 esters such as ethyl acetate.

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

In some embodiments, the nanostructured film is part of a 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 microLEDs.

In some embodiments, the nanostructure layer is disposed on the light source element. In some embodiments, the nanostructure layer includes a patterned nanostructure layer. Patterned nanostructure layers may be prepared by any known method in the art. In one embodiment, the patterned nanostructure layer is prepared by inkjet printing of a solution of nanostructures. Suitable solvents for the solution include, but are not limited to, dipropylene glycol monomethyl ether acetate (DPMA), polyglycidyl methacrylate (PGMA), diethylene glycol monoethyl ether acetate (EDGAC), and propylene glycol methyl ether acetate (PGMEA). can be mentioned. Volatile solvents can also be used in inkjet printing because they allow rapid drying. Examples of volatile solvents include ethanol, methanol, 1-propanol, 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and tetrahydrofuran. Alternatively, "solventless" inks in which AIGS nanostructures are dispersed in the ink monomers may 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 the ligand that coats the AIGS surface. In some embodiments, at least one monomer is an acrylate. In some embodiments, the acrylate is at least one of ethyl acrylate, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, or isobornyl acrylate. AIGS nanostructures treated with at least one monomer during ligand exchange provide better compatibility with HDDA, a common monomer used in inkjet printable inks, and improve QY and blue light absorption. was found to improve.

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

In some embodiments, the nanostructure display device exhibits a PCE of at least 32%. In some embodiments, the nanostructured compact exhibits a PCE of 32-40%. In some embodiments, the nanostructured compact is 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- PCE of 38%, 33-37%, 34-37%, 35-37%, 36-37%, 33-36%, 34-36%, 35-36%, 33-35%, or 34-35% shows.

In some embodiments, the optical film that includes the nanostructure layer is substantially free of cadmium. As used herein, the term "substantially free of cadmium" intends that the nanostructure composition contains less than 100 ppm by weight of cadmium. RoHS compliance definitions require 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) and are at the parts per billion (ppb) level. In some embodiments, a "substantially cadmium-free" optical film contains 10-90 ppm cadmium. In other embodiments, the substantially cadmium-free optical film contains less than about 50 ppm, less than about 20 ppm, less than about 10 ppm, or less than about 1 ppm cadmium.

Nanostructured Molded Objects In some embodiments, the present disclosure provides
(a) a first barrier layer;
(b) a second barrier layer;
(c) a nanostructured layer between the first barrier layer and the second barrier layer, the nanostructured layer comprising a population of nanostructures including AIGS nanostructures; and at least one organic resin. A nanostructure molded body is provided.

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

In some embodiments, at least 80% of the emission is band edge emission. In other embodiments, at least 90% of the emission is band edge emission. In other embodiments, at least 95% of the emission is band edge emission. In some embodiments, 92-98% of the emission is band edge emission. In some embodiments, 93-96% of the emission is band edge emission. In some embodiments, the nanostructured compact exhibits a PCE of at least 32%. In some embodiments, the nanostructured compact exhibits a PCE of 32-40%. In some embodiments, the nanostructured compact is 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- PCE of 38%, 33-37%, 34-37%, 35-37%, 36-37%, 33-36%, 34-36%, 35-36%, 33-35%, or 34-35% shows.

Barrier Layer In some embodiments, the nanostructured compact includes one or more barrier layers disposed on either one or both sides of the nanostructure layer. Suitable barrier layers protect the nanostructured layer and nanostructured compact from environmental conditions such as high temperature, oxygen, and moisture. Suitable barrier materials include non-yellowing transparent optics that are hydrophobic, chemically and mechanically compatible with nanostructured moldings, exhibit optical and chemical stability, and can withstand high temperatures. Examples include materials. In some embodiments, one or more barrier layers are index matched to the nanostructured compact. In some embodiments, the matrix material of the nanostructured compact and the one or more adjacent barrier layers are such that a majority of the light transmitted through the barrier layer toward the nanostructured compact is from the barrier layer to the nanostructured compact. The refractive index is matched to have a similar refractive index so that the refractive index is transmitted within the refractive index. This refractive index matching reduces optical loss at the interface between barrier and matrix materials.

The barrier layer is preferably a solid material and may be a hardened liquid, gel, or polymer. The barrier layer can include flexible or non-flexible materials depending on the particular application. Barrier layers are generally planar layers and can include any suitable shape and surface area configuration, depending on the particular lighting application. In some embodiments, the one or more barrier layers are compatible with laminated film processing techniques, such that the nanostructure layer is disposed on at least a first barrier layer and on at least a second barrier layer. are disposed on the nanostructured layer opposite the nanostructured layer to form a nanostructured compact according to an embodiment of the invention. Suitable barrier materials include any suitable barrier materials known in the art. For example, suitable barrier materials include glasses, polymers, and oxides. Suitable barrier layer materials include polymers such as polyethylene terephthalate (PET) and oxides such as silicon oxide, titanium oxide, or aluminum oxide (e.g., SiO ₂ , Si ₂ O ₃ , TiO ₂ , or Al ₂ O ₃ ). and suitable combinations thereof, but are not limited to these. In some embodiments, each barrier layer of the nanostructured compact includes at least two layers comprising different materials or compositions, such that the multilayer barrier eliminates or reduces alignment of pinhole defects in the barrier layer. and provides an effective barrier to oxygen and moisture penetration into the nanostructured layer. The nanostructured layer can include any suitable material or combination of materials and any suitable number of barrier layers on one or both sides of the nanostructured layer. The material, thickness, and number of barrier layers depend on the particular application and are suitably selected to maximize the barrier protection and brightness of the nanostructured layer while minimizing the thickness of the nanostructured compact. . In some embodiments, each barrier layer comprises a laminated film, in some embodiments a double-laminated film, and the thickness of each barrier layer is adjusted to eliminate wrinkles in roll-to-roll or laminated manufacturing processes. thick enough. The number or thickness of barriers may further depend on legal toxicity guidelines in embodiments where the nanostructures include heavy metals or other toxic materials, 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, such as two or three layers on each side of the nanostructured layer or two or more barrier layers on each side of the nanostructured layer. Contains two barrier layers. In some embodiments, each barrier layer comprises a thin glass sheet, such as a glass sheet having a thickness of about 100 μm, less than 100 μm, or less than 50 μm.

Each barrier layer of the nanostructured film of the present invention depends on the specific requirements and characteristics of the lighting device and application, as well as the individual film components, such as the barrier layer and the nanostructured layer, as understood by those skilled in the art. It can have any suitable thickness. 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 is an oxide coating that can include materials such as silicon oxide, titanium oxide, and aluminum oxide (e.g., SiO ₂ , Si ₂ O ₃ , TiO ₂ , or Al ₂ O ₃ ). including. 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 comprises 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 upper and/or lower barrier may consist of a thin oxide coating or may include a thin oxide coating and one or more additional material layers.
Display device with nanostructured color conversion layer

In some embodiments, the invention provides:
(a) a display panel that emits a first light;
(b) a backlight unit that provides first light to the display panel;
(c) a color filter including at least one pixel region including a color conversion layer.

In some embodiments, the color filter comprises at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 pixel regions. When blue light is incident on the color filter, red light, white light, green light, and/or blue light is emitted through the pixel area. In some embodiments, color filters are described in US Pat. 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 conversion layer includes nanostructures described herein configured to convert incident light to light of a first color. In some embodiments, the color conversion layer includes 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 one color conversion layer that includes the nanostructures described herein. In some embodiments, the display device includes two color conversion layers that include the nanostructures described herein. In some embodiments, the display device includes three color conversion layers that include the nanostructures described herein. In some embodiments, the display device includes four color conversion layers that include 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 a thickness of about 3 μm to about 10 μm, about 3 μm to about 8 μm, about 3 μm to about 6 μm, about 6 μm to about 10 μm, about 6 μm to about 8 μm, or about 8 μm to about 10 μm. It has a certain quality. In some embodiments, the color conversion layer has a thickness of about 3 μm to about 10 μm.

The nanostructured color conversion layer can be applied by, but not limited to, painting, spray coating, solvent atomization, wet coating, adhesive coating, spin coating, tape coating, roll coating, flow coating, inkjet printing, photoresist patterning, drop casting, blading. It may be deposited by any suitable method known in the art, including 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 compositions further include one or more ligands. Ligands include amino-ligands, polyamino-ligands, mercapto-ligands, phosphino-ligands, silane ligands, and polymeric or oligomeric chains such as polyethylene glycols having amine and silane groups.

式中、
ｘは、１～１００であり、
ｙは、０～１００であり、
Ｒ^２は、Ｃ_１－２０アルキルである。 In some embodiments, the amino ligand has Formula I,

During the ceremony,
x is 1 to 100,
y is 0 to 100,
R ² is C _1-20 alkyl.

In some embodiments, the polyamino-ligand is a polyaminoalkane, polyamine-cycloalkane, polyamino heterocycle, polyamino-functionalized silicone, or polyamino-substituted ethylene glycol. In some embodiments, the polyamino ligand is a C 2-20 alkane or a C _2-20 alkane substituted with two or three amino groups and optionally containing one or two amino groups in place of _carbon groups. It is a cycloalkane. In some embodiments, the polyamino ligand is ethylenediamine, 1,2-diaminopropane, 1,2-diamino-2-methylpropane, N-methylethylenediamine, N-ethyl-ethylenediamine, N-isopropylethylenediamine, N-cyclohexyl - Ethylenediamine, N-cyclohexyl-ethylenediamine, N-octylethylenediamine, N-decylethylenediamine, N-dodecyl-ethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N'-diethyl-ethylenediamine, N, N'-diisopropylethylenediamine, N,N,N'-trimethyl-ethylenediamine, diethylenetriamine, N-isopropyl-diethylenetriamine, N-(2-aminoethyl)-1,3-propanediamine, triethylenetetramine, N,N'- Bis(3-aminopropyl)ethylenediamine, N,N'-bis(2-aminoethyl)-1,3-propanediamine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, 2-( 2-Aminoethylamino)ethanol, N,N-bis(hydroxyethyl)ethylenediamine, N-(hydroxyethyl)diethylenetriamine, N-(hydroxyethyl)triethylenetetramine, piperazine, 1-(2-aminoethyl)piperazine, 4 -(2-aminoethyl)morpholine, polyethyleneimine, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diminopemane, 2,2-dimethyl-1,3-propane Diamine, 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(hexanediamine) methylene)triamine, N,N',N"-trimethyl-bis(hexamethylene)triamine, 4-amino-1,8-octanediamine, N,N'-bis(3-aminopropyl)-1,3-propylene Diamine, spermine, 4,4'-methylenebis(cyclohexylamine), 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-cyclohexanebis(methylamine), 1,4-cyclohexanebis(methylamine) , 1,2-bis(aminoethoxy)ethane, 4,9-dioxa-1,12-dodecanediamine, 4,7,10-trioxa-1,13-tridecanediamine, 1,3-diamino-hydroxy-propane , 4,4-methylenedipiperidine, 4-(aminomethyl)piperidine, 3-(4-aminobutyl)piperidine, or polyallylamine. In some embodiments, the polyamino-ligand is 1,3-cyclohexanebis(methylamino), 2,2-dimethyl-1,3-propanediamine, or tris(2-aminoethyl)amine.

In some embodiments, the polyamino-ligand is a polyamino heterocyclic compound. In some embodiments, the polyamino heterocyclic compound is 2,4-diamino-6-phenyl-1,3,5-triazi, 6-methyl-1,3,5-triazi-2,4-diamine, 2,4-diamino-6-diethylamino-1,3,5-triazi, 2-N,4-N,6-N-tripropyl-1,3,5-triazi-2,4,6-triamine, 2 ,4-diaminopyrimidine, 2,4,6-triaminopyrimidine, 2,5-diaminopyridine, 2,4,5,6-tetraminopyrimidine, 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)-phenylmethylidene]-1H- Imidazole-1,2-diamine, 2-phenyl-1H-imidazole-4,5-diamine, 1H-imidazole-2,4,5-triamine, 1H-pyrrole-2,5-diamine, 1,2,4, 5-tetrazine-3,6-diamine, N,N'-dicyclohexyl-1,2,4,5-tetrazine-3,6-diamine, N3-propyl-1H-1,2,4-triazole-3 ,5-diamine, or N,N'-bis(2-methoxybenzyl)-1H-1,2,4-triazole-3,5-diamine.

のうちの１つである。 In some embodiments, the polyamino-ligand is a polyamino-functionalized silicone. In some embodiments, the polyamino functionalized silicone is

This is one of them.

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

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

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

In some embodiments, the ligand includes amino-polyalkylene oxide (e.g., about m.w. 1000), (3-aminopropyl)trimethoxysilane), (3-mercaptopropyl)triethoxysilane, DL- α-lipoic acid, 3,6-dioxa-1,8-octanedithiol, 6-mercapto-1-hexanol, methoxypolyethylene glycolamine (approx. m.w. 500), poly(ethylene glycol) methyl ether thiol (approx. .w.800), diethylphenylphosphonite, dibenzyl N,N-diisopropylphosphoramidite, di-tert-butyl N,N-diisopropylphosphoramidite, tris(2-carboxyethyl)phosphine hydrochloride, poly(ethylene glycol) ) methyl ether thiol (about m.w. 2000), methoxypolyethylene glycolamine (about m.w. 750), acrylamide, and polyethyleneimine.

Particular combinations of ligands include amino-polyalkylene oxide (about m.w. 1000) and methoxypolyethylene glycolamine (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 glycolamine (about m.w. 500), which provided excellent dispersibility and thermal stability. See Example 9.

Films containing AIGS nanostructures and polyamino ligands exhibited higher film light conversion efficiency (PCE) and less wrinkling of the film compared to AIGS-containing films without polyamino ligands and compared to monoamino ligands. and exhibit less delamination. Compositions containing AIGS-polyamino-ligands are therefore uniquely suitable for use in nanostructured color conversion layers.

The following examples are illustrative of, but not limiting, 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 in view of this disclosure are within the spirit and scope of the invention.

Example 1: AIGS Core _Synthesis Sample ID1 was prepared using the following representative synthesis of AIGS core: 4 mL of 0.06 M _CH3CO2Ag in oleylamine, ₁ mL of 0.2 M InCl3 in ethanol, 1 mL of 0.95 M sulfur in oleylamine and 0.5 mL of dodecanethiol were injected into a flask containing 5 mL of degassed octadecene, 300 mg of trioctylphosphine oxide, and 170 mg of gallium acetylacetonate. The mixture was heated to 40°C for 5 minutes, then the temperature was increased to 210°C and held for 100 minutes. After cooling to 180° C., 5 mL of trioctylphosphine was added. The reaction mixture was transferred to a glove box and diluted with 5 mL of toluene. The final AIGS product was precipitated by adding 75 mL of ethanol, centrifuged, and redispersed in toluene. Samples ID2 and 3 were also prepared using this method. The optical properties of the AIGS core were measured and summarized in Table 2. The size and morphology of AIGS cores were characterized by transmission electron microscopy (TEM).

Example 2: AIGS Nanostructures with Ion Exchange Treatment Sample ID4 was prepared using the following typical ion exchange treatment. 2 mL of a 0.3 M gallium oleate solution in octadecene and 12 mL of oleylamine were introduced into the flask and degassed. The mixture was heated to 270°C. A premixed solution of 1 mL of a 0.95 M sulfur solution in oleylamine and 1 mL of isolated AIGS core (15 mg/mL) was co-injected. The reaction was stopped after 30 minutes. The final product was transferred to a glove box, washed with toluene/ethanol, centrifuged, and redispersed in toluene. Samples ID4-8 were also prepared using this method. The optical properties of the AIGS nanostructures thus produced are summarized in Table 3. Ion exchange with gallium ions resulted in nearly complete band-edge emission. An increase in average particle size was observed by TEM.

Example: ₃ Ion exchange treatment of gallium halide and trioctylphosphine AIGS nano A room temperature ion exchange reaction with the structure was performed. This treatment resulted in significant enhancement of band edge emission, summarized in Table 4, while substantially preserving peak wavelength (PWL).

The composition changes before and after _GaI addition were monitored by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and energy dispersive X-ray spectroscopy (EDS) as summarized in Table 4. A composite image of In and Ga element distribution before and after _GaI3 /TOP treatment shows a radial distribution of In vs. Ga, and thus the ion exchange treatment results in a larger amount of gallium near the surface of the nanostructures and a higher amount of gallium in the center of the nanostructures. This results in a gradient of smaller amounts of gallium.

Example 4: AIGS ion exchange treatment using an oxygen-free Ga source Samples ID14 and 15 were prepared using the following representative treatment of AIGS nanoparticles using an oxygen-free Ga source. To 8 mL of degassed oleylamine was added 400 mg of GaCl ₃ dissolved in 400 μL of toluene, followed by 40 mg of AIGS core, then 1.7 mL of 0.95 M sulfur in oleylamine. After heating to 240°C, the reaction was held for 2 hours and then cooled. The final product was transferred to a glove box, washed with toluene/ethanol, centrifuged, and dispersed in toluene. Samples ID15 and 16 were also prepared using this method. Samples ID11-13 were prepared using the method of Example 2. The optical properties of the treated AIGS material are shown in Table 5.

As shown in Table 5, the quantum yield of treated AIGS nanostructures is higher than Ga(III) chloride but not Ga(III) acetylacetonate or gallium oleate when oleylamine is used as the solvent. can be improved by using The final material subjected to ion exchange using Ga(III) chloride gave similar size and similar band edge versus trap emission properties as the starting nanostructures. Therefore, the increase in quantum yield (QY) is not simply due to an increase in the trapped emission component. It was also unexpectedly 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. Ta.

High-resolution TEM with energy-dispersive X-ray spectroscopy (EDS) of sample 14 shows that the nanostructures likely contain a slight gradient that decreases In from the center of the AIGS nanostructures to the surface. , this results from a process in which treatment under these conditions causes In to exit the AIGS structure and be replaced by Ga, while Ag is present throughout the structure rather than growing a separate layer of GS. Show that. This may also contribute to improving the quantum yield of the nanostructures due to less distortion.

Example 5: AIGS core from hot injection of pre-formed Ag ₂ S nanostructures mixed with pre-formed In-Ga reagent To create Ag ₂ S nanostructures, ₀ Add .5 g of AgI and 2 mL of oleylamine to a 20 mL vial and stir at 58° C. until a clear solution is obtained. In a separate 20 mL vial, 5 mL of DDT and 9 mL of 0.95 M sulfur in oleylamine were mixed. Add the DDT+S-OYA mixture to the AgI solution and stir at 58° C. for 10 minutes. The obtained Ag ₂ S nanoparticles were used without washing.

To make the In-Ga reagent mixture, 1.2 g Ga(acetylacetonate) ₃ , 0.35 g InCl ₃ , 2.5 mL oleylamine, and 2.5 mL ODE were placed in a 100 mL flask. Heat to 210° C. and hold for 10 minutes under N ₂ atm. 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, the solvent mixture is heated to 210° C. over 40 minutes. In a 40 mL vial, mix the Ag ₂ S and In-Ga reagent mixture from above at 58° C. and transfer to a syringe. The Ag-In-Ga mixture is then injected into the solvent mixture at 210°C and held for 3 hours. After cooling to 180° C., 5 mL of trioctylphosphine was added. The reaction mixture was transferred to a glove box and diluted with 50 mL of toluene. The final product was precipitated by adding 150 mL of ethanol, centrifuged, and redispersed in toluene. The AIGS nanostructures were then ion-exchanged by the method described in Example 4. The optical properties of materials produced by this method at scales up to 24 times the above are shown in Table 6.

Example 7 Repeated gallium ion exchange improves photoluminescence stability of AIGS nanostructures.

7.1 First Ion Exchange Process Oleylamine (OYA, 2.5 L) is degassed under vacuum at 40° C. for 40 minutes. Add AIGS nanostructures (25.4 g in toluene) followed by GaCl ₃ (127 g in minimal toluene) and sulfur dissolved in OYA (0.95 M, 570 mL). The mixture is heated to 240° C. over 40 minutes and held for 4 hours. After cooling, the mixture is diluted with 1 volume of toluene. After centrifugation to remove some byproducts, the material is washed with 2 volumes of ethanol, collected by centrifugation, and redissolved in toluene. After the second wash, the nanostructures are dissolved in heptane for storage.

7.2 Second Ion Exchange Process Oleylamine (OYA, 960 mL) is degassed under vacuum at 40° C. for 20 minutes. AIGS ion-exchange nanostructures (12 g in heptane) as from Example 7.1 were added to OYA, followed by _GaCl (22.5 g in minimum volume of toluene) and then sulfur (0.95 M) dissolved in OYA. , 100 mL). The mixture is heated to 240° C. over 40 minutes and held for 3 hours. After cooling, the mixture is diluted with 1 vol of toluene, then washed (precipitated with 1.6 vol of ethanol and centrifuged) and redispersed in toluene or heptane as required. When performing ligand exchange for ink formulation, a further ethanol wash is applied to redisperse the QDs in heptane.

7.3 Alternating Second Ion Exchange Process Oleylamine (15 mL) is degassed under vacuum at 60° C. for 20 minutes. GaCl ₃ (360 mg in minimum volume of toluene) was added to OYA, followed by AIGS (200 mg in heptane) as from Example 7.1, followed by sulfur (0.95 M, 1.6 mL) dissolved in OYA. Add. The mixture is heated to 240° C. over 40 minutes and held for 3 hours. After cooling, the mixture is washed as described in Example 7.1.

7.4 Alternating Second Ion Exchange Process This example was carried out as described for Example 7.3, but on a 3x scale.

7.5 Alternating Second Ion Exchange Process Oleylamine (10 mL) and oleic acid (5 mL) are degassed under vacuum at 90° C. for 20 minutes. (Ga( _NMe3 ) ₃ ) ₂ (206 mg) and _GaCl3 (180 mg in a minimum volume of toluene) are added followed by AIGS (200 mg in heptane) as from Example 7.1. After heating to 130° C., TMS ₂ S (0.65 mL of a 50% solution in ODE) is added over 20 minutes and the mixture is held for 2.5 hours. After cooling, the mixture is washed as described in Example 7.1.

7.6 Results AIGS nanostructures were subjected to an ion exchange process where In was exchanged with Ga. Compared to core growth, the higher temperature used in this process (240 °C vs. 210 °C) results in ripening such that the average size is larger than the untreated nanostructures. Nanostructures do not have well-defined shell structures. This can be observed in cross-sectional TEM elemental mapping. The lack of a higher bandgap shell 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 (Figures 2A-2C), but TEM elemental mapping showed that a clearer gradient towards the Ga-rich (higher bandgap) region occurred in the QDs. I have proven that I did it.

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

The properties of the ion-exchanged AIGS nanostructures are shown in Table 8. Metal ratios are molar ratios determined by ICP.

The film PCE retained after UV curing and 180° C. bake is significantly improved by the second ion exchange process, as shown in Table 9. This is believed to be because the process of increasing the Ga concentration in the outer layer of the nanostructure results in a gradient to the higher bandgap region introduced by ion exchange.

Example 8 - Composition Comprising AIGS Nanostructures and Polyamino Ligands Abbreviation - Jeffamine - Jeffamine M-1000
・HDDA-1-6 hexanediol diacrylate ・Bismethylamine-1,3 cyclohexane bismethylamine ・PCE-Photon conversion efficiency

The crude AIGS QD growth solution was purified by washing with ethanol and redispersing in heptane (solution 1). 6-mercapto-1-hexanol was added to solution 1, heated at 50° C. for 30 minutes, washed with ethanol, and redispersed in heptane (solution 2). 2 μL of 6-mercapto-1-hexanol was added per 100 mg of QD inorganic solid. To solution 2, Jeffamine and HDDA were added for the ligand exchange step, heated at 80° C. for 1 hour, precipitated with heptane and redispersed in HDDA (solution 3). 83 mg of Jeffamine was added per 100 mg of QD inorganic solids. 0.42 g HDDA was added per 100 mg QD inorganic solids. Solution 3 and HDDA were added to an inkjet ink composition containing 10% by weight TiO ₂ and 90% by weight monomer. The inkjet formulation has a composition of 10 wt% QD inorganic mass, 4 wt% _TiO2 , the remaining 86 wt% being ligands (bound and unbound), HDDA, monomers, photoinitiators, and QDs. It was a combination of various other organics that remained from the solution. This ink formulation was Solution 4.

To Solution 4, the polyamino ligand bismethylamine (50 mg bismethylamine per 100 mg QD inorganic solids) was added and the composition was then cast as a film.

Film Casting Solution 4 was spin coated onto a 2 inch x 2 inch glass substrate. The film was cured with a UV LED curing lamp. Next, film light conversion efficiency (PCE), a measure of brightness, was tested. The film was then baked on a hot plate set at 180° C. for 30 minutes at a slightly higher temperature than the hot plate. Alternatively, the film was baked for 10 minutes using a hot plate set at 180° C. in direct contact with the hot place surface.

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

PCE is the ratio of the number of forward-emitting green photons to the number of blue photons generated by the test platform. Although the emission spectrum from 484 nm to 700 nm is used to calculate PCE, it is expected that the green emission has a peak wavelength between 484 and 545 nm, with the majority of the emission being below 588 nm. PCE, LRR and film morphology are reported in Table 10. Unexpectedly, the presence of the ligands 1,3-cyclohexanebis(methylamine), tris(2-aminoethyl)amine and 2,2-dimethyl-1,3-propanediamine compared to films without ligands , resulted in high retention of PCE after 180°C baking, high LRR and no wrinkles.

Figure 1 shows the effect of diamine addition on film morphology. The films in Figure 1 are from left to right: no additive (wrinkled), 2,2-dimethyl-1,3-propanediamine (diamine, wrinkled), cyclohexanemethylamine (monoamine, wrinkled), and tris (wrinkled). 2-aminoethyl)amine (triamine, wrinkle free). From left to right, the first and third films without diamine exhibited extensive wrinkling. In contrast, the second and fourth films showed no wrinkles. Unexpectedly, the use of diamino ligands in AIGS films resulted in a significant reduction in film wrinkling.

Example 9 - Testing of Additional Ligands for AIGS Nanostructures In this experiment, additional ligands for AIGS nanoparticles were tested for enhanced QY, high compatibility and good thermal stability. Additionally, these ligands were evaluated for protecting AIGS nanostructures from degradation and oxidation. We also tested combinations of ligands that can be incorporated into AIGS ink compositions.

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

AIGS nanostructures are ligand-exchanged with ligands containing polymeric or oligomeric chains such as polyethylene glycol with amine and silane groups and soft bases such as phosphino-, mercapto- and combinations thereof for co-passivation. Ta.

FIG. 4 shows quantum yield values for a number of individual ligands and AIGS nanostructures subjected to a single ion exchange treatment as described herein. In this graph, NG: natural AIGS, NG-NL1: amino-polyalkylene oxide, about m.p.m. w. 1000, NG-NL2: (3-aminopropyl)trimethoxysilane), NG-NL3: (3-mercaptopropyl)triethoxysilane, NG-NL4: DL-α-lipoic acid, NG-NL5: 3,6- Dioxa-1,8-octanedithiol, NG-NL6: 6-mercapto-1-hexanol, NG-NL7: Methoxypolyethylene glycolamine 500, NG-NL8: Poly(ethylene glycol) methyl ether thiol Mn800, NG-NL9: Diethyl Phenylphosphonite, NG-NL10: dibenzyl N,N-diisopropylphosphoramidite, NG-NL11: di-tert-butyl N,N-diisopropylphosphoramidite, NG-NL12: tris(2-carboxyethyl)phosphine hydrochloride , NG-NL13: poly(ethylene glycol) methyl ether thiol Mn2000, NG-NL14: methoxypolyethylene glycolamine 750, NG-NL15: acrylamide, and NG-NL16: polyethyleneimine).

As seen in Figure 4, AIGS nanostructures were synthesized using 3-mercaptopropyl)triethoxysilane (NL3), 3,6-dioxa-1,8-octanedithiol (NL5), and 6-mercapto-1-hexanol (NL6). ), high QY (73.7%, 72.9% and 76.1%, respectively) was obtained. Accordingly, the present invention provides AIGS nanostructure compositions that include at least one mercapto-substituted ligand that provides improved QY. Mercapto-substituted ligands are believed to provide high QY by passivating the surface of AIGS nanostructures and reducing defect emission. Amino-substituted ligands also improved QY.

In this single-ligand study, polyethylene glycolamine-substituted ligands (L1, L7, L8, and L13), thiol-substituted ligands (L3, L5, and L6), and silane ligand (L2) compared favorably to native AIGS nanostructures. It showed a QY. Also, ligands L1, L7 and L8 provided better compatibility with monomers when dispersed in HDDA.

FIG. 5 is a graph showing the QY% of various two-ligand combinations that gave improved QY% (good combinations) and reduced QY% (bad combinations). Surface defects can be reduced by adding thiol ligands. The combination of L6 and L7 gave better stability than the others. However, for ink compositions that are relatively hydrophilic, better ligands are relatively hydrophilic ligands such as methoxypolyethylene glycolamine and poly(ethylene glycol) methyl ether thiol. This thiol also improves QY by passivating surface defects.

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

Table 11 shows the relative changes in QY, PWL, and FWHM before and after ligand exchange with multiple ligands. Table 11 shows that L6 and L7 were the most effective ligand combinations for the ink formulations, especially when combined with acrylate monomers. Combinations of L2 and L7, L2 and L6, and L2 and L3, L6 and L7 provided excellent dispersibility and thermal stability. Please refer to FIG.

Combinations of ligands that provided good thermal stability when heated to 180° C. for 30 minutes in a glove box were further investigated. The ligand combinations L6 & L7, L2 & L6, and L2 & L3 provided better stability than the single ligand L1. Please refer to FIG.

We also studied the effect of combinations of different ratios of ligands on QY. The weight ratio of the ligands was varied, but the total amount of ligands was fixed. The best QY was achieved with an L6 to L7 ratio of 7:3. Please refer to FIG. All combinations with L6 and L7 showed enhanced QY compared to native AIGS nanostructures, except for the 9:1 ratio. Even if the mixture showed a high QY, it was difficult to purify as no precipitation occurred. Mixtures of L6&L2, L3&L7, and L5&L7 are good ligand mixtures for AIGS nanostructures. Combinations of these ligands include tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane, diethylene glycol ethyl ether acrylate, isobornyl acrylate, hydroxypropyl acrylate, 2-(acryloyloxy) ) ethyl hydrogen succinate, and 1,6-hexanediol diacrylate.

Example 10 - Improving PCE in AIGS Films AIGS QDs coated with appropriate ligands containing one or more monomers, _TiO scattering particles, and photoinitiator in a glove box filled with _N2 mixed into ink. Films were cast by spin coating these inks and then cured using UV radiation. The film was then baked on a hot plate at 180° C. for 30 minutes to remove the remaining volatile components. All these processes were performed in an inert atmosphere in a glove box filled with _N2 .

Typically, at this stage the film is measured in air by placing it film side up over a blue LED light source. An integrating sphere connected to a spectrophotometer is placed above the QD film (see Figures 3A and 3B) to capture the emission spectrum of the film. Repeat the measurements using a blank glass substrate (no QDs). The blue light absorption and photon conversion efficiency (PCE) of QD films are measured using the following equation:
Blue absorption = number of blue photons transmitted through the QD film / number of incident blue photons PCE = number of forward-emitting green photons (484-588 nm) / number of incident blue photons

To study the effects of air and moisture during measurements, the baked QD films were encapsulated before being 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 coverslip and curing the adhesive by UV irradiation. QD films thus sealed using glass and adhesive were measured in air using the method described above.

The results show that encapsulating the QD film before measurement in air is important to achieve high photon conversion efficiency (PCE). Table 12 shows the results from a set of films measured with and without encapsulation. For comparison, PCE values from a typical QDCC film containing InP QDs are also shown. When measured in encapsulation, films containing AIGS nanostructures had higher post-bake PCE values than InP at much lower QD loadings. Further improvement in PCE was achieved by irradiating the film by placing it on a blue light source (approximately 6 mW/cm ² ) for 1 hour. In addition, QDCC films made with AIGS QDs exhibit a much narrower emission (FWHM ~30 nm) compared to films made with InP QDs (FWHM 36 nm). This is a result of the lower FWHM of AIGS QDs in solution (34 nm vs. 39 nm) combined with the use of mono- and poly-amino ligands that allow for better dispersion in the ink resin.

Figure 8 shows the effects of encapsulation and blue light treatment over a much wider range of samples. Unexpectedly, the PCE values achieved with encapsulation were significantly higher (>32%) than without encapsulation.

FIG. 9 shows the emission linewidth (FWHM) of the film after a 180° C. bake step and subsequent encapsulation. The median FWHM of the film baked at 180° C. is 30.5 nm, which further narrows to 30.1 nm upon encapsulation. This narrowing may be a result of the film becoming brighter upon encapsulation.

Although the samples in this study were encapsulated using glass and adhesive, this improvement in 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 surface layers, encapsulation will likely be performed using a vapor deposition process. A typical process flow in this case is inkjet printing of the QD layer, followed by curing by UV irradiation, baking at 180 °C to remove volatiles, deposition of an organic planarization layer, then deposition of an inorganic barrier layer. including. The techniques used for the deposition of inorganic layers are atomic layer deposition (ALD), molecular layer deposition (MLD), chemical vapor deposition (CVD) (with or without plasma enhancement), pulsed vapor deposition (PVD), It can include sputtering or metal vapor deposition. Other potential encapsulation methods include solution processing or printed organic layers, UV or thermosetting adhesives, lamination with barrier films, etc.

Example 11 - AIGS Ink Containing Monomers Incorporated into Ligands Coating AIGS Surfaces Ligand exchange (LE) of AIGS nanostructures in the presence of monomers compared to LE performed purely in solvent. It has been discovered that higher solution QY results in better compatible inks and better film performance. This was demonstrated through LE and film evaluation using 16 different media.

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

This procedure can be used for LE of AIGS nanostructures as well, with high retention of QY. However, this approach usually results in poor dispersion of the nanostructures in the monomer upon removal of the solvent. Good dispersion of AIGS nanostructures in the ink and efficient passivation of the nanostructure surface by ligands are necessary to maintain film performance through harsh processing conditions such as UV irradiation, high temperature bake, etc. Therefore, AIGS nanostructures that are ligand-exchanged using conventional processes are not suitable for QDCC applications.

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

Some solvents, PGMEA, ethyl acetate, toluene and DCM, were very effective in maintaining QY after LE. In particular, LE at room temperature resulted in higher QY than LE at 80°C. Other solvents tested such as acetone, chloroform, DMF and ethanol resulted in lower QY.

However, as shown in Table 13 (o = clear dispersion; Δ = turbid dispersion), AIGS nanostructures ligand-exchanged in solvent at room temperature are commonly used in inkjet printable inks. The compatibility with HDDA, which is a monomer, was low. AIGS nanostructures ligand-exchanged at 80 °C had better compatibility with HDDA but lower QY. Therefore, it has been difficult to find effective LE conditions that provide high QY and good compatibility with HDDA.

The LE studies were repeated using a series of common monomers (shown in Table 14) as vehicles instead of organic solvents. LE was performed by mixing the starting AIGS nanostructures (in heptane) with monomers, then adding Jeffamine M1000 and heating at 80 °C.

Figure 11 shows the QY after LE in the presence of monomer. In all 16 cases, the QY increased upon LE and was also higher than the QY achieved by LE in organic solvents.

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

All 16 AIGS samples were dispersed in HDDA and then mixed into an ink containing scattering media and photoinitiator. Unlike nanostructures that were ligand-exchanged in solvent, all 16 samples tested here showed 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 monomers M2, M3, M4, M5, M6 and M8 exhibit high film EQE and can be good LE media for AIGS QDs.

Figure 13 shows the blue absorption of AIGS nanostructures film spun at 800 RPM. M7, M10, M13, M15 and M16 provided very high blue absorption.

Example 12 Increased Blue Absorption by Polyamino Ligands Typical film deposition processes involve a hard bake at very high temperatures, typically around 200° C., to completely remove any residual solvents and volatile components. This hard bake prevents outgassing while depositing other layers on top of the QDCC layer. This harsh bake can result in very low EQE. Also, the nanostructures are damaged by high temperatures or the ligands detach from the nanostructures, resulting in aggregation. Table 15 shows the EQE of a typical AIGS film after UV curing and 180° C. hard bake. The EQE was good, higher than 33% after UV curing, but decreased to less than 19% after hard bake at 180° C. for 30 minutes. The light retention ratio (LRR), which is the ratio of post-bake EQE to pre-bake EQE, was very low at less than 60%, meaning that the film performance decreased by more than 40% after baking.

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

To keep the AIGS nanostructures uniformly dispersed throughout the film and prevent agglomeration, diamine (1,3-bis(aminomethyl)cyclohexane) was added to the AIGS-monomer dispersion before ink formulation. Alternatively, other ink components such as the scattering medium and photoinitiator can be mixed into the AIGS monomer dispersion and then added to the ink formulation. As seen in Figure 14, addition of diamine to the AIGS-monomer dispersion before ink formulation increased the EQE after UV curing and POB. When the diamine was added in an amount of 5% w/w of the AIGS inorganic mass, the EQE after UV curing increased by 3%. Further addition of diamine did not further improve the EQE. The effect of diamines on improving EQE was even higher after POB. The EQE was improved by 5% with the addition of 5% diamine compared to no diamine in the monomer. With 30% diamine addition, the EQE increases from 25% to 32% and the LRR is 92%, which is similar to the results seen with the InP green QD film. A side effect of the diamine was an increase in viscosity, as seen in Figure 15. However, for monomers such as ethyl acrylate, ink viscosity decreased dramatically to levels below 20 cP at room temperature.

Better AIGS surface passivation with diamines was attempted as an alternative approach to increase EQE. As shown in Figure 16, the QY of AIGS nanostructures ligand-exchanged in the presence of diamine was enhanced by more than 12% immediately after LE. It should be noted that the QY of the AIGS nanostructures was also improved after heat treatment simulating a hard bake at 180 °C for 30 min in the presence of monomer. The decrease in QY after 30 minutes at 180°C became smaller as the amount of diamine added to LE increased. With 50% w/w diamine in LE, the QY before and after thermal processing was approximately equal, and the QY after thermal processing was higher when 70% diamine was used in LE.

The performance of QDCC films using these AIGS nanostructures is plotted in Figure 17. The EQE of the film is better with diamine in LE compared to without diamine in LE, and the improvement is further enhanced with the addition of more diamine up to 50%. it was high. The EQE obtained with 70% diamine addition and LE was lower than 30% and 50%. If more diamine is used for LE, the amount of diamine incorporated onto the AIGS surface increases, but this is presumed to decrease the amount of ligand and/or monomer on the AIGS surface. The observed decrease in QD mass after LE with diamines is likely a result of fewer ligands and/or monomers on the QD surface. This also occurs when diamines are added to the monomer for LE, resulting in an increase in ink viscosity.

As seen in Figure 19, when using these two approaches to improve film EQE, the effect of diamine on film EQE was highest when diamine was added to both the ligand exchange and monomer dispersion. Viscosity does not necessarily depend on the total amount of diamine in the ink. The sample with the highest amount of diamine, in which diamine was used in both the LE and the monomer dispersion, had an intermediate viscosity. This viscosity was lower than when the same amount of diamine was used in LE alone.

EQE enhancement using diamines in LE and/or monomer dispersions was tested with 1,3-bis(aminomethyl)cyclohexane and five additional other additives listed in Table 16. All additives had a similar effect on the initial EQE, with A1, A5 and A6 slightly better than the others when added directly with the monomer. However, after hard bake, A1 and A6 were the two best additives in the final film EQE. In addition, good EQE was obtained among the listed amines without using the same additives in LE and monomer addition. Even when the same diamine is used in LE and monomer addition, its effectiveness in improving EQE can be different. For example, as seen in Figure 23, A6 was as effective at preserving EQE as A1 when used in monomer addition, but not as effective when A1 was used in LE. .

While various embodiments have been described above, it is to be understood that they are 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 detail may be made without departing from the spirit and scope of the invention. Accordingly, width and range should not be limited by any of the exemplary embodiments described above, but should be defined only in accordance with the following claims and their equivalents.

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 each individual publication, patent or patent application is incorporated by reference. Incorporated herein by reference to the same extent as specifically and individually indicated.

Claims (46)

comprising Ag, In, Ga, and S (AIGS) nanostructures and at least one ligand, with a peak emission wavelength of 480-545 nm when excited using a blue light source with a wavelength of about 450 nm. Films that exhibit superior conversion efficiency (PCE). 2. 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. A film according to any preceding claim, wherein the nanostructures have a quantum yield (QY) of 80-99.9%. 7. The film of claim 6, wherein the nanostructures have a QY of 85-95%. A film according to any preceding claim, wherein the nanostructures have a QY of about 86-94%. Film according to any one of claims 1 to 8, wherein the nanostructures have an OD ₄₅₀ /mass (mL ^. mg ^−1. cm ⁻¹ ) of 0.8 or more. 10. The film of claim 9, wherein the nanostructures have an OD ₄₅₀ /mass (mL ^. mg ^−1. cm ⁻¹ ) in the range of 0.8 to 2.5 (inclusive). 11. The film of claim 10, wherein the nanostructures have an OD ₄₅₀ /mass (mL ^. mg ^−1. cm ⁻¹ ) in the range of 0.87 to 1.9 (inclusive). Film according to any of the preceding claims, wherein the nanostructures have an average diameter of less than 10 nm by TEM. 13. The film of claim 12, wherein the average diameter is about 5 nm. A film according to any preceding claim, wherein at least about 80% of the emission is band edge emission. A film according to any preceding claim, wherein at least about 90% of the emission is band edge emission. 16. The film of claim 15, wherein 92-98% of the emission is band edge emission. 16. The film of claim 15, wherein 93-96% of the emission is band edge emission. A film according to any one of claims 1 to 17, wherein the at least one ligand is a polyamino ligand. 19. The film of claim 18, wherein the at least one polyamino ligand is a polyaminoalkane, a polyaminocycloalkane, a polyamino heterocycle, a polyamino functionalized silicone, or a polyamino substituted ethylene glycol. 2. The polyamino ligand is a C _2-20 alkane or a C _2-20 cycloalkane substituted with 2 or 3 amino groups and optionally containing 1 or 2 amino groups instead of carbon groups. The film according to item 18. The polyamino ligand is 1,3-cyclohexanebis(methylamino), 2,2-dimethyl-1,3-propadiamine, tris(2-aminoethyl)amine, or 2-methyl-1,5-diaminopentane. 21. The film of claim 20. said at least one ligand is a compound of formula I;

During the ceremony,
x is 1 to 100,
y is 0 to 100,
A film according to any one of claims 1 to 17, wherein R ² is C _1-20 alkyl. 23. The film of claim 22, wherein x=19, y=3, and ^R2 = _-CH3 . The at least one ligand is (3-aminopropyl)trimethoxysilane), (3-mercaptopropyl)triethoxysilane, DL-α-lipoic acid, 3,6-dioxa-1,8-octanedithiol, 6- Mercapto-1-hexanol, methoxypolyethylene glycolamine (approx. m.w. 500), poly(ethylene glycol) methyl ether thiol (approx. m.w. 800), diethylphenylphosphonite, dibenzyl N,N-diisopropylphosphoramidite , di-tert-butyl N,N-diisopropylphosphoramidite, tris(2-carboxyethyl)phosphine hydrochloride, poly(ethylene glycol) methyl ether thiol (about m.w. 2000), methoxypolyethylene glycolamine (about m.w. .w.750), acrylamide, or polyethyleneimine. The at least one ligand may include amino-polyalkylene oxide (about m.w. 1000) and methoxypolyethylene glycolamine (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 glycolamine (about m.w. 500) ) The film according to any one of claims 1 to 17, which is a combination of the following. Film according to any one of claims 1 to 25, further comprising at least one organic resin. 27. The film composition of claim 26, wherein the at least one organic resin is cured. The film composition according to any one of claims 1 to 27, wherein the film has a thickness of 5 to 15 μm. 29. The film composition of any one of claims 1-28, further comprising at least one monomer incorporated into the at least one ligand coating the AIGS surface. 30. The film composition of claim 29, wherein the at least one monomer is an acrylate. 30. The monomer according to claim 29, wherein the monomer is at least one of ethyl acrylate, HDDA, tetrahydrofurfuryl acrylate, tri(propylene glycol) diacrylate, 1,4-bis(acryloyloxy)butane or isobornyl acrylate. The film composition described. A film composition according to any one of claims 1 to 31, exhibiting a blue light absorption of greater than 95% at 450 nm. 33. The film composition of any one of claims 1-32, wherein the AIGS nanostructure comprises a gradient from increased gallium from the surface of the nanostructure to decreased gallium at the center of the nanostructure. A method for preparing a film according to any one of claims 26 to 33, said method comprising:
(a) providing an AIGS nanostructure and at least one ligand coating the AIGS nanostructure surface;
(b) mixing at least one organic resin with the AIGS nanostructures of (a);
(c) 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 a first barrier layer;
(d) curing the film;
(e) encapsulating the first film between the first barrier layer and the second barrier layer;
The method, wherein the encapsulated film exhibits a photon conversion efficiency (PCE) of greater than 32% at a peak emission wavelength of 480-545 nm when excited using a blue light source having a wavelength of about 450 nm. 35. The method of claim 34, wherein the method is performed prior to exposing the encapsulated film to a blue LED light source in air. 35. The method of claim 34, wherein the method is performed under an inert atmosphere. The method includes:
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 said mixture of (b); and/or adding at least one oxygen-reactive material to said mixture of (b) forming a second film comprising a material on the first film prepared in (c) and/or a sacrificial barrier layer temporarily blocking oxygen and/or water prepared in (c); 35. The method of claim 34, further comprising forming a sacrificial barrier layer on the first film, measuring the PCE of the film, and then removing the sacrificial barrier layer. 35. The method of claim 34, wherein the two barrier layers exclude oxygen and/or water. 39. A method according to any one of claims 34 to 38, wherein the at least one ligand is a polyamino ligand. 40. The method of any one of claims 34-39, further comprising incorporating at least one monomer into the at least one ligand coating the AIGS surface. A device comprising a film according to any one of claims 1 to 33. A nanostructured molded body,
(a) a first conductive layer;
(b) a second conductive layer;
(c) the nanostructured molded article, comprising: the film according to any one of claims 1 to 33, between the first conductive layer and the second conductive layer. A nanostructured color converter,
backplane and
a display panel disposed on the backplane;
34. The nanostructured color converter, comprising a film according to any one of claims 1 to 33, disposed on the display panel. 44. The nanostructured color converter of claim 43, wherein the film comprises patterned AIGS nanostructures. 44. The nanostructured color converter of claim 43, wherein the film comprises AIGS nanostructures and at least one monomer incorporated into the at least one ligand coating the AIGS surface. 44. The nanostructured color converter of claim 43, wherein the backplane includes an LED, LCD, OLED, or microLED.

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