Inorganic nanophosphor and application thereof in field of optoelectronics

Abstract

Disclosed in the present invention is an inorganic nanophosphor, including a core formed by an inorganic semiconductor, and at least one ligand, wherein at least one of the ligands includes the structure of an organic compound H1. Further disclosed in the present invention is a composition, including the inorganic nanophosphor, an organic solvent and / or an organic resin. The composition helps to form a thin film by means of printing or coating, and a solid film is formed by means of heating. The inorganic nanophosphor can be used in a color converter, wherein the ligand including the structure of the organic compound H1 absorbs light from an excitation light source, transfers energy to the core of the inorganic nanophosphor, and then emits light having a relatively narrow half-peak width. The core of the inorganic nanophosphor is preferably a quantum dot with a photoluminescence spectrum, the wave crest position of which can be adjusted by means of the components and size of the core, such that light of different colors can be emitted. These narrow-half-peak-width light emission devices of different colors can be used to produce a display device with a high color gamut.

Description

An inorganic nanoluminescent body and its application in the field of optoelectronics Technical Field

[0001] The present invention relates to the field of inorganic nano-luminescent materials and technologies, and in particular to an inorganic nano-luminescent body, a composition thereof, a functional film, a photoelectric device and applications thereof in the photoelectric field. Background Art

[0002] According to the principles of colorimetry, the narrower the half-width at half-maximum of light entering the human eye, the higher the color purity and the brighter the color. Display devices made with red, green, and blue primary colors with narrow half-width at half-maximum display a wide color gamut, realistic images, and high-quality images.

[0003] Currently, there are two mainstream methods for achieving full-color displays. The first is that the display device actively emits light in the three primary colors of red, green, and blue, a typical example being RGB-OLED displays. The currently mature technology uses vacuum evaporation of fine metal masks to produce light-emitting devices in these three colors. This process is complex, costly, and difficult to achieve high-resolution displays exceeding 600ppi. The second method uses a color converter to convert the single color light emitted by the light-emitting device into multiple colors, thereby achieving full-color display. An example is Samsung's blue OLED plus red and green quantum dot (QD) films as color converters (hereinafter referred to as QD-OLED). The light-emitting device in this method has simple manufacturing processes and high color purity. Moreover, the color converter can be implemented through various technologies such as inkjet printing, transfer printing, and photolithography. It can be applied to display products with different resolution requirements, ranging from as low as 50ppi for large-screen TVs to as high as 3000ppi and above for silicon-based microdisplays.

[0004] Currently, the most promising color-conversion materials used in color converters are inorganic nanoluminescent materials, commonly known as quantum dots. These are nanoparticles of inorganic semiconductor materials (such as InP, CdSe, CdS, and ZnSe) with diameters ranging from 2nm to 10nm. Due to the limitations of current quantum dot synthesis and separation technologies, the half-width (FWHM) of the emission peak of Cd-containing quantum dots currently ranges from 20nm to 40nm, with color purity that meets NTSC display requirements. The FWHM of Cd-free quantum dots ranges from 35nm to 75nm. However, due to the generally low extinction coefficient of quantum dots, thicker films—typically over 10 microns—are required to fully absorb blue light. This poses a significant challenge to mass production, particularly for Samsung's QD-OLED technology.

[0005] Therefore, from an industrial perspective, there is an urgent need to find a material solution for color converters that can maintain the narrow emission spectrum of quantum dots while reducing the thickness of the film.

[0006] Meanwhile, QLEDs, or electroluminescent diodes (QLEDs) that use quantum dots as light sources, have also made significant progress recently (see DOI: 10.1038 / s41566-019-0364-z). However, the stability, or operating life, of QLEDs, particularly blue QLEDs, remains far from commercially viable. Therefore, the development of new, more stable QDs is urgently needed. Summary of the Invention

[0007] Based on this, the purpose of the present invention is to provide an inorganic nanoluminescent body, a composition thereof, a functional film, a photoelectric device and its application in the photoelectric field.

[0008] The specific technical solutions are as follows:

[0009] The present invention provides an inorganic nanoluminescent body comprising a core composed of an inorganic semiconductor and at least one ligand, wherein at least one of the ligands comprises a structure of an organic compound H1, wherein 1) the luminescence spectrum of the organic compound H1 and the absorption spectrum of the core at least partially overlap with each other; 2) the luminescence spectrum peak of the organic compound H1 is on the short-wavelength side of the luminescence spectrum peak of the core; and 3) the full width at half maximum (FWHM) of the luminescence spectrum of the inorganic nanoluminescent body is less than or equal to 45 nm.

[0010] In the above-mentioned inorganic nanoluminescent body, the core is selected from quantum dots or nanorods with a single distribution.

[0011] In the above-mentioned inorganic nanoluminescent body, the core is selected from one or any combination of CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe, CdZnSe, InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe, ZnCdSe, PbSe, PbTe, PbS, PbSnTe, and Tl2SnTe5.

[0012] The present invention also provides a composition comprising the inorganic nanoluminescent body as described above, an organic solvent and / or an organic resin.

[0013] The present invention also provides a functional film, comprising the inorganic nanoluminescent body as described above or prepared using the composition as described above.

[0014] The present invention also provides a photoelectric device comprising the inorganic nanoluminescent body or the functional film as described above.

[0015] Beneficial effects: According to the inorganic nanoluminescent body of the present invention, the organic compound H1 as a ligand has a large extinction coefficient, the core of the inorganic nanoluminescent body has a high luminous efficiency and a narrow luminous half-width, and the distance between the organic compound H1 and the core is short, and the energy transfer efficiency is high, thereby realizing the separation and optimization of the absorption and luminescence functions, facilitating the preparation of a thin and high-efficiency color converter, and facilitating the realization of a display with a high color gamut; in addition, in QLED, the inorganic nanoluminescent body containing the organic compound H1 as a ligand can realize the separation of the two processes of exciton formation and luminescence, thereby facilitating the realization of high efficiency and long life. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1: A red, green, and blue display device;

[0017] FIG2 is a graph showing a comparison of absorption spectra of conventional quantum dots (QD(OA)) and quantum dots according to the present invention (QD(LA1)). DETAILED DESCRIPTION

[0018] To facilitate understanding of the present invention, the present invention will be described more fully below with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the accompanying drawings. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and comprehensive understanding of the present disclosure.

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used herein in the specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0020] In the description of the embodiments of the present invention, a numerical range represented by “~” refers to a range that includes the numerical values ​​described before and after “~” as the lower limit and the upper limit.

[0021] In the description of the embodiments of the present invention, a substituent may be further substituted by a substituent, and "substituted group a" may refer to group a being substituted by a substituent, and the substituent may be substituted by at least one further substituent or may be unsubstituted.

[0022] In this disclosure, the term "and / or" describes the relationship between associated objects, indicating that three possible relationships exist. For example, "A and / or B" can represent: A exists alone, A and B exist simultaneously, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0023] In the present invention, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can each be single or plural.

[0024] It should be understood that in various embodiments of the present invention, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present invention.

[0025] The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The singular forms "a", "an", "the" and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

[0026] The term "OLED" is an abbreviation for "Organic Light Emitting Diode," which stands for organic electroluminescent diode, also known as organic electric laser display or organic light-emitting semiconductor (Organic Electroluminescence Display, OLED). OLED is a current-type organic light-emitting device that emits light through the injection and recombination of carriers, and the luminous intensity is proportional to the injected current. Under the action of the electric field, the holes generated by the anode and the electrons generated by the cathode will move, and are injected into the hole transport layer and the electron transport layer respectively, and migrate to the light-emitting layer. When the two meet in the light-emitting layer, energy excitons are generated, which excite the light-emitting molecules and ultimately produce visible light.

[0027] The term "TADF," short for "Thermally Activated Delayed Fluorescence," refers to thermally activated delayed fluorescence, which occurs when the triplet excited state and singlet excited state are close in energy, allowing the triplet excited state to transition to the singlet excited state through thermally activated reverse intersystem crossing (ISC). Conventional luminescence occurs as fluorescence and phosphorescence, respectively, where the exciton returns to the ground state via radiative emission from the singlet and triplet states. Furthermore, the energy difference between the lower singlet and triplet states is typically large, resulting in an inability to return the exciton to the singlet state once it reaches the triplet state through ISC.

[0028] In the present invention, main body material, matrix material, host material and matrix material have the same meaning and can be interchanged.

[0029] In the present invention, composition, printing ink, ink and ink have the same meaning and can be interchanged.

[0030] The present invention provides an inorganic nanoluminescent body comprising a core composed of an inorganic semiconductor and at least one ligand, wherein at least one of the ligands comprises a structure of an organic compound H1, wherein 1) the luminescence spectrum of the organic compound H1 and the absorption spectrum of the core at least partially overlap with each other; 2) the luminescence spectrum peak of the organic compound H1 is on the short-wavelength side of the luminescence spectrum peak of the core; and 3) the full width at half maximum (FWHM) of the luminescence spectrum of the inorganic nanoluminescent body is less than or equal to 45 nm.

[0031] In a preferred embodiment, the full width at half maximum (FWHM) of the light emission spectrum of the inorganic nanoluminescent body is ≤40 nm, preferably ≤35 nm, more preferably ≤30 nm, even better ≤25 nm, and most preferably ≤22 nm.

[0032] In another preferred embodiment, the inorganic nanoluminescent body has a fluorescence quantum efficiency (PLQY) of ≥60%, preferably ≥65%, more preferably ≥70%, and most preferably ≥80%.

[0033] In some preferred embodiments, the core of the inorganic nanoluminescent body is selected from quantum dots or nanorods with a single distribution.

[0034] In some preferred embodiments, the core of the inorganic nanoluminescent body is selected from one or any combination of CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe, CdZnSe, InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe, ZnCdSe, PbSe, PbTe, PbS, PbSnTe, and Tl2SnTe5.

[0035] In some embodiments, the core of the inorganic nanoluminescent body is a heterojunction structure comprising two different semiconductors, and the heterojunction structure is a core / shell structure having at least one outer shell.

[0036] In a preferred embodiment, the core of the inorganic nanoluminescent body is a semiconductor nanocrystal.

[0037] In certain embodiments, the average grain size of semiconductor nanocrystal is approximately in the 1nm to 1000nm scope. In certain embodiments, the average grain size of semiconductor nanocrystal is approximately in the 1nm to 100nm. In certain embodiments, the average grain size of semiconductor nanocrystal is approximately in the 1nm to 20nm, preferably from 1nm to 10nm.

[0038] The semiconductor forming the semiconductor nanocrystals may comprise a Group IV element, a group of Group II-VI compounds, a group of Group II-V compounds, a group of Group III-VI compounds, a group of Group III-V compounds, a group of Group IV-VI compounds, a group of Group I-III-VI compounds, a group of Group II-IV-VI compounds, a group of Group II-IV-V compounds, an alloy comprising any of the foregoing, and / or a mixture comprising the foregoing compounds, and / or a ternary / quaternary mixture or alloy. A non-limiting list of examples includes zinc oxide, zinc sulfide, zinc selenide, zinc telluride, cadmium oxide, cadmium sulfide, cadmium selenide, cadmium telluride, magnesium sulfide, magnesium selenide, gallium arsenide, gallium nitride, gallium phosphide, gallium selenide, gallium antimonide, mercury oxide, mercury sulfide, mercury selenide, mercury telluride, indium arsenide, indium nitride, indium phosphide, indium antimonide, aluminum arsenide, aluminum nitride, aluminum phosphide, aluminum antimonide, titanium nitride, titanium phosphide, titanium arsenide, titanium antimonide, lead oxide, lead sulfide, lead selenide, lead telluride, germanium, silicon, an alloy comprising any of the foregoing, and / or a mixture comprising any of the foregoing, including ternary / quaternary mixtures or alloys.

[0039] In a preferred embodiment, the semiconductor nanocrystals comprise a II-VI semiconductor material, preferably selected from CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe, CdZnSe, and any combination thereof. In a suitable embodiment, CdSe is used as an inorganic nanoluminescent material for visible light due to its relatively mature synthesis.

[0040] In another preferred embodiment, the semiconductor nanocrystals comprise III-V semiconductor materials, preferably selected from InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe, ZnCdSe and any combination thereof.

[0041] In another preferred embodiment, the semiconductor nanocrystals comprise a Group IV-VI semiconductor material, preferably selected from PbSe, PbTe, PbS, PbSnTe, Tl2SnTe5 and any combination thereof.

[0042] The shapes of semiconductor nanocrystals and other nanoparticles can include spheres, rods, disks, crosses, T-shapes, other shapes, or mixtures thereof. There are many methods for producing semiconductor nanocrystals, and a preferred method is the controlled growth solution phase colloidal method. For details of this method, see Alivisatos, AP, Science 1996, 271, p933; X. Peng et al., J. Am. Chem. Soc. 1997, 119, p7019; and CB Murray et al., J. Am. Chem. Soc. 1993, 115, p8706. The contents of the above-listed documents are hereby incorporated by reference. In these methods, an organometallic precursor (containing an M donor and an X donor, as described below) that undergoes pyrolysis at high temperature is rapidly injected into a hot solution containing a surfactant (coordinating solvent). These precursors decompose at high temperature and react to form nanocrystal nuclei. After this initial discrete nucleation stage, the growth stage is initiated by adding monomers to the growing crystals. The product is free-standing crystalline nanoparticles in solution, which have organic surfactant molecules coating their surfaces. The synthesis method involves initial discrete nucleation in seconds, followed by crystal growth at elevated temperatures over several minutes. The nature and course of the reaction can be altered by varying parameters such as temperature, surfactant type, precursor amount, and surfactant-to-monomer ratio. Temperature controls the nucleation process, precursor decomposition rate, and growth rate. The organic surfactant molecules regulate solubility and control nanocrystal shape. The ratios of surfactant to monomer, surfactant to surfactant, monomer to monomer, and the concentration of each monomer strongly influence the grain growth kinetics. By appropriately controlling the reaction parameters, the resulting semiconductor nanocrystals have a narrow distribution, known as a monodisperse distribution of particle sizes. Monodisperse diameters can also be used as a measure of grain size. In the present invention, at least 60% of the grains in a monodisperse collection of grains have a particle size within a specified range. A preferred monodisperse crystal has a diameter deviation of less than 15% rms, more preferably less than 10% rms, and most preferably less than 5% rms. The terms "monodispersed nanocrystals", "nanodots" and "quantum dots" are readily understood by those skilled in the art to refer to the same structure and are used interchangeably in the present invention.

[0043] In a preferred embodiment, the semiconductor nanocrystal or quantum dot comprises a core composed of a first semiconductor material and a shell composed of a second semiconductor material, wherein the shell is deposited on at least a portion of the surface of the core. A semiconductor nanocrystal comprising a core and a shell is also referred to as a "core / shell" semiconductor nanocrystal or quantum dot.

[0044] In semiconductor nanocrystals, light emission is produced by the band edge state of the nanocrystal. The band edge emission from the luminescent nanocrystal competes with the radiation and non-radiative decay channels derived from the surface electronic state. Surface defects such as dangling bonds provide non-radiative recombination centers, thereby reducing luminous efficiency. An effective method for passivating and removing the surface defect state is to epitaxially grow inorganic shell materials on the surface of the nanocrystal (see X. Peng et al., J. Am. Chem. Soc. Vol 119, 7019-7029 (1997)). The shell material can be selected so that the shell / core constitutes an I-type semiconductor heterojunction structure, which can confine electrons and holes, and the excitons formed by their compound, to the core, thereby reducing the probability of non-radiative recombination. A core-shell structure is obtained by adding an organometallic precursor containing the shell material to the reaction mixture containing the core nanocrystal. In this case, instead of growing after the nucleation event, the core plays the role of a crystal nucleus and grows a shell from their surface. The temperature of the reaction should be kept appropriately low to facilitate the addition of the shell material monomer to the core surface while preventing the nanocrystal of the shell material from independently nucleating. The presence of a surfactant in the reaction mixture is to guide the controlled growth of the shell material and to ensure solubility. When there is a low lattice mismatch between the two materials, a uniform and epitaxially grown shell is obtained. In addition, the spherical shape plays a role in minimizing the interfacial strain energy from a large radius of curvature, thereby preventing the formation of dislocations that can degrade the optical properties of the nanocrystal.

[0045] For example, a semiconductor nanocrystal can include a core having the general chemical formula MX, where M can be cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, thallium, or a mixture thereof, and X can be oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, or a mixture thereof. Examples of materials suitable for use as the core of a semiconductor nanocrystal include, but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe, InAs, InN, InP, InSb, AlAs, AlN, AlP, AlSb, TIN, TIP, TlAs, TlSb, PbO, PbS, PbSe, PbTe, Ge, Si, an alloy or mixture comprising any of the foregoing materials, including ternary / quaternary mixtures or alloys.

[0046] The semiconductor material comprising the shell can be the same as or different from that of the core. The shell of a semiconductor nanocrystal is a coating covering the core surface, and its material can include a group of Group IV elements, a group of Group II-VI compounds, a group of Group II-V compounds, a group of Group III-VI compounds, a group of Group III-V compounds, a group of Group IV-VI compounds, a group of Group I-III-VI compounds, a group of Group II-IV-VI compounds, a group of Group II-IV-V compounds, an alloy comprising any of the foregoing, and / or a mixture of the foregoing compounds. Examples include, but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe, InAs, InN, InP, InSb, AlAs, AlN, AlP, AlSb, TIN, TIP, TlAs, TlSb, PbO, PbS, PbSe, PbTe, Ge, Si, an alloy and / or mixture comprising any of the foregoing.

[0047] For example, a ZnS, ZnSe or CdS shell can be grown on a CdSe or CdTe semiconductor nanocrystal. For example, U.S. Patent No. 6,322,901 discloses a method for shell growth. By adjusting the temperature of the reaction mixture during shell growth and monitoring the core absorption spectrum, "core / shell" semiconductor nanocrystals or quantum dots with high quantum efficiency and narrow particle size distribution can be prepared. The shell can include one or more layers. The shell includes at least one semiconductor material that is the same or different from the core composition. Preferably, the shell has a thickness of about 1 to 10 monolayers. A shell can also have a thickness greater than 10 monolayers. In certain embodiments, more than one shell can be wrapped around a core.

[0048] In some embodiments, the outer "shell" material may have a band gap larger than that of the core material. Preferably, the core / shell has a type I heterojunction structure.

[0049] In certain embodiments, shell can be selected so that there is an atomic distance close to " core ". In some other embodiments, shell and core material can have the same crystal structure. " Core / shell " semiconductor nanocrystal or quantum dot include, for example but not limited to: red (such as " CdSe / ZnS "), green (such as " CdZnSe / CdZnS "), blue (such as " CdS / CdZnS "). The narrow particle size distribution of semiconductor nanocrystal or quantum dot makes it possible to emit light with a narrow width spectrum. The detailed description of quantum dot can be found in the following documents: Murray et al. (J.Am.Chem.Soc, 1993, 115, p8706), Christopher Murray's paper " Synthesis and Characterization of II-VI Quantum Dots and Their Assembly into 3-D Quantum Dot Superlattices " Massachusetts Institute of Technology September 1995, and U.S. Patent No. 6,322,901, which are hereby incorporated by reference in their entirety.

[0050] In some embodiments, two or more shells can be introduced, such as CdSe / CdS / ZnS and CdSe / ZnSe / ZnS core / shell / shell structures (J.Phys.Chem.B 2004, 108, p18826). By placing an intermediate shell (CdS or ZnSe) between the cadmium selenide core and the zinc sulfide shell, the stress inside the nanocrystal can be effectively reduced. Because the lattice parameters of CdS and ZnSe are between those of CdSe and ZnS, nearly defect-free nanocrystals can be obtained.

[0051] Controlled growth in a coordinating solvent and annealing of the semiconductor nanocrystals after nucleation can also lead to uniform surface derivatization and a uniform core structure. As the particle size distribution narrows, the temperature can be increased to maintain stable growth. The growth cycle can be shortened by adding more M or X donors. The M donor can be an inorganic compound, an organometallic compound, or a metallic element. M can be cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, or thallium. The X donor is a compound that reacts with the M donor to form a material with the general formula MX. The X donor can be a chalcogen donor or a pnictide donor, such as a phosphine chalcogenide, dioxygen, an ammonium salt, or trisilane phosphide. Suitable X donors include dioxygen, bis(trimethylsilyl)selenide ((TMS)2Se), trialkyl phosphine selenides such as (tri-n-octylphosphine)selenide (TOPSe) or (tri-n-butylphosphine)selenide (TBPSe), trialkyl phosphine tellurides such as (tri-n-octylphosphine)telluride (TOPTe) or hexapropylphosphorustriamide telluride (HPPTTe), bis(trimethylsilyl)telluride ((TMS)2Te), bis(trimethylsilyl)sulfide ((TMS)2S), a trialkyl phosphine sulfide such as (tri-n-octylphosphine)sulfide (TOPS), an ammonium salt such as an ammonium halide ( halide) (such as NH4Cl), tris(trimethylsilyl)phosphide((TMS)3P), tris(trimethylsilyl)arsenide((TMS)3As), or tris(trimethylsilyl)antimonide((TMS)3Sb).

[0052] In a preferred embodiment, the M donor and the X donor can be contained in the same molecule.

[0053] A coordinating solvent can help control the growth of semiconductor nanocrystals. A coordinating solvent is a compound with a lone pair donor, for example, a lone pair of electrons that can coordinate to the surface of a growing semiconductor nanocrystal. This coordinating effect of the solvent can stabilize the growth of the semiconductor nanocrystal. Examples of coordinating solvents include alkyl phosphines, alkyl phosphine oxides, alkyl phosphonic acids, or alkyl phosphinic acids. However, other coordinating solvents, such as pyridines, furans, and amines may also be suitable for growing semiconductor nanocrystals. Examples of other suitable coordinating solvents include pyridine, tri-n-octyl phosphine (TOP), tri-n-octyl phosphine oxide (TOPO), and trishydroxylpropylphosphine (tHPP), tributylphosphine, tri(dodecyl)phosphine, dibutyl-phosphate, tributyl phosphate, trioctadecyl phosphate, trilauryl phosphate, tris(tridecyl)phosphate, triisodecyl phosphate, and tris(tridecyl)phosphate. phosphate), bis(2-ethylhexyl)phosphate, tris(tridecyl)phosphate, hexadecylamine, 9-octadecylamine, octadecylamine, bis(2-ethylhexyl)amine, octylamine, dioctylamine, trioctylamine, dodecylamine, didodecylamine, tridodecylamine, hexadecylamine, dioctadecylamine,trioctadecylamine, phenylphosphonic acid, hexylphosphonic acid, tetradecylphosphonic acid, octylphosphonic acid, octadecylphosphonic acid, propylenediphosphonic acid, phenylphosphonic acid, aminohexylphosphonic acid, dioctyl ether, diphenyl ether, methyl myristate, octyl octanoate, and hexyl octanoate. In certain embodiments, industrial TOPO can be used.

[0054] The size distribution in the reaction process of the growth stage can be estimated by monitoring the width of the particle absorption or emission spectral line. The correction of the reaction temperature corresponding to the particle absorption spectrum change can allow a sharp particle size distribution to be arranged in the whole growth process. In the crystal growth process, reactant can be added to the nucleation solution and grow larger grains. For example, for cadmium selenide and cadmium telluride, by terminating growth when the average diameter of specific semiconductor nanocrystals, and selecting suitable semiconductor material to form, the emission spectrum of semiconductor nanocrystals can be continuously regulated in the scope of 300nm to 1500nm, and particularly preferably from 400nm to 800nm.

[0055] The size distribution of semiconductor nanocrystals can be further refined by selective precipitation using poor solvents, such as methanol / butanol as described in U.S. Patent No. 6,322,901 B1. For example, semiconductor nanocrystals can be dispersed in a solution of 10% butanol in n-hexane. Methanol can be added dropwise to this stirred solution until opalescence persists. The supernatant is separated by centrifugation and flocculation to produce a precipitate rich in large crystals. This process can be repeated until no further sharpening of the optical absorption spectrum is observed. Size selective precipitation can be performed in a variety of solvent / non-solvent pairs, including pyridine / n-hexane, chloroform / methanol, etc. The size-selective collection of semiconductor nanocrystals preferably has no more than 15% rms or less, more preferably 10% rms or less, and most preferably 5% rms or less.

[0056] For the purposes of the present invention, the semiconductor nanocrystals have ligands attached thereto.

[0057] In certain embodiments, the ligands can be derived from the coordinating solvent used during the growth process. Surface modification can be achieved by repeatedly exposing the nanocrystal to a coating containing an excess of competing coordinating groups. For example, a dispersion of encapsulated semiconductor nanocrystals can be treated with a coordinating organic compound, such as pyridine, resulting in grains that are readily dispersible in pyridine, methanol, and aromatic solvents, but no longer dispersible in aliphatic solvents. This surface exchange process can be performed with any compound that can coordinate or bind to the outer surface of the semiconductor nanocrystal. Examples of such compounds include phosphines, thiols, amines, and phosphates. The semiconductor nanocrystals can also be exposed to a short-chain polymer that has an affinity for the semiconductor nanocrystals at one end and a group at the other end that has an affinity for the liquid medium in which the semiconductor nanocrystals are dispersed. This affinity improves suspension stability and hinders flocculation of the semiconductor nanocrystals. In addition, in certain embodiments, the semiconductor nanocrystals can also be prepared using a non-coordinating solvent.

[0058] More specifically, according to the semiconductor nanocrystal of the present invention, its ligand has the structure of the following chemical formula (I):

[0059] wherein k is 2, 3, 4 or 5, and n is 1, 2, 3, 4 or 5, such that kn is not less than zero; X ​​is selected from O, OS, O-Se, ON, OP, O-As, S, S=O, SO2, Se, Se=O, N, N=O, P, P=O, O=C=As, or As=O; each Y and L is independent of each other and can be H, OH, an aryl group, a heteroaryl group, or a linear or branched hydrocarbon containing a C2 to C18 carbon chain; and at least one of Y and L comprises a structure of an organic compound H1.

[0060] In certain embodiments, the hydrocarbon may optionally contain at least one double bond, or at least one triple bond, or at least one double bond and triple bond; wherein the hydrocarbon chain may be optionally substituted with one or more of the following groups: C1-C4 alkyl and C2-C4 alkenyl and C2-C4 alkyne, C1-C4 alkoxy, hydroxy, halo, amino, nitro, cyano, C3-C5 cycloalkyl, 3-5 membered heterocycloalkyl, aryl, heteroaryl, C1-C4 alkylcarbonyloxy, C1-C4 alkyloxycarbonyl, C1-C4 alkylcarbonyl, or formyl. The hydrocarbon chain may be optionally interrupted by -O-, -S-, -N(Ra)-, -N(Ra)-C(O)-O-, -OC(O)-N(Ra)-, -N(Ra)-C(O)-N(Rb)-, -OC(O)-O-, -P(Ra)-, or -P(O)(Ra)-, where each Ra and Rb, independently of one another, may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyl, or haloalkyl. An aryl group is a substituted or unsubstituted cyclic aromatic group. Examples include benzene, naphthalene, toluene, anthracenyl, nitrobenzene, or halophenyl. A heteroaryl group is an aromatic group having one or more heteroatoms, such as a furan ring, pyridine, pyrrole, or phenanthrenyl.

[0061] A suitable coordinating ligand can be purchased commercially or prepared by conventional organic synthesis techniques, for example, as described by J. March in Advanced Organic Chemistry, the entire reference of which is incorporated herein by reference. Other ligands are disclosed in U.S. Pat. No. 7,160,613, the entire contents of which are hereby incorporated herein by reference.

[0062] The luminescence spectrum of semiconductor nanocrystals or quantum dots can be narrow Gaussian. By adjusting the size of the semiconductor nanocrystals, the composition of the semiconductor nanocrystals, or both, the luminescence spectrum of the semiconductor nanocrystals or quantum dots can be continuously tuned across the entire wavelength range of the ultraviolet, visible, or infrared spectra. For example, a quantum dot containing CdSe can be tuned within the visible region, and a semiconductor nanocrystal or quantum dot containing indium arsenide can be tuned within the infrared region. The narrow particle size distribution of a luminescent semiconductor nanocrystal or quantum dot results in a narrow luminescence spectrum. The collection of grains can be monodisperse, preferably with a diameter deviation of less than 15% rms, more preferably less than 10% rms, and most preferably less than 5% rms. For semiconductor nanocrystals or quantum dots that emit visible light, the luminescence spectrum is within a narrow range, generally no greater than 75 nm, preferably no greater than 60 nm, more preferably no greater than 40 nm, and most preferably no greater than 30 nm in full width at half maximum (FWHM). For infrared-emitting semiconductor nanocrystals or quantum dots, the luminescence spectrum may have a full width at half maximum (FWHM) of no more than 150 nm, or a full width at half maximum (FWHM) of no more than 100 nm. The luminescence spectrum narrows as the width of the quantum dot size distribution narrows.

[0063] Semiconductor nanocrystal or quantum dot can have for example greater than 10%, 20%, 30%, 40%, 50%, 60% quantum efficiency of luminescence.In a preferred embodiment, the quantum efficiency of luminescence of semiconductor nanocrystal or quantum dot is greater than 70%, better is greater than 80%, preferably greater than 90%.

[0064] The small half-width at half maximum of quantum dots results in luminescence with saturated colors. Using a single material, luminescence with widely adjustable, saturated colors can be achieved across the entire visible light range, a feat unmatched by any other organic chromophore (see, for example, Dabbousi et al., J. Phys. Chem. 1997, 101, p9463). Quantum dots emit light over a narrow wavelength range. A pattern comprising more than one quantum dot can emit light within more than one narrow luminescence range. The color of light perceived by humans can be controlled by selecting the appropriate combination of quantum dot size and material. Transmission electron microscopy (TEM) can provide information on the size, shape, and grain distribution of quantum dots. Powder X-ray diffraction (XRD) patterns can provide the most complete information on grain type and quality. Grain size can also be estimated using the X-ray coherence length, where the particle diameter is inversely proportional to the peak width. For example, the diameter of a quantum dot can be measured directly from a transmission electron microscope or estimated from X-ray diffraction data using, for example, the Scherrer equation. It can also be estimated from UV / visible absorption spectra.

[0065] Other materials, techniques, methods, applications and information that may be useful for the present invention are described in the following patent documents: WO2007 / 117698, WO2008 / 13366, WO2007 / 143197, US6207229, US6426513, US6576291, US7138098, US7470379, WO2006134599A1, and the entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0066] In another preferred embodiment, the semiconductor light-emitting nanocrystal is a nanorod. The characteristics of the nanorod are different from those of the spherical nanocrystal. For example, the luminescence of the nanorod is polarized along the long rod axis, while the luminescence of the spherical crystal is non-polarized (see Woggon et al., Nano Lett., 2003, 3, p509). Nanorods have excellent optical gain characteristics, making them possible to be used as laser gain materials (see Banin et al., Adv. Mater. 2002, 14, p317). In addition, the luminescence of the nanorod can be reversibly turned on and off under the control of an external electric field (see Banin et al., Nano Lett. 2005, 5, p1581). These characteristics of nanorods can be preferentially incorporated into the device of the present invention under certain circumstances. Examples of preparing semiconductor nanorods include WO03097904A1, US2008188063A1, US2009053522A1, and KR20050121443A, and the entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0067] In certain embodiments, according to the inorganic nanoluminescent material of the present invention, at least one ligand has a structure represented by the following chemical formula (II):

[0068] Wherein, n is an integer greater than or equal to 1, preferably 1 or 2, more preferably 1; L0 is a single bond or a connecting group, L1 is a terminal functional group capable of binding to the surface of the core, preferably L1 is a terminal functional group capable of binding to the surface of the semiconductor light-emitting nanocrystal; when L0 and L1 appear multiple times, they may be the same or different.

[0069] In certain embodiments, L0, when it occurs multiple times, may be the same or different and selected from a linear alkyl, haloalkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy, or silyl group having 3 to 20 carbon atoms, or a keto group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or an arylamine or heteroarylamine group having 5 to 40 ring atoms, a disubstituted unit at any position of the above groups, or a combination of these groups.

[0070] In a preferred embodiment, L0 is a single bond, and at least one ligand has a structure represented by the following chemical formula (II-1):

[0071] In a more preferred embodiment, the above-mentioned L1 is selected from -OH, -SH, -NH2, -COOH, -P(O)(OH)2, -P(O)OH or -SO3H.

[0072] For the purpose of the present invention, if the ligand represented by chemical formula (II) is replaced with n hydrogen atoms, i.e., organic compound H1, -[L0-L1]n, organic compound H1 is obtained. For example, if the ligand of the following formula contains a structure of benzene, the corresponding organic compound H1 is benzene; this also means that the ligand described in the present invention contains the structure of organic compound H1.

[0073] According to the inorganic nanoluminescent material of the present invention, the organic compound H1 has a relatively high extinction coefficient. The extinction coefficient is also called the molar extinction coefficient, which refers to the absorption coefficient when the concentration is 1 mol / L, and is represented by the symbol ε, and the unit is Lmol. -1 cm -1 , the preferred extinction coefficient: ε≥1*10 3 ; More preferably: ε≥1*10 4 ; Particularly preferred: ε≥3*10 4 ; Most preferred: ε≥5*10 4 Preferably, the extinction coefficient refers to the extinction coefficient at the wavelength corresponding to the absorption peak.

[0074] In certain embodiments, the absorption spectrum of the organic compound H1 is between 380 nm and 620 nm.

[0075] In certain embodiments, the absorption spectrum of the organic compound H1 is between 380 nm and 580 nm.

[0076] In certain embodiments, the absorption spectrum of the organic compound H1 is between 380 nm and 500 nm.

[0077] In some preferred embodiments, the luminescence spectrum of the organic compound H1 is between 440 nm and 510 nm.

[0078] In some preferred embodiments, the luminescence spectrum of the organic compound H1 is between 510 nm and 600 nm.

[0079] In a preferred embodiment, the wavelength corresponding to the peak of the luminescence spectrum of the organic compound H1 is less than 500 nm.

[0080] In other preferred embodiments, the wavelength corresponding to the peak of the luminescence spectrum of the organic compound H1 is between 500 nm and 580 nm.

[0081] In a preferred embodiment, the organic compound H1 is a non-DA structure.

[0082] In the present invention, the energy level structure of organic materials, including the triplet energy level (T1) and singlet energy level (S1), HOMO, LUMO, and the resonance factor intensity f, have a significant impact on their optoelectronic properties and stability. The following describes how to determine these parameters.

[0083] HOMO and LUMO energy levels can be measured by photoelectric effects, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy), or by cyclic voltammetry (CV). Recently, quantum chemical methods, such as density functional theory (DFT), have also become effective methods for calculating molecular orbital energy levels.

[0084] The triplet energy level T1 of the organic material can be measured by low-temperature time-resolved luminescence spectroscopy, or obtained by quantum simulation calculation (such as by Time-dependent DFT), such as by the commercial software Gaussian 09W (Gaussian Inc.), and the specific simulation method is described below.

[0085] The singlet energy level S1 of an organic material can be determined by absorption or emission spectroscopy, or obtained by quantum simulation calculations (such as Time-dependent DFT); the resonance factor intensity f can also be obtained by quantum simulation calculations (such as Time-dependent DFT).

[0086] It should be noted that the absolute values ​​of HOMO, LUMO, T1, and S1 depend on the measurement or calculation method used. Even for the same method, different evaluation methods, such as the starting point and peak point on the CV curve, can give different HOMO / LUMO values. Therefore, reasonable and meaningful comparisons should be made using the same measurement and evaluation methods. In the description of the embodiments of the present invention, the values ​​of HOMO, LUMO, T1, and S1 are based on time-dependent DFT simulations, but this does not affect the application of other measurement or calculation methods.

[0087] For the purposes of this invention, (HOMO-1) is defined as the second-highest occupied molecular orbital energy level, (HOMO-2) is the third-highest occupied molecular orbital energy level, and so on. (LUMO+1) is defined as the second-lowest unoccupied molecular orbital energy level, (LUMO+2) is the third-lowest occupied molecular orbital energy level, and so on; these energy levels can be determined by the simulation method described below.

[0088] In a preferred embodiment, the organic compound H1 has a larger ΔHOMO and / or ΔLUMO, generally ≥0.20 eV, preferably ≥0.30 eV, more preferably ≥0.40 eV, even better ≥0.45 eV, and most preferably ≥0.50 eV; wherein ΔHOMO = HOMO-(HOMO-1), ΔLUMO = (LUMO+1)-LUMO.

[0089] In a more preferred embodiment, the organic compound H1 has a larger resonance factor f(Sn) (n≥1); generally f(S1)≥0.20eV, preferably ≥0.30eV, more preferably ≥0.40eV, even better ≥0.50eV, and most preferably ≥0.60eV.

[0090] In certain embodiments, the organic compound H1 has a relatively low HOMO, generally ≤-5.0 eV, preferably ≤-5.1 eV, more preferably ≤-5.2 eV, even more preferably ≤-5.3 eV, and most preferably ≤-5.4 eV.

[0091] In other embodiments, the organic compound H1 has a relatively high LUMO, which is generally ≥-3.0 eV, preferably ≥-2.9 eV, more preferably ≥-2.8 eV, even more preferably ≥-2.7 eV, and most preferably -2.6 eV.

[0092] Suitable organic compound H1 can be selected from organic small molecules, polymers or metal complexes.

[0093] In certain preferred embodiments, the organic compound H1 can be selected from aromatic hydrocarbon compounds containing rings, such as benzene, biphenyl, triphenylbenzene, triphenylene, naphthalene, anthracene, phenanthrene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indole, carbazole, pyridine, indole, pyrrole, dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, , indoleazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalide, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furandipyridine, benzothiophene pyridine, thiophene dipyridine, benzoselenophene pyridine and selenophene dipyridine; containing groups having 2 to 10 ring structures, which can be cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups of the same or different types, and are linked to each other directly or through at least one of the following groups, such as oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups.

[0094] In other embodiments, the organic compound H1 is selected from compounds having a long conjugated π electron system. To date, there have been many examples, such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729A1, and indenofluorene and its derivatives disclosed in WO2008 / 006449 and WO2007 / 140847.

[0095] In a preferred embodiment, the organic compound H1 can be selected from monostyrylamine, distyrylamine, tristyrylamine, tetrastyrylamine, styrylphosphine, styryl ether or aromatic amine.

[0096] A monostyrylamine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrylamine is a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tert-styrylamine is a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tetrastyrylamine is a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A preferred styrene is diphenylethylene, which may be further substituted. The corresponding phosphines and ethers are defined similarly to the amines. An arylamine or aromatic amine is a compound comprising three unsubstituted or substituted aromatic or heterocyclic rings directly attached to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Preferred examples include aromatic anthracenamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, and aromatic chrysenediamines. An aromatic anthracenamine is a compound in which a diarylamine group is directly attached to anthracene, preferably at the 9-position. An aromatic anthracenediamine is a compound in which two diarylamine groups are directly attached to anthracene, preferably at the 9- and 10-positions. Aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysamines, and aromatic chrysenediamines are similarly defined, with the diarylamine groups preferably attached to the 1- or 1,6-positions of the pyrene group.

[0097] Examples of organic compounds H1 based on vinylamine and aromatic amine can be found in the following patent documents: WO2006 / 000389, WO2007 / 065549, US7250532B2, DE102005058557A1, CN1583691A, JP08053397A, US6251531B1, US2006 / 210830A, EP1957606A1 and US2008 / 0113101A1. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0098] Examples of organic compounds H1 based on stilbene and its derivatives are given in US Pat. No. 5,121,029.

[0099] Further preferred organic compounds H1 can be selected from indenofluorene-amine and indenofluorene-diamine, as disclosed in WO2006 / 122630, benzoindenofluorene-amine and benzoindenofluorene-diamine, as disclosed in WO2008 / 006449, and dibenzoindenofluorene-amine and dibenzoindenofluorene-diamine, as disclosed in WO2007 / 140847.

[0100] Other materials that can be used as organic compound H1 include polycyclic aromatic hydrocarbon compounds, especially derivatives of the following compounds: anthracene such as 9,10-di(2-naphthyl)anthracene, naphthalene, tetracene, xanthene, phenanthrene, pyrene (such as 2,5,8,11-tetra-t-butylperylene), indenopyrene, benzo-fused ring such as (4,4'-bis(9-ethyl-3-carbazolylvinyl)-1,1'-biphenyl), diindenopyrene, decacycloene, hexabenzophenone, fluorene, spirobifluorene, arylpyrene (such as US20060222886), arylene vinyl (such as US512 1029, US Pat. No. 5,130,603), cyclopentadiene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4-(dicyanomethylene)-6-(4-(p-dimethylaminophenyl)-2-methyl)-4H-pyran (DCM), thiopyran, bis(azinyl)imine boron compounds (US Pat. No. 2007 / 0092753A1), bis(azinyl)methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles, and diketopyrrolopyrroles. Some materials for singlet emitters can be found in the following patent documents: US Pat. No. 20070252517A1, US Pat. No. 4,769,292, and US Pat. No. 6,020,078. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0101] The organic functional materials publications appearing above are incorporated herein by reference for disclosure purposes.

[0102] In a more preferred embodiment, the inorganic nanoluminescent body, wherein the organic compound H1 is selected from any one of the following chemical formulas (III-1) to (III-21):

[0103] wherein: X is selected from O, S, SO2, NR1 or CR2R3; Ar1-Ar4, when they occur multiple times, may be the same or different and be selected from aromatic or heteroaromatic groups having 5 to 60 ring atoms; R0-R3, when they occur each time, may be the same or different and be selected from H or D, or a linear alkyl, haloalkyl, alkoxy, thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy group, silyl group having 3 to 20 carbon atoms, or a keto group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms group, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, I, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or an arylamine or heteroarylamine group having 5 to 40 ring atoms, a disubstituted unit at any position of the above groups or a combination of these groups, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which the group is bonded.

[0104] Some examples of suitable ligands comprising the structure of organic compound H1 are listed below (but are not limited thereto), which may be further substituted with any desired substitutions:

[0105] According to the inorganic nanoluminescent body of the present invention, the absorption spectrum of the inorganic nanoluminescent body core and the emission spectrum of the organic compound H1 have a large overlap, and a relatively efficient energy transfer can be achieved between them ( Resonance Energy Transfer(FRET)).

[0106] In certain preferred embodiments, the luminescence spectrum of the inorganic nanoluminescent body is completely derived from the core of the inorganic nanoluminescent body, that is, complete energy transfer is achieved between the core of the inorganic nanoluminescent body and the organic compound H1.

[0107] In certain embodiments, the inorganic nanoluminescent body comprises the structures of two or more organic compounds H1.

[0108] In one embodiment, the inorganic nanoluminescent body has a light emission wavelength range from UV to near infrared, preferably from 350 nm to 850 nm, more preferably from 380 nm to 800 nm, and most preferably from 380 nm to 680 nm.

[0109] The present invention also relates to a method for preparing the inorganic nanoluminescent material. The following describes a method for preparing hybrid quantum dots QD(LA) using quantum dots QD(OA) with oleic acid (OA) as a ligand as an example (without loss of generality), as shown in the following formula:

[0110] Hybrid quantum dots can be prepared by ligand exchange reaction of oleic acid (OA) with carboxylic acid derivatives of organic light-emitting materials (LA, luminescent acid):

[0111] 1) A luminescent acid ligand (LA) dissolved in an organic solvent (such as toluene) is added to a QD (OA) solution at a certain concentration; the resulting solution is mixed by shaking to achieve ligand exchange and obtain QD (LA).

[0112] 2) Transfer the mixture to a dialysis membrane (molecular cut-off: 3500 g / mol) and purify it with an organic solvent (e.g., toluene). Exchange the toluene with fresh toluene at regular intervals until free ligand is no longer detected.

[0113] 3) The QD(LA) solution was concentrated to 5 mL to prepare the QD(LA) stock solution.

[0114] The present invention further relates to a composition comprising the inorganic nanoluminescent body, an organic solvent and / or an organic resin.

[0115] For the purpose of the present invention, the organic resin refers to a resin prepolymer or a resin formed after crosslinking or curing.

[0116] In a preferred embodiment, the composition comprises two or more organic resins.

[0117] Organic resins suitable for the present invention include, but are not limited to, polystyrene, polyacrylate, polymethacrylate, polycarbonate, polyurethane, polyvinyl pyrrolidone, polyvinyl acetate, polybutylene, polyethylene glycol, polysiloxane, epoxy resin, polyvinyl alcohol, polyacrylonitrile, polyvinylidene chloride (PVDC), polystyrene-acrylonitrile (SAN), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl butyrate (PVB), polyvinyl chloride (PVC), polyamide, polyoxymethylene, polyimide, polyetherimide, or mixtures thereof.

[0118] Furthermore, organic resins suitable for the present invention include but are not limited to those formed by homopolymerization or copolymerization of the following monomers (resin prepolymers): styrene derivatives, acrylate derivatives, acrylonitrile derivatives, acrylamide derivatives, vinyl ester derivatives, vinyl ether derivatives, maleimide derivatives, and conjugated diene derivatives.

[0119] Examples of styrene derivatives include alkylstyrenes such as α-methylstyrene, o-, m- and p-methylstyrene, p-butylstyrene, especially p-tert-butylstyrene, and alkoxystyrenes such as p-methoxystyrene, p-butoxystyrene and p-tert-butoxystyrene.

[0120] Examples of acrylate derivatives include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl meth ...ethyl acrylate, 2-hydroxypropyl acrylate 2-Hydroxybutyl methacrylate, 2-Hydroxybutyl methacrylate, 3-Hydroxybutyl acrylate, 3-Hydroxybutyl methacrylate, 4-Hydroxybutyl acrylate, 4-Hydroxybutyl methacrylate, Allyl acrylate, Allyl methacrylate, Benzyl acrylate, Benzyl methacrylate, Cyclohexyl acrylate, Cyclohexyl methacrylate, Phenyl acrylate, Phenyl methacrylate, 2-Methoxyethyl acrylate, 2-Methoxyethyl methacrylate, 2-Phenoxyethyl acrylate, 2-Phenoxyethyl methacrylate, Methoxydiglycol acrylate, Methoxydiglycol methacrylate, Methoxytriglycol acrylate, Methoxy Oxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glyceryl monoacrylate and glyceryl monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate Methylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, N,N-dimethyl-1,3-propylenediamine benzyl (meth)acrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate, glycidyl acrylate and glycidyl methacrylate.

[0121] Examples of the acrylonitrile derivatives are acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide.

[0122] Examples of the acrylamide derivatives are acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethylmethacrylamide.

[0123] Examples of vinyl ester derivatives are vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate.

[0124] Examples of the vinyl ether derivatives are vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether.

[0125] Examples of maleimide derivatives include maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide.

[0126] Examples of conjugated diene derivatives are 1,3-butadiene, isoprene and chloroprene.

[0127] The homopolymer or copolymer can be prepared by, for example, free radical polymerization, cationic polymerization, anionic polymerization or organometallic catalytic polymerization (such as Ziegler-Natta catalysis). The polymerization process can be suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization.

[0128] The organic resin generally has an average molar mass Mn (determined by GPC) of 10,000 g / mol to 1,000,000 g / mol, preferably 20,000 g / mol to 750,000 g / mol, more preferably 30,000 g / mol to 500,000 g / mol.

[0129] In some preferred embodiments, the organic resin is a thermosetting resin or a light-curable resin. In certain preferred embodiments, the organic resin is a UV-curable resin. In some embodiments, the organic resin is cured using a method that facilitates roll-to-roll processing.

[0130] Thermosetting resins require curing, during which they undergo irreversible molecular crosslinking, which 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-formaldehyde resin, an unsaturated polyester resin, a polyurethane resin, an allyl resin, an acrylic resin, a polyamide resin, a polyamide-imide resin, a phenolamine polycondensation resin, a urea-melamine polycondensation resin, or a combination thereof.

[0131] In some embodiments, the thermosetting resin is an epoxy resin. Epoxy resins cure easily without volatile emissions or byproducts from a wide range of chemicals. Epoxy resins are also compatible with most substrates and tend to wet surfaces easily. See Boyle, MA et al., "Epoxy Resins," Composites, Vol. 21, ASM Handbook, pages 78-89 (2001).

[0132] In some embodiments, the organic resin is a silicone thermosetting resin. In some embodiments, the silicone thermosetting resin is 0E6630A or 0E6630B (Dow Corning Corporation (Auburn, Michigan)).

[0133] In some embodiments, a thermal initiator is used. In some embodiments, the thermal initiator is AIBN [2,2'-azobis(2-methylpropionitrile)] or benzoyl peroxide.

[0134] UV curable resins are polymers that cure and harden rapidly when exposed to light of a specific wavelength. In some embodiments, the UV curable resin is a resin having free radical polymerizable groups, such as (meth)acryloyloxy groups, vinyloxy groups, styryl groups, or vinyl groups, or cationic polymerizable groups as functional groups; the free radical polymerizable groups are, for example, epoxy groups, thioepoxy groups, vinyloxy groups, or oxetane groups; and the cationic polymerizable groups are, for example, epoxy groups, thioepoxy groups, vinyloxy groups, or oxetane groups. In some embodiments, the UV curable resin is a polyester resin, a polyether resin, a (meth)acrylic resin, an epoxy resin, a polyurethane resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, or a thioolefin resin.

[0135] In some embodiments, the UV curable resin is selected from polyurethane acrylate, allyloxylated cyclohexyl diacrylate, bis(acryloyloxyethyl)hydroxyisocyanurate, bis(acryloyloxyneopentyl glycol) adipate, bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, dicyclopentyl diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, di(trimethylolpropane) tetraacrylate, triethylene glycol dimethacrylate, glyceryl methacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol hydroxypivalic acid diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate. Acrylates, phosphoric acid dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, tetrabromobisphenol A diacrylate, triethylene glycol divinyl ether, triglycerol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, tris(acryloyloxyethyl) isocyanurate, phosphoric acid triacrylate, phosphoric acid diacrylate, monopropyl acrylate, vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated difluoromethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane, monomethacryloxypropyl-terminated polydimethylsiloxane, monovinyl-terminated polydimethylsiloxane, monoallyl-monotrimethylsiloxy-terminated polyethylene oxide, and combinations thereof.

[0136] In some embodiments, the UV curable resin is a thiol functional compound that can be cross-linked with an isocyanate, an epoxy resin, or an unsaturated compound under UV curing conditions. In some embodiments, the thiol functional compound is a polythiol. In some embodiments, the polythiol is pentaerythritol tetrakis (3-mercaptopropionate) (PETMP); trimethylolpropane tris (3-mercaptopropionate) (TMPMP); ethylene glycol di (3-mercaptopropionate) (GDMP); tris [25- (3-mercapto-propionyloxy) ethyl] isocyanurate (TEMPIC); dipentaerythritol hexa (3-mercaptopropionate) (Di-PETMP); ethoxylated trimethylolpropane tris (3-mercaptopropionate) (ETTMP 1300 and ETTMP 700); polycaprolactone tetrakis (3-mercaptopropionate) (PCL4MP1350); pentaerythritol tetrakis mercaptoacetate (PETMA); trimethylolpropane tris mercaptoacetate (TMPMA); or ethylene glycol dimercaptoacetate (GDMA). These compounds are commercially available from Bruno Bock (Malschacht, Germany) under the trade name sell.

[0137] In some embodiments, the UV curable resin further comprises a photoinitiator. The photoinitiator initiates a crosslinking and / or curing reaction of the photosensitive material during exposure to light. In some embodiments, the photoinitiator is an acetophenone-based, benzoin-based, or thioxanthone-based compound that can initiate polymerization, crosslinking, and curing of the monomer.

[0138] In some embodiments, the UV curable resin comprises a mercapto functional compound and a methacrylate, an acrylate, an isocyanate, or a combination thereof. In some embodiments, the UV curable resin comprises a polythiol and a methacrylate, an acrylate, an isocyanate, or a combination thereof.

[0139] In some embodiments, the photoinitiator is MINS-311RM (Minuta Technology Co., Ltd (Korea)).

[0140] In some embodiments, the photoinitiator is 127. 184. 184D, 2022, 2100, 250, 270, 2959, 369, 369EG, 379, 500, 651, 754, 784, 819, 819DW, 907, 907FF, OxeOl, TPO-L, 1173, 1173D, 4265, BP or MBF (BASF Corporation (Wyandotte, Michigan)). In some embodiments, the photoinitiator is TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) or MBF (methyl benzoylformate).

[0141] In some embodiments, the organic resin has a weight ratio between 20 wt % and 99 wt %.

[0142] In some embodiments, the organic resin is present in an amount by weight (weight / weight) of about 20% to about 99%, about 20% to about 95%, about 20% to about 90%, about 20% to about 85%, about 20% to about 80%, about 20% to about 70%, about 20% to about 60%, about 40% to about 99%, about 40% to about 95%, about 40% to about 90%, about 40% to about 85%, about 40% to about 80%, about 40% to about 70%, about 70% to about 99%, about 70% to about 95%, about 70% to about 90%, about 70% to about 85%, about 70% to about 80%, about 80% to about 99%, about 80% to about 95%, about 80% to about 90%, about 80% to about 85%, about 85% to about 99%, about 85% to about 95%, about 85% to about 90%, about 90% to about 99%, about 90% to about 95%, or about 95% to about 99%.

[0143] In a preferred embodiment, the composition according to the present invention is a solution.

[0144] In another preferred embodiment, the composition according to the present invention is a suspension.

[0145] The composition in the embodiment of the present invention may include 0.01wt% to 20wt% of the inorganic nano-luminescent body, preferably 0.1wt% to 20wt%, more preferably 0.2wt% to 20wt%, and most preferably 2wt% to 15wt% of the inorganic nano-luminescent body.

[0146] The composition of the present invention can be used to form a color conversion layer using methods such as inkjet printing, transfer printing, and photolithography. In this case, the inorganic nanoluminescent material is dissolved alone or together with other materials in a resin (prepolymer) and / or an organic solvent to form an ink. The mass concentration of the inorganic nanoluminescent material in the ink is not less than 0.1 wt%.

[0147] In a preferred embodiment, the inorganic nanoluminescent material according to the present invention is used as a color conversion material. The color conversion capability of the color conversion layer can be improved by adjusting the concentration of the color conversion material in the ink and the thickness of the color conversion layer. Generally speaking, the higher the concentration of the color conversion material or the thicker the color conversion layer, the higher the color conversion efficiency of the color conversion layer.

[0148] In some preferred embodiments, the solvent is selected from water, alcohol, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, or inorganic ester compounds such as borate or phosphate, or a mixture of two or more solvents.

[0149] In other embodiments, suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, diols or polyols.

[0150] In other embodiments, alcohols represent an appropriate class of solvents. Preferred alcohols include alkylcyclohexanols, particularly methylated aliphatic alcohols, naphthols, and the like.

[0151] Other examples of suitable alcohol solvents include: dodecanol, phenyl tridecanol, benzyl alcohol, ethylene glycol, ethylene glycol methyl ether, glycerol, propylene glycol, propylene glycol ethyl ether and the like.

[0152] The solvent may be used alone or as a mixture of two or more organic solvents.

[0153] Further, examples of organic solvents include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetralin, decalin, indene and / or mixtures thereof.

[0154] In some preferred embodiments, according to the composition of the present invention, the organic solvent is selected from aromatic or heteroaromatic compounds, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, alicyclic or olefinic compounds, or inorganic ester compounds such as borate or phosphate esters, or a mixture of two or more solvents.

[0155] Examples of aromatic or heteroaromatic solvents according to the present invention include, but are not limited to: 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, 1-methylnaphthalene, 1,2,4 -Trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, diphenyl ether, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.

[0156] In other embodiments, suitable and preferred solvents are aliphatic, alicyclic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers.

[0157] The solvent may be a cycloalkane, such as decalin.

[0158] In other preferred embodiments, a composition according to the present invention comprises at least 50 wt% of an alcohol solvent, preferably at least 80 wt% of an alcohol solvent, and particularly preferably at least 90 wt% of an alcohol solvent.

[0159] In some preferred embodiments, the solvents particularly suitable for the present invention are solvents having a Hansen solubility parameter within the following ranges:

[0160] δ d (Dispersion force) at 17.0 MPa 1 / 2 ~23.2MPa 1 / 2 range, especially at 18.5MPa 1 / 2 ~21.0MPa 1 / 2 scope;

[0161] δ p (Polar force) at 0.2MPa 1 / 2 ~12.5MPa 1 / 2 range, especially at 2.0MPa 1 / 2 ~6.0MPa 1 / 2 scope;

[0162] δ h (Hydrogen bond force) at 0.9MPa 1 / 2 ~14.2MPa 1 / 2 range, especially at 2.0MPa 1 / 2 ~6.0MPa 1 / 2 range.

[0163] In the composition of the present invention, the organic solvent should be selected based on its boiling point. In the present invention, the boiling point of the organic solvent is ≥150°C; preferably ≥180°C; more preferably ≥200°C; even more preferably ≥250°C; and most preferably ≥275°C or ≥300°C. Boiling points within these ranges are beneficial for preventing nozzle clogging in inkjet printheads. The organic solvent can be evaporated from the solvent system to form a film containing the functional material.

[0164] In some preferred embodiments, the composition according to the present invention is characterized in that

[0165] 1) Its viscosity @25℃ is in the range of 1cps to 100cps, and / or

[0166] 2) Its surface tension @25℃ is in the range of 19 dyne / cm to 50 dyne / cm.

[0167] In the composition of the present invention, the surface tension parameters of the resin (prepolymer) or organic solvent should be considered when selecting. The appropriate surface tension parameters are tailored to the specific substrate and printing method. For example, for inkjet printing, in a preferred embodiment, the surface tension of the resin (prepolymer) or organic solvent at 25°C is approximately in the range of 19 dyne / cm to 50 dyne / cm; more preferably, in the range of 22 dyne / cm to 35 dyne / cm; and most preferably, in the range of 25 dyne / cm to 33 dyne / cm.

[0168] In a preferred embodiment, the surface tension of the composition according to the present invention at 25°C is in the range of about 19 dyne / cm to 50 dyne / cm; more preferably in the range of 22 dyne / cm to 35 dyne / cm; and most preferably in the range of 25 dyne / cm to 33 dyne / cm.

[0169] According to the composition of the present invention, the viscosity parameters of the ink need to be considered when selecting the resin (prepolymer) or organic solvent. The viscosity can be adjusted by different methods, such as by selecting a suitable resin (prepolymer) or organic solvent and the concentration of the functional material in the ink. In a preferred embodiment, the viscosity of the resin (prepolymer) or organic solvent is less than 100 cps; more preferably less than 50 cps; and most preferably 1.5 to 20 cps. The viscosity here refers to the viscosity at the ambient temperature during printing, generally 15°C-30°C, preferably 18°C-28°C, more preferably 20°C-25°C, and most preferably 23°C-25°C. The composition thus formulated will be particularly suitable for inkjet printing.

[0170] In a preferred embodiment, the composition according to the present invention has a viscosity at 25°C in the range of about 1 cps to 100 cps; more preferably in the range of 1 cps to 50 cps; and most preferably in the range of 1.5 cps to 20 cps.

[0171] The ink obtained from the resin (prepolymer) or organic solvent that satisfies the above-mentioned boiling point, surface tension parameters, and viscosity parameters can form a functional thin film with uniform thickness and composition properties.

[0172] The present invention further relates to a functional film, which comprises an inorganic nanoluminescent body as described above or is prepared using a composition as described above.

[0173] The present invention also provides a method for preparing the functional film, comprising the following steps:

[0174] 1) preparing a composition comprising an inorganic nanoluminescent body according to the present invention;

[0175] 2) coating the composition on a substrate to form a thin film by printing or coating, wherein the printing or coating method is selected from inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roll printing, offset printing, flexographic printing, rotary printing, spray coating, brush coating, pad printing, or slot die coating;

[0176] 3) The obtained film is heated at at least 50° C. to remove the solvent and form a solid film.

[0177] The thickness of the functional film is generally 50nm-200μm, preferably 100nm-150μm, and most preferably 500nm-100μm.

[0178] In another preferred embodiment, the thickness of the functional film is 20nm-50μm, preferably 20nm-40μm, more preferably 20nm-30μm, very preferably 20nm-20μm, particularly preferably 20nm-10μm, and most preferably 20nm-5μm.

[0179] The present invention also provides the application of the inorganic nano-luminescent body and the functional film in optoelectronic devices.

[0180] In certain embodiments, the optoelectronic device may be selected from an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic light emitting field effect transistor (OLED), an organic laser, or a color converter.

[0181] Furthermore, the present invention provides a photoelectric device comprising an inorganic nanoluminescent body or functional film as described above.

[0182] Preferably, the optoelectronic device is an electroluminescent device, such as an organic light emitting cell (OLEEC), an organic light emitting field effect tube, a perovskite light emitting diode (PeLED), and a quantum dot light emitting diode (QD-LED), wherein the light emitting layer contains one of the above-mentioned inorganic nanoluminescent bodies.

[0183] In a preferred embodiment, the optoelectronic device is an electroluminescent device comprising two electrodes and a light-emitting layer, wherein the light-emitting layer is located between the two electrodes, wherein the light-emitting layer comprises an inorganic nanoluminescent body as described above.

[0184] In another preferred embodiment, the optoelectronic device comprises a light-emitting unit and a color conversion layer, wherein the color conversion layer comprises an inorganic nanoluminescent body or functional film as described above or is prepared using a composition as described above.

[0185] In certain preferred embodiments, the light-emitting unit is selected from a solid-state light-emitting device. The solid-state light-emitting device is preferably selected from a light-emitting diode (LED), an organic light-emitting diode (OLED), an organic light-emitting cell (OLEEC), an organic light-emitting field-effect transistor (OLED), a perovskite light-emitting diode (PeLED), and a quantum dot light-emitting diode (QD-LED).

[0186] In a preferred embodiment, the light emitting unit emits blue light, which is converted into green light or red light by the color conversion layer.

[0187] In some embodiments, the light emitting unit emits green light or yellow light, which is converted into red light by the color conversion layer.

[0188] The present invention further relates to a display comprising at least three types of pixels: red, green, and blue. As shown in FIG1 , the blue pixel comprises a blue light emitting unit, and the red and green pixels comprise a blue light emitting unit and corresponding red and green color conversion layers.

[0189] Example

[0190] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should realize that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0191] Example 1: Preparation of Luminescent Acid (LA1)

[0192] Under inert conditions, 9,10-dibromoanthracene 1 (5 g, 14.88 mmol), phenylacetylene 2 (1.52 g, 14.88 mol), Pd (PPh 3 ) 2 Cl 2 (2%) and CuI (4%) were dissolved in a mixture of toluene (100 mL) and triethylamine (20 mL) and heated to 80° C. overnight. After cooling to room temperature, the mixture was diluted with DCM and washed with 2M hydrochloric acid and water. The organic matter was dried over magnesium sulfite and the solvent was removed in vacuo. The crude product was purified by recrystallization from DCM / hexane to give the product 3 (1.81 g, 34%) as a bright yellow solid.

[0193] 4-bromobenzoic acid methyl ester 4 (10g, 46.5mmol), Pd (PPh 3 ) 2Cl 2 (1%) and CuI (2%) are dissolved in the mixture of 200mL toluene and 50mL triethylamine. Exchange air with nitrogen, then add trimethylsilyl acetylene 5 (9.13g, 93mmol) with syringe. The gained mixture was stirred 16 hours at 80 ℃. The reaction soln was cooled to room temperature, and washed with 2M hydrochloric acid and water. Use rotary evaporation to remove solvent, and obtain light brown waxy solid product 6 (10g) by filtering the raw material with silica gel. With 12mL tetrabutylammonium fluoride (1M THF) the alkyne product 6 (2.32g, 10mmol is dissolved among the 100mL DCM) of trimethylsilyl protection deprotection. Use TLC to monitor the reaction. Make the reaction quenching by adding water, extract with DCM and dry with magnesium sulfate. After removal of the solvent in vacuo, the resulting crude product was purified using silica gel chromatography (10% DCM in hexanes) to afford the product 7 (1.5 g, 94%) as a colorless solid.

[0194] Under inert condition, with product 3 (1g, 2.8mmol), product 7 (0.9g, 5.6mmol), Pd (PPh ) Cl (5%) and CuI (10%) are dissolved in the mixture of 20mL toluene and 5mL triethylamine.Mixture was stirred 24 hours down at 80 ℃, then cooled to room temperature and diluted with DCM again.Organic matter is washed with 2M hydrochloric acid and water, and dried over magnesium sulfate.Under reduced pressure, remove solvent, and use 20%DCM in hexane as the crude product that obtains by silica gel column chromatography purification of eluent.Realize further purification by recrystallization from DCM / hexane mixture, thereby obtain the product 8 (892mg, 73%) of orange solid.

[0195] Product 8 (500 mg, 1.15 mmol) was placed in a round-bottom flask and 30 mL of ethanol was added. The dispersion was treated with 10 mL of a 10% NaOH aqueous solution and stirred at 80° C. for one day until it became a clear solution. After cooling to room temperature, a 10% HCl aqueous solution was added, the formed precipitate was filtered out and washed with water. The solid was dried in vacuo to obtain product 9 (LA1) as a bright orange solid (370 mg, 76%).

[0196] Synthetic intermediate A-1

[0197] Under inert conditions, a mixture of 4-bromo-6-tert-butyldibenzo[b,d]furan (30.3 g, 100 mmol), 2-aminotoluene (10.5 g, 98 mmol), NaOtBu (28.8 g, 300 mmol), tBu3P (1.01 g, 5 mmol), and Pd(OAc)2 (0.56 g, 2.5 mmol) was dissolved in 500 mL of toluene and stirred at 120°C for 12 hours. After the reaction was cooled to room temperature, dichloromethane was added, and the organic layer was washed with water and separated. The organic layer was dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography (2% ethyl acetate in n-hexane) to obtain the target intermediate A-1 as a light yellow compound (24.9 g, 77%).

[0198] Synthetic intermediate A-2

[0199] Under inert conditions, iodobenzene (20.4 g, 100 mmol), ethyl 4-aminobenzoate (16.2 g, 98 mmol), NaOtBu (28.8 g, 300 mmol), tBu3P (1.01 g, 5 mmol), and Pd(OAc)2 (0.56 g, 2.5 mmol) were dissolved in 500 mL of toluene and heated to 120°C for 4 hours. After the reaction was cooled to room temperature, dichloromethane was added, the mixture was washed with water, and the layers were separated. The organic material was dried over sodium sulfate, filtered, and evaporated under reduced pressure. The crude product was chromatographed on a silica gel column using 10% ethyl acetate in hexane as the eluent to obtain Intermediate A-2 (12.9 g, 53%) as a white solid.

[0200] Synthetic intermediate A-3

[0201] A mixture of 1-bromo-2,4-dimethylbenzene (18.5 g, 100 mmol), 1-amino-2,4-dimethylbenzene (11.9 g, 98 mmol), NaOtBu (28.8 g, 300 mmol), tBu3P (1.01 g, 5 mmol), and Pd(OAc)2 (0.56 g, 2.5 mmol) was dissolved in 500 mL of toluene solution and heated to 120°C under a nitrogen atmosphere for 6 hours. After cooling to room temperature, dichloromethane was added, and the mixture was washed with water and separated. The organic material was dried over sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The resulting crude product was purified by silica gel column chromatography (2% ethyl acetate in n-hexane) to obtain intermediate A-3 (15.2 g, 69%) as a white solid.

[0202] Synthesis of compounds 1-4

[0203] Fluorene 1-1 (3.1 g, 10 mmol), intermediate A-1 (3.3 g, 10 mmol), NaOtBu (2.9 g, 30 mmol), tBu3P (0.101 g, 0.5 mmol) and Pd(OAc)2 (56 mg, 0.25 mmol) were dissolved in 50 mL of toluene under a protective gas atmosphere and heated at 120°C for 12 hours. The mixture was cooled to room temperature and diluted with DCM. The organic matter was washed with water and separated. Sodium sulfate was added to the organic matter, dried, filtered, and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography (5% ethyl acetate in hexane) to give intermediate 1-2 as a light yellow powder (2.06 g, 37%).

[0204] Under inert conditions, a mixture of Intermediate 1-2 (1.11 g, 2 mmol), Intermediate A-2 (531 mg, 2.2 mmol), NaOtBu (577 mg, 6 mmol), XPhos (95 mg, 0.2 mmol), and Pd2dba3 (92 mg, 0.1 mmol) was dissolved in 20 mL of toluene and stirred at 120°C for 24 hours. After cooling to room temperature, DCM was added, the mixture was washed with water, and the liquids were separated. The organic material was dried over sodium sulfate and filtered. The solvent was removed by rotary evaporation, and the product was purified by silica gel column chromatography using 10% ethyl acetate in hexane as the eluent. The target product, Intermediate 1-3, was obtained as a light yellow powder (822 mg, 54%).

[0205] Intermediate 1-3 (761 mg, 1 mmol) was dispersed in 20 mL of ethanol and 5 mL of 50% w / w aqueous NaOH solution was added. The resulting mixture was stirred at 80°C for 5 hours to form a clear solution. The solution was washed with ether and concentrated hydrochloric acid was added to form a solid, which was filtered and washed with water. The solid was dissolved in DCM, washed with water, and the liquids were separated. Sodium sulfate was added to the organic material and dried, and filtered. After evaporation of the solvent, the residue was recrystallized from ethanol to obtain product 1-4 as a yellow solid (682 mg, 93%).

[0206] Synthesis of compounds 2-4

[0207] A mixture of indene 2-1 (9.4 g, 20 mmol), diphenylamine (1.7 g, 10 mmol), NaOtBu (2.9 g, 30 mmol), tBu3P (101 mg, 0.5 mmol) and Pd(OAc)2 (56 mg, 0.25 mmol) was dissolved in 50 mL of toluene and heated to 120°C under nitrogen for 6 hours. After cooling to room temperature, the mixture was diluted with DCM, rinsed with water, and separated. The organic material was dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (5% ethyl acetate in hexane) to obtain the target compound 2-2 as a light yellow solid (2.4 g, 43%).

[0208] Under inert conditions, compound 2-2 (1.11 g, 2 mmol), intermediate A-2 (531 mg, 2.2 mmol), NaOtBu (57 mg, 6 mmol), tBu3P (40 mg, 0.2 mmol), and Pd(OAc)2 (22 mg, 0.1 mmol) were dissolved in 20 mL of toluene and heated at 120°C for 20 hours. The reaction was cooled to room temperature, diluted with DCM, rinsed with water, and the layers separated. The organic material was dried over sodium sulfate, filtered, and the solvent evaporated to afford a brown product. Silica gel column chromatography using 10% ethyl acetate in hexane as the eluent afforded the desired product, indenylene 2-3, as a yellow solid (1061 mg, 74%).

[0209] Indene 2-3 (717 mg, 1 mmol) was dispersed in 20 mL of ethanol and 5 mL of 50% w / w aqueous NaOH solution was added. The reaction was stirred at 80°C until clear, and the solution was washed with ether at room temperature. Concentrated hydrochloric acid was then added to form a precipitate, which was filtered, rinsed with water, and dissolved in DCM. The organic phase was washed with water and separated. The organic phase was dried over sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The residue was recrystallized from ethanol to give the product compound 2-4 as a yellow powder (613 mg, 89%).

[0210] Synthesis of compound 3-4

[0211] Under inert conditions, a mixture of compound 3-1 (14.0 g, 20 mmol), intermediate A-3 (2.3 g, 10 mmol), NaOtBu (2.9 g, 30 mmol), tBu3P (101 mg, 0.5 mmol) and Pd(OAc)2 (56 mg, 0.25 mmol) was dissolved in 50 mL of toluene and heated at 120°C for 8 hours. The reaction was cooled to room temperature, diluted with DCM, rinsed with water, and the liquids were separated. The organics were dried over sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The resulting product was purified by silica gel column chromatography and purified with 10% DCM in hexane to obtain the product compound 3-2 as a yellow solid (2.87 g, 37%).

[0212] Under a protective gas atmosphere, a mixture of compound 3-2 (1.11 g, 2 mmol), intermediate A-2 (531 mg, 2.2 mmol), NaOtBu (57 mg, 6 mmol), tBu3P (40 mg, 0.2 mmol), and Pd(OAc)2 (22 mg, 0.1 mmol) was dissolved in 20 mL of toluene solution and stirred at 120°C for 24 hours. After cooling to room temperature, DCM was added, the mixture was washed with water, and the layers were separated. The organic material was dried over sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. The raw material was subjected to silica gel column chromatography using 10% DCM and 10% ethyl acetate in hexane as eluents to obtain the product compound 3-3 as a bright yellow solid (1.37 g, 79%).

[0213] Compound 3-3 (867 mg, 1 mmol) was dispersed in 20 mL of ethanol, 5 mL of aqueous NaOH solution (50% w / w) was added, and the mixture was heated at 80°C for 12 hours. After cooling to room temperature, the mixture was washed with DCM and concentrated hydrochloric acid was added to form a precipitate. The solid was filtered off, rinsed with water, and dissolved in DCM. The organic phase was washed with water and separated. Sodium sulfate was added to the organic phase for drying, filtering, and concentrating in vacuo. The residue was recrystallized from DCM and ethanol to give the target compound 3-4 as yellow crystals (713 mg, 85%).

[0214] Synthesis of compound 4-4

[0215] Under inert conditions, a mixture of 9,10-dibromoanthracene 4-1 (6.7 g, 20 mmol), intermediate A-3 (2.3 g, 10 mmol), NaOtBu (2.9 g, 30 mmol), tBu3P (101 mg, 0.5 mmol), and Pd(OAc)2 (56 mg, 0.25 mmol) was dissolved in 50 mL of toluene and heated at 120°C for 20 hours. After cooling to room temperature, DCM was added, the mixture was rinsed with water, and the layers were separated. The organic material was dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure. The remaining liquid was purified by silica gel column chromatography (10% DCM in hexane) to obtain the product aminoanthracene 4-2 as a yellow solid (2.26 g, 47%).

[0216] Under nitrogen, aminoanthracene 4-2 (961 mg, 2 mmol), intermediate A-2 (531 mg, 2.2 mmol), NaOtBu (577 mg, 6 mmol), tBu3P (40 mg, 0.2 mmol), and Pd(OAc)2 (22 mg, 0.1 mmol) were dissolved in 20 mL of toluene and stirred at 120°C for 24 hours. The reaction was cooled to room temperature, diluted with DCM, rinsed with water, and the layers separated. The organics were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The raw material was chromatographed on a silica gel column using 10% DCM in hexane as the eluent to afford the product diaminoanthracene 4-3 as a yellow solid (859 mg, 67%).

[0217] Diaminoanthracene 4-3 (641 mg, 1 mmol) was suspended in 20 mL of ethanol and 5 mL of aqueous NaOH (50% w / w) was added. The mixture was refluxed until a clear solution was obtained. The solution was washed with ether and concentrated hydrochloric acid (aq) was carefully added until a precipitate was formed. The solid was filtered off, rinsed with water, and dissolved in DCM. The organic phase was washed with water and separated. Sodium sulfate was added to the organic phase and dried, and the product was filtered. The solvent was evaporated and recrystallized from DCM / ethanol to give compound 4-4 as a light yellow solid (576 mg, 94%).

[0218] Synthesis of compound 5-4

[0219] Dibromo A mixture of 5-1 (7.7 g, 20 mmol), intermediate A-3 (2.3 g, 10 mmol), NaOtBu (2.9 g, 30 mmol), tBu3P (101 mg, 0.5 mmol) and Pd(OAc)2 (56 mg, 0.25 mmol) was dissolved in 50 mL of toluene under inert conditions and heated at 120°C for 8 hours. After cooling to room temperature, DCM was added, washed with water, and the liquids were separated. Sodium sulfate was added to the organic matter to dry it, filtered, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (10% DCM in hexane) to obtain the product amino 5-2 was a yellow powder (2.22 g, 43%).

[0220] Under inert conditions, the amino 5-2 (1610 mg, 2 mmol), intermediate A-2 (531 mg, 2.2 mmol), NaOtBu (577 mg, 6 mmol), tBu3P (40 mg, 0.2 mmol), and Pd(OAc)2 (22 mg, 0.1 mmol) were dissolved in 20 mL of toluene and stirred at 120°C for 24 hours. DCM was added at room temperature, and the organic matter was washed with water and separated. Sodium sulfate was added to the organic matter to dry it, filtered, and the solution was evaporated and subjected to silica gel column chromatography with 10% ethyl acetate as the eluent. The synthetic product, compound 5-3, was obtained as a yellow powder (1.2 g, 87%).

[0221] Compound 5-3 (691 mg, 1 mmol) was dispersed in 20 mL of ethanol and 5 mL of aqueous NaOH (50% w / w) was added. The resulting mixture was refluxed for 12 hours. Then, after cooling to room temperature, the resulting solution was washed with DCM and concentrated hydrochloric acid (aq) was added to form a precipitate. The solid was filtered off, rinsed with water, and dissolved in DCM. The organic matter was washed with water and separated. Sodium sulfate was added to the organic matter, dried, filtered, and the solvent was removed under reduced pressure. The product compound 5-4 was obtained as a yellow solid (636 mg, 96%) after recrystallization from DCM / ethanol.

[0222] Synthesis of compound 6-4

[0223] In a three-necked flask, pyrene 6-1 (7.2 g, 20 mmol), intermediate A-3 (2.3 g, 10 mmol), NaOtBu (2.9 g, 30 mmol), tBu3P (101 mg, 0.5 mmol) and Pd(OAc)2 (56 mg, 0.25 mmol) were dissolved in 250 mL of toluene and heated to 120°C for 20 hours under a nitrogen atmosphere. After cooling to room temperature, DCM was added, the solution was rinsed with water, and the liquids were separated. The organic matter was dried over sodium sulfate, filtered, and evaporated under reduced pressure. The product was purified by silica gel column chromatography (10% DCM in hexane) to obtain the product aminopyrene 6-2 as a yellow solid (1.36 g, 27%).

[0224] A mixture of aminopyrene 6-2 (1080 mg, 2 mmol), intermediate A-2 (531 mg, 2.2 mmol), NaOtBu (577 mg, 6 mmol), tBu3P (40 mg, 0.2 mmol) and Pd(OAc)2 (22 mg, 0.1 mmol) was dissolved in 40 mL of toluene under inert conditions and heated at 120°C for 24 hours. The reaction was cooled to room temperature before adding DCM. The solution was rinsed with water and separated. The organic material was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The raw material was chromatographed on a silica gel column (20% DCM in hexane) to give the product pyrene 6-3 as a yellow solid (638 mg, 48%).

[0225] 5 mL of NaOH aqueous solution (50% w / w) was added to a dispersion of pyrene 6-3 (665 mg, 1 mmol), added to 20 mL of ethanol, and heated to 80 ° C for 24 hours. After cooling to room temperature, it was washed with DCM and a 37% w / w hydrochloric acid solution was added to form a yellow precipitate. The solid was filtered off, rinsed with water, and dissolved in DCM. The organic matter was washed with water and separated. Sodium sulfate was added to the organic matter, dried, filtered, and evaporated under reduced pressure to give the product compound 6-4 as a yellow-brown solid (636 mg, 99%).

[0226] Synthesis of compound 7-3

[0227] Under inert conditions, a mixture of anthracenecarboxylic acid 7-1 (6.0 g, 20 mmol), dibenzofuran boronic acid 7-2 (8.0 g, 30 mmol), potassium carbonate (200 mmol) and Pd(PPh3)4 (5%) was dissolved in 200 mL of 1,4-dioxane and 50 mL of water and heated to 100 ° C for 24 hours. After cooling to room temperature, it was washed with DCM and hydrochloric acid was added to form a yellow precipitate. The solid was filtered off, washed with water, and then dried in vacuo. The solid was recrystallized from ethanol to give the product compound 7-3 as yellow crystals (3.0 g, 34%).

[0228] Synthesis of compound 8-4

[0229] A solution of compound 8-1 (11.3 g, 20 mmol), intermediate A-3 (2.3 g, 10 mmol), NaOtBu (2.9 g, 30 mmol), tBu3P (101 mg, 0.5 mmol) and Pd(OAc)2 (56 mg, 0.25 mmol) was dissolved in 50 mL of toluene under inert conditions and stirred at 120°C for 6 hours. The reaction was cooled to room temperature and DCM was added. The organic phase was washed with water and separated. Sodium sulfate was added to the organic matter, dried, filtered, and evaporated under reduced pressure. The crude material was purified by silica gel column chromatography (10% ethyl acetate in hexane) to give the product compound 8-2 as a yellow solid (3.4 g, 48%).

[0230] In a three-necked flask, compound 8-2 (1.42 g, 2 mmol), intermediate A-2 (531 mg, 2.2 mmol), NaOtBu (577 mg, 6 mmol), tBu3P (40 mg, 0.2 mmol) and Pd(OAc)2 (22 mg, 0.1 mmol) were dissolved in 20 mL of toluene under a nitrogen atmosphere. The resulting mixture was stirred at 120°C for 16 hours and then cooled to room temperature. DCM was added, washed with water, and the liquids were separated. The organic material was dried over sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The residue was subjected to silica gel column chromatography (10% ethyl acetate in hexane) to afford the target compound 8-3 as a yellow solid (1.52 g, 87%).

[0231] Compound 8-3 (871 mg, 1 mmol) was dispersed in 20 mL of ethanol and 5 mL of aqueous NaOH (50% w / w) was added. The resulting mixture was stirred at 80 ° C for 4 hours and then washed with DCM at room temperature. Hydrochloric acid (37% water) was then added to form a white precipitate, which was filtered off and washed with water. The solid was dissolved in DCM, washed with water, and separated. Sodium sulfate was added to the organic matter and dried, filtered, and the solvent was removed under reduced pressure. The remaining solid was recrystallized from ethanol to obtain the product compound 8-4 as a light yellow solid (733 mg, 87%).

[0232] Synthesis of compound 9-4

[0233] Under inert conditions, compound 9-1 (11.3 g, 20 mmol), intermediate A-3 (2.3 g, 10 mmol), NaOtBu (2.9 g, 30 mmol), tBu3P (101 mg, 0.5 mmol), and Pd(OAc)2 (56 mg, 0.25 mmol) were dissolved in 50 mL of toluene and heated at 120°C for 6 hours. After the reaction was cooled to room temperature, DCM was added, and the organics were washed with water and separated. The organics were dried over sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The remaining material was purified by silica gel column chromatography (10% ethyl acetate in hexane) to obtain the product, compound 9-2, as a light yellow powder (2.35 g, 33%).

[0234] Compound 9-2 (1.42 g, 2 mmol), intermediate A-2 (531 mg, 2.2 mmol), NaOtBu (577 mg, 6 mmol), tBu3P (40 mg, 0.2 mmol) and Pd(OAc)2 (22 mg, 0.1 mmol) were dissolved in 20 mL of toluene and heated to 120°C for 20 hours under a protective gas atmosphere. The mixture was cooled to room temperature and diluted with DCM. The organic phase was washed with water and separated. Sodium sulfate was added to the organic matter and dried, filtered, and the solvent was removed under reduced pressure. The residue was chromatographed on a silica gel column (10% ethyl acetate in hexane) to give the product compound 9-3 as a yellow solid (1.6 g, 92%).

[0235] Compound 9-3 (871 mg, 1 mmol) was dispersed in 20 mL of ethanol and 5 mL of aqueous NaOH solution (50% w / w) was added. The mixture was stirred at 80 ° C for 6 hours, then became a clear solution and was cooled to room temperature. The solution was washed with DCM and 37% aqueous hydrochloric acid was added. The formed solid was filtered off, rinsed with water, and then dissolved in DCM. The organic phase was washed with water and separated. Sodium sulfate was added to the organic matter, dried, filtered, and concentrated in vacuo. The product compound 9-4 was recrystallized from ethanol as yellow crystals (565 mg, 67%).

[0236] Synthesis of compound 10-1

[0237] Magnesium (100 mg) and a small piece of solid iodine were placed in a three-necked flask equipped with a dropping funnel and a condenser, the air was exchanged with argon, and the funnel was filled with 10 mL of a dry solution of compound 1-2 (2 mmol) in 2-methyltetrahydrofuran. A small amount of the solution was added to the magnesium, which was then heated with an air gun. Once the reaction started, the remaining solution was added dropwise to keep the reaction going. After complete addition, the reaction was heated after stirring for 20 hours and then cooled. The Grignard solution was then transferred to a new three-necked flask, cooled to 0°C, and carbon dioxide gas was injected into the solution for 2 hours. The pH of the solution was raised to 12 with an aqueous NaOH solution, and the resulting mixture was washed with ether. HCl was then added to the water to reduce the pH to 2, ether was added, and the organic matter was washed with water. The solvent was removed under reduced pressure, and the residue was recrystallized from ethanol to give the product compound 10-1 as a yellow solid (136 mg, 12%).

[0238] Synthesis of compound 11-1

[0239] Magnesium (100 mg) and a small piece of solid iodine were placed in a three-necked flask equipped with a dropping funnel and a condenser, the air was exchanged with argon, and compound 2-2 (2 mmol) was dissolved in 10 mL of dry 2-methyltetrahydrofuran and filled into the dropping funnel. When a small amount of solution covered the magnesium, the reaction was started by heating with an air gun. The remaining solution was added dropwise, and the reaction was kept at reflux until the addition was complete. The reaction was then refluxed overnight, and the solution was then transferred to a dry flask filled with argon and cooled to 0°C. Gaseous carbon dioxide was then injected into the solution for two hours. Hydrochloric acid was added and extracted with ether. The solvent was removed under reduced pressure, and the residue was recrystallized from ethanol to obtain the product compound 11-1 as a solid (177 mg, 17%).

[0240] Example 2: Preparation of QD (LA1)

[0241] A quantum dot QD(OA) solution with oleic acid as a ligand was provided by Hefei Funa Technology Co., Ltd. The QD has a CdSe / ZnS core-shell structure, a particle size of about 10 nm, and the solvent is toluene.

[0242] To 0.5 mL of a 30 mg / mL QD(OA) toluene solution, add 4 mL (concentration 2 mg / mL) of LA1 toluene solution; the resulting solution is mixed by shaking to obtain a mixture of QD(LA1) and LA1. The mixture is transferred to a dialysis membrane (molecular cutoff: 3500 g / mol) and purified with pure toluene. The toluene is exchanged with fresh toluene several times until no free ligand is detected. The QD(LA1) solution is concentrated to 0.5 mL and used as the QD(LA1) stock solution.

[0243] QD(1-4)-QD(11-1) was prepared according to the same method as above.

[0244] Example 3: Measurement of the Absorption Spectrum of QD (LA1)

[0245] The absorption spectra of QD(OA) and QD(LA1) at the same concentration (0.6 mg / mL) in toluene solution were measured using a Pulse T9 UV / Vis spectrophotometer. The results are shown in Figure 2. At 460 nm, the absorption of QD(LA1) is 0.427, while that of QD(OA) is 0.126, more than three times that of QD(LA1). The data for QD(LA1), QD(OA), and QD(1-4)-QD(11-1) are shown in Table 1.

[0246] Table 1: Absorbance of 0.6 mg / ml QD toluene solution at 460 nm

[0247] Example 4: Light-emitting device

[0248] 30 mg of QD (LA1) was dissolved in 1 mL of resin solution and stirred for 30 minutes. The stirred solution was then dropped onto a glass substrate, spin-coated, and heated to cure to obtain a color conversion film with a thickness of 6 μm. The color conversion film was placed above an OLED blue light (460 nm) device and the spectrum was tested. The results showed an emission peak of 533 nm, a half-width of 25 nm, and a blue light absorptivity of 99%. The technical features of the above-described embodiments can be combined arbitrarily. To keep the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0249] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. An inorganic nanoluminescent material comprising a core composed of an inorganic semiconductor and at least one ligand, wherein at least one of the ligands comprises a structure of an organic compound H1, characterized in that: 1) the luminescence spectrum of the organic compound H1 and the absorption spectrum of the core at least partially overlap with each other; 2) the luminescence spectrum peak of the organic compound H1 is on the short-wavelength side of the luminescence spectrum peak of the core; 3) The half-peak width of the luminescence spectrum of the inorganic nano-luminescent body is less than or equal to 45 nm.

2. The inorganic nanoluminescent material according to claim 1, characterized in that The core is selected from one or any combination of CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe, CdZnSe, InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe, ZnCdSe, PbSe, PbTe, PbS, PbSnTe, and Tl2SnTe5.

3. The inorganic nanoluminescent material according to claim 1 or 2, characterized in that: The core is a heterojunction structure comprising two different semiconductors, and the heterojunction structure is a core / shell structure having at least one outer shell.

4. The inorganic nanoluminescent material according to any one of claims 1 to 3, characterized in that: At least one of the ligands has a structure represented by the following chemical formula (II): Wherein, n is an integer greater than or equal to 1, L0 is a single bond or a connecting group, and L1 is a terminal functional group capable of binding to the surface of the core.

5. The inorganic nanoluminescent material according to claim 4, characterized in that L1 may be the same or different in multiple occurrences and is selected from -OH, -SH, -NH2, -COOH, -P(O)(OH)2, -P(O)OH or -SO3H.

6. The inorganic nanoluminescent material according to any one of claims 1 to 5, characterized in that: The organic compound H1 is selected from any one of the following chemical formulas (III-1) to (III-21): in: X is selected from O, S, SO2, NR1 or CR2R3; Ar1-Ar4, when present multiple times, may be identical or different and may be selected from aromatic or heteroaromatic groups having 5 to 60 ring atoms; R0-R3, when present, may be identical or different and be selected from H or D, or a linear alkyl, haloalkyl, alkoxy, thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy group, silyl group having 3 to 20 carbon atoms, or a keto group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, or a 1-20 carbon atom alkyl group. The present invention also includes but is not limited to: a hydroxyl group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, I, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or an arylamine or heteroarylamine group having 5 to 40 ring atoms, a disubstituted unit at any position of the above groups, or a combination of these groups, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which the groups are bonded.

7. A composition comprising an inorganic nanoluminescent body as claimed in any one of claims 1 to 6, an organic solvent and / or an organic resin.

8. The composition according to claim 7, characterized in that The organic resin is a thermosetting resin or a light-curing resin.

9. A functional film comprising an inorganic nanoluminescent body as claimed in any one of claims 1 to 6 or prepared using a composition as claimed in any one of claims 7 to 8.

10. A photoelectric device comprising an inorganic nanoluminescent body according to any one of claims 1 to 6 or a functional film according to claim 9.

11. The optoelectronic device according to claim 10, wherein: The optoelectronic device comprises a light-emitting unit and a color conversion layer, wherein the color conversion layer comprises an inorganic nanoluminescent body as described in any one of claims 1 to 6 or is prepared using a composition as described in any one of claims 7 to 8.

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