Thermally stable polythiol ligands with pendant solubilizing moieties

Abstract

The present invention provides nanostructure compositions and methods for producing the nanostructure compositions. The nanostructure compositions include a population of nanostructures that include polythiol ligands with pendant moieties. The polythiol ligands with pendant moieties improve the solubility of the nanostructures in solvents and resins. The present invention also provides nanostructure films that include the nanostructure compositions and methods for making nanostructure films using the nanostructure compositions.

Description

[Technical Field]

[0001] The present invention provides nanostructure compositions and methods for producing the nanostructure compositions. The nanostructure compositions include a population of nanostructures that include polythiol ligands with pendant moieties. The polythiol ligands with pendant moieties improve the solubility of the nanostructures in solvents and resins. The present invention also provides nanostructure films that include the nanostructure compositions and methods for making nanostructure films using the nanostructure compositions. [Background technology]

[0002] A synthetic method that allows for the preparation of quantum dots with precise control over their properties provides nanocrystals whose surfaces are 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 nanocrystal surface with appropriate molecular ligands. For example, a series of poly(ethylene glycol)-based bidentate ligands have been produced that exhibit strong interactions with CdSe / ZnS (core / shell) quantum dots and gold nanoparticles, facilitating their dispersion in aqueous solutions. Bing, C.M., et al., Nature Protocols 4:412-423 (2009). However, Owen, J.S., et al., J. Am. Chem. Soc. 130(37):12279-12281 (2008) found that ligand exchange of octadecylphosphonate ligands with -S-(CH2CH2O)4OCH3 allowed thiols to be attached to the nanoparticle surface, but caused quenching of nanoparticle fluorescence.

[0003] Organic molecules bind to the inorganic surface of quantum dots to provide colloidal stability and also terminate the material's crystal lattice, reducing the number of surface trapping states caused by dangling bonds. As-synthesized quantum dots produced by the reaction of metal carboxylates (i.e., metal oleates, stearates, laurates, etc.) with chalcogenide precursors result in the formation of metal-rich quantum dot surfaces terminated primarily by metal carboxylate ligands. Additionally, in reactions utilizing primary alkyl thiols as sulfur precursors, unreacted thiol species can also serve as ligands.

[0004] The natural ligand sets for most quantum dots (including metal carboxylates, metal thiolates, and thiols) are hydrophobic and therefore inherently insoluble in a wide range of organic media. Surface ligand replacement is typically required to confer solubility in these media. Ligand exchange procedures have been performed using polyethylene glycol (PEG)-based polymeric ligands functionalized with either amines or carboxylic acids. For some quantum dots, amine-functionalized PEG-based polymeric ligands cannot be used because exposure to primary amines results in a severe loss of photoluminescence quantum yield. Ligand exchange with carboxylic acid-functionalized polymeric ligands results in some solubility in various resin formulations, but challenges remain regarding full-width-at-half-maximum (FWHM) broadening upon ligand exchange, reliability of QDEF products under high-flux test conditions, and initial fluctuations in emission intensity (i.e., burn-in). These concerns may be due to the fact that exposure to thiol functional groups present in many resin formulations can lead to the elimination of carboxylate groups and disruption of quantum dot colloidal stability.

[0005] Metal-thiolate bonds have been found to be stronger than both metal-carboxylate and metal-phosphonate bonds, and exposure to thiols or the corresponding deprotonated thiolates results in the displacement of carboxylate ligands from the surface as carboxylic acids. Furthermore, thiols can also bind to the nanocrystal surface as neutral L-shaped ligands, occupying sites left vacant by surface packing of metal-carboxylate ligands. Either mechanism—displacement of polymeric carboxylic acid ligands by multifunctional thiol molecules present in the resin formulation, or aggregation of multiple quantum dots—can lead to undesirable degradation of quantum dot optical properties.

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

[0007] Provided is a nanostructure composition comprising: (a) nanostructures; and (b) Polythiol ligands dispersed on the surface of the nanostructure. wherein the polythiol ligand comprises Formula I: [ka] [During the ceremony, CM is the central part; X1 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X2 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X3 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X4 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X5 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X6 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; 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 bond or C 1-12 is alkylene; X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B are independently H or C 1-20 is alkyl; R 2 is C 1-20 Alkyl, or C 1-20 It is an alkoxy. a is 2 to 10; b is 0 to 10; c is 2 to 10; d is 0 to 10; e is between 1 and 100; f is between 0 and 100; a+b+c+d≧3 The nanostructure composition has the following structure:

[0008] In some embodiments, the polythiol ligand has Formula II: [ka] [During the ceremony, CM is the central part; X1 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X2 is a bond, -C(=O)-, C 1-10Alkylene, or C 2-10 is heteroalkylene; X3 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; 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 bond or C 1-12 is alkylene; X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B are independently H or C 1-20 is alkylene; R 2 is C 1-20 Alkylene, or C 1-20 It is an alkoxy. a is 2 to 10; c is 2 to 10; e is between 1 and 100; f is between 0 and 100; a+c≧3 It has.

[0009] In some embodiments, CM is selected from the group consisting of an alkane, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, and (propane-2,2-diylbis(4,1-phenylene))bis(λ′-oxy).

[0010] In some embodiments, the nanostructure comprises a core selected from the group consisting of InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP.

[0011] In some embodiments, the nanostructure comprises at least one shell.

[0012] In some embodiments, X1, X2, and X3 are bonds.

[0013] In some embodiments, X1 is -C(=O)- and X2 is C 1-10 is alkylene, and X3 is a bond.

[0014] In some embodiments, X is C 2-10 heteroalkylene, X2 is —C(═O)—, and X3 is C 1-10 It is alkylene.

[0015] In some embodiments, X is substituted C 2-10 It is heteroalkylene, X2 is a bond, and X3 is a bond.

[0016] In some embodiments, B is —CH 2 —CH 2 —.

[0017] In some embodiments, X7 is C 1-10 It is alkylene, and X8 is -C(=O)-O-.

[0018] In some embodiments, R 1A is H, e is 1 to 100, a is 2, and c is 2.

[0019] In some embodiments, the nanostructure composition is soluble in a solvent selected from the group consisting of 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.

[0020] Also provided is a method of replacing a first ligand on a nanostructure with a second ligand, the method comprising combining a reaction mixture comprising a population of nanostructures having a first ligand non-covalently bound to the nanostructures with a second ligand, the second ligand being a polythiol ligand, such that the second ligand replaces the first ligand and becomes non-covalently bound to the nanostructures, the polythiol ligand having a structure represented by Formula I: [ka] [During the ceremony, CM is the central part; X1 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X2 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X3 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X4 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X5 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X6 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; 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 bond or C 1-12 is alkylene; X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1Bare independently H or C 1-20 is alkyl; R 2 is C 1-20 Alkyl, or C 1-20 It is an alkoxy. a is 2 to 10; b is 0 to 10; c is 2 to 10; d is 0 to 10; e is between 1 and 100; f is between 0 and 100; a+b+c+d≧3 The method has the following features:

[0021] In some embodiments, CM is selected from the group consisting of an alkane, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, and (propane-2,2-diylbis(4,1-phenylene))bis(λ′-oxy).

[0022] In some embodiments, the nanostructure comprises a core selected from the group consisting of InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP.

[0023] Also provided is a nanostructured film layer comprising: (a) Nanostructures; (b) a polythiol ligand dispersed on the surface of the nanostructure, the polythiol ligand having Formula I: [ka] [During the ceremony, CM is the central part; X1 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X2 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X3 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X4 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X5 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X6 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; 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 bond or C 1-12 is alkylene; X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B are independently H or C 1-20 is alkyl; R 2 is C 1-20 Alkyl, or C 1-20 It is an alkoxy. a is 2 to 10; b is 0 to 10; c is 2 to 10; d is 0 to 10; e is between 1 and 100; f is between 0 and 100; a+b+c+d≧3 the polythiol ligand having (c) at least one organic resin The nanostructure film layer comprises:

[0024] In some embodiments, CM is selected from the group consisting of an alkane, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, and (propane-2,2-diylbis(4,1-phenylene))bis(λ′-oxy).

[0025] In some embodiments, the nanostructure film layer exhibits a light conversion efficiency of about 20% to about 40%.

[0026] Also provided are polythiols of formula III: [ka] [During the ceremony, CM is the central part; X1 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X2 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X3 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X4 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X5 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X6 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; a is 2 to 10; b is 0 to 10; a+b≧3 with a poly(alkylene oxide) of formula V: [ka] [During the ceremony, FG is an acrylate group, a methacrylate group, an acrylamide group, an isocyanate group, an alkene group, or a glycidyl ether group; X7 is a bond or C 1-12 is alkylene; X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B are independently H or C 1-20 is alkyl; e is between 1 and 100; f is between 0 and 100; R 2 is C 1-20 Alkyl, or C 1-20 alkoxy] A method for preparing the polythiol ligand described above, comprising reacting

[0027] The accompanying drawings, which are incorporated in and form a part of this specification, illustrate the invention and, together with the description, serve to explain the principles of the invention and to enable one skilled in the art to make and use the invention. [Brief explanation of the drawings]

[0028] [Figure 1] 1 is a flow chart showing the ligand exchange procedure of Example 2. In the first step, the PETMP-PEG-480 ligand and quantum dots containing the native ligand are added to propylene glycol methyl ether acetate, which is then heated to 80° C. for 1 hour. In the second step, the solution is cooled to room temperature, and then heptane is added to precipitate the quantum dots. In the third step, the precipitate is centrifuged to produce a quantum dot pellet that can be redispersed in propylene glycol methyl ether acetate. [Figure 2] Schematic diagram of a base-catalyzed Michael addition reaction, where EWG is an electron-withdrawing group. DETAILED DESCRIPTION OF THE INVENTION

[0029] Unless otherwise defined, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The following definitions supplement those in the art and are directed to this application and should not be attributed to any related or unrelated matter, such as any commonly owned patent or application. Although any methods and materials similar or equivalent to those described herein can actually be used for testing, the preferred materials and methods are described herein. Therefore, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0030] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include the plural references unless the context clearly indicates otherwise. Thus, for example, reference to a "nanostructure" includes a plurality of such nanostructures.

[0031] As used herein, the term "about" indicates that a given quantity value varies by ±10% of the value. For example, "about 100 nm" encompasses a range of sizes from 90 nm to 110 nm, inclusive.

[0032] A "nanostructure" is a structure having at least one region or characteristic dimension that is less than about 500 nm. In some embodiments, nanostructures have dimensions that are less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm. The region or characteristic dimension will typically be along the shortest axis of the structure. Examples of such structures include nanowires, nanorods, nanotubes, branched nanostructures, nanotetrapods, tripods, bipods, nanocrystals, nanodots, quantum dots, nanoparticles, and the like. Nanostructures can be, for example, substantially crystalline, substantially monocrystalline, polycrystalline, amorphous, or a combination thereof. In some embodiments, each of the three dimensions of a nanostructure is 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.

[0033] The term "heterostructure" when used with respect to nanostructures refers to a nanostructure characterized by at least two different and / or distinguishable material species. Typically, one region of the nanostructure comprises a first material species, while another region of the nanostructure comprises a second material species. In certain embodiments, the nanostructure comprises a core of a first material and at least one shell of a second (or third, etc.) material, with the different material species distributed radially, for example, along the long axis of a nanowire, the long axes of the arms of a branched nanowire, or around the center of a nanocrystal. A shell may, but does not necessarily completely, coat adjacent materials to be considered a shell, or for a nanostructure to be considered a heterostructure; for example, a nanocrystal characterized by a core of one material coated with islands of another material is a heterostructure. In other embodiments, the different material species are distributed at different locations within the nanostructure, for example, along the long axis of a nanowire or the long axes of the arms of a branched nanowire. Within a heterostructure, different regions may comprise entirely different materials, or different regions may comprise a substrate (eg, silicon) with different dopants or different concentrations of the same dopant.

[0034] As used herein, the "diameter" of a nanostructure refers to the diameter of a cross section perpendicular to the first axis of the nanostructure, where the first axis is most different in length from the second and third axes (the second and third axes being the two axes most similar in length). The first axis is not necessarily the longest axis of the nanostructure; for example, in the case of a disk-shaped nanostructure, the cross section would be a substantially circular cross section perpendicular to the short longitudinal axis of the disk. If the cross section is not circular, the diameter is the average of the long and short axes of the cross section. In the case of elongated or high aspect ratio nanostructures, such as nanowires, the diameter is measured across a cross section perpendicular to the longest axis of the nanowire. In the case of spherical nanostructures, the diameter is measured from one side through the center of the sphere to the other side.

[0035] The terms "crystalline" or "substantially crystalline," when used with respect to nanostructures, refer to the fact that the nanostructures typically exhibit 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 a particular nanostructure, as the order of a single crystal may not extend beyond the boundaries of the crystal. In this case, "long-range order" will refer to substantial order across at least most of the dimensions of the nanostructure. In some cases, nanostructures may possess a coating, such as an oxide, or may be composed of a core and at least one shell. In such cases, it will be recognized that the oxide, shell(s), or other coating may, but need not, exhibit such order (e.g., it may be amorphous, polycrystalline, or otherwise). In such cases, the phrases "crystalline," "substantially crystalline," "substantially monocrystalline," or "monocrystalline" refer to the central core of the nanostructure (excluding any coating layers or shells). As used herein, the terms "crystalline" or "substantially crystalline" are intended to encompass structures containing various defects, stacking faults, atomic substitutions, and the like, so long as the structure exhibits substantial long-range order (e.g., order over at least about 80% of the length of at least one axis of the nanostructure or its core). In addition, it will be recognized that the interface between the core and the exterior of the nanostructure, or between the core and an adjacent shell, or between a shell and a second adjacent shell, may contain non-crystalline regions, or may even be amorphous. This does not prevent the nanostructure from being crystalline or substantially crystalline as defined herein.

[0036] The term "monocrystalline" when used in reference to a nanostructure indicates that the nanostructure is substantially crystalline and comprises substantially a single crystal. When used in reference to a nanostructure heterostructure comprising a core and one or more shells, "monocrystalline" indicates that the core is substantially crystalline and comprises substantially a single crystal.

[0037] A "nanocrystal" is a nanostructure that is substantially monocrystalline. Thus, a nanocrystal has at least one region or characteristic dimension that is less than about 500 nm in dimension. In some embodiments, a nanocrystal has a dimension less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 20 nm, or less than about 10 nm. The term "nanocrystal" is intended to encompass substantially monocrystalline nanostructures that contain various defects, stacking faults, atomic substitutions, and the like, as well as nanostructures that are substantially monocrystalline without such defects, 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 monocrystalline, but the shell(s) are not necessarily so. In some embodiments, each of the three dimensions of the nanocrystal is 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.

[0038] The term "quantum dot" (or "dot") refers to a nanocrystal that exhibits quantum or exciton confinement. Quantum dots can be substantially homogeneous in material properties, or in certain embodiments, can be heterogeneous, e.g., comprising a core and at least one shell. The optical properties of quantum dots can be affected by their particle size, chemical composition, and / or surface composition, and can be determined by suitable optical tests available in the art. The ability to tune nanocrystal diameters, e.g., in the range of about 1 nm to about 15 nm, allows for photoemission coverage across the entire optical spectrum, providing great versatility in color rendering.

[0039] A "ligand" is a molecule that can interact (whether weakly or strongly) with one or more crystalline faces of a nanostructure, for example, through covalent, ionic, van der Waals, or other molecular interactions with the surface of the nanostructure.

[0040] "Photoluminescence quantum yield" is the ratio of photons emitted to photons absorbed, for example, by a nanostructure or population of nanostructures. As known in the art, quantum yield is typically determined by comparative methods using well-characterized standards with known quantum yield values.

[0041] As used herein, the term "shell" refers to the material resulting from a single deposition of shell material onto a core or onto a previously deposited shell of the same or different composition. The exact shell thickness depends on the material, as well as the precursor input and conversion rate, and may be reported in nanometers or monolayers. As used herein, "target shell thickness" refers to the intended shell thickness used to calculate the amount of precursor required. As used herein, "actual shell thickness" refers to the amount of shell material actually deposited after synthesis and may be measured by methods known in the art. For example, actual shell thickness may be measured by comparing particle sizes determined by transmission electron microscope (TEM) images of nanocrystals before and after shell synthesis.

[0042] As used herein, the term "solubilizing group" refers to a substantially non-polar 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 chloride), chloroform, dimethylformamide, and N-methylpyrrolidone. In some embodiments, the solubilizing group is a long chain alkyl, long chain heteroalkyl, long chain alkenyl, long chain alkynyl, cycloalkyl, or aryl.

[0043] As used herein, the term "stable" refers to a mixture or composition that resists change or decomposition due to internal reaction or due to the action of air, heat, light, pressure, or other natural conditions.

[0044] As used herein, the term "full width at half maximum" (FWHM) is a measure of the particle 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 an idea of ​​the particle size distribution. A smaller FWHM corresponds to a narrower quantum dot nanocrystal size distribution. The FWHM also depends on the emission wavelength maximum.

[0045] As used herein, the term "functional group equivalent weight" (FGEW) is used to determine the proportion of reactive functional groups in a polymer. The FGEW of a polymer is defined as the ratio of the number average molecular weight (NAMW) to the number of functional groups (n) in the polymer. It is the weight of the polymer containing one formula weight of functional groups. FGEW is calculated by counting the number of reactive functional groups using end group analysis and dividing the number average molecular weight: FGEW=NAMW / n where n=number of reactive functional groups in the monomer.

[0046] As used herein, the term "polythiol" refers to a simple or complex organic compound containing at least two --SH groups per molecule.

[0047] As used herein, the term "alkane" refers to a saturated straight-chain, branched, or cyclic hydrocarbon having only single bonds. In some embodiments, an alkane contains 1 to 20 carbon atoms. In some embodiments, an alkane is ethane, propane, butane, pentane, hexane, heptane, octane, nonane, or decane. An alkane group may contain one or more substituents, such as hydroxyl, halogen, amino, nitro, C 1-20 Alkyl or C 1-20 It may be substituted with alkoxy.

[0048] As used herein, the term "alkene" refers to an unsaturated hydrocarbon containing one or more carbon-carbon double bonds. In some embodiments, the alkene contains 2 to 20 carbon atoms. In some embodiments, the alkene is ethene, propene, butene, pentene, hexene, heptene, octene, nonene, or decene. The alkene group may contain one or more substituents, such as hydroxyl, halogen, amino, nitro, C 1-20 Alkyl or C 1-20 It may be substituted with alkoxy.

[0049] As used herein, the term "alkyl" refers to a straight-chain or branched saturated aliphatic radical having the indicated number of carbon atoms. In some embodiments, alkyl is a C 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, C 1-9 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 It is an alkyl group. For example, C 1-6 Alkyl includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl. In some embodiments, alkyl is octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or icosanyl. Unless otherwise specified, the term "alkyl" can include "alkylene" groups.

[0050] As used herein, the term "heteroalkyl" refers to an alkyl moiety that is optionally substituted with one or more functional groups and contains one or more oxygen, sulfur, nitrogen, phosphorus, or silicon atoms, e.g., in place of carbon atoms.

[0051] As used herein, the term "cycloalkyl" refers to a monovalent or divalent group of 3 to 8 carbon atoms, preferably 3 to 5 carbon atoms, derived from a saturated cyclic hydrocarbon. Cycloalkyl groups can be monocyclic or polycyclic. Cycloalkyl refers to any group selected from the group consisting of C 1-3 It may be substituted with an alkyl group or a halogen.

[0052] As used herein, the term "alkylene" refers to a saturated aliphatic group derived from a straight or branched chain saturated hydrocarbon having from 1 to about 20 carbon atoms and attached at two or more positions. In some embodiments, alkylene is a 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 C 18-20 Alkylene. For example, C 1-6Alkylene includes, but is not limited to, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, tert-butylene, pentylene, isopentylene, and hexylene. In some embodiments, alkylene is octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, or icosanylene. The alkylene group may have one or more substituents, such as hydroxyl, halogen, amino, nitro, C 1-20 Alkyl or C 1-20 It may be substituted with alkoxy.

[0053] As used herein, the term "heteroalkylene" refers to an alkylene group in which one or more carbon atoms in the backbone are replaced by heteroatoms such as oxygen, nitrogen, phosphorus, silicon, and sulfur, including, for example, oligomeric ethylene glycol moieties. Heteroalkylene groups may contain one or more substituents, such as hydroxyl, halogen, amino, nitro, C 1-20 Alkyl or C 1-20 It may be substituted with alkoxy.

[0054] As used herein, the term "amino" refers to --NH.sub.2.

[0055] As used herein, the term "alkylamino" refers to a group of the formula (-NR K 2) "substituted amino" and R in the formula K are independently hydrogen or an optionally substituted alkyl group as defined herein, and the nitrogen moiety is directly attached to the parent molecule.

[0056] As used herein, the term "halo" or "halogen" refers to F, Cl, Br, or I.

[0057] As used herein, the term "alkoxy" refers to a straight or branched chain -O-alkyl group having 1 to 20 carbon atoms. In some embodiments, alkoxy is 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, C 14-20 Alkoxy, C 16-20 Alkoxy or C 18-20 In some embodiments, the alkoxy is methoxy, ethoxy, n-propoxy, isopropoxy, or t-butoxy.

[0058] As used herein, the term "acrylate" or "acrylate group" refers to a compound possessing at least one moiety having the structure -OC(=O)-CH=CH2. In some embodiments, the acrylate is a methacrylate.

[0059] As used herein, the term "methacrylate" or "methacrylate group" refers to a compound possessing at least one moiety having the structure -OC(=O)-C(CH3)=CH2.

[0060] As used herein, the term "acrylamide" or "acrylamide group" refers to a compound possessing at least one moiety having the structure -NH-C(=O)-CH=CH2. In some embodiments, the acrylamide is methacrylamide.

[0061] As used herein, the term "methacrylamide" or "methacrylamide group" refers to a compound possessing at least one moiety having the structure -NH-C(=O)-C(CH3)=CH2.

[0062] As used herein, the term "glycidyl ether" or "glycidyl ether group" refers to a group having the structure [ka] refers to a compound having at least one moiety having the formula:

[0063] As used herein, the term "isocyanate" or "isocyanato group" refers to a compound that possesses at least one moiety with the structure --N.dbd.C.dbd.O.

[0064] Unless expressly stated otherwise, ranges recited herein include the endpoints.

[0065] Various other terms are defined or characterized throughout this specification.

[0066] Nanostructure composition In some embodiments, the present invention provides a nanostructure composition comprising: (a) nanostructures; and (b) a polythiol ligand attached to the surface of the nanostructure, the polythiol ligand comprising a poly(ethylene oxide) / poly(propylene oxide) block copolymer, a poly(ethylene oxide) block copolymer, or a poly(propylene oxide) block copolymer. The nanostructure composition comprises:

[0067] In some embodiments, the present invention provides a nanostructure composition comprising: (a) nanostructures; and (b) Polythiol ligands dispersed on the surface of the nanostructure. wherein the polythiol ligand comprises Formula I: [ka] [During the ceremony, CM is the central part; X1 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X2 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X3 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X4 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X5 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X6 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; 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 bond or C 1-12 is alkylene; X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B are independently H or C 1-20 is alkyl; R 2 is C 1-20 Alkyl, or C 1-20 It is an alkoxy. a is 2 to 10; b is 0 to 10; c is 2 to 10; d is 0 to 10; e is between 1 and 100; f is between 0 and 100; a+b+c+d≧3 The nanostructure composition has:

[0068] In some embodiments, the present invention provides a nanostructure composition comprising: (a) nanostructures; and (b) Polythiol ligands dispersed on the surface of the nanostructure. wherein the polythiol ligand comprises Formula II: [ka] [During the ceremony, CM is the central part; X1 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X2 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X3 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; 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 bond or C 1-12 is alkylene; X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B are independently H or C 1-20 is alkyl; R 2 is C 1-20 Alkyl, or C 1-20 It is an alkoxy. a is 2 to 10; c is 2 to 10; e is between 1 and 100; f is between 0 and 100; a+c≧3 The nanostructure composition has:

[0069] In some embodiments, the present invention provides a nanostructure composition comprising: (a) at least one population of nanostructures, wherein about 20 to about 100 mole percent of the ligands in the at least one population of nanostructures comprise polythiol ligands bound to the nanostructures; and (b) at least one organic resin The nanostructure composition comprises:

[0070] In some embodiments, the nanostructure composition further comprises a solvent, hi some embodiments, the nanostructure composition further comprises a polar organic solvent.

[0071] In some embodiments, the nanostructures are quantum dots.

[0072] In some embodiments, the present invention provides a nanostructure film kit comprising: (a) a first composition comprising at least one population of nanostructures, wherein about 20 to about 100 mole percent of the ligands in the at least one population of nanostructures comprise polythiol ligands bound to the nanostructures; (b) a second composition comprising at least one organic resin; and (c) Instructions for fabricating nanostructured films The nanostructure film kit includes:

[0073] In some embodiments, the nanostructure film kit further comprises a solvent. In some embodiments, the nanostructure film kit further comprises a polar organic solvent.

[0074] In some embodiments, the nanostructures are quantum dots.

[0075] Nanostructured Film Layer In some embodiments, the present invention provides a nanostructure film layer comprising: (a) at least one population of nanostructures, wherein about 20 to about 100 mole percent of the ligands in the at least one population of nanostructures comprise polythiol ligands bound to the nanostructures; and (b) at least one organic resin The present invention provides a nanostructure film layer comprising:

[0076] In some embodiments, the nanostructures are quantum dots.

[0077] Nanostructured molded products In some embodiments, the present invention provides a nanostructured article, comprising: (a) at least one population of nanostructures, wherein about 20 to about 100 mole percent of the ligands in the at least one population of nanostructures comprise polythiol ligands bound to the nanostructures; and (b) at least one organic resin The nanostructure molded article includes:

[0078] In some embodiments, the molded article is a film, a display substrate, or a light emitting diode.

[0079] In some embodiments, the nanostructures are quantum dots.

[0080] In some embodiments, the present invention provides a nanostructure film comprising: (a) First barrier layer; (b) a second barrier layer; and (c) a nanostructure layer between the first and second barrier layers, the nanostructure layer comprising: at least one population of nanostructures, wherein about 20 to about 100 mole percent of the ligands in the at least one population of nanostructures comprise polythiol ligands bound to the nanostructures; and at least one organic resin. The nanostructure film includes:

[0081] In some embodiments, the nanostructures are quantum dots.

[0082] nanostructures 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.

[0083] The number of monolayers will dictate the size of the core / shell(s) nanostructure. The size of the core / shell(s) nanostructure can be determined using techniques known to those skilled in the art. In some embodiments, the size of the core / shell(s) nanostructure is determined using TEM. In some embodiments, the core / shell(s) nanostructures have a size of about 1 nm to about 15 nm, about 1 nm to about 10 nm, about 1 nm to about 9 nm, about 1 nm to about 8 nm, about 1 nm to about 7 nm, about 1 nm to about 6 nm, about 1 nm to about 5 nm, about 5 nm to about 15 nm, about 5 nm to about 10 nm, about 5 nm to about 9 nm, about 5 nm to about 8 nm, about 5 nm to about 7 nm, about 5 nm to about 6 nm, about 6 nm In some embodiments, the core / shell(s) nanostructure(s) have an average diameter of about 6 nm to about 7 nm.

[0084] Nanostructure Core In some embodiments, 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, SiN, GeN, AlO, AlOC, or a combination thereof.

[0085] In some embodiments, the core is a III-V nanostructure. In some embodiments, the core is a III-V nanocrystal selected from the group consisting of BN, BP, BAs, BSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb. In some embodiments, the core is an InP nanocrystal.

[0086] The synthesis of Group III-V nanostructures is 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, and U.S. Patent Application Publication No. 2015 / 236195. Synthesis of Group III-V nanostructures is also described in Wells, R.L., et al., "The use of tris(trimethylsilyl)arsine to prepare gallium arsenide and indium arsenide," Chem. Mater. 1:4-6 (1989), and Guzelian, A.A., et al., "Colloidal chemical synthesis and characterization of InAs nanocrystal quantum dots," Appl. Phys. Lett. 69:1432-1434 (1996).

[0087] Regarding the synthesis of InP-based nanostructures, 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, O. I., et al., “Core-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 X. Peng, “Formation of high quality InP and InAs nanocrystals in a noncoordinating solvent,” Nano Letters 2: 1027-1030 (2002), Kim, S., et al., “Highly luminescent 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: A nanophotocathode for hydrogen 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)、CrosGagneux,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 GaInP2quantum 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 a non-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 had limited success in producing InP nanostructures with high quantum yields.

[0088] In some embodiments, the core is doped. In some embodiments, the dopant of the nanocrystalline core comprises a metal, including one or more transition metals. In some embodiments, the dopant is a transition metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and combinations thereof. In some embodiments, the dopant comprises a non-metal. In some embodiments, the dopant is ZnS, ZnSe, ZnTe, CdSe, CdS, CdTe, HgS, HgSe, HgTe, CuInS2, CuInSe2, AlN, AlP, AlAs, GaN, GaP, or GaAs.

[0089] In some embodiments, the core is a II-VI nanocrystal selected from the group consisting of ZnO, ZnSe, ZnS, ZnTe, CdO, CdSe, CdS, CdTe, HgO, HgSe, HgS, and HgTe. In some embodiments, the core is a nanocrystal selected from the group consisting of ZnSe, ZnS, CdSe, and CdS. The synthesis of Group II-VI nanostructures is 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 Publication Nos. 2011 / 0262752 and 2011 / 0263062.

[0090] In some embodiments, the cores are purified before depositing the shell, hi some embodiments, the cores are filtered to remove precipitates from the core solution.

[0091] In some embodiments, the core is subjected to an acid etching step before the shell is deposited.

[0092] In some embodiments, the core diameter is determined using quantum confinement. Quantum confinement in zero-dimensional nanocrystallites, such as quantum dots, arises from the spatial confinement of electrons within the crystallite boundaries. Quantum confinement can be observed when the diameter of a material is on the same scale as the de Broglie wavelength of the wave function. The electronic and optical properties of nanoparticles deviate significantly from those of bulk materials. When the confinement dimension is large compared to the wavelength of the particle, the particle behaves as if it were a free particle. During this state, the band gap remains at its original energy because the energy states are continuous. However, as the confinement dimension decreases to a certain limit, typically the nanoscale, the energy spectrum becomes discrete. As a result, the band gap becomes size-dependent. Size can be determined as known in the art, for example, using transmission electron microscopy and / or physical modeling.

[0093] In some embodiments, the diameter of the core nanostructure is from about 1 nm to about 9 nm, from about 1 nm to about 8 nm, from about 1 nm to about 7 nm, from about 1 nm to about 6 nm, from about 1 nm to about 5 nm, from about 1 nm to about 4 nm, from about 1 nm to about 3 nm, from about 1 nm to about 2 nm, from about 2 nm to about 9 nm, from about 2 nm to about 8 nm, from about 2 nm to about 7 nm, from about 2 nm to about 6 nm, from about 2 nm to about 5 nm, from about 2 nm to about 4 nm, from about 2 nm to about 3 nm, from about 3 nm to about 9 nm, from about 3 nm to about 8 nm, 3 nm to about 7 nm, about 3 nm to about 6 nm, about 3 nm to about 5 nm, about 3 nm to about 4 nm, about 4 nm to about 9 nm, about 4 nm to about 8 nm, about 4 nm to about 7 nm, about 4 nm to about 6 nm, about 4 nm to about 5 nm, about 5 nm to about 9 nm, about 5 nm to about 8 nm, about 5 nm to about 7 nm, about 5 nm to about 6 nm, about 6 nm to about 9 nm, about 6 nm to about 8 nm, about 6 nm to about 7 nm, about 7 nm to about 9 nm, about 7 nm to about 8 nm, or about 8 nm to about 9 nm. In some embodiments, the diameter of the core nanostructure is about 7 nm.

[0094] Nanostructure shell layer The shell may, 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 shell material.

[0095] In some embodiments, a shell comprising a mixture of Group II and Group VI elements is deposited on the core or on the core / shell(s). 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 comprised 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, sulfur and selenium; or cadmium, zinc, sulfur and selenium.

[0096] 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 an alloy 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.

[0097] In some embodiments, the shell comprises more than one monolayer of shell material. The number of monolayers is an average across all nanostructures; therefore, the number of monolayers in a shell can be small. In some embodiments, the number of monolayers in a shell is 0.25-10, 0.25-8, 0.25-7, 0.25-6, 0.25-5, 0.25-4, 0.25-3, 0.25-2, 2-10, 2-8, 2-7, 2-6, 2-5, 2-4, 2-3, 3-10, 3-8, 3-7, 3-6, 3-5, 3-4, 4-10, 4-8, 4-7, 4-6, 4-5, 5-10, 5-8, 5-7, 5-6, 6-10, 6-8, 6-7, 7-10, 7-8, or 8-10. In some embodiments, the shell comprises 3-5 monolayers.

[0098] 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 nanostructures before and after the addition of each shell. In some embodiments, the average diameter of the nanostructures before and after the addition of each shell is determined by TEM.

[0099] In some embodiments, each shell has a diameter of about 0.05 nm to about 3.5 nm, about 0.05 nm to about 2 nm, about 0.05 nm to about 0.9 nm, about 0.05 nm to about 0.7 nm, about 0.05 nm to about 0.5 nm, about 0.05 nm to about 0.3 nm, about 0.05 nm to about 0.1 nm, about 0.1 nm to about 3.5 nm, about 0.1 nm to about 2 nm, about 0.1 nm to about 0.9 nm, about 0.1 nm to about 0.7 nm, about 0.1 nm to about 0.5 nm, about 0.1 nm to about 0.3 nm, or about 0. The thickness is 3 nm to about 3.5 nm, about 0.3 nm to about 2 nm, about 0.3 nm to about 0.9 nm, about 0.3 nm to about 0.7 nm, about 0.3 nm to about 0.5 nm, about 0.5 nm to about 3.5 nm, about 0.5 nm to about 2 nm, about 0.5 nm to about 0.9 nm, about 0.5 nm to about 0.7 nm, about 0.7 nm to about 3.5 nm, about 0.7 nm to about 2 nm, about 0.7 nm to about 0.9 nm, about 0.9 nm to about 3.5 nm, about 0.9 nm to about 2 nm, or about 2 nm to about 3.5 nm.

[0100] Ligand exchange The present disclosure relates to methods of 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.

[0101] In some embodiments, the present disclosure relates to a method for replacing a first ligand on a nanostructure with a second ligand, the method comprising combining a reaction mixture comprising a population of nanostructures having a first ligand bound to the nanostructure with at least one second ligand, such that the second ligand replaces the first ligand and binds to the nanostructure.

[0102] In some embodiments, the nanostructures are quantum dots.

[0103] In some embodiments, the blending is carried out at a temperature of about 0°C to about 200°C, about 0°C to about 150°C, about 0°C to about 100°C, about 0°C to about 80°C, about 20°C to about 200°C, about 20°C to about 150°C, about 20°C to about 100°C, about 20°C to about 80°C, about 50°C to about 200°C, about 50°C to about 150°C, about 50°C to about 100°C, about 50°C to about 80°C, about 80°C to about 200°C, about 80°C to about 150°C, about 80°C to about 100°C, about 100°C to about 200°C, about 100°C to about 150°C, or about 150°C to about 200°C. In some embodiments, the blending is carried out at a temperature of about 20°C to about 100°C. In some embodiments, the blending is carried out at a temperature of about 22°C. In some embodiments, the blending is carried out at a temperature of about 70°C.

[0104] In some embodiments, the blending may be from about 1 minute to about 6 hours, from about 1 minute to about 2 hours, from about 1 minute to about 1 hour, from about 1 minute to about 40 minutes, from about 1 minute to about 30 minutes, from about 1 minute to about 20 minutes, from about 1 minute to about 10 minutes, from about 10 minutes to about 6 hours, from about 10 minutes to about 2 hours, from about 10 minutes to about 1 hour, from about 10 minutes to about 40 minutes, from about 10 minutes to about 30 minutes, from about 10 minutes to about 20 minutes, or from about 20 minutes to about 6 hours. The treatment is carried out over a period of about 1 hour, about 20 minutes to about 2 hours, about 20 minutes to about 1 hour, about 20 minutes to about 40 minutes, about 20 minutes to about 30 minutes, about 30 minutes to about 6 hours, about 30 minutes to about 2 hours, about 30 minutes to about 1 hour, about 30 minutes to about 40 minutes, about 40 minutes to about 6 hours, about 40 minutes to about 2 hours, about 40 minutes to about 1 hour, about 1 hour to about 6 hours, about 1 hour to about 2 hours, or about 2 hours to about 6 hours.

[0105] In some embodiments, the reaction mixture further comprises a solvent. In some embodiments, the solvent is selected from the group consisting of 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, monomethyl ether glycol esters, gamma-butyrolactone, methyl acetate-3-ethyl ether, butyl carbitol, butyl carbitol acetate, propanediol monomethyl ether, propanediol acetate monomethyl ether, cyclohexane, toluene, xylene, isopropyl alcohol, 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.

[0106] The percentage of second ligands bound to nanostructures in a population of nanostructures is 1 The amount of bound secondary ligand can be measured by 1 H NMR and the amount of bound secondary ligand is calculated using (bound secondary ligand) / (bound+free secondary ligand).

[0107] In some embodiments, the molar percentage of second ligands bound to the population of nanostructures 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%.

[0108] First Ligand In some embodiments, each shell is synthesized in the presence of at least one nanostructure ligand. The ligand may, for example, enhance the miscibility of the nanostructures in the solvent or polymer (allowing the nanostructures to be distributed throughout the composition so that they do not clump together), improve the quantum yield of the nanostructures, and / or maintain nanostructure emission (e.g., when the nanostructures are incorporated into a matrix). In some embodiments, the ligand(s) for core synthesis and shell synthesis are the same. In some embodiments, the ligand(s) for core synthesis and shell synthesis are different. After synthesis, any ligands on the surface of the nanostructures can be exchanged for different ligands with other desirable 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.

[0109] In some embodiments, the first ligand is a fatty acid selected from the group consisting of lauric acid, caproic acid, myristic acid, palmitic acid, stearic acid, and oleic acid. In some embodiments, the first ligand is an organophosphine or organophosphine oxide selected from trioctylphosphine oxide, trioctylphosphine, diphenylphosphine, triphenylphosphine oxide, and tributylphosphine oxide. In some embodiments, the first ligand is an amine selected from the group consisting of dodecylamine, oleylamine, hexadecylamine, dioctylamine, and octadecylamine. In some embodiments, the first ligand is selected from the group consisting of trioctylphosphine, trioctylphosphine oxide, trihydroxypropylphosphine, tributylphosphine, tridodecylphosphine, dibutyl phosphite, tributyl phosphite, octadecyl phosphite, trilauryl phosphite, didodecyl phosphite, triisodocyl phosphite, bis(2-ethylhexyl) phosphate, tridecyl phosphate, hexadecylamine, oleylamine, octadecylamine, dioctadecylamine, octacosamine, bis(2-ethylhexyl)amine, octylamine, dioctylamine, trioctylamine, dodecylamine, didodecylamine, hexadecylamine, phenyl phosphoric acid, hexylphosphoric acid, tetradecylphosphonic acid, octyl phosphoric acid, acid), n-octadecylphosphonic acid, propenyldiphosphonic acid, dioctyl ether, diphenyl ether, octyl mercaptan, dodecyl mercaptan, oleate, or octanethiol. In some embodiments, the first ligand is oleate, trioctylphosphine, or octanethiol.

[0110] Secondary Ligand In some embodiments, the second ligand is a polythiol ligand comprising at least one -SH group. In some embodiments, the at least one -SH group may be attached to the II-VI nanocrystal surface as a neutral L-type binding ligand (e.g., R-COOH). In some embodiments, the at least one -SH group may be attached to the II-VI nanocrystal surface as an electron-donating X-type ligand (e.g., R-COOH). - ) can be attached to the surface of II-VI nanocrystals.

[0111] In some embodiments, the polythiol ligand is prepared by reacting a polythiol with a poly(alkylene oxide) compound containing an acrylate group, a methacrylate group, an acrylamide group, an isocyanate group, an alkene group, or a glycidyl ether group to produce the polythiol ligand.

[0112] Polythiol In some embodiments, the polythiol has Formula III: [ka] [During the ceremony, CM is the central part; X1 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X2 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X3 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X4 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X5 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X6 is a bond, -C(=O)-, C 1-10 Alkylene, or C2-10 is heteroalkylene; a is 2 to 10; b is 0 to 10; a+b≧3 It has.

[0113] In some embodiments, when b in Formula III is 0, the polythiol has Formula IV: [ka] [During the ceremony, CM is the central part; X1 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X2 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X3 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; a is 3 to 10. It has.

[0114] In some embodiments, CM is an alkene, 1,3,5-triazine, pentaerythritol, 1,3,5-triazine-2,4,6-trione, trimethylolpropane, or (propane-2,2-diylbis(4,1-phenylene))bis(λ'-oxy). In some embodiments, CM is propane.

[0115] In some embodiments, X is a bond. In some embodiments, X is -C(=O)-. In some embodiments, X is a substituted or unsubstituted C 1-10 In some embodiments, X is an unsubstituted C 1-10 In some embodiments, X is substituted C 1-10 In some embodiments, X is substituted or unsubstituted C 1-10In some embodiments, X is an unsubstituted C 1-10 In some embodiments, X is a substituted C 1-10 In some embodiments, the substituent on X is -SH.

[0116] In some embodiments, X2 is a bond. In some embodiments, X2 is -C(=O)-. In some embodiments, X2 is a substituted or unsubstituted C 1-10 In some embodiments, X2 is an unsubstituted C 1-10 In some embodiments, X2 is a substituted C 1-10 In some embodiments, X2 is substituted or unsubstituted C 1-10 In some embodiments, X2 is an unsubstituted C 1-10 In some embodiments, X2 is a substituted C 1-10 In some embodiments, the substituent on X2 is -SH.

[0117] In some embodiments, X3 is a bond. In some embodiments, X3 is -C(=O)-. In some embodiments, X3 is a substituted or unsubstituted C 1-10 In some embodiments, X is an unsubstituted C 1-10 In some embodiments, X is a substituted C 1-10 In some embodiments, X is substituted or unsubstituted C 1-10 In some embodiments, X is an unsubstituted C 1-10 In some embodiments, X is a substituted C 1-10 In some embodiments, the substituent on X3 is -SH.

[0118] In some embodiments, X4 is a bond. In some embodiments, X4 is -C(=O)-. In some embodiments, X4 is a substituted or unsubstituted C1-10 In some embodiments, X4 is an unsubstituted C 1-10 In some embodiments, X4 is a substituted C 1-10 In some embodiments, X4 is substituted or unsubstituted C 1-10 In some embodiments, X4 is an unsubstituted C 1-10 In some embodiments, X4 is a substituted C 1-10 In some embodiments, the substituent on X4 is -SH.

[0119] In some embodiments, X5 is a bond. In some embodiments, X5 is -C(=O)-. In some embodiments, X5 is a substituted or unsubstituted C 1-10 In some embodiments, X5 is an unsubstituted C 1-10 In some embodiments, X5 is a substituted C 1-10 In some embodiments, X5 is substituted or unsubstituted C 1-10 In some embodiments, X5 is an unsubstituted C 1-10 In some embodiments, X5 is a substituted C 1-10 In some embodiments, the substituent on X5 is -SH.

[0120] In some embodiments, X6 is a bond. In some embodiments, X6 is -C(=O)-. In some embodiments, X6 is a substituted or unsubstituted C 1-10 In some embodiments, X6 is an unsubstituted C 1-10 In some embodiments, X6 is a substituted C 1-10 In some embodiments, X6 is substituted or unsubstituted C 1-10 In some embodiments, X6 is an unsubstituted C 1-10 In some embodiments, X6 is a substituted C 1-10In some embodiments, the substituent on X6 is -SH.

[0121] In some embodiments, a is 2 to 10. In some embodiments, a is 3 to 10. In some embodiments, a is 2 to 10, 2 to 8, 2 to 6, 2 to 4, 2 to 3, 3 to 10, 3 to 8, 3 to 6, 3 to 4, 4 to 10, 4 to 8, 4 to 6, 6 to 10, 6 to 8, or 8 to 10.

[0122] In some embodiments, b is 0 to 10. In some embodiments, b is 0 to 10, 0 to 8, 0 to 6, 0 to 4, 3 to 10, 3 to 8, 3 to 6, 6 to 10, 6 to 8, or 8 to 10. In some embodiments, b is 0.

[0123] In some embodiments, X 1 , X 2 and X 3 are bonds and b is 0.

[0124] In some embodiments, X1 is -C(=O)- and X2 is an unsubstituted C 1-10 It is alkylene and b is 0.

[0125] In some embodiments, X1 is -C(=O)- and X2 is a branched unsubstituted C 1-10 It is alkylene, X3 is a bond, and b is 0.

[0126] In some embodiments, X is C 1-10 heteroalkylene, X2 is —C(═O)—, and X3 is an unsubstituted C 1-10 It is alkylene and b is 0.

[0127] In some embodiments, X1 is a substituted C 1-10 It is heteroalkylene and b is 0.

[0128] In some embodiments, X is C 1-10 alkylene, X2 is —C(═O)—, and X3 is an unsubstituted C 1-10It is alkylene, a is 2, and b is 1.

[0129] In some embodiments, the polythiol is a commercially available polythiol.

[0130] In some embodiments, the polythiol is [Table 1-1] [Table 1-2] [Table 1-3] is selected from the group consisting of:

[0131] Poly(alkylene oxide) In some embodiments, the poly(alkylene oxide) comprises at least one functional group attached to the poly(alkylene oxide) backbone. In some embodiments, the poly(alkylene oxide) is a poly(alkylene oxide) comprising one functional group attached to the poly(alkylene oxide) backbone.

[0132] In some embodiments, at least one functional group is an acrylate group, a methacrylate group, an acrylamide group, an isocyanate group, an alkene group, or a glycidyl ether group.

[0133] In some embodiments, the poly(alkylene oxide) is a mixture of functionally terminated poly(alkylene oxide), copolymers of alkylene oxide, and combinations thereof. In some embodiments, the functionally terminated poly(alkylene oxide) comprises a copolymer of alkylene oxide. 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.

[0134] In some embodiments, the poly(alkylene oxide) comprises a random copolymer of ethylene oxide and propylene oxide, a poly(ethylene oxide)-poly(propylene oxide) diblock copolymer, a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer, a poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) triblock copolymer, or a combination thereof.

[0135] In some embodiments, the poly(alkylene oxide) comprises a copolymer of PO and EO. In some embodiments, the ratio of ethylene oxide groups to propylene oxide groups is high enough so that the poly(alkylene oxide) ligand has a high degree of hydrophilicity. In some embodiments, the ratio of ethylene oxide groups to propylene oxide groups is low enough so that the ligand has a desired elasticity. In some embodiments, the ratio of ethylene oxide groups to propylene oxide groups is about 15:1 to about 1:15, about 15:1 to about 1:10, about 15:1 to about 1:5, about 10:1 to 1:15, about 10:1 to 1:10, about 10:1 to 1:5, about 5:1 to 1:15, about 5:1 to 1:10, or about 5:1 to 1:5.

[0136] In some embodiments, the poly(alkylene oxide) has the structure of Formula V: [ka] [During the ceremony, FG is an acrylate group, a methacrylate group, an acrylamide group, an isocyanate group, an alkene group, or a glycidyl ether group; X7 is a bond or C 1-12 is alkylene; X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B are independently H or C 1-20 is alkyl; e is between 1 and 100; f is between 0 and 100; R 2 is C 1-20 Alkyl, or C 1-20 alkoxy] It has.

[0137] 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 alkene 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=CH2. In some embodiments, FG is -N=C=O. In some embodiments, FG is -CH=CH2. In some embodiments, FG is [ka] is.

[0138] In some embodiments, X7 is a bond. In some embodiments, X7 is C 1-12 It is alkylene.

[0139] 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 amide.

[0140] In some embodiments, R 1A is H. In some embodiments, R 1A is C 1-20 In some embodiments, R 1A is C 1-10 In some embodiments, R 1A is C 1-5 In some embodiments, R 1A is -CH3.

[0141] In some embodiments, R 1B is H. In some embodiments, R 1B is C 1-20 In some embodiments, R 1B is C 1-10 In some embodiments, R 1B is C 1-5 In some embodiments, R 1B is -CH3.

[0142] In some embodiments, R 1A is H and R 1B is -CH3. In some embodiments, R 1A is -CH3 and R 1B is H. In some embodiments, R 1A is H and R 1B is H. In some embodiments, R 1A is -CH3 and R 1B is -CH3.

[0143] 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.

[0144] The value of e should be understood to be modified by the word "about." Thus, a value of e=1 is understood to mean e=1±0.1. For example, a value of e=1 is understood to mean 0.9 to 1.1.

[0145] 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.

[0146] The value of f should be understood to be modified by the word "about." Therefore, a value of f=1 is understood to mean f=1±0.1. For example, a value of f=1 is understood to mean 0.9 to 1.1.

[0147] In some embodiments, the ratio of e to f is about 15:1 to about 1:15, about 15:1 to about 1:10, about 15:1 to about 1:5, about 10:1 to about 1:15, about 10:1 to about 1:10, about 10:1 to about 1:5, about 5:1 to about 1:15, about 5:1 to about 1:10, or about 5:1 to about 1:5.

[0148] In some embodiments, R 2 is C 1-20 In some embodiments, R 2 is C 1-10 In some embodiments, R 2 is C 1-5 In some embodiments, R 2 is -CH2CH3.

[0149] In some embodiments where FG is —OC(═O)—CH═CH and X7 and X8 are bonds in Formula V, the poly(alkylene oxide) has the structure of Formula VI: [ka] [During the ceremony, R 1A and R 1B are independently H or C 1-20 is alkyl; e is between 1 and 100; f is between 0 and 100; R 2 is C 1-20 Alkyl, or C 1-20 alkoxy] It has.

[0150] 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, 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.

[0151] 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 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.

[0152] In some embodiments, the ratio of e to f is about 15:1 to about 1:15, about 15:1 to about 1:10, about 15:1 to about 1:5, about 10:1 to 1:15, about 10:1 to 1:10, about 10:1 to 1:5, about 5:1 to 1:15, about 5:1 to 1:10, or about 5:1 to 1:5.

[0153] In some embodiments, R 1A is H. In some embodiments, R 1A is C 1-20 In some embodiments, R 1A is C 1-10 In some embodiments, R 1A is C 1-5 In some embodiments, R 1A is -CH3.

[0154] In some embodiments, R 1B is H. In some embodiments, R 1B is C 1-20 In some embodiments, R 1B is C 1-10 In some embodiments, R 1B is C 1-5 In some embodiments, R 1B is -CH3.

[0155] In some embodiments, R 2 is C 1-20 In some embodiments, R 2 is C 1-10 In some embodiments, R 2 is C 1-5 In some embodiments, R 2 is -CH2CH3. In some embodiments, R 2 is -CH3.

[0156] In Formula V, FG is —OC(═O)—CH═CH, X and X are bonds, f is 0, and R 2In some embodiments, where is —CH3, the poly(alkylene oxide) has the structure of Formula VII: [ka] [During the ceremony, R 1A is H or C 1-20 is alkyl; e is 1 to 100. It has.

[0157] In some embodiments, R 1A is H. In some embodiments, R 1A is C 1-20 In some embodiments, R 1A is C 1-10 In some embodiments, R 1A is C 1-5 In some embodiments, R 1A is -CH3.

[0158] 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.

[0159] Polythiol Ligands In some embodiments, the polythiol ligand has Formula I: [ka] [During the ceremony, CM is the central part; X1 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X2 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X3 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X4 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X5 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X6 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; 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 bond or C 1-12 is alkylene; X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B are independently H or C 1-20 is alkyl; R 2 is C 1-20 Alkyl, or C 1-20 It is an alkoxy. a is 2 to 10; b is 0 to 10; c is 2 to 10; d is 0 to 10; e is between 1 and 100; f is between 0 and 100; a+b+c+d≧3 It has.

[0160] 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-diylbis(4,1-phenylene))bis(λ'-oxy). In some embodiments, CM is propane.

[0161] In some embodiments, X is a bond. In some embodiments, X is -C(=O)-. In some embodiments, X is a substituted or unsubstituted C 1-10 In some embodiments, X is an unsubstituted C 1-10 In some embodiments, X is substituted C 1-10 In some embodiments, X is substituted or unsubstituted C 1-10 In some embodiments, X is an unsubstituted C 1-10 In some embodiments, X is a substituted C 1-10 In some embodiments, the substituent on X is -SH.

[0162] In some embodiments, X2 is a bond. In some embodiments, X2 is -C(=O)-. In some embodiments, X2 is a substituted or unsubstituted C 1-10 In some embodiments, X2 is an unsubstituted C 1-10 In some embodiments, X2 is a substituted C 1-10 In some embodiments, X2 is substituted or unsubstituted C 1-10 In some embodiments, X2 is an unsubstituted C 1-10 In some embodiments, X2 is a substituted C 1-10 In some embodiments, the substituent on X2 is -SH.

[0163] In some embodiments, X3 is a bond. In some embodiments, X3 is -C(=O)-. In some embodiments, X3 is a substituted or unsubstituted C 1-10 In some embodiments, X is an unsubstituted C 1-10 In some embodiments, X is a substituted C 1-10 In some embodiments, X is substituted or unsubstituted C 1-10 In some embodiments, X is an unsubstituted C 1-10 In some embodiments, X is a substituted C 1-10 In some embodiments, the substituent on X3 is -SH.

[0164] In some embodiments, X4 is a bond. In some embodiments, X4 is -C(=O)-. In some embodiments, X4 is a substituted or unsubstituted C 1-10 In some embodiments, X4 is an unsubstituted C 1-10 In some embodiments, X4 is a substituted C 1-10 In some embodiments, X4 is substituted or unsubstituted C 1-10 In some embodiments, X4 is an unsubstituted C 1-10 In some embodiments, X4 is a substituted C 1-10 In some embodiments, the substituent on X4 is -SH.

[0165] In some embodiments, X5 is a bond. In some embodiments, X5 is -C(=O)-. In some embodiments, X5 is a substituted or unsubstituted C 1-10 In some embodiments, X5 is an unsubstituted C 1-10 In some embodiments, X5 is a substituted C 1-10 In some embodiments, X5 is substituted or unsubstituted C 1-10 In some embodiments, X5 is an unsubstituted C1-10 In some embodiments, X5 is a substituted C 1-10 In some embodiments, the substituent on X5 is -SH.

[0166] In some embodiments, X6 is a bond. In some embodiments, X1 is -C(=O)-. In some embodiments, X6 is a substituted or unsubstituted C 1-10 In some embodiments, X6 is an unsubstituted C 1-10 In some embodiments, X6 is a substituted C 1-10 In some embodiments, X6 is substituted or unsubstituted C 1-10 In some embodiments, X6 is an unsubstituted C 1-10 In some embodiments, X6 is a substituted C 1-10 In some embodiments, the substituent on X6 is -SH.

[0167] In some embodiments, B is -CH-CH-C(=O)-O-. In some embodiments, B is -CH-CH(CH)-C(=O)-O-. In some embodiments, B is -CH-CH-C(=O)-N-. In some embodiments, B is -C(=O)-NH-. In some embodiments, B is -CH-CH-. In some embodiments, B is -CH-CH(OH)-CH-O-. In some embodiments, B is -CH-CH(OH)-.

[0168] In some embodiments, X7 is a bond. In some embodiments, X7 is a substituted or unsubstituted C 1-12 In some embodiments, X7 is an unsubstituted C 1-12 In some embodiments, X7 is a substituted C 1-12 It is alkylene.

[0169] In some embodiments, X8 is a bond. In some embodiments, X8 is -O-. In some embodiments, X8 is -C(=O)-O-. In some embodiments, X8 is -C(=O)-N-.

[0170] In some embodiments, R 1A is H. In some embodiments, R 1A is C 1-20 In some embodiments, R 1A is C 1-10 In some embodiments, R 1A is C 1-5 In some embodiments, R 1A is -CH3.

[0171] In some embodiments, R 1B is H. In some embodiments, R 1B is C 1-20 In some embodiments, R 1B is C 1-10 In some embodiments, R 1B is C 1-5 In some embodiments, R 1B is -CH3.

[0172] In some embodiments, R 2 is C 1-20 In some embodiments, R 2 is C 1-10 In some embodiments, R 2 is C 1-5 In some embodiments, R 2 is -CH2CH3. In some embodiments, R 2 is -CH3.

[0173] In some embodiments, a is 2 to 10. In some embodiments, a is 2 to 10, 2 to 8, 2 to 6, 2 to 4, 2 to 3, 3 to 10, 3 to 8, 3 to 6, 3 to 4, 4 to 10, 4 to 8, 4 to 6, 6 to 10, 6 to 8, or 8 to 10. In some embodiments, a is 3. In some embodiments, a is 4. In some embodiments, a is 5. In some embodiments, a is 6.

[0174] In some embodiments, b is 0 to 10. In some embodiments, b is 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, 2 to 10, 2 to 8, 2 to 6, 2 to 4, 2 to 3, 3 to 10, 3 to 8, 3 to 6, 3 to 4, 4 to 10, 4 to 8, 4 to 6, 6 to 10, 6 to 8, or 8 to 10. In some embodiments, b is 3. In some embodiments, b is 4. In some embodiments, b is 5. In some embodiments, b is 6.

[0175] In some embodiments, c is 2 to 10. In some embodiments, a is 2 to 10, 2 to 8, 2 to 6, 2 to 4, 2 to 3, 3 to 10, 3 to 8, 3 to 6, 3 to 4, 4 to 10, 4 to 8, 4 to 6, 6 to 10, 6 to 8, or 8 to 10. In some embodiments, c is 3. In some embodiments, c is 4. In some embodiments, c is 5. In some embodiments, c is 6.

[0176] In some embodiments, d is 0 to 10. In some embodiments, b is 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, 2 to 10, 2 to 8, 2 to 6, 2 to 4, 2 to 3, 3 to 10, 3 to 8, 3 to 6, 3 to 4, 4 to 10, 4 to 8, 4 to 6, 6 to 10, 6 to 8, or 8 to 10. In some embodiments, d is 3. In some embodiments, d is 4. In some embodiments, d is 5. In some embodiments, d is 6.

[0177] 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, 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.

[0178] 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 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.

[0179] In some embodiments where b is 0 and d is 0 in Formula I, the polythiol ligand has the structure of Formula IX: [ka] [During the ceremony, CM is the central part; X1 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X2 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; X3 is a bond, -C(=O)-, C 1-10 Alkylene, or C 2-10 is heteroalkylene; 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 bond or C 1-12 is alkylene; X8 is a bond, -O-, -C(=O)-O-, or -C(=O)-N-; R 1A and R 1B are independently H or C 1-20 is alkylene; R 2 is C 1-20 Alkylene, or C 1-20 It is an alkoxy. a is 2 to 10; c is 2 to 10; e is between 1 and 100; f is between 0 and 100; a+c≧3 It has.

[0180] 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-diylbis(4,1-phenylene))bis(λ'-oxy). In some embodiments, CM is propane.

[0181] In some embodiments, X is a bond. In some embodiments, X is -C(=O)-. In some embodiments, X is a substituted or unsubstituted C 1-10 In some embodiments, X is an unsubstituted C 1-10 In some embodiments, X is substituted C 1-10 In some embodiments, X is substituted or unsubstituted C 1-10 In some embodiments, X is an unsubstituted C 1-10In some embodiments, X is a substituted C 1-10 In some embodiments, the substituent on X is -SH.

[0182] In some embodiments, X2 is a bond. In some embodiments, X2 is -C(=O)-. In some embodiments, X2 is a substituted or unsubstituted C 1-10 In some embodiments, X2 is an unsubstituted C 1-10 In some embodiments, X2 is a substituted C 1-10 In some embodiments, X2 is substituted or unsubstituted C 1-10 In some embodiments, X2 is an unsubstituted C 1-10 In some embodiments, X2 is a substituted C 1-10 In some embodiments, the substituent on X2 is -SH.

[0183] In some embodiments, X3 is a bond. In some embodiments, X3 is -C(=O)-. In some embodiments, X3 is a substituted or unsubstituted C 1-10 In some embodiments, X is an unsubstituted C 1-10 In some embodiments, X is a substituted C 1-10 In some embodiments, X is substituted or unsubstituted C 1-10 In some embodiments, X is an unsubstituted C 1-10 In some embodiments, X is a substituted C 1-10 In some embodiments, the substituent on X3 is -SH.

[0184] In some embodiments, B is -CH-CH-C(=O)-O-. In some embodiments, B is -CH-CH(CH)-C(=O)-O-. In some embodiments, B is -CH-CH-C(=O)-N-. In some embodiments, B is -C(=O)-NH-. In some embodiments, B is -CH-CH-. In some embodiments, B is -CH-CH(OH)-CH-O-. In some embodiments, B is -CH-CH(OH)-.

[0185] In some embodiments, X7 is a bond. In some embodiments, X7 is a substituted or unsubstituted C 1-12 In some embodiments, X7 is an unsubstituted C 1-12 In some embodiments, X7 is a substituted C 1-12 It is alkylene.

[0186] In some embodiments, X8 is a bond. In some embodiments, X8 is -O-. In some embodiments, X8 is -C(=O)-O-. In some embodiments, X8 is -C(=O)-N-.

[0187] In some embodiments, R 1A is H. In some embodiments, R 1A is C 1-20 In some embodiments, R 1A is C 1-10 In some embodiments, R 1A is C 1-5 In some embodiments, R 1A is -CH3.

[0188] In some embodiments, R 1B is H. In some embodiments, R 1B is C 1-20 In some embodiments, R 1B is C 1-10 In some embodiments, R1B is C 1-5 In some embodiments, R 1B is -CH3.

[0189] In some embodiments, R 2 is C 1-20 In some embodiments, R 2 is C 1-10 In some embodiments, R 2 is C 1-5 In some embodiments, R 2 is -CH2CH3. In some embodiments, R 2 is -CH3.

[0190] In some embodiments, a is 2 to 10. In some embodiments, a is 2 to 10, 2 to 8, 2 to 6, 2 to 4, 2 to 3, 3 to 10, 3 to 8, 3 to 6, 3 to 4, 4 to 10, 4 to 8, 4 to 6, 6 to 10, 6 to 8, or 8 to 10. In some embodiments, a is 3. In some embodiments, a is 4. In some embodiments, a is 5. In some embodiments, a is 6.

[0191] In some embodiments, c is 2 to 10. In some embodiments, a is 2 to 10, 2 to 8, 2 to 6, 2 to 4, 2 to 3, 3 to 10, 3 to 8, 3 to 6, 3 to 4, 4 to 10, 4 to 8, 4 to 6, 6 to 10, 6 to 8, or 8 to 10. In some embodiments, c is 3. In some embodiments, c is 4. In some embodiments, c is 5. In some embodiments, c is 6.

[0192] 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, 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.

[0193] 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 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.

[0194] Preparation of polythiol ligands Polythiol ligands can be prepared by a base-catalyzed Michael addition reaction between at least one thiol on a polythiol and at least one functional group on a poly(alkylene oxide), where the at least one functional group is an acrylate, methacrylate, or acrylamide. An example of a Michael reaction is the 1,4-addition to an α,β-unsaturated carbonyl compound, as shown in Figure 2. See Chatani, S., et al., "Relative reactivity and selectivity of vinyl sulfones and acrylates toward the thiol-Michael addition reaction and polymerization," Polym. Chem. 4:1048-1055 (2013).

[0195] In some embodiments, the base catalyst is selected from the group consisting of N,N-dimethylformamide, triethylamine, pyridine, tetrabutylammonium chloride, or N-methylimidazole, hi some embodiments, the base catalyst is triethylamine.

[0196] In some embodiments, the reaction is carried out at a temperature of about -20°C to about 100°C. In some embodiments, the base-catalyzed reaction is carried out at a temperature of about -20°C to about 100°C, about -20°C to about 80°C, about -20°C to about 60°C, about -20°C to about 40°C, about -20°C to about 20°C, about 20°C to about 100°C, about 20°C to about 80°C, about 20°C to about 60°C, about 20°C to about 40°C, about 40°C to about 100°C, about 40°C to about 80°C, about 40°C to about 60°C, about 60°C to about 100°C, about 60°C to about 80°C, or about 80°C to about 100°C. In some embodiments, the reaction is carried out at a temperature of about 60°C to about 100°C.

[0197] In some embodiments, the polythiol ligand is prepared from a polythiol and an acrylate-terminated poly(alkylene oxide) by the reaction shown in Scheme 1. [ka]

[0198] In some embodiments, the polythiol ligand is prepared from a polythiol and a methacrylate-terminated poly(alkylene oxide) by the reaction shown in Scheme 2. [ka]

[0199] In some embodiments, the polythiol ligand is prepared from a polythiol and an acrylamide-terminated poly(alkylene oxide) by the reaction shown in Scheme 3. [ka]

[0200] 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(alkylene oxide), where the at least one functional group is an isocyanate or a glycidyl ether. See Nguyen, L.-TT, et al., Polym. Chem. 4:5527-5536 (2013).

[0201] In some embodiments, the base catalyst is selected from the group consisting of N,N-dimethylformamide, triethylamine, pyridine, tetrabutylammonium chloride, or N-methylimidazole, hi some embodiments, the base catalyst is triethylamine.

[0202] In some embodiments, the reaction is carried out at a temperature of about -20°C to about 100°C. In some embodiments, the base-catalyzed reaction is carried out at a temperature of about -20°C to about 100°C, about -20°C to about 80°C, about -20°C to about 60°C, about -20°C to about 40°C, about -20°C to about 20°C, about 20°C to about 100°C, about 20°C to about 80°C, about 20°C to about 60°C, about 20°C to about 40°C, about 40°C to about 100°C, about 40°C to about 80°C, about 40°C to about 60°C, about 60°C to about 100°C, about 60°C to about 80°C, or about 80°C to about 100°C. In some embodiments, the reaction is carried out at a temperature of about 60°C to about 100°C.

[0203] In some embodiments, the polythiol ligand is prepared from a polythiol and an isocyanate-terminated poly(alkylene oxide) by the reaction shown in Scheme 4. [ka]

[0204] In some embodiments, polythiol ligands are prepared from a polythiol and a glyidyl ether-terminated poly(alkylene oxide) by the reaction shown in Scheme 5. [ka]

[0205] 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(alkylene oxide), where the at least one functional group is an alkene. See Nguyen, L.-TT, et al., Polym. Chem. 4:5527-5536 (2013).

[0206] In some embodiments, the radical mediator is a photoinitiator, for example, dimethoxy-2-phenylacetophenone.

[0207] In some embodiments, polythiol ligands are prepared from polythiols and alkene-terminated poly(alkylene oxides) by the reaction shown in Scheme 6. [ka]

[0208] Ligand exchange In some embodiments, the present invention relates to methods of exchanging ligands on nanostructures. In some embodiments, the present invention relates to methods of 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.

[0209] In some embodiments, the first ligands on the nanostructure dots are replaced with polythiol ligands. The thiol groups replace the nanostructure's natural hydrophobic ligands and provide stable anchoring of the ligands on the nanocrystal surface. In some embodiments, the nanostructures are quantum dots.

[0210] In some embodiments, the present invention provides a method for replacing a first ligand on a nanostructure with a second ligand, the method comprising: combining a reaction mixture containing a population of nanostructures having a first ligand bound thereto with a second ligand, the second ligand being a polythiol ligand, such that the second ligand displaces the first ligand and binds to the nanostructures; The present invention relates to a method comprising the steps of:

[0211] In some embodiments, the nanostructures are quantum dots.

[0212] In some embodiments, the first ligand is covalently bound to the nanostructure. In some embodiments, the first ligand is non-covalently bound to the nanostructure.

[0213] In some embodiments, the second ligand is covalently bound to the nanostructure. In some embodiments, the second ligand is non-covalently bound to the nanostructure.

[0214] In some embodiments, the blending is carried out at a temperature of about 0°C to about 200°C, about 0°C to about 150°C, about 0°C to about 100°C, about 0°C to about 80°C, about 20°C to about 200°C, about 20°C to about 150°C, about 20°C to about 100°C, about 20°C to about 80°C, about 50°C to about 200°C, about 50°C to about 150°C, about 50°C to about 100°C, about 50°C to about 80°C, about 80°C to about 200°C, about 80°C to about 150°C, about 80°C to about 100°C, about 100°C to about 200°C, about 100°C to about 150°C, or about 150°C to about 200°C. In some embodiments, the blending is carried out at a temperature of about 50°C to about 100°C. In some embodiments, the blending is carried out at a temperature of about 80°C.

[0215] In some embodiments, the blending may be from about 1 minute to about 6 hours, from about 1 minute to about 2 hours, from about 1 minute to about 1 hour, from about 1 minute to about 40 minutes, from about 1 minute to about 30 minutes, from about 1 minute to about 20 minutes, from about 1 minute to about 10 minutes, from about 10 minutes to about 6 hours, from about 10 minutes to about 2 hours, from about 10 minutes to about 1 hour, from about 10 minutes to about 40 minutes, from about 10 minutes to about 30 minutes, from about 10 minutes to about 20 minutes, or from about 20 minutes to about 6 hours. The blending is carried out for a period of about 1 hour, about 20 minutes to about 2 hours, about 20 minutes to about 1 hour, about 20 minutes to about 40 minutes, about 20 minutes to about 30 minutes, about 30 minutes to about 6 hours, about 30 minutes to about 2 hours, about 30 minutes to about 1 hour, about 30 minutes to about 40 minutes, about 40 minutes to about 6 hours, about 40 minutes to about 2 hours, about 40 minutes to about 1 hour, about 1 hour to about 6 hours, about 1 hour to about 2 hours, or about 2 hours to about 6 hours. In some embodiments, the blending is carried out for a period of about 40 minutes to about 2 hours. In some embodiments, the blending is carried out for a period of about 1 hour.

[0216] In some embodiments, the reaction mixture further comprises a solvent. In some embodiments, the solvent is selected from the group consisting of 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, monomethyl ether glycol esters, gamma-butyrolactone, methyl acetate-3-ethyl ether, butyl carbitol, butyl carbitol acetate, propanediol monomethyl ether, propanediol monomethyl ether acetate, cyclohexane, toluene, xylene, isopropyl alcohol, propylene glycol methyl ether acetate, hexanediol methacrylate, and combinations thereof. In some embodiments, the solvent is propylene glycol methyl ether acetate.

[0217] Optical density is a measure of a material's absorbance at a specific wavelength and is calculated by the formula: CD=-log 10 * (I OUT / I IN ) where: I OUT = the intensity of radiation passing through the cell; and I IN = Intensity of radiation hitting the cell The optical density of the material can be measured using a UV-Visible spectrometer.

[0218] 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, 5.0 mg / mL / OD 460 To achieve a quantum dot to polythiol ligand concentration ratio of 2.5 mg / mL / OD, 200 mg of polythiol ligand is added to 4.0 mL of quantum dot stock solution with an optical density of 10 (measured at 460 nm in a 1 cm path length cuvette). 460 To achieve a quantum dot to polythiol ligand concentration ratio of 100 mg, 100 mg of polythiol ligand is added to 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).

[0219] In some embodiments, the concentration ratio of quantum dots to polythiol ligands, as measured by optical density (at a wavelength of about 450 nm to about 600 nm), is about 0.25 mg / mL to about 10 mg / mL, about 0.25 mg / mL to about 5 mg / mL, about 0.25 mg / mL to about 1 mg / mL, about 0.25 mg / mL to about 0.5 mg / mL, about 0.5 mg / mL to about 10 mg / mL, about 0.5 mg / mL to about 5 mg / mL, about 0.5 mg / mL to about 1 mg / mL, about 1 mg / mL to about 10 mg / mL, about 1 mg / mL to about 5 mg / mL, or about 5 mg / mL to about 10 mg / mL. In some embodiments, the concentration ratio of quantum dots to polythiol ligands, as measured by optical density (at a wavelength of about 450 nm), is about 0.25 mg / mL to about 10 mg / mL, about 0.25 mg / mL to about 5 mg / mL, about 0.25 mg / mL to about 1 mg / mL, about 0.25 mg / mL to about 0.5 mg / mL, about 0.5 mg / mL to about 10 mg / mL, about 0.5 mg / mL to about 1 mg / mL, about 1 mg / mL to about 10 mg / mL, about 1 mg / mL to about 5 mg / mL, or about 5 mg / mL to about 10 mg / mL. In some embodiments, the concentration ratio of quantum dots to polythiol ligands, as measured by optical density (at a wavelength of about 450 nm), is about 1 mg / mL to about 5 mg / mL.

[0220] In some embodiments, the ratio of quantum dots to polythiol ligands, as measured by optical density (at wavelengths of about 600 nm and about 750 nm), is about 0.25 mg / mL to about 10 mg / mL, about 0.25 mg / mL to about 5 mg / mL, about 0.25 mg / mL to about 1 mg / mL, about 0.25 mg / mL to about 0.5 mg / mL, about 0.5 mg / mL to about 10 mg / mL, about 0.5 mg / mL to about 5 mg / mL, about 0.5 mg / mL to about 1 mg / mL, about 1 mg / mL to about 10 mg / mL, about 1 mg / mL to about 5 mg / mL, or about 5 mg / mL to about 10 mg / mL.

[0221] The percentage of primary ligands replaced by polythiol ligands is 1In some embodiments, the mole 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%.

[0222] The percentage of nanostructures in a population of nanostructures that contain polythiol ligands is 1 The molar percentage of the ligands constituting the polythiol ligand can be measured by H NMR. In some embodiments, the molar percentage of the ligands constituting the polythiol ligand is about 20% to about 100%, about 20% to about 80%, about 20% to about 60%, about 20% to about 40%, about 25% to about 100%, about 25% to about 80%, about 25% to about 60%, about 25% to about 40%, about 30% to about 100%, about 30% to about 80%, about 30% to about 60%, about 30% to about 40%, about 40% to about 100%, about 40% to about 80%, about 40% to about 60%, about 60% to about 100%, about 60% to about 80%, or about 80% to about 100%.

[0223] Improved solubility In some embodiments, the polythiol ligand is soluble in a polar solvent or a combination of solvents comprising at least one polar solvent. In some embodiments, the nanostructures comprising the polythiol ligand dispersed thereon are soluble in a polar solvent or a combination of solvents comprising at least one polar solvent.

[0224] A polythiol ligand is soluble in a polar solvent if at least 1 gram of the polythiol ligand dissolves in 1000 mL or less of the polar solvent at room temperature with stirring. The amount of polythiol ligand that dissolves can be determined by visual inspection.

[0225] In some embodiments, the polar solvent is selected from the group consisting of 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, benzonitrile, cyclohexanone, chloroform, ethyl acetate, propylene glycol methyl ether acetate, and dichloromethane.

[0226] organic resin In some embodiments, the organic resin is a thermosetting resin or an ultraviolet (UV) curable resin. In some embodiments, the organic resin is cured using a method that facilitates roll-to-roll processing.

[0227] Thermosetting resins require curing to undergo an irreversible molecular crosslinking process that renders the resin infusible. In some embodiments, the thermosetting resin is an epoxy resin, a phenolic resin, a vinyl resin, a melamine resin, a urea resin, an unsaturated polyester resin, a polyurethane resin, an allylic resin, an acrylic resin, a polyamide resin, a polyamide-imide resin, a polyamine condensation polymerization resin, a urea-melamine condensation polymerization resin, or a combination thereof.

[0228] In some embodiments, the thermosetting resin is an epoxy resin. Epoxy resins cure easily with a wide range of chemicals without generating volatiles or by-products. Epoxy resins are also compatible with most substrates and tend to wet surfaces easily. See Boyle, MA, et al., "Epoxy Resins," Composites, Vol. 21, ASM Handbook, pages 78-89 (2001).

[0229] In some embodiments, the organic resin is a silicone thermoset. In some embodiments, the silicone thermoset is OE6630A or OE6630B (Dow Corning Corporation, Auburn, MI).

[0230] In some embodiments, a thermal initiator is used, hi some embodiments, the thermal initiator is [2,2'-azobis(2-methylpropionitrile)] (AIBN) or benzoyl peroxide.

[0231] UV-curable resins are polymers that cure and rapidly cure when exposed to specific wavelengths of light. In some embodiments, the UV-curable resin is a resin having a radical polymerizable group, such as a (meth)acryloxy group, a vinyloxy group, a styryl group, or a vinyl group, or a cationically polymerizable group, such as an epoxy group, a thioepoxy group, a vinyloxy group, or an oxetanyl group, as a functional group. In some embodiments, the UV-curable resin is a polyester resin, a polyether resin, a (meth)acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, or a polythiolpolyene resin.

[0232] In some embodiments, the UV curable resin is selected from the group consisting of isobornyl acrylate (IBOA), urethane acrylate, allyloxylated cyclohexyl diacrylate, bis(acryloxyethyl)hydroxyl isocyanurate, bis(acryloxyneopentyl glycol) adipate, bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, diacrylamidopropyl ... Dicyclopentanyl acrylate, 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 diacrylate hydroxypivalate, pentaerythritol triacrylate, pentaerythritol tetraacrylate The monomer is selected from the group consisting of erythritol, dimethacrylate phosphate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, tetrabromobisphenol A diacrylate, triethylene glycol divinyl ether, triglycerol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, tris(acryloylethyl) isocyanurate, triacrylate phosphate, diacrylate phosphate, acrylic acid propargyl ester, 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.

[0233] In some embodiments, the UV curable resin is a thiol- or polythiol-functionalized resin that can be crosslinked with isocyanate, epoxy, or unsaturated compounds under UV curing conditions.

[0234] In some embodiments, the polythiol-functionalized resin is selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate) (PTMP), trimethylolpropane tri(3-mercaptopropionate) (TMPMP), glycol di(3-mercaptopropionate) (GDMP), tris[25-(3-mercaptopropionyloxy)ethyl] isocyanurate (TEMPIC), dipentaerythritol hexa(3-mercaptopropionate) (Di-PETMP), ethoxylated trimethylolpropane tri(3-mercaptopropionate) (ETTMP 1300, and ETTMP 700), polycaprolactone tetra(3-mercaptopropionate) (PCL4MP), and ethylenediaminetetraacetic acid (EETA). 1350), pentaerythritol tetramercaptoacetate (PETMA), trimethylolpropane trimercaptoacetate (TMPMA), or glycol dimercaptoacetate (GDMA). These compounds are sold under the trade name THIOCURE® by Bruno Bock, Marschacht, Germany.

[0235] 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 the group consisting of ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), and combinations thereof. In some embodiments, the polythiol-functionalized resin is PETMP.

[0236] In some embodiments, the UV-curable resin is a thiol-ene 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-ene formulation comprising PETMP and TTT.

[0237] In some embodiments, the UV-curable resin further comprises a photoinitiator, which initiates the curing reaction of the photosensitive material during exposure to light. In some embodiments, the photoinitiator is an acetophenone, benzoin, or thioxanthenone.

[0238] In some embodiments, the photoinitiator is MINS-311RM (Minuta Technology Co., Ltd, Korea).

[0239] In some embodiments, the photoinitiator is selected from the group consisting of IRGACURE 127, IRGACURE 184, IRGACURE 184D, IRGACURE 2022, IRGACURE2100, IRGACURE 250, IRGACURE 270, IRGACURE 2959, IRGACURE 369, IRGACURE 369 EG, IRGACURE 379, IRGACURE 500, IRGACURE 651, IRGACURE 754, IRGACURE 784, IRGACURE 819, IRGACURE 819Dw, IRGACURE 907, IRGACURE 907 FF, IRGACURE Oxe01, IRGACURE TPO-L, IRGACURE 1173, IRGACURE 1173D, IRGACURE 4265, IRGACURE 500Dw, IRGACURE 500E, IRGACURE 500F, IRGACURE 500G, IRGACURE 500H ... BP, or IRGACURE MBF (BASF Corporation, Wyandotte, MI). In some embodiments, the photoinitiator is TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) or MBF (methyl benzoylformate).

[0240] In some embodiments, the weight percentage of the organic resin in the nanostructure composition is about 5% to about 50%, about 5% to about 40%, about 5% to about 30%, about 5% to about 20%, about 5% to about 10%, about 10% to about 50%, about 10% to about 40%, about 10% to about 30%, about 10% to about 20%, about 20% to about 50%, about 20% to about 40%, about 20% to about 30%, about 30% to about 50%, about 30% to about 40%, or about 40% to about 50%.

[0241] In some embodiments, the weight percentage of the organic resin in the nanostructure molded article is about 0.01% to about 50%, about 0.01% to about 25%, about 0.01% to about 20%, about 0.01% to about 15%, about 0.01% to about 10%, about 0.01% to about 5%, about 0.01% to about 2%, about 0.01% to about 1%, about 1% to about 50%, about 1% to about 25%, about 1% to about 20%, about 1% to about 15%, about 1% to about 10%, about 1% to about 5%, about 1% to about 2%, or about 2% to about 50%. %, about 2% to about 25%, about 2% to about 20%, about 2% to about 15%, about 2% to about 10%, about 2% to about 5%, 5% to about 50%, about 5% to about 25%, about 5% to about 20%, about 5% to about 15%, about 5% to about 10%, about 10% to about 50%, about 10% to about 25%, about 10% to about 20%, about 10% to about 15%, about 15% to about 50%, about 15% to about 25%, about 15% to about 20%, about 20% to about 50%, about 20% to about 25%, or about 25% to about 50%.

[0242] In some embodiments, when more than one organic resin is used, the organic resins are added and mixed together, hi some embodiments, a first organic resin and a second organic resin are added and mixed together.

[0243] In some embodiments, the first organic resin is mixed with the second organic resin at a stirring speed of about 100 rpm to about 10,000 rpm, about 100 rpm to about 5,000 rpm, about 100 rpm to about 3,000 rpm, about 100 rpm to about 1,000 rpm, about 100 rpm to about 500 rpm, about 500 rpm to about 10,000 rpm, about 500 rpm to about 5,000 rpm, about 500 rpm to about 3,000 rpm, about 500 rpm to about 1,000 rpm, about 1,000 rpm to about 10,000 rpm, about 1,000 rpm to about 5,000 rpm, about 1,000 rpm to about 3,000 rpm, about 3,000 rpm to about 10,000 rpm, about 3,000 rpm to about 10,000 rpm, or about 5,000 rpm to about 10,000 rpm.

[0244] In some embodiments, the range is from about 10 minutes to about 24 hours, from about 10 minutes to about 20 hours, from about 10 minutes to about 15 hours, from about 10 minutes to about 10 hours, from about 10 minutes to about 5 hours, from about 10 minutes to about 1 hour, from about 10 minutes to about 30 minutes, from about 30 minutes to about 24 hours, from about 30 minutes to about 20 hours, from about 30 minutes to about 15 hours, from about 30 minutes to about 10 hours, from about 30 minutes to about 5 hours, from about 30 minutes to about 1 hour, from about 1 hour to about 24 hours, from about 1 hour to about The first organic resin is mixed with the second organic resin for a period of 20 hours, about 1 hour to about 15 hours, about 1 hour to about 10 hours, about 1 hour to about 5 hours, about 5 hours to about 24 hours, about 5 hours to about 20 hours, about 5 hours to about 15 hours, about 5 hours to about 10 hours, about 10 hours to about 24 hours, about 10 hours to about 20 hours, about 10 hours to about 15 hours, about 15 hours to about 24 hours, about 15 hours to about 20 hours, or about 20 hours to about 24 hours.

[0245] Preparation of nanostructure compositions The present invention provides methods of making a nanostructure composition, the methods comprising combining at least one population of nanostructures with at least one organic resin. In some embodiments, about 20 to about 100 mole percent of the ligands in the population of nanostructures comprise polythiol ligands. In some embodiments, the at least one organic resin is a thiol-functionalized resin.

[0246] The present invention provides a method for preparing a nanostructure composition, comprising the steps of: (a) providing a composition comprising at least one population of nanostructures, wherein about 20 to about 100 mole percent of the ligands in the population of nanostructures comprise polythiol ligands bound to the nanostructures; and (b) mixing at least one organic resin, the at least one organic resin being soluble in a polar solvent, with the composition of (a); The method includes:

[0247] In some embodiments, the population of nanostructures emits red, green, or blue light, and in some embodiments, the portions of each of the red, green, and blue light can be controlled to achieve a desired white point for the white light emitted by a display device incorporating the nanostructure film.

[0248] In some embodiments, the nanostructure composition comprises at least one population of nanostructure materials. In some embodiments, the nanostructure composition comprises 1-5, 1-4, 1-3, 1-2, 2-5, 2-4, 2-3, 3-5, 3-4, or 4-5 populations of nanostructure materials. Populations of quantum dots can be combined in any suitable ratio to produce desired nanostructure composition characteristics. In some embodiments, the nanostructures are quantum dots.

[0249] In some embodiments, the nanostructure composition comprises at least one organic resin. In some embodiments, the nanostructure composition comprises 1-5, 1-4, 1-3, 1-2, 2-5, 2-4, 2-3, 3-5, 3-4, or 4-5 organic resins. In some embodiments, the nanostructure composition comprises 1-3, 1-2, or 2-3 organic resins. In some embodiments, the nanostructure composition comprises 1 organic resin. In some embodiments, the nanostructures are quantum dots.

[0250] In some embodiments, the weight percentage of the nanostructure population in the nanostructure composition is about 0.001% to about 2%, about 0.001% to about 1%, about 0.001% to about 0.5%, about 0.001% to about 0.1%, about 0.001% to about 0.01%, about 0.01% to about 2%, about 0.01% to about 1%, about 0.01% to about 0.5%, about 0.01% to about 0.1%, about 0.1% to about 2%, about 0.1% to about 1%, about 0.1% to about 0.5%, about 0.5% to about 2%, about 0.5% to about 1%, or about 1% to about 2%. In some embodiments, the nanostructures are quantum dots.

[0251] In some embodiments, the weight percentage of the organic resin in the nanostructure composition is about 5% to about 50%, about 5% to about 40%, about 5% to about 30%, about 5% to about 20%, about 5% to about 10%, about 10% to about 50%, about 10% to about 40%, about 10% to about 30%, about 10% to about 20%, about 20% to about 50%, about 20% to about 40%, about 20% to about 30%, about 30% to about 50%, about 30% to about 40%, or about 40% to about 50%.

[0252] In some embodiments, the rotation speed is about 100 rpm to about 10,000 rpm, about 100 rpm to about 5,000 rpm, about 100 rpm to about 3,000 rpm, about 100 rpm to about 1,000 rpm, about 100 rpm to about 500 rpm, about 500 rpm to about 10,000 rpm, about 500 rpm to about 5,000 rpm, about 500 rpm to about 3,000 rpm, or about 500 rpm to about 1,000 The at least one organic resin is mixed with the at least one population of nanostructures at a stirring speed of about 1,000 rpm to about 10,000 rpm, about 1,000 rpm to about 5,000 rpm, about 1,000 rpm to about 3,000 rpm, about 3,000 rpm to about 10,000 rpm, about 3,000 rpm to about 10,000 rpm, or about 5,000 rpm to about 10,000 rpm.

[0253] In some embodiments, the at least one organic resin is combined with the at least one population of nanostructures at a temperature of about −5° C. to about 100° C., about −5° C. to about 75° C., about −5° C. to about 50° C., about −5° C. to about 23° C., about 23° C. to about 100° C., about 23° C. to about 75° C., about 23° C. to about 50° C., about 50° C. to about 100° C., about 50° C. to about 75° C., or about 75° C. to about 100° C. In some embodiments, the at least one organic resin is combined with the at least one population of nanostructures at a temperature of about 23° C. to about 50° C.

[0254] In some embodiments, the range is from about 10 minutes to about 24 hours, from about 10 minutes to about 20 hours, from about 10 minutes to about 15 hours, from about 10 minutes to about 10 hours, from about 10 minutes to about 5 hours, from about 10 minutes to about 1 hour, from about 10 minutes to about 30 minutes, from about 30 minutes to about 24 hours, from about 30 minutes to about 20 hours, from about 30 minutes to about 15 hours, from about 30 minutes to about 10 hours, from about 30 minutes to about 5 hours, from about 30 minutes to about 1 hour, from about 1 hour to about 24 hours, from about 1 hour to about 20 hours, or from about 1 hour. The at least one organic resin is admixed with the at least one population of nanostructures for a period of about 1 hour to about 15 hours, about 1 hour to about 10 hours, about 1 hour to about 5 hours, about 5 hours to about 24 hours, about 5 hours to about 20 hours, about 5 hours to about 15 hours, about 5 hours to about 10 hours, about 10 hours to about 24 hours, about 10 hours to about 20 hours, about 10 hours to about 15 hours, about 15 hours to about 24 hours, about 15 hours to about 20 hours, or about 20 hours to about 24 hours.

[0255] In some embodiments, the blending further comprises a solvent, in some embodiments, the solvent is selected from the group consisting of 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, monomethyl ether glycol esters, gamma-butyrolactone, methyl acetate-3-ethyl ether, butyl carbitol, butyl carbitol acetate, propanediol monomethyl ether, propanediol monomethyl ether acetate, cyclohexane, toluene, xylene, isopropyl alcohol, and combinations thereof.

[0256] Improved solubility of nanostructure compositions containing polythiol ligands The polythiol ligand provides improved stability to the population of nanostructures in the organic resin, allowing for storage of the nanostructures for extended periods of time. In some embodiments, at least one population of nanostructures is immersed in an organic resin at a temperature of about 10° C. to about 90° C. for about 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, about 1 day to about 15 days, about It can be stored for 15 days to about 3 years, about 15 days to about 12 months, about 15 days to about 6 months, about 15 days to about 3 months, about 15 days to about 1 month, about 1 month to about 3 years, about 1 month to about 12 months, about 1 month to about 6 months, about 1 month to about 3 months, about 3 months to about 3 years, about 3 months to about 12 months, about 3 months to about 6 months, about 6 months to about 3 years, about 6 months to about 12 months, or about 12 months to about 3 years.

[0257] The polythiol ligand provides improved stability to the population of nanostructures in the organic resin, allowing for storage of the nanostructures for extended periods of time. In some embodiments, at least one population of nanostructures is immersed in an organic resin at a temperature of about 30° C. to about 90° C. for about 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, about 1 day to about 15 days, about It can be stored for 15 days to about 3 years, about 15 days to about 12 months, about 15 days to about 6 months, about 15 days to about 3 months, about 15 days to about 1 month, about 1 month to about 3 years, about 1 month to about 12 months, about 1 month to about 6 months, about 1 month to about 3 months, about 3 months to about 3 years, about 3 months to about 12 months, about 3 months to about 6 months, about 6 months to about 3 years, about 6 months to about 12 months, or about 12 months to about 3 years.

[0258] Fabrication of nanostructured layers The nanostructures used in the present invention can be embedded in a polymer matrix using any suitable method. As used herein, the term "embedded" is used to describe a nanostructure population that is encapsulated or enclosed by a polymer that constitutes the majority of the matrix's components. In some embodiments, at least one nanostructure population is preferably uniformly distributed throughout the matrix. In some embodiments, at least one nanostructure population is distributed according to an application-specific distribution. In some embodiments, the nanostructures are mixed into a polymer and applied to the surface of a substrate.

[0259] Deposition of the nanostructure composition may be accomplished by any suitable method known in the art, including, but not limited to, painting, spray coating, solvent spraying, wet coating, adhesive coating, spin coating, tape coating, roll coating, flow coating, inkjet vapor jetting, drop casting, blade coating, mist deposition, or a combination thereof. Preferably, the nanostructure composition is cured after deposition. Suitable curing methods include photocuring, e.g., UV curing, and thermal curing. Conventional layer-by-layer film processing methods, tape coating, and / or roll-to-roll manufacturing methods may be employed to form the nanostructure film. The nanostructure composition may be coated directly onto a desired layer of the substrate. Alternatively, the nanostructure composition may be cast into a solid layer as a separate element and then applied to the substrate. In some embodiments, the nanostructure composition may be deposited onto one or more barrier layers.

[0260] Spin coating In some embodiments, the nanostructure composition is deposited onto a substrate using spin coating. Spin coating typically involves depositing a small amount of material at the center of a substrate mounted on a vacuum-mounted machine called a spinner. The spinner applies high-speed rotation to the substrate, creating a centripetal force that spreads the material from the center to the edges of the substrate. While most of the material will be shaken off, some will remain on the substrate, forming a thin film of material on the surface as rotation continues. The final thickness of the film depends on the parameters selected for spin processing, such as spin speed, acceleration, and spin time, as well as the properties of the deposited material and the substrate. For typical films, spin speeds of 1500-6000 rpm are used with spin times of 10-60 seconds.

[0261] Mist accumulation In some embodiments, mist deposition is used to deposit the nanostructure composition onto a substrate. Mist deposition occurs at room temperature and atmospheric pressure, allowing for precise control over film thickness by varying process conditions. During mist deposition, a liquid source material is converted into a very fine mist and carried into the deposition chamber by nitrogen gas. The mist is then attracted to the wafer surface by a high-voltage potential between an electric field shield and a wafer holder. Once the droplets coalesce on the wafer surface, the wafer is removed from the chamber and thermally cured to evaporate the solvent. The liquid precursor is a mixture of solvent and the material to be deposited. It is carried into the atomizer by pressurized nitrogen gas. Price, SC, et al., “Formation of Ultra-Thin Quantum Dot Films by Mist Deposition,” ESC Transactions 11:89-94 (2007).

[0262] Spray coating In some embodiments, the nanostructure composition is deposited onto the substrate using spray coating. Typical equipment for spray coating includes a spray nozzle, a sprayer, a precursor solution, and a carrier gas. In the spray deposition process, the precursor solution is atomized into micro-sized droplets by a carrier gas or by atomization (e.g., ultrasonic, air blast, or electrostatic). The droplets emerging from the sprayer are accelerated through the nozzle by the substrate surface with the aid of a carrier gas that is controlled and adjusted as desired. The relative movement between the spray nozzle and the substrate is dictated by a design aimed at covering the entire substrate.

[0263] In some embodiments, the application of the nanostructure composition further comprises a solvent. In some embodiments, the solvent for application of the nanostructure composition is water, an organic solvent, an inorganic solvent, a halogenated organic solvent, or a mixture thereof. Exemplary solvents include, but are not limited to, water, DO, acetone, ethanol, dioxane, ethyl acetate, methyl ethyl ketone, isopropanol, anisole, γ-butyrolactone, dimethylformamide, N-methylpyrroldinone, dimethylacetamide, hexamethylphosphoramide, toluene, dimethyl sulfoxide, cyclopentanone, tetramethylene sulfoxide, xylene, ε-caprolactone, tetrahydrofuran, tetrachloroethylene, chloroform, dichlorobenzene, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, or a mixture thereof.

[0264] In some embodiments, the nanostructure composition is thermally cured to form the nanostructure layer. In some embodiments, the composition is cured using UV light. In some embodiments, the nanostructure composition is coated directly onto the barrier layer of the nanostructure film, and then an additional barrier layer is deposited onto the nanostructure layer to create the nanostructure film. A support substrate may be employed below the barrier film for additional strength, stability, and coating uniformity, as well as to prevent material imperfections, bubble formation, and wrinkling or creasing of the barrier layer material or other materials. In addition, one or more barrier layers are preferably deposited above the nanostructure layer to seal the material between the upper and lower barrier layers. Deposition of the barrier layers may be suitably performed as a stack film, and optical sealing or further processing may be performed before the nanostructure film is incorporated into a specific lighting device. As will be understood by those skilled in the art, the nanostructure composition deposition process may include additional or modified components. Such embodiments may enable in-line process tuning of nanostructure emission characteristics, such as brightness and color (e.g., to adjust the white point of a quantum dot film), as well as nanostructure film thickness and other characteristics. Additionally, these embodiments would allow for periodic inspection of nanostructure film properties during production and any toggling necessary to achieve precise nanostructure film properties. Such inspection and adjustments may be achieved without changing the mechanical layout of the processing line, since a computer program can be employed to electronically vary the amounts of each of the compounds to be used in forming the nanostructure film.

[0265] Barrier layer In some embodiments, the nanostructured article includes one or more barrier layers disposed on either or both sides of the nanostructured layer. Suitable barrier layers protect the nanostructured layer and the nanostructured article from environmental conditions such as high temperatures, oxygen, and moisture. Suitable barrier layers include non-yellowing, transparent optical materials that are hydrophobic, chemically and mechanically compatible with the nanostructured article, exhibit optical and chemical stability, and can withstand high temperatures. Preferably, the one or more barrier layers are index-matched to the nanostructured article. In preferred embodiments, the matrix material of the nanostructured article and one or more adjacent barrier layers are index-matched such that a large proportion of light transmitted through the barrier layer toward the nanostructured article is transmitted from the barrier layer into the nanostructured layer. This index-matching reduces optical loss at the interface between the barrier layer and the matrix material.

[0266] The barrier layer is preferably a solid material and may be a hardened liquid, gel, or polymer. The barrier layer may comprise a flexible or non-flexible material depending on the particular application. The barrier layer is preferably a flat layer and may comprise any suitable shape and surface area configuration depending on the particular lighting application. In a preferred embodiment, one or more barrier layers will be adapted to a laminate film processing technique, whereby a nanostructure layer is disposed on at least a first barrier layer and at least a second barrier layer is disposed on the nanostructure layer on the opposite side to form a nanostructured article according to one embodiment. Suitable barrier materials include any suitable barrier material 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, SiO3, TiO2, or Al2O3); and suitable combinations thereof. Preferably, each barrier layer of the nanostructure article comprises at least two layers comprising different materials or compositions, such that the multi-layer barrier eliminates or reduces alignment of pinhole defects in the barrier layer to provide an effective barrier against oxygen and moisture permeation into the nanostructure layer. The nanostructure layer may comprise any suitable material or combination of materials, and may include any suitable number of barrier layers on either or both sides of the nanostructure layer. The material, thickness, and number of barrier layers will depend on the specific application and will preferably be selected to maximize barrier protection and brightness of the nanostructure layer while minimizing the thickness of the nanostructure article. In preferred embodiments, each barrier layer comprises a laminate film, preferably a bilaminate film, with each barrier layer being thick enough to eliminate wrinkling during roll-to-roll or laminate manufacturing processes. The number or thickness of the barriers may further be determined by regulatory toxicological guidelines in embodiments in which the nanostructures contain heavy metals or other hazardous materials, which may require more or thicker barrier layers. Additional barrier considerations include cost, availability, and mechanical strength.

[0267] In some embodiments, the nanostructure film comprises two or more barrier layers adjacent to either side of the nanostructure layer, e.g., two or three layers on each side of the nanostructure layer, or two barrier layers on each side. In some embodiments, each barrier layer comprises a thin glass sheet, e.g., a glass sheet having a thickness of about 100 μm, 100 μm or less, or 50 μm or less.

[0268] Each barrier layer of the nanostructured film can have any suitable thickness, which will depend on the specific requirements and characteristics of the lighting device and application, as well as the individual film components, e.g., the barrier layer and the nanostructured layer, as will be understood by those skilled in the art. In some embodiments, each barrier layer can have a thickness of 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, or 15 μm or less. In certain embodiments, the barrier layer includes an oxide coating, which can include materials such as silicon oxide, titanium oxide, and aluminum oxide (e.g., SiO, SiO, TiO, or AlO). The oxide coating can have a thickness of about 10 μm or less, 5 μm or less, 1 μm or less, or 100 nm or less. In certain embodiments, the barrier includes a thin oxide coating having a thickness of about 100 nm or less, 10 nm or less, 5 nm or less, or 3 nm or less. The upper and / or lower barriers can consist of a thin oxide coating, or can include a thin oxide coating and one or more additional material layers.

[0269] Improved properties of nanostructured films Films prepared using nanostructure compositions comprising a population of nanostructures comprising polythiol ligands in an organic resin provide improved stability at high temperatures. In some embodiments, films prepared using the nanostructure compositions exhibit improved stability at temperatures between 40°C and 100°C for about 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, about 1 day to about 15 days, or about 15 days. It can be stably stored for about 3 years, about 15 days to about 12 months, about 15 days to about 6 months, about 15 days to about 3 months, about 15 days to about 1 month, about 1 month to about 3 years, about 1 month to about 12 months, about 1 month to about 6 months, about 1 month to about 3 months, about 3 months to about 3 years, about 3 months to about 12 months, about 3 months to about 6 months, about 6 months to about 3 years, about 6 months to about 12 months, or about 12 months to about 3 years.

[0270] Films prepared using nanostructure compositions comprising a population of nanostructures comprising polythiol ligands in an organic resin provide improved stability at high humidity levels. In some embodiments, films prepared using the nanostructure compositions exhibit improved stability at relative humidity levels of about 60% to about 100% for about 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, about 1 day to about 15 days, about 1 minute to about 1 day. It can be stably stored for 5 days to about 3 years, about 15 days to about 12 months, about 15 days to about 6 months, about 15 days to about 3 months, about 15 days to about 1 month, about 1 month to about 3 years, about 1 month to about 12 months, about 1 month to about 6 months, about 1 month to about 3 months, about 3 months to about 3 years, about 3 months to about 12 months, about 3 months to about 6 months, about 6 months to about 3 years, about 6 months to about 12 months, or about 12 months to about 3 years.

[0271] Films fabricated using nanostructure compositions containing a population of nanostructures comprising polythiol ligands in an organic resin exhibit improved light conversion efficiencies (LCEs). In some embodiments, films fabricated using the nanostructure compositions exhibit light conversion efficiencies of about 20% to about 40%, about 20% to about 30%, about 20% to about 25%, about 20% to about 22.5%, about 22.5% to about 40%, about 22.5% to about 30%, about 22.5% to about 25%, about 25% to about 40%, about 25% to about 30%, or about 30% to about 40%. In some embodiments, films fabricated using the nanostructure compositions exhibit color conversion efficiencies of about 20% to about 25%.

[0272] Nanostructure Film Features and Embodiments In some embodiments, the nanostructure films are used to form display devices. As used herein, display device refers to any system with an illuminated display. Such devices include, but are not limited to, devices that contain a liquid crystal display (LCD), televisions, computers, mobile phones, smart phones, personal digital assistants (PDAs), gaming devices, electronic readers, digital cameras, and the like. [Example]

[0273] The following examples are illustrative, but not limiting, of the products and methods described herein. Suitable modifications and adaptations of the various conditions, formulations and other parameters normally encountered in the art and obvious to those skilled in the art in light of this disclosure are within the spirit and scope of the present invention.

[0274] Example 1 [ka] Synthesis of PETMP-PEG480 A solution of 78.582 g of poly(ethylene glycol) methyl ether acrylate (average Mn 480 (Sigma Aldrich, St. Louis, MO)) (PEG480) and 1.092 mL of trimethylamine (TEA) was added to a round-bottom flask at room temperature and stirred for 5 minutes until homogeneous. To the solution, 80 g of tetrakis(3-mercaptopropionate) pentaerythritol (Evans Chemetics LP, Waterloo, NY) (PETMP) was added, and the mixture was stirred at room temperature for 30 minutes. The reaction was exothermic, causing the temperature to rise 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 the TEA was removed by applying a vacuum (100 mTorr) for 2 hours. FTIR and H spectra confirmed the C=CH stretching and consumption of proton signals. 1 The final product was characterized by -NMR.

[0275] Example 2 Ligand exchange with PETMP-PEG480 ligand To a 100 mL round-bottom flask, 6.0 mL of hexane containing QDs, 0.379 g of PETMP-PEG-480, and 12.0 mL of degassed polypropylene glycol methyl ether acetate (PGMEA) were added under nitrogen. The flask was heated to 80 °C with stirring for 1 h. The hazy solution clarified during the ligand exchange. The solution was cooled to room temperature, and then 36 mL of degassed heptane (four times the total volume of the ligand exchange solution) was added in a TEFLON® centrifuge bottle to precipitate the QDs with bound PETMP-PEG-480 ligands. The cloudy suspension of QDs with bound PETMP-PEG-480 ligands was centrifuged at 4000 rpm for 15 min to obtain a pellet and a clear supernatant phase. The supernatant was discarded, and the QDs with bound PETMP-PEG-480 ligands were redispersed in 0.948 mL of degassed PGMEA by stirring. Before the ligand exchange, the QDs were not soluble in PGMEA.

[0276] Example 3 Ligand exchange with PEG1000-CA ligand Quantum dots containing bound carboxylic acid-terminated PEG-1000 (PEG-1000-CA) ligands were prepared using the method of Example 2, substituting PEG1000-CA for PETMP-PEG480. The carboxylic acid-terminated PEG-1000 ligands were prepared using the method described in International Patent Application Publication No. WO 2019 / 084119, which is incorporated herein by reference in its entirety.

[0277] Example 4 Quantum yield results for different ratios of PETMP-PEG480 or PEG1000-CA Quantum dots containing PETMP-PEG-480 ligands and PEG-1000-CA were prepared using different ligand-to-quantum dot concentration ratios. The ligand concentration (mg / mL) and quantum dot concentration were determined by measuring the optical density (OD) of the ligand dispersion or quantum dot dispersion at a wavelength of 450 nm using a UV-Vis spectrometer. The ligand-to-quantum dot ratio was calculated from the individual concentration measurements using the formula: Ligand / Quantum Dot Ratio = OD 450 Ligand / OD 450 quantum dots The quantum yield measurements of quantum dots containing PETMP-PEG-480 conjugated at three different ligand / quantum dot ratios and quantum dots containing PEG-1000-CA conjugated are shown in Table 1. [Table 2]

[0278] As shown in Table 1, quantum dots containing PETMP-PEG-480 ligands at a ratio of 1 resulted in a quantum yield of 87.4%, which decreased as the ligand / quantum dot ratio increased, resulting in a quantum yield of 83.9% for quantum dots containing PETMP-PEG-480 ligands. The quantum yield obtained with quantum dots containing PETMP-PEG-480 ligands was comparable to that obtained with quantum dots containing PEG-1000-CA ligands at the same ligand / quantum dot ratio.

[0279] Example 5 Fabrication of quantum dot films A PGMEA solution of quantum dots containing PETMP-PEG-480 ligands (or PEG-1000-CA ligands) was added to the polymer formulation (also soluble in PGMEA). The solution was processed into films by solvent evaporation at 100 °C followed by thermal curing at 180 °C. As shown in Table 2, films made using quantum dots containing PETMP-PEG-480 ligands exhibited improved luminance compared to films made using quantum dots containing PEG-1000-CA ligands. The luminance of the quantum dot films was measured as the light conversion efficiency (LCE). [Table 3]

[0280] Example 6 Weight loss of quantum dot films after thermal heating The weights of the quantum dots with conjugated PETMP-PEG-480 ligands and the quantum dots with conjugated PEG-1000-CA ligands were measured before and after thermal curing at 180° C. for 30 minutes. The results are shown in Table 3. [Table 4]

[0281] As shown in Table 3, the QDs containing the PETMP-PEG-480 ligand are much more thermally stable than those containing the PEG-1000-CA ligand, and the improved thermal stability is believed to contribute to the improved film brightness of the QDs containing the PETMP-PEG-480 ligand.

[0282] Example 7 QDCF (Quantum Dot Color Filter) Compound Examples Formulations for QDCF applications are prepared by combining the QD solution with other ingredients used in the ink. Examples are shown in Table 4. [Table 5]

[0283] Film deposition can be achieved by spin-coating the above formulation onto a pre-cleaned 2" x 2" glass substrate at three different speeds (e.g., 200, 400, and 600 rpm). Films can be deposited by heating (150 °C in N2 for 20-40 min) or UV light irradiation (1000-2000 mJ / cm2), depending on the ink type. 2 ) can be cured.

[0284] The film can be transferred to an optical bench for measurement of blue transmittance and photoconversion efficiency (PCE). Film thickness can be measured using a profilometer.

[0285] While various embodiments have been described above, it should be understood that they have been presented by way of example only, and not by way of limitation. It will be apparent to those skilled in the relevant art that various changes in form and detail can be made therein without departing from the spirit and scope of the present invention. Accordingly, the breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments, but should instead be defined only by the following claims and their equivalents.

[0286] All publications, patents, and patent applications mentioned in this specification are indicative of the level of skill of those skilled in the art to which this invention pertains and are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.

Claims

1. 1. A nanostructure composition comprising: (a) nanostructures; and (b) polythiol ligands dispersed on the surface of the nanostructures; wherein the polythiol ligand comprises Formula I: 【Chemistry 1】 [During the ceremony, CM is the central part; X １ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ２ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ３ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ４ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ５ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ６ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; B is -CH ２ -CH ２ -C(=O)-O-, -CH ２ -C(CH ３ ) ２ -C(=O)-O-, -CH ２ -CH(CH ３ )-C(=O)-NH-, -C(=O)-NH-, -CH ２ -CH ２ - or -CH ２ -CH(OH)-CH ２ -O-; X ７ is a bond, or C １－１２ alkylene; X ８ is a bond, —O—, —C(═O)—O—, or —C(═O)—N—; R １Ａ and R １Ｂ are independently H, or C １－２０ is alkyl; R ２ is C １－２０ Alkyl, or C １－２０ It is an alkoxy. a is 2 to 4; b is 0 to 2; c is 2 to 4; d is 0 to 2; e is 1 to 100; f is 0 to 100; 6≧a+b+c+d≧4 The nanostructure composition having the following structure.

2. The polythiol ligand has Formula II: 【Chemistry 2】 [During the ceremony, CM is the central part; X １ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ２ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ３ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; B is -CH ２ -CH ２ -C(=O)-O-, -CH ２ -C(CH ３ ) ２ -C(=O)-O-, -CH ２ -CH(CH ３ )-C(=O)-NH-, -C(=O)-NH-, -CH ２ -CH ２ - or -CH ２ -CH(OH)-CH ２ -O-; X ７ is a bond, or C １－１２ alkylene; X ８ is a bond, —O—, —C(═O)—O—, or —C(═O)—N—; R １Ａ and R １Ｂ are independently H, or C １－２０ is alkyl; R ２ is C １－２０ Alkyl, or C １－２０ It is an alkoxy. a is 2 to 4; c is 2 to 4; e is 1 to 100; f is 0 to 100; 6 ≧ a + c ≧ 4 10. The nanostructure composition of claim 1, comprising:

3. The commercial, 3. The nanostructure composition of claim 1 or claim 2, which is pentaerythritol.

4. The nanostructure is InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP The nanostructure according to any one of claims 1 to 3, comprising a core selected from the group consisting of: composition.

5. The nanostructure composition of any one of claims 1 to 4, wherein the nanostructure comprises at least one shell.

6. X １ , X ２ and X ３ The nanostructure composition according to any one of claims 1 to 5, wherein is a bond.

7. X １ is —C(═O)—, and X ２ is C １－１０ alkylene, and X ３ The nanostructure composition according to any one of claims 1 to 5, wherein is a bond.

8. X １ is C ２－１０ is heteroalkylene, and X ２ is —C(═O)—, and X ３ is C １－１０ The nanostructure composition according to any one of claims 1 to 5, wherein the alkylene is alkylene.

9. X １ is substituted C ２－１０ is heteroalkylene, and X ２ is a bond, and X ３ The nanostructure composition according to any one of claims 1 to 5, wherein is a bond.

10. B is -CH ２ -CH ２ The nanostructure composition according to any one of claims 1 to 9, wherein

11. X ７ is C １－１０ alkylene, and X ８ The nanostructure composition according to any one of claims 1 to 10, wherein is -C(=O)-O-.

12. R １Ａ The nanostructure composition according to any one of claims 1 to 11, wherein is H, e is 1 to 100, a is 2, and c is 2.

13. The nanostructure composition comprises: 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 The nanostructure composition according to any one of claims 1 to 12, which is soluble in a solvent selected from the group consisting of:

14. 1. A method of replacing a first ligand on a nanostructure with a second ligand, comprising: combining a reaction mixture containing a population of nanostructures having first ligands non-covalently bound to said nanostructures with a second ligand, said second ligand being a polythiol ligand, such that said second ligand displaces said first ligand and non-covalently binds to said nanostructures; wherein the polythiol ligand comprises Formula I: 【Transformation 3】 [During the ceremony, CM is the central part; X １ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ２ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ３ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ４ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ５ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ６ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; B is -CH ２ -CH ２ -C(=O)-O-, -CH ２ -C(CH ３ ) ２ -C(=O)-O-, -CH ２ -CH(CH ３ )-C(=O)-NH-, -C(=O)-NH-, -CH ２ -CH ２ - or -CH ２ -CH(OH)-CH ２ -O-; X ７ is a bond, or C １－１２ alkylene; X ８ is a bond, —O—, —C(═O)—O—, or —C(═O)—N—; R １Ａ and R １Ｂ are independently H, or C １－２０ is alkyl; R ２ is C １－２０ Alkyl, or C １－２０ It is an alkoxy. a is 2 to 4; b is 0 to 2; c is 2 to 4; d is 0 to 2; e is 1 to 100; f is 0 to 100; 6≧a+b+c+d≧4 The method comprising:

15. The commercial, 15. The method of claim 14, wherein the sugar is pentaerythritol.

16. The nanostructure is InP, InZnP, InGaP, CdSe, CdS, CdSSe, CdZnSe, CdZnS, ZnSe, ZnSSe, InAs, InGaAs, and InAsP 16. The method of claim 14 or claim 15, comprising a core selected from the group consisting of:

17. A nanostructure film layer comprising: (a) nanostructures; (b) polythiol ligands dispersed on the surface of the nanostructures, said polythiol ligands having Formula I: 【Chemistry 4】 [During the ceremony, CM is the central part; X １ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ２ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ３ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ４ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ５ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ６ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; B is -CH ２ -CH ２ -C(=O)-O-, -CH ２ -C(CH ３ ) ２ -C(=O)-O-, -CH ２ -CH(CH ３ )-C(=O)-NH-, -C(=O)-NH-, -CH ２ -CH ２ - or -CH ２ -CH(OH)-CH ２ -O-; X ７ is a bond, or C １－１２ alkylene; X ８ is a bond, —O—, —C(═O)—O—, or —C(═O)—N—; R １Ａ and R １Ｂ are independently H, or C １－２０ is alkyl; R ２ is C １－２０ Alkyl, or C １－２０ It is an alkoxy. a is 2 to 4; b is 0 to 2; c is 2 to 4; d is 0 to 2; e is 1 to 100; f is 0 to 100; 6≧a+b+c+d≧4 the polythiol ligand having (c) at least one organic resin The nanostructure film layer comprising:

18. The commercial, 18. The nanostructure film layer of claim 17 which is pentaerythritol.

19. 19. The nanostructure film layer of claim 17 or claim 18, wherein the nanostructure film layer exhibits a light conversion efficiency of 20% to 40%.

20. A method for preparing the polythiol ligand of claim 1, comprising: Polythiols of Formula III: 【Transformation 5】 [During the ceremony, CM is the central part; X １ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ２ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ３ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ４ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ５ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; X ６ is a bond, -C(=O)-, C １－１０ Alkylene, or C ２－１０ is heteroalkylene; a is 2 to 4; b is 0 to 2; 6 ≧ a + b ≧ 4 with a poly(alkylene oxide) of formula V: 【Transformation 6】 [During the ceremony, FG is an acrylate group, a methacrylate group, an acrylamide group, an isocyanate group, an alkene group, or a glycidyl ether group; X ７ is a bond, or C １－１２ alkylene; X ８ is a bond, —O—, —C(═O)—O—, or —C(═O)—N—; R １Ａ and R １Ｂ are independently H, or C １－２０ is alkyl; e is 1 to 100; f is 0 to 100; R ２ is C １－２０ Alkyl, or C １－２０ alkoxy] A method for preparing a polythiol ligand, comprising reacting a

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