Thermally stable polythiol ligands having pendant solubilizing moieties

Abstract

The present invention provides nanostructure compositions and methods of making nanostructure compositions. The nanostructure compositions comprise a population of nanostructures comprising a polythiol ligand having a pendant moiety. The polythiol ligand having a pendant moiety improves the solubility of the nanostructures in solvents and resins. The present invention also provides nanostructure films comprising the nanostructure compositions and methods of making nanostructure films using the nanostructure compositions.

Description

Technical Field

[0001] This invention provides nanostructured compositions and methods for producing nanostructured compositions. The nanostructured compositions comprise groups of nanostructures containing polythiol ligands with overhanging portions. The polythiol ligands with overhanging portions improve the solubility of the nanostructures in solvents and resins. This invention also provides nanostructured films comprising the nanostructured compositions and methods for preparing nanostructured films using the nanostructured compositions. Background Technology

[0002] Synthetic methods capable of preparing quantum dots while precisely controlling their properties can provide nanocrystals with a surface coated with a layer of highly hydrophobic molecular ligands. Therefore, these quantum dots are only (moderately) soluble in polar organic solvents such as toluene, hexane, or chloroform. However, some applications of quantum dots require water-soluble nanocrystals. This goal can be achieved by functionalizing the surface of nanocrystals with suitable molecular ligands. For example, a series of poly(ethylene glycol)-based bidentate ligands have been produced, which exhibit strong interactions with CdSe / ZnS (core / shell) quantum dots and gold nanoparticles, promoting their dispersion in aqueous solutions. Bing, CM, et al., Nature Protocols 4:412-423 (2009). However, Owen, JS, et al., J.Am.Chem.Soc.130(37):12279-12281 (2008) found that ligand exchange between octadecylphosphonate ligands and -S-(CH2CH2O)4OCH3 resulted in thiol binding to the nanoparticle surface, but caused quenching of the nanoparticle fluorescence.

[0003] Organic molecules binding to the inorganic surface of quantum dots provide colloidal stability and terminate the material's lattice, thereby reducing the number of surface trap states caused by dangling bonds. Synthetic quantum dots produced by the reaction of metal carboxylates (i.e., metal oleates, stearates, laurates, etc.) with chalcogenide precursors lead to the formation of metal-rich quantum dot surfaces primarily terminated by metal carboxylate ligands. Furthermore, for reactions utilizing primary alkyl thiols as sulfur precursors, unreacted thiols can also act as ligands.

[0004] Most quantum dots (QDs) have a natural ligand set (including metal carboxylates, metal thiols, and thiols) that is hydrophobic and therefore inherently insoluble in a wide range of organic media. Typically, surface ligand replacement is required to impart solubility in these media. Ligand exchange processes have been performed using amine- or carboxylic acid-functionalized polyethylene glycol (PEG)-based polymeric ligands. For some QDs, PEG-based polymeric ligands with amine functional groups cannot be used because exposure to primary amines leads to severe quenching of the photoluminescence quantum yield. Ligand exchange with carboxylic acid-functionalized polymeric ligands results in nominal solubility in a variety of resin formulations; however, challenges remain regarding the broadening of the full width at half maximum (FWHM) during ligand exchange, the reliability of QDEF products under high-flow-rate testing conditions, and early changes in emission power (i.e., aging). One potential cause of these concerns is that exposure to thiol functional groups present in many resin formulations can lead to the substitution of carboxylic acid groups and the degradation of the colloidal stability of the quantum dots.

[0005] Metal thiolate bonds have been found to be stronger than metal carboxylate and metal phosphonate bonds, and exposure to thiols or their corresponding deprotonated forms leads to the replacement of carboxylate ligands with carboxylic acids from the surface. Furthermore, thiols can also bind to the nanocrystal surface as neutral L-type ligands, occupying open sites left by the accumulation of metal carboxylate ligands. Regardless of the mechanism (replacement by polymerized carboxylic acid ligands or aggregation of multiple quantum dots caused by polyfunctional thiols in the resin formulation), the optical properties of the quantum dots are undesirably degraded.

[0006] There is a need to prepare nanostructure compositions and / or resin mixtures that have improved stability and result in improved optical properties when used to prepare nanostructured films. Summary of the Invention

[0007] A nanostructure composition is provided, the nanostructure composition comprising:

[0008] (a) Nanostructures; and

[0009] (b) Polythiol ligands dispersed on the surface of the nanostructure, the polythiol ligands having formula I:

[0010]

[0011] in:

[0012] CM is the central part;

[0013] X1 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0014] X2 is a key, -C (=O)-, C 1-10 Alkylene or C2-10 Heteroalkyl;

[0015] X3 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0016] X4 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0017] X5 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0018] X6 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0019] B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-;

[0020] X7 is a key or C. 1-12 Alkylene;

[0021] X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-;

[0022] R 1A and R 1B Independently, it is H or C 1-20 alkyl;

[0023] R 2 It is C 1-20 Alkyl or C 1-20 Alkyl group.

[0024] a is 2 to 10;

[0025] b is between 0 and 10;

[0026] c is between 2 and 10;

[0027] d is between 0 and 10;

[0028] e is from 1 to 100; and

[0029] f is between 0 and 100;

[0030] Where a+b+c+d≥3.

[0031] In some implementations, the polythiol ligand has formula II:

[0032]

[0033] in:

[0034] CM is the central part;

[0035] X1 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0036] X2 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0037] X3 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0038] B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-;

[0039] X7 is a key or C. 1-12 Alkylene;

[0040] X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-;

[0041] R 1A and R 1B Independently, it is H or C 1-20 Alkylene;

[0042] R 2 It is C 1-20 Alkylene or C 1-20 Alkyl group.

[0043] a is 2 to 10;

[0044] c is between 2 and 10;

[0045] e is from 1 to 100; and

[0046] f is between 0 and 100;

[0047] Where a+c≥3.

[0048] In some embodiments, CM is selected from alkanes, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, and (propane-2,2-dimethylbis(4,1-phenylene))bis(λ'-oxy).

[0049] In some embodiments, the nanostructure comprises a core selected from InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP.

[0050] In some implementations, the nanostructure includes at least one shell.

[0051] In some implementations, X1, X2, and X3 are keys.

[0052] In some implementations, X1 is -C (=O)-, and X2 is C. 1-10 Alkylene, and X3 is a bond.

[0053] In some implementations, X1 is C 2-10 Heteroalkylene, X2 is -C(=O)-, and X3 is C 1-10 Alkylene.

[0054] In some implementations, X1 is a replacement for C. 2-10 Heteroalkyl, X2 is a bond and X3 is a bond.

[0055] In some implementations, B is -CH2-CH2-.

[0056] In some implementations, X7 is C 1-10 Alkylene, and X8 is -C(=O)-O-.

[0057] In some implementation schemes, R 1A H is a number, e is 1 to 100, a is 2, and c is 2.

[0058] In some embodiments, the nanostructure composition is soluble in solvents selected from water, methanol, ethanol, acetone, methyl ethyl ketone, isopropanol, n-propanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, ethylene glycol, diethylene glycol, benzonitrile, cyclohexane, chloroform, ethyl acetate, propylene glycol methyl acetate, and dichloromethane.

[0059] A method for replacing a first ligand on a nanostructure with a second ligand is also provided. This method includes mixing a reaction mixture comprising a group of nanostructures having a first ligand non-covalently bonded to the nanostructure and a second ligand being a polythiol ligand, such that the second ligand replaces the first ligand and becomes non-covalently bonded to the nanostructure, wherein the polythiol ligand has Formula I:

[0060]

[0061] in:

[0062] CM is the central part;

[0063] X1 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0064] X2 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0065] X3 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0066] X4 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0067] X5 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0068] X6 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0069] B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-;

[0070] X7 is a key or C. 1-12 Alkylene;

[0071] X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-;

[0072] R 1A and R 1B Independently, it is H or C 1-20 alkyl;

[0073] R 2 It is C 1-20 Alkyl or C 1-20 Alkyl group.

[0074] a is 2 to 10;

[0075] b is between 0 and 10;

[0076] c is between 2 and 10;

[0077] d is between 0 and 10;

[0078] e is from 1 to 100; and

[0079] f is between 0 and 100;

[0080] Where a+b+c+d≥3.

[0081] In some embodiments, CM is selected from alkanes, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, and (propane-2,2-dimethylbis(4,1-phenylene))bis(λ'-oxy).

[0082] In some embodiments, the nanostructure comprises a core selected from InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP.

[0083] A nanostructured film is also provided, comprising:

[0084] (a) Nanostructure;

[0085] (b) Polythiol ligands dispersed on the surface of the nanostructure, the polythiol ligands having formula I:

[0086]

[0087] in:

[0088] CM is the central part;

[0089] X1 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0090] X2 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0091] X3 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0092] X4 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0093] X5 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0094] X6 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0095] B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-;

[0096] X7 is a key or C. 1-12 Alkylene;

[0097] X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-;

[0098] R 1A and R 1B Independently, it is H or C 1-20 alkyl;

[0099] R 2 It is C 1-20 Alkyl or C 1-20 Alkyl group.

[0100] a is 2 to 10;

[0101] b is between 0 and 10;

[0102] c is between 2 and 10;

[0103] d is between 0 and 10;

[0104] e is from 1 to 100; and

[0105] f is between 0 and 100;

[0106] Where a+b+c+d≥3; and

[0107] (c) At least one organic resin.

[0108] In some embodiments, CM is selected from alkanes, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, and (propane-2,2-dimethylbis(4,1-phenylene))bis(λ'-oxy).

[0109] In some implementations, the nanostructured film exhibits a light conversion efficiency between approximately 20% and approximately 40%.

[0110] A method for preparing the above-mentioned polythiol ligand is also provided, the method comprising reacting the following two substances: polythiol of formula III:

[0111]

[0112] in:

[0113] CM is the central part;

[0114] X1 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0115] X2 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0116] X3 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0117] X4 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0118] X5 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0119] X6 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0120] a is 2 to 10; and

[0121] b is between 0 and 10;

[0122] Where a+b≥3;

[0123] Poly(epoxide) of formula V:

[0124]

[0125] in:

[0126] FG is an acrylate group, a methacrylate group, an acrylamide group, an isocyanate group, an olefin group, or a glycidyl ether group;

[0127] X7 is a key or C. 1-12 Alkylene;

[0128] X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-;

[0129] R 1A and R 1B Independently, it is H or C 1-20alkyl;

[0130] e is from 1 to 100;

[0131] f is between 0 and 100; and

[0132] R 2 It is C 1-20 Alkyl or C 1-20 Alkyl group. Attached Figure Description

[0133] The accompanying drawings, which are incorporated herein and form a part of the specification, illustrate the invention and, together with the description, further serve to explain the principles of the invention and enable those skilled in the art to implement and use the invention.

[0134] Figure 1 This is a flowchart illustrating the ligand exchange process of Example 2. In the first step, PETMP-PEG-480 ligand and quantum dots containing the natural ligand were added to propylene glycol methyl ether acetate, and then heated to 80°C for 1 hour. In the second step, the solution was cooled to room temperature, and then heptane was added to precipitate the quantum dots. In the third step, the precipitate was centrifuged to provide quantum dot spheres, which could be redispersed in propylene glycol methyl ether acetate.

[0135] Figure 2 This is a schematic diagram illustrating a base-catalyzed Michael addition reaction, where EWG is an electron-withdrawing group. Detailed Implementation

[0136] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The following definitions supplement those in the art and are specific to the present application and should not be attributed to any related or unrelated cases, such as any co-owned patents or applications. While any methods and materials similar to or equivalent to those described herein may be used in practice for testing, preferred materials and methods are described herein. Therefore, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0137] As used in this specification and the appended claims, the singular forms "an" and "the" include the plural forms unless the context clearly indicates otherwise. Thus, for example, a reference to "nanostructure" includes a plurality of such nanostructures, and so on.

[0138] As used herein, the term “about” indicates that the value of a given quantity varies within ±10% of that value. For example, “about 100 nm” covers a size range from 90 nm to 110 nm (inclusive).

[0139] A “nanostructure” is a structure having at least one region or feature size less than about 500 nm. In some embodiments, the nanostructure has a size less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm. Typically, this region or feature size will be along the smallest axis of the structure. Examples of such structures include nanowires, nanorods, nanotubes, branched nanostructures, nanotetrapods, tripartites, bipods, nanocrystals, nanodots, quantum dots, nanoparticles, and so on. Nanostructures can be, for example, substantially crystalline, substantially single-crystal, polycrystalline, amorphous, or a combination thereof. In some embodiments, each of the three dimensions of the nanostructure has a size less than about 500 nm, less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm.

[0140] When used in the context of nanostructures, the term "heterogeneous structure" refers to a nanostructure characterized by at least two different and / or distinguishable material types. Typically, one region of the nanostructure contains a first material type, while a second region contains a second material type. In some embodiments, the nanostructure comprises a core of a first material and a shell of at least one second (or third, etc.) material, wherein, for example, the different material types are radially distributed around the long axis of a nanowire, the long axis of an arm of a branched nanowire, or the center of a nanocrystal. The shell may, but does not need to, completely cover the adjacent material to be considered a shell or, for the nanostructure, a heterostructure; for example, a nanocrystal characterized by a core of one material covered by islands of a second material is a heterostructure. In other embodiments, the different material types are distributed at different locations within the nanostructure; for example, along the main (long) axis of a nanowire or along the long axis of an arm of a branched nanowire. Different regions within a heterostructure may contain entirely different materials, or different regions may contain a substrate material (e.g., silicon) with different dopants or different concentrations of the same dopant.

[0141] As used herein, the “diameter” of a nanostructure refers to the diameter of a cross-section perpendicular to the nanostructure’s first axis, which has the largest length difference relative to the second and third axes (the second and third axes being the two axes whose lengths are closest to each other). The first axis is not necessarily the longest axis of the nanostructure; for example, for a disk-shaped nanostructure, its cross-section would be a substantially circular cross-section perpendicular to the disk’s shorter longitudinal axis. When the cross-section is not circular, the diameter is the average of the principal and secondary axes of that cross-section. For elongated or high aspect ratio nanostructures, such as nanowires, the diameter is measured on a cross-section perpendicular to the nanowire’s longest axis. For spherical nanostructures, the diameter is measured from one side to the other through the center of the sphere.

[0142] When used in relation to nanostructures, the term "crystalline" or "substantially crystalline" refers to the fact that a nanostructure typically exhibits long-range order across one or more dimensions of the structure. Those skilled in the art will understand that the term "long-range order" will depend on the absolute size of the particular nanostructure, as the order of a single crystal cannot extend beyond the crystal boundaries. In this case, "long-range order" will mean substantially ordered across at least a majority of the dimensions of the nanostructure. In some cases, the nanostructure may have oxides or other coatings, or may consist of a core and at least one shell. In this case, it will be understood that the oxide, shell, or other coating may, but does not need to, exhibit such order (e.g., it may be amorphous, polycrystalline, or otherwise). In this case, the phrases "crystalline," "substantially crystalline," "substantially single-crystal," or "single-crystal" refer to the central core of the nanostructure (excluding coatings or shells). As used herein, the term "crystalline" or "substantially crystalline" is intended to also encompass structures containing various defects, stacking faults, atomic substitutions, etc., as long as the structure exhibits substantially long-range order (e.g., ordered along at least about 80% of the length of at least one axis of the nanostructure or its core). Furthermore, it will be understood that the interfaces between the core and the outer shell of a nanostructure, or between the core and an adjacent shell, or between a shell and a second adjacent shell, may contain amorphous regions, or even be amorphous. This does not preclude the nanostructure from being crystalline or substantially crystalline as defined herein.

[0143] When used in the context of nanostructures, the term "single crystal" indicates that the nanostructure is substantially crystalline and essentially comprises a single crystal. When used in the context of heterostructures that include a core and one or more shells, "single crystal" indicates that the core is substantially crystalline and essentially comprises a single crystal.

[0144] "Nanocrystal" is a substantially single-crystal nanostructure. Therefore, a nanocrystal has at least one region or feature size smaller than about 500 nm. In some embodiments, the nanocrystal has a size smaller than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm. The term "nanocrystal" is intended to cover substantially single-crystal nanostructures containing various defects, stacking faults, atomic substitutions, etc., as well as substantially single-crystal nanostructures without such defects, stacking faults, or substitutions. In the case of nanocrystal heterostructures comprising a core and one or more shells, the core of the nanocrystal is typically substantially single-crystal, but the shell need not be. In some embodiments, each of the three dimensions of the nanocrystal has a size smaller than about 500 nm, less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm.

[0145] The term "quantum dot" (or "dot") refers to a nanocrystal exhibiting quantum confinement or exciton confinement. Quantum dots can be substantially homogeneous in material properties, or in some embodiments, can be heterogeneous, for example, comprising a core and at least one shell. The optical properties of quantum dots can be influenced by their particle size, chemical composition, and / or surface composition, and can be determined by suitable optical tests available in the art. The ability to tune the size of nanocrystals, for example, in the range of about 1 nm to 15 nm, enables light emission to cover the entire optical spectrum, thus providing great versatility in terms of color rendering.

[0146] A "ligand" is a molecule that can interact (whether weakly or strongly) with one or more surfaces of a nanostructure, for example, through covalent, ionic, van der Waals, or other molecular interactions with the surface of the nanostructure.

[0147] "Photoluminescence quantum yield" is, for example, the ratio of photons emitted by a nanostructure or group of nanostructures to the number of photons absorbed. As is known in the art, quantum yield is typically determined by comparison with standard samples that have well-characterized quantum yield values.

[0148] As used herein, the term "shell" refers to material deposited on the core or on a previously deposited shell of the same or different composition, and is produced by a single deposition of shell material. The precise shell thickness depends on the material as well as the precursor input and transformation, and can be reported in nanoscale or monolayer form. As used herein, "target shell thickness" refers to the expected shell thickness used to calculate the desired amount of precursor. As used herein, "actual shell thickness" refers to the actual amount of shell material deposited after synthesis, which can be measured by methods known in the art. For example, actual shell thickness can be measured by comparing the particle diameter determined by transmission electron microscopy (TEM) images of nanocrystals before and after shell synthesis.

[0149] As used herein, the term "solubilizing group" refers to a substantially nonpolar group that has low solubility in water and high solubility in organic solvents such as hexane, pentane, toluene, benzene, diethyl ether, acetone, ethyl acetate, dichloromethane (methylene dichloro), chloroform, dimethylformamide, and N-methylpyrrolidone. In some embodiments, the soubilizing group is a long-chain alkyl, long-chain heteroalkyl, long-chain alkenyl, long-chain alkynyl, cycloalkyl, or aryl group.

[0150] As used herein, the term "stable" means a mixture or composition that resists change or decomposition due to internal reactions or due to the effects of air, heat, light, pressure or other natural conditions.

[0151] As used herein, the term "full width at half maximum" (FWHM) is a measure of the size distribution of quantum dots. The emission spectrum of quantum dots typically has the shape of a Gaussian curve. The width of the Gaussian curve is defined as the FWHM and gives the concept of the particle size distribution. A smaller FWHM corresponds to a narrower size distribution of the quantum dot nanocrystals. FWHM also depends on the maximum emission wavelength.

[0152] As used herein, the term “functional equivalent weight” (FGEW) is used to determine the ratio of reactive functional groups in a polymer. The FGEW of a polymer is defined as the ratio of its average molecular weight (NAMW) to the number of functional groups (n) in the polymer. It is the weight of a polymer containing one stoichiometric amount of functional groups. FGEW is calculated using end-group analysis by calculating the number of reactive functional groups and dividing by the number-average molecular weight:

[0153] FGEW = NAMW / n

[0154] Where n = the number of reactive functional groups in the monomer.

[0155] As used herein, the term "polythiol" refers to a simple or complex organic compound containing at least two SH groups per molecule.

[0156] As used herein, the term "alkane" refers to a saturated straight-chain, branched, or cyclic hydrocarbon containing only single bonds. In some embodiments, the alkane comprises 1 to 20 carbon atoms. In some embodiments, the alkane is ethane, propane, butane, pentane, hexane, heptane, octane, nonane, or decane. The alkane group may be substituented by one or more substituents such as hydroxyl, halogen, amino, nitro, C- group, etc. 1-20 Alkyl or C 1-20 Alkyl groups are substituted.

[0157] As used herein, the term "olefin" refers to an unsaturated hydrocarbon comprising one or more carbon-carbon double bonds. In some embodiments, the olefin comprises 2 to 20 carbon atoms. In some embodiments, the olefin is ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, or decene. The olefinic group may be substituented by one or more substituents such as hydroxyl, halogen, amino, nitro, C- group, etc. 1-20 Alkyl or C 1-20 Alkyl groups are substituted.

[0158] As used herein, the term "alkyl" refers to a straight-chain or branched saturated aliphatic hydrocarbon group having the indicated number of carbon atoms. In some embodiments, the alkyl group is C1000. 1-2 Alkyl, C 1-3 Alkyl, C 1-4 Alkyl, C 1-5 Alkyl, C 1-6 Alkyl, C 1-7 Alkyl, C 1-8 Alkyl, C1-9 Alkyl, C 1-10 Alkyl, C 1-12 Alkyl, C 1-14 Alkyl, C 1-16 Alkyl, C 1-18 Alkyl, C 1-20 Alkyl, C 8-20 Alkyl, C 12-20 Alkyl, C 14-20 Alkyl, C 16-20 Alkyl or C 18-20 Alkyl group. For example, C 1-6 Alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl. In some embodiments, the alkyl group is octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonyl, or tridecyl. Unless otherwise specified, the term "alkyl" may include "alkylene" groups.

[0159] As used herein, the term "heteroalkyl" refers to an alkyl moiety that is optionally substituted with one or more functional groups and contains, for example, one or more oxygen, sulfur, nitrogen, phosphorus or silicon atoms that have substituted carbon atoms.

[0160] As used herein, the term "cycloalkyl" refers to a monovalent or divalent group derived from a saturated cyclic hydrocarbon, consisting of 3 to 8 carbon atoms, preferably 3 to 5 carbon atoms. The cycloalkyl group can be monocyclic or polycyclic. Cycloalkyl groups can be C16-3 ... 1-3 Alkyl groups or halogens are substituted.

[0161] As used herein, the term "alkylene" refers to a saturated aliphatic group derived from a straight-chain or branched saturated hydrocarbon having 1 to 20 carbon atoms attached at two or more positions. In some embodiments, the alkylene is C 1-2 Alkylene, C 1-3 Alkylene, C 1-4 Alkylene, C 1-5 Alkylene, C 1-6 Alkylene, C 1-7 Alkylene, C 1-8 Alkylene, C 1-9 Alkylene, C 1-10 Alkylene, C 1-12 Alkylene, C 1-14 Alkylene, C 1-16 Alkylene, C 1-18 Alkylene, C 1-20 Alkylene, C 8-20 Alkylene, C 12-20 Alkylene, C 14-20 Alkylene, C 16-20 Alkylene or C18-20 Alkylene. For example, C 1-6 Alkylenes include, but are not limited to, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, secondary butylene, tert-butylene, pentylene, isopentylene, and hexylene. In some embodiments, the alkyl group is octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecanylene, octadecylene, nonadecanylene, or eicosylene. The alkylene group may be substituented by one or more substituents such as hydroxyl, halogen, amino, nitro, C 1-20 Alkyl or C 1-20 Alkyl groups are substituted.

[0162] As used herein, the term "heteroalkylene" refers to an alkylene group in which one or more carbon atoms in its main chain are replaced by heteroatoms such as oxygen, nitrogen, phosphorus, silicon, and sulfur, including, for example, oligomeric glycol moieties. Heteroalkylene groups may be substituented by one or more substituents such as hydroxyl, halogen, amino, nitro, C... 1-20 Alkyl or C 1-20 Alkyl groups are substituted.

[0163] As used in this article, the term "amino" refers to -NH2.

[0164] As used herein, the term "alkylamino" refers to the formula (-NR) K 2) "Substituted amino group", where R K It is independently hydrogen or optionally substituted alkyl groups, as defined herein, and the nitrogen moiety is directly attached to the parent molecule.

[0165] As used in this article, the term "halogenated" or "halogen" refers to F, Cl, Br, or I.

[0166] As used herein, the term "alkoxy group" refers to a straight-chain or branched -O-alkyl group consisting of 1 to 20 carbon atoms. In some embodiments, the alkoxy group is C 1-2 Alkoxy, C 1-3 Alkoxy, C 1-4 Alkoxy, C 1-5 Alkoxy, C 1-6 Alkoxy, C 1-7 Alkoxy, C 1-8 Alkoxy, C 1-9 Alkoxy, C 1-10 Alkoxy, C 1-12 Alkoxy, C 1-14 Alkoxy, C 1-16 Alkoxy, C 1-18 Alkoxy, C 1-20 Alkoxy, C 8-20 Alkoxy, C 12-20 Alkoxy, C14-20 Alkoxy, C 16-20 Alkoxy or C 18-20 Alkoxy group. In some embodiments, the alkoxy group is methoxy, ethoxy, n-propoxy, isopropoxy, or tert-butoxy.

[0167] As used herein, the term "acrylate" or "acrylate group" refers to a compound having at least one moiety having the structure -OC(=O)-CH=CH2. In some embodiments, the acrylate is a methacrylate.

[0168] As used herein, the term "methacrylate" or "methacrylate group" refers to a compound having at least one moiety having the structure -OC(=O)-C(CH3)=CH2.

[0169] As used herein, the term "acrylamide" or "acrylamide group" refers to a compound having at least one moiety having the structure -NH-C(=O)-CH=CH2. In some embodiments, acrylamide is methacrylamide.

[0170] As used herein, the term "methacrylamide" or "methacrylamide group" refers to a compound having at least one moiety having the structure -NH-C(=O)-C(CH3)=CH2.

[0171] As used herein, the term "glycidyl ether" or "glycidyl ether group" refers to a substance containing at least one structurally distinct group. Some of the compounds.

[0172] As used herein, the term "isocyanate" or "isocyanate group" refers to a compound having at least one part having the structure N=C=O.

[0173] Unless otherwise expressly stated, the scope outlined in this document is inclusive.

[0174] This document defines or otherwise characterizes various additional terms.

[0175] Nanostructured Compositions

[0176] In some embodiments, the present invention provides a nanostructure composition comprising:

[0177] (a) Nanostructures; and

[0178] (b) A polythiol ligand bonded to the surface of a nanostructure, wherein the polythiol ligand comprises a poly(ethylene oxide) / poly(propylene oxide) block copolymer, a poly(ethylene oxide) block copolymer, or a poly(propylene oxide) block copolymer.

[0179] In some embodiments, the present invention provides a nanostructure composition comprising:

[0180] (a) Nanostructures; and

[0181] (b) Polythiol ligands dispersed on the surface of the nanostructure, the polythiol ligands having formula I:

[0182]

[0183] in:

[0184] CM is the central part;

[0185] X1 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0186] X2 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0187] X3 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0188] X4 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0189] X5 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0190] X6 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0191] B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-;

[0192] X7 is a key or C. 1-12 Alkylene;

[0193] X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-;

[0194] R 1A and R 1B Independently, it is H or C 1-20 alkyl;

[0195] R 2 It is C 1-20 Alkyl or C 1-20 Alkyl group.

[0196] a is 2 to 10;

[0197] b is between 0 and 10;

[0198] c is between 2 and 10;

[0199] d is between 0 and 10;

[0200] e is from 1 to 100; and

[0201] f is between 0 and 100;

[0202] Where a+b+c+d≥3.

[0203] In some embodiments, the present invention provides a nanostructure composition comprising:

[0204] (a) Nanostructures; and

[0205] (b) Polythiol ligands dispersed on the surface of the nanostructure, the polythiol ligands having formula II:

[0206]

[0207] in:

[0208] CM is the central part;

[0209] X1 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0210] X2 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0211] X3 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0212] B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-;

[0213] X7 is a key or C. 1-12 Alkylene;

[0214] X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-;

[0215] R 1A and R 1B Independently, it is H or C 1-20 alkyl;

[0216] R 2 It is C 1-20 Alkyl or C 1-20 Alkyl group.

[0217] a is 2 to 10;

[0218] c is between 2 and 10;

[0219] e is from 1 to 100; and

[0220] f is between 0 and 100;

[0221] Where a+c≥3.

[0222] In some embodiments, the present invention provides a nanostructure composition comprising:

[0223] (a) At least one nanostructure group, wherein about 20 mol% to about 100 mol% of the ligands in the at least one nanostructure group comprises polythiol ligands bonded to the nanostructures; and

[0224] (b) At least one organic resin.

[0225] In some embodiments, the nanostructure composition further comprises a solvent. In some embodiments, the nanostructure composition further comprises a polar organic solvent.

[0226] In some implementations, the nanostructure is a quantum dot.

[0227] In some embodiments, the present invention provides a nanostructured membrane kit comprising:

[0228] (a) A first composition comprising at least one nanostructure group, wherein about 20 mol% to about 100 mol% of the ligands in the at least one nanostructure group comprises polythiol ligands bonded to the nanostructures;

[0229] (b) a second composition comprising at least one organic resin; and

[0230] (c) Explanation of the preparation of nanostructured membranes.

[0231] In some embodiments, the nanostructured membrane kit also includes a solvent. In some embodiments, the nanostructured membrane kit also includes a polar organic solvent.

[0232] In some implementations, the nanostructure is a quantum dot.

[0233] Nanostructured film

[0234] In some embodiments, the present invention provides a nanostructured film layer comprising:

[0235] (a) At least one nanostructure group, wherein about 20 mol% to about 100 mol% of the ligands in the at least one nanostructure group comprises polythiol ligands bonded to the nanostructures; and

[0236] (b) At least one organic resin.

[0237] In some implementations, the nanostructure is a quantum dot.

[0238] Nanostructured molded products

[0239] In some embodiments, the present invention provides a nanostructured molded article comprising:

[0240] (a) At least one nanostructure group, wherein about 20 mol% to about 100 mol% of the ligands in the at least one nanostructure group comprises polythiol ligands bonded to the nanostructures; and

[0241] (b) At least one organic resin.

[0242] In some implementations, the molded article is a film, a display substrate, or a light-emitting diode.

[0243] In some implementations, the nanostructure is a quantum dot.

[0244] In some embodiments, the present invention provides a nanostructured membrane comprising:

[0245] (a) First barrier layer;

[0246] (b) the second barrier layer; and

[0247] (c) A nanostructured layer between the first barrier layer and the second barrier layer, wherein the nanostructured layer comprises at least one nanostructure group, wherein about 20 mol% to about 100 mol% of the ligands in the at least one nanostructure group comprises polythiol ligands bonded to the nanostructure; and at least one organic resin.

[0248] In some implementations, the nanostructure is a quantum dot.

[0249] Nanostructures

[0250] In some embodiments, the nanostructure comprises a core and at least one shell. In some embodiments, the nanostructure comprises a core and 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 shells. In some embodiments, the nanostructure comprises a core and one shell. In some embodiments, the nanostructure comprises a core and two shells. In some embodiments, the nanostructure comprises a core and three shells. In some embodiments, the nanostructure comprises at least two shells, wherein the two shells are different.

[0251] The number of monolayers determines the size of the core / shell nanostructure. The size of the core / shell nanostructure can be determined using techniques known to those skilled in the art. In some embodiments, the size of the core / shell nanostructure is determined using TEM. In some embodiments, the average diameter of the core / shell nanostructure is between about 1 nm and about 15 nm, between about 1 nm and about 10 nm, between about 1 nm and about 9 nm, between about 1 nm and about 8 nm, between about 1 nm and about 7 nm, between about 1 nm and about 6 nm, between about 1 nm and about 5 nm, between about 5 nm and about 15 nm, between about 5 nm and about 10 nm, between about 5 nm and about 9 nm, between about 5 nm and about 8 nm, between about 5 nm and about 7 nm, between about 5 nm and about 6 nm, and about 6 nm. Between approximately 15 nm, between approximately 6 nm and approximately 10 nm, between approximately 6 nm and approximately 9 nm, between approximately 6 nm and approximately 8 nm, between approximately 6 nm and approximately 7 nm, between approximately 7 nm and approximately 15 nm, between approximately 7 nm and approximately 10 nm, between approximately 7 nm and approximately 9 nm, between approximately 7 nm and approximately 8 nm, between approximately 8 nm and approximately 15 nm, between approximately 8 nm and approximately 10 nm, between approximately 8 nm and approximately 9 nm, between approximately 9 nm and approximately 15 nm, between approximately 9 nm and approximately 10 nm, or between approximately 10 nm and approximately 15 nm. In some embodiments, the average diameter of the core / shell nanostructure is between approximately 6 nm and approximately 7 nm.

[0252] Nanostructured core

[0253] In some implementations, the core comprises Si, Ge, Sn, Se, Te, B, C, P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si3N4, Ge3N4, Al2O3, Al2OC, or combinations thereof.

[0254] In some embodiments, the core is a group III-V nanostructure. In some embodiments, the core is a group III-V nanocrystal selected from BN, BP, BAs, BSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb. In some embodiments, the core is an InP nanocrystal.

[0255] The synthesis of III-V nanostructures has been described in U.S. Patent Nos. 5,505,928, 6,306,736, 6,576,291, 6,788,453, 6,821,337, 7,138,098, 7,557,028, 8,062,967, 7,645,397, and 8,282,412, as well as U.S. Patent Application Publication No. 2015 / 236195. The synthesis of group III-V nanostructures has also been described in Wells, RL et al., "The use of tris(trimethylsilyl)arsine to prepare gallium arsenide and indium arsenide," Chem. Mater. 1:4-6 (1989) and Guzelian, AA et al., "Colloidal chemical synthesis and characterization of InAs nanocrystal quantum dots," Appl. Phys. Lett. 69:1432-1434 (1996).

[0256] The synthesis of InP-based nanostructures has been described in, for example, Xie, R. et al., "Colloidal InP nanocrystals as efficient emitters covering blue to near-infrared," J. Am. Chem. Soc. 129: 15432-15433 (2007); Micic, OI et al., "C millito-shell quantum dots of lattice-matched ZnCdSe2 shells on InP cores: Experiment and theory," J. Phys. Chem. B 104: 12149-12156 (2000); Liu, Z. et al., "Coreduction colloidal synthesis of III-V nanocrystals: The case of InP," Angew. Chem. Int. Ed. Engl. 47: 3540-3542 (2008); Li, L. et al., "Economic synthesis of high quality InP nanocrystals using calcium phosphide." as the phosphorus precursor," Chem. Mater. 20: 2621-2623 (2008); D. Battaglia and InP / GaP / ZnS nanocrystals and their application to white light-emitting diodes," J.Am.Chem.Soc.134:3804-3809(2012); Nann, T. et al., "Water splitting by visible light: Ananophotocathode forhydrogen production," Angew.Chem.Int.Ed.49:1574-1577(2010); Borchert, H.et al., "Investigation of ZnS passivated InP nanocrystals by XPS," Nano Letters 2:151-154(2002); L. Li and P. Reiss, "One-pot synthesis of highly luminescent InP / ZnS nanocrystals without precursor injection," J. Am. Chem. Soc. 130:11588-11589(2008); Hussain, S. et al., "One-pot fabrication of high-quality InP / ZnS(core / shell) quantum dots and their application to cellular imaging," Chemphyschem. 10:1466-1470(2009); Xu, S. et al., "Rapid synthesis of high-quality InP nanocrystals," J. Am. Chem. Soc. 128:1054-1055(2006); Micic, O. I. et al., "Size-dependent spectroscopy of InP quantum dots," J. Phys. Chem. B 101:4904-4912(1997); Haubold, S. et al., "Strongly luminescent InP / ZnS core-shell nanoparticles," Chemphyschem. 5:331-334(2001); Cros Gagneux, A. et al., "Surface chemistry of InP quantum dots: A comprehensive study," J. Am. Chem. Soc. 132:18147-18157(2010); Micic, O. I. et al., "Synthesis and characterization of InP, GaP, and GaInP2 quantum dots," J. Phys. Chem. 99:7754-7759(1995); Guzelian, A. A. et al., "Synthesis of size-selected, surface-passivated InP nanocrystals," J. Phys. Chem.100:7212-7219 (1996); Lucey, DW et al., "Monodispersed InP quantum dots prepared by colloidal chemistry in anon-coordinating solvent," Chem. Mater. 17:3754-3762 (2005); Lim, J. et al., "InP@ZnSeS,core@composition gradient shell quantum dots with enhanced stability," Chem. Mater. 23:4459-4463 (2011); and Zan, F. et al., "Experimental studies on blinking behavior of single InP / ZnS quantum dots: Effects of synthetic conditions and UV irradiation," J. Phys. Chem. C 116:394-3950 (2012). However, such efforts have only achieved limited success in producing InP nanostructures with high quantum yields.

[0257] In some embodiments, the core is doped. In some embodiments, the dopant of the nanocrystal core comprises a metal, including one or more transition metals. In some embodiments, the dopant is a transition metal selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and combinations thereof. In some embodiments, the dopant comprises a nonmetal. In some embodiments, the dopant is ZnS, ZnSe, ZnTe, CdSe, CdS, CdTe, HgS, HgSe, HgTe, CuInS2, CuInSe2, AlN, AlP, AlAs, GaN, GaP, or GaAs.

[0258] In some embodiments, the core is a group II-VI nanocrystal selected from ZnO, ZnSe, ZnS, ZnTe, CdO, CdSe, CdS, CdTe, HgO, HgSe, HgS, and HgTe. In some embodiments, the core is a nanocrystal selected from ZnSe, ZnS, CdSe, and CdS. The synthesis of group II-VI nanostructures has been described in U.S. Patent Nos. 6,225,198, 6,322,901, 6,207,229, 6,607,829, 7,060,243, 7,374,824, 6,861,155, 7,125,605, 7,566,476, 8,158,193, and 8,101,234, and U.S. Patent Application Publications Nos. 2011 / 0262752 and 2011 / 0263062.

[0259] In some embodiments, the nuclei are purified prior to the deposition of the shell. In some embodiments, the nuclei are filtered to remove precipitates from the nuclei solution.

[0260] In some implementations, the core undergoes an acid etching step before the deposited shell.

[0261] In some implementations, quantum confinement is used to determine the diameter of the nucleus. Quantum confinement in zero-dimensional nanocrystals such as quantum dots arises from the spatial confinement of electrons within the crystallite boundaries. Quantum confinement can be observed once the diameter of the material is on the same order of magnitude as the de Broglie wavelength of the wavefunction. The electronic and optical properties of nanoparticles differ significantly from those of bulk materials. When the confinement size is large compared to the wavelength of the particle, the particle behaves as if it were free. In this state, the band gap remains at its original energy due to the continuous energy state. However, as the confinement size decreases and reaches a certain limit (typically at the nanoscale), the energy spectrum becomes discrete. Therefore, the band gap becomes size-dependent. The size can be determined, for example, using transmission electron microscopy and / or physical modeling, as is known in the art.

[0262] In some implementations, the diameter of the nuclear nanostructure is between about 1 nm and about 9 nm, between about 1 nm and about 8 nm, between about 1 nm and about 7 nm, between about 1 nm and about 6 nm, between about 1 nm and about 5 nm, between about 1 nm and about 4 nm, between about 1 nm and about 3 nm, between about 1 nm and about 2 nm, between about 2 nm and about 9 nm, between about 2 nm and about 8 nm, between about 2 nm and about 7 nm, between about 2 nm and about 6 nm, between about 2 nm and about 5 nm, between about 2 nm and about 4 nm, between about 2 nm and about 3 nm, between about 3 nm and about 9 nm, between about 3 nm and about 8 nm, and about 3 nm. The diameter of the nuclear nanostructure is between approximately 7 nm and approximately 3 nm and approximately 6 nm, between approximately 3 nm and approximately 5 nm, between approximately 3 nm and approximately 4 nm, between approximately 4 nm and approximately 9 nm, between approximately 4 nm and approximately 8 nm, between approximately 4 nm and approximately 7 nm, between approximately 4 nm and approximately 6 nm, between approximately 4 nm and approximately 5 nm, between approximately 5 nm and approximately 9 nm, between approximately 5 nm and approximately 8 nm, between approximately 5 nm and approximately 7 nm, between approximately 5 nm and approximately 6 nm, between approximately 6 nm and approximately 9 nm, between approximately 6 nm and approximately 8 nm, between approximately 6 nm and approximately 7 nm, between approximately 7 nm and approximately 9 nm, between approximately 7 nm and approximately 8 nm, or between approximately 8 nm and approximately 9 nm. In some embodiments, the diameter of the nuclear nanostructure is approximately 7 nm.

[0263] Nanostructured shell

[0264] The shell can, for example, improve the quantum yield and / or stability of the nanostructure. In some embodiments, the core and shell comprise different materials. In some embodiments, the nanostructure comprises a shell of a different material.

[0265] In some embodiments, a shell comprising a mixture of Group II and Group VI elements is deposited on the core or a core / shell structure. In some embodiments, the shell is deposited from a mixture of at least two of a zinc source, a selenium source, a sulfur source, a tellurium source, and a cadmium source. In some embodiments, the shell is deposited from a mixture of two of a zinc source, a selenium source, a sulfur source, a tellurium source, and a cadmium source. In some embodiments, the shell is deposited from a mixture of three of a zinc source, a selenium source, a sulfur source, a tellurium source, and a cadmium source. In some embodiments, the shell is composed of: zinc and sulfur; zinc and selenium; zinc, sulfur, and selenium; zinc and tellurium; zinc, tellurium, and sulfur; zinc, tellurium, and selenium; zinc, cadmium, and sulfur; zinc, cadmium, and selenium; cadmium and sulfur; cadmium and selenium; cadmium, selenium, and sulfur; cadmium, zinc, and sulfur; cadmium, zinc, and selenium; or cadmium, zinc, sulfur, and selenium.

[0266] In some embodiments, at least one shell comprises CdS, CdSe, CdO, CdTe, ZnS, ZnO, ZnSe, ZnTe, MgTe, GaAs, GaSb, GaN, HgO, HgS, HgSe, HgTe, InAs, InSb, InN, AlAs, AlN, AlSb, AlS, PbS, PbO, PbSe, PbTe, MgO, MgS, MgSe, MgTe, CuCl, Ge, Si, or alloys thereof. In some embodiments, at least one shell comprises ZnSe. In some embodiments, at least one shell comprises ZnS. In some embodiments, at least one shell comprises a first shell comprising ZnSe and a second shell comprising ZnS.

[0267] In some implementations, the shell comprises more than one monolayer of shell material. The number of monolayers is an average of all nanostructures; therefore, the number of monolayers in the shell can be a fraction. In some embodiments, the number of single layers in the shell is between 0.25 and 10, 0.25 and 8, 0.25 and 7, 0.25 and 6, 0.25 and 5, 0.25 and 4, 0.25 and 3, 0.25 and 2, 2 and 10, 2 and 8, 2 and 7, 2 and 6, 2 and 5, 2 and 4, 2 and 3, 3 and 10, 3 and 8, 3 and 7, 3 and 6, 3 and 5, 3 and 4, 4 and 10, 4 and 8, 4 and 7, 4 and 6, 4 and 5, 5 and 10, 5 and 8, 5 and 7, 5 and 6, 6 and 10, 6 and 8, 6 and 7, 7 and 10, 7 and 8, or 8 and 10. In some embodiments, the shell comprises between 3 and 5 single layers.

[0268] The thickness of each shell can be determined using techniques known to those skilled in the art. In some embodiments, the thickness of each shell is determined by comparing the average diameter of the nanostructure before and after the addition of each shell. In some embodiments, the average diameter of the nanostructure before and after the addition of each shell is determined by TEM.

[0269] In some implementations, the thickness of each shell is between approximately 0.05 nm and approximately 3.5 nm, between approximately 0.05 nm and approximately 2 nm, between approximately 0.05 nm and approximately 0.9 nm, between approximately 0.05 nm and approximately 0.7 nm, between approximately 0.05 nm and approximately 0.5 nm, between approximately 0.05 nm and approximately 0.3 nm, between approximately 0.05 nm and approximately 0.1 nm, between approximately 0.1 nm and approximately 3.5 nm, between approximately 0.1 nm and approximately 2 nm, between approximately 0.1 nm and approximately 0.9 nm, between approximately 0.1 nm and approximately 0.7 nm, between approximately 0.1 nm and approximately 0.5 nm, between approximately 0.1 nm and approximately 0.3 nm, and approximately... Between 0.3nm and approximately 3.5nm, between approximately 0.3nm and approximately 2nm, between approximately 0.3nm and approximately 0.9nm, between approximately 0.3nm and approximately 0.7nm, between approximately 0.3nm and approximately 0.5nm, between approximately 0.5nm and approximately 3.5nm, between approximately 0.5nm and approximately 2nm, between approximately 0.5nm and approximately 0.9nm, between approximately 0.5nm and approximately 0.7nm, between approximately 0.7nm and approximately 3.5nm, between approximately 0.7nm and approximately 2nm, between approximately 0.7nm and approximately 0.9nm, between approximately 0.9nm and approximately 3.5nm, between approximately 0.9nm and approximately 2nm, or between approximately 2nm and approximately 3.5nm.

[0270] ligand exchange

[0271] This disclosure relates to a method for replacing a first ligand on a nanostructure with a second ligand. In some embodiments, the second ligand is a polythiol ligand. In some embodiments, the nanostructure is a quantum dot.

[0272] In some embodiments, this disclosure relates to a method of replacing a first ligand on a nanostructure with a second ligand, the method comprising mixing a reaction mixture comprising a group of nanostructures having a first ligand bonded to the nanostructure and at least one second ligand such that the second ligand replaces the first ligand and becomes bonded to the nanostructure.

[0273] In some implementations, the nanostructure is a quantum dot.

[0274] In some embodiments, mixing is carried out at temperatures between about 0°C and about 200°C, between about 0°C and about 150°C, between about 0°C and about 100°C, between about 0°C and about 80°C, between about 20°C and about 200°C, between about 20°C and about 150°C, between about 20°C and about 100°C, between about 20°C and about 80°C, between about 50°C and about 200°C, between about 50°C and about 150°C, between about 50°C and about 100°C, between about 50°C and about 80°C, between about 80°C and about 200°C, between about 80°C and about 150°C, between about 80°C and about 100°C, between about 100°C and about 200°C, between about 100°C and about 150°C, or between about 150°C and about 200°C. In some embodiments, mixing is carried out at temperatures between about 20°C and about 100°C. In some embodiments, compounding is carried out at a temperature of about 22°C. In some embodiments, compounding is carried out at a temperature of about 70°C.

[0275] In some implementations, mixing occurs between approximately 1 minute and approximately 6 hours, between approximately 1 minute and approximately 2 hours, between approximately 1 minute and approximately 1 hour, between approximately 1 minute and approximately 40 minutes, between approximately 1 minute and approximately 30 minutes, between approximately 1 minute and approximately 20 minutes, between approximately 1 minute and approximately 10 minutes, between approximately 10 minutes and approximately 6 hours, between approximately 10 minutes and approximately 2 hours, between approximately 10 minutes and approximately 1 hour, between approximately 10 minutes and approximately 40 minutes, between approximately 10 minutes and approximately 30 minutes, between approximately 10 minutes and approximately 20 minutes, and between approximately 20 minutes and approximately 6 hours. The time period is between approximately 20 minutes and approximately 2 hours, between approximately 20 minutes and approximately 1 hour, between approximately 20 minutes and approximately 40 minutes, between approximately 20 minutes and approximately 30 minutes, between approximately 30 minutes and approximately 6 hours, between approximately 30 minutes and approximately 2 hours, between approximately 30 minutes and approximately 1 hour, between approximately 30 minutes and approximately 40 minutes, between approximately 40 minutes and approximately 6 hours, between approximately 40 minutes and approximately 2 hours, between approximately 40 minutes and approximately 1 hour, between approximately 1 hour and approximately 6 hours, between approximately 1 hour and approximately 2 hours, or between approximately 2 hours and approximately 6 hours.

[0276] In some embodiments, the reaction mixture further comprises a solvent. In some embodiments, the solvent is selected from chloroform, acetone, butanone, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, methyl isobutyl ketone, ethylene glycol monomethyl ether, γ-butyrolactone, methylacetic acid-3-ethyl ether, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, toluene, xylene, isopropanol, N-methylformamide, and combinations thereof. In some embodiments, the solvent is toluene. In some embodiments, the solvent is N-methylformamide. In some embodiments, the solvent is a mixture of toluene and N-methylformamide.

[0277] The percentage of second ligands bonded to the nanostructures in the nanostructure group can be determined by... 1 HNMR measurements, where the bonded ligand is calculated using the following formula: (bonded second ligand) / (bonded second ligand + free second ligand).

[0278] In some embodiments, the molar percentage of the second ligand bonded to the nanostructure group is between about 20% and about 100%, between about 20% and about 80%, between about 20% and about 60%, between about 20% and about 40%, between about 25% and about 100%, between about 25% and about 80%, between about 25% and about 60%, between about 25% and about 40%, between about 30% and about 100%, between about 30% and about 80%, between about 30% and about 60%, between about 30% and about 40%, between about 40% and about 100%, between about 40% and about 80%, between about 40% and about 60%, between about 60% and about 100%, between about 60% and about 80%, or between about 80% and about 100%.

[0279] First ligand

[0280] In some embodiments, each shell is synthesized in the presence of at least one nanostructure ligand. The ligand can, for example, enhance the miscibility of the nanostructure in a solvent or polymer (allowing the nanostructure to distribute throughout the composition so that it does not aggregate), increase the quantum yield of the nanostructure, and / or maintain the luminescence of the nanostructure (e.g., when the nanostructure is bound to a matrix). In some embodiments, the ligand used for core synthesis and the ligand used for shell synthesis are the same. In some embodiments, the ligand used for core synthesis and the ligand used for shell synthesis are different. After synthesis, any ligand on the surface of the nanostructure can be replaced with a different ligand having other desired properties. Examples of ligands are disclosed in U.S. Patent Nos. 7,572,395, 8,143,703, 8,425,803, 8,563,133, 8,916,064, 9,005,480, 9,139,770, and 9,169,435 and U.S. Patent Application Publication No. 2008 / 0118755.

[0281] In some embodiments, the first ligand is a fatty acid selected from lauric acid, hexanoic acid, myristic acid, palmitic acid, stearic acid, and oleic acid. In some embodiments, the first ligand is an organophosphorus or organophosphorus oxide selected from trioctylphosphine oxide, trioctylphosphine, diphenylphosphine, triphenylphosphine oxide, and tributylphosphine oxide. In some embodiments, the first ligand is an amine selected from dodecylamine, oleylamine, hexadecylamine, dioctylamine, and octadecylamine. In some embodiments, the first ligand is trioctylphosphine, trioctylphosphine oxide, trihydroxypropylphosphine, tributylphosphine, tridecylphosphine, dibutyl phosphite, tributyl phosphite, octadecyl phosphite, trilauryl phosphite, dodecyl phosphite, triisooctyl phosphite, di(2-ethylhexyl) phosphate, triacontyl phosphate, hexadecylamine, oleylamine, octadecylamine, dioctadecylamine, octadecyl oleate, di(2-ethylhexyl)amine, octylamine, dioctylamine, trioctylamine, dodecylamine, didodecylamine, hexadecylamine, phenyl phosphate, hexyl phosphate, tetradecylphosphonic acid, octyl phosphate, n-octadecylphosphonic acid, propenyl diphosphonic acid, dioctyl ether, diphenyl ether, n-octyl mercaptan, dodecyl mercaptan, or octyl mercaptan. In some embodiments, the first ligand is oleic acid, trioctylphosphine, or octyl mercaptan.

[0282] Second ligand

[0283] In some embodiments, the second ligand is a polythiol ligand containing at least one SH group. In some embodiments, at least one SH group may act as a neutral L-type binding ligand (e.g., R-COOH) bound to the surface of II-VI nanocrystals. In some embodiments, at least one SH group may act as an electron-donating X-type ligand (e.g., R-COOH). - It is incorporated into the surface of II-VI nanocrystals.

[0284] In some embodiments, the polythiol ligand is prepared by reacting a polythiol with a poly(epoxide) compound containing acrylate groups, methacrylate groups, acrylamide groups, isocyanate groups, olefin groups, or glycidyl ether groups to generate the polythiol ligand.

[0285] polythiol

[0286] In some implementations, polythiol has formula III:

[0287]

[0288] in:

[0289] CM is the central part;

[0290] X1 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0291] X2 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0292] X3 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0293] X4 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0294] X5 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0295] X6 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0296] a is 2 to 10; and

[0297] b is between 0 and 10;

[0298] And where a+b≥3.

[0299] In some implementations, when b in Formula III is 0, the polythiol has Formula IV:

[0300] CM-(X1-X2-X3-SH) a (IV)

[0301] in:

[0302] CM is the central part;

[0303] X1 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0304] X2 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0305] X3 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; and

[0306] a is 3 to 10.

[0307] In some embodiments, CM is an alkane, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, or (propane-2,2-dimethylbis(4,1-phenylene))bis(λ'-oxy). In some embodiments, CM is propane.

[0308] In some implementations, X1 is a bond. In some implementations, X1 is -C (=O)-. In some implementations, X1 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X1 is an unsubstituted C1. 1-10 Alkylene. In some embodiments, X1 is a substituted C 1-10 Alkylene. In some embodiments, X1 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X1 is an unsubstituted C1. 1-10 Heteroalkyl. In some embodiments, X1 is a substituted C 1-10 Heteroalkyl. In some embodiments, the substituent on X1 is -SH.

[0309] In some implementations, X2 is a bond. In some implementations, X2 is -C (=O)-. In some implementations, X2 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X2 is an unsubstituted C 1-10 Alkylene. In some embodiments, X2 is a substituted C 1-10 Alkylene. In some embodiments, X2 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X2 is an unsubstituted C 1-10 Heteroalkyl. In some embodiments, X2 is a substituted C 1-10 Heteroalkyl. In some embodiments, the substituent on X2 is -SH.

[0310] In some implementations, X3 is a bond. In some implementations, X3 is -C (=O)-. In some implementations, X3 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X3 is an unsubstituted C 1-10 Alkylene. In some embodiments, X3 is a substituted C 1-10 Alkylene. In some embodiments, X3 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X3 is an unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X3 is a substituted C. 1-10 Heteroalkyl. In some embodiments, the substituent on X3 is -SH.

[0311] In some implementations, X4 is a bond. In some implementations, X4 is -C (=O)-. In some implementations, X4 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X4 is an unsubstituted C4. 1-10 Alkylene. In some embodiments, X4 is a substituted C. 1-10 Alkylene. In some embodiments, X4 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X4 is an unsubstituted C 1-10 Heteroalkyl. In some embodiments, X4 is a substituted C. 1-10 Heteroalkyl. In some embodiments, the substituent on X4 is -SH.

[0312] In some implementations, X5 is a bond. In some implementations, X5 is -C (=O)-. In some implementations, X5 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X5 is an unsubstituted C 1-10 Alkylene. In some embodiments, X5 is a substituted C 1-10 Alkylene. In some embodiments, X5 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X5 is an unsubstituted C 1-10 Heteroalkyl. In some embodiments, X5 is a substituted C. 1-10 Heteroalkyl. In some embodiments, the substituent on X5 is -SH.

[0313] In some implementations, X6 is a bond. In some implementations, X6 is -C (=O)-. In some implementations, X6 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X6 is an unsubstituted C 1-10 Alkylene. In some embodiments, X6 is a substituted C. 1-10 Alkylene. In some embodiments, X6 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X6 is an unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X6 is a substituted C. 1-10 Heteroalkyl. In some embodiments, the substituent on X6 is -SH.

[0314] In some implementations, a is between 2 and 10. In some implementations, a is between 2 and 10. In some implementations, a is between 2 and 10, between 2 and 8, between 2 and 6, between 2 and 4, between 2 and 3, between 3 and 10, between 3 and 8, between 3 and 6, between 3 and 4, between 4 and 10, between 4 and 8, between 4 and 6, between 6 and 10, between 6 and 8, or between 8 and 10.

[0315] In some implementations, b is between 0 and 10. In some implementations, b is between 0 and 10, between 0 and 8, between 0 and 6, between 0 and 4, between 3 and 10, between 3 and 8, between 3 and 6, between 6 and 10, between 6 and 8, or between 8 and 10. In some implementations, B is 0.

[0316] In some implementations, X1, X2, and X3 are keys and b is 0.

[0317] In some implementations, X1 is -C (=O)-, and X2 is unsubstituted C. 1-10 Alkylene, and b is 0.

[0318] In some implementations, X1 is -C (=O)-, and X2 is an unsubstituted C from a branched chain. 1-10 Alkylene, X3 is a bond, and b is 0.

[0319] In some implementations, X1 is C 1-10 Heteroalkyl, X2 is -C(=O)-, X3 is unsubstituted C 1-10 Alkylene, and b is 0.

[0320] In some implementations, X1 is a replacement for C. 1-10 Heteroalkyl, wherein the substituent is -SH and b is 0.

[0321] In some implementations, X1 is C 1-10 Alkylene, X2 is -C(=O)-, X3 is unsubstituted C 1-10 Alkylene, a is 2 and b is 1.

[0322] In some implementations, the polythiol is a commercially available polythiol.

[0323] In some implementations, the polythiol is selected from:

[0324]

[0325]

[0326]

[0327] Poly(epoxide)

[0328] In some embodiments, the poly(epoxide) comprises at least one functional group attached to the poly(epoxide) backbone. In some embodiments, the poly(epoxide) is a poly(epoxide) comprising at least one functional group attached to the poly(epoxide) backbone.

[0329] In some embodiments, at least one functional group is an acrylate group, a methacrylate group, an acrylamide group, an isocyanate group, an olefin group, or a glycidyl ether group.

[0330] In some embodiments, the poly(epoxide) is a mixture of functionalized end-capped poly(epoxide), epoxide copolymers, and combinations thereof. In some embodiments, the functionalized end-capped poly(epoxide) comprises epoxide copolymers. In some embodiments, the copolymer is a random copolymer or a block copolymer. In some embodiments, the block copolymer is a diblock copolymer or a triblock copolymer. In some embodiments, the copolymer is based on propylene oxide (PO), ethylene oxide (EO), or a mixture of PO and EO. In some embodiments, the copolymer is a mixture of PO and EO.

[0331] In some embodiments, the poly(epoxide) includes random copolymers of ethylene oxide and propylene oxide, poly(ethylene oxide)-poly(propylene oxide) diblock copolymers, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers, poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) triblock copolymers, or combinations thereof.

[0332] In some embodiments, the poly(epoxyalkane) comprises a copolymer of PO and EO. In some embodiments, the ratio of ethylene oxide groups to propylene oxide groups is high enough to give the poly(epoxyalkane) ligand high hydrophilicity. In some embodiments, the ratio of ethylene oxide groups to propylene oxide groups is low enough to give the ligand the desired elasticity. In some embodiments, the ratio of ethylene oxide groups to propylene oxide groups is between about 15:1 and about 1:15, between about 15:1 and about 1:10, between about 15:1 and about 1:5, between about 10:1 and 1:15, between about 10:1 and 1:10, between about 10:1 and 1:5, between about 5:1 and 1:15, between about 5:1 and 1:10, or between about 5:1 and 1:5.

[0333] In some implementations, the poly(epoxide) has the structure of formula V:

[0334]

[0335] in:

[0336] FG is an acrylate group, a methacrylate group, an acrylamide group, an isocyanate group, an olefin group, or a glycidyl ether group;

[0337] X7 is a key or C. 1-12 Alkylene;

[0338] X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-;

[0339] R 1A and R 1B Independently, it is H or C 1-20 alkyl;

[0340] e is from 1 to 100;

[0341] f is between 0 and 100; and

[0342] R 2 It is C 1-20 Alkyl or C 1-20 Alkyl group.

[0343] In some embodiments, FG is an acrylate group. In some embodiments, FG is a methacrylate group. In some embodiments, FG is an acrylamide group. In some embodiments, FG is an isocyanate group. In some embodiments, FG is an olefin group. In some embodiments, FG is a glycidyl ether group. In some embodiments, FG is -OC(=O)-CH=CH2. In some embodiments, FG is -OC(=O)-C(CH3)=CH2. In some embodiments, FG is -NC(=O)-CH=CH 2。 In some implementations, FG is -N=C=O. In some implementations, FG is -CH=CH2. In some implementations, FG is...

[0344]

[0345] In some implementations, X7 is a key. In some implementations, X7 is a C. 1-12 Alkylene.

[0346] In some embodiments, X8 is a bond. In some embodiments, X8 is -O-. In some embodiments, X8 is -OC(=O)-. In some embodiments, X8 is an amino group.

[0347] In some implementation schemes, R 1A It is H. In some implementations, R 1A It is C 1-20 Alkyl group. In some embodiments, R 1A It is C 1-10Alkyl group. In some embodiments, R 1A It is C 1-5 Alkyl group. In some embodiments, R 1A It is -CH3.

[0348] In some implementation schemes, R 1B It is H. In some implementations, R 1B It is C 1-20 Alkyl group. In some embodiments, R 1B It is C 1-10 Alkyl group. In some embodiments, R 1B It is C 1-5 Alkyl group. In some embodiments, R 1B It is -CH3.

[0349] In some implementation schemes, R 1A It is H, and R 1B It is -CH3. In some implementations, R 1A It is -CH3 and R 1B It is H. In some implementations, R 1A It is H and R 1B It is H. In some implementations, R 1A It is -CH3 and R 1B It is -CH3.

[0350] In some embodiments, e is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100. In some embodiments, e is 10 to 50. In some embodiments, e is 10 to 20.

[0351] The value of e should be understood as being modified by the word "approximately". Therefore, the value of e = 1 is understood as meaning e = 1 ± 0.1. Therefore, the value of e = 1 is understood as meaning 0.9 to 1.1.

[0352] In some embodiments, f is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100. In some embodiments, f is 1 to 30. In some embodiments, f is 1 to 10.

[0353] The value of f should be understood as being modified by the word "approximately". Therefore, the value of f = 1 is understood to mean f = 1 ± 0.1. For example, the value of f = 1 is understood to mean 0.9 to 1.1.

[0354] In some implementations, the ratio of e to f is between approximately 15:1 and approximately 1:15, between approximately 15:1 and approximately 1:10, between approximately 15:1 and approximately 1:5, between approximately 10:1 and approximately 1:15, between approximately 10:1 and approximately 1:10, between approximately 10:1 and approximately 1:5, between approximately 5:1 and approximately 1:15, between approximately 5:1 and approximately 1:10, or between approximately 5:1 and approximately 1:5.

[0355] In some implementation schemes, R 2 It is C 1-20 Alkyl group. In some embodiments, R 2 It is C 1-10 Alkyl group. In some embodiments, R 2 It is C 1-5 Alkyl group. In some embodiments, R 2 It is -CH2CH3.

[0356] In some embodiments, where FG is -OC(=O)-CH=CH2 and X7 and X8 are bonds in formula V, the poly(epoxide) has the structure of formula VI:

[0357]

[0358] in:

[0359] R 1A and R 1B Independently, it is H or C 1-20 alkyl;

[0360] e is from 1 to 100;

[0361] f is between 0 and 100; and

[0362] R 2 It is C 1-20 Alkyl or C 1-20 Alkyl group.

[0363] In some implementations, e is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100. In some implementations, f is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100.

[0364] In some implementations, f is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100.

[0365] In some implementations, the ratio of e to f is between approximately 15:1 and approximately 1:15, between approximately 15:1 and approximately 1:10, between approximately 15:1 and approximately 1:5, between approximately 10:1 and 1:15, between approximately 10:1 and 1:10, between approximately 10:1 and 1:5, between approximately 5:1 and 1:15, between approximately 5:1 and 1:10, or between approximately 5:1 and 1:5.

[0366] In some implementation schemes, R 1A It is H. In some implementations, R 1A It is C 1-20 Alkyl group. In some embodiments, R 1A It is C 1-10 Alkyl group. In some embodiments, R 1A It is C 1-5 Alkyl group. In some embodiments, R 1A It is -CH3.

[0367] In some implementation schemes, R 1B It is H. In some implementations, R 1B It is C 1-20 Alkyl group. In some embodiments, R 1B It is C 1-10 Alkyl group. In some embodiments, R 1B It is C 1-5 Alkyl group. In some embodiments, R 1B It is -CH3.

[0368] In some implementation schemes, R 2 It is C 1-20 Alkyl group. In some embodiments, R 2 It is C 1-10 Alkyl group. In some embodiments, R 2 It is C 1-5 Alkyl group. In some embodiments, R 2 It is -CH2CH3. In some implementations, R 2 It is -CH3.

[0369] In some implementations, FG is -OC(=O)-CH=CH2, X7 and X8 are bonds, f is 0, and R 2 The -CH3 in formula V indicates that poly(epoxide) has the structure of formula VII:

[0370]

[0371] in:

[0372] R 1A Is it H or C? 1-20 Alkyl; and

[0373] e is from 1 to 100.

[0374] In some implementation schemes, R 1A It is H. In some implementations, R 1A It is C 1-20 Alkyl group. In some embodiments, R 1A It is C 1-10 Alkyl group. In some embodiments, R 1A It is C 1-5 Alkyl group. In some embodiments, R 1A It is -CH3.

[0375] In some embodiments, e is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100. In some embodiments, e is 10 to 50. In some embodiments, e is 10 to 20. In some embodiments, e is 10. In some embodiments, e is 9. In some embodiments, e is 6.

[0376] polythiol ligands

[0377] In some implementations, the polythiol ligand has formula I:

[0378]

[0379] in:

[0380] CM is the central part;

[0381] X1 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0382] X2 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0383] X3 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0384] X4 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0385] X5 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0386] X6 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0387] B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-;

[0388] X7 is a key or C. 1-12 Alkylene;

[0389] X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-;

[0390] R 1A and R 1B Independently, it is H or C 1-20 alkyl;

[0391] R 2 It is C 1-20 Alkyl or C 1-20 Alkyl group.

[0392] a is 2 to 10;

[0393] b is between 0 and 10;

[0394] c is between 2 and 10;

[0395] d is between 0 and 10;

[0396] e is from 1 to 100; and

[0397] f is between 0 and 100;

[0398] Where a+b+c+d≥3.

[0399] In some embodiments, CM is an alkane, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, or (propane-2,2-dimethylbis(4,1-phenylene))bis(λ'-oxy). In some embodiments, CM is propane.

[0400] In some implementations, X1 is a bond. In some implementations, X1 is -C (=O)-. In some implementations, X1 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X1 is an unsubstituted C1. 1-10 Alkylene. In some embodiments, X1 is a substituted C 1-10 Alkylene. In some embodiments, X1 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X1 is an unsubstituted C1. 1-10 Heteroalkyl. In some embodiments, X1 is a substituted C 1-10 Heteroalkyl. In some embodiments, the substituent on X1 is -SH.

[0401] In some implementations, X2 is a bond. In some implementations, X2 is -C (=O)-. In some implementations, X2 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X2 is an unsubstituted C 1-10 Alkylene. In some embodiments, X2 is a substituted C 1-10 Alkylene. In some embodiments, X2 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X2 is an unsubstituted C 1-10 Heteroalkyl. In some embodiments, X2 is a substituted C 1-10 Heteroalkyl. In some embodiments, the substituent on X2 is -SH.

[0402] In some implementations, X3 is a bond. In some implementations, X3 is -C (=O)-. In some implementations, X3 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X3 is an unsubstituted C 1-10 Alkylene. In some embodiments, X3 is a substituted C 1-10 Alkylene. In some embodiments, X3 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X3 is an unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X3 is a substituted C. 1-10 Heteroalkyl. In some embodiments, the substituent on X3 is -SH.

[0403] In some implementations, X4 is a bond. In some implementations, X4 is -C (=O)-. In some implementations, X4 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X4 is an unsubstituted C4. 1-10 Alkylene. In some embodiments, X4 is a substituted C. 1-10 Alkylene. In some embodiments, X4 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X4 is an unsubstituted C 1-10 Heteroalkyl. In some embodiments, X4 is a substituted C. 1-10 Heteroalkyl. In some embodiments, the substituent on X4 is -SH.

[0404] In some implementations, X5 is a bond. In some implementations, X5 is -C (=O)-. In some implementations, X5 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X5 is an unsubstituted C 1-10 Alkylene. In some embodiments, X5 is a substituted C 1-10 Alkylene. In some embodiments, X5 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X5 is an unsubstituted C 1-10 Heteroalkyl. In some embodiments, X5 is a substituted C. 1-10 Heteroalkyl. In some embodiments, the substituent on X5 is -SH.

[0405] In some implementations, X6 is a bond. In some implementations, X1 is -C (=O)-. In some implementations, X6 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X6 is an unsubstituted C 1-10 Alkylene. In some embodiments, X6 is a substituted C. 1-10 Alkylene. In some embodiments, X6 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X6 is an unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X6 is a substituted C. 1-10 Heteroalkyl. In some embodiments, the substituent on X6 is -SH.

[0406] In some embodiments, B is -CH2-CH2-C(=O)-O-. In some embodiments, B is -CH2-CH(CH3)-C(=O)-O-. In some embodiments, B is -CH2-CH2-C(=O)-N-. In some embodiments, B is -C(=O)-NH-. In some embodiments, B is -CH2-CH2-. In some embodiments, B is -CH2-CH(OH)-CH2-O. In some embodiments, B is -CH2-CH(OH)-.

[0407] In some implementations, X7 is a key. In some implementations, X7 is a substituted or unsubstituted C. 1-12 Alkylene. In some embodiments, X7 is an unsubstituted C. 1-12 Alkylene. In some embodiments, X7 is a substituted C. 1-12 Alkylene.

[0408] In some implementations, X8 is a key. In some implementations, X8 is -O-. In some implementations, X8 is -C(=O)-O-. In some implementations, X8 is -C(=O)-N-.

[0409] In some implementation schemes, R 1A It is H. In some implementations, R 1A It is C 1-20 Alkyl group. In some embodiments, R 1A It is C 1-10 Alkyl group. In some embodiments, R 1A It is C 1-5 Alkyl group. In some embodiments, R 1A It is -CH3.

[0410] In some implementation schemes, R 1B It is H. In some implementations, R 1B It is C 1-20 Alkyl group. In some embodiments, R 1B It is C 1-10 Alkyl group. In some embodiments, R 1B It is C 1-5 Alkyl group. In some embodiments, R 1B It is -CH3.

[0411] In some implementation schemes, R 2 It is C 1-20 Alkyl group. In some embodiments, R 2 It is C 1-10 Alkyl group. In some embodiments, R 2 It is C 1-5 Alkyl group. In some embodiments, R2 It is -CH2CH3. In some implementations, R 2 It is -CH3.

[0412] In some implementations, a is between 2 and 10. In some implementations, a is between 2 and 10, 2 and 8, 2 and 6, 2 and 4, 2 and 3, 3 and 10, 3 and 8, 3 and 6, 3 and 4, 4 and 10, 4 and 8, 4 and 6, 6 and 10, 6 and 8, or 8 and 10. In some implementations, a is 3. In some implementations, a is 4. In some implementations, a is 5. In some implementations, a is 6.

[0413] In some implementations, b is between 0 and 10. In some implementations, b is between 1 and 10, 1 and 8, 1 and 6, 1 and 4, 1 and 3, 2 and 10, 2 and 8, 2 and 6, 2 and 4, 2 and 3, 3 and 10, 3 and 8, 3 and 6, 3 and 4, 4 and 10, 4 and 8, 4 and 6, 6 and 10, 6 and 8, or 8 and 10. In some implementations, b is 3. In some implementations, b is 4. In some implementations, b is 5. In some implementations, b is 6.

[0414] In some implementations, c is between 2 and 10. In some implementations, a is between 2 and 10, 2 and 8, 2 and 6, 2 and 4, 2 and 3, 3 and 10, 3 and 8, 3 and 6, 3 and 4, 4 and 10, 4 and 8, 4 and 6, 6 and 10, 6 and 8, or 8 and 10. In some implementations, c is 3. In some implementations, c is 4. In some implementations, c is 5. In some implementations, c is 6.

[0415] In some implementations, d is between 0 and 10. In some implementations, b is between 1 and 10, 1 and 8, 1 and 6, 1 and 4, 1 and 3, 2 and 10, 2 and 8, 2 and 6, 2 and 4, 2 and 3, 3 and 10, 3 and 8, 3 and 6, 3 and 4, 4 and 10, 4 and 8, 4 and 6, 6 and 10, 6 and 8, or 8 and 10. In some implementations, d is 3. In some implementations, d is 4. In some implementations, d is 5. In some implementations, d is 6.

[0416] In some implementations, e is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100. In some implementations, f is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100.

[0417] In some implementations, f is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100.

[0418] In some embodiments, where b is 0 and d is 0 in Formula I, the polythiol ligand has the structure of Formula IX:

[0419]

[0420] in:

[0421] CM is the central part;

[0422] X1 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0423] X2 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0424] X3 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl;

[0425] B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-;

[0426] X7 is a key or C. 1-12 Alkylene;

[0427] X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-;

[0428] R 1A and R 1B Independently, it is H or C 1-20 Alkylene;

[0429] R 2 It is C 1-20 Alkylene or C 1-20 Alkyl group.

[0430] a is 2 to 10;

[0431] c is between 2 and 10;

[0432] e is from 1 to 100; and

[0433] f is between 0 and 100;

[0434] Where a+c≥3.

[0435] In some embodiments, CM is an alkane, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, or (propane-2,2-dimethylbis(4,1-phenylene))bis(λ'-oxy). In some embodiments, CM is propane.

[0436] In some implementations, X1 is a bond. In some implementations, X1 is -C (=O)-. In some implementations, X1 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X1 is an unsubstituted C1. 1-10 Alkylene. In some embodiments, X1 is a substituted C 1-10 Alkylene. In some embodiments, X1 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X1 is an unsubstituted C1. 1-10 Heteroalkyl. In some embodiments, X1 is a substituted C 1-10 Heteroalkyl. In some embodiments, the substituent on X1 is -SH.

[0437] In some implementations, X2 is a bond. In some implementations, X2 is -C (=O)-. In some implementations, X2 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X2 is an unsubstituted C 1-10 Alkylene. In some embodiments, X2 is a substituted C 1-10 Alkylene. In some embodiments, X2 is a substituted or unsubstituted C. 1-10Heteroalkyl. In some embodiments, X2 is an unsubstituted C 1-10 Heteroalkyl. In some embodiments, X2 is a substituted C 1-10 Heteroalkyl. In some embodiments, the substituent on X2 is -SH.

[0438] In some implementations, X3 is a bond. In some implementations, X3 is -C (=O)-. In some implementations, X3 is a substituted or unsubstituted C. 1-10 Alkylene. In some embodiments, X3 is an unsubstituted C 1-10 Alkylene. In some embodiments, X3 is a substituted C 1-10 Alkylene. In some embodiments, X3 is a substituted or unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X3 is an unsubstituted C. 1-10 Heteroalkyl. In some embodiments, X3 is a substituted C. 1-10 Heteroalkyl. In some embodiments, the substituent on X3 is -SH.

[0439] In some embodiments, B is -CH2-CH2-C(=O)-O-. In some embodiments, B is -CH2-CH(CH3)-C(=O)-O-. In some embodiments, B is -CH2-CH2-C(=O)-N-. In some embodiments, B is -C(=O)-NH-. In some embodiments, B is -CH2-CH2-. In some embodiments, B is -CH2-CH(OH)-CH2-O-. In some embodiments, B is -CH2-CH(OH)-.

[0440] In some implementations, X7 is a key. In some implementations, X7 is a substituted or unsubstituted C. 1-12 Alkylene. In some embodiments, X7 is an unsubstituted C. 1-12 Alkylene. In some embodiments, X7 is a substituted C. 1-12 Alkylene.

[0441] In some implementations, X8 is a key. In some implementations, X8 is -O-. In some implementations, X8 is -C(=O)-O-. In some implementations, X8 is -C(=O)-N-.

[0442] In some implementation schemes, R 1A It is H. In some implementations, R 1A It is C 1-20 Alkyl group. In some embodiments, R 1A It is C 1-10 Alkyl group. In some embodiments, R1A It is C 1-5 Alkyl group. In some embodiments, R 1A It is -CH3.

[0443] In some implementation schemes, R 1B It is H. In some implementations, R 1B It is C 1-20 Alkyl group. In some embodiments, R 1B It is C 1-10 Alkyl group. In some embodiments, R 1B It is C 1-5 Alkyl group. In some embodiments, R 1B It is -CH3.

[0444] In some implementation schemes, R 2 It is C 1-20 Alkyl group. In some embodiments, R 2 It is C 1-10 Alkyl group. In some embodiments, R 2 It is C 1-5 Alkyl group. In some embodiments, R 2 It is -CH2CH3. In some implementations, R 2 It is -CH3.

[0445] In some implementations, a is between 2 and 10. In some implementations, a is between 2 and 10, 2 and 8, 2 and 6, 2 and 4, 2 and 3, 3 and 10, 3 and 8, 3 and 6, 3 and 4, 4 and 10, 4 and 8, 4 and 6, 6 and 10, 6 and 8, or 8 and 10. In some implementations, a is 3. In some implementations, a is 4. In some implementations, a is 5. In some implementations, a is 6.

[0446] In some implementations, c is between 2 and 10. In some implementations, a is between 2 and 10, 2 and 8, 2 and 6, 2 and 4, 2 and 3, 3 and 10, 3 and 8, 3 and 6, 3 and 4, 4 and 10, 4 and 8, 4 and 6, 6 and 10, 6 and 8, or 8 and 10. In some implementations, c is 3. In some implementations, c is 4. In some implementations, c is 5. In some implementations, c is 6.

[0447] In some implementations, e is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100. In some implementations, f is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100.

[0448] In some implementations, f is 1 to 100, 1 to 50, 1 to 20, 1 to 10, 1 to 5, 5 to 100, 5 to 50, 5 to 20, 5 to 10, 10 to 100, 10 to 50, 10 to 20, 20 to 100, 20 to 50, or 50 to 100.

[0449] Preparation of polythiol ligands

[0450] Polythiol ligands can be prepared by a base-catalyzed Michael addition reaction of at least one thiol on a polythiol with at least one functional group on a poly(epoxide), wherein the at least one functional group is an acrylate, a methacrylate, or an acrylamide. An example of the Michael reaction is the 1,4-addition of α,β-unsaturated carbonyl compounds, such as... Figure 2 shown. See Chatani, S. et al., "Relative reactivity and selectivity of vinyl sulfones and acrylates towards the thiol-Michael addition reaction and polymerization," Polym. Chem. 4:1048-1055 (2013).

[0451] In some embodiments, the base catalyst is selected from N,N-dimethylformamide, triethylamine, pyridine, tetrabutylammonium chloride, or N-methylimidazole. In some embodiments, the base catalyst is triethylamine.

[0452] In some embodiments, the reaction is carried out at a temperature between about -20°C and about 100°C. In some embodiments, the base-catalyzed reaction is carried out at temperatures between about -20°C and about 100°C, between about -20°C and about 80°C, between about -20°C and about 60°C, between about -20°C and about 40°C, between about -20°C and about 20°C, between about 20°C and about 100°C, between about 20°C and about 80°C, between about 20°C and about 60°C, between about 20°C and about 40°C, between about 40°C and about 100°C, between about 40°C and about 80°C, between about 40°C and about 60°C, between about 60°C and about 100°C, between about 60°C and about 80°C, or between about 80°C and about 100°C. In some embodiments, the reaction is carried out at a temperature between about 60°C and about 100°C.

[0453] In some embodiments, the polythiol ligand is prepared from polythiol and acrylate-terminated poly(epoxide) via the reaction shown in Scheme 1.

[0454] Option 1

[0455]

[0456] In some embodiments, the polythiol ligand is prepared from polythiol and methacrylate-terminated poly(epoxide) via the reaction shown in Scheme 2.

[0457] Option 2

[0458]

[0459] In some embodiments, the polythiol ligand is prepared from polythiol and acrylamide-terminated poly(epoxide) via the reaction shown in Scheme 3.

[0460] Option 3

[0461]

[0462] Polythiol ligands can also be prepared by a base-catalyzed reaction of at least one thiol on a polythiol with at least one functional group on a poly(epoxyalkane), wherein at least one functional group is an isocyanate or a glycidyl ether. See Nguyen, L.-TT et al., Polym. Chem. 4:5527-5536 (2013).

[0463] In some embodiments, the base catalyst is selected from N,N-dimethylformamide, triethylamine, pyridine, tetrabutylammonium chloride, or N-methylimidazole. In some embodiments, the base catalyst is triethylamine.

[0464] In some embodiments, the reaction is carried out at a temperature between about -20°C and about 100°C. In some embodiments, the base-catalyzed reaction is carried out at temperatures between about -20°C and about 100°C, between about -20°C and about 80°C, between about -20°C and about 60°C, between about -20°C and about 40°C, between about -20°C and about 20°C, between about 20°C and about 100°C, between about 20°C and about 80°C, between about 20°C and about 60°C, between about 20°C and about 40°C, between about 40°C and about 100°C, between about 40°C and about 80°C, between about 40°C and about 60°C, between about 60°C and about 100°C, between about 60°C and about 80°C, or between about 80°C and about 100°C. In some embodiments, the reaction is carried out at a temperature between about 60°C and about 100°C.

[0465] In some embodiments, the polythiol ligand is prepared by reacting polythiol and isocyanate-terminated poly(epoxide) as shown in Scheme 4.

[0466] Option 4

[0467]

[0468] In some embodiments, the polythiol ligand is prepared from polythiol and glycidyl ether-terminated poly(epoxide) via the reaction shown in Scheme 5.

[0469] Option 5

[0470]

[0471] Polythiol ligands can also be prepared by a radical-mediated reaction of at least one thiol on a polythiol with at least one functional group on a poly(epoxide), wherein at least one functional group is an olefin. See Nguyen, L.-TT et al., Polym. Chem. 4:5527-5536 (2013).

[0472] In some implementations, the free radical mediator is a photoinitiator, such as dimethoxy-2-phenylacetophenone.

[0473] In some embodiments, the polythiol ligand is prepared by reacting polythiol and olefin-terminated poly(epoxide) as shown in Scheme 6.

[0474] Option 6

[0475]

[0476] ligand exchange

[0477] In some embodiments, the present invention relates to a method for exchanging ligands on a nanostructure. In some embodiments, the present invention relates to a method for replacing a first ligand on a nanostructure with a second ligand. In some embodiments, the second ligand is a polythiol ligand. In some embodiments, the nanostructure is a quantum dot.

[0478] In some embodiments, the first ligand on the nanostructure dot is exchanged with a polythiol ligand. The thiol group replaces the natural hydrophobic ligand of the nanostructure, and stably anchors the ligand to the nanocrystal surface. In some embodiments, the nanostructure is a quantum dot.

[0479] In some embodiments, the present invention relates to a method for replacing a first ligand on a nanostructure with a second ligand, the method comprising:

[0480] A compounding reaction mixture comprising a group of nanostructures having a first ligand bonded to a nanostructure and a second ligand, wherein the second ligand is a polythiol ligand, such that the second ligand replaces the first ligand and becomes bonded to the nanostructure.

[0481] In some implementations, the nanostructure is a quantum dot.

[0482] In some embodiments, the first ligand is covalently bonded to the nanostructure. In other embodiments, the first ligand is non-covalently bonded to the nanostructure.

[0483] In some embodiments, the second ligand is covalently bonded to the nanostructure. In other embodiments, the second ligand is non-covalently bonded to the nanostructure.

[0484] In some embodiments, mixing is carried out at temperatures between about 0°C and about 200°C, between about 0°C and about 150°C, between about 0°C and about 100°C, between about 0°C and about 80°C, between about 20°C and about 200°C, between about 20°C and about 150°C, between about 20°C and about 100°C, between about 20°C and about 80°C, between about 50°C and about 200°C, between about 50°C and about 150°C, between about 50°C and about 100°C, between about 50°C and about 80°C, between about 80°C and about 200°C, between about 80°C and about 150°C, between about 80°C and about 100°C, between about 100°C and about 200°C, between about 100°C and about 150°C, or between about 150°C and about 200°C. In some embodiments, mixing is carried out at temperatures between about 50°C and about 100°C. In some implementations, mixing is carried out at a temperature of about 80°C.

[0485] In some implementations, mixing occurs between approximately 1 minute and approximately 6 hours, between approximately 1 minute and approximately 2 hours, between approximately 1 minute and approximately 1 hour, between approximately 1 minute and approximately 40 minutes, between approximately 1 minute and approximately 30 minutes, between approximately 1 minute and approximately 20 minutes, between approximately 1 minute and approximately 10 minutes, between approximately 10 minutes and approximately 6 hours, between approximately 10 minutes and approximately 2 hours, between approximately 10 minutes and approximately 1 hour, between approximately 10 minutes and approximately 40 minutes, between approximately 10 minutes and approximately 30 minutes, between approximately 10 minutes and approximately 20 minutes, and between approximately 20 minutes and approximately 6 hours. The mixing can be carried out within the following time periods: approximately 20 minutes to approximately 2 hours, approximately 20 minutes to approximately 1 hour, approximately 20 minutes to approximately 40 minutes, approximately 20 minutes to approximately 30 minutes, approximately 30 minutes to approximately 6 hours, approximately 30 minutes to approximately 2 hours, approximately 30 minutes to approximately 1 hour, approximately 30 minutes to approximately 40 minutes, approximately 40 minutes to approximately 6 hours, approximately 40 minutes to approximately 2 hours, approximately 40 minutes to approximately 1 hour, approximately 1 hour to approximately 6 hours, approximately 1 hour to approximately 2 hours, or approximately 2 hours to approximately 6 hours. In some embodiments, mixing is carried out within a time period of approximately 40 minutes to approximately 2 hours. In some embodiments, mixing is carried out within a time period of approximately 1 hour.

[0486] In some embodiments, the reaction mixture further comprises a solvent. In some embodiments, the solvent is selected from chloroform, acetone, butanone, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, γ-butyrolactone, methylacetic acid-3-ethyl ether, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, toluene, xylene, isopropanol, propylene glycol methyl ether acetate, hexanediol methacrylate, and combinations thereof. In some embodiments, the solvent is propylene glycol methyl ether acetate.

[0487] Optical density is a measure of the absorption of a material at a specific wavelength, and its formula is:

[0488] OD = -log 10 *(I OUT / I IN )

[0489] in:

[0490] I OUT =Radiation intensity passing through the cell; and

[0491] I IN = The intensity of radiation irradiating the unit.

[0492] The optical density of a material can be measured using a UV-Vis spectrometer.

[0493] The ratio of quantum dots to polythiol ligands can be determined by measuring the optical density of the stock solution at the desired wavelength. For example, to achieve 5.0 mg / mL / OD... 460 The concentration ratio of quantum dots to polythiol ligands was determined by combining 4.0 mL of a quantum dot stock solution with an optical density of 10 (measured at 460 nm in a 1 cm path length cuvette) with 200 mg of polythiol ligands. Furthermore, to achieve a concentration ratio of 2.5 mg / mL / OD... 460 The concentration ratio of quantum dots to polythiol ligands can be determined by combining 4.0 mL of quantum dot stock solution with an optical density of 10 (measured at 460 nm wavelength in a cuvette with an optical path length of 1 cm) with 100 mg of polythiol ligands.

[0494] In some embodiments, the concentration ratio of quantum dots to polythiol ligands, measured by optical density (at wavelengths between about 450 nm and about 600 nm), is between about 0.25 mg / mL and about 10 mg / mL, between about 0.25 mg / mL and about 5 mg / mL, between about 0.25 mg / mL and about 1 mg / mL, between about 0.25 mg / mL and about 0.5 mg / mL, between about 0.5 mg / mL and about 10 mg / mL, between about 0.5 mg / mL and about 5 mg / mL, between about 0.5 mg / mL and about 1 mg / mL, between about 1 mg / mL and about 10 mg / mL, between about 1 mg / mL and about 5 mg / mL, or between about 5 mg / mL and about 10 mg / mL. In some embodiments, the concentration ratio of quantum dots to polythiol ligands, measured by optical density (at a wavelength of about 450 nm), is between about 0.25 mg / mL and about 10 mg / mL, between about 0.25 mg / mL and about 5 mg / mL, between about 0.25 mg / mL and about 1 mg / mL, between about 0.25 mg / mL and about 0.5 mg / mL, between about 0.5 mg / mL and about 10 mg / mL, between about 0.5 mg / mL and about 4 mg / mL, between about 0.5 mg / mL and about 1 mg / mL, between about 1 mg / mL and about 10 mg / mL, between about 1 mg / mL and about 5 mg / mL, or between about 5 mg / mL and about 10 mg / mL. In some embodiments, the concentration ratio of quantum dots to polythiol ligands, measured by optical density (at a wavelength of about 450 nm), is between about 1 mg / mL and about 5 mg / mL.

[0495] In some embodiments, the ratio of quantum dots to polythiol ligands, measured by optical density (at wavelengths between about 600 nm and about 750 nm), is between about 0.25 mg / mL and about 10 mg / mL, between about 0.25 mg / mL and about 5 mg / mL, between about 0.25 mg / mL and about 1 mg / mL, between about 0.25 mg / mL and about 0.5 mg / mL, between about 0.5 mg / mL and about 10 mg / mL, between about 0.5 mg / mL and about 5 mg / mL, between about 0.5 mg / mL and about 1 mg / mL, between about 1 mg / mL and about 10 mg / mL, between about 1 mg / mL and about 5 mg / mL, or between about 4 mg / mL and about 10 mg / mL.

[0496] The percentage of the first ligand replaced by the polythiol ligand can be determined by... 1 H NMR measurements. In some embodiments, the molar percentage of the first ligand replaced by the polythiol ligand is between about 20% and about 100%, between about 20% and about 80%, between about 20% and about 60%, between about 20% and about 40%, between about 25% and about 100%, between about 25% and about 80%, between about 25% and about 60%, between about 25% and about 40%, between about 30% and about 100%, between about 30% and about 80%, between about 30% and about 60%, between about 30% and about 40%, between about 40% and about 100%, between about 40% and about 80%, between about 40% and about 60%, between about 60% and about 100%, between about 60% and about 80%, or between about 80% and about 100%.

[0497] The percentage of nanostructures in a nanostructure group containing polythiol ligands can be determined by... 1 HNMR measurements. In some embodiments, the molar percentage of ligands in the nanostructure group containing polythiol ligands is between about 20% and about 100%, between about 20% and about 80%, between about 20% and about 60%, between about 20% and about 40%, between about 25% and about 100%, between about 25% and about 80%, between about 25% and about 60%, between about 25% and about 40%, between about 30% and about 100%, between about 30% and about 80%, between about 30% and about 60%, between about 30% and about 40%, between about 40% and about 100%, between about 40% and about 80%, between about 40% and about 60%, between about 60% and about 100%, between about 60% and about 80%, or between about 80% and about 100%.

[0498] Increased solubility

[0499] In some embodiments, the polythiol ligand is soluble in a polar solvent or a combination of solvents containing at least one polar solvent. In some embodiments, the nanostructure containing the polythiol ligand dispersed on the nanostructure is soluble in a polar solvent or a combination of solvents containing at least one polar solvent.

[0500] A polythiol ligand is considered soluble in a polar solvent if at least 1 gram dissolves in 1000 mL or less of the solvent under stirring at room temperature. The amount of dissolved polythiol ligand can be determined by visual inspection.

[0501] In some embodiments, the polar solvent is selected from water, deuterium oxide, methanol, ethanol, acetone, methyl ethyl ketone, isopropanol, n-propanol, n-butanol, acetonitrile, dimethyl sulfoxide, deuterated dimethyl sulfoxide, dimethylformamide, ethylene glycol, pyridine, diethylene glycol, benzyl nitrile, cyclohexanone, chloroform, ethyl acetate, propylene glycol methyl ether acetate, and dichloromethane.

[0502] organic resin

[0503] In some embodiments, the organic resin is a thermosetting resin or an ultraviolet (UV) curable resin. In some embodiments, the organic resin is cured using a method that facilitates roll-to-roll processing.

[0504] Thermosetting resins require curing, during which they undergo an irreversible molecular cross-linking process, making the resin infusible. In some embodiments, the thermosetting resin is an epoxy resin, phenolic resin, vinyl resin, melamine resin, urea resin, unsaturated polyester resin, polyurethane resin, allyl resin, acrylic resin, polyamide resin, polyamide-imide resin, phenolic amine condensation resin, urea-melamine condensation resin, or a combination thereof.

[0505] In some embodiments, the thermosetting resin is an epoxy resin. Epoxy resins are easy to cure and do not produce volatiles or a variety of chemical byproducts. Epoxy resins are also compatible with most substrates and readily wet surfaces. See Boyle, MA et al., "Epoxy Resins," Composites, Vol. 21, ASM Handbook, pp. 78-89 (2001).

[0506] In some embodiments, the organic resin is a silicone thermosetting resin. In some embodiments, the silicone thermosetting resin is OE6630A or OE6630B (Dow Corning Corporation, Auburn, MI).

[0507] In some embodiments, a thermal initiator is used. In some embodiments, the thermal initiator is [2,2'-azobis(2-methylpropionitrile)](AIBN) or benzoyl peroxide.

[0508] UV-curable resins are polymers that cure and harden rapidly when exposed to a specific wavelength of light. In some embodiments, UV-curable resins are resins having the following functional groups: free radical polymerizable groups, such as (meth)acryloyloxy groups, ethyleneoxy groups, styryl groups, or vinyl groups; or cationic polymerizable groups, such as epoxy groups, thioepoxy groups, ethyleneoxy groups, or oxetyl groups. In some embodiments, UV-curable resins are polyester resins, polyether resins, (meth)acrylic resins, epoxy resins, polyurethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, or polythiol polyene resins.

[0509] In some embodiments, the UV-curable resin is selected from isobornyl acrylate (IBOA), polyurethane acrylate, allyloxycyclohexyl diacrylate, bis(acryloyloxyethyl)hydroxyisocyanurate, bis(acryloyloxyneopentyl glycol) adipate, bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, dicyclopentyl diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, di(trimethylolpropane)tetraacrylate, ethylene glycol dimethacrylate, glycerol methacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol hydroxyneopentate diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dimethacrylate phosphate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, tetrabromobisphenol A diacrylate, triethylene glycol divinyl ether, triglyceride diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, tri(acryloyloxyethyl) isocyanurate, triacrylate phosphate, diacrylate phosphate, propargyl acrylate, vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated trifluoromethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane, monomethacryloyloxypropyl-terminated polydimethylsiloxane, monovinyl-terminated polydimethylsiloxane, monoallyl-monotrimethylsiloxy-terminated polyethylene oxide, and combinations thereof.

[0510] In some embodiments, the UV-curable resin is a thiol-functionalized resin or a polythiol-functionalized resin that can be crosslinked with isocyanate, epoxy resin or unsaturated compound under UV curing conditions.

[0511] In some embodiments, the polythiol-functionalized resin is pentaerythritol tetra(3-mercaptopropionate) (PTMP); trimethylolpropane tri(3-mercaptopropionate) (TMPMP); ethylene glycol di(3-mercaptopropionate) (GDMP); tris[25-(3-mercaptopropionyloxy)ethyl]isocyanurate (TEMPIC); di-pentaerythritol hexa(3-mercaptopropionate) (Di-PETMP); ethoxylated trimethylolpropane tri(3-mercaptopropionate) (ETTMP 1300 and ETTMP 700); polycaprolactone tetra(3-mercaptopropionate) (PCL4MP 1350); pentaerythritol tetramercaptoacetate (PETMA); trimethylolpropane trimercaptoacetate (TMPMA); or ethylene glycol dimercaptoacetate (GDMA). These compounds are marketed under trade names by Bruno Bock GmbH of Marschacht, Germany. sell.

[0512] In some embodiments, the UV-curable resin is a polythiol-functionalized resin. In some embodiments, the UV-curable resin is a polythiol-functionalized compound selected from ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tri(thioglycolate), trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra(thioglycolate), pentaerythritol tetra(3-mercaptopropionate) (PETMP), and combinations thereof. In some embodiments, the polythiol-functionalized resin is PETMP.

[0513] In some embodiments, the UV-curable resin is a thiol-olefin formulation comprising a polythiol-functionalized resin and 1,3,5-triallyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (TTT). In some embodiments, the UV-curable resin is a thiol-olefin formulation comprising PETMP and TTT.

[0514] In some embodiments, the UV-curable resin also includes a photoinitiator. The photoinitiator initiates the curing reaction of the photosensitive material during exposure to light. In some embodiments, the photoinitiator is acetophenone-based, benzoin-based, or thioxanthone-based.

[0515] In some implementations, the photoinitiator is MINS-311RM (Minuta Technology Co., Ltd, Korea).

[0516] In some embodiments, the photoinitiator is IRGACURE 127, IRGACURE 184, IRGACURE 184D, IRGACURE 2022, IRGACURE 2100, IRGACURE 250, IRGACURE 270, IRGACURE 2959, IRGACURE 369, IRGACURE 369EG, IRGACURE 379, IRGACURE 500, IRGACURE 651, IRGACURE 754, IRGACURE 784, IRGACURE 819, IRGACURE 819Dw, IRGACURE 907, IRGACURE 907FF, IRGACUREOxe01, IRGACURE TPO-L, IRGACURE 1173, IRGACURE 1173D, IRGACURE 4265, IRGACURE BP or IRGACURE MBF (BASF Corporation, Wyandotte, MI). In some embodiments, the photoinitiator is TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) or MBF (methyl benzoylformate).

[0517] In some embodiments, the weight percentage of the organic resin in the nanostructure composition is between about 5% and about 50%, between about 5% and about 40%, between about 5% and about 30%, between about 5% and about 20%, between about 5% and about 10%, between about 10% and about 50%, between about 10% and about 40%, between about 10% and about 30%, between about 10% and about 20%, between about 20% and about 50%, between about 20% and about 40%, between about 20% and about 30%, between about 30% and about 50%, between about 30% and about 40%, or between about 40% and about 50%.

[0518] In some embodiments, the weight percentage of organic resin in the nanostructured molded article is between about 0.01% and about 50%, between about 0.01% and about 25%, between about 0.01% and about 20%, between about 0.01% and about 15%, between about 0.01% and about 10%, between about 0.01% and about 5%, between about 0.01% and about 2%, between about 0.01% and about 1%, between about 1% and about 50%, between about 1% and about 25%, between about 1% and about 20%, between about 1% and about 15%, between about 1% and about 10%, between about 1% and about 5%, between about 1% and about 2%, between about 2% and about 50%, and about 2%... Between % and approximately 25%, between approximately 2% and approximately 20%, between approximately 2% and approximately 15%, between approximately 2% and approximately 10%, between approximately 2% and approximately 5%, between 5% and approximately 50%, between approximately 5% and approximately 25%, between approximately 5% and approximately 20%, between approximately 5% and approximately 15%, between approximately 5% and approximately 10%, between approximately 10% and approximately 50%, between approximately 10% and approximately 25%, between approximately 10% and approximately 20%, between approximately 10% and approximately 15%, between approximately 15% and approximately 50%, between approximately 15% and approximately 25%, between approximately 15% and approximately 20%, between approximately 20% and approximately 50%, between approximately 20% and approximately 25%, or between approximately 25% and approximately 50%.

[0519] In some embodiments, if more than one organic resin is used, the organic resins are added and mixed together. In some embodiments, the first organic resin and the second organic resin are added and mixed together.

[0520] In some embodiments, the first organic resin and the second organic resin are mixed at speeds between approximately 100 rpm and approximately 10,000 rpm, between approximately 100 rpm and approximately 5,000 rpm, between approximately 100 rpm and approximately 3,000 rpm, between approximately 100 rpm and approximately 1,000 rpm, between approximately 100 rpm and approximately 500 rpm, between approximately 500 rpm and approximately 10,000 rpm, between approximately 500 rpm and approximately 5,000 rpm, and between approximately 500 rpm and approximately 3,000 rpm. Mix at stirring rates between approximately 1,000 rpm, approximately 500 rpm and approximately 1,000 rpm, approximately 1,000 rpm and approximately 10,000 rpm, approximately 1,000 rpm and approximately 5,000 rpm, approximately 1,000 rpm and approximately 3,000 rpm, approximately 3,000 rpm and approximately 10,000 rpm, approximately 3,000 rpm and approximately 10,000 rpm, or approximately 5,000 rpm and approximately 10,000 rpm.

[0521] In some embodiments, the mixing time of the first organic resin and the second organic resin is between about 10 minutes and about 24 hours, between about 10 minutes and about 20 hours, between about 10 minutes and about 15 hours, between about 10 minutes and about 10 hours, between about 10 minutes and about 5 hours, between about 10 minutes and about 1 hour, between about 10 minutes and about 30 minutes, between about 30 minutes and about 24 hours, between about 30 minutes and about 20 hours, between about 30 minutes and about 15 hours, between about 30 minutes and about 10 hours, between about 30 minutes and about 5 hours, and between about 30 minutes and about 1 hour. Between, approximately 1 hour and approximately 24 hours, approximately 1 hour and approximately 20 hours, approximately 1 hour and approximately 15 hours, approximately 1 hour and approximately 10 hours, approximately 1 hour and approximately 5 hours, approximately 5 hours and approximately 24 hours, approximately 5 hours and approximately 20 hours, approximately 5 hours and approximately 15 hours, approximately 5 hours and approximately 10 hours, approximately 10 hours and approximately 24 hours, approximately 10 hours and approximately 20 hours, approximately 10 hours and approximately 15 hours, approximately 15 hours and approximately 24 hours, approximately 15 hours and approximately 20 hours, or approximately 20 hours and approximately 24 hours.

[0522] Preparation of nanostructured compositions

[0523] This invention provides a method for preparing a nanostructure composition, the method comprising compounding at least one nanostructure group with at least one organic resin. In some embodiments, the ligands in the nanostructure group, ranging from about 20 mol% to about 100 mol%, comprise polythiol ligands. In some embodiments, the at least one organic resin is a thiol-functionalized resin.

[0524] This invention provides a method for preparing a nanostructure composition, the method comprising:

[0525] (a) A composition comprising at least one nanostructure group, wherein about 20 mol% to about 100 mol% of the ligands in the nanostructure group comprises a polythiol ligand bonded to the nanostructure; and

[0526] (b) Mixing at least one organic resin with the composition of (a), wherein at least one organic resin is soluble in a polar solvent.

[0527] In some implementations, the nanostructure clusters emit red, green, or blue light. In some implementations, the individual portions of the red, green, and blue light can be controlled to achieve the desired white point of the white light emitted by the display device incorporating the nanostructure film.

[0528] In some embodiments, the nanostructure composition comprises at least one group of nanostructure materials. In some embodiments, the nanostructure composition comprises a group consisting of between 1 and 5, 1 and 4, 1 and 3, 1 and 2, 2 and 5, 2 and 4, 2 and 3, 3 and 5, 3 and 4, or 4 and 5 nanostructure materials. Any suitable proportion of quantum dot groups can be combined to produce the desired nanostructure composition characteristics. In some embodiments, the nanostructure is a quantum dot.

[0529] In some embodiments, the nanostructure composition comprises at least one organic resin. In some embodiments, the nanostructure composition comprises one to five, one to four, one to three, one to two, two to five, two to four, two to three, three to five, three to four, or four to five organic resins. In some embodiments, the nanostructure composition comprises one to three, one to two, or two to three organic resins. In some embodiments, the nanostructure composition comprises one organic resin. In some embodiments, the nanostructure is a quantum dot.

[0530] In some embodiments, the weight percentage of the nanostructure group in the nanostructure composition is between about 0.001% and about 2%, between about 0.001% and about 1%, between about 0.001% and about 0.5%, between about 0.001% and about 0.1%, between about 0.001% and 0.01%, between about 0.01% and about 2%, between about 0.01% and about 1%, between about 0.01% and about 0.5%, between about 0.01% and about 0.1%, between about 0.1% and about 2%, between about 0.1% and about 1%, between about 0.1% and about 0.5%, between about 0.5% and about 2%, between about 0.5% and about 1%, or between about 1% and about 2%. In some embodiments, the nanostructure is a quantum dot.

[0531] In some embodiments, the weight percentage of the organic resin in the nanostructure composition is between about 5% and about 50%, between about 5% and about 40%, between about 5% and about 30%, between about 5% and about 20%, between about 5% and about 10%, between about 10% and about 50%, between about 10% and about 40%, between about 10% and about 30%, between about 10% and about 20%, between about 20% and about 50%, between about 20% and about 40%, between about 20% and about 30%, between about 30% and about 50%, between about 30% and about 40%, or between about 40% and about 50%.

[0532] In some embodiments, at least one organic resin is mixed with at least one nanostructure group at speeds between about 100 rpm and about 10,000 rpm, between about 100 rpm and about 5,000 rpm, between about 100 rpm and about 3,000 rpm, between about 100 rpm and about 1,000 rpm, between about 100 rpm and about 500 rpm, between about 500 rpm and about 10,000 rpm, between about 500 rpm and about 5,000 rpm, and between about 500 rpm and about 10,000 rpm. Mix at stirring rates between approximately 3,000 rpm, between approximately 500 rpm and approximately 1,000 rpm, between approximately 1,000 rpm and approximately 10,000 rpm, between approximately 1,000 rpm and approximately 5,000 rpm, between approximately 1,000 rpm and approximately 3,000 rpm, between approximately 3,000 rpm and approximately 10,000 rpm, between approximately 3,000 rpm and approximately 10,000 rpm, or between approximately 5,000 rpm and approximately 10,000 rpm.

[0533] In some embodiments, at least one organic resin is compounded with at least one group of nanostructures at a temperature between about -5°C and about 100°C, between about -5°C and about 75°C, between about -5°C and about 50°C, between about -5°C and about 23°C, between about 23°C and about 100°C, between about 23°C and about 75°C, between about 23°C and about 50°C, between about 50°C and about 100°C, between about 50°C and about 75°C, or between about 75°C and about 100°C. In some embodiments, at least one organic resin is compounded with at least one group of nanostructures at a temperature between about 23°C and about 50°C.

[0534] In some embodiments, the mixing time of at least one organic resin with at least one nanostructure group is between about 10 minutes and about 24 hours, between about 10 minutes and about 20 hours, between about 10 minutes and about 15 hours, between about 10 minutes and about 10 hours, between about 10 minutes and about 5 hours, between about 10 minutes and about 1 hour, between about 10 minutes and about 30 minutes, between about 30 minutes and about 24 hours, between about 30 minutes and about 20 hours, between about 30 minutes and about 15 hours, between about 30 minutes and about 10 hours, between about 30 minutes and about 5 hours, between about 30 minutes and about 1 hour. Between 1 hour, between approximately 1 hour and approximately 24 hours, between approximately 1 hour and approximately 20 hours, between approximately 1 hour and approximately 15 hours, between approximately 1 hour and approximately 10 hours, between approximately 1 hour and approximately 5 hours, between approximately 5 hours and approximately 24 hours, between approximately 5 hours and approximately 20 hours, between approximately 5 hours and approximately 15 hours, between approximately 5 hours and approximately 10 hours, between approximately 10 hours and approximately 24 hours, between approximately 10 hours and approximately 20 hours, between approximately 10 hours and approximately 15 hours, between approximately 15 hours and approximately 24 hours, between approximately 15 hours and approximately 20 hours, or between approximately 20 hours and approximately 24 hours.

[0535] In some embodiments, the compound further comprises a solvent. In some embodiments, the solvent is selected from chloroform, acetone, butanone, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, γ-butyrolactone, methylacetic acid-3-ethyl ether, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexane, toluene, xylene, isopropanol, and combinations thereof.

[0536] Improved stability of nanostructured compositions containing polythiol ligands

[0537] Polythiol ligands provide enhanced stability to nanostructure groups in organic resins and allow for longer storage times. In some embodiments, at least one nanostructure group can be stored with the organic resin at temperatures between about 10°C and about 90°C for approximately 1 minute to about 3 years, approximately 1 minute to about 12 months, approximately 1 minute to about 6 months, approximately 1 minute to about 3 months, approximately 1 minute to about 1 month, approximately 1 minute to about 15 days, approximately 1 minute to about 1 day, approximately 1 day to about 3 years, approximately 1 day to about 12 months, approximately 1 day to about 6 months, approximately 1 day to about 3 months, approximately 1 day to about 1 month, and approximately 1 day to about 3 years. Between 15 days, between approximately 15 days and approximately 3 years, between approximately 15 days and approximately 12 months, between approximately 15 days and approximately 6 months, between approximately 15 days and approximately 3 months, between approximately 15 days and approximately 1 month, between approximately 1 month and approximately 3 years, between approximately 1 month and approximately 12 months, between approximately 1 month and approximately 6 months, between approximately 1 month and approximately 3 months, between approximately 3 months and approximately 3 years, between approximately 3 months and approximately 12 months, between approximately 3 months and approximately 6 months, between approximately 6 months and 3 years, between approximately 6 months and 12 months, or between approximately 12 months and approximately 3 years.

[0538] Polythiol ligands provide enhanced stability to nanostructure groups in organic resins and allow for longer storage times. In some embodiments, at least one nanostructure group can be stored with the organic resin at temperatures between about 30°C and about 90°C for approximately 1 minute to about 3 years, approximately 1 minute to about 12 months, approximately 1 minute to about 6 months, approximately 1 minute to about 3 months, approximately 1 minute to about 1 month, approximately 1 minute to about 15 days, approximately 1 minute to about 1 day, approximately 1 day to about 3 years, approximately 1 day to about 12 months, approximately 1 day to about 6 months, approximately 1 day to about 3 months, approximately 1 day to about 1 month, approximately 1 day ...3 years, approximately 1 day to about 1 month, approximately 1 day to about 3 years, approximately 1 day to about 12 months, approximately 1 day to about 6 months, approximately 1 day to about 3 months, approximately 1 day to about 1 month, approximately 1 day to about 3 years, approximately 1 day to about 15 days, approximately 1 minute to about 1 day, approximately 1 day to about 15 days, approximately 1 minute to about 1 day, approximately 1 day to about 15 days, approximately 1 minute to about 1 day, approximately 1 day to about 15 days, approximately 1 minute to about 1 day, approximately 1 day to about 15 years, approximately 1 day to about 1 day, approximately 1 day to about 15 years, approximately 1 day to about 15 years, approximately 1 day to about 15 years, approximately 1 day to about 15 years, approximately 1 day to about 15 years, approximately 1 day to about 15 years, approximately 1 day Between 15 days, between approximately 15 days and approximately 3 years, between approximately 15 days and approximately 12 months, between approximately 15 days and approximately 6 months, between approximately 15 days and approximately 3 months, between approximately 15 days and approximately 1 month, between approximately 1 month and approximately 3 years, between approximately 1 month and approximately 12 months, between approximately 1 month and approximately 6 months, between approximately 1 month and approximately 3 months, between approximately 3 months and approximately 3 years, between approximately 3 months and approximately 12 months, between approximately 3 months and approximately 6 months, between approximately 6 months and 3 years, between approximately 6 months and 12 months, or between approximately 12 months and approximately 3 years.

[0539] Preparation of nanostructured layers

[0540] The nanostructures used in this invention can be embedded in a polymer matrix using any suitable method. As used herein, the term "embedded" is used to indicate that a group of nanostructures is surrounded or encapsulated by a polymer constituting a majority of the matrix component. In some embodiments, at least one group of nanostructures is suitably and uniformly distributed throughout the matrix. In some embodiments, at least one group of nanostructures is distributed according to a specific application. In some embodiments, the nanostructures are mixed in a polymer and applied to the surface of a substrate.

[0541] Nanostructured compositions can be deposited by any suitable method known in the art, including but not limited to smearing, spraying, solvent spraying, wet coating, adhesive coating, spin coating, tape coating, roll coating, flow coating, inkjet vapor jetting, drop casting, doctor blade coating, fog deposition, or combinations thereof. Preferably, the nanostructured composition is cured after deposition. Suitable curing methods include photocuring such as UV curing and thermal curing. Conventional lamination, tape coating, and / or roll-to-roll manufacturing methods can be used to form nanostructured films. The nanostructured composition can be directly coated onto the desired layer of a substrate. Alternatively, the nanostructured composition can be formed as a solid layer as an independent element and subsequently applied to the substrate. In some embodiments, the nanostructured composition can be deposited on one or more barrier layers.

[0542] Spin coating

[0543] In some implementations, spin coating is used to deposit nanostructured compositions onto a substrate. During spin coating, a small amount of material is typically deposited at the center of the substrate, which is mounted on a machine called a spin coater, held in place by a vacuum. The spin coater applies high-speed rotation to the substrate, generating a centripetal force that causes the material to diffuse from the center to the edges of the substrate. While most of the material is ejected, a certain amount remains on the substrate, forming a thin film on the surface as rotation continues. The final thickness of the film is determined by the properties of the deposited material and the substrate, as well as the parameters chosen for the spin process, such as rotation speed, acceleration, and spin time. For typical films, rotation speeds of 1500 rpm to 6000 rpm and spin times of 10 to 60 seconds are used.

[0544] Fog deposition

[0545] In some implementations, mist deposition is used to deposit nanostructure compositions onto a substrate. Mist deposition is performed at room temperature and atmospheric pressure, allowing for precise control of film thickness by varying process conditions. During mist deposition, the liquid source material is atomized into a very fine mist and carried to the deposition chamber by nitrogen gas. The mist is then drawn onto the wafer surface by a high voltage potential between the field screen and the wafer holder. Once the droplets have condensed on the wafer surface, the wafer is removed from the chamber and thermally cured to allow the solvent to evaporate. The liquid precursor is a mixture of solvent and material to be deposited. It is carried to the atomizer by pressurized nitrogen gas. Price, SC et al., "Formation of Ultra-Thin Quantum Dot Films by MistDeposition," ESC Transactions 11:89-94 (2007).

[0546] Spraying

[0547] In some implementations, spraying is used to deposit nanostructured compositions onto a substrate. Typical equipment for spraying includes a nozzle, an atomizer, a precursor solution, and a carrier gas. In a spray deposition process, the precursor solution is atomized into micron-sized droplets using a carrier gas or by atomization (such as ultrasonic, air jet, or electrostatic). Droplets exiting the atomizer are accelerated through the nozzle onto the substrate surface with the aid of a carrier gas that is controlled and regulated as needed. The relative movement between the nozzle and the substrate is defined by design to ensure complete coverage of the substrate.

[0548] In some embodiments, the application of the nanostructure composition further includes a solvent. In some embodiments, the solvent used for the application of the nanostructure composition is water, an organic solvent, an inorganic solvent, a halogenated organic solvent, or a mixture thereof. Exemplary solvents include, but are not limited to, water, D2O, acetone, ethanol, dioxane, ethyl acetate, methyl ethyl ketone, isopropanol, anisole, γ-butyrolactone, dimethylformamide, N-methylpyrroledione, dimethylacetamide, hexamethylphosphoramide, toluene, dimethyl sulfoxide, cyclopentanone, tetramethyl sulfoxide, xylene, ε-caprolactone, tetrahydrofuran, tetrachloroethylene, chloroform, chlorobenzene, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, or a mixture thereof.

[0549] In some embodiments, the nanostructure composition is thermally cured to form a nanostructure layer. In some embodiments, a UV-curable composition is used. In some embodiments, the nanostructure composition is directly coated onto a barrier layer of the nanostructure film, followed by the deposition of an additional barrier layer on the nanostructure layer to form the nanostructure film. To increase strength, stability, and coating uniformity, and to prevent material inconsistencies, bubble formation, and wrinkling or folding of the barrier layer material or other materials, a support substrate may be used under the barrier film. Furthermore, it is preferable to deposit one or more barrier layers on the nanostructure layer to seal the material between the top and bottom barrier layers. Suitably, the barrier layer may be deposited as a laminate and optionally sealed or further processed before the nanostructure film is incorporated into a specific lighting device. Those skilled in the art will understand that the nanostructure composition deposition process may include additional or different components. Such embodiments will allow for in-line process tuning of nanostructure emission characteristics such as brightness and color (e.g., adjusting the white point of a quantum dot film) and nanostructure film thickness and other characteristics. Furthermore, these embodiments will allow for periodic testing of nanostructure film characteristics during production, and for making any necessary switchovers to achieve precise nanostructure film characteristics. Such tests and adjustments can also be performed without altering the mechanical configuration of the processing line, as computer programs can electronically change the respective amounts of the mixtures used to form nanostructured films.

[0550] Barrier layer

[0551] In some embodiments, the nanostructured molded article includes one or more barrier layers disposed on one or both sides of the nanostructured layer. Suitable barrier layers protect the nanostructured layer and the nanostructured molded article from environmental conditions such as high temperature, oxygen, and moisture. Suitable barrier materials include non-yellowing transparent optical materials that are hydrophobic, chemically and mechanically compatible with the nanostructured molded article, exhibit optical and chemical stability, and can withstand high temperatures. Preferably, one or more barrier layers have a refractive index matched to the nanostructured molded article. In a preferred embodiment, the matrix material of the nanostructured molded article has a refractive index matched to one or more adjacent barrier layers to have similar refractive indices, such that most of the light transmitted through the barrier layers toward the nanostructured molded article is transmitted from the barrier layers to the nanostructured layer. This refractive index matching reduces optical losses at the interface between the barrier material and the matrix material.

[0552] The barrier layer is suitably a solid material and can be a cured liquid, gel, or polymer. The barrier layer may comprise flexible or non-flexible materials, depending on the specific application. The barrier layer is preferably a planar layer and can include any suitable shape and surface area configuration, depending on the specific lighting application. In a preferred embodiment, one or more barrier layers will be compatible with a lamination process, wherein a nanostructured layer is disposed on at least a first barrier layer, and at least a second barrier layer is disposed on the nanostructured layer on the side opposite to the nanostructured layer, to form a nanostructured molded article according to one embodiment. Suitable barrier materials include any suitable barrier materials known in the art. For example, suitable barrier materials include glass, polymers, and oxides. Suitable barrier layer materials include, but are not limited to, polymers such as polyethylene terephthalate (PET); oxides such as silicon oxide, titanium oxide, or aluminum oxide (e.g., SiO2, Si2O3, TiO2, or Al2O3); and suitable combinations thereof. Preferably, each barrier layer of the nanostructured molded article comprises at least two layers containing different materials or compositions, such that the multilayer barrier layers eliminate or reduce pinhole defect alignment in the barrier layers, thereby providing an effective barrier against oxygen and moisture penetration into the nanostructured layer. The nanostructured layer may comprise any suitable material or combination of materials on either side or both sides of the nanostructured layer and any suitable number of barrier layers. The material, thickness, and number of barrier layers will depend on the specific application and will be appropriately selected to maximize the barrier protection and brightness of the nanostructured layer while minimizing the thickness of the nanostructured molded article. In a preferred embodiment, each barrier layer comprises a laminate, preferably a double-laminated laminate, wherein each barrier layer is thick enough to eliminate wrinkling during roll-to-roll or lamination manufacturing processes. In embodiments where the nanostructure contains heavy metals or other toxic materials, the number or thickness of the barrier layers may also depend on statutory toxicity guidelines, which may require more or thicker barrier layers. Other considerations for barrier layers include cost, availability, and mechanical strength.

[0553] In some embodiments, the nanostructured film includes two or more barrier layers adjacent to each side of the nanostructured layer, for example, two or three layers on each side or two barrier layers on each side of the nanostructured layer. In some embodiments, each barrier layer includes a thin glass sheet, for example, a glass sheet with a thickness of about 100 μm, 100 μm or less, or 50 μm or less.

[0554] Each barrier layer of the nanostructured film can have any suitable thickness, depending on the specific requirements and characteristics of the lighting device and application, as well as the individual film components such as the barrier layer and the nanostructured layer, as will be understood by those skilled in the art. In some embodiments, each barrier layer may have a thickness of 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, or 15 μm or less. In some embodiments, the barrier layer comprises an oxide coating, which may contain materials such as silicon oxide, titanium oxide, and aluminum oxide (e.g., SiO2, Si2O3, TiO2, or Al2O3). The oxide coating may have a thickness of about 10 μm or less, 5 μm or less, 1 μm or less, or 100 nm or less. In some embodiments, the barrier layer comprises a thin oxide coating with a thickness of about 100 nm or less, 10 nm or less, 5 nm or less, or 3 nm or less. The top and / or bottom barrier layers may consist of a thin oxide coating, or may comprise a thin oxide coating and one or more additional material layers.

[0555] Improved properties of nanostructured films

[0556] Membranes prepared using nanostructure compositions comprising nanostructure groups in organic resins offer enhanced stability at high temperatures, wherein the nanostructures comprise polythiol ligands. In some embodiments, membranes prepared using nanostructure compositions can be stably stored at temperatures between 40°C and 100°C for approximately 1 minute to approximately 3 years, approximately 1 minute to approximately 12 months, approximately 1 minute to approximately 6 months, approximately 1 minute to approximately 3 months, approximately 1 minute to approximately 1 month, approximately 1 minute to approximately 15 days, approximately 1 minute to approximately 1 day, approximately 1 day to approximately 3 years, approximately 1 day to approximately 12 months, approximately 1 day to approximately 6 months, approximately 1 day to approximately 3 months, approximately 1 day to approximately 1 month, and approximately 1 day to approximately 3 years. Between 15 days, between approximately 15 days and approximately 3 years, between approximately 15 days and approximately 12 months, between approximately 15 days and approximately 6 months, between approximately 15 days and approximately 3 months, between approximately 15 days and approximately 1 month, between approximately 1 month and approximately 3 years, between approximately 1 month and approximately 12 months, between approximately 1 month and approximately 6 months, between approximately 1 month and approximately 3 months, between approximately 3 months and approximately 3 years, between approximately 3 months and approximately 12 months, between approximately 3 months and approximately 6 months, between approximately 6 months and 3 years, between approximately 6 months and 12 months, or between approximately 12 months and approximately 3 years.

[0557] Membranes prepared using nanostructure compositions comprising nanostructure groups in organic resins offer enhanced stability at high humidity levels, wherein the nanostructures comprise polythiol ligands. In some embodiments, membranes prepared using nanostructure compositions can be stably stored at relative humidity levels between about 60% and about 100% for approximately 1 minute to about 3 years, about 1 minute to about 12 months, about 1 minute to about 6 months, about 1 minute to about 3 months, about 1 minute to about 1 month, about 1 minute to about 15 days, about 1 minute to about 1 day, about 1 day to about 3 years, about 1 day to about 12 months, about 1 day to about 6 months, about 1 day to about 3 months, about 1 day to about 1 month, and about 1... The time between approximately 15 days and approximately 3 years, between approximately 15 days and approximately 12 months, between approximately 15 days and approximately 6 months, between approximately 15 days and approximately 3 months, between approximately 15 days and approximately 1 month, between approximately 1 month and approximately 3 years, between approximately 1 month and approximately 12 months, between approximately 1 month and approximately 6 months, between approximately 1 month and approximately 3 months, between approximately 3 months and approximately 3 years, between approximately 3 months and approximately 12 months, between approximately 3 months and approximately 6 months, between approximately 6 months and 3 years, between approximately 6 months and 12 months, or between approximately 12 months and approximately 3 years.

[0558] Films prepared using nanostructure compositions comprising nanostructure groups in an organic resin provide improved light conversion efficiency (LCE), wherein the nanostructures comprise polythiol ligands. In some embodiments, films prepared using nanostructure compositions exhibit light conversion efficiencies between about 20% and about 40%, between about 20% and about 30%, between about 20% and about 25%, between about 20% and about 22.5%, between about 22.5% and about 40%, between about 22.5% and about 30%, between about 22.5% and about 25%, between about 25% and about 40%, between about 25% and about 30%, or between about 30% and about 40%. In some embodiments, films prepared using nanostructure compositions exhibit color conversion efficiencies between about 20% and about 25%.

[0559] Nanostructured membrane characteristics and implementation scheme

[0560] In some implementations, the nanostructured film is used to form a display device. As used herein, a display device refers to any system with an illuminated display. Such devices include, but are not limited to, devices encompassing liquid crystal displays (LCDs), televisions, computers, mobile phones, smartphones, personal digital assistants (PDAs), gaming devices, e-readers, digital cameras, and the like.

[0561] Example

[0562] The following examples are illustrative and non-limiting descriptions of the products and methods described herein. Suitable modifications and adjustments to various conditions, formulations, and other parameters that are commonly encountered in the art and will be apparent to those skilled in the art in view of this disclosure are within the spirit and scope of the invention.

[0563] Example 1

[0564]

[0565] Synthesis of PETMP-PEG480

[0566] 78.582 g of a poly(ethylene glycol) methyl ether acrylate (average Mn 480 (Sigma Aldrich, St. Louis, MO)) (PEG480) solution and 1.092 mL of trimethylamine (TEA) were added to a round-bottom flask at room temperature and stirred for 5 minutes until homogeneous. 80 g of pentaerythritol tetra(3-mercaptopropionate (Evans Chemetics LP, Waterloo, NY)) (PETMP) was added to this solution, and the mixture was stirred at room temperature for 30 minutes. Due to the exothermic nature of the reaction, the temperature rose to approximately 40 °C. The flask was further heated at 80 °C for 1.5 hours. The flask was then cooled to 60 °C, and TEA was removed by applying a vacuum (100 mTorr) for 2 hours. The flask was analyzed by FTIR and H₂O. 1 -NMR characterization of the final product confirmed C=CH stretching and proton signal depletion.

[0567] Example 2

[0568] Ligand exchange with PETMP-PEG480 ligand

[0569] Add 6.0 mL of quantum dots in heptane, 0.379 g of PETMP-PEG-480, and 12.0 mL of degassed polypropylene glycol methyl ether acetate (PGMEA) under nitrogen to a 100 mL round-bottom flask. Heat the flask to 80 °C with stirring for 1 hour. The mist solution becomes clear during ligand exchange. Cool the solution to room temperature, and then add 36 mL of degassed heptane (4 x the total volume of the ligand exchange solution) to a TEFLON centrifuge flask to precipitate quantum dots containing bonded PETMP-PEG-480 ligands. Centrifuge the turbid suspension of quantum dots containing bonded PETMP-PEG-480 ligands at 4000 rpm for 15 min to obtain pellets and a clear supernatant. Discard the supernatant and redisperse the quantum dots containing bonded PETMP-PEG-480 ligands in 0.948 mL of degassed PGMEA with stirring. The quantum dots are insoluble in PGMEA prior to ligand exchange.

[0570] Example 3

[0571] Ligand exchange with PEG1000-CA ligand

[0572] Quantum dots containing bonded carboxylic acid-terminated PEG-1000 (PEG-1000-CA) ligands were prepared using the method of Example 2, with PEG1000-CA used instead of PETMP-PEG480. The carboxylic acid-terminated PEG-1000 ligands were prepared using the method described in International Patent Application Publication No. WO 2019 / 084119, the entire contents of which are incorporated herein by reference.

[0573] Example 4

[0574] Quantum yield results of PETMP-PEG480 or PEG1000-CA at different ratios

[0575] Quantum dots containing bonded PETMP-PEG-480 ligands and quantum dots containing bonded PEG-1000-CA were prepared using different ligand-to-quantum-dot concentration ratios. The concentrations of the ligands (mg / mL) and quantum dots were determined by measuring the optical density (OD) of the ligand or quantum dot dispersions at 450 nm using a UV-VIS spectrometer. Based on the measured concentrations, the ligand-to-quantum-dot ratio was measured using the following formula:

[0576] Ligand / Quantum Dot Ratio = OD 450 ligand / OD 450 quantum dots

[0577] Table 1 shows the quantum yield measurements for quantum dots containing bonded PETMP-PEG-480 and quantum dots containing bonded PEG-1000-CA at three different ligand / quantum dot ratios.

[0578] Table 1.

[0579] ligands ligand / quantum dot ratio Quantum yield PETMP-PEG-480 1 87.4％ PETMP-PEG-480 2.5 85.2％ PETMP-PEG-480 5 83.9％ PEG-1000-CA 1 87.0％

[0580] As shown in Table 1, quantum dots containing bonded PETMP-PEG-480 ligands at a ratio of 1 provided a quantum yield of 87.4%, and the quantum yield decreased with increasing ligand / quantum dot ratio, with quantum dots containing bonded PETMP-PEG-480 ligands providing a quantum yield of 83.9%. At the same ligand / quantum dot ratio, the quantum yield obtained with quantum dots containing bonded PETMP-PEG-480 ligands was comparable to that obtained with quantum dots containing bonded PEG-1000-CA ligands.

[0581] Example 5

[0582] Preparation of quantum dot films

[0583] A solution of quantum dots containing bonded PETMP-PEG-480 ligands (or PEG-1000-CA ligands) in PGMEA was added to a polymer formulation (also dissolved in PGMEA). The solution was processed into a film by evaporating the solvent at 100°C and then thermally curing it at 180°C. As shown in Table 2, the film prepared using quantum dots containing bonded PETMP-PEG-480 ligands exhibited improved brightness compared to the film prepared using quantum dots containing bonded PEG-1000-CA ligands. The brightness of the quantum dot film is a measure of light conversion efficiency (LCE).

[0584] Table 2.

[0585]

[0586] Example 6

[0587] Weight loss of quantum dot film after heating

[0588] The weights of quantum dots containing bonded PETMP-PEG-480 ligands and quantum dots containing bonded PEG-1000-CA ligands were measured before and after heat curing at 180°C for 30 minutes. The results are shown in Table 3.

[0589] Table 3.

[0590] ligands Ligand / quantum dot ratio (mg / OD) Weight loss PETMP-PEG-480 1 2.0％ PEG-1000-CA 1 23.1％

[0591] As shown in Table 3, quantum dots containing bonded PETMP-PEG-480 ligands exhibit significantly better thermal stability than those containing bonded PEG-1000-CA ligands. It is believed that this improved thermal stability contributes to enhanced film brightness from quantum dots containing bonded PETMP-PEG-480 ligands.

[0592] Example 7

[0593] QDCF (Quantum Dot Color Filter) Formulation Examples

[0594] Formulations for QDCF applications are prepared by combining the QD solution with other components used in the ink. Examples are shown in Table 4.

[0595] Table 4.

[0596]

[0597] The above formulation can be deposited by spin-coating onto a 2" x 2" pre-cleaned glass substrate at three different speeds (e.g., 200 rpm, 400 rpm, and 600 rpm). Depending on the type of ink, the film can be deposited by heating (at 150°C in N2 for 20 to 40 minutes) or by irradiation with UV light (1000 mJ / cm). 2 Up to 2000mJ / cm 2 The membrane is then cured.

[0598] The film can be transferred to an optical platform to measure blue light transmittance and photon conversion efficiency (PCE). Film thickness can be measured using a profilometer.

[0599] While various embodiments have been described above, it should be understood that they are presented by way of example only and not by way of limitation. It will be apparent to those skilled in the art that various changes in form and detail can be made therein without departing from the spirit and scope of the invention. Therefore, its breadth and scope should not be limited by any of the exemplary embodiments described above, but should be defined only by the following claims and their equivalents.

[0600] All publications, patents, and patent applications mentioned in this specification demonstrate the skill of a person skilled in the art to which this invention pertains and are incorporated herein by reference to the extent that each individual publication, patent, or patent application is specifically and individually indicated to be incorporated by reference.

Claims

1. A nanostructure composition, said nanostructure composition comprising: (b) Nanostructures; and (b) A polythiol ligand dispersed on the surface of the nanostructure, the polythiol ligand having formula I: in: CM is the central part, selected from alkanes, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, and (propane-2,2-dimethylbis(4,1-phenylene))bis(λ'-oxy); X1 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X2 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X3 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X4 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X5 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X6 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-; X7 is a key or C. 1-12 Alkylene; X8 is a key, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B Independently, it is H or C 1-20 alkyl; R 2 It is C 1-20 Alkyl or C 1-20 Alkoxy; a is 2 to 4; b is between 0 and 2; c is 2 to 4; d is between 0 and 2; e is from 1 to 20; and f is between 0 and 20; Where 6≥a+b+c+d≥4.

2. The nanostructure composition of claim 1, wherein the polythiol ligand has formula II: in: CM is the central part, selected from alkanes, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, and (propane-2,2-dimethylbis(4,1-phenylene))bis(λ'-oxy); X1 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X2 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X3 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-; X7 is a key or C. 1-12 Alkylene; X8 is a key, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B Independently, it is H or C 1-20 Alkylene; R 2 It is C 1-20 Alkylene or C 1-20 Alkoxy; a is 2 to 4; c is 2 to 4; e is from 1 to 20; and f is between 0 and 20; Where 6≥a+c≥4.

3. The nanostructure composition of claim 1 or 2, wherein the nanostructure comprises a core selected from InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP.

4. The nanostructure composition of claim 1 or 2, wherein the nanostructure comprises at least one shell.

5. The nanostructure composition of claim 1 or 2, wherein X1, X2 and X3 are bonds.

6. The nanostructure composition of claim 1 or 2, wherein X1 is -C(=O)- and X2 is C 1-10 Alkylene, and X3 is a bond.

7. The nanostructure composition of claim 1 or 2, wherein X1 is C 2-10 Heteroalkylene, X2 is -C(=O)-, and X3 is C 1-10 Alkylene.

8. The nanostructure composition of claim 1 or 2, wherein X1 is a substituted C 2-10 Heteroalkyl, X2 is a bond and X3 is a bond.

9. The nanostructure composition of claim 1 or 2, wherein B is -CH2-CH2-.

10. The nanostructure composition of claim 1 or 2, wherein X7 is C 1-10 Alkylene, and X8 is -C(=O)-O-.

11. The nanostructure composition of claim 1 or 2, wherein R 1A H is a, e is 1 to 20, a is 2, and c is 2.

12. The nanostructure composition of claim 1 or 2, wherein the nanostructure composition is soluble in a solvent selected from water, methanol, ethanol, acetone, methyl ethyl ketone, isopropanol, n-propanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, ethylene glycol, diethylene glycol, benzonitrile, cyclohexane, chloroform, ethyl acetate, methyl propylene glycol acetate, and dichloromethane.

13. A method for replacing a first ligand on a nanostructure with a second ligand, the method comprising mixing a reaction mixture comprising a group of nanostructures having a first ligand non-covalently bonded to the nanostructure and a second ligand being a polythiol ligand, such that the second ligand replaces the first ligand and becomes non-covalently bonded to the nanostructure, wherein the polythiol ligand has Formula I: in: CM is the central part, selected from alkanes, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, and (propane-2,2-dimethylbis(4,1-phenylene))bis(λ'-oxy); X1 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X2 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X3 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X4 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X5 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X6 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-; X7 is a key or C. 1-12 Alkylene; X8 is a key, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B Independently, it is H or C 1-20 alkyl; R 2 It is C 1-20 Alkyl or C 1-20 Alkoxy; a is 2 to 4; b is between 0 and 2; c is 2 to 4; d is between 0 and 2; e is from 1 to 20; and f is between 0 and 20; Where 6≥a+b+c+d≥4.

14. The method of claim 13, wherein the nanostructure comprises a core selected from InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP.

15. A nanostructured film, the nanostructured film comprising: (b) Nanostructures; (b) A polythiol ligand dispersed on the surface of the nanostructure, the polythiol ligand having formula I: in: CM is the central part, selected from alkanes, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, and (propane-2,2-dimethylbis(4,1-phenylene))bis(λ'-oxy); X1 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X2 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X3 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X4 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X5 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X6 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; B is -CH2-CH2-C(=O)-O-, -CH2-C(CH3)2-C(=O)-O-, -CH2-CH(CH3)-C(=O)-NH-, -C(=O)-NH-, -CH2-CH2- or -CH2-CH(OH)-CH2-O-; X7 is a key or C. 1-12 Alkylene; X8 is a key, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B Independently, it is H or C 1-20 alkyl; R 2 It is C 1-20 Alkyl or C 1-20 Alkoxy; a is 2 to 4; b is between 0 and 2; c is 2 to 4; d is between 0 and 2; e is from 1 to 20; and f is between 0 and 20; Where 6≥a+b+c+d≥4; and (c) At least one organic resin.

16. The nanostructured film of claim 15, wherein the nanostructured film exhibits a light conversion efficiency between 20% and 40%.

17. A method for preparing the polythiol ligand as claimed in claim 1, the method comprising reacting two substances: a polythiol of formula III: in: CM is the central part, selected from alkanes, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, and (propane-2,2-dimethylbis(4,1-phenylene))bis(λ'-oxy); X1 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X2 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X3 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X4 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X5 is a key, -C (=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; X6 is a key, -C(=O)-, C 1-10 Alkylene or C 2-10 Heteroalkyl; a is 2 to 4; and b is between 0 and 2; And where 6 ≥ a + b ≥ 4; Poly(epoxide) of formula V: in: FG is an acrylate group, a methacrylate group, an acrylamide group, an isocyanate group, an olefin group, or a glycidyl ether group; X7 is a key or C. 1-12 Alkylene; X8 is a key, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B Independently, it is H or C 1-20 alkyl; e is from 1 to 20; f is between 0 and 20; and R 2 It is C 1-20 Alkyl or C 1-20 Alkyl group.

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